JPS6059890B2 - Production method of isobutyric acid - Google Patents
Production method of isobutyric acidInfo
- Publication number
- JPS6059890B2 JPS6059890B2 JP53085834A JP8583478A JPS6059890B2 JP S6059890 B2 JPS6059890 B2 JP S6059890B2 JP 53085834 A JP53085834 A JP 53085834A JP 8583478 A JP8583478 A JP 8583478A JP S6059890 B2 JPS6059890 B2 JP S6059890B2
- Authority
- JP
- Japan
- Prior art keywords
- isobutyric acid
- alkali metal
- reaction
- isobutyraldehyde
- producing
- 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
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
Description
【発明の詳細な説明】 本発明は、イソ醋酸の製造法に関するものである。[Detailed description of the invention] The present invention relates to a method for producing isoacetic acid.
更に詳しくは、本発明は、イソブチルアルデヒドを分
子状酸素含有ガスで酸化してイソ醋酸を製造する方法に
関するものてある。More specifically, the present invention relates to a method for producing isoacetic acid by oxidizing isobutyraldehyde with a molecular oxygen-containing gas.
イソ酩酊は、食品添加物あるいはメタクリル酸、メタ
クリル酸メチルの製造原料として有用な化合物である。Iso-drunkenness is a compound useful as a food additive or a raw material for the production of methacrylic acid and methyl methacrylate.
このイソ醋酸の製造法として、イソブチルアルデヒド
を触媒の存在下で分子状酸素を用いて酸化する方法が知
られている。例えば、ジャーナルオブ ジ オーガニッ
ク ケミストリー ２６巻５６５（１９６ハ、英国特許
第８２４１１６号明細書、特公昭５２−３９川■号公報
にこの方法が記載されている。 しカルながら、これら
の方法は、イソ醋酸の選択率、イソブチルアルデヒドの
転化率、副生物（アセトン（以下、ＡＴと略称する。）
、過酸化物（以下、Ｐｏと略称する。）、イソプロピル
アルコール（以下、ＩＰＡと略称する。）等）の生成量
に於て、十分なものではなかつた。 本発明者等は、こ
れらの点に鑑み鋭意研究を行つた結果、本発明に到達し
た。As a method for producing this isoacetic acid, a method is known in which isobutyraldehyde is oxidized using molecular oxygen in the presence of a catalyst. For example, this method is described in Journal of the Organic Chemistry Vol. Selectivity of acetic acid, conversion rate of isobutyraldehyde, by-product (acetone (hereinafter abbreviated as AT))
, peroxide (hereinafter abbreviated as Po), isopropyl alcohol (hereinafter abbreviated as IPA), etc.) were not sufficient. The present inventors conducted extensive research in view of these points, and as a result, arrived at the present invention.
即ち、本発明は、アルカリ金属化合物の存在下、イソブ
チルアルデヒドを液相で分子状酸素又は分子状酸素含有
ガスで連続的に酸化してイソ酪酸を製造するに際し、仕
込イソブチルアルデヒドに対する仕込酸素のモル比を０
．５以上とすることを特徴とするイソ酪酸の製造法に存
する。That is, in the present invention, when producing isobutyric acid by continuously oxidizing isobutyraldehyde in the liquid phase with molecular oxygen or molecular oxygen-containing gas in the presence of an alkali metal compound, the molar ratio of the charged oxygen to the charged isobutyraldehyde is ratio to 0
．． 5 or more.
次に本発明を更に詳細に説明する。Next, the present invention will be explained in more detail.
反応系に存在させるアルカリ金属化合物としては、カリ
ウム、ナトリウム等のアルカリ金属の塩特にイソ酪酸の
アルカリ金属塩、具体的にはイソ酪酸カリウム、イソ酪
酸ナトリウムが挙げられる。アルカリ金属化合物の存在
量は反応液に対し、０．０１〜１ｍ０１１ｅ好ましくは
０．０５〜０．５ｍ０１Ｉ′である。Examples of the alkali metal compound to be present in the reaction system include salts of alkali metals such as potassium and sodium, particularly alkali metal salts of isobutyric acid, specifically potassium isobutyrate and sodium isobutyrate. The amount of the alkali metal compound present is 0.01 to 1 m01e, preferably 0.05 to 0.5 m01I', based on the reaction solution.
これらのアルカリ金属化合物は、アルカリ金属の炭酸塩
や水酸化物を反応系に添加することにより存在させるこ
とができる。These alkali metal compounds can be made to exist by adding an alkali metal carbonate or hydroxide to the reaction system.
イソブチルアルデヒドの酸化に使用される分子状酸素含
有ガスとしては、通常、Ｎ２ガスのような不活性ガスで
希釈した、酸素含有量５％以上のものが用いられる。The molecular oxygen-containing gas used to oxidize isobutyraldehyde is usually a gas containing 5% or more of oxygen and diluted with an inert gas such as N2 gas.
反応温度は５０〜７０℃好ましくは５５〜６５゜Ｃ反応
圧力は常圧〜１０ｋ９１ｃＩｔＧ好ましくは３〜８ｋ９
１ｄＧてある。The reaction temperature is 50 to 70°C, preferably 55 to 65°C, and the reaction pressure is normal pressure to 10k91cItG, preferably 3 to 8k9
There is 1dG.
平均滞留時間は、１〜１時間好ましくは２〜８時間であ
る。The average residence time is 1 to 1 hour, preferably 2 to 8 hours.
酸化反応器としては、攪拌機付槽型反応器や気泡塔など
が用いられる。As the oxidation reactor, a tank reactor with a stirrer, a bubble column, etc. are used.
本願発明では、仕込イソブチルアルデヒドに対．する仕
込酸素のモル比を０．５以上、好ましくは０．５Ｇ上と
することを必須要件とする。In the present invention, for the charged isobutyraldehyde. It is an essential requirement that the molar ratio of the charged oxygen be 0.5 or more, preferably 0.5G or more.
イソブチルアルデヒドの酸化のような液相酸化反応ては
、転化率の低い場合には酸素吸収速度が律速になるほど
反応速度は速い。In a liquid phase oxidation reaction such as the oxidation of isobutyraldehyde, when the conversion rate is low, the reaction rate is so fast that the oxygen absorption rate becomes rate limiting.
反応が進むと反こ応速度は極端に遅くなるので転化率を
１００％近くにするには、温度を上げたり、滞留時間を
長くする等反応条件を厳しくしないと反応が進まない。
よつて、反応器を２種用い反応条件を変えて前段で反応
の速い部分、後段で反応の遅い部分を反ｔ応させること
が経済的に有利である。速い部分で、イソブチルアルデ
ヒドを９０〜９５％転化させるが、この場合の仕込イソ
ブチルアルデヒドに対する仕込０２のモル比は化学量論
的には、０．４５〜０．４７５である。As the reaction progresses, the reaction rate becomes extremely slow, so in order to achieve a conversion rate of nearly 100%, the reaction will not proceed unless the reaction conditions are made stricter, such as by raising the temperature or lengthening the residence time.
Therefore, it is economically advantageous to use two types of reactors and change the reaction conditions so that the fast-reacting part is reacted in the first stage and the slow-reacting part is reacted in the latter stage. In the fast section, the isobutyraldehyde is converted to 90-95%, where the molar ratio of charge 02 to charge isobutyraldehyde is stoichiometrically 0.45-0.475.
また、気相部の爆発を防止するには酸素はできるだけ少
なく仕込み、出口ガスの０２濃度をできるだけ低くする
必要がある。Furthermore, in order to prevent an explosion in the gas phase, it is necessary to charge as little oxygen as possible and to lower the 02 concentration of the outlet gas as much as possible.
よつて、これらの点を考慮すると仕込イソブチルアルデ
ヒドに対する仕込酸素のモル比を０．５以下で反応させ
るとよいだろうことが予測される。Therefore, in consideration of these points, it is predicted that the reaction should be carried out at a molar ratio of charged oxygen to charged isobutyraldehyde of 0.5 or less.
然しながら、０．５より低いと、副生物の量が多く、イ
ソブチルアルデヒドの転化率、イソ酪酸の）選択率が低
下し経済的に不利である。該モル比が余り大きくなると
爆発の危険性が生じるし、またコスト面からの制約もあ
るので、反応器廃ガスの酸素濃度が爆発範囲外となるよ
う調整することが好ましい。However, if it is lower than 0.5, the amount of by-products will be large and the conversion rate of isobutyraldehyde and selectivity (of isobutyric acid) will decrease, which is economically disadvantageous. If the molar ratio becomes too large, there will be a risk of explosion, and there will also be cost constraints, so it is preferable to adjust the oxygen concentration of the reactor waste gas so that it is outside the explosive range.
反応器廃ガスの酸素濃度は１容量％以上、好ましくは３
〜８容量％である。The oxygen concentration of the reactor waste gas is 1% by volume or more, preferably 3% by volume.
~8% by volume.
また、反応系の水分量は、反応器出口の反応液中の水分
が２．５重量％、特に２．鍾量％以下とするのが好まし
い。The water content of the reaction system is 2.5% by weight, especially 2.5% by weight in the reaction liquid at the outlet of the reactor. It is preferable that the amount is less than 1%.
本発明によれば、反応速度が大きいにもかかわらず、副
生物量を低く押えることができ、原料イソブチルアルデ
ヒドからイソ酪酸を高選択率、高収率で得ることができ
る。According to the present invention, although the reaction rate is high, the amount of byproducts can be kept low, and isobutyric acid can be obtained from raw material isobutyraldehyde with high selectivity and high yield.
以下、実施例に従つて、本発明を具体的に説明するが、
本発明はその要旨を超えない限り、以下の実施例に限定
されない。The present invention will be specifically explained below with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例１
容量３００ｍｔ（：１）攪拌機を備えたジャケット付き
反応器に０．１ｍ０１１ｅのカリウムを含むイソ酪酸（
以下１ＢＡｃと略称する。Example 1 Isobutyric acid containing 0.1 m011e of potassium in a jacketed reactor equipped with a capacity 300 mt (:1) stirrer
Hereinafter, it will be abbreviated as 1BAc.
）を２５０ｍｔ仕込み、６０℃まて昇温した。これに下
記組成の液を１００ｃｃ′Ｈｒ．（滞留時間：３時間）
、空気を５６．２Ｎｅ１ｈｒ．（仕込み時の０２／Ｎ３
Ｄモル比：０．５４）て供給し、５ｋ９１ｃＩｔＧ加圧
下連続反応を行つた。) was charged and the temperature was raised to 60°C. Add a solution of the following composition to this for 100cc'Hr. (Residence time: 3 hours)
, air at 56.2 Ne1hr. (02/N3 during preparation
D molar ratio: 0.54) was supplied, and continuous reaction was carried out under pressure with 5k91cItG.
イソブチノげルデヒド（以下１ＢＤと略称ｊこ″）″″
反応器から抜き出した反応混合物は、コンデンサーを通
した後、気液分離した。Isobutynol geldehyde (hereinafter abbreviated as 1BD)''
The reaction mixture taken out from the reactor was passed through a condenser and then separated into gas and liquid.
反応液及び、ガスはそれぞれガスクロマトグラフィーに
よりその組成を測定した。ＡＴ，．ＰＯ．．ＩＰＡの選
択率仕込ＩＢＤ（７）ＩＢＡｃへの選択率及びＩＢＤ転
化率を下記表一１に示す。実施例２
空気の供給量を６９．９Ｎ′１ｈｒ．（仕込み時の０２
／１ＢＤモル比：０．６７）とした以外は実施例１と同
様にして反応を行なつた。The compositions of the reaction solution and gas were each measured by gas chromatography. AT,. P.O. ．． Selectivity of IPA to IBD (7) IBAc and IBD conversion rate are shown in Table 1 below. Example 2 Air supply amount was set to 69.9N'1hr. (02 at the time of preparation)
/1BD molar ratio: 0.67) The reaction was carried out in the same manner as in Example 1.
得られた反応混合物中のＡＴ．．ＰＯ．．ＩＰＡの選択
率、仕込１ＢＤ（７）ＩＢＡｃへの選択率及びＩＢＤ転
化率を下記表−１に示す。実施例３供給液中の水分濃度
を３．６鍾量％、空気の供給量を６１．７ＮｅＩｈｒ．
とした以外は実施例１と同様にして反応を行なつた。AT. ．． P.O. ．． The selectivity of IPA, the selectivity to charge 1BD (7) IBAc, and the IBD conversion rate are shown in Table 1 below. Example 3 The water concentration in the feed liquid was 3.6%, and the air supply amount was 61.7 NeIhr.
The reaction was carried out in the same manner as in Example 1 except for the following.
８実施例４
原料組成液を１８６ｃｃ′Ｈｒ．（滞留時間：１．６時
間）、空気を２０３．２Ｎｅ１ｈｒ．で供給した以外は
実施例１と同様にして反応を行なつた。8 Example 4 The raw material composition liquid was heated to 186 cc'Hr. (residence time: 1.6 hours), air was pumped at 203.2 Ne1hr. The reaction was carried out in the same manner as in Example 1, except that the solution was supplied as follows.
実施例５
空気の供給量を５５．６ＮｆＩｈｒ．とした以外は実施
例１と同様にして反応を行なつた。Example 5 The air supply amount was set to 55.6NfIhr. The reaction was carried out in the same manner as in Example 1 except for the following.
比較例１
空気の量を５４．９Ｎｆ１ｈｒ．（仕込時の０２／ＩＢ
Ｄモリレ比：０．４７）とした以外は実施例１と同様に
して反応を行なつた。Comparative Example 1 The amount of air was 54.9Nf1hr. (02/IB during preparation
The reaction was carried out in the same manner as in Example 1 except that the D-Morille ratio was 0.47).
Claims (1)
デヒドを液相で分子状酸素又は分子状酸素含有ガスで連
続的に酸化してイソ酪酸を製造するに際し、仕込イソブ
チルアルデヒドに対する仕込酸素のモル比を０．５以上
とすることを特徴とするイソ酪酸の製造法。 ２ アルカリ金属含有化合物がアルカリ金属塩であるこ
とを特徴とする特許請求の範囲第１項記載のイソ酪酸の
製造法。 ３ アルカリ金属含有化合物がイソ酪酸のアルカリ金属
塩であることを特徴とする特許請求の範囲第１項又は第
２項記載のイソ酪酸の製造法。 ４ アルカリ金属含有化合物がカリウム又はナトリウム
含有化合物であることを特徴とする特許請求の範囲第１
ないし３項のいずれかに記載のイソ酪酸の製造法。 ５ アルカリ金属含有化合物がイソ酪酸カリウム又はイ
ソ酪酸ナトリウムであることを特徴とする特許請求の範
囲第３項記載の方法。 ６ 分子状酸素含有ガスが空気であることを特徴とする
特許請求の範囲第１ないし３項のいずれかに記載のイソ
酪酸の製造法。 ７ 仕込イソブチルアルデヒドに対する仕込酸素のモル
比を０．５４以上とすることを特徴とする特許請求の範
囲第１ないし６項のいずれかに記載のイソ酪酸の製造法
。 ８ 酸化反応が連続的に行われることを特徴とする特許
請求の範囲第１ないし７項のいずれかに記載のイソ酪酸
の製造法。[Claims] 1. When producing isobutyric acid by continuously oxidizing isobutyraldehyde in the liquid phase with molecular oxygen or molecular oxygen-containing gas in the presence of an alkali metal-containing compound, A method for producing isobutyric acid, characterized in that the molar ratio of isobutyric acid is 0.5 or more. 2. The method for producing isobutyric acid according to claim 1, wherein the alkali metal-containing compound is an alkali metal salt. 3. The method for producing isobutyric acid according to claim 1 or 2, wherein the alkali metal-containing compound is an alkali metal salt of isobutyric acid. 4. Claim 1, characterized in that the alkali metal-containing compound is a potassium- or sodium-containing compound.
The method for producing isobutyric acid according to any one of items 3 to 3. 5. The method according to claim 3, wherein the alkali metal-containing compound is potassium isobutyrate or sodium isobutyrate. 6. The method for producing isobutyric acid according to any one of claims 1 to 3, wherein the molecular oxygen-containing gas is air. 7. The method for producing isobutyric acid according to any one of claims 1 to 6, characterized in that the molar ratio of charged oxygen to charged isobutyraldehyde is 0.54 or more. 8. The method for producing isobutyric acid according to any one of claims 1 to 7, characterized in that the oxidation reaction is carried out continuously.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53085834A JPS6059890B2 (en) | 1978-07-14 | 1978-07-14 | Production method of isobutyric acid |
| US06/052,590 US4350829A (en) | 1978-07-14 | 1979-06-27 | Process for preparing isobutyric acid |
| DE19792928002 DE2928002A1 (en) | 1978-07-14 | 1979-07-11 | METHOD FOR PRODUCING ISOBUTTERIC ACID |
| CS487879A CS210694B2 (en) | 1978-07-14 | 1979-07-12 | Method of isobutyric acid preparation |
| FR7918299A FR2430929A1 (en) | 1978-07-14 | 1979-07-13 | PROCESS FOR PREPARING ISOBUTYRIC ACID |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53085834A JPS6059890B2 (en) | 1978-07-14 | 1978-07-14 | Production method of isobutyric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5513223A JPS5513223A (en) | 1980-01-30 |
| JPS6059890B2 true JPS6059890B2 (en) | 1985-12-27 |
Family
ID=13869876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53085834A Expired JPS6059890B2 (en) | 1978-07-14 | 1978-07-14 | Production method of isobutyric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6059890B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100843594B1 (en) * | 2005-09-07 | 2008-07-03 | 주식회사 엘지화학 | Preparation of organic acids from aldehyde compounds by means of liquid phase oxidation reaction |
| CA2861524A1 (en) * | 2013-09-16 | 2014-11-03 | Armstrong World Industries, Inc. | Methods for preparing methacrylic acid from biobased starting materials |
| CN113185395B (en) * | 2021-04-09 | 2022-12-23 | 润泰新材料股份有限公司 | Process for the production of isobutyric acid |
-
1978
- 1978-07-14 JP JP53085834A patent/JPS6059890B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5513223A (en) | 1980-01-30 |
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