WO2015056657A1 - 複合アミン吸収液、ｃｏ２又はｈ２ｓ又はその双方の除去装置及び方法 - Google Patents

複合アミン吸収液、ｃｏ２又はｈ２ｓ又はその双方の除去装置及び方法 Download PDF

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WO2015056657A1
WO2015056657A1 PCT/JP2014/077264 JP2014077264W WO2015056657A1 WO 2015056657 A1 WO2015056657 A1 WO 2015056657A1 JP 2014077264 W JP2014077264 W JP 2014077264W WO 2015056657 A1 WO2015056657 A1 WO 2015056657A1
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compound
amine
amine compound
group
disulfide
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English (en)
French (fr)
Japanese (ja)
Inventor
田中　裕士
琢也 平田
大石　剛司
遠藤　崇彦
晋平 川▲崎▼
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Kansai Electric Power Co Inc
Mitsubishi Heavy Industries Ltd
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Kansai Electric Power Co Inc
Mitsubishi Heavy Industries Ltd
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Priority to CA2924300A priority Critical patent/CA2924300A1/en
Priority to AU2014335384A priority patent/AU2014335384B2/en
Priority to EP14853761.6A priority patent/EP3034152A4/en
Priority to US15/022,125 priority patent/US20160220947A1/en
Publication of WO2015056657A1 publication Critical patent/WO2015056657A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20405—Monoamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/2041—Diamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20421—Primary amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20426—Secondary amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20431—Tertiary amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20442—Cyclic amines containing a piperidine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20447—Cyclic amines containing a piperazine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B01D2252/20484—Alkanolamines with one hydroxyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B01D2252/20489—Alkanolamines with two or more hydroxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2056—Sulfur compounds, e.g. Sulfolane, thiols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/502—Combinations of absorbents having two or more functionalities in the same molecule other than alkanolamine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/604—Stabilisers or agents inhibiting degradation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a composite amine absorbing solution that absorbs CO 2 and / or H 2 S in a gas, or both, and an apparatus and method for removing CO 2 and / or H 2 S or both.
  • the regeneration step consumes a large amount of heat energy, so it is necessary to make it an energy saving process as much as possible.
  • Patent Document 3 In order to improve the performance of the CO 2 absorbent, there is a proposal of an absorbent that contributes to the improvement of the absorption performance (Patent Document 3).
  • the CO 2 absorption liquid is important not only for its absorption performance but also for its release ability when regenerating the absorption liquid.
  • many of the conventional CO 2 absorption liquids have been designed to improve the absorption performance and have good regeneration performance. There are few studies on this.
  • an object of the present invention is to provide an apparatus and method for removing a composite amine absorbent, CO 2 and / or H 2 S, or both, which have not only absorption capacity but also regeneration capacity.
  • the first invention of the present invention for solving the above-mentioned problems is an absorption liquid that absorbs CO 2 and / or H 2 S in gas, or both, and includes 1) at least one amine compound and 2) absorption.
  • the composite amine absorbing liquid is characterized in that a disulfide compound which is an oxidative degradation inhibitor of the liquid is dissolved in water, and the disulfide compound is a compound represented by the following chemical formula (I).
  • R 1 -SSR 2 (I)
  • R 1 or R 2 is any one of an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, a carboxyethyl group, a cyclohexyl group, and a dibutylthiocarbamoyl group.
  • the composite amine absorbing liquid according to the first invention wherein the disulfide compound is added in an amount of 1 to 20% by weight based on the amine compound.
  • the amine compound is at least one primary amine compound, or at least one secondary amine compound, or at least one tertiary amine compound, or a mixture thereof. It is in the composite amine absorption liquid characterized by these.
  • a fourth invention provides a disulfide compound as the oxidative degradation inhibitor when the amine compound is at least one primary amine compound, or at least one secondary amine compound, or a mixture thereof in the third invention.
  • a tertiary amine compound is contained, and the tertiary amine compound is a compound represented by the following chemical formula (II).
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 4 is an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group
  • R 5 is an alkyl group having 2 to 4 carbon atoms.
  • the disulfide compound and the tertiary amine compound are added in an amount of 1 to 20% by weight based on the primary amine compound, the secondary amine compound, or a mixture thereof.
  • the composite amine absorbent is characterized in that.
  • a disulfide compound is used as the oxidative degradation inhibitor.
  • the composite amine absorbing liquid further comprises at least one piperidine compound, wherein the piperidine compound is a compound represented by the following chemical formula (III) (excluding piperidine).
  • R 6 is H, an alkyl group having 1 to 4 carbon atoms, a 2-aminoethyl group, or a 3-aminopropyl group
  • R 7 is any one of H and an alkyl group having 1 to 4 carbon atoms. .
  • a seventh invention is characterized in that, in the sixth invention, the disulfide compound and the piperidine compound are added in an amount of 1 to 20% by weight based on the primary amine compound, the secondary amine compound or a mixture thereof. It is in the composite amine absorbing solution.
  • the eighth invention is an absorbent that absorbs CO 2 or H 2 S or both in a gas, and 1) at least one primary amine compound, or at least one secondary amine compound, or a mixture thereof. And 2) an oxidative degradation inhibitor of the absorbing solution, dissolved in water, wherein the oxidative degradation inhibitor is a piperidine compound having the structure of the following chemical formula (III) and excluding piperidine: It is in the composite amine absorbent.
  • R 6 is H, an alkyl group having 1 to 4 carbon atoms, a 2-aminoethyl group, or a 3-aminopropyl group
  • R 7 is any one of H and an alkyl group having 1 to 4 carbon atoms. .
  • a ninth invention is the composite amine according to the eighth invention, wherein the piperidine compound is added in an amount of 1 to 20% by weight to the primary amine compound, the secondary amine compound or a mixture thereof. In the absorbent.
  • a tenth aspect of the invention is an absorption tower that removes CO 2 or H 2 S or both by bringing a gas containing CO 2 and / or H 2 S or both into contact with an absorbent, and CO 2 or H 2 S or a regenerator for reproducing a solution which has absorbed the both regenerator in a CO 2 or H 2 S or CO 2 removal or H 2 S or both reusing solution was regenerated to remove both of the absorption tower
  • An eleventh aspect of the invention is an absorption tower for removing CO 2 or H 2 S or both by bringing a gas containing CO 2 or H 2 S or both into contact with an absorbing solution, and CO 2 or H 2 S or a regenerator for reproducing a solution which has absorbed the both regenerator in a CO 2 or H 2 S or CO 2 removal or H 2 S or both reusing solution was regenerated to remove both of the absorption tower a method, composite amine absorbent CO 2 or H 2 S or both, and removing CO 2 or H 2 S or both using any one invention of the first to ninth In the removal method.
  • the oxidation reaction proceeds faster than the amine absorbing solution, the substance involved in the reaction is made a stable compound, and the amine absorbing solution is protected from oxidative degradation. Yes.
  • the addition of the disulfide compound can suppress deterioration due to oxidation of the amine absorbing solution due to oxygen or the like in the gas.
  • FIG. 1 is a diagram showing a performance index of an oxidation degradation inhibitor of a disulfide compound.
  • FIG. 2 is a diagram showing a figure of merit of an oxidation degradation inhibitor of a piperidine compound.
  • FIG. 3 is a diagram showing the results of a test example and a comparative example depending on whether or not a disulfide compound is added.
  • FIG. 4 is a diagram showing the results of a test example and a comparative example depending on whether or not an oxidation inhibitor is added.
  • FIG. 5 is a diagram showing the results of a test example and a comparative example depending on whether or not a piperidine compound is added.
  • FIG. 6 is a schematic diagram illustrating the configuration of the CO 2 recovery device according to the third embodiment.
  • the composite amine absorption liquid according to Example 1 of the present invention is an absorption liquid that absorbs CO 2 and / or H 2 S in gas, or both, and includes 1) at least one amine compound and 2) oxidation of the absorption liquid.
  • a disulfide compound which is a deterioration inhibitor is dissolved in water, and the disulfide compound is a compound represented by the following chemical formula (I).
  • R 1 or R 2 is any one of an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, a carboxyethyl group, a cyclohexyl group, and a dibutylthiocarbamoyl group.
  • the at least one amine compound of 1) is a known absorbing liquid that absorbs CO 2 or H 2 S, and is at least one primary amine compound, at least one secondary amine compound, or at least one tertiary amine. A compound, or a mixture thereof.
  • the primary amine for example, monoethanolamine (MEA), 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) can be mentioned.
  • MEA monoethanolamine
  • 2-amino-1-propanol (2A1P
  • AMB 2-amino-3-methyl-1-butanol
  • 1-amino-2-propanol 1, 1-amino-2-butanol (1A2B)
  • AMP 2-amino-2-methyl-1-propanol
  • the secondary amine compound is preferably any one of a secondary monoamine and a secondary diamine, or a mixture thereof.
  • secondary monoamines examples include 2-methylaminoethanol, 2-ethylaminoethanol, 2-n-propylaminoethanol, 2-n-butylaminoethanol, 2-n-pentylaminoethanol, 2-isopropylaminoethanol, 2
  • a compound selected from at least one of -sec-butylaminoethanol and 2-isobutylaminoethanol can be exemplified, but the present invention is not limited thereto.
  • Examples of secondary diamines include piperazine, 2-methylpiperazine, 2,3-dimethylpiperazine, 2,5-dimethylpiperazine, N, N′-dimethylethanediamine, N, N′-dimethylpropanediamine, N, Examples include compounds selected from at least one of N′-diethylethylenediamine, N, N′-diethylpropanediamine, N, N′-diisopropylethylenediamine, and N, N′-ditertiarybutylethanediamine. Is not limited to this.
  • the tertiary amine compound is a compound represented by the following chemical formula (II).
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 4 is an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group
  • R 5 is an alkyl group having 2 to 4 carbon atoms.
  • tertiary amine compounds include N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-di-n-butylaminoethanol, N-ethyl-N- Examples include methylethanolamine, 3-dimethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, and 4-dimethylamino-1-butanol, but the present invention is not limited thereto. is not.
  • the tertiary amine compound functions as an oxidative degradation inhibitor as described later, but can also be used as an absorbing solution.
  • disulfide compound that is an oxidative degradation inhibitor examples include diethyl disulfide, dipropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, bis (2-hydroxyethyl) disulfide, 2-carboxyethyl disulfide, and dicyclohexyl disulfide.
  • diethyl disulfide dipropyl disulfide
  • dibutyl disulfide di-tert-butyl disulfide
  • bis (2-hydroxyethyl) disulfide 2-carboxyethyl disulfide
  • dicyclohexyl disulfide examples include diethyl disulfide, dipropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, bis (2-hydroxyethyl) disulfide, 2-carboxyethyl disulfide, and dicyclohexyl disul
  • FIG. 1 is a diagram showing a performance index of an oxidation degradation inhibitor of a disulfide compound.
  • the figure of merit of the oxidative degradation inhibitor refers to the difference between the radical reaction rate possessed by the amine absorbent and the radical reaction rate possessed by the oxidative degradation inhibitor. As shown in FIG.
  • the disulfide compound advances the oxidation reaction faster than the amine absorption liquid, and the substance involved in the reaction is made a stable compound to protect the amine absorption liquid from oxidative deterioration.
  • the addition of the disulfide compound can suppress deterioration due to oxidation of the amine absorbing solution due to oxygen or the like in the gas.
  • the proportion of the disulfide compound added to the amine compound is preferably 1 to 20% by weight, more preferably 2 to 10% by weight.
  • a tertiary amine compound is further added to the disulfide compound as an oxidative degradation inhibitor.
  • the tertiary amine compound is a compound represented by the following chemical formula (II).
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 4 is an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group
  • R 5 is an alkyl group having 2 to 4 carbon atoms.
  • tertiary amine compounds include N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-di-n-butylaminoethanol, N-ethyl-N- Examples include methylethanolamine, 3-dimethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, and 4-dimethylamino-1-butanol, but the present invention is not limited thereto. is not.
  • a disulfide compound and a tertiary amine compound are used as an oxidative degradation inhibitor, 1 to 20% by weight, more preferably 2 to 10% by weight, based on the primary amine compound, the secondary amine compound, or a mixture thereof. It is preferable to add it.
  • the mixing ratio of the disulfide compound and the tertiary amine compound is preferably 70:30 to 30:70.
  • At least one piperidine compound is further added to the disulfide compound.
  • the piperidine compound is a compound represented by the following chemical formula (III) (excluding piperidine).
  • R 6 is H, an alkyl group having 1 to 4 carbon atoms, a 2-aminoethyl group, or a 3-aminopropyl group
  • R 7 is any one of H and an alkyl group having 1 to 4 carbon atoms.
  • Examples of the piperidine compound represented by the chemical formula (III) include 1-methylpiperidine, 1-ethylpiperidine, 1-propylpiperidine, 1-butylpiperidine, 2-methylpiperidine, 2-ethylpiperidine, 2-propylpiperidine, Examples include 2-butylpiperidine, 1- (2-aminoethyl) -2-methylpiperidine, and 1- (3-aminopropyl) -2-methylpiperidine, but the present invention is not limited thereto. .
  • a disulfide compound and a piperidine compound are used as an oxidation inhibitor, they are added in an amount of 1 to 20% by weight, more preferably 2 to 10% by weight, based on the primary amine compound, the secondary amine compound, or a mixture thereof. Preferably it is.
  • the mixing ratio of the disulfide compound and the piperidine compound is preferably 70:30 to 30:70.
  • FIG. 2 is a diagram showing a performance index of an oxidation degradation inhibitor of a piperidine compound.
  • a piperidine compound 1-methylpiperidine (P-1), 1-ethylpiperidine (P-2), 1-propylpiperidine (P-3), 1-butylpiperidine (P-4), 2-methyl Piperidine (P-5), 2-ethylpiperidine (P-6), 2-propylpiperidine (P-7), 2-butylpiperidine (P-8), 1- (2-aminoethyl) -2-methylpiperidine In (P-9) and 1- (3-aminopropyl) -2-methylpiperidine (P-10), an effect of suppressing oxidative degradation was confirmed. Therefore, the addition of the piperidine compound can suppress deterioration due to oxidation of the amine absorbing solution due to oxygen or the like in the gas.
  • Test example Below, the test example which shows the effect of a present Example is demonstrated.
  • Test Examples 1 and 2 In this test example, a secondary monoamine was used as the amine absorbent, and a piperazine compound was used as the secondary diamine to form a secondary amine composite absorbent. Next, by using dibutyl disulfide (D-3) and bis (2-hydroxyethyl) disulfide (D-5) in FIG. Test Example 1 and Test Example 2 (Trial-1, Trial-2) were used. For comparison, the case where the disulfide compound represented by the chemical formula (I) is not added is Comparative Example 1 (ratio-1), and the case where a tertiary amine compound (methyldiethanolamine (MDEA)) is added is Comparative Example 2 (ratio- 2).
  • FIG. 3 is a diagram showing the results of a test example and a comparative example depending on whether or not a disulfide compound is added.
  • the oxidation deterioration rate ratio means the ratio of the oxidation deterioration rate of the amine absorbent when the oxidation deterioration inhibitor is added to the oxidation deterioration rate of the amine absorbent when the oxidation deterioration inhibitor is not added.
  • FIG. 4 is a diagram showing the results of test examples and comparative examples depending on whether or not an oxidation inhibitor is added.
  • the composite amine absorbing liquid according to Example 2 according to the present invention is an absorbing liquid that absorbs CO 2 and / or H 2 S in gas, or both, and 1) at least one primary amine compound, or at least one 2 A secondary amine compound, or a mixture thereof, and 2) an oxidative degradation inhibitor of the absorbing solution, which are dissolved in water.
  • the oxidative degradation inhibitor has the structure of the following chemical formula (III) and excludes piperidine It is a piperidine compound.
  • R 6 is H, an alkyl group having 1 to 4 carbon atoms, a 2-aminoethyl group, or a 3-aminopropyl group
  • R 7 is any one of H and an alkyl group having 1 to 4 carbon atoms.
  • the piperidine compound is preferably added in an amount of 1 to 20% by weight, more preferably 2 to 10% by weight, based on the primary amine compound, the secondary amine compound or a mixture thereof.
  • Test example Below, the test example which shows the effect of a present Example is demonstrated.
  • FIG. 5 is a diagram showing the results of a test example and a comparative example depending on whether or not a piperidine compound is added.
  • the process that can be employed in the method for removing CO 2 and / or H 2 S in the gas of the present invention is not particularly limited, but an example of a removal apparatus for removing CO 2 will be described with reference to FIG.
  • the gas to be treated by the present invention such as coal gasification gas, syngas, coke oven gas, petroleum gas, natural gas, there may be mentioned a combustion exhaust gas or the like, but the invention is not limited to, CO 2 Any gas may be used as long as it contains an acidic gas such as H 2 S.
  • FIG. 6 is a schematic diagram illustrating the configuration of the CO 2 recovery device according to the third embodiment.
  • the CO 2 recovery device 12 according to the first embodiment cools an exhaust gas 14 containing CO 2 and O 2 discharged from an industrial combustion facility 13 such as a boiler or a gas turbine with cooling water 15.
  • an industrial combustion facility 13 such as a boiler or a gas turbine with cooling water 15.
  • an exhaust gas cooling device 16 which, CO 2 absorbing solution for absorbing the exhaust gas 14 and CO 2 containing the cooled CO 2 (hereinafter, also referred to as "absorbing solution”.) 17 and is contacted with by the CO 2 from the exhaust gas 14 and the CO 2 absorber 18 having a CO 2 recovery unit 18A to be removed, CO 2 absorbent having absorbed CO 2 (hereinafter, also referred to as "rich solvent”.) 19 to release CO 2 from the reproduction of CO 2 absorbing solution
  • an absorption liquid regeneration tower 20 that performs the following operation.
  • the absorbent regenerator 20 in reproducing the CO 2 absorbing liquid to remove CO 2 (hereinafter, also referred to as "lean solvent”.) 17 as a CO 2 absorbing solution in the CO 2 absorber 18 Reuse.
  • reference numeral 13a is a flue
  • 13b is a chimney
  • 34 is steam condensed water.
  • the CO 2 recovery device may be provided later in order to recover CO 2 from an existing exhaust gas source, or may be provided at the same time as a new exhaust gas source.
  • the chimney 13b is provided with a door that can be opened and closed, and is closed when the CO 2 recovery device 12 is in operation. Although the exhaust gas source is running, when stopping the operation of the CO 2 recovering apparatus 12 is set to open.
  • the exhaust gas 14 from the industrial combustion facility 13 such as a boiler or gas turbine containing CO 2 is pressurized by the exhaust gas blower 22, and then the exhaust gas cooling device. 16, where it is cooled by cooling water 15 and sent to a CO 2 absorption tower 18.
  • the exhaust gas 14 is the CO 2 absorbing liquid 17 and countercurrent contact with an amine absorbent solution according to the present embodiment, CO 2 in the exhaust gas 14 is absorbed into the CO 2 absorbing solution 17 by a chemical reaction Is done.
  • CO 2 flue gas after CO 2 is removed in the CO 2 recovery unit 18A, the cleaning water 21 circulating containing CO 2 absorbing liquid supplied from the nozzle at the water washing section 18B in the CO 2 absorber 18 and a gas-liquid contact with, CO 2 absorbing liquid 17 accompanying the CO 2 flue gas is recovered, then the exhaust gas 23 from which CO 2 has been removed is released out of the system.
  • the rich solution is CO 2 absorbing liquid 19 that has absorbed CO 2, boosted by the rich solution pump 24, the rich-lean solution heat exchanger 25, which is reproduced in the absorbent regenerator 20 CO 2 absorbing solution 17 And is supplied to the absorption liquid regeneration tower 20.
  • the rich solution 19 released to the inside from the upper part of the absorption liquid regeneration tower 20 generates an endothermic reaction with water vapor supplied from the bottom, and releases most of CO 2 .
  • the CO 2 absorbent that has released a part or most of CO 2 in the absorbent regeneration tower 20 is called a semi-lean solution.
  • This semi-lean solution becomes a CO 2 absorbent (lean solution) 17 from which almost all of the CO 2 has been removed by the time it reaches the bottom of the absorbent regeneration tower 20.
  • a part of the lean solution 17 is superheated by the steam 27 in the regeneration superheater 26, and the steam is supplied into the absorbent regeneration tower 20.
  • the CO 2 entrained gas 28 accompanied by the water vapor released from the rich solution 19 and the semi-lean solution is led out in the tower, the water vapor is condensed by the condenser 29, and the separation drum 30. Then, the water is separated and the CO 2 gas 40 is discharged out of the system, and is separately compressed and recovered by the compressor 41.
  • the compressed / recovered CO 2 gas 42 passes through the separation drum 43 and is then injected into an oil field using an enhanced oil recovery (EOR) method or stored in an aquifer for warming. Measures are being taken.
  • the reflux water 31 separated and refluxed from the CO 2 entrained gas 28 accompanied by water vapor by the separation drum 30 is supplied to the upper part of the absorption liquid regeneration tower 20 and the circulating wash water 21 side by the reflux water circulation pump 35.
  • the regenerated CO 2 absorbing solution (lean solution) 17 is cooled by the rich solution 19 in the rich / lean solution heat exchanger 25, subsequently pressurized by the lean solution pump 32, and further by the lean solution cooler 33. After cooling, it is supplied into the CO 2 absorption tower 18.
  • the outline is only described, and a part of the attached devices is omitted.
  • the composite amine absorbing liquid of this embodiment as the amine absorbing liquid, deterioration due to oxidation of the amine absorbing liquid due to oxygen in the gas can be suppressed, and further deterioration of the absorbing liquid It is possible to reduce the absorption liquid loss due to the above.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2014/077264 2013-10-15 2014-10-10 複合アミン吸収液、ｃｏ２又はｈ２ｓ又はその双方の除去装置及び方法 Ceased WO2015056657A1 (ja)

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CA2924300A CA2924300A1 (en) 2013-10-15 2014-10-10 Composite amine absorbent, and apparatus and method for removing co2 and/or h2s
AU2014335384A AU2014335384B2 (en) 2013-10-15 2014-10-10 Composite amine absorption solution, and method and device for removing CO2 and/or H2S
EP14853761.6A EP3034152A4 (en) 2013-10-15 2014-10-10 COMPOUND AMINE ABSORPTION SOLUTION AND PROCESS AND DEVICE FOR REMOVING CO2 AND / OR H2S
US15/022,125 US20160220947A1 (en) 2013-10-15 2014-10-10 Composite amine absorbent, and apparatus and method for removing co2 and/or h2s

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CA3003795A1 (en) * 2015-11-09 2017-05-18 Shell Internationale Research Maatschappij B.V. Process for removing mercaptans from a gas stream
US10710020B2 (en) * 2017-06-30 2020-07-14 Uop Llc Processes for gas separation by solvent or absorbent
CN108854459B (zh) * 2018-09-25 2022-03-15 天津工业大学 一种低能耗无水co2相变吸收剂及再生方法和应用
JP7178911B2 (ja) * 2019-01-24 2022-11-28 三菱重工エンジニアリング株式会社 複合アミン吸収液、ｃｏ２又はｈ２ｓ又はその双方の除去装置及び方法
JP2025086680A (ja) * 2023-11-28 2025-06-09 川崎重工業株式会社 固体吸収材ならびにそれを用いた酸性ガスの吸収および脱離方法

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AU2014335384B2 (en) 2017-03-16
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JP2015077537A (ja) 2015-04-23
EP3034152A1 (en) 2016-06-22
AU2014335384A1 (en) 2016-04-07
US20160220947A1 (en) 2016-08-04
CA2924300A1 (en) 2015-04-23

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