JPS6161637A - Methanol reforming catalyst - Google Patents
Methanol reforming catalystInfo
- Publication number
- JPS6161637A JPS6161637A JP59183632A JP18363284A JPS6161637A JP S6161637 A JPS6161637 A JP S6161637A JP 59183632 A JP59183632 A JP 59183632A JP 18363284 A JP18363284 A JP 18363284A JP S6161637 A JPS6161637 A JP S6161637A
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- JP
- Japan
- Prior art keywords
- oxide
- nickel
- carrier
- catalyst
- copper
- 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.)
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Links
Abstract
Description
【発明の詳細な説明】
く産業上のぷり用分野〉
不発明にメタノール改質用触媒に関するものである。更
に詳しく扛、メタノール又はメタノールと水の混合液會
原料として水素を含有するガスを製造する方法において
、晶活性、高選択性、長寿命のメタノール改質用触８奮
提供するものである。[Detailed Description of the Invention] Industrial Purification Field The present invention relates to a methanol reforming catalyst. More specifically, the present invention provides a catalyst for methanol reforming with crystal activity, high selectivity, and long life in a method for producing a gas containing hydrogen as a raw material from methanol or a mixture of methanol and water.
現在１発電用ボイラ、内燃機関などに用いらｎる液体燃
料や気体燃料及び還元ガス製造用原料には原油及びそれ
から精製された石油類が使用されているが、最近の石油
価格の高騰のため燃料の多様１しが指向されて、原油以
外の化石燃料７）ｈら合成さ几るメタノールがこれら燃
料及び還元ガス製造用原料として注目されている。Currently, crude oil and petroleum products refined from it are used as raw materials for producing liquid fuel, gaseous fuel, and reducing gas used in power generation boilers, internal combustion engines, etc., but due to the recent rise in oil prices, As fuels become increasingly diverse, methanol, which is synthesized from fossil fuels other than crude oil, is attracting attention as a raw material for producing these fuels and reducing gases.
また、メタノールはナフサエ９はるかに低温で水素、−
酸化炭素！−含むガスに、さらには水を共存させること
にＬｖ水累言肩量の高いガスに改質さｎるので上記改質
反応の熱源として、廃熱の利用が可能であるとい９優位
性全もっている。この工うな改質反応框次の（１）、
＋２）式のとおりである。Also, methanol is hydrogen at a much lower temperature than naphtha9, -
Carbon oxide! -By allowing water to coexist with the contained gas, it is reformed into a gas with a high level of water content, so it is possible to use waste heat as a heat source for the above reforming reaction.9 Advantages: I have it. This modification reaction frame is as follows (1):
+2) is as shown in the formula.
０Ｈ３０Ｈ４００＋２Ｈ，ΔＨ２５℃＝ ２１．７ Ｋ
ｃ ａｔ／ｒｎｏｔ・・・ （１ン
ＯＨ３０Ｈ＋Ｈ２Ｏ→Ｃ０２＋ ５ Ｈ２ΔＨ２５℃＝
１１． ａ ｘｃａｔ７ｍｏｔ・・・（２）
この反応で生成した改質ガスは、改質反応の吸隔世（Δ
■）相当分だけ改質ガスの発熱量が増加するという利点
と、さらにこの生成した改質ガスに冒オクタン価で高出
力設計の内燃機関に適用すると圧縮沈金あげて熱効率全
改善することや、メタノール燃焼時のアルデヒド頌など
の排出もなく、クリーン燃焼が可能などの利点があり、
自動車用さらには発電用無公賓燃料としての利用が可能
である。0H30H400+2H, ΔH25℃= 21.7K
c at/rnot... (1 OH30H+H2O→C02+ 5 H2ΔH25℃=
11. a xcat7mot...(2) The reformed gas generated in this reaction is
■) The advantage is that the calorific value of the reformed gas increases by a corresponding amount, and when applied to an internal combustion engine with a high-output design due to the high octane value of the generated reformed gas, the thermal efficiency is completely improved by increasing the compression precipitate, and methanol It has the advantage of being able to burn cleanly without emitting aldehydes or other substances during combustion.
It can be used for automobiles and even as a non-official fuel for power generation.
さらに上記反応（１）、 （２）にエフ生成した改質ガ
ス〃）ら水素全分離し、この水素を燃料電池発電用燃料
として、又石油鞘製工業における各Ｎ有機化付物の水素
化反応などの水素源として利用できる。Furthermore, hydrogen is completely separated from the reformed gas produced in reactions (1) and (2) above, and this hydrogen is used as a fuel for fuel cell power generation, and for hydrogenation of various N organic adducts in the oil sheath manufacturing industry. Can be used as a hydrogen source for reactions, etc.
このように、メタノール改質用触媒は、燃料あるいに水
素源としてのメタノール改質反応一般に広く利用できる
。Thus, the methanol reforming catalyst can be widely used in general methanol reforming reactions as a fuel or hydrogen source.
く従来の技術〉
従来、メタノール全分解する触媒としては、アルミナな
どの担体に白金などの白金属元素又は銅、ニッケル、ク
ロム、亜鉛などの卑金浅元素及びその酸化物など全担持
した触媒、亜鉛、クロムさらには銅を＠有するメタノー
ル合成用触媒（分解反応にも使用できる）などが提案さ
れており、まｔメタノールと水との反応にエフ水素含有
量の高いガスを得る１こめの触媒としては、銅−クロム
−マンガン酸化物（特公昭５４−１１２７４号公報）、
又に銅−亜鉛酸化物。Conventional technology> Conventionally, catalysts for total decomposition of methanol include catalysts that fully support platinum metal elements such as platinum or base metal elements such as copper, nickel, chromium, and zinc and their oxides on carriers such as alumina; Catalysts for methanol synthesis containing zinc, chromium, and even copper (which can also be used for decomposition reactions) have been proposed, and they are also a single catalyst for producing gas with a high hydrogen content in the reaction between methanol and water. Examples include copper-chromium-manganese oxide (Japanese Patent Publication No. 54-11274),
Also copper-zinc oxide.
亜鉛−クロム酸化物、銅−亜鉛−クロム酸化物（特開昭
５７−５６３０２号公報）などの水素化・脱水素用触媒
、−酸化炭素転化用触媒、メタノール合成用触媒等が提
案されている。Hydrogenation/dehydrogenation catalysts such as zinc-chromium oxide and copper-zinc-chromium oxide (JP-A-57-56302), -carbon oxide conversion catalysts, methanol synthesis catalysts, etc. have been proposed. .
〈発明が解決しょうとする問題点〉
し〃為し、上記の従来公知の触媒は、低温活性に乏しく
、また副反応が起こりや丁く、耐熱性に乏しいため寿命
が短いという問題点がある。<Problems to be Solved by the Invention> However, the above-mentioned conventionally known catalysts have the problems of poor low-temperature activity, side reactions that easily occur, and poor heat resistance, resulting in a short life. .
本発明の目的に上記の如き問題点を解決し、高活性、高
選択性、かつ長寿命のメタノール改質用触媒全提供する
にある。The object of the present invention is to solve the above-mentioned problems and provide a catalyst for methanol reforming that has high activity, high selectivity, and a long life.
く問題点全解決するための手段〉 本発明者らに、上記の問題点全解決すべく。Means to solve all problems〉 The present inventors aim to solve all of the above problems.
鋭意実験検討′にＭねｔ結果、銅、クロムの酸化物全含
有する担体に、ニッケルの酸化物さらに塩基性酸化物を
担持しｔ触媒がメタノール改質反応に対し、高活性でか
つ選択性に非常に優れており、さらにはカーボン析出が
ないため長寿命でφることを見出し、本発明に至った。Extensive experimental studies have shown that the catalyst has high activity and selectivity for the methanol reforming reaction by supporting nickel oxide and basic oxide on a carrier containing all copper and chromium oxides. The inventors have discovered that this material has excellent properties, and furthermore, has a long life and φ due to the absence of carbon precipitation, leading to the present invention.
すなわち本発明は、銅、クロムの酸化物で官有する担体
又μマンガン、バリウムからなる群の一種以上の酸化物
と銅、クロムの酸化物全含有する担体にニッケルの酸化
物又はニッケルの酸化物と塩基性酸化物を担持したこと
を特徴とするメタノール改質用触媒を提供する。That is, the present invention provides a carrier containing an oxide of copper or chromium, or a carrier containing all of the oxides of copper and chromium and one or more oxides of the group consisting of μ manganese and barium, and a carrier containing an oxide of nickel or nickel. Provided is a methanol reforming catalyst characterized by supporting a basic oxide and a basic oxide.
メタノール改質用触媒として高活性か要求さ詐ることは
当然ながら選択性が重要視されるのは、下記（３）〜（
５）式
％式％（３）
などの副反応にＬり、ジメチルエーテル、メタン、炭酸
ガスなどが生成すると、分離操作に工って水素のみ、−
酸化炭素のみ又はこれらの混合ガスを製品として得↓う
とする場合に、分離工程が複雑となり製造コストの上昇
につながるからである。It goes without saying that high activity is required as a methanol reforming catalyst, but selectivity is important in the following (3) to (
5) When dimethyl ether, methane, carbon dioxide gas, etc. are produced due to side reactions such as formula % formula % (3), the separation operation is carried out to remove only hydrogen, -
This is because when trying to obtain only carbon oxide or a mixed gas of these as a product, the separation process becomes complicated, leading to an increase in manufacturing costs.
さらににメタノールの分解反応（ＯＨ３０Ｈ４００＋２
Ｈ２）又は水蒸気改質反応（ＯＨ３０Ｈ−）−Ｈ２０→
５ Ｈ２＋ＣＯｚ ） ｋ利用して燃料の発熱量全増加
させＪ：りとする場合、上記（３）〜（５）の副反応は
発熱反応であるため、副反応の反応熱分だけ、発熱量が
低下するといり問題があるからである。Furthermore, methanol decomposition reaction (OH30H400+2
H2) or steam reforming reaction (OH30H-)-H20→
5 H2+COz ) k is used to increase the total calorific value of the fuel J: Since the side reactions in (3) to (5) above are exothermic reactions, the calorific value increases by the reaction heat of the side reactions. This is because there is a problem if it decreases.
本発明のメタノール改質用触媒は、銅、クロムの酸化物
を含有する担体又にマンガン、バリウムからなる群の一
種以上の酸化物と銅、クロムの酸化物全含有する担体に
、ニッケルの酸化物又はニッケルの酸化物と塩基性酸化
物を担持したことｔ特徴とするものである。The methanol reforming catalyst of the present invention has a carrier containing oxides of copper and chromium, or a carrier containing all oxides of copper and chromium and one or more oxides of the group consisting of manganese and barium. It is characterized by supporting an oxide of nickel or nickel and a basic oxide.
本発明の触媒における担体の組成に、銅の酸化物及びク
ロムの酸化物の含有量がそ：ｎ−！ ｔＬｌ。In the composition of the carrier in the catalyst of the present invention, the content of copper oxide and chromium oxide is n-! tLl.
Ｎ量チ以上のものが好ましく、さらにマンガンの酸化物
及び／又はバリウムの酸化物老Ｃ１，１素置弔以上含有
するものも好ましい。特に好ましくは、銅の酸化物の割
合が２０〜９０重量％、クロムの酸化物の割合が１０〜
８０重量％、マ／ガンの酸化物及び／又はバリウムの酸
化物の割合が１５〜１０重量％の範囲である。It is preferable that the N content is at least 100%, and it is also preferable that the N content is at least 1,1% of manganese oxide and/or barium oxide. Particularly preferably, the proportion of copper oxide is 20 to 90% by weight, and the proportion of chromium oxide is 10 to 90% by weight.
80% by weight, the proportion of oxide of magenta/ganese and/or oxide of barium is in the range of 15-10% by weight.
また、これら担体に担持するニッケルの酸化物の割＠は
ａ１重量％以上が好ましく、塩基性酸化物の割合にα０
１重量％以上が好ましく、特に好ましくは、ニッケルの
酸化物の割合が０５〜１０重量％、塩基性酸化物の割合
がＩＩＬｏ５〜５重量係の範囲である。Further, the proportion of nickel oxide supported on these carriers is preferably a1% by weight or more, and the proportion of basic oxide is α0
It is preferably 1% by weight or more, and particularly preferably, the proportion of nickel oxide is in the range of 05 to 10% by weight, and the proportion of basic oxide is in the range of IILo5 to 5% by weight.
銅、クロムの酸化物さらにはマンガン、バリウムからな
る群の一種以上の酸化物′に含有する担体全調製する具
体的方法としては、例えば下記の方法がある。As a specific method for preparing the entire carrier containing oxides of copper and chromium, as well as one or more oxides of the group consisting of manganese and barium, there is, for example, the following method.
■粉末あるいはペースト状の銅の酸化物又は水酸化物及
びクロムの酸化物又は水酸化物の混合物に適量の水を加
え、工く混合しｔ後、乾燥・焼成する。上記混合物にマ
ンガン及び／又はバリウムの酸化物又は水酸化物全添加
しても良い。(2) Add an appropriate amount of water to a powder or paste mixture of copper oxide or hydroxide and chromium oxide or hydroxide, mix well, and then dry and bake. All of the oxides or hydroxides of manganese and/or barium may be added to the above mixture.
■ 硝酸鋼など銅の化合物及び硝酸クロムなどクロムの
化合物を含有する水溶液に、炭酸ソーダ水溶液などのア
ルカリ全顎え良く混合して沈殿を作った後、洗浄・乾燥
・焼成する。■ An aqueous solution containing copper compounds such as steel nitrate and chromium compounds such as chromium nitrate is thoroughly mixed with an alkali such as an aqueous solution of soda carbonate to form a precipitate, which is then washed, dried, and fired.
上記混合水溶液にマンガン及び／又はバリウムの化合物
の水溶液？添加しても艮い。An aqueous solution of manganese and/or barium compounds in the above mixed aqueous solution? It doesn't matter if you add it.
■ 硝酸銅、硫酸銅など銅の化合物水溶液に重クロム酸
ソーダとアンモニア水の混合水溶液を加え良く混合して
沈殿を生成させた後、洗浄・乾燥・焼成する。上記沈殿
調製時に硝酸マ／ガ／、硫酸マンガンなどマンガンの化
合物及び／又は硝酸バリウム、クロム酸バリウムなどバ
リウムの化合−物を添加しても良い。■ Add a mixed aqueous solution of sodium dichromate and aqueous ammonia to an aqueous solution of copper compounds such as copper nitrate and copper sulfate, mix well to form a precipitate, and then wash, dry, and bake. At the time of preparing the above-mentioned precipitation, manganese compounds such as nitric acid, manganese sulfate, and/or barium compounds such as barium nitrate and barium chromate may be added.
以上の■〜■の方法では粉末状の触媒が得られるが、バ
インダーを添加して底型する方法も用いられる。この場
合、バインダーとしては、グラファイト、ポリビニルア
ルコール、ホウ酸、ケイソウ土などが用いられる。Although a powdered catalyst can be obtained by the above methods (1) to (2), a method in which a binder is added and molded into a bottom mold is also used. In this case, graphite, polyvinyl alcohol, boric acid, diatomaceous earth, etc. are used as the binder.
以上はあくまでも例示であって２本発明？特に限定する
ものではない。The above is just an example, and are there two inventions? It is not particularly limited.
次にこの工うにして得らＩｆ”Ｌ７を担体にニッケルの
酸化物又ｈニッケルの酸化物と塩基性酸化物全担持する
方法は、従来から用いられている方法で良く、例えばニ
ッケルの酸化物全担持する場合、硝酸ニッケルなどニッ
ケル化合物の水溶液に担体を浸漬後、焼成することによ
り容易に得られる。Next, the method of supporting If'L7 obtained in this way on a carrier with nickel oxide or all of the nickel oxide and basic oxide may be any conventional method, such as nickel oxide. When the entire substance is supported, it can be easily obtained by immersing the carrier in an aqueous solution of a nickel compound such as nickel nitrate and then firing it.
ここで塩基性酸化物とはアルカリ金属元素、アルカリ土
類金属元素、希土類元素、 ■ｂ族元累からなる群の一
種以上の元素の酸化物であり。Here, the basic oxide is an oxide of one or more elements from the group consisting of alkali metal elements, alkaline earth metal elements, rare earth elements, and group (1) b group elements.
塩基性酸化物を担持する場合、上記元素の化合物例えば
硝酸塩水浴液に浸漬後暁成することにエフ容易に得られ
る。When a basic oxide is supported, a compound of the above elements, for example, can be easily obtained by immersion in a nitrate water bath solution and subsequent formation.
ニッケルの酸化物と塩基性酸化物全担持する場合、ニッ
ケルの酸化物？あらかじめ担持してから塩基性酸化物を
担持する方法、逆の順序に担持する方法、又は同時に担
持する方法が用いられる。Nickel oxide and basic oxide When fully supported, is it nickel oxide? A method is used in which the basic oxide is supported in advance and then the basic oxide is supported, a method in which the basic oxide is supported in the reverse order, or a method in which the basic oxide is supported at the same time.
なお本発明でいうメタノール又はメタノールと水の混合
液とＩ’ｊ、 Ｈ２０／ＣＨ３０Ｈのモル比が０〜１
００の範囲であり１本発明の触奴ケ用いるメタノール改
質反応の反応条件としては、圧カニ０〜５０ ｋｇ７ｃ
ｍ２、温度＝１５０〜６００℃の範囲が好ましい。In the present invention, methanol or a mixture of methanol and water and I'j, the molar ratio of H20/CH30H is 0 to 1.
The reaction conditions for the methanol reforming reaction using the catalyst of the present invention are as follows: pressure crab 0-50 kg7c
m2 and temperature are preferably in the range of 150 to 600°C.
〈実施例〉
以下実施例にエフ本発明のメタノール改質用触媒を具体
的に説明する。<Example> The methanol reforming catalyst of the present invention will be specifically explained in the following example.
実施例１
Ａｄｋｉｎｓ法 と呼ばれる調製法、即ち硝酸銅の水溶
液に重クロム酸ソーダとアンモニア水との混合水溶ｗｒ
加え、工〈混合して生成させｔ沈殿Ｏｕ（ＮＨ４）ＯＨ
Ｃｒ２０４’ｊｚ洗浄、乾繰後５５０℃で焼成すること
に工９０ｕＯ・Ｃ３ｕ Ｃｒ２０４の組成の担体１全調
製した。Example 1 A preparation method called the Adkins method, that is, a mixed aqueous solution of sodium dichromate and aqueous ammonia in an aqueous solution of copper nitrate.
Add and mix to form precipitate O(NH4)OH
A carrier 1 having a composition of 90 uO.C3u Cr204 was prepared by cleaning and drying the carrier and firing it at 550°C.
上記担体１を調製する時にさらに硝酸マンガン全添加し
て調製した担体２（（！ｕｏ：０ｒ２０３ ：ＭｎＯ２
の−Ｆ−ル比＝１０＝１０：１）、硝酸バリウム全添加
して調製し窺担体５ （Ｃ！ｕｏ：０ｒ２０３ ：Ｂａ
Ｏのモル比＝１０：１０：１）、また硫酸マンガン及び
クロム酸バリウムを添加して調製した担体４ （ＣｕＯ
：（！ｒ２０３ ：ＭｎＯ２：ＢａＯのモル比＝１０
： １０ ： ０．５ ：α５）全担体１と同じ方法で
調製した、
以上の１９にして得られた担体１〜４の各々を硝酸ニッ
ケルの水溶液に浸渋し、乾燥後５００℃で５時間焼成し
て１．０重量％の酸化ニッケルを担持した触媒１〜４ｔ
、また硝酸ニッケル及び硝酸カリウムの水溶液に浸漬し
乾燥後５００℃で５時間焼成して１．０重量％の酸化ニ
ッケル、１．０重量％の酸化カリウム會担持した触媒５
〜ｓｒ！Ｊ！ｌ！！した。Carrier 2 ((!uo:0r203 :MnO2
-F-ru ratio = 10 = 10:1), the carrier was prepared by adding all barium nitrate (C!uo:0r203:Ba
Support 4 prepared by adding manganese sulfate and barium chromate (CuO
:(!r203 :MnO2:BaO molar ratio=10
: 10 : 0.5 : α5) Each of the carriers 1 to 4 obtained in step 19 above, prepared in the same manner as all carriers 1, was immersed in an aqueous solution of nickel nitrate, dried, and then heated at 500°C for 5 hours. 1 to 4 tons of calcined catalyst supporting 1.0% by weight of nickel oxide
, Catalyst 5 was immersed in an aqueous solution of nickel nitrate and potassium nitrate, dried, and then calcined at 500°C for 5 hours to support 1.0% by weight of nickel oxide and 1.0% by weight of potassium oxide.
~sr! J! l! ! did.
また上記担体１〜４の各々を硝酸カリウムの水溶液に浸
漬し、乾燥後５００℃で３時間焼成して１．Ｏｉ量うの
酸化カリウムを担持した担体９〜１２を、ｔた硝酸バリ
ウムの水溶液に浸漬し、乾燥ｖｋｓｏｏ℃で３時間焼成
してα５重重量％酸化バリウムを担持した担体１３〜１
６ｊ？調製した。Further, each of the above-mentioned carriers 1 to 4 was immersed in an aqueous solution of potassium nitrate, dried, and then baked at 500°C for 3 hours. Carriers 9 to 12 carrying Oi weight potassium oxide were immersed in an aqueous solution of barium nitrate and baked at dry temperature for 3 hours to obtain carriers 13 to 1 carrying α5 wt % barium oxide.
6j? Prepared.
以上の工うにして得らｎた担体？〜１６の各々全硝酸ニ
ッケルの水ｆｇ液に浸漬し、乾燥後５ｏｏｃで５時間焼
成してｚＯ重量％の段化ニッケルを担持した触媒９〜１
６ｇ調製した。Is the carrier obtained through the above process? Catalysts 9 to 1, each of which was immersed in a water fg solution of total nickel nitrate, dried, and calcined at 5 ooc for 5 hours to support zO weight % of staged nickel.
6g was prepared.
上記触媒１〜１６欠２００℃で１０時間２％水素気流中
で還元し、メタノール９９．９％以上を原料に、常圧、
ＬＨＩ３Ｖ（液空間速度） ： ２ｈ−’反応温度５０
０℃で活性評価試験を行った結果全表１に示した。The above catalysts 1 to 16 were reduced at 200°C for 10 hours in a 2% hydrogen stream, using methanol 99.9% or more as a raw material, at normal pressure,
LHI3V (liquid hourly space velocity): 2h-'reaction temperature 50
The results of the activity evaluation test conducted at 0°C are shown in Table 1.
実施例２
実施例１で調製した触媒１〜１６ｉ２００℃ −で１０
時間２％水累気流中で還元し、メタノ−／Ｌｌ ト水＋
７） ａ合？ｌＩ （Ｈ２０１０Ｈｉ ＯＨ＝ １．５
） ｆ原料に圧力１５ Ｋｇ／ｃｍ２Ｇ、ＬＨ８Ｖ：
１ｈ−１、反応温度２８０℃で活性評価試験を行った
結果全表２に示した。Example 2 Catalysts 1 to 16 prepared in Example 1 at 200°C - 10
Time 2% water reduced in cumulative air stream, methanol/Ll water+
7) A match? lI (H2010Hi OH= 1.5
) Pressure on f raw material: 15 Kg/cm2G, LH8V:
An activity evaluation test was conducted at a reaction temperature of 280° C. for 1 h-1, and the results are shown in Table 2.
表 ２
実施例３
実施例１でＦＡｉＡシｙｔ触媒６ （Ｎｉｐ、 Ｋ２Ｏ
１０１１０・Ｃｒ２Ｏ３・ＭｎＯ２） ｆ対象に実施例
１と同様に還元し、た後、表３のように反応条件’ｋｆ
えて活性評価試験全行つ１こ。試験結果も表３にまとめ
て示す。Table 2 Example 3 In Example 1, FAiA catalyst 6 (Nip, K2O
10110・Cr2O3・MnO2) The f target was reduced in the same manner as in Example 1, and then the reaction conditions 'kf
All activity evaluation tests were conducted once. The test results are also summarized in Table 3.
上記条件２，１１，１４．１７の反応条件で２０００時
間の連続試験を行つｔが、活性低下はみられなかった。A continuous test was conducted for 2000 hours under the reaction conditions 2, 11, 14, and 17 above, but no decrease in activity was observed.
従来の触媒の寿命が１０００時間以下であったに比べ１
本発明の触媒寿命は倍以上長いことがわかる。Compared to the lifespan of conventional catalysts, which was less than 1,000 hours,
It can be seen that the catalyst life of the present invention is more than twice as long.
実施例４
実施例１で調製し１ζ担体２を硝酸ナトリウム、硝酸去
ルシウム、硝酸マグネシウム、硝酸ランタン、硝酸セリ
ウム、硝酸亜鉛の各水溶液に夫々浸漬し乾燥後５００℃
で３時間焼成し、酸化ナトリウム、酸化カルシウム、酸
化マグネシウム、酸化ランタン、散化七すウム、酸化亜
鉛それぞれが１．０重量係担持された担体１７〜２２全
調製し友。Example 4 The 1ζ carrier 2 prepared in Example 1 was immersed in each aqueous solution of sodium nitrate, lucium nitrate, magnesium nitrate, lanthanum nitrate, cerium nitrate, and zinc nitrate, and dried at 500°C.
The carriers 17 to 22 were prepared by firing for 3 hours and carrying 1.0 weight of each of sodium oxide, calcium oxide, magnesium oxide, lanthanum oxide, heptasium oxide, and zinc oxide.
以上の工うにして得られた担体１７〜２２の各々を硝酸
ニッケルの水溶液に浸＠ｊ７、乾燥後５００℃で５時間
焼成して１１口重−ｋｔ、ｓの酸化二し
ツケルを担持した触媒１７〜２２を調製した。Each of the supports 17 to 22 obtained in the above manner was immersed in an aqueous solution of nickel nitrate @j7, dried, and then calcined at 500°C for 5 hours to support nickel oxide with a weight of 11 -kt, s. Catalysts 17-22 were prepared.
実施例１で調製した担体３會１０゛ＯＭ量部に対してホ
ウ酸５重量部、グラファイト２重量部バインダーとして
混合し、３門φ、３間高さの円筒状に成型し７Ｃ，こｆ
Ｌｔ−硝酸カリウムの水溶液に浸漬し乾燥後５００℃で
５時間焼成して１．０重量％の酸化カリウムを担持した
担体２３を得た。この担体を硝酸ニッケルの水溶液に浸
漬し、酸化ニッケル担持量Ｑ、５，１，２，５．１０重
量％−の触媒２３〜２７ｉ調製しｔ０
銅及びクロムの硝酸塩の混合水溶液に炭酸ソーダ水溶？
［−加え沈殿？調製し、乾燥後５００℃３時間焼成し、
ＯｕＯ：０ｒ２０３０重量比 ８０ ： ２０の担体２
４１ １ ５０：５０の担体２５ｔｒ
ｔｔ ２０：８０の担体２６會調製した。5 parts by weight of boric acid and 2 parts by weight of graphite were mixed as a binder with 10 OM parts of the carrier prepared in Example 1, and the mixture was molded into a cylindrical shape with a diameter of 3 holes and a height of 3 holes.
The carrier 23 was immersed in an aqueous solution of Lt-potassium nitrate, dried, and then calcined at 500° C. for 5 hours to obtain a carrier 23 supporting 1.0% by weight of potassium oxide. This carrier was immersed in an aqueous solution of nickel nitrate to prepare catalysts 23-27i with a supported amount of nickel oxide Q, 5, 1, 2, 5.10% by weight.
[-Additional precipitation? After drying and baking at 500°C for 3 hours, OuO:0r2030 weight ratio 80:20 carrier 2 was prepared.
41 1 50:50 carrier 25tr
26 carriers were prepared at tt 20:80.
こ几らの担体２４〜２６の各々を硝酸カリウムの水溶液
に浸漬し、乾燥後５００℃で３時間焼成して１．０重量
−の酸化カリウムを担持した担体２８〜３０業調製した
。Each of the carriers 24 to 26 of Kohori et al. was immersed in an aqueous solution of potassium nitrate, dried, and then calcined at 500° C. for 3 hours to prepare carriers 28 to 30 carrying 1.0 weight of potassium oxide.
以上の工うにして得ら；ｎた担体２８〜３０の各々を硝
酸ニッケルの水溶液に浸漬し、乾燥後５００℃で３時間
焼成して２，０重量％の酸化ニッケルを担持した触媒２
８〜５０デ調製し７Ｃ。Catalyst 2 obtained by the above process; each of the carriers 28 to 30 was immersed in an aqueous solution of nickel nitrate, dried and calcined at 500°C for 3 hours to support 2.0% by weight of nickel oxide.
Prepare 8 to 50 centimeters and 7C.
上記触媒１７〜５０７．（２００℃で１０時間２係水素
気流中で還元し、メタノールと水の混合液（Ｈ２ｏｌｏ
Ｈ３０Ｈのモル比＝（Ｌｌ）を原料に圧力１５ ｋｌ
ｉｌ／ｃｒｎ２Ｇ、 ＬＨ８Ｖ ＝ １ ｈ−’ 、反
応温度３００℃で活性評価試験２行った結果を表４に示
し１ζ。The above catalysts 17 to 507. (Reduced at 200°C for 10 hours in a dihydrogen stream, and a mixture of methanol and water (H2olo
Molar ratio of H30H = (Ll) as raw material, pressure 15 kl
Table 4 shows the results of activity evaluation test 2 conducted at il/crn2G, LH8V = 1 h-', and reaction temperature of 300°C.
比較例
粒径２〜４閣φのｒ−Ａｌ２Ｏ２担体ケ硝酸ニッケル水
溶液又は塩化白金酸水溶液に浸漬し、乾燥後５００℃で
３時間焼成して１０重量％の酸化ニッケルを担持した。Comparative Example An r-Al2O2 carrier having a particle size of 2 to 4 mm was immersed in an aqueous solution of nickel nitrate or an aqueous solution of chloroplatinic acid, dried, and then calcined at 500 DEG C. for 3 hours to support 10% by weight of nickel oxide.
触媒、３１．（Ｌ５重ｔ％の白金を担持した触媒３２を
比較例として調製した。Catalyst, 31. (Catalyst 32 supporting L5% by weight of platinum was prepared as a comparative example.
触媒３１ｔｌ！２００℃で１０時間２％水素気流中で還
元、また触媒３２は４５０℃で５時間２悌水累気流中で
還元し、実施例１と同じ条件で活性評価を行った結果を
表５に示した。Catalyst 31tl! The catalyst 32 was reduced at 200°C for 10 hours in a 2% hydrogen stream, and the catalyst 32 was reduced at 450°C for 5 hours in a 2% water stream, and the activity was evaluated under the same conditions as in Example 1. The results are shown in Table 5. Ta.
表 ５
表５から明らかな工すに、比較例の触媒のメタノール反
応ｙＩＧは、本発明の触媒に比べ大幅に低く、生底ガス
組成も、副反応によるものが多い。Table 5 As is clear from Table 5, the methanol reaction yIG of the catalyst of the comparative example is significantly lower than that of the catalyst of the present invention, and the raw bottom gas composition is also largely due to side reactions.
〈発明の効果〉
以上、実施例お工び比較例の結果から明らかなごとく、
本発明のメタノール改質用触媒は、メタノール又はメタ
ノールと水の混合液全原料として水素ｋｍ造する反応に
おいて、低温で高活性、高選択性、たつ長寿命の非常に
優Ａ７ｔ、触媒である。<Effects of the Invention> As is clear from the results of the Examples and Comparative Examples,
The methanol reforming catalyst of the present invention is an extremely effective A7t catalyst that has high activity, high selectivity, and long life at low temperatures in a reaction that produces hydrogen km as the total raw material for methanol or a mixture of methanol and water.
復代理人 内 １） 明 復代理人 萩 原 亮 −Sub-agent: 1) Akira Sub-agent Ryo Hagi Hara -
Claims (1)
ウムからなる群の一種以上の酸化物と銅、クロムの酸化
物を含有する担体にニッケルの酸化物又はニッケルの酸
化物と塩基性酸化物を担持したことを特徴とするメタノ
ール改質用触媒。Adding a nickel oxide or a nickel oxide and a basic oxide to a carrier containing an oxide of copper or chromium or one or more oxides of the group consisting of manganese or barium and a carrier containing an oxide of copper or chromium. A methanol reforming catalyst characterized by being supported.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59183632A JPS6161637A (en) | 1984-09-04 | 1984-09-04 | Methanol reforming catalyst |
| AU46959/85A AU4695985A (en) | 1984-09-04 | 1985-09-02 | Process for reforming methanol |
| DE19853531757 DE3531757A1 (en) | 1984-09-04 | 1985-09-03 | METHOD FOR REFORMING METHANOL |
| US07/011,371 US4780300A (en) | 1984-09-04 | 1987-02-04 | Process for reforming methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59183632A JPS6161637A (en) | 1984-09-04 | 1984-09-04 | Methanol reforming catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6161637A true JPS6161637A (en) | 1986-03-29 |
| JPH0425064B2 JPH0425064B2 (en) | 1992-04-28 |
Family
ID=16139167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59183632A Granted JPS6161637A (en) | 1984-09-04 | 1984-09-04 | Methanol reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6161637A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07299791A (en) * | 1994-12-02 | 1995-11-14 | Teijin Seiki Co Ltd | Deceleration device for joint drive of industrial robot |
| US6072752A (en) * | 1992-04-27 | 2000-06-06 | Citizen Watch Co., Ltd. | Hand display-type electronic timepiece |
| JP2002173302A (en) * | 2000-12-04 | 2002-06-21 | Mitsubishi Gas Chem Co Inc | Method of producing gaseous mixture of carbon monoxide with hydrogen |
| WO2002078840A1 (en) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| JP2014124628A (en) * | 2012-12-27 | 2014-07-07 | Sekisui Chem Co Ltd | Catalyst for c2 oxygen compound synthesis, apparatus and method for producing c2 oxygen compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156194A (en) * | 1976-06-22 | 1977-12-26 | Nippon Soken | Catalysts for reforming methyl alchol |
| JPS5310389A (en) * | 1976-07-15 | 1978-01-30 | Nippon Soken | Catalysts for reforming methyl alchol |
| JPS5372795A (en) * | 1976-12-10 | 1978-06-28 | Nippon Soken | Ethyl alcohol reforming catalyst |
| JPS57174138A (en) * | 1981-04-21 | 1982-10-26 | Mitsubishi Heavy Ind Ltd | Catalyst for modification of methanol |
| JPS57174139A (en) * | 1981-04-21 | 1982-10-26 | Mitsubishi Heavy Ind Ltd | Catalyst for modification of methanol |
| JPS59123533A (en) * | 1982-12-29 | 1984-07-17 | Nissan Motor Co Ltd | Catalyst for reforming methanol |
-
1984
- 1984-09-04 JP JP59183632A patent/JPS6161637A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156194A (en) * | 1976-06-22 | 1977-12-26 | Nippon Soken | Catalysts for reforming methyl alchol |
| JPS5310389A (en) * | 1976-07-15 | 1978-01-30 | Nippon Soken | Catalysts for reforming methyl alchol |
| JPS5372795A (en) * | 1976-12-10 | 1978-06-28 | Nippon Soken | Ethyl alcohol reforming catalyst |
| JPS57174138A (en) * | 1981-04-21 | 1982-10-26 | Mitsubishi Heavy Ind Ltd | Catalyst for modification of methanol |
| JPS57174139A (en) * | 1981-04-21 | 1982-10-26 | Mitsubishi Heavy Ind Ltd | Catalyst for modification of methanol |
| JPS59123533A (en) * | 1982-12-29 | 1984-07-17 | Nissan Motor Co Ltd | Catalyst for reforming methanol |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6072752A (en) * | 1992-04-27 | 2000-06-06 | Citizen Watch Co., Ltd. | Hand display-type electronic timepiece |
| JPH07299791A (en) * | 1994-12-02 | 1995-11-14 | Teijin Seiki Co Ltd | Deceleration device for joint drive of industrial robot |
| JP2002173302A (en) * | 2000-12-04 | 2002-06-21 | Mitsubishi Gas Chem Co Inc | Method of producing gaseous mixture of carbon monoxide with hydrogen |
| WO2002078840A1 (en) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| US7378368B2 (en) | 2001-03-29 | 2008-05-27 | Idemitsu Kosan, Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| US7892417B2 (en) | 2001-03-29 | 2011-02-22 | Idemitsu Kosan, Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| JP2014124628A (en) * | 2012-12-27 | 2014-07-07 | Sekisui Chem Co Ltd | Catalyst for c2 oxygen compound synthesis, apparatus and method for producing c2 oxygen compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0425064B2 (en) | 1992-04-28 |
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