JPS6121533B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for producing a hybrid ether from alcohol, carbon monoxide, and hydrogen.

Conventionally, most of the ethers produced industrially are single ethers represented by the general formula ROR. For example, dimethyl ether can be obtained by a dehydration reaction of methanol using aluminum phosphate as a catalyst. Diethyl ether is also obtained by dehydrating ethanol or as a by-product when producing ethanol from ethylene. Similarly, diisopropyl ether, di-n-butyl ether, etc. are also obtained by dehydrating the corresponding alcohol. These ethers can be used as solvents, extractants, coolants, aerosol propellants,
It has useful uses as an anesthetic.

On the other hand, a hybrid ether represented by the general formula ROR'(R' is an alkyl group with one or more carbon atoms more than R), which has different alkyl groups via an oxygen atom, is synthesized by Williamson's method as follows. can get.

Alternatively, it can be obtained by reacting sodium alkoxide with an alkyl halide or dialkyl sulfate.

RONa+R'X→ROR'+NaX 2RONa+R' ₂ SO ₄ →2ROR'+Na ₂ SO _4The method for producing the above-mentioned hybrid ether has the disadvantages of being complicated, using alcohols with different carbon numbers as raw materials, and using expensive raw materials.

We were able to produce a hybrid ether using a new method whose technical philosophy is completely different from those methods. That is, they overcame the disadvantages of the conventional method by producing a hybrid ether from only one type of alcohol and inexpensively available synthesis gas.

The present invention involves producing an ether, particularly a hybrid ether, by reacting an alcohol represented by the general formula ROH (R is an alkyl group having 1 to 5 carbon atoms) with carbon monoxide and hydrogen in the presence of a cobalt, ruthenium, or iodine catalyst. It's a method.

Many reaction examples are known for the reaction of alcohol with carbon monoxide and hydrogen, and so-called homologation is carried out as a method for producing aldehydes and alcohols with increased carbon chains.

The present invention is a novel method for obtaining a mixed ether as a reaction product with high selectivity while using similar raw materials. Although some alcohols with increased carbon chains are produced, the aldehydes that are thought to have been produced as intermediates can ultimately be prevented from remaining in the reaction solution by adjusting the amount of catalyst.

JP-A-54-73708 shows that a mixed ether is produced by reacting alcohol, carbon monoxide, and hydrogen.
and JP-A-54-125605 (both catalysts are cobalt and iodine or bromine), but as stated in the footnotes, it is stated as the total amount of single ether and mixed ether. , the ratio of single ether to hybrid ether is not clear, and it is difficult to recognize that this is a selective production method for hybrid ether. Furthermore, in terms of yield, the production of ethanol is overwhelmingly large, and the production of ethers, especially mixed ethers, is small.

Furthermore, in JP-A-55-92330, ethanol is obtained by reacting methanol, carbon monoxide and hydrogen in the presence of, for example, cobalt acetylacetonate, tri-para-tolyl phosphite, iodine and ruthenium acetylacetonate. Although the production of dimethyl ether and diethyl ether as ethers is described, methyl ethyl ether as a mixed ether is not recognized.

Therefore, the present invention is a new production method for obtaining a hybrid ether with a high selectivity not found in conventional methods.

Embodiments of the present invention will be described in detail below.

The alcohol used in the present invention is an aliphatic alcohol having 1 to 5 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, n
-butanol, iso-butanol, sec-butanol, tert-butanol, n-amyl alcohol,
iso-amyl alcohol and tert-amyl alcohol. Methanol and ethanol, which have a small number of carbon atoms and have a high reaction rate, are preferable, but the raw materials should of course be selected depending on the desired mixed ether.

A wide range of ratios of carbon monoxide and hydrogen can be used, but CO:H ₂ (molar ratio) = 1:10 to
in the range of 10:1, particularly preferably from 1:2 to 2:1
Various gases can be used as raw materials.

Reaction temperature is 100-300℃, preferably 120-250℃
℃, more preferably 150 to 200℃. If the reaction temperature is low, the reaction will be difficult to proceed and will require a long time.
In addition, when the reaction temperature becomes high, undesirable by-products,
For example, methane and single ether increase, and the selectivity of the target ether decreases.

The reaction pressure is also related to the reaction temperature and the amount of catalyst added. Practically speaking, the sum of the partial pressures of carbon monoxide and hydrogen is 50 to 500 Kg/cm ² , preferably 100 to 300 Kg/cm ² .

The catalyst in the present invention contains cobalt, ruthenium and iodine as active ingredients. Cobalt may be metal cobalt or a cobalt compound containing cobalt. Similarly, ruthenium may be metal ruthenium or a ruthenium compound containing ruthenium.

Cobalt oxide is a typical example of cobalt compounds.
cobalt hydroxide, cobalt chloride, cobalt bromide,
cobalt iodide, cobalt carbonate, cobalt formate,
These include cobalt acetate, cobalt naphthenate, cobalt acetylacetonate and octacarbonyl dicobalt. Representative examples of ruthenium compounds include ruthenium oxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium acetate, and dodecacarbonyl triruthenium.

Iodine includes not only simple iodine ( ₂ ) but also iodine compounds such as hydrogen iodide, methyl iodide,
Alkyl iodides such as ethyl iodide, metal iodides such as lithium iodide, sodium iodide, and calcium iodide are used. When iodine is bonded to the catalyst metal, it may not be necessary to add iodine or iodide. Iodine may escape from the system during the reaction, but in such cases a trowel can be used to replenish it.

The cobalt/ruthenium atomic ratio is from 10/1 to 1/10, but is particularly preferably around 1/1. If the amount of ruthenium is less than that of cobalt, aldehydes and their derivatives will remain and the yield of ether will not improve.
Further, even if a large amount of ruthenium is added, the effect is not necessarily exhibited.

Using the catalysts described above, the reaction can be carried out batchwise, semi-continuously or continuously. Naturally, when the reaction is carried out in a continuous manner in a fixed bed, there is no particular restriction on the amount of catalyst used. When carrying out the reaction in a batch method or in a completely mixed method such as a suspended bed or a fluidized bed, the amount of catalyst used is 1
Cobalt and ruthenium combined 0.01 to mol
100 milligram atoms, preferably 0.1 to 10 milligram atoms. If it is less than 0.01 milligram atom, the reaction rate is too low to be practical. Moreover, if the amount exceeds 100 milligram atoms, there will be no problem with the reaction, but it will be disadvantageous mainly from an economic point of view.

The amount of iodine used in the present invention is the total amount of aldehyde metals (cobalt and ruthenium) used.
0.1 to 10 milligram atoms, preferably 0.5 to milligram atoms per milligram atom. These catalyst components can be used in the form of powder by being mixed with the reaction raw materials. Further, the catalyst may be mixed with a carrier such as clay or diatomaceous earth or supported on a carrier to form a catalyst, or the catalyst component itself may be used as a shaped catalyst.

In the present invention, alcohol can also serve as a solvent, but there is no problem in using an inert solvent such as a hydrocarbon in the reaction. Furthermore, in order to prevent the by-production of aliphatic carboxylic acids or esters thereof, it is preferable to add the aliphatic carboxylic acids or esters thereof that will be by-produced.

In the present invention, it has become possible to obtain a highly valuable mixed ether with high selectivity by using one type of inexpensive alcohol as a raw material.

The present invention will be explained in more detail below with reference to Examples.

A shaking stainless steel autoclave with an internal volume of 50 ml was charged with 15.6 g (487 mmol) of methanol, 1 mmol of cobalt iodide, and 1/3 mmol of dodecacarbonyl triruthenium, and then charged with carbon monoxide:hydrogen (examples with molar ratios below). But the same) is 50:
A mixed gas of 50% was injected under pressure up to 200Kg/cm ² . The reaction was carried out by heating to 150°C. Shows maximum pressure 260Kg/cm ² ,
It decreased to 195Kg/cm ² in 60 minutes of reaction time. It was allowed to cool, evacuated and the resulting reaction mixture was analyzed by gas chromatography. The conversion rate of methanol was 13.3%, and the molar selectivity for various products was 41.1% for methyl ethyl ether, ethanol
39.7%, methyl acetate 9.0%, dimethyl ether 10.2
It was %.

Example 2 Using the same autoclave as Example 1,
Methanol 7.8g (243 mmol), methyl acetate 9.4
g (127 mmol), cobalt iodide 1 mmol,
Filled with 0.5 mmol of basic ruthenium acetate, then 200% carbon monoxide:hydrogen mixed gas 50:50
It was press-fitted up to Kg/cm ² . The mixture was heated to 150°C and reacted.
The maximum pressure is 270Kg/cm ² and the reaction time is 240Kg/cm2 at 60 minutes.
It went down to ^cm2 . The conversion rate of methanol is 14.0%, and the molar selectivity is 47.2 to methyl ethyl ether.
%, ethanol 46.3%, dimethyl ether 6.5%
It was hot. Substantially no acetic acid groups were produced.

Example 3 A magnetically stirred titanium autoclave with an internal volume of 100 ml was filled with 31.2 g (677 mmol) of ethanol, 2 mmol of cobalt iodide, and 1 mmol of basic ruthenium acetate, and then mixed with carbon monoxide:hydrogen in a ratio of 50:50.
A mixed gas of up to 160Kg/cm ² was injected under pressure. The reaction was carried out by heating to 150°C. The maximum pressure was 215Kg/cm ² , which decreased to 177Kg/cm ² in 180 minutes of reaction time. The conversion rate of ethanol was 11.4%, and the molar selectivity was 42.6% for ethyl propyl ether, 43.9% for propanol,
Diethyl ether was 13.5%.

Example 4 Using an autoclave similar to Example 3, n
- Filled with 31.4 g (522 mmol) of propanol, 2 mmol of cobalt iodide, and 1 mmol of basic ruthenium acetate, then carbon monoxide:hydrogen 50:50
A mixed gas of up to 140Kg/cm ² was injected under pressure. The mixture was heated to 170°C and reacted. The maximum pressure was 203Kg/cm ² , which decreased to 192Kg/cm ² in 210 minutes of reaction time. The conversion rate of n-propanol was 3.6%, and the molar selectivity was 40.9% for propyl butyl ether and butyl alcohol.
42.8% and dipropyl ether 16.3%.

Example 5 Using an autoclave similar to Example 1, 15.6 g (487 mmol) of methanol and 1 cobalt acetate were added.
After that, a 50:50 mixed gas of carbon monoxide and hydrogen was injected under pressure at 200 kg/cm ² . The reaction was carried out by heating to 160°C. The maximum pressure was 270Kg/cm ² , which decreased to 195Kg/cm ² in 60 minutes of reaction time. The conversion rate of methanol is
The molar selectivity is 15.6% and the molar selectivity is methyl ethyl ether.
41.0%, ethanol 41.2%, methyl acetate 8.8%, and dimethyl ether 9.0%.

Example 6 Using an autoclave similar to Example 1, 15.6 g (487 mmol) of methanol and 1 cobalt acetate were added.
mmol, basic ruthenium acetate 0.5 mmol,
Fill with 1 mmol of iodine and then carbon monoxide:
A mixed gas containing 45:55 hydrogen was injected to a pressure of 200 kg/cm ² . The reaction was carried out by heating to 150°C. Maximum pressure 260
Kg/cm ² , which decreased to 185 Kg/cm ² in 60 minutes of reaction time. The conversion rate of methanol was 13.8%, and the molar selectivity was 40.9% for methyl ethyl ether, 39.5% for ethanol, 9.3% for methyl acetate, and 10.3% for dimethyl ether.

Claims (1)

[Claims] 1 Alcohol represented by the general formula ROH (R represents an alkyl group having 1 to 5 carbon atoms), carbon monoxide, and hydrogen to the general formula ROR'(R' represents an alkyl group having 1 or more carbon atoms than R). ) A method for producing an ether, which comprises using a catalyst containing cobalt, ruthenium, and iodine as active ingredients.