JP3918640B2 - Process for producing aliphatic dicarboxylic acids - Google Patents

Description

【００２３】
実施例１１から１４
反応温度を４０℃〜８０℃の範囲で代えた以外は，実施例１と同様の反応をおこなった。
その結果を表２にまとめて示した。
【００２４】
【表２】

【００２５】
実施例１５〜２７
セリウム化合物およびコバルト化合物の使用量およびその使用割合を代えた以外は実施例１と同様の反応をおこなった。
その結果を表３にまとめて示した。
【００２６】
【表３】

【００２７】
実施例２８
シクロヘキサノンの酸化によるアジピン酸合成
シクロドデカノンの代わりに、シクロヘキサノンを使用し、実施例１に準じて液相酸化を行った。なお、反応条件は反応温度４０℃で５時間とした。
反応条件および反応結果を表４にまとめて示した。
なお、反応結果の分析は、実施例１に準じてガスクロマトグラフィーおよび液体クロマトグラフィーにて行った。
【００２８】
実施例２９
反応温度を室温とし、反応時間を７２時間で行った以外は実施例２８に準じて液相酸化を行った。反応条件および反応結果を表４に示した。
【００２９】
比較例５〜７
先行文献の追試として、セリウム化合物単独系、マンガン化合物とコバルト化合物の組み合わせ系、およびセリウム化合物とマンガン化合物の組み合わせ系の反応条件と反応結果を表４にまとめて示した。
【００３０】
【表４】

【００３１】
【発明の効果】
本発明により、シクロアルカノン化合物を分子状酸素で液相酸化して対応する脂肪族ジカルボン酸を製造する方法において、より安全に取り扱うことが可能な触媒系で、かつ高収率で、対応する脂肪族ジカルボン酸を製造することが可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an aliphatic dicarboxylic acid useful as a raw material for nylon or polyester.
[0002]
[Prior art]
Several methods are known for producing a corresponding aliphatic dicarboxylic acid by liquid-phase oxidation of a cycloalkanone compound with molecular oxygen.
Specifically, as a method for producing dodecanedicarboxylic acid, GB1164506 (1967) uses cobalt (II) acetate and manganese (II) acetate as catalysts, and dodecanedicarboxylic acid is obtained with a selectivity of 50 mol%. Is disclosed. As a by-product of this reaction, the production of undecanedicarboxylic acid, decanedicarboxylic acid, etc., which are short-chain dicarboxylic acids with a cleaved carbon chain, has been confirmed, and the deterioration of the quality of dodecanedicarboxylic acid due to them is a major problem. .
Also, WO 01/87815 uses manganese nitrate (II) and cobalt nitrate (II) as a catalyst, and cyclododecanone conversion is 98.6%, and dodecanedicarboxylic acid is obtained with a selectivity of 92.3 mol%. Has been reported. However, as a result of the additional test under the same conditions, the cyclododecanone conversion was 99.3%, but the selectivity for dodecanedicarboxylic acid was only 67.7 mol%, and the undecanedicarboxylic acid with the carbon chain cleaved. The acid was produced at a selectivity of 15.9 mol% and the decanedicarboxylic acid was produced at a selectivity of 4.1 mol%, and the results of the patent could not be confirmed.
Further, as a method for producing adipic acid, SU Patent Nos. 407876, 415038 and JP-A-51-29427 disclose a method for producing adipic acid by liquid phase oxidation of cyclohexanone using cerium compound or cerium compound and manganese compound as a catalyst. Is disclosed. However, the former Russian patent has a cyclohexanone conversion of 99% and adipic acid selectivity of 70 to 86 mol%, and the latter Japanese patent has a cyclohexanone conversion of 76% and adipic acid selectivity of 75 mol%.
Thus, it cannot be said that satisfactory results have been obtained with a conventional catalyst system using a combination of a cobalt compound and a manganese compound, or a combination of a cerium compound and a manganese compound.
Furthermore, manganese has a risk of causing manganese poisoning, and it is necessary to give due consideration to handling.
[0003]
[Problems to be solved by the invention]
The present invention relates to a method for producing a corresponding aliphatic dicarboxylic acid by oxidizing a cycloalkanone compound with molecular oxygen in a liquid phase, which can be handled more safely and in a high yield. It is an object of the present invention to provide a method for producing a group dicarboxylic acid.
[0004]
[Means for Solving the Invention]
As a result of intensive studies on the above problems, the present inventors have found that if a cycloalkanone compound is catalytically oxidized with molecular oxygen in a liquid phase in which a cerium compound and a cobalt compound coexist as a catalyst, a short reaction occurs. The present inventors have found that the production amount of chain dicarboxylic acids can be greatly reduced and the selectivity of the intended aliphatic dicarboxylic acid can be improved, and the present invention has been achieved.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The cycloalkanone compound used in the present invention is preferably an alicyclic compound having 6 to 12 carbon atoms, and may have 0 to 2 carbon-carbon double bonds.
Specific examples include cyclohexanone, cyclohexenone, cyclooctanone, cyclooctenone, cyclodecanone, cyclodecenone, cyclododecanone, cyclododecenone, and cyclododecadienone.
Preferred are cyclohexanone, cyclooctanone, cyclodecanone and cyclododecanone, and more preferred are cyclohexanone and cyclododecanone.
The corresponding aliphatic dicarboxylic acids obtained in the present invention include adipic acid, hexene dicarboxylic acid, octane dicarboxylic acid, octene dicarboxylic acid, decanedicarboxylic acid, decenedicarboxylic acid, dodecanedicarboxylic acid, dodecenedicarboxylic acid, dodecadiene dicarboxylic acid Is mentioned.
[0006]
The molecular oxygen used in the present invention is pure oxygen, air, or oxygen diluted with a gas inert to the reaction such as nitrogen. The oxygen partial pressure is preferably 1 to 100% with respect to the total pressure, and the reaction pressure is not particularly limited, but is preferably 0.1 to 20 kg / cm ² . Usually, the operation under atmospheric pressure is preferable.
As a method for introducing molecular oxygen, an oxygen-containing gas may be bubbled in the reaction system or may be used as a reaction atmosphere.
[0007]
The reaction solvent used in the present invention is not particularly limited as long as it is a compound that is stable against oxygen oxidation, but is preferably an organic carboxylic acid having 1 to 12 carbon atoms, more preferably an aliphatic carboxylic acid having 2 to 4 carbon atoms. It is an acid.
Specific examples include acetic acid, propionic acid and butyric acid.
The usage-amount of a solvent is 1-100 weight times with respect to the cycloalkanone compound which is a substrate, Preferably it is 2-30 weight times, More preferably, it is 5-20 weight times.
[0008]
Examples of the cerium compound used in the present invention include cerium trivalent or tetravalent halides, nitrates, sulfates, carbonates, perchlorates, and organic carboxylates. Nitrate and halide salts are preferred, and nitrates are more preferred.
Specifically, cerium (III) nitrate, cerium ammonium nitrate (IV), cerium acetate (IV), acetylacetone cerium (III), cerium bromide (III), cerium carbonate (III), cerium chloride (III), fluoride Cerium (III), Cerium hydroxide (IV), Cerium iodide (III), Cerium oxalate (III), Cerium perchlorate (III), Cerium phosphate (III), Cerium stearate (III), Cerium sulfate ( III), cerium trifluoroacetate (III) and the like. There is no problem even if these are used as hydrates.
Although there is no restriction | limiting in particular as the usage-amount of a catalyst, Preferably it is 0.01-30 mol% with respect to the cycloalkanone compound which is a substrate, More preferably, it is 1-10 mol%.
Although there is no restriction | limiting in particular also about the catalyst density | concentration in a solvent, Preferably it is 0.004-15 wt%, More preferably, it is 0.4-5 wt%. If the catalyst concentration is too high, side reactions may proceed, and if it is too low, the reactivity decreases.
[0009]
Examples of the cobalt compound used in the present invention include cobalt divalent or trivalent halide salts, nitrates, sulfates, carbonates, perchlorates, and organic carboxylates. Nitrate and halide salts are preferred, and nitrates are more preferred.
Specifically, cobalt nitrate (II), cobalt acetate (II), acetylacetone cobalt (II), acetylacetone cobalt (III), cobalt bromide (II), cobalt carbonate (II), cobalt chloride (II), citric acid Cobalt (II), cobalt fluoride (II), hexafluoroacetylacetone cobalt (III), cobalt hydroxide (II), cobalt iodide (II), cobalt naphthenate (II), cobalt perchlorate (II), phosphoric acid Cobalt (II), cobalt phthalocyanine (II), cobalt (II) stearate, cobalt (II) sulfate, cobalt (II) sulfide, cobalt (II) thiocyanate, cobalt (II) tungstate, hexaammonium cobalt chloride (III) ) And the like. There is no problem even if these are used as hydrates.
Although there is no restriction | limiting in particular as the usage-amount of a catalyst, Preferably it is 0.0005-15 mol% with respect to the cycloalkanone compound which is a substrate, Most preferably, it is 0.005-5 mol%.
The catalyst concentration in the solvent is not particularly limited, but is preferably 0.00015 to 4.5 wt%, more preferably 0.0015 to 1.5 wt%.
[0010]
Although there is no restriction | limiting in particular about the usage-amount of cerium and cobalt, if both are not made to coexist, the target oxidation reaction will not advance. The proportion of cobalt used with respect to cerium is preferably 0.05 to 500 mol%.
[0011]
Further, in the present invention, nitric acid may be added as an additive, and the amount thereof is 20 mol% or less, preferably 0.1 to 15 mol%, more preferably 1 to 10 mol, based on the substrate cyclododecanone. %.
[0012]
Although there is no restriction | limiting in particular as reaction temperature of this invention, Preferably it is 20-100 degreeC, More preferably, it is 40-70 degreeC. If the reaction temperature is too low, the reaction rate is significantly reduced. On the other hand, if the reaction temperature is too high, the selectivity of the aliphatic dicarboxylic acid is greatly lowered, which is not preferable.
[0013]
The aliphatic dicarboxylic acid obtained in the present invention is purified and separated by recrystallization or the like, and is used, for example, as a raw material for nylon or polyester.
[0014]
【Example】
The present invention will be specifically described below with reference to examples and comparative examples.
[0015]
Example 1
Synthesis of dodecanedicarboxylic acid by oxidation of cyclododecanone Cyclododecanone (4.57 g, 25 mmol), cerium nitrate hexahydrate (0.22 g, 0.5 mmol) and nitric acid were added to a three-necked flask (50 ml) equipped with a condenser tube. Cobalt hexahydrate (0.15 g, 0.5 mmol) was weighed, acetic acid (25 ml) was added, and oxygen was introduced into the reaction system by an oxygen balloon (5 L). Next, the reaction vessel was transferred to an oil bath (60 ° C.) and stirred for 5 hours (1400 rpm). When the reaction solution is cooled to room temperature, crystals of dodecanedicarboxylic acid are precipitated. Therefore, a part of the reaction solution was taken out from the reaction mixture and the reaction product was analyzed by gas chromatography and high performance liquid chromatography. The conversion of cyclododecanone was 99.2%, the selectivity for the target compound dodecanedicarboxylic acid was 74.8 mol%, the selectivity for undecanedicarboxylic acid was 9.7 mol%, and a trace amount of decanedicarboxylic acid was obtained. It was.
[GC condition]
Analysis method: Internal standard method (dodecanedicarboxylic acid diethyl ester was used as an internal standard)
GC: Shimadzu GC-14A
Column: G-column, G-250 (40 mx 1.2 mm, df 1.0 μm)
Inlet temperature: 280 ° C
Detector temperature: 280 ° C
Column temperature: 100 ° C. → 10 ° C./min→240° C./16 min The respective retention times under the above analysis conditions are as follows.
Dodecane dicarboxylic acid diethyl ester (internal standard, 25.2 minutes), cyclododecanone (17.2 minutes).
[HPLC conditions]
Analytical method: Internal standard method (using tetradecanedicarboxylic acid as internal standard)
GC: Shimadzu LC-10
Column: Tosoh ODS-80TS
(4.6 mm (ID) x 250 mm (L))
Eluent: Water: Acetonitrile: Tetrahydrofuran = 2: 1: 1
Potassium dihydrogen phosphate 15 mmol / L,
Trifluoroacetic acid 10mmol / L
Flow rate: 0.8ml / min
Column temperature: 40 ° C
Detector: UV detection (λ = 220 nm)
Each retention time under the above analysis conditions is as follows.
Decanedicarboxylic acid (5.7 minutes), undecanedicarboxylic acid (6.7 minutes),
Dodecanedicarboxylic acid (8.0 min),
Tetradecanedicarboxylic acid (internal standard, 12.7 minutes).
[0016]
Comparative Example 1
The reaction was carried out in the same manner as in Example 1 using only cerium nitrate hexahydrate (0.22 g, 0.5 mmol) as a catalyst. As a result, the conversion of cyclododecanone was 3.4%, and the target compound dodecanedicarboxylic acid was not obtained.
[0017]
Comparative Example 2
The reaction was carried out in the same manner as in Example 1 using only cobalt nitrate hexahydrate (0.15 g, 0.5 mmol) as a catalyst. As a result, the conversion of cyclododecanone was 1% or less, and the target compound dodecanedicarboxylic acid was not obtained.
[0018]
Comparative Example 3
The reaction was carried out in the same manner as in Example 1 using cerium nitrate hexahydrate (0.22 g, 0.5 mmol) and manganese nitrate hexahydrate (0.14 g, 0.5 mmol) as catalysts. As a result, the conversion of cyclododecanone was 98.1%, the selectivity of the target compound dodecanedicarboxylic acid was 63.2 mol%, the selectivity of other undecanedicarboxylic acid was 15.5 mol%, and the selectivity of decanedicarboxylic acid was 4. A result of 0 mol% was obtained.
[0019]
Comparative Example 4 (WO01 / 87815 supplementary test)
Manganese nitrate hexahydrate (0.14 g, 0.5 mmol), cobalt nitrate hexahydrate (0.15 g, 0.5 mmol) and nitric acid (0.11 mL, 1.5 mmol) were used as catalysts. The reaction was carried out in the same manner as in Example 1. As a result, the conversion of cyclododecanone was 99.3%, the selectivity of the target compound dodecanedicarboxylic acid was 67.7 mol%, the selectivity of other undecanedicarboxylic acid was 15.9 mol%, and the selectivity of decanedicarboxylic acid was 4. A result of 1 mol% was obtained.
[0020]
The results of Example 1 and Comparative Examples 1 to 4 are summarized in Table 1.
[0021]
Examples 2-10
Furthermore, the reaction similar to Example 1 was performed except having changed the combination of the cerium compound and the cobalt compound as shown in Table 1.
The results are also shown in Table 1.
[0022]
[Table 1]

[0023]
Examples 11 to 14
The same reaction as in Example 1 was performed except that the reaction temperature was changed in the range of 40 ° C to 80 ° C.
The results are summarized in Table 2.
[0024]
[Table 2]

[0025]
Examples 15-27
The same reaction as in Example 1 was carried out except that the amount of cerium compound and cobalt compound used and the proportion of the compound used were changed.
The results are summarized in Table 3.
[0026]
[Table 3]

[0027]
Example 28
Synthesis of adipic acid by oxidation of cyclohexanone Instead of cyclododecanone, cyclohexanone was used, and liquid phase oxidation was performed according to Example 1. The reaction conditions were a reaction temperature of 40 ° C. and 5 hours.
The reaction conditions and reaction results are summarized in Table 4.
The reaction results were analyzed by gas chromatography and liquid chromatography according to Example 1.
[0028]
Example 29
Liquid phase oxidation was performed according to Example 28 except that the reaction temperature was room temperature and the reaction time was 72 hours. The reaction conditions and reaction results are shown in Table 4.
[0029]
Comparative Examples 5-7
Table 4 summarizes the reaction conditions and results of a cerium compound single system, a combination system of a manganese compound and a cobalt compound, and a combination system of a cerium compound and a manganese compound.
[0030]
[Table 4]

[0031]
【The invention's effect】
According to the present invention, in a method for producing a corresponding aliphatic dicarboxylic acid by liquid phase oxidation of a cycloalkanone compound with molecular oxygen, a catalyst system that can be handled more safely and in a high yield can be obtained. It became possible to produce aliphatic dicarboxylic acids.

Claims (4)

A process for producing a corresponding aliphatic dicarboxylic acid by contacting a cycloalkanone compound and molecular oxygen in a liquid phase, wherein an oxidation reaction is performed in the presence of a cerium compound and a cobalt compound. Acid production method. The process for producing an aliphatic dicarboxylic acid according to claim 1, wherein the cycloalkanone compound is cyclohexanone or cyclododecanone. 2. The process for producing an aliphatic dicarboxylic acid according to claim 1, wherein at least one of the catalyst components selected from a cerium compound and a cobalt compound is a nitrate. The process for producing an aliphatic dicarboxylic acid according to claim 1, wherein nitric acid is added to the reaction system.