[0001]　The present invention is a composite amine absorbent, CO 2 or H 2 about S or removing apparatus and method for both.
[0002]In recent years, as one of the causes of the global warming phenomenon, CO 2 greenhouse effect has been pointed out by, international also the measures on protecting the global environment has become an urgent task. CO 2 as the source of Oyobi by any human activities combusting fossil fuels, there are increasing demands for its emissions. To the target power generation facilities such as thermal power plants using large amounts of fossil fuels with which the flue gas of a boiler amine CO 2 is contacted with the absorption liquid, CO in the combustion exhaust gas 2 how to remove and recover and the recovered CO 2 method of storing without releasing to the atmosphere have been studied extensively. Moreover, CO, such as the 2 with absorbing solution, CO from flue gas 2 as the process of removing and recovering, in the absorption tower combustion exhaust gas and CO 2 is brought into contact with absorption liquid, CO 2 and absorbing liquid that has absorbed was heated in the regeneration tower, CO 2 which circulated and reused again absorption column reproduces the absorbing liquid together to release is employed (e.g., see Patent Document 1).
[0003]
　The CO 2 CO, such as flue gas with absorption liquid and process 2 CO -containing gas 2 in the method of absorbing removing and recovering, since these processes are installed in addition to combustion equipment, its operating costs also it must be reduced as much as possible. Especially among the processes, the regeneration step so consumes a large amount of heat energy, it is necessary to make the energy-saving process as much as possible.
[0004]
　Therefore, conventionally, for example from the regeneration tower extracting a portion of the semi-lean solution to the outside, causes heat exchange lean solution heat exchanger, and then is heat exchanged with steam condensate and the heat exchanger, the lower side of the position withdrawn back, raising the temperature of the semi-lean solution to be supplied to the lower side to the regenerator, it has been proposed to reduce the steam consumption (e.g., see Patent Document 2 (example 8, FIG. 17)).
[0005]
　On the other hand, CO 2 absorbing solution in order to improve its performance, there is a proposal of contributing absorption liquid to improve the absorbing performance (Patent Documents 3-5).
CITATION
Patent Document
[0006]
Patent Document 1: JP-A-7-51537 JP
Patent Document 2: Patent No. 4690659 Patent Publication
Patent Document 3: JP 2008-13400 JP
Patent Document 4: JP 2008-307519 Patent Publication
Patent Document 5: JP 2013- 236,987 JP
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　However, CO 2 absorbing solution is not the absorption performance only, but release capability when regenerating the absorption liquid is also important, in addition to the improvement of the absorption performance has been studied most conventionally, reproduction performance good absorption liquid proposal is also a problem present situation.
[0008]
　Therefore, CO from the exhaust gas 2 Upon recovery, because it requires the as steam, for the purpose of operating cost, the desired CO with a small amount of steam 2 for expressing the energy saving can be achieved recovery amount, absorption capacity only the emergence of not not playback capability combines the absorption liquid has been desired.
[0009]
　In view of the above problems, the absorption capacity not only reproduction capability composite amine absorbent that combines, CO 2 or H 2 and to provide an S or removing apparatus and method for both.
Means for Solving the Problems
[0010]
　The first aspect of the present invention to solve the problems described above, CO in the gas 2 or H 2 An absorbent solution to absorb S or both, and (1) straight chain monoamine, (2) a diamine If there (3) and amide group-containing compound, the composite amine absorbent, characterized in that dissolved in water.
[0011]
　A second aspect of the invention is combined in the first aspect, linear monoamines (1) is a primary straight-chain monoamines, secondary linear monoamines, characterized in that it comprises at least one tertiary linear monoamines in the amine absorbent.
[0012]
　The third invention is the invention of the first or 2, diamine (2) is a primary straight-chain polyamine, secondary linear polyamines, composite amine absorbent, characterized in that it comprises at least one cyclic polyamine It is in.
[0013]
　It a fourth invention, in any one invention of the first to third, and linear monoamine (1), the concentration sum of the diamine (2) is 40 to 60 wt% of the total absorbing solution in composite amine absorbent, wherein.
[0014]
　A fifth invention, in any one invention of the first to fourth, with respect to a straight-chain monoamines (1), the mixing ratio of the amide group-containing compound (2) diamine and (3), ( diamine + amide group-containing compound) / in composite amine absorbent, wherein the linear monoamine is 0.16 to 2.1.
[0015]
　It is 54: a sixth invention, in any one invention of the first to fifth, mixing ratio of the amide group-containing compound (2) diamine and (3) is 1: 0.4-1 in composite amine absorbent, wherein.
[0016]
　A seventh aspect of the present invention is, CO 2 or H 2 S or both contacting the gas containing the absorbed liquid and CO Part 2 or H 2 and S or absorption tower to remove the both, CO 2 or H 2 S or both of the and a absorbent regenerator for reproducing the absorbed solution, wherein the absorbent regenerator with CO 2 or H 2 reuse S or solution was regenerated to remove both of the above absorption tower, CO 2 or H 2 a S or removal device of the both, CO and characterized by using the composite amine absorbent of any one invention of the first to sixth 2 or H 2 removal of S or both apparatus is in.
[0017]
　Advantageously, in the seventh invention, the absorption temperature of the absorption tower, along with a 30 ~ 80 ° C., the regeneration temperature of the absorbent solution regeneration tower, CO and wherein the at 110 ° C. or higher 2 or H 2 S or removal device of both.
[0018]
　A ninth aspect of the invention, CO 2 or H 2 S or both is contacted with a gas containing the absorbed liquid CO 2 or H 2 S or removed in the absorption tower the both, CO 2 or H 2 S or reproduces the solution which has absorbed the both absorption solution regeneration tower, the absorbing solution regeneration tower with CO 2 or H 2 reuse S or solution was regenerated to remove both of the above absorption tower, CO 2 or H 2 a S or method of removing the both, CO using the composite amine absorbent of any one invention of the first to sixth 2 or H 2 CO, characterized in that the removal of S or both 2 or H 2 in the S or method for removing both.
[0019]
　A tenth invention is, CO Aspect 9, the absorption temperature of the absorption tower, along with a 30 ~ 80 ° C., the regeneration temperature of the absorbent regenerator, characterized in that at 110 ° C. or higher 2 H or 2 in S or method for removing both.
Effect of the invention
[0020]
　According to the present invention, (1) and linear monoamine, and diamine (2), and amide group-containing compound (3), by which dissolved in water to absorb liquid, entangled composite, these synergistic effects, CO 2 or H 2 with S or absorbent that both are good, absorbed CO during regeneration of the absorbent 2 or H 2 dissipation of S becomes favorable, CO 2 recovery it is possible to reduce the amount of water vapor used during the absorption liquid regeneration in facilities.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
[1] Figure 1, CO according to Example 1 2 is a schematic diagram showing the structure of a recovery device.
FIG. 2 is the dielectric constant and the CO 2 is a diagram showing the relationship between the saturation solubility index.
FIG. 3 is a diagram showing a reboiler heat reduction rate according to Test Example 1-4.
[4] FIG. 4 is a diagram showing a reboiler heat reduction rate according to Test Example 5-10.
FIG. 5 is a diagram showing a reboiler heat reduction rate according to the Test Example 11-12.
FIG. 6 is a diagram showing a reboiler heat reduction rate according to the Test Example 13-14.
[7] FIG. 7 is a diagram showing a reboiler heat reduction rate according to the Test Example 15-16.
[8] FIG. 8 is a diagram showing the ratio of reboiler heat reduction rate according to Test Example 17.
DESCRIPTION OF THE INVENTION
[0022]
　With reference to the accompanying drawings, illustrating preferred embodiments of the present invention in detail. It is not intended the invention be limited by this example, also, if the embodiment there are a plurality, i.e., an constitute a combination of each embodiment.
Example 1
[0023]
　Composite amine absorbent according to an embodiment of the present invention, CO in the gas 2 or H 2 An absorbent solution to absorb S or both, and (1) a straight-chain monoamine (a component), (2) and diamine (b component), those obtained by dissolving the amide group-containing compound (3) and (d component), water (c component). In the present invention, (1) and linear monoamine, and diamine (2), and amide group-containing compound (3), by which dissolved in water to absorb liquid, entangled composite, these by synergistic effect, CO 2 or H 2 with S or absorbent that both are good, the absorption liquid of the absorbed CO during reproduction 2 or H 2 is dissipation of S becomes favorable, CO 2 in the recovery facility it is possible to reduce the amount of steam used during the absorption solution regeneration.
[0024]
　Here, linear monoamine, primary linear monoamines, secondary linear monoamines are those which include at least one tertiary linear monoamines. Further, primary linear monoamine and 2 combined components linear amine and secondary linear monoamines, primary linear monoamine and a combination of two components linear amine with tertiary linear monoamines, more primary linear monoamines, may be three combinations of components linear amine of secondary linear monoamines and tertiary straight-chain monoamine.
[0025]
　As the primary linear monoamines, preferably lower amine or hindered high amine sterically hindered. Wherein at least in one primary linear monoamines, as the low amine sterically hindered, such as monoethanolamine (MEA), 3- amino-1-propanol, 4-amino-1-butanol, selected from diglycolamine kind can be mentioned. Incidentally, it is also possible to combine these.
[0026]
　Moreover, in primary linear monoamines, as the primary monoamine highly sterically hindered, it is preferably a compound represented by the chemical formula (1) shown below "Formula 1".
[Formula 1]

[0027]
　Specifically, the high primary amine sterically hindered, such as 2-amino-1-propanol (2A1P), 2- amino-1-butanol (2A1B), 2- amino-3-methyl-1-butanol (AMB), 1-amino-2-propanol (1A2P), 1- amino-2-butanol (1A2B), 2- amino-2-methyl-1-propanol (AMP) a compound selected from at least one of such an Although not intended the invention be limited thereto can be exemplified. Incidentally, it is also possible to combine these.
[0028]
　As the secondary linear monoamine is preferably a compound represented by the chemical formula (2) shown below "Formula 2".
[Formula 2]

[0029]
　Specifically, the secondary linear monoamines, such as N- methylamino ethanol, N- ethylamino ethanol, N- propylamino ethanol, and the like selected compounds from at least one of such N- butylamino ethanol it is not intended the invention be limited thereto. Incidentally, it is also possible to combine these.
[0030]
　As the tertiary linear monoamine is preferably a compound represented by the chemical formula (3) shown below "Formula 3".
[Formula 3]

[0031]
　Specifically, the tertiary linear monoamines, such as N- methyldiethanolamine, N- ethyldiethanolamine, N- butyl diethanolamine, 4-dimethylamino-1-butanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2 - di -n- butyl aminoethanol, N- ethyl -N- methyl-ethanolamine, 3-dimethylamino-1-propanol, 2-dimethylamino-2-methyl-1 compound selected from at least one of propanol and Although not intended the invention be limited thereto can be exemplified. Incidentally, it is also possible to combine these.
[0032]
　Here, the formulation of two-component linear monoamines mentioned above, preferably the following formulation. The weight ratio of the sterically hindered high primary linear monoamine (a2 component) / hindered low primary linear monoamine (a1 component), (a2) / (a1) = 0.3 ~ 2.5 preferably in the range. Further, more preferably in the range of 0.3-1.2, more preferably it is in the range of 0.3-0.7. This is because the rate other than the above, in order to decrease the absorption performance than when referenced to 30 wt% of the absorbent performance as a conventional generally monoethanolamine used (MEA) concentration.
[0033]
　As the weight ratio of tertiary linear monoamine (a4 component) / secondary linear monoamine (a3 component), preferably in the range of (a4) / (a3) ​​= 0.3 ~ 2.5. Further, more preferably in the range of 0.6-1.7, more preferably it is in the range of 0.6-1.0. This is lower than the above range lowers reproduction performance is higher than the above range is due to the absorption performance is deteriorated.
[0034]
　As the weight ratio of sterically hindered high primary linear monoamine (a2 component) / secondary linear monoamine (a3 component), and a range of (a2) / (a3) ​​= 0.3 ~ 2.5 it is preferable to. Further, more preferably in the range of 0.6-1.7, more preferably it is in the range of 0.6-1.0. This is lower than the above range lowers reproduction performance is higher than the above range is due to the absorption performance is deteriorated.
[0035]
　As the weight ratio of sterically hindered high primary linear monoamine (a2 component) / tertiary linear monoamine (a4 component), and a range of (a2) / (a4) = 0.3 ~ 2.5 it is preferable to. Further, more preferably in the range of 0.6-1.7, more preferably it is in the range of 0.6-1.0. This is lower than the above range is absorbing performance decreases, is higher than the above range in order to worse reproduction performance.
[0036]
　The diamine (2) (b component), primary linear polyamines, secondary linear polyamine is preferably one containing at least one cyclic polyamine.
[0037]
　Here, a primary or as a secondary linear polyamine group, such as ethylene diamine (EDA), N, N'-dimethylethylenediamine (DMEDA), N, N'-diethyl ethylenediamine (DEEDA), propanediamine (PDA), N , N'- dimethyl propanediamine (DMPDA) compound selected from at least one, and the like, but the present invention is not limited thereto. Incidentally, it is also possible to combine these.
[0038]
　As the cyclic polyamine, for example piperazine (PZ), 1-methylpiperazine (1MPZ), 2- methylpiperazine (1MPZ), 2,5- dimethylpiperazine (DMPZ), 1- (2- aminoethyl) piperazine (AEPRZ ), 1- (2-hydroxyethyl) piperazine (HEP) compound selected from at least one, and the like, but the present invention is not limited thereto. Incidentally, it is also possible to combine these.
[0039]
　Further, that the amide The group-containing compound (d component), and a boiling point under atmospheric pressure is 130 ° C. or higher, and the relative dielectric constant of 25 ° C. contains 20 or more amide groups Compound (3) preferable.
[0040]
　Here, (3) Examples of the amide group-containing compound, such as N- methyl formamide, N- ethyl formamide, N- methylacetamide, N- ethylacetamide, N, N- dimethylformamide, N, N- dimethylacetamide, N , N- diethylformamide, N, N- diethylacetamide, there may be mentioned a compound selected from at least one of such N- methylpyrrolidone present invention is not limited thereto. Incidentally, it is also possible to combine these.
[0041]
　2, the dielectric constant and the CO 2 is a diagram showing the relationship between the saturation solubility index. The horizontal axis of FIG. 2 is the relative dielectric constant (25 ° C.), the vertical axis represents CO when the 2 shows the saturated solubility index.
　The dielectric constant of the horizontal axis shows the value of the static dielectric constant of the low frequency condition (100 MHz or less).
　As shown in FIG. 2, the relative dielectric constant value of 20 or more conditions of the horizontal axis, vertical axis of CO 2 increase in the saturation solubility index slowed, CO 2 saturated solubility index a generally constant high value in the area Become. The relative dielectric constant, a polar indicator of the compounds, the specific dielectric low index region, increasing polarity CO 2 contributes significantly to the saturation dissolution capability, the polarity becomes sufficiently high area, such as solvent interactions CO equal 2 for the contribution of non-dissolution is increased, CO due to an increase in the dielectric constant 2 that the effect of the saturation solubility increases hardly expressed considered as contributing.
[0042]
　Therefore, Similarly for reboiler heat, the relative dielectric constant sufficiently high region (e.g., 40 or higher), reboiler heat reduction effect by the dielectric constant increases is presumed to be slowed. Here, in the measurement of the relative dielectric constant was measured relative dielectric constant at 25 ° C..
[0043]
　A linear monoamine (a component) of (1), the concentration sum of the diamine (2) (b component) is preferably 40 to 60 wt% of the total absorbing solution, and more preferably, the absorbing liquid preferably the entire 47 to 55 wt%.
　This range is out because not satisfactorily function as an absorbing liquid.
[0044]
　The mixing ratio of the relative linear monoamine (a component), an amide group-containing compound of the diamine (b component) and (3) of (2) (d component) (1), (b + d) / a = is preferably set to 0.16 to 2.1 of the formulation.
　Reboiler heat reduction effect at low concentrations blending conditions of this formulation is the limiting, whereas at higher concentrations blending conditions there is no efficient in practical use, such as increased liquid viscosity.
[0045]
　Compounding ratio of diamine (2) and (b component) and the amide group-containing compound (3) (d component), b: d = 1: 0.4 ~ 1: It is preferable to 54.
　Reboiler heat reduction effect at a low ratio conditions of the blending ratio becomes limited, whereas a high proportion condition there is no efficient in practical use, such as increased liquid viscosity.
[0046]
　In the present invention, CO 2 absorption temperature of the absorption tower at the time of contact with the exhaust gas containing the like, preferably in the range of usually 30 ~ 80 ° C.. The absorption liquid used in the present invention, the corrosion inhibitor as needed, such as anti-deterioration agent is added.
[0047]
　In the present invention, CO 2 from the absorbing solution that has absorbed the like, CO 2 regeneration temperature in the regenerator to emit the like, when reproducing tower pressure is 130 ~ 200 kPa (absolute pressure), it is 110 ° C. or higher preferable. This is because reproduction in less than 110 ° C., it becomes necessary to increase the circulation amount of the absorption liquid in the system, is not preferable from the viewpoint of regeneration efficiency. More preferably reproduction at 115 ° C. or more.
[0048]
　The gas to be treated by the present invention, such as coal gasification gas, syngas, coke oven gas, petroleum gas, there may be mentioned a natural gas, etc., is not limited to these, CO 2 and H 2 if gas containing acid gas S such as may be any gas.
[0049]
　CO in the gas of the present invention 2 or H 2 processes that can be employed in the methods of removing S, or both is not particularly limited, CO 2 an example of a removal device for removing be described with reference to FIG.
[0050]
　1, CO according to Example 1 2 is a schematic diagram showing the structure of a recovery device. As shown in FIG. 1, CO according to Example 1 2 recovering apparatus 12, CO discharged from industrial combustion facility 13, such as boilers and gas turbines 2 and O 2 cools the flue gas 14 containing a by cooling water 15 an exhaust gas cooling device 16 for the cooled CO 2 gas 14 and CO containing 2 CO absorbs 2 absorbing solution (hereinafter, also referred to as "absorbing solution".) 17 and is brought into contact with and CO from the exhaust gas 14 2 a CO removing 2 CO having a recovery section 18A 2 and the absorption tower 18, CO 2 CO absorbed 2 absorbing solution (hereinafter, also referred to as "rich solvent".) 19 CO from 2 to release by CO 2 play absorbing solution and an absorbent regenerator 20. Then, the CO 2 in the recovery device 12, in the absorbent regenerator 20 CO 2Play CO removing the 2 absorbing solution (hereinafter, also referred to as "lean solvent".) 17 CO 2 CO in absorption tower 18 2 is reused as the absorption liquid.
[0051]
　1, reference numeral 13a flue, 13b are chimney 34 is steam-condensate. The CO 2 recovering apparatus 12, CO from the exhaust gas source of the existing 2 and a case when it is provided in retrofitted and, which is co-attached to the new exhaust gas source to recover. Incidentally, in the line of the exhaust gas 14 has established an openable dampers, CO 2 during the operation of the recovery device 12 is opened. Although the exhaust gas source is running, CO 2 when stopping the operation of the recovery device 12 is set to close.
[0052]
　The CO 2 recovering apparatus 12 CO using 2 In recovery method, first, CO 2 gas 14 from industrial combustion facility 13 of the boiler and a gas turbine or the like containing, after being boosted by the exhaust gas blower 22, the exhaust gas cooling device is sent to 16 where it is cooled by cooling water 15, CO 2 is fed to the absorption tower 18.
[0053]
　The CO 2 in the absorption tower 18, the exhaust gas 14 CO is an amine absorbent solution according to the present embodiment 2 absorbing solution 17 and then countercurrent contact, CO in the exhaust gas 14 2 is, CO by chemical reaction 2 absorbed into the absorbing solution 17 It is.
　CO 2 CO in the recovery portion 18A 2 CO after was removed 2 removing exhaust gases, CO 2 CO supplied from the nozzle washing section 18B in the absorption tower 18 2 wash water 21 circulating containing absorption liquid and gas-liquid contact with, CO 2 CO accompanying the flue gas 2 absorbing liquid 17 is recovered, then CO 2 gas 23 that has been removed is discharged out of the system.
　Moreover, CO 2 CO was absorbed 2 rich solution which is an absorption liquid 19 is pressurized by the rich solution pump 24, the rich-lean solution heat exchanger 25, the absorbing solution was regenerated in the regeneration tower 20 CO 2Is heated by the lean solution is an absorption liquid 17 is supplied to the absorbent regenerator 20.
[0054]
　Rich solution 19 emitted from the upper inside of the absorbing solution regeneration tower 20, caused an endothermic reaction by steam supplied from the bottom, most of the CO 2 releasing. CO some or most in absorbent regenerator within 20 2 CO were released 2 absorbing solution is called semi-lean solvent. The semi-lean solution, the time to reach the bottom of the absorbing solution regeneration tower 20, almost all of the CO 2 CO has been removed 2 becomes absorbing solution (lean solution) 17. The lean solution 17 is partially overheated by steam 27 in reboiler 26, CO inside the absorbent regenerator 20 2 supplies steam for desorption. 1, reference numeral 27 is a steam introduction pipe for introducing steam into the reboiler 26, 30 gas-liquid separator, 34 is respectively illustrated a condensed water drain pipe for discharging the condensed water separated by the gas-liquid separator 30 .
[0055]
　On the other hand, from the top of the absorbing solution regeneration tower 20, CO accompanied by water vapor released from the rich solution 19 and semi-lean solution in the tower 2 carrier gas 28 is led out, the steam is condensed by the condenser 29, the separation drum 30 with water is separated, CO 2 gas 40 is released out of the system, it is compressed by a separate compressor 41 and recovered. CO The compressed and recovered 2 gas 42, after passing through the separation drum 43, enhanced oil recovery method (EOR: Enhanced Oil Recovery) or pressed into oil was used to stored in an aquifer, warming It is aimed measures.
　CO accompanied by steam 2 reflux water 31 separated reflux in the separation drum 30 from carrier gas 28 are respectively supplied to the upper and the cleaning water 21 side of the absorbent solution regeneration column 20 at a reflux water circulation pump 35.
　Regenerated CO 2 absorbing solution (lean solution) 17, at the rich-lean solution heat exchanger 25, is cooled by the rich solution 19 is pressurized by a lean solution pump 32 Subsequently, further in the lean solution cooler 33 after being cooled, CO 2 is fed into the absorption tower 18. In this embodiment, which only explaining the outline has been described with partial omission accompanying equipment.
[0056]
　Hereinafter, a description will be given of a preferred test examples showing the effects of the present invention, the present invention is not limited thereto.
[0057]
[Test Example]
　using unillustrated absorption test apparatus, CO 2 was absorbed. Figure 3-7 composite amine absorbent ternary in Test Example 1-16 (straight monoamine (a component), the diamine (b component), amide group-containing compound (d component) in water (c component) it is a diagram illustrating a reboiler heat reduction rate of dissolved ones). Here, the sum of linear monoamine (a component) with a diamine (b component) of the test examples were in the range from 47 wt% to 55 wt%. Here, the comparative example, except that it does not include an amide group-containing compound (d component) from each formulation sought reboiler heat in the same conditions as in Test Example, the reboiler heat reduction ratio relative to the reboiler heat of the comparative example ( %) was determined. It should be noted, it shows the component list of the test examples in the following "Table 1".
[0058]
[Table 1]

[0059]

　In Test Example 1, a linear monoamine (a component), using N- ethylamino ethanol, using 2-methylpiperazine as a diamine (b component), amide group-containing compound (d component) as, N, N- dimethylacetamide using a dissolved mixture of water and with each of the absorption liquid.
　N, the value of N- dimethylacetamide dielectric constant of (d component) (25 ° C.) is 38 (hereinafter the same).
[0060]
　In Test Example 2, as a straight monoamine (a component), using N- ethylamino ethanol, using piperazine as the diamine (b component), amide group-containing compound as (d component), using N, the N- dimethylacetamide , dissolved mixture of water and with each of the absorption liquid.
[0061]
　In Test Example 3, as a straight monoamine (a component), using N- butylamino ethanol, using 2-methylpiperazine as a diamine (b component), as an amide group-containing compound (d component), N, N- dimethyl with acetamide, was dissolved mixture of water and with each of the absorption liquid.
[0062]
　In Test Example 4, the linear monoamine (a component), using N- butylamino ethanol, using piperazine as the diamine (b component), amide group-containing compound as (d component), using N, the N- dimethylacetamide , dissolved mixture of water and with each of the absorption liquid.
[0063]
　In the test examples 1-4, the addition weight ratio of the amide group-containing compound (d component) and water (c component) ((d) / (c + d)) was 0.5.
[0064]
　Absorption conditions in this test, 40 ° C., 10KPaCO 2 and, also, reproduction conditions are set to 120 ° C., was determined reboiler heat reduction rate (%).
[0065]
　The results of this test example 1-4 in FIG.
　As shown in FIG. 3, Test Example 1 was near reboiler heat reduction ratio is 10%, Test Examples 2, 3 and 4 are more than 10% of the reboiler heat reduction rate, Test Example 4 in which greater than 15% there were.
[0066]

　In Experimental Example 5, 2 as a linear monoamine (a component) of two used, the use of monoethanolamine as a first linear monoamine, a second linear monoamines (1) - using amino-2-methyl-1-propanol.
　Further, using propane as the diamine (b component) (2), (3) an amide group-containing compound (d component) as N, using N- dimethylacetamide, and water dissolved mixing each of the absorbent did.
[0067]
　In Test Example 6, straight monoamine (a component) of two used, the use of monoethanolamine as a first linear monoamine, a 2-amino-2-methyl-1-propanol as a second linear monoamines Using.
　Further, using propane as the diamine (b component), N, the N- diethylacetamide used as an amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
　N, the value of N- diethylacetamide dielectric constant of (d component) (25 ° C.) is 31 (hereinafter the same).
[0068]
　In Test Example 7, straight monoamine (a component) of two used, the use of monoethanolamine as a first linear monoamine, a 2-amino-2-methyl-1-propanol as a second linear monoamines Using.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
[0069]
　In the test examples 5-7, the addition weight ratio of the amide group compounds and (d component) and water (c component) ((d) / (c + d)) was 0.25.
[0070]
　Further, in Test Example 8-10, except for changing the addition weight ratio of the amide group compounds and (d component) and water (c component) and ((d) / (c + d)) and 0.5, the test was the same formulation as in example 5-7.
[0071]
　Absorption conditions in this test, 40 ° C., 10KPaCO 2 and, also, reproduction conditions are set to 120 ° C., was determined reboiler heat reduction rate (%).
　The results of this test example 5-10 in FIG.
　As shown in FIG. 4, Test Example 5-7 is near reboiler heat reduction ratio is 7-9%, Test Examples 8, 9 and 10 were those reboiler heat reduction rate exceeds 16%.
[0072]

　In Test Example 11, (1) a straight-chain monoamine (a component) of two used, the use of N- ethylamino ethanol as the first linear monoamine, a second linear monoamines using N- methyldiethanolamine as.
　Further, using piperazine as diamine (2) (b component) and N, N-dimethylacetamide with a dissolved mixture of water each of the absorbing liquid as an amide group-containing compound (d component) (3) .
[0073]
　In Test Example 12, straight monoamine (a component) of two used, the use of N- butylamino ethanol as the first linear monoamines, using N- methyldiethanolamine as a second linear monoamines.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
[0074]
　In Test Example 13, straight monoamine (a component) of two used, the use of N- ethylamino ethanol as the first linear monoamines, 2-amino-2-methyl as a second linear monoamine-1- using propanol.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
[0075]
　In Test Example 14, straight monoamine (a component) of two used, the use of N- butylamino ethanol as the first linear monoamines, 2-amino-2-methyl as a second linear monoamine-1- using propanol.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
[0076]
　In Test Example 15, straight monoamine (a component) of two used, the use of N- methyldiethanolamine as a first linear monoamines, 2-amino-2-methyl-1-propanol as a second linear monoamines It was used.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
[0077]
　In Test Example 16, a linear monoamine (a component) of two used, the use of 4-dimethylamino-1-butanol as the first linear monoamines, 2-amino-2-methyl as a second linear monoamines -1 using propanol.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
[0078]
　In the Test Examples 11-16, the addition weight ratio of the amide group-containing compound (d component) and water (c component) ((d) / (c + d)) was 0.5.
[0079]
　Absorption conditions in this test, 40 ° C., 10KPaCO 2 and, also, reproduction conditions are set to 120 ° C., was determined reboiler heat reduction rate (%).
　Figure 5 The results of this test example 11-12, in Figure 6 the results of Test Example 13-14, respectively show the results of Test Example 15-16 in FIG.
　As shown in FIG. 5, Test Examples 11 and 12 are reboiler heat reduction ratio is more than 10%, as shown in FIG. 6, the test examples 13 and 14 were those reboiler heat reduction rate exceeds 10%.
　As shown in FIG. 7, the test examples 15 and 16 were those reboiler heat reduction ratio exceeds 7%.
[0080]
　As described above, according to the present invention, a straight-chain monoamine (a component) of (1), a diamine (b component) (2), and amide group-containing compound (3) (d component), water ( since dissolved in component c), with respect to the prior art, it can provide excellent composite amine absorbent to energy saving, CO in the gas 2 or H 2 when reproducing the S or absorbing solution which has absorbed the both it can be reduced reboiler heat.
[0081]

　Test Example 17 is the same blending as in Test Example 16, straight monoamine (a component) of two used, the use of 4-dimethylamino-1-butanol as the first linear monoamines , using 2-amino-2-methyl-1-propanol as a second linear monoamines.
　Further, using piperazine as the diamine (b component), N, the N- dimethylacetamide used as amide group-containing compound (d component), was dissolved mixture of water and with each of the absorption liquid.
　As a comparative example 17-1 of Test Example 17, N of the amide group-containing compound from Test Example 17 (d component) and do not blended N- dimethylacetamide.
　As a comparative example 17-2 of Test Example 17, in which not blended piperazine diamine (b component) from Test Example 17. Incidentally, increasing concentrations of decrease only 4-dimethylamino-1-butanol diamine (b component), were set the same as the total concentration of Test Example 17.
　As a comparative example 17-3 of Test Example 17, N of diamine from Test Examples 17 piperazine and amide group-containing compound (b component) (d component) and do not blended N- dimethylacetamide.
[0082]
　Absorption conditions in this test, 40 ° C., 10KPaCO 2 and, also, reproduction conditions are set to 120 ° C., was determined reboiler heat reduction rate (%).
[0083]
　Reduction ratio of the reboiler heat was defined as the following equation.
Reboiler heat reduction ratio = (amide reboiler heat reduction rate Test Example 17 for Comparative Example 17-1 containing no group-containing compound (%)) / (diamine for Comparative Example 17-3 containing no diamine and amide group-containing compound the reboiler heat reduction rate of Comparative example 17-2 free (%))
　the results are shown in Figure 8. Figure 8 is a diagram showing the ratio of reboiler heat reduction rate in Test Example 17 and Comparative Example.
[0084]
　As shown in FIG. 8, Test Example 17 containing diamine, with respect to Comparative Example 17-2 containing no diamine, has a great effect reboiler heat reduction ratio is 1.3 times or more. This effect is not only excellent absorption performance of the diamine (b component), improved playback performance containing steam latent heat quantity reduction of the outlet gas from the absorbent regenerator 20 by interaction with the amide group-containing compound (d component) it is due to the effect of.
　As described above, those effects of the diamine (b component) amide group-containing compounds during the content (d component) addition is not readily occur only from vapor-liquid equilibrium, the result of intensive studies to reboiler heat was achieved for the first time it is.
DESCRIPTION OF SYMBOLS
[0085]
　12 CO 2 recovery unit
　13 industrial combustion facility
　14 exhaust
　16 exhaust gas cooler
　17 CO 2 absorbing solution (lean
　solution) 18 CO 2 absorption tower
　19 CO 2 CO absorbed 2 absorbing solution (rich
　solution) 20 absorbent regenerator
　21 wash water　

WE CLAIM

CO in the gas 2 or H 2 A S or absorbent that absorbs both,
　(1) with linear monoamine,
　and (2) a diamine,
　and (3) an amide group-containing compound, was dissolved in water composite amine absorbent, characterized by comprising.
[Requested item 2]
　According to claim 1,
　(1) a linear monoamine, primary linear monoamines, secondary linear monoamines, composite amine absorbent, characterized in that it comprises at least one tertiary linear monoamines.
[Requested item 3]
　According to claim 1 or 2,
　(2) a diamine of, primary linear polyamines, secondary linear polyamines, composite amine absorbent, characterized in that it comprises at least one cyclic polyamine.
[Requested item 4]
　In any one of claims 1 to 3,
　composite amine, wherein (1) the linear monoamines, the concentration sum of the diamine (2) is 40 to 60 wt% of the total absorbing solution absorbing liquid.
[Requested item 5]
　In any one of claims 1 to 4,
　(1) relative to the linear monoamines, blending ratio of the amide group-containing compound (2) diamine and (3), (diamine + amide group-containing compound ) / composite amine absorbent to a straight monoamine is characterized in that a 0.16 to 2.1.
[Requested item 6]
　In any one of claims 1 to 5,
　mixing ratio of the amide group-containing compound (2) diamine and (3) is 1: 0.4 to 1: 54 composite amine, which is a absorbing liquid.
[Requested item 7]
　CO 2 or H 2 S or a gas containing absorbing solution and is contacted with and CO that both 2 or H 2 and S or absorption tower to remove the both, CO 2 or H 2 solution having absorbed S or both, and a absorbent regenerator for reproducing, the absorbing solution regeneration tower with CO 2 or H 2 reuse S or solution was regenerated to remove both of the above absorption tower, CO 2 or H 2 S or a removal device of the both,
　CO is characterized by using any one of a composite amine absorbent of claims 1 to 6 2 or H 2 S or both of the removal device.
[Requested item 8]
　In claim 7,
　the absorption temperature of the absorption tower, along with a 30 ~ 80 ° C., the regeneration temperature of the absorbent solution regeneration tower, CO and wherein the at 110 ° C. or higher 2 or H 2 S or both removal device.
[Requested item 9]
　CO 2 or H 2 S or by contacting the gas with absorbing liquid containing both of CO 2 or H 2 S or both, was removed in the absorption tower, CO 2 or H 2 was absorbed S, or both the solution was reproduced in the absorbing solution regeneration tower, the absorbing solution regeneration tower with CO 2 or H 2 reuse S or solution was regenerated to remove both of the above absorption tower, CO 2 or H 2 S or a both method for removing,
　according to claim 1 to 6 or one composite amine absorbent CO using a 2 or H 2 S or CO, and removing the both 2 or H 2 S or both the method of removing the.
[Requested item 10]
　In claim 9,
　the absorption temperature of the absorption tower, along with a 30 ~ 80 ° C., the regeneration temperature of the absorbent solution regeneration tower, CO and wherein the at 110 ° C. or higher 2 or H 2 S or both the method of removal.