JPS6150639A - Methanol reforming catalyst - Google Patents
Methanol reforming catalystInfo
- Publication number
- JPS6150639A JPS6150639A JP16874984A JP16874984A JPS6150639A JP S6150639 A JPS6150639 A JP S6150639A JP 16874984 A JP16874984 A JP 16874984A JP 16874984 A JP16874984 A JP 16874984A JP S6150639 A JPS6150639 A JP S6150639A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oxide
- cerium
- weight
- amount
- 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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明はメタノールを水素ならびに一酸化炭素に改質
するための高耐久性メタノール改質用触媒に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to a highly durable methanol reforming catalyst for reforming methanol into hydrogen and carbon monoxide.
（従来の技術）
従来、メタノール改質用触媒は種々提案されており、本
出願人も特開昭５８−６７８４４号公報に開示されてい
る触媒を提案した。この触媒は例えば活性アルミナベレ
ットに硝酸セリウムを含浸乾燥した後、空気中で焼成し
、酸化セリウム付アルミナベレットとし、次いで白金を
担持させたものである。(Prior Art) Various catalysts for methanol reforming have been proposed in the past, and the present applicant also proposed a catalyst disclosed in Japanese Patent Application Laid-Open No. 58-67844. This catalyst is, for example, an activated alumina pellet impregnated with cerium nitrate and dried, then calcined in air to form an alumina pellet with cerium oxide, and then supported with platinum.
（発明が解決しようとする問題点）
この触媒により同じ白金量が担持されそれまでの触媒よ
り触媒の活性、耐久性並びに水素と一酸化炭素への反応
選択性は改善されたものの尚耐久性が満足されないとい
う問題点があった。(Problems to be Solved by the Invention) This catalyst supports the same amount of platinum and has improved catalyst activity, durability, and reaction selectivity to hydrogen and carbon monoxide compared to previous catalysts, but the durability is still poor. There was a problem that they were not satisfied.
（問題点を解決するための手段）
発明者らは上記問題点を解決すべく、従来法によるメタ
ノール改質用触媒を耐久試験をしていたところ、途中で
性能が劣化したため、そのサンプルをＸ線光電子分光に
かけた所、セリウム酸化物が３価および４価の混合物で
あることが判明し、劣化がこれに起因するのではないか
と考え、そこ１で触媒を白金とし、その付着量を０．１
重量％、０．２重量％、０．４重量％と変えて触媒性能
とセリウム酸化物の価数の関係を調べたところ、第１図
に示すように４１価のセリウムの多い担体を出発物質と
したサンプル程、すなわちセリウム原子の数の比として
４価の酸化セリウム１０に対して３価の酸化セリウムが
（１，５未満で性能が高くかつ劣化が少ないことを確か
めた。次いでセリウムがすべて４９価である酸化セリウ
ムの微粉末をコロイダルベーマイトアルミナゾルと混合
し、さらに粉砕したものを、活性アルミナの表面に付着
させ乾燥焼したアルミナペレットを担体として用いたと
ころ高耐久性のメタノール改質効果媒が得らねた。(Means for solving the problem) In order to solve the above problem, the inventors conducted an durability test on a methanol reforming catalyst using a conventional method. When subjected to line photoelectron spectroscopy, it was found that cerium oxide was a mixture of trivalent and tetravalent cerium oxides, and we thought that this might be the cause of the deterioration, so we used platinum as the catalyst and reduced the amount of adhesion to 0. .1
When we investigated the relationship between the catalyst performance and the valence of cerium oxide by changing the amounts by weight%, 0.2% by weight, and 0.4% by weight, we found that as shown in Figure 1, the carrier containing a large amount of 41-valent cerium was It was confirmed that the sample had higher performance and less deterioration when the ratio of the number of cerium atoms was less than 1.5 for tetravalent cerium oxide to 10 for tetravalent cerium oxide. By mixing fine powder of 49-valent cerium oxide with colloidal boehmite alumina sol, pulverizing the powder, adhering it to the surface of activated alumina, and using dry-fired alumina pellets as a carrier, a highly durable methanol reforming effective medium was obtained. I didn't get it.
従ってこの発明のメタノール改質用触媒は、活性アルミ
ナを主成分とする無機酸化物にセリウム酸化物を付着さ
刊た担体に、白金およびパラジウムの内の少くとも１種
が担持されたメタノール改質ＩＩ峡媒であって、セリウ
ム酸化物の大部分が４価のセリウムの酸化物だけである
こと、すなわちセリウムσ１ ｆ’４１ ｉｔ：、物の
うち、４価のセリウムの数１（）に対して８価のセリウ
ムの数が０．５未満の比率であることを特徴とする。Therefore, the methanol reforming catalyst of the present invention is a methanol reforming catalyst in which at least one of platinum and palladium is supported on a carrier in which cerium oxide is attached to an inorganic oxide mainly composed of activated alumina. II isthmus medium, and most of the cerium oxides are only oxides of tetravalent cerium, that is, cerium σ1 f'41 it:, for the number 1 () of tetravalent cerium among the things. The ratio of the number of octavalent cerium is less than 0.5.
この発明の触媒における４価のセリウムの酸化物の担体
への付着量は、０．１〜１０ 、ｆｆＩ ｉｔ％とする
のが好ましい。０．１重置％より少ないと添加した、効
果がなく、１０重量％を越えると得られる触媒の性能が
かえって低下するので好ましくない。In the catalyst of the present invention, the amount of tetravalent cerium oxide deposited on the carrier is preferably 0.1 to 10%, ffI it%. If it is less than 0.1% by weight, there is no effect, and if it exceeds 10% by weight, the performance of the resulting catalyst will deteriorate, which is not preferable.
次に白金（ｐｔ）の担持量は０．１〜１．０重量％が好
ましい。０．１重量％より少ないと十分なメタノール改
質効果が得られず、一方１．０重量％より多くしても分
散性のためと考えられるが増量効果がなく不経済である
。Next, the amount of platinum (pt) supported is preferably 0.1 to 1.0% by weight. If it is less than 0.1% by weight, a sufficient methanol reforming effect cannot be obtained, while if it is more than 1.0% by weight, it is uneconomical because there is no increase in weight, although this is thought to be due to dispersibility.
またパラジウム（Ｐｄ）の担持量は０．２〜１．０重量
％が好ましい。０．２重量％より少ないと十分なメタノ
ール改質効果が得られず、一方１．０重量％より多くし
ても分散性のためと思われるが、増量効果がなく不経済
である。Further, the amount of palladium (Pd) supported is preferably 0.2 to 1.0% by weight. If it is less than 0.2% by weight, a sufficient methanol reforming effect cannot be obtained, while if it is more than 1.0% by weight, there is no weight increase effect and it is uneconomical, although this may be due to dispersibility.
（実施例）
実施例１
Ｐ［ｌｌ’ｌコンデア社製ベーマイトアルミナ粉末デイ
スビューラル１００９を純水７７４９に分散させ攪拌し
ながら１０重量％硝酸１２６ｇを徐々に投入し、ベーマ
イトアルミナゾルとした。信越化学工業（株）制酸化セ
リウム粉末１００りおよび仏画ローヌブ・−ラン製活性
アルミナペレット（粒径３關）１００９を上記ゾル中へ
投入し １ボールミルにて１１３ Ｏｒｐｍで１４
時時間分粉砕し、スラリーとした。前記活性アルミナペ
レット（粒径８ ａｍ ） ］ ｌ （８２０り）を回
転円盤皿状造粒機に取り、前記スラリーの一部を徐々に
添加しなから造粒機を１２ Ｏｒｐｍで回転させ酸化セ
リウムおよびアルミナゾルの混合物をペレットの表面に
まぶした。次いで別の回転円盤皿状造粒機に移し、赤外
線ランプにて加熱乾燥し、空気炉中６５０’Ｃで２時間
焼成し、表面に酸化セリウムをコーティングしたアルミ
ナペレットとした。酸化セリウムの付着量は金属セリウ
ム換算で２重量％とした。(Example) Example 1 Boehmite alumina powder Disbural 1009 manufactured by Condea was dispersed in pure water 7749, and 126 g of 10% by weight nitric acid was gradually added while stirring to obtain a boehmite alumina sol. Cerium antaoxide powder (Shin-Etsu Chemical Co., Ltd.) 100g and activated alumina pellets (particle size 3cm) made by French Painting Rhoneve-Lin 1009 were added to the above sol and milled using a ball mill at 113 orpm for 14 hours.
It was ground for hours to make a slurry. The activated alumina pellets (particle size 8 am)] 1 (820 ml) were taken into a rotary disc-shaped granulator, and a portion of the slurry was gradually added, and the granulator was rotated at 12 Orpm to form cerium oxide. and alumina sol were sprinkled on the surface of the pellets. The mixture was then transferred to another rotary disc-shaped granulator, heated and dried with an infrared lamp, and calcined in an air oven at 650'C for 2 hours to obtain alumina pellets whose surfaces were coated with cerium oxide. The amount of cerium oxide deposited was 2% by weight in terms of metallic cerium.
次に塩化白金酸（Ｈ，ＰｔＯ／６・６Ｈ，Ｏ） ８．７
１９を純□水２８０（１９に溶解し、生成した溶液を加
熱器により加熱した。この溶液に２．７４りのチオ硫酸
アンモニウム（（ＮＨ，）、 Ｓ、０８）を添加し、白
金とイオウのモル比を］：２として塩化白金酸と反応さ
せた後、攪拌しながら担体に含浸を行なった。こ□の含
浸処理した担体を水切後空気オーブン中２００°Ｃで担
体の乾燥が均一になるように担体を動かしながら水分含
有率１０重量％以下まで乾燥した。Next, chloroplatinic acid (H, PtO/6.6H, O) 8.7
19 was dissolved in 280 mL of pure water (19), and the resulting solution was heated with a heater. 2.74 parts of ammonium thiosulfate ((NH,), S, 08) was added to this solution to dissolve platinum and sulfur. After reacting with chloroplatinic acid at a molar ratio of ]:2, the carrier was impregnated with stirring. After draining the impregnated carrier, it was placed in an air oven at 200°C to ensure uniform drying of the carrier. The carrier was dried to a moisture content of 10% by weight or less while moving it in this manner.
しかる後水蒸気気流中５５０°Ｃで９０分間焼成し、水
素化ホウ素す） ＩＪウム（ＳＢＩ（）０．１重量％水
溶液で処理し、乾燥し触媒Ａを得た。この触媒Ａは。Thereafter, it was calcined for 90 minutes at 550°C in a stream of steam, treated with a 0.1% by weight aqueous solution of boron hydride (SBI), and dried to obtain catalyst A.
金属換算でセリウムを２重量％、白金を０．４（１重量
％含有していた。It contained 2% by weight of cerium and 0.4% (1% by weight of platinum) in terms of metal.
比較例１
実施例］で用いた仏国ローヌブーラン社製活性アルミナ
ペレット１００ｇと硝酸セリウム（Ｏｓ（ＮＯ，）、・
６Ｈ，Ｏ） ２５８．４９を純水ｚ ａ Ｏｇ Ｇ、Ｌ
溶解したものをボールミル中に取り、十分に混合粉砕し
た後、空気オーブン中２ｏｏ″Ｃで乾燥し、空気炉中６
００°Ｃで２時間加熱し、２００ｇのブ町。Comparative Example 1 100 g of activated alumina pellets manufactured by Rhone Boulin, France used in Example] and cerium nitrate (Os(NO,),
6H, O) 258.49 to pure water z a Og G, L
The dissolved material was taken into a ball mill, thoroughly mixed and pulverized, and then dried in an air oven at 2oo''C.
Heated at 00°C for 2 hours and weighed 200g.
ツクを得た。また***国コンデア社製のベーマイトアル
ミナ粉末デイスピーラル１００９を純水７７４りに分散
させ、攪拌しながら】０重Ｉｔ％硝酸１２ｆｌを徐々に
投入しベーマイトアルミナゾルとした。I got a trick. Further, boehmite alumina powder Dispiral 1009 manufactured by Condea, West Germany, was dispersed in 774ml of pure water, and while stirring, 12 fl of 0 weight It% nitric acid was gradually added to form a boehmite alumina sol.
前記ブロック２００９をこのゾル中へ投入し、ボールミ
ルにて１０ Ｏｒｐｍで１４時時間分粉砕し、スラリー
とした。The block 2009 was put into this sol and ground in a ball mill at 10 Orpm for 14 hours to form a slurry.
以下実施例１と全く同様にして触媒Ｂを得た。Thereafter, Catalyst B was obtained in exactly the same manner as in Example 1.
この触媒Ｂは金属換算でセリウムを２重計％、白金を０
．４０重量％含有していた。This catalyst B contains 2% cerium and 0% platinum in metal terms.
．． It contained 40% by weight.
比較例２
比較例１で用いたブロック２００９の代りに、このブロ
ック１３０り、信越化学工業（株）制酸化セリウム８５
９および仏国ローヌブーラン社製活性アルミナペレット
（粒径３ ｎ ） ８５９を混ぜたものを比較例１と同
様のゾル中へ投入し、以下比較例】と全く同様にして触
媒０を得た。触媒Ｃは金属換算でセリウムを２重量％、
白金を０．４０重量％含有していた。Comparative Example 2 Instead of the block 2009 used in Comparative Example 1, this block 130 was prepared by using Cerium Antoxide 85 manufactured by Shin-Etsu Chemical Co., Ltd.
A mixture of 9 and activated alumina pellets (particle size 3 n) 859 manufactured by Rhone-Bouland, France, was added to the same sol as in Comparative Example 1, and the same procedure as in Comparative Example] was carried out to obtain Catalyst 0. Catalyst C contains 2% by weight of cerium in terms of metal.
It contained 0.40% by weight of platinum.
比較例８
比較例］で用いたブロック２００９の代りに、このブロ
ック７０９、比較例２で用いた酸化セリウム６５９およ
び活性アルミナペレット（粒径８關）６５りを混ぜたも
のを比較例１と同様のゾル÷中へ投入し、以下比較例］
と全く同様にして触媒りを得た。この触媒りは金属換算
でセリウムを２重量％、白金を０．４重量％含有してい
た。Comparative Example 8 Instead of the block 2009 used in Comparative Example], a mixture of this block 709, 659 cerium oxide used in Comparative Example 2, and 65 ml of activated alumina pellets (particle size 8) was used in the same manner as in Comparative Example 1. Comparative example below]
A catalyst was obtained in exactly the same manner. This catalyst contained 2% by weight of cerium and 0.4% by weight of platinum in terms of metal.
′ 実施例２
実施例１で用いたセリア付アルミナペレットを、・塩化
パラジウム（Ｐｄ０Ｉ、 ） ６．５０りを純水２８０
０ 。' Example 2 The ceria-coated alumina pellets used in Example 1 were mixed with 6.50 g of palladium chloride (Pd0I) and 280 g of pure water.
0.
りに溶解した溶液にて含浸した。この含浸した担体を水
切後空気オーブン中２００″Ｃで担体の乾燥が均一にな
るように相体を動かしながら水分含有率５％まで乾燥し
た。しかる後水蒸気気流中５５０°Ｃで９０分間焼成し
、５ＢＨ０，１重臘％水溶液で処理し、乾燥しＰｄ ０
１４０重量％担持した触媒Ｅを得た。It was impregnated with a solution dissolved in water. After draining, the impregnated carrier was dried in an air oven at 200"C to a moisture content of 5% while moving the phase to uniformly dry the carrier. Thereafter, it was calcined in a stream of steam at 550°C for 90 minutes. , treated with 5BH0,1% aqueous solution, dried and Pd 0
Catalyst E with 140% by weight supported was obtained.
比較例４
比較例］で用いたセリア付アルミナペレットを１・・用
い、実施例２と全く同様に処理し、Ｐｄ Ｏ，４０重量
％担持した触媒Ｆを得た。Comparative Example 4 The ceria-coated alumina pellets used in Comparative Example 1 were treated in exactly the same manner as in Example 2 to obtain catalyst F carrying 40% by weight of Pd 2 O.
試験例１
前記実施例］および比較例１〜８で得られた触媒Ａ、Ｂ
、ＧおよびＤをＸ線光電子分光にかけた。１得た結果を
第１図〜第４図に示す。但し図中のＳは（３ｅ ４＋の
サテライトピークを示す。触媒Ａは全て４価の酸化セリ
ウムであるが、触媒Ｂは８価および４価の酸化セリウム
の混合物（その重量比率はＣｅ’”／（３ｅ ａ ＋
−１ｏ／４ ）であり、触媒Ｃは触媒Ｂより、また触媒
りは触媒Ｃよりさらに４Ｉｉｌｌｉの酸化１セリウムカ
増、ｔている（触媒ＣはＯｅ ’７０ｅ ８ ＋−ＩＶ
２．５、触媒りはＣｅ′”／（３ａ８＋−］ ０／１．
５） カ、全テカ４価（ｉ’）酸化セリウムではないこ
とがわかる。Test Example 1 Catalysts A and B obtained in the above Examples and Comparative Examples 1 to 8
, G and D were subjected to X-ray photoelectron spectroscopy. 1 The results obtained are shown in FIGS. 1 to 4. However, S in the figure indicates a satellite peak of (3e 4+). Catalyst A is all tetravalent cerium oxide, but catalyst B is a mixture of octavalent and tetravalent cerium oxide (the weight ratio is Ce'''/ (3e a +
-1o/4), and catalyst C has 4Iilli more cerium oxide than catalyst B, and catalyst C has Oe '70e 8 + -IV
2.5, the catalyst ratio is Ce'"/(3a8+-) 0/1.
5) It can be seen that it is not all Teca(i') cerium oxide.
試験例２ 実施例１〜２、比較例１〜４で得られた触媒Ａ。Test example 2 Catalyst A obtained in Examples 1-2 and Comparative Examples 1-4.
Ｂ、Ｏ，Ｄ、ＥおよびＦを、それぞれ下記の条件で耐久
し、耐久前後の活性を測定し、得た結果を第１表に示す
。B, O, D, E, and F were each subjected to durability under the following conditions, and their activities before and after the durability were measured. The results are shown in Table 1.
耐 久 条 件
触 媒 量 ２ 〇−
触媒床渇変 ４０．０″Ｃ
空間速Ｗ ２０００ Ｈｒ−１
耐久時間 ４００ Ｈｒ
使用メタノール 工業用メタノール
触媒の活性評価
工業用メタノール（１００％）を蒸発器（エバポレータ
ー）により蒸発させ、触媒床温度８００゛Ｃ・・として
蒸発したメタノール蒸気を触媒床に導入し・た。触媒床
通過後のメタノール分解率を水素（Ｈ２）濃度により測
定した。理論的にはＴ（１１７１１度、−酸化炭素（０
０）７ｍ！１度３８．８％となる（ ０Ｈ８０Ｈ→２Ｈ
２＋ＯＯ）。Durability conditions Catalyst amount 2 〇- Catalyst bed depletion 40.0''C Space velocity W 2000 Hr-1 Durability time 400 Hr Methanol used Evaluation of the activity of industrial methanol catalyst Industrial methanol (100%) was added to the evaporator ( The vaporized methanol vapor was introduced into the catalyst bed at a catalyst bed temperature of 800°C.The methanol decomposition rate after passing through the catalyst bed was measured by the hydrogen (H2) concentration.Theoretically, T (11711 degrees, - carbon oxide (0
0) 7m! 1 degree becomes 38.8% (0H80H→2H
2+OO).
Ｈ２濃度測定はガスクロマトグラフを用いた。また測定
時の触媒量は２（］耐、空間速度は２１００Ｈｒ”であ
る。A gas chromatograph was used to measure the H2 concentration. Further, the amount of catalyst at the time of measurement was 2 (2) hours, and the space velocity was 2100 hours.
第１表より本発明のメタノール改質用触媒Ａは比較例の
触媒Ｂ〜Ｄに対し、また触媒Ｅは触媒Ｆに対し明らかに
耐久後の性能がそれぞれ高いことがわかる。From Table 1, it can be seen that catalyst A for methanol reforming of the present invention has clearly higher performance after durability than catalysts B to D of comparative examples, and catalyst E has clearly higher performance than catalyst F.
試験例３
（イ）実施例１の方法に準じ、付着セリウム量を０．０
０５ 、０．１ 、０．５ 、１．０ 、２．０ 、５
．０ 、１０．０゜１５．０ 、２０．１１重量％に変
化させたサンプルを作り、
（ロ）実施例１の方法に準じ、付着白金量をｏ、０．０
５＋１）、１ 、０，２ 、０．４ 、０．ｆｌ 、
１，０ 、２．０ 、５．０重量％に変化させたサンプ
ルを作り、
（ハ）更に実施例２の方法に準じ、付着パラジウム量を
上記白金量と同様に変化させたサンプルを作り、
各サンプルを試験例２と同様に耐久評価した。Test Example 3 (a) According to the method of Example 1, the amount of cerium deposited was 0.0.
05, 0.1, 0.5, 1.0, 2.0, 5
．． 0, 10.0°, 15.0°, 20.11% by weight, and (b) Following the method of Example 1, the amount of deposited platinum was changed to o, 0.0%.
5+1), 1, 0,2, 0.4, 0. fl,
(c) Furthermore, according to the method of Example 2, samples were prepared in which the amount of deposited palladium was changed in the same manner as the amount of platinum, Each sample was evaluated for durability in the same manner as in Test Example 2.
得た結果をそれぞれ第５図および第６図に示す。・これ
等の図面よりセリウム置は０．１〜１０重量％、白金量
は０．１〜１．０重量％、パラジウム量は２．０〜１．
０重世％が好ましいことがわかる。The obtained results are shown in FIG. 5 and FIG. 6, respectively. - From these drawings, the amount of cerium is 0.1 to 10% by weight, the amount of platinum is 0.1 to 1.0% by weight, and the amount of palladium is 2.0 to 1.0% by weight.
It can be seen that 0 times % is preferable.
（発明の効果）
以上説明してきたように、この発明のメタノール改質用
触媒は、活性アルミナを主成分とする無・機酸化物に、
白金およびパラジウムの内の少くとも１種の触媒金属と
セリウムの４価の酸化物が大部分であるセリウムの酸化
物を担持させた構成としたことにより耐久後の性能が極
めて向上したという効果が得られた。(Effects of the Invention) As explained above, the methanol reforming catalyst of the present invention has an inorganic oxide containing activated alumina as a main component.
By adopting a structure in which at least one catalyst metal selected from platinum and palladium and cerium oxides, most of which are tetravalent oxides of cerium, are supported, the performance after durability has been significantly improved. Obtained.
第１〜４図はそれぞれ触媒Ａ〜ＤのＸＩＩＩ光電子分光
によるセリウムの束縛エネルギーの変化を示す曲線図、
第５図はセリウム付着量と耐久後の水素濃度との関係を
示す曲線図、
第６図は白金、パラジウム各付着量と耐久後の水素濃度
との関係を示す曲線図、
第７図は３価のセリウムと４価のセリウムの比よと水素
濃度との関係を示す曲線図である。
？１５ ａ） ＃５’ ＃ ８９５ 婢Ｗ ｆｌｌｌ
９１５ （ｎｌｌ東縛工子ｌレギー（ｅＶン
汀θ１１０ ａｓ ＃ ｔｓｓ ｑａａ ｗ ｑｔａ
ｑｔ５ 箸１７５１１１０１１１５ ｍ） １１９！；
蝮９０５９１０９１５９２０乗１時１ネルギ’−（ｅ
Ｖ）
＃５ ｆｍ ８５ ＃ ＩＫ ９ｏｏ ９ｔＭ ｍ ９
ｔｔ （ｍ第５図
ビリクＡｌＦ（ｆ；！ｉ月−Ｉ）（タ量幻第６図
第７図
Ｃ５−：ツ子数北Figures 1 to 4 are curve diagrams showing changes in the binding energy of cerium by XIII photoelectron spectroscopy of catalysts A to D, respectively. Figure 5 is a curve diagram showing the relationship between the amount of cerium deposited and the hydrogen concentration after durability. The figure is a curve diagram showing the relationship between the amount of platinum and palladium deposited and the hydrogen concentration after durability. Figure 7 is a curve diagram showing the relationship between the ratio of trivalent cerium and tetravalent cerium and hydrogen concentration. . ? 15 a) #5'#895 婢W flll
915 (nll Tobakuko l leggi (eVn ti θ110 as # tss qaa w qta
qt5 chopsticks 17511101115 m) 119! ;
Viper905910915920 power 1:1 energy'-(e
V) #5 fm 85 #IK 9oo 9tM m 9
tt (m Fig. 5 Birik AlF (f;!i month-I) (Ta quantity illusion Fig. 6 Fig. 7 C5-: Tsuko number north
Claims (1)
酸化物を付着させた担体に、白金およびパラジウムの内
の少くとも１種が担持されたメタノール改質用触媒であ
つて、セリウム酸化物が４価のセリウムの酸化物が大部
分であることを特徴とするメタノール改質用触媒。1. A methanol reforming catalyst in which at least one of platinum and palladium is supported on a carrier in which cerium oxide is attached to an inorganic oxide mainly composed of activated alumina, and the cerium oxide is A methanol reforming catalyst characterized in that most of the content is an oxide of tetravalent cerium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16874984A JPS6150639A (en) | 1984-08-14 | 1984-08-14 | Methanol reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16874984A JPS6150639A (en) | 1984-08-14 | 1984-08-14 | Methanol reforming catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6150639A true JPS6150639A (en) | 1986-03-12 |
Family
ID=15873709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16874984A Pending JPS6150639A (en) | 1984-08-14 | 1984-08-14 | Methanol reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6150639A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014175097A1 (en) * | 2013-04-25 | 2014-10-30 | 日産自動車株式会社 | Catalyst, method for producing same, and electrode catalyst layer using said catalyst |
| WO2014175098A1 (en) * | 2013-04-25 | 2014-10-30 | 日産自動車株式会社 | Catalyst, electrode catalyst layer using said catalyst, membrane electrode assembly, and fuel cell |
| US10367218B2 (en) | 2014-10-29 | 2019-07-30 | Nissan Motor Co., Ltd. | Electrode catalyst layer for fuel cell, method for producing the same, and membrane electrode assembly and fuel cell using the catalyst layer |
-
1984
- 1984-08-14 JP JP16874984A patent/JPS6150639A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014175097A1 (en) * | 2013-04-25 | 2014-10-30 | 日産自動車株式会社 | Catalyst, method for producing same, and electrode catalyst layer using said catalyst |
| WO2014175098A1 (en) * | 2013-04-25 | 2014-10-30 | 日産自動車株式会社 | Catalyst, electrode catalyst layer using said catalyst, membrane electrode assembly, and fuel cell |
| JPWO2014175098A1 (en) * | 2013-04-25 | 2017-02-23 | 日産自動車株式会社 | ELECTRODE CATALYST FOR FUEL CELL AND ELECTRODE CATALYST LAYER, MEMBRANE ELECTRODE ASSEMBLY AND FUEL CELL |
| US10535881B2 (en) | 2013-04-25 | 2020-01-14 | Nissan Motor Co., Ltd. | Catalyst and electrode catalyst layer, membrane electrode assembly, and fuel cell using the catalyst |
| US10573901B2 (en) | 2013-04-25 | 2020-02-25 | Tanaka Kikinzoku Kogyo K.K. | Catalyst and manufacturing method thereof, and electrode catalyst layer using the catalyst |
| US11031604B2 (en) | 2013-04-25 | 2021-06-08 | Nissan Motor Co., Ltd. | Catalyst and electrode catalyst layer, membrane electrode assembly, and fuel cell using the catalyst |
| US10367218B2 (en) | 2014-10-29 | 2019-07-30 | Nissan Motor Co., Ltd. | Electrode catalyst layer for fuel cell, method for producing the same, and membrane electrode assembly and fuel cell using the catalyst layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gonzalez et al. | A comparative study of the water gas shift reaction over platinum catalysts supported on CeO2, TiO2 and Ce-modified TiO2 | |
| KR100460249B1 (en) | A Process for the Oxidation of Ammonia | |
| Kayo et al. | The effect of preparation method on the acidic and catalytic properties of iron oxide | |
| Ozaki | Development of alkali-promoted ruthenium as a novel catalyst for ammonia synthesis | |
| US4331565A (en) | Method for forming high surface area catalyst carrier and catalyst using same | |
| Pernicone et al. | Wustite as a new precursor of industrial ammonia synthesis catalysts | |
| US3928238A (en) | Exhaust gas purifying catalyst and process of making and using same | |
| JP3329839B2 (en) | Catalyst for steam reforming of hydrocarbons | |
| US4511673A (en) | Catalyst for reforming of methanol and process of preparing same | |
| Johnson Jr et al. | The nature and effects of platinum in perovskite catalysts | |
| Le et al. | Synergy effects between bismuth molybdate catalyst phases (Bi/Mo from 0.57 to 2) for the selective oxidation of propylene to arcrolein | |
| Plyusnin et al. | Synthesis of bimetallic AuPt/CeO 2 catalysts and their comparative study in CO oxidation under different reaction conditions | |
| CN108160105B (en) | Molecular sieve catalyst for methane selective catalytic reduction and synthesis method thereof | |
| JPS6150639A (en) | Methanol reforming catalyst | |
| Moens et al. | Enhancement of total oxidation of isobutene on bismuth-promoted tin oxide catalysts | |
| JPS5929633B2 (en) | Low-temperature steam reforming method for hydrocarbons | |
| CN111054326A (en) | Supported catalyst, preparation method thereof and application of supported catalyst in catalyzing synthesis of indole from ethylene glycol and aniline | |
| Mărginean et al. | Metal/oxide support effects in the H2 H2O deuterium exchange reaction catalyzed by nickel | |
| US4029602A (en) | Catalyst system for catalytic heaters | |
| Wachowski | The activity of LaMeO3 oxides obtained by various methods for the catalytic oxidation of CO and 1-butene | |
| Ganguly | Catalytic Properties of Transition Metal Oxide Perovskite | |
| Luu et al. | The role of carriers in properties and performance of Pt-CuO nanocatalysts in low temperature oxidation of CO and p-xylene | |
| UA72543C2 (en) | Combination comprising lead compounds upstream of the copper-containing catalyst, and method for carrying out the catalytic reaction using the catalyst | |
| Yoon et al. | Oxidative coupling of methane over sodium-salt-promoted zirconia catalysts prepared by the mixed solution method | |
| JPS6142330A (en) | Methanol reforming catalyst |