JP3837520B2

JP3837520B2 - Catalyst for CO shift reaction

Info

Publication number: JP3837520B2
Application number: JP2002293179A
Authority: JP
Inventors: 昌弘斉藤; 功高原; 和久村田; 仁稲葉
Original assignee: National Institute of Advanced Industrial Science and Technology AIST
Current assignee: National Institute of Advanced Industrial Science and Technology AIST
Priority date: 2002-10-07
Filing date: 2002-10-07
Publication date: 2006-10-25
Anticipated expiration: 2022-10-07
Also published as: JP2004122063A

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Ｈ_２／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Ｈ_２ＯからＨ_２とＣＯ_２を生成する反応である。
【化１】
ＣＯ＋Ｈ_２Ｏ → ＣＯ_２＋Ｈ_２
これまでに、このようなＣＯシフト反応用触媒としては、高温反応用として、鉄・クロム系触媒が、低温反応用として、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、低温ＣＯシフト反応に用いられている銅／酸化亜鉛系触媒の触媒活性を更に改善・向上し得る新たな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、酸化アルミニウムおよび酸化マンガンを必須成分とする触媒により、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、酸化アルミニウムおよび酸化マンガンを必須成分とする、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、酸化アルミニウムおよび酸化マンガンを必須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１〜２５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、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、酸化アルミニウムおよび酸化マンガンを必須成分とすることを特徴とする。
【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％、酸化マンガンが１〜２５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、酸化アルミニウムおよび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焼成することにより製造できる。触媒前駆体の焼成温度は、特に限定しないが、３００〜６５０℃の範囲が好ましく、３５０℃〜６００℃が特に好ましい。
【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１５０〜３００℃、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１，０００〜１００，０００（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３．３ｇ、硝酸アルミニウム九水和物２．８ｇ、硝酸マンガン六水和物１．３ｇ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１２．６ｇ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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．４重量％、酸化亜鉛３２．３重量％、酸化ジルコニウム１８．５重量％、酸化アルミニウム４．６重量％、二酸化マンガン４．２重量％であった。
【００１７】
得られた触媒０．５ｍｌ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３００℃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％、ＣＯ２１８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、２５０℃、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３５，０００（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５６％であった（表１参照）。
【００１８】
実施例２
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、４００℃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。
【００１９】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５８％であった（表１参照）。
【００２０】
実施例３
硝酸銅三水和物１０．１ｇ、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２．７ｇ、硝酸アルミニウム九水和物２．８ｇ、硝酸マンガン六水和物２．２ｇ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１３．０ｇ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、４００℃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３２．４重量％、酸化ジルコニウム１５．０重量％、酸化アルミニウム４．６重量％、二酸化マンガン７．５重量％であった。
【００２１】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５６％であった（表１参照）。
【００２２】
実施例４
硝酸銅三水和物１０．１ｇ、硝酸亜鉛六水和物９．７ｇ、オキシ硝酸ジルコニウム二水和物２．１ｇ、硝酸アルミニウム九水和物２．８ｇ、硝酸マンガン六水和物３．０ｇ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１３．３ｇ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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．６重量％、酸化亜鉛３２．５重量％、酸化ジルコニウム１２．１重量％、酸化アルミニウム４．６重量％、二酸化マンガン１０．２重量％であった。
【００２３】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５８％であった（表１参照）。
【００２４】
実施例５
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、４００℃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。
【００２５】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５６％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９．５ｇ、オキシ硝酸ジルコニウム二水和物０．８ｇ、硝酸アルミニウム九水和物２．７ｇ、硝酸マンガン六水和物４．８ｇ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１４．１ｇ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に粒度調製した後、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．９重量％、酸化亜鉛３２．６重量％、酸化ジルコニウム４．７重量％、酸化アルミニウム４．７重量％、二酸化マンガン１７．１重量％であった。
【００２７】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５７％であった（表１参照）。
【００２８】
比較例１
硝酸銅三水和物８．５ｇ、硝酸亜鉛六水和物８．２ｇ、硝酸アルミニウム九水和物１４．１ｇ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１３．９ｇ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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．３重量％、酸化亜鉛３２．２重量％、酸化アルミニウム２７．６重量％であった。
【００２９】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、ＣＯシフト反応を行った。その結果、反応経過時間２時間後において、ＣＯ転化率３０％であった（表１参照）。
【００３０】
比較例２
硝酸銅三水和物８．５ｇ、硝酸亜鉛六水和物８．２ｇ、オキシ硝酸ジルコニウム二水和物１４．１ｇ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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．３重量％、酸化亜鉛３２．２重量％、酸化ジルコニウム２７．６重量％であった。
【００３１】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、ＣＯシフト反応を行った。その結果、反応経過時間２時間後において、ＣＯ転化率５２％であった（表１参照）。
【００３２】
比較例３
硝酸銅三水和物１０．７ｇ、硝酸亜鉛六水和物１０．３ｇ、オキシ硝酸ジルコニウム二水和物４．４ｇ、硝酸マンガン六水和物１．３ｇ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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．４重量％、酸化亜鉛３２．３重量％、酸化ジルコニウム２３．１重量％、二酸化マンガン４．２重量％であった。
【００３３】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５０％であった（表１参照）。
【００３４】
比較例４
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３．３ｇ、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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４０．４重量％、酸化亜鉛３２．３重量％、酸化ジルコニウム１８．５重量％、酸化アルミニウム４．６重量％であった。
【００３５】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５３％であった（表１参照）。
【００３６】
比較例５
硝酸銅三水和物９．７ｇ、硝酸亜鉛六水和物９．４ｇ、硝酸アルミニウム九水和物２．７ｇ、硝酸マンガン六水和物６．０ｇ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、４００℃で再度焼成して触媒とした。この触媒の組成は、酸化銅４１．１重量％、酸化亜鉛３２．８重量％、酸化アルミニウム４．７重量％、二酸化マンガン２１．４重量％であった。
【００３７】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、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５３％であった（表１参照）。
【００３８】
比較例６
硝酸銅三水和物８．８ｇ、硝酸亜鉛六水和物８．５ｇ、硝酸アルミニウム九水和物１１．２ｇ、硝酸マンガン六水和物１．５ｇ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、４００℃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％、酸化アルミニウム２１．３重量％、二酸化マンガン５．９重量％であった。
【００３９】
得られた触媒０．５ｍｌを反応管に充填し、実施例１と同様にして、ＣＯシフト反応を行った。その結果、反応経過時間４時間後において、ＣＯ転化率１８％であった（表１参照）。
【００４０】
【表１】

【００４１】
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、酸化アルミニウムおよび酸化マンガンを必須成分とする触媒を用いれば、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。
【００４２】
【発明の効果】
本発明の触媒は、ＣＯシフト反応において、優れた触媒活性を示し、従来の低温反応用のＣＯシフト反応用触媒である、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／クロムの酸化物に比べＣＯ転化率が高いものである。従って、ＣＯシフト反応特に低温下におけるＣＯシフト反応をを工業的に有利に実施することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for water gas conversion reaction, and more specifically, CO shift used when carbon monoxide and water vapor are reacted to produce carbon dioxide and hydrogen (referred to as CO shift reaction or water gas shift reaction). The present invention relates to a reaction catalyst.
[0002]
[Prior art]
Conventionally, it is known that the CO shift reaction is an important reaction for removing CO in hydrogen production from hydrocarbons or adjusting the H ₂ / CO ratio in methanol synthesis or oxo synthesis. Attention has been focused on as one of the main processes for producing hydrogen with 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.
[Chemical 1]
CO + H ₂ O → CO ₂ + H ₂
Up to now, as such a catalyst for CO shift reaction, an iron / chromium-based catalyst for high temperature reaction, a catalyst made of copper / zinc / aluminum oxide or a copper / zinc / chromium catalyst for low temperature reaction. Catalysts made of oxides have been developed and implemented industrially (for example, see Non-Patent Document 1).
However, the present situation is that the CO conversion rate of any catalyst is not yet satisfactory, and the development of a high-performance catalyst is an important technical development subject.
[0003]
[Non-Patent Document 1]
"Catalyst Lecture" 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 CO shift reaction that can further improve and improve the catalytic activity of the copper / zinc oxide catalyst used in the low temperature CO shift reaction. The main purpose is to do.
[0005]
[Means for Solving the Problems]
As a result of various studies on a catalyst containing copper, the present inventor has found that the problem can be solved by a catalyst containing copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components. .
[0006]
That is, according to the present invention, first, there is provided a catalyst exhibiting high performance in a CO shift reaction comprising copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components.
Second, in the first invention, a catalyst having copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components, and when the total amount of the catalyst is 100% by weight, the content of each component is In this order, the catalyst for CO shift reaction is provided which is 20 to 70% by weight, 10 to 60% by weight, 1 to 50% by weight, 1 to 50% by weight and 1 to 25% by weight.
Third, there is provided a CO shift reaction method characterized by contacting carbon monoxide and water vapor with the first or second catalyst.
Fourth, there is provided a method for producing carbon dioxide and hydrogen, wherein carbon monoxide and water vapor are brought into contact with the first or second catalyst to cause a shift reaction.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0008]
The catalyst for CO shift reaction of the present invention is characterized by containing copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components.
[0009]
The ratio of each catalyst component is not particularly limited, but 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, oxidation Aluminum is 1 to 50% by weight and manganese oxide is 1 to 25% by weight. In such a quantitative range, by appropriately determining the composition according to the reaction conditions, catalyst performance suitable for the reaction conditions can be obtained.
The catalyst for CO shift reaction of the present invention contains copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components, but contains other substances as long as the reaction of the present invention is not impaired. Also good. Examples of such a substance include calcium oxide, magnesium oxide, silicon oxide, lanthanum oxide, cerium oxide, and the like.
[0010]
As raw materials for copper oxide, zinc oxide, zirconium oxide, aluminum oxide, and manganese oxide, which are catalyst components of the present invention, respective nitrates, hydrochlorides, lead sulfates, organic acid salts, hydroxides, and the like can be used. For the catalyst, a catalyst precursor 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 combination of these methods. It can be manufactured by firing. Although the calcination temperature of a catalyst precursor is not specifically limited, The range of 300-650 degreeC is preferable and 350 degreeC-600 degreeC is especially preferable.
[0011]
The catalyst thus produced is used as it is or after being granulated or tableted by an appropriate method. The particle diameter 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]
The catalyst after calcination may be obtained by previously reducing copper oxide in the catalyst to metallic copper before use in the reaction. However, even when this reduction is not performed, the copper oxide is naturally reduced by carbon monoxide or hydrogen in the reaction gas, and therefore a prior reduction operation is not essential.
[0013]
The reaction conditions in the CO shift reaction method of carbon monoxide with water vapor 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 150 to 300 ° 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%, one in the water vapor and the raw material gas. The molar ratio of carbon oxide is suitably 1 to 100, and the space velocity of the raw material gas (excluding water vapor) is suitably in the range of 1,000 to 100,000 (1 / h).
[0015]
【Example】
Hereinafter, the features of the present invention will be further clarified by giving examples.
[0016]
Example 1
Copper nitrate trihydrate 10.2 g, zinc nitrate hexahydrate 9.8 g, zirconium oxynitrate dihydrate 3.3 g, aluminum nitrate nonahydrate 2.8 g, manganese nitrate hexahydrate 1.3 g Was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 12.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.4% by weight of copper oxide, 32.3% by weight of zinc oxide, 18.5% by weight of zirconium oxide, 4.6% by weight of aluminum oxide, and 4.2% by weight of manganese dioxide.
[0017]
0.5 ml of the obtained catalyst is filled in a reaction tube, and a mixed gas of helium and hydrogen (90% by volume of helium, 10% by volume of hydrogen) is supplied at a flow rate of 300 ml / min and hydrogen of copper oxide in the catalyst at 300 ° C. Reduction was performed. After the reduction of the catalyst, the reaction was carried out by supplying raw material gas (CO 10% by volume, CO2 18% by volume, hydrogen 72% by volume) and water vapor into the reaction tube. The reaction conditions were temperature, 250 ° C., pressure, 0.15 MPa, the volume ratio of water vapor to the raw material gas was 0.3, and the space velocity of the raw material gas (excluding water vapor) was 35,000 (1 / h). The reaction product gas was analyzed by gas chromatography. As a result, the CO conversion was 56% at a reaction time of 10 hours (see Table 1).
[0018]
Example 2
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. On the other hand, 12.8 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° 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.
[0019]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, CO conversion was 58% after 10 hours of reaction elapsed time (see Table 1).
[0020]
Example 3
Copper nitrate trihydrate 10.1 g, zinc nitrate hexahydrate 9.8 g, zirconium oxynitrate dihydrate 2.7 g, aluminum nitrate nonahydrate 2.8 g, manganese nitrate hexahydrate 2.2 g Was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 13.0 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.5% by weight of copper oxide, 32.4% by weight of zinc oxide, 15.0% by weight of zirconium oxide, 4.6% by weight of aluminum oxide, and 7.5% by weight of manganese dioxide.
[0021]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, CO conversion was 56% after 10 hours of reaction elapsed time (see Table 1).
[0022]
Example 4
Copper nitrate trihydrate 10.1 g, zinc nitrate hexahydrate 9.7 g, zirconium oxynitrate dihydrate 2.1 g, aluminum nitrate nonahydrate 2.8 g, manganese nitrate hexahydrate 3.0 g Was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 13.3 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.6% by weight of copper oxide, 32.5% by weight of zinc oxide, 12.1% by weight of zirconium oxide, 4.6% by weight of aluminum oxide, and 10.2% by weight of manganese dioxide.
[0023]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, CO conversion was 58% after 10 hours of reaction elapsed time (see Table 1).
[0024]
Example 5
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. On the other hand, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° 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.
[0025]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, CO conversion was 56% after 10 hours of reaction elapsed time (see Table 1).
[0026]
Example 6
Copper nitrate trihydrate 10.0 g, zinc nitrate hexahydrate 9.5 g, zirconium oxynitrate dihydrate 0.8 g, aluminum nitrate nonahydrate 2.7 g, manganese nitrate hexahydrate 4.8 g Was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 14.1 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.9% by weight of copper oxide, 32.6% by weight of zinc oxide, 4.7% by weight of zirconium oxide, 4.7% by weight of aluminum oxide, and 17.1% by weight of manganese dioxide.
[0027]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, the CO conversion rate was 57% after 10 hours of reaction elapsed time (see Table 1).
[0028]
Comparative Example 1
8.5 g of copper nitrate trihydrate, 8.2 g of zinc nitrate hexahydrate, and 14.1 g of aluminum nitrate nonahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 13.9 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.3% by weight of copper oxide, 32.2% by weight of zinc oxide, and 27.6% by weight of aluminum oxide.
[0029]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, after 2 hours of reaction elapsed time, the CO conversion was 30% (see Table 1).
[0030]
Comparative Example 2
8.5 g of copper nitrate trihydrate, 8.2 g of zinc nitrate hexahydrate, and 14.1 g of zirconium oxynitrate dihydrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.3% by weight of copper oxide, 32.2% by weight of zinc oxide, and 27.6% by weight of zirconium oxide.
[0031]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, the CO conversion was 52% after 2 hours of reaction elapsed (see Table 1).
[0032]
Comparative Example 3
10.7 g of copper nitrate trihydrate, 10.3 g of zinc nitrate hexahydrate, 4.4 g of zirconium oxynitrate dihydrate, and 1.3 g of manganese nitrate hexahydrate were dissolved in distilled water to give a 100 ml aqueous solution. To prepare a solution A. On the other hand, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.4% by weight of copper oxide, 32.3% by weight of zinc oxide, 23.1% by weight of zirconium oxide, and 4.2% by weight of manganese dioxide.
[0033]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, the CO conversion was 50% after 10 hours of reaction elapsed time (see Table 1).
[0034]
Comparative Example 4
Dissolve 10.2 g of copper nitrate trihydrate, 9.8 g of zinc nitrate hexahydrate, 3.3 g of zirconium oxynitrate dihydrate, and 2.8 g of aluminum nitrate nonahydrate in distilled water, and add 100 ml of an aqueous solution. To prepare a solution A. On the other hand, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 40.4% by weight of copper oxide, 32.3% by weight of zinc oxide, 18.5% by weight of zirconium oxide, and 4.6% by weight of aluminum oxide.
[0035]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, after 10 hours of reaction elapsed time, the CO conversion was 53% (see Table 1).
[0036]
Comparative Example 5
Dissolve 9.7 g of copper nitrate trihydrate, 9.4 g of zinc nitrate hexahydrate, 2.7 g of aluminum nitrate nonahydrate, and 6.0 g of manganese nitrate hexahydrate in distilled water. It prepared and it was set as A liquid. On the other hand, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° C. to obtain a catalyst. The composition of this catalyst was 41.1% by weight of copper oxide, 32.8% by weight of zinc oxide, 4.7% by weight of aluminum oxide, and 21.4% by weight of manganese dioxide.
[0037]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, after 10 hours of reaction elapsed time, the CO conversion was 53% (see Table 1).
[0038]
Comparative Example 6
Dissolve 8.8 g of copper nitrate trihydrate, 8.5 g of zinc nitrate hexahydrate, 11.2 g of aluminum nitrate nonahydrate, and 1.5 g of manganese nitrate hexahydrate in distilled water. It prepared and it was set as the A liquid. On the other hand, 13.6 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 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 and then pulverized to adjust the particle size to 250 to 600 μm, and then fired again at 400 ° 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, 21.3% by weight of aluminum oxide, and 5.9% by weight of manganese dioxide.
[0039]
0.5 ml of the obtained catalyst was filled into a reaction tube, and a CO shift reaction was carried out in the same manner as in Example 1. As a result, after 4 hours of reaction elapsed time, the CO conversion was 18% (see Table 1).
[0040]
[Table 1]

[0041]
From the results shown in Table 1, it is clear that a high CO conversion can be obtained in the CO shift reaction by using the catalyst of the present invention containing copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components. It is.
[0042]
【The invention's effect】
The catalyst of the present invention exhibits excellent catalytic activity in the CO shift reaction, and is a conventional catalyst for CO shift reaction for low temperature reaction, a catalyst made of copper / zinc / aluminum oxide or copper / zinc / chromium. CO conversion is higher than that of oxide. Therefore, the CO shift reaction, particularly the CO shift reaction at a low temperature, can be advantageously carried out industrially.

Claims

A catalyst for CO shift reaction comprising copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components.

A catalyst comprising copper oxide, zinc oxide, zirconium oxide, aluminum oxide and manganese oxide as essential components, and when the total catalyst is 100% by weight, the content of each component is 20 to 70% by weight in the above order, The catalyst for CO shift reaction according to claim 1, wherein the catalyst is 10 to 60 wt%, 1 to 50 wt%, 1 to 50 wt%, and 1 to 25 wt%.

A CO shift reaction method comprising contacting carbon monoxide and water vapor with the catalyst according to claim 1 or 2.

A method for producing carbon dioxide and hydrogen, wherein carbon monoxide and water vapor are brought into contact with the catalyst of claim 1 or 2 to cause a shift reaction.