JPS5983919A - Manufacture of heat treated carbon - Google Patents

Manufacture of heat treated carbon

Info

Publication number
JPS5983919A
JPS5983919A JP58168479A JP16847983A JPS5983919A JP S5983919 A JPS5983919 A JP S5983919A JP 58168479 A JP58168479 A JP 58168479A JP 16847983 A JP16847983 A JP 16847983A JP S5983919 A JPS5983919 A JP S5983919A
Authority
JP
Japan
Prior art keywords
surface area
carbon
heating
temperature
heat treatment
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.)
Granted
Application number
JP58168479A
Other languages
Japanese (ja)
Other versions
JPS6241163B2 (en
Inventor
ジヨン・ジエ−ムズ・マツカ−ロ−ル
ジヨン・トレバ−・ケント・クラ−ク
スチ−フアン・ロバ−ト・テニソン
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP PLC
Original Assignee
BP PLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BP PLC filed Critical BP PLC
Publication of JPS5983919A publication Critical patent/JPS5983919A/en
Publication of JPS6241163B2 publication Critical patent/JPS6241163B2/ja
Granted legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/415—Catalytic processes with metals
    • C07C5/417—Catalytic processes with metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B01J35/60—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • B01J35/615—
    • B01J35/617—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/58—Platinum group metals with alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 〔発明の属する技術分野〕 本発明は、新規な形態のカーボン、特に触媒担体として
優れた性質を有する熱処理カーボンの製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a method for producing a new form of carbon, particularly heat-treated carbon that has excellent properties as a catalyst carrier.

〔発明の目的並びに要点〕[Purpose and main points of the invention]

この発明の１目的は、（１）基礎平面表面積が少なくと
も１００？ｉ’／ｊ’であり、（２１Ｂ　Ｂ　Ｔ表面二
対基礎平面表面積の比が５：１より多くなく、かつ（５
）基礎平面表面積対エツジ表面積の比が少なくとも５：
１の新規な形態のグラファイト含有カーボンを提供する
ことである。One object of this invention is to (1) have a basic plane surface area of at least 100? i'/j', and the ratio of the two B T surfaces to the basic plane surface area is not more than 5:1, and (5
) The ratio of base plane surface area to edge surface area is at least 5:
An object of the present invention is to provide a novel form of graphite-containing carbon.

グラファイト含有カーボンは、成分原子が複数の層を形
成している結晶性層構造を包含しており、この層は、比
較的弱いグアノ　デル　ヴアールス　分数力によって互
いＰこ結合している。Graphite-containing carbons include a crystalline layered structure in which the component atoms form multiple layers, which are bonded to each other by relatively weak guano del vuals fractional forces.

この物質の結晶の表面積は、殆んど層の基礎平面によシ
形成され、層の縁部により形成される表面積は少ない。The surface area of the crystals of this material is mostly formed by the basal planes of the layers, with less surface area formed by the edges of the layers.

通常結晶性物質と一緒に幾らかの無定形の炭素が存在し
２ている・ 基礎表面積は、ｎ−へブタンからのｎ−トドリアコンタ
ンの吸着熱を測定し１．００ＪＶ　　　は基礎表面積１
９３ｍ″タ　　として測らｔＬる。同様にエツジ表面積
は、ｎ−へブタンからのｎ−ブタノールの吸着熱′ｆｒ
：測定し、１．［１ＯＪｊｌ　　　はエツジ表面積６．
７ｍｉ　　として測定される。There is usually some amorphous carbon present along with the crystalline material.2 The basic surface area is determined by measuring the heat of adsorption of n-todolyacontane from n-hebutane and is 1.00 JV, which is the basic surface area of 1.
Similarly, the edge surface area is determined by the heat of adsorption of n-butanol from n-hebutane 'fr
: Measure, 1. [1OJjl is the edge surface area6.
Measured as 7mi.

吸着熱は、“ケミストリー　アンド　インダストリー”
２０，３，１９６５．　　Ｐ４８２〜４８５に記載され
ている流体マイクロカロリメーターを用いて測定するこ
とができる。Adsorption heat is “chemistry and industry”
20, 3, 1965. It can be measured using the fluidic microcalorimeter described in P482-485.

ＩＪＥＴ表面積ｅよ、　Ｊ　、Ａｍ　、　Ｃｈｅｍ　、
　Ｓｏｃ　６０゜３０９、（１９３Ｂ＞Ｋｎｔ：載され
ているプルチー。IJET surface area e, J, Am, Chem,
Soc 60°309, (193B>Knt: Pluchie listed.

ｘ　ｉ　ツ）　ｋ　Ｌびチー　チー　（１３ｒｕｎａｕ
ｅｒ　、飾ｍｅｔａｎｄ　’Ｉ’ｅＪｌｅｒ　）の窒素
吸着法により測定された表面積である。これは、全表面
積、即ち結晶の基礎平面表面積、結晶のエツジ表面積お
よび不定形炭素部分の表面積に相当する。x i tsu) k Lbi chi chi (13runau
er, surface area measured by the nitrogen adsorption method (Metand'I'eJler). This corresponds to the total surface area, ie the basic planar surface area of the crystal, the edge surface area of the crystal and the surface area of the amorphous carbon portions.

この新らしい形のグラファイト含有カーｄインは、白金
族金属用触媒担体として使用することが出来、この担持
された金属触媒は、水素転移反応に有効である。This new form of graphite-containing cardin can be used as a catalyst support for platinum group metals, and the supported metal catalysts are effective in hydrogen transfer reactions.

かくて、この発明の他の態様によれば、（１）担体とし
ての（ａｔ基礎平面表面積が少なくとも１００ｍ’ｉｐ
であり、（ｂ）ＢＥＴ表面積対、基礎平面表面積の比が
５：１以上でなく、かつ（ｃｌ基礎平面表面積二対ツジ
表面積の比が少なくとも５：１のグラファイト含有カー
ボンが提供される。Thus, according to another aspect of the invention, (1) the carrier (at a basic planar surface area of at least 100 m'ip
and (b) a graphite-containing carbon having a ratio of BET surface area to basal planar surface area of not greater than 5:1 and a ratio of (cl basal planar surface area to 2 basal planar surface area of at least 5:1) is provided.

グラファイト含有カーボンの基礎平面表面積は、１５０
ｍ’／Ｐ乃至１０００ｍ”／Ｆの範囲内にあるのが好ま
しい。若し、この面積が１０００ｍ′／　Ｐよυも大き
い場合には、触媒担体として充分な強度を有しない。The basic plane surface area of graphite-containing carbon is 150
It is preferable that the area is within the range of m'/P to 1000 m''/F. If this area is as large as 1000 m'/P, it will not have sufficient strength as a catalyst carrier.

ＪＪ　Ｅ　Ｔ表面二対基礎平面表面積の比が、理論的な
最小値である１に近い程、その物質の品質は高くなる。The closer the ratio of JJ ET surface 2 to base plane surface area is to the theoretical minimum value of 1, the higher the quality of the material.

即ち、結晶性物質の割合が高くなシ、そして無定形物の
割合が低くなるｎ夾際上の理由から、この比は２対１乃
至ｉ、ｏｌ：１の範囲内にあるのが好ましい。That is, this ratio is preferably in the range of 2:1 to i,ol:1 for reasons such as a high proportion of crystalline substances and a low proportion of amorphous substances.

基礎平面表面積対エツジ表面積の比は１０：１より大き
いのが好ましく、３００：１よシ大きいのが最も好まし
い。Preferably, the ratio of base planar surface area to edge surface area is greater than 10:1, and most preferably greater than 300:1.

グラファイト含有カーボン担体は、５乃至９の範囲内の
Ｊ）Ｈを有しているのが好ましく、６乃至８のｐＨがよ
シ好ましく、約７であるのが最も好ましく、かつ１重量
％以下の吸着酸素を含有しているのか好ましく、０．５
重量％以下の吸着酸素を含有しているのがよシ好ましい
。吸着されている酸素が低ければ低い程、ｐＨは７に近
くなる。Preferably, the graphite-containing carbon support has a Preferably, it contains adsorbed oxygen, 0.5
More preferably, it contains less than % by weight of adsorbed oxygen. The lower the oxygen adsorbed, the closer the pH will be to 7.

グラファイト含有カーボンは高純度のものでなければな
らない。囲えば、灰分含有量は０．１重量−以下でなけ
ればならず、０．０５　％以下が好ましく、０．０２％
以下がより好ましいｅグラファイト含有カーボンの粒子
の大きさは重要でなく５その使用目的との関連で既知の
方法で制量することができる。こまかい粒子範囲のもの
けスラリー法に用いられ、粒状のものは同定床法で用い
られる。The graphite-containing carbon must be of high purity. If the
The following is more preferred: e The size of the graphite-containing carbon particles is not critical and can be controlled by known methods in relation to its intended use. It is used in the Mononoke slurry method with fine particles, and the granular one is used in the identified bed method.

グラファイトは、（ａｌココナツト炭、石炭、泥炭等か
ら誘導された活性炭、（ｈｌカーボンブラック類、（Ｃ
）石油残置のコーキングにより製造さ！またカーボン類
、および（ｆ３）英国特許第１１６８７８５号記載の方
法で製造される如き親油性グラファイトを包含する、多
くのイ」々の形態のカーボンから製造されうる、 担体は、１００乃至３０００ゴ／Ｐの範囲内のＢＥＴ表
面積を有するカーボンを、不活性雰囲気中で、９００℃
乃至３３００℃、好ましくけ１５００℃乃至２７００℃
の温度で、グラファイト含有カーボンを生成するのに十
分な時間加熱する仁とにより製造することができる。Graphite includes activated carbon derived from (al coconut charcoal, coal, peat, etc.), (hl carbon blacks, (C
) Manufactured by caulking with petroleum residue! The carrier can also be made from many different forms of carbon, including carbons and (f3) lipophilic graphite, such as made by the method described in GB 1168785. Carbon having a BET surface area within the range of P was heated at 900°C in an inert atmosphere.
〜3300℃, preferably 1500℃〜2700℃
The graphite-containing carbon can be produced by heating the carbon at a temperature of

出発原料とＥ〜て用いられるカーボンは、前述の熱処理
前に、約１０００℃において、少なくとも５００ザ／Ｐ
の１３　ＪＤ　Ｔ表面積を有するものが好ましい。The carbon used as the starting material is heated at a temperature of at least 500 °C/P at about 1000°C prior to the heat treatment described above.
Those having a surface area of 13 JD T are preferred.

グラノアイト含有カーボンの訓整祉、選択されたカーボ
ンの種類およびＢ　Ｐ３　Ｔ’対基礎乎面表面積ならび
に基礎平面表面積対エツジ表面積の比を最適のものにす
る為に選択される不活性ならびに酸化条件下の熱処理の
結合使用に依存して変化する。The preparation of the granoite-containing carbon, the type of carbon selected and the inert and oxidizing conditions selected to optimize the ratio of B P3 T' to basal planar surface area and basal planar surface area to edge surface area. The heat treatment will vary depending on the bond used.

不活性ガス中における加熱によりグラファイト性物質の
割合が増加する。即ち、はじめの比が減少し、そして第
２番目の比が増加する。、最も多くの形態のカーボンは
、この処理により全表面積が著しく減少されるが、常に
そうではなく、いくらかの形態のカーボンは加熱に際し
比較的少しの表面積の減少しか示さない、注意深く制御
された条件下における酸化は、比較において表面積を増
加する。Heating in an inert gas increases the proportion of graphitic material. That is, the first ratio decreases and the second ratio increases. , most forms of carbon have their total surface area significantly reduced by this treatment, but this is not always the case, and some forms of carbon show relatively little surface area loss upon heating under carefully controlled conditions. Oxidation below increases surface area in comparison.

カーボン担体の調製は、典型的におよび一般Ｋ（次の）
６つの工程を包含している。（１）不活性ガス中におけ
る９００℃乃至３３００℃の間の温度での最初の熱処理
、　（２１３００℃乃至１２００℃の間の温度ＶＣおい
て行なう酸化工程および（３）不活性ガス中における１
０００’Ｃ乃至３０００℃の閣の温度で、かつ好ましく
ｌｉ最初の熱処理の温度より高くない温度で行なう、再
度の熱処理 （１）および（３）の工程において、１０００℃までの
温度において用いるのに適する芽囲気としては窒素があ
げらＪｌ−る。この温度以上では、不活性ガスとして、
例えば、アルゴンまたはヘリウムを用いるのが好ましい
。工程（２）における適当な酸化媒体としては、空気、
水蒸気および二酸化炭素が包含される。若し空気を用い
る場合には、３００℃乃至４５０℃の範囲内の温度が好
ましく、水蒸気または二酸化炭素を用いる場合には、８
００℃乃至１２００℃の範囲内の温度が好ましい・ 不活性雰囲気中において加熱する間、カーボンの少なく
とも一部はグラファイトに変換されそしてケトン類、ヒ
ドロキシル、カルボン酸類および類似物の如き、吸着さ
れている有機酸素含有基が除去されると思われる。処理
されたカーボン中に有機酸素含有基が存在しないこと（
１チ以下）は、この炭素を相体として用いた触媒の選択
性との関連で重要なことである。何となれば、酸素含有
基は副反応を促進することが報告されているからである
。The preparation of carbon supports is typically and generally K (next)
It includes six steps. (1) an initial heat treatment in an inert gas at a temperature between 900°C and 3300°C; (3) an oxidation step carried out at a temperature VC between 21300°C and 1200°C;
For use at temperatures up to 1000°C, in steps (1) and (3) of the second heat treatment, carried out at temperatures between 000'C and 3000°C, and preferably at a temperature not higher than the temperature of the first heat treatment. Nitrogen is a suitable bud surround atmosphere. Above this temperature, as an inert gas,
For example, it is preferable to use argon or helium. Suitable oxidizing media in step (2) include air,
Water vapor and carbon dioxide are included. If air is used, the temperature is preferably within the range of 300°C to 450°C, and if water vapor or carbon dioxide is used, the temperature is preferably within the range of 80°C to 450°C.
Temperatures in the range 00°C to 1200°C are preferred. During heating in an inert atmosphere, at least a portion of the carbon is converted to graphite and adsorbed, such as ketones, hydroxyls, carboxylic acids and the like. It is believed that organic oxygen-containing groups are removed. The absence of organic oxygen-containing groups in the treated carbon (
1 H) is important in relation to the selectivity of catalysts using this carbon as a phase. This is because oxygen-containing groups have been reported to promote side reactions.

〔発明の実施例〕[Embodiments of the invention]

実施例１ カボット　コーポレーション（ＣａｂｏｔＣｏｒｐｏｒ
ａｔｉｏｎ　　）から“ブラック　ノ（−ルス７１１１
（Ｂｌａｃｋ　Ｐｅａｒｌｓ　７１　）という商標名で
販売されているカーボン　プラック　４５Ｆを揮発物を
除く為に窒累雰囲気下で１０００℃に加熱しそして室温
に冷却した（重量損失１１．４ｆｉ）。Example 1 Cabot Corporation
ation) from “Black No(-Rus7111
Carbon Plaque 45F, sold under the tradename Black Pearls 71, was heated to 1000° C. under a nitrogen atmosphere to remove volatiles and cooled to room temperature (weight loss 11.4 fi).

ついでこのサンプルをアルゴン雰囲気中で室温から２７
００℃に加熱し、この温度に約３０分間保持し、ついで
冷却した（さらに２．３俤の重量損失１０この第２回目
の加熱および冷却処理は約３時間かかった。冷却後カー
ボンは黒色と灰色のまだらな外端を有し、そして次の分
析値を有していた。This sample was then heated from room temperature to 27°C in an argon atmosphere.
This second heating and cooling process took about 3 hours. After cooling, the carbon turned black. It had a mottled gray outer edge and the following analysis values:

ＢＥＴ表面ｆｉｌｌ　　　　　　　　１８０ｍ、’／ｌ
’基礎表面精　　　　　　　１５０ｙｒ＋″／！縁部表
面積　　　　　　　０．３６７７１”／ＰＢ　ｇ　Ｔ　
／基礎比　　　　　　１．２　：　１基礎／縁部比　　
　　　　４２７：１ ｐＨ７（水とスラリーにして測定） ％　グラファイト　３０重Ｂ％（Ｘ−線回折）俤　無定
形カーボン　　　７０重景気 全金属含有量　　　　　　１３ｐｐｍ 灰分含有量　　　　　　　　　ゼロ 俤　吸着された酸素　　　　　ゼロ 加熱処理した結果、全Ｍ貴損失は１３．７重量係であっ
た。BET surface fill 180m,'/l
'Basic surface precision 150yr+''/!Edge surface area 0.36771''/PB g T
/Foundation ratio 1.2: 1Foundation/Edge ratio
427:1 pH 7 (measured as a slurry with water) % Graphite 30% by weight (X-ray diffraction) Amorphous carbon 70% Total metal content 13 ppm Ash content Zero Adsorbed oxygen Zero Result of heat treatment , the total M loss was 13.7% by weight.

このカーボンは、２００−４０ＯＡの直径を有する球形
であって、これは外部にグラファイトの皮を有している
ものと考えられる。The carbon is believed to be spherical with a diameter of 200-40 OA and has an outer graphite skin.

触媒の製造 ９０℃で４時間、１／、。モルのｐｔ　（ＮＨ，ｌ　４
（ＯＨ）２の水性溶液で含浸させ、ついで１２０℃で２
時間乾燥さぜることによｐ、０，７重Ｊｔ％の白金を担
体に添加した。Preparation of catalyst 4 hours at 90°C, 1/. moles of pt (NH,l 4
impregnation with an aqueous solution of (OH)2 and then at 120°C.
P, 0.7 weight Jt% of platinum was added to the carrier by dry stirring for an hour.

ついで、この含浸さｉｔた物質の一部を、１を当りソジ
ウムカーボネートを０．７４グラム含有している水性溶
液を用いて９０℃で２時間含浸させ、ついで１１０℃で
２時間乾燥した後、４Ｏ−１００ＤＢＳメツシユの大き
さに篩分けし、ついで５００℃で、４０００Ｖ／Ｖ／時
の流動水素流中で２時間還元した。得られた触媒は６０
０ｐｐｍのソジウムを含有していた。これは白金の７３
原子％に相当する。A portion of this impregnated material was then impregnated with an aqueous solution containing 0.74 grams of sodium carbonate per part for 2 hours at 90°C and then dried at 110°C for 2 hours. , 40-100 DBS mesh size and then reduced for 2 hours at 500° C. in a flowing hydrogen stream of 4000 V/V/hr. The catalyst obtained was 60
It contained 0 ppm of sodium. This is Shirokane's 73
Corresponds to atomic percent.

白金およびソジウムの含浸中ならびにつゾいて水を除去
する間中、両成分を触媒ペレット中ならびにペレツＨ１
ｆｌに均一に分配するのを確実圧する為に触媒を連続的
に攪拌した。During impregnation with platinum and sodium and during soaking to remove water, both components were added to the catalyst pellets and pellets H1.
The catalyst was continuously stirred to ensure uniform distribution over fl.

触媒担体として上述のように製造１−たカーボンの使用 （１）０．２２５Ｆの触媒を、ミクロリアクター中で５
００℃、大気圧下で、水素対ｎ−ヘキザンのモル比７：
１ならびに液空間速度４ｖ／ｖ／時で、ｎ−ヘキサンの
脱水素環化反応に使用した。ミクロリアクターは、０゜
４５＃Ｉ／の触媒用容量を有していた。Use of carbon produced as described above as catalyst support (1) Catalyst at 0.225 F was heated to
At 00°C and atmospheric pressure, the molar ratio of hydrogen to n-hexane is 7:
It was used in the dehydrocyclization reaction of n-hexane at a liquid hourly space velocity of 1 and a liquid hourly space velocity of 4 v/v/hour. The microreactor had a catalyst capacity of 0°45 #I/.

（２）　　ンジウムの添加工程を省略しまた上述の触媒
の１部についても亦同じ条件下でテストを行った。その
結果は次の通シである。(2) A portion of the above-mentioned catalyst was also tested under the same conditions, with the addition step omitted. The result is the following passage.

実施例２ カボット　コーポレーションから商標名“ブラック　パ
ールス　２′″として販売されているカーボン　ブラッ
クのサンプルを実施例１ｈ己載の如く２段階で加熱し、
そして冷却した（全重陽損失３２重債％）。Example 2 A sample of carbon black sold by Cabot Corporation under the trade name "Black Pearls 2'" was heated in two stages as described in Example 1h.
Then it was cooled (total loss of 32%).

冷却後カーボンは黒と灰色のまだらの外観を有し、そし
て次の分析値を有していた。After cooling, the carbon had a mottled black and gray appearance and had the following analytical values:

ＢＥＴ表面積　　　　　　　２３５ゴ／Ｐ基礎表面積　
　　　　　　　２５０ｍ”ＩＰ縁部表面積　　　　　　
　　　０．３　ｍ”／　ｊｉＢ　Ｎ　’ｒ　／基礎比　
　　　　　１．０２　：　１基礎／縁部比　　　　　　
　７６６：１ｐＨ７ 全金属含有量　　　　　　　　１３ｐｐｍ灰分含有員　
　　　　　　　　　ゼロ 係　吸着されている酸素　　　　　　ゼロ係　グラファ
イト　　　　　　　　３０ｆｂｑｂ　　無定形炭素　　
　　　　　７０％前述の担体を、実施例１中に記載され
ている如く処理することにより、０．７重ｉ％の白金お
よび６００ｐｐｍのソジウムを含有している触媒を製造
した。BET surface area 235 Go/P basic surface area
250m” IP edge surface area
0.3 m”/jiB N'r/base ratio
1.02 : 1 base/edge ratio
766:1 pH7 Total metal content 13ppm Ash content
Zero factor Adsorbed oxygen Zero factor Graphite 30fbqb Amorphous carbon
A catalyst containing 0.7 wt% platinum and 600 ppm sodium was prepared by treating the 70% support described above as described in Example 1.

（１）ｎ−ヘキサンを実施例１記載のように脱水素環化
した。(1) n-hexane was dehydrocyclized as described in Example 1.

Ｑ）上述のように製造したがソジウム添加工程を省略し
た触媒についても亦同じ条件下でテストを行なった。結
果は次の通りであった。Q) A catalyst prepared as described above but omitting the sodium addition step was also tested under the same conditions. The results were as follows.

参考ゼ１１１ 実施例２記載のソジウム含有触媒を、実施例１の操作条
件下で連＃ｌ！４２時間、ｎ−ヘキサンのベンゼンへの
脱水素環化に使用した。Reference Ze111 The sodium-containing catalyst described in Example 2 was used in series #1 under the operating conditions of Example 1! 42 hours was used for the dehydrocyclization of n-hexane to benzene.

この反応中得らｔｔ７を結果は、次の通シであった。The results of tt7 obtained during this reaction were as follows.

参考例２ 商業的に入手しうる数種の異なった脱水素環化触媒（先
ついて、実施例１の操作条件下にテストを行ない、その
活性およびベンゼンの収量を実施ｆ１１２記載のソジウ
ム含有触媒のそれらと比較した。Reference Example 2 Several different commercially available dehydrocyclization catalysts were previously tested under the operating conditions of Example 1 to determine their activity and benzene yield. compared with them.

その結果は次の通りである。The results are as follows.

実施例３ ノーリット　フライデスブール　リミテッド（Ｎｏｒｌ
ｔ　Ｃ１ｙｄｅｓｄａｌｅ　Ｌｔｄ、）から商標名ノー
リット　エクストラ（Ｎｏｒｉｔ　Ｅｘｔｒａ　　）と
して販売されている活性炭のサンプルをアルゴン中で１
５００’Ｃで加熱し、部分的にグラファイト化した。こ
の物質ｔｉ部分的に崩壊されていた。即ち、その全表面
積は可成減少されていた。Example 3 Norl Freydesbourg Limited (Norl
A sample of activated carbon sold under the trade name Norit Extra by Clydesdale Ltd.
It was heated at 500'C to partially graphitize. This material ti had partially disintegrated. That is, its total surface area has been significantly reduced.

ついで、その２Ｆを表面積を増加する為に５０ｍ１１分
の割合で流れている空気中で、４５０℃の温度で５時間
加熱することにより酸化した。The 2F was then oxidized by heating at a temperature of 450° C. for 5 hours in air flowing at a rate of 50 ml/min to increase the surface area.

次の結果が得られた。The following results were obtained.

酸化前＋１７）ＢＥＴ表面ｆ１４　　　　７４　ＣＪｒ
ｎ”／７酸化後のＢＥＴ表面ｙ４　　　１３５０ｍ”／
ｊ’酸化酸化基礎表面積　　　　　１６９７７１”／Ｐ
酸化彼の基礎表面積　　　　　４３０ｍ“／ｌ酸酸化前
縁部表面積　　　　　　２．５　ｍ’／　Ｆ酸化後の縁
部表面積　　　　　　３５　ｍ、”／　ｊ’ＮＩ：終曲
な１３　Ｅ　Ｔ　／基礎比　　　　　３：１最終的な基
礎／縁部比　　　　　１２：１加熱処理による全京貴損
失は１６．７％であった。ｐＨは７であった。Before oxidation +17) BET surface f14 74 CJr
n”/7 BET surface after oxidation y4 1350m”/
j' Oxidation oxidation basic surface area 169771"/P
Basal surface area of oxidation 430 m"/l Acid oxidation front edge surface area 2.5 m'/F Edge surface area after oxidation 35 m,"/j'NI: final 13 E T /basal ratio 3:1 final The total loss due to heat treatment with a base/edge ratio of 12:1 was 16.7%. pH was 7.

実施例４ ライムホルン　ケミカルス　リミテッド（Ｗｌｍｂｏｒ
ｎｅ　Ｃｈｅｍｉｃａｌｓ　Ｌｉｄ、　）　　から訪標
名ニスニーニスシー１３　（８Ａ８Ｃ１３）として販売
されている活性炭のサンプルを、実施例３と同様に処理
した。たゾアルゴン雰囲気中での最初の熱処理を１９０
０℃で行なった点で異なっていた。Example 4 Limehorn Chemicals Limited (Wlmbor
A sample of activated carbon sold under the trade name Nisni Nisci 13 (8A8C13) by New Chemicals Lid, Inc. was treated as in Example 3. The first heat treatment in an argon atmosphere was carried out at 190°C.
The difference was that it was carried out at 0°C.

次の表にｈα載した結果が得られた。The results listed hα in the following table were obtained.

実施例５ ケトジエン　カーボン　エフＯブイ（ＫｅｔｊｅｎＣａ
ｒｌ）ｏｎ　Ｎ、Ｖ、）　から商標名　ケトジエン　　
イーｖ−１ｂ　（Ｋｅｔｊｅｎ　ＥＣｉｂ）　　として
販売されている活性炭を実施例６と同様に処理した。Example 5 KetjenCa
rl) on N, V,) to trade name ketodiene
Activated carbon sold as Ketjen ECib was treated in the same manner as in Example 6.

得らＪした結果を次の表に示す。The results obtained are shown in the following table.

実施例６ フＩＪティシュ　セカ　コンパニー　リミテッド（Ｂｒ
１ｔ１ｓｈ　Ｃｅｃａ　Ｃｏ、　Ｌｔｄ、　）から商標
名アンチ　カーボン　ニーシー　ａＯ（ＡｎｔｉＣａｒ
ｂｏｎｅ　ＡＣ４Ｑ　）として販売されている活性炭を
実施例６と同様に処理し念。Example 6 IJ Tissue Seka Company Limited (Br
1t1sh Ceca Co, Ltd.) to the trade name Anti Carbon Nice aO (AntiCar
Activated carbon sold as bone AC4Q) was treated in the same manner as in Example 6.

得らｉｔた結果を次の表に示す。The results obtained are shown in the following table.

実施例７ 本発明に係る製造方法で得た熱処理カーボン及び規定外
のカーボンにつき、表面性質と触媒活性を比較した。Example 7 The surface properties and catalytic activity of heat-treated carbon and non-specified carbon obtained by the production method according to the present invention were compared.

八〇４０として販売される活性炭につき３種類の熱処理
を実施した。Three types of heat treatments were performed on activated carbon sold as 8040.

７−■　アルゴン中で９００’Ｃ，１Ｊｒｌ熱し、次に
空気中４５０℃で５時間加熱した。7-■ Heated at 900'C for 1 Jrl in argon, then heated at 450°C in air for 5 hours.

７−■　７−■と同様に熱処理をし、次に不活性ガス中
１５０００に加熱した。7-■ Heat treatment was carried out in the same manner as in 7-■, and then heated to 15,000 ℃ in an inert gas.

７−■　７−■と同様に熱処理をし、次に不活性ガス中
１７００℃に加熱した。7-■ Heat treatment was carried out in the same manner as in 7-■, and then heated to 1700°C in an inert gas.

ここに得られたカーボンに０．７％白金担持触媒を調製
し、ミクロ反応器に充填し、ｎ−ヘキサンと水素を送入
して脱水素環化を行なわせた。A 0.7% platinum-supported catalyst was prepared on the carbon thus obtained, filled in a microreactor, and n-hexane and hydrogen were introduced to carry out dehydrogenation cyclization.

反応条件： ｎ−ヘキサンの液空間速度（マ／Ｖ／時）　　　２温　
　度　　　　　　　　　（Ｃ）　　　　　　５００圧　
　力　　　　（給体バール）　　　　１Ｈ２／ヘキサン
　　　　（モル比＞　　　１０：１反応結果の表示： 結果は次の通ジである。Reaction conditions: Liquid hourly space velocity of n-hexane (ma/v/hour) 2 temperatures
degree (C) 500 pressure
Power (feed bar) 1H2/hexane (mole ratio > 10:1 Reaction result display: The results are as follows.

７−■のカーボンのように不活性ガス中１５００℃以上
の加熱処理をせず、基礎平面表面積／エツジ表面積が５
以下で規定外のカーボンは触媒性能が劣り、ベンゼン収
率が悪いことが示されている。Unlike the carbon in 7-■, it is not heat treated at 1500℃ or higher in an inert gas, and the basic plane surface area / edge surface area is 5.
It is shown below that non-specified carbon has poor catalytic performance and poor benzene yield.

特許出願人 ザ　ブリティッシュ　ビトローリアム コンパ二一　リミテッド し−１１ト・ 第１頁の続き 優先権主張　＠　１９７４年９月２日■イギリス（ＧＢ
）■３８１８３ ０発　明　者　スチーファン・ロバート・テニソン 英国サリー州ニュー・ホー・フ ァーレイ・ロード６２番Patent Applicant: The British Vitroleum Company Limited - 11th Page 1 Continued Priority Claim @ September 2, 1974 ■ United Kingdom (GB
)■38183 0 Inventor Stephen Robert Tennyson 62 New Haw Farley Road, Surrey, UK

Claims (1)

【特許請求の範囲】 （１＋ＢＤＴ表面積が１００〜３０００ｍ”；／ｆの範
囲内のカーボンを不活性雰囲気中にて１５００℃以上よ
Ｊ）２７００’Ｃ，の範囲内のｍ度で加熱することから
なる加熱処理によって（１）少なくとも１００ｍ’／ｊ
’の基礎平面表面積、Ｔ２１　Ｂ　ＢＩ　Ｔ表面積対基
礎平面表面積の比が５：１以下、かつ已）基礎平面表面
積対エツジ表面積の比が少なくとも５：１であるグラフ
ァイト含有カーボンに変換することを特徴とする不活性
雰囲気中でカーボンを加熱することによる加熱処理力〜
ボンの製造方法・ （２）加熱処理は゛またカーボンを酸化雰囲気中で加熱
することからなることを特徴とする特許請求の範囲第１
項記載の熱処理カーボンの製造方法。 （３）カーボンは、（１）不活性雰囲気中にて１５００
℃以上２７００℃の範囲内の温度で加熱し、　（２）酸
化雰囲気中にて３００〜１２００℃の範囲内の温度で加
熱し、引続き（３）不活性雰囲気中にて１５００℃以上
２７００℃の範囲内の温度て加熱する工程からなる加熱
処理に付することを特徴とする特許請求の範囲第１項記
載の熱処理カーボンの製造方法。 （４）　　カーボンを空気よりなる酸化雰囲気中にて６
００〜４５０℃の範囲内の温度で加熱することを特徴と
する特許請求の範囲第２項または第３項に記載の熱処理
カーボンの製造方法。 （５）出発原料として使用するカーボンは加熱処理前に
少なくとも５００ｍ”／ＰのＢＥＴ表面積を有する特許
請求の範囲第１乃至第６項のいずれかに記載の熱処理カ
ーボンの製造方法。 （６）熱処理はＢＥＴ表面積対基礎平面表面積の比が２
＝１からｔｏｌ：１であるカーボンが得られる時間と温
度を用いて実施されることを特徴とする特許請求の範囲
第１乃至第５項のいずれかに記載の熱処理カーボンの製
造方法Ｏ （ハ　熱処理ｔｊ、基礎基礎平面表面二対エツジ表面積
が１０＝１以上であるカーボンが得られる時間と温度を
用いて実施されることを特徴とする特許請求の範囲第１
乃至第６項のいずれかに記載の熱処理カーボンの製造方
法。[Claims] From heating carbon having a surface area of 1+BDT in the range of 100 to 3000 m''; (1) At least 100 m'/j
', the ratio of the basal plane surface area to the basal plane surface area of T21 BBI T is 5:1 or less, and 3) the ratio of the basal plane surface area to the edge surface area is at least 5:1. Heat treatment power by heating carbon in an inert atmosphere ~
Claim 1, characterized in that (2) the heat treatment also consists of heating the carbon in an oxidizing atmosphere.
A method for producing heat-treated carbon as described in Section 1. (3) Carbon is (1) 1500 in an inert atmosphere.
(2) Heating at a temperature within the range of 300 to 1200°C in an oxidizing atmosphere, followed by (3) Heating at a temperature of 1500°C to 2700°C in an inert atmosphere. 2. The method for producing heat-treated carbon according to claim 1, wherein the heat-treated carbon is subjected to a heat treatment comprising a step of heating at a temperature within a range. (4) Carbon in an oxidizing atmosphere consisting of air.
The method for producing heat-treated carbon according to claim 2 or 3, characterized in that heating is performed at a temperature within the range of 00 to 450°C. (5) The method for producing heat-treated carbon according to any one of claims 1 to 6, wherein the carbon used as a starting material has a BET surface area of at least 500 m''/P before heat treatment. (6) Heat treatment has a ratio of BET surface area to basic plane surface area of 2
The method for producing heat-treated carbon according to any one of claims 1 to 5, characterized in that the method is carried out using a time and temperature that yields carbon with tol=1 to tol:1. Claim 1, characterized in that the heat treatment tj is carried out using a time and temperature that yields carbon having a two-to-edge surface area of 10=1 or more.
7. The method for producing heat-treated carbon according to any one of items 6 to 6.
JP58168479A 1974-09-02 1983-09-14 Manufacture of heat treated carbon Granted JPS5983919A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB38182/1974 1974-09-02
GB3818274A GB1471233A (en) 1974-09-02 1974-09-02 Platinum group metal catalysts
GB38183/1974 1974-09-02

Publications (2)

Publication Number Publication Date
JPS5983919A true JPS5983919A (en) 1984-05-15
JPS6241163B2 JPS6241163B2 (en) 1987-09-01

Family

ID=10401783

Family Applications (2)

Application Number Title Priority Date Filing Date
JP58168480A Granted JPS5980617A (en) 1974-09-02 1983-09-14 Hydrogen transition
JP58168479A Granted JPS5983919A (en) 1974-09-02 1983-09-14 Manufacture of heat treated carbon

Family Applications Before (1)

Application Number Title Priority Date Filing Date
JP58168480A Granted JPS5980617A (en) 1974-09-02 1983-09-14 Hydrogen transition

Country Status (3)

Country Link
JP (2) JPS5980617A (en)
BE (1) BE832993A (en)
GB (1) GB1471233A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8321255D0 (en) * 1983-08-06 1983-09-07 British Petroleum Co Plc Methanol conversion process
GB8613672D0 (en) * 1986-06-05 1986-07-09 Bp Benzin Und Petroleum Ag Chemical process
JP4764866B2 (en) * 2007-04-25 2011-09-07 関西熱化学株式会社 Catalyst carrier, catalyst, method for producing catalyst carrier, and method for producing catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5926333A (en) * 1982-08-03 1984-02-10 Nissan Motor Co Ltd Seat for automobile

Also Published As

Publication number Publication date
GB1471233A (en) 1977-04-21
BE832993A (en) 1976-03-02
JPS6241163B2 (en) 1987-09-01
JPS5980617A (en) 1984-05-10
JPS6332334B2 (en) 1988-06-29

Similar Documents

Publication Publication Date Title
US4163775A (en) Process for the synthesis of ammonia using catalysts supported on graphite containing carbon
US4055628A (en) Method for preparing graphite containing carbon
JPS6339634A (en) Conversion of synthetic gas using ror-activated catalyst
JPS60501104A (en) Gas phase hydrogenation of esters
US6479027B1 (en) Process for the preparation of ammonia and ammonia synthesis gas
WO2018056126A1 (en) Porous carbon material, method for producing same, and synthesis reaction catalyst
US4122040A (en) Platinum group metal catalyst
US4476250A (en) Catalytic process for the production of methanol
JPH021416A (en) Preparation of 2-ethylhexanol by hydrogenating 2-ethylhexenal in liquid phase, and catalyst used therein
CN113976119A (en) Cobalt-based monatomic dehydrogenation catalyst having improved thermal stability and process for producing olefin from corresponding paraffin using same
JPS5926333B2 (en) hydrogen transfer catalyst
US2292570A (en) Process for the production of catalysts
JPS5983919A (en) Manufacture of heat treated carbon
Imamura et al. Methanation activity of catalysts formed by treating intermetallic compounds nickel-silicon (Ni5Si2), nickel-silicon (Ni2Si), and cobalt-silicon (Co2Si) with oxygen
US4510071A (en) Methanol conversion process
JPS63224737A (en) Titanium oxide carrying palladium catalyst
US3948760A (en) Catalytic conversion of hydrocarbons by improved zeolite catalyst
Arai et al. Synthetic smectite-like materials containing different divalent cations as catalysts and supports for gas-phase hydrogenation of acetonitrile
JPH03173840A (en) Production of chlorotrifluoroethylene
JP3860625B2 (en) Hydrogen oxidation catalyst, hydrogen selective oxidation method, and hydrocarbon dehydrogenation method
US2407814A (en) Catalysts
EP0190307A1 (en) Fischer-tropsch catalyst
JP3135539B2 (en) Improved steam reforming catalyst for hydrocarbons
GB2033776A (en) Catalyst for the production of ammonia
JPS62269701A (en) Method for synthesizing needle-like diamond particle