CO2 RECOVERY UNIT AND CO2 RECOVERY METHOD

Abstract

A CO2 recovery unit and a CO2 recovery method capable of having an excellent CO2 absorption rate and saving energy are provided. A CO2 recovery unit of the invention includes: a CO2 absorber which includes an upper CO2 absorption unit obtaining a CO2 absorbent by causing a flue gas containing CO2 to contact a CO2 absorbent and a lower CO2 absorption unit obtaining a CO2 absorbent by causing the CO2 absorbent to contact a flue gas containing CO2; a CO2 absorbent regenerator which obtains the CO2 absorbent by heating the CO2 absorbent a thermometer which measures a temperature of the CO2 absorbent supplied from the CO2 absorber to the CO2 absorbent regenerator; and a control device which controls a temperature of the CO2 absorbent supplied to the lower CO2 absorption unit based on the temperature of the CO2 absorbent measured by the thermometer.

Description

FIELD

The present invention relates to a CO₂ recovery unit and a CO₂ recovery method and particularly to a CO₂ recovery unit and a CO₂ recovery method which recover CO₂ in a gas to be treated by using a CO₂ absorbent.

BACKGROUND

Hitherto, there has been proposed a direct-reduced iron reduction system including an acid gas removing device for removing an acid element in a reducing furnace flue gas corresponding to a synthetic gas discharged from a direct reducing furnace (for example, see Patent Literature 1). In this direct-reduced iron reduction system, the reducing furnace flue gas having a high CO₂ partial pressure (for example, 50 kPa to 200 kPa) and discharged from the direct reducing furnace is caused to contact an acid gas absorbent in an acid gas element-absorber so that an acid gas element in the reducing furnace flue gas is removed therefrom. The acid gas absorbent having the acid gas element absorbed thereto is heated in a regenerator to discharge the acid gas element in the acid gas absorbent therefrom so that the acid gas absorbent is regenerated. Further, there is also proposed an acid gas removing facility which removes an acid element contained in a natural gas (for example, see Non Patent-Literature 1).

CITATION LIST

Patent Literature

Patent Literature 1: Japanese Laid-open Patent Publication No. 2013-108109

Non Patent Literature

Non Patent Literature 1: Liquefying Plant Essential Knowledge For Understanding LNG Business (http://oilgas-info.jogmec.go.jp/pdf/0/598/200503_001a.pdf)

SUMMARY

Technical Problem

Incidentally, a CO₂ recovery unit which recovers CO₂ in a combustion flue gas having a relatively low CO₂ partial pressure (for example, 10 kPa to 15 kPa) and discharged from a boiler or the like by using a CO₂ absorbent is used in a thermal power station or the like. Likewise, various methods have been examined in order to save energy. In recent years, it is desirable to develop a technology capable of having a small CO₂ recovery heat amount involved with a steam consumption amount and realizing energy saving even when CO₂ in a synthetic gas having a relatively high CO₂ partial pressure is recovered by a CO₂ absorbent or CO₂ in a natural gas (a methane gas) containing CO₂ is recovered by a CO₂ absorbent.

This invention is contrived in view of such circumstances and an object of the invention is to provide a CO₂ recovery unit and a CO₂ recovery method capable of both having an excellent CO₂ absorption rate and saving energy.

Solution to Problem

A CO₂ recovery unit according to the present invention comprising: a CO₂ absorber which includes a first CO₂ absorption unit obtaining a first CO₂ absorbent by causing a CO₂ containing gas to be treated to contact a CO₂ absorbent so that CO₂ contained in the gas to be treated is absorbed to the CO₂ absorbent and a second CO₂ absorption unit obtaining a second CO₂ absorbent by causing the first CO₂ absorbent to contact a CO₂ containing gas to be treated so that CO₂ contained in the gas to be treated is absorbed to the first CO₂ absorbent; a CO₂ absorbent regenerator which regenerates a CO₂ absorbent by heating the second CO₂ absorbent so that CO₂ is discharged from the second CO₂ absorbent; a temperature measurement device which measures a temperature of the second CO₂ absorbent supplied from the CO₂ absorber to the CO₂ absorbent regenerator; and a control device which controls a temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit based on the temperature of the second CO₂ absorbent measured by the temperature measurement device.

According to this configuration, since the temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit is controlled based on the temperature of the second CO₂ absorbent supplied to the CO₂ absorbent regenerator, the CO₂ absorption rate of the CO₂ absorbent in the second CO₂ absorption unit can be increased. Accordingly, the CO₂ recovery unit can have an excellent CO₂ absorption rate and save energy even when a synthetic gas having a high CO₂ partial pressure in a gas to be treated is treated. Here, the absorption rate indicates a CO₂ absorption molar amount per 1 mol of an absorbent.

In the CO₂ recovery unit according to present invention, it is preferable that the control device controls the temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit so that the temperature is equal to or higher than 50° C. and equal to or lower than 60° C. With this configuration, since the CO₂ recovery unit controls the temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit within an appropriate range, the CO₂ absorption rate of the gas to be treated in the second CO₂ absorption unit is further improved and the circulation amount of the CO₂ absorbent can be decreased in accordance with the improved CO₂ absorption rate. Accordingly, the amount of steam necessary to regenerate the CO₂ absorbent can be decreased. With this configuration, the temperature of the CO₂ absorbent supplied to the CO₂ absorbent regenerator can be appropriately increased and thus an effect of decreasing a steam consumption amount is expected.

In the CO₂ recovery unit according to present invention, it is preferable that a CO₂ partial pressure of the CO₂ containing gas to be treated is 50 kPa or more. With this configuration, since the CO₂ recovery unit controls the CO₂ partial pressure in the gas to be treated within an appropriate range, the CO₂ absorption rate using the first CO₂ absorbent in the second CO₂ absorption unit is further improved.

In the CO₂ recovery unit according to present invention, it is preferable that a ratio (the first CO₂ absorption unit:the second CO₂ absorption unit) between a filling material charging height in the first CO₂ absorption unit and a filling material charging height in the second CO₂ absorption unit is equal to or larger than 1:3 and equal to or smaller than 3:1. With this configuration, since the CO₂ absorption rate in the gas to be treated using the CO₂ absorbent is further improved, energy can be saved.

A CO₂ recovery method according to the present invention comprising: obtaining a first CO₂ absorbent by causing a CO₂ containing gas to be treated to contact a CO₂ absorbent in a first CO₂ absorption unit of a CO₂ absorber so that CO₂ contained in the gas to be treated is absorbed to the CO₂ absorbent and obtaining a second CO₂ absorbent by causing the first CO₂ absorbent to contact the CO₂ containing gas to be treated in a second CO₂ absorption unit of the CO₂ absorber so that CO₂ contained in the gas to be treated is absorbed to the first CO₂ absorbent; regenerating a CO₂ absorbent by heating the second CO₂ absorbent in a CO₂ absorbent regenerator so that CO₂ is discharged from the CO₂ absorbent; and measuring a temperature of the second CO₂ absorbent supplied from the CO₂ absorber to the CO₂ absorbent regenerator and controlling a temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit based on the measured temperature of the second CO₂ absorbent.

According to this method, since the temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit is controlled based on the temperature of the second CO₂ absorbent supplied to the CO₂ absorbent regenerator, the CO₂ absorption rate of the CO₂ absorbent in the second CO₂ absorption unit can be increased. Accordingly, the CO₂ recovery method can have an excellent CO₂ absorption rate and save energy even when a synthetic gas having a high CO₂ partial pressure in a gas to be treated is treated.

In the CO₂ recovery method according to present invention, it is preferable that the temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit is controlled so that the temperature is equal to or higher than 50° C. and equal to or lower than 60° C. With this method, since the CO₂ recovery unit controls the temperature of the first CO₂ absorbent supplied to the second CO₂ absorption unit within an appropriate range, the CO₂ absorption rate of the gas to be treated in the second CO₂ absorption unit is further improved and the circulation amount of the CO₂ absorbent can be decreased in accordance with the improved CO₂ absorption rate. Accordingly, the amount of steam necessary to regenerate the CO₂ absorbent can be decreased. With this configuration, the temperature of the CO₂ absorbent supplied to the CO₂ absorbent regenerator can be appropriately increased and thus an effect of decreasing a steam consumption amount is expected.

In the CO₂ recovery method according to present invention, it is preferable that a CO₂ partial pressure of the CO₂ containing gas to be treated is 50 kPa or more. With this method, since the CO₂ recovery method controls the CO₂ partial pressure in the gas to be treated within an appropriate range, the CO₂ absorption rate in the gas to be treated using the first CO₂ absorbent in the second CO₂ absorption unit is further improved.

In the CO₂ recovery method according to present invention, it is preferable that a ratio (the first CO₂ absorption unit:the second CO₂ absorption unit) between a filling material charging height in the first CO₂ absorption unit and a filling material charging height in the second CO₂ absorption unit is equal to or larger than 1:3 and equal to or smaller than 3:1. With this method, since the CO₂ absorption rate in the gas to be treated using the CO₂ absorbent is further improved, energy can be saved.

Advantageous Effects of Invention

According to the invention, it is possible to realize a CO₂ recovery unit and a CO₂ recovery method both having an excellent CO₂ absorption rate and realizing energy saving.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram illustrating a CO₂ recovery unit according to an embodiment of the invention.

FIG. 2 is a diagram illustrating a relation between a temperature of a CO₂ absorbent (a semi-rich solution) supplied to a lower CO₂ absorption unit and a ratio of a CO₂ absorption rate of a rich solution.

FIG. 3 is a diagram illustrating a relation between a temperature of a CO₂ absorbent (a semi-rich solution) supplied to a lower CO₂ absorption unit and a ratio of a heat amount necessary to regenerate the CO₂ absorbent.

FIG. 4 is a diagram illustrating a relation between a temperature of a CO₂ absorbent (a semi-rich solution) supplied to a lower CO₂ absorption unit and a temperature of a CO₂ absorbent (a rich solution) supplied to a CO₂ absorbent regenerator.

FIG. 5 is a diagram illustrating a relation of filling material charging height ratios of a lower CO₂ absorption unit and an upper CO₂ absorption unit of a CO₂ absorber with respect to a ratio of a CO₂ absorption rate of a rich solution.

DESCRIPTION OF EMBODIMENTS

The present inventors have paid attention to a conventional CO₂ recovery unit which recovers CO₂ from a gas having a relatively low CO₂ partial pressure (for example, 10 kPa to 15 kPa) such as a combustion flue gas discharged from a boiler of a thermal power station and does not recover CO₂ from a synthetic gas having a relatively high CO₂ partial pressure (for example, 50 kPa to 200 kPa) and discharged from a direct reducing furnace. Then, the present inventors have found that a CO₂ recovery unit and a CO₂ recovery method capable of both having an excellent CO₂ absorption rate and saving energy are obtained by a configuration in which a CO₂ absorber is provided with a plurality of CO₂ absorption units and a temperature of a CO₂ absorbent supplied to the plurality of CO₂ absorption units is controlled based on a temperature of a CO₂ absorbent supplied to a CO₂ absorbent regenerator when CO₂ is recovered from a synthetic gas having a relatively high CO₂ partial pressure, whereby the invention is obtained.

Hereinafter, an embodiment of the invention will be described in detail with reference to the accompanying drawings. The invention is not limited to the embodiments below and can be appropriately modified. Further, the components of the CO₂ recovery unit according to the embodiments below can be appropriately combined with one another.

FIG. 1 is a schematic diagram illustrating a CO₂ recovery unit according to an embodiment of the invention. As illustrated in FIG. 1, a CO₂ recovery unit 1 is an apparatus which recovers CO₂ in a reducing furnace flue gas (a gas to be treated) 11A, corresponding to a synthetic gas discharged from a direct reducing furnace, in the form of a high-concentration CO₂ gas. The CO₂ recovery unit 1 includes a cooling tower 12 which cools a flue gas 11A containing CO₂ discharged from a direct reducing furnace, a CO₂ absorber 14 which is provided at a rear stage of the cooling tower 12 and causes the cooled flue gas 11A to contact a CO₂ absorbent 13 so that CO₂ in the flue gas 11A is absorbed to the CO₂ absorbent 13 to be removed from the flue gas, and a CO₂ absorbent regenerator 15 which is provided at a rear stage of the CO₂ absorber 14 and discharges CO₂ from a CO₂ absorbent 13C having CO₂ absorbed thereto to regenerate the CO₂ absorbent 13.

In the CO₂ recovery unit 1, the CO₂ absorbent 13 is circulated between the CO₂ absorber 14 and the CO₂ absorbent regenerator 15. The CO₂ absorbent 13 (a lean solution) is supplied as the CO₂ absorbent 13C having CO₂ absorbed thereto (a rich solution) in the CO₂ absorber 14 to the CO₂ absorbent regenerator 15. Further, CO₂ is removed from the CO₂ absorbent 13C (the rich solution) by the CO₂ absorbent regenerator 15 and a resultant gas is supplied as the regenerated CO₂ absorbent 13 (the lean solution) to the CO₂ absorber 14.

The cooling tower 12 includes a cooling unit 121 which cools the flue gas 11A. Further, a circulation line L₁ is provided between a bottom portion of the cooling tower 12 and a top portion of the cooling unit 121. The circulation line L₁ is provided with a heat exchanger 122 which cools cooling water W₁, a circulation pump 123 which circulates the cooling water W₁ in the direction line L₁, and an adjustment valve 124 which adjusts the amount of a waste liquid separated as a liquid from the circulation line L₁ and discharged therefrom.

In the cooling unit 121, the flue gas 11A is cooled by a counterflow contact between the flue gas 11A and the cooling water W₁ and thus a cooled flue gas 11B is obtained. The heat exchanger 122 cools the cooling water W₁ which is heated by exchanging heat with the flue gas 11A. The circulation pump 123 supplies the cooling water W₁ flowing down to the bottom portion of the cooling tower 12 through the heat exchanger 122 to a top portion of the cooling unit 121. In the cooling tower 12, when the amount of moisture in the flue gas 11A is small, a liquid level of the cooling tower 12 decreases and thus water is supplied from a tower top portion. Further, when the amount of the moisture in the flue gas 11A is large, the liquid level of the cooling tower 12 increases and thus a part of the cooling water W₁ circulated in the circulation line L₁ is separated as waste liquid.

The CO₂ absorber 14 includes a CO₂ absorption unit 141 which is provided in a lower portion of the CO₂ absorber 14 and to which the CO₂ absorbent 13 and the flue gas 11B cooled by the cooling tower 12 are supplied, and a water washing unit 142 which is provided in an upper portion of the CO₂ absorber 14.

The CO₂ absorption unit 141 includes a lower CO₂ absorption unit (a second CO₂ absorption unit) 141A which is provided in a lower portion of the CO₂ absorption unit 141 and an upper CO₂ absorption unit 141B (a first CO₂ absorption unit) which is provided in an upper portion of the CO₂ absorption unit 141. A filling material is charged into the lower CO₂ absorption unit 141A at a charging height H1. A filling material is charged into the upper CO₂ absorption unit 141B at a charging height H2. The CO₂ absorbent 13 which is regenerated by the CO₂ absorbent regenerator 15 is supplied to the upper CO₂ absorption unit 141B. A CO₂ absorbent 13B which absorbs CO₂ in a flue gas 11C by the upper CO₂ absorption unit 141B is supplied to the lower CO₂ absorption unit (the second CO₂ absorption unit) 141A.

A liquid storage unit 143A, which stores a CO₂ absorbent (a first CO₂ absorbent) 13A flowing down from the upper CO₂ absorption unit 141B and staying at a lower portion of the upper CO₂ absorption unit 141B, and a chimney tray 143B are provided between the lower CO₂ absorption unit 141A and the upper CO₂ absorption unit 141B. The liquid storage unit 143A is provided with an extraction line L₁₁ which extracts the CO₂ absorbent 13A stored in the liquid storage unit 143A from the CO₂ absorber 14 and supplies the liquid to the lower CO₂ absorption unit 141A.

The extraction line L₁₁ is provided with a heat exchanger 24 which cools the CO₂ absorbent 13A to obtain the cooled CO₂ absorbent 13B and a pump 25 which supplies the CO₂ absorbent 13A as the CO₂ absorbent 13B to the lower CO₂ absorption unit 141A. The heat exchanger 24 is configured to adjust a refrigerant supply amount by a control device 101. Further, the pump 25 is configured to adjust the amount of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A by the control device 101. The control device 101 can be realized by, for example, a general or dedicated computer such as a CPU (Central Processing Unit), a ROM (Read Only Memory)/and a RAM (Random Access Memory) and a program operated on this computer.

A bottom portion of the water washing unit 142 is provided with a liquid storage unit 144A which stores washing water W₂ for washing a flue gas 11D obtained by removing CO₂ therefrom in the flue gas 11C. A circulation line L₂ which supplies the washing water W₂ containing the CO₂ absorbent 13 recovered by the liquid storage unit 144A from a top portion of the water washing unit 142 so that the washing water is circulated is provided between the liquid storage unit 144A and the water washing unit 142. The circulation line L₂ is provided with a heat exchanger 21 which cools the washing water W₂ and a circulation pump 22 which circulates the washing water W₂ containing the CO₂ absorbent 13 recovered by the liquid storage unit 144A through the heat exchanger 21 so that the washing water is circulated in the circulation line L₂. Further, the circulation line L₂ is provided with an extraction line L₃ which extracts a part (washing water W₃) of the washing water W₂ and supplies the water to the CO₂ absorbent 13 (the lean solution). The extraction line L₃ is provided with an adjustment valve 23 which adjusts the amount of the washing water W₃ supplied to the CO₂ absorbent 13.

In the CO₂ absorption unit 141, a counterflow contact between the flue gas 11A containing CO₂ by the upper CO₂ absorption unit 141B and the CO₂ absorbent 13 containing alkanolamine occurs. Accordingly, CO₂ in the flue gas 11C is absorbed to the CO₂ absorbent 13 by a chemical reaction expressed in the following formula. As a result, CO₂ in the flue gas 11C is removed so that the flue gas 11C becomes the flue gas 11D obtained by removing CO₂ therefrom and the CO₂ absorbent 13 becomes the CO₂ absorbent 13A. Then, in the lower CO₂ absorption unit 141A, a counterflow contact between the flue gas 11B containing CO₂ and the CO₂ absorbent 13B having CO₂ absorbed thereto occurs. Accordingly, CO₂ in the flue gas 11B is absorbed to the CO₂ absorbent 13B by the chemical reaction expressed in the following formula. As a result, CO₂ in the flue gas 11B is removed so that the flue gas 11B becomes the flue gas 11C of which a CO₂ concentration is decreased and the CO₂ absorbent 13B becomes the CO₂ absorbent 13C. In this way, when the flue gas 11B containing CO₂ passes through the CO₂ absorption unit 141, the flue gas 11D obtained by removing CO₂ therefrom is obtained. Further, the CO₂ absorbent 13 absorbs CO₂ to become the CO₂ absorbent 13B (the semi-rich solution) in the upper CO₂ absorption unit 141B and the CO₂ absorbent 13B further absorbs CO₂ to become the CO₂ absorbent 13C (the rich solution) in the lower CO₂ absorption unit 141A.

R—NH₂+H₂O+CO₂→R—NH₃HCO₃

In the water washing unit 142, the flue gas 11D obtained by removing CO₂ therefrom after passing through the upper CO₂ absorption unit 141B rises through a chimney tray 144B. Then, a gas-liquid contact occurs between the flue gas 11D and the washing water W₂ supplied from the top portion of the water washing unit 142 so that a flue gas 11B is obtained by recovering the CO₂ absorbent 13 accompanied by the flue gas 11D through circulating and washing processes. After mist in the flue gas 11E is trapped by a mist eliminator 145, the flue gas is discharged to the outside from a tower top portion 14a of the CO₂ absorber 14.

A rich solution supply pipe 50 which supplies the CO₂ absorbent 13C having CO₂ absorbed thereto (the rich solution) in the CO₂ absorber 14 to an upper portion of the CO₂ absorbent regenerator 15 is provided between a tower bottom portion 14b of the CO₂ absorber 14 and the upper portion of the CO₂ absorbent regenerator 15. The rich solution supply pipe 50 is provided with a thermometer (a temperature measurement device) 102 which measures a temperature of the CO₂ absorbent 13C, a rich solution pump 51 which supplies the CO₂ absorbent 13C having CO₂ absorbed thereto in the CO₂ absorber 14 to the CO₂ absorbent regenerator 15, and a rich-lean solution heat exchanger 52 which heats the CO₂ absorbent 13C by the CO₂ absorbent 13 (the lean solution) heated by the CO₂ absorbent regenerator 15 to remove CO₂ therefrom. The control device 101 adjusts the amount of a refrigerant supplied to the heat exchanger 24 based on a temperature of the CO₂ absorbent 13C measured by the thermometer 102 and controls the amount of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A by the pump 25. Additionally, the thermometer 102 may be provided at a position where the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A can be controlled by the control device 101. For example, the thermometer may be provided at a rear stage of the heat exchanger 24 of the extraction line L₁₁.

A CO₂ absorbent supply unit 151 to which the CO₂ absorbent 13C having CO₂ absorbed thereto is supplied is provided at a enter portion of the CO₂ absorbent regenerator 15. A tower bottom portion 15b of the CO₂ absorbent regenerator 15 is provided with a circulation line L₄ which circulates the CO₂ absorbent 13C flowing down to the tower bottom portion. The circulation line L₄ is provided with a regenerating heater 31 which heats the CO₂ absorbent 13 by saturated steam S, an adjustment valve 32 which supplies the saturated steam S to the regenerating heater 31, and a circulation pump 33 which supplies the CO₂ absorbent 13 of a tower bottom portion of the CO₂ absorbent regenerator 15 to a lower portion of the CO₂ absorbent supply unit 151 of the CO₂ absorbent regenerator 15 through the regenerating heater 31.

A tower top portion 15a of the CO₂ absorbent regenerator 15 is provided with a gas discharge line L₅ which discharges a CO₂ gas 41 accompanying steam. The gas discharge line L₅ is provided with a condenser 42 which condenses moisture in the CO₂ gas 41 and a separation drum 43 which separates water W₅ condensed by the CO₂ gas 41. A CO₂ gas 44 from which the condensed water W₅ is separated is discharged to the outside from the upper portion of the separation drum 43. A condensed water line L₆ which supplies the condensed water W₅ separated in the separation drum 43 to an upper portion of the CO₂ absorbent regenerator 15 is provided between the bottom portion of the separation drum 43 and the upper portion of the CO₂ absorbent regenerator 15. The condensed water line L₆ is provided with a condensed water circulation pump 45 which supplies the condensed water W₅ separated in the separation drum 43 to the upper portion of the CO₂ absorbent regenerator 15. An adjustment valve 46 which controls the amount of the condensed water W₅ supplied to the CO₂ absorbent regenerator 15 is provided between the condensed water circulation pump 45 and the CO₂ absorbent regenerator 15. Further, a re-circulation line L₁₂ which divides a part of the condensed water W₅ supplied to the CO₂ absorbent regenerator 15 and re-circulates the condensed water W₅ supplied to the water washing unit 142 of the CO₂ absorber 14 is provided between the condensed water circulation pump 45 and the circulation line L₂. The re-circulation line L₁₂ is provided with an adjustment valve 47 which adjusts the amount of the condensed water W₅ supplied to the water washing unit 142.

Further, the tower bottom portion of the CO₂ absorbent regenerator 15 and the upper portion of the CO₂ absorption unit 141 of the CO₂ absorber 14 are provided with a lean solution supply pipe 53 which supplies the CO₂ absorbent 13 (the lean solution) of the tower bottom portion of the CO₂ absorbent regenerator 15 to the upper portion of the CO₂ absorption unit 141. The lean solution supply pipe 53 is provided with the rich-lean solution heat exchanger 52 which heats the CO₂ absorbent 13C having CO₂ absorbed thereto (the rich solution) by the CO₂ absorbent 13 (the lean solution) heated by the steam in the CO₂ absorbent regenerator 15 so that CO₂ is removed therefrom, a lean solution pump 54 which supplies the CO₂ absorbent 13 of the tower bottom portion of the CO₂ absorbent regenerator 15 to the upper portion of the CO₂ absorption unit 141, and a cooling unit 55 which cools the CO₂ absorbent 13 (the lean solution) to a predetermined temperature.

Next, a relation between a CO₂ absorption rate and a temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A of the CO₂ absorber 14 in the CO₂ recovery unit 1 according to the embodiment will be described with reference to FIG. 2. FIG. 2 is a diagram illustrating a relation between the temperature of the CO₂ absorbent 13B (the semi-rich solution) supplied to the lower CO₂ absorption unit and a ratio of the CO₂ absorption rate of the rich solution. Additionally, in FIG. 2, a horizontal axis indicates the temperature of the CO₂ absorbent 13B and a vertical axis indicates the ratio of the CO₂ absorption rate of the rich solution. Further, in FIG. 2, a case where a flue gas having a low CO₂ partial pressure (for example, about 10 kPa) such as a combustion flue gas discharged from a boiler is used is indicated by a dotted line and a case where a flue gas having a high CO₂ partial pressure (for example, about 60 kPa) such as a synthetic gas discharged from a direct reducing furnace is used is indicated by a solid line. Additionally, a plot indicates an analysis value. Further, in FIG. 2, the flue gas having a low CO₂ partial pressure and the flue gas having a high CO₂ partial pressure are displayed on the same axes at a ratio in which a maximal value of the absorption rate is 1 in a temperature range equal to or higher than 40° C. and equal to or lower than 70° C., but have different maximal values of the absorption rates.

As indicated by the dotted line of FIG. 2, when the flue gas having a low CO₂ partial pressure is used, the CO₂ absorption rate of the CO₂ absorbent 13B increases in accordance with a decrease in temperature. For this reason, it is desirable to decrease a temperature of the CO₂ absorbent 13B in order to efficiently recover CO₂ in the flue gas having a low CO₂ partial pressure.

Meanwhile, when the flue gas having a high CO₂ partial pressure is used as indicated by the solid line of FIG. 2, the CO₂ absorption rate has a different tendency from the case where the flue gas having a low CO₂ partial pressure is used. When the flue gas having a high CO₂ partial pressure is used, the CO₂ absorption rate becomes maximal at about 55° C., and the CO₂ absorption rate decreases as the temperature falls from 55° C. However, in the embodiment, compared with the case where the flue gas having a low CO₂ partial pressure is used, it is possible to improve the CO₂ absorption rate in the lower CO₂ absorption unit 141A by controlling the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A in an operation state and to decrease the heat amount of the CO₂ absorbent 13C in the CO₂ absorbent regenerator 15 by decreasing the circulation amount of the CO₂ absorbent. Accordingly, energy saving is realized.

As illustrated in FIG. 2, in the CO₂ recovery unit 1 according to the embodiment, it is desirable to control the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A in a range equal to or higher than 50° C. and equal to or lower than 60° C. by the control device 101. Accordingly, the CO₂ recovery unit 1 can set the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A within an appropriate range. For this reason, it is possible to further improve the CO₂ absorption rate of the flue gas 11A by the CO₂ absorbent 13B in the lower CO₂ absorption unit 141A and to decrease the circulation amount of the CO₂ absorbent 13B in accordance with the improved CO₂ absorption rate. Thus, it is possible to decrease the amount of the saturated steam S consumed to regenerate the CO₂ absorbent 13C. Further, the CO₂ recovery unit 1 can set the temperature of the CO₂ absorbent 13C supplied to the CO₂ absorbent regenerator 15 to an appropriately high temperature and thus an effect of decreasing a steam consumption amount is obtained.

Additionally, in the embodiment, the CO₂ partial pressure of the flue gas 11B is desirably equal to or higher than 50 kPa and equal to or lower than 200 kPa. When the CO₂ partial pressure is equal to or higher than 50 kPa, the CO₂ absorption rate of the lower CO₂ absorption unit 141A has a different tendency when the CO₂ partial pressure is low (for example, about 10 kPa) as indicated by the solid line of FIG, 2. Further, when the CO₂ partial pressure is equal to or lower than 200 kPa, the amount of CO₂ in the flue gas 11B can be sufficiently decreased by the CO₂ absorber 14. From the viewpoint of improving the above-described operations and effects, the CO₂ partial pressure of the flue gas 11B is more desirably 55 kPa or more, further desirably 60 kPa or more, more desirably 150 kPa or less, and further desirably 100 kPa or less. When the above-described fact is taken into consideration, the CO₂ partial pressure of the flue gas 11B is more desirably equal to or higher than 55 kPa and equal to or lower than 150 kPa and further desirably equal to or higher than 60 kPa and equal to or lower than 100 kPa.

Next, a relation between the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A in the CO₂ recovery unit 1 according to the embodiment and the heat amount necessary to regenerate the CO₂ absorbent 13 in the CO₂ absorbent regenerator 15 will be described with reference to FIG. 3. FIG. 3 is a diagram illustrating a relation between the temperature of the CO₂ absorbent 13B (the semi-rich solution) supplied to the lower CO₂ absorption unit 141A and a ratio of the heat amount necessary to regenerate the CO₂ absorbent 13. Further, in FIG. 3, a horizontal axis indicates the temperature of the CO₂ absorbent 13B and a vertical axis indicates the ratio of the heat amount necessary to regenerate CO₂ . Further, in FIG. 3, the flue gas having a high CO₂ partial pressure is displayed as a ratio in which a minimal value of the heat amount necessary to regenerate the CO₂ absorbent 13B is 1 in a temperature range equal to or higher than 40° C. and equal to or lower than 70° C. Additionally, a plot indicates an analysis value.

As illustrated in FIG. 3, when the flue gas having a high CO₂ partial pressure is used, the heat amount necessary to regenerate the CO₂ absorbent 13B in the CO₂ absorbent regenerator 15 becomes minimal at about 55° C. and the heat amount necessary to regenerate the CO₂ absorbent 13C increases as the temperature falls from 55° C. Thus, in the embodiment, as illustrated in FIG. 2, when the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A is set to a range in which the CO₂ absorption rate of the flue gas 11A using the CO₂ absorbent 13B of the lower CO₂ absorption unit 141A is high, it is possible to decrease the amount of the saturated steam S consumed to regenerate the CO₂ absorbent 13C. This is because the circulation amount of the CO₂ absorbent 13 can be decreased in accordance with improvement in absorption rate.

FIG. 4 is a diagram illustrating a relation between the temperature of the CO₂ absorbent 13B (the semi-rich solution) supplied to the lower CO₂ absorption unit 141A and the temperature of the CO₂ absorbent 13C (the rich solution) supplied to the CO₂ absorbent regenerator 15. Further, in FIG. 4, a vertical axis indicates the temperature of the CO₂ absorbent 13C supplied to the CO₂ absorbent regenerator 15 and a horizontal axis indicates the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A.

As illustrated in FIG. 4, in the embodiment, there is a direct proportional relation between the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A and the temperature of the CO₂ absorbent 13C supplied to the CO₂ absorbent regenerator 15. Thus, when the control device 101 controls the amount of the refrigerant supplied to the heat exchanger 24 and the amount of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A by the pump 25 so that the temperature of the CO₂ absorbent 13C supplied to the CO₂ absorbent regenerator 15 is measured by the thermometer 102 and the measured temperature falls within a predetermined range (for example, a range equal to or higher than 62° C. and equal to or lower than 67° C.), it is possible to control the CO₂ absorbent 13B of the lower CO₂ absorption unit 141A at a desired temperature. Accordingly, it is possible to obtain a high CO₂ absorption rate and to decrease a heat amount necessary to heat the CO₂ absorbent 13C in the CO₂ absorbent regenerator 15.

FIG. 5 is a diagram illustrating a relation of filling material charging height ratios H1 and H2 of the lower CO₂ absorption unit and the upper CO₂ absorption unit of the CO₂ absorber with respect to a ratio of the CO₂ absorption rate of the rich solution. Additionally, in FIG. 5, a case where the filling material charging height ratios (the upper CO₂ absorption unit 141B:the lower CO₂ absorption unit 141A) H1 and H2 of the lower CO₂ absorption unit 141A and the upper CO₂ absorption unit 141B are changed in a range of 1:3 to 3:1 is displayed at a ratio in which a maximal value of the CO₂ absorption rate is 1.

As illustrated in FIG. 5, in the embodiment, when the filling material charging height ratios of the lower CO₂ absorption unit 141A and the upper CO₂ absorption unit 141B are changed, the CO₂ absorption rate changes. For this reason, in the embodiment, it is desirable that the charging height ratio (the upper CO₂ absorption unit 141B:the lower CO₂ absorption unit 141A) between the charging height of the filling material the filling material H2 in the upper CO₂ absorption unit 141B and the charging height of the filling material H1 in the lower CO₂ absorption unit 141A be equal to or larger than 1:3 and equal to or smaller than 3:1. Accordingly, since the absorption efficiency for CO₂ in the flue gas 11A of the upper CO₂ absorption unit 141B and the absorption efficiency for CO₂ in the flue gas 11A of the lower CO₂ absorption unit 141A are respectively improved, it is possible to further improve a CO₂ absorption rate and to save energy. As the charging height ratio, 1:1 is more desirable from the viewpoint of further improving the above-described operations and effects.

Next, an overall operation of the CO₂ recovery unit 1 according to the embodiment will be described. The flue gas 11A such as a synthetic gas containing CO₂ discharged from the direct reducing furnace is introduced into the cooling tower 12 and is cooled by a counterflow contact with respect to the cooling water W₁ to become the flue gas 11B. The cooled flue gas 11B is introduced into the CO₂ absorber 14 through a flue gas duct 16 and a flow rate of the flue gas 11B introduced into the CO₂ absorber 14 is measured. A counterflow contact occurs between the flue gas 11B introduced into the CO₂ absorber 14 and the CO₂ absorbent 13 containing alkanolamine in the lower CO₂ absorption unit 141A and the upper CO₂ absorption unit 141B of the CO₂ absorption unit 141 so that CO₂ in the flue gas 11B is absorbed to the CO₂ absorbent 13 and the flue gas 11D is obtained by removing CO₂ therefrom.

The flue gas 11D obtained by removing CO₂ therefrom rises through the chimney tray 144B and causes a gas-liquid contact with respect to the washing water W₂ supplied from the top portion of the water washing unit 142 so that the flue gas 11E is obtained by recovering the CO₂ absorbent 13 accompanied by the flue gas 11D through a circulating and washing process. Mist is the flue gas 11E is trapped by the mist eliminator 145 and the flue gas is discharged to the outside from the tower top portion 14a of the CO₂ absorber 14.

The CO₂ absorbent 13C having CO₂ absorbed thereto in the CO₂ absorber 14 exchanges heat with the CO₂ absorbent 13 (the lean solution) in the rich-lean solution heat exchanger 52 through the rich solution supply pipe 50 and is supplied to the upper portion of the CO₂ absorbent regenerator 15 by the rich solution pump 51. Here, in the embodiment, the CO₂ absorbent 13C flowing in the rich solution supply pipe 50 is measured at all times by the thermometer 102 and the measured temperature of the CO₂ absorbent 13C is transmitted to the control device 101. The control device 101 adjusts the amount of the refrigerant supplied to the heat exchanger 24 and the amount of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A by the pump 25 so that the temperature of the CO₂ absorbent 13C measured by the thermometer 102 falls within a predetermined range.

CO₂ is removed from the CO₂ absorbent 13C supplied to the CO₂ absorbent regenerator 15 while the CO₂ absorbent 13C flows down to the tower bottom portion through the CO₂ absorbent supply unit 151 and thus a semi-lean solution is obtained. This semi-lean solution is circulated in the circulation line L₄ by the circulation pump 33 and is heated by the saturated steam S in the regenerating heater 31 so that the CO₂ absorbent 13 (the lean solution) is obtained. The heated saturated steam S becomes the steam condensed water The CO₂ gas 41 removed from the CO₂ absorbent 13 passes through the condenser 42 so that moisture is removed therefrom and is discharged as the CO₂ gas 44, from which the condensed water W₅ is separated, to the outside from the upper portion of the separation drum 43, The separated condensed water W₅ is supplied to the CO₂ absorbent regenerator 15 and a part of the water is divided so that the water is supplied to the water washing unit 142 of the CO₂ absorber 14 through the re-circulation line L₁₂.

The CO₂ absorbent 13 (the lean solution) of the tower bottom portion 15b of the CO₂ absorbent regenerator 15 exchanges heat with the CO₂ absorbent 13C (the rich solution) by the rich-lean solution heat exchanger 52 through the lean solution supply pipe 53 and is supplied to the upper portion of the CO₂ absorption unit 141 of the CO₂ absorber 14 by the lean solution pump 54. The CO₂ absorbent 13 supplied to the CO₂ absorption unit 141 absorbs CO₂ of the flue gas 11A in the upper CO₂ absorption unit 141B to become the CO₂ absorbent (the semi-rich solution) 13A and is extracted from the lower portion of the upper CO₂ absorption unit 141B to the extraction line L₁₁. The extracted CO₂ absorbent 13A is cooled to a predetermined temperature range by the heat exchanger 24 to become the CO₂ absorbent (the semi-rich solution) 13B and is supplied to the lower CO₂ absorption unit 141A by the pump 25 to absorb CO₂ in the flue gas 11B by the lower CO₂ absorption unit 141A so that the CO₂ absorbent (the rich solution) 13C is obtained. The CO₂ absorbent (the rich solution) 13C is extracted from the tower bottom portion 14b of the CO₂ absorber 14 and is supplied to the CO₂ absorbent regenerator 15.

As described above, according to the embodiment, since the temperature of the CO₂ absorbent 13B supplied to the lower CO₂ absorption unit 141A is controlled based on the temperature of the CO₂ absorbent 13C supplied to the CO₂ absorbent regenerator 15, the CO₂ absorption rate of the flue gas 11B of the lower CO₂ absorption unit 141A can be increased. Accordingly, since the CO₂ recovery unit 1 has an excellent CO₂ absorption rate even when the synthetic gas having a high CO₂ partial pressure in the flue gas 11B is treated, energy can be saved.

Additionally, in the above-described embodiment, an example of treating the flue gas 11A such as a synthetic gas containing CO₂ discharged from a direct reducing furnace has been described, but the invention can be applied to various gases including a natural gas (a methane gas) containing CO₂.

REFERENCE SIGNS LIST

• 1, 2 CO₂ Recovery Unit
• 11A, 11B, 11C, 11D, 11E Flue Gas
• 12 Cooling Tower
• 121 Cooling Unit
• 122 Heat Exchanger
• 123 Circulation Pump
• 124 Adjustment Value
• 13 CO₂ Absorbent (Lean Solution)
• 13A CO₂ Absorbent
• 13B CO₂ Absorbent (Semi-Rich Solution)
• 13C CO₂ Absorbent (Rich Solution)
• 14 CO₂ Absorber
• 14 a Tower Top Portion
• 14 b Tower Bottom Portion
• 141 CO₂ Absorption Unit
• 142 Water Washing Unit
• 143A Liquid Storage Unit
• 143B Chimney Tray
• 144A Liquid Storage Unit
• 144B Chimney Tray
• 145 Mist Eliminator
• 15 CO₂ Absorbent Regenerator
• 15 a Tower Top Portion
• 151 CO₂ Absorbent Supply Unit
• 16 Flue Gas Duct
• 21 Heat Exchanger
• 22 Circulation Pump
• 23 Adjustment Valve
• 24 Heat Exchanger
• 31 Regenerating Heater
• 32 Adjustment Valve
• 33 Circulation Pump
• 41, 44 CO₂ Gas
• 42 Condenser
• 43 Separation Drum
• 45 Condensed Water Circulation Pump
• 46, 47 Adjustment Valve
• 50 Rich Solution Supply Pipe
• 51 Rich Solution Pump
• 52 Rich-Lean Solution Heat Exchanger
• 53 Lean Solution Supply Pipe
• 54 Lean Solution Pump
• 55 Cooling Unit
• 101 Control Device
• 102 Thermometer (Temperature Measurement Device)
• L₁, L₂, L₄ Circulation Line
• L₃, L₁₁ Extraction Line
• L₅ Gas Discharge Line
• L₆ Condensed Water Line
• L₁₂ Re-Circulation Line
• S Saturation Steam
• W₁ Cooling Water
• W₂, W₃ Washing Water
• W₄ Steam Condensed Water
• W₅ Condensed Water

Claims

1. A CO2 recovery unit comprising: a CO2 absorber which includes a first CO2 absorption unit obtaining a first CO2 absorbent by causing a CO2 containing gas to be treated to contact a CO2 absorbent so that CO2 contained in the gas to be treated is absorbed to the CO2 absorbent and a second CO2 absorption unit obtaining a second CO2 absorbent by causing the first CO2 absorbent to contact a CO2 containing gas to be treated so that CO2 contained in the gas to be treated is absorbed to the first CO2 absorbent;a CO2 absorbent regenerator which regenerates a CO2 absorbent by heating the second CO2 absorbent so that CO2 is discharged from the second CO2 absorbent;a temperature measurement device which measures a temperature of the second CO2 absorbent supplied from the CO2 absorber to the CO2 absorbent regenerator; anda control device which controls a temperature of the first CO2 absorbent supplied to the second CO2 absorption unit based on the temperature of the second CO2 absorbent measured by the temperature measurement device.

2. The CO2 recovery unit according to claim 1, wherein the control device controls the temperature of the first CO2 absorbent supplied to the second CO2 absorption unit so that the temperature is equal to or higher than 50° C. and equal to or lower than 60° C.

3. The CO2 recovery unit according to claim 1, wherein a CO2 partial pressure of the CO2 containing gas to be treated is 50 kPa or more.

4. The CO2 recovery unit according to claim 1, wherein a ratio (the first CO2 absorption unit:the second CO2 absorption unit) between a filling material charging height in the first CO2 absorption unit and a filling material charging height in the second CO2 absorption unit is equal to or larger than 1:3 and equal to or smaller than 3:1.

5. A CO2 recovery method comprising: obtaining a first CO2 absorbent by causing a CO2 containing gas to be treated to contact a CO2 absorbent in a first CO2 absorption unit of a CO2 absorber so that CO2 contained in the gas to be treated is absorbed to the CO2 absorbent and obtaining a second CO2 absorbent by causing the first CO2 absorbent to contact the CO2 containing gas to be treated in a second CO2 absorption unit of the CO2 absorber so that CO2 contained in the gas to be treated is absorbed to the first CO2 absorbent;regenerating a CO2 absorbent by heating the second CO2 absorbent in a CO2 absorbent regenerator so that CO2 is discharged from the CO2 absorbent; andmeasuring a temperature of the second CO2 absorbent supplied from the CO2 absorber to the CO2 absorbent regenerator and controlling a temperature of the first CO2 absorbent supplied to the second CO2 absorption unit based on the measured temperature of the second CO2 absorbent.

6. The CO2 recovery method according to claim 5, wherein the temperature of the first CO2 absorbent supplied to the second CO2 absorption unit is controlled so that the temperature is equal to or higher than 50° C. and equal to or lower than 60° C.

7. The CO2 recovery method according to claim 5, wherein a CO2 partial pressure of the CO2 containing gas to be treated is 50 kPa or more.

8. The CO2 recovery method according to claim 5, wherein a ratio (the first CO2 absorption unit:the second CO2 absorption unit) between a filling material charging height in the first CO2 absorption unit and a filling material charging height in the second CO2 absorption unit is equal to or larger than 1:3 and equal to or smaller than 3:1.