WO2014073801A1 - 반용매를 포함하는 이산화탄소 흡수용 조성물 및 이를 사용하는 이산화탄소 흡수 방법 및 장치 - Google Patents

반용매를 포함하는 이산화탄소 흡수용 조성물 및 이를 사용하는 이산화탄소 흡수 방법 및 장치 Download PDF

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Publication number
WO2014073801A1
WO2014073801A1 PCT/KR2013/009327 KR2013009327W WO2014073801A1 WO 2014073801 A1 WO2014073801 A1 WO 2014073801A1 KR 2013009327 W KR2013009327 W KR 2013009327W WO 2014073801 A1 WO2014073801 A1 WO 2014073801A1
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Prior art keywords
carbon dioxide
absorbing
composition
absorption
solution
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PCT/KR2013/009327
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English (en)
French (fr)
Inventor
정태성
김종남
범희태
한상섭
윤형철
김교희
홍원희
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한국에너지기술연구원
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Priority to US14/398,500 priority Critical patent/US20150290581A1/en
Publication of WO2014073801A1 publication Critical patent/WO2014073801A1/ko

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/302—Alkali metal compounds of lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • 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
    • B01D2252/202—Alcohols or their derivatives
    • 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
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2021—Methanol
    • 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
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2023—Glycols, diols or their derivatives
    • 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
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2023—Glycols, diols or their derivatives
    • B01D2252/2025—Ethers or esters of alkylene glycols, e.g. ethylene or propylene carbonate
    • 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
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2023—Glycols, diols or their derivatives
    • B01D2252/2026—Polyethylene glycol, ethers or esters thereof, e.g. Selexol
    • 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
    • B01D2252/20468—Cyclic amines containing a pyrrolidone-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
    • B01D2252/50—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
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes
    • 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
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/606—Anticorrosion agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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

  • Carbon dioxide absorption composition comprising anti-solvent and carbon dioxide absorption method and apparatus using same
  • the present invention relates to a carbon dioxide absorption composition comprising an antisolvent and a carbon dioxide absorption method and apparatus using the same. More specifically, the present invention relates to carbon dioxide from a mixed gas containing carbon dioxide such as combustion exhaust gas of a coal-fired power plant. In a process and apparatus for separating and regenerating bicarbonate slurry containing a large amount of carbon dioxide at high pressure, by using a carbon dioxide absorption composition prepared by mixing an aqueous antisolvent with an inorganic salt carbon dioxide absorption solution containing an alkali metal.
  • a composition for absorbing carbon dioxide including antisolvents and carbon dioxide absorption methods and apparatus using the same, which can reduce the sensible heat, latent heat and renewable energy costs required for the regeneration, cooling and heating of carbon dioxide absorbing solutions by increasing the yield of carbonate slurry. It's about.
  • the removal and recovery method is a process in which the absorbent solution and the mixed gas are brought into direct contact with the absorbent in the absorbent solution and the carbon dioxide is combined with carbon dioxide to remove carbon dioxide and obtain a purified gas.
  • energy is supplied to the solution, carbon dioxide is separated and recovered from the absorbent, and the absorbing solution is regenerated to absorb carbon dioxide again.
  • Absorption solutions used in the carbon dioxide absorption process are amine and alkali metal absorption solution. Carbon dioxide absorption process using alkali metal absorption solution as absorption solution is more expensive and thermochemical safety of absorbent than absorption process using amine. In terms of advantages, the absorbed carbon dioxide is removed from the stripping column, especially since the renewable energy is small and stable at high temperature and high pressure.
  • Alkaline metal or bicarbonate crystallization method (International Patent Publication) is a method to reduce the amount of absorbent liquid to be sent to the regeneration tower.
  • the purpose of the present invention is to solve the problems of the prior art described above, to absorb carbon dioxide from a mixed gas containing carbon dioxide, such as combustion exhaust gas of a coal-fired power plant, and to separate the carbon dioxide-rich bicarbonate slurry.
  • a composition for absorbing carbon dioxide comprising an anti-solvent, which can reduce the sensible heat, latent heat and renewable energy costs required for the regeneration, cooling and heating of the carbon dioxide absorption solution by increasing the yield of bicarbonate slurry.
  • the present invention contains carbon dioxide.
  • a carbon dioxide absorption composition used in a process including absorbing carbon dioxide from a mixed gas, separating a high carbon dioxide-containing bicarbonate slurry, and regenerating it at high pressure, and including an inorganic salt carbon dioxide absorption solution and an aqueous antisolvent. It provides a composition for absorbing carbon dioxide.
  • an inorganic salt carbon dioxide absorption solution is used for sodium, potassium, lithium, rubidium, and Use a solution of a monovalent inorganic salt that contains one selected from the group consisting of sesame seeds.
  • the concentration of monovalent inorganic salt is 30% by weight for inorganic salts containing sodium, 50% by weight for inorganic salts containing potassium, and 2% for inorganic salts containing lithium. %, 30% by weight for inorganic salts containing rubidium, 70% by weight for inorganic salts containing sage is preferred.
  • the water-soluble antisolvent in the invention is methane, ethanol, propanol, ethylene glycol,
  • One selected from the group consisting of propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, N-methylpyrrolidone, propylene carbonate, ethylene carbonate and mixtures thereof can be used.
  • the water-soluble antisolvent is preferably included in an amount of more than 0 to 30% by weight based on the total weight of the carbon dioxide absorption composition.
  • composition may further comprise one or two or more compounds selected from absorption rate enhancers, antioxidants and anticorrosion agents, as desired.
  • the present invention comprises the steps of absorbing carbon dioxide by contacting a mixed gas containing carbon dioxide with the composition for absorbing carbon dioxide; forming a bicarbonate slurry by recognizing the carbon dioxide absorbing composition absorbing the carbon dioxide; and Separation of the solid slurry from the bicarbonate slurry and the liquid absorbent solution containing the anti-solvent, and then the anti-solvent is separated from the absorbing solution and recovered, while heating the solid slurry at high temperature to separate carbon dioxide. And a playback method.
  • the present invention provides an absorption tip for selectively absorbing carbon dioxide from combustion exhaust gas using the composition for absorbing carbon dioxide; a carbon dioxide absorbing composition containing the carbon dioxide absorbed by cooling by using a cooler or a heat exchanger and having a bicarbonate slurry. Crystallizer to form; the bicarbonate
  • the present invention includes carbon dioxide such as combustion exhaust gas of coal-fired power plant.
  • Carbon dioxide of the present invention prepared by mixing an aqueous antisolvent with an inorganic salt carbon dioxide absorption solution containing an alkali metal in a process and apparatus for absorbing carbon dioxide from a mixed gas and separating a high carbon dioxide-rich bicarbonate slurry.
  • Bicarbonate Slurry Formation Using Absorption Composition By increasing the yield and separating and regenerating only the solid slurry, it is possible to reduce the sensible heat, latent heat and renewable energy costs required for the regeneration of the carbon dioxide absorption solution and the cooling and heating of the carbon dioxide absorption solution.
  • FIG. 1 is a process diagram schematically showing a carbon dioxide absorption and regeneration device using a carbon dioxide absorption composition comprising an anti-solvent of the present invention according to an embodiment of the present invention, and a process using the same.
  • Figure 2 comprises an antisolvent of the invention according to another embodiment of the invention
  • FIG. 3 (A) of Figure 3 is a photograph of the phase-separated state after crystallization of the composition for absorbing carbon dioxide containing the anti-solvent in Test Example 1 of the present invention
  • Figure 3 (b) is a phase-separated bicarbonate slurry and reference material This is a graph measured using an infrared spectrometer.
  • Carbon dioxide absorption composition according to the present invention is a carbon dioxide absorption composition used in the process comprising the step of absorbing carbon dioxide from a mixed gas containing carbon dioxide, separating the bicarbonate slurry containing a large amount of carbon dioxide and regeneration at high pressure.
  • Salt Carbon Dioxide Absorption and Water Solubility Includes antisolvents.
  • the term 'inorganic salt carbon dioxide absorption solution silver means an aqueous solution containing a monovalent inorganic salt such as sodium, potassium, lithium, rubidium, cesium that can absorb carbon dioxide.
  • the inorganic salt concentration of the inorganic carbon dioxide absorbing solution is 30% by weight for inorganic salts containing sodium, 50% by weight for inorganic salts containing potassium, 2% by weight for inorganic salts containing lithium, rubidium
  • the inorganic salt containing 30 wt% of the inorganic salt containing cesium is preferably 70% by weight.
  • the higher the concentration of the inorganic salt may be advantageous to increase the amount of carbon dioxide absorbed, but exceed the inorganic salt concentration.
  • supersaturation of carbonate may be induced from the absorbent solution to the absorption tower, and solid sludge may be generated in the absorption tower, which may be referred to as a material transfer. Delivery is inefficient and difficult to remove the heat of absorption reaction.
  • composition for absorbing carbon dioxide according to the present invention includes an aqueous antisolvent with an inorganic salt carbon dioxide absorbing solution.
  • composition for absorbing carbon dioxide improves the yield of bicarbonate, including an aqueous antisolvent with an inorganic salt carbon dioxide absorbing solution, thereby forming a solid slurry without significantly lowering the cooling temperature. It can absorb and recover carbon dioxide.
  • the water-soluble antisolvent used in the present invention is selected from polar protic solvents such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, diethylene glycol,
  • N-methylpyridone, propylene carbonate selected as an alcohol-based, glycol-based, polar aprotic solvent such as triethylene glycol, polyethylene glycol,
  • It may be selected from the group consisting of ethylene carbonate and their mixtures, and more preferably selected from ethanol and ⁇ methylpyrrolidone is preferable in the yield of bicarbonate production.
  • the water-soluble antisolvent is contained in an amount of more than 0 to 30% by weight based on the total weight of the carbon dioxide absorbing composition. If included, the amount of carbon dioxide absorbing solution separated from the anti-solvent decreases, which may be called carbon dioxide absorption in the absorption tower.
  • composition for absorbing carbon dioxide according to the present invention may further include one or two or more kinds of compounds selected from absorption rate enhancers, antioxidants and anticorrosion agents as necessary.
  • Absorption rate enhancers included in the composition for absorbing carbon dioxide according to the present invention can be used, for example, piperazine and piperazine derivatives, amino acids, borate salts, and the like.
  • Potassium, nickel, iron, copper, chromium ions, 2-aminothiophenol and A 1-hydroxy acetylene-1,1-diphosphonic acid mixture can be used, but is not limited to this.
  • the present invention is a dine-based for absorbing carbon dioxide by contacting a mixed gas containing carbon dioxide with the composition for absorbing carbon dioxide; Forming a bicarbonate slurry by injecting the carbon dioxide absorbing composition into which the carbon dioxide is absorbed; And separating the solid absorption slurry and the liquid absorption solution containing the antisolvent from the bicarbonate slurry, separating and recovering the antisolvent from the absorption solution, and heating the solid slurry to a high temperature to separate carbon dioxide. It provides a carbon dioxide absorption and regeneration method comprising.
  • FIG. 1 A schematic process diagram of the apparatus and process for distilling carbon dioxide is shown in FIG. 1.
  • the carbon dioxide absorption and regeneration device according to the present invention from the combustion exhaust gas (1) using the carbon dioxide absorption composition (11) according to the present invention
  • Absorption tower (2) for selectively absorbing carbon dioxide
  • a crystallizer (5) for forming a carbonated carbonate slurry by refining the carbon dioxide absorbing solution (3) in which carbon dioxide is absorbed by using a heat exchanger or a heat exchanger (6)
  • a filter (8) for separating solid sludge ( ⁇ ) from the resulting bicarbonate slurry (7) solution;
  • a mixed gas containing carbon dioxide such as combustion exhaust gas 1
  • the carbon dioxide is absorbed by contact with the composition for absorbing carbon dioxide (U).
  • the absorption tower (2) is for absorbing the carbon dioxide at atmospheric pressure and 60 ⁇ 80 ° C conditions
  • composition (U) By spraying the composition (U) with a nozzle at the top, carbon dioxide is absorbed and the carbon dioxide absorbing composition (3) with the carbon dioxide absorbed at the bottom is discharged.
  • a filler is used inside the absorption tower (2).
  • composition (1 1) for the carbon dioxide absorption using a configuration or a spray nozzle, but the injection method is not limited.
  • composition for absorbing carbon dioxide absorbing the carbon dioxide (3) is cooled to form a bicarbonate slurry.
  • the composition for absorbing carbon dioxide absorbing carbon dioxide (3) is transferred to the crystallizer (5) and cooled to 10 to 50 o C using a cooler or heat exchanger (6) to induce supersaturation of the bicarbonate crystals.
  • the cooler or heat exchanger 6 may be located inside or outside the crystallizer 5, and an agitator may be further configured to increase the heat transfer efficiency of the composition for absorbing carbon dioxide 3. If there is flow or small particles inside the device, Crystallizers that separate and remove by heating to increase the size of slurry particles are advantageous, but there are no limitations on the types of crystallizers.
  • the water-soluble antisolvent included in the composition for absorbing carbon dioxide (11) improves the yield of bicarbonate crystals and forms bicarbonate slurry solution without significantly lowering the cooling temperature.
  • the produced bicarbonate slurry solution is filtered through a filter (8).
  • a solid slurry containing a relatively large amount of carbon dioxide (13) and a liquid absorbing solution (9) containing an antisolvent containing a small amount of carbon dioxide are separated.
  • the filter (8) is a filter capable of separating solid and liquid phases. Can be cyclone, sedimentation light.
  • the solid slurry (13) and the liquid absorption solution (9) containing the antisolvent are separated from the bicarbonate slurry, and the solid slurry (13) is heated with silver to separate carbon dioxide.
  • the separated solid slurry (13) is transferred to a regenerator (14) and separated into carbon dioxide, moisture, and inorganic carbon dioxide absorbing solution under conditions of l-20 bar and 100-250 o C.
  • a regenerator (14) At the bottom of the regenerator (14) Steam is composed of the recycling machine (15) to disassemble the slurry, the condenser (16) is formed on top of the regenerator (14), and the evaporation of moisture is expanded.
  • the regenerator (14) may be in the form of a column with filler therein or may consist of a stirring pressure reaction tank, but is not necessarily limited thereto.
  • the regenerated absorbent solution (18) recovered in) contains little carbon dioxide and is circulated through the heat exchanger (19) to the absorption tower (2), i.e., the regenerated carbon dioxide separated at the bottom of the regenerator (14)
  • the absorbing solution 18 is separated from the top of the D. regenerator 14, which is recovered to the absorption tower 2, to remove water using the condenser 16, and the water is refluxed and regenerated to the regenerator 14
  • High purity carbon dioxide (17) is recovered as a product.
  • the step of separating the aqueous anti-solvent by performing a liquid-liquid separation process for the liquid absorption liquid separated from the bicarbonate slurry.
  • a liquid-liquid separation device 10 for selectively separating the anti-solvent may be further configured.
  • the separated anti-solvent 12 is separated from the liquid absorbing solution 9 including the same in a filter to form a crystallizer ( 5) Re-supplied and separated liquid phase
  • the absorption solution 9 can be supplied to the absorption tower 2.
  • the low temperature liquid absorption solution (9) discharged from the filter (8) and the carbon dioxide absorption composition (3) absorbing carbon dioxide discharged from the absorption tower (2) can recover heat through a heat exchanger.
  • the heat exchanger can be additionally configured in the process to increase the heat exchange efficiency.
  • FIG. 2 shows the case where the liquid-absorbing solution 9 containing the anti-solvent can be circulated to the absorption tower 2 without additional configuration of the liquid-liquid separator 10.
  • the anti-solvent is atmospheric pressure And low vapor pressure under the conditions of 60 ⁇ 80 o C It can be used as a composition for absorbing carbon dioxide by including anti-solvent in the liquid absorbing solution (9).
  • Test Example 1 3 ⁇ 4 Purification of Carbon Dioxide Groove Composition Containing Anti-Solvent

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

본 발명은 석탄화력발전소의 연소 배가스와 같은 이산화탄소를 포함하는 혼합기체로부터 이산화탄소를 흡수하고, 이산화탄소를 많이 포함하는 중탄산염 슬러리를 분리하여 고압으로 재생하는 공정 및 장치에서, 중탄산염 슬러리 생성 수율을 높여 이산화탄소 흡수용액의 재생 및 냉각과 가열에 소요되는 현열, 잠열 및 재생에너지 비용을 감소시킬 수 있는 반용매를 포함하는 이산화탄소 흡수용 조성물 및 이를 사용하는 이산화탄소 흡수 및 재생 방법 및 이에 사용되는 장치에 관한 것이다.

Description

명세서
발명의명칭：반용매를포함하는이산화탄소흡수용조성물및 이를사용하는이산화탄소흡수방법및장치 기술분야
[1] 본발명은반용매를포함하는이산화탄소흡수용조성물및이를사용하는 이산화탄소흡수방법및장치에관한것이다.보다상세하게는본발명은 석탄화력발전소의연소배가스와같은이산화탄소를포함하는흔합기체로부터 이산화탄소를흡수하고，이산화탄소를많이포함하는중탄산염슬러리를 분리하여고압으로재생하는공정및장치에서，알칼리금속을함유하는무기염 이산화탄소흡수용액에수용성반용매를흔합하여제조된이산화탄소흡수용 조성물을사용함으로써증탄산염슬러리생성수율을높여이산화탄소 흡수용액의재생및냉각과가열에소요되는현열，잠열및재생에너지비용을 감소시킬수있는,반용매를포함하는이산화탄소흡수용조성물및이를 사용하는이산화탄소흡수방법및장치에관한것이다.
[2]
배경기술
[3] 흡수용액을사용하여연소배가스와같은흔합기체내의이산화탄소를
제거하고회수하는방법으로는,흡수용액과흔합기체를직접 접촉시켜 흡수용액의흡수제가이산화탄소와결합함으로써이산화탄소를제거하고 정제된기체를얻어내는공정이대표적이다.이러한공정에서,흡수공정을거친 흡수용액에에너지를공급하면흡수제에서이산화탄소가분리되어회수되고, 흡수용액은다시이산화탄소를흡수할수있도록재생된다.
[4] 이러한이산화탄소흡수공정에사용되는흡수용액으로는아민，알칼리금속계 흡수용액이대표적이다.흡수용액으로서알칼리금속계흡수용액을이용한 이산화탄소흡수공정은아민을이용한흡수공정에비해흡수제의가격과 열화학적안전성측면에서유리한장점이있다.특히,재생에너지가작고 고온고압에서안정하기때문에,흡수된이산화탄소를탈거탑에서
흡수용액으로부터분리시킬때고압에서고순도이산화탄소의재생이 가능하디-.분리를통해생산된이산화탄소를이송시키기위해서는 50 bar이상의 압력으로압축하여부피를줄여야하는데,압축기의단수가증가할수록 에너지가크게소요된다.
[5] 따라서 1~20 bar이상의고압의이산화탄소를생산할수있는알칼리금속계 흡수용액을이용한흡수공정의경우，이산화탄소압축에필요한압축기 장치비용과운전비용을크게감소시킬수있는장점이 있다.그러나알칼리 금속계흡수용액을고압에서재생할때상압에비해재비기온도가상승하고 다량의흡수용액을재생해야하므로,흡수제재생에필요한현열,증발잠열및 반웅열등에너지가많이소요되는단점이있다.
[6] 재생탑에서재생해야하는흡수용액의양을줄이게되면재생에필요한
에너지를저감할수있다.재생탑으로이송하는흡수액의양을줄이는 방법으로는알칼리메탈이은중탄산염결정화방법 (국제특허공개
제 2011/130796 A1,미국특허출원제 12/448252호)이보고된바있다.상기 방법에서는이산화탄소를포함하는흔합기체로부터흡수탑에서알칼리수용액 흡수제를이용하여이산화탄소를분리하고,분리된흡수용액을냉각시켜 중탄산염슬러리용액을제조하고이를이산화탄소가많이함유된슬러리와 이산화탄소가적게함유된흡수용액으로분리한뒤슬러리는고온의
재생기에서재생하여이산화탄소를분리하고남은용액과상술한이산화탄소가 적게함유된흡수용액을흔합하여흡수탑으로희수하는방법이다.상기방법의 경우흡수탑에서배출되는이산화탄소를포함하는다량의흡수용액을낮은 온도로냉각시켜야결정화수율이높아져중탄산염슬러리가생성되므로 냉각에너지와냉각속도의문제로열교환기및냉각결정화기의장치비와 운전비가필요하게된다.또한결정화기에서배출되는 K)~30oC의흡수용액을 60~80°C로운전되는흡수탑으로그리고낮은온도의슬러리는 100~250°C로 운전되는흡수탑으로이송해야하므로,온도차에의한현열에너지가상승하는 큰문제점이있다.
[7]
발명의상세한설명
기술적과제
[8] 따라서，본발명의목적은，상술한종래기술의문제점을해결하기위하여, 석탄화력발전소의연소배가스와같은이산화탄소를포함하는흔합기체로부터 이산화탄소를흡수하고,이산화탄소를많이포함하는중탄산염슬러리를 분리하여고압으로재생하는공정및장치에서,중탄산염슬러리생성수율을 높여이산화탄소흡수용액의재생및냉각과가열에소요되는현열，잠열및 재생에너지비용을감소시킬수있는반용매를포함하는이산화탄소흡수용 조성물및이를사용하는이산화탄소흡수및재생방법및이에사용되는 장치를제공하는것이다.
[9]
과제해결수단
[10] 상기본발명의목적을달성하기위해，본발명은이산화탄소를포함하는
흔합기체로부터이산화탄소를흡수하고,이산화탄소를많이포함하는중탄산염 슬러리를분리하여고압으로재생하는단계를포함하는공정에서사용되는 이산화탄소흡수용조성물로서，무기염이산화탄소흡수용액및수용성 반용매를포함하는것을특징으로하는이산화탄소흡수용조성물을제공한다.
[11] 본발명에서무기염이산화탄소흡수용액으로나트륨，칼륨,리튬,루비듐，및 세슴으로이루어진군으로부터선택되는것을포함하는 1가무기염이용해된 용액을사용한다.
[12] 상기무기염이산화탄소흡수용액에서 1가무기염의농도는나트륨이포함된 무기염인경우 30증량 %，칼륨이포함된무기염인경우 50중량 %，리튬이포함된 무기염인경우 2증량 %，루비듐이포함된무기염인경우 30중량 %，세슴이 포함된무기염인경우 70중량 %인것이바람직하다.
[13] 발명에서수용성반용매는메탄을,에탄올，프로판올，에틸렌글리콜,
프로필렌글리콜,디에틸렌글리콜，트리에티렌글리콜，폴리에틸렌글리콜, N-메틸피롤리돈，프로필렌카보네이트,에틸렌카보네이트및이의흔합물로 이루어진군으로부터선택된것을사용할수있다.
[14] 상기수용성반용매는이산화탄소흡수용조성물전체중량에대해 0초과〜 30 증량 %로포함되는것이바람직하다.
[15] 본발명의바람직한구현예에 있어서，본발명의이산화탄소흡수용
조성물에는필요에따라흡수속도증진제，산화방지제및부식방지제로부터 선택되는 1종또는 2종이상의흔합물이더포함될수있다.
[16] 또한,본발명은이산화탄소를포함하는흔합기체를상기이산화탄소흡수용 조성물과접촉시켜이산화탄소를흡수하는단계；상기이산화탄소를흡수한 이산화탄소흡수용조성물을넁각시켜중탄산염슬러리를형성하는단계;및 상기중탄산염슬러리로부터고상의슬러리와반용매가포함된액상의 흡수용액을분리한후,반용매를흡수용액으로부터분리하여회수하는한편 고상의슬러리를고온으로가열하여이산화탄소를분리하는단계를포함하는 이산화탄소흡수및재생방법을제공한다.
[17] 또한,본발명은연소배가스로부터이산화탄소를상기이산화탄소흡수용 조성물을사용하여선택적으로흡수하기위한흡수팁-；상기이산화탄소가 흡수된이산화탄소흡수용조성물을냉각기또는열교환기를이용하여 냉각시켜중탄산염슬러리를형성시키는결정화기;상기중탄산염
슬러리로부터고상의슬러리및반용매가포함된액상의흡수용액을분리하기 위한여과기;반용매를수용액으로부터분리하는액-액분리징 -치;및상기 고상의슬러리를고온으로가열하여이산화탄소를분리하는재생기를포함하는 이산화탄소흡수및재생장치를제공한다.
[18]
발명의효과
[19] 본발명은석탄화력발전소의연소배가스와같은이산화탄소를포함하는
흔합기체로부터이산화탄소를흡수하고，이산화탄소를많이포함하는중탄산염 슬러리를분리하여고압으로재생하는공정및장치에서,알칼리금속을 함유하는무기염이산화탄소흡수용액에수용성반용매를흔합하여제조된본 발명의이산화탄소흡수용조성물을사용함으로써중탄산염슬러리생성 수율을높이고고상의슬러리만분리및재생하여，이산화탄소흡수용액의재생 및이산화탄소흡수용액의냉각과가열에소요되는현열，잠열및재생에너지 비용을저감할수있다.
[20]
도면의간단한설명
[21] 도 1은본발명의일실시양태에따른본발명의반용매를포함하는이산화탄소 흡수용조성물을사용하는이산화탄소흡수및재생장치와이를사용하는 공정을개략적으로보여주는공정도이다.
[22] 도 2는본발명의다른실시양태에따른본발명의반용매를포함하는
이산화탄소흡수용조성물을사용하는이산화탄소흡수및재생장치와이를 사용하는공정을개략적으로보여주는공정도이디-.
[23] 도 3의 (a)는본발명의시험예 1에서반용매를포함하는이산화탄소흡수용 조성물의결정화후상분리된상태의사진이고,도 3의 (b)는상분리된증탄산염 슬러리및참조물질에대해적외선분광기를이용하여측정한그래프이다.
[24] 도 4는본발명의시험예 1에서반용매의종류에따른증탄산염결정생성
수율을나타내는그래프이다.
[25] 도 5는본발명의시험예 1에서반용매의농도에따른중탄산염결정생성
수율을나타내는그래프이다.
[26] [부호의설명]
[27] *도면의주요부분에대한부호설명
[28] 1：연소배가스 3, 11：이산화탄소흡수용조성물
[29] 2：흡수탑 12：반용매
[30] 4：처리연소배가스 13：고상의슬러리
[31] 5:냉각결정화기 14:재생기
[32] 6:열교환기 (냉각기) 15：재비기
[33] 7:슬러리용액 16:웅축기
[34] 8：여과기 17：이산화탄소
[35] 9：반용매포함액상의흡수용액 18：재생된흡수용액
[36] 10：액-액분리장치 19：열교환기
[37]
발명의실시를위한형태
[38] 이하，본발명을상세히설명한다.
[39]
본발명에따른이산화탄소흡수용조성물은이산화탄소를포함하는 흔합기체로부터이산화탄소를흡수하고,이산화탄소를많이포함하는중탄산염 슬러리를분리하여고압으로재생하는단계를포함하는공정에서사용되는 이산화탄소흡수용조성물로서,무기염이산화탄소흡수용엑및수용성 반용매를포함한다.
[41] 본발명에서용어 '무기염이산화탄소흡수용액，은이산화탄소를흡수할수 있는나트륨，칼륨,리튬,루비듐，세슘등의 1가무기염을포함하는수용액을 의미한다.
[42] 상기무기염이산화탄소흡수용액의무기염농도는나트륨이포함된무기염인 경우 30중량 %,칼륨이포함된무기염인경우 50중량 %,리튬어포함된무기염인 경우 2중량 %，루비듐이포함된무기염인경우 30중량 세슘이포함된 무기염인경우 70중량 %인것이바람직하다.상기무기염의농도가높을수록 흡수되는이산화탄소의양이증가하여유리할수있으나，상기무기염농도를 초과할때에는흡수탑으로이송되는흡수용액에서탄산염의과포화가유발되어 흡수탑내부에고상의슬러리가발생하여물질전달에불리할수있다.또한, 무기염의농도를초과하여흡수용액의물이적을경우기-액물질전달이 비효율적이고흡수반응열을제거하기어렵다.
[43] 본발명에따른이산화탄소흡수용조성물은무기염이산화탄소흡수용액과 함께수용성반용매를포함한다.
[44] 본발명에따른이산화탄소흡수용조성물은무기염이산화탄소흡수용액과 함께수용성반용매를포함하여중탄산염생성수율을향상시킴으로써냉각 온도를크게낮출필요없이고상의슬러리를형성할수있으며,이로부터 고순도의이산화탄소를흡수및회수할수있다.
[45] 본발명에서사용되는수용성반용매는극성양자성용매로선택되는메탄올， 에탄올，프로판올,에틸렌글리콜,프로필렌글리콜,디에틸렌글리콜,
트리에티렌글리콜,폴리에틸렌글리콜등의알콜계및글리콜계과극성 비양자성용매로선택되는 N-메틸피를리돈，프로필렌카보네이트,
에틸렌카보네이트및이들의흔합물로이루어진군으로부터선택될수있으며, 보다바람직하게는에탄올및 ^메틸피롤리돈으로부터선택되는것이중탄산염 생성수율에있어서바람직하다.
[46] 상기수용성반용매는이산화탄소흡수용조성물전체중량에대해 0초과 ~30 중량 %로포함되는것이바람직하다.상기수용성반용매는과포화를높이가 때문에첨가량이많을수록유리하나，상기함량범위를초과하여과량으로 포함될경우반용매로부터분리되는이산화탄소흡수용액의양이적어져 흡수탑내에서이산화탄소흡수에불리할수있디-.
[47] 본발명에따른이산화탄소흡수용조성물은필요에따라흡수속도증진제， 산화방지제및부식방지제로부터선택되는 i종또는 2종이상의흔합물을더 포함할수있다.
[48] 본발명에따른이산화탄소흡수용조성물에포함되는흡수속도증진제로는 예컨대피페라진및피페라진유도체，아미노산,붕산염등을사용할수있고， 산화방지제및부식방지제로는예컨대산화바나듐，산화안티몬,중크롬산 칼륨，니켈，철，구리，크롬이온，그리고 2-아미노티오페놀및 1-하이드록시에 틸리 덴 -1,1-디포스폰산 흔합물 둥을 사용할 수 있으나，반드시 이 에 제한되는 것은 아니다.
[49] 또한 본 발명은 이산화탄소를 포함하는 흔합기 체를 상기 이산화탄소 흡수용 조성물과 접촉시켜 이산화탄소를 흡수하는 딘 -계 ; 상기 이산화탄소를 흡수한 이산화탄소 흡수용 조성물을 넁각시켜 중탄산염 술러 리를 형 성하는 단계 ; 및 상기 중탄산염 슬러 리로부터 고상의 슬러리와 반용매가 포함된 액상의 흡수용액을 분리 한 후, 반용매를 흡수용액으로부터 분리하여 회수하는 한편 고상의 슬러 리를 고온으로 가열하여 이산화탄소를 분리하는 단계를 포함하는 이산화탄소 흡수 및 재 생방법을 제공한다.
[50] 이하에서 도면을 참조하여 본 발명 에 따른 이산화탄소 흡수 및 재생방법을
설명한다.
[51] 본 발명에 따른 이산화탄소 흡수용 조성물의 수용성 반용매를 통해 증탄산염 슬러 리를 결정화하고 이로부터 분리되는 고상의 슬러 리를 재 생하여
이산화탄소를 희수하는 장치 및 공정의 개략적 인 공정도를 도 1에 나타내었다.
[52] 도 1을 참조하면, 본 발명 에 따른 이산화탄소 흡수 및 재생장치는 본 발명에 따른 이산화탄소 흡수용 조성물 (11)을 이용하여 연소배가스 (1)로부터
이산화탄소를 선택적으로 흡수하기 위 한 흡수탑 (2); 이산화탄소가 흡수된 이산화탄소 흡수용액 (3)을 넁각기 또는 열교환기 (6)를 이용하여 넁각시켜 증탄산염 슬러 리를 형 성시키는 결정화기 (5); 생성된 중탄산염 슬러 리 (7) 용액으로부터 고상의 슬러 리 (Π)를 분리하기 위한 여과기 (8); 고상의
슬러 리 (13)를 고온으로 가열하여 이산화탄소를 분리하는 재생기 (14); 재생기 (14) 하단의 재비 기 (15); 및 재생기 (14) 상단의 수분 응축기 (16)를 포함하여 구성됨을 특징으로 한다.
[53] 우선, 이산화탄소를 포함하는 혼합기 체，예컨대 연소배가스 (1)를 상기
이산화탄소 흡수용 조성물 (U)과 접촉시켜 이산화탄소를 흡수한다.
[54] 상기 흡수탑 (2)은 대기 압 및 60~80°C의 조건에서 상기 이산화탄소 흡수용
조성물 (U)을 상단에서 노즐을 이용하여 분사함으로써 이산화탄소를 흡수하고 하단에서 이산화탄소가 흡수된 이산화탄소 흡수용 조성물 (3)을 배출한다. 기-액 접촉에 의 한 물질전달을 향상하기 위해 흡수탑 (2) 내부에는 충진제를
구성하거나 분사식 노즐을 이용하여 이산화탄소 흡수용 조성물 (1 1)을 분사할 수 있으나 분사 방식에 한정 이 있는 것은 아니다.
[55] 다음으로，상기 이산화탄소를 흡수한 이산화탄소 흡수용 조성물 (3)을 냉각시 켜 중탄산염 슬러 리를 형성한다.
[56] 이산화탄소를 흡수한 이산화탄소 흡수용 조성물 (3)은 결정화기 (5)로 이송하여 냉각기 또는 열교환기 (6)를 이용하여 이를 10~50oC로 냉각시켜 증탄산염 결정의 과포화를 유발시 킨다. 냉각기 또는 열교환기 (6)는 결정화기 (5) 내부 또는 외부에 위치할 수 있으며，이산화탄소 흡수용 조성물 (3)의 열전달 효율을 높이기 위해 교반기가 추가로 구성될 수 있다. 장치 내부에 유동이 있거나 작은 입자를 분리하여가열을통해제거하여슬러리입자의크기를증가시키는결정화기가 유리하나，결정화기의종류에한정이 있는것은아니다.
[57] 이산화탄소흡수용조성물 (11)에포함된수용성반용매는중탄산염결정의 생성수율을향상시켜냉각온도를크게낮출필요없이중탄산염슬러리용액을 형성시킨다.생성된중탄산염슬러리용액은여과기 (8)를통해이산화탄소를 상대적으로많이포함하고있는고상의슬러리 (13)와,이산화탄소를적게 포함하고있는반용매가포함된액상의흡수용액 (9)으로분리된다.여과기 (8)는 고상과액상을분리할수있는필터,싸이클론，침전조등이될수있다.
[58] 다음으로,상기중탄산염슬러리로부터고상의슬러리 (13)와반용매가포함된 액상의흡수용액 (9)을분리한후，고상의슬러리 (13)를고은으로가열하여 이산화탄소를분리한다.
[59] 분리된고상의슬러리 (13)는재생기 (14)로이송하여 l~20bar, 100~250oC의 조건에서이산화탄소와수분，무기염이산화탄소흡수용액으로분리된다.이때 재생기 (14)하단에스팀이공급되는재비기 (15)를구성하여슬러리를분해하고, 재생기 (14)상단에응축기 (16)를구성하껴증발하는수분을웅축시켜
재생기 (14)에환류하고고순도의 이산화탄소 (17)를회수한다.재생기 (14)는 내부에충진제를포함하는컬럼형태이거나교반압력반웅탱크로구성할수 있으나,반드시이에한정되는것은아니다.재생기 (14)에서회수된재생된 흡수용액 (18)은이산화탄소를적게포함하고있으며,열교환기 (19)를거쳐 흡수탑 (2)으로순환된다.즉,재생기 (14)의하단에서이산화탄소가분리된 재생된흡수용액 (18)은흡수탑 (2)으로회수된디-.재생기 (14)의상단으로부터 분리된이산화탄소는응축기 (16)를이용하여물을제거하고물은재생기 (14)로 환류되고재생된고순도의이산화탄소 (17)는제품으로회수된디-.
[60] 추가적으로,상기중탄산염슬러리로부터분리된액상의흡수용액에대해 액-액분리공정을수행하여수용성반용매를분리하는단계를더수행할수 있다.
[61] 따라서，여과기 (8)에서분리된반용매가포함된액상의흡수용액 (9)중
반용매를선택적으로분리하기위한액-액분리장치 (10)를추가적으로구성할 수있다.상기분리된반용매 (12)는이를포함하는액상의흡수용액 (9)으로부터 여과기에서분리되어결정화기 (5)로다시공급되고분리된액상의
흡수용액 (9)은흡수탑 (2)으로공급될수있다.
[62] 한편，여과기 (8)로부터배출되는저온의액상의흡수용액 (9)과흡수탑 (2)에서 배출되는이산화탄소를흡수한이산화탄소흡수용조성물 (3)은열교환기를통해 열을회수할수있으며，열교환효율을높이기위해열교환기는공정에 추가적으로구성될수있다.
[63] 도 2는액-액분리장치 (10)의추가적인구성없이，상기반용매가포함된액상의 흡수용액 (9)이흡수탑 (2)으로순환될수있는경우를나타낸다.상기반용매가 대기압및 60~80oC의조건에서증기압이낮아용매의증발량이적을경우 액상의흡수용액 (9)에반용매를포함시켜이산화탄소흡수용조성물로이용이 가능하다.
[64]
[65] 시험예 1:반용매를포함하는이산화탄소홈수용조성물의 ¾정화
[66] 25°C에서포화된중탄산칼륨용액 9 g올에탄올 1 g과함께흔합한뒤밀폐 용기에두고 70oC로가열한뒤 25°C로냉각시켰다.도 3은냉각후의흔합용액을 나타내며， (ii)의상층부는투명한상등액이， (i)의하층부에는슬러리가침전된 용액으로상분리가되었다. (i)의슬러리용액을적외선분광기를이용하여 측정하면,참조물질탄산칼륨 (Hi)보다참조물질인중탄산칼륨 (iv)과같은 형태인것이확인되었다. (ii)의상충부를측정하면，참조물질인순수한 에탄올 (V)과일치하는것으로나타났다.반용매는중탄산칼륨용액에포함되지 않고상분리되어쉽게분리가되는것으로나타난다.한편,넁각결정화에의해 생성된슬러리는결정의크기가약 500 이므로쉽게침전이되어고-액분리가 용이하다.
[67] 도 4는수용성반용매인메탄올,에탄올, 1-프로판올， 2-프로판올,
에틸렌글리콜，폴리에틸렌글리콜, N-메틸피롤리돈,프로필렌카보네이트등을 적용시용액 g당생성된결정의 g을나타낸다.반용매가존재하지않는조건에 비해중탄산염결정생성수율이높아졌으며특히，에탄올， N-메틸피를리돈등이 존재할때중탄산염결정의수율이높은것으로나타났다.도 5는에탄올,
N-메틸피롤리돈의농도가높아질수록석출되는결정의양이증가함을 나타내며,이를통해반용매를사용하는경우중탄산염의결정수율을높일수 있다는것을알수있다.

Claims

청구범위
[청구항 1] 이산화탄소를포함하는흔합기체로부터이산화탄소를흡수하고, 이산화탄소를많이포함하는중탄산염슬러리를분리하여 고압으로재생하는단계를포함하는공정에서사용되는 이산화탄소흡수용조성물로서，
무기염이산화탄소흡수용액및수용성반용매를포함하는것을 특징으로하는이산화탄소흡수용조성물.
[청구항 2] 제 1항에 있어서,
상기무기염이산화탄소흡수용액은나트륨，칼륨，리튬,루비듬및 세슘으로이루어진군으로부터선택되는것을포함하는 1가 무기염이용해된용액인것을특징으로이산화탄소흡수용 조성물.
[청구항 3] 제 1항에있어서，
상기무기염이산화탄소흡수용액은칼륨이용해된용액인것을 특징으로하는이산화탄소흡수용조성물.
[청구항 4] 제 1항에있어서,
상기무기염이산화탄소흡수용액의무기염농도는나트륨이 포함된무기염인경우 30중량 %,칼륨이포함된무기염인경우 50 중량 %，리튬이포함된무기염인경우 2중량 %,루비듐이포함된 무기염인경우 30증량 %,세슘이포함된무기염인경우 70 중량 %인것을특징으로하는이산화탄소흡수용조성물.
[청구항 5] 제 1항에있어서,
상기수용성반용매는메탄올,에탄올,프로판올,에틸렌글리콜， 프로필렌글리콜,디에틸렌글리콜,트리에티렌글리콜，
폴리에틸렌글리콜， N-메틸피를리돈,프로필렌카보네이트， 에틸렌카보네이트및이의흔합물로이루어진군으로부터 선택되는것을특징으로하는이산화탄소흡수용조성물.
[청구항 6] 제 5항에있어서,
상기수용성반용매는에탄올또는 N-메틸피롤리돈인것을 특징으로하는이산화탄소흡수용조성물.
[청구항 7] 제 5항에있어서,
상기수용성반용매는이산화탄소흡수용조성물전체중량에 대해 0초과〜 30중량 %로포함되는것을특징으로하는이산화탄소 흡수용조성물.
[청구항 8] 제 1항에있어서,
상기흡수속도증진제,산화방지제및부식방지제로부터선택되는 1종또는 2종이상의흔합물을더포함하는특징으로하는 이산화탄소흡수용조성물.
[청구항 9] 이산화탄소를포함하는흔할기체를제 1항내지제 8항중어느 한항에따른이산화탄소흡수용조성물과접촉시켜이산화탄소를 흡수하는단계 ;
상기이산화탄소를흡수한이산화탄소흡수용조성물을냉각시켜 중탄산염슬러리를형성하는단계;및
상기중탄산염슬러리로부터고상의슬러리와반용매가포함된 액상의흡수용액을분리한후반용매를흡수용액으로부터 분리하여회수하는한편,고상의슬러리를고온으로가열하여 이산화탄소를분리하는단계;
를포함하는이산화탄소흡수및재생방법 .
[청구항 10] 제 9항에있어서，
상기이산화탄소를포함하는흔합기체를이산화탄소흡수용 조성물과접촉시키는단계는대기압및 60~80oC의조건에서상기 이산화탄소흡수용조성물을이산화탄소를포함하는흔합기체에 분사시킴으로써수행되는것을특징으로하는이산화탄소흡수및 재생방법.
[청구항 11] 제 9항에있어서，
상기이산화탄소를흡수한이산화탄소흡수용조성물을
10~50oC로넁각시켜중탄산염슬러리를형성하는것을특징으로 하는이산화탄소흡수및재생방법 .
[청구항 12] 제 9항에 있어서,
상기중탄산염슬러리로부터분리된고상의슬러리를 l~20bar, 100~250oC의조건에서가열하여이산화탄소를분리하는것을 특징으로하는이산화탄소흡수및재생방법 .
[청구항 13] 제 9항에있어서,
상기중탄산염슬러리로부터분리된반용매가포함된액상의 흡수용액에대해액-액분리공정을수행하여수용성반용매를 분리하는단계를더포함하는것을특징으로하는이산화탄소 흡수및재생방법.
[청구항 14] 연소배가스로부터이산화탄소를제 1항내지제 8항중어느한 항에따른이산화탄소흡수용조성물을사용하여선택적으로 흡수하기위한흡수탑 (2);
상기이산화탄소가흡수된이산화탄소흡수용조성물을냉각기 또는열교환기를이용하여냉각시켜중탄산염슬러리를 형성시키는결정화기 (5);
상기중탄산염슬러리로부터고상의슬러리및반용매가포함된 액상의흡수용액을분리하기위한여과기 (8);및 상기 고상의 슬러 리를 고온으로 가열하여 이산화탄소를 분리하는 재생기 (14);
를 포함하는 이산화탄소 흡수 및 재생 장치 .
[청구항 15] 제 I4 항에 있어서 ,
상기 반용매가 포함된 액상의 흡수용액으로부터 수용성 반용매를 분리하기 위 한 액-액 분리장치 (10)를 더 포함하는 것을 특징으로 하는 이산화탄소 흡수 및 재 생 장치 .
[청구항 16] 제 14 항에 있어서，
상기 재생기 (14)는 고상의 슬러 리를 분해하는 재비기 (15) 및 수분과 이산화탄소를 분리하는 응축기 (16)를 포함하는 것을 특징으로 하는 이산화탄소 흡수 및 재생 장치 .
PCT/KR2013/009327 2012-11-09 2013-10-18 반용매를 포함하는 이산화탄소 흡수용 조성물 및 이를 사용하는 이산화탄소 흡수 방법 및 장치 WO2014073801A1 (ko)

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Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
KR20160063768A (ko) 2014-11-27 2016-06-07 한국에너지기술연구원 쿠엣-테일러 냉각 결정화기를 이용한 이산화탄소 분리방법 및 장치
KR101634539B1 (ko) * 2014-12-30 2016-06-29 한국에너지기술연구원 마그네슘을 포함하는 이산화탄소 흡수액을 이용한 이산화탄소 흡수 방법 및 장치
KR101670289B1 (ko) * 2014-12-30 2016-10-28 한국에너지기술연구원 칼슘을 포함하는 이산화탄소 흡수액을 이용한 이산화탄소 흡수 방법 및 장치
KR101796236B1 (ko) * 2015-11-27 2017-11-09 주식회사 포스코 산성 가스 내 이산화탄소 제거 방법 및 그 장치
EP3914376A4 (en) * 2019-01-28 2023-02-15 Richardson, Robert George CHEMICAL SEQUESTRATION OF CO2, NOX AND SO2
GB202010908D0 (en) * 2020-07-15 2020-08-26 C-Capture Ltd Rate enhancement of gas capture processes
CN114307803A (zh) * 2020-09-30 2022-04-12 新疆天运化工有限公司 一种co2吸收液及其配制装置与工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006272143A (ja) * 2005-03-29 2006-10-12 Mitsubishi Materials Corp 酸性ガスを含む混合ガスの精製方法及びその装置並びにその精製に用いられる酸性ガスの吸収液
US20100034724A1 (en) * 2008-06-20 2010-02-11 David Keith Carbon Dioxide Capture
WO2011130796A1 (en) * 2010-04-23 2011-10-27 Co2Crc Technologies Pty Ltd A process and plant for removing acid gases
KR101157141B1 (ko) * 2009-12-28 2012-06-22 한국에너지기술연구원 입체장애 시클릭 아민이 첨가된 알칼리탄산염계 이산화탄소 흡수제 및 이를 이용한 이산화탄소 제거방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017350A (en) * 1989-06-02 1991-05-21 Union Carbide Canada Limited Gas scrubbing process
US7192468B2 (en) * 2002-04-15 2007-03-20 Fluor Technologies Corporation Configurations and method for improved gas removal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006272143A (ja) * 2005-03-29 2006-10-12 Mitsubishi Materials Corp 酸性ガスを含む混合ガスの精製方法及びその装置並びにその精製に用いられる酸性ガスの吸収液
US20100034724A1 (en) * 2008-06-20 2010-02-11 David Keith Carbon Dioxide Capture
KR101157141B1 (ko) * 2009-12-28 2012-06-22 한국에너지기술연구원 입체장애 시클릭 아민이 첨가된 알칼리탄산염계 이산화탄소 흡수제 및 이를 이용한 이산화탄소 제거방법
WO2011130796A1 (en) * 2010-04-23 2011-10-27 Co2Crc Technologies Pty Ltd A process and plant for removing acid gases

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