JPS58135828A - Preparation of ethanol - Google Patents

Abstract

PURPOSE:To prepare ethanol, easily, in high selectivity, by reacting methanol, CO and H2 in an inert solvent using a catalyst containing Co, Pd and/or Pt and an alkyl phosphine as active components. CONSTITUTION:Ethanol is prepared by pressing a mixed gas of H2 and CO (the molar ratio of H2/CO is 1:2-3:1) under 150-450kg/cm<2> into an inert solvent such as toluene, dioxane, etc. containing methanol, a Co compound such as dicobalt octacarbonyl, a Pd compound such as palladium chloride, Pd-activated charcoal, etc. and/or a Pt compound such as chloroplatinic acid, and an alkyl phosphine such as tri-n-butyl phosphine, and reacting the components together at 200-260 deg.C. The atomic ratios of Co:(pd or Pt):(p in the alkyl phosphine) are 1:(0.05-0.4):(0.5-1.5).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for selectively producing ethanol from methanol, -carbon oxide and hydrogen. A method for producing ethanol by reacting in the presence of is disclosed in JP-A-51-1
Also known as Copal F and other 8th
Group metal, iodine or bromine, and reacted in the presence of a tertiary phosphine catalyst 1 to 16 methods @lInn112,056.75
It is known as 9. However, in such a method, K other than the target ethanol is used.

Many by-products such as 1-methyl ethyl ether, diethylethyl, acetaldehyde, dimethoxyethane, acetic acid, methyl acetate, ethyl acetate, methyl formate, and other compounds of CS or higher are simultaneously generated in dimethyl ether, and the conversion to free ethanol It has disadvantages such as low selectivity and complicated steps to separate ethanol from the reaction product.

The present invention eliminates these drawbacks and provides a method for producing ethanol with few by-products and high selectivity.
methanol, - carbon oxide and hydrogen in an inert solvent, (
1) Koparsi, (2) Paratu 1 and 1/11 Shirokane and 1
(2) A method in which the reaction is carried out in the presence of a catalyst containing fins as an active ingredient in an aquifer. Although the presence of element is not necessary in the present invention, the iodine/cobalt atomic ratio is 0.1 or less. If it is, there will be no negative effect on the selectivity of ethanol.

Cobalt catalysts used in the present invention include cobalt carbonyls such as dicobalt octacarbonyl and cobalt hydride tetracarbonyl, inorganic cobalt compounds such as cobalt monohydroxide, cobalt carbonate, basic cobalt carbonate, and cobalt halides, and cobalt organic Various cobalt compounds that produce cobalt carbonyl in the reaction system can be used, such as organic cobalt compounds such as cobalt salts, cobalt heptamines, copal) 7 cetyl acetate, etc. However, when cobalt iodide is used, other cobalt compounds can be used. It is necessary to use a cobalt compound button in combination with the abrasive grain to copal f) II ratio of 0.1 or less.

The amount of the cobalt compound to be used is 1 to 300 sys, preferably 5 to 1 sy, in terms of cobalt atoms, per 1 mole of methanol.
00 one atom. If the amount is less than this range, the reaction will proceed, but the reaction rate will be slow; if the amount is more than this range, there will be no adverse effects, but it will not be economical.

As palladium or platinum in the present invention, any material containing palladium or platinum can be used, such as metallic palladium, halogenated palladium, palladium acetate, palladium chloride, metallic platinum, halogenated platinum, or halogenated palladium. These include platinic acid and its salts, and these can be used alone or supported on an inert carrier such as activated carbon, diatomaceous earth, or alumina. However, when using an iodine compound, the atomic ratio of iodine to cobalt must be 0.1 or less. The amount of palladium or platinum used is 0.1 per mole of methanol in terms of palladium or platinum atoms. ~1 (10m
11 [child, preferably 0.5 to 50 IIIPm].

Examples of the furkylphosphine in this practice include dolly-n-butylphosphine, triphenylphosphine,
) Para-tolylphosphine, tricyclohexylphos 747.1.4-bistriphenylphos 74butane, 1,6-pisdryphenylhydrosphinohexane, etc. are available.

The amount of alkyl phosphine used is 1 mole of methanol,
The amount of phosphorus atoms is from 2 to 4001 lg atoms, preferably from 10 to 200 mg atoms. If it is less than this range, there will be little effect of suppressing the by-product of ether chains and esters, and if it is more than this range, the methanol reaction rate and ethanol selectivity will decrease, which is undesirable. This invention is suitable Kl! The atomic ratio of cobalt pudgecum or platinum phosphorus that can be applied is 110.01 to 0.530.1 to 2, preferably 110.05 to 0.410. S~1.5. Outside this range, the by-products of ether steel, esters, and high boiling point products increase, which is undesirable.

The non-soakable solvent in HoW14 means a solvent that does not adversely affect the reaction, and is preferably a hydrocarbon or an ether chain.Examples of hydrocarbon solvents include aromatic hydrocarbons such as benzene%F toluene and xylene. , aliphatic hydrocarbons such as hexane, octane, and cycloaliphatic hydrocarbons such as cyclohexane are used. As the ether solvent, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, etc. are used.

The amount of sm used is 0.01 to 5 mol, preferably 0.1 to 2 mol, per mol of methanol. If the amount is less than this, the effect of coexistence will be small.

If the amount is higher than this, there is no problem with the reaction, but the space-time yield becomes small and it is not practical.10 The reaction temperature varies depending on the catalyst system used and other reaction conditions, but is generally 150°C.
The reaction proceeds at temperatures below 0 to 500°C, preferably from 200°C to 260°C, but the degree of summer reaction is delayed.

If it exceeds this range, the number of rigid organisms will increase, which is not preferable.

What is the reaction pressure? It is sufficient if i0 is 9/- or more, and there is no particular upper limit, but a range of 150 to 450 kl/32 is practically preferable. - The molar ratio of oxidized bulk hydrogen is 411 to 1
14, preferably in the range of 2'l'1 to ill 41N used in the reaction - For the carbon suroxide and hydrogen, a gas inert to the reaction, such as argon, nitrogen, acid gas, methane and ethane, is used. However, in this case, it is necessary to make the partial pressures of carbon monoxide and water correspond to the above pressure range 11.

The method of the present invention can be carried out either in a batch method or a continuous method.According to the present invention, ethanol can be selectively produced from methanol, -carbon oxide, and water μ.

The methanol conversion rate, ethanol selectivity, actual methanol conversion rate, and realizable ethanol selectivity in the Examples and Comparative Examples shown below are defined as follows.

Methanol reaction rate (*) Charged methanol, mole (charged methanol - unreacted methanol), mole actual methanol conversion rate (LIi) Charged methanol, mole Realizable ethanol selectivity (-) Note 1) Dimethoxymethane, methyl ester 0 means the amount of methanol recovered by the volume of IKmm by hydrolysis. Note 2) 0 refers to the amount of ethanol recovered by the hydrogenation or hydrolysis of free ethanol and acetaldehyde, xyethane, ethyl ester, etc. Example 1 In a stainless steel shaker-type osciflape with an internal volume of 100-), Nord 1op (0,3121 mol), Dicoparciotata luponyl 2f (o, nos @ mol), Palladium chloride 0°! $5t (0,002 mol), tri-1-butylphosphine 5? (0,0148 mol) and 10 t (0,1086 mol) of toluene were charged,
Next, the mixed gas of water and carbon monoxide (H2/co molar ratio ■
1) Inject 200kll/aa2 and heat to 250℃75
Allowed time to react.

After the reaction, cool the autoclave and leave it! The gas was purged, and the reaction product tK was analyzed using the internal standard method using Gastaloma Shidaraf.

As a result, the methanol reaction rate was 21.6g, the free ethanol selectivity was 72.6g, and the selectivity to other components was 2.01g of methyl formate.

Butyl ethyl ether 2.11 methyl acetate 1,s- and traces of dimethoxyethane. This is a realizable ethanol selectivity of 8O,S* at an actual methanol conversion rate of 21.2-.Example 2 5-palladium-activated carbon catalyst instead of palladium chloride
The reaction was carried out in the same manner as in Example 1 except that 2t was used. As a result, methanol conversion rate -20,5-1 selectivity to free ethanol 49. The selectivity for each of the other components was 82.3 gIn for methyl formate -15-1 methyl ethyl ether, 0.1 gIn for methyl acetate, and 5.9 gIn for dimethoxyethane.The actual methanol conversion rate was 18 , 411, the selectivity to ethanol is achievable.
The reaction was carried out in the same manner as in Example 1 except that 01 mol) was used. As a result, the notanol reaction rate was 31,111
The selectivity to G% free ethanol was 70.4 s, and the other components were refluxed in the same manner as in Example 1 except that dioxane 10) (0°11N5 mol) was used instead of toluene. As a result, the methanol reaction rate was 71, and the selectivity to free ethanol was 68.1-, and the selectivity to other components was 0.9-%, methyl ethyl ether, 2.5%, and methyl acetate. 0.5 thi and dimethoxyethane 2.9 thi. This corresponds to an actual methanol conversion rate of 29,696 and a realizable selectivity to ethanol of 74.5%.

Comparative Examples 1 to 4 Using Dicopal F octacarbonyl as a main catalyst in the coexistence of one or two selected from palladium, platinum or their compounds, sily-l-butylphosphine or toluene, Examples The reaction was carried out under the same conditions as in Example 1.

The results are shown in Table 1, and if the four components of dicopalsioctacarbonyl, palladium, platinum or their compounds, ) substitute butylphosphine and toluene do not coexist, one biological substance such as ethers or esters is used. It is rare that the selectivity to free ethanol and realizable ethanol is low.

Claims (1)

[Claims] Methanol, - carbon oxide and hydrogen in an inert solvent - (
l) copal), (!l palladium and or platinum, l bi(!l)
3) A method for producing ethanol characterized by carrying out the reaction in the presence of a catalyst containing furkylphosphine as an active ingredient 4