WO2010106953A1 - 炭酸ガスの処理方法 - Google Patents

炭酸ガスの処理方法 Download PDF

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Publication number
WO2010106953A1
WO2010106953A1 PCT/JP2010/054025 JP2010054025W WO2010106953A1 WO 2010106953 A1 WO2010106953 A1 WO 2010106953A1 JP 2010054025 W JP2010054025 W JP 2010054025W WO 2010106953 A1 WO2010106953 A1 WO 2010106953A1
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WO
WIPO (PCT)
Prior art keywords
calcium
carbon dioxide
solution
calcium carbonate
dioxide gas
Prior art date
Application number
PCT/JP2010/054025
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English (en)
French (fr)
Japanese (ja)
Inventor
脇本佳季
小山敏之
皆木肇
萩原輝行
蜂須賀譲二
Original Assignee
アイシン精機株式会社
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Publication date
Application filed by アイシン精機株式会社 filed Critical アイシン精機株式会社
Publication of WO2010106953A1 publication Critical patent/WO2010106953A1/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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a carbon dioxide gas treatment method in which carbon dioxide is brought into contact with a calcium solution to produce calcium carbonate.
  • a gas containing carbon dioxide is brought into contact with an aqueous solution obtained from water, an alkaline earth metal-containing substance, and a salt of a weak base and a strong acid to thereby form an alkaline earth metal.
  • a method for producing carbonate is known (for example, see Patent Document 1).
  • this method in order to treat carbon dioxide gas inexpensively and easily, natural minerals, waste materials, by-products discharged in the manufacturing process, concrete solidified with cement hydrated solids, and concrete are used as alkaline earth metal-containing substances.
  • the use of building waste materials or pulverized materials, steel slag, soda lime glass, potash lime glass, coal ash, incinerated ash, dust, etc. is being studied.
  • the carbonate produced by this method is, for example, in the case of calcium carbonate, an auxiliary material for iron making, a raw material for cement, a refractory material, a paper filler, a ground improvement material, a fertilizer, a raw material for environmental purification process, a filler, Used for industrial raw materials.
  • the present invention has been devised in view of the above problems, and provides a carbon dioxide gas treatment method capable of controlling grain growth of the produced calcium carbonate in a carbon dioxide gas treatment method in which calcium carbonate is produced as a carbonate. Objective.
  • the first characteristic means of the carbon dioxide gas treatment method according to the present invention is the carbon dioxide gas treatment method for producing calcium carbonate by bringing carbon dioxide gas into contact with a calcium solution having a pH of 7 or higher.
  • the solution is maintained at a calcium concentration that depends on pH for the promotion and suppression of the grain growth of the calcium carbonate, and the pH of the calcium solution is maintained within a predetermined range to control the grain growth of the calcium carbonate. is there.
  • the particle diameter of the calcium carbonate to be generated can be easily controlled only by adjusting the calcium concentration of the calcium solution (hereinafter sometimes referred to as [Ca 2+ ]) and the pH. Moreover, since carbon dioxide having a particle size corresponding to the intended use can be provided while treating carbon dioxide, the added value of calcium carbonate is increased, and the processing cost can be reduced as a whole.
  • the second characteristic means of the method for treating carbon dioxide gas according to the present invention is that calcium hydroxide is added to the calcium solution to maintain the pH of the calcium solution in the predetermined range.
  • the third characteristic means of the carbon dioxide gas treatment method according to the present invention is that the calcium concentration of the calcium solution is maintained at 1.0 ⁇ 10 ⁇ 8.3 ⁇ [Ca 2+ ] (mol / L).
  • the fourth characteristic means of the method for treating carbon dioxide gas according to the present invention is that the pH of the calcium solution is maintained in the range of 10 to 12.8.
  • the fifth characteristic means of the carbon dioxide treatment method according to the present invention is that the pH of the calcium solution is maintained in the range of 7-9.
  • the particle growth of the calcium carbonate to be generated can be promoted and the particle size of the calcium carbonate can be easily controlled.
  • the carbon dioxide treatment method according to the present invention is a carbon dioxide treatment method in which carbon dioxide is brought into contact with a calcium solution having a pH of 7 or more to produce calcium carbonate.
  • the calcium solution is used to promote the growth of calcium carbonate grains. Inhibition is maintained at a calcium concentration that depends on the pH, and the pH of the calcium solution is maintained within a predetermined range to control grain growth of the calcium carbonate. That is, the present inventors paid attention to a calcium solution in contact with carbon dioxide gas, and found that the particle size of the generated calcium carbonate changes depending on the calcium concentration and pH of the calcium solution. According to this method, the particle diameter of the calcium carbonate to be generated can be controlled by contacting the carbon dioxide gas while maintaining the calcium concentration and pH of the calcium solution in a predetermined range. Moreover, since carbon dioxide having a particle size corresponding to the intended use can be provided while treating carbon dioxide, the added value of calcium carbonate is increased, and the processing cost can be reduced as a whole.
  • the carbon dioxide gas in the present invention is not limited to pure carbon dioxide gas, and any gas containing carbon dioxide gas can be applied.
  • gaseous fuel such as liquefied natural gas (LNG) and liquefied petroleum gas (LP)
  • liquid fuel such as gasoline and light oil
  • combustion exhaust gas generated by burning solid fuel such as coal
  • solid fuel such as coal
  • the calcium solution used in the present invention is not particularly limited, but for example, it can be prepared by pulverizing slag such as cupola slag and blast furnace slag to about 20 to 500 ⁇ m and dissolving in acid or water.
  • the slag is particularly preferably used after being pulverized to 20 to 100 ⁇ m.
  • calcium content appears on the surface of the pulverized product, so that it can be preferably dissolved in water without using acid.
  • a calcium solution can also be prepared by adding a conventionally known calcium compound such as calcium hydroxide.
  • the calcium solution is set to a calcium concentration at which pH dependence occurs in the grain growth of the generated calcium carbonate.
  • the pH of the calcium solution is lowered by the formation of calcium carbonate, it is maintained in a predetermined range of 7 or more.
  • the pH is preferably maintained in the range of 7-9.
  • carbon dioxide gas is brought into contact while changing the pH of the calcium solution from the range of 10 to 12.8 to the range of 7 to 9, the formation of calcium carbonate particles is accelerated in the range of pH from 10 to 12.8.
  • the pH is in the range of 7-9, the grain growth of the generated calcium carbonate is promoted.
  • the pH of the calcium solution becomes alkaline with a pH of 7 or more by dissolving the slag, it can be arbitrarily adjusted by changing the dissolved amount of the slag.
  • the pH can also be adjusted by adding a conventionally known pH adjusting agent such as acid or alkali. If the pH of the calcium solution decreases with the formation of calcium carbonate, add slag, calcium-containing basic substance, or a solution containing calcium-containing substance and base (such as calcium hydroxide). By doing so, the pH can be maintained within a predetermined range.
  • the pH can be maintained within a predetermined range by adding a pH adjuster
  • calcium can be replenished at the same time by adding a slag, a calcium-containing basic substance, or a solution containing a calcium-containing substance and a base as components. You can also The calcium solution may be mixed with other various additives and impurities.
  • the contact of carbon dioxide with the calcium solution can be performed by a conventionally known method, and there is no particular limitation.
  • a method of bubbling (blowing) carbon dioxide into a calcium solution a method of shaking a calcium solution and carbon dioxide enclosed in the same container, and the like can be mentioned.
  • combustion exhaust gas etc. as a carbon dioxide gas
  • it can also pass an adsorption filter etc., and can remove gas other than dust and a carbon dioxide gas.
  • the calcium solution can be used at any temperature, but the higher the temperature, the more difficult the carbon dioxide gas dissolves.
  • Calcium carbonate produced by the carbon dioxide treatment method of the present invention can be recovered by a conventionally known method such as filtration.
  • the recovered calcium carbonate can be used as a filler in industries such as papermaking, pigments, paints, plastics, rubber, woven and knitted fabrics.
  • Carbon dioxide treatment was performed with the apparatus shown in FIG. That is, while putting a calcium solution into the reaction vessel 1 and stirring with a stirrer 2 at 400 rpm, a simulated combustion exhaust gas was introduced into the calcium solution as bubbling carbon dioxide, and the precipitated calcium carbonate was examined.
  • the reaction state between the carbon dioxide gas and the calcium solution was examined by measuring the redox potential and pH of the calcium solution with the measuring instrument 7.
  • the concentration of carbon dioxide gas that was not absorbed by the calcium solution after introduction was measured by a gas chromatograph 8.
  • 9 is a backflow prevention apparatus
  • 3 is a water bath which adjusts the temperature of a calcium solution.
  • the calcium solution was used at room temperature by adding calcium hydroxide (Ca (OH) 2 ) to 500 ml of distilled water to adjust the calcium (Ca) concentration and pH.
  • Ca (OH) 2 calcium hydroxide
  • a mixed gas of carbon dioxide (CO 2 ) and nitrogen (N 2 ) gas was used as the simulated combustion exhaust gas.
  • the simulated combustion exhaust gas is supplied with carbon dioxide gas and nitrogen gas mixed at a predetermined mixing ratio in the mixing device 6 with the flow rate adjusted by the flow rate adjusters 4 and 5, respectively.
  • the simulated combustion exhaust gas was adjusted to 10 vol% CO 2 -90 vol% N 2 and introduced into the calcium solution at 1 liter / min.
  • the relationship between the calcium concentration and pH of the calcium solution and the particle size of the generated calcium carbonate is as shown in FIG. That is, the calcium concentration that depends on pH for the promotion / suppression of the grain growth of calcium carbonate is 0.04 mol / 500 mL or less, and when the pH increases from pH 10 to 10-12.8, grain growth does not occur.
  • the generation of particles is prioritized, and when the pH is reduced as in the case of 7 to 9, grain growth is promoted.
  • the calcium concentration exceeds 0.04 mol / 500 mL grain growth is promoted regardless of pH.
  • the calcium concentration is preferably maintained in the range of 0.5 ⁇ 10 ⁇ 8.3 ⁇ [Ca 2+ ] (mol / 500 mL) ⁇ 0.04. ⁇ [Ca 2+ ] (mol / 500 mL) ⁇ 0.04 is more preferably maintained.
  • the carbon dioxide treatment method of the present invention can be applied to the treatment of carbon dioxide in combustion exhaust gas.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Geology (AREA)
  • Biomedical Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Gas Separation By Absorption (AREA)
PCT/JP2010/054025 2009-03-17 2010-03-10 炭酸ガスの処理方法 WO2010106953A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009064843A JP5637345B2 (ja) 2009-03-17 2009-03-17 炭酸ガスの処理方法
JP2009-064843 2009-03-17

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013095662A (ja) * 2011-10-27 2013-05-20 Korea Inst Of Geoscience & Mineral Resources 二酸化炭素固定化方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101254978B1 (ko) 2011-05-18 2013-04-17 재단법인 포항산업과학연구원 모델식을 이용한 이산화탄소 포집공정의 반응생성물 농도 예측방법 및 이를 이용한 포집 반응기
JP6266989B2 (ja) 2014-01-31 2018-01-24 フタバ産業株式会社 二酸化炭素施用装置
JP6359881B2 (ja) * 2014-06-10 2018-07-18 フタバ産業株式会社 二酸化炭素施用装置
JP5931253B1 (ja) * 2014-06-30 2016-06-08 本部三慶株式会社 高度サラシ粉からカルシウム成分を除去し、低塩素臭の液体塩素酸化物を得る方法
US11041420B2 (en) * 2016-09-21 2021-06-22 M-Trigen, Inc. Carbon capture system, apparatus, and method
JP6442014B1 (ja) * 2017-09-13 2018-12-19 株式会社流機エンジニアリング 被処理液の処理装置及び処理方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03197318A (ja) * 1989-12-26 1991-08-28 Okutama Kogyo Kk 凝集炭酸カルシウムの製造方法
JP2002234726A (ja) * 2001-02-01 2002-08-23 Okutama Kogyo Co Ltd 炭酸カルシウムの連続製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03197318A (ja) * 1989-12-26 1991-08-28 Okutama Kogyo Kk 凝集炭酸カルシウムの製造方法
JP2002234726A (ja) * 2001-02-01 2002-08-23 Okutama Kogyo Co Ltd 炭酸カルシウムの連続製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013095662A (ja) * 2011-10-27 2013-05-20 Korea Inst Of Geoscience & Mineral Resources 二酸化炭素固定化方法
US20130287672A1 (en) * 2011-10-27 2013-10-31 Korea Institute Of Geoscience And Mineral Resources Method for Increasing Efficiency in Mineral Carbonation Using Furnace Slag as Industrial Byproduct

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JP2010214303A (ja) 2010-09-30

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