JPH0959190A - Production of 1,4-butanediol and/or tetrahydrofuran - Google Patents
Production of 1,4-butanediol and/or tetrahydrofuranInfo
- Publication number
- JPH0959190A JPH0959190A JP7208752A JP20875295A JPH0959190A JP H0959190 A JPH0959190 A JP H0959190A JP 7208752 A JP7208752 A JP 7208752A JP 20875295 A JP20875295 A JP 20875295A JP H0959190 A JPH0959190 A JP H0959190A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- noble metal
- supported
- hydrogenation
- 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
Landscapes
- Furan Compounds (AREA)
- 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、マレイン酸類を原
料として、接触水素化反応することにより１，４−ブタ
ンジオール及び／又はテトラヒドロフランを製造する方
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。また、テトラヒド
ロフランは、沸点が低く優れた溶解力をもつため溶媒と
して使用されるほか、ポリテトラメチレンエーテルグリ
コール、テトラヒドロチオフェン等の原料として使用さ
れている。TECHNICAL FIELD The present invention relates to a method for producing 1,4-butanediol and / or tetrahydrofuran by catalytic hydrogenation reaction using maleic acids as raw materials. 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. Tetrahydrofuran is used as a solvent because it has a low boiling point and an excellent dissolving power, and is also used as a raw material for polytetramethylene ether glycol, tetrahydrothiophene 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
化水素を水素化する方法は数多く報告されており、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ないため、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、
また、一般に２００気圧以上の水素加圧下で反応を行う
ので、エネルギー的にも設備的にも不利な方法である。2. Description of the Related Art Conventionally, many methods for hydrogenating oxygen-containing C 4 hydrocarbons such as maleic anhydride have been reported, and 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 therefore the carboxylic acid must be once converted into an ester and then reduced.
Further, since the reaction is generally performed under hydrogen pressure of 200 atm or more, it is a disadvantageous method 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おり、例えば、特開
昭６３−２１８６３６号公報及び米国特許第４，６５
９，６８６号明細書には、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
ドロフラン又はγ−ブチロラクトンを製造する方法が記
載されている。しかしながら、前者に記載の方法では反
応基質濃度が低く、米国特許明細書に記載の方法では、
反応を行う際に１５０気圧以上の水素圧力が必要であ
る。また、米国特許第４，８２７，００１号明細書に
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、この方法において
は、１，４−ブタンジオール、テトラヒドロフラン、γ
−ブチロラクトンの選択率が十分でない。On the other hand, some catalysts capable of directly reducing a carboxylic acid such as maleic acid have been proposed, for example, JP-A-63-218636 and US Pat. No. 4,65.
No. 9,686 describes a method for producing tetrahydrofuran or γ-butyrolactone from an aqueous maleic acid solution using a palladium-rhenium catalyst supported on activated carbon. However, the method described in the former has a low reaction substrate concentration, and the method described in the U.S. Pat.
A hydrogen pressure of 150 atm or higher is required when carrying out the reaction. US Pat. No. 4,827,001 proposes a method for directly reducing maleic acid using ruthenium-iron oxide as a catalyst. In this method, 1,4-butanediol, Tetrahydrofuran, γ
-The butyrolactone selectivity is not sufficient.
【０００４】さらに、プロセスの見地から検討された特
許もいくつか開示されており、例えば米国特許第５，１
９６，６０２号明細書には、マレイン酸もしくはマレイ
ン酸無水物を２段で水素化する方法において、後段の反
応をＲｕ−Ｃｏ−Ｎｉ−Ｚｎ系触媒を用いて行う方法が
記載されているが、実施例の結果では活性は低いレベル
にとどまっている。また、特開平５−２３８９７１号公
報には、コバルト含有触媒を用いて無水マレイン酸を２
段で水素化する１，４−ブタンジオールの製法が開示さ
れているが、反応が２００〜３５０バールと非常な高圧
を要するという欠点があった。一方、特開平５−２４６
９１５号公報には、カルボン酸類の水素化反応には、第
VIII族の貴金属を多孔質炭素からなる担体に担持した触
媒が高活性で優れた成績を示すこと、及び、第２金属成
分として錫等を共存させると選択性が向上することが開
示されている。In addition, several patents have been disclosed which were considered from a process perspective, eg US Pat. No. 5,1.
Although the specification of 96,602 describes a method of hydrogenating maleic acid or maleic anhydride in two steps, a method in which the reaction in the latter step is carried out using a Ru-Co-Ni-Zn-based catalyst is described. The results of the examples show that the activity remains at a low level. Further, in Japanese Patent Laid-Open No. 5-238971, a maleic anhydride containing a cobalt-containing catalyst is used.
Although a process for producing 1,4-butanediol which is hydrogenated in stages is disclosed, it has a drawback that the reaction requires a very high pressure of 200 to 350 bar. On the other hand, JP-A-5-246
No. 915, the hydrogenation reaction of carboxylic acids is described in
It is disclosed that a catalyst in which a noble metal of Group VIII is supported on a support made of porous carbon has high activity and excellent performance, and that coexistence of tin or the like as the second metal component improves the selectivity. .
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記特
開平５−２４６９１５号公報に担持型触媒として具体的
に記載されているＲｕ−Ｓｎ系触媒は無水マレイン酸類
の水素化反応に使用すると、徐々にＳｎが溶出してくる
という問題があり、工業的には触媒活性の長期安定性の
点で改善が望まれている。However, when the Ru-Sn type catalyst specifically described as a supported catalyst in the above-mentioned JP-A-5-246915 is used for the hydrogenation reaction of maleic anhydride, it gradually increases. There is a problem that Sn elutes, and industrially, improvement is desired in terms of long-term stability of catalytic activity.
【０００６】このように、従来は、いずれの方法におい
ても工業的に不十分であり、マレイン酸類を水素化し、
高収率で目的物である１，４−ブタンジオール及び／又
はテトラヒドロフランを得るためには、反応性を高める
ために比較的高い水素圧下に反応を行う必要があった。
本発明は、反応活性の高い触媒を効率的に利用して、温
和な条件下マレイン酸類を水素化し、高収率で且つ安定
的に１，４−ブタンジオール及び／又はテトラヒドロフ
ランを製造する方法を提供することを目的とする。As described above, any of the conventional methods is industrially insufficient, and hydrogenates maleic acids,
In order to obtain the desired products of 1,4-butanediol and / or tetrahydrofuran in high yield, it was necessary to carry out the reaction under a relatively high hydrogen pressure in order to enhance the reactivity.
The present invention provides a method for efficiently producing a 1,4-butanediol and / or tetrahydrofuran in a high yield by hydrogenating maleic acids under mild conditions by efficiently utilizing a catalyst having high reaction activity. The purpose is to provide.
【０００７】[0007]
【課題を解決するための手段】本発明は、水素化触媒の
存在下にマレイン酸類を２段で水素化して１，４−ブタ
ンジオール及び／又はテトラヒドロフランを製造するに
際し、第１段水素化工程にてマレイン酸類をＣ＝Ｃ二重
結合還元能を有する触媒の存在下に水素化反応に付し、
第２段水素化工程にて、第１段水素化反応生成物を担持
型貴金属−Ｓｎ系触媒の存在下に水素化反応に付すこと
を特徴とする１，４−ブタンジオール及び／又はテトラ
ヒドロフランの製造方法を提供するものである。According to the present invention, when a maleic acid is hydrogenated in two stages in the presence of a hydrogenation catalyst to produce 1,4-butanediol and / or tetrahydrofuran, the first stage hydrogenation step is carried out. And a hydrogenation reaction of maleic acids in the presence of a catalyst having a C = C double bond reducing ability,
In the second-stage hydrogenation step, the first-stage hydrogenation reaction product is subjected to a hydrogenation reaction in the presence of a supported noble metal-Sn-based catalyst, which comprises 1,4-butanediol and / or tetrahydrofuran. A manufacturing method is provided.
【０００８】[0008]
【発明の実施の形態】以下に本発明について詳細に説明
する。本発明の方法では、マレイン酸類（無水マレイン
酸、マレイン酸、及びマレイン酸のエステル、又はこれ
らの混合物）を反応の原料とする。第１段水素化工程
は、マレイン酸類のＣ＝Ｃ二重結合を還元する能力が有
る公知の水素化触媒の存在下に行われる。例えば、担持
型Ｐｄ系、Ｒｕ系、Ｐｔ系、Ｒｈ系触媒、Ｃｕ−クロマ
イト系触媒、Ｃｕ−Ｚｎ−Ａｌ酸化物系触媒等が使用さ
れる。これら触媒は、単独でも、複数組み合わせ用いて
も良い。中でも担持型Ｐｄ系触媒が好適に用いられる。
担持型触媒の場合の担体は、水素化反応条件下で安定に
存在できることを条件に自由に選択できる、例えば、活
性炭、けいそう土、シリカ、アルミナ、チタニア、ジル
コニア等の多孔質担体を単独又は２種以上を組み合わせ
て用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the method of the present invention, maleic acids (maleic anhydride, maleic acid, an ester of maleic acid, or a mixture thereof) are used as raw materials for the reaction. The first stage hydrogenation step is carried out in the presence of a known hydrogenation catalyst capable of reducing the C = C double bond of maleic acids. For example, supported Pd-based, Ru-based, Pt-based, Rh-based catalysts, Cu-chromite-based catalysts, Cu-Zn-Al oxide-based catalysts and the like are used. These catalysts may be used alone or in combination. Above all, a supported Pd-based catalyst is preferably used.
The carrier in the case of a supported catalyst can be freely selected under the condition that it can stably exist under hydrogenation reaction conditions, for example, activated carbon, diatomaceous earth, silica, alumina, titania, zirconia, or other porous carrier. Two or more kinds can be used in combination.
【０００９】中でも特に活性の面から、活性炭担持型Ｐ
ｄ触媒が好適に使用される。その場合のＰｄ金属の担持
量は、０．０１重量％以上で有れば良く、担持量の上限
はないが、経済性を考えると１０重量％以下がよい。使
用される触媒の量は、回分反応の場合、マレイン酸類の
反応原料１００重量部に対し０．０１〜１００重量部で
あることが望ましいが、反応温度又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で任意に
選ぶことができる。[0009] Above all, from the viewpoint of activity, activated carbon-supporting P
d catalysts are preferably used. In this case, the amount of Pd metal supported may be 0.01% by weight or more, and there is no upper limit of the amount supported, but 10% by weight or less is preferable in consideration of economy. In the case of a batch reaction, the amount of the catalyst used is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the reaction raw material of maleic acid, but depending on various conditions such as reaction temperature or reaction pressure, it is practical. It can be arbitrarily selected within the range in which a specific reaction rate is obtained.
【００１０】反応温度は、２０℃〜２５０℃の範囲内、
好適には、３０℃〜２００℃、更に好適には５０℃〜１
８０℃の範囲内である。反応圧力は、０．１ＭＰａ〜２
０ＭＰａの範囲、好適には０．１ＭＰａ〜１０ＭＰａの
範囲である。反応方式は、液相懸濁反応又は固定床反応
のいずれであってもよい。また反応は、無溶媒で行って
もよいし、必要に応じて、反応に悪影響を与えない種類
の溶媒を使用してもよい。The reaction temperature is in the range of 20 ° C to 250 ° C,
Preferably, 30 ° C to 200 ° C, more preferably 50 ° C to 1
It is within the range of 80 ° C. The reaction pressure is 0.1 MPa to 2
It is in the range of 0 MPa, preferably in the range of 0.1 MPa to 10 MPa. The reaction system may be either a liquid phase suspension reaction or a fixed bed reaction. The reaction may be carried out without a solvent, or, if necessary, a type of solvent that does not adversely affect the reaction may be used.
【００１１】使用できる溶媒としては、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挙げられる。特
に、マレイン酸類を、テトラヒドロフラン、γ−ブチロ
ラクトン、及び水から選ばれる少なくとも１種の溶媒に
溶解すると、マレイン酸類の溶解度が高く、供給が行な
い易くなり好ましい。その濃度は反応又は供給時の温度
における飽和濃度以下であれば任意の濃度を選択できる
が、生産性を考えると１５重量％以上が好ましい。マレ
イン酸類の初期濃度は通常は約２０〜６０重量％程度で
ある。The solvent that can be used is not particularly limited, but specifically, water; alcohols such as methanol, ethanol, octanol and dodecanol; ethers such as tetrahydrofuran, dioxane and tetraethylene glycol dimethyl ether; other, hexane, Hydrocarbons such as cyclohexane and decalin are included. Particularly, it is preferable to dissolve maleic acid in at least one solvent selected from tetrahydrofuran, γ-butyrolactone, and water because the maleic acid has high solubility and can be easily supplied. Although the concentration can be selected as desired as long as it is equal to or lower than the saturation concentration at the temperature during reaction or supply, it is preferably 15% by weight or more in view of productivity. The initial concentration of maleic acid is usually about 20 to 60% by weight.
【００１２】第１段水素化工程においては、マレイン酸
類のエチレン性二重結合（Ｃ＝Ｃ）を水素化して、反応
基質の酸性度を低下させる。マレイン酸類の変換率は９
０モル％以上、好ましくは９５モル％であることが望ま
しい。第２段水素化反応に用いる触媒中のＳｎの流出を
防止するため反応基質の酸性度を十分に低下させる必要
性を勘案すると、具体的には第２段水素化工程に供給さ
れる水素化反応処理物中の残留マレイン酸類の濃度を１
０重量％以下、好ましくは５重量％以下とすることが望
ましい。In the first stage hydrogenation step, the ethylenic double bond (C = C) of maleic acid is hydrogenated to reduce the acidity of the reaction substrate. The conversion rate of maleic acids is 9
It is desirable that the content is 0 mol% or more, preferably 95 mol%. Considering the necessity of sufficiently lowering the acidity of the reaction substrate in order to prevent the outflow of Sn in the catalyst used for the second stage hydrogenation reaction, specifically, the hydrogenation supplied to the second stage hydrogenation step Set the concentration of residual maleic acid in the reaction product to 1
It is desirable that the amount is 0% by weight or less, preferably 5% by weight or less.
【００１３】マレイン酸類のＣ＝Ｃ結合の水素化による
酸性度の低下は、例えば、マレイン酸のｐＫａは、１．
７５と５．８３であるのに対して、コハク酸では、４．
００と５．２４であり、水素化反応生成物中のマレイン
酸類の残重量濃度１０％以下とすることにより、第２段
水素化工程への供給原料の酸性度を大幅に低下させる。
第２段水素化工程の担持型Ｒｕ−Ｓｎ触媒は、マレイン
酸に直接接すると、反応条件によってはその強い酸性に
より、Ｓｎが反応液中に溶出する危険がある。第１段水
素化工程でマレイン酸類のＣ＝Ｃ二重結合を水素化して
酸性度を低下させておくことは非常に重要であり、それ
により第２段水素化工程での触媒中のＳｎの溶出を完全
に回避し、触媒の性能を十分引き出すことができる。The decrease in acidity due to hydrogenation of the C = C bond of maleic acids is caused by, for example, the pKa of maleic acid being 1.
75 and 5.83, whereas for succinic acid, 4.
00 and 5.24, and by setting the residual weight concentration of maleic acids in the hydrogenation reaction product to 10% or less, the acidity of the feedstock to the second stage hydrogenation step is significantly reduced.
When the supported Ru-Sn catalyst in the second stage hydrogenation step is brought into direct contact with maleic acid, there is a risk that Sn will be eluted into the reaction solution due to its strong acidity depending on the reaction conditions. It is very important to hydrogenate the C = C double bond of the maleic acids to reduce the acidity in the first stage hydrogenation step, so that Sn in the catalyst in the second stage hydrogenation step Elution can be completely avoided, and the performance of the catalyst can be fully obtained.
【００１４】第２段水素化工程は、第１工程で得られた
水素化反応生成物を目的物である１，４−ブタンジオー
ル及び／又はテトラヒドロフランまで変換するために、
担持型貴金属−Ｓｎ系触媒、特にＲｕ−Ｓｎ系触媒もし
くはこれにＰｔ及びＲｈから選ばれる少なくとも１種の
金属を組み合わせて担持した触媒の存在下に行う。第１
段反応において溶媒を使用する場合、第２段水素化工程
に供給される第１段水素化反応生成物の溶液は必要あれ
ば濃縮してもよく、通常２０重量％以上、好ましくは３
０重量％以上の生成物を含む溶液が用いられる。In the second stage hydrogenation step, in order to convert the hydrogenation reaction product obtained in the first step to the target 1,4-butanediol and / or tetrahydrofuran,
It is carried out in the presence of a supported noble metal-Sn catalyst, particularly a Ru-Sn catalyst, or a catalyst in which at least one metal selected from Pt and Rh is supported in combination. First
When a solvent is used in the two-stage reaction, the solution of the first-stage hydrogenation reaction product supplied to the second-stage hydrogenation step may be concentrated if necessary, and is usually 20% by weight or more, preferably 3% by weight.
A solution containing 0% by weight or more of the product is used.
【００１５】該担持型触媒の担体としては、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
の多孔質担体を単独又は２種以上を組み合わせて用いる
ことができる。該触媒の活性を十分に得るためには、担
体が高表面積であると良いので、上記した中でも、特に
活性炭、及びシリカがより好ましい。なお、貴金属成分
とＳｎ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、酸化物又は、一般に知られている
有機金属化合物や錯塩も使用することもできる。As the carrier of the supported catalyst, a porous carrier such as activated carbon, diatomaceous earth, silica, alumina, titania and zirconia can be used alone or in combination of two or more kinds. In order to obtain sufficient activity of the catalyst, it is preferable that the carrier has a high surface area. Therefore, activated carbon and silica are particularly preferable among the above. As the noble metal component and the raw material compound of Sn, 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 generally Known organometallic compounds and complex salts can also be used.
【００１６】担体に金属成分を担持する方法としては、
浸漬法、イオン交換法、ゾル−ゲル法、など通常の調製
法で採用されている方法はいずれも適用可能である。中
でも特に簡便な浸漬法が好ましく採用される。浸漬法に
よるときは、通常、担持する金属の原料化合物を水等の
該化合物を溶解可能な溶媒に溶解して、金属化合物の溶
液とし、これに別途調製した多孔質担体を浸漬して担体
に触媒成分を担持させる。As a method for supporting the metal component on the carrier,
Any of the methods employed in ordinary preparation methods such as the dipping method, the ion exchange method, and the sol-gel method can be applied. Of these, a particularly simple dipping method is preferably adopted. When the dipping method is used, usually, the raw material compound of the metal to be supported is dissolved in a solvent capable of dissolving the compound, such as water, to obtain a solution of the metal compound, and a separately prepared porous carrier is immersed in the solution to form a carrier. The catalyst component is supported.
【００１７】担体に各金属成分を担持する順序について
は特に制限はなく、全ての金属成分を一度に同時に担持
しても、各成分を個別に担持しても、また成分のいくつ
かを組み合わせて複数回にわたって担持してもよい。し
かし、まずＲｕとＳｎを先に担体に担持して乾燥、還元
処理し、その後にＰｔ及び／又はＲｈを追加して担体に
担持すると反応活性をさらに高める事ができる。このＰ
ｔ及び／又はＲｈを後から担持する事による活性向上の
理由は、詳しくは解っていないが、水素の活性化能もし
くは水素化反応活性の高いＰｔ及び／又はＲｈを後から
担持することで、これらの金属が触媒表面に担持でき、
この表面の金属が水素化反応において有効に機能してい
るためと推定している。The order of loading each metal component on the carrier is not particularly limited, and all the metal components may be loaded simultaneously at the same time, each component may be loaded individually, or some of the components may be combined. You may carry in multiple times. However, it is possible to further increase the reaction activity by first supporting Ru and Sn on the carrier, drying and reducing them, and then adding Pt and / or Rh and supporting them on the carrier. This P
The reason why the activity is improved by supporting t and / or Rh afterwards is not understood in detail, but by supporting afterwards Pt and / or Rh having high hydrogen activating ability or hydrogenation reaction activity, These metals can be supported on the catalyst surface,
It is presumed that the metal on this surface functions effectively in the hydrogenation reaction.
【００１８】貴金属成分及びＳｎ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。Ｐｔ及び／又はＲｈは、Ｒｕに対
して０．０１〜１０重量倍量共存させるのが活性向上の
観点から好ましい。Ｓｎは、貴金属成分に対して、通常
０．１〜５重量倍量共存させるのが、生成物の選択性向
上の観点から好ましい。The loading amounts of the noble metal component and Sn are respectively
It is usually 0.5 to 50% by weight, preferably 1 based on the carrier.
-20% by weight. It is preferable that Pt and / or Rh coexist in an amount of 0.01 to 10 times by weight relative to Ru from the viewpoint of improving the activity. It is preferable that Sn is present in an amount of usually 0.1 to 5 times by weight with respect to the noble metal component from the viewpoint of improving the selectivity of the product.
【００１９】金属成分の溶液を浸漬担持した後には（複
数回に亘って浸漬担持する場合にはその都度）、乾燥を
行う。乾燥は、２００℃以下の温度で、減圧下、もしく
は空気や不活性ガス等の乾燥ガスを通気しながら行う。
その後、必要に応じて焼成、還元処理を行う。焼成処理
は、通常１００〜６００℃の温度範囲で行われる。ま
た、還元処理を行う場合には、公知の液相還元法、気相
還元法が採用され、気相還元法の場合、通常１００〜５
００℃の温度範囲、好ましくは２００〜３５０℃の範囲
で行われる。還元処理を行った後の触媒の構造の詳細は
不明であるが、上記の還元条件では、貴金属成分は実質
的に全てが金属に還元されると推定され、Ｓｎは、一部
分が２価又は４価で残存すると推定される。After the solution of the metal component is dipped and carried (whenever it is dipped and carried out a plurality of times, each time), it is dried. Drying is performed at a temperature of 200 ° C. or lower under reduced pressure or while aeration with a dry gas such as air or an inert gas.
After that, firing and reduction are performed as necessary. The firing treatment is usually performed in a temperature range of 100 to 600 ° C. In addition, when performing the reduction treatment, a known liquid phase reduction method or gas phase reduction method is adopted, and in the case of the gas phase reduction method, it is usually 100 to 5
It is carried out in the temperature range of 00 ° C, preferably in the range of 200 to 350 ° C. Although details of the structure of the catalyst after the reduction treatment are unknown, it is presumed that under the above-mentioned reducing conditions, substantially all of the noble metal component is reduced to metal, and Sn is partially divalent or tetravalent. It is estimated that the price will remain.
【００２０】回分反応の場合には、使用される触媒の量
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
度又は反応圧力等の諸条件に応じ、実用的な反応速度が
得られる範囲内で任意に選ぶことができる。第２段水素
化工程の反応条件に関して、温度は、通常１３０〜３５
０℃、好ましくは１６０〜３００℃、反応圧は、通常１
〜３０ＭＰａ、好ましくは５〜２０ＭＰａの条件が採用
される。In the case of the batch reaction, the amount of the catalyst used 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 the reaction temperature or the reaction pressure. Can be arbitrarily selected within the range where a practical reaction rate can be obtained according to the various conditions. Regarding the reaction conditions of the second stage hydrogenation step, the temperature is usually 130 to 35.
0 ° C, preferably 160 to 300 ° C, the reaction pressure is usually 1
The condition of -30 MPa, preferably 5-20 MPa is adopted.
【００２１】反応方式は、液相懸濁反応又は固定床反応
のいずれであってもよい。また反応は、無溶媒で行って
もよいし、必要に応じて、反応に悪影響を与えない種類
の溶媒を使用してもよい。この際使用できる溶媒として
は、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
素類が挙げられる。The reaction system may be either a liquid phase suspension reaction or a fixed bed reaction. The reaction may be carried out without a solvent, or, if necessary, a type of solvent that does not adversely affect the reaction may be used. The solvent that can be used at this time is not particularly limited, and specific examples thereof include water; alcohols such as methanol, ethanol, octanol, and dodecanol; ethers such as tetrahydrofuran, dioxane, and tetraethylene glycol dimethyl ether; and hexane and cyclohexane. And hydrocarbons such as decalin.
【００２２】また、第１段、第２段の各水素化工程は、
上記構成を満たす限りにおいて各々の反応工程を複数の
反応器で構成した多段階に分割して行っても良い。な
お、本発明による方法で製造した１，４−ブタンジオー
ル及び／又はテトラヒドロフランは、蒸留等の公知の方
法により分離精製される。また、この分離精製後に残る
未反応原料又は反応中間体としてのγ−ブチロラクトン
等は、反応原料として再使用することができる。The hydrogenation steps of the first and second stages are
As long as the above constitution is satisfied, each reaction process may be divided into multiple stages composed of a plurality of reactors. The 1,4-butanediol and / or tetrahydrofuran produced by the method of the present invention is separated and purified by a known method such as distillation. Unreacted raw materials remaining after the separation and purification or γ-butyrolactone as a reaction intermediate can be reused as a reaction raw material.
【００２３】[0023]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り詳細に説明するが、本発明はその要旨を超えない限
り、以下の実施例の記載に限定されるものではない。な
お、以下において特に記載のないかぎり、「％」は「重
量％」を示す。EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the description of the following Examples unless it exceeds the gist. In the following, "%" means "% by weight" unless otherwise specified.
【００２４】参考例１（第１水素化工程において使用可
能な触媒の例） エヌ・イー ケムキャット社製担持触媒（それぞれ３０
０℃、２時間水素還元したもの）を用い、次記の条件で
無水マレイン酸の水素化反応を行い、得られた値に基づ
きマレイン酸に０次の反応速度定数ｋ及びマレイン酸が
９０モル％変換するのに要する反応時間を計算した結果
を表１に示す。 （反応）無水マレイン酸３ｇを水７ｇに溶解し、触媒
０．２２ｇと共に７０ｍｌスピナー攪拌オートクレーブ
に仕込んだ。次に系内を水素で充分置換した後、室温下
３ＭＰａの水素を圧入し、８０℃で１時間反応を行っ
た。反応終了後、触媒をろ別してから、ろ液を液体クロ
マトグラフィーにより分析した。Reference Example 1 (Example of catalyst that can be used in the first hydrogenation step) Supported catalyst manufactured by NE Chemcat (each 30
The hydrogenation reaction of maleic anhydride was carried out under the following conditions at 0 ° C. for 2 hours with hydrogen reduction), and the reaction rate constant k of the 0th-order maleic acid and 90 mol of maleic acid were calculated based on the obtained values. Table 1 shows the result of calculating the reaction time required for the conversion. (Reaction) 3 g of maleic anhydride was dissolved in 7 g of water and charged with 0.22 g of a catalyst in a 70 ml spinner stirring autoclave. Next, after thoroughly replacing the inside of the system with hydrogen, hydrogen of 3 MPa was injected at room temperature and the reaction was carried out at 80 ° C. for 1 hour. After completion of the reaction, the catalyst was filtered off and the filtrate was analyzed by liquid chromatography.
【００２５】[0025]
【表１】 [Table 1]
【００２６】参考例２（第２段水素化工程用触媒の調製
例） （１）５Ｎ−ＨＣｌ水溶液３．６１ｍｌに、ＲｕＣｌ3
・３Ｈ2 Ｏを１．５７８ｇ、Ｈ2 ＰｔＣｌ6 ・６Ｈ2 Ｏ
を０．９０３ｇ、ＳｎＣｌ2 ・２Ｈ2 Ｏを０.９５０ｇ
を加えて溶解した後、この混合溶液に担体としてＳｉＯ
2 （富士デヴィソン社製、スペシャルグレード１２ 比
表面積６７９ｍ2 ／ｇ、細孔容量０．３７ｍｌ／ｇ）を
８．５５ｇを加え良くかき混ぜ、含浸させた。このもの
を回転減圧乾燥器で６０℃、２５ｍｍＨｇ下で溶媒の水
を除去した後、窒素雰囲気下１５０℃で２時間乾燥処理
し、ついで水素雰囲気下、３００℃で２時間還元処理し
て、６．１％Ｒｕ−３．４％Ｐｔ−５．０％Ｓｎ／Ｓｉ
Ｏ2 の触媒を調製した。 （２）上記した手順と同様の手法で、５．１％Ｒｕ−
３．４％Ｐｔ−３．０％Ｓｎ／ＳｉＯ2 の触媒を調製し
た。Reference Example 2 (Preparation Example of Catalyst for Second Step Hydrogenation Step) (1) RuCl 3 was added to 3.61 ml of 5N-HCl aqueous solution.
・ 1.5Hg of 3H 2 O, H 2 PtCl 6 .6H 2 O
0.903 g, SnCl 2 .2H 2 O 0.950 g
After adding and dissolving, SiO 2 as a carrier was added to this mixed solution.
2 (manufactured by Fuji Davison, special grade 12, specific surface area 679 m 2 / g, pore volume 0.37 ml / g) was added in an amount of 8.55 g and thoroughly stirred to impregnate. After removing water as a solvent at 60 ° C. and 25 mmHg in a rotary vacuum dryer, this was dried at 150 ° C. for 2 hours in a nitrogen atmosphere, and then reduced at 300 ° C. for 2 hours in a hydrogen atmosphere. .1% Ru-3.4% Pt-5.0% Sn / Si
A catalyst of O 2 was prepared. (2) In the same manner as the above procedure, 5.1% Ru-
A 3.4% Pt-3.0% Sn / SiO 2 catalyst was prepared.
【００２７】実施例１ ＜第１段水素化工程＞無水マレイン酸５０ｇを水５０ｇ
に溶解し、２％Ｐｄ／Ｃ（エヌ・イー ケムキャット社
製）０．５ｇを２００℃、２時間水素還元したものと共
に２０0 ｍｌ誘導攪拌式オートクレーブに仕込んだ。次
に系内を水素で充分置換した後、水素圧７ＭＰａ、８０
℃で１時間反応を行った。反応終了後、触媒をろ別して
から、ろ液を液体クロマトグラフィーにより分析した。
その結果、無水マレイン酸の転化率は１００モル％で、
コハク酸の選択率は９９．６モル％、フマル酸の選択率
は０．１モル％であった。Example 1 <First Step Hydrogenation Step> 50 g of maleic anhydride and 50 g of water
And 0.5 g of 2% Pd / C (manufactured by NE Chemcat) were hydrogen-reduced at 200 ° C. for 2 hours and charged in a 200 ml induction stirring autoclave. Next, after the system was sufficiently replaced with hydrogen, the hydrogen pressure was 7 MPa and 80
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, the catalyst was filtered off and the filtrate was analyzed by liquid chromatography.
As a result, the conversion rate of maleic anhydride was 100 mol%,
The selectivity of succinic acid was 99.6 mol% and the selectivity of fumaric acid was 0.1 mol%.
【００２８】＜第２段水素化工程＞第１段水素化工程で
得られた反応生成物に水を加えコハク酸濃度５０重量％
の水溶液を調製し、容量２００ｍｌのオートクレーブ
に、得られたコハク酸水溶液５０ｇを入れ、更に参考例
２（１）で調製した触媒４ｇを仕込み、攪拌しつつ２Ｍ
Ｐａの水素を圧入し、２４０℃まで昇温した。オートク
レーブ内温を２４０℃に維持しつつ、水素を圧入して水
素圧を７ＭＰａまで高め、消費される分の水素を絶えず
補いながらこの圧力保ち２時間反応を行った。反応終了
後、反応生成物をガスクロマトグラフィで分析したとこ
ろ、コハク酸の変換率は１００モル％であり、対コハク
酸収率としてＴＨＦが６７．８モル％、γ−ブチロラク
トンが１０．５モル％、１，４−ブタンジオールが４．
６モル％で、また、対無水マレイン酸通算収率で夫々６
７．６モル％、１０．５モル％、４．６モル％で得られ
た。なお、反応生成物の中には、副生成物として対コハ
ク酸収率でプロパノールが３．０モル％、ブタノールが
５．１モル％で、また、無水マレイン酸通算収率では夫
々３．０モル％、５．１モル％含まれており、また気相
部から、仕込んだコハク酸のＣを基準として７．３％対
コハク酸収率、無水マレイン酸通算収率では７．３モル
％のガス成分（メタン、エタン、プロパン、ブタン）が
検出された。<Second Step Hydrogenation Step> Water is added to the reaction product obtained in the first step hydrogenation step to obtain a succinic acid concentration of 50% by weight.
50 g of the obtained aqueous solution of succinic acid was placed in an autoclave having a capacity of 200 ml, and 4 g of the catalyst prepared in Reference Example 2 (1) was further charged into the autoclave having a volume of 200 ml and stirred to 2M.
Hydrogen of Pa was injected under pressure and the temperature was raised to 240 ° C. While maintaining the internal temperature of the autoclave at 240 ° C., hydrogen was introduced under pressure to raise the hydrogen pressure to 7 MPa, and the reaction was carried out for 2 hours while keeping this pressure while constantly supplementing the consumed hydrogen. After completion of the reaction, the reaction product was analyzed by gas chromatography to find that the conversion rate of succinic acid was 100 mol%, and the yield of succinic acid was 67.8 mol% for THF and 10.5 mol% for γ-butyrolactone. , 1,4-butanediol is 4.
6 mol% and a total yield of maleic anhydride to 6 respectively
It was obtained at 7.6 mol%, 10.5 mol% and 4.6 mol%. Among the reaction products, by-product yields were 3.0 mol% of propanol and 5.1 mol% of butanol as by-products, and the total yield of maleic anhydride was 3.0 mol%. Mol%, 5.1 mol%, and, based on the C of succinic acid charged from the gas phase, 7.3% relative to succinic acid yield, and total maleic anhydride yield is 7.3 mol%. Gas components (methane, ethane, propane, butane) were detected.
【００２９】実施例２ ＜第１段水素化工程＞無水マレイン酸１５ｇを水３５ｇ
に溶解し、５％Ｐｄ／Ｃ（エヌ・イー ケムキャット社
製）０．２ｇを３００℃、２時間水素還元したものと共
に２００ｍｌ誘導攪拌式オートクレーブに仕込んだ。次
に系内を水素で充分置換した後、水素圧１ＭＰａ、８０
℃で１時間反応を行った。反応終了後、触媒をろ別して
から、ろ液を液体クロマトグラフィーにより分析した。
その結果、無水マレイン酸の転化率は１００モル％で、
コハク酸の選択率は１００モル％であった。Example 2 <First Stage Hydrogenation Step> 15 g of maleic anhydride and 35 g of water
And 0.2 g of 5% Pd / C (manufactured by NE Chemcat) were hydrogen-reduced at 300 ° C. for 2 hours, and then charged in a 200 ml induction stirring autoclave. Next, after thoroughly replacing the inside of the system with hydrogen, the hydrogen pressure was 1 MPa and 80
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, the catalyst was filtered off and the filtrate was analyzed by liquid chromatography.
As a result, the conversion rate of maleic anhydride was 100 mol%,
The selectivity of succinic acid was 100 mol%.
【００３０】＜第２段水素化工程＞容量２００ｍｌのオ
ートクレーブに、第１段水素化工程で得られたコハク酸
水溶液を５０重量％水溶液に濃縮したもの５０ｇを入
れ、更に参考例２（１）で調製した触媒４ｇを加え、室
温下攪拌しつつ２ＭＰａの水素を圧入し、２４０℃まで
昇温した。オートクレーブ内温を２４０℃に維持しつ
つ、水素を圧入して水素圧を７ＭＰａまで高め、水素を
反応器出口で３０ノルマルリットル／時間で流通させ、
この圧力で２時間反応を行った。この間、流通するＨ2
に同伴されてＴＨＦ等の軽沸成分が反応系から分離され
て得られた。反応終了後、反応生成物をガスクロマトグ
ラフィーで分析したところ、コハク酸の変換率は１００
モル％であり、対コハク酸収率でＴＨＦが８４．１モル
％、γ−ブチロラクトンが０．４モル％で得られた。ま
た、反応生成物の中には、副生成物としてプロパノール
が収率４．３モル％、ブタノールが収率３．９モル％で
含まれており、また気相部から、仕込んだコハク酸のＣ
を基準として８．２％のガス成分（メタン、エタン、プ
ロパン、ブタン）が検出された。なお、これらの生成物
の無水マレイン酸通算収率も同様であった。<Second-stage hydrogenation step> 50 g of a 50 wt% aqueous solution of the succinic acid aqueous solution obtained in the first-step hydrogenation step was placed in an autoclave having a capacity of 200 ml, and further, Reference Example 2 (1). 4 g of the catalyst prepared in Step 2 was added, 2 MPa of hydrogen was injected under pressure at room temperature with stirring, and the temperature was raised to 240 ° C. While maintaining the internal temperature of the autoclave at 240 ° C., hydrogen was injected to increase the hydrogen pressure to 7 MPa, and hydrogen was circulated at the reactor outlet at 30 normal liters / hour,
The reaction was carried out at this pressure for 2 hours. During this period, H 2 is distributed
And the light-boiling components such as THF were separated from the reaction system. After completion of the reaction, the reaction product was analyzed by gas chromatography to find that the conversion rate of succinic acid was 100.
The yield was 84.1 mol% and γ-butyrolactone was 0.4 mol% with respect to the yields of succinic acid. In addition, the reaction product contained propanol as a by-product in a yield of 4.3 mol% and butanol in a yield of 3.9 mol% as a by-product. C
Gas components (methane, ethane, propane, butane) of 8.2% were detected based on the above. The total maleic anhydride yields of these products were similar.
【００３１】実施例３（金属成分溶出試験） 触媒の安定性を示す以下の金属成分溶出試験を行った。
なお、この溶出試験は、水素雰囲気下で行うと、例え
ば、マレイン酸からコハク酸への反応が進行するなどし
て、適正な評価ができないため、窒素雰囲気下で行っ
た。Example 3 (Metal Component Elution Test) The following metal component elution test showing the stability of the catalyst was carried out.
In addition, when this elution test is performed in a hydrogen atmosphere, a proper evaluation cannot be performed because, for example, a reaction from maleic acid to succinic acid proceeds, so that the elution test was performed in a nitrogen atmosphere.
【００３２】（１）無水マレイン酸４．５ｇ、水１０．
５ｇ、および参考例（２）で調製した触媒０．４ｇを７
０ｍｌオートクレーブに仕込み、内部を窒素で置換した
後、窒素１気圧で、２４０℃、１時間処理した。この処
理液から触媒を除去した後、誘導結合プラズマ発光分析
法（ＩＣＰ−ＡＥＳ）により処理液中に溶出した金属成
分の量を定量したところ、ＲｕとＰｔは検出限界以下
（担持量の０．１重量％以下）であったが、Ｓｎは担持
量の３．８重量％が溶出しており、この条件ではＲｕ−
Ｐｔ−Ｓｎ／ＳｉＯ2 触媒は安定に存在できない事が判
明した。 （２）無水マレイン酸を無水コハク酸に変えた以外は、
上記（１）と同様の処理を行った。Ｒｕ、Ｐｔ、Ｓｎ全
ての金属の溶出はＩＣＰ−ＡＥＳの検出限界以下であっ
た。この結果から、コハク酸の存在下ではＲｕ−Ｐｔ−
Ｓｎ／ＳｉＯ2 触媒は金属成分の溶出もなく安定に存在
する事が判明した。 （３）無水マレイン酸１０ｇ、水１０ｇ、５％Ｐｄ／Ｃ
（エヌ・イー ケムキャット社製）０．４４ｇを７０ｍ
ｌオートクレーブに仕込み、内部を窒素で置換した後、
窒素１気圧で、８０℃、１時間処理し、同様にして処理
液中に溶出したＰｄの量を定量したところ、検出限界以
下であり、＜０．０５ｐｐｍである事が分かった。 （４）上記（３）と同様にして、７時間処理を行った
が、Ｐｄの溶出は認められなかった。 以上の結果より、本発明の方法が、触媒の安定性の維持
に大きく寄与し、触媒を長期に渡って安定に使用する事
ができると判断される。(1) Maleic anhydride 4.5 g, water 10.
5 g and 0.4 g of the catalyst prepared in Reference Example (2)
After charging in a 0 ml autoclave and replacing the inside with nitrogen, the mixture was treated with nitrogen at 1 atm at 240 ° C. for 1 hour. After removing the catalyst from the treatment liquid, the amount of the metal component eluted in the treatment liquid was quantified by the inductively coupled plasma emission spectrometry (ICP-AES). As a result, Ru and Pt were below the detection limit (the supported amount of 0. 1 wt% or less), but 3.8 wt% of the carried amount of Sn was eluted, and Ru-
Pt-Sn / SiO 2 catalyst was found to be not be able to exist stably. (2) except that maleic anhydride was changed to succinic anhydride
The same process as the above (1) was performed. The elution of all metals of Ru, Pt, and Sn was below the detection limit of ICP-AES. From this result, in the presence of succinic acid, Ru-Pt-
It was found that the Sn / SiO 2 catalyst existed stably without elution of metal components. (3) Maleic anhydride 10 g, water 10 g, 5% Pd / C
(Manufactured by NE Chemcat) 0.44 g to 70 m
After charging in an autoclave and replacing the inside with nitrogen,
When the amount of Pd eluted in the treatment liquid was quantified in the same manner by treating with nitrogen at 1 atm at 80 ° C. for 1 hour, it was found to be below the detection limit and <0.05 ppm. (4) The same treatment as in (3) above was performed for 7 hours, but no Pd elution was observed. From the above results, it is judged that the method of the present invention greatly contributes to maintaining the stability of the catalyst, and the catalyst can be stably used for a long period of time.
【００３３】[0033]
【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、γ−ブチロ
ラクトン又はこれらの混合物を原料とし、接触水素化反
応により比較的温和な反応条件下で、１，４−ブタンジ
オール及び／又はテトラヒドロフランを長期に亘り安定
して高収率で製造することができ、その工業的利用価値
は極めて大である。According to the method of the present invention, maleic anhydride, maleic acid, succinic anhydride, succinic acid, γ-butyrolactone or a mixture thereof is used as a raw material, and the reaction is carried out under relatively mild reaction conditions by catalytic hydrogenation reaction. Thus, 1,4-butanediol and / or tetrahydrofuran can be stably produced in a high yield over a long period of time, and its industrial utility value is extremely large.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 29/149 Ｃ０７Ｃ 29/149 29/17 29/17 Ｃ０７Ｄ 307/08 Ｃ０７Ｄ 307/08 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 29/149 C07C 29/149 29/17 29/17 C07D 307/08 C07D 307/08 // C07B 61/00 300 C07B 61/00 300
Claims (10)
段で水素化して１，４−ブタンジオール及び／又はテト
ラヒドロフランを製造するに際し、第１段水素化工程に
てマレイン酸類をＣ＝Ｃ二重結合還元能を有する触媒の
存在下に水素化反応に付し、第２段水素化工程にて第１
段水素化反応生成物を担持型貴金属−Ｓｎ系触媒の存在
下に水素化反応に付すことを特徴とする１，４−ブタン
ジオール及び／又はテトラヒドロフランの製造方法。1. A maleic acid is added in the presence of a hydrogenation catalyst.
When 1,4-butanediol and / or tetrahydrofuran is hydrogenated in a stage, maleic acids are subjected to a hydrogenation reaction in the presence of a catalyst having a C = C double bond reducing ability in the first stage hydrogenation step. Attached in the 2nd stage hydrogenation process
A process for producing 1,4-butanediol and / or tetrahydrofuran, which comprises subjecting a step hydrogenation reaction product to a hydrogenation reaction in the presence of a supported noble metal-Sn catalyst.
属系触媒、Ｃｕ−クロマイト系触媒、Ｃｕ−Ｚｎ−Ａｌ
を含む酸化物触媒の群から選ばれるものである請求項１
に記載の方法。2. The catalyst of the first stage hydrogenation step is a supported noble metal catalyst, Cu-chromite catalyst, Cu-Zn-Al.
2. A catalyst selected from the group of oxide catalysts containing
The method described in.
ｔ及びＲｈの群から選ばれる貴金属を含有する担持型触
媒である請求項２に記載の方法。3. A supported precious metal-based catalyst is Pd, Ru, P.
The method according to claim 2, which is a supported catalyst containing a noble metal selected from the group of t and Rh.
いものである請求項３に記載の方法。4. The method according to claim 3, wherein the supported noble metal catalyst does not contain Sn.
る請求項４に記載の方法。5. The method according to claim 4, wherein the supported noble metal-based catalyst is a Pd-based catalyst.
項５に記載の方法。6. The method according to claim 5, wherein the Pd-based catalyst is a Pd / C-based catalyst.
Ｒｕ、Ｐｔ及びＲｈから選ばれるものである請求項１に
記載の方法。7. The noble metal of the supported type noble metal-Sn catalyst is
The method according to claim 1, wherein the method is selected from Ru, Pt and Rh.
ｎ系触媒である請求項７に記載の方法。8. The supported noble metal-Sn catalyst is Ru-S.
The method according to claim 7, which is an n-based catalyst.
から選ばれる少なくとも１種の金属を組み合わせて担持
した触媒である請求項８に記載の方法。9. The Ru—Sn catalyst further comprises Pt and Rh.
The method according to claim 8, wherein the catalyst is a catalyst supporting a combination of at least one metal selected from the group consisting of:
ン、γ−ブチロラクトン、及び水から選ばれる少なくと
も１種の溶液として供給する請求項１に記載の方法。10. The method according to claim 1, wherein the maleic acid is supplied as a solution of at least one selected from tetrahydrofuran, γ-butyrolactone, and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20875295A JP3704758B2 (en) | 1995-08-16 | 1995-08-16 | Process for producing 1,4-butanediol and / or tetrahydrofuran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20875295A JP3704758B2 (en) | 1995-08-16 | 1995-08-16 | Process for producing 1,4-butanediol and / or tetrahydrofuran |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0959190A true JPH0959190A (en) | 1997-03-04 |
| JP3704758B2 JP3704758B2 (en) | 2005-10-12 |
Family
ID=16561499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20875295A Expired - Fee Related JP3704758B2 (en) | 1995-08-16 | 1995-08-16 | Process for producing 1,4-butanediol and / or tetrahydrofuran |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3704758B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6008384A (en) * | 1998-03-03 | 1999-12-28 | E. I. Du Pont De Nemours And Company | Method and Ru,Re,Sn/carbon catalyst for hydrogenation in aqueous solution |
| JP2004507516A (en) * | 2000-08-29 | 2004-03-11 | ザ・スタンダード・オイル・カンパニー | Two-stage method for hydrogenating maleic acid to 1,4-butanediol |
| JP2013527835A (en) * | 2010-04-07 | 2013-07-04 | ロディア オペレーションズ | Method for producing lactone |
-
1995
- 1995-08-16 JP JP20875295A patent/JP3704758B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6008384A (en) * | 1998-03-03 | 1999-12-28 | E. I. Du Pont De Nemours And Company | Method and Ru,Re,Sn/carbon catalyst for hydrogenation in aqueous solution |
| JP2004507516A (en) * | 2000-08-29 | 2004-03-11 | ザ・スタンダード・オイル・カンパニー | Two-stage method for hydrogenating maleic acid to 1,4-butanediol |
| JP2013527835A (en) * | 2010-04-07 | 2013-07-04 | ロディア オペレーションズ | Method for producing lactone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3704758B2 (en) | 2005-10-12 |
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