JP6413408B2 - Co2除去装置 - Google Patents
Co2除去装置 Download PDFInfo
- Publication number
- JP6413408B2 JP6413408B2 JP2014141002A JP2014141002A JP6413408B2 JP 6413408 B2 JP6413408 B2 JP 6413408B2 JP 2014141002 A JP2014141002 A JP 2014141002A JP 2014141002 A JP2014141002 A JP 2014141002A JP 6413408 B2 JP6413408 B2 JP 6413408B2
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- gas
- capture
- removal apparatus
- reaction vessel
- concentration
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 285
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 284
- 239000007789 gas Substances 0.000 claims description 185
- 239000000463 material Substances 0.000 claims description 149
- 238000006243 chemical reaction Methods 0.000 claims description 108
- 238000010438 heat treatment Methods 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 238000007599 discharging Methods 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 5
- 101100114828 Drosophila melanogaster Orai gene Proteins 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003546 flue gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 49
- 229910000420 cerium oxide Inorganic materials 0.000 description 29
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 28
- 238000001179 sorption measurement Methods 0.000 description 26
- 238000003795 desorption Methods 0.000 description 23
- 229910021536 Zeolite Inorganic materials 0.000 description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 21
- 239000010457 zeolite Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229920006395 saturated elastomer Polymers 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical group 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000005192 partition Methods 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical class 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
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- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
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Description
層状複水酸化物を合成する方法としては、含浸法、混練法、共沈法、及びゾルゲル法などの調製方法が挙げられる。例えば、MgとAlの硝酸塩を含んだ溶液に、炭酸ナトリウムを添加した後、アンモニア水、水酸化Na、及び水酸化Caなどの塩基性の化合物を加えることでpHを8〜11に調整して、沈殿させて得てもよい。本沈殿で得られる物質は層状複水酸化物であるため、金属酸化物及び金属の複合酸化物を得るためには焼成してもよい。焼成温度はどのような温度でも構わないが、例えば400℃以上で焼成した場合に金属酸化物を得られる。
精製水1080gに硝酸セリウム六水和物26.05gを室温で激しく撹拌しながら溶解させた。前記水溶液を撹拌しながら28重量%のアンモニア水溶液を滴下しpHを9.0とした。8時間撹拌した後、1時間静置し、沈殿物を洗浄ろ過により収集した。その後、沈殿物を乾燥炉にて120℃で乾燥させ、大気雰囲気下の電気炉にて400℃で1時間焼成し、得られたセリウム酸化物をCO2捕捉材とした。
第一稀元素製のジルコニウム酸化物(RSC−100)をCO2捕捉材とした。
以下に、H2Oを流通させずにCO2を吸着させた場合の試験条件を示す。
CO2捕捉材は直径40mmの金型を使用して、プレス機により200kgfでペレット化し、破砕したのち篩を用いて0.5〜1.0mmの粒状に整粒した。その後、メスシリンダーを用いて1.0mlを測り、石英ガラス製反応管中に固定した。
150ml/分でHeを流通させながら、電気炉を用いてCO2捕捉材の温度を400℃に上昇させて1時間保持して不純物及び捕捉材に吸着したガスを除去した。
加熱前処理後、冷却してCO2捕捉材温度を50℃まで下げた。
電気炉で試料温度を50℃に保ちながらCO2パルス捕捉試験によりCO2捕捉量を測定した。サンプルガスとして12体積%のCO2と88体積%のHeからなる混合ガス10mlをパルス状で4分おきに2分間導入し、反応管出口のCO2濃度をガスクロマトグラフィにより測定した。パルス導入は反応管出口で測定されるCO2が飽和するまで実施した。また、キャリアガスとしてHeを使用した。
電気炉で試料温度を昇温速度10℃/分で400℃まで加熱してCO2の脱離量を測定した。
H2Oを流通させた後にCO2を吸着させた場合の試験条件を示す。CO2吸着試験−H2O流通なし、における測定方法において、冷却の後、吸着の前においてH2O流通処理を行った以外は同様の方法でCO2吸着量を評価した。
25℃の水が入ったバブラー容器において、150ml/分でHeを1時間流通させた。処理中のCO2捕捉材温度は電気炉で50℃に設定した。
×1.41(kg/L)×(Td−50)(K)×382(J/K・kg)・・・(2)
本結果から、H2O流通がある方が加熱に要するエネルギーが低くできることがわかった。
実施例1のセリウム酸化物におけるBET(Brunauer−Emmett−Teller)法を用いて−196℃での窒素の吸着等温線を測定し、比表面積を測定した。前処理として、真空引きを行いながら200℃で加熱した。実施例1の比表面積は130m2/gであった。
実施例1のセリウム酸化物におけるH2O吸着等温線を計測した。前処理として、真空引きを行いながら200℃で加熱した。その後真空引きを行いながら冷却し、試料温度は25℃で保持しながらH2Oを吸着させた。
実施例1のセリウム酸化物における表面にH2O単分子層を形成するための吸着量Qmlを算出した。前記BET法で求めた比表面積をSA、アボガドロ数をNA=6.02×1023、H2Oの吸着断面積を1.25×10-19m2とし、下記式(3)を用いて算出した。
本計算の結果、H2O単分子層吸着量Qmlは1.8mol/kgと算出された。
103 加熱用ガス
301、302、303、304 配管
401、402、403、404 弁
501 凝縮器
601 H2O濃度計
701 反応容器
801、802 CO2捕捉材
901 加熱器
Claims (10)
- ガス中のH2O及びCO2を捕捉する捕捉材と、
前記捕捉材が内部に設置され、2つ以上有する反応容器と、
前記ガス中のH2O濃度を計測するためのH2O計測器と、
前記H2O計測器で得た情報を基にH2O濃度を調整するH2O濃度調整機器と、
前記H2O濃度調整機器から前記反応容器にH 2 O及びCO 2 を含む前記ガスを導入して前記捕捉材に接触させるためのガス導入路と、
前記ガスを前記捕捉材に接触させた後に前記反応容器から排出するための第一のガス排出路と、
前記捕捉材から脱離したガスを前記反応容器から排出するための第二のガス排出路と、を含み、
前記捕捉材は、セリウムを含む酸化物もしくは複合酸化物を含む捕捉材Aと、少なくともゼオライトを含む捕捉材Bと、を含み、
前記ガスからCO2もしくはH2Oもしくはその両方を除去する場合において、前記ガスの流通方向が前記捕捉材Aから前記捕捉材Bの方向であることを特徴とするCO2除去装置。 - 請求項1に記載のCO2除去装置において、
前記捕捉材を加熱する加熱手段を有することを特徴とするCO2除去装置。 - 請求項1に記載のCO2除去装置において、
加熱用流体が前記捕捉材に接触するように構成され、
前記加熱用流体が、CO2、水蒸気、N2、燃焼排ガス、及び、大気から取り込んだ後に加熱して得たガス、から選ばれる少なくとも1つのガスを含む流体であることを特徴とするCO2除去装置。 - 請求項3に記載のCO2除去装置であって、
前記ガスの流通方向と、前記加熱流体の流通方向が同一方向であることを特徴とするCO2除去装置。 - 請求項3に記載のCO2除去装置であって、
前記ガスの流通方向と、前記加熱流体の流通方向が逆方向であることを特徴とするCO2除去装置。 - 請求項1に記載のCO2除去装置において、
前記捕捉材よりも高温の熱媒を伝熱機器に流通させ、伝熱機器からの伝熱により前記捕捉材を加熱するための機器を含むことを特徴とするCO2除去装置。 - 請求項2に記載のCO2除去装置において、
前記加熱手段は、電力により加熱する機器であることを特徴とするCO2除去装置。 - 請求項1〜7の何れかに記載のCO2除去装置において、
前記反応容器を減圧するための減圧機器を有することを特徴とするCO2除去装置。 - 請求項1〜8の何れかに記載のCO2除去装置において、
前記反応容器を加圧するための加圧機器を有することを特徴とするCO2除去装置。 - 請求項1〜9の何れかに記載のCO2除去装置において、
前記ガスが周辺の大気圧よりも高圧であることを特徴とするCO2除去装置。
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JP2014141002A JP6413408B2 (ja) | 2014-07-09 | 2014-07-09 | Co2除去装置 |
CN201580011119.1A CN106170330B (zh) | 2014-07-09 | 2015-07-08 | Co2除去装置 |
US15/301,099 US10035099B2 (en) | 2014-07-09 | 2015-07-08 | CO2 removal device |
PCT/JP2015/069584 WO2016006620A1 (ja) | 2014-07-09 | 2015-07-08 | Co2除去装置 |
EP15818650.2A EP3167951A4 (en) | 2014-07-09 | 2015-07-08 | Co2 removal device |
CA2941022A CA2941022C (en) | 2014-07-09 | 2015-07-08 | Co2 removal device |
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JP5664674B2 (ja) | 2013-01-31 | 2015-02-04 | 住友大阪セメント株式会社 | 光学素子 |
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