JPH09225311A - Modified raney nickel catalyst and production of diol compound thereby - Google Patents
Modified raney nickel catalyst and production of diol compound therebyInfo
- Publication number
- JPH09225311A JPH09225311A JP8039730A JP3973096A JPH09225311A JP H09225311 A JPH09225311 A JP H09225311A JP 8039730 A JP8039730 A JP 8039730A JP 3973096 A JP3973096 A JP 3973096A JP H09225311 A JPH09225311 A JP H09225311A
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- Prior art keywords
- hydroxy
- catalyst
- weight
- reaction
- hydrogenation reaction
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Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、改質ラニーニッケ
ル触媒とその触媒によるジオール化合物の製造方法に関
する。本発明の改質ラニーニッケルは、ヒドロキシ−ア
ルデヒドとヒドロキシ環状エーテルの水素添加反応、特
に、４−ヒドロキシ−ブタナール、２−ヒドロキシ−テ
トラヒドロフランおよび２−メチル−３−ヒドロキシ−
プロパナールの水素添加反応の際に有用な触媒として最
も良く用いられる。TECHNICAL FIELD The present invention relates to a modified Raney nickel catalyst and a method for producing a diol compound by the catalyst. The modified Raney nickel of the present invention is a hydrogenation reaction of hydroxy-aldehyde and hydroxy cyclic ether, especially 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-.
It is most often used as a useful catalyst in the hydrogenation reaction of propanal.
【０００２】[0002]
【従来の技術】従来、４−ヒドロキシ−ブタナール（４
−ｈｙｄｒｏｘｙ−ｂｕｔａｎａｌ）、２−ヒドロキシ
−テトラヒドロフラン（２−ｈｙｄｒｏｘｙ−ｔｅｔｒ
ａ−ｈｙｄｒｏｆｕｒａｎ）および２−メチル−３−ヒ
ドロキシ−プロパナール（２−ｍｅｔｈｙｌ−３−ｈｙ
ｄｒｏｘｙｐｒｏｐａｎａｌ）の製造方法として、アリ
ル−アルコール（ａｌｌｙｌ ａｌｃｏｈｏｌ）、一酸
化炭素と水素を原料とするゲルマニウム触媒の存在下
で、ヒドロホルミル化反応（Ｈｙｄｒｏ−ｆｏｒｍｙｌ
ａｔｉｏｎ）による下記に挙げる方法が知られている。Conventionally, 4-hydroxy-butanal (4
-Hydroxy-butanal), 2-hydroxy-tetrahydrofuran (2-hydroxy-tetr)
a-hydrofuran) and 2-methyl-3-hydroxy-propanal (2-methyl-3-hy)
As a method for producing droxypropanal, a hydroformylation reaction (Hydro-formyl) in the presence of an allyl alcohol and a germanium catalyst using carbon monoxide and hydrogen as raw materials is used.
The following methods are known.
【０００３】[0003]
【化１】 Embedded image
【０００４】そして、上記に挙げる方法により得られた
４−ヒドロキシ−ブタナールと２−ヒドロキシ−テトラ
ヒドロフラン及び２−メチル−３−ヒドロキシ−プロパ
ナールは、それぞれさらに水素添加反応（ｈｙｄｒｏｇ
ｅｎａｔｉｏｎ）により、１，４−ブタンジオール
（１，４−ｂｕｔａｎｅｄｉｏｌ）及び２−メチル−
１，３−プロパンジオール（２−ｍｅｔｈｙｌ−１，３
−ｐｒｏｐａｎｅｄｉｏｌ）の製造に際し、必要な中間
原料として有用な化合物である。上記水素添加反応とし
て下記の反応式が挙げられている。Then, 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal obtained by the above-mentioned methods are further subjected to a hydrogenation reaction (hydrolog).
1,4-butanediol and 2-methyl-
1,3-propanediol (2-methyl-1,3
-Propanediol) is a useful compound as a necessary intermediate raw material. The following reaction formula is mentioned as the above hydrogenation reaction.
【０００５】[0005]
【化２】 Embedded image
【０００６】前記の４−ヒドロキシ−ブタナールと２−
メチル−３−ヒドロキシ−プロパナールの水素添加反応
はカルボニル基（ｃａｒｂｏｎｙｌ ｇｒｏｕｐ）の水
素添加反応によるもので、一般にはカルボニ基の水素添
加反応に用いられる貴重金属（Ｐｒｅｃｉｏｕｓ ｍｅ
ｔａｌ）を含む触媒、例えばパラジウム触媒〔Ｂｉｏｃ
ｈｅｍｉｓｔｒｙ Ｊｏｕｒｎａｌ，３７，７２６（１
９４３）〕、白金触媒〔Ｊｏｕｒｎａｌ ｏｆ Ａｍｅ
ｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，７
０，６６４（１９４８）〕、ルテニウム触媒（ＵＳＰ第
３１４４４９０号公報）、レニウム触媒〔Ｊｏｕｒｎａ
ｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ，２
４，１８４７（１９５９）〕、酸化銅−クロマイト触媒
〔Ｉｎｄｕｓｔｒｉａｌ ａｎｄ Ｅｎｇｉｎｅｅｒｉ
ｎｇ Ｃｈｅｍｉｓｔｒｙ，３８，２５１，（１９４
６）〕、銅触媒（ＢＰ第６５９９８１号公報）、ニッケ
ル触媒〔工業化学雑誌、第４６巻、９０１頁、（１９４
３）〕、ラニーニッケル触媒〔Ｊｏｕｒｎａｌ ｏｆ
Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔ
ｙ，７０，６９５（１９４８）〕、ラニーコバルト触媒
（Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｃｈｅｍｉ
ｓｔｒｙ，８，４９２（１９５８）〕などか用いられて
いる。The above 4-hydroxy-butanal and 2-
The hydrogenation reaction of methyl-3-hydroxy-propanal is based on the hydrogenation reaction of a carbonyl group, and is generally a precious metal used in the hydrogenation reaction of a carbonyl group.
tal) containing catalysts such as palladium catalysts [Bioc
chemistry Journal, 37, 726 (1
943)], platinum catalyst [Journal of Ame
rican Chemical Society, 7
0,664 (1948)], ruthenium catalyst (USP No. 3144490), rhenium catalyst [Journa
l of Organic Chemistry, 2
4, 1847 (1959)], copper oxide-chromite catalyst [Industrial and Engineering]
ng Chemistry, 38, 251, (194
6)], copper catalyst (BP 659981), nickel catalyst [Industrial Chemistry, Vol. 46, page 901, (194)
3)], Raney nickel catalyst [Journal of
American Chemical Societ
y, 70, 695 (1948)], Raney cobalt catalyst (Journal of Applied Chemi).
stry, 8, 492 (1958)] or the like is used.
【０００７】[0007]
【発明が解決しようとする課題】本発明者らの多年にわ
たる上記４−ヒドロキシ−ブタナール、２−ヒドロキシ
−テトラヒドロフランと２−メチル−３−ヒドロキシ−
プロパナールの水素添加反応にかかわる研究の結果、本
系列の水素添加反応と通常のカルボニル基の水素添加反
応は異なることを見出した。即ち、実験に用いたパラジ
ウム触媒と酸化銅亜鉛触媒は上記反応系においてほとん
ど活性がみられず、さらにルテニウム触媒と酸化銅−ク
ロマイト触媒にいたっては、上記反応系では活性が非常
に低く、実用価値のないものである。ただニッケル触媒
とラニーニッケル触媒のみ、本反応系において高い活性
を示す。さらに鋭意検討したところ、ニッケル触媒、ラ
ニーニッケル触媒とも反応活性の低下が非常にはやく、
触媒として重複使用した場合、その使用寿命は短かく、
３３バッチ或いは３０時間の連続的使用で、その反応活
性は使用に耐えないものとなり、工業的には実用化に遠
いものであった。SUMMARY OF THE INVENTION The 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-above-mentioned for many years of the present inventors.
As a result of research on hydrogenation reaction of propanal, it was found that the hydrogenation reaction of this series is different from the usual hydrogenation reaction of carbonyl group. That is, the palladium catalyst and the copper-zinc oxide catalyst used in the experiment showed almost no activity in the above reaction system, and the ruthenium catalyst and the copper oxide-chromite catalyst had very low activity in the above reaction system, and were practically used. It is worthless. Only nickel catalyst and Raney nickel catalyst show high activity in this reaction system. As a result of further study, the reaction activity of both the nickel catalyst and the Raney nickel catalyst was very low,
When it is used repeatedly as a catalyst, its service life is short,
With 33 batches or continuous use for 30 hours, the reaction activity became unusable, and industrially far from practical use.
【０００８】このように、公知のいずれの触媒によって
も上記の反応系の水素添加反応を工業的に有利に行なう
ことは困難であった。As described above, it has been difficult to industrially advantageously carry out the hydrogenation reaction of the above reaction system with any known catalyst.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記の状
況に鑑み、有用な触媒を提供すべく鋭意検討をした。そ
の結果、従来のラニーニッケル触媒に鉄或いは鉄とクロ
ム、モリブデン、タングステン、コバルト、マンガン、
チタンなどの金属より選出した少なくとも一種或いは二
種以上の金属を添加したところ、非常に高い反応活性を
示し、かつ反応活性の低下も少ない。即ち、再三重複使
用した場合、触媒としての寿命も非常に長く、工業的に
も有用な改質ラニーニッケル触媒を見出した。In view of the above situation, the present inventors have made earnest studies to provide a useful catalyst. As a result, iron or iron and chromium, molybdenum, tungsten, cobalt, manganese,
When at least one metal or two or more metals selected from metals such as titanium are added, a very high reaction activity is exhibited and the reaction activity is not significantly reduced. That is, a modified Raney nickel catalyst was found to be industrially useful, since it has a very long life as a catalyst when it is used repeatedly.
【００１０】さらに本発明者らは、上記の改質ラニーニ
ッケル触媒を用いることにより、４−ヒドロキシ−ブタ
ナール、２−ヒドロキシ−テトラヒドロフランと２−メ
チル−３−ヒドロキシ−プロパナールを原料として水素
添加反応を行ない、１，４−−ブタンジオールと２−メ
チル−１，３−プロパンジオールを工業的に有利に製造
できることを見出し、本発明を完成するに至った。Further, the inventors of the present invention use the above modified Raney nickel catalyst to carry out hydrogenation reaction using 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal as raw materials. The present invention was completed by finding out that 1,4-butanediol and 2-methyl-1,3-propanediol can be industrially advantageously produced.
【００１１】本発明の第１の目的は、改質ラニーニッケ
ル触媒を提供し、即ち、ヒドロキシ−アルデヒド、特に
４−ヒドロキシ−ブタナール、２−ヒドロキシ−テトラ
ヒドロフランと２−メチル−３−ヒドロキシ−プロパナ
ールの水素添加反応に用いられる触媒を提供する。The first object of the present invention is to provide a modified Raney nickel catalyst, ie a hydroxy-aldehyde, especially 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal. A catalyst used in the hydrogenation reaction of 1.
【００１２】さらに、本発明の次の目的は、上記の改質
ラニーニッケル触媒を用いたジオール化合物の製造方法
を提供する。Further, the next object of the present invention is to provide a method for producing a diol compound using the above modified Raney nickel catalyst.
【００１３】本発明は、一種の改質ラニーニッケル触媒
に関したものであり、ヒドロキシ−アルデヒドの水素添
加反応、特に４−ヒドロキシ−ブタナール、２−ヒドロ
キシ−テトラヒドロフランと２−メチル−３−ヒドロキ
シ−プロパナールの水素添加反応に用いられる触媒を提
供することを特徴とする。The present invention relates to a kind of modified Raney nickel catalyst, which is a hydrogenation reaction of hydroxy-aldehyde, especially 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-proton. It is characterized by providing a catalyst used in the hydrogenation reaction of Panhard.
【００１４】さらに本発明は、上記の触媒を用いたジオ
ール化合物の製造方法に関するものである。Further, the present invention relates to a method for producing a diol compound using the above catalyst.
【００１５】本発明の改質ラニーニッケル触媒における
ニッケルの含有量は、４０〜９８重量％、アルミニウム
の含有量は１〜５０重量％、鉄の含有量は０．０５〜１
５重量％である。In the modified Raney nickel catalyst of the present invention, the nickel content is 40 to 98% by weight, the aluminum content is 1 to 50% by weight, and the iron content is 0.05 to 1%.
5% by weight.
【００１６】本発明の改質ラニーニッケル触媒は、前記
必須成分のニッケル、アルミニウムと鉄に加え、必要に
応じて、さらにクロム、モリブデン、タングステン、コ
バルト、マンガン、チタンなどの金属より任意に選んだ
１種或いは１種以上の金属を０．０５〜１０重量％加え
ることができる。The modified Raney nickel catalyst of the present invention is arbitrarily selected from the metals such as chromium, molybdenum, tungsten, cobalt, manganese and titanium in addition to the above-mentioned essential components nickel, aluminum and iron. 0.05 to 10% by weight of one or more metals can be added.
【００１７】本発明の改質ラニーニッケル触媒の製造方
法は、公知の製造方法に準じて製造することができる。The modified Raney nickel catalyst of the present invention can be produced according to a known production method.
【００１８】例えば、所定量のニッケル、アルミニウム
と鉄、さらに必要に応じてクロム、モリブデン、コバル
ト、タングステン、マンガン、チタンなどの金属より任
意に選ばれた１種或いは１種以上を適宜配合した混合物
を１２００〜２０００℃の温度下で加熱融解し、本発明
の改質ラニーニッケル触媒の前駆合金を製造し、静置、
冷却した後に適当な粒度（通常は粒状あるいは粉末とし
て）に粒砕し、次に水酸化アルカリ金属水溶液中で分散
し、さらに蒸留水あるいはイオン交換水を用いて洗浄す
ることにより本発明の改質ラニーニッケル触媒を得る。For example, a predetermined amount of nickel, aluminum and iron, and, if necessary, one kind or a mixture of one or more kinds arbitrarily selected from metals such as chromium, molybdenum, cobalt, tungsten, manganese and titanium. Is heated and melted at a temperature of 1200 to 2000 ° C. to produce a precursor alloy of the modified Raney nickel catalyst of the present invention, which is allowed to stand,
After cooling, it is crushed to a suitable particle size (usually as a granule or powder), then dispersed in an aqueous alkali metal hydroxide solution, and further washed with distilled water or ion-exchanged water to modify the present invention. A Raney nickel catalyst is obtained.
【００１９】本発明による改質ラニーニッケル触媒はヒ
ドロキシ−アルデヒド、特に４−ヒドロキシ−ブタナー
ル、２−ヒドロキシ−テトラヒドロフランと２−メチル
−３−ヒドロキシ−プロパナールの水素添加反応の触媒
として最も良く用いられる。The modified Raney nickel catalyst according to the invention is best used as a catalyst for the hydrogenation reaction of hydroxy-aldehydes, especially 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal. .
【００２０】また、本発明の改質ラニーニッケル触媒に
よるジオール化合物の製造方法は、例えば本発明の改質
ラニーニッケル触媒の存在下で、ヒドロキシ−アルデヒ
ドを５０〜２００℃、好ましくは７０〜１５０℃の温度
下で、１０〜２００ｋｇ／ｃｍ2 Ｇの加圧、好ましくは
２０〜８０ｋｇ／ｃｍ2 Ｇの反応加圧下で水素添加反応
を行うことにより目的とするジオール化合物が得られ
る。The method for producing a diol compound using the modified Raney nickel catalyst of the present invention is, for example, in the presence of the modified Raney nickel catalyst of the present invention, hydroxy-aldehyde is added at 50 to 200 ° C., preferably 70 to 150 ° C. The desired diol compound can be obtained by carrying out the hydrogenation reaction under the pressure of 10 to 200 kg / cm 2 G, and preferably under the reaction pressure of 20 to 80 kg / cm 2 G under the temperature of
【００２１】上記水素添加反応の際に用いる反応器は、
使用する触媒によって異なるが、一般に粉末状の触媒を
用いた場合、スラリー床式反応槽（ｓｌｕｒｒｙ ｂｅ
ｄｒｅａｃｔｏｒ）を用い、粒状の触媒を用いた場合
は、固定床式反応槽（ｆｉｘｅｄ ｂｅｄ ｒｅａｃｔ
ｏｒ）が良く利用される。上記反応は、バッチ・プロセ
ス（ｂａｔｃｈ ｐｒｏｃｅｓｓ）或いは連続式操作
（ｃｏｎｔｉｎｕｏｕｓｐｒｏｃｅｓｓ）の任意の方法
が用いられる。The reactor used in the above hydrogenation reaction is
Depending on the catalyst used, in general, when a powdery catalyst is used, a slurry bed reactor (slurry beer) is used.
fixed bed reactor when a granular catalyst is used.
or) is often used. For the above reaction, any method of batch process or continuous process is used.
【００２２】本発明の触媒の使用量は、スラリー床式反
応系において、反応液重量に対して、通常０．５〜２０
重量％を用いる。固定床式反応系の場合は、０．１〜１
０ｈｒ-1の液量空間速度（ｌｉｑｕｉｄ ｈｏｕｒｌｙ
ｓｐａｃｅ ｖｅｌｏｃｉｔｙ、以下ＬＨＳＶと略す
る）で触媒を投入する。The amount of the catalyst of the present invention used is usually 0.5 to 20 relative to the weight of the reaction liquid in the slurry bed type reaction system.
Use% by weight. 0.1 to 1 for fixed bed reaction system
Liquid hourly velocity of 0 hr -1
The catalyst is charged at a space velocity (hereinafter abbreviated as LHSV).
【００２３】本発明の水素添加反応に用いられる原料化
合物のヒドロキシ−アルデヒドとして、例えば４−ヒド
ロキシ−ブタナール、２−ヒドロキシ−テトラヒドロフ
ランと２−メチル−３−ヒドロキシ−プロパナールなど
が挙げられる。Examples of the hydroxy-aldehyde of the raw material compound used in the hydrogenation reaction of the present invention include 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal.
【００２４】本発明の改質ラニーニッケル触媒は活性が
高く、かつ触媒として長期間利用できるものである。The modified Raney nickel catalyst of the present invention has high activity and can be used as a catalyst for a long period of time.
【００２５】以下に、実施例により本発明をさらに詳し
く説明するが、本発明は、これらの実施例に何等限定さ
れるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００２６】[0026]
１．粉末状スラリー床反応系 1. Powder slurry bed reaction system
【００２７】[0027]
【実施例１】撹拌機を附した耐圧ガラス反応容器に、カ
ルボニルヒドロトリス（トリフェニルホスフィン）ロジ
ウム０．７８１ｇ、トリフェニルホスフィン２１．６
ｇ、アリルアルコール５５．４ｇとトルエン７３．６ｇ
を加え、反応系の温度を６０℃に保ちながら、一酸化炭
素と水素ガスの混合物（１：１モル比）を導入し、それ
により反応系の内圧を７ｋｇ／ｃｍ2 Ｇに保ち、アルデ
ヒド化反応を６．５時間続ける。反応終了後、精製水を
反応液に加えて抽出、分液する。上層に触媒を含むトル
エン液と下層に４−ヒドロキシ−ブタナール、２−ヒド
ロキシ−テトラヒドロフランと２−メチル−３−ヒドロ
キシ−プロパナールを含む水層とに分かれる。Example 1 0.781 g of carbonylhydrotris (triphenylphosphine) rhodium and 21.6 triphenylphosphine were placed in a pressure-resistant glass reaction vessel equipped with a stirrer.
g, allyl alcohol 55.4 g and toluene 73.6 g
And a mixture of carbon monoxide and hydrogen gas (1: 1 molar ratio) was introduced while maintaining the temperature of the reaction system at 60 ° C., thereby maintaining the internal pressure of the reaction system at 7 kg / cm 2 G and performing aldehyde formation. The reaction is continued for 6.5 hours. After completion of the reaction, purified water is added to the reaction solution for extraction and separation. It is divided into a toluene solution containing a catalyst in the upper layer and an aqueous layer containing 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal in the lower layer.
【００２８】水素添加触媒の調製として、ニッケル３
８．５重量％、アルミニウム５８．４重量％、鉄１．４
重量％、クロム１．７重量％よりなるアロイを１６５０
℃で熔解、冷却して製造した後、これを２０〜１５０μ
ｍに粒砕する。別に、水酸化ナトリウム３０ｇを水１５
０ｍｌに溶解し、撹拌しながら５０〜６０℃に冷却す
る。次に上記アロイ粉末２０ｇを前記の水酸化ナトリウ
ム水溶液中に加え、温度を５０〜１００℃に上昇させ、
撹拌しながら３０〜１２０分間分散を行なう。その後、
精製水を用い洗浄液がｐＨ８〜９になる迄洗浄して、ニ
ッケル８５．０重量％、アルミニウム９．５重量％、鉄
２．５重量％とクロム３．０重量％を含有する本発明の
改質ラニーニッケル触媒を得る。For the preparation of the hydrogenation catalyst, nickel 3
8.5% by weight, aluminum 58.4% by weight, iron 1.4
1650 alloy consisting of 1% by weight and 1.7% chromium
After melting and cooling at ℃, and manufacturing, this is 20-150μ
Grind to m. Separately, 30 g of sodium hydroxide is added to 15 g of water.
Dissolve in 0 ml and cool to 50-60 ° C. with stirring. Next, 20 g of the above alloy powder is added to the above aqueous sodium hydroxide solution to raise the temperature to 50 to 100 ° C.,
Disperse for 30 to 120 minutes with stirring. afterwards,
It was washed with purified water until the pH of the washing liquid reached 8 to 9, and the modified form of the present invention containing 85.0% by weight nickel, 9.5% by weight aluminum, 2.5% by weight iron and 3.0% by weight chromium. Quality Raney nickel catalyst is obtained.
【００２９】次に、４−ヒドロキシ−ブタナール、２−
ヒドロキシ−テトラヒドロフランと２−メチル−３−ヒ
ドロキシ−プロパナールを含む上記の水溶液４２０ｍｌ
を撹拌機を附したステンレス・ジャケット式反応容器に
加え、反応容器内に金属粉末か燒装置を設置し、上記の
水素添加触媒９．３８ｇ（粒径５０μｍ以下６５％）を
添加し、１１５℃に加温、水素ガスを導入しながら反応
系内圧を６０ｋｇ／ｃｍ2 Ｇに維持し、撹拌を続け、２
時間水素添加反応を行なう。反応後、水素ガスの供給と
撹拌を止め、３０分間静置して触媒を沈澱させ、水素ガ
ス圧を上記か燒装置の中心より放圧した後、上澄液約４
００ｍｌを反応系より取り出す。ガスクロマトグラフィ
の分析結果、１，４−ブタンジオール１６．６４重量
％、２−メチル−１，３−プロパンジオール３．２５重
量％、その他の反応生成物と水溶液８０．１１重量％よ
りなることを知る。さらに４−ヒドロキシ−ブタナー
ル、２−ヒドロキシ−テトラヒドロフランと２−メチル
−３−ヒドロキシ−プロパナールなどを含む水溶液４０
０ｍｌを反応容器内に補給し、上記と同じ反応条件下で
２時間水素添加反応を再度行ない、このようにして五十
回（ｂａｔｃｈ）水素添加反応の操作を連続した結果、
平均９５〜９８％の転化率を維持した状態を示した。上
記の転化率は下記の式により計算される。Next, 4-hydroxy-butanal, 2-
420 ml of the above aqueous solution containing hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal
Was added to a stainless steel jacket type reaction vessel equipped with a stirrer, a metal powder or a burning device was installed in the reaction vessel, 9.38 g of the above hydrogenation catalyst (particle size 50 μm or less 65%) was added, and 115 ° C. While heating and introducing hydrogen gas, the internal pressure of the reaction system was maintained at 60 kg / cm 2 G and stirring was continued for 2
The hydrogenation reaction is performed for an hour. After the reaction, supply of hydrogen gas and stirring were stopped, the catalyst was allowed to stand for 30 minutes, the hydrogen gas pressure was released from the center of the above-mentioned burning apparatus, and the supernatant liquid was about 4
Remove 00 ml from the reaction system. As a result of analysis by gas chromatography, it was found that it was composed of 16.64% by weight of 1,4-butanediol, 3.25% by weight of 2-methyl-1,3-propanediol, 80.11% by weight of other reaction products and an aqueous solution. know. Further, an aqueous solution containing 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran, 2-methyl-3-hydroxy-propanal, etc. 40
0 ml was replenished in the reaction vessel, and the hydrogenation reaction was performed again for 2 hours under the same reaction conditions as described above. As a result, the operation of the 50th hydrogenation reaction was continued in this way,
An average conversion rate of 95 to 98% was maintained. The above conversion rate is calculated by the following formula.
【００３０】[0030]
【数１】 ＨＢＡ１：水素添加反応前の反応液中、ガスクロ分析に
よる４−ヒドロキシ−ブタナール＋２−ヒドロキシ−テ
トラヒドロフラン＋２−メチル−３−ヒドロキシ−プロ
パナールの濃度を示す。 ＨＢＡ２：水素添加反応後の反応液中、ガスクロ分析に
よる４−ヒドロキシ−ブタナール＋２−ヒドロキシ−テ
トラヒドロフラン＋２−メチル−３−ヒドロキシ−プロ
パナールの濃度を示す。[Equation 1] HBA1: shows the concentration of 4-hydroxy-butanal + 2-hydroxy-tetrahydrofuran + 2-methyl-3-hydroxy-propanal in the reaction solution before hydrogenation reaction by gas chromatography analysis. HBA2: shows the concentration of 4-hydroxy-butanal + 2-hydroxy-tetrahydrofuran + 2-methyl-3-hydroxy-propanal in the reaction solution after the hydrogenation reaction by gas chromatography analysis.
【００３１】[0031]
【実施例２】水素添加反応に用いる触媒中、粒径５０μ
ｍ以下に占める比を５７％、かつ触媒の組成をニッケル
８７．１重量％、アルミニウム９．９重量％、鉄３．０
重量％に変えた以外は、実施例１と同様にして水素添加
反応を行ない、５０回（ｂａｔｃｈ）連続操作をしたと
ころ、その転化率は、平均９３〜９８％の範囲を維持し
た。Example 2 Particle size of 50 μm in a catalyst used for hydrogenation reaction
The ratio of m to m is 57%, and the composition of the catalyst is nickel 87.1% by weight, aluminum 9.9% by weight, iron 3.0.
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the weight ratio was changed to 50 times (batch), and the conversion rate was maintained in the range of 93 to 98% on average.
【００３２】[0032]
【実施例３】水素添加反応に用いる触媒中、粒径８７μ
ｍ以下に占める比を９０％、かつ触媒の組成をニッケル
８７．０重量％、アルミニウム９．９重量％、鉄０．１
重量％、クロム３．０重量％に変えた以外は、実施例１
と同様にして水素添加反応を行ない、４６回（ｂａｔｃ
ｈ）連続操作をしたところ、その転化率は平均９０〜９
８％の範囲を維持した。Example 3 Particle size of 87 μm in a catalyst used for hydrogenation reaction
90% of m or less, and the composition of the catalyst is 87.0% by weight of nickel, 9.9% by weight of aluminum, and 0.1 of iron.
Example 1 except that the weight% and chromium 3.0% were changed.
The hydrogenation reaction was carried out in the same manner as in, and was carried out 46 times (batc
h) When the continuous operation was performed, the conversion rate was 90 to 9 on average.
The range of 8% was maintained.
【００３３】[0033]
【実施例４】水素添加反応に用いる触媒中、粒径１６２
μｍ以下に占める比を９０％、かつ触媒の組成をニッケ
ル９２．０重量％、アルミニウム６．１重量％、鉄０．
７重量％、モリブデン１．２重量％に変えた以外は、実
施例１と同様にして水素添加反応を行ない、４５回（ｂ
ａｔｃｈ）連続操作をしたところ、その転化率は平均９
０〜９８％の範囲を維持した。Example 4 Particle size 162 in catalyst used for hydrogenation reaction
90% by weight, and the composition of the catalyst is 92.0% by weight of nickel, 6.1% by weight of aluminum, and 0.1% by weight of iron.
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the amount of hydrogen was changed to 7% by weight and 1.2% by weight of molybdenum.
When the continuous operation was performed, the conversion rate was 9 on average.
The range of 0-98% was maintained.
【００３４】[0034]
【実施例５】水素添加反応に用いる触媒中、粒径５０μ
ｍ以下に占める比を６５％、かつ触媒の組成をニッケル
８６．０重量％、アルミニウム９．５重量％、鉄０．５
重量％、チタン２．０重量％、タングステン２．０重量
％に変えた以外は、実施例１と同様にして水素添加反応
を行ない、４０回（ｂａｔｃｈ）連続操作をしたとこ
ろ、その転化率は平均９０〜９８％の範囲を維持した。Example 5 Particle size of 50 μm in catalyst used for hydrogenation reaction
The ratio of 65% to m or less, and the composition of the catalyst is 86.0% by weight of nickel, 9.5% by weight of aluminum, and 0.5 of iron.
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the weight ratio was changed to 2.0% by weight of titanium and 2.0% by weight of tungsten, and the continuous operation was repeated 40 times (batch). The average range of 90-98% was maintained.
【００３５】[0035]
【実施例６】水素添加反応に用いる触媒中、粒径４４μ
ｍ以下に占める比を４６．８％、かつ触媒の組成をニッ
ケル８７．０重量％、アルミニウム１１．６重量％、鉄
１．２重量％、マンガン２．０重量％に変えた以外は、
実施例１と同様にして水素添加反応を行い、３８回（ｂ
ａｔｃｈ）連続操作をしたところ、その転化率は平均９
０〜９８％の範囲を維持した。Example 6 Particle size of 44 μm in catalyst used for hydrogenation reaction
except that the ratio of m to m is 46.8%, and the composition of the catalyst is changed to nickel 87.0 wt%, aluminum 11.6 wt%, iron 1.2 wt% and manganese 2.0 wt%.
The hydrogenation reaction was carried out in the same manner as in Example 1, 38 times (b
When the continuous operation was performed, the conversion rate was 9 on average.
The range of 0-98% was maintained.
【００３６】[0036]
【比較例１】水素添加反応に用いる触媒中、粒径５０μ
ｍ以下に占める比を８３％、但し触媒の組成をニッケル
９２．７重量％、アルミニウム６．１重量％、モリブデ
ン１．２重量％に変え、実施例１と同様にして水素添加
反応を行い、３３回（ｂａｔｃｈ）連続操作をしたとこ
ろ、その転化率は９０％より７０％に低下した。[Comparative Example 1] Particle size of 50μ in a catalyst used for hydrogenation reaction
The proportion of m or less is 83%, except that the composition of the catalyst is changed to nickel 92.7% by weight, aluminum 6.1% by weight, molybdenum 1.2% by weight, and hydrogenation reaction is performed in the same manner as in Example 1, After continuous operation for 33 times (batch), the conversion rate decreased from 90% to 70%.
【００３７】[0037]
【比較例２】水素添加反応に用いる触媒の組成をニッケ
ル８７．２重量％、アルミニウム３．６重量％、マンガ
ン９．２重量％に変え、実施例１と同様にして水素添加
反応を行ない、１５回（ｂａｔｃｈ）連続操作をしたと
ころ、その転化率は９０％より３０％に低下した。Comparative Example 2 The composition of the catalyst used in the hydrogenation reaction was changed to nickel 87.2% by weight, aluminum 3.6% by weight and manganese 9.2% by weight, and the hydrogenation reaction was carried out in the same manner as in Example 1, After continuous operation for 15 times (batch), the conversion rate decreased from 90% to 30%.
【００３８】[0038]
【比較例３】水素添加反応に用いる触媒中、粒径５０μ
ｍ以下に占める比を６０％、但し触媒の組成をニッケル
９２．７重量％、アルミニウム７．３重量％に変えて、
実施例１と同様にして水素添加反応を行ない、１０回
（ｂａｔｃｈ）連続操作をしたところ、その転化率は８
０％より３０％に低下した。[Comparative Example 3] Particle size of 50 μm in the catalyst used for hydrogenation reaction
The ratio of m or less is 60%, except that the composition of the catalyst is changed to 92.7% by weight of nickel and 7.3% by weight of aluminum,
Hydrogenation reaction was carried out in the same manner as in Example 1 and continuous operation was carried out 10 times (batch).
It decreased from 0% to 30%.
【００３９】[0039]
【比較例４】水素添加反応にドイツＨｏｅｃｈｓｔ社製
の触媒ＲＣＨ５５／１０を用い、その組成をニッケル５
５重量％を硅藻土に維持した以外は、実施例１と同様に
して水素添加反応を行ない、３回（ｂａｔｃｈ）連続操
作をしたところ、その転化率は８０％より２０％に低下
した。[Comparative Example 4] A catalyst RCH55 / 10 manufactured by Hoechst in Germany was used for the hydrogenation reaction, and the composition was changed to nickel 5
The hydrogenation reaction was carried out in the same manner as in Example 1 except that diatomaceous earth was maintained at 5% by weight, and the conversion was repeated 3 times (batch), and the conversion rate decreased from 80% to 20%.
【００４０】[0040]
【比較例５】水素添加反応にアメリカＨａｒｓｈａｗ社
製の触媒Ｎｉ−１４０４Ｐを用い、触媒の粒径を１００
μｍ以下に占める比を１００％とし、その触媒の組成を
ニッケル６６重量％をシリカ−アルミナ（ＳｉＯ2−Ａ
ｌ2Ｏ3 ）上に載持した以外は、実施例１と同様にして
水素添加反応を行ない、３回（ｂａｔｃｈ）連続操作を
したところ、その転化率は８５％より３５％に低下し
た。[Comparative Example 5] The catalyst Ni-1404P manufactured by Harshaw, USA was used for the hydrogenation reaction, and the particle size of the catalyst was 100.
The ratio of the catalyst in 100 μm or less is 66% by weight of nickel and silica-alumina (SiO 2 -A).
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the reaction was carried out on 1 2 O 3 ) and the operation was carried out continuously for 3 times (batch). As a result, the conversion rate decreased from 85% to 35%.
【００４１】[0041]
【比較例６】水素添加反応に用いる触媒として、イギリ
スのＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ社製の触媒１９Ａ
を用い、その組成をルテニウム５重量％を活性炭に載持
した以外は、実施例１と同様にして、一回だけ水素添加
反応を行なった。その転化率は１６％と低いものであっ
た。[Comparative Example 6] As a catalyst used in the hydrogenation reaction, catalyst 19A manufactured by Johnson Matthey of England
Was used, and the hydrogenation reaction was carried out only once in the same manner as in Example 1 except that 5% by weight of ruthenium was loaded on the activated carbon. The conversion rate was as low as 16%.
【００４２】[0042]
【比較例７】水素添加反応に用いる触媒として、日本Ｎ
ｉｋｋｉ社製の触媒Ｎ−２０３ＳＤを用い、該触媒組成
を、第二酸化銅と酸化クロム（Ｃｒ2Ｏ3）よりなる以外
は、実施例１と同様にして、一回だけ水素添加反応を行
なったところ、その転化率は９％と非常に低い値を示し
た。[Comparative Example 7] Japan N was used as a catalyst for the hydrogenation reaction.
A hydrogenation reaction was performed only once in the same manner as in Example 1 except that a catalyst N-203SD manufactured by ikki was used and the catalyst composition consisted of cupric oxide and chromium oxide (Cr 2 O 3 ). However, the conversion rate was a very low value of 9%.
【００４３】[0043]
【比較例８】水素添加反応に用いる触媒として、日本Ｇ
ｉｒｄｌｅｒ社製の触媒Ｇ−６６Ｄを用い、該触媒組成
を酸化銅３３重量％、酸化亜鉛６５重量％とする以外
は、実施例１と同様にして、一回だけ水素添加反応を行
なったところ、その転化率は０％であった。Comparative Example 8 As a catalyst used in the hydrogenation reaction, Japan G
A hydrogenation reaction was carried out only once in the same manner as in Example 1 except that the catalyst composition G-66D manufactured by Irdler was used and the catalyst composition was 33% by weight of copper oxide and 65% by weight of zinc oxide. The conversion rate was 0%.
【００４４】[0044]
【比較例９】水素添加反応に用いる触媒として、日本Ｅ
ｎｇｅｌｈａｒｄ社製の触媒を用い、触媒組成をパラジ
ウム２重量％をアルミナ上に載持する以外は、実施例１
と同様にして、一回だけ水素添加反応を行なったとこ
ろ、その転化率も０％であった。[Comparative Example 9] Japan E was used as a catalyst for the hydrogenation reaction.
Example 1 except that a catalyst manufactured by Ngelhard was used and the catalyst composition was 2% by weight of palladium loaded on alumina.
When the hydrogenation reaction was carried out only once in the same manner as above, the conversion rate was 0%.
【００４５】上記触媒組成、転化率と操作回数などを併
せ得た結果を第１表に示す。Table 1 shows the results obtained by combining the above-mentioned catalyst composition, conversion rate and number of operations.
【００４６】[0046]
【表１】 [Table 1]
【００４７】２．粒状触媒固定床反応系2. Granular catalyst fixed bed reaction system
【００４８】[0048]
【実施例７】撹拌機を附した耐圧ガラス反応容器に、カ
ルボニルヒドロトリス（トリフェニルホスフィン）ロジ
ウム０．７８１ｇ、トリフェニルホスフィン２１．６
ｇ、アリルアルコール５５．４ｇとトルエン７３．６ｇ
を加え、反応系の温度を６０℃に保ち、さらに一酸化炭
素と水素（１：１モル比）の混合ガスを導入し、これに
より反応系の内圧を７ｋｇ／ｃｍ2 Ｇに維持して６．５
時間反応を続けた。反応終了後、精製水を用いて抽出、
分液、上層にアルデヒド化反応触媒を含むトルエン溶液
層と、下層に４−ヒドロキシ−ブタナール、２−ヒドロ
キシ−テトラヒドロフランと２−メチル−３−ヒドロキ
シ−プロパナールなどを含む水溶液層とに分かれる。Example 7 0.781 g of carbonylhydrotris (triphenylphosphine) rhodium and 21.6 triphenylphosphine were placed in a pressure-resistant glass reaction vessel equipped with a stirrer.
g, allyl alcohol 55.4 g and toluene 73.6 g
Was added to maintain the temperature of the reaction system at 60 ° C., and a mixed gas of carbon monoxide and hydrogen (1: 1 molar ratio) was further introduced to maintain the internal pressure of the reaction system at 7 kg / cm 2 G. .5
The reaction was continued for hours. After completion of the reaction, extraction with purified water,
Liquid separation is divided into a toluene solution layer containing an aldehyde conversion catalyst in the upper layer and an aqueous solution layer containing 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal in the lower layer.
【００４９】水素添加触媒の調製として、ニッケル４０
重量％、アルミニウム５８重量％、鉄０．５重量％、ク
ロム１．５重量％よりなるアロイを１６０℃で熔解、冷
却して製造した後、これを３〜１０ｍｅｓｈに粉砕す
る。別に、水酸化ナトリウム８０ｇを水４００ｍｌに溶
解し、撹拌しながら５０〜６０℃に冷却する。次に上記
製造した粒状のアロイを前記の水酸化ナトリウム水溶液
に加え、温度を５０〜１００℃に上昇し、撹拌しながら
３０〜１２０分間分散を行ない、その後精製水で分散液
を洗浄し、洗浄液がｐＨ８〜９を示す迄洗浄し、これに
よりニッケル５７．０重量％、アルミニウム４０．２重
量％、鉄０．７重量％、クロム２．１重量％を含む本発
明の改質ラニーニッケル触媒を得る。To prepare the hydrogenation catalyst, nickel 40
An alloy composed of 50% by weight, 58% by weight of aluminum, 0.5% by weight of iron, and 1.5% by weight of chromium is melted at 160 ° C. and manufactured by cooling, and then crushed to 3 to 10 mesh. Separately, 80 g of sodium hydroxide is dissolved in 400 ml of water and cooled to 50-60 ° C with stirring. Next, the above-prepared granular alloy is added to the above-mentioned sodium hydroxide aqueous solution, the temperature is raised to 50 to 100 ° C., dispersion is carried out for 30 to 120 minutes while stirring, and then the dispersion is washed with purified water to obtain a washing liquid. Was washed until it showed a pH of 8-9, whereby a modified Raney nickel catalyst of the present invention containing 57.0% by weight of nickel, 40.2% by weight of aluminum, 0.7% by weight of iron and 2.1% by weight of chromium was obtained. obtain.
【００５０】次に、４−ヒドロキシ−ブタナール、２−
ヒドロキシ−テトラヒドロフランと２−メチル−３−ヒ
ドロキシ−プロパナールなどを含む水溶液を、ポンプに
より、１．５ｍｌ／ｍｉｎの流速で、内径１ｃｍのシリ
ンダー状反応液に加え、さらに前記の粒状水素添加触媒
３０ｍｌを添加し、１１５℃に昇温し、水素ガスを導入
しながら、反応系の内圧を６０ｋｇ／ｃｍ2 Ｇに保ち、
水素添加反応を行なう。ガスクロマトグラフィにより反
応第１日目の反応液中の生成物を分析したところ、１，
４−ブタンジオール１７．３８重量％、２−メチル−
１，３−プロパンジオール１．９８重量％とその他の生
成物を含む水溶液８０．６４重量％よりなることを知
る。Next, 4-hydroxy-butanal, 2-
An aqueous solution containing hydroxy-tetrahydrofuran and 2-methyl-3-hydroxy-propanal was added to the cylindrical reaction liquid having an inner diameter of 1 cm by a pump at a flow rate of 1.5 ml / min, and further 30 ml of the granular hydrogenation catalyst. Was added and the temperature was raised to 115 ° C., while introducing hydrogen gas, the internal pressure of the reaction system was maintained at 60 kg / cm 2 G,
Carry out hydrogenation reaction. When the products in the reaction solution on the first day of the reaction were analyzed by gas chromatography,
17.38 wt% 4-butanediol, 2-methyl-
It is known that it consists of 1.98% by weight of 1,3-propanediol and 80.64% by weight of an aqueous solution containing other products.
【００５１】さらに２０日間連続反応し、その転化率を
調べたところ、すべて９６〜１００％範囲内に維持した
結果を得る。The reaction was continued for 20 more days, and the conversion rate was examined. As a result, all the results were maintained within the range of 96 to 100%.
【００５２】[0052]
【実施例８】水素添加反応触媒の組成をニッケル５０．
４重量％、アルミニウム４７重量％、鉄２．６重量％に
変えた以外は、実施例７と同様にして水素添加反応を２
０日間続けて、その転化率を調べた結果９５〜１００％
を示した。Example 8 The composition of the hydrogenation reaction catalyst was nickel 50.
The hydrogenation reaction was carried out in the same manner as in Example 7 except that the amounts were changed to 4% by weight, 47% by weight of aluminum and 2.6% by weight of iron.
As a result of checking the conversion rate continuously for 0 days, 95 to 100%
showed that.
【００５３】[0053]
【実施例９】水素添加反応触媒の組成をニッケル５３．
５重量％、アルミニウム４２．４重量％、鉄０．１重量
％、モリブデン４．０重量％に変えた以外は、実施例７
と同様にして水素添加反応を２０日間続けて、その転化
率を調べた結果９４〜１００％を維持していた。Example 9 The composition of the hydrogenation reaction catalyst was nickel 53.
Example 7 except that the amounts were changed to 5% by weight, 42.4% by weight of aluminum, 0.1% by weight of iron, and 4.0% by weight of molybdenum.
The hydrogenation reaction was continued for 20 days in the same manner as above, and the conversion rate was examined. As a result, it was maintained at 94 to 100%.
【００５４】[0054]
【実施例１０】水素添加反応触媒の組成をニッケル４
７．５重量％、アルミニウム４８．０重量％、鉄０．５
重量％、マンガン３．０重量％、コバルト１．０重量％
に変えた以外は、実施例７と同様にして水素添加反応を
２０日間続けて、その転化率を調べたところ、９０〜１
００％範囲内に維持した結果を得る。Example 10 The composition of the hydrogenation reaction catalyst was nickel 4
7.5% by weight, aluminum 48.0% by weight, iron 0.5
% By weight, 3.0% by weight of manganese, 1.0% by weight of cobalt
The hydrogenation reaction was continued for 20 days in the same manner as in Example 7 except that the conversion ratio was changed to 90-1.
The result obtained is maintained within the range of 00%.
【００５５】[0055]
【比較例１０】水素添加反応触媒の組成をニッケル５２
重量％、アルミニウム４８重量％に変えた以外は、実施
例７と同様にして水素添加反応を１．５日間行なったと
ころ、その転化率は９０％より２５％に低下した。Comparative Example 10 The composition of the hydrogenation reaction catalyst was nickel 52.
When the hydrogenation reaction was carried out for 1.5 days in the same manner as in Example 7 except that the amounts were changed to 80% by weight and 48% by weight of aluminum, the conversion rate decreased from 90% to 25%.
【００５６】[0056]
【比較例１１】水素添加反応触媒の組成をニッケル４
８．７重量％、アルミニウム４８．４重量％、コバルト
２．９重量％に変えた以外は、実施例７と同様にして水
素添加反応を１．５日間行なった結果、その転化率は６
０％より２０％に低下した。Comparative Example 11 The composition of the hydrogenation reaction catalyst was nickel 4
The hydrogenation reaction was conducted for 1.5 days in the same manner as in Example 7 except that the amounts were changed to 8.7% by weight, aluminum 48.4% by weight, and cobalt 2.9% by weight. As a result, the conversion rate was 6%.
It fell from 0% to 20%.
【００５７】[0057]
【比較例１２】水素添加触媒として、アメリカＭａｌｌ
ｉｎｃｋｒａｄｔ社製品の触媒Ｅ−１１３Ｔを用いた。
その触媒の組成は銅−クロムよりなり、粒度１／８″を
示すものである。水素添加反応を連続４時間行なったと
ころ、その転化率は１０％より０％に低下した。[Comparative Example 12] US Mall as a hydrogenation catalyst
The catalyst E-113T manufactured by inckradt was used.
The composition of the catalyst was copper-chromium and had a particle size of 1/8 ". When the hydrogenation reaction was carried out continuously for 4 hours, the conversion rate decreased from 10% to 0%.
【００５８】[0058]
【比較例１３】水素添加触媒として、イギリスＪｏｈｎ
ｓｏｎ Ｍｅｔｔｈｅｙ社製の触媒５０Ａを用いた。そ
の触媒組成は、パラジウム０．５重量％をアルミナに載
持したものよりなる。実施例７と同様にして４時間反応
を続けた結果、その転化率は０％を示した。[Comparative Example 13] As a hydrogenation catalyst, England John
The catalyst 50A manufactured by Son Metsey was used. The catalyst composition consists of 0.5% by weight of palladium on alumina. As a result of continuing the reaction for 4 hours in the same manner as in Example 7, the conversion rate was 0%.
【００５９】上記触媒組成、転化率と反応時間などの結
果を併せて第２表に示す。The results of the catalyst composition, conversion rate and reaction time are shown in Table 2.
【００６０】[0060]
【表２】 [Table 2]
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Claims (9)
シ環状エーテルの水添触媒としてニッケル４０〜９８重
量％、アルミニウム１〜５０重量％と鉄０．０５〜１５
重量％よりなることを特徴とする改質ラニーニッケル触
媒。1. As a hydrogenation catalyst for hydroxy-aldehyde or hydroxy cyclic ether, 40 to 98% by weight of nickel, 1 to 50% by weight of aluminum and 0.05 to 15 of iron are used.
A modified Raney-nickel catalyst, characterized in that it comprises 1% by weight.
バルト、マンガン、チタンなどより任意の一種あるいは
一種以上の金属物質を更に０．０５〜１０重量％含む請
求項１記載の改質ラニーニッケル触媒。2. The modified Raney nickel catalyst according to claim 1, further comprising 0.05 to 10% by weight of any one or more metal substances selected from chromium, molybdenum, tungsten, cobalt, manganese, titanium and the like.
ロキシ−ブタナールまたは２−メチル−３−ヒドロキシ
−プロパナールである請求項１記載の改質ラニーニッケ
ル触媒。3. The modified Raney nickel catalyst according to claim 1, wherein the hydroxy-aldehyde is 4-hydroxy-butanal or 2-methyl-3-hydroxy-propanal.
ロキシ−テトラヒドロフランである請求項１記載の改質
ラニーニッケル触媒。4. The modified Raney nickel catalyst according to claim 1, wherein the hydroxy cyclic ether is 2-hydroxy-tetrahydrofuran.
０ｋｇ／ｃｍ2 Ｇの反応圧力で、請求項１或いは２に記
載の改質ラニーニッケル触媒を用いてヒドロキシ−アル
デヒドまたはヒドロキシ環状エーテルを水素添加反応さ
せることを特徴とするその対応するジオール化合物の製
造方法。5. A reaction temperature of 50 to 200 ° C. and a temperature of 10 to 20.
Preparation of its corresponding diol compound, characterized in that a hydroxy-aldehyde or hydroxy cyclic ether is hydrogenated with a modified Raney nickel catalyst according to claim 1 or 2 at a reaction pressure of 0 kg / cm 2 G. Method.
ロキシ−ブタナールまたは２−メチル−３−ヒドロキシ
−プロパナールである請求項５記載の対応するジオール
化合物の製造方法。6. The method for producing a corresponding diol compound according to claim 5, wherein the hydroxy-aldehyde is 4-hydroxy-butanal or 2-methyl-3-hydroxy-propanal.
ブタンジオール或いは２−メチル−１，３−プロパンジ
オールである請求項６の製造方法。7. The corresponding diol compound is 1,4-
The production method according to claim 6, which is butanediol or 2-methyl-1,3-propanediol.
ロキシ−テトラヒドロフランである請求項５記載の対応
するジオール化合物の製造方法。8. The method for producing a corresponding diol compound according to claim 5, wherein the hydroxy cyclic ether is 2-hydroxy-tetrahydrofuran.
ブタンジオールである請求項８記載の製造方法。9. The corresponding diol compound is 1,4-
The production method according to claim 8, which is butanediol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8039730A JP3016727B2 (en) | 1996-02-27 | 1996-02-27 | Modified Raney nickel catalyst and method for producing diol compound using the catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8039730A JP3016727B2 (en) | 1996-02-27 | 1996-02-27 | Modified Raney nickel catalyst and method for producing diol compound using the catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09225311A true JPH09225311A (en) | 1997-09-02 |
| JP3016727B2 JP3016727B2 (en) | 2000-03-06 |
Family
ID=12561099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8039730A Expired - Lifetime JP3016727B2 (en) | 1996-02-27 | 1996-02-27 | Modified Raney nickel catalyst and method for producing diol compound using the catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3016727B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001056963A1 (en) * | 2000-02-04 | 2001-08-09 | Daicel Chemical Industries, Ltd. | High-purity 1,3-butylene glycol, process for producing 1,3-butylene glycol, and process for producing by-product butanol and butyl acetate |
| JP2001288131A (en) * | 2000-02-04 | 2001-10-16 | Daicel Chem Ind Ltd | Method for producing purified 1,3-butylene glycol |
| KR100420453B1 (en) * | 1998-11-05 | 2004-03-02 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Raney Iron Catalyst and a Process for Hydrogenating Organic Compounds Using Said Catalyst |
| JP2008524326A (en) * | 2004-12-20 | 2008-07-10 | ライオンデル ケミカル テクノロジー、 エル．ピー． | Production of butanediol |
| FR2993557A1 (en) * | 2012-07-23 | 2014-01-24 | Arkema France | SYNTHESIS OF METHYL PROPANE DIOL FROM ALLYL ALCOHOL |
-
1996
- 1996-02-27 JP JP8039730A patent/JP3016727B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100420453B1 (en) * | 1998-11-05 | 2004-03-02 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Raney Iron Catalyst and a Process for Hydrogenating Organic Compounds Using Said Catalyst |
| WO2001056963A1 (en) * | 2000-02-04 | 2001-08-09 | Daicel Chemical Industries, Ltd. | High-purity 1,3-butylene glycol, process for producing 1,3-butylene glycol, and process for producing by-product butanol and butyl acetate |
| JP2001288131A (en) * | 2000-02-04 | 2001-10-16 | Daicel Chem Ind Ltd | Method for producing purified 1,3-butylene glycol |
| US6900360B2 (en) | 2000-02-04 | 2005-05-31 | Daicel Chemical Industries, Ltd. | High-purity 1,3-butylen glycol, process for producing 1,3-butylene glycol, and process for producing by-product butanol and butyl acetate |
| JP2008524326A (en) * | 2004-12-20 | 2008-07-10 | ライオンデル ケミカル テクノロジー、 エル．ピー． | Production of butanediol |
| JP4913752B2 (en) * | 2004-12-20 | 2012-04-11 | ライオンデル ケミカル テクノロジー、 エル．ピー． | Production of butanediol |
| FR2993557A1 (en) * | 2012-07-23 | 2014-01-24 | Arkema France | SYNTHESIS OF METHYL PROPANE DIOL FROM ALLYL ALCOHOL |
| WO2014016491A1 (en) * | 2012-07-23 | 2014-01-30 | Arkema France | Synthesising of methyl propanediol from allyl alcohol |
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|---|---|
| JP3016727B2 (en) | 2000-03-06 |
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