# Patent

## Title
Absorbing solution, method and device for absorbing CO2 or H2S or both

## Abstract

An absorbing solution according to the present invention is an absorbing solution that absorbs CO2 or H2S in gas or both of CO2 and H2S. The absorbing solution is formed by adding desirably 1 to 20 weight percent of tertiary monoamine to a secondary-amine composite absorbent such as a mixture of secondary monoamine and secondary diamine. Consequently, it is possible to control degradation in absorbing solution amine due to oxygen or the like in gas. As a result, it is possible to realize a reduction in an absorption loss, prevention of malfunction, and a reduction in cost. This absorbing solution is suitably used in an apparatus for removing CO2 or H2S or both of CO2 and H2S.

## Background
TECHNICAL FIELD
The present invention relates to an absorbing solution that removes any one of carbon dioxide (CO2) and hydrogen sulfide (H2S) or both of CO2 and H2S contained in gas, and an apparatus and a method that removes any one of CO2 and H2S or both of CO2 and H2S by using the absorbing solution.
BACKGROUND ART
Conventionally, have been studied a method of collecting and removing acid gases, in particular, CO2 that are contained in gases (treatment object gases), for example various industrial gases manufactured in chemical plants such as a natural gas and a synthesis gas and flue gases, and various methods have been proposed.
For example, for the flue gases, have been actively studied a method of bringing CO2 in a flue gas into contact with an alkanolamine solution or the like to remove and collect CO2, and a method of storing CO2 without emitting CO2 to the atmosphere.
As the alkanolamine, it is possible to use monoethanolamine (MEA), 2-methylaminoethanol, 2-ethylaminoethanol, 2-propylaminoethanol, n-buthylaminoethanol, 2-(isopropylamino)ethanol, and 3-ethylaminoethanol.
For example, an absorbing-solution formed of a mixture of secondary amine or a mixture of secondary amine and tertiary amine is disclosed in a United States Patent specification. It is proposed that this mixed absorbing-solution is an advantageous absorbing-solution because an absorbing ability and regeneration energy are substantially improved in the mixed absorbing solution compared with an MEA single absorbing solution (Patent Document 1).
When a monoethanolamine (MEA) absorbing solution is used, there is a problem in that degradation in the absorbing-solution severely progresses because of oxygen or the like in gas.
Therefore, conventionally, a method has been proposed for stabilizing an absorbing-solution by adding, for example, trialkanolamine or methyldiethanolamine (MDEA) to the absorbing-solution (Patent Document 2 and Patent Document 3).
Patent Document 1: U.S. Pat. No. 5,618,506 specification
Patent Document 2: U.S. Pat. No. 3,535,260 specification
Patent Document 3: U.S. Pat. No. 4,840,777 specification
DISCLOSURE OF INVENTION
Problem to Be Solved by the Invention
However, in the patent documents, disclosed are demonstrations for the absorbing ability and the like for the absorbing-solution formed of the mixture of secondary amine. However, not disclosed is a method of preventing degradation in the absorbing-solution due to oxygen or the like in gas. Further control of degradation in the absorbing-solution still remains a problem to solve.
Taking the problem into consideration, it is an object of the present invention to provide an absorbing-solution which can prevent self-degradation due to oxygen or the like that is present in gas, and a method and an apparatus for removing any one of CO2 and H2S or both.
Means for Solving Problem
To overcome the above problems, according to claim 1, an absorbing-solution that absorbs any one of CO2 and H2S or both that are present in gas includes secondary-amine composite absorbent; and tertiary monoamine that is added to the secondary-amine composite absorbent.
According to claim 2, the absorbing-solution according to claim 1, wherein the secondary-amine composite absorbent is a mixture of secondary monoamine and secondary diamine.
According to claim 3, the absorbing-solution according to claim 2, wherein the secondary monoamine is a compound that is selected from at least one kind of 2-methylaminoethanol, 2-ethylaminoethanol, 2-n-propylaminoethanol, 2-n-buthylaminoethanol, 2-n-penthylaminoethanol, 2-isopropylaminoethanol, 2-sec-buthyleamnoethanol, and 2-isobuthylaminoethanol, and the secondary diamine is a compound that is selected from at least one kind of piperazine, 2-metylpiperazine, 2,3-dimethylpiperazine, 2,5-dimethylpiperazine, N,N′-dimethylethanediamine, N,N′-dimethylpropanediamine, N,N′-diethylethylenediamine, N,N′-diethylpropanediamine, N,N′-diisopropylethylenediamine, and N,N′-ditartiary-buthylethanediamine.
According to claim 4, the absorbing-solution according to claim 1, wherein 1 to 20 weight percent of the tertiary monoamine is added to the secondary-amine composite absorbent.
According to claim 5, the absorbing-solution according to claim 2, wherein 2.5 to 100 weight percent of the secondary diamine is added to the secondary monoamine.
According to claim 6, a removing apparatus that removes any one of CO2 and H2S or both includes an absorber that brings therein the gas that includes any one of CO2 and H2S or both into an absorbing-solution to contact so as to remove any one of CO2 and H2S or both; and a regenerator that regenerates a solution that absorbs any one of CO2 and H2S or both, wherein the absorber re-uses the solution that is regenerated by the regenerator to remove any one of CO2 and H2S or both, the absorbing-solution being any one of that according to claims 1 to 5.
According to claim 7, a method for a removing apparatus to remove any one of CO2 and H2S or both includes bringing gas that includes any one of C02 and H2S or both into an absorbing-solution to contact; removing any one of CO2 and H2S or both in an absorber; regenerating the solution that absorbs any one of CO2 and H2S or both at the removing in a regenerator; and re-using the solution that is regenerated at the regenerating in the absorber, wherein the removing includes removing any one of CO2 and H2S or both by using an absorbing-solution that is according to any one of claims 1 to 5.
Effects of the Invention
According to the embodiment of the present invention, it is possible to reduce a loss of an absorbing-solution due to degradation in amine used as the absorbing-solution, to prevent deterioration of performance, and to reduce a cost.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a diagram for explaining an example of a process that can be adopted in the present invention.



EXPLANATIONS OF LETTERS OR NUMERALS


    1 Decarbonator
    15 Absorbing-solution regenerator


BEST MODE(S) FOR CARRYING OUT THE INVENTION
Exemplary embodiment of the present invention is explained in detail below with reference to the drawings. The present invention is not limited by the embodiment and an example. Components in the embodiment and the example include components that those skilled in the art can easily anticipate, or include components that are substantially identical with the components that those skilled in the art can easily anticipate.
Embodiment of the Invention
An absorbing solution according to an embodiment of the present invention is an absorbing solution that absorbs any one of CO2 and H2S or both of CO2 and H2S in gas. The absorbing solution is formed by adding tertiary monoamine to a secondary-amine composite absorbent. Consequently, it is possible to control degradation in amine in the absorbing solution due to oxygen or the like in gas.
It is desirable that the secondary-amine composite absorbent is a mixture of secondary monoamine and secondary diamine.
The secondary monoamine is of an amine compound represented by Formula (1) below.

R1CHR2NHCH2CH2OH  (1)

In the formula, R1 represents a lower alkyl group with a hydrogen or carbon number 1. to 4 and R2 represents a hydrogen or methyl group.
Specifically, examples of the secondary monoamine include a compound selected from at least one kind of 2-methylaminoethanol, 2-ethylaminoethanol, 2-n-propylaminoethanol, 2-n-buthylaminoethanol, 2-n-penthylaminoethanol, 2-isopropylaminoethanol, 2-sec-butyleamnoethanol 2-sec-buthyleamnoethanol, and 2-isobuthylaminoethanol. However, the present invention is not limited to this.
Examples of the secondary diamine include a compound selected from at least one kind of piperazine, 2-methylpiperazine, 2,3-dimethylpiperazine, 2,5-dimethylpiperazine, N,N′-dimethylethanediamine, N,N′-dimethylpropanediamine, N,N′-diethylethylenediamine, N,N′-diethylpropanediamine, N,N′-diisopropylethylenediamine, and N,N′-ditartiary-buthylethanediamine. However, the present invention is not limited to this.
It is assumed that the tertiary monoamine is an amine compound indicated by Formula (2) below.

R3R4NR5OH  (2)

R3 is a lower alkyl group with a carbon number 1 to 4, R4 is a lower alkyl group or hydroxyethyl group with a carbon number 1 to 4, and R5 is a lower alkyl group with a carbon number 2 to 4.
As the tertiary monoamine indicated by Formula (2), it is desirable to use, for example, N-methyldiethanolamine (MDEA), N-ethyldiethanolamine, N-butyldiethanolamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-di-n-butylaminoethanol, N-ethyl-N-methylethanolamine, 3-dimethylanimo-1-propanol, 2-dimethylamino-2-methyl-1-propanol, or 4-dimethylamino-1-butanol. However, the present invention is not limited to this.
It is desirable to set a percentage of addition of tertiary monoamine to the secondary-amine composite absorbent to 1 to 20 weight percent.
This is because, as indicated by Table 1 below, when the percentage exceeds 20 weight percent, a fall in an absorption capacity undesirably increases.
On the other hand, when the percentage is lower than 1 weight percent, undesirably, it is impossible to eliminate an influence of contaminant.
Table 1







TABLE 1







(50° C., 10 mol % dry CO2 condition)










Tertiary amine concentration with respect




to a mixture of secondary monoamine and
Absorption



secondary diamine (weight %)
capacity ratio














0
1 (reference)



10
0.99



20
0.96



30
0.93










A percentage of addition of secondary diamine to secondary monoamine is not specifically limited. However, it is desirable to add 2.5 to 100 weight % of secondary diamine.
A process that can be adopted in the method of removing CO2 or H2S in a flue gas or both of CO2 and H2S according to the present invention is not specifically limited. An example of the process is explained with reference to FIG. 1.
In FIG. 1, only main equipment is shown and additional equipment is not shown. In FIG. 1, reference numeral 1 denotes a decarbonator; 2, a lower filling unit; 3, an upper filling unit or a tray; 4, a decarbonator flue-gas supply port; 5, a decarbonator flue-gas exhaust port; 6, an absorbing-solution supply port; 7, nozzles; 8, a flue gas cooler provided when needed; 9, nozzles; 10, a filling unit; 11, a humidifying-coolant circulation pump; 12, a makeup-water supply line; 13, an absorbing-solution discharge pump for an absorbing-solution in which CO2 is absorbed; 14, a heat exchanger; 15, an absorbing-solution regenerator; 16, nozzles; 17, a lower filling unit; 18, a reboiler; 19, an upper filling unit; 20, a reflux water pump; 21, a CO2 separator; 22, a collected CO2 exhaust line; 23, a regenerator reflex cooler; 24, nozzles; 25, a regenerator reflux-water supply line; 26, a flue-gas supply blower; 27, a cooler, and 28, a regenerator reflux-water supply port.
In FIG. 1, a flue gas is squeezed into the flue gas cooler 8 by the flue-gas supply blower [translator's comment: reference numeral 26 should be affixed]. The flue gas comes into contact with a humidifying coolant from the nozzles 9 in the filling unit 10 and is humidified and cooled and led to the decarbonator 1 through the decarbonator flue-gas supply port 4. The humidifying coolant coming into contact with the flue gas accumulates in a lower part of the flue gas cooler 8 and is circulated to the nozzles 9 by the pump 11 and used. Since the humidifying coolant is gradually lost by humidifying and cooling the flue gas, the humidifying coolant is filled by the makeup-water supply line 12.
The flue gas squeezed into the decarbonator 1 is brought into counter-contact with an absorbing-solution of a fixed concentration supplied from the nozzles 7 in the lower filling unit 2. CO2 in-the decarbonated flue gas is absorbed and removed by the absorbing-solution and the decarbonated flue gas flows to the upper filling unit 3. The absorbing-solution supplied to the decarbonator 1 absorbs CO2. Temperature of the absorbing-solution usually rises to be higher than temperature in the absorbing-solution supply port 6 because of reaction heat due to the absorption. The absorbing-solution is sent to the heat exchanger 14 by the absorbing-solution discharge pump 13 for the absorbing-solution in which CO2 is absorbed. The absorbing-solution is heated and led to the absorbing-solution regenerator 5. It is possible to perform temperature adjustment for the absorbing-solution regenerated using the heat exchanger 14 or the cooler 27 provided between the heat exchanger 14 and the absorbing-solution supply port' 6 as required.
In the absorbing-solution regenerator 15, the absorbing-solution is regenerated in the lower filling unit 17 according to heating by the reboiler 18, cooled by the heat exchanger 14, and returned to the decarbonator 1. In an upper part of the absorbing-solution regenerator 15, CO2 separated from the absorbing-solution comes into contact with a reflux water supplied from the nozzles 24 in the upper filling unit 19 and cooled by the regenerator reflux cooler 23. Water vapor accompanying CO2 is separated from the condensed reflux water by the CO2 separator 21 and led to a CO2 collection process from the collected CO2 exhaust line 22. The reflux water is partially refluxed to the regenerator by the reflux water pump 20 and partially supplied to the regenerator reflux-water supply port 28 of the decarbonator 1 through the regenerator reflux-water supply line 25. Since a small quantity of absorbing-solution is contained in this regenerated reflux water, the absorbing-solution comes into contact with exhaust gas in the upper filling unit 3 of the decarbonator 1 and contributes to removal of a small quantity of CO2 contained in the exhaust gas.
EXAMPLE
An example according to the present invention is explained.
In the example, temperature was set to 60° C. and oxygen concentration in gas was set to 20 mol %.
As a compounding ratio, concentration of tertiary amine with respect to a mixture of secondary monoamine and a secondary diamine was set to 2 weight percent.
In this example, secondary monoamine was used and a piperazine compound was used as secondary diamine to form a secondary-amine composite absorbent. 2 weight percent of methyldiethanolamine (MDEA) was added to the secondary-amine composite absorbent as tertiary monoamine. Thereafter, a predetermined quantity of water was added to the secondary-amine composite absorbent to form a CO2 absorbing-solution. Concentration of a decomposition product (a vapor-like basic compound) in the CO2 absorbing-solution obtained was 8 ppm.
On the other hand, concentration of a decomposition product (a vapor-like basic compound) in a CO2 absorbing-solution formed of a secondary monoamine and a piperazine compound, which was a comparative example in which 2 weight percent of methyldiethanolamine (MDEA) was not added to the secondary-amine composite absorbent as tertiary monoamine, was 15 ppm
Thus, it was found that, when tertiary monoamine was added to the secondary-amine composite absorbent, it is possible to control degradation due to oxygen in exhaust gas.
INDUSTRIAL APPLICABILITY
As described above, the absorbing-solution according to the present invention is suitably used in a facility that removes CO2 or H2S in a flue gas or both of CO2 and H2S, in which a reduction in a loss of an absorbing-solution due to degradation in absorbing-solution amine, prevention of malfunction, and a reduction in cost can be realized.

## Claims

1. An absorbing-solution that absorbs at least one of CO2 and H2S that are present in a gas, the absorbing-solution comprising:
a secondary-amine composite absorbent which is a mixture of a secondary monoamine and a secondary diamine; and
a tertiary monoamine that is added to the secondary-amine composite absorbent,
wherein the tertiary monoamine concentration with respect to the mixture of secondary monoamine and secondary diamine is set to 1 to 20 weight percent.

2. The absorbing-solution according to claim 1, wherein
the secondary monoamine is at least one member selected from the group consisting of 2-methylaminoethanol, 2-ethylaminoethanol, 2-n-propylaminoethanol, 2-n-butylaminoethanol, 2-n-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec-butylaminoethanol, and 2-isobutylaminoethanol, and
the secondary diamine is at least one member selected from the group consisting of piperazine, 2-methylpiperazine, 2,3-dimethylpiperazine, 2,5-dimethylpiperazine, N,N′-dimethylethanediamine, N,N′-dimethylpropanediamine, N,N′-diethylethanediamine, N,N′-diethylpropanediamine, N,N′-diisopropylethylenediamine, and N,N′-ditertiary-butylethanediamine.

3. The absorbing-solution according to claim 1, wherein
the secondary monoamine is at least one member selected from the group consisting of 2-methylaminoethanol, 2-ethylaminoethanol, 2-n-propylaminoethanol, 2-n-butylaminoethanol, 2-n-pentylaminoethanol, 2-isopropylaminoethanol, 2-sec-butylaminoethanol, and 2-isobutylaminoethanol, and
the secondary diamine is at least one member selected from the group consisting of piperazine, 2-methylpiperazine, 2,3-dimethylpiperazine, and 2,5-dimethylpiperazine.

4. The absorbing-solution according to claim 1, wherein 2.5 weight percent to less than 100 weight percent of the secondary diamine is added to the secondary monoamine.

5. A removing apparatus which removes at least one of CO2 and H2S that are present in a gas, the removing apparatus comprising:
an absorber that receives the gas and causes the gas to come into contact with an absorbing-solution whereby at least one of CO2 and H2S is absorbed by the absorbing-solution; and
a regenerator that regenerates the absorbing-solution which has absorbed at least one of CO2 and H2S by removing any one of CO2 and H2S or both from the absorbing-solution, and that supplies the absorbing-solution from which at least one of CO2 and H2S has been removed to the absorber,
wherein the absorbing-solution includes a secondary-amine composite absorbent which is a mixture of a secondary monoamine and a secondary diamine and a tertiary monoamine that is added to the secondary-amine composite absorbent, wherein the tertiary monoamine concentration with respect to the mixture of secondary monoamine and secondary diamine is set to 1 to 20 weight percent.

6. The removing apparatus according to claim 5, wherein the mixture contains 2.5 to less than 100 weight percent of the secondary diamine based on the secondary monoamine.

7. A method of removing apparatus to remove at least one of CO2 and H2S that are present in a gas, the method comprising:
causing the gas to come into contact with an absorbing-solution whereby at least one of CO2 and H2S is absorbed by the absorbing-solution; and
regenerating the absorbing-solution that absorbed any one of CO2 and H2S by removing at least one of CO2 and H2S from the absorbing-solution,
wherein the causing step includes causing the gas to come into contact with an absorbing-solution that is regenerated in the regenerating step, and
wherein the absorbing-solution includes a secondary-amine composite absorbent which is a mixture of a secondary monoamine and a secondary diamine, and 1 to 20 weight-percent, based on the weight of said secondary-amine composite absorbent, of a tertiary monoamine that is added to the secondary-amine composite absorbent.

8. The method according to claim 7, wherein the mixture contains 2.5 to less than 100 weight percent of the secondary diamine based on the secondary monoamine.