JPH0653692B2 - Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol - Google Patents

Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol

Info

Publication number
JPH0653692B2
JPH0653692B2 JP62031153A JP3115387A JPH0653692B2 JP H0653692 B2 JPH0653692 B2 JP H0653692B2 JP 62031153 A JP62031153 A JP 62031153A JP 3115387 A JP3115387 A JP 3115387A JP H0653692 B2 JPH0653692 B2 JP H0653692B2
Authority
JP
Japan
Prior art keywords
reaction
mpd
mvl
mhp
present
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.)
Expired - Fee Related
Application number
JP62031153A
Other languages
Japanese (ja)
Other versions
JPS63198639A (en
Inventor
康雄 時任
典昭 吉村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
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Filing date
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Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP62031153A priority Critical patent/JPH0653692B2/en
Publication of JPS63198639A publication Critical patent/JPS63198639A/en
Publication of JPH0653692B2 publication Critical patent/JPH0653692B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)
  • Pyrane Compounds (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、β−メチル−δ−バレロラクトン(以下、こ
れをMVLと称する)および3−メチルペンタン−1,
5−ジオール(以下、これをMPDと称する)の製造法
に関し、詳しくは2−ヒドロキシ−4−メチルテトラヒ
ドロピラン(以下、これをMHPと称する)を特定の条
件下で反応させてMVLおよびMPDを製造するMVL
およびMPDの製造法に関する。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to β-methyl-δ-valerolactone (hereinafter, referred to as MVL) and 3-methylpentane-1,
Regarding a method for producing 5-diol (hereinafter referred to as MPD), specifically, 2-hydroxy-4-methyltetrahydropyran (hereinafter referred to as MHP) is reacted under specific conditions to give MVL and MPD. MVL to be manufactured
And a method for manufacturing MPD.

〔従来の技術〕[Conventional technology]

従来、MVLの製造法としては、β,β−ジメチルアク
リル酸エチルエステルをコバルト系触媒の存在下高温、
高圧で水素と一酸化炭素との混合ガスにより処理するこ
とにする方法(Chemische Berichte
97巻1964年発行863頁など参照)、あるいはM
PDを銅クロム酸化物触媒の存在下に200℃の温度に
おいて酸化脱水素する方法(Organic Synt
heses35巻87頁参照)などが提案されている。
また、MVLに類似する化合物の製造法として、Bul
l.Chem.Soc.Japan,35,986(1
962)には2−ヒドロキシテトラヒドロピラン(δ−
オキシバレロアルデヒド)を銅亜鉛酸化物、銅クロム酸
化物または銅クロム亜鉛酸化物を触媒として使用し、2
20〜230℃の温度下に連続気相反応させてδ−バレ
ロラクトンを得たことが記載されている。
Conventionally, as a method for producing MVL, β, β-dimethylacrylic acid ethyl ester was used at high temperature in the presence of a cobalt-based catalyst,
A method of treating with a mixed gas of hydrogen and carbon monoxide at high pressure (Chemische Berichte
Vol. 97, 1964, p. 863), or M
Method for oxidative dehydrogenation of PD at a temperature of 200 ° C. in the presence of a copper chromium oxide catalyst (Organic Synt
(See "heses 35", page 87).
In addition, as a method for producing a compound similar to MVL, Bul
l. Chem. Soc. Japan, 35, 986 (1
962) includes 2-hydroxytetrahydropyran (δ-
Oxyvaleraldehyde) is used as a catalyst for copper zinc oxide, copper chromium oxide or copper chromium zinc oxide.
It is described that δ-valerolactone was obtained by continuous gas phase reaction at a temperature of 20 to 230 ° C.

一方、MPDの製造法としてはMHPを水素化触媒の存
在下に高められた温度および高められた圧力において水
素化する方法(特公昭58−40533号公報参照)な
どが提案されている。
On the other hand, as a method for producing MPD, a method has been proposed in which MHP is hydrogenated in the presence of a hydrogenation catalyst at an elevated temperature and an elevated pressure (see Japanese Patent Publication No. 58-40533).

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

上述のMVL又はMPDの製造に係る従来公知の文献に
は、MVLとMPDとが同時に生成するという報告はな
されていない。このように、従来、MVLとMPDとを
同時に取得することは全く認識されておらず、工業的に
極めて利用価値の高いMVLおよびMPDの双方の取得
が要求される場合には、独立した2つの製造プロセスを
利用する必要があると考えられてきた。そして、実際そ
のような場合にはMVL又はMPDは全く別個のプロセ
スにより製造されていた。
There is no report that the MVL and the MPD are produced at the same time in the conventionally known documents relating to the production of the MVL or MPD. As described above, conventionally, it has not been recognized at all to simultaneously acquire MVL and MPD, and when it is required to acquire both MVL and MPD which are industrially extremely valuable, two independent MVLs and MPDs are required. It has been considered necessary to utilize manufacturing processes. And in fact, in such cases the MVL or MPD was manufactured by a completely separate process.

MVLおよびMPDを同時に効率よく製造できれば、共
通の原料および単一の反応を利用できる点で工業的に有
利であり、本発明者らは、かかる製造法について検討し
た結果、MHPを特定の条件下、銅、クロムおよび亜鉛
から選ばれる少なくとも一種以上の金属から成る酸化物
触媒の存在下に反応させると、MVLおよびMPDを製
造することができることを見い出し、先に特願昭60−
178928号として特許出願を行なつた。しかしなが
ら、上記発明において、生成物であるMVLおよび/ま
たはMPDを反応溶媒としてMHPを反応させてMVL
およびMPDを製造する場合には、多量の高沸点化合物
が生成し、収率の低下を招くことが判明した。この問題
は、反応に対して不活性な溶媒を約50重量%以上使用
することによつて低減できるが、工業的観点から見た場
合には、別途に溶媒を使用しないで反応生成物自体を溶
媒の一部として反応させるのが、溶媒回収が不要であり
かつ同一反応装置で比較した場合の生産性が高く、極め
て有利である。
If MVL and MPD can be efficiently produced at the same time, it is industrially advantageous in that a common raw material and a single reaction can be utilized, and as a result of studying such a production method, the present inventors have determined that MHP can be produced under specific conditions. It was found that MVL and MPD can be produced by reacting in the presence of an oxide catalyst composed of at least one metal selected from copper, chromium and zinc.
A patent application was filed as No. 178928. However, in the above-mentioned invention, MHP is reacted with the product MVL and / or MPD as a reaction solvent to produce MVL.
It was found that a large amount of high-boiling compounds are produced in the case of producing MPD and MPD, which causes a decrease in yield. This problem can be reduced by using about 50% by weight or more of a solvent inert to the reaction, but from an industrial viewpoint, the reaction product itself can be obtained without using a solvent. Reacting as a part of the solvent is extremely advantageous because the solvent recovery is unnecessary and the productivity is high when compared in the same reaction apparatus.

従つて本発明の目的は、共通の原料を使用し、反応生成
物を反応溶媒とする溶媒の存在下において、高い総合収
率でMVLおよびMPDを製造することのできる生産性
の高いMVLおよびMPDの製造法を提供することにあ
る。
Therefore, an object of the present invention is to provide a highly productive MVL and MPD capable of producing MVL and MPD in a high overall yield in the presence of a solvent using a common raw material and a reaction product as a reaction solvent. To provide a manufacturing method of.

又、本発明の別の目的は、比較的簡単な操作によつて、
高い総合収率でMVLおよびMPDを製造することので
きる生産性の高い工業的に有利なMVLおよびMPDの
製造法を提供することにある。
Another object of the present invention is to provide a relatively simple operation.
An object of the present invention is to provide a highly productive industrially advantageous method for producing MVL and MPD, which is capable of producing MVL and MPD with a high overall yield.

〔問題点を解決するための手段〕[Means for solving problems]

本発明者らは、上記目的を達成するため、MVLおよび
MPDを製造する際に生成される副生成物の生成経路お
よびその物性について詳細に検討を重ね、副生成物はM
PDとMVLが反応して生成された各種の化合物であ
り、該化合物は加熱により再びMPDとMVLに分解す
ること、およびMPDとMVLの高沸点化合物への生成
反応と、該化合物のMPDとMVLへの分解反応が、反
応条件に依存して一定の平衡組成を示すことに着眼し、
本発明を完成するに至つた。すなわち本発明は、銅、ク
ロムおよび亜鉛から選ばれる少くとも一種以上の金属か
らなる酸化物を用いて非酸化性ガスの雰囲気下にMHP
を反応させてMVLおよびMPDを製造するにあたり、
反応混合液からMVLとMPDを留去した残液を反応系
に循環させることを特徴とするMVLおよびMPDの製
造法である。
In order to achieve the above object, the present inventors have made detailed studies on the production route and physical properties of by-products produced during the production of MVL and MPD.
Various compounds produced by the reaction of PD and MVL, which are decomposed into MPD and MVL again by heating, and the reaction of MPD and MVL to form a high boiling point compound, and the MPD and MVL of the compound. Focusing on the fact that the decomposition reaction to give a constant equilibrium composition depending on the reaction conditions,
The present invention has been completed. That is, the present invention uses an oxide composed of at least one metal selected from copper, chromium and zinc in a non-oxidizing gas atmosphere under MHP.
When producing MVL and MPD by reacting
In the method for producing MVL and MPD, the residual liquid obtained by distilling MVL and MPD from the reaction mixture is circulated in the reaction system.

本発明においては、反応混合液から例えば蒸留等の公知
の手段によりMVLおよびMPDを留去した高沸点化合
物を含有する残液を反応系に循環させることが必要であ
る。通常、高沸点化合物を循環させないで反応させた場
合には約5〜30重量%の高沸点副生成物が生成する
が、MVLおよびMPDを留去した後、反応で生成した
高沸点化合物を反応系に循環させると、それ以降の反応
ではもはやこれ以上の高沸点化合物の蓄積は見られなく
なり、反応系では常に高沸点化合物の濃度は反応条件に
依存した一定値に保たれる。本発明において循環させる
高沸点化合物は同一の反応器で生成したものをそのまま
使用することができるが、別の反応器で合成し、反応系
に添加して、反応をスタートさせても何らさしつかえな
い。この場合、反応系で生成する平衡量より多くの高沸
点化合物を添化しても平衡量以上の高沸点化合物は分解
してMVLとMPDになるのでとくに問題はない。この
ように、本発明においては、高沸点化合物はMVLおよ
びMPDと一定の平衡組成を示すため、反応が定常にな
つた時点では見かけ上もはや高沸点化合物の生成はなく
なり、仕込み原料MHPに対して高い総合収率でMVL
およびMPDを生産することができる。ここでいう総合
収率とはMVLとMPDの合計の収率を意味する。従
来、均一系触媒反応などにおいて触媒を含む高沸成分を
反応系に循環することがよく行われているが、触媒の循
環再使用だけを目的とした一般的な反応においては、反
応成績が向上することはなく、むしろ循環回数が増すに
従つて高沸点副成物の蓄積が毎回加算され、反応成績自
体も少しずつ低下してくる傾向を示す。しかしながら、
本発明においては、本質的に触媒の循環が不必要であ
り、従来とはまつたく違つた本発明の反応の系に特有の
効果が認められる。本発明の反応は、著しく大きな副反
応を伴なう反応であるにもかかわらず、触媒の循環の有
無に関係なく、高沸点化合物の循環のみを積極的に行な
うことによりむしろ高沸点化合物の生成が抑制され、反
応成績が向上して高いMVLとMPDの総合収率が達成
されるということは全く驚くべきことである。
In the present invention, it is necessary to circulate in the reaction system the residual liquid containing the high boiling point compound obtained by distilling MVL and MPD from the reaction mixture by a known means such as distillation. Usually, when the high boiling point compound is reacted without being circulated, about 5 to 30% by weight of a high boiling point by-product is produced, but after the MVL and MPD are distilled off, the high boiling point compound produced by the reaction is reacted. When it is circulated in the system, no further accumulation of high-boiling compounds is observed in the subsequent reactions, and the concentration of high-boiling compounds is always kept in the reaction system at a constant value depending on the reaction conditions. The high boiling point compound to be circulated in the present invention can be the one produced in the same reactor as it is, but it does not matter even if it is synthesized in another reactor and added to the reaction system to start the reaction. . In this case, even if a high-boiling-point compound in an amount larger than the equilibrium amount produced in the reaction system is added, the high-boiling-point compound in an equilibrium amount or more is decomposed into MVL and MPD, and there is no particular problem. As described above, in the present invention, the high-boiling compound has a constant equilibrium composition with MVL and MPD, so that when the reaction reaches a steady state, the high-boiling compound is apparently no longer produced, and the high-boiling compound is not added to the feed material MHP. High overall yield MVL
And MPD can be produced. The total yield here means the total yield of MVL and MPD. Conventionally, it has been common to circulate high boiling components, including catalysts, in the reaction system in homogeneous catalytic reactions, etc., but in general reactions for the purpose of recycling and reuse of the catalyst, the reaction results are improved. Rather, as the circulation number increases, the accumulation of high-boiling by-products is added every time, and the reaction performance itself tends to gradually decrease. However,
In the present invention, the circulation of the catalyst is essentially unnecessary, and the effect peculiar to the reaction system of the present invention, which is completely different from the conventional one, is recognized. Although the reaction of the present invention is a reaction involving a remarkably large side reaction, regardless of the presence or absence of the circulation of the catalyst, the circulation of the high-boiling compound is positively performed to form a high-boiling compound. It is quite surprising that the reaction is suppressed, the reaction performance is improved, and a high combined yield of MVL and MPD is achieved.

また、本発明において触媒を懸濁状態で反応させた場合
には、高沸点化合物と同時に触媒を循環させることがで
きるので、工業的に好ましい。失活した触媒の更新等の
目的で高沸点化合物の一部を抜き出した場合には、その
直後の反応においてのみ抜き取り量に見合つた高沸点化
合物の生成が認められることは言うまでもない。
Further, when the catalyst is reacted in a suspended state in the present invention, the catalyst can be circulated at the same time as the high boiling point compound, which is industrially preferable. Needless to say, when a part of the high boiling point compound is extracted for the purpose of renewing the deactivated catalyst, the formation of the high boiling point compound commensurate with the extracted amount is recognized only in the reaction immediately thereafter.

本発明の方法に従う反応は、反応原料および生成物の酸
化を回避するために非酸化性ガスの雰囲気下において行
われる。好ましい非酸化性ガスの代表例としては窒素、
ヘリウム、アルゴンなどの不活性ガスおよび水素ガスを
挙げることができる。これらの非酸化性ガスは一種のガ
スだけを用いてもよく、又二種以上のガスを混合して用
いてもよい。なかでも窒素ガス又は水素ガスを使用する
のが工業的な面から好ましい。
The reaction according to the method of the present invention is carried out under an atmosphere of non-oxidizing gas in order to avoid oxidation of the reaction raw materials and products. Nitrogen is a typical example of a preferable non-oxidizing gas,
Inert gases such as helium, argon and hydrogen gas may be mentioned. As these non-oxidizing gases, only one kind of gas may be used, or two or more kinds of gas may be mixed and used. Among them, it is preferable to use nitrogen gas or hydrogen gas from the industrial viewpoint.

本発明の方法において、反応を窒素ガスの雰囲気下で行
う場合、MVLとMPDの生成比は1/1以上の割合で実
施することが可能であり、水素ガスの雰囲気下で行う場
合、該生成比は1/1未満の割合で実施することが可能で
ある。
In the method of the present invention, when the reaction is carried out in an atmosphere of nitrogen gas, the production ratio of MVL and MPD can be carried out at a ratio of 1/1 or more. The ratio can be implemented at a ratio of less than 1/1.

本発明の方法に従う反応は、圧力があまり高いとMVL
の収率が低くなる傾向を示すので、50絶対気圧以下の
圧力で実施するのが好ましい。又、反応は減圧下に実施
することもできるが、MVLおよびMPDを実質的な損
失なく単離するには0.01〜20絶対気圧の範囲内で
実施するのがさらに好ましい。
The reaction according to the method of the present invention is
It is preferable to carry out the treatment at a pressure of 50 absolute atmospheric pressure or less, since the yield of the above tends to be low. The reaction can also be carried out under reduced pressure, but it is more preferable to carry out the reaction within the range of 0.01 to 20 absolute atmospheric pressure in order to isolate MVL and MPD without substantial loss.

本発明の方法に従う反応は、温度があまり低いと反応速
度が低くなる傾向にあり、又あまり高いとMPDの収率
が低下する傾向にあるので好ましくは110〜190℃
(さらに好ましくは130〜180℃)で実施される。
In the reaction according to the method of the present invention, if the temperature is too low, the reaction rate tends to be low, and if it is too high, the yield of MPD tends to be low, and therefore the temperature is preferably 110 to 190 ° C.
(More preferably 130 to 180 ° C.).

本発明の方法に従う反応には、銅、クロムおよび亜鉛か
ら選ばれる少なくとも一種以上の金属からなる酸化物が
用いられる。このような酸化物の具体例としては銅クロ
ム酸化物、銅亜鉛酸化物又は銅クロム亜鉛酸化物をあげ
ることができる。これらの金属酸化物は単独で用いるこ
とも可能であるが、アルミナ、シリカ、ケイソウ土等の
担体に担持して用いることも可能である。又、金属酸化
物はタングステン、モリブデン、レニウム、ジルコニウ
ム、マンガン、チタン、鉄、バリウム、マグネシウム、
カルシウム等から選ばれる他の金属又はこれらの金属の
化合物で部分的に変性されていてもよい。担持されてい
てもよく、又部分的に変性されていてもよい金属酸化物
は水素化又は脱水素などの反応に用いられる触媒として
商業生産されており、容易に入手することができるほ
か、例えばOrganic Syntheses Co
ll.Vol.II,142(1943)、J.Am.C
hem.Soc.,54,1138(1932)、J.
Am.Chem.Soc.,58,1053(193
6)、Ind.Eng.Chem.,27,134(1
935)、Ind.Eng.Chem.,21,105
2(1929)などに記載されている方法に従つて調製
することもできる。かかる金属酸化物は、その種類によ
つては使用に先立つて水素処理すれば触媒活性が向上す
る場合がある。これらの金属酸化物は通常一種のみで用
いられるが、二種もしくはそれ以上を組み合せて用いる
こともできる。
In the reaction according to the method of the present invention, an oxide composed of at least one metal selected from copper, chromium and zinc is used. Specific examples of such oxides include copper chromium oxide, copper zinc oxide, and copper chromium zinc oxide. These metal oxides can be used alone, but can also be used by supporting them on a carrier such as alumina, silica, or diatomaceous earth. The metal oxides are tungsten, molybdenum, rhenium, zirconium, manganese, titanium, iron, barium, magnesium,
It may be partially modified with another metal selected from calcium or the like or a compound of these metals. The metal oxide, which may be supported or partially modified, is commercially produced as a catalyst used in a reaction such as hydrogenation or dehydrogenation, and is easily available. Organic Syntheses Co
ll. Vol. II, 142 (1943), J. Am. C
hem. Soc. 54, 1138 (1932), J.
Am. Chem. Soc. , 58, 1053 (193
6), Ind. Eng. Chem. , 27, 134 (1
935), Ind. Eng. Chem. , 21, 105
2 (1929) and the like. Depending on the type of the metal oxide, the catalytic activity may be improved if it is treated with hydrogen prior to use. These metal oxides are usually used alone, but it is also possible to use two or more kinds in combination.

本発明の方法において出発原料として用いられるMHP
は、たとえば公知の方法に従つて3−メチル−3−ブテ
ン−1−オールをロジウム錯化合物の存在下に水素と一
酸化炭素との混合ガスによつてヒドロホルミル化するこ
とによつて容易に得ることができる(特公昭58−40
533号公報、特公昭60−4832号公報、特開昭6
0−19781号公報など参照)。
MHP used as starting material in the process of the invention
Can be easily obtained, for example, by hydroformylating 3-methyl-3-buten-1-ol by a known method in the presence of a rhodium complex compound with a mixed gas of hydrogen and carbon monoxide. It is possible (Japanese Patent Publication Sho 58-40
No. 533, Japanese Patent Publication No. 60-4832, and Japanese Patent Laid-Open No. 6
0-19781, etc.).

本発明の方法に従う反応は液相で実施される。本発明に
おいて、反応生成物以外の有機溶媒を積極的に存在させ
る必要はないが、反応に対して不活性な有機溶媒を使用
してもよい。この場合、該有機溶媒があまり多いと本発
明のメリットがそれ程顕著に発現しないので、40重量
%以下で用いるのが好ましい。このような有機溶媒の具
体例としては流動パラフイン、ヘキサン、ヘプタン、オ
クタン、シクロヘキサン、ベンゼン、トルエン、キシレ
ン、ビフエニル、ジフエニルエーテル、ジエチレングリ
コールジメチルエーテル、トリエチレングリコールジメ
チルエーチル、ジオクチルフタレートなどの飽和脂肪族
炭化水素、飽和脂環式炭化水素、芳香族炭化水素、エー
テルおよびエステルなどを挙げることができる。これら
の有機溶媒の選定に際しては、所望の反応温度および反
応圧力ならびにMHP、MVLおよびMPDと有機溶媒
との沸点差について考慮が払われるべきであることは言
うまでもない。又、このような有機溶媒は存在させずに
反応を実施する方が工業的に有利であることは前述した
とおりであり、本発明においてはこのような有機溶媒が
存在しない場合にとくに効果が発揮される。
The reaction according to the method of the present invention is carried out in the liquid phase. In the present invention, it is not necessary to positively allow an organic solvent other than the reaction product to exist, but an organic solvent inert to the reaction may be used. In this case, if the amount of the organic solvent is too large, the merit of the present invention is not so remarkable, so that it is preferably used at 40% by weight or less. Specific examples of such organic solvents include liquid paraffin, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, biphenyl, diphenyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ethyl, saturated aliphatic such as dioctyl phthalate. Examples thereof include hydrocarbons, saturated alicyclic hydrocarbons, aromatic hydrocarbons, ethers and esters. It goes without saying that in selecting these organic solvents, consideration should be given to the desired reaction temperature and reaction pressure and the boiling point difference between MHP, MVL and MPD and the organic solvent. Further, as described above, it is industrially advantageous to carry out the reaction in the absence of such an organic solvent, and in the present invention, the effect is particularly exerted in the absence of such an organic solvent. To be done.

本発明の方法に従う反応は懸濁床または固定床のいずれ
の接触方式で行うことも、また回分式または連続式のい
ずれの操作方式によつて行うこともできる。副反応を抑
制するためには、MHPを反応系に連続的に供給するな
どの方法により反応系中におけるMHPの濃度があまり
高くならないようにして反応させることが好ましい。ま
た、反応時間または滞留時間としてはMHPの転化率が
100%にならないような時間範囲を選んでもよく、M
HPの転化率が100%になるような時間範囲を選んで
もよい。本発明の方法に従う反応においては、金属酸化
物の種類および濃度、反応温度、反応圧力、反応雰囲気
中における水素ガスの分圧、反応時間(または滞留時
間)などの反応条件を選択することによつて、MVLと
MPDをMVL/MPD(モル比)で通常9/1〜1/
9の範囲内における任意の割合で同時に生成させること
が可能である。かかる反応によつて得られた反応混合物
中のMVL、MPDおよび場合によつて存在する未反応
のMHPは、それぞれ反応混合物から金属酸化物を除去
したのち通常の分離操作、例えば蒸留操作によつて容易
に分離取得することができる。
The reaction according to the method of the present invention can be carried out by either a contact system of a suspension bed or a fixed bed, or a batch or continuous operation system. In order to suppress the side reaction, it is preferable to carry out the reaction so that the concentration of MHP in the reaction system does not become too high by a method such as continuously supplying MHP to the reaction system. As the reaction time or the residence time, a time range in which the conversion of MHP does not reach 100% may be selected.
A time range may be selected so that the HP conversion rate is 100%. In the reaction according to the method of the present invention, by selecting the reaction conditions such as the kind and concentration of the metal oxide, the reaction temperature, the reaction pressure, the partial pressure of hydrogen gas in the reaction atmosphere, the reaction time (or the residence time), etc. Regarding MVL and MPD, MVL / MPD (molar ratio) is usually 9/1 to 1 /
It is possible to simultaneously generate at an arbitrary ratio within the range of 9. The MVL, MPD and optionally the unreacted MHP present in the reaction mixture obtained by such a reaction can be removed by conventional separation operations, for example distillation operations, after removal of the metal oxides from the reaction mixture. Can be easily acquired separately.

反応は原料MHPのみを仕込んでバツチ反応させること
もできるが、工業的には生成物を反応溶媒としてMHP
を連続フイードして反応させるのが好ましい。
In the reaction, the batch reaction can be carried out by charging only the raw material MHP, but industrially, the product is used as a reaction solvent for MHP.
Is preferably fed continuously for reaction.

〔実施例〕〔Example〕

以下、実施例により本発明を具体的に説明するが、本発
明はこれら実施例により何ら制限されるものではない。
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

〔実施例〕〔Example〕

実施例1 MHPフイード口、ガス供給口、サンプリング口を備え
た内容500mlの電磁攪拌式オートクレーブ中に、粉末
状の銅クロム酸化物触媒(CuO−Cr2O3,0.5wt%Mn
O2日揮化学社製N−203)3.0gおよびMPD15
0gを仕込み、水素ガスにて系内を充分に置換した後、
水素圧力10kg/cm2G、オフガス流量15Nl/hrに保ち
ながら攪拌下に160℃まで昇温した。次いで、MHP
150gを定量フイードポンプにより2.5時間かけて
フイードした。フイード終了後、さらに30分反応を続
けて反応を完結させた。サンプリング口より内圧を利用
して少量の反応混合液を抜き取り、ガスクロマトグラフ
イーによつて分析した結果、反応混合液は未反応MHP
0.5重量%、MVL17.0重量%、MPD71.0
重量%および高沸点化合物10.5重量%から成つてい
た。MHPの転化率は99モル%であり、生成したMV
LおよびMPDの反応したMHP基準での選択率はそれ
ぞれ35モル%および44モル%(MVLとMPDの合
計選択率79モル%)であり、MVLおよびMPDの総
合収率は78モルであつた。
Example 1 A powdered copper chromium oxide catalyst (CuO—Cr 2 O 3 , 0.5 wt% Mn) was placed in a 500 ml electromagnetic stirring autoclave equipped with an MHP feed port, a gas supply port, and a sampling port.
O 2 JGC Chemical Co., Ltd. N-203) 3.0 g and MPD15
After charging 0 g and thoroughly replacing the inside of the system with hydrogen gas,
The temperature was raised to 160 ° C. with stirring while maintaining the hydrogen pressure at 10 kg / cm 2 G and the off gas flow rate at 15 Nl / hr. Then MHP
150 g was fed through a quantitative feed pump for 2.5 hours. After the feed was completed, the reaction was continued for another 30 minutes to complete the reaction. Using the internal pressure from the sampling port, a small amount of the reaction mixture was withdrawn and analyzed by gas chromatography. As a result, the reaction mixture was unreacted MHP.
0.5 wt%, MVL17.0 wt%, MPD71.0
% Of high-boiling compounds and 10.5% by weight of high-boiling compounds. The conversion rate of MHP was 99 mol%,
Selectivities of L and MPD on the basis of reacted MHP were 35 mol% and 44 mol% (total selectivity of MVL and MPD was 79 mol%), respectively, and the total yield of MVL and MPD was 78 mol.

実施例1 比較例1の反応混合液をワイパー式薄膜蒸発装置を使用
して140℃、10Torrの減圧下に処理して約半分
を留出させ、触媒、高沸点化合物およびMPDを含む液
152gを得た。この液をガスクロマトグラフイーで分
析した結果MPD77.3重量%が検出され、残りは触
媒および高沸点化合物であつた。
Example 1 The reaction mixture of Comparative Example 1 was treated using a wiper type thin film evaporator under reduced pressure of 140 ° C. and 10 Torr to distill about half, and 152 g of a liquid containing a catalyst, a high boiling point compound and MPD was obtained. Obtained. As a result of analyzing this liquid by gas chromatography, 77.3% by weight of MPD was detected, and the rest was a catalyst and a high boiling point compound.

触媒、高沸点化合物およびMPDを含む上記蒸発残液を
比較例1の装置に仕込み、比較例1と同一条件でMHP
150gを反応させた。反応終了後、サンプリング口よ
り反応混合液の一部をサンプリングしガスクロマトグラ
フイーで分析した結果、反応混合液はMHP0.2重量
%、MVL20.4重量%、MPD67.4重量%およ
び高沸点化合物11.0重量%から成つていた。MHP
の転化率は99.5モル%であり、生成したMVLおよ
びMPDの反応したMHP基準での選択率はそれぞれ4
1モル%および58モル%(MVLとMPDの合計選択
率99モル%)であり、MVLおよびMPDの総合収率
は99モル%であつた。
The above-mentioned evaporation residual liquid containing a catalyst, a high boiling point compound and MPD was charged into the apparatus of Comparative Example 1, and MHP was performed under the same conditions as in Comparative Example 1.
150 g was reacted. After completion of the reaction, a part of the reaction mixture was sampled from the sampling port and analyzed by gas chromatography. As a result, the reaction mixture was 0.2% by weight of MHP, 20.4% by weight of MVL, 67.4% by weight of MPD and 11 of the high boiling point compound. It consisted of 0.0% by weight. MHP
Of 99.5 mol% and the selectivity of the produced MVL and MPD based on the reacted MHP was 4 respectively.
1 mol% and 58 mol% (total selectivity of MVL and MPD 99 mol%), and the overall yield of MVL and MPD was 99 mol%.

実施例2 実施例1の実験を8回くり返し行なつた。4回目と8回
目の反応成績を第1表に示す。第1表より高沸点化合物
の副生はほとんど認められないことがわかる。
Example 2 The experiment of Example 1 was repeated 8 times. The results of the 4th and 8th reactions are shown in Table 1. It can be seen from Table 1 that almost no by-product of the high boiling point compound is observed.

実施例3 下記第2表に示した金属酸化物を使用し、第2表示に示
した反応温度およびガス雰囲気を採用する以外は比較例
1と同様に実験を行い、実施例1と同様に処理および高
沸副生物の循環を行なつて反応させた。得られた2回目
の反応結果を第2表に示した。
Example 3 An experiment was conducted in the same manner as in Comparative Example 1 except that the metal oxides shown in Table 2 below were used and the reaction temperatures and gas atmospheres shown in Table 2 were adopted, and the same treatment as in Example 1 was performed. The reaction was carried out by circulating a high boiling by-product. The results of the second reaction obtained are shown in Table 2.

実施例8 比較例1において反応終了後、反応混合液から触媒をガ
ラスフイルターで除去した。液は減圧蒸留装置を使用
して7Torr、120〜140℃で処理して約半分を
留出させ、MPDおよび高沸点化合物を含む残液147
gを得た。この液をガスクロマトグラフイーで分析した
結果、MPD78.5重量%、残りは高沸点化合物であ
つた。比較例1と同一の装置に銅クロム酸化物触媒(N
−203)3.0gおよび蒸発残液150gを仕込み、
比較例1と同一条件でMHP150gを反応させた。反
応終了後、反応混合液をガスクロマトグラフイーで分析
した結果、反応混合液はMHP0.5重量%、MVL2
0.8重量%、MPD66.8重量%および高沸点化合
物10.9重量%から成つていた。これらの結果からM
HPの転化率は99モル%であり、生成したMVLおよ
びMPDの反応したMHP基準での選択率はそれぞれ4
2モル%および57モル%(MVLとMPDの合計選択
率99モル%)であり、MVLおよびMPDの総合収率
は98モル%であつた。
Example 8 After the completion of the reaction in Comparative Example 1, the catalyst was removed from the reaction mixture with a glass filter. The liquid was treated at 7 Torr and 120 to 140 ° C. using a vacuum distillation apparatus to distill about half, and a residual liquid 147 containing MPD and a high boiling point compound.
g was obtained. As a result of analyzing this liquid by gas chromatography, MPD was 78.5% by weight, and the rest was a high boiling point compound. Copper chrome oxide catalyst (N
-203) 3.0 g and evaporation residual liquid 150 g were charged,
Under the same conditions as in Comparative Example 1, 150 g of MHP was reacted. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and as a result, the reaction mixture was found to have MHP of 0.5% by weight and MVL2.
It consisted of 0.8% by weight, 66.8% by weight of MPD and 10.9% by weight of high-boiling compounds. From these results M
The conversion of HP was 99 mol%, and the selectivity of the produced MVL and MPD on the basis of the reacted MHP was 4 respectively.
2 mol% and 57 mol% (total selectivity of MVL and MPD 99 mol%), and the overall yield of MVL and MPD was 98 mol%.

〔発明の効果〕〔The invention's effect〕

本発明の方法によれば、ポリウレタンの原料、塗料の変
性剤や樹脂の改質剤として有用な高分子化合物に誘導さ
れうる原料として、又医薬、農薬、香料などの中間体と
しても有用な化合物であるMVLや、ポリエステル、ポ
リウレタンなどの原料となるMPDを高い生産性と高い
収率で得ることができ、本発明の有用性は極めて大き
い。
According to the method of the present invention, a compound useful as a raw material of polyurethane, a raw material which can be derived into a polymer compound useful as a modifier for a coating material or a modifier for a resin, and as an intermediate for medicines, agricultural chemicals, perfumes, etc. It is possible to obtain MVL as a raw material, MPD as a raw material for polyester, polyurethane and the like with high productivity and high yield, and the utility of the present invention is extremely large.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 B01J 23/72 X 8017−4G 23/80 X 8017−4G 23/86 X 8017−4G C07B 61/00 300 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location B01J 23/72 X 8017-4G 23/80 X 8017-4G 23/86 X 8017-4G C07B 61 / 00 300

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】銅、クロムおよび亜鉛から選ばれる少くと
も一種以上の金属からなる酸化物を用いて非酸化性ガス
の雰囲気下に2−ヒドロキシ−4−メチルテトラヒドロ
ピランを反応させてβ−メチル−δ−バレロラクトンお
よび3−メチルペンタン−1,5−ジオールを製造する
にあたり、反応混合液からβ−メチル−δ−バレロラク
トンと3−メチルペンタン−1,5−ジオールを留去さ
せた残液を反応系に循環させることを特徴とするβ−メ
チル−δ−バレロラクトンおよび3−メチルペンタン−
1,5−ジオールの製造法。
1. β-Methyl by reacting 2-hydroxy-4-methyltetrahydropyran in an atmosphere of a non-oxidizing gas using an oxide composed of at least one metal selected from copper, chromium and zinc. In producing -δ-valerolactone and 3-methylpentane-1,5-diol, the residue obtained by distilling β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol from the reaction mixture The liquid is circulated in the reaction system, β-methyl-δ-valerolactone and 3-methylpentane-
Process for producing 1,5-diol.
JP62031153A 1987-02-12 1987-02-12 Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol Expired - Fee Related JPH0653692B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62031153A JPH0653692B2 (en) 1987-02-12 1987-02-12 Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62031153A JPH0653692B2 (en) 1987-02-12 1987-02-12 Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol

Publications (2)

Publication Number Publication Date
JPS63198639A JPS63198639A (en) 1988-08-17
JPH0653692B2 true JPH0653692B2 (en) 1994-07-20

Family

ID=12323496

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62031153A Expired - Fee Related JPH0653692B2 (en) 1987-02-12 1987-02-12 Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol

Country Status (1)

Country Link
JP (1) JPH0653692B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103081902A (en) * 2012-10-17 2013-05-08 王浅肃 Method for detoxicating pesticide residue

Also Published As

Publication number Publication date
JPS63198639A (en) 1988-08-17

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