JPS6369542A - Methanol reforming catalyst - Google Patents
Methanol reforming catalystInfo
- Publication number
- JPS6369542A JPS6369542A JP21478386A JP21478386A JPS6369542A JP S6369542 A JPS6369542 A JP S6369542A JP 21478386 A JP21478386 A JP 21478386A JP 21478386 A JP21478386 A JP 21478386A JP S6369542 A JPS6369542 A JP S6369542A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methanol
- catalyst
- alumina
- activity
- 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 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 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 32
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 6
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 230000000694 effects Effects 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000006057 reforming reaction Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 150000001340 alkali metals Chemical class 0.000 description 10
- 229910002090 carbon oxide Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000047 product Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- -1 rubylum Chemical compound 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance 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
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
イ、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、特にメタノー
ルから選択的に水素及び−酸化炭素を生成するメタノー
ル改質用触媒に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a methanol reforming catalyst, and more particularly to a methanol reforming catalyst that selectively produces hydrogen and carbon oxide from methanol.
口、従来技術
る方法が注目されている。メタノールは、輸送が簡便で
あって天然ガス輸送に於けるような液体、高圧容器、バ
イブライン建設等の必要がなく、取扱いが簡単で、また
水素は、自動車等小規模の発有望である。しかも、メタ
ノールが天然ガスの主成分であるメタンから容易に大量
合成が可能であり、多量の天然ガスが無為に放散、焼却
処分されている現状から見ても、メタノールのエネルギ
ーとしての利用は有意義なことと言わねばならない。However, conventional methods are attracting attention. Methanol is easy to transport and does not require the construction of liquids, high-pressure containers, vibrating lines, etc. that are required for natural gas transportation, and is easy to handle.Hydrogen is also promising for small-scale generation, such as in automobiles. Moreover, methanol can be easily synthesized in large quantities from methane, the main component of natural gas, and considering the current situation where large amounts of natural gas are wastefully dissipated and incinerated, the use of methanol as energy is meaningful. I have to say that.
上述のようなメタノール改質用触媒としては、従来、活
性アルミナ、シリカゲル、チタニア等の無機酸化物担体
に、銅、ニッケル、クロム、亜鉛等の金属元素若しくは
これらの酸化物を担持させたものが提案されている。し
かし、このような触媒は水素又は−酸化炭素生成反応へ
の選択性が低く、低温活性が乏しい。また、触媒の表面
状態の関係で焼結等が生じやすいため耐熱性、耐久性に
劣り、即ち高温での使用や繰返し使用によって触媒特性
が劣化するので、上記したように反応が高温で行われる
こととも相俟って、問題となっていた。Conventionally, the above-mentioned methanol reforming catalysts have been made by supporting metal elements such as copper, nickel, chromium, zinc, or oxides of these on inorganic oxide supports such as activated alumina, silica gel, and titania. Proposed. However, such catalysts have low selectivity to hydrogen or carbon oxide production reactions and poor low temperature activity. In addition, due to the surface condition of the catalyst, sintering tends to occur, resulting in poor heat resistance and durability.In other words, the catalyst properties deteriorate due to use at high temperatures or repeated use, so as mentioned above, the reaction is carried out at high temperatures. Combined with this, it became a problem.
また、前記無機酸化物担体に白金等の貴金属元素を担持
させたものも提案されているが、このような触媒を用い
た場合、多量の貴金属を必要とするため経済性に問題が
あり、資源的にも制約を受けていて、実用的ではない。In addition, catalysts in which noble metal elements such as platinum are supported on the inorganic oxide carrier have been proposed, but when such catalysts are used, there are economical problems as they require a large amount of precious metals, and resource It is also subject to physical limitations and is not practical.
上述の問題を解決したメタノール改質用触媒は、未だ提
案されておらず、知られてもいない。A methanol reforming catalyst that solves the above-mentioned problems has not yet been proposed or known.
ハ９発明の目的
本発明は、上記の事情に鑑みてなされたものであって、
メタノール改質反応に対する活性及び高い選択性を示す
メタノール改質用触媒を提供することを目的としている
。C.9 Purpose of the Invention The present invention has been made in view of the above circumstances, and includes:
An object of the present invention is to provide a methanol reforming catalyst that exhibits activity and high selectivity for methanol reforming reactions.
二１発明の構成
本発明は、アルミナを主成分とする担体に、カリウム、
ナトリウム、リチウム、ルビジウム及びセシウムの１種
又は２種以上が担持されたメタノール改質用触媒に係る
。21 Structure of the Invention The present invention provides a method for adding potassium and
The present invention relates to a methanol reforming catalyst that supports one or more of sodium, lithium, rubidium, and cesium.
ホ０発明の作用効果 最初に、メタノール改質反応について簡単に説明する。Effects of Ho0 invention First, the methanol reforming reaction will be briefly explained.
本発明の通用されるメタノール改質反応は、下記の反応
式（１）に示す反応であり、これにより一酸化炭素及び
目的物の水素が得られる。The methanol reforming reaction commonly used in the present invention is the reaction shown in the following reaction formula (1), whereby carbon monoxide and hydrogen, which is the target product, are obtained.
ＣＨ３０Ｈ−２Ｈｚ＋ＣＯ・・・・・・・・・（１１上
記（１）式の反応には副反応が伴い、副生成物としてメ
タン、二酸化炭素、メチルエーテル、水などが生成する
。CH30H-2Hz+CO (11) The reaction of formula (1) above involves side reactions, and methane, carbon dioxide, methyl ether, water, etc. are produced as by-products.
本発明者は、上記メタノール改質反応に使用するに好適
な触媒に関する研究の過程で、アルミナを主成分とする
担体に、カリウム、ナトリウム、リチウム、ルビラム及
びセシウムの１種又は２種以上が担持された触媒は、メ
タノール改質反応用触媒として前記（１）式の反応に対
し活性及び高い選択性を示し、低温活性に富み、高い耐
熱性、耐久性を有することを見出した。In the course of research on a catalyst suitable for use in the methanol reforming reaction, the present inventor discovered that one or more of potassium, sodium, lithium, rubylum, and cesium was supported on a support mainly composed of alumina. It has been found that the resulting catalyst exhibits activity and high selectivity for the reaction of formula (1) as a catalyst for methanol reforming reaction, is rich in low-temperature activity, and has high heat resistance and durability.
上記担体としては、アルミナに他の担体成分を混合した
ものでも良く、アルミナのみでも良い。The carrier may be a mixture of alumina and other carrier components, or may be alumina alone.
アルミナはＴ−アルミナが一般的である。アルミナ以外
の上記担体成分としては、例えばシリカゲル、チタニア
等の無機酸化物が好適である。The alumina is generally T-alumina. As the carrier component other than alumina, for example, inorganic oxides such as silica gel and titania are suitable.
こうしたアルミナを主成分とする担体は、それ自体メタ
ノール分解反応用触媒として活性であるが、後に例示す
るように、この反応においては目的とするメタノール改
質反応即ち水素及び−酸化質用触媒としての使用には不
都合である。Such a support mainly composed of alumina is itself active as a catalyst for the methanol decomposition reaction, but as will be illustrated later, in this reaction, it is used as a catalyst for the target methanol reforming reaction, that is, for hydrogen and -oxidants. It is inconvenient to use.
本発明者は、上記ｍ体に前記アルカリ金属を担持させる
ことにより、メタノール改質用触媒として良好な特性を
付与しうろことを見出し、本発明をなすに至った。The present inventors have discovered that by supporting the alkali metal on the m-form, good characteristics can be imparted as a catalyst for methanol reforming, and the present invention has been completed.
即ち、アルミナを主成分とする担体に、アルカリ金属を
担持させたメタノール改質用触媒を用いることにより、
メタノール改質反応の選択性は著しく向上し、同反応の
活性もまた高まり、目的物でない水、メタン等の生成を
抑えることができる。That is, by using a methanol reforming catalyst in which an alkali metal is supported on a support mainly composed of alumina,
The selectivity of the methanol reforming reaction is significantly improved, the activity of the same reaction is also increased, and the production of unintended substances such as water and methane can be suppressed.
このような効果は、上記担体にナトリウム又はカリウム
を担持させたときに殊に顕著である。Such effects are particularly remarkable when sodium or potassium is supported on the carrier.
また、上記触媒は４５０℃付近で良好な触媒特性を有し
ていて低温活性に優れ、また、触媒表面の微細構造が比
較的単純なことから、焼結等が起こりにくく耐熱性、繰
返し使用に対する耐久性に優れている。In addition, the above catalyst has good catalytic properties at around 450°C and has excellent low-temperature activity.Also, since the fine structure of the catalyst surface is relatively simple, sintering etc. do not easily occur, making it heat resistant and suitable for repeated use. Excellent durability.
メタノール改質用触媒は、アルミナを主成分とする担体
を、例えばアルカリ金属の水酸化物の水溶液に浸漬し、
濾過、乾燥の後、酸素雰囲気下高温で焼成することによ
り作成することができる。The catalyst for methanol reforming is prepared by immersing a support mainly composed of alumina in an aqueous solution of an alkali metal hydroxide,
After filtration and drying, it can be produced by firing at a high temperature in an oxygen atmosphere.
本発明の触媒を用いた場合の触媒表面における反応機構
は、次のように推測される。The reaction mechanism on the catalyst surface when using the catalyst of the present invention is estimated as follows.
図面は、カリウムを担持したＴ−アルミナ触媒表面での
、吸着型メタノール（ＣＤ３０Ｄ）の赤外線吸収スペク
トルの温度依存性を示すグラフである。グラフの横軸は
波数、縦軸は透過率である。The figure is a graph showing the temperature dependence of the infrared absorption spectrum of adsorbed methanol (CD30D) on the surface of a T-alumina catalyst supporting potassium. The horizontal axis of the graph is the wave number, and the vertical axis is the transmittance.
ここで、メタノールを用いず重メタノールを使用したの
は、観察の便宜のためであって、重メタノールがメタノ
ールと同様の化学的挙動を示すであろうことは、言うま
でもない。Here, heavy methanol was used instead of methanol for the convenience of observation, and it goes without saying that heavy methanol would exhibit the same chemical behavior as methanol.
グラフ中の吸収（波数２１７５ｃｏ＋−’ 、２０４５
Ｃ１１−’、１１４０ｃｍ−１，１０４５ｃｍ−’ ）
から、触媒表面において重メトキシド（ＣＤ３０ ）
が存在すること、及び重メトキシドが反応温度４００℃
まで安定に存在することが解る。この重メトキシドは温
度４５０℃においては消滅するが、これは後に実施例の
項で述べるように、反応温度を４００℃から４５０℃に
上げたときに触媒活性が著しく増加することと照応して
おり、重メトキシド（即ち、メタノールを用いた場合は
メトキシド）が重メタノール（メタノール）改質反応の
中間体であることを裏付けていると考えられる。Absorption in the graph (wave number 2175co+-', 2045
C11-', 1140cm-1,1045cm-')
From, heavy methoxide (CD30) on the catalyst surface
is present, and the reaction temperature of heavy methoxide is 400°C.
It can be seen that it exists stably until This heavy methoxide disappears at a temperature of 450°C, which is consistent with the fact that the catalyst activity increases significantly when the reaction temperature is raised from 400°C to 450°C, as will be described later in the Examples section. This is considered to confirm that heavy methoxide (that is, methoxide when methanol is used) is an intermediate in the heavy methanol (methanol) reforming reaction.
また、重メタノールの酸素と重水素との結合を示す吸収
（波数２５６０ｃｍ−１）は、反応温度２００℃におい
て既にほとんど検出されず、触媒表面の活性点に吸着さ
れた重メタノール（メタノール）が反応して消滅してい
ることが解る。In addition, the absorption (wavenumber 2560 cm-1) indicating the bond between oxygen and deuterium in heavy methanol is hardly detected at the reaction temperature of 200°C, and heavy methanol (methanol) adsorbed on the active sites on the catalyst surface is reacted. It can be seen that it disappears.
上述の結果などから、触媒表面における反応機構は、次
のように推測される。From the above results, the reaction mechanism on the catalyst surface is estimated as follows.
まず、アルカリ金属（ここではカリウム）を担持したア
ルミナを主成分とする触媒の表面の活性点に、メタノー
ル分子が吸着されると、次式に示すような反応が起こり
、水素とカリウムが交換される。First, when methanol molecules are adsorbed to the active sites on the surface of a catalyst whose main component is alumina that supports an alkali metal (potassium in this case), a reaction occurs as shown in the following equation, and hydrogen and potassium are exchanged. Ru.
触媒表面におけるメトキシド（重メトキシド）の存在は
、前述のように確認されている。The presence of methoxide (heavy methoxide) on the catalyst surface has been confirmed as described above.
メタノール吸着点において、上記（２）式の反応が生じ
た後には、次に（３）式で示す反応か又は（４）式で示
す反応のいずれかが生ずると推測される。After the reaction of formula (2) occurs at the methanol adsorption point, it is presumed that either the reaction of formula (3) or the reaction of formula (4) occurs next.
ＡＩ Ｋ −ＡＮ Ｋ
ハ
ＡＩ Ｋ＋ＣＨ３０Ｈ・・・・・・・・・（３）ＡＮ
Ｋ −ＡＮ Ｋ
一←Ａｎ Ｋ＋ＣＯ＋２Ｈ２・・・・・・・・・（４
）上記（３）式に示すように、メトキシド／７Ｉの酸素
が、アルミナに結合している水素を攻撃した場合は、元
のメタノール分子とカリウムを担持したアルミナとが再
生され、メタノール分子は次の活性点に吸着されるまで
運動を続ける。このメタノール分子が再び触媒表面の活
性点に吸着されると、前記（２）式で示した反応を再び
起こし、次いで上記（３）式で示す反応又は（４）式で
示す反応のいずれかが生ずることとなる。このとき、（
３）式に示す反応が生じた場合は、再び上述したことが
繰り返されることとなる。AI K -AN K AI K+CH30H・・・・・・・・・(3)AN
K -AN K 1←An K+CO+2H2・・・・・・・・・(4
) As shown in equation (3) above, when the oxygen of methoxide/7I attacks the hydrogen bonded to alumina, the original methanol molecule and the alumina supporting potassium are regenerated, and the methanol molecule becomes The movement continues until it is adsorbed to the active site. When this methanol molecule is adsorbed again to the active sites on the catalyst surface, the reaction shown in the above equation (2) occurs again, and then either the reaction shown in the above equation (3) or the reaction shown in the above equation (4) occurs. will occur. At this time,(
3) If the reaction shown in the formula occurs, the above steps will be repeated again.
これに対し、上記（４）式に示すように、アルミナの酸
素がメトキシドの水素を攻撃した場合は、メトキシドが
分解して目的物である水素及び−酸化炭素を生じ、カリ
ウムを担持したアルミナは再生され、次のメタノール分
子の吸着を待って、前記（２）式に示す反応を再び生ず
る。On the other hand, as shown in equation (4) above, when the oxygen of alumina attacks the hydrogen of methoxide, the methoxide decomposes to produce the target hydrogen and -carbon oxide, and the potassium-supported alumina After being regenerated and waiting for the next methanol molecule to be adsorbed, the reaction shown in equation (2) above occurs again.
本発明のアルカリ金属を担持した触媒を用いた場合は、
前記（１１式の反応が、上述のように通常のアルミナを
用いた場合とは異なる反応機構を通じ、メトキシドを中
間体として容易に進行し、他の目的としない副反応が抑
制されるので、メタノール改質反応の活性が向上し、選
択性が著しく高まるのだと推定される。When using the alkali metal supported catalyst of the present invention,
The reaction of formula (11) proceeds easily with methoxide as an intermediate through a reaction mechanism different from that when using ordinary alumina as described above, and other unintended side reactions are suppressed. It is presumed that the activity of the reforming reaction is improved and the selectivity is significantly increased.
本発明の触媒を用いたメタノール改質反応には、固定床
式反応器、流動床式反応器又は移動床式反応器のいずれ
を用いても良い。For the methanol reforming reaction using the catalyst of the present invention, any of a fixed bed reactor, a fluidized bed reactor, or a moving bed reactor may be used.
反応の例を挙げると、メタノール改質用触媒及びメタノ
ールを含む混合ガスを閉ｔｊ１循環型装置に導入し、所
定温度に加熱すれば、反応器出口において水素及び−酸
化炭素の存在比を高めることができる。To give an example of a reaction, if a mixed gas containing a methanol reforming catalyst and methanol is introduced into a closed TJ1 circulation type device and heated to a predetermined temperature, the abundance ratio of hydrogen and -carbon oxide can be increased at the outlet of the reactor. Can be done.
こうしたメタノール改質反応の反応条件は、圧力が１気
圧から５０気圧、反応温度は３５０℃から５００℃とす
る。The reaction conditions for such a methanol reforming reaction are a pressure of 1 atm to 50 atm, and a reaction temperature of 350°C to 500°C.
以上述べてきたように、本発明は、高価で資源的にも制
約を受けている貴金属触媒を用いず、かつ前述の方法に
より簡便に調製でき、活性及び高い選択性を示すメタノ
ール改質用触媒を提供するものであって、その工業的価
値は大きい。As described above, the present invention provides a methanol reforming catalyst that does not use expensive and resource-constrained precious metal catalysts, can be easily prepared by the method described above, and exhibits activity and high selectivity. , and its industrial value is great.
ヘ、実施例 以下、本発明の実施例について説明する。F. Example Examples of the present invention will be described below.
本例の触媒は、粒状γ−アルミナを水酸化カリウム、水
酸化ナトリウム、水酸化リチウム等の水酸化アルカリ金
属水溶液に１２時間前後浸漬し、これを濾過して１２０
℃で２時間前後乾燥して開裂した。これら触媒をメタノ
ール分解反応に用いるときは、使用に先立って酸素雰囲
気中で４５０℃に１時間加熱して焼成し、更に同温度で
１時間排気処理する。The catalyst of this example was prepared by immersing granular γ-alumina in an aqueous alkali metal hydroxide solution such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. for about 12 hours, and filtering the solution.
It was dried at ℃ for about 2 hours and cleaved. When these catalysts are used in a methanol decomposition reaction, prior to use, they are fired by heating to 450° C. for 1 hour in an oxygen atmosphere, and then subjected to exhaust treatment at the same temperature for 1 hour.
メタノール分解反応は、３００ ｒａｇの前記触媒を収
容する閉鎖循環型装置に７ＱＴｏｒｒのメタノールを導
入して４５０℃で行い、反応開始後１時間の時点で少量
の反応ガスを採取し、これをガスクロマトグラフによっ
て分析し、触媒活性及び選択性を調べた。分析に使用し
たカラムはガスクロ工業社製ＭＳ−５Ａ及びガスクロ工
業社製パラバックＴ（ＰａｒａｐａｃｋＴ ）である０
反応生成物は水素、−酸化炭素、二酸化炭素、メタン、
メチルエーテル及び水である。なお、Ｔ−アルミナ中の
アルカリ全屈濃度は、原子吸光法によって分析した。The methanol decomposition reaction was carried out at 450°C by introducing methanol at 7QTorr into a closed circulation type device containing 300 rag of the catalyst, and a small amount of reaction gas was collected one hour after the start of the reaction, and this was analyzed using a gas chromatograph. The catalytic activity and selectivity were determined by analysis. The columns used in the analysis were MS-5A manufactured by Gascro Industries and Parapack T manufactured by Gascro Industries.
The reaction products are hydrogen, carbon oxide, carbon dioxide, methane,
Methyl ether and water. Note that the total alkali concentration in T-alumina was analyzed by atomic absorption spectrometry.
上記のようにして求めたメタノール分解反応の分解率及
び各生成物の割合は、下記表に示す通りである０表には
比較のために、アルカリ金属を担持しないγ−アルミナ
触媒について同様の測定をした結果が併記しである。The decomposition rate and the proportion of each product in the methanol decomposition reaction determined as above are shown in the table below. The results are also listed.
（以下余白、次頁に続く。）
表から、アルカリ金属を担持しないＴ−アルミナは、メ
タノール分解率は高いが、メタン及び水の生成が多く、
水素、−酸化炭素へのメタノール分解反応の選択性は甚
だ低い。これに対してアルカリ金属担持γ−アルミナは
、分解率は低下する傾向が見られるものの、メタンや水
の生成が少なく、水素及び−酸化炭素が主な生成物とな
り、著しい選択性向上が見られる。メタノール分解率の
低下は、特にアルカリ金属（この例ではカリウム）の量
が０．２９重量％と低い場合に見られるが、カリウムの
量が３．６重量％、４．６重量％に迄高くなると、高い
選択性を保持した侭無担持γ−アルミナと略同程度の高
い分解率を示している。同様な傾向はナトリウム又はリ
チウム担持γ−アルミナ触媒にも見られ、約３重量％ナ
トリウム又は３重量％以下のリチウム担持Ｔ−アルミナ
触媒でもメタノール分解率をそれ程低下させずに選択性
が向上している。このように、γ−アルミナにアルカリ
金属を担持させることにより、水素及び−酸化炭素への
メタノール分解反応の選択性が向上し、アルカリ金屈担
持量を増すと分解率の低下が極めて少なく高活性で而も
高選択性を示す触媒を調製できる。(The following margins continue on the next page.) From the table, T-alumina that does not support alkali metal has a high methanol decomposition rate, but produces a lot of methane and water.
The selectivity of the methanol decomposition reaction to hydrogen and carbon oxide is extremely low. On the other hand, with alkali metal-supported γ-alumina, although the decomposition rate tends to decrease, it produces less methane and water, and the main products are hydrogen and carbon oxide, resulting in a marked improvement in selectivity. . A decrease in methanol decomposition rate is especially seen when the amount of alkali metal (potassium in this example) is as low as 0.29% by weight, but when the amount of potassium is as high as 3.6% and 4.6% by weight. As a result, the decomposition rate is almost as high as that of unsupported γ-alumina which maintains high selectivity. A similar trend is observed with sodium or lithium-supported γ-alumina catalysts; approximately 3 wt.% sodium or 3 wt.% lithium-supported T-alumina catalysts also improve selectivity without significantly reducing the methanol decomposition rate. There is. In this way, by supporting an alkali metal on γ-alumina, the selectivity of the methanol decomposition reaction to hydrogen and carbon oxide is improved, and when the amount of alkali metal supported is increased, the decomposition rate is extremely small and the activity is high. However, catalysts with high selectivity can be prepared.
カリウムの担持量が０．２９重量％では、反応開始から
１時間の時点での分解率は３２％程度であるが、この時
点での分解は、主として前記（２）式及び（４）式の反
応によっており、他の反応は比較的僅かしか進行してい
ない、更に反応時間を延長すれば、前ＣＨ３０Ｈからも
（２）式及び（４）式の反応でＣＯ＋２Ｈ２０が生成し
、分解率は高（なるものと考えられる。表の結果から短
時間の反応で高い分解率を得ようとするには、アルカリ
金属の担持量は３重量％以上とするのが好ましいことが
解る。When the amount of potassium supported is 0.29% by weight, the decomposition rate at one hour from the start of the reaction is about 32%, but the decomposition at this point is mainly due to the equations (2) and (4) above. If the reaction time is further extended, CO+2H20 will be generated from the previous CH30H in the reactions of equations (2) and (4), and the decomposition rate will be high. (This is considered to be the case.) From the results in the table, it can be seen that in order to obtain a high decomposition rate in a short reaction time, it is preferable that the amount of alkali metal supported be 3% by weight or more.
以上の結果は反応温度４５０℃での結果であるが、反応
温度を４５０℃とした場合は、反応温度４００℃の場合
に較べて改質反応の活性及び選択性が上昇していた。The above results were obtained at a reaction temperature of 450°C, but when the reaction temperature was 450°C, the activity and selectivity of the reforming reaction were higher than when the reaction temperature was 400°C.
なお、カリウム、ナトリウム、リチウム以外のルビジウ
ム、セシウムでは、リチウムと略同程度の活性及び選択
性を示した。また、Ｔ−アルミナにアルカリ金属を担持
させる方法としては、前記のようなアルカリ金属水酸化
物水溶液中にγ−アルミナを浸漬する方法のほか、これ
らの炭酸塩等の水溶液中にγ−アルミナを浸漬する方法
も採用可能である。Note that rubidium and cesium, other than potassium, sodium, and lithium, showed approximately the same activity and selectivity as lithium. In addition, as a method for supporting an alkali metal on T-alumina, in addition to the method of immersing γ-alumina in an aqueous solution of alkali metal hydroxide as described above, γ-alumina is immersed in an aqueous solution of these carbonates, etc. A method of immersion can also be adopted.
図面はカリウム担持γ−アルミナ触媒表面での吸着型メ
タノールの赤外線スペクトルの温度依存性を示すグラフ
である。The figure is a graph showing the temperature dependence of the infrared spectrum of adsorbed methanol on the surface of a potassium-supported γ-alumina catalyst.
Claims (1)
ウム、リチウム、ルビジウム及びセシウムの１種又は２
種以上が担持されたメタノール改質用触媒。1. One or two of potassium, sodium, lithium, rubidium, and cesium on a carrier mainly composed of alumina
A catalyst for methanol reforming that supports more than one species.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21478386A JPS6369542A (en) | 1986-09-11 | 1986-09-11 | Methanol reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21478386A JPS6369542A (en) | 1986-09-11 | 1986-09-11 | Methanol reforming catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6369542A true JPS6369542A (en) | 1988-03-29 |
Family
ID=16661463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21478386A Pending JPS6369542A (en) | 1986-09-11 | 1986-09-11 | Methanol reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6369542A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7966966B2 (en) | 2005-07-29 | 2011-06-28 | Mikado Technos Co., Ltd. | Vacuum high pressure filling equipment |
-
1986
- 1986-09-11 JP JP21478386A patent/JPS6369542A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7966966B2 (en) | 2005-07-29 | 2011-06-28 | Mikado Technos Co., Ltd. | Vacuum high pressure filling equipment |
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