JPH06239778A - Production of 1,4-butanediol - Google Patents
Production of 1,4-butanediolInfo
- Publication number
- JPH06239778A JPH06239778A JP5028013A JP2801393A JPH06239778A JP H06239778 A JPH06239778 A JP H06239778A JP 5028013 A JP5028013 A JP 5028013A JP 2801393 A JP2801393 A JP 2801393A JP H06239778 A JPH06239778 A JP H06239778A
- Authority
- JP
- Japan
- Prior art keywords
- butanediol
- reaction
- acid
- metal compound
- catalyst
- 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.)
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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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、無水マレイン酸、マレ
イン酸、無水コハク酸、コハク酸またはγ−ブチロラク
トンから選ばれる含酸素Ｃ4 炭化水素を接触水素化する
ことによる１，４−ブタンジオールの製造方法に関す
る。１，４−ブタンジオールは、主にポリブチレンテレ
フタレートやポリウレタン等のプラスチック原料として
使用されるほか、ピロリジン、アジピン酸等の製造中間
体等として使用されている。The present invention relates to 1,4-butanediol obtained by catalytic hydrogenation of an oxygen-containing C 4 hydrocarbon selected from maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone. Manufacturing method. 1,4-butanediol is mainly used as a raw material for plastics such as polybutylene terephthalate and polyurethane, and is also used as a production intermediate for pyrrolidine, adipic acid and the like.
【０００２】[0002]
【従来の技術】従来、無水マレイン酸等の含酸素Ｃ4 炭
化水素を水素化して１，４−ブタンジオールを製造する
方法は数多く報告されている。例えば、最も良く知られ
ている方法として銅系の触媒を用いる方法がある。しか
しながら、この方法では、マレイン酸等の有機カルボン
酸を直接還元することができず、カルボン酸を一旦エス
テルに転換後還元しなければならず、製造工程が高くな
る。また、この方法では、一般に２００気圧以上の水素
圧下で反応を行うので、エネルギー的にも設備的にも不
経済な方法である。2. Description of the Related Art Heretofore, many methods have been reported for producing 1,4-butanediol by hydrogenating oxygen-containing C 4 hydrocarbons such as maleic anhydride. For example, the best known method is to use a copper-based catalyst. However, in this method, an organic carboxylic acid such as maleic acid cannot be directly reduced, and the carboxylic acid must be once converted into an ester and then reduced, resulting in a high manufacturing process. Further, in this method, the reaction is generally carried out under a hydrogen pressure of 200 atm or higher, which is uneconomical in terms of energy and equipment.
【０００３】一方、マレイン酸等のカルボン酸を直接還
元できる触媒もいくつか提案されている。例えば、特開
昭６３−２１８６３６号あるいは米国特許４、６５９、
６８６号には、活性炭に担持したパラジウム−レニウム
触媒を用いてマレイン酸水溶液からテトラヒドロフラン
またはγ−ブチロラクトンを製造する方法が記載されて
いる。この方法では、１，４−ブタンジオールの選択率
が非常に低い。On the other hand, some catalysts which can directly reduce carboxylic acids such as maleic acid have been proposed. For example, JP-A-63-218636 or US Pat. No. 4,659,
No. 686 describes a method for producing tetrahydrofuran or γ-butyrolactone from an aqueous maleic acid solution using a palladium-rhenium catalyst supported on activated carbon. With this method, the selectivity of 1,4-butanediol is very low.
【０００４】また、米国特許４、８２７、００１号には
ルテニウム−鉄酸化物を触媒としてマレイン酸を直接還
元する方法が提案されているが、該方法においては１，
４−ブタンジオールの選択率が十分でない。US Pat. No. 4,827,001 proposes a method for directly reducing maleic acid using ruthenium-iron oxide as a catalyst.
The selectivity of 4-butanediol is not sufficient.
【０００５】[0005]
【発明が解決しようとする課題】このように、従来、マ
レイン酸等の水素化反応の方法においては、反応性を高
めるために比較的に高水素圧の条件下での反応にする必
要があった。また、水素化による種々の反応生成物が生
じるため、１，４−ブタンジオールを高選択率で得るこ
とは困難であり、テトラヒドロフランの副生は不可避的
なものであった。As described above, in the conventional method for hydrogenation reaction of maleic acid or the like, it is necessary to carry out the reaction under relatively high hydrogen pressure condition in order to enhance the reactivity. It was Further, since various reaction products are generated by hydrogenation, it is difficult to obtain 1,4-butanediol with high selectivity, and the by-product of tetrahydrofuran is unavoidable.
【０００６】[0006]
【課題を解決するための手段】本発明者等は上記問題点
に鑑み鋭意検討を重ねた結果、マレイン酸等を触媒の存
在下で接触水素化反応を行う際に、触媒として周期律表
第VIII族の貴金属と錫の担持触媒を用い、かつ、特定物
質の存在下で反応を行った場合において、１，４−ブタ
ンジオールの生成が飛躍的に増大することを見い出し、
本発明に到達したものである。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, when a catalytic hydrogenation reaction of maleic acid or the like is carried out in the presence of a catalyst, the catalyst of the periodic table It was found that the production of 1,4-butanediol dramatically increases when the reaction is carried out in the presence of a specific substance using a supported catalyst of a Group VIII noble metal and tin,
The present invention has been reached.
【０００７】即ち、本発明の要旨は無水マレイン酸、マ
レイン酸、無水コハク酸、コハク酸またはγ−ブチロラ
クトンを接触水素化して１，４−ブタンジオールを製造
する方法において、該接触水素化を（１）周期律表第VI
II族の貴金属及び錫を担体に担持してなる担持触媒と
（２）アルカリ金属化合物、アルカリ土類金属化合物ま
たは窒素塩基化合物の存在下で行うことを特徴とする
１，４−ブタンジオールの製造方法、及び、無水マレイ
ン酸、マレイン酸、無水コハク酸、コハク酸またはγ−
ブチロラクトンを接触水素化して１，４−ブタンジオー
ルを製造する方法において、該接触水素化を（１）周期
律表第VIII族の貴金属及び錫、並びに（２）アルカリ金
属化合物またはアルカリ土類金属化合物、を担体に担持
してなる担持触媒の存在下で行うことを特徴とする１，
４−ブタンジオールの製造方法に存する。That is, the gist of the present invention is to provide a method for producing 1,4-butanediol by catalytic hydrogenation of maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone. 1) Periodic Table VI
Production of 1,4-butanediol characterized in that it is carried out in the presence of a supported catalyst in which a noble metal of group II and tin are supported on a carrier and (2) an alkali metal compound, an alkaline earth metal compound or a nitrogen base compound. Method and maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-
In the method for producing 1,4-butanediol by catalytic hydrogenation of butyrolactone, the catalytic hydrogenation is carried out by (1) a noble metal and tin of Group VIII of the periodic table, and (2) an alkali metal compound or an alkaline earth metal compound. Is carried out in the presence of a supported catalyst formed by supporting on a carrier 1,
It exists in a method for producing 4-butanediol.
【０００８】以下に本発明について詳細に説明する。本
発明の反応原料は、無水マレイン酸、マレイン酸、無水
コハク酸、コハク酸またはγ−ブチロラクトンあるいは
これらの混合物である。本発明の水素化反応では、反応
機構あるいは反応生成物の分析結果等からみて、（無
水）マレイン酸が水素化し、（無水）コハク酸となり、
次いで、γ−ブチロラクトンとなり、更に１，４−ブタ
ンジオールを生成するものと考えられるからである。従
って、本発明では、上記の化合物のいずれをも反応原料
として用いることができるし、２種以上の混合物であっ
てもよい。The present invention will be described in detail below. The reaction raw material of the present invention is maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone, or a mixture thereof. In the hydrogenation reaction of the present invention, the (anhydrous) maleic acid is hydrogenated to become (anhydrous) succinic acid in view of the reaction mechanism or the analysis result of the reaction product,
This is because it is considered that it then becomes γ-butyrolactone and further produces 1,4-butanediol. Therefore, in the present invention, any of the above compounds can be used as a reaction raw material, and a mixture of two or more kinds may be used.
【０００９】本発明で使用される触媒を構成する周期律
表第VIII族の貴金属としては、ルテニウム（Ｒｕ）、パ
ラジウム（Ｐｄ）、白金（Ｐｔ）、ロジウム（Ｒｈ）、
及びイリジウム（Ｉｒ）が挙げられる。これらの貴金属
の中でルテニウムが好適に用いられる。また、本発明に
おいては上記貴金属の他に錫を用いることが必須であ
る。これら金属成分を担体に担持してなる担持触媒とし
て使用する。The noble metal of Group VIII of the Periodic Table, which constitutes the catalyst used in the present invention, includes ruthenium (Ru), palladium (Pd), platinum (Pt), rhodium (Rh),
And iridium (Ir). Among these precious metals, ruthenium is preferably used. Further, in the present invention, it is essential to use tin in addition to the above noble metal. These metal components are used as a supported catalyst which is supported on a carrier.
【００１０】貴金属及び錫を担持させる担体としては活
性炭、けいそう土、シリカ、アルミナ、チタニア、ジル
コニア等を単独あるいは２種以上を組み合わせて用いる
ことができる。貴金属成分、錫成分の原料化合物をこれ
ら担体と接触させる方法は特に制限はないが、通常、浸
漬法が採用される。即ち、例えば、原料化合物を溶解可
能な溶媒、例えば、水に溶解して溶液とし、この溶液に
多孔質担体を浸漬して含浸担持させる。担持後は乾燥
し、必要に応じて焼成、還元を行う。焼成は、通常１０
０〜６００℃で行われる。また、還元処理としては、公
知の液相還元、気相還元が用いられ、気相還元の場合、
通常１００〜５００℃、好ましくは２００〜３５０℃で
行われる。As a carrier for supporting a noble metal and tin, activated carbon, diatomaceous earth, silica, alumina, titania, zirconia or the like can be used alone or in combination of two or more kinds. The method of bringing the raw material compounds of the noble metal component and tin component into contact with these carriers is not particularly limited, but the dipping method is usually employed. That is, for example, the raw material compound is dissolved in a solvent capable of dissolving it, for example, water to form a solution, and the porous carrier is immersed in this solution and impregnated and supported. After loading, it is dried and, if necessary, calcined and reduced. Firing is usually 10
It is carried out at 0 to 600 ° C. As the reduction treatment, known liquid-phase reduction or gas-phase reduction is used. In the case of gas-phase reduction,
It is usually carried out at 100 to 500 ° C, preferably 200 to 350 ° C.
【００１１】貴金属及び錫の担持量はそれぞれ、担体に
対して、通常０．５〜５０重量％、好ましくは１〜２０
重量％である。また、錫の担持量は、貴金属に対して、
通常０．１〜５重量倍量共存させるのが、生成物の選択
性向上の面で好ましい。なお、貴金属成分と錫の原料化
合物としてはそれらの金属の硝酸、硫酸、塩酸等の鉱酸
塩が一般的に使用されるが、酢酸等の有機酸塩、水酸化
物、酸化物あるいは錯塩も使用することもできる。The amount of each of the noble metal and tin supported is usually 0.5 to 50% by weight, preferably 1 to 20% with respect to the carrier.
% By weight. Also, the amount of tin supported is
Usually, it is preferable to coexist in an amount of 0.1 to 5 times by weight in order to improve the selectivity of the product. As the raw material compound of the noble metal component and tin, nitric acid, sulfuric acid, hydrochloric acid and other mineral acid salts of these metals are generally used, but organic acid salts such as acetic acid, hydroxides, oxides or complex salts are also used. It can also be used.
【００１２】以上の触媒はそれのみを用いても前記の反
応原料の水素化活性を充分有するものであるが、１，４
−ブタンジオールを高選択率で得るためには、アルカリ
金属化合物、アルカリ土類金属化合物または窒素塩基化
合物を反応系に存在させる必要がある。アルカリ金属化
合物、アルカリ土類金属化合物とは、アルカリ金属また
はアルカリ土類金属の硝酸、塩酸、硫酸等との鉱酸塩、
酢酸、シュウ酸等の有機酸塩、水酸化物、酸化物等であ
り、ＬｉＮＯ3 、ＬｉＣｌ、ＬｉＯＡｃ、ＮａＯＡｃ、
ＫＯＡｃ、ＣｓＯＡｃ、Ｍｇ（ＯＡｃ）2 、Ｃａ（ＯＡ
ｃ）2 、Ｓｒ（ＯＡｃ） 2 、Ｂａ（ＯＡｃ）2 、ＬｉＯ
Ｈ等が挙げられる。[0012] The above catalyst, even if used alone
Although it has sufficient hydrogenation activity of the reaction raw material, 1,4
-In order to obtain butanediol with high selectivity, alkali
Metal compounds, alkaline earth metal compounds or nitrogen-based
The compound must be present in the reaction system. Alkali metallization
Compounds and alkaline earth metal compounds mean alkali metal or
Is a mineral acid salt with alkaline earth metal nitric acid, hydrochloric acid, sulfuric acid, etc.,
Organic acid salts such as acetic acid and oxalic acid, hydroxides and oxides
LiNO3, LiCl, LiOAc, NaOAc,
KOAc, CsOAc, Mg (OAc)2, Ca (OA
c)2, Sr (OAc) 2, Ba (OAc)2, LiO
H etc. are mentioned.
【００１３】また、窒素塩基化合物とは、アンモニア、
有機アミン、及びそれらの塩、あるいはピーロール、ピ
ロリジン、ピリジン、ピペリジン、インドール、キノリ
ン等の窒素含有複素環式化合物及びその塩であり、酢酸
アンモニウム、トリエチルアミン、ピリジン、ピロリ
ン、Ｎ−メチルピロリジン等が挙げられる。アルカリ金
属化合物、アルカリ土類金属化合物または窒素塩基化合
物を反応系に存在させる方法としては、特に制限はな
く、反応系にこれらの化合物を直接添加すればよい。添
加量は、触媒１００重量部に対して、通常０．１〜１０
０重量部、好ましくは１〜５０重量部である。The nitrogen base compound is ammonia,
Organic amines and salts thereof, or nitrogen-containing heterocyclic compounds such as pyrrole, pyrrolidine, pyridine, piperidine, indole and quinoline, and salts thereof, such as ammonium acetate, triethylamine, pyridine, pyrroline and N-methylpyrrolidine. To be The method for allowing the alkali metal compound, alkaline earth metal compound or nitrogen base compound to be present in the reaction system is not particularly limited, and these compounds may be added directly to the reaction system. The addition amount is usually 0.1 to 10 with respect to 100 parts by weight of the catalyst.
It is 0 part by weight, preferably 1 to 50 parts by weight.
【００１４】また、アルカリ金属化合物、アルカリ土類
金属化合物については、上記の反応系に直接添加する方
法の他、これらを金属成分として触媒成分とともに担体
に担持する方法も可能である。担体に担持させる方法
は、前述の触媒成分の担持方法と同じように、通常、ア
ルカリ金属化合物等の水溶液を担体に含浸させる方法が
採用される。担持後は乾燥し、必要に応じて、焼成、還
元を行う。アルカリ金属またはアルカリ土類金属の担持
量は、触媒１００重量部に対して、通常０．１〜１００
重量部、好ましくは１〜５０重量部である。Regarding the alkali metal compound and the alkaline earth metal compound, in addition to the method of directly adding to the above reaction system, a method of supporting them as a metal component together with a catalyst component on a carrier is also possible. As the method for supporting the carrier, a method of impregnating the carrier with an aqueous solution of an alkali metal compound or the like is usually adopted, as in the above-described method for supporting the catalyst component. After loading, it is dried, and if necessary, calcined and reduced. The amount of alkali metal or alkaline earth metal supported is usually 0.1 to 100 relative to 100 parts by weight of the catalyst.
Parts by weight, preferably 1 to 50 parts by weight.
【００１５】本発明での接触水素化反応は、通常、温度
１３０〜３５０℃、好ましくは１６０〜３００℃、水素
圧１０〜３００ｋｇ／ｃｍ2 、好ましくは５０〜２００
ｋｇ／ｃｍ2 の範囲で行われる。反応に使用される触媒
量は、無水マレイン酸等の反応原料１００重量部に対し
０．１〜１００重量部であることが望ましいが、反応温
度または反応圧力等の諸条件に応じ、実用的な反応速度
が得られる範囲内において任意に選択できる。The catalytic hydrogenation reaction in the present invention is usually carried out at a temperature of 130 to 350 ° C., preferably 160 to 300 ° C., a hydrogen pressure of 10 to 300 kg / cm 2 , preferably 50 to 200.
It is performed in the range of kg / cm 2 . The amount of the catalyst used in the reaction is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the reaction raw material such as maleic anhydride, but is practical depending on various conditions such as reaction temperature or reaction pressure. It can be arbitrarily selected within the range where the reaction rate is obtained.
【００１６】反応方式としては液相懸濁反応或いは固定
床反応のいずれも採用できる。また、反応は、無触媒で
行っても良いし、必要に応じて、溶媒を用いても良い。
溶媒を用いる場合、溶媒としては、反応に悪影響を与え
ない物であれば良く、特に制限されないが、具体的に
は、水；メタノール、エタノール、オクタノール、ドデ
カノール等のアルコール類；テトラヒドロフラン、ジオ
キサン、テトラエチレングリコールジメチルエーテル等
のエーテル類；その他、ヘキサン、シクロヘキサン、デ
カリン等の炭化水素類が例示される。As the reaction system, either liquid phase suspension reaction or fixed bed reaction can be adopted. Further, the reaction may be carried out without a catalyst or, if necessary, a solvent may be used.
When a solvent is used, the solvent is not particularly limited as long as it does not adversely affect the reaction, and specifically, water; alcohols such as methanol, ethanol, octanol and dodecanol; tetrahydrofuran, dioxane and tetra Examples thereof include ethers such as ethylene glycol dimethyl ether; and hydrocarbons such as hexane, cyclohexane and decalin.
【００１７】なお、反応で生成した１，４−ブタンジオ
ールは蒸留等の公知の方法により分離精製される。ま
た、該分離後に残る反応原料あるいは反応中間体として
のγ−ブチロラクトン等は反応原料として再度反応系に
循環して利用することができる。The 1,4-butanediol produced by the reaction is separated and purified by a known method such as distillation. Further, the reaction raw material remaining after the separation or γ-butyrolactone or the like as a reaction intermediate can be reused as a reaction raw material by recirculating to the reaction system.
【００１８】[0018]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明するが、本発明はその要旨を超えない限
り以下の実施例に限定されるものではない、なお、以下
において「％」は「重量％」を示す。The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. "%" Indicates "% by weight".
【００１９】実施例１〜８ 塩化ルテニウム（III ）と塩化錫（II）を５Ｎ−ＨＣｌ
水溶液とエタノール（１／１容積比）に溶解し、担体と
してＳｉＯ2 （富士デビソン社製、比表面積６０９ｍ2
／ｇ、細孔容量０．３７ｍｌ／ｇ）を加え回転減圧乾燥
器で溶媒を除去した後、窒素雰囲気下１５０℃で２時間
焼成し、ついで水素雰囲気下、３００℃で２時間還元し
て、７％Ｒｕ−５％Ｓｎ／ＳｉＯ2 触媒を得た。無水マ
レイン酸０．５ｇを水９．５ｇに溶解し、上記方法で調
製した触媒０．２ｇと表−１に示す添加物０．３ｍｍｏ
ｌと共に７０ｍｌスピンナー撹拌オートクレーブに仕込
み、室温下１００ｋｇ／ｃｍ2 の水素を圧入し、２００
℃で３時間反応を行った。反応物につきガスクロマトグ
ラフィーで分析を行った結果を表−１に示す。Examples 1 to 8 Ruthenium (III) chloride and tin (II) chloride were added to 5N-HCl.
Dissolved in an aqueous solution and ethanol (1/1 volume ratio) and used as a carrier for SiO 2 (manufactured by Fuji Devison, specific surface area 609 m 2
/ G, pore volume 0.37 ml / g) was added and the solvent was removed by a rotary vacuum dryer, followed by firing at 150 ° C. for 2 hours in a nitrogen atmosphere and then reducing at 300 ° C. for 2 hours in a hydrogen atmosphere. It was obtained 7% Ru-5% Sn / SiO 2 catalyst. 0.5 g of maleic anhydride was dissolved in 9.5 g of water, and 0.2 g of the catalyst prepared by the above method and 0.3 mmo of the additives shown in Table-1.
It was charged into a 70 ml spinner stirring autoclave together with 1, and 100 kg / cm 2 of hydrogen was pressure-injected at room temperature.
The reaction was carried out at ℃ for 3 hours. The results of gas chromatography analysis of the reaction products are shown in Table 1.
【００２０】比較例１ 実施例１の触媒を用い、添加物を加えない以外は実施例
１と同様にして反応を行った結果を表−１に示す。Comparative Example 1 The results of carrying out the reaction in the same manner as in Example 1 except that the catalyst of Example 1 was used and no additives were added are shown in Table 1.
【００２１】[0021]
【表１】 ＣＭＬ：無水マレイン酸 ＴＨＦ：テトラヒドロフラン ＧＢＬ：γ−ブチロラクトン ＢＤＯ：１，４−ブタンジオール[Table 1] CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol
【００２２】実施例９ ＬｉＯＡｃを水に溶解し、これに実施例１で得られた７
％Ｒｕ−５％Ｓｎ／ＳｉＯ2 を加え、回転減圧乾燥器で
溶媒を除去した後、窒素雰囲気下１５０℃で２時間焼成
し、ついで水素雰囲気下、３００℃で２時間還元して、
７％Ｒｕ−５％Ｓｎ−０．３％Ｌｉ／ＳｉＯ2 触媒を得
た。無水マレイン酸１５ｇを水３５ｇに溶解し、上記方
法で調製した触媒４ｇと共に２００ｍｌオートクレーブ
に仕込み、室温下２０ｋｇ／ｃｍ2 の水素を圧入し、２
４０℃まで昇温した。次に、２４０℃で水素を１００ｋ
ｇ／ｃｍ2 まで加え２時間反応を行った。結果を表−２
に示す。Example 9 LiOAc was dissolved in water, to which 7 obtained in Example 1 was added.
% Ru-5% Sn / SiO 2 was added, the solvent was removed by a rotary vacuum drier, the mixture was calcined in a nitrogen atmosphere at 150 ° C. for 2 hours, and then reduced in a hydrogen atmosphere at 300 ° C. for 2 hours.
It was obtained 7% Ru-5% Sn- 0.3% Li / SiO 2 catalyst. Maleic acid 15g is dissolved in water 35 g, were charged to a 200ml autoclave together with the catalyst 4g prepared by the method described above, press-fitted hydrogen at room temperature under 20 kg / cm 2, 2
The temperature was raised to 40 ° C. Next, at 240 ° C, hydrogen is added to 100 k
It was added to g / cm 2 and reacted for 2 hours. The results are shown in Table-2.
Shown in.
【００２３】比較例２ 実施例１の触媒を用い、添加物を加えず実施例９と同様
に反応を行った。結果を表−２に示す。Comparative Example 2 Using the catalyst of Example 1, the reaction was carried out in the same manner as in Example 9 without adding any additives. The results are shown in Table-2.
【００２４】[0024]
【表２】 ＣＭＬ：無水マレイン酸 ＴＨＦ：テトラヒドロフラン ＧＢＬ：γ−ブチロラクトン ＢＤＯ：１，４−ブタンジオール[Table 2] CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol
【００２５】[0025]
【発明の効果】本発明の方法によれば、無水マレイン
酸、マレイン酸、無水コハク酸、コハク酸またはγ−ブ
チロラクトンを原料とする接触水素化反応により、比較
的温和な反応条件下で、テトラヒドロフラン等の副生が
極めて少なく、高選択率、高収率にて１，４−ブタンジ
オールを製造することができる。According to the method of the present invention, a catalytic hydrogenation reaction using maleic anhydride, maleic acid, succinic anhydride, succinic acid, or γ-butyrolactone as a raw material gives tetrahydrofuran under relatively mild reaction conditions. It is possible to produce 1,4-butanediol with a high selectivity and a high yield.
Claims (2)
ク酸、コハク酸またはγ−ブチロラクトンを接触水素化
して１，４−ブタンジオールを製造する方法において、
該接触水素化を（１）周期律表第VIII族の貴金属及び錫
を担体に担持してなる担持触媒と（２）アルカリ金属化
合物、アルカリ土類金属化合物または窒素塩基化合物の
存在下で行うことを特徴とする１，４−ブタンジオール
の製造方法。1. A method for producing 1,4-butanediol by catalytic hydrogenation of maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone,
Carrying out the catalytic hydrogenation in the presence of (1) a supported catalyst in which a noble metal of Group VIII of the Periodic Table and tin are supported on a carrier and (2) an alkali metal compound, an alkaline earth metal compound or a nitrogen base compound. A method for producing 1,4-butanediol, which comprises:
ク酸、コハク酸またはγ−ブチロラクトンを接触水素化
して１，４−ブタンジオールを製造する方法において、
該接触水素化を（１）周期律表第VIII族の貴金属及び
錫、並びに（２）アルカリ金属化合物またはアルカリ土
類金属化合物、を担体に担持してなる担持触媒の存在下
で行うことを特徴とする１，４−ブタンジオールの製造
方法。2. A method for producing 1,4-butanediol by catalytic hydrogenation of maleic anhydride, maleic acid, succinic anhydride, succinic acid or γ-butyrolactone,
The catalytic hydrogenation is carried out in the presence of a supported catalyst in which (1) a noble metal and tin of Group VIII of the periodic table and (2) an alkali metal compound or an alkaline earth metal compound are supported on a carrier. And a method for producing 1,4-butanediol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02801393A JP3206183B2 (en) | 1993-02-17 | 1993-02-17 | Method for producing 1,4-butanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02801393A JP3206183B2 (en) | 1993-02-17 | 1993-02-17 | Method for producing 1,4-butanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06239778A true JPH06239778A (en) | 1994-08-30 |
| JP3206183B2 JP3206183B2 (en) | 2001-09-04 |
Family
ID=12236895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02801393A Expired - Lifetime JP3206183B2 (en) | 1993-02-17 | 1993-02-17 | Method for producing 1,4-butanediol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3206183B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985789A (en) * | 1997-03-27 | 1999-11-16 | E. I. Du Pont De Nemours And Company | Ru, Sn/oxide catalyst and process for hydrogenation in acidic aqueous solution |
| WO2013005748A1 (en) * | 2011-07-04 | 2013-01-10 | 三菱化学株式会社 | Method for producing 1,4-butanediol |
| WO2013012048A1 (en) * | 2011-07-20 | 2013-01-24 | 三菱化学株式会社 | Method for producing 1,4-butanediol |
| JP2013079395A (en) * | 2005-04-22 | 2013-05-02 | Mitsubishi Chemicals Corp | Polyester derived from biomass resource and method for production thereof |
| JP2018502857A (en) * | 2015-01-09 | 2018-02-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing tetrahydrofuran, 1,4-butanediol or γ-butyrolactone |
-
1993
- 1993-02-17 JP JP02801393A patent/JP3206183B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985789A (en) * | 1997-03-27 | 1999-11-16 | E. I. Du Pont De Nemours And Company | Ru, Sn/oxide catalyst and process for hydrogenation in acidic aqueous solution |
| JP2013079395A (en) * | 2005-04-22 | 2013-05-02 | Mitsubishi Chemicals Corp | Polyester derived from biomass resource and method for production thereof |
| US10287393B2 (en) | 2005-04-22 | 2019-05-14 | Mitsubishi Chemical Corporation | Biomass-resource-derived polyester and production process thereof |
| US10870727B2 (en) | 2005-04-22 | 2020-12-22 | Mitsubishi Chemical Corporation | Biomass-resource-derived polyester and production process thereof |
| US11560449B2 (en) | 2005-04-22 | 2023-01-24 | Mitsubishi Chemical Corporation | Biomass-resource-derived polyester and production process thereof |
| US11732087B2 (en) | 2005-04-22 | 2023-08-22 | Mitsubishi Chemical Corporation | Biomass-resource-derived polyester and production process thereof |
| WO2013005748A1 (en) * | 2011-07-04 | 2013-01-10 | 三菱化学株式会社 | Method for producing 1,4-butanediol |
| JP2013032350A (en) * | 2011-07-04 | 2013-02-14 | Mitsubishi Chemicals Corp | Method for producing 1,4-butanediol |
| US10144687B2 (en) | 2011-07-04 | 2018-12-04 | Mitsubishi Chemical Corporation | Method for producing 1,4-butanediol |
| WO2013012048A1 (en) * | 2011-07-20 | 2013-01-24 | 三菱化学株式会社 | Method for producing 1,4-butanediol |
| JP2018502857A (en) * | 2015-01-09 | 2018-02-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing tetrahydrofuran, 1,4-butanediol or γ-butyrolactone |
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|---|---|
| JP3206183B2 (en) | 2001-09-04 |
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