JP5550715B2 - Coシフト触媒、coシフト反応装置及びガス化ガスの精製方法 - Google Patents
Coシフト触媒、coシフト反応装置及びガス化ガスの精製方法 Download PDFInfo
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- JP5550715B2 JP5550715B2 JP2012501852A JP2012501852A JP5550715B2 JP 5550715 B2 JP5550715 B2 JP 5550715B2 JP 2012501852 A JP2012501852 A JP 2012501852A JP 2012501852 A JP2012501852 A JP 2012501852A JP 5550715 B2 JP5550715 B2 JP 5550715B2
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- catalyst
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- gasification gas
- gas
- gasification
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- 239000003054 catalyst Substances 0.000 title claims description 94
- 238000002309 gasification Methods 0.000 title claims description 50
- 238000006243 chemical reaction Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 14
- 238000000746 purification Methods 0.000 title description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 91
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 91
- 239000007789 gas Substances 0.000 claims description 62
- 239000003245 coal Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- -1 Next Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052573 porcelain Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910017318 Mo—Ni Inorganic materials 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 238000005486 sulfidation Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- TVAATYMJWZHIQJ-UHFFFAOYSA-N molybdenum;tetrahydrate Chemical compound O.O.O.O.[Mo] TVAATYMJWZHIQJ-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910015711 MoOx Inorganic materials 0.000 description 1
- 229910003185 MoSx Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SUOTZEJYYPISIE-UHFFFAOYSA-N iron(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SUOTZEJYYPISIE-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
一方、石炭を付加価値の高いエネルギー媒体として、変換するためには石炭ガス化技術、ガス精製技術など高度な技術が必要とされる。
このガス化ガスを用いて発電する石炭ガス化複合発電システムが提案されている(特許文献1)。
この石炭ガス化複合発電(Integrated coal Gasification Combined Cycle:IGCC)とは、石炭を高温高圧のガス化炉で可燃性ガスに転換し、そのガス化ガスを燃料としてガスタービンと蒸気タービンとによる複合発電を行うシステムをいう。
図3に示すように、この石炭ガス化発電プラント100−1は、石炭101をガス化炉102でガス化し、生成ガスであるガス化ガス103を得た後、脱塵装置104で除塵した後、COS変換装置105でCOSをH2Sに変換した後、COシフト反応装置106でCOシフト反応を起こさせた後、H2S/CO2回収装置107でCO2を回収すると共に、ガス中のH2Sの除去をおこなっている。なお、図中、符号120は空気、121は空気を窒素(N2)と酸素(O2)とに分離する空気分離装置、122はガス化空気圧縮機、123はガス化空気、124は水蒸気、125はH2S/CO2処理系を各々図示する。
このCOシフト反応は、下記式(1)の反応により有用成分であるCO2とH2とを得るようにしている。
CO+H2O→CO2+H2…(1)
湿式スクラバ装置によりガス化ガスを浄化し、次いで、ガス化ガス中の二酸化炭素及び硫化水素を除去し、次いで、第1の発明のCOシフト触媒を用いて、H 2 S濃度が0.1〜100ppmの低濃度の硫化水素下において、ガス化ガス中のCOをCO2に変換するCOシフト反応させ精製ガスを得ることを特徴とするガス化ガスの精製方法にある。
図1に示すように、ガス化ガス精製システム10は、燃料Fである石炭をガス化するガス化炉11と、生成ガスであるガス化ガス12中の煤塵を除去するフィルタ13と、フィルタ13を通過した後のガス化ガス12中のハロゲンを除去する湿式スクラバ装置14と、熱交換後のガス化ガス12中のCO2及びH2Sを吸収除去する吸収塔15Aと再生する再生塔15Bからなると共に再生塔15B側に再生過熱器16を備えたガス精製装置15と、ガス化ガス12の温度を上げる第1の熱交換器17及び第2の熱交換器18と、温度が300℃に上昇されたガス化ガス12中のCOをCO2に変換して精製ガス22とするCOシフト触媒19を備えたCOシフト反応装置20と、を具備するものである。なお、図1中、符号21は水蒸気を図示する。
ここで、得られる複合酸化物としては、例えばTiO2-ZrO2、TiO2-CeO2、CeO2-ZrO2、等の複合酸化物を例示することができる。
下記式(2)は、酸化モリブデンが硫化水素を反応して硫化モリブデンとなる反応式である。
MoOx+xH2S⇔MoSx+xH2O(x=0〜3)…(2)
2)ここで、触媒活性と硫化度合い(硫化物の割合を示す)とは相関関係を有し、硫化度合いが小さければ、触媒活性も低いこととなる。
3)ルシャトリエの法則から、系内のH2S分圧が小さければ、平衡組成は上記式(2)において、左側に傾くので、硫化モリブデンの量が減少し、活性も低くなる傾向となる。
4)本発明のMo−Ni系触媒では、副成分としてNi元素を含んでいるので、低H2S濃度でも硫化モリブデンを安定させることができるので、H2S分圧が小さい場合であっても、平衡組成は式(2)において、左側に傾くことが抑制され、触媒活性も維持できると、推察される。
図2に示すように、本発明に係るMo−Ni系触媒では、H2S濃度が0.1ppm程度と極めて低い場合でも触媒活性が示され、H2S濃度が10〜1000ppmでは、相対値0.9以上の高い活性を示している。
これに対して、Co−Mo系触媒では、H2S濃度10〜100ppmでは、相対値0.3以下と低い活性を示している。
これにより、本発明に係るMo−Ni系触媒は、H2S濃度が極めて低い場合でも触媒活性が示されることとなることが判明した。
以下、本発明の効果を示す試験例について説明する。
1)触媒1の製法[含浸(IMP)法]
石原産業製酸化チタン(TiO2(「MC−90」商品名))を100g磁製皿に入れ、150mlの水に溶かした硝酸ニッケル・6水和物(NN)とモリブデン酸アンモニウム・4水和物(MA)を、最終的に得られる全粉末量に対してNiOが5重量%、MoO3が15重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。
得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして触媒1を得た。
石原産業製酸化チタン(TiO2(「MC−90」商品名))を100g、3Lの水が入ったビーカーに入れ、その中に硝酸ニッケル・6水和物を最終的に得られる全粉末量に対してNiOが5重量%となるように添加する。
ビーカー内を攪拌して硝酸ニッケルを溶解後、攪拌を継続した状態で炭酸ナトリウム2.5mol%を水2Lに溶解させた溶液を滴下し、沈殿させる。
次に、モリブデン酸アンモニウム・4水和物を最終的に得られる全粉末量に対してMoO3が15重量%担持されるように添加し、攪拌溶解する。
そして、攪拌を継続した状態で1Nの硝酸水溶液を滴下し、沈殿させる。
最後に、遠心分離機で洗浄ろ過、乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。
得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして触媒2を得た。
第一希元素製10重量%ZrO2/TiO2を100g磁製皿に入れ、150mlの水に溶かした硝酸ニッケル・6水和物とモリブデン酸アンモニウム・4水和物を、最終的に得られる全粉末量に対してNiOが5重量%、MoO3が15重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。
得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして触媒3を得た。
第一希元素製CeO2を100g磁製皿に入れ、150mlの水に溶かした硝酸ニッケル・6水和物とモリブデン酸アンモニウム・4水和物を、最終的に得られる全粉末量に対してNiOが6重量%、MoO3が20重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。
得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして触媒4を得た。
第一希元素製80重量%CeO2/ZrO2を100g磁製皿に入れ、150mlの水に溶かした硝酸ニッケル・6水和物とモリブデン酸アンモニウム・4水和物を、最終的に得られる全粉末量に対してNiOが6重量%、MoO3が14重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして触媒5を得た。
石原産業製酸化チタン(TiO2(「MC−90」商品名))を100g磁製皿に入れ、100mlの水に溶かした硝酸ルテニウム(RN)水溶液と硝酸鉄(II)・6水和物(FN)を、最終的に得られる全粉末量に対してRuが1重量%、FeOが17重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして参考触媒1を得た。
第一希元素製10重量%CeO2/TiO2を100g磁製皿に入れ、100mlの水に溶かした硝酸ニッケル・6水和物(NN)と硝酸鉄(III)・6水和物(FN)を、最終的に得られる全粉末量に対してNiが9重量%、Fe2O3が17重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして参考触媒2を得た。
住友化学製γ−Al2O3(A−11)を100g磁製皿に入れ、150mlの水に溶かした硝酸コバルト・6水和物(CN)とモリブデン酸アンモニウム・4水和物(MA)を、最終的に得られる全粉末量に対してCoOが4重量%、MoO3が13重量%担持されるように添加後、磁製皿上で蒸発乾固含浸した。そして、得られた粉末を乾燥器で完全に乾燥後、500℃で3時間(昇温速度100℃/h)焼成を施すことにより粉末触媒を得た。
得られた触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして比較触媒1(比1)を得た。
炭酸ナトリウムを水2Lに溶解させ、60℃に保温してこのアルカリ溶液を溶液Aとした。次に硝酸アルミニウム及び硝酸亜鉛を水400mlに溶解させ、60℃に保温した酸性溶液を溶液Bとした。また、硝酸銅(CUN)を水400mlに溶かして60℃に保温した酸性溶液を溶液Cとした。なお、硝酸アルミニウム、硝酸亜鉛及び硝酸銅の比率は金属酸化物の形態で50:15:35重量%となるように配合し、炭酸ナトリウムは硝酸アルミニウム、硝酸亜鉛及び硝酸銅の添加モル量の2倍量とした。さらに上記配合で調製する触媒量は理論換算で100gとなるように原料を添加した。
調製方法は、攪拌しながら溶液Aに溶液Bを30分にわたり均一に滴下し、沈殿生成液Dを得た。次に、溶液Cを前記の沈殿生成液Dに30分にわたり均一に滴下し、アルミニウム、亜鉛及び銅を含有した沈殿生成液Fを得た。
沈殿生成液Fを、2時間そのまま攪拌することにより熟成を行い、次に沈殿生成液Fのろ液及びNaイオン、NOイオンが検出されないように、十分に洗浄した。さらに、100℃で24時間乾燥し、その後、300℃で3時間焼成することにより比較触媒粉末を得た。得られた比較触媒粉末を30tonの加圧成形器で粉末を固定化させた後、粒径が2〜4mmの範囲となるように破砕後篩い分けして比較触媒2(比2)を得た。
評価試験は、内径14mmの管型反応管に触媒を3.3cc充填し、流通式マイクロリアクタ装置により触媒活性を評価した。触媒活性の比較は、触媒層入口、出口のガス流量変化で、下記表2に示すCO転化率と定義するパラメータで整理した。
ガス組成は、H2/CO/CO2/H2O=17/24/11/48モル%、H2S=20ppm、S/CO=2.0とし、0.9MPa、温度250℃の条件で試験した。評価条件については表2に示す。CO転化率は表2の下段の式による。
これに対し、比較例にかかる比較触媒1は、CO転化率が大幅に低下した。比較触媒2は殆ど活性が無かった。
11 ガス化炉
12 ガス化ガス
13 フィルタ
14 湿式スクラバ装置
15A 吸収塔
15B 再生塔
15 ガス精製装置
16 再生過熱器
17 第1の熱交換器
18 第2の熱交換器
19 COシフト触媒
20 COシフト反応装置
22 精製ガス
Claims (3)
- 石炭ガス化ガス中のH2SをH2S回収装置により除去したH2S濃度が0.1〜100ppmのガス化ガス中の一酸化炭素(CO)を改質するCOシフト触媒であって、
モリブデン(Mo)を主成分とすると共に、ニッケル(Ni)を副成分とする活性成分と、
この活性成分を担持するチタン(Ti)、ジルコニウム(Zr)及びセリウム(Ce)の少なくとも二種の元素が存在する複合酸化物を含む担体とを有し、
前記活性成分の主成分の担持量が0.1〜25重量%であると共に、副成分の担持量が0.01〜10重量%であることを特徴とするCOシフト触媒。 - 請求項1のCOシフト触媒を反応塔内に充填してなることを特徴とするCOシフト反応装置。
- 石炭ガス化炉で得られたガス化ガス中の煤塵をフィルタで除去した後、
湿式スクラバ装置によりガス化ガスを浄化し、
次いで、ガス化ガス中の二酸化炭素及び硫化水素を除去し、
次いで、請求項1のCOシフト触媒を用いて、H 2 S濃度が0.1〜100ppmの低濃度の硫化水素下において、ガス化ガス中のCOをCO2に変換するCOシフト反応させ精製ガスを得ることを特徴とするガス化ガスの精製方法。
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JP5535990B2 (ja) * | 2010-08-27 | 2014-07-02 | 株式会社日立製作所 | シフト触媒、ガス精製方法及び設備 |
JP5450540B2 (ja) * | 2011-09-12 | 2014-03-26 | 株式会社日立製作所 | Co2回収装置を備えたボイラーの熱回収システム |
JP2013129787A (ja) * | 2011-12-22 | 2013-07-04 | Mitsubishi Heavy Ind Ltd | Coシフト反応装置およびcoシフト反応方法 |
JP5826066B2 (ja) | 2012-02-27 | 2015-12-02 | 三菱重工業株式会社 | Coシフト反応装置及びガス化ガス精製システム |
JP5705156B2 (ja) * | 2012-03-30 | 2015-04-22 | 三菱日立パワーシステムズ株式会社 | ガス精製方法及び石炭ガス化プラント |
JP5988728B2 (ja) * | 2012-06-27 | 2016-09-07 | 大阪瓦斯株式会社 | 高カロリーガスの製造方法及び高カロリーガスの製造装置 |
AU2012397690B2 (en) * | 2012-12-28 | 2016-04-21 | Mitsubishi Heavy Industries Engineering, Ltd. | CO shift catalyst, CO shift reactor, and method for purifying gasification gas |
EP2939739B1 (en) * | 2012-12-28 | 2023-12-20 | Mitsubishi Heavy Industries, Ltd. | Co shift catalyst |
WO2014103075A1 (ja) * | 2012-12-28 | 2014-07-03 | 三菱重工業株式会社 | Coシフト触媒、coシフト反応装置及びガス化ガスの精製方法 |
JP6025603B2 (ja) * | 2013-02-21 | 2016-11-16 | 三菱重工業株式会社 | Coシフト反応装置及びcoシフト変換方法 |
JP6005251B2 (ja) * | 2013-02-27 | 2016-10-12 | 三菱重工業株式会社 | Coシフト触媒の製造方法及びガス化ガスの精製方法 |
US10774278B2 (en) | 2013-02-27 | 2020-09-15 | Mitsubishi Heavy Industries Engineering, Ltd. | CO shift catalyst, CO shift reaction apparatus, and method for purifying gasified gas |
CN107118810A (zh) * | 2017-05-05 | 2017-09-01 | 北京清创晋华科技有限公司 | 一种将出洗涤塔合成气升温除液态水的方法 |
JP6934437B2 (ja) * | 2018-03-14 | 2021-09-15 | 三菱重工エンジニアリング株式会社 | ガス精製装置 |
JP7020306B2 (ja) * | 2018-06-13 | 2022-02-16 | 日本製鉄株式会社 | 水性ガスシフト反応触媒の製造方法、水性ガスシフト反応触媒、及び水素の製造方法 |
CN114177913A (zh) * | 2021-12-03 | 2022-03-15 | 浙江皇马科技股份有限公司 | 一种用于合成聚醚胺的负载型催化剂、制备方法及应用 |
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