JPH11244700A - Carbon monoxide conversion catalyst - Google Patents
Carbon monoxide conversion catalystInfo
- Publication number
- JPH11244700A JPH11244700A JP10051927A JP5192798A JPH11244700A JP H11244700 A JPH11244700 A JP H11244700A JP 10051927 A JP10051927 A JP 10051927A JP 5192798 A JP5192798 A JP 5192798A JP H11244700 A JPH11244700 A JP H11244700A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carbon monoxide
- oxide
- fired body
- cesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は一酸化炭素転化反応
のための触媒に関する。[0001] The present invention relates to a catalyst for a carbon monoxide conversion reaction.
【０００２】[0002]
【従来の技術】一酸化炭素と水蒸気との反応により水素
と二酸化炭素を生成する反応は、化学工業における重要
な反応であり、現在でもアンモニア合成プロセス、石油
化学プロセス、低カロリー都市ガス製造プロセス、リン
酸型燃料電池プロセスなどで水素製造の基幹反応として
広く使用されている。この反応は熱力学的には発熱反応
であるため低温ほど有利である。2. Description of the Related Art The reaction of producing hydrogen and carbon dioxide by the reaction between carbon monoxide and water vapor is an important reaction in the chemical industry. Even today, ammonia synthesis process, petrochemical process, low calorie city gas production process, It is widely used as a key reaction in hydrogen production in phosphoric acid type fuel cell processes and the like. Since this reaction is thermodynamically exothermic, the lower the temperature, the more advantageous.
【０００３】工業的に使用されている一酸化炭素転化触
媒としては２種類あり、一つは鉄、クロム系で比較的高
温（３２０℃〜５１０℃）で用いられるため高温転化触
媒ともいわれている。もう一つは銅、亜鉛系触媒であ
り、これは耐熱性には劣るが比較的低温（１８０℃〜２
９０℃）で高活性を示すため低温転化触媒といわれてい
る。There are two types of carbon monoxide conversion catalysts used industrially. One is an iron or chromium-based catalyst which is used at a relatively high temperature (320 ° C. to 510 ° C.) and is also called a high temperature conversion catalyst. . The other is a copper or zinc-based catalyst, which is inferior in heat resistance but relatively low in temperature (180 ° C to 2 ° C).
It is called a low-temperature conversion catalyst because of its high activity at 90 ° C).
【０００４】炭化水素を原料とするリン酸型燃料電池で
は、電池燃料に用いられる水素の収率を高めるため、お
よび一酸化炭素による電池の被毒劣化を防止するため、
一酸化炭素転化触媒が用いられている。特に、電池の被
毒劣化を防止するためには、燃料水素中の一酸化炭素濃
度を１％未満（乾燥状態）まで下げる必要性があり、炭
化水素を原料とするリン酸型燃料電池においては、高活
性の銅、亜鉛系低温転化触媒が用いられるのが一般的で
ある。In a phosphoric acid fuel cell using hydrocarbon as a raw material, in order to increase the yield of hydrogen used for cell fuel and to prevent the poisoning deterioration of the cell due to carbon monoxide,
A carbon monoxide conversion catalyst has been used. In particular, in order to prevent poisoning deterioration of the battery, it is necessary to reduce the concentration of carbon monoxide in the fuel hydrogen to less than 1% (dry state). In general, a low activity, high activity copper or zinc conversion catalyst is used.
【発明が解決しようとする課題】しかしながら、従来知
られている高活性の銅、亜鉛系転化触媒を、例えば燃料
電池プロセス中一酸化炭素転化工程等に適用し、反応速
度の遅い比較的低温（２００℃）で使用する場合、多く
の触媒量を必要とし、一酸化炭素転化器は大きな容積を
占めている。そのため一酸化炭素転化器の大きさが燃料
電池の小型化、低コスト化をはばんでいる。この問題は
燃料電池システムのみならずその他のアンモニア合成プ
ロセス、石油化学プロセス、低カロリー都市ガス製造プ
ロセス等にも同様に当てはまる問題である。係る問題の
一つの解決方法としては、触媒活性を向上させ、使用す
る触媒量を少なくすることである。したがって、燃料電
池はもちろん、その他種々のシステムの小型化、低コス
ト化の面からも触媒活性の向上が望まれている。However, a conventionally known high-activity copper / zinc conversion catalyst is applied to, for example, a carbon monoxide conversion step in a fuel cell process, and a relatively low temperature (low reaction rate) is required. (200 ° C.) requires a large amount of catalyst and the carbon monoxide converter occupies a large volume. Therefore, the size of the carbon monoxide converter has reduced the size and cost of the fuel cell. This problem applies not only to fuel cell systems but also to other ammonia synthesis processes, petrochemical processes, low-calorie city gas production processes, and the like. One solution to this problem is to improve the catalyst activity and reduce the amount of catalyst used. Therefore, improvement in catalytic activity is desired not only for fuel cells, but also for miniaturization and cost reduction of various other systems.
【０００５】本発明はこのような事情に鑑みなされたも
のであり、低温環境下でより高活性の一酸化炭素転化触
媒を提供することを目的とする。The present invention has been made in view of such circumstances, and has as its object to provide a carbon monoxide conversion catalyst having higher activity under a low temperature environment.
【０００６】本発明は、さらに上記特性に加え、耐熱性
に優れた一酸化炭素転化触媒を提供することを 目的と
する。Another object of the present invention is to provide a carbon monoxide conversion catalyst having excellent heat resistance in addition to the above characteristics.
【０００７】[0007]
【課題を解決するための手段】すなわち本発明は酸化
銅、酸化亜鉛およびアルミナからなる酸化物焼成体に、
金属元素として表した場合に、セシウムまたはストロン
チウム金属元素の少なくとも１種が含有されてなる一酸
化炭素転化触媒に関する。That is, the present invention provides an oxide fired body comprising copper oxide, zinc oxide and alumina,
The present invention relates to a carbon monoxide conversion catalyst containing at least one cesium or strontium metal element when expressed as a metal element.
【０００８】酸化銅、酸化亜鉛およびアルミナからなる
酸化物焼成体は既に知られているものを使用することが
でき、基本的に酸化銅が約２０〜約５０重量％、酸化亜
鉛が約２５〜約６０重量％およびアルミナが約５〜約３
０重量％含有されている構成をしている。[0008] As the oxide fired body composed of copper oxide, zinc oxide and alumina, known ones can be used. Basically, copper oxide is about 20 to about 50% by weight and zinc oxide is about 25 to 25% by weight. About 60% by weight and about 5 to about 3 alumina
It is configured to contain 0% by weight.
【０００９】本発明はそのよな焼成体に、金属元素とし
て表した場合に、セシウムおよびストロンチウムからな
る群から選択される金属元素の少なくとも１種、特に好
ましくはセシウムを含有させてなることを特徴としてい
る。The present invention is characterized in that such a fired body contains, when expressed as a metal element, at least one metal element selected from the group consisting of cesium and strontium, particularly preferably cesium. And
【００１０】それらの金属元素の含有量は、金属元素に
換算した値で、焼結体に対して約１〜約５重量％、好ま
しくは約１〜約４重量％、より好ましくは約２〜約３重
量％とする。The content of the metal element is about 1 to about 5% by weight, preferably about 1 to about 4% by weight, more preferably about 2 to about 5% by weight, based on the metal element. It is about 3% by weight.
【００１１】本発明の一酸化炭素転化触媒の製造方法
は、特に限定されるものではないが、例えば以下のよう
にして製造することができる。Although the method for producing the carbon monoxide conversion catalyst of the present invention is not particularly limited, it can be produced, for example, as follows.
【００１２】銅化合物（例えば硝酸銅、酢酸銅等）、お
よび亜鉛化合物（例えば硝酸亜鉛、酢酸亜鉛等）を含む
水溶液に水酸化アルミニウムを加え、その混合溶液を、
約６０℃程度に保ったアルカリ物質（例えば炭酸ナトリ
ウム、炭酸カリウム等）の水溶液に攪拌下に滴下して沈
殿を生成させる。この沈殿を生成させる工程は、溶液を
加える順序を逆にして、すなわちアルカリ物質の水溶液
に銅化合物、亜鉛化合物および水酸化アルミニウムの混
合溶液を添加させてもよい。また水酸化アルミニウムは
アルカリ物質の溶液に加えておいて、この溶液と銅化合
物および亜鉛化合物を含む水溶液を添加混合して沈殿を
生成させてもよい。Aluminum hydroxide is added to an aqueous solution containing a copper compound (eg, copper nitrate, copper acetate, etc.) and a zinc compound (eg, zinc nitrate, zinc acetate, etc.).
A precipitate is formed by adding dropwise to an aqueous solution of an alkaline substance (eg, sodium carbonate, potassium carbonate, etc.) maintained at about 60 ° C. with stirring. In the step of forming the precipitate, the order of adding the solution may be reversed, that is, a mixed solution of a copper compound, a zinc compound and aluminum hydroxide may be added to an aqueous solution of an alkaline substance. Alternatively, aluminum hydroxide may be added to a solution of an alkali substance, and this solution and an aqueous solution containing a copper compound and a zinc compound may be added and mixed to form a precipitate.
【００１３】生成した沈殿物は充分に水で洗浄し、濾
過、乾燥する。次にこの乾燥物を２７０℃から４００℃
で焼成し、一旦、水でスラリーとする。得られたスラリ
ーを濾過、乾燥し、酸化銅−酸化亜鉛−酸化アルミニウ
ムの焼結体を得る。さらに、必要に応じて本発明の効果
を損なわない範囲で助剤（例えばグラファイト等）を加
えて所望の形状、大きさに成形し、本発明の触媒前駆焼
成体を得る。The resulting precipitate is thoroughly washed with water, filtered and dried. Next, the dried product is heated from 270 ° C to 400 ° C.
And once slurried with water. The obtained slurry is filtered and dried to obtain a sintered body of copper oxide-zinc oxide-aluminum oxide. Further, if necessary, an auxiliary agent (for example, graphite or the like) is added to the extent that the effects of the present invention are not impaired, and the mixture is shaped into a desired shape and size to obtain a fired catalyst precursor of the present invention.
【００１４】このようにして得られた前駆焼結体に、セ
シウムおよびストロンチウム化合物（例えば硝酸塩、炭
酸塩等）が、セシウムおよびストロンチウム金属元素で
換算して、焼結体に対して約１〜約５重量％、好ましく
は約１〜約４重量％、より好ましくは約２〜約３重量％
となるような量で含有される水溶液を全量に吸収させ
る。得られた金属塩吸収焼結体を乾燥、焼成して本発明
の一酸化炭素添加触媒を得る。この時、焼成は２７０〜
４００℃程度で行えばよい。In the precursor sintered body thus obtained, a cesium and strontium compound (for example, nitrate, carbonate, etc.) is converted into about 1 to about 5% by weight, preferably about 1 to about 4% by weight, more preferably about 2 to about 3% by weight
The aqueous solution contained in such an amount as to be absorbed into the whole amount. The obtained metal salt absorption sintered body is dried and fired to obtain the carbon monoxide-added catalyst of the present invention. At this time, firing is 270-
It may be performed at about 400 ° C.
【００１５】以上のようにして得られた本発明の一酸化
炭素転化触媒は、酸化銅−酸化亜鉛−アルミナ系一酸化
炭素転化触媒と同様に、予め水素還元して使用に供す
る。The carbon monoxide conversion catalyst of the present invention obtained as described above is subjected to hydrogen reduction in advance, similarly to the copper oxide-zinc oxide-alumina carbon monoxide conversion catalyst, before use.
【００１６】触媒前駆焼成体の調製硝酸銅、硝酸亜鉛お
よび水酸化アルミニウムを１：１：０．３のモル比で含
有する混合水溶液を、約６０℃に保った炭酸ナトリウム
水溶液に攪拌下滴下し、沈殿を生ぜしめた。得られた沈
殿を充分に水で洗浄し、濾過、乾燥した。Preparation of Catalyst Prefired Body A mixed aqueous solution containing copper nitrate, zinc nitrate and aluminum hydroxide at a molar ratio of 1: 1: 0.3 was added dropwise with stirring to an aqueous sodium carbonate solution maintained at about 60 ° C. , Resulting in precipitation. The obtained precipitate was sufficiently washed with water, filtered and dried.
【００１７】乾燥した沈殿物を２７０℃で焼成し、一旦
水でスラリーとした後、濾過乾燥した。成形剤（グラフ
ァイト）を添加し、直径１／８インチ×長さ１／８イン
チの固体に成形した触媒前駆焼成体を得た。The dried precipitate was calcined at 270 ° C., once slurried with water, and filtered and dried. A molding agent (graphite) was added to obtain a catalyst precursor fired body formed into a solid having a diameter of 1/8 inch and a length of 1/8 inch.
【００１８】実施例１ 得られた触媒前駆焼成体を１ｍｍ〜２ｍｍに粉砕した。
粉砕焼成体１０ｇに対して２重量％のセシウムを含有す
る硝酸セシウム水溶液の全量を、該１０ｇの焼成体に全
量吸収させた。この硝酸セシウム吸収物を３００℃で焼
成して目的とする本発明の一酸化炭素転化触媒を得た。Example 1 The obtained fired catalyst precursor was pulverized to 1 mm to 2 mm.
The entire amount of the cesium nitrate aqueous solution containing 2% by weight of cesium per 10 g of the pulverized fired body was absorbed by the 10 g of the fired body. The cesium nitrate absorbent was calcined at 300 ° C. to obtain a target carbon monoxide conversion catalyst of the present invention.
【００１９】上記で得られた触媒を内径１０ｍｍの石英
製反応管に充填して、下記試験条件で一酸化炭素転化反
応を行った。The catalyst obtained above was filled in a quartz reaction tube having an inner diameter of 10 mm, and a carbon monoxide conversion reaction was carried out under the following test conditions.
【００２０】試験条件 触媒充填量： １ｍｌ 触媒活性化条件：２ｖｏｌ％Ｈ2／Ｎ2ガス３００ｍｌに
て２００℃で２時間還元 原料ガス組成： １１．５ｖｏｌ％ＣＯ、７．５
ｖｏｌ％ＣＯ2、０．７５ｖｏｌ％ＣＨ4、２２．８ｖｏ
ｌ％Ｈ2Ｏ、残りＨ2 原料ガス流量： ３３８ｍｌ／ｍｉｎ． ＧＨＳＶ： ２０２８０ｈ-1 圧力： 大気圧 温度： １７０℃ 結果を下記表１に示した。Test conditions Catalyst loading amount: 1 ml Catalyst activation condition: 2 vol% H 2 / N 2 gas reduced at 200 ° C. for 2 hours at 200 ° C. Raw material gas composition: 11.5 vol% CO, 7.5
vol% CO 2 , 0.75 vol% CH 4 , 22.8 vo
1% H 2 O, remaining H 2 raw material gas flow rate: 338 ml / min. GHSV: 20280 h -1 Pressure: atmospheric pressure Temperature: 170 ° C. The results are shown in Table 1 below.
【００２１】実施例２ 触媒前駆焼成体に対して２重量％のセシウムを含有する
炭酸セシウム水溶液を吸収させた以外は、実施例１と同
様に触媒を得た。また得られた触媒を実施例１と同じ試
験条件で一酸化炭素転化反応を行った。結果を表１に示
した。Example 2 A catalyst was obtained in the same manner as in Example 1 except that a cesium carbonate aqueous solution containing 2% by weight of cesium was absorbed with respect to the catalyst precursor fired body. The obtained catalyst was subjected to a carbon monoxide conversion reaction under the same test conditions as in Example 1. The results are shown in Table 1.
【００２２】実施例３ 触媒前駆焼成体に対して２重量％のセシウムを含有する
水酸化セシウム水溶液を吸収させた以外は、実施例１と
同様に触媒を得た。また得られた触媒を実施例１と同じ
試験条件で一酸化炭素転化反応を行った。結果を表１に
示した。Example 3 A catalyst was obtained in the same manner as in Example 1 except that a cesium hydroxide aqueous solution containing 2% by weight of cesium was absorbed with respect to the catalyst precursor fired body. The obtained catalyst was subjected to a carbon monoxide conversion reaction under the same test conditions as in Example 1. The results are shown in Table 1.
【００２３】実施例４ 触媒前駆焼成体に対して２重量％のストロンチウムを含
有する硝酸ストロンチウム水溶液を吸収させた以外は、
実施例１と同様に触媒を得た。また得られた触媒を実施
例１と同じ試験条件で一酸化炭素転化反応を行った。結
果を表１に示した。Example 4 A strontium nitrate aqueous solution containing 2% by weight of strontium with respect to a catalyst precursor calcined product was absorbed.
A catalyst was obtained in the same manner as in Example 1. The obtained catalyst was subjected to a carbon monoxide conversion reaction under the same test conditions as in Example 1. The results are shown in Table 1.
【００２４】実施例５ 触媒前駆焼成体に対して１重量％のセシウムを含有する
硝酸セシウム水溶液を吸収させた以外は、実施例１と同
様に触媒を得た。また得られた触媒を実施例１と同じ試
験条件で一酸化炭素転化反応を行った。結果を表１に示
した。Example 5 A catalyst was obtained in the same manner as in Example 1 except that an aqueous cesium nitrate solution containing 1% by weight of cesium was absorbed with respect to the catalyst precursor fired body. The obtained catalyst was subjected to a carbon monoxide conversion reaction under the same test conditions as in Example 1. The results are shown in Table 1.
【００２５】実施例６ 触媒前駆焼成体に対して３重量％のセシウムを含有する
硝酸セシウム水溶液を吸収させた以外は、実施例１と同
様に触媒を得た。また得られた触媒を実施例１と同じ試
験条件で一酸化炭素転化反応を行った。結果を表１に示
した。Example 6 A catalyst was obtained in the same manner as in Example 1 except that a cesium nitrate aqueous solution containing 3% by weight of cesium was absorbed with respect to the catalyst precursor fired body. The obtained catalyst was subjected to a carbon monoxide conversion reaction under the same test conditions as in Example 1. The results are shown in Table 1.
【００２６】比較例１ 実施例１で得られた１ｍｍ〜２ｍｍに粉砕した焼成体
を、そのまま３００℃で焼成して触媒を得た。また得ら
れた触媒を実施例１と同じ試験条件で一酸化炭素転化反
応を行った。結果を表１に示した。Comparative Example 1 The fired body obtained in Example 1 and ground to 1 mm to 2 mm was fired at 300 ° C. as it was to obtain a catalyst. The obtained catalyst was subjected to a carbon monoxide conversion reaction under the same test conditions as in Example 1. The results are shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】なお、一酸化炭素の転化率は、下記式によ
り算出した。The conversion of carbon monoxide was calculated by the following equation.
【数１】 上記式中、ＣＯoutは出口ＣＯ濃度、ＣＯ2outは出口Ｃ
Ｏ2の濃度、ＣＯinは入口ＣＯ濃度、ＣＯ2inは入口ＣＯ
2濃度を表す。(Equation 1) In the above formula, CO out is the outlet CO concentration, CO 2out exit C
O 2 concentration, CO in is inlet CO concentration, CO 2in is inlet CO
2 represents the concentration.
【００２９】表１より本発明の触媒はＣＯ転化率が高い
ことがわかる。Table 1 shows that the catalyst of the present invention has a high CO conversion.
【００３０】実施例７ 触媒前駆焼成体１０ｇに対して２重量％のセシウムを含
有する硝酸セシウム水溶液の全量を、該１０ｇの焼成体
に全量吸収させた。この硝酸セシウム吸収物を３００℃
で焼成して目的とする本発明の一酸化炭素転化触媒を得
た。Example 7 The entire amount of the cesium nitrate aqueous solution containing 2% by weight of cesium per 10 g of the fired catalyst precursor was absorbed by the fired body of 10 g. This cesium nitrate absorbent is heated to 300 ° C.
To obtain the desired carbon monoxide conversion catalyst of the present invention.
【００３１】上記で得られた触媒を内径３０ｍｍの石英
製反応管に充填して、下記試験条件で一酸化炭素転化反
応を行い、１時間後と１２６時間後のＣＯ転化率を測定
した。The above-obtained catalyst was filled in a quartz reaction tube having an inner diameter of 30 mm, a carbon monoxide conversion reaction was performed under the following test conditions, and the CO conversion rates after 1 hour and 126 hours were measured.
【００３２】試験条件 触媒充填量： ５ｍｌ 触媒活性化条件：２ｖｏｌ％Ｈ2／Ｎ2ガス１５００ｍｌ
にて２００℃で２時間還元 原料ガス組成： １２．１ｖｏｌ％ＣＯ、７．９ｖｏｌ
％ＣＯ2、０．７８ｖｏｌ％ＣＨ4、１７．２ｖｏｌ％Ｈ
2Ｏ、残りＨ2 原料ガス流量： １８６００ｍｌ／ｍｉｎ． ＧＨＳＶ： ２２３２００ｈ-1 圧力： 大気圧 温度： ３５０℃ 結果を下記表２に示した。Test conditions Catalyst filling amount: 5 ml Catalyst activation condition: 2 vol% H 2 / N 2 gas 1500 ml
At 200 ° C. for 2 hours Raw material gas composition: 12.1 vol% CO, 7.9 vol
% CO 2 , 0.78 vol% CH 4 , 17.2 vol% H
2 O, remaining H 2 raw material gas flow rate: 18600 ml / min. GHSV: 223200 h -1 Pressure: Atmospheric pressure Temperature: 350 ° C. The results are shown in Table 2 below.
【００３３】比較例２ 触媒前駆焼成体をそのまま触媒として用いた以外は、実
施例７と同じ試験条件により一酸化炭素転化反応を行っ
た。結果を表２に示す。Comparative Example 2 A carbon monoxide conversion reaction was carried out under the same test conditions as in Example 7 except that the fired catalyst precursor was used as a catalyst. Table 2 shows the results.
【００３４】[0034]
【表２】 [Table 2]
【００３５】表２より、本発明の触媒は高温環境下でも
良好なＣＯ転化率を維持でき、耐久性に優れたものであ
ることがわかる。From Table 2, it can be seen that the catalyst of the present invention can maintain a good CO conversion even under a high temperature environment and has excellent durability.
【００３６】実施例８ 図１は本実施例で使用した１００ｋＷリン酸型燃料電池
発電システムの概略フロー構成図を示す。Embodiment 8 FIG. 1 shows a schematic flow diagram of a 100 kW phosphoric acid fuel cell power generation system used in this embodiment.
【００３７】原燃料（都市ガス）１は一酸化炭素変成器
６ａより導かれる水素を主成分とする燃料ガスと適宜な
混合比に混合されて、脱硫器２に導入され付臭剤中の硫
黄が除去される。脱硫された原燃料１は混合器３で気水
分離器１８から生成した水蒸気と適宜の混合比で混合さ
れた後、水蒸気改質器５に導入され、水蒸気改質反応に
付されて水素を主成分とする燃料ガスに変換される。水
蒸気改質器５から排出される水素を主成分とする燃料ガ
スは、一酸化炭素変成器６ａに送られ、一酸化炭素含有
量を減少させるとともに水素含有量が高められる。この
一酸化炭素変成器６ａに本発明の一酸化炭素転化触媒６
ｂが充填されている。次いで、一酸化炭素変成器６ａか
ら排出された燃料ガスは、電池７の燃料極８に送られ、
空気ブロワー９より空気極１１に流入している空気１０
中の酸素と電気化学的反応を行い、その結果燃料ガスの
一部が消費されて電気エネルギーが得られ、水が副生す
る。なお、燃料極７から排出された燃料ガスは、バーナ
ー１２に送り、燃焼させて水蒸気改質器の加熱源として
利用する。The raw fuel (city gas) 1 is mixed with a fuel gas containing hydrogen as a main component, which is led from a carbon monoxide converter 6a, at an appropriate mixing ratio. Is removed. The desulfurized raw fuel 1 is mixed with the steam generated from the steam separator 18 at an appropriate mixing ratio in the mixer 3 and then introduced into the steam reformer 5 where it is subjected to a steam reforming reaction to remove hydrogen. It is converted into fuel gas as the main component. The fuel gas containing hydrogen as a main component discharged from the steam reformer 5 is sent to the carbon monoxide converter 6a to reduce the carbon monoxide content and increase the hydrogen content. The carbon monoxide conversion catalyst 6 of the present invention is
b is filled. Next, the fuel gas discharged from the carbon monoxide converter 6a is sent to the fuel electrode 8 of the battery 7,
The air 10 flowing from the air blower 9 to the air electrode 11
An electrochemical reaction occurs with oxygen in the fuel, and as a result, a part of the fuel gas is consumed, electric energy is obtained, and water is by-produced. The fuel gas discharged from the fuel electrode 7 is sent to the burner 12, where it is burned and used as a heating source for the steam reformer.
【００３８】本システムで使用された触媒は、以下の通
りである。直径１／４インチ×長さ１／８インチに成形
した以外は触媒前駆焼成体の調製と同様に作製し、触媒
前駆焼成体を調製し、３００℃で焼成した。得られた焼
成体をそのまま１５０リットルを用いて、図１に示す１
００ｋＷリン酸型燃料電池発電システムの一酸化炭素転
化反応器に充填した。、次いで１３Ａ都市ガスを原料と
して該燃料電池を運転し、定格負荷での一酸化炭素転化
反応器出口での一酸化炭素濃度を測定したところ０．６
１容量％（乾燥状態）であった。The catalyst used in the present system is as follows. A catalyst precursor fired body was prepared in the same manner as in the preparation of the catalyst precursor fired body except that the catalyst precursor fired body was formed to have a diameter of 1/4 inch and a length of 1/8 inch, and fired at 300 ° C. Using the obtained fired body as it is, using 150 liters,
A 00 kW phosphoric acid fuel cell power generation system was charged into a carbon monoxide conversion reactor. Then, the fuel cell was operated using 13A city gas as a raw material, and the carbon monoxide concentration at the outlet of the carbon monoxide conversion reactor at the rated load was measured.
It was 1% by volume (dry state).
【００３９】一方、直径１／４インチ×長さ１／８イン
チに成形した以外は触媒前駆焼成体の調製と同様に作製
し、触媒前駆焼成体を得た。該焼成体に対して２重量％
のセシウムを含有する硝酸セシウム水溶液を焼成体に全
量吸収させ、この硝酸セシウム吸収物を３００℃で焼成
して本発明の一酸化炭素転化触媒を得た。得られた触媒
１２０リットルを用いて、１００ｋＷリン酸型燃料電池
用の一酸化炭素転化反応器に充填した。次いで１３Ａ都
市ガスを原料として該燃料電池を運転し、定格負荷での
一酸化炭素転化反応器出口での一酸化炭素濃度を測定し
たところ０．６０容量％であった。On the other hand, a catalyst precursor fired body was prepared in the same manner as in the preparation of the catalyst precursor fired body except that it was formed to have a diameter of 1/4 inch and a length of 1/8 inch. 2% by weight based on the fired body
The cesium nitrate aqueous solution containing cesium was completely absorbed by the calcined body, and the cesium nitrate absorbent was calcined at 300 ° C. to obtain a carbon monoxide conversion catalyst of the present invention. Using 120 liters of the obtained catalyst, it was charged into a carbon monoxide conversion reactor for a 100 kW phosphoric acid type fuel cell. Next, the fuel cell was operated using 13A city gas as a raw material, and the carbon monoxide concentration at the outlet of the carbon monoxide conversion reactor at the rated load was measured to be 0.60% by volume.
【００４０】以上から、本発明の触媒は、従来の触媒よ
りも少ない触媒量で従来の触媒と同等の性能が得られる
ことがわかる。From the above, it can be seen that the catalyst of the present invention can achieve the same performance as the conventional catalyst with a smaller amount of the catalyst than the conventional catalyst.
【００４１】なお、上記フロー図中における、都市ガス
の組成、スチーム添加後のガス組成、改質器５で改質後
のガス組成、ＣＯ変成器６ａでの変成後のガス組成、未
反応ガス組成を表３に示した。In the above flow chart, the composition of the city gas, the gas composition after the addition of steam, the gas composition after the reforming in the reformer 5, the gas composition after the conversion in the CO converter 6a, the unreacted gas The composition is shown in Table 3.
【００４２】[0042]
【表３】 [Table 3]
【００４３】さらに本発明の触媒を充填したシステムで
運転した時のＣＯ変成器６ａにおける温度分布とＣＯ濃
度を触媒層長に対してプロットした図を図２に示す。FIG. 2 is a diagram plotting the temperature distribution and the CO concentration in the CO converter 6a with respect to the catalyst layer length when the system is operated with the system filled with the catalyst of the present invention.
【００４４】図２において温度分布はガス入り口付近で
入り口温度より上昇し約３５０℃近くまで達している。
これはＣＯ変成器６ａにおけるＣＯ転化反応が発熱反応
でありその時生じる熱による温度上昇を表している。そ
の後、温度が徐々に下がっているのは冷却水で熱交換し
ているためである。このように、燃料電池発電システム
に本発明の触媒を使用する場合、入口付近の触媒温度が
３５０℃にまで達するので、その温度に対する耐熱性が
要求されるのである。この耐熱性があることを実施例７
は示すものであり、本発明の触媒は燃料電池システムに
好適に使用できることが示されている。In FIG. 2, the temperature distribution near the gas inlet rises from the inlet temperature and reaches about 350 ° C.
This indicates that the CO conversion reaction in the CO converter 6a is an exothermic reaction and the temperature rise due to the heat generated at that time. Thereafter, the temperature is gradually lowered because heat is exchanged with the cooling water. As described above, when the catalyst of the present invention is used in a fuel cell power generation system, the catalyst temperature near the inlet reaches 350 ° C., so that heat resistance to that temperature is required. Example 7 shows that this heat resistance exists.
Shows that the catalyst of the present invention can be suitably used for a fuel cell system.
【００４５】[0045]
【発明の効果】本発明の一酸化炭素転化触媒は低温環境
下で高活性である。また本発明の一酸化炭素転化触媒は
左記特性に加え、耐熱性および耐久性に優れている。The carbon monoxide conversion catalyst of the present invention has high activity under a low temperature environment. Further, the carbon monoxide conversion catalyst of the present invention is excellent in heat resistance and durability in addition to the properties described on the left.
【図１】 実施例で使用した燃料電池発電システムの概
略フロー構成図。FIG. 1 is a schematic flow configuration diagram of a fuel cell power generation system used in an example.
【図２】 ＣＯ変成器６ａにおける温度分布とＣＯ濃度
を触媒層長に対してプロットしたグラフ。FIG. 2 is a graph in which the temperature distribution and the CO concentration in the CO converter 6a are plotted against the catalyst layer length.
１：原燃料（都市ガス） ２：脱硫器 ３：混合器 ４：熱交換器 ５：水蒸気改質器 ６ａ：一酸化炭素変成器 ６ｂ：一酸化炭素転化触媒 ７：電池 ８：燃料極 ９：空気ブロワー １０：空気 １１：空気極 １２：バーナー １３：熱交換器 １４：凝縮器 １５：給水ライン １６：給水ポンプ １７：冷却水ポンプ １８：気水分離器 1: Raw fuel (city gas) 2: Desulfurizer 3: Mixer 4: Heat exchanger 5: Steam reformer 6a: Carbon monoxide converter 6b: Carbon monoxide conversion catalyst 7: Battery 8: Fuel electrode 9: Air blower 10: Air 11: Air electrode 12: Burner 13: Heat exchanger 14: Condenser 15: Water supply line 16: Water supply pump 17: Cooling water pump 18: Air / water separator
フロントページの続き (72)発明者 安田 征雄 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 (72)発明者 張 華民 京都府京都市下京区中堂寺南町17 京都リ サーチパーク株式会社関西新技術研究所内Continued on the front page (72) Inventor Yasuo Yasuda 4-1-2-1, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Prefecture Inside Osaka Gas Co., Ltd. Search Park Co., Ltd.
Claims (2)
る酸化物焼成体に、金属元素として表した場合に、セシ
ウムおよび／またはストロンチウム金属元素が含有され
てなる一酸化炭素転化触媒。1. A carbon monoxide conversion catalyst comprising an oxide fired body comprising copper oxide, zinc oxide and alumina, when expressed as a metal element, containing a cesium and / or strontium metal element.
金属元素が、酸化物焼成体に対して金属元素換算で１〜
５重量％含有されている請求項３記載の一酸化炭素転化
触媒。2. A cesium and / or strontium metal element is 1 to 1 in terms of a metal element with respect to an oxide fired body.
The carbon monoxide conversion catalyst according to claim 3, which is contained in an amount of 5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10051927A JPH11244700A (en) | 1998-03-04 | 1998-03-04 | Carbon monoxide conversion catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10051927A JPH11244700A (en) | 1998-03-04 | 1998-03-04 | Carbon monoxide conversion catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11244700A true JPH11244700A (en) | 1999-09-14 |
Family
ID=12900520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10051927A Pending JPH11244700A (en) | 1998-03-04 | 1998-03-04 | Carbon monoxide conversion catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11244700A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001078892A1 (en) * | 2000-04-19 | 2001-10-25 | Osaka Gas Co., Ltd. | Method for preparing catalyst for reforming methanol |
| JP2006223985A (en) * | 2005-02-17 | 2006-08-31 | Catalysts & Chem Ind Co Ltd | Water gas shift reaction catalyst |
| JP2006239557A (en) * | 2005-03-03 | 2006-09-14 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction |
| JP2007313487A (en) * | 2006-05-29 | 2007-12-06 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction, and method for water gas shift reaction using the same |
| JP2009241036A (en) * | 2008-03-31 | 2009-10-22 | Idemitsu Kosan Co Ltd | Carbon monoxide conversion catalyst comprising composition for carbon monoxide conversion catalyst, and method of removing carbon monoxide using the same |
-
1998
- 1998-03-04 JP JP10051927A patent/JPH11244700A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001078892A1 (en) * | 2000-04-19 | 2001-10-25 | Osaka Gas Co., Ltd. | Method for preparing catalyst for reforming methanol |
| US6844292B1 (en) | 2000-04-19 | 2005-01-18 | Osaka Gas Co., Ltd. | Method for preparing catalyst for reforming methanol |
| JP2006223985A (en) * | 2005-02-17 | 2006-08-31 | Catalysts & Chem Ind Co Ltd | Water gas shift reaction catalyst |
| JP2006239557A (en) * | 2005-03-03 | 2006-09-14 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift 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 |
| JP2007313487A (en) * | 2006-05-29 | 2007-12-06 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction, and method for water gas shift reaction using the same |
| JP2009241036A (en) * | 2008-03-31 | 2009-10-22 | Idemitsu Kosan Co Ltd | Carbon monoxide conversion catalyst comprising composition for carbon monoxide conversion catalyst, and method of removing carbon monoxide using the same |
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