JP4447152B2 - Production method of ketones - Google Patents
Production method of ketones Download PDFInfo
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- JP4447152B2 JP4447152B2 JP2000372458A JP2000372458A JP4447152B2 JP 4447152 B2 JP4447152 B2 JP 4447152B2 JP 2000372458 A JP2000372458 A JP 2000372458A JP 2000372458 A JP2000372458 A JP 2000372458A JP 4447152 B2 JP4447152 B2 JP 4447152B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、アルコールとメチルケトンとを反応させてケトン類を製造する方法に関する。
【０００２】
【従来の技術】
ケトン類は、溶剤、可塑剤等や工業用製品の原料等として有用である。ケトン類を製造する方法としては、例えば、触媒の存在下に第一級アルコールとアセトン等のメチルケトンとから製造する方法が知られている。
例えば、米国特許第４７３９１２２号にはアルミナを担体とした銅触媒の存在下、アセトンおよびイソプロパノールとブタノールとを、２１６〜２５４℃の温度で反応させることにより２−ヘプタノンを５．９〜１８．３％の収率で製造する方法が開示されている。
【０００３】
また、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，７，１８９（１９４２）は、アルミナを担体とした銅−亜鉛触媒の存在下、アセトンとブタノールを、３０９℃で反応させることにより２−ヘプタノンを製造する方法を記載している。
しかしながら、前記のいずれの方法でも反応時に２１０℃以上の高温が必要である。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、アルコールとメチルケトンとを反応させてケトン類を製造する方法において、高温を必要としない工業的に有利なケトン類の製造法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明は、式（Ｉ）
【０００６】
【化８】
（式中、Ｒ1はアルキルを表す）で表されるアルコールと式（ＩＩ）
【０００８】
【化９】
（式中、Ｒ2はアルキルを表す）で表されるメチルケトンとを担体に担持されたニッケル触媒の存在下で反応させることを特徴とする式（ＩＩＩ）
【００１０】
【化１０】
（式中、Ｒ1およびＲ2はそれぞれ前記と同義である）で表されるケトン類の製造法を提供する（この製造法を本発明の製造法１と表現することもある）。
以下、本明細書中においては、式（Ｉ）で表されるアルコールを単にアルコールと、式（ＩＩ）で表されるメチルケトンを単にメチルケトンと、式（ＩＩＩ）で表されるケトン類を単にケトン類と、担体に担持されたニッケル触媒を本発明における触媒と表現することもある。
【００１２】
【発明の実施の形態】
式（Ｉ）〜（ＩＩＩ）の基の定義において、アルキルとしては、直鎖または分枝状の炭素数１〜２０の、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、イソペンチル、ネオペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、ペンタデシル、エイコシル等があげられるが、中でも炭素数１〜８のものが好ましい。また、メチルケトンとしてはアセトンが好ましい。
【００１３】
原料であるアルコールの好ましい具体例としては、例えば、エタノール、プロパノール、２−メチルプロパノール、ブタノール、ペンタノール、２−メチルブタノール、３−メチルブタノール、ヘキサノール、ヘプタノール、オクタノール、２−エチルヘキサノール等があげられる。
本発明の製造法１におけるメチルケトンとアルコールのモル比は、特に限定されないが、１：０．０５〜１０であるのが好ましく、１：０．２〜２であるのがより好ましい。
【００１４】
本発明における触媒において、その担体としては、例えば、シリカ、シリカ−アルミナ、アルミナ、ケイソウ土、ゼオライト、ベントナイト、活性白土、酸性白土、ケイ酸マグネシウム、カオリン、酸化マグネシウム、シリカ−酸化マグネシウム、タルク等があげられるが、中でも、シリカ、シリカ−アルミナ、ケイソウ土、シリカ−酸化マグネシウムが好ましく、さらには、シリカ−酸化マグネシウムがより好ましく使用される。さらにシリカ−酸化マグネシウムの中でも、シリカと酸化マグネシウムの重量比が、８：２〜６：４のものがより好ましく使用される。
【００１５】
本発明における触媒において、ニッケルの含量が３０〜７０重量％であるものが好ましく使用される。
本発明における触媒は、通常は、市販品として入手することが可能であり、例えば、日揮化学製のＮ−１０１Ｆ、Ｎ−１０２Ｆ、Ｎ−１０３Ｆ、セラニーズ社製のｃｅｌＡｃｔｉｖｅ Ｎｉ５５／５、 ｃｅｌＡｃｔｉｖｅ Ｎｉ６０／１５、エンゲルハルド社製のＮｉ−３２８８、 Ｎｉ − ５２５６等があげられる。また、本発明における触媒は、公知の方法〔元素別触媒便覧（触媒工学講座10）、474〜482頁、地人書館、昭和４２年２月２５日発行 等〕等により調製することも可能である。
【００１６】
本発明における触媒は、前記にあげた市販品をそのまま使用してもよいが、予め、水素で還元した後に使用してもよい。この場合の還元条件は、使用する触媒によって異なるが、水素のガス空間速度ＧＨＳＶ［本発明における触媒（ｃｍ3）に対するガスの流速（ｃｍ3／時間）］は１０〜５００（／時間）であるのが好ましい。
【００１７】
本発明の製造法１における反応は、バッチ方式で行うことも可能であるが、本発明における触媒を固定床触媒として、連続的に反応を行うことも可能である。バッチ方式の場合の、本発明における触媒の使用量は、原料（メチルケトン＋アルコール）に対して５〜３０％であるのが好ましい。また、本発明における触媒を固定床触媒として、連続的に反応を行う場合には、本発明における触媒の使用量は特に限定されないが、原料（メチルケトン＋アルコール）の液空間速度ＬＨＳＶ［本発明における触媒（ｃｍ3）に対する原料液の流速（ｃｍ3／時間）］が０．１〜１０（／時間）であるのが好ましく、０．５〜４．０（／時間）であるのがより好ましい。
【００１８】
反応温度は、特には限定されないが、１００〜２００℃であるのが好ましい。
反応圧力は、０．１〜５ＭＰａであるのが好ましい。
また、反応は、通常、無溶媒で行うか、不活性な溶媒の存在下、行ってもよく、その不活性な溶媒の具体例としては、ジイソプロピルエーテル等のエーテル類、ヘプタン、オクタン等の脂肪族炭化水素、トルエン、キシレン等の芳香族炭化水素等があげられる。
【００１９】
また、反応は、前記以外の方法として回分式、半回分式等のいずれの方式でも行うことができる。
また、原料としてメチルケトンの一部をメチルケトンと対応する式（ＩＶ）
【００２０】
【化１１】
（式中、Ｒ2は前記と同義である）で表される２級アルコールに置きかえてもよく、この場合のメチルケトンと式（ＩＶ）で表される２級アルコールのモル比は、１：０．０１〜０．８であるのが好ましく、１：０．１〜０．４であるのがより好ましい。従って、本発明は、式（Ｉ）で表されるアルコールと、式（ＩＩ）で表されるメチルケトンと式（ＩＶ）で表される２級アルコールの混合液とを担体に担持されたニッケル触媒の存在下で反応させることを特徴とする式（ＩＩＩ）で表されるケトン類の製造法も提供する（この製造法を本発明の製造法２と表現することもある）。この場合、式（ＩＩ）で表されるメチルケトンがアセトンであり、式（ＩＶ）で表される２級アルコールがイソプロピルアルコールであるのが好ましい。本発明の製造法２における反応条件等は、前記で説明した本発明の製造法１の反応条件等と同様に設定することができる。
【００２２】
本発明の製造法１および２は、副生成物の生成が少ないという長所を有する。前記のようにして得られたケトン類を含む反応液は、触媒を濾過等により分離した後、蒸留等による精製に付すことができる。
本発明の製造法１または２により得られるケトン類は、溶剤、可塑剤等や工業用製品の原料等として有用である。
【００２３】
【実施例】
参考例１：触媒の前処理
５〜７メッシュに破砕したＮ−１０１Ｆ触媒〔日揮化学製：Ni（55.5%）、SiO2（12.0%）、MgO（5.2%）〕１００ｍｌを内径２．３ｃｍの金属製反応器に充填し、室温下で窒素をＧＨＳＶ＝１２で流し０．４ＭＰａに加圧し、さらにブタノールをＬＨＳＶ＝１．０で通液する。次に５０℃／時間で１２０℃まで昇温し、水素をＧＨＳＶ＝１２で流して、触媒還元を７０時間行った後、窒素を止め、水素のみで２．０ＭＰａまで昇圧し、１８０℃まで昇温して、さらに７０時間触媒還元を行った。この還元された触媒を実施例１〜６で使用した。
【００２４】
実施例１
参考例１で得られた触媒を反応器に入れ、窒素をＧＨＳＶ＝６０で流し２．０ＭＰａに加圧し、さらにアセトンとブタノールの混合液（モル比１：０．５）をＬＨＳＶ＝１．８で通液し、反応温度を１８０℃に昇温して反応を行った。反応生成物をガスクロマトグラフィーで分析した結果、ブタノールの転化率は４９％で、２−ヘプタノンの選択率は７３％であった。また、アセトンからの転化率は２３％で、２−ヘプタノンの選択率は７０％であった。ガスクロマトグラフィーの分析条件は以下の通りである（以下の実施例においても同様の条件でガスクロマトグラフィー分析を行った）。
（ガスクロマトグラフィー分析条件）
カラム：DB-5(ジェー・アンド・ダブリュ・サイエンティフィック社製）とHP-INNOWax（ヒューレット パッカード社製）を直列につないだ。
カラム温度：50℃で10分間保持後、6℃/分で110℃まで昇温後、同温度で10分間保持、さらに、10℃/分で220℃まで昇温後、同温度で９分間保持。
注入口：250℃
検出器：ＦＩＤ（水素炎イオン検出器）
【００２５】
実施例２
アセトンとブタノールのモル比を１：１、液空間速度ＬＨＳＶを１．０、反応温度を１６０℃とする以外は実施例１と同様に反応を行った。反応生成物を分析した結果、ブタノールの転化率は２３％で、２−ヘプタノンの選択率は７５％であった。また、アセトンからの転化率は２５％で、２−ヘプタノンの選択率は７０％であった。
【００２６】
実施例３
ブタノールの代わりにエタノールを用い、ＬＨＳＶ＝１．０、反応温度１６０℃とする以外は実施例１と同様に反応を行った。反応生成物を分析した結果、エタノールの転化率は２９％で、２−ペンタノンの選択率は７６％であった。また、アセトンからの転化率は１８％で、２−ペンタノンの選択率は７９％であった。
【００２７】
実施例４
ブタノールの代わりに２−エチルヘキサノールを用い、アセトンと２−エチルヘキサノールのモル比を１：０．３５とする以外は実施例１と同様に反応を行った。反応生成物を分析した結果、２−エチルヘキサノールの転化率は５１％で、５−エチル−２−ノナノンの選択率は６１％であった。また、アセトンからの転化率は２５％で、５−エチル−２−ノナノンの選択率は４２％であった。
【００２８】
実施例５
ブタノールの代わりに２−メチルプロパノールを用いる以外は実施例１と同様に反応を行った。反応生成物を分析した結果、２−メチルプロパノールの転化率は４３％で、５−メチル−２−ヘキサノンの選択率は６９％であった。また、アセトンからの転化率は２７％であり、５−メチル−２−ヘキサノンの選択率は５９％であった。
【００２９】
実施例６
アセトンの代わりにアセトンとイソプロパノールの混合液（モル比＝１：０．２）を用いる以外は実施例１と同様に反応を行った。反応生成物を分析した結果、ブタノールの転化率は４９％で、２−ヘプタノンの選択率は７３％であった。また、アセトンからの転化率は２３％で、２−ヘプタノンの選択率は７５％であった。
【００３０】
【発明の効果】
本発明によれば、アルコールとメチルケトンとを反応させてケトン類を製造する方法において、高温を必要としない工業的に有利なケトン類の製造法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing ketones by reacting alcohol and methyl ketone.
[0002]
[Prior art]
Ketones are useful as solvents, plasticizers, raw materials for industrial products, and the like. As a method for producing ketones, for example, a method for producing primary ketones and methyl ketones such as acetone in the presence of a catalyst is known.
For example, US Pat. No. 4,739,122 discloses 2-heptanone 5.9 to 18.3 by reacting acetone, isopropanol and butanol at a temperature of 216 to 254 ° C. in the presence of an alumina-supported copper catalyst. A method of manufacturing with a yield of% is disclosed.
[0003]
In addition, J.H. Org. Chem. , 7 , 189 (1942) describe a process for producing 2-heptanone by reacting acetone and butanol at 309 ° C. in the presence of a copper-zinc catalyst using alumina as a support.
However, any of the above methods requires a high temperature of 210 ° C. or higher during the reaction.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an industrially advantageous method for producing ketones which does not require high temperature in a method for producing ketones by reacting alcohol with methyl ketone.
[0005]
[Means for Solving the Problems]
The present invention relates to a compound of formula (I)
[0006]
[Chemical 8]
(Wherein R 1 represents alkyl) and the formula (II)
[0008]
[Chemical 9]
(Wherein R 2 represents alkyl) is reacted with methyl ketone represented by the formula (III) in the presence of a nickel catalyst supported on a carrier.
[0010]
[Chemical Formula 10]
(Wherein, R 1 and R 2 have the same meanings as described above), respectively, are provided (this production method may be expressed as Production Method 1 of the present invention).
Hereinafter, in the present specification, the alcohol represented by formula (I) is simply alcohol, the methyl ketone represented by formula (II) is simply methyl ketone, and the ketone represented by formula (III) is simply ketone. And a nickel catalyst supported on a carrier may be expressed as a catalyst in the present invention.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
In the definition of the groups of the formulas (I) to (III), alkyl includes straight-chain or branched C 1-20, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert- Examples thereof include butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosyl, etc. Among them, those having 1 to 8 carbon atoms are preferable. As the methyl ketone, acetone is preferable.
[0013]
Preferable specific examples of the alcohol as a raw material include, for example, ethanol, propanol, 2-methylpropanol, butanol, pentanol, 2-methylbutanol, 3-methylbutanol, hexanol, heptanol, octanol, 2-ethylhexanol and the like. It is done.
The molar ratio of methyl ketone and alcohol in production method 1 of the present invention is not particularly limited, but is preferably 1: 0.05 to 10 and more preferably 1: 0.2 to 2.
[0014]
In the catalyst of the present invention, examples of the carrier include silica, silica-alumina, alumina, diatomaceous earth, zeolite, bentonite, activated clay, acidic clay, magnesium silicate, kaolin, magnesium oxide, silica-magnesium oxide, talc and the like. Among them, silica, silica-alumina, diatomaceous earth, and silica-magnesium oxide are preferable, and silica-magnesium oxide is more preferably used. Furthermore, among silica-magnesium oxides, those having a weight ratio of silica to magnesium oxide of 8: 2 to 6: 4 are more preferably used.
[0015]
In the catalyst of the present invention, those having a nickel content of 30 to 70% by weight are preferably used.
The catalyst in the present invention can be usually obtained as a commercial product, for example, N-101F, N-102F, N-103F manufactured by JGC Chemical, celActive Ni55 / 5 manufactured by Celanese, celActive Ni60 / 15, Ni-3288 manufactured by Engelhard, Ni-5256, and the like. The catalyst in the present invention can also be prepared by a known method [catalyst manual for each element (Catalyst Engineering Course 10), pages 474 to 482, Jinjinshokan, issued on February 25, 1967, etc.]. is there.
[0016]
As the catalyst in the present invention, the above-mentioned commercial products may be used as they are, but they may be used after reducing with hydrogen in advance. The reduction conditions in this case vary depending on the catalyst used, but the hydrogen gas space velocity GHSV [gas flow rate (cm 3 / hour) relative to the catalyst (cm 3 ) in the present invention] is 10 to 500 (/ hour). Is preferred.
[0017]
The reaction in the production method 1 of the present invention can be performed in a batch system, but it is also possible to perform the reaction continuously using the catalyst in the present invention as a fixed bed catalyst. In the batch method, the amount of the catalyst used in the present invention is preferably 5 to 30% with respect to the raw material (methyl ketone + alcohol). In addition, when the catalyst in the present invention is used as a fixed bed catalyst and the reaction is continuously performed, the amount of the catalyst used in the present invention is not particularly limited, but the liquid space velocity LHSV of the raw material (methyl ketone + alcohol) [in the present invention] The flow rate of the raw material liquid (cm 3 / hour) relative to the catalyst (cm 3 )] is preferably 0.1 to 10 (/ hour), more preferably 0.5 to 4.0 (/ hour). .
[0018]
Although reaction temperature is not specifically limited, It is preferable that it is 100-200 degreeC.
The reaction pressure is preferably 0.1 to 5 MPa.
The reaction may be usually carried out without a solvent or in the presence of an inert solvent. Specific examples of the inert solvent include ethers such as diisopropyl ether, fats such as heptane and octane. Aromatic hydrocarbons such as aromatic hydrocarbons, toluene and xylene.
[0019]
The reaction can be carried out by any method other than the above, such as a batch method or a semi-batch method.
In addition, formula (IV) corresponding to methyl ketone as a part of methyl ketone as a raw material
[0020]
Embedded image
(Wherein R 2 has the same meaning as described above), and the molar ratio of methyl ketone to secondary alcohol represented by formula (IV) in this case is 1: 0. 0.01 to 0.8 is preferable, and 1: 0.1 to 0.4 is more preferable. Accordingly, the present invention provides a nickel catalyst in which an alcohol represented by the formula (I), a mixed liquid of methyl ketone represented by the formula (II) and a secondary alcohol represented by the formula (IV) is supported on a carrier. There is also provided a method for producing a ketone represented by the formula (III) characterized in that the reaction is carried out in the presence of (this production method may be expressed as production method 2 of the present invention). In this case, the methyl ketone represented by the formula (II) is preferably acetone, and the secondary alcohol represented by the formula (IV) is preferably isopropyl alcohol. The reaction conditions and the like in the production method 2 of the present invention can be set similarly to the reaction conditions and the like of the production method 1 of the present invention described above.
[0022]
The production methods 1 and 2 of the present invention have an advantage that there are few by-products. The reaction solution containing ketones obtained as described above can be subjected to purification by distillation or the like after the catalyst is separated by filtration or the like.
The ketones obtained by the production method 1 or 2 of the present invention are useful as solvents, plasticizers and the like, and raw materials for industrial products.
[0023]
【Example】
Reference Example 1: N-101F catalyst was crushed before treatment 5-7 mesh catalyst [Nikki Kagaku: Ni (55.5%), SiO 2 (12.0%), MgO (5.2%) ] 100ml of internal diameter 2.3cm A metal reactor is charged, nitrogen is flowed at GHSV = 12, pressurized to 0.4 MPa, and butanol is further passed at LHSV = 1.0 at room temperature. Next, the temperature was raised to 120 ° C. at 50 ° C./hour, hydrogen was allowed to flow at GHSV = 12, and catalytic reduction was performed for 70 hours. Then, nitrogen was stopped, the pressure was increased to 2.0 MPa only with hydrogen, and the temperature was raised to 180 ° C. The catalyst was reduced for an additional 70 hours. This reduced catalyst was used in Examples 1-6.
[0024]
Example 1
The catalyst obtained in Reference Example 1 was put into a reactor, nitrogen was flowed at GHSV = 60, and the pressure was increased to 2.0 MPa. Further, a mixed liquid of acetone and butanol (molar ratio 1: 0.5) was LHSV = 1.8. And the reaction temperature was raised to 180 ° C. to carry out the reaction. As a result of analyzing the reaction product by gas chromatography, the conversion of butanol was 49% and the selectivity for 2-heptanone was 73%. The conversion from acetone was 23%, and the selectivity for 2-heptanone was 70%. The analysis conditions of gas chromatography are as follows (gas chromatography analysis was performed under the same conditions in the following examples).
(Gas chromatography analysis conditions)
Column: DB-5 (manufactured by J & W Scientific) and HP-INNOWax (manufactured by Hewlett-Packard) were connected in series.
Column temperature: Hold at 50 ° C for 10 minutes, then heat up to 110 ° C at 6 ° C / minute, hold at the same temperature for 10 minutes, further heat up to 220 ° C at 10 ° C / minute, and hold at the same temperature for 9 minutes .
Inlet: 250 ° C
Detector: FID (hydrogen flame ion detector)
[0025]
Example 2
The reaction was performed in the same manner as in Example 1 except that the molar ratio of acetone to butanol was 1: 1, the liquid space velocity LHSV was 1.0, and the reaction temperature was 160 ° C. As a result of analyzing the reaction product, the conversion of butanol was 23% and the selectivity for 2-heptanone was 75%. The conversion from acetone was 25%, and the selectivity for 2-heptanone was 70%.
[0026]
Example 3
The reaction was performed in the same manner as in Example 1 except that ethanol was used in place of butanol, LHSV = 1.0, and the reaction temperature was 160 ° C. As a result of analyzing the reaction product, the conversion of ethanol was 29% and the selectivity for 2-pentanone was 76%. The conversion from acetone was 18%, and the selectivity for 2-pentanone was 79%.
[0027]
Example 4
The reaction was performed in the same manner as in Example 1 except that 2-ethylhexanol was used instead of butanol and the molar ratio of acetone to 2-ethylhexanol was 1: 0.35. As a result of analyzing the reaction product, the conversion rate of 2-ethylhexanol was 51% and the selectivity of 5-ethyl-2-nonanone was 61%. The conversion from acetone was 25%, and the selectivity for 5-ethyl-2-nonanone was 42%.
[0028]
Example 5
The reaction was performed in the same manner as in Example 1 except that 2-methylpropanol was used instead of butanol. As a result of analyzing the reaction product, the conversion of 2-methylpropanol was 43% and the selectivity of 5-methyl-2-hexanone was 69%. The conversion rate from acetone was 27%, and the selectivity for 5-methyl-2-hexanone was 59%.
[0029]
Example 6
The reaction was performed in the same manner as in Example 1 except that a mixed liquid of acetone and isopropanol (molar ratio = 1: 0.2) was used instead of acetone. As a result of analyzing the reaction product, the conversion of butanol was 49% and the selectivity for 2-heptanone was 73%. Moreover, the conversion from acetone was 23% and the selectivity of 2-heptanone was 75%.
[0030]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of industrially advantageous ketones which does not require high temperature in the method of making alcohol react with methyl ketone and manufacturing ketones is provided.
Claims (8)
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