JPS6245215B2 - - Google Patents
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- JPS6245215B2 JPS6245215B2 JP57111542A JP11154282A JPS6245215B2 JP S6245215 B2 JPS6245215 B2 JP S6245215B2 JP 57111542 A JP57111542 A JP 57111542A JP 11154282 A JP11154282 A JP 11154282A JP S6245215 B2 JPS6245215 B2 JP S6245215B2
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- catalyst
- methyl ethyl
- ethyl ketone
- butene
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Description
本発明はオレフインからカルボニル化合物を製
造する方法に関し、詳しくは特定の触媒の存在下
にオレフインを酸化して効率よくカルボニル化合
物を製造する方法に関するものである。
オレフインの酸化によるカルボニル化合物の製
造方法としては、いわゆるヘキストワツカー法が
知られており（特公昭36−7869号）、エチレン、
プロピレンについては既に工業的にも実施されて
いる。このヘキストワツカー法では触媒として塩
化パラジウムおよび塩化第２銅水溶液が用いられ
ている。しかしながら、この方法では可成りの塩
化物が生成する、炭素数４個以上のオレフインで
は転化率が低いなどの欠点があつた。また、この
ような欠点を改良すべく提案されたPdあるいは
RhとFe、Co、Ni、Mnなどとを組合せた触媒
（特公昭51−6643号、特開昭53−43686号）では活
性が低いという新たな問題点があつた。
本発明者らは、このような問題点を解消すべ
く、使用する触媒について検討を重ねた結果、ロ
ジウム化合物とバナジウム化合物を組合せた新規
な触媒を用いることによつて良好な転化率で、し
かも塩化物を副生することなくカルボニル化合物
を製造できることを見出し、本発明に到達したの
である。
本発明は、ロジウム化合物とバナジウム化合物
を担体に担持した触媒を用いて、オレフインと酸
素または酸素含有ガスを水の存在下で反応させる
ことを特徴とするカルボニル化合物の製造法であ
る。
本発明に用いる触媒は、触媒成分であるロジウ
ム化合物とバナジウム化合物を担体に担持させた
ものである。ここでロジウム化合物としては特に
制限はないが、水溶液、アルコール等に溶け易い
塩が好ましく、たとえばハロゲン化物、硫酸塩、
硝酸塩、塩素酸塩、酢酸塩、モノクロル酢酸塩な
どを挙げることができ、これらの中ではロジウム
のハロゲン化物、とりわけ塩化物が好適である。
また、バナジウム化合物についても特に制限され
ないが、具体的にはV2O5、シユウ酸バナジル、
NH4VO3、VOCl2などがある。
次に、本発明に用いる触媒の担体としてはシリ
カ、アルミナ、シリカ−アルミナ、ゼオライト、
活性炭などの無機酸化物があり、これらの中では
γ−アルミナが好ましく、特に予め塩酸処理した
γ−アルミナが好適である。なお、担体は比表面
積が30m2／ｇ以上、特に50〜1000m2／ｇのものが
好ましい。
触媒成分の担体への担持量は特に制限はなく各
種の条件によつて異なるが、通常はロジウム化合
物の担持率を、金属として0.1〜10重量％、好ま
しくは0.2〜５重量％とし、バナジウム化合物の
担持率を、金属として0.1〜30重量％、好ましく
は0.5〜20重量％とすべきである。ここで担持率
とは生成触媒中の触媒成分の含有率を示すもので
ある。
触媒成分を担体に担持させる方法としては、た
とえば通常の含浸法、吸着法などのほか触媒成分
の水溶液とコロイド状の担体とを混合し濃縮、固
化後成形する方法など任意の方法を採用すること
ができる。触媒成分を担持した担体は乾燥後100
〜500℃、好ましくは150〜400℃の温度で空気、
窒素、アルゴンなどの不活性ガスや塩素ガスなど
の雰囲気下で１〜10時間焼成することによつて活
性が高く、しかも安定した触媒を得ることができ
る。
上記のようにして得られた触媒を用いることに
よつてオレフインから対応するカルボニル化合物
を効率よく製造することができる。
本発明に用いることができるオレフインとして
はエチレン、プロピレン、ｎ−ブテン−１、ｎ−
ブテン−２、ｎ−ヘキセンなどの脂肪族直鎖オレ
フイン；３−メチルブテン−１・３−メチルペン
テン−１などの側鎖を有する脂肪族オレフイン；
１・３−ブタジエン、シクロヘキサジエンなどの
ジオレフイン；シクロペンテン、シクロヘキセン
などの脂環族オレフイン等を挙げることができ
る。また、これらのオレフインにはｎ−ブテン−
１、ｎ−ブテン−２などの混合物やｎ−ブタン、
イソブタンなどの飽和炭化水素や窒素が混在した
ものを用いることもできる。
原料のオレフインからカルボニル化合物を製造
するには、原料オレフインを酸素または酸素含有
ガスと混合し、水（通常は水蒸気）の存在下で50
〜250℃、好ましくは100〜180℃の温度および50
Kg／cm2程度までの圧力にて上記触媒と接触せしめ
る。なお、この反応は固定床、流動床、移動床の
いずれの方式で行なうこともでき、さらに気相
法、気液混合法、液相法などにより行なわれる
が、好ましくは気相反応で流通式にて行なう。特
に気相反応を行なうと、生成物の分離、精製の点
で有利である。オレフイン、酸素または酸素含有
ガスおよび水の混合比は原料オレフインの種類な
どを考慮して決定すべきであり、一般的には容量
比でオレフイン１に対して酸素または酸素含有ガ
ス１〜4.0、水１〜40の割合が適当である。ま
た、これら混合物と触媒の接触時間は３〜30秒、
好ましくは５〜20秒である。なお、酸素含有ガス
としては、空気または酸素と不活性ガス（窒素な
ど）との混合ガスなどが適当であり、水は予熱層
を通して気化し水蒸気として反応系に導入するこ
とが望ましい。
本発明によれば、アセトアルデヒド、アセト
ン、メチルエチルケトンなどの有用なカルボニル
化合物を効率よく製造することができる。特にブ
テンのような反応性の低いオレフインからメチル
エチルケトンを高収率で得られることは本発明の
大きな特色である。また、塩化物などのハロゲン
化物が生成しないため、装置の腐食がなく、工業
的にすぐれた方法である。
次に、本発明の実施例を示す。
実施例 １
3.6ｇのV2O5を飽和シユウ酸水溶液（シユウ酸
15ｇを含む）100mlに溶かし、この溶液に100ｇの
γ−Al2O3（表面積200m2／ｇ）を浸漬して蒸発
乾固させた（バナジウム担持率２重量％）。これ
を空気流通下、500℃にて４時間焼成し、さらに
金属として担持率１重量％に相当するRhCl3を水
溶液にて含浸せしめ、乾燥し、空気流通下、200
℃で４時間焼成して触媒を調製した。
この触媒30mlを内径25mmのガラス製反応管に充
填し、１−ブテン7.5％、酸素５％、窒素17.5％
および水70％（容量組成）からなる混合ガスを
135℃、常圧下に接触時間９秒で流通して反応さ
せた。その結果、１−ブテンの転化率は49モル
％、メチルエチルケトンの選択率は55モル％、メ
チルエチルケトンの収率は27モル％であつた。ま
た、塩素化合物の生成は認められなかつた。
実施例 ２
実施例１のシユウ酸水溶液の代りにシユウ酸15
ｇと濃塩酸15mlを溶かした水溶液100mlを用いた
こと以外は実施例１と同様にして触媒を調製し、
この触媒を用いて反応させた。その結果、１−ブ
テンの転化率は60モル％、メチルエチルケトンの
選択率は50モル％、メチルエチルケトンの収率は
30モル％であつた。また、塩素化合物の生成は認
められなかつた。
実施例 ３
実施例１のシユウ酸水溶液の代りに濃塩酸20ml
を溶かした水溶液100mlを使用したこと以外は実
施例１と同様に行なつた。その結果、１−ブテン
の転化率は50モル％、メチルエチルケトンの選択
率は68モル％、メチルエチルケトンの収率は34モ
ル％であり、塩素化合物の生成は認められなかつ
た。
実施例 ４
実施例１において触媒成分のバナジウムの担持
率を４重量％（V2O57.2ｇ）としたこと以外は実
施例１と同様に行なつた。その結果、１−ブテン
の転化率は49モル％、メチルエチルケトンの選択
率は67モル％、メチルエチルケトンの収率は33モ
ル％であり、塩素化合物の生成は認められなかつ
た。
実施例 ５
実施例３においてγ−Al2O3の代りに予め塩酸
処理したγ−Al2O3を使用したこと以外は同様に
行なつた。その結果、１−ブテンの転化率は62モ
ル％、メチルエチルケトンの選択率は65モル％、
メチルエチルケトンの収率は40モル％であり、塩
素化合物の生成は認められなかつた。
実施例 ６
実施例２において触媒成分のロジウムの担持率
を1.5重量％としたこと以外は同様に行なつた。
その結果、１−ブテンの転化率は58モル％、メチ
ルエチルケトンの選択率は68モル％、メチルエチ
ルケトンの収率は40モル％であつた。
実施例 ７
実施例１においてV2O5の代りにVOCl2を用
い、かつシユウ酸水溶液の代りに蒸留水を用いた
こと以外は同様にして行なつた。その結果、１−
ブテンの転化率は55モル％、メチルエチルケトン
の選択率は55モル％、メチルエチルケトンの収率
は30モル％であつた。
実施例 ８および９
実施例７においてVOCl2の代りにNH4VO3また
はシユウ酸バナジルを使用したこと以外は同様に
行なつた。結果を第１表に示す。
The present invention relates to a method for producing carbonyl compounds from olefins, and more particularly to a method for efficiently producing carbonyl compounds by oxidizing olefins in the presence of a specific catalyst. The so-called Hoechstwatzker process is known as a method for producing carbonyl compounds by oxidizing olefins (Japanese Patent Publication No. 36-7869),
Propylene has already been used industrially. In this Hoechstwatzker method, palladium chloride and an aqueous cupric chloride solution are used as catalysts. However, this method has drawbacks such as a considerable amount of chloride being produced and a low conversion rate for olefins having 4 or more carbon atoms. In addition, Pd or
Catalysts that combine Rh with Fe, Co, Ni, Mn, etc. (Japanese Patent Publication No. 6643/1983, Japanese Patent Application Laid-Open No. 43686/1982) had a new problem of low activity. In order to solve these problems, the inventors of the present invention have repeatedly studied the catalysts to be used, and have found that by using a new catalyst that combines a rhodium compound and a vanadium compound, a good conversion rate can be achieved. The present invention was achieved by discovering that carbonyl compounds can be produced without producing chloride as a by-product. The present invention is a method for producing a carbonyl compound, which is characterized by reacting an olefin and oxygen or an oxygen-containing gas in the presence of water using a catalyst in which a rhodium compound and a vanadium compound are supported on a carrier. The catalyst used in the present invention is one in which a rhodium compound and a vanadium compound, which are catalyst components, are supported on a carrier. Here, the rhodium compound is not particularly limited, but salts that are easily soluble in aqueous solutions, alcohol, etc. are preferred, such as halides, sulfates,
Examples include nitrates, chlorates, acetates, monochloroacetates, and among these, rhodium halides, particularly chlorides, are preferred.
Further, vanadium compounds are not particularly limited, but specifically include V 2 O 5 , vanadyl oxalate,
Examples include NH 4 VO 3 and VOCl 2 . Next, examples of carriers for the catalyst used in the present invention include silica, alumina, silica-alumina, zeolite,
There are inorganic oxides such as activated carbon, and among these, γ-alumina is preferred, and γ-alumina that has been previously treated with hydrochloric acid is particularly preferred. The carrier preferably has a specific surface area of 30 m 2 /g or more, particularly 50 to 1000 m 2 /g. The amount of the catalyst component supported on the carrier is not particularly limited and varies depending on various conditions, but usually the supported ratio of the rhodium compound is 0.1 to 10% by weight, preferably 0.2 to 5% by weight as metal, The loading should be between 0.1 and 30% by weight as metal, preferably between 0.5 and 20% by weight. The term "support rate" used herein refers to the content of catalyst components in the produced catalyst. As a method for supporting the catalyst component on the carrier, any method may be used, such as the usual impregnation method, adsorption method, or a method in which an aqueous solution of the catalyst component and a colloidal carrier are mixed, concentrated, solidified, and then shaped. Can be done. After drying, the carrier supporting the catalyst component is 100%
Air at a temperature of ~500℃, preferably 150-400℃
By calcining for 1 to 10 hours in an atmosphere of an inert gas such as nitrogen or argon, or chlorine gas, a highly active and stable catalyst can be obtained. By using the catalyst obtained as described above, a corresponding carbonyl compound can be efficiently produced from an olefin. Olefins that can be used in the present invention include ethylene, propylene, n-butene-1, n-
Aliphatic linear olefins such as butene-2 and n-hexene; aliphatic olefins having side chains such as 3-methylbutene-1 and 3-methylpentene-1;
Examples include diolefins such as 1,3-butadiene and cyclohexadiene; and alicyclic olefins such as cyclopentene and cyclohexene. Additionally, these olefins contain n-butene-
1, mixtures such as n-butene-2 and n-butane,
It is also possible to use a mixture of saturated hydrocarbons such as isobutane and nitrogen. To produce carbonyl compounds from raw olefins, the raw olefins are mixed with oxygen or an oxygen-containing gas and heated for 50 min in the presence of water (usually steam).
Temperature of ~250℃, preferably 100-180℃ and 50℃
It is brought into contact with the above catalyst at a pressure of up to about Kg/cm 2 . This reaction can be carried out in a fixed bed, fluidized bed, or moving bed, and may also be carried out in a gas phase, gas-liquid mixing method, liquid phase, etc., but it is preferable to use a gas phase reaction in a flow system. I'll do it at In particular, gas phase reaction is advantageous in terms of product separation and purification. The mixing ratio of olefin, oxygen or oxygen-containing gas, and water should be determined taking into account the type of raw material olefin, etc. Generally, the volume ratio is 1 to 4.0 of oxygen or oxygen-containing gas to 1 of olefin, and 1 to 4.0 of oxygen or oxygen-containing gas, water. A ratio of 1 to 40 is appropriate. In addition, the contact time between these mixtures and the catalyst was 3 to 30 seconds;
Preferably it is 5 to 20 seconds. Note that air or a mixed gas of oxygen and an inert gas (such as nitrogen) is suitable as the oxygen-containing gas, and water is preferably vaporized through a preheating layer and introduced into the reaction system as water vapor. According to the present invention, useful carbonyl compounds such as acetaldehyde, acetone, and methyl ethyl ketone can be efficiently produced. In particular, it is a major feature of the present invention that methyl ethyl ketone can be obtained in high yield from an olefin with low reactivity such as butene. Furthermore, since halides such as chlorides are not produced, there is no corrosion of equipment, making it an excellent method industrially. Next, examples of the present invention will be shown. Example 1 3.6 g of V 2 O 5 was dissolved in a saturated oxalic acid aqueous solution (oxalic acid
100 g of γ-Al 2 O 3 (surface area: 200 m 2 /g) was immersed in this solution and evaporated to dryness (vanadium loading rate: 2% by weight). This was calcined at 500°C for 4 hours under air circulation, impregnated with an aqueous solution of RhCl 3 corresponding to a metal loading of 1% by weight, dried, and heated at 200°C under air circulation.
A catalyst was prepared by calcining at ℃ for 4 hours. 30 ml of this catalyst was packed into a glass reaction tube with an inner diameter of 25 mm, and the mixture contained 7.5% of 1-butene, 5% of oxygen, and 17.5% of nitrogen.
and water at 70% (volume composition).
The reaction was carried out at 135° C. under normal pressure for a contact time of 9 seconds. As a result, the conversion rate of 1-butene was 49 mol%, the selectivity of methyl ethyl ketone was 55 mol%, and the yield of methyl ethyl ketone was 27 mol%. Further, no formation of chlorine compounds was observed. Example 2 Oxalic acid 15 was used instead of the oxalic acid aqueous solution of Example 1.
A catalyst was prepared in the same manner as in Example 1, except that 100 ml of an aqueous solution containing 15 ml of concentrated hydrochloric acid and 15 ml of concentrated hydrochloric acid was used.
A reaction was carried out using this catalyst. As a result, the conversion rate of 1-butene was 60 mol%, the selectivity of methyl ethyl ketone was 50 mol%, and the yield of methyl ethyl ketone was
It was 30 mol%. Further, no formation of chlorine compounds was observed. Example 3 20ml of concentrated hydrochloric acid instead of the oxalic acid aqueous solution of Example 1
Example 1 was carried out in the same manner as in Example 1, except that 100 ml of an aqueous solution containing . As a result, the conversion rate of 1-butene was 50 mol %, the selectivity of methyl ethyl ketone was 68 mol %, the yield of methyl ethyl ketone was 34 mol %, and no formation of chlorine compounds was observed. Example 4 The same procedure as in Example 1 was carried out except that the loading rate of vanadium as a catalyst component in Example 1 was changed to 4% by weight (7.2 g of V 2 O 5 ). As a result, the conversion rate of 1-butene was 49 mol %, the selectivity of methyl ethyl ketone was 67 mol %, the yield of methyl ethyl ketone was 33 mol %, and no formation of chlorine compounds was observed. Example 5 The same procedure as in Example 3 was carried out except that γ-Al 2 O 3 previously treated with hydrochloric acid was used instead of γ-Al 2 O 3 . As a result, the conversion rate of 1-butene was 62 mol%, the selectivity of methyl ethyl ketone was 65 mol%,
The yield of methyl ethyl ketone was 40 mol%, and no formation of chlorine compounds was observed. Example 6 The same procedure as in Example 2 was carried out except that the supported ratio of rhodium as a catalyst component was changed to 1.5% by weight.
As a result, the conversion rate of 1-butene was 58 mol%, the selectivity of methyl ethyl ketone was 68 mol%, and the yield of methyl ethyl ketone was 40 mol%. Example 7 The procedure of Example 1 was repeated except that VOCl 2 was used instead of V 2 O 5 and distilled water was used instead of the oxalic acid aqueous solution. As a result, 1-
The conversion rate of butene was 55 mol%, the selectivity of methyl ethyl ketone was 55 mol%, and the yield of methyl ethyl ketone was 30 mol%. Examples 8 and 9 Example 7 was repeated except that NH 4 VO 3 or vanadyl oxalate was used instead of VOCl 2 . The results are shown in Table 1.
【表】
バナジル
実施例 10
実施例１においてバナジウムを担体に担持させ
た後の焼成温度を700℃としたこと以外は同様に
行なつた。その結果、１−ブテンの転化率は51モ
ル％、メチルエチルケトンの選択率は64モル％、
メチルエチルケトンの収率は33モル％であつた。
実施例 11〜16
実施例９の触媒を使用し、反応条件を第２表に
示した如く変化させた。このときの結果を第２表
に示す。[Table] Vanadyl Example 10 The same procedure as in Example 1 was carried out except that the firing temperature after supporting vanadium on the carrier was 700°C. As a result, the conversion rate of 1-butene was 51 mol%, the selectivity of methyl ethyl ketone was 64 mol%,
The yield of methyl ethyl ketone was 33 mol%. Examples 11-16 The catalyst of Example 9 was used and the reaction conditions were varied as shown in Table 2. The results at this time are shown in Table 2.
【表】
実施例 17
実施例１と同様にしてロジウムを担持率２重量
％およびバナジウムを担持率２重量％とした触媒
を調製し、１−ブテン7.5容量％、酸素５容量％
および水87.5容量％の原料ガスを接触時間９秒で
供給し、135℃で反応させた。その結果、１−ブ
テンの転化率は85モル％、メチルエチルケトの選
択率は56モル％、メチルエチルケトンの収率は48
モル％であつた。
実施例 18
実施例９の触媒を使用し、１−ブテン7.5容量
％、酸素５容量％、窒素17.5容量％および水70容
量％の原料ガスを接触時間９秒で供給し、温度
185℃、圧力５Kg／cm2（ゲージ圧、以下同様）の
条件で反応させたところ以下のような結果が得ら
れた。[Table] Example 17 In the same manner as in Example 1, a catalyst with a loading rate of 2% by weight of rhodium and a loading rate of vanadium of 2% by weight was prepared, and 7.5% by volume of 1-butene and 5% by volume of oxygen.
A raw material gas containing 87.5% by volume of water and water was supplied for a contact time of 9 seconds, and the reaction was carried out at 135°C. As a result, the conversion rate of 1-butene was 85 mol%, the selectivity of methyl ethyl ketone was 56 mol%, and the yield of methyl ethyl ketone was 48 mol%.
It was in mol%. Example 18 Using the catalyst of Example 9, feed gas containing 7.5% by volume of 1-butene, 5% by volume of oxygen, 17.5% by volume of nitrogen and 70% by volume of water was supplied for a contact time of 9 seconds, and the temperature
When the reaction was carried out under the conditions of 185°C and a pressure of 5 Kg/cm 2 (gauge pressure, hereinafter the same), the following results were obtained.
【表】
実施例 19
実施例１の触媒を用い、cis−２−ブテン7.5容
量％、酸素５容量％、窒素17.5容量％および水70
容量％の原料ガスを接触時間９秒で供給し、温度
165℃、圧力３Kg／cm2の条件で反応させた。その
結果、cis−２−ブテンの転化率は56モル％、メ
チルエチルケトンの選択率は46モル％、メチルエ
チルケトンの収率は26モル％であつた。
実施例 20
実施例１の触媒を用い、ブタジエン7.5容量
％、酸素５容量％、窒素17.5容量％および水70容
量％の原料ガスを接触時間９秒で供給し、温度
135℃、圧力１Kg／cm2で反応させた。その結果、
メチルエチルケトンの収率は２モル％、クロトン
アルデヒドの収率は４モル％であつた。なお、上
記実施例６〜20の場合はいずれも塩素化合物の生
成は認められなかつた。
比較例 １〜４
実施例１と同様な方法で第４表に示す金属担持
率をもつ触媒を調製し、実施例１と同様に反応さ
せた。結果を第４表に示す。[Table] Example 19 Using the catalyst of Example 1, 7.5% by volume of cis-2-butene, 5% by volume of oxygen, 17.5% by volume of nitrogen and 70% by volume of water.
% by volume of raw material gas was supplied for a contact time of 9 seconds, and the temperature
The reaction was carried out at 165°C and a pressure of 3 kg/cm 2 . As a result, the conversion rate of cis-2-butene was 56 mol%, the selectivity of methyl ethyl ketone was 46 mol%, and the yield of methyl ethyl ketone was 26 mol%. Example 20 Using the catalyst of Example 1, feed gas containing 7.5% by volume of butadiene, 5% by volume of oxygen, 17.5% by volume of nitrogen and 70% by volume of water was supplied for a contact time of 9 seconds, and the temperature
The reaction was carried out at 135° C. and a pressure of 1 Kg/cm 2 . the result,
The yield of methyl ethyl ketone was 2 mol%, and the yield of crotonaldehyde was 4 mol%. In addition, in the cases of Examples 6 to 20 above, no formation of chlorine compounds was observed. Comparative Examples 1 to 4 Catalysts having the metal loading rates shown in Table 4 were prepared in the same manner as in Example 1, and reacted in the same manner as in Example 1. The results are shown in Table 4.
【表】
なお、比較例２および４の場合、凝縮液面およ
び底に油状物質が認められ、ガスクロマトグラフ
分析の結果、炭素数３個および４個の塩化物であ
ることが判つた。
比較例 ５
γ−Al2O3の代りにα−Al2O3を用いたこと以
外は実施例１と同様にして行なつた。その結果、
１−ブテンの転化率は３モル％、メチルエチルケ
トンの選択率は２モル％、メチルエチルケトンの
収率は0.1モル％であつた。
実施例 21
実施例１と同様にしてロジウムを担持率２重量
％およびバナジウムを担持率２重量％とした触媒
を調製し、シクロヘキセン7.5容量％、酸素５容
量％、窒素17.5容量％および水70容量％の原料ガ
スを接触時間９秒で供給して135℃で反応させ
た。
その結果、シクロヘキセンの転化率は20モル
％、選択率は20モル％、シクロヘキサノンの收率
は４モル％であつた。
実施例 22
実施例１と同様にしてロジウムを担持率２重量
％およびバナジウムを担持率２重量％とした触媒
を調製し、実施例１の１−ブテンに代えて１−ヘ
キセンを使用したこと以外は同様の操作をした。
その結果、１−ヘキセンの転化率は15モル％、
ヘキサノンの選択率は45モル％、ヘキサノンの收
率は6.8モル％であつた。
実施例 23
実施例１と同様にしてロジウムを担持率２重量
％およびバナジウムを担持率２重量％とした触媒
を調製し、実施例の１−ブテンに代えてエチレン
を使用したこと以外は同様の操作をした。
その結果、エチレンの転化率は32モル％、アセ
トアルデヒドの選択率は52モル％、アセトアルデ
ヒドの收率は16モル％であつた。[Table] In the case of Comparative Examples 2 and 4, oily substances were observed on the surface and bottom of the condensed liquid, and as a result of gas chromatography analysis, it was determined that they were chlorides having 3 and 4 carbon atoms. Comparative Example 5 The same procedure as in Example 1 was carried out except that α-Al 2 O 3 was used instead of γ-Al 2 O 3 . the result,
The conversion rate of 1-butene was 3 mol %, the selectivity of methyl ethyl ketone was 2 mol %, and the yield of methyl ethyl ketone was 0.1 mol %. Example 21 A catalyst with a loading rate of 2% by weight of rhodium and a loading rate of vanadium of 2% by weight was prepared in the same manner as in Example 1, and 7.5% by volume of cyclohexene, 5% by volume of oxygen, 17.5% by volume of nitrogen, and 70% by volume of water. % raw material gas was supplied for a contact time of 9 seconds, and the reaction was carried out at 135°C. As a result, the conversion rate of cyclohexene was 20 mol%, the selectivity was 20 mol%, and the yield of cyclohexanone was 4 mol%. Example 22 A catalyst with a rhodium loading rate of 2% by weight and a vanadium loading rate of 2% by weight was prepared in the same manner as in Example 1, except that 1-hexene was used in place of 1-butene in Example 1. performed the same operation. As a result, the conversion rate of 1-hexene was 15 mol%,
The selectivity of hexanone was 45 mol%, and the yield of hexanone was 6.8 mol%. Example 23 A catalyst with a rhodium loading rate of 2% by weight and a vanadium loading rate of 2% by weight was prepared in the same manner as in Example 1, except that ethylene was used instead of 1-butene in Example 1. I did the operation. As a result, the conversion rate of ethylene was 32 mol%, the selectivity of acetaldehyde was 52 mol%, and the yield of acetaldehyde was 16 mol%.
Claims (1)
担持した触媒を用いて、オレフインと酸素または
酸素含有ガスを水の存在下で反応させることを特
徴とするカルボニル化合物の製造法。1. A method for producing a carbonyl compound, which comprises reacting an olefin and oxygen or an oxygen-containing gas in the presence of water using a catalyst in which a rhodium compound and a vanadium compound are supported on a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57111542A JPS595134A (en) | 1982-06-30 | 1982-06-30 | Production method of carbonyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57111542A JPS595134A (en) | 1982-06-30 | 1982-06-30 | Production method of carbonyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS595134A JPS595134A (en) | 1984-01-12 |
| JPS6245215B2 true JPS6245215B2 (en) | 1987-09-25 |
Family
ID=14564006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57111542A Granted JPS595134A (en) | 1982-06-30 | 1982-06-30 | Production method of carbonyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS595134A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565430A (en) * | 1979-06-26 | 1981-01-20 | Mitsui Petrochem Ind Ltd | Cooxidation |
| JPS5872531A (en) * | 1981-10-28 | 1983-04-30 | Idemitsu Kosan Co Ltd | Preparation of carbonyl compound |
-
1982
- 1982-06-30 JP JP57111542A patent/JPS595134A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS595134A (en) | 1984-01-12 |
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