Absorbing solution for separating and capturing carbon dioxide, and method for separating and capturing carbon dioxide in which same is used

Abstract

Disclosed is an absorbing liquid for separating and capturing carbon dioxide from a carbon dioxide-containing gas, the absorbing liquid containing: at least one alkanolamine represented by formula (1) ##STR00001##
wherein R.sup.1 represents hydrogen or C.sub.1-4 alkyl, R.sup.2 and R.sup.3 are identical or different and each represent hydrogen or C.sub.1-3 alkyl, R.sup.1, R.sup.2, and R.sup.3 are not all hydrogen, and n is 1 or 2; a low-molecular-weight diol compound and/or glycerin; and water.

Claims

1. An absorbing liquid for separating and capturing carbon dioxide from a carbon dioxide-containing gas, the liquid comprising: at least one alkanolamine represented by formula (1) ##STR00004## wherein R.sup.1 represents hydrogen or C.sub.1-4 alkyl, R.sup.2 and R.sup.3 are identical or different and each represent hydrogen or C.sub.1-3 alkyl, R.sup.1, R.sup.2, and R.sup.3 are not all hydrogen, and n is 1 or 2, wherein the at least one alkanolamine represented by formula (1) is an amine mixture of N-isopropylaminoethanol and 2-amino-2-methyl-1-propanol; a low-molecular-weight diol compound and/or glycerin, wherein the low-molecular-weight diol compound and/or glycerin is ethylene glycol and is present in an amount of from 10 wt % to 20 wt %; and water.

2. A method for separating and capturing carbon dioxide from a carbon dioxide-containing gas, the method comprising: bringing the absorbing liquid according to claim 1 into contact with a carbon dioxide-containing gas to obtain the absorbing liquid that has absorbed carbon dioxide from the carbon dioxide-containing gas; and heating the absorbing liquid that has absorbed carbon dioxide to desorb and regenerate carbon dioxide from the absorbing liquid and capture the desorbed carbon dioxide.

3. The method according to claim 2, wherein the absorbing liquid that has absorbed carbon dioxide is heated at a temperature of from 80 C. to 95 C. to desorb carbon dioxide.

4. The method of claim 2, wherein the carbon dioxide regenerated from the absorbing liquid is at least 99 vol %.

Description

DESCRIPTION OF EMBODIMENTS

(1) The following describes the present invention in detail.

(2) Absorbing Solution for Separating and Capturing Carbon Dioxide

(3) The absorbing liquid of the present invention comprises: at least one alkanolamine represented by formula (1)

(4) ##STR00003##
wherein R.sup.1 represents hydrogen or C.sub.1-4 alkyl, R.sup.2 and R.sup.3 are identical or different and each represent hydrogen or C.sub.1-3 alkyl, R.sup.1, R.sup.2, and R.sup.3 are not all hydrogen, and n is 1 or 2; a low-molecular-weight diol compound and/or glycerin; and water.

(5) R.sup.1 in formula (1) may be any of hydrogen or C.sub.1-4 linear or branched alkyl, and may specifically be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, or the like. Of these, hydrogen, ethyl, n-propyl, isopropyl, and n-butyl are preferable, with isopropyl being more preferable.

(6) In formula (1), n is 1 or 2, and more preferably 1.

(7) In formula (1), R.sup.2 and R.sup.3 may be any of hydrogen or C.sub.1-3 linear or branched alkyl, and may specifically be hydrogen, methyl, ethyl, n-propyl, or isopropyl. Of these, hydrogen and methyl are preferable.

(8) Specific alkanolamines represented by formula (1) include N-ethylaminoethanol, N-n-propylaminoethanol, N-isopropylaminoethanol, N-n-butylaminoethanol, 2-amino-1-propanol, N-isobutylaminoethanol, 2-amino-2-methyl-1-propanol, 3-ethylamino-1-propanol, 3-n-propylamino-1-propanol, 3-isopropylamino-1-propanol, 3-n-butylamino-1-propanol, and 3-isobutylamino-1-propanol. These can also be used on an industrial scale.

(9) The absorbing liquid of the present invention comprises at least one alkanolamine represented by formula (1) or an amine mixture containing two or more alkanolamines represented by formula (1).

(10) Examples of amine mixtures include amine mixtures of (I) an alkanolamine wherein R.sup.1 represents methyl, ethyl, n-propyl, isopropyl, or n-butyl, R.sup.2 and R.sup.3 each represent hydrogen, and n is 1 or 2, and (II) an alkanolamine wherein R.sup.1 represents hydrogen, R.sup.2 and R.sup.3 each represent methyl, and n is 1. Of these, an amine mixture of N-isopropylaminoethanol and 2-amino-2-methyl-1-propanol is preferable.

(11) The following describes the total amount of alkanolamine(s) in the absorbing liquid of the present invention.

(12) Typically, as the concentration of the amine component increases, the absorption amount, absorption rate, desorption amount, and desorption rate of carbon dioxide per unit volume of the liquid increase, and from the standpoint of energy consumption, plant equipment size, and efficiency, a higher concentration of the amine component is preferable. However, a weight concentration of the amine component exceeding 70% is likely to cause problems such as decreases in the absorption amount of carbon dioxide, decreases in the degree of mixedness of the amine component, and increases in viscosity, perhaps due to decreased surfactant action of water.

(13) In the absorbing liquid of the present invention as well, the total amount of alkanolamine(s) is preferably 60 wt % or less, given the problems such as decreases in the degree of mixedness of the amine component and increases in viscosity. From the standpoint of practical absorption performance and desorption performance, the total amount of alkanolamine(s) is preferably 30 wt % or more. The total amount of the alkanolamine(s) in the absorbing liquid of the present invention is selected from the range of preferably 30 to 60 wt %, more preferably 30 to 55 wt %, and particularly preferably 40 to 55 wt %.

(14) Examples of the low-molecular-weight diol compound include C.sub.2-8 aliphatic diol compounds (e.g., ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol), and ethylene glycol is preferable.

(15) The absorbing liquid of the present invention comprises at least either a low-molecular-weight diol compound or glycerin. When a low-molecular-weight diol compound is added, the low-molecular-weight diol compound for use may be a single low-molecular-weight diol compound or a combination of two or more low-molecular-weight diol compounds. Of the low-molecular-weight diol compound and glycerin, ethylene glycol is preferable. The total amount of the low-molecular-weight diol compound and glycerin in the absorbing liquid of the present invention is preferably 5 to 30 wt %, and more preferably 5 to 20 wt %.

(16) The absorbing liquid of the present invention comprises water.

(17) The content of water in the absorbing liquid of the present invention is not particularly limited, and the remaining liquid may be water.

(18) The water for use in the absorbing liquid of the present invention is not particularly limited, and distilled water, ion-exchanged water, tap water, groundwater, etc. can be suitably used.

(19) The absorbing liquid of the present invention may optionally comprise components other than the alkanolamine represented by formula (1), the low-molecular-weight diol, glycerin, and water as long as the effects of the present invention are not impaired. Other components include stabilizers for ensuring chemical or physical stability of the liquid (e.g., side reaction inhibitors such as antioxidants), degradation inhibitors for inhibiting the degradation of materials of devices or equipment used with the liquid of the present invention (e.g., corrosion inhibitors), and antifoaming agents (e.g., surfactants). The content of these components is not particularly limited as long as the effects of the present invention are not impaired.

(20) Examples of the carbon dioxide-containing gas include exhaust gases from thermal power plants using fuels such as heavy oil and natural gas, factory boilers, cement plant kilns, ironworks blast furnaces for reducing iron oxide with coke, and ironworks converters for burning carbon contained in pig iron to manufacture steel. The concentration of carbon dioxide in the gas is not particularly limited, and may typically be about 5 to 30 vol %, and particularly about 10 to 20 vol %. The concentration of carbon dioxide within these numerical ranges allows the effects of the present invention to be suitably achieved. The carbon dioxide-containing gas may contain impurity gases derived from sources such as water vapor and CO, in addition to carbon dioxide.

(21) Method for Absorbing and Capturing Carbon Dioxide

(22) The method for separating and capturing carbon dioxide of the present invention comprises step A of bringing the absorbing liquid into contact with a carbon dioxide-containing gas to obtain the absorbing liquid that has absorbed carbon dioxide from the carbon dioxide-containing gas, and step B of heating the absorbing liquid that has absorbed carbon dioxide obtained in step A to desorb and regenerate carbon dioxide from the absorbing liquid, and capturing the desorbed carbon dioxide.

(23) Step A: Step of Absorbing Carbon Dioxide

(24) In the present invention, the absorbing liquid is brought into contact with a carbon dioxide-containing gas, and the liquid thereby absorbs carbon dioxide. The method for bringing the absorbing liquid into contact with a carbon dioxide-containing gas to absorb carbon dioxide is not particularly limited, and examples include a method comprising bubbling a carbon dioxide-containing gas in the absorbing liquid to absorb carbon dioxide, a method comprising mist-spraying the absorbing liquid over a carbon dioxide-containing gas stream (misting or spraying method), and a method comprising bringing a carbon dioxide-containing gas into countercurrent contact with the absorbing liquid in an absorption tower containing a porcelain or metal mesh filler.

(25) Carbon dioxide in a carbon dioxide-containing gas is absorbed into the absorbing liquid at a temperature of typically about 60 C. or less, preferably about 50 C. or less, and more preferably in the range of about 20 to 45 C.

(26) As the temperature at which carbon dioxide in a carbon dioxide-containing gas is absorbed into the absorbing liquid decreases, the absorption amount of carbon dioxide increases. However, how far the temperature should be lowered is determined in accordance with the gas temperature of the carbon dioxide-containing gas, the heat recovery target, and the like. Because the absorption of carbon dioxide by amines is an exothermic reaction, increasing the absorption amount of carbon dioxide at low temperatures requires energy for cooling the absorbing liquid. Thus, the step of absorbing carbon dioxide is typically performed at a temperature of around 40 C.

(27) The step of absorbing carbon dioxide is typically performed under substantially atmospheric pressure. Although the absorption step can be performed under increased pressure to increase the performance in absorbing carbon dioxide, the step is preferably performed under atmospheric pressure to save energy consumption for increasing pressure.

(28) Step B: Step of Desorbing and Regenerating Carbon Dioxide

(29) In the present invention, the absorbing liquid that has absorbed carbon dioxide obtained in step A is heated to desorb carbon dioxide, and the desorbed pure or high-concentration carbon dioxide is captured.

(30) Examples of the method for desorbing and regenerating carbon dioxide from the absorbing liquid that has absorbed carbon dioxide include a method comprising heating and boiling the absorbing liquid in a vessel to desorb carbon dioxide, and a method comprising heating the absorbing liquid in a tray distillation tower, spray tower, or regeneration tower containing a porcelain or metal mesh filler to increase the liquid contact interface. These methods desorb carbon dioxide present in the form of bicarbonate ions in the absorbing liquid and regenerate the carbon dioxide as molecular carbon dioxide.

(31) When carbon dioxide is desorbed and regenerated from an absorbing liquid, and the absorbing liquid is a conventional aqueous liquid, the absorbing liquid is set to about 100 to 120 C. As the temperature of the absorbing liquid rises, the amount of desorbed carbon dioxide increases. However, raising the temperature requires additional energy to heat the absorbing liquid. The temperature is thus determined depending on the gas temperature, heat recovery target, and the like in the process of exhausting carbon dioxide-containing gases.

(32) In the present invention, when carbon dioxide is desorbed and regenerated from the absorbing liquid, the absorbing liquid may be about 70 to 120 C., or 70 to 95 C. For example, by optimizing the design of the regeneration tower to use low-grade waste heat, a sufficient amount of carbon dioxide can be desorded at a low temperature in the range of 80 to 95 C.

(33) The absorbing liquid from which carbon dioxide has been desorbed and captured in step B can be sent back to step A, and recycled.

(34) Action

(35) While substantially maintaining a high capture amount of carbon dioxide captured from a carbon dioxide-containing gas, the present invention can improve the amount of carbon dioxide desorbed at low temperatures from the absorbing liquid that has absorbed carbon dioxide. In particular, the present invention can achieve a sufficient desorption amount at temperatures within the range of 80 to 95 C., which is significantly lower than in the prior art.

(36) In addition, the present invention increases the desorption rate of carbon dioxide and the desorption amount of carbon dioxide relative to the absorption amount of carbon dioxide (which hereinafter may be referred to as regeneration efficiency in this specification), meaning that carbon dioxide can be captured at lower energy costs. The thus-captured carbon dioxide is highly pure (typically 99 vol % or more), and has applications in chemical and food industries. The carbon dioxide can also be sequestered underground in EOR (enhanced oil recovery) or CCS (carbon dioxide capture and storage), the commercial viability of which is currently being studied.

EXAMPLES

(37) The following Examples describe the present invention in more detail. However, the present invention is not limited to the Examples.

(38) In the Examples, alkanolamines, low-molecular-weight diol compounds, and glycerin for use are denoted as below. EGL: ethylene glycol Gly: glycerin 1,2-PD: 1,2-propanediol 1,3-PD: 1,3-propanediol 1,2-BD: 1,2-butanediol 1,4-BD: 1,4-butanediol TEG: triethylene glycol IPAE: N-isopropylaminoethanol AMP: 2-amino-2-methyl-1-propanol EAE: N-ethylaminoethanol NBAE: N-n-butylaminoethanol 2A1P: 2-amino-1-propanol

Example 1

(39) Ethylene glycol, water, and IPAE were mixed at a weight ratio of 10:35:55, thereby obtaining an absorbing liquid.

Example 2

(40) Ethylene glycol, water, and IPAE were mixed at a weight ratio of 20:25:55, thereby obtaining an absorbing liquid.

Example 3

(41) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 10:30:45:15, thereby obtaining an absorbing liquid.

Example 4

(42) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 10:35:47.5:7.5, thereby obtaining an absorbing liquid.

Example 5

(43) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 20:25:45:10, thereby obtaining an absorbing liquid.

Example 6

(44) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 10:35:42.5:12.5, thereby obtaining an absorbing liquid.

Example 7

(45) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 5:40:40:15, thereby obtaining an absorbing liquid.

Example 8

(46) Glycerin, water, IPAE, and AMP were mixed at a weight ratio of 5:40:40:15, thereby obtaining an absorbing liquid.

Examples 9 and 10

(47) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 10:35:40:15, thereby obtaining an absorbing liquid.

Examples 11 to 14

(48) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 15

(49) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 25:20:40:15, thereby obtaining an absorbing liquid.

Example 16

(50) 1,2-Propanediol, water, IPAE, and AMP were mixed at a weight ratio of 10:35:40:15, thereby obtaining an absorbing liquid.

Example 17

(51) 1,2-Butanediol, water, IPAE, and AMP were mixed at a weight ratio of 10:35:40:15, thereby obtaining an absorbing liquid.

Example 18

(52) Glycerin, water, IPAE, and AMP were mixed at a weight ratio of 10:35:40:15, thereby obtaining an absorbing liquid.

Example 19

(53) 1,2-Butanediol, water, IPAE, and AMP were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 20

(54) 1,3-Propanediol, water, IPAE, and AMP were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 21

(55) 1,4-Butanediol, water, IPAE, and AMP were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 22

(56) Triethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 23

(57) Ethylene glycol, water, IPAE, and AMP were mixed at a weight ratio of 20:35:35:10, thereby obtaining an absorbing liquid.

Example 24

(58) Ethylene glycol, water, IPAE, and EAE were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 25

(59) Ethylene glycol, water, IPAE, and NBAE were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Example 26

(60) Ethylene glycol, water, IPAE, and 2A1P were mixed at a weight ratio of 20:25:40:15, thereby obtaining an absorbing liquid.

Comparative Example 1

(61) Water and IPAE were mixed at a weight ratio of 45:55, thereby obtaining an absorbing liquid.

Comparative Example 2

(62) Water, IPAE, and AMP were mixed at a weight ratio of 45:40:15, thereby obtaining an absorbing liquid.

Comparative Example 3

(63) Water, IPAE, and AMP were mixed at a weight ratio of 45:40:15, thereby obtaining an absorbing liquid.

Comparative Example 4

(64) Water, IPAE, and EAE were mixed at a weight ratio of 45:40:15, thereby obtaining an absorbing liquid.

Comparative Example 5

(65) Water, IPAE, and NBAE were mixed at a weight ratio of 45:40:15, thereby obtaining an absorbing liquid.

Comparative Example 6

(66) Water, IPAE, and 2A1P were mixed at a weight ratio of 45:40:15, thereby obtaining an absorbing liquid.

(67) The alkanolamines, low-molecular-weight diol compounds, and glycerin used in the Examples and Comparative Examples above are brand-name reagent products from Tokyo Chemical Industry Co., Ltd., and other companies, and products of general purity were used. For IPAE, a product with a purity of 99% or more manufactured by Koei Chemical Co., Ltd., was used. The water for use was ion-exchanged water.

Test Example 1

(68) The absorbing liquids of Examples and Comparative Examples were measured for the absorption amount, desorption amount, and desorption rate of carbon dioxide. The measurement was performed with a carbon dioxide absorption and desorption apparatus to which a carbon dioxide gas cylinder (purity: 99.9%) and a nitrogen gas bottle (purity: 99.9%), a carbon dioxide gas flow rate controller and a nitrogen gas flow rate controller, a glass reactor (0.5 L), a mechanical stirrer and a temperature controller, a gas flowmeter, a chiller, and a carbon dioxide analyzer (Yokogawa, IR100) were sequentially connected.

(69) The glass reactor outside was surrounded by an inbuilt electric heater, so that the temperature of the absorbing liquid in the glass reactor could be freely controlled with the temperature controller.

(70) 0.1 L of an absorbing liquid was added to the glass reactor, and the gas in the upper part of the glass reactor was replaced by nitrogen gas. The absorbing liquid in the glass reactor was maintained at 40 C. While the liquid was fully stirred at a rotation frequency of 700 rpm, carbon dioxide gas at a flow rate of 0.14 L/min and nitrogen gas at a flow rate of 0.56 L/min were blown into the absorbing liquid in the glass reactor to start step A, and step A continued for 2 hours.

(71) After completion of step A, the absorbing liquid in the glass reactor was subsequently heated to 80 C. to 95 C. to start step B, and step B continued for 2 hours.

(72) In steps A and B, the exhaust gas from the glass reactor was analyzed with the carbon dioxide analyzer. The amount of carbon dioxide dissolved in the absorbing liquid (i.e., the absorption amount) was determined from a change in carbon dioxide concentration over time measured with the carbon dioxide analyzer. The amount of carbon dioxide desorbed from the absorbing liquid by heating was defined as a value determined by deducting the amount of desorbed carbon dioxide after 2 hours from the start of step B from the amount of absorbed carbon dioxide after 2 hours from the start of step A. The desorption rate of carbon dioxide desorbed from the absorbing liquid was defined as a change in the absorption amount of carbon dioxide per unit time during 10 minutes after the start of desorption of carbon dioxide in step B.

(73) Table 1 shows the compositions and measurement results of the absorbing liquids of the Examples and Comparative Examples.

(74) Absorbing liquids of the Examples exhibited significantly higher performance in the desorption rate and regeneration efficiency of carbon dioxide than the absorbing liquids of the Comparative Examples.

(75) The results reveal that absorbing liquids that comprise at least one alkanolamine represented by formula (1), a low-molecular-weight diol compound and/or glycerin, and water for separating and capturing carbon dioxide from a carbon dioxide-containing gas have excellent performance in the desorption rate and regeneration efficiency of carbon dioxide, as compared with conventional aqueous solutions, and that the absorbing liquids show promise for their excellent desorption performance particularly at low temperatures.

(76) TABLE-US-00001 TABLE 1 Regeneration Absorption Efficiency Tem- Absorption Desorption Desorption (%) Amount of Amount perature- Amount Rate Amount (Desorption Diol and of Desorption (g-CO.sub.2/kg- (g-CO.sub.2/kg- (g-CO.sub.2/kg- Amount/ Others Water Amine Composition Temperature Absorbing Absorbing Absorbing Absorption (wt %) (wt %) (wt %) ( C.) Liquid) Liquid/min) Liquid) Amount) Example 1 EGL_10 35 IPAE_55 40-90 120 11.2 115 96 Example 2 EGL_20 25 IPAE_55 40-90 109 10.4 100 92 Example 3 EGL_10 30 IPAE_45 + AMP_15 40-90 125 8.7 104 83 Example 4 EGL_10 35 IPAE_47.5 + AMP_7.5 40-90 123 10.6 110 89 Example 5 EGL_20 25 IPAE_45 + AMP_10 40-90 122 11.2 113 92 Example 6 EGL_10 35 IPAE_42.5 + AMP_12.5 40-90 124 10.8 120 97 Example 7 EGL_5 40 IPAE_40 + AMP_15 40-90 133 10.4 115 87 Example 8 Gly_5 40 IPAE_40 + AMP_15 40-90 131 10.4 109 84 Example 9 EGL_10 35 IPAE_40 + AMP_15 40-95 126 11.2 111 89 Example 10 EGL_10 35 IPAE_40 + AMP_15 40-90 125 10.8 114 91 Example 11 EGL_20 25 IPAE_40 + AMP_15 40-95 126 12.8 124 99 Example 12 EGL_20 25 IPAE_40 + AMP_15 40-90 123 11.6 122 99 Example 13 EGL_20 25 IPAE_40 + AMP_15 40-85 125 10.5 118 95 Example 14 EGL_20 25 IPAE_40 + AMP_15 40-80 123 7.8 101 82 Example 15 EGL_25 20 IPAE_40 + AMP_15 40-90 110 9.7 97 88 Example 16 1,2-PD_10 35 IPAE_40 + AMP_15 40-90 125 9.8 105 84 Example 17 1,2-BD_10 35 IPAE_40 + AMP_15 40-90 121 9.7 108 89 Example 18 Gly_10 35 IPAE_40 + AMP_15 40-90 120 9.5 105 88 Example 19 1,2-PD_20 25 IPAE_40 + AMP_15 40-90 120 10.0 107 89 Example 20 1,3-PD_20 25 IPAE_40 + AMP_15 40-90 118 8.6 110 94 Example 21 1,4-BD_20 25 IPAE_40 + AMP_15 40-90 117 9.1 112 96 Example 22 TEG_20 25 IPAE_40 + AMP_15 40-90 112 9.5 101 90 Example 23 EGL_20 35 IPAE_35 + AMP_10 40-90 113 9.3 97 86 Example 24 EGL_20 25 IPAE_40 + EAE_15 40-90 126 9.6 107 85 Example 25 EGL_20 25 IPAE_40 + NBAE_15 40-90 111 7.6 99 89 Example 26 EGL_20 25 IPAE_40 + 2A1P_15 40-90 134 9.4 106 79 Comparative 0 45 IPAE_55 40-90 140 9.4 122 87 Example 1 Comparative 0 45 IPAE_40 + AMP_15 40-90 137 6.5 117 85 Example 2 Comparative 0 45 IPAE_40 + AMP_15 40-80 139 5.1 99 71 Example 3 Comparative 0 45 IPAE_40 + EAE_15 40-90 150 4.8 100 67 Example 4 Comparative 0 45 IPAE_40 + NBAE_15 40-90 136 5.2 96 71 Example 5 Comparative 0 45 IPAE_40 + 2A1P_15 40-90 143 5.2 95 66 Example 6