JPS637843A - Catalyst for reforming methanol - Google Patents
Catalyst for reforming methanolInfo
- Publication number
- JPS637843A JPS637843A JP61153473A JP15347386A JPS637843A JP S637843 A JPS637843 A JP S637843A JP 61153473 A JP61153473 A JP 61153473A JP 15347386 A JP15347386 A JP 15347386A JP S637843 A JPS637843 A JP S637843A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- platinum
- rhodium
- palladium
- methanol
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002407 reforming Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 17
- 239000010948 rhodium Substances 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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〕
本発明はメタノール改質用触媒に関するものである。更
に詳しくはメタノールを水素及び−酸化炭素を含むガス
に改質する触媒として低温で高活性、高選択性を賦与し
ているためカーボン析出のない長寿命の触媒を提供する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for methanol reforming. More specifically, as a catalyst for reforming methanol into a gas containing hydrogen and carbon oxide, it provides a long-life catalyst that does not deposit carbon because it has high activity and high selectivity at low temperatures.
メタノールは石炭、天然ガスなどから合成ガスを経由し
て、大規模に製造することができ。Methanol can be produced on a large scale from coal, natural gas, etc. via synthetic gas.
しかも輸送が容易であることから将来石油に代る二ネμ
ギー源あるいは種々化学工業原料として大きな関心がも
たれている。その利用法の一つとしてメタノールを水素
と一酸化炭素を含むガスに分解し、これを自動車用無公
害燃料あるいは還元ガス製造用原料として利用する方法
がある。In addition, because it is easy to transport, it will become an alternative to petroleum in the future.
It is of great interest as a source of energy or as a raw material for various chemical industries. One method of using it is to decompose methanol into a gas containing hydrogen and carbon monoxide, and use this as a pollution-free fuel for automobiles or as a raw material for producing reducing gas.
一方、この分解ガスから水素を分離し、この水素を燃料
電池発電用燃料として、又９石油精製工業における各種
有機化合物の水素化などの水素源として利用でき、−酸
化炭素についても。On the other hand, hydrogen can be separated from this cracked gas and used as a fuel for fuel cell power generation and as a hydrogen source for hydrogenation of various organic compounds in the petroleum refining industry.
各種有機化合物のカルボニル化プロセスに利用できる。It can be used in the carbonylation process of various organic compounds.
メタノールの分解反応は、熱力学的には比較的低温で起
こりうるが、これを経済的に行わせるためには触媒の存
在が不可欠である。Thermodynamically, the decomposition reaction of methanol can occur at relatively low temperatures, but the presence of a catalyst is essential in order to carry it out economically.
従来、メタノールを分解する触媒としては。Traditionally, it has been used as a catalyst to decompose methanol.
アルミナ（以下ｒ Ａｌ２Ｏ３Ｊと記す）などの担体に
、白金などの白金属元素又は銅、ニッケル。A platinum metal element such as platinum, copper, or nickel on a carrier such as alumina (hereinafter referred to as rAl2O3J).
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。Catalysts supporting base metal elements such as chromium and zinc and their oxides have been proposed.
これらの触媒は低温活性に乏しくまた耐熱性がないなど
現在までのところ多くの問題点を残している。例えばγ
−Ａ１２０３又はアナターゼ型のチタニアなどをそのま
ま担体として用い、白金を担持した触媒については目的
の反応■のみが起こるという選択性が低く、ジメチルエ
ーテル、メタン、カーボンなどの生成する副反応■が起
こりやすいという問題がある。These catalysts still have many problems to date, such as poor low-temperature activity and lack of heat resistance. For example, γ
- Catalysts that use A1203 or anatase-type titania as a carrier and support platinum have low selectivity in that only the desired reaction (■) occurs, and side reactions (■) that produce dimethyl ether, methane, carbon, etc. are likely to occur. There's a problem.
主反応■ ０Ｍ３０Ｈ→２Ｈ２＋ｃ。Main reaction ■ 0M30H→2H2+c.
副反応（り ２ＣＨ３０Ｈ−＋ＣＨ３０ＣＨ３＋ Ｈ
２０ＣＨ３０Ｈ−Ｃ−１−Ｈ２＋Ｈ２０
ＣＨ３ＱＨ−４−Ｈ２→Ｃ）（４＋ Ｈ２０ＣＨ，ＯＩ
＝［−１−Ｃｏ−＋ＣＨ４−１−Ｃｏ２上記反応のうち
、■はメタノール分解の主反応で、この際生成した分解
ガスは分解反応の吸熱量相当分（約２２にＣａｌ／Ｆｎ
ｏｌ ）だけ分解ガスの発熱量が増加するという利点が
あり熱効率改善につながる。Side reaction (2CH30H−+CH30CH3+ H
20CH30H-C-1-H2+H20 CH3QH-4-H2→C) (4+ H20CH, OI
=[-1-Co-+CH4-1-Co2 Among the above reactions, ■ is the main reaction of methanol decomposition, and the cracked gas generated at this time is equivalent to the endothermic amount of the decomposition reaction (approximately 22% of Cal/Fn
This has the advantage that the calorific value of the decomposed gas increases by an amount equal to .ol), which leads to an improvement in thermal efficiency.
しかし９反応■のような副反応が起こるとこの反応はい
ずれも発熱反応であるため熱効率の面からはむしろ損失
となる。However, if a side reaction such as 9 reaction ① occurs, this reaction is an exothermic reaction, and therefore results in a loss in terms of thermal efficiency.
さらにこの分解ガスを各種プロセスの水素源などに利用
する場合１反応■によって副生ずる水、エーテル類など
は分離、精製を困難にする要因となる。また反応■のう
ちカーボン生成反応は、触媒の劣化あるいはりアクタ−
の閉塞などをきたし、長期安定操業の妨げとなる。Furthermore, when this cracked gas is used as a hydrogen source for various processes, water, ethers, etc. produced as by-products in one reaction (2) become a factor that makes separation and purification difficult. In addition, among reactions (2), the carbon production reaction is due to catalyst deterioration or
This can lead to blockages, etc., and impede long-term stable operations.
本発明は、上記の問題点を解消し、低温活性が高く、メ
タノールからの水素、−酸化炭素を含むガスへの分解反
応において活性９選択性。The present invention solves the above problems, has high low-temperature activity, and has 9 selectivity in the decomposition reaction of methanol to gas containing hydrogen and carbon oxide.
寿命とも極めて優れた触媒を提供することを目的とした
ものである。The purpose is to provide a catalyst with extremely excellent longevity.
従来、触媒担体として用いられている比表面積の大キい
酸性作用のあるアナターゼ型のチタニア担体を、高温で
熱処理することによりルチル型に結晶転移させると、比
表面積は小さくなるが酸性作用が殆んどなくなり、脱水
素反応（主反応■）により選択性が向上すること、さら
に、活性金属としての白金又はパラジウムに第２成分と
してロジウムを加えれば、低温活性向上に効果があるこ
とを見出した。すなわち９氷上
発明はルチル型の戸タニアを含有する担体にロジウムと
白金、又はロジウムとパラジウムとを担持させたことを
特徴とす°るメタノール改質用触媒を提案するものであ
る。If the anatase type titania support, which has been conventionally used as a catalyst support and has a large specific surface area and has a strong acidic effect, is crystallized into a rutile type by heat treatment at high temperature, the specific surface area will be small but the acidic effect will be almost nonexistent. They found that the selectivity was improved by the dehydrogenation reaction (main reaction ■), and that adding rhodium as a second component to platinum or palladium as the active metal was effective in improving low-temperature activity. . That is, the invention on ice proposes a methanol reforming catalyst characterized in that rhodium and platinum, or rhodium and palladium are supported on a carrier containing rutile-type dotania.
ここで／Ｌ／−！−ル型のチタニアを含有する担体は。 Here /L/-! - A carrier containing titania of the type.
アナターゼ型のチタニア又は、アルミナ担体にチタニア
をコーティングもたものなどを、６００°Ｃ以上の温度
、好ましくは８００−１０００°Ｃの温度範囲で焼成す
ることで容易に得られる。It can be easily obtained by firing anatase-type titania or an alumina carrier coated with titania at a temperature of 600°C or higher, preferably in the temperature range of 800-1000°C.
次にこのようにして得られた担体にロジウム。Next, rhodium was added to the support thus obtained.
白金、パラジウムなどの活性金属を担持させる方法は常
法でよく２例えば上記金属の硝酸塩又は塩化物などの化
合物の水溶液に担体を浸した後、乾燥焼成することによ
り容易に得られる。Active metals such as platinum and palladium may be supported by conventional methods.2 For example, active metals such as platinum and palladium can be easily obtained by soaking the support in an aqueous solution of a compound such as a nitrate or chloride of the metal, followed by drying and firing.
活性体としての白金、パラジウムの担持量は０．１〜５
ｗｔ％（触媒全重量基準）が好ましく、これに第２成分
として添加するロジウムは白金。The supported amount of platinum and palladium as active substances is 0.1 to 5.
Wt% (based on the total weight of the catalyst) is preferable, and the rhodium added as a second component is platinum.
又はパラジウムに対し１０ｗｔ％以下では効果がなく、
５０ｗｔ％以上ではコスト高となるため、 １０〜５Ｑ
ｗｔ％の範囲とすることが好ましい。以上のようにし
て、ロジウムと白金又はロジウムとパラジウムを担持さ
せた後、水素還元処理を行うとロジウム、白金、パラジ
ウムが酸化物状態から金属状態に変わシ初期活性が発現
する。Or, it is not effective if it is less than 10 wt% with respect to palladium,
10-5Q as the cost will be high if it exceeds 50wt%
It is preferable to set it as the range of wt%. After supporting rhodium and platinum or rhodium and palladium as described above, when hydrogen reduction treatment is performed, rhodium, platinum, and palladium change from an oxide state to a metal state and exhibit initial activity.
またロジウム、白金、パラジウムの酸化状態でもメタノ
ールと反応させると初期活性は低いが生成する水素、−
酸化炭素によって数時間後にはロジウム、白金、パラジ
ウムは還元され活性が発現する。In addition, even in the oxidized state of rhodium, platinum, and palladium, when they are reacted with methanol, the initial activity is low, but hydrogen, -
After several hours, rhodium, platinum, and palladium are reduced by carbon oxide and their activity is expressed.
但し、この場合、メタノールとの反応条件によっては急
激な発熱を起こす場合があり、これによって失活するこ
とがある。However, in this case, depending on the reaction conditions with methanol, rapid heat generation may occur, which may lead to deactivation.
従って、この発熱を防止するためにも予め水素還元処理
を行うことが好ましい。Therefore, in order to prevent this heat generation, it is preferable to perform a hydrogen reduction treatment in advance.
以上のようにして得られた触媒はメタノールを水素、−
酸化炭素を含むガスに改質する反応に対し目的の反応の
選択性に優れａｏｏ’ｃという低温で高活性、高選択性
を示すものである。The catalyst obtained as described above converts methanol into hydrogen, -
It has excellent selectivity for the desired reaction in the reaction of reforming into a gas containing carbon oxide, and exhibits high activity and high selectivity at a low temperature of AOO'C.
以下、実施例により９本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
〔実施例１〕
粒径２〜４ｍｍのアナターゼ型のチタニア担体を８００
’Ｃで２４時間焼成を行い、／Ｉ／チ〜型のチタニア担
体を得た。ルチル型に結晶転移していることはＸ線回折
によシ同定した。このルチル型チタニア担体を塩化ロジ
ウム及び塩化白金酸の混合水溶液に浸漬し、乾燥後５０
０’Ｃで３時間焼成しテｐｔ ０．４ ｗｔ％、 Ｒｈ
Ｏ，１ｗｔ％（触媒全重量基準）を担持した触媒１を
調製した。この触媒を４００℃で８時間３．５％水素気
液中で還元し表１に示す条件で活性評価試験を行い表２
の結果を得た。なお比較触媒として従来の７チターゼ型
のｆｌｙ’ニア担体にｐｔｏ、４ｗｔ％、 Ｒｈ ｏ、
１ ｗｔ％（触媒全重量基準）を担持した触媒を調製し
１反応温度４００°Ｃでの活性評価試験を行った結果を
表２に併せて示した。[Example 1] Anatase type titania carrier with a particle size of 2 to 4 mm was
Calcination was performed for 24 hours at 'C' to obtain a /I/C type titania support. The crystal transition to rutile type was confirmed by X-ray diffraction. This rutile type titania support was immersed in a mixed aqueous solution of rhodium chloride and chloroplatinic acid, and after drying,
Calcined at 0'C for 3 hours, Tept 0.4 wt%, Rh
Catalyst 1 supporting 1 wt% of O (based on the total weight of the catalyst) was prepared. This catalyst was reduced in a 3.5% hydrogen gas liquid at 400°C for 8 hours, and an activity evaluation test was conducted under the conditions shown in Table 1.
The results were obtained. As a comparative catalyst, pto, 4 wt%, Rho,
A catalyst supporting 1 wt% (based on the total weight of the catalyst) was prepared and an activity evaluation test was conducted at a reaction temperature of 400° C. The results are also shown in Table 2.
表１゜
表２゜
〔実施例２〕
実施例１と同じ方法で得たルチル型チタニア担体を、塩
化ロジウムと塩化白金酸及び塩化ロジウムと塩化パラジ
ウムの水溶液に各々浸漬し。Table 1 Table 2 [Example 2] A rutile titania support obtained in the same manner as in Example 1 was immersed in an aqueous solution of rhodium chloride and chloroplatinic acid and rhodium chloride and palladium chloride.
乾燥後５００’Ｃで８時間焼成して表３に示す組成の触
媒２〜１３を調製した。これらの触媒について実施例１
と同様にして水素還元処理した後。After drying, catalysts 2 to 13 having the compositions shown in Table 3 were prepared by calcining at 500'C for 8 hours. Example 1 for these catalysts
After hydrogen reduction treatment in the same manner as above.
反応温度を８５０’Ｃにした以外は表１に示す条件で活
性評価試験を行い表３の結果を得た。The activity evaluation test was conducted under the conditions shown in Table 1, except that the reaction temperature was 850'C, and the results shown in Table 3 were obtained.
また白金、パラジウムを各々Ｑ５ ｗｔ％（触媒全重量
基準）担持した触媒１４．１５を調製し同様に水素還元
処理した後、４００°Ｃでの活性評価試験を行い結果を
表３に併せて示した。In addition, a catalyst 14.15 carrying Q5 wt% of platinum and palladium (based on the total weight of the catalyst) was prepared and subjected to hydrogen reduction treatment in the same manner, followed by an activity evaluation test at 400°C, and the results are also shown in Table 3. Ta.
夙下企白
表 ３
〔実施例３〕
実施例１で得たルチル型チタニア担体を塩化ロジウムの
水溶液中に浸漬した後、乾燥し１次いで硝酸白金の水溶
液に浸漬してこれを乾燥。Table 3 [Example 3] The rutile type titania support obtained in Example 1 was immersed in an aqueous solution of rhodium chloride, dried, and then immersed in an aqueous solution of platinum nitrate and dried.
焼成（５００°Ｃで３時間）してＲｈ Ｑ、１ ｗｔ％
、 Ｐｔ□、４ｗｔ％（触媒全重量基準）を含有する触
媒を調製した。この触媒について実施例１と同じ方法で
水素還元処理をし反応温度を４００°Ｃに変えた以外は
表１に示す条件と同じ方法で活性評価試験を行った結果
、触媒１と同様の性能が得られた。Calcined (3 hours at 500°C) to give RhQ, 1 wt%
, Pt□, 4 wt% (based on the total weight of the catalyst). This catalyst was subjected to hydrogen reduction treatment in the same manner as in Example 1, and an activity evaluation test was conducted under the same conditions as shown in Table 1, except that the reaction temperature was changed to 400°C. As a result, the same performance as Catalyst 1 was found. Obtained.
〔実施例４〕
実施例１で調製した触媒ｌをステンレス製の反応管に５
ｃｃ充填し４００°Ｃでメタノールを５ｃｃ／ｈ連続供
給し２００時間の耐久性試験を行った。この結果メタノ
ール反応率及び分解ガス組成とも初期と殆んど変化がな
く、触媒表面へのカーボン析出もないことを確認した。[Example 4] 5 l of the catalyst prepared in Example 1 was placed in a stainless steel reaction tube.
A durability test was conducted for 200 hours by filling the tube with cc and continuously supplying methanol at 5 cc/h at 400°C. As a result, it was confirmed that there was almost no change in the methanol reaction rate and cracked gas composition from the initial stage, and that there was no carbon precipitation on the catalyst surface.
以上の実施例では粒状触媒について記述しであるが、触
媒の形状を特に限定するものではなく、ハニカム状、板
状などの触媒形状で用いて良いことは云うまでもない。Although granular catalysts are described in the above embodiments, the shape of the catalyst is not particularly limited, and it goes without saying that catalyst shapes such as honeycomb shapes and plate shapes may be used.
又実施例では、メタノール単独の場合について記述しで
あるが、水蒸気、空気などを含有したガスとの共存下で
メタノール改質を行わせても良い。Further, in the examples, the case where methanol alone is used is described, but methanol reforming may be performed in the coexistence with a gas containing water vapor, air, etc.
以上の実施例の結果から明らかなように１本発明の触媒
はメタノールを水素、−酸化炭素を含むガスに改質する
反応に対し、目的とする反応の選択性に優れ、かつ３０
０°Ｃという低温においても高活性を示し、長時間の運
転でも活性の低下が少ない触媒である。As is clear from the results of the above examples, the catalyst of the present invention has excellent selectivity for the desired reaction in the reaction of reforming methanol into a gas containing hydrogen and carbon oxide, and
This catalyst shows high activity even at low temperatures of 0°C, and its activity does not decrease much even during long-term operation.
Claims (1)
又はロジウムとパラジウムとを担持させたことを特徴と
するメタノール改質用触媒。A methanol reforming catalyst characterized in that rhodium and platinum or rhodium and palladium are supported on a carrier containing rutile-type titania.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61153473A JPS637843A (en) | 1986-06-30 | 1986-06-30 | Catalyst for reforming methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61153473A JPS637843A (en) | 1986-06-30 | 1986-06-30 | Catalyst for reforming methanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS637843A true JPS637843A (en) | 1988-01-13 |
Family
ID=15563339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61153473A Pending JPS637843A (en) | 1986-06-30 | 1986-06-30 | Catalyst for reforming methanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS637843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292704A (en) * | 1989-05-01 | 1994-03-08 | Allied-Signal Inc. | Catalyst for destruction of organohalogen compounds |
-
1986
- 1986-06-30 JP JP61153473A patent/JPS637843A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292704A (en) * | 1989-05-01 | 1994-03-08 | Allied-Signal Inc. | Catalyst for destruction of organohalogen compounds |
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