JPH0515778A - Methanol reforming catalyst - Google Patents
Methanol reforming catalystInfo
- Publication number
- JPH0515778A JPH0515778A JP3168005A JP16800591A JPH0515778A JP H0515778 A JPH0515778 A JP H0515778A JP 3168005 A JP3168005 A JP 3168005A JP 16800591 A JP16800591 A JP 16800591A JP H0515778 A JPH0515778 A JP H0515778A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- layer
- methanol
- porous alumina
- palladium
- 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.)
- Withdrawn
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002407 reforming Methods 0.000 title claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000007769 metal material Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000002344 surface layer Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 11
- 239000010410 layer Substances 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 abstract description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001593 boehmite Inorganic materials 0.000 abstract description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- -1 for example Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はメタノール改質用触媒に
関し、さらに詳しくはメタノール又はメタノールと水の
混合物を水素含有ガスに改質する触媒に関する。FIELD OF THE INVENTION The present invention relates to a catalyst for reforming methanol, and more particularly to a catalyst for reforming methanol or a mixture of methanol and water into a hydrogen-containing gas.
【０００２】[0002]
【従来の技術】従来のメタノールを改質する触媒として
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、亜鉛などの卑金属元素及びその酸化
物などを担持した触媒が提案されている。又、上述した
金属担持法による触媒とは別に沈殿法による調製法があ
り、この方法で調製される触媒の代表例としては、亜
鉛、クロムさらには銅を含有してなるメタノールの改質
触媒がある。2. Description of the Related Art Conventional catalysts for reforming methanol include a carrier such as alumina and a white metal element such as platinum or copper,
A catalyst supporting a base metal element such as nickel, chromium or zinc and an oxide thereof has been proposed. In addition to the above-mentioned metal-supporting catalyst, there is a precipitation method. A typical example of a catalyst prepared by this method is a methanol reforming catalyst containing zinc, chromium and copper. is there.
【０００３】[0003]
【発明が解決しようとする課題】従来、エンジン、ガス
タービンなどの排ガスの顕熱を熱源として利用し、メタ
ノール又はメタノールと水の混合物を原料として分解又
は水蒸気改質反応を行わせる場合、排ガス温度は周知の
ごとく２００℃から７００℃程度まで変化するため、幅
広い温度範囲にわたって内燃機関に搭載できる程度の少
量の触媒で改質でき、かつ例えば上記の７００℃程度の
高温下におかれていても、改質性能を劣化しない改質方
法並びに安定した触媒が必要である。Conventionally, when the sensible heat of exhaust gas from an engine, a gas turbine or the like is used as a heat source and a decomposition or steam reforming reaction is carried out using methanol or a mixture of methanol and water as a raw material, the exhaust gas temperature As is well known, since it changes from about 200 ° C to about 700 ° C, it can be reformed with a small amount of catalyst that can be mounted on an internal combustion engine over a wide temperature range, and even if it is exposed to the high temperature of about 700 ° C, for example. A reforming method that does not deteriorate the reforming performance and a stable catalyst are required.
【０００４】従来のメタノールを改質する触媒は、先に
述べた金属担持法や沈殿法によって調製される触媒が提
案されているが、これらの触媒は低温活性に乏しく、熱
的劣化を起こしやすいなど現在のところ多くの問題点を
残している。As a conventional catalyst for reforming methanol, a catalyst prepared by the above-mentioned metal supporting method or precipitation method has been proposed, but these catalysts have poor low temperature activity and are liable to be thermally deteriorated. As of now, many problems remain.
【０００５】また反応器としてはシェル・アンド・チュ
ーブ型の熱交換器型式となっており、チューブ内に触媒
を充填し、原料のメタノール蒸気又はメタノールと水の
混合蒸気は触媒との接触反応により水素含有ガスに改質
される。この改質反応は大きな吸熱反応であり、必要な
反応熱はシェル側の熱媒から供給されるが、伝熱速度が
あまり大きくないため、触媒層内の温度が反応熱により
低くなり、反応速度を大きくすることが難しいという問
題がある。The reactor is a shell-and-tube type heat exchanger type, in which a catalyst is filled in a tube, and the raw material methanol vapor or a mixed vapor of methanol and water is produced by a catalytic reaction with the catalyst. Reformed into hydrogen-containing gas. This reforming reaction is a large endothermic reaction, and the necessary reaction heat is supplied from the heat medium on the shell side, but since the heat transfer rate is not so high, the temperature inside the catalyst layer becomes lower due to the reaction heat, and the reaction rate There is a problem that it is difficult to increase.
【０００６】[0006]
【課題を解決するための手段】本発明は少なくとも１０
μｍのアルミニウムの表面層を有する金属又は合金材料
の表面上に、陽極酸化法により多孔質アルミナ皮膜を形
成させ、次いで焼成処理を施した後、該多孔質アルミナ
皮膜上に、白金及び／又はパラジウムを熱水処理により
担持させてなることを特徴とするメタノール改質用触媒
である。The present invention provides at least 10
A porous alumina film is formed on the surface of a metal or alloy material having a surface layer of aluminum having a thickness of μm by an anodic oxidation method, and then subjected to a firing treatment, and then platinum and / or palladium is formed on the porous alumina film. Is a catalyst for reforming methanol, which is carried by hot water treatment.
【０００７】そして、上記構成における金属又は合金材
料として、伝熱管そのものを使用することを好ましい態
様とするものである。The heat transfer tube itself is preferably used as the metal or alloy material in the above structure.
【０００８】以下、本発明について詳細に説明する。本
発明における少なくとも１０μｍのアルミニウムの表面
層を有する金属又は合金材料とは、アルミニウム、アル
ミニウムを含有する合金又はアルミニウムを含有しない
合金（鉄、銅、亜鉛、コバルト、ニッケルまたはそれら
の合金）に予め少なくとも１０μｍのアルミニウムの表
面層を形成させたものをいう。The present invention will be described in detail below. The metal or alloy material having a surface layer of aluminum of at least 10 μm in the present invention means at least aluminum, an alloy containing aluminum or an alloy not containing aluminum (iron, copper, zinc, cobalt, nickel or alloys thereof) in advance. It means that a surface layer of aluminum having a thickness of 10 μm is formed.
【０００９】アルミニウムを含有しない合金に、少なく
とも１０μｍのアルミニウムの表面層を形成させる方法
としては非水メッキ、圧着、蒸着、溶融メッキ等の公知
の方法の中から適宜用いることができる。As a method for forming a surface layer of aluminum having a thickness of at least 10 μm on an aluminum-free alloy, any known method such as non-water plating, pressure bonding, vapor deposition, and hot dipping can be used.
【００１０】これらのアルミニウム層表面上に陽極酸化
法により多孔質アルミナ層を形成させる。この陽極酸化
の技術は公知であり、処理液として、例えばクロム酸、
臭酸、硫酸等の水溶液が使用できる。本発明において陽
極酸化の処理液温度を常温〜５０℃、特に３０〜４０℃
とすることが好ましい。一方５０℃を越えると表面皮膜
の溶解が激しく、経済的ではない。A porous alumina layer is formed on the surface of these aluminum layers by the anodic oxidation method. This anodic oxidation technique is known, and as a treatment liquid, for example, chromic acid,
An aqueous solution of bromic acid, sulfuric acid or the like can be used. In the present invention, the treatment liquid temperature for anodic oxidation is room temperature to 50 ° C., particularly 30 to 40 ° C.
It is preferable that On the other hand, if the temperature exceeds 50 ° C, the surface film is severely dissolved, which is not economical.
【００１１】この陽極酸化法により形成された多孔質ア
ルミナ層はベ−マイトを主とする無定形のアルミナであ
り、焼成処理によりγ−アルミナを形成させる。本発明
における焼成処理の条件としては空気中で３００〜５０
０℃（好ましくは３５０〜４００℃）、数時間処理す
る。The porous alumina layer formed by this anodic oxidation method is an amorphous alumina mainly containing boehmite, and γ-alumina is formed by a firing treatment. The conditions for the firing treatment in the present invention are 300 to 50 in air.
Treat at 0 ° C. (preferably 350 to 400 ° C.) for several hours.
【００１２】上記の如く、金属又は合金材料の表面上に
形成された多孔質アルミナ皮膜上に白金及び／又はパラ
ジウムを熱水処理により担持させるとは、アルミナ皮膜
の比表面積を増大させる処理とメタノール改質における
触媒活性を有する白金及び／又はパラジウムを担持せし
める処理とを同時に処理することであり、所定のｐＨ、
液濃度、温度条件下の白金及び／又はパラジウムの塩化
物又はアルミン錯体の水溶液中に、上記方法で得た多孔
質アルミナ皮膜が形成された金属又は合金材料を浸漬
し、乾燥、焼成しさらに還元することにより該皮膜上に
白金及び／又はパラジウムを担持する。熱水処理におけ
る水溶液のｐＨについてはアルカリ溶液を用いて７以上
特に９〜１２とすることが好ましく、温度については３
０〜１００℃特に６０〜８５℃とすることが好ましい。[0012] As mentioned above, carrying platinum and / or palladium by hydrothermal treatment on the porous alumina coating formed on the surface of the metal or alloy material means a treatment for increasing the specific surface area of the alumina coating and methanol. That is, a treatment for supporting platinum and / or palladium having catalytic activity in the reforming is performed at the same time, and a predetermined pH,
The metal or alloy material having the porous alumina film formed by the above method is dipped in an aqueous solution of chloride and / or aluminium complex of platinum and / or palladium under the conditions of liquid concentration and temperature, dried, calcined and further reduced. By doing so, platinum and / or palladium is supported on the film. The pH of the aqueous solution in the hot water treatment is preferably 7 or more, especially 9 to 12 using an alkaline solution, and the temperature is 3
It is preferably 0 to 100 ° C., particularly 60 to 85 ° C.
【００１３】なお本発明でいう水素含有ガスとは、水素
を５０％以上、一酸化炭素を３５％以下含有するガスで
ある。また本発明のメタノール改質用触媒を用いてのメ
タノール改質方法における反応条件は以下のようであ
る。The hydrogen-containing gas in the present invention is a gas containing 50% or more of hydrogen and 35% or less of carbon monoxide. The reaction conditions in the methanol reforming method using the methanol reforming catalyst of the present invention are as follows.
【００１４】反応温度：２００〜７００℃ 特に
好ましくは３００〜６００℃ 反応圧力：０〜３０ｋｇ／ｃｍ2 Ｇ 特に好ましくは０
〜１５ｋｇ／ｃｍ2 Ｇ メタノール１モルに対する水の供給モル比：１０以下
特に好ましくは３以下Reaction temperature: 200 to 700 ° C., particularly preferably 300 to 600 ° C. Reaction pressure: 0 to 30 kg / cm 2 G, particularly preferably 0.
~ 15 kg / cm 2 G Molar ratio of water supply to 1 mol of methanol: 10 or less
Particularly preferably 3 or less
【００１５】[0015]
【実施例】以下、実施例により本発明を具体的に説明す
る。EXAMPLES The present invention will be specifically described below with reference to examples.
【００１６】（実施例１） 〇多孔質アルミナ皮膜の形成 １００ｍｍ×１００ｍｍ×０．６ｍｍ（厚さ）のアルミ
ニウム板（ＪＩＳ Ａ−１０８０、アルミニウム純度９
８．５％）を脱脂洗浄後、５重量％のクロム酸水溶液
で、液温４０℃、電流密度０．２Ａ／ｄｍ2 で８時間陽
極酸化を行い、約１７μｍの多孔質アルミナ皮膜を形成
させた後、空気中で４００℃、３時間焼成処理を行っ
た。Example 1 Formation of Porous Alumina Film 100 mm × 100 mm × 0.6 mm (thickness) aluminum plate (JIS A-1080, aluminum purity 9)
(8.5%) after degreasing and washing with a 5% by weight aqueous chromic acid solution at a liquid temperature of 40 ° C. and a current density of 0.2 A / dm 2 for 8 hours to form a porous alumina film of about 17 μm. After that, baking treatment was performed in air at 400 ° C. for 3 hours.
【００１７】〇触媒の調製 上記方法で得られた多孔質アルミナ皮膜が形成されたア
ルミニウム板を、塩化白金酸水溶液）０．２５ｍｇ−白
金／ｃｃ、ｐＨ＝１０、８０℃）に浸漬し、２時間熱水
処理を行い、乾燥後、４００℃で３時間焼成し、触媒１
を調製した。Preparation of catalyst The aluminum plate on which the porous alumina film obtained by the above method is formed is immersed in chloroplatinic acid aqueous solution) 0.25 mg-platinum / cc, pH = 10, 80 ° C.), and 2 After hot water treatment for 2 hours, dry and calcination at 400 ℃ for 3 hours, catalyst 1
Was prepared.
【００１８】塩化白金酸水溶液の代わりに、塩化パラジ
ウム水溶液（０．５ｍｇ−パラジウム／ｃｃ、ｐＨ＝１
０、８０℃）を用いた以外は上記方法と同じ方法で触媒
２を調製した。Instead of the aqueous solution of chloroplatinic acid, an aqueous solution of palladium chloride (0.5 mg-palladium / cc, pH = 1
Catalyst 2 was prepared by the same method as above except that (0, 80 ° C.) was used.
【００１９】〇触媒の活性評価 上記触媒１，２を反応器に充填し、下記表１に示す条件
で触媒活性評価を行い、その結果を表２に示す。Evaluation of Catalyst Activity The above catalysts 1 and 2 were filled in a reactor, the catalyst activity was evaluated under the conditions shown in Table 1 below, and the results are shown in Table 2.
【表１】 [Table 1]
【表２】 [Table 2]
【００２０】なお、生成ガス組成（ｍｏｌ％−ドライベ
ースでＨ2 Ｏ，ＣＨ3 ＯＨを除外した組成：以下同じ）
は次の通りであった。 （１）メタノール原料 Ｈ2 ： ６４〜６７％ ＣＯ ： ３１〜３３％ ＣＯ2 ： ０．１〜２％ ＣＨ4 ： ０．０２〜２％Composition of generated gas (mol% -composition excluding H 2 O and CH 3 OH on a dry basis: the same applies hereinafter)
Was as follows: (1) Methanol feed H 2: 64~67% CO: 31~33 % CO 2: 0.1~2% CH 4: 0.02~2%
【００２１】（２）メタノール・水混合液原料 Ｈ2 ： ６２〜７０％ ＣＯ ： ２２〜２８％ ＣＯ2 ： ２〜８％ ＣＨ4 ： ０．０１〜２％(2) Methanol / water mixed liquid raw material H 2 : 62 to 70% CO: 22 to 28% CO 2 : 2 to 8% CH 4 : 0.01 to 2%
【００２２】（実施例２） 〇多孔質アルミナ皮膜の形成 １５ｍｍ×７０ｍｍ×２ｍｍ（厚さ）のＳＵＳ３０４板
に、約３０μｍの厚さにアルミニウムをメッキし、その
後実施例１と同様に処理を行い、ＳＵＳ３０４板上に多
孔質アルミナ皮膜を形成させた。Example 2 Formation of Porous Alumina Film A 15 mm × 70 mm × 2 mm (thickness) SUS304 plate was plated with aluminum to a thickness of about 30 μm, and then treated in the same manner as in Example 1. Then, a porous alumina film was formed on the SUS304 plate.
【００２３】〇触媒の調製 上記方法で得られた多孔質アルミナ皮膜が形成されたＳ
ＵＳ３０４板に、塩化パラジウム水溶液の代りに塩化白
金と塩化パラジウムの混合水溶液（０．５ｍｇ−白金、
０．５ｍｇ−パラジウム／ｃｃ、ｐＨ＝１１、７０℃）
を用いた以外は、触媒２の調製と同様にして触媒３を調
製した。Preparation of catalyst S on which the porous alumina film obtained by the above method is formed
On a US304 plate, instead of the aqueous solution of palladium chloride, a mixed aqueous solution of platinum chloride and palladium chloride (0.5 mg-platinum,
0.5 mg-palladium / cc, pH = 11, 70 ° C.)
A catalyst 3 was prepared in the same manner as the preparation of the catalyst 2, except that was used.
【００２４】〇触媒の活性評価 上記触媒３を反応器に充填し、下記表３に示す条件で触
媒活性評価を行い、その結果を表４に示す。Evaluation of catalyst activity The catalyst 3 was filled in a reactor and the catalyst activity was evaluated under the conditions shown in Table 3 below. The results are shown in Table 4.
【表３】 [Table 3]
【表４】 [Table 4]
【００２５】（実施例３）外径１０．５ｍｍ、長さ１０
０ｍのＳＵＳ３０４管の管外壁（外表面積３３ｃｍ2 ）
に実施例２と同様にして処理を行い多孔質アルミナ皮膜
を形成し、実施例２と同様にして触媒４を調製した。(Embodiment 3) Outer diameter 10.5 mm, length 10
Outer wall of 0m SUS304 tube (outer surface area 33cm 2 )
Was treated in the same manner as in Example 2 to form a porous alumina film, and Catalyst 4 was prepared in the same manner as in Example 2.
【００２６】上記触媒４を反応管として反応管の内側を
熱媒で加熱することにより昇温し、熱媒温度を２００〜
４００℃にし、反応管外表面に水素３％（窒素バラン
ス）ガスを供給して還元処理を行った後、熱媒を昇温
し、熱媒温度を４５０℃に一定にし、反応管外表面に４
５０℃のメタノールと水の混合蒸気｛Ｈ2Ｏ／ＣＨ3 Ｏ
Ｈ＝１．５（ｍｏｌ／ｍｏｌ）｝を１５（ｃｃ／ｈ）の
流量で供給した結果、メタノール反応率は９７％であっ
た。By using the catalyst 4 as a reaction tube and heating the inside of the reaction tube with a heating medium, the temperature is raised to a heating medium temperature of 200 to
After the temperature is set to 400 ° C., 3% hydrogen (nitrogen balance) gas is supplied to the outer surface of the reaction tube to carry out the reduction treatment, the temperature of the heating medium is raised and the temperature of the heating medium is kept constant at 450 ° C. Four
Mixed steam of methanol and water at 50 ° C {H 2 O / CH 3 O
As a result of supplying H = 1.5 (mol / mol)} at a flow rate of 15 (cc / h), the methanol reaction rate was 97%.
【００２７】一方同じ触媒外表面積になるように、従来
のペレット型触媒を二重管の外側に充填し、内側に熱媒
を通すような反応管として同じように反応させた結果、
メタノール反応率は９０％程度であった。これより、本
発明による反応管は伝熱速度が大きいため、メタノール
反応率が大きいことがわかった。On the other hand, a conventional pellet type catalyst was filled in the outside of the double tube so that the outer surface area of the catalyst was the same, and the same reaction was performed as a reaction tube in which a heating medium was passed through the inside.
The methanol reaction rate was about 90%. From this, it was found that the reaction tube according to the present invention has a high heat transfer rate and thus a high methanol reaction rate.
【００２８】[0028]
【発明の効果】以上の実施例からも明らかなように本発
明による伝熱機能の優れた触媒を用いることによりメタ
ノール皮膜反応においてメタノール又はメタノールと水
の混合物から水素を含有するガスが効率よく製造される
ことがわかった。As is clear from the above examples, by using the catalyst of the present invention having an excellent heat transfer function, a gas containing hydrogen can be efficiently produced from methanol or a mixture of methanol and water in a methanol film reaction. I knew it would be done.
Claims (1)
面層を有する金属又は合金材料の表面上に、陽極酸化法
により多孔質アルミナ皮膜を形成させ、次いで焼成処理
を施した後、該多孔質アルミナ皮膜上に、白金及び／又
はパラジウムを熱水処理により担持させてなることを特
徴とするメタノール改質用触媒。Claim: What is claimed is: 1. A porous alumina film is formed on a surface of a metal or alloy material having a surface layer of aluminum having a thickness of at least 10 μm by an anodic oxidation method, and then a calcination treatment is performed. A catalyst for reforming methanol, characterized in that platinum and / or palladium is supported on a porous alumina film by hot water treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3168005A JPH0515778A (en) | 1991-07-09 | 1991-07-09 | Methanol reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3168005A JPH0515778A (en) | 1991-07-09 | 1991-07-09 | Methanol reforming catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0515778A true JPH0515778A (en) | 1993-01-26 |
Family
ID=15860039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3168005A Withdrawn JPH0515778A (en) | 1991-07-09 | 1991-07-09 | Methanol reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0515778A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005082777A1 (en) * | 2004-03-01 | 2005-09-09 | Dai Nippon Printing Co., Ltd. | Micro-reactor and method of manufacturing the same |
| JP2007326078A (en) * | 2006-06-09 | 2007-12-20 | Hitachi Metals Ltd | Hydrogen producing substrate and its manufacturing method |
| KR100828489B1 (en) * | 2004-03-01 | 2008-05-13 | 다이니폰 인사츠 가부시키가이샤 | Micro?reactor and method of manufacturing the same |
| EP3060335A4 (en) * | 2013-10-22 | 2017-07-19 | SDCMaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
-
1991
- 1991-07-09 JP JP3168005A patent/JPH0515778A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005082777A1 (en) * | 2004-03-01 | 2005-09-09 | Dai Nippon Printing Co., Ltd. | Micro-reactor and method of manufacturing the same |
| JP2005246115A (en) * | 2004-03-01 | 2005-09-15 | Dainippon Printing Co Ltd | Microreactor and its manufacturing method |
| KR100828489B1 (en) * | 2004-03-01 | 2008-05-13 | 다이니폰 인사츠 가부시키가이샤 | Micro?reactor and method of manufacturing the same |
| JP4580664B2 (en) * | 2004-03-01 | 2010-11-17 | 大日本印刷株式会社 | Microreactor and manufacturing method thereof |
| US7857874B2 (en) | 2004-03-01 | 2010-12-28 | Dai Nippon Printing Co., Ltd. | Micro-reactor and method of manufacturing the same |
| JP2007326078A (en) * | 2006-06-09 | 2007-12-20 | Hitachi Metals Ltd | Hydrogen producing substrate and its manufacturing method |
| EP3060335A4 (en) * | 2013-10-22 | 2017-07-19 | SDCMaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
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