WO2026029286A1 - Absorbant de capture de dioxyde de carbone comprenant un inhibiteur d'évaporation - Google Patents

Absorbant de capture de dioxyde de carbone comprenant un inhibiteur d'évaporation

Info

Publication number
WO2026029286A1
WO2026029286A1 PCT/KR2024/020476 KR2024020476W WO2026029286A1 WO 2026029286 A1 WO2026029286 A1 WO 2026029286A1 KR 2024020476 W KR2024020476 W KR 2024020476W WO 2026029286 A1 WO2026029286 A1 WO 2026029286A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon dioxide
absorbent
ether
dioxide absorbent
evaporation inhibitor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/KR2024/020476
Other languages
English (en)
Korean (ko)
Inventor
강성신
정재철
최현철
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hanwha TotalEnergies Petrochemical Co Ltd
Original Assignee
Hanwha TotalEnergies Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hanwha TotalEnergies Petrochemical Co Ltd filed Critical Hanwha TotalEnergies Petrochemical Co Ltd
Publication of WO2026029286A1 publication Critical patent/WO2026029286A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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

Definitions

  • the present invention relates to a carbon dioxide absorbent, and more particularly, to a carbon dioxide absorbent that reduces heat consumed in the carbon dioxide removal process during a carbon dioxide wet absorption process through an evaporation inhibitor.
  • CO2 capture is a method that directly reduces CO2 emissions. It separates CO2 from exhaust gas and reduces CO2 emissions.
  • carbon dioxide in exhaust gas is reduced by absorbing it and capturing it within the absorbent through a reaction between the amine and carbon dioxide contained in the absorbent.
  • the absorbent containing carbon dioxide is then heated to remove the carbon dioxide and regenerated. Furthermore, high-purity carbon dioxide is produced during the regeneration process.
  • the heat consumed during the regeneration process accounts for the largest portion, and therefore, reducing the amount of renewable energy used for regeneration is very important from an economic perspective for the absorption process.
  • the present invention was derived to solve the above-mentioned problem, and the purpose of the present invention is to provide an absorbent that reduces heat consumption by suppressing evaporation of water during the carbon dioxide removal process through improvement of the carbon dioxide absorbent.
  • the present invention provides a carbon dioxide absorbent comprising a triamine, an ether, water, and an evaporation inhibitor, wherein the evaporation inhibitor is a polyol.
  • Another aspect of the present invention for achieving the above object is to provide a carbon dioxide capture method, characterized by including a first step of capturing carbon dioxide from a mixed gas containing carbon dioxide using the carbon dioxide absorbent; and a second step of removing carbon dioxide from the carbon dioxide absorbent in which carbon dioxide has been absorbed.
  • the carbon dioxide absorbent including the evaporation inhibitor according to the present invention unlike the carbon dioxide absorbent of a conventional wet carbon dioxide capture process, suppresses the evaporation of water within the absorbent, thereby reducing the heat consumed in the carbon dioxide removal process and thus reducing the process operating cost.
  • evaporation inhibitors can reduce environmental pollution and reduce the cost of reducing it by suppressing the evaporation of amine substances and thus the emission of hazardous substances.
  • Figure 1 is a schematic diagram illustrating a carbon dioxide capture process.
  • Figure 2 is a schematic diagram of a device for measuring carbon dioxide absorption capacity according to an embodiment of the invention.
  • the present invention is a carbon dioxide absorbent comprising a triamine, an ether, water, and an evaporation inhibitor, wherein the evaporation inhibitor is a polyol.
  • the above carbon dioxide absorbent is a material used in a carbon dioxide wet capture process, and by including the evaporation inhibitor, the vapor pressure of the absorbent is lowered during the carbon dioxide removal process.
  • the absorbent with the lowered vapor pressure is prevented from evaporating through heating in the regeneration tower, thereby reducing the outflow of the absorbent and reducing the heat of evaporation, thereby reducing heat consumption in the regeneration tower, ultimately reducing process costs.
  • the above evaporation inhibitor is a polyol, more preferably ethylene glycol or glycerol.
  • the above triamine is preferably a compound represented by the following [chemical formula 1].
  • n and m are each independently an integer between 1 and 10, and preferably an integer between 2 and 4.
  • R 1 to R 5 are each independently hydrogen or a C1-C10 alkyl group, and preferably hydrogen or a C1-C5 alkyl group.
  • alkyl group described in the present invention means a monovalent straight-chain or branched saturated hydrocarbon radical composed only of carbon and hydrogen atoms, and examples of such alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, nonyl, and the like.
  • the above triamine more preferably includes at least one selected from the group consisting of 2,2'-iminobis(N,N-dimethylethylamine), 2,2'-iminobis(N,N-diethylethylamine), 3,3'-iminobis(N,N-dimethylpropylamine), 3,3'-iminobis(N,N-diethylpropylamine), but is not limited thereto.
  • the above ether is preferably a compound represented by the following [chemical formula 2].
  • o is an integer between 1 and 10, and preferably an integer between 2 and 4.
  • R 6 and R 7 are each independently hydrogen or a C1-C10 alkyl group, preferably a C1-C3 alkyl group.
  • the above ether more preferably includes at least one selected from the group consisting of tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropylene ether, tetraethylene glycol methylethyl ether, tetraethylene glycol methylpropyl ether, tetraethylene glycol ethylpropyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropylene ether, triethylene glycol methylethyl ether, triethylene glycol methylpropyl ether, and triethylene glycol ethylpropyl ether, but is not limited thereto.
  • the evaporation inhibitor is included in an amount of 5 to 50 wt%, preferably 10 to 40 wt%, of the total amount of the carbon dioxide absorbent. If the amount of the evaporation inhibitor is less than 5 wt%, the evaporation inhibition effect of the water within the absorbent becomes poor, and if it exceeds 50 wt%, there is a problem of poor carbon dioxide absorption performance.
  • triamine is included in an amount of 20 to 50 wt%, preferably 25 to 45 wt%, of the total amount of the carbon dioxide absorbent. If the amount of triamine is less than 20 wt%, the carbon dioxide absorption effect is small, and if it exceeds 50 wt%, it causes a decrease in absorption performance and an increase in the viscosity of the absorbent.
  • ether is included in an amount of more than 0% by weight and less than or equal to 20% by weight, preferably 2% to 15% by weight, of the total amount of the carbon dioxide absorbent. If ether is not present, there is a problem of a low absorption rate, and if the amount of ether exceeds 20% by weight, there is a problem of a reduced absorption capacity.
  • water comprises 20 to 50 wt% of the total amount of the carbon dioxide absorbent. If the amount of water is less than 20 wt%, the viscosity of the absorbent solution increases, and if it exceeds 50 wt%, the viscosity of the absorbent decreases, but the carbon dioxide absorption capacity decreases.
  • the present invention provides, as one embodiment, a method for capturing carbon dioxide, the method comprising: a first step of capturing carbon dioxide from a mixed gas containing carbon dioxide using the carbon dioxide absorbent; and a second step of removing carbon dioxide from the carbon dioxide absorbent in which carbon dioxide has been absorbed.
  • carbon dioxide removal according to the present invention can be accomplished using the device of FIG. 1.
  • the removal method is divided into two stages: 1) a first stage in which carbon dioxide is absorbed into an absorbent in a gas containing carbon dioxide, and 2) a second stage in which the absorbent containing carbon dioxide is heated to remove carbon dioxide and the absorbent is regenerated.
  • flue gas (101) is injected into the bottom of the absorption tower (100) and discharged to the top.
  • Absorbent (103) is injected into the top of the absorption tower. As the flue gas passes through the absorption tower, it comes into contact with the absorbent injected from the top and flowing down, and in this process, carbon dioxide is absorbed by the absorbent.
  • the flue gas (104) from which the absorbent has been removed is discharged to the top of the absorption tower.
  • the absorbent (102) containing carbon dioxide is discharged to the bottom of the absorption tower, heated through a heat exchanger (220), and then the heated absorbent (201) is injected to the top of the regeneration tower.
  • the absorbent (201) containing carbon dioxide injected into the upper part of the regeneration tower descends to the lower part of the regeneration tower, and the lower part of the regeneration tower is heated through a reboiler (210). Due to the heating, the solubility of carbon dioxide in the absorbent decreases, and the carbon dioxide is removed. The removed carbon dioxide (205) is discharged in a gaseous state through the upper part of the regeneration tower.
  • the absorbent (202) regenerated by removing carbon dioxide is cooled through a heat exchanger (220), and then injected back into the absorption tower (100).
  • the temperature of the first step is preferably in the range of 30 to 60°C. If the temperature is below 30°C, there is a problem in that cooling with cooling water is difficult in the summer, and if the temperature exceeds 60°C, the solubility of carbon dioxide decreases, resulting in a decrease in absorption performance.
  • the temperature of the second step is preferably in the range of 80 to 150°C. If the absorption temperature is less than 80°C, the solubility of carbon dioxide does not decrease significantly, resulting in low stripping efficiency. If the temperature exceeds 150°C, solvent leakage may occur due to thermal denaturation and evaporation of the solvent.
  • the pressure of the second step is preferably 10 atm or less. If the pressure exceeds 10 atm, the temperature for carbon dioxide removal increases, causing thermal denaturation of the solvent. In addition, high-pressure steam or a heat source is required, making it economically inefficient.
  • the evaporation inhibitor reduces the amount of heat consumed in the reboiler (210) of the second stage.
  • the heat injected from the reboiler is used to heat the absorbent that has captured carbon dioxide.
  • the heated absorbent emits carbon dioxide due to the difference in carbon dioxide solubility according to temperature change, and the emitted carbon dioxide is removed from the top of the regeneration tower.
  • the heated absorbent evaporates according to the vapor pressure of the absorbent and is emitted together with the carbon dioxide. This causes the outflow of the absorbent, and the vaporization heat consumed when the absorbent evaporates causes additional heat consumption.
  • the evaporation inhibitor proposed in the present invention is a substance that lowers the vapor pressure of the absorbent, and the evaporation of the absorbent with the lowered vapor pressure is suppressed through heating in the regeneration tower. This reduces the outflow of the absorbent, reduces the heat of vaporization, and thus reduces the heat consumption in the regeneration tower.
  • the heat used in the regeneration tower can be reduced by using a carbon dioxide absorbent including an evaporation inhibitor, and the problem caused by absorbent leakage can be solved.
  • An absorbent was prepared by mixing 45 wt% of 3,3'-ibininobis(N,N-dimethylpropylamine) (CAS No. 6711-48-4) as a triamine, 5 wt% of tetraethylene glycol dimethyl ether, 30 wt% of water, and 20 wt% of glycerol as an evaporation inhibitor.
  • An absorbent was prepared by mixing 30 wt% of 3,3'-ibininobis(N,N-dimethylpropylamine) (CAS No. 6711-48-4) as a triamine, 5 wt% of tetraethylene glycol dimethyl ether, 35 wt% of water, and 30 wt% of glycerol as an evaporation inhibitor.
  • An absorbent was prepared in the same manner as in Example 1, except that the evaporation inhibitor was changed to ethylene glycol.
  • An absorbent was prepared in the same manner as in Example 1, except that the evaporation inhibitor was changed to 1,3-propanediol.
  • An absorbent was prepared in the same manner as in Example 1, except that the evaporation inhibitor was changed to 1,4-butanediol.
  • An absorbent was prepared by mixing 45 wt% of 3,3'-ibininobis(N,N-dimethylpropylamine) (CAS No. 6711-48-4) as triamine, 0 wt% of ether, and 55 wt% of water.
  • An absorbent was prepared by mixing 40 wt% of 3,3'-ibininobis(N,N-dimethylpropylamine) (CAS No. 6711-48-4) as triamine, 20 wt% of tetraethylene glycol dimethyl ether, and 40 wt% of water.
  • An absorbent was prepared by mixing 45 wt% of 3,3'-ibininobis(N,N-dimethylpropylamine) (CAS No. 6711-48-4) as triamine, 5 wt% of tetraethylene glycol dimethyl ether, 30 wt% of water, and 20 wt% of 1,6-hexanediol.
  • the evaporation suppression effect of the absorbent can be confirmed by measuring the vapor pressure of the absorbent.
  • the vapor pressure of the absorbent was calculated using a commercial simulator, Aspen Plus.
  • the thermodynamic parameters used in the process simulator were derived from both built-in values and experimentally obtained values.
  • the vapor pressures of different absorbents were compared during the stripping process, depending on their composition.
  • Carbon dioxide absorption capacity was measured using the device of Fig. 2. 50 ml of a pre-prepared absorbent was injected into a device maintained under vacuum using a vacuum pump. CO2 was injected through an MFC, and the temperature of the device was adjusted to a constant temperature T using a circulator injected with silicone oil. The device was maintained for more than 1 hour to allow evaporation of the absorbent, and when the pressure was maintained constant while the temperature was maintained at T, nitrogen was injected so that the internal pressure of the device became the target pressure P 0 (T) and recorded. The target pressure P 0 (T) was set to 1 atm.
  • Carbon dioxide is injected at a constant rate through an MFC into a device where the temperature is T and the pressure is maintained at P 0 (T). After the injection for a certain period of time, the pressure in the device is maintained constant, and the pressure (P 1 (T)) of the device is recorded. This is used to calculate the partial pressure of carbon dioxide, the amount of carbon dioxide absorbed, and the absorption capacity.
  • the temperature unit is °C, and the pressure unit is kPa.
  • M CO2,l M CO2,overall - M CO2,v
  • V V V equip - V abs
  • V equip internal volume of the device (ml)
  • ⁇ ⁇ (T abs, P CO2 (T abs )) - ⁇ (T des, P CO2 (T des ))
  • Table 2 shows the results of measuring the cyclic absorption capacity under adsorption conditions (40°C, 10 kPa) and desorption conditions (120°C, 101.325 kPa).
  • Examples 1-3 are absorbents containing ethylene glycol or glycerol as an evaporation inhibitor, while Comparative Examples 1 and 2 contained glycol-based substances, and Comparative Examples 3 and 4 are absorbents that do not contain glycol-based substances or glycerol.
  • the cyclic absorption capacities did not differ significantly, and even when an evaporation inhibitor was included, there was no significant change in the cyclic absorption capacity, confirming that the performance was maintained even when an evaporation inhibitor was added.
  • Example 2 it was confirmed that when the ratio of absorbent was adjusted by adding an evaporation inhibitor, the absorption capacity increased due to the addition of an evaporation inhibitor, and the absorbent performance increased compared to the existing absorbent without an evaporation inhibitor.
  • Carbon dioxide (the removed carbon dioxide is discharged through the top of the regeneration tower in a gaseous state)

Landscapes

  • 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)

Abstract

Un absorbant de dioxyde de carbone comprenant un inhibiteur d'évaporation selon la présente invention est un absorbant utilisé dans un procédé de capture de dioxyde de carbone humide. L'absorbant comprenant un inhibiteur d'évaporation peut absorber efficacement le dioxyde de carbone et supprimer l'évaporation pour réduire la consommation d'énergie de régénération en raison de la chaleur latente de l'eau consommée dans un processus d'élimination, ce qui permet d'augmenter l'efficacité énergétique.
PCT/KR2024/020476 2024-07-29 2024-12-17 Absorbant de capture de dioxyde de carbone comprenant un inhibiteur d'évaporation Pending WO2026029286A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2024-0100242 2024-07-29
KR1020240100242A KR102831229B1 (ko) 2024-07-29 2024-07-29 증발 억제제를 포함한 이산화탄소 포집 흡수제

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WO2026029286A1 true WO2026029286A1 (fr) 2026-02-05

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090069271A (ko) * 2006-08-10 2009-06-30 유니버시티 오브 써던 캘리포니아 공기를 포함하는 가스 혼합물로부터 이산화탄소를 분리하기위한 나노 구조의 지지 고형 재생성 폴리아민 및 폴리아민폴리올 흡착제
CN101734658A (zh) * 2009-12-30 2010-06-16 清华大学 一种二氧化碳的吸收分离方法
KR20170129920A (ko) * 2015-03-26 2017-11-27 신닛테츠스미킨 카부시키카이샤 이산화탄소를 분리 회수하기 위한 흡수액 및 그것을 사용한 이산화탄소를 분리 회수하는 방법
KR20190101052A (ko) * 2018-02-22 2019-08-30 서강대학교산학협력단 이산화탄소 흡수제와 이를 이용한 이산화탄소의 분리방법
CN116139657A (zh) * 2023-03-01 2023-05-23 昆明理工大学 一种用于捕集二氧化碳的胺类非水吸收剂及其使用方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110099466A (ko) 2010-03-02 2011-09-08 현대자동차주식회사 이산화탄소 흡수제
KR102445742B1 (ko) * 2021-11-08 2022-09-21 주식회사 씨이텍 변성방지제를 포함하는 이산화탄소 흡수제

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090069271A (ko) * 2006-08-10 2009-06-30 유니버시티 오브 써던 캘리포니아 공기를 포함하는 가스 혼합물로부터 이산화탄소를 분리하기위한 나노 구조의 지지 고형 재생성 폴리아민 및 폴리아민폴리올 흡착제
CN101734658A (zh) * 2009-12-30 2010-06-16 清华大学 一种二氧化碳的吸收分离方法
KR20170129920A (ko) * 2015-03-26 2017-11-27 신닛테츠스미킨 카부시키카이샤 이산화탄소를 분리 회수하기 위한 흡수액 및 그것을 사용한 이산화탄소를 분리 회수하는 방법
KR20190101052A (ko) * 2018-02-22 2019-08-30 서강대학교산학협력단 이산화탄소 흡수제와 이를 이용한 이산화탄소의 분리방법
CN116139657A (zh) * 2023-03-01 2023-05-23 昆明理工大学 一种用于捕集二氧化碳的胺类非水吸收剂及其使用方法

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