JPH0551333A - Catalyst for hydroformylation reaction - Google Patents
Catalyst for hydroformylation reactionInfo
- Publication number
- JPH0551333A JPH0551333A JP3235570A JP23557091A JPH0551333A JP H0551333 A JPH0551333 A JP H0551333A JP 3235570 A JP3235570 A JP 3235570A JP 23557091 A JP23557091 A JP 23557091A JP H0551333 A JPH0551333 A JP H0551333A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- hydroformylation reaction
- ethylene
- hydroformylation
- 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
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な触媒を用いるオ
レフィンのヒドロホルミル化反応によるアルデヒドおよ
びアルコールを製造する方法に関する。より詳細には、
コバルト化合物およびイリジウム化合物を無機酸化物上
に担持して調製した不均一触媒を用いることを特徴とす
る、オレフィンのヒドロホルミル化反応によるアルデヒ
ドあるいはアルコール類を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing aldehydes and alcohols by olefin hydroformylation reaction using a novel catalyst. More specifically,
It relates to a method for producing an aldehyde or an alcohol by a hydroformylation reaction of an olefin, which comprises using a heterogeneous catalyst prepared by supporting a cobalt compound and an iridium compound on an inorganic oxide.
【０００２】[0002]
【従来の技術】種々のオレフィン類に一酸化炭素と水素
を作用させるヒドロホルミル化反応はアルデヒドあるい
はアルコール類を合成する方法として現在の化学工業界
で実施されている重要な反応の一つである。しかしなが
らこの反応はすべてロジウム錯体あるいはコバルト錯体
を触媒とする液相均一反応によって行われており、触媒
と反応生成物あるいは溶媒との分離が困難であり、また
各種の溶媒を用いることによる生産コストの上昇、触媒
の回収、再生、寿命などの点において大きな問題を抱え
ている。2. Description of the Related Art The hydroformylation reaction of carbon monoxide and hydrogen on various olefins is one of the important reactions currently practiced in the chemical industry as a method for synthesizing aldehydes or alcohols. However, all of this reaction is carried out by a liquid phase homogeneous reaction using a rhodium complex or a cobalt complex as a catalyst, it is difficult to separate the catalyst from the reaction product or solvent, and the production cost due to the use of various solvents increases. There are major problems in terms of temperature rise, catalyst recovery, regeneration, and life.
【０００３】これらの問題点を解決する一つの有効な方
法として、不均一触媒を用いる反応系について種々検討
がなされてきた。例えばこれまでにロジウムを種々の無
機酸化物上に担持した触媒を用いてのエチレンやプロピ
レン等のヒドロホルミル化反応についての報告が幾つか
なされている。例えば、ゼオライト担持ロジウム触媒に
よるエチレン、プロピレンのヒドロホルミル化（Ｊ．Ｃ
ａｔａｌ、７５、１８８（１９８２））や酸化ジルコニ
ウム担持セレン修飾ロジウム触媒によるエチレンのヒド
ロホルミル化反応（Ｊ．Ｃｈｅｍ．Ｓｏｃ．、Ｃｈｅ
ｍ．Ｃｏｍｍｕｎ．、１３２７（１９８８））が報告さ
れている。また金属クラスターを前駆体とするシリカ担
持ロジウム触媒によるエチレンのヒドロホルミル化反応
（Ｃｈｅｍ．Ｌｅｔｔ．、１９１７（１９８８））も報
告されている。As one effective method for solving these problems, various studies have been made on a reaction system using a heterogeneous catalyst. For example, some reports have hitherto been made on hydroformylation reactions of ethylene, propylene and the like using a catalyst in which rhodium is supported on various inorganic oxides. For example, hydroformylation of ethylene and propylene by a zeolite-supported rhodium catalyst (J.C.
atal, 75 , 188 (1982)) and a hydroformylation reaction of ethylene with a selenium-modified rhodium catalyst supporting zirconium oxide (J. Chem. Soc., Che.
m. Commun. , 1327 (1988)). Further, a hydroformylation reaction of ethylene using a silica-supported rhodium catalyst using a metal cluster as a precursor (Chem. Lett., 1917 (1988)) has also been reported.
【０００４】これらは高価なロジウムを主成分とする触
媒であるが、そのヒドロホルミル化選択率は高々４０％
程度で活性も低い。また、ロジウム以外の豊富で廉価な
金属を主成分とする不均一触媒の開発も種々検討されて
きた。例えば各種酸化物に担持したニッケル触媒による
エチレンヒドロホルミル化反応（Ｐｒｏｃｅｅｄｉｎｇ
ｓ ｏｆ ９ｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏ
ｎｇｒｅｓｓ ｏｎＣａｔａｌｙｓｉｓ ５１３（１９
８８））、ナトリウムで修飾したパラジウム、ルテニウ
ム、白金、ニッケルあるいはロジウム触媒によるプロピ
レンのヒドロホルミル化（触媒、３０、４８８（１９８
８）；Ｊ．Ｃｈｅｍ．Ｓｏｃ．、Ｃｈｅｍ．Ｃｏｍｍｕ
ｎ．、１４０３（１９８９））が報告されている。ま
た、［ＮＥｔ4］［ＨＲｕ3（ＣＯ）11］、［ＮＥｔ4］
［Ｒｕ3Ｃｏ（ＣＯ）13］、［Ｈ3Ｒｕ3Ｃｏ（Ｃ
Ｏ）12］、ＨＲｕＣｏ3（ＣＯ）12などのルテニウムク
ラスターあるいはルテニウム−コバルト混合クラスター
化合物を活性炭に担持した触媒（Ｃｈｅｍ．Ｌｅｔ
ｔ．、９４１（１９８７））やトリルテニウムケテニリ
デンクラスター（［ＰＰｎ］2［Ｒｕ3（ＣＯ）9（ＣＣ
Ｏ）］）をマグネシア、シリカ、シリカアルミナに担持
した触媒系（Ｃａｔａｌ．Ｌｅｔｔ．、６、３６１（１
９９０））も試みられている。These are expensive rhodium-based catalysts, but their hydroformylation selectivity is at most 40%.
The activity is also low. In addition, various studies have been conducted on the development of heterogeneous catalysts containing abundant and inexpensive metals other than rhodium as a main component. For example, ethylene hydroformylation reaction (Proceeding) using nickel catalysts supported on various oxides.
s of 9th International Co
ngless on Catalysis 513 (19
88)), hydroformylation of propylene with sodium-modified palladium, ruthenium, platinum, nickel or rhodium catalysts (catalyst, 30 , 488 (198).
8); Chem. Soc. Chem. Commu
n. 1403 (1989)) has been reported. In addition, [NEt 4 ] [HRu 3 (CO) 11 ], [NEt 4 ]
[Ru 3 Co (CO) 13 ], [H 3 Ru 3 Co (C
O) 12 ], HRuCo 3 (CO) 12 and other ruthenium clusters or ruthenium-cobalt mixed cluster compounds supported on activated carbon (Chem. Let.
t. , 941 (1987)) and triruthenium ketenylidene cluster ([PPn] 2 [Ru 3 (CO) 9 (CC
O)]) is supported on magnesia, silica, and silica-alumina (Cal. Lett., 6 , 361 (1
990)) has also been tried.
【０００５】しかしながら、ロジウム以外の金属を主成
分とするこれらの触媒ではオレフィンの水素化能がヒド
ロホルミル化能よりも著しく高く、アルデヒドやアルコ
ールの収率はきわめて低いものであった。However, in these catalysts containing a metal other than rhodium as a main component, the hydrogenation ability of olefins was significantly higher than the hydroformylation ability, and the yields of aldehydes and alcohols were extremely low.
【０００６】[0006]
【発明が解決しようとする課題】解決しようとする課題
は、オレフィンのヒドロホルミル化反応に高活性かつ高
選択的な安価で豊富に産する元素を主成分とする不均一
触媒を調製することである。The problem to be solved is to prepare an inexpensive and abundantly produced heterogeneous catalyst mainly composed of elements which is highly active and highly selective for the hydroformylation reaction of olefins. ..
【０００７】[0007]
【課題を解決するための手段】本発明は、コバルト化合
物およびイリジウム化合物をシリカなどの無機酸化物に
複合担持させ、さらに水素などで還元処理して調製した
不均一触媒を用いることを特徴とする、オレフィンのヒ
ドロホルミル化反応において高い選択性および活性でア
ルデヒドあるいはアルコールを製造する新規な方法であ
る。The present invention is characterized by the use of a heterogeneous catalyst prepared by carrying a composite of a cobalt compound and an iridium compound on an inorganic oxide such as silica, and further subjecting it to a reduction treatment with hydrogen or the like. , Is a novel method for producing aldehydes or alcohols with high selectivity and activity in the hydroformylation reaction of olefins.
【０００８】本発明において用いられる触媒はコバルト
化合物およびイリジウム化合物を無機酸化物担体に担持
・乾燥し、次いで水素などの適当な還元剤で処理して調
製した触媒である。The catalyst used in the present invention is a catalyst prepared by supporting and drying a cobalt compound and an iridium compound on an inorganic oxide carrier and then treating with a suitable reducing agent such as hydrogen.
【０００９】コバルトおよびイリジウム化合物として
は、これらの元素の酢酸塩、硝酸塩、ハロゲン化物（塩
化物、フッ化物、臭化物、ヨウ化物）、カルボニル化合
物、酸化物などが用いられる。これらの化合物を水ある
いは各種有機溶媒に溶解し、上記担体用無機酸化物と混
合し、溶媒を蒸発させて担体上に担持する。昇華性があ
る化合物（例えばイリジウムカルボニルなど）の場合、
減圧下で担体と混合攪拌して担持することもできる。コ
バルトおよびイリジウムは同時に担持してもよく、また
順次担持してもよい。コバルトおよびイリジウムの担持
量は、好ましくは担体重量に対して０．１〜３０重量
％、より好ましくは０．３〜１０重量％である。担体と
しては触媒成分を触媒成分を効率よく分散させるに足る
比表面積および細孔容積を持つ種々の無機酸化物が用い
られる。例えば通常担体として用いられるシリカやアル
ミナの他に、不定形シリカ−アルミナ、ゼオライト、シ
リカライト、ジルコニア、チタニア、マグネシア、カル
シア、酸化ストロンチウム、酸化バリウム、酸化ニオ
ブ、酸化ネオジウム等を用いることができる。As the cobalt and iridium compounds, acetates, nitrates, halides (chlorides, fluorides, bromides and iodides) of these elements, carbonyl compounds and oxides are used. These compounds are dissolved in water or various organic solvents, mixed with the above inorganic oxide for a carrier, and the solvent is evaporated to be loaded on the carrier. For sublimable compounds (eg iridium carbonyl),
It is also possible to mix and stir the carrier under reduced pressure to carry it. Cobalt and iridium may be loaded simultaneously or sequentially. The supported amount of cobalt and iridium is preferably 0.1 to 30% by weight, and more preferably 0.3 to 10% by weight, based on the weight of the carrier. As the carrier, various inorganic oxides having a specific surface area and a pore volume sufficient to efficiently disperse the catalyst component are used. For example, in addition to silica and alumina usually used as a carrier, amorphous silica-alumina, zeolite, silicalite, zirconia, titania, magnesia, calcia, strontium oxide, barium oxide, niobium oxide, neodymium oxide and the like can be used.
【００１０】反応原料のオレフィンとしては、炭素数２
〜２０のオレフィン類、すなわちエチレン、プロピレ
ン、ブテン、ブタジエン、ペンテン、ヘキセン等の脂肪
族オレフィン類、シクロブテン、シクロペンテン、シク
ロヘキセン、シクロペンタジエン、シクロオクタジエン
等の脂環式オレフィン類、スチレン、インデン、スチル
ベン、メチルスチレン等の芳香族オレフィン類等が上げ
られるが、これらに限るものではない。The olefin used as the reaction raw material has 2 carbon atoms.
To 20 olefins, that is, aliphatic olefins such as ethylene, propylene, butene, butadiene, pentene, and hexene, alicyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cyclopentadiene, and cyclooctadiene, styrene, indene, stilbene. , Aromatic olefins such as methyl styrene, and the like, but not limited thereto.
【００１１】反応方法としては、固定床あるいは流動床
式の気相流通反応装置を用い、オレフィン、一酸化炭
素、水素の混合ガスを触媒に接触させるか、またはバッ
チ式あるいは液相流通反応装置を用いる方法があり、反
応基質および生成物によって最適な方法が用いられる。
なお、液相反応装置を用いる場合には、適当な溶媒を用
いることにより反応を制御することもできる。As the reaction method, a fixed bed or fluidized bed type gas phase flow reactor is used, and a mixed gas of olefin, carbon monoxide and hydrogen is brought into contact with the catalyst, or a batch type or liquid phase flow reactor is used. There is a method to be used, and an optimum method is used depending on a reaction substrate and a product.
When using a liquid phase reactor, the reaction can be controlled by using an appropriate solvent.
【００１２】反応温度は、好ましくは１００〜２５０
℃、より好ましくは１２０〜２１０℃の範囲が適当であ
り、反応方法、反応基質等により適宜選択される。反応
圧力は、好ましくは５〜１００ｋｇ／ｃｍ2、より好ま
しくは８〜５０ｋｇ／ｃｍ2であり、反応基質、反応様
式によって触媒活性、選択率等を勘案して選択される。The reaction temperature is preferably 100 to 250.
C., more preferably in the range of 120 to 210.degree. C., is appropriately selected depending on the reaction method, reaction substrate and the like. The reaction pressure is preferably 5 to 100 kg / cm 2 , more preferably 8 to 50 kg / cm 2 , and is selected in consideration of the catalytic activity, selectivity and the like depending on the reaction substrate and reaction mode.
【００１３】以上に述べた反応条件等は、必ずしもこれ
に限られるものではなく、反応基質、反応様式の他に、
経済性、技術的容易さ等を考慮の上、適宜選択されるも
のである。The reaction conditions and the like described above are not necessarily limited to these, and in addition to the reaction substrate and reaction mode,
It is appropriately selected in consideration of economical efficiency and technical ease.
【００１４】[0014]
【実施例】次に実施例によって、本発明をさらに詳細に
説明する。 実施例１ 粒状シリカゲル（富士ダビソン社製 No.５７）１ｇをフ
ラスコ中、２００℃で２時間真空加熱した。冷却後、こ
れに酢酸コバルト（和光純薬製、Ｃｏ（ＯＣＯＣＨ3）2
・４Ｈ2Ｏ）２１１．３ｍｇを含む水溶液１．２ｍｌを
減圧下で加え、約一昼夜静置した。その後、減圧下、１
２０℃で２時間乾燥し、次いで水素気流中、３００℃で
３時間加熱処理をした。（これをＣｏ（Ａ）／ＳｉＯ2
触媒と略す。）このＣｏ（Ａ）／ＳｉＯ2触媒と所定量
のテトライリジウムドデカカルボニル（アルドリッチ社
製、Ｉｒ4（ＣＯ）12）を混合し、減圧下、１５０℃で
攪拌してイリジウムを担持し、次いで水素気流中、４５
０℃で３時間処理した。（これをＣｏ（Ａ）−Ｉｒ（Ｃ
Ｏ）／ＳｉＯ2触媒と略す。）EXAMPLES Next, the present invention will be described in more detail with reference to examples. Example 1 1 g of granular silica gel (Fuji Davison No. 57) was heated in a flask at 200 ° C. for 2 hours under vacuum. After cooling, cobalt acetate (manufactured by Wako Pure Chemical Industries, Co (OCOCH 3 ) 2
1.2 ml of an aqueous solution containing 211.3 mg of 4H 2 O) was added under reduced pressure, and the mixture was allowed to stand for about 24 hours. Then, under reduced pressure, 1
It was dried at 20 ° C. for 2 hours and then heat-treated in a hydrogen stream at 300 ° C. for 3 hours. (This is Co (A) / SiO 2
Abbreviated as catalyst. ) This Co (A) / SiO 2 catalyst and a predetermined amount of tetriridium dodecacarbonyl (manufactured by Aldrich, Ir 4 (CO) 12 ) are mixed and stirred under reduced pressure at 150 ° C. to carry iridium and then hydrogen. 45 in the airflow
It was treated at 0 ° C. for 3 hours. (This is Co (A) -Ir (C
O) / SiO 2 catalyst. )
【００１５】この触媒をＳＵＳ−３１６ステンレス製固
定床流通型反応管に移し、もう一度４５０℃で３時間水
素処理を行い、その後アルゴン（内部標準ガス）：一酸
化炭素：水素：エチレンの混合ガスを所定の圧力、流量
で導入し、反応温度１５０〜２１０℃で触媒と接触させ
た。反応管出口からの混合ガスを直接ガスクロマトグラ
フに導入し、エチレンの転化率および生成物選択率を求
めた。結果を表１の実施例１に示す。This catalyst was transferred to a fixed-bed flow type reaction tube made of SUS-316 stainless steel, subjected to hydrogen treatment again at 450 ° C. for 3 hours, and then mixed gas of argon (internal standard gas): carbon monoxide: hydrogen: ethylene. It was introduced at a predetermined pressure and flow rate and brought into contact with the catalyst at a reaction temperature of 150 to 210 ° C. The mixed gas from the outlet of the reaction tube was directly introduced into the gas chromatograph, and the conversion rate of ethylene and the product selectivity were determined. The results are shown in Example 1 of Table 1.
【００１６】実施例２ 実施例１と同様にＣｏ（Ａ）／ＳｉＯ2触媒を調製し、
これに塩化イリジウム（アルドリッチ社製、ＩｒＣ
ｌ3）８０．２ｍｇを含む１．２ｍｌの水溶液を減圧下
で加え、乾燥した後、水素処理を行った。（この触媒を
Ｃｏ（Ａ）−Ｉｒ（Ｃｌ）／ＳｉＯ2触媒と略す。）こ
の触媒を用いて実施例１と同様にエチレンのヒドロホル
ミル化反応を行った。結果を表１の実施例２に示す。Example 2 A Co (A) / SiO 2 catalyst was prepared in the same manner as in Example 1,
Iridium chloride (Aldrich, IrC
l 3) an aqueous solution of 1.2ml was added under reduced pressure comprising 80.2 mg, dried and subjected to hydrogen treatment. (This catalyst is abbreviated as Co (A) -Ir (Cl) / SiO 2 catalyst.) Using this catalyst, a hydroformylation reaction of ethylene was carried out in the same manner as in Example 1. The results are shown in Example 2 in Table 1.
【００１７】実施例３ 実施例１と同様に、粒状シリカゲル１ｇに、硝酸コバル
ト（半井化学製、Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ）２４６．
９ｍｇを含む水溶液１．２ｍｌを減圧下で加え、静置、
乾燥、水素処理をした。（これをＣｏ（Ｎ）／ＳｉＯ2
触媒と略す。）さらにこれに実施例１と同様にテトライ
リジウムドデカカルボニル２９．６ｍｇを減圧下で担持
し、次いで水素処理を行った。（この触媒をＣｏ（Ｎ）
−Ｉｒ（ＣＯ）／ＳｉＯ2触媒と略す。）この触媒を用
いて実施例１と同様にエチレンのヒドロホルミル化反応
を行った。結果を表１の実施例３に示す。[0017] Similarly to Example 3 Example 1, the particulate silica gel 1g, cobalt nitrate (Nakarai Chemical Co., Co (NO 3) 2 · 6H 2 O) 246.
1.2 ml of an aqueous solution containing 9 mg was added under reduced pressure and allowed to stand,
It was dried and treated with hydrogen. (This is Co (N) / SiO 2
Abbreviated as catalyst. ) Further, in the same manner as in Example 1, 29.6 mg of tetriridium dodecacarbonyl was carried under reduced pressure, and then hydrogen treatment was carried out. (This catalyst is Co (N)
Abbreviated as -Ir (CO) / SiO 2 catalyst. ) Using this catalyst, a hydroformylation reaction of ethylene was carried out in the same manner as in Example 1. The results are shown in Example 3 in Table 1.
【００１８】実施例４ 実施例１と同様に、粒状シリカゲル１ｇに、塩化コバル
ト（半井化学製、ＣｏＣｌ2・６Ｈ2Ｏ）２０１．９ｍｇ
を含む水溶液１．２ｍｌを減圧下で加え、静置、乾燥、
水素処理をした。（これをＣｏ（Ｃｌ）／ＳｉＯ2触媒
と略す。）さらにこれに実施例１と同様にテトライリジ
ウムドデカカルボニル２９．６ｍｇを担持し、次いで水
素処理を行った。（これをＣｏ（Ｃｌ）−Ｉｒ（ＣＯ）
／ＳｉＯ2触媒と略す。）この触媒を用いて実施例１と
同様にエチレンのヒドロホルミル化反応を行った。結果
を表１の実施例４に示す。Example 4 In the same manner as in Example 1, 201.9 mg of cobalt chloride (manufactured by Hanai Chemical Co., CoCl 2 .6H 2 O) was added to 1 g of granular silica gel.
1.2 ml of an aqueous solution containing
It was treated with hydrogen. (This is abbreviated as Co (Cl) / SiO 2 catalyst.) Further, as in Example 1, 29.6 mg of tetriridium dodecacarbonyl was carried on this, and then hydrogen treatment was carried out. (This is Co (Cl) -Ir (CO)
/ SiO 2 catalyst. ) Using this catalyst, a hydroformylation reaction of ethylene was carried out in the same manner as in Example 1. The results are shown in Example 4 of Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】比較例１ 実施例１と同様に調製したＣｏ（Ａ）／ＳｉＯ2触媒を
用いてエチレンのヒドロホルミル化反応を行った。結果
を表２の比較例１に示す。Comparative Example 1 A hydroformylation reaction of ethylene was carried out using a Co (A) / SiO 2 catalyst prepared in the same manner as in Example 1. The results are shown in Comparative Example 1 in Table 2.
【００２１】比較例２ 実施例３と同様に調製したＣｏ（Ｎ）／ＳｉＯ2触媒を
用いてエチレンのヒドロホルミル化反応を行った。結果
を表２の比較例２に示す。Comparative Example 2 A Co (N) / SiO 2 catalyst prepared in the same manner as in Example 3 was used to carry out a hydroformylation reaction of ethylene. The results are shown in Comparative Example 2 in Table 2.
【００２２】比較例３ 実施例４と同様に調製したＣｏ（Ｃｌ）／ＳｉＯ2触媒
を用いてエチレンのヒドロホルミル化反応を行った。結
果を表２の比較例３に示す。Comparative Example 3 Hydroformylation reaction of ethylene was carried out using a Co (Cl) / SiO 2 catalyst prepared in the same manner as in Example 4. The results are shown in Comparative Example 3 in Table 2.
【００２３】比較例４ 実施例１と同様に粒状シリカゲル１ｇをフラスコ中、２
００℃で２時間真空加熱した。冷却後、これにテトライ
リジウムドデカカルボニル７４．２ｍｇを混合し、減圧
下、１５０℃で攪拌してイリジウムを担持し、次いで水
素気流中、４５０℃で３時間処理した。（これをＩｒ
（ＣＯ）／ＳｉＯ2触媒と略す。）この触媒を実施例１
と同様にエチレンのヒドロホルミル化反応を行った。結
果を表２の比較例４に示す。Comparative Example 4 In the same manner as in Example 1, 1 g of granular silica gel was placed in a flask for 2 times.
It was heated in vacuum at 00 ° C. for 2 hours. After cooling, this was mixed with 74.2 mg of tetriridium dodecacarbonyl and stirred under reduced pressure at 150 ° C to carry iridium, and then treated at 450 ° C for 3 hours in a hydrogen stream. (This is Ir
Abbreviated as (CO) / SiO 2 catalyst. ) This catalyst was used in Example 1
The hydroformylation reaction of ethylene was carried out in the same manner as in. The results are shown in Comparative Example 4 in Table 2.
【００２４】比較例５ 実施例１と同様に粒状シリカゲル１ｇをフラスコ中、２
００℃で２時間真空加熱した。冷却後、これに塩化イリ
ジウム８０．２ｍｇを含む１．２ｍｌの水溶液を減圧下
で加え、乾燥した後、水素処理を行った。（これをＩｒ
（Ｃｌ）／ＳｉＯ2触媒と略す。）この触媒を用いて実
施例１と同様にエチレンのヒドロホルミル化反応を行っ
た。結果を表２の比較例５に示す。Comparative Example 5 As in Example 1, 1 g of granular silica gel was placed in a flask for 2
It was heated in vacuum at 00 ° C. for 2 hours. After cooling, 1.2 ml of an aqueous solution containing 80.2 mg of iridium chloride was added under reduced pressure, dried, and then hydrogenated. (This is Ir
Abbreviated as (Cl) / SiO 2 catalyst. ) Using this catalyst, a hydroformylation reaction of ethylene was carried out in the same manner as in Example 1. The results are shown in Comparative Example 5 in Table 2.
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【発明の効果】以上説明したように本発明のコバルト化
合物およびイリジウム化合物を無機酸化物上に担持して
調製した不均一触媒はオレフィンのヒドロホルミル化反
応に高い活性および選択性を示し、アルデヒドあるいは
アルコールを高収率で製造することができる。INDUSTRIAL APPLICABILITY As described above, the heterogeneous catalyst prepared by supporting the cobalt compound and the iridium compound of the present invention on the inorganic oxide shows high activity and selectivity for the hydroformylation reaction of olefins, and the aldehyde or alcohol. Can be produced in high yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ (72)発明者 杉 義弘 茨城県つくば市東１丁目１番地 工業技術 院化学技術研究所内 (72)発明者 朝賀 裕之 千葉県野田市山崎2641番地 東京理科大学 理工学部内 (72)発明者 阿部 芳首 千葉県野田市山崎2641番地 東京理科大学 理工学部内 (72)発明者 御園生 尭久 千葉県野田市山崎2641番地 東京理科大学 理工学部内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication location // C07B 61/00 300 (72) Inventor Yoshihiro Sugi 1-chome, Higashi 1-chome, Tsukuba-shi, Ibaraki Industrial Technology Institute In the Institute of Chemical Research (72) Hiroyuki Asaga, 2641 Yamazaki, Noda, Chiba Prefecture, Faculty of Science and Engineering, Tokyo University of Science (72) Inventor, Yoshikazu Abe 2641, Yamazaki, Noda, Chiba Prefecture, Faculty of Science and Engineering, Tokyo University of Science (72) Inventor Misono Takahisa 2641 Yamazaki, Noda, Chiba Prefecture Tokyo University of Science Faculty of Science and Engineering
Claims (3)
調製した不均一コバルト触媒にさらにイリジウムを添加
した触媒を用いることを特徴とする、（１）式で表され
るオレフィンのヒドロホルミル化反応によるアルデヒド
及びアルコール類を合成する方法。 【化１】 1. A hydroformylation reaction of an olefin represented by formula (1), characterized in that a heterogeneous cobalt catalyst prepared by supporting a cobalt compound on an inorganic oxide is further added with iridium. A method for synthesizing aldehydes and alcohols. [Chemical 1]
原料オレフィンとしてエチレン（Ｒ1＝Ｒ2＝Ｒ3＝Ｒ4＝
Ｈ）を用い、ヒドロホルミル化反応によりプロピオンア
ルデヒドあるいはプロパノールを合成する方法。2. The method according to claim 1, wherein the reaction raw material olefin is ethylene (R 1 = R 2 = R 3 = R 4 =
H) is used to synthesize propionaldehyde or propanol by a hydroformylation reaction.
の担体用無機酸化物としてシリカゲルを用いる方法。3. The method according to claim 1, wherein silica gel is used as an inorganic oxide for a catalyst carrier.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3235570A JPH0774174B2 (en) | 1991-08-22 | 1991-08-22 | Hydroformylation catalyst |
| US07/931,965 US5409877A (en) | 1991-08-22 | 1992-08-19 | Catalyst for producing aldehyde and alcohol from olefin, carbon monoxide and hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3235570A JPH0774174B2 (en) | 1991-08-22 | 1991-08-22 | Hydroformylation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0551333A true JPH0551333A (en) | 1993-03-02 |
| JPH0774174B2 JPH0774174B2 (en) | 1995-08-09 |
Family
ID=16987952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3235570A Expired - Lifetime JPH0774174B2 (en) | 1991-08-22 | 1991-08-22 | Hydroformylation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774174B2 (en) |
-
1991
- 1991-08-22 JP JP3235570A patent/JPH0774174B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774174B2 (en) | 1995-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3092072B1 (en) | A process for vapor-phase methanol carbonylation to methyl formate | |
| EP0736326A1 (en) | Fischer-Tropsch catalysts containing iron and cobalt | |
| CN1024666C (en) | Production of alcohols and ethers by the catalysed hydrogenation of esters | |
| JP2000061306A (en) | Supported catalyst usable in conversion reaction of organic compound | |
| JPH0623269A (en) | Catalyst containing group viii and iiia metal supported on carrier thereof | |
| US20040225168A1 (en) | Selective hydrogenation of cyclododecatriene to cyclododecene | |
| US5409877A (en) | Catalyst for producing aldehyde and alcohol from olefin, carbon monoxide and hydrogen | |
| KR20050072119A (en) | CATALYST FOR α,β-UNSATURATED CARBOXYLIC ACID PRODUCTION, PROCESS FOR PRODUCING THE SAME, AND PROCESS FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID | |
| JPH0551333A (en) | Catalyst for hydroformylation reaction | |
| US4018831A (en) | Production of 2-ethyl hexanal | |
| JPH0597731A (en) | Production of oxygen-containing compound and catalyst therefor | |
| JPS5941974B2 (en) | Hydrogenation method for α,β-unsaturated aldehydes | |
| JP3744023B2 (en) | Process for producing 1,4-butanediol and / or tetrahydrofuran | |
| JPH0687978B2 (en) | Olefin hydroformylation reaction catalyst and method using the same | |
| JP2001010987A (en) | Production of cyclopentene | |
| CN115487821B (en) | Application of inorganic oxide supported multi-metal catalyst in catalyzing hydrogenation reaction of hydroquinone or bisphenol A | |
| JPS6039653B2 (en) | Method for producing oxygen-containing hydrocarbon compound | |
| CN114917900B (en) | Eggshell type silver-silicon catalyst and preparation method and application thereof | |
| JPH09118638A (en) | Production of cycloolefin | |
| JPH0735346B2 (en) | Hydroformylation catalyst | |
| CN1143733C (en) | C2-C7 fraction selective hydrogenation catalyst | |
| JPS6160621A (en) | Production of carbonyl compound | |
| US4022840A (en) | Process and catalyst for the preparation of linear mono-olefines by catalytic dehydrogenation of linear paraffins | |
| Cao et al. | Catalytic behavior of silica-supported polyalumazane-Co-Ru bimetallic complex for the hydroformylation of cyclohexene | |
| CN115990490A (en) | Dual-function catalyst, preparation method thereof and application thereof in ethylene purification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |