JPS6130545A - Hydrogenation of unsaturated carbonyl compound - Google Patents

Abstract

PURPOSE:To produce the titled compound easily, in high purity, by the liqid- phase hydrogenation of an unsaturated carbonyl compound in the presence of a catalyst containing specific amounts of palladium and an alkali metal as active components of the catalyst. CONSTITUTION:The objective compound is produced by the liquid-phase hydrogenation of an unsaturated carboxyl compound at 40-200 deg.C under atmospheric pressure -50kg/cm<2> in the presence of a catalyst containing palladium and an alkali metal supported on a carrier and having alkali metal/palladium atomic ratio of 0.7-3.5, especially 1.0-2.0 determined by X-ray photo-electron spectrometry at the surface of the catayst. The catalyst can be prepared e.g. by supporting a soluble palladium salt, e.g. palladium chloride, etc. as a palladium component on a carrier, reducing the supported palladium compound to obtain a palladium-supported catalyst, and then applying an alkali metal salt, etc. as the alkali metal component from a solution to the palladium catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for selectively obtaining a saturated carbonyl compound by hydrogenating an unsaturated carbonyl compound.

[Conventional technology]

This is a reaction that hydrogenates carbon-carbon multiple bonds in olefins, acetylene compounds, etc. and converts them into compounds with a low degree of unsaturation.This reaction is also important from an industrial perspective, and numerous studies have been conducted to date. Many metals, oxides, sulfides, etc. have been proposed as effective catalysts for this group of reactions, and noble metal catalysts such as platinum, rhodium, palladium, ruthenium, nickel, cobalt, copper, etc. are used as main active ingredients. The catalyst system it contains has extremely high activity and is widely used. In addition to carbon-carbon multiple bonds, compounds that have a return element-oxygen unsaturated bond, especially a carbonyl group, in one molecule (aldehydes, ketones, etc., are selectively hydrogenated only on the carbon-carbon unsaturated bonds to form saturated carbonyl groups. It is well known that palladium is particularly effective among the above-mentioned active ingredients when producing compounds.

For example, various noble metal catalysts (
platinum, ruthenium and palladium) in equal amounts of t-methyl-3-pentene-! The results of measuring the hydrogen absorption rate with -one and one methyl-λ-pentanone show the selectivity characteristics of palladium for the hydrogenation of carbon-carbon unsaturated bonds, as shown in Table 1.

Table: Hydrogen absorption by noble metal catalyst IIY, rate (liquid phase suspended bed, normal pressure, temperature 0°C) Also, the low hydrogenation ability of palladium for carbonyl bonds was also reported by Tanaka et al. It has been reported (B
ull.

Ohem, Sac, Japan sr, , 227
j (/FJj)).

Furthermore, [Practical Catalysts by Reaction] (published by Kagaku Kogyosha, many wI'o
] Supervised by Kimio, Showa Guj)/ffg page contains 5%Pd/
When tei-methyl-copentanone is hydrogenated in various solvents at room temperature and pressure using an activated carbon catalyst, water, methanol, methyl acetate and 0.3 N He! It is described that the reaction does not proceed in 4, but hydrogenation to ≠-methyl-2-pentanol gradually proceeds in θ,jN-NaOH.

That is, the alkali in the solution lowers the selectivity to the desired product, the saturated carbonyl compound. Furthermore, in a smooth-phase hydrogenation reaction, the reactivity is affected by the solvent.

Therefore, when producing a saturated carbonyl compound from an unsaturated carbonyl compound by hydrogenating a carbon-carbon unsaturated bond, palladium is the most effective catalyst component, and platinum and ruthenium can further hydrogenate the carbonyl group, and alcohol (
This is not preferable because hydrogenation proceeds to ≠-methyl-2-pentanol).

USP 3,734. Core A7 is a method for producing a radium catalyst supported on activated carbon, in which a basic substance is added to an aqueous solution of soluble palladium salt containing a powdered activated carbon carrier slurry to adjust the pH to 2 or more and palladium is added in the form of hydroxide. He proposes a method of depositing and then applying several layers. In this case, as a basic substance, an alkali or alkaline earth hydroxide,
Preferably Ll, Na%, Ba%Os hydroxide s-s.

It is preferable to use an aqueous solution of water, and the use of carbonates and bicarbonates is disadvantageous because the pH increases only up to io. The catalyst is then boiled in an aqueous medium, and then isolated by filtration, washing, and diversion. It is also stated that this cocoon production method increases the activity as a hydrogenation catalyst.

Also, USF 3. l'0hiro, 772re, USF 3,
736,246, the carbon carrier slurry in acidic palladium mass aqueous solution was prepared under very basic conditions (pH 3.0~
4.0), a method for producing a supported palladium catalyst with high rigidity against sulfur by reduction, separation, and washing is reported. The basic compounds used here include alkali or alkaline earth metal hydroxides, ammonium hydroxide and quaternary ammonium compounds, alkali metal carbonates and bicarbonates, and sodium carbonate is particularly preferred. It is said that it is.

In these catalysts, the alkali is separated and removed during the filtration and washing process, so it is normal for most of it to remain in the catalyst, but if the alkali is washed with an aqueous alkali solution, or if the washing is insufficient There is a possibility that some alkali may remain in the materials. However, their patent specifications only describe the general hydrogenation activity of palladium catalysts or the improvement of resistance to sulfur. There is no suggestion of increasing selectivity to the compound.

[Problem that the invention seeks to solve]

There have been several proposals for improving the selective hydrogenation of carbon-carbon unsaturated bonds using the palladium catalyst described above. However, none of these methods were satisfactory due to the disadvantages that a large amount of solvent was used and excessive hydrides such as alcohol were produced as by-products. For example, Chapter 2 (Chapter 1) of “Catalysts for Reactions”
//~331 pages), the hydrogenation of mesityl oxide using a 3% Pd/alumina catalyst was carried out at 200 °C.
It is said that methyl isobutyl ketone was obtained with a yield of 27% by this process, but even with such a yield, there are still disadvantages such as the need to increase the reflux ratio of the rectification column to remove impurities during purification. there were.

Also, Tokko Sho≠7-15. In the Ori, the use of palladium -carbon catalysts with alkaline metal acetate adhered as a method of selectively synthesizing methylinbutyl ketone by adding meshyloxide. This catalyst is produced by impregnating and depositing a soluble alkali metal acetate as a solution onto a palladium-carbon catalyst prepared in advance. The reaction was carried out in the gas phase, and a conversion ratio of 1, methyl isobutyl ketone selectivity, r% (Example-1), or a selectivity of 7.7% (Example-2) was obtained. However, it is still insufficient in terms of conversion rate and (industrially, it is desirable that the concentration of both raw materials and impurities be less than 1,000 ppm), and although the performance is industrially satisfactory, it is still insufficient. There wasn't. According to the studies conducted by the present inventors, the causes of this lack of performance are thought to be both the fact that the process was carried out in a single-reaction gas phase and the amount of alkali used was inappropriate. However, considering that alkali metal acetates are soluble in organic solvents,
It seems that it would have been impossible to use a catalyst containing a high concentration of alkali in a liquid phase reaction.

In addition, when conventional palladium-supported catalysts such as those mentioned above are used, hydrogenation of unsaturated carbonyl compounds produces neutral compounds, that is, unreacted raw material unsaturated carbonyl compounds and saturated alcohols as excess hydrides. 20 each
0~/0.000 ppm and/,000~jO,0
There was still a problem in terms of selectivity because about 1,000 ppm of nitrate was produced.

For example, the reaction results according to Example 7 described in the above-mentioned Japanese Patent Publication Sho Guar No. 3,1107 are as follows: conversion rate (unreacted menthyl oxide/0.000 ppm), selectivity of methyl isobutyl ketone, 3%, and low boiling point. The total amount of decomposition products and methylinbutylcarbinol (saturated alcohol) is said to have been less than 0.2%. 44 Kimiaki 4'7
According to table No.-/3102, the amount of by-products of low-boiling compounds below the boiling point of acetone is 0.102% or less, so
The amount of methylimbutylcarbinol is Q, l ~ 00.2
% (/,000-2,000 ppm).

[Means for solving problems]

The present inventors discovered that palladium is a catalyst for selectively hydrogenating unsaturated carbonyl compounds to saturated carbonyl compounds using a medium. The present invention was completed based on the discovery that the supported catalyst is extremely effective and that high selectivity can be maintained even when the conversion rate is set to a very high level of Tata or Tati or higher.

That is, the purpose of the present invention is to further improve the selectivity of the reaction when hydrogenating an unsaturated carbonyl compound to produce a saturated carbonyl compound, and to suppress to the utmost the by-product production of saturated alcohol. The above is a method for hydrogenating an unsaturated carbonyl compound in a liquid phase in the presence of a catalyst to obtain a saturated carbonyl compound, wherein the catalyst contains palladium and an alkali metal supported on a carrier as active components, and the surface alkali metal/palladium atomic ratio determined by X-ray photoelectron spectroscopy is 0.7 to 3.
6. A method for hydrogenating an unsaturated carbonyl compound, characterized in that the compound is within the range of 6.

The present invention will be explained in more detail below.

In the method for hydrogenating unsaturated carbonyl compounds of the present invention, a catalyst containing palladium and an alkali metal supported on a carrier is used as an active component.

As the carrier, activated carbon, alumina, silica, carbon dioxide, other oxides, carbonates, sulfates, etc. are used. Any of these powders, small lumps, granules, etc. may be used, but powdered activated carbon is the most common.

The above catalyst may be supported on a carrier as a palladium component, reduced to produce a palladium-supported catalyst, and then supported on an alkali support as an alkali metal R component.

The catalyst used in the method of the present invention contains palladium and an alkali metal as supported active ingredients, and in particular, the alkali metal may be present in an amount within the range of one foot in the -1 supported palladium catalyst. Effective.

For example, when sodium or lithium is used as the alkali metal, the preferred alkali metal/palladium atomic ratio range is 0. /! S-≠, preferably 0.2 to 3.5.

Further, for other potassium, cesium, etc., the bulk composition is preferably in the range of O, Co to i, S. Among the alkali metals, sodium is the most effective.

The above-mentioned palladium and alkali metal are preferably supported on the surface of the catalyst particles. In the above-mentioned bulk composition, the carrier itself may contain a small amount of alkali metal, and surface-supported particles are not necessarily clearly expressed. For example, X-ray photoelectron spectroscopy (IEIOA)
) It can be estimated by surface composition analysis by &C.

According to the studies conducted by the present inventors, the atomic ratio of alkali gold F4/palladium was 0.00 in surface composition analysis using K80A.
7 to J, j is particularly effective when it is /, 0 to 2.0, and high activity and high selectivity can be stably achieved.

On the other hand, the preferred supporting ratio of palladium is (7
, J ~/Owt%, more preferably /-7wt%. As mentioned above, the proportion of alkali metals is determined based on the amount of palladium supported.

By the method of the present invention, unsaturated carbonyl compounds can be totally selectively hydrogenated to obtain carbonyl compounds with saturation>0. For example, butyraldehyde can be obtained from crotonaldehyde, cyclohexanone can be obtained from cyclohexenone, and methyl-3-penten°-coion can yield +-menal-2-pentanone.

The method of the invention is carried out in the liquid phase. Although a suitable reaction solvent such as alcohol, ester, ether, or aromatic compound vIJ may be used, the reaction is preferably carried out without a solvent. The reaction temperature is usually aO~-i! It is a cape of 00 degrees Celsius. As the pressure condition, normal pressure to jOky/dl is used.

Furthermore, since the target saturated carbonyl compound can be obtained with extremely high purity in the raw H obtained by hydrogenating an unsaturated carbonyl compound according to the method of the present invention, the target product can be extracted by simple distillation or the like. I can do it.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention does not exceed its gist.

The following examples are not intended to be limiting.

In addition, X! The alkali gold R/palladium atomic ratio on the surface of the catalyst in the present invention was determined by surface composition analysis using photoelectron spectroscopy (ICEIOA) according to the following method.

Pi411 of the sample to be measured! The catalyst powder is directly dried under reduced pressure at room temperature.

After drying, the catalyst powder was fixed on a sample holder using double-sided adhesive tape and used for the following measurements.

Measurement and analysis method @: KRATO8g XBAM 100
Excitation source: AtKα1ip (/4LKVX20mA)
Measurement mode: Fixed reduction ratio (1Fixad RetlLr
dingRatio) C, pa, d * ” Scanning width for each level of 1B, 4p O
By computer control in eV? I411. The peak plane of the obtained spectrum ItJt f:rh', #)i
Calculate by subtracting the baseline. The obtained peak plane & is corrected by the elemental heat ratio to obtain the molar ratio (atomic ratio).

(This method provides analytical values for the surface up to approximately jθ in the depth direction.) Pdad /I1. / Na, so, 6119 Ktp O, J j atomic ratio Example/, 2 and Comparative Examples 1 to 3 Aqueous solution containing palladium chloride, sodium carbonate aqueous solution,
An activated carbon catalyst containing sodium ions and atomic palladium was prepared using activated carbon powder and a reducing agent. Catalysts with various sodium contents were prepared by repeatedly washing this catalyst with demineralized water and gradually extracting and removing the sodium component. Supported amount of sodium component (bulk composition) of the obtained catalyst, Na / P d atomic ratio (bulk composition), and Na / P d atomic ratio of the catalyst surface determined by xiPil photoelectron spectroscopy, Table 2 It was Oshi as shown in . Furthermore, the palladium loading rate (based on dry catalyst) is 1wt.
It was Chi. A 200 ml autoclave with vertical stirring was charged with ≠-methyl-3-pente/-2-off 30f and the prepared catalyst (approximately JO water content).
Hydrogenation was carried out by reacting for 2 hours at jtO 0 C and hydrogen pressure O 0 MFa.

After the catalyst was separated by sedimentation using a product device, the supernatant components were analyzed and the results are shown in Table λ. Catalysts W and XI were prepared in the same manner as in Example 1 except that the ratios were changed as shown in Table 3.

Using the prepared catalyst, a reaction was carried out under the same conditions as in Example. The results are shown in Table-3.

〔effect〕

When an unsaturated carbonyl compound is hydrogenated by the method of the present invention, the resulting reaction product solution can be extracted with high purity.

in the saturated carbonyl form (target product) Patent applicant: Sankyo Kasei Kogyo Co., Ltd. Representative: Patent Attorney Hase - 1 other person

Claims (2)

[Claims] (1) In a method of hydrogenating an unsaturated carbonyl compound in a liquid phase in the presence of a catalyst to obtain a saturated carbonyl compound,
The catalyst contains palladium and an alkali metal supported on a carrier as active components, and the surface alkali metal/palladium atomic ratio determined by X-ray photoelectron spectroscopy is 0.7 to 3.5. A method for hydrogenating an unsaturated carbonyl compound, characterized in that the hydrogenation method is within the range of (2) A method for hydrogenating an unsaturated carbonyl compound according to claim 1, wherein the unsaturated carbonyl compound is 4-methyl-3-penten-2-one.