Aqueous solution which efficiently absorbs and recovers carbon dioxide in exhaust gas, and method for recovering carbon dioxide using same

Abstract

Disclosed is an aqueous solution for absorbing and recovering carbon dioxide from a carbon dioxide-containing gas, the aqueous solution containing an amino alcohol compound represented by Formula 1 and an amine compound represented by Formula 2, ##STR00001## wherein R represents an alkyl group having 1 to 5 carbon atoms; and n represents 1 or 2, ##STR00002## wherein X represents NR1R2; Y represents NR3R4; R1, R2, R3 and R4 may be the same or different, and each represents an alkyl group having 1 to 3 carbon atoms; and m represents an integer of 3 to 7.

Claims

1. An aqueous solution for absorbing and recovering carbon dioxide from a carbon dioxide-containing gas, the aqueous solution comprising an amino alcohol compound represented by Formula 1 and an amine compound represented by Formula 2, ##STR00007## wherein R represents an alkyl group having 1 to 5 carbon atoms, and n represents 1 or 2, ##STR00008## wherein X represents NR1R2; Y represents NR3R4; R1, R2, R3 and R4 may be the same or different, and each represents an alkyl group having 1 to 3 carbon atoms; and m represents an integer of 3 to 7.

2. The aqueous solution according to claim 1 wherein the amino alcohol compound and the amine compound have a total concentration of 20 to 80% by weight; the amino alcohol compound has a concentration of 10 to 70% by weight; and the amine compound has a concentration of 1 to 50% by weight.

3. The aqueous solution according to claim 2 wherein the amino alcohol compound has a concentration of 30 to 60% by weight; and the amine compound has a concentration of 1 to 40% by weight.

4. The aqueous solution according to claim 1 wherein R of the amino alcohol compound represents an alkyl group having 2 to 4 carbon atoms; and m of the amine compound represents an integer of 5 to 7.

5. A method for absorbing and recovering carbon dioxide, the method comprising the steps of: (1) bringing the aqueous solution according to claim 1 into contact with a carbon dioxide-containing gas to absorb carbon dioxide from the gas; and (2) heating the aqueous solution obtained in step (I) containing absorbed carbon dioxide therein to release the carbon dioxide, thereby recovering the carbon dioxide.

Description

DESCRIPTION OF EMBODIMENTS

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

(2) Aqueous Solution for Absorbing and Recovering Carbon Dioxide

(3) The aqueous solution for absorbing and recovering CO.sub.2 from a CO.sub.2-containing gas according to the present invention contains an amino alcohol compound represented by Formula 1 and an amine compound represented by Formula 2,

(4) ##STR00005##
wherein R represents an alkyl group having 1 to 5 carbon atoms, and n represents 1 or 2,

(5) ##STR00006##
wherein X represents NR1R2; Y represents NR3R4; R1, R2, R3 and R4 may be the same or different, and each represents an alkyl group having 1 to 3 carbon atoms; and m represents an integer of 3 to 7.

(6) The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, and isopentyl. Preferably, R is an alkyl group having 2 to 4 carbon atoms, and examples thereof include ethyl, n-propyl, isopropyl, n-butyl, and isobutyl, with isopropyl, n-butyl, and isobutyl being more preferable.

(7) The alkyl group having 1 to 3 carbon atoms may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, and isopropyl. Preferably, R1, R2, R3, and R4 are methyl or ethyl.

(8) Preferably, m is 5 to 7, with 5 being more preferable.

(9) Examples of the amino alcohol compound represented by Formula 1 include N-ethylethanolamine, N-n-propylethanolamine, N-isopropylethanolamine, N-n-butylethanolamine, N-isobutylethanolamine, 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 be used in industrial applications.

(10) Examples of the amine compound represented by Formula 2 include N,N,N,N-tetramethyl-1,4-butanediamine, N,N,N,N-tetramethyl-1,5-pentanediamine, N,N,N,N-tetramethyl-1,6-hexanediamine, N,N,N,N-tetramethyl-1,8-octanediamine, N,N,N,N-tetraethyl-1,4-butanediamine, N,N,N,N-tetraethyl-1,5-pentanediamine, N,N,N,N-tetraethyl-1,6-hexanediamine, and N,N,N,N-tetraethyl-1,8-octanediamine. These can be used in industrial applications.

(11) The amino alcohol compound represented by Formula 1 and the amine compound represented by Formula 2 preferably have a total concentration of 20 to 80% by weight; the amino alcohol compound represented by Formula 1 preferably has a concentration of 10 to 70% by weight; and the amine compound represented by Formula 2 preferably has a concentration of 1 to 50% by weight. The amino alcohol compound represented by Formula 1 more preferably has a concentration of 30 to 60% by weight, and the amine compound represented by Formula 2 more preferably has a concentration of 1 to 40% by weight.

(12) If desired, the aqueous solution according to the present invention may contain a stabilizer (e.g., an antioxidant) to ensure the chemical or physical stability of the aqueous solution, or an inhibitor (e.g., a corrosion inhibitor) to prevent the deterioration of the materials of devices and equipment in which the aqueous solution of the present invention is used.

(13) The amino alcohol compound represented by Formula 1 and the amine compound represented by Formula 2 are commercially available, or are produced by known methods.

(14) Examples of the CO.sub.2-containing gas include: exhaust gases from thermal power plants, boilers of factories, kilns of cement factories using coal, heavy oil, natural gas or the like as a fuel, blast furnaces of ironworks where iron oxide is reduced with coke, converter furnaces of steel mills where carbon in pig iron is combusted to produce steel, integrated coal gasification combined cycle facilities, and the like; raw natural gases; and reformed gases. The gases typically have a concentration of CO.sub.2 in the range of about 5 to 30 vol %, and particularly about 6 to 25 vol %. When the concentration of CO.sub.2 is within such a range, the effect of the present invention is advantageously produced. The CO.sub.2-containing gas may contain, in addition to CO.sub.2, gases such as water vapor, CO, H.sub.2S, COS, SO.sub.2, NO.sub.2, hydrogen, and the like.

(15) Method for Absorbing and Recovering Carbon Dioxide

(16) The method for absorbing and recovering CO.sub.2 according to the present invention includes the following steps:

(17) (1) bringing the above-described aqueous solution into contact with a CO.sub.2-containing gas to absorb CO.sub.2 from the gas; and

(18) (2) heating the aqueous solution obtained in step (1) containing absorbed CO.sub.2 therein to release and recover CO.sub.2.

(19) Step of Absorbing Carbon Dioxide

(20) The method according to the present invention includes the step of bringing the above-described aqueous solution into contact with a CO.sub.2-containing gas to absorb CO.sub.2 from the gas. The method for bringing the aqueous solution of the present invention into contact with a CO.sub.2-containing gas to absorb CO.sub.2 is not particularly limited. Examples include a method comprising bubbling a CO.sub.2-containing gas in the aqueous solution to absorb CO.sub.2, a method comprising mist-spraying the aqueous solution over a CO.sub.2-containing gas stream (misting or spraying method), or a method comprising bringing the aqueous solution into countercurrent contact with a CO.sub.2-containing gas in an absorption tower that contains a porcelain or metal mesh filler.

(21) A CO.sub.2-containing gas is absorbed into the aqueous solution at a temperature typically in the range of from room temperature to 60 C., preferably 50 C. or less, and more preferably in the range of about 20 to 45 C. The lower the temperature, the larger the absorption amount. However, how far the temperature should be lowered is determined in accordance with the gas temperature of the exhaust gas, the heat recovery target, or the like. Carbon dioxide is typically absorbed at atmospheric pressure. Although it is possible to increase the pressure to a higher level in order to improve the absorption capacity, it is preferable to effect absorption at atmospheric pressure to suppress the energy consumption required for compression.

(22) The CO.sub.2-containing gas is the same as the aforementioned gas.

(23) Step of Releasing Carbon Dioxide

(24) The method according to the present invention includes the step of heating the aqueous solution obtained in the step of absorbing CO.sub.2 to thereby release and recover CO.sub.2.

(25) Examples of methods for recovering pure or high-concentration CO.sub.2 by releasing CO.sub.2 from an aqueous solution containing absorbed CO.sub.2 therein include a method comprising heating and boiling the aqueous solution in a vessel as in distillation, and a method comprising heating the aqueous solution in a plate distillation column, spray tower, or release tower containing a porcelain or metal mesh filler to increase the liquid contact interface. CO.sub.2 is thereby liberated and released from bicarbonate ions.

(26) CO.sub.2 is released at a solution temperature of typically 70 C. or more, preferably 80 C. or more, and more preferably about 90 to 120 C. The higher the temperature, the larger the absorption amount; however, an increase in temperature results in an increase in energy necessary for heating the absorbing solution. Therefore, the temperature is determined in accordance with the gas temperature during the process, the heat recovery target, or the like. The amine aqueous solution from which CO.sub.2 has been released is again sent to the CO.sub.2-absorbing step to recycle it. During this period, the heat applied in the CO.sub.2-releasing step is effectively used in the recycling process to increase the temperature of an aqueous solution that is to be sent to the CO.sub.2-releasing step through heat exchange, thereby resulting in the reduction of energy consumption in the entire recovery process.

(27) The thus recovered CO.sub.2 has a purity of typically 99 vol % or more, which means that it is extremely pure and can be used in the chemical industry or food industry. Further, the recovered CO.sub.2 can also be stored underground for EOR (Enhanced Oil Recovery) or CCS, which are presently being considered for practical use.

EXAMPLES

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

Example 1

(29) A glass-made gas washing bottle was immersed into a constant temperature water bath whose liquid temperature was set at 40 C. This bottle was filled with 50 g of an aqueous solution containing 50 wt % of 2-(isopropylamino)ethanol (IPAE, manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 wt % of N,N,N,N-tetramethyl-1,6-hexanediamine (TMHA, manufactured by Tokyo Chemical Industry Co., Ltd.). Into the aqueous solution, a gas mixture of 20 vol % of carbon dioxide and 80 vol % of nitrogen was introduced at a rate of 0.7 L/min at atmospheric pressure through a glass filter having a pore size of 100 m and a diameter of 13 mm to disperse the gas in the form of bubbles and effect absorption for 60 minutes.

(30) The CO.sub.2 concentration in the gas was continuously measured at the inlet and outlet of the absorbing solution using an infrared carbon dioxide meter (HORIBA GAS ANALYZER VA-3000), and the amount of absorbed CO.sub.2 was determined from the difference in the flow amount of CO.sub.2 between the inlet and the outlet. Where necessary, the amount of inorganic carbon in the absorbing solution was measured with a total organic carbon analyzer for gas chromatography (SHIMADZU TOC-VCSH), and compared with the value obtained by using the infrared carbon dioxide meter. The saturated absorption amount is defined as the amount of CO.sub.2 absorbed until the CO.sub.2 concentration at the outlet of the absorbing solution became equal to that at the inlet. Because the absorption rate varies depending on the absorption amount, the absorption rate at the time point at which CO.sub.2 was absorbed in an amount equal to of the saturated absorption amount was measured and compared. Subsequently, the temperature of the solution was increased to 70 C. over a few minutes in the same gas stream, and the amount of released CO.sub.2 was measured for 60 minutes under the same conditions.

(31) The quantity of heat generation was determined by diffusing at 40 C. a predetermined amount of CO.sub.2 into one of the reactors of two absorption devices of the same shape, each of which was equipped with a stirrer, and measuring, during this period, the difference in the quantity of generated heat between the two reactors using a differential calorimeter (DRC Evolution manufactured by SETARAM).

Examples 2 to 5

(32) Following the procedure of Example 1 and using an aqueous solution containing IPE and TMHA at the concentrations shown in Table 1 in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, quantity of heat generation, and released amount of CO.sub.2 were measured.

Example 6

(33) Following the procedure of Example 1 and using an aqueous solution containing 3-isopropylamino-1-propanol (IPAP) and TMHA at the concentrations shown in Table 2 in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, quantity of heat generation, and released amount of CO.sub.2 were measured.

Examples 7 to 9

(34) Following the procedure of Example 1 and using an aqueous solution containing IPAP and TMHA at the concentrations shown in Table 1 in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, and released amount of CO.sub.2 were measured.

Examples 10 to 12

(35) Following the procedure of Example 1 and using an aqueous solution containing 2-ethylamino-1-ethanol (EAE) and TMHA at the concentrations shown in Table 1 in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, and released amount of CO.sub.2 were measured.

(36) EAE is readily available commercially and is inexpensive as compared with IPAE; thus, EAE is advantageous in terms of the cost of absorbing solutions. As is apparent from the comparison with Comparative Examples 8 and 9, even when using EAE, the addition of the amine compound according to the present invention significantly increases the amount of CO.sub.2 released, which is a very important property or absorbing solutions.

Examples 13 to 15

(37) Following the procedure of Example 1 and using an aqueous solution containing IPAE and N,N,N,N-tetramethyl-1,4-butanediamine (TMBA, manufactured by Tokyo Chemical Industry Co., Ltd.) in place of the aqueous solution containing IPAE and TMHA, the saturated absorption amount and released amount of CO.sub.2 were measured. The results revealed that the saturated absorption amount and released amount of CO.sub.2 per unit amount of the absorbing solution were improved as compared with the use of an aqueous solution containing only IPAE.

Comparative Examples 1 to 3

(38) Following the procedure of Example 1 and using aqueous solutions individually containing 30, 55, and 60 wt % of IPAE only in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, quantity of heat generation, and released amount of CO.sub.2 were measured.

Comparative Example 4

(39) Following the procedure of Example 1 and using an aqueous solution containing 52 wt % of IPAE and 3 wt % of piperazine (PZ) in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, quantity of heat generation, and released amount of CO.sub.2 were measured.

Comparative Examples 5 and 6

(40) Following the procedure of Example 1 and using aqueous solutions individually containing 30 wt % and 50 wt % of TMHA in place of the aqueous solution containing 50 wt % of IPAE and 10 wt % of TMHA, the saturated absorption amount, absorption rate, quantity of heat generation, and released amount of CO.sub.2 were measured.

Comparative Example 7

(41) Following the procedure of Example 1 and using an aqueous solution containing 30 wt % of IPAP in place of the aqueous solution containing 50 wt % of IPAP and 10 wt % of TMHA, the saturated absorption amount, and released amount of CO.sub.2 were measured.

Comparative Examples 8 and 9

(42) Following the procedure of Example 1 and using aqueous solutions individually containing 30 wt % and 54 wt % of EAE in place of the aqueous solution containing 50 wt % of EAE and 10 wt % of TMHA, the saturated absorption amount, and released amount of CO.sub.2 were measured.

(43) Table 1 shows the results of Examples 1 to 15 and Comparative Examples of 1 to 9. The symbol % used in Table 1 denotes wt %.

(44) TABLE-US-00001 TABLE 1 CO.sub.2 Absorption Performance CO.sub.2 Release at 40 C. Performance CO.sub.2 Saturated Quantity of at 70 C. Composition of Aqueous Solution Absorption CO.sub.2 Absorption Heat Released (by Weight) Amount (g/kg Rate Generation Amount (g/kg Compound 1 Compound 2 Aqueous Solution) (g/kg/min) (kj/mol CO.sub.2) Aqueous Solution) Example 1 IPAE 50% TMHA 10% 156 4.6 65.0 91 Example 2 IPAE 55% TMHA 15% 132 4.0 91 Example 3 IPAE 40% TMHA 5% 146 5.0 67.6 68 Example 4 IPAE 20% TMHA 30% 121 4.5 77 Example 5 IPAP 53% TMHA 2% 154 4.1 76.6 84 Example 6 IPAP 50% TMHA 1% 146 5.0 70.8 54 Example 7 IPAP 50% TMHA 10% 148 3.2 56 Example 8 IPAP 45% TMHA 7.5% 147 3.0 55 Example 9 IPAP 35% TMHA 20% 138 4.3 63 Example 10 EAE 50% TMHA 10% 157 5.2 30 Example 11 EAE 45% TMHA 7.5% 149 5.3 34 Example 12 EAE 35% TMHA 20% 156 5.1 42 Example 13 IPAE 60% TMBA 10% 150 3.5 85 Example 14 IPAE 45% TMBA 7.5% 148 4.2 80 Example 15 IPAE 40% TMBA 5% 143 4.8 69 Comp. Ex 1 IPAE 30% 98.6 5.0 76.6 35 Comp. Ex 2 IPAE 55% 100.0 3.2 72.8 32 Comp. Ex 3 IPAE 60% 100.6 2.9 71.5 29 Comp. Ex 4 IPAE 52% PZ 3% 136.2 4.6 76.2 48 Comp. Ex 5 TMHA 30% 73 3.8 67.2 13 Comp. Ex 6 TMHA 50% 102 2.2 36 Comp. Ex 7 IPAP 30% 98 19 Comp. Ex 8 EAE 30% 102 21 Comp. Ex 9 EAE 54% 150 23

Results of Example 1

(45) The saturated absorption amount of CO.sub.2 was 156 g per kg of the aqueous solution at a temperature of 40 C. The released amount of CO.sub.2 was 91 g per kg of the absorbing solution at a temperature of 70 C. The recovered CO.sub.2 had a purity of 99.8%. The results revealed that the saturated absorption amount and released amount per unit amount of the absorbing solution were significantly larger than those of Comparative Example 1. Thus, the performance of the absorbing solution of the present invention was recognized.

Results of Comparative Examples 1 to 3

(46) The absorption rate was high at a low concentration of 30 wt %; however, a significant decrease in the absorption rate was observed at a concentration of 60 wt %. All of the solutions of Comparative Examples 1 to 3 exhibited a lower saturated absorption amount and released amount than those of Examples 1 to 5.

Results of Comparative Example 4

(47) Piperazine is known as a reaction activator for the absorption of CO.sub.2 by using an alkanolamine aqueous solution, and exerts an improving effect on the saturated absorption amount and absorption rate. The results shown in Table 1 reveal that the solutions of Examples 1 to 5 are advantageous in terms of the released amount.

Results of Comparative Examples 5 and 6

(48) The aqueous solutions containing only TMHA did not exert a sufficient effect on the released amount at a concentration of 30 wt %. The absorption rate was considerably decreased at a concentration of 50 wt %. The results shown in Table 1 reveal that the solutions of the Examples were advantageous.

Results of Comparative Example 7

(49) The released amount was smaller than that of Examples 6 to 9.

Results of Comparative Examples 8 and 9

(50) The solutions of Comparative Examples 8 and 9 both exhibited smaller released amounts than those of Examples 10 to 12.

Test Example 1

(51) The aqueous solution of Example 1 was tested for corrosion of an SS400 metal test piece. The test was conducted using a Hastelloy autoclave under a CO.sub.2-saturated atmosphere at 130 C. for 48 hours. As a result, the corrosion caused by the aqueous solution of Example 1 on the SS400 was total corrosion, and the calculated corrosion rate was 0.13 mm/year. The results revealed that the aqueous solution of Example 1 is slightly corrosive.