JP2004329976A - High temperature CO shift reaction catalyst - Google Patents
High temperature CO shift reaction catalyst Download PDFInfo
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- JP2004329976A JP2004329976A JP2003124824A JP2003124824A JP2004329976A JP 2004329976 A JP2004329976 A JP 2004329976A JP 2003124824 A JP2003124824 A JP 2003124824A JP 2003124824 A JP2003124824 A JP 2003124824A JP 2004329976 A JP2004329976 A JP 2004329976A
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- 239000007809 chemical reaction catalyst Substances 0.000 title claims description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005751 Copper oxide Substances 0.000 claims abstract description 16
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010586 diagram Methods 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- -1 organic acid salts Chemical class 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
【課題】一酸化炭素を水蒸気と反応させて水素と二酸化炭素に変換するための高温ＣＯシフト反応において、高活性を発揮する触媒を提供する。
【解決手段】酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、二酸化マンガンを任意成分とする触媒であり、かつ、５００℃〜６５０℃という高温にて焼成された触媒であって、好ましくは触媒全体を１００重量％とするとき、各成分の含有量が、上記の順に、２０〜７０重量％、１０〜６０重量％、１〜５０重量％、１〜５０重量％および０〜２５重量％であること高温ＣＯシフト反応用触媒。
【選択図】なしAn object of the present invention is to provide a catalyst exhibiting high activity in a high-temperature CO shift reaction for converting carbon monoxide with water vapor to convert it into hydrogen and carbon dioxide.
A catalyst comprising copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components, and manganese dioxide as an optional component, and a catalyst calcined at a high temperature of 500 ° C to 650 ° C, Preferably, when the entire catalyst is 100% by weight, the content of each component is preferably from 20 to 70% by weight, 10 to 60% by weight, 1 to 50% by weight, 1 to 50% by weight and 0 to 25% in the above order. The catalyst for the high-temperature CO shift reaction to be in wt%.
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、水性ガス転化反応用触媒に関し、更に詳しくは一酸化炭素と水蒸気を反応させて、二酸化炭素および水素を製造する（ＣＯシフト反応あるいは水性ガスシフト反応などと呼ばれる）際に使用されるＣＯシフト反応用触媒に関する。
【０００２】
【従来の技術】
従来より、ＣＯシフト反応は、炭化水素からの水素製造におけるＣＯ除去あるいはメタノール合成やオキソ合成におけるＨ２／ＣＯ比の調整のための重要な反応であることが知られており、さらに、最近では、燃料電池用のＣＯ含有量が低い水素を、炭化水素などから製造するための主要な工程の一つとして注目されている。
このシフト反応は下記反応式に示されるように、ＣＯとＨ２ＯからＨ２とＣＯ２を生成する反応である。
【化１】
ＣＯ ＋ Ｈ２Ｏ → ＣＯ２ ＋ Ｈ２
これまでに、このようなＣＯシフト反応用触媒としては、高温反応用（３２０℃〜４００℃にて実施される）として鉄・クロム系触媒、低温反応用（１５０℃〜３００℃にて実施される）として銅／亜鉛／アルミニウムの酸化物からなる触媒あるいは銅／亜鉛／クロムの酸化物からなる触媒が開発され、工業的に実施されている（例えば非特許文献１参照）。
しかしながら、何れの触媒もＣＯ転化率が未だ満足すべきでないのが現状であり、高性能な触媒の開発が重要な技術開発課題となっている。
【０００３】
【非特許文献１】
「触媒講座」第８巻、２５１頁〜２６２頁 触媒学会編、講談社発行（１９８５）。
【０００４】
【発明が解決しようとする課題】
本発明は、このような実情に鑑みなされたものであり、高温ＣＯシフト反応に用いられている鉄・クロム系触媒の触媒活性よりも高い活性を示す新たな高温ＣＯシフト反応用触媒を提供することを主な目的とする。
【０００５】
【課題を解決するための手段】
本発明者は、銅を含む触媒について種々の研究を行った結果、酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、二酸化マンガンを任意成分とする触媒であって、かつ、５００℃〜６５０℃という高温にて焼成された触媒により、その課題を解決し得ることを見い出した。
【０００６】
即ち、本発明によれば、第一に、酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、二酸化マンガンを任意成分とする触媒であって、かつ、５００℃〜６５０℃という高温にて焼成されたことを特徴とする、高温ＣＯシフト反応において高い性能を示す触媒が提供される。
第二に、第一の発明において、酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、二酸化マンガンを任意成分とする触媒であって、触媒全体を１００重量％とするとき、各成分の含有量が、上記の順に２０〜７０重量％、１０〜６０重量％、１〜５０重量％、１〜５０重量％および０〜２５重量％であることを特徴とするＣＯシフト反応用触媒が提供される。
第三に、一酸化炭素および水蒸気を上記第一又は第二の触媒に接触させることを特徴とする高温ＣＯシフト反応方法が提供される。
第四に、一酸化炭素および水蒸気を上記第一又は第二の触媒に接触させ、高温ＣＯシフト反応させることを特徴とする二酸化炭素及び水素の製造方法が提供される。
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【０００８】
本発明の高温ＣＯシフト反応用触媒は、酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、二酸化マンガンを任意成分とする触媒であり、かつ、５００℃〜６５０℃という高温にて焼成されたものであることを特徴とする。
本発明においては、焼成温度を５００℃〜６５０℃に設定することが重要である。焼成温度が５００℃未満であると、触媒成分間の相互作用が弱いなどの理由により、触媒活性が低く、また、焼成温度が６５０℃を越えると、触媒成分の結晶化などの理由により、触媒活性が低くなるため、本発明の所期の目的を達成できない。
【０００９】
各触媒成分の割合は、特に限定されないが、触媒全体を１００重量％とするとき、酸化銅が２０〜７０重量％、酸化亜鉛が１０〜６０重量％、酸化ジルコニウムが１〜５０重量％、酸化アルミニウムが１〜５０重量％、二酸化マンガンが０〜２５重量％とされる。このような量的範囲において、組成を反応条件に応じて適切に定めることにより、その反応条件に適した触媒性能を得ることができる。また、本発明の高温ＣＯシフト反応用触媒は、酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、二酸化マンガンを必須成分とするが、本発明の反応を損なわない範囲で、他の物質を含んでいても良い。このような物質としては、たとえば、酸化カルシウム、酸化マグネシウム、酸化珪素、酸化ランタン、酸化セリウムなどが挙げられる。
【００１０】
本発明の触媒成分となる酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムおよび二酸化マンガンの原料としては、それぞれの硝酸塩、塩酸塩、硫酸鉛、有機酸塩、水酸化物等を用いることができる。触媒は、共沈法、含浸法、混合法、逐次沈殿法、アルコキシド法等の方法により、あるいは、これらの方法を組み合わせた方法により触媒前駆体を調製し、次いで、触媒前駆体を空気中で５００〜６５０℃で焼成することにより製造できる。
【００１１】
このようにして製造された触媒は、そのままで、あるいは適当な方法により造粒または打錠成型して用いる。触媒の粒子径や形状は、反応方式、反応器の形状によって任意に選択できる。すなわち、本発明による触媒は、固定床、流動床等いずれの反応方式においても用いることができる。
【００１２】
焼成後の触媒は、反応に使用する前に触媒中の酸化銅を金属銅に予め還元しても良い。但し、この還元を行わない場合にも、反応ガス中の一酸化炭素や水素により酸化銅は自然に還元されるので、事前の還元操作は必須ではない。
【００１３】
上記本発明にかかる触媒を用いる、一酸化炭素の水蒸気による高温ＣＯシフト反応方法における反応条件は、原料ガス中の一酸化炭素や水素の濃度や触媒成分の含有量などにより異なり得る。
【００１４】
通常、反応温度は３５０〜４５０℃、反応圧力は１〜１００気圧（絶対圧力）、原料ガス中（水蒸気を除く）の一酸化炭素のモル濃度は１〜３０％、水蒸気と原料ガス中の一酸化炭素のモル比は１〜１００、原料ガス（水蒸気を除く）の空間速度は１，０００〜５００，０００（１／ｈ）の範囲が適当である。
【００１５】
【実施例】
以下、実施例をあげて本発明の特徴とするところをより一層明確にする。
【００１６】
実施例１
硝酸銅三水和物１１．７ｇ、硝酸亜鉛六水和物８．４ｇ、オキシ硝酸ジルコニウム二水和物４．２ｇ、硝酸アルミニウム九水和物２．８ｇを蒸留水に溶解し、１００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム１２．１ｇを蒸留水に溶解し、１００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した３００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、３５０℃で２時間焼成した。次に、焼成後の酸化物を圧縮成型後、粉砕し、２５０〜６００μｍに粒度調整した後、５００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４５．５重量％、酸化亜鉛２７．３重量％、酸化ジルコニウム２２．７重量％、酸化アルミニウム４．５重量％であった。
【００１７】
得られた触媒０．２ｍｌを反応管に充填し、ヘリウムと水素の混合ガス（ヘリウム９０容量％、水素１０容量％）を毎分３００ｍｌの流速で供給し４５０℃で触媒中の酸化銅の水素還元を行った。触媒の還元後、反応管に、原料ガス（ＣＯ１０容量％、ＣＯ２ １８容量％、水素７２容量％）と水蒸気を供給し、反応を行った。反応条件は、温度、４００℃、圧力、０．１５ＭＰａ、水蒸気と原料ガスの容量比は０．３、原料ガス（水蒸気を除く）の空間速度は９０，０００（１／ｈ）であった。反応生成ガスをガスクロマトグラフにより分析した。その結果、反応時間１０時間においてＣＯ転化率は２５％であった（表１参照）。
【００１８】
実施例２
実施例１で得た２５０〜６００μｍに粒度調整した酸化物を、５５０℃で再度焼成して触媒とした。この触媒の組成は、実施例１と同じであった。
【００１９】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２５％であった（表１参照）。
【００２０】
実施例３
実施例１で得た２５０〜６００μｍに粒度調整した酸化物を、６００℃で再度焼成して触媒とした。この触媒の組成は、実施例１と同じであった。
【００２１】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２６％であった（表１参照）。
【００２２】
実施例４
実施例１で得た２５０〜６００μｍに粒度調整した酸化物を、６５０℃で再度焼成して触媒とした。この触媒の組成は、実施例１と同じであった。
【００２３】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２５％であった（表１参照）。
【００２４】
実施例５
硝酸銅三水和物１０．２ｇ、硝酸亜鉛六水和物９．８ｇ、オキシ硝酸ジルコニウム二水和物３．０ｇ、硝酸アルミニウム九水和物２．８ｇ、硝酸マンガン六水和物１．８ｇを蒸留水に溶解し、１００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム１２．８ｇを蒸留水に溶解し、１００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した３００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、３５０℃で２時間焼成した。次に、焼成後の酸化物を圧縮成型後、粉砕し、２５０〜６００μｍに粒度調製した後、６００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．５重量％、酸化亜鉛３２．３重量％、酸化ジルコニウム１６．６重量％、酸化アルミニウム４．６重量％、二酸化マンガン５．９重量％であった。
【００２５】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２６％であった（表１参照）。
【００２６】
実施例６
硝酸銅三水和物１０．０ｇ、硝酸亜鉛六水和物９．６ｇ、オキシ硝酸ジルコニウム二水和物１．６ｇ、硝酸アルミニウム九水和物２．８ｇ、硝酸マンガン六水和物３．７ｇを蒸留水に溶解し、１００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム１３．６ｇを蒸留水に溶解し、１００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した３００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、３５０℃で２時間焼成した。次に、焼成後の酸化物を圧縮成型後、粉砕し、２５０〜６００μｍに粒度調製した後、６００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．７重量％、酸化亜鉛３２．５重量％、酸化ジルコニウム９．３重量％、酸化アルミニウム４．６重量％、二酸化マンガン１２．８重量％であった。
【００２７】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２６％であった（表１参照）。
【００２８】
比較例１
実施例１で得た２５０〜６００μｍに粒度調整した酸化物を、４００℃で再度焼成して触媒とした。この触媒の組成は、実施例１と同じであった。
【００２９】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２２％であった（表１参照）。
【００３０】
比較例２
実施例１で得た２５０〜６００μｍに粒度調整した酸化物を、７００℃で再度焼成して触媒とした。この触媒の組成は、実施例１と同じであった。
【００３１】
得られた触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は２１％であった（表１参照）。
【００３２】
比較例３
工業的に用いられている鉄・クロム系触媒０．２ｍｌを反応管に充填し、実施例１と同様にして、高温ＣＯシフト反応を行った。その結果、反応経過時間１０時間後において、ＣＯ転化率は１２％であった（表１参照）。
【００３３】
表１に示す結果から、本発明の酸化銅、酸化亜鉛、酸化ジルコニウム、酸化アルミニウムを必須成分とし、酸化マンガンを任意成分とする触媒であって、かつ、かつ、５００℃〜６５０℃という高温にて焼成された触媒を用いれば、高温ＣＯシフト反応において、高いＣＯ転化率を得ることができることが明らかである。
【００３５】
【発明の効果】
本発明の触媒は、高温ＣＯシフト反応において、極めて高い触媒活性を示すものである。従って、高温ＣＯシフト反応を工業的有利に実施することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a catalyst for a water gas shift reaction, and more particularly, to a method of reacting carbon monoxide with water vapor to produce carbon dioxide and hydrogen (referred to as a CO shift reaction or a water gas shift reaction). The present invention relates to a catalyst for a shift reaction.
[0002]
[Prior art]
Conventionally, it has been known that the CO shift reaction is an important reaction for removing CO in the production of hydrogen from hydrocarbons or adjusting the H 2 / CO ratio in methanol synthesis or oxo synthesis. It is receiving attention as one of the main processes for producing hydrogen having a low CO content for fuel cells from hydrocarbons and the like.
This shift reaction is a reaction for generating H 2 and CO 2 from CO and H 2 O as shown in the following reaction formula.
Embedded image
CO + H 2 O → CO 2 + H 2
To date, such CO shift reaction catalysts include iron-chromium catalysts for high-temperature reactions (implemented at 320 ° C. to 400 ° C.) and catalysts for low-temperature reactions (implemented at 150 ° C. to 300 ° C.). A catalyst comprising an oxide of copper / zinc / aluminum or a catalyst comprising an oxide of copper / zinc / chromium has been developed and industrially implemented (see Non-Patent Document 1, for example).
However, at present, the CO conversion rate of any of the catalysts is not yet satisfactory, and the development of a high-performance catalyst is an important technical development task.
[0003]
[Non-patent document 1]
"Catalyst Course", Vol. 8, pp. 251-262, edited by The Catalysis Society of Japan, published by Kodansha (1985).
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and provides a new catalyst for a high-temperature CO shift reaction that exhibits an activity higher than the catalytic activity of an iron / chromium-based catalyst used in a high-temperature CO shift reaction. Its main purpose is to:
[0005]
[Means for Solving the Problems]
The present inventor has conducted various studies on a catalyst containing copper. As a result, the catalyst containing copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components and manganese dioxide as an optional component, and having a temperature of 500 ° C. It has been found that a catalyst calcined at a high temperature of ６650 ° C. can solve the problem.
[0006]
That is, according to the present invention, first, a catalyst containing copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components and manganese dioxide as an optional component, and at a high temperature of 500 ° C to 650 ° C. A catalyst that exhibits high performance in a high-temperature CO shift reaction, characterized in that the catalyst is calcined.
Second, in the first invention, a catalyst containing copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components and manganese dioxide as an optional component. Is 20 to 70% by weight, 10 to 60% by weight, 1 to 50% by weight, 1 to 50% by weight and 0 to 25% by weight in the above order. Provided.
Third, there is provided a high-temperature CO shift reaction method characterized by contacting carbon monoxide and steam with the first or second catalyst.
Fourth, there is provided a method for producing carbon dioxide and hydrogen, wherein carbon monoxide and steam are brought into contact with the first or second catalyst to cause a high-temperature CO shift reaction.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0008]
The catalyst for a high-temperature CO shift reaction of the present invention is a catalyst containing copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components and manganese dioxide as an optional component, and is calcined at a high temperature of 500 ° C. to 650 ° C. It is characterized by having been done.
In the present invention, it is important to set the firing temperature at 500 ° C to 650 ° C. If the calcination temperature is lower than 500 ° C., the catalytic activity is low because the interaction between the catalyst components is weak, and if the calcination temperature exceeds 650 ° C., the catalyst component is crystallized and the like. Due to the low activity, the intended object of the present invention cannot be achieved.
[0009]
The proportion of each catalyst component is not particularly limited. When the total catalyst is 100% by weight, copper oxide is 20 to 70% by weight, zinc oxide is 10 to 60% by weight, zirconium oxide is 1 to 50% by weight, Aluminum is 1 to 50% by weight, and manganese dioxide is 0 to 25% by weight. In such a quantitative range, by appropriately determining the composition according to the reaction conditions, it is possible to obtain a catalyst performance suitable for the reaction conditions. The catalyst for the high-temperature CO shift reaction of the present invention contains copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components, and manganese dioxide as an essential component, but other components within a range that does not impair the reaction of the present invention. May contain substances. Examples of such a substance include calcium oxide, magnesium oxide, silicon oxide, lanthanum oxide, and cerium oxide.
[0010]
As a raw material of copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese dioxide which are the catalyst components of the present invention, respective nitrates, hydrochlorides, lead sulfates, organic acid salts, hydroxides and the like can be used. The catalyst is prepared by a method such as a coprecipitation method, an impregnation method, a mixing method, a sequential precipitation method, an alkoxide method, or a method combining these methods, and then the catalyst precursor is prepared in the air. It can be manufactured by firing at 500 to 650 ° C.
[0011]
The catalyst thus produced is used as it is or after granulation or tableting by an appropriate method. The particle size and shape of the catalyst can be arbitrarily selected depending on the reaction system and the shape of the reactor. That is, the catalyst according to the present invention can be used in any reaction system such as a fixed bed and a fluidized bed.
[0012]
After the calcined catalyst, the copper oxide in the catalyst may be reduced to metallic copper before use in the reaction. However, even when this reduction is not performed, a prior reduction operation is not essential because copper oxide is naturally reduced by carbon monoxide and hydrogen in the reaction gas.
[0013]
The reaction conditions in the high-temperature CO shift reaction method using water vapor of carbon monoxide using the catalyst according to the present invention may vary depending on the concentration of carbon monoxide and hydrogen in the raw material gas, the content of the catalyst component, and the like.
[0014]
Usually, the reaction temperature is 350 to 450 ° C., the reaction pressure is 1 to 100 atm (absolute pressure), the molar concentration of carbon monoxide in the raw material gas (excluding water vapor) is 1 to 30%, The molar ratio of carbon oxide is suitably in the range of 1 to 100, and the space velocity of the raw material gas (excluding water vapor) is suitably in the range of 1,000 to 500,000 (1 / h).
[0015]
【Example】
Hereinafter, features of the present invention will be further clarified with reference to examples.
[0016]
Example 1
11.7 g of copper nitrate trihydrate, 8.4 g of zinc nitrate hexahydrate, 4.2 g of zirconium oxynitrate dihydrate and 2.8 g of aluminum nitrate nonahydrate were dissolved in distilled water, and 100 ml of an aqueous solution was dissolved. Was prepared and used as solution A. Separately, anhydrous sodium carbonate (12.1 g) was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. The solution A and the solution B were simultaneously dropped into 300 ml of room temperature distilled water, which was well stirred at a rate of 8 ml / min, to obtain a precipitate. This precipitate was aged at room temperature for one day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 350 ° C. for 2 hours. Next, the oxide after firing was compression-molded, pulverized, adjusted to a particle size of 250 to 600 μm, and fired again at 500 ° C. to obtain a catalyst. The composition of the catalyst was 45.5% by weight of copper oxide, 27.3% by weight of zinc oxide, 22.7% by weight of zirconium oxide, and 4.5% by weight of aluminum oxide.
[0017]
A reaction tube was filled with 0.2 ml of the obtained catalyst, and a mixed gas of helium and hydrogen (helium 90% by volume, hydrogen 10% by volume) was supplied at a flow rate of 300 ml / min. Reduction was performed. After the reduction of the catalyst, a raw material gas (10% by volume of CO, 18% by volume of CO 2 , and 72% by volume of hydrogen) and steam were supplied to the reaction tube to perform a reaction. The reaction conditions were as follows: temperature, 400 ° C., pressure, 0.15 MPa, volume ratio of steam to raw material gas was 0.3, and space velocity of raw material gas (excluding water vapor) was 90,000 (1 / h). The reaction product gas was analyzed by gas chromatography. As a result, the CO conversion was 25% at a reaction time of 10 hours (see Table 1).
[0018]
Example 2
The oxide obtained in Example 1 and having a particle size adjusted to 250 to 600 μm was calcined again at 550 ° C. to obtain a catalyst. The composition of this catalyst was the same as in Example 1.
[0019]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 25% (see Table 1).
[0020]
Example 3
The oxide having a particle size adjusted to 250 to 600 μm obtained in Example 1 was calcined again at 600 ° C. to obtain a catalyst. The composition of this catalyst was the same as in Example 1.
[0021]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 26% (see Table 1).
[0022]
Example 4
The oxide whose particle size was adjusted to 250 to 600 μm obtained in Example 1 was calcined again at 650 ° C. to obtain a catalyst. The composition of this catalyst was the same as in Example 1.
[0023]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 25% (see Table 1).
[0024]
Example 5
Copper nitrate trihydrate 10.2 g, zinc nitrate hexahydrate 9.8 g, zirconium oxynitrate dihydrate 3.0 g, aluminum nitrate nonahydrate 2.8 g, manganese nitrate hexahydrate 1.8 g Was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. Separately, 12.8 g of anhydrous sodium carbonate was dissolved in distilled water to prepare 100 ml of an aqueous solution, which was used as solution B. The solution A and the solution B were simultaneously dropped into 300 ml of room temperature distilled water, which was well stirred at a rate of 8 ml / min, to obtain a precipitate. This precipitate was aged at room temperature for one day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 350 ° C. for 2 hours. Next, the oxide after firing was compression-molded, pulverized, adjusted to a particle size of 250 to 600 μm, and fired again at 600 ° C. to obtain a catalyst. The composition of this catalyst was 40.5% by weight of copper oxide, 32.3% by weight of zinc oxide, 16.6% by weight of zirconium oxide, 4.6% by weight of aluminum oxide, and 5.9% by weight of manganese dioxide.
[0025]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 26% (see Table 1).
[0026]
Example 6
Copper nitrate trihydrate 10.0 g, zinc nitrate hexahydrate 9.6 g, zirconium oxynitrate dihydrate 1.6 g, aluminum nitrate nonahydrate 2.8 g, manganese nitrate hexahydrate 3.7 g Was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. Separately, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare 100 ml of an aqueous solution, which was used as solution B. The solution A and the solution B were simultaneously dropped into 300 ml of room temperature distilled water, which was well stirred at a rate of 8 ml / min, to obtain a precipitate. This precipitate was aged at room temperature for one day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 350 ° C. for 2 hours. Next, the oxide after firing was compression-molded, pulverized, adjusted to a particle size of 250 to 600 μm, and fired again at 600 ° C. to obtain a catalyst. The composition of this catalyst was 40.7% by weight of copper oxide, 32.5% by weight of zinc oxide, 9.3% by weight of zirconium oxide, 4.6% by weight of aluminum oxide, and 12.8% by weight of manganese dioxide.
[0027]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 26% (see Table 1).
[0028]
Comparative Example 1
The oxide whose particle size was adjusted to 250 to 600 μm obtained in Example 1 was calcined again at 400 ° C. to obtain a catalyst. The composition of this catalyst was the same as in Example 1.
[0029]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 22% (see Table 1).
[0030]
Comparative Example 2
The oxide whose particle size was adjusted to 250 to 600 μm obtained in Example 1 was calcined again at 700 ° C. to obtain a catalyst. The composition of this catalyst was the same as in Example 1.
[0031]
0.2 ml of the obtained catalyst was filled in a reaction tube, and a high-temperature CO shift reaction was performed in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 21% (see Table 1).
[0032]
Comparative Example 3
A reaction tube was filled with 0.2 ml of an industrially used iron-chromium catalyst, and a high-temperature CO shift reaction was carried out in the same manner as in Example 1. As a result, 10 hours after the reaction elapsed time, the CO conversion was 12% (see Table 1).
[0033]
From the results shown in Table 1, it is a catalyst containing copper oxide, zinc oxide, zirconium oxide, and aluminum oxide as essential components and manganese oxide as an optional component, and at a high temperature of 500 ° C. to 650 ° C. It is apparent that a high CO conversion can be obtained in the high-temperature CO shift reaction by using the catalyst calcined by the above method.
[0035]
【The invention's effect】
The catalyst of the present invention exhibits extremely high catalytic activity in a high-temperature CO shift reaction. Therefore, the high-temperature CO shift reaction can be carried out industrially advantageously.
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| JP (1) | JP4012965B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006239557A (en) * | 2005-03-03 | 2006-09-14 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas conversion reaction |
| JP2007209976A (en) * | 2006-02-10 | 2007-08-23 | Samsung Sdi Co Ltd | WATER GAS CONVERSION OXIDATION CATALYST FOR REFORMER OF FUEL CELL SYSTEM, MANUFACTURING METHOD THEREOF, AND FUEL CELL SYSTEM |
| JP2007313487A (en) * | 2006-05-29 | 2007-12-06 | National Institute Of Advanced Industrial & Technology | Water gas conversion reaction catalyst and water gas conversion reaction method using the same. |
| GB2422615B (en) * | 2004-03-18 | 2009-01-28 | Gen Motors Corp | High activity water gas shift catalyst |
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|---|---|---|---|---|
| CN103949268B (en) * | 2014-04-17 | 2016-01-20 | 中国科学院山西煤炭化学研究所 | The synthesis copper Mn catalyst of methyl formate and method for making and application |
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2003
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2422615B (en) * | 2004-03-18 | 2009-01-28 | Gen Motors Corp | High activity water gas shift catalyst |
| JP2006239557A (en) * | 2005-03-03 | 2006-09-14 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas conversion reaction |
| JP4512748B2 (en) * | 2005-03-03 | 2010-07-28 | 独立行政法人産業技術総合研究所 | Catalyst for water gas conversion reaction |
| JP2007209976A (en) * | 2006-02-10 | 2007-08-23 | Samsung Sdi Co Ltd | WATER GAS CONVERSION OXIDATION CATALYST FOR REFORMER OF FUEL CELL SYSTEM, MANUFACTURING METHOD THEREOF, AND FUEL CELL SYSTEM |
| JP4686486B2 (en) * | 2006-02-10 | 2011-05-25 | 三星エスディアイ株式会社 | WATER GAS CONVERSION OXIDATION CATALYST FOR REFORMER OF FUEL CELL SYSTEM, MANUFACTURING METHOD THEREOF, AND FUEL CELL SYSTEM |
| JP2007313487A (en) * | 2006-05-29 | 2007-12-06 | National Institute Of Advanced Industrial & Technology | Water gas conversion reaction catalyst and water gas conversion reaction method using the same. |
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| JP4012965B2 (en) | 2007-11-28 |
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