JPH06247954A - Production of lactone - Google Patents
Production of lactoneInfo
- Publication number
- JPH06247954A JPH06247954A JP5038351A JP3835193A JPH06247954A JP H06247954 A JPH06247954 A JP H06247954A JP 5038351 A JP5038351 A JP 5038351A JP 3835193 A JP3835193 A JP 3835193A JP H06247954 A JPH06247954 A JP H06247954A
- Authority
- JP
- Japan
- Prior art keywords
- lactone
- dicarboxylic acid
- hydrogen
- acid diester
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な固体触媒を使用
して、ジカルボン酸ジエステルと水素との接触反応によ
り、高選択率、高収量でラクトンを製造する方法に関す
る。ジカルボン酸ジエステルから生成するラクトンは、
ポリエステルや香料の原料として、また、洗剤のビルダ
−や生分解性ポリマ−等の製造のための中間体として、
工業上非常に重要な化合物である。TECHNICAL FIELD The present invention relates to a method for producing a lactone with a high selectivity and a high yield by a catalytic reaction of a dicarboxylic acid diester and hydrogen using a novel solid catalyst. The lactone produced from the dicarboxylic acid diester is
As a raw material for polyesters and fragrances, and as an intermediate for the production of detergent builders, biodegradable polymers, etc.
It is a very important compound in industry.
【０００２】[0002]
【従来の技術】ラクトンの工業的製造法としては、環状
の酸無水物またはジカルボン酸ジエステルを水素により
水素化する方法が、米国特許第３，０６５，２４３号に
開示されている。しかしながら、この方法は、触媒活性
が低く、原料である環状の酸無水物またはジカルボン酸
ジエステルの反応層への供給速度も小さいため、反応速
度的には工業的製造法として満足できるものではない。
また、ラクトンの選択率を上げるには、環状の酸無水物
またはジカルボン酸ジエステルに対する水素のモル比を
５０以上に上げる、反応温度を上げるなど、苛酷な反応
条件が必要であった。更に、触媒として銅−クロム系触
媒を使用しているため、使用後は廃触媒からクロムの回
収・処理を行うことが必要であるが、その工程でクロム
を効率良く回収して、排水等にクロムが同伴しないよう
にすることは極めて困難であり、環境衛生上からも、毒
性が極めて強いクロムを使用しない製造法が望まれてい
た。2. Description of the Related Art As an industrial production method of lactone, a method of hydrogenating a cyclic acid anhydride or dicarboxylic acid diester with hydrogen is disclosed in US Pat. No. 3,065,243. However, this method is unsatisfactory in terms of reaction rate as an industrial production method because the catalyst activity is low and the feed rate of the cyclic acid anhydride or dicarboxylic acid diester as a raw material is small.
Further, in order to increase the selectivity of the lactone, harsh reaction conditions such as increasing the molar ratio of hydrogen to the cyclic acid anhydride or dicarboxylic acid diester to 50 or higher and raising the reaction temperature have been required. Furthermore, since a copper-chromium-based catalyst is used as a catalyst, it is necessary to recover and treat chromium from the waste catalyst after use, but in that process chromium can be efficiently recovered and used in wastewater, etc. It is extremely difficult to prevent chromium from accommodating, and from the viewpoint of environmental hygiene, a manufacturing method that does not use chromium, which is extremely toxic, has been desired.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、クロ
ム等の公害問題となりうる成分を含有しない新規な固体
触媒を使用して、温和な反応条件下でジカルボン酸ジエ
ステルの水素による気相水素化反応を行って、高選択
率、高収量でラクトンを製造しうる、工業的に好適なラ
クトンの製造法を提供することにある。DISCLOSURE OF THE INVENTION The object of the present invention is to use a novel solid catalyst containing no components such as chromium, which may cause pollution problems, under a mild reaction condition to produce hydrogen gas of dicarboxylic acid diester in a gas phase. The object of the present invention is to provide an industrially suitable method for producing a lactone, which is capable of producing a lactone with a high selectivity and a high yield by carrying out a chemical reaction.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、従来公知
のラクトンの製造法における前述したような問題点を克
服すべく、水素化触媒の存在下、ジカルボン酸ジエステ
ルと水素との気相水素化反応によってラクトンを製造す
る反応について鋭意検討した結果、新規な水素化触媒を
使用して、温和な反応条件下、気相でジカルボン酸ジエ
ステルの水素化反応を行うことにより、極めて高い選択
率および空時収量で目的生成物のラクトンが得られるこ
とを見出して本発明に到達した。In order to overcome the above-mentioned problems in the conventionally known lactone production methods, the present inventors have investigated the gas phase of dicarboxylic acid diester and hydrogen in the presence of a hydrogenation catalyst. As a result of extensive studies on the reaction for producing a lactone by a hydrogenation reaction, an extremely high selectivity can be obtained by carrying out the hydrogenation reaction of a dicarboxylic acid diester in a gas phase under a mild reaction condition using a novel hydrogenation catalyst. The present invention has been accomplished by finding that the desired product lactone can be obtained with a space-time yield.
【０００５】即ち、本発明は、ジカルボン酸ジエステル
を、水素により気相で水素化反応させてラクトンを製造
する方法において、一般式Ｒn2・（ＣＯＯＲn1）2 （但
し、式中のＲn1は炭素数１〜６の低級アルキル基を、Ｒ
n2は炭素数１〜１２の炭化水素基を示す）で表されるジ
カルボン酸ジエステルを、少なくとも銅金属および銀金
属が担体に担持されている固体触媒の存在下、水素によ
り気相で水素化反応させてラクトンを合成することを特
徴とするラクトンの製造法に関する。That is, the present invention provides a method for producing a lactone by hydrogenating a dicarboxylic acid diester with hydrogen in a gas phase, wherein R n2 · (COOR n1 ) 2 (where R n1 in the formula is A lower alkyl group having 1 to 6 carbon atoms is represented by R
(n2 represents a hydrocarbon group having 1 to 12 carbon atoms), a dicarboxylic acid diester represented by the formula (2) is used to hydrogenate a dicarboxylic acid diester in the gas phase with hydrogen in the presence of a solid catalyst in which at least copper metal and silver metal are supported on a carrier. The present invention relates to a method for producing a lactone, which comprises synthesizing a lactone.
【０００６】以下に本発明の方法を詳しく説明する。本
発明で使用されるジカルボン酸ジエステルとしては、コ
ハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリ
ン酸、アゼライン酸、セバシン酸、ウンデカンジカルボ
ン酸、ドデカンジカルボン酸などの脂肪族飽和カルボン
酸、マレイン酸、フマール酸などの脂肪族不飽和カルボ
ン酸、シクロペンタンジカルボン酸、シクロヘキサンジ
カルボン酸などの脂環式カルボン酸、フタル酸、ナフタ
レンジカルボン酸などの芳香族カルボン酸と炭素数１〜
６の低級脂肪族アルコ−ルとのジエステルが挙げられる
が、これらのジカルボン酸ジエステルのうち、特に好適
に使用される化合物は、Ｒn2が炭素数２〜６の脂肪族炭
化水素基で示されるものである。なお、上記のジカルボ
ン酸ジエステルを使用した場合、反応生成物としては、
γ−ブチロラクトン、δ−バレロラクトン、ε−カプロ
ラクトン、７−ヘプタノリド、８−オクタノリド、９−
ノナノリド、１０−デカノリド、１１−ウンデカノリ
ド、１２−ドデカノリドなどをそれぞれ得ることができ
る。The method of the present invention will be described in detail below. Examples of the dicarboxylic acid diester used in the present invention include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and other saturated saturated carboxylic acids, and maleic acid. , Aliphatic unsaturated carboxylic acids such as fumaric acid, cyclopentanedicarboxylic acid, alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, aromatic carboxylic acids such as phthalic acid and naphthalenedicarboxylic acid, and 1 to 1 carbon atoms
Examples thereof include diesters of 6 with lower aliphatic alcohols. Among these dicarboxylic acid diesters, the compounds that are particularly preferably used are those in which R n2 is an aliphatic hydrocarbon group having 2 to 6 carbon atoms. It is a thing. When the above dicarboxylic acid diester is used, as the reaction product,
γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octanolide, 9-
Nonanolide, 10-decanolide, 11-undecanolide, 12-dodecanolide and the like can be obtained, respectively.
【０００７】本発明の水素化反応に使用される新規な固
体触媒は、少なくとも銅金属および銀金属がシリカ、ア
ルミナ、チタニア、ケイソウ土、酸化亜鉛、酸化ランタ
ン、活性炭などの担体に担持されている固体触媒であ
り、更に前記銅金属および銀金属に加えて、銅化合物お
よび／または銀化合物が担持されている固体触媒であっ
てもよい。銅金属および銀金属の担持量は、担体に対し
て、金属換算で、銅が５〜５０重量％、特に５〜３０重
量％であり、銀が０．０１〜２０重量％、特に０．０２
〜１０重量％であることが好ましい。The novel solid catalyst used in the hydrogenation reaction of the present invention has at least copper metal and silver metal supported on a carrier such as silica, alumina, titania, diatomaceous earth, zinc oxide, lanthanum oxide and activated carbon. It may be a solid catalyst, and may be a solid catalyst supporting a copper compound and / or a silver compound in addition to the copper metal and the silver metal. The supported amounts of copper metal and silver metal are 5 to 50% by weight, particularly 5 to 30% by weight, and 0.01 to 20% by weight, particularly 0.02% of silver, in terms of metal, with respect to the carrier.
It is preferably from 10 to 10% by weight.
【０００８】また、上記の担体は、粉末、粒状のもの、
もしくは成型体が使用されるが、そのサイズについて
は、特に限定されるものではなく、粉末の場合は通常用
いられる２０〜１００μｍのもの、粒状の場合は４〜２
００メッシュ程度のもの、成型体の場合は数ｍｍのもの
が好適に用いられる。Further, the above-mentioned carrier is a powder, a granular one,
Alternatively, a molded product is used, but its size is not particularly limited, and a powder having a particle size of 20 to 100 μm which is usually used, and a granular product having a particle size of 4 to 2 are used.
Those having a mesh size of about 00 mesh and several mm in the case of a molded product are preferably used.
【０００９】本発明で水素化反応に使用される固体触媒
は、銅および銀の硫酸塩，硝酸塩，塩化物、錯塩などの
水溶性化合物が溶解している銅化合物および銀化合物の
水溶液を調製して、これに上記の担体を添加して適当な
方法で銅化合物および銀化合物を担体に担持させた後、
水素ガスなどで担体に担持されている銅化合物および銀
化合物を還元することによって調製される。The solid catalyst used in the hydrogenation reaction of the present invention is prepared by preparing an aqueous solution of a copper compound and a silver compound in which water-soluble compounds such as sulfates, nitrates, chlorides and complex salts of copper and silver are dissolved. Then, after adding the above carrier to this and supporting the copper compound and the silver compound on the carrier by a suitable method,
It is prepared by reducing a copper compound and a silver compound supported on a carrier with hydrogen gas or the like.
【００１０】触媒成分を担体に担持する方法は、特別な
ものである必要はなく、通常実施される方法、即ち、含
浸法（浸漬吸着法）、混練法、沈着法、蒸発乾固法、共
沈法等でよいが、簡便であることから、共沈法、含浸法
または蒸発乾固法が望ましい。なお、上記の各成分の担
体への担持は、同時に行ってもまたは逐次に行ってもよ
い。The method of loading the catalyst component on the carrier does not have to be special, and it is usually carried out, that is, impregnation method (immersion adsorption method), kneading method, deposition method, evaporation dryness method, Although a precipitation method or the like may be used, a coprecipitation method, an impregnation method or an evaporation-drying method is preferable because it is simple. The above components may be loaded on the carrier at the same time or sequentially.
【００１１】触媒成分が担持された担体の還元は、水素
ガスまたはヒドラジン等の一般的な還元剤を用いて行わ
れるが、水素ガスを用いる還元処理では、ジカルボン酸
ジエステルの水素化反応に先立って、１５０〜４００℃
の温度で、還元時間を１〜２０時間とする一般的な水素
ガスによる還元処理を行って、銅金属および銀金属が主
として担持されている固体触媒を製造することが好まし
い。The reduction of the carrier carrying the catalyst component is carried out by using a general reducing agent such as hydrogen gas or hydrazine. In the reduction treatment using hydrogen gas, the hydrogenation reaction of the dicarboxylic acid diester is carried out prior to the hydrogenation reaction. , 150-400 ℃
It is preferable to carry out a reduction treatment with a general hydrogen gas at a temperature of 1 to 20 hours for a reduction time of 1 to 20 hours to produce a solid catalyst on which copper metal and silver metal are mainly supported.
【００１２】なお、前記の還元処理を行った後の固体触
媒において、還元が充分にされなかった銅化合物および
／または銀化合物が、銅金属および銀金属と共に、少な
い割合（担体上に担持された金属および金属化合物成分
の全量に対する銅化合物および銀化合物の合計量の割合
で示す残留割合が２０重量％以下、特に１０重量％以下
である割合）で担持されていても、本発明のジカルボン
酸ジエステルの水素化反応には支障はなく、そのまま固
体触媒として使用できる。また、本発明の固体触媒は、
銅金属および銀金属と共に、銅金属および銀金属以外の
他の金属またはその化合物が触媒成分として担持されて
いてもよい。In the solid catalyst after the above reduction treatment, the copper compound and / or the silver compound, which has not been sufficiently reduced, is contained in a small proportion together with the copper metal and the silver metal (supported on the carrier). The dicarboxylic acid diester of the present invention is supported even if the residual ratio shown by the ratio of the total amount of the copper compound and the silver compound to the total amount of the metal and the metal compound component is 20% by weight or less, particularly 10% by weight or less. There is no hindrance to the hydrogenation reaction, and it can be used as it is as a solid catalyst. Further, the solid catalyst of the present invention,
In addition to copper metal and silver metal, a metal other than copper metal and silver metal or a compound thereof may be supported as a catalyst component.
【００１３】上述の方法などで調製された、少なくとも
銅金属および銀金属が担持されている固体触媒は、水素
化反応の活性（例えば、空時収量：ＳＴＹ）が高いレベ
ルで継続して維持され、触媒としての機械的強度も高く
崩壊がないため、長期間安定に使用することができ、本
発明のジカルボン酸ジエステルの水素化反応に好適な触
媒である。The solid catalyst prepared by the above-mentioned method and loaded with at least copper metal and silver metal is continuously maintained at a high level for the activity of hydrogenation reaction (for example, space-time yield: STY). Since it has a high mechanical strength as a catalyst and does not collapse, it can be used stably for a long period of time and is a catalyst suitable for the hydrogenation reaction of the dicarboxylic acid diester of the present invention.
【００１４】更に、この触媒を用いれば、反応を非常に
温和な条件下でも行うことができる。即ち、ジカルボン
酸ジエステルと水素との接触水素化反応は、反応温度が
１００〜３００℃、好ましくは１００〜２６０℃であっ
て、反応圧が常圧〜約３０ｋｇ／ｃｍ2 Ｇ程度の条件で
実施することができる。また、固体触媒の充填された反
応管に導入される水素とジカルボン酸ジエステルとのモ
ル比（水素／ジカルボン酸ジエステル）は、２〜１０
０、特に４〜５０であることが好ましく、固体触媒との
接触時間は、０．０１〜２０秒、特に０．２〜８秒程度
であることが好ましい。Furthermore, by using this catalyst, the reaction can be carried out under extremely mild conditions. That is, the catalytic hydrogenation reaction of dicarboxylic acid diester and hydrogen is carried out at a reaction temperature of 100 to 300 ° C., preferably 100 to 260 ° C., and a reaction pressure of normal pressure to about 30 kg / cm 2 G. can do. Further, the molar ratio of hydrogen introduced into the reaction tube filled with the solid catalyst and dicarboxylic acid diester (hydrogen / dicarboxylic acid diester) is from 2 to 10
It is preferably 0, particularly 4 to 50, and the contact time with the solid catalyst is preferably 0.01 to 20 seconds, particularly preferably 0.2 to 8 seconds.
【００１５】原料ガスの水素およびジカルボン酸ジエス
テルは、メタノ−ル、エタノ−ルなどの低級アルコ−ル
蒸気または窒素ガス等の不活性ガスで希釈して前記の水
素化用の固体触媒にフィ−ドされることが望ましい。そ
の組成としては、反応上からは特に限定されるものでは
ないが、例えば、ジカルボン酸ジエステルは、濃度が１
０〜４０重量％、特に１５〜３５％重量％であるジカル
ボン酸ジエステルのアルコ−ル溶液を蒸発させて、水素
ガスと共に固体触媒上へ供給されることが好ましい。な
お、このとき、アルコ−ルにはジカルボン酸ジエステル
のアルコキシ基と同じアルキル基を持つアルコ−ルを使
用することが望ましい。Hydrogen as a raw material gas and dicarboxylic acid diester are diluted with a lower alcohol vapor such as methanol or ethanol or an inert gas such as nitrogen gas, and then fed to the above-mentioned solid catalyst for hydrogenation. It is desirable to be read. The composition thereof is not particularly limited from the viewpoint of reaction, but for example, dicarboxylic acid diester has a concentration of 1
It is preferred that the alcoholic solution of dicarboxylic acid diester, which is 0 to 40% by weight, in particular 15 to 35% by weight, is evaporated and fed with hydrogen gas onto the solid catalyst. At this time, it is preferable to use an alcohol having the same alkyl group as the alkoxy group of the dicarboxylic acid diester.
【００１６】このようにしてラクトンの合成反応を行っ
て、反応器から、目的生成物のラクトンの他に、ヒドロ
キシカルボン酸エステル等の副生物、アルコール、未反
応の水素、不活性ガスなどを含む反応ガスが導出される
が、ラクトンはこの反応ガスを冷却した後、凝縮液から
蒸留等の常法により分離・精製することができる。な
お、副生物のヒドロキシカルボン酸エステルはラクトン
に誘導して利用することもできる。By carrying out the lactone synthesis reaction in this manner, the reaction product contains by-products such as hydroxycarboxylic acid ester, alcohol, unreacted hydrogen, and inert gas, in addition to the desired product, lactone. Although the reaction gas is discharged, the lactone can be separated and purified from the condensate by a conventional method such as distillation after cooling the reaction gas. The by-product hydroxycarboxylic acid ester can also be used by derivatizing it into a lactone.
【００１７】[0017]
【実施例】次に、実施例を挙げて、本発明の方法を具体
的に説明するが、これらは、本発明の方法を何ら限定す
るものではない。なお、各実施例における反応条件のう
ち、液空間速度（ｇ／ｍｌ・ｈｒ）：ＬＨＳＶ、空間速
度（ｈｒ-1）：ＳＶは、下記の式により求めた。EXAMPLES Next, the method of the present invention will be specifically described with reference to examples, but these do not limit the method of the present invention in any way. The liquid space velocity (g / ml · hr): LHSV and the space velocity (hr −1 ): SV among the reaction conditions in each example were determined by the following formulas.
【００１８】[0018]
【数１】 [Equation 1]
【００１９】[0019]
【数２】 [Equation 2]
【００２０】また、各実施例におけるジカルボン酸ジエ
ステルの転化率（％）、およびラクトン、ヒドロキシカ
ルボン酸エステル、ジオールの選択率（％）は、次式に
より求めた。The conversion (%) of dicarboxylic acid diester and the selectivity (%) of lactone, hydroxycarboxylic acid ester and diol in each example were determined by the following equations.
【００２１】[0021]
【数３】 [Equation 3]
【００２２】[0022]
【数４】 [Equation 4]
【００２３】[0023]
【数５】 [Equation 5]
【００２４】[0024]
【数６】 [Equation 6]
【００２５】更に、各実施例における空時収量（ｇ／ｌ
・ｈｒ）：ＳＴＹは、次式により求めた。Further, the space-time yield (g / l) in each Example
* Hr): STY was calculated by the following equation.
【００２６】[0026]
【数７】 [Equation 7]
【００２７】実施例１〜４ 〔触媒の調製〕硝酸銅〔Ｃｕ（ＮＯ3 ）2 ・３Ｈ2 Ｏ〕
３９．２ｇと、硝酸銀（ＡｇＮＯ3 ）２．１ｇを水２０
０ｍｌに溶解し、これに市販のシリカゾル（触媒化成
製；キャタロイドＳ３０Ｌ）６６．６ｇを加えて攪拌し
た。この溶液に、予め炭酸アンモニウム１４．４ｇを水
８５ｍｌに溶解した液を、３０分間で攪拌しながらゆっ
くり滴下した。滴下終了後、攪拌しながら反応物を１．
５時間熟成した後、生成した沈殿物を濾過し分離した。
分離した沈殿物は、約５００ｍｌの水で、水洗・濾過を
３回繰り返した。得られた青白色のケ−キを取り出し、
１４０℃で１２時間乾燥して、銅化合物および銀化合物
が担体に担持されている担持体（固体触媒の前駆体）を
形成し、更に、この担持体を、水素気流中、３５０℃で
２時間還元処理して、銅金属および銀金属が担持されて
いる固体触媒（平均粒子径：１〜２ｍｍ）を調製した。[0027] Examples 1-4 [Preparation of Catalyst] copper nitrate [Cu (NO 3) 2 · 3H 2 O ]
39.2 g and 2.1 g of silver nitrate (AgNO 3 ) in water 20
It was dissolved in 0 ml, and 66.6 g of commercially available silica sol (manufactured by Catalysts &Chemicals; Cataloid S30L) was added and stirred. A solution prepared by previously dissolving 14.4 g of ammonium carbonate in 85 ml of water was slowly added dropwise to this solution while stirring for 30 minutes. After completion of dropping, the reaction product was stirred with stirring.
After aging for 5 hours, the formed precipitate was filtered and separated.
The separated precipitate was washed with water and filtered three times with about 500 ml of water. Take out the obtained pale white cake,
It is dried at 140 ° C. for 12 hours to form a carrier (a precursor of a solid catalyst) in which a copper compound and a silver compound are supported on a carrier, and the carrier is further heated in a hydrogen stream at 350 ° C. for 2 hours. Reduction treatment was carried out to prepare a solid catalyst (average particle diameter: 1 to 2 mm) supporting copper metal and silver metal.
【００２８】〔ラクトンの合成〕上記で得られた固体触
媒１０ｍｌを、内径２０ｍｍ、長さ７００ｍｍのガラス
製気相反応管に充填した後、この反応管を電気炉中に垂
直に設置して固体触媒層内の温度が表１に示す温度にな
るようにそれぞれ加熱制御した。これらの反応管の上部
から、表１に示す液空間速度（ＬＨＳＶ）および空間速
度（ＳＶ）で、水素とコハク酸ジメチルとのモル比が２
０〜４０となるように、水素、およびコハク酸ジメチル
とメタノ−ルとの溶液（２５重量％コハク酸ジメチルの
メタノ−ル溶液）を供給しながら、前記固体触媒層内の
温度で、常圧下、コハク酸ジメチルの水素化反応を行っ
て、これらの反応管を通過した反応生成物を氷冷したト
ラップ中に捕集した。得られた捕集液をガスクロマトグ
ラフィ−によって分析した結果から、コハク酸ジメチル
の転化率、γ−ブチロラクトンの選択率および空時収量
（ＳＴＹ）、１，４−ブタンジオ−ルの選択率を求め
て、表１にそれぞれ示した。[Synthesis of Lactone] 10 ml of the solid catalyst obtained above was filled in a glass vapor phase reaction tube having an inner diameter of 20 mm and a length of 700 mm, and the reaction tube was placed vertically in an electric furnace to prepare a solid. The heating was controlled so that the temperature in the catalyst layer became the temperature shown in Table 1. From the top of these reaction tubes, the molar ratio of hydrogen to dimethyl succinate was 2 at the liquid hourly space velocity (LHSV) and the hourly space velocity (SV) shown in Table 1.
While supplying hydrogen and a solution of dimethyl succinate and methanol (25 wt% dimethyl succinate solution in methanol) so as to be 0 to 40, the temperature in the solid catalyst layer under normal pressure Hydrogenation reaction of dimethyl succinate was carried out, and the reaction products passing through these reaction tubes were collected in an ice-cooled trap. From the analysis results of the obtained collected liquid by gas chromatography, the conversion of dimethyl succinate, the selectivity of γ-butyrolactone and the space-time yield (STY), and the selectivity of 1,4-butanediol were determined. , And shown in Table 1, respectively.
【００２９】実施例５〜７ 〔ラクトンの合成〕実施例１〜４と同様に調製した触媒
を使用して、実施例１〜４におけるコハク酸ジメチルを
アジピン酸ジメチルに、水素とアジピン酸ジメチルとの
モル比を４６．９に、温度、液空間速度（ＬＨＳＶ）、
空間速度（ＳＶ）を表２に示す条件に変えたことの他
は、実施例１〜４と同様にしてアジピン酸ジメチルの水
素化反応を行った。得られた各捕集液をガスクロマトグ
ラフィ−によって分析した結果から、アジピン酸ジメチ
ルの転化率、ε−カプロラクトンの選択率および空時収
量（ＳＴＹ）、１，６−ヘキサンジオ−ルの選択率、ヒ
ドロキシカプロン酸メチルの選択率を求めて、表２にそ
れぞれ示した。Examples 5 to 7 [Synthesis of lactone] Using the catalysts prepared in the same manner as in Examples 1 to 4, dimethyl succinate in Examples 1 to 4 was converted to dimethyl adipate, hydrogen and dimethyl adipate. To a molar ratio of 46.9, temperature, liquid hourly space velocity (LHSV),
The hydrogenation reaction of dimethyl adipate was performed in the same manner as in Examples 1 to 4 except that the space velocity (SV) was changed to the conditions shown in Table 2. The obtained collected liquids were analyzed by gas chromatography, and as a result, conversion of dimethyl adipate, selectivity of ε-caprolactone and space-time yield (STY), selectivity of 1,6-hexanediol, hydroxy The selectivity of methyl caproate was calculated and shown in Table 2.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【発明の作用効果】本発明の方法により、クロムを含有
しない新規な固体触媒を使用して、温和な反応条件下
で、水素により気相でジカルボン酸ジエステルの水素化
反応を行って、従来公知のラクトンの製造法における、
ラクトンの選択率および収量が低い、触媒にクロム等の
公害問題となりうる成分を含有している、という工業的
に望ましくない点を克服して、高選択率、高収量でラク
トンを製造することができる。According to the method of the present invention, a novel solid catalyst containing no chromium is used to carry out a hydrogenation reaction of a dicarboxylic acid diester with hydrogen in a gas phase under mild reaction conditions, and the conventional method is known. In the lactone production method of
It is possible to manufacture lactones with high selectivity and high yield by overcoming the industrially undesirable point that the selectivity and yield of lactone are low, and that the catalyst contains components that may cause pollution problems such as chromium. it can.
───────────────────────────────────────────────────── 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 Ｃ０７Ｄ 313/18 9360−4Ｃ 315/00 9360−4Ｃ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C07D 313/18 9360-4C 315/00 9360-4C // C07B 61/00 300
Claims (1)
相で水素化反応させてラクトンを製造する方法におい
て、一般式Ｒn2・（ＣＯＯＲn1）2 （但し、式中のＲn1
は炭素数１〜６の低級アルキル基を、Ｒn2は炭素数１〜
１２の炭化水素基を示す）で表されるジカルボン酸ジエ
ステルを、少なくとも銅金属および銀金属が担体に担持
されている固体触媒の存在下、水素により気相で水素化
反応させてラクトンを合成することを特徴とするラクト
ンの製造法。1. A method for producing a lactone by subjecting a dicarboxylic acid diester to hydrogenation reaction with hydrogen in a gas phase, wherein a compound represented by the general formula R n2. (COOR n1 ) 2 (where R n1
Is a lower alkyl group having 1 to 6 carbon atoms, and R n2 is 1 to 6 carbon atoms.
A dicarboxylic acid diester represented by 12), which is a hydrocarbon group of 12), is subjected to a hydrogenation reaction in the gas phase with hydrogen in the presence of a solid catalyst in which at least copper metal and silver metal are supported on a carrier to synthesize a lactone. A method for producing a lactone characterized by the following:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05038351A JP3132532B2 (en) | 1993-02-26 | 1993-02-26 | Lactone production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05038351A JP3132532B2 (en) | 1993-02-26 | 1993-02-26 | Lactone production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06247954A true JPH06247954A (en) | 1994-09-06 |
| JP3132532B2 JP3132532B2 (en) | 2001-02-05 |
Family
ID=12522866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05038351A Expired - Fee Related JP3132532B2 (en) | 1993-02-26 | 1993-02-26 | Lactone production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3132532B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495706B2 (en) | 2000-06-07 | 2002-12-17 | Kao Corporation | Process for producing hydroxycarboxylic acid ester |
| KR100457067B1 (en) * | 2002-04-23 | 2004-11-12 | 애경유화 주식회사 | Complicated metal oxide catalyst, preparation thereof, and method for the preparation of phthalide from phthalic ester using the catalyst |
| KR100910165B1 (en) * | 2008-09-18 | 2009-07-30 | (주) 제노텍 | Purification method of lactone compounds containing unsaturated alkyl group by extraction with silver ion solution |
| JP2010227893A (en) * | 2009-03-30 | 2010-10-14 | Yamaguchi Univ | Silver-supporting catalyst used for reduction of carboxylic acid ester to aldehyde |
-
1993
- 1993-02-26 JP JP05038351A patent/JP3132532B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495706B2 (en) | 2000-06-07 | 2002-12-17 | Kao Corporation | Process for producing hydroxycarboxylic acid ester |
| KR100457067B1 (en) * | 2002-04-23 | 2004-11-12 | 애경유화 주식회사 | Complicated metal oxide catalyst, preparation thereof, and method for the preparation of phthalide from phthalic ester using the catalyst |
| KR100910165B1 (en) * | 2008-09-18 | 2009-07-30 | (주) 제노텍 | Purification method of lactone compounds containing unsaturated alkyl group by extraction with silver ion solution |
| WO2010032919A1 (en) * | 2008-09-18 | 2010-03-25 | 제노텍 | Method for purifying lactone compound having unsaturated alkyl group by extraction with silver ion solution |
| US8193345B2 (en) | 2008-09-18 | 2012-06-05 | Genotech Corp. | Purification method of lactone compounds containing unsaturated alkyl group by extraction with silver ion solution |
| JP2010227893A (en) * | 2009-03-30 | 2010-10-14 | Yamaguchi Univ | Silver-supporting catalyst used for reduction of carboxylic acid ester to aldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3132532B2 (en) | 2001-02-05 |
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