JPS59110635A - Preparation of monohydric alcohol - Google Patents

Abstract

PURPOSE:To prepare the objective compound, in high selectivity, from and ether, carbon monoxide and hydrogen, by using a catalyst containing cobalt, ruthenium and iodine as active components. CONSTITUTION:The monohydric alcohol of formula II and III can be prepared under mild condition in high selectivity by reacting the ether of formula I (R1 and R2 are 1-10C straight or branched alkyl) with carbon monoxide and hydrogen in the presence of a catalyst containing (A) cobalt, (B) ruthenium and (C) iodine and optionally (D) iron, as active components, preferably at 130-200 deg.C and 100-500kg/cm<2> pressure. The recovery and reuse of the catalyst can be carried out easily, and the process is extremely advantageous from industrial viewpoint. The preferably amount of the component (A) is 1-50mg-atom per 1mol of methanol, and the atomic ratios of B, C and D to A are preferably 0.1-1, 0.1-10 and 0.25-2, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for selectively producing monohydric alcohols by reacting ethers, -carbon oxide, and hydrogen.

The reaction for producing monovalent alpour from ethers, -carbon oxide and hydrogen is shown by the following formula.

R1-0-R2+■+2H2=Kug10H+R2CH20
H Previously, as a method similar to the present invention, U.S. Patent No. 4,0
There are 62,898. When producing ethanol from acetal, carbon oxide and hydrogen,
A catalyst system containing cyto, ruthenium, and iodine is shown, but it has poor selectivity to ethanol, and in addition to the target ethanol, acetaldehyde, methyl acetate, n
-There is a drawback that many products such as propatool, ethyl acetate, dimethyl ether, etc. are produced.

Furthermore, JP-A No. 56-127326 proposes a method of using an alkyl phosphine as a ligand in the above catalyst system in the production of monohydric or polyhydric alcohols from acetals or ethers, carbon monoxide and hydrogen. There is. However, even in this method, the selectivity to the desired alcohol is not sufficient, and ligands such as tertiary phosphines are thermally unstable, so decomposition or deterioration within the reaction system may occur. It is difficult to directly recover and reuse the active species of the catalyst. Furthermore, even if a method were adopted in which each catalyst component was recovered, the catalyst system would be complicated, requiring complicated processes, and the loss associated with recovery would be large, and the catalyst would be expensive. There are drawbacks.

As a result of extensive research into a method for producing m alcohols from ethers, carbon oxide, and hydrogen, the present inventor discovered a catalyst containing cobalt, ruthenium, and iodine, or cobalt, ruthenium, iron, and iodine as active ingredients. The present invention was completed based on the discovery that the desired alcohol can be obtained with high selectivity by reacting in the presence of.

That is, the present invention provides ethers represented by the general formula R1-0-R2 (where R1 and R2 are linear or branched alkyl groups having 1 to 10 carbon atoms that are the same or different from each other), This is a method in which carbon and hydrogen are reacted in the presence of cobalt, ruthenium, and iodine, or a catalyst containing cobalt, ruthenium, iron, and iodine as active ingredients.

Examples of ethers (m alcohols obtained from them) that can be used as raw materials in the present invention include dimethyl ether (methanol, ethanol), methyl ethyl ether (methanol, ethanol), diethyl ether (ethanol, propatool), and ethyl ether. Propyl ether (ethanol, propatool, butanol), dipropyl ether (proptool, butanol), t-butyl methyl ether (methanol, ethanol, 3-methylbutanol), t-butyl ethyl ether (ethanol, 3-methylbutanol) etc.

In addition, the cobalt component used as a catalyst in the present invention includes metallic cobalt, cobalt iodide, cobalt bromide,
These include cobalt chloride, cobalt oxide, cobalt acetylacetonate, and cobalt carbonyl. Examples of the ruthenium component include metal ruthenium, ruthenium iodide, ruthenium chloride, ruthenium hydroxide, ruthenium acetate, and ruthenium carbonyl. Iron components include metallic iron, iron iodide, iron chloride, iron oxide, iron acetylacetonate, iron carbonyl, and the like. Examples of the iodine component include iodine, hydrogen pentatide, cantilever iodide, sodium iodide, potassium iodide, calcium iodide, lithium iodide, and iodides of the above-mentioned metal components.

The amount of catalyst used for suitably carrying out the method of the present invention is 0.1 to 500 cobalt atoms per mole of methanol.
Mi! + Durham atoms, preferably 1 to 50 milligram atoms. When the amount is less than this, the reaction rate becomes low, and when it is more than this, there is no adverse effect but it is not economical, and the above range is economical.

The atomic ratio of iron to cobalt is between 0.1 and 4, preferably between 0.25 and 2.

When the amount is less than this, the selectivity becomes low, and when it is more than this, the reaction rate becomes low.

The atomic ratio of ruthenium to cobalt is between 0.05 and 2, preferably between 0.1 and 1. If it is less than this, the amount of by-products will increase, and if it is more than this, the reaction rate will be reduced.

The amount of iodine used is in the range of 0.05 to 20 atomic ratios, preferably 0.1 to 10 atomic ratios, relative to cobalt. If the amount is less than this, the reaction rate will decrease,
In addition, if the amount is too large, by-products will increase and selectivity will decrease.

The process according to the invention is preferably carried out in a solvent. As a solvent, aromatic hydrocarbons, cyclic ethers, methyl acetate,
Water or a mixed solvent thereof is particularly excellent. Examples of aromatic hydrocarbons include benzene, toluene, O, m1
p-xylene, mixed xylene, ethylbenzene, 1,2
These include 3-trimethylbenzene, 0-methylethylpenzene, 0-diethylbenzene, and isopropylbenzene. As the cyclic ether, the general formula (R-0)n
A compound represented by, especially tetrahydrofuran, 1
．． 3-dioxane and 1,4-dioxane are preferred. The amount of this solvent used is usually 0.0 per volume of ether.
It ranges from 5 to 20 volumes, preferably from 0.1 to 10 volumes.

The reaction temperature is in the range of 100-250°C, preferably 160-200°C. At temperatures lower than this, the reaction rate is too low to be practical, and at higher temperatures side reactions increase.

The molar ratio of CO to H2 in the synthesis gas ranges from 4:1 to 1=4, preferably from 1!2 to 1=3.

The reaction pressure may be 5[1'19/cm2 or higher, and there is no particular upper limit on the upper limit, but it is practically 100 to 5
A range of 00 to &/α2 is suitable. In synthesis gas,
A gas inert to the reaction, such as Ar.

N2, CO2, CH4, etc. may be mixed, but in this case, the partial pressures of CO and H2 must correspond to the above pressure range.

According to the method of the present invention, not only can monohydric alcohols be produced from ethers, CO and H2 under mild conditions and with high selectivity, but also the catalyst system does not use unstable ligands. The catalyst can be easily recovered and reused, making it an extremely advantageous alcohol coating method industrially.

The method of the present invention can be suitably carried out either by a batch method or by a continuous method.

The reaction rate of ethers and the selectivity of alcohol in the following Examples and Comparative Examples are defined as follows.

Ether reaction rate (mol 96) Each alcohol selectivity C mol %) Example 1 Methyl ethyl ether 5t1 Penzea 12i,
Water 21, Co 2 (Co) sCl as a catalyst,
3ay, Fe(Co)5 0.547, RuC1s
・3H2 (0,2Of, and I2 0.88P) were sealed in a sealed container.Next, they were pressurized into synthesis gas (H2/Co = 2 molar ratio) t'240kg/cIrL2 (gauge pressure) and heated at 150℃ for 3 hours. The reaction was carried out. After the reaction, the auto
The crepe was cooled and residual gas was purged, and the reaction product liquid was analyzed using a gas chromatograph. As a result, the selectivity to ethanol was 91.296 and the selectivity to methanol was 2.1096 at a methyl ethyl ether conversion rate of 31.4%, and almost no other by-products were produced.

Examples 2 to 5 As in Example 1, methyl ethyl ether was used as the raw material, and the catalyst species, catalyst composition, H2/CO molar ratio, pressure, temperature, and solvent species were varied, and the results are shown in Table 1.

Examples 6-7 Table 1 shows the results of reacting dimethyl nitride with CO and H2 in the same manner as in Example 1.

Comparative Example 1 In a stainless steel shaking autoclave with contents of 1 m1aarrrt, 5 parts of methyl ethyl ether and 1 part of benzene were placed.
2, water 2, as a catalyst Q) 2 (Co) 8o,
”roy, RuC1!s・3Hzo 0, 2 Of
, yo1i0. 1.82 ff of BBfi-yohittriphenylphosphine was charged and the container was sealed. Next, synthesis gas (H
2/Co = 2 (-R ratio) to 240 kg/cm
2 (gauge pressure) and allowed to react at 150° C. for 3 hours.

After the reaction, the autoclave was cooled and residual gas was purged, and the reaction product liquid was analyzed using a Gasc p-Madograph. As a result, the methyl ethyl ether reaction rate was 25.3
In 96, the selectivity to ethanol was 48.89r) and the selectivity to methanol was 3.21%. In addition, many by-products such as acetaldehyde and dimethoxyethane were produced.

Comparative Example 2 By the same method as Comparative Example 1, dimethyl ether and CO
and H2 were reacted. About the reaction product liquid
-r) As a result of graphical analysis, the selectivity to ethanol was 39.9% at a dimethyl ether conversion rate of 11.896.
1%, and the selectivity to methanol was 15.4%.

Example 8.9 The raw materials were varied in the same manner as in Example 1. Second result
Shown in the table.

Claims (1)

[Claims] 1) Ethers represented by the general formula R1-0-R2 (wherein Rs and R2 are linear or branched alkyl groups having 1 to 10 carbon atoms that are the same or different from each other), -carbon oxide and hydrogen 2) General formula R1-0
-Ethers represented by R2 (wherein R1 and R2 are linear or branched alkyl groups having 1 to 10 carbon atoms, which are the same or different from each other), -urea oxide and hydrogen, cobalt, ruthenium, iron and a method for producing monovalent furfur, which is characterized by carrying out the reaction in the presence of a catalyst containing iodine as an active ingredient.