JPS6014007B2 - Ethanol manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ethanol using carbon monoxide and hydrogen as raw materials in the presence of a catalyst.

Ethanol is a substance that has a wide range of uses as an intermediate raw material for commercial chemicals and as a solvent, and it is highly desirable to produce ethanol selectively and in high yield from carbon monoxide and hydrogen. A method of producing ethanol by reacting carbon monoxide and hydrogen at high temperature and high pressure is known. For example, ■ carbon monoxide and hydrogen in a carboxylic acid solvent using a ruthenium and/or osmium catalyst;
A method of producing methyl acetate, ethyl acetate and ethylene glycol diacetate by reacting at a temperature of 100 to 350°C and a pressure of at least 34 atmospheres (Samurai Kaisho 55-9 Pimura No. 9), and ■50 Temperature of ~400℃ and sia of 50 (35.15kg/) ~15
Production of ethylene glycol, methanol, ethanol or their carboxylate derivatives from carbon monoxide and hydrogen using a solvent containing a ruthenium carbonyl compound having a dielectric constant of at least 2 in 00 other sia (1054.6k9/ground) How to do it (Tokukan Sho 55-11
(No. 5834 Publication), furthermore, (1) using a catalyst consisting of ruthenium and at least one metal of the skin group of the periodic table, in which the molar ratio of ruthenium is at least 50% in relation to the other blood group metals; 150~ in liquid solvent
Ethylene glycol, methanol, from carbon monoxide and hydrogen at a temperature of 300°C and a pressure of 200-3000 bar.
There are methods for producing ethanol and/or their esters (Japanese Patent Application Laid-open No. 123925/1983).

However, these proposed methods are still not satisfactory and have various drawbacks, which need to be improved.

That is, in the proposed methods using ruthenium compounds as catalysts, the main product is methanol, and the selectivity for ethanol is generally low.

For example, in methods (1) and (2) above, the molar ratio of ethanol to methanol in the product is 1 or less.
- In addition, it has been shown that in the proposed methods (1) and (2), the selectivity to ethanol is high when a carboxylic acid such as acetic acid or a glyme such as tetraglyme is used as a solvent.

However, carboxylic acid solvents and glymes are known to be hydrogenolyzed to alcohols such as ethanol under similar reaction conditions, and are therefore not preferred as solvents. As described above, the known methods produce a large amount of methanol, the selectivity for ethanol is generally low, and the carboxylic acid solvent and glyme solvent themselves decompose and are consumed, making them unsuitable for industrial ethanol production. do not have. The present inventors investigated a method for selectively producing ethanol using carbon monoxide and hydrogen as raw materials, and produced ethanol by coexisting a ruthenium compound with a platinum compound, a tin compound and/or a lead compound, and a phosphonium compound. They discovered that the selectivity was greatly improved and completed the present invention.

That is, the present invention deals with the treatment of carbon monoxide and hydrogen under high temperature and high pressure with a low polarity compound containing a ruthenium compound, a platinum halide, a tin halide and/or a lead halide, and a quaternary phosphonium halide. This is a method for producing ethanol, which is characterized by carrying out the reaction in a solvent.

According to the method of the present invention, a stable solvent can be used even under the reaction conditions, and the selectivity to ethanol can be increased. The ruthenium compound used in the method of the present invention forms a chain with carbon monoxide as a ligand, and under reaction conditions becomes a ruthenium chain with a carbon monoxide ligand, and the liquid medium used It dissolves in

This collar body can be produced under reaction conditions using various ruthenium compounds as precursors. Any ruthenium compound can be used as the precursor as long as it produces a ruthenium body having a carbon monoxide ligand under the reaction conditions. Examples of these include, in addition to ruthenium metal, ruthenium oxides such as ruthenium dioxide and ruthenium tetroxide, their hydrates, mineral salts of ruthenium such as ruthenium chloride, ruthenium iodide, and ruthenium nitrate, and acetic acid. Examples include ruthenium and organic acid salts of ruthenium such as ruthenium propionate. Ruthenium compounds can also be used directly in the form of coordination compounds, examples of which include:
Examples include ruthenium carbonyl such as triruthenium dodecacarbonyl, ruthenium chains in which ruthenium is coordinated with ligands containing oxygen, sulfur, halogen, nitrogen, phosphorus, arsenic, antimony, bismuth, etc., and their salts. It will be done. Among these ruthenium compounds, ruthenium oxide, ruthenium halide, ruthenium carbonyl, or a ruthenium key body in which at least some of the carbon monoxide ligands of ruthenium carbonyl are replaced with other ligands are preferable. .

The platinum halides used in the method of the present invention include potassium platinum chloride, potassium chloroplatinate, platinum (0) chloride, platinum (W) chloride, sodium platinum chloride,
Potassium bromide platinum, tetraamine platinum (0) chloride, cis-dichlorbis(tri-n-butylphosphine) platinum (0), and the like can be mentioned. In addition, the tin compound or lead compound used in the present invention includes:
A halide of tin or lead, such as stannous chloride, dibutyltin dichloride, triphenyltin chloride, diphenyltin dichloride, phenyltin trichloride, lead chloride, lead dichlordiphenyl, lead triphenyl bromide, etc. .

Furthermore, tin bodies containing platinum and tin or platinum and lead can also be used. Examples of these include PtC12(P(C mountain 5)3)2-SnC12, Pt
C12 (P (C6 public) 3) 21 12 on P, 12 on P (P
(C6 day 5) 3) 2-SnC14, P old r2 (P(C6
Day 5) 3) 21 S Hawk r2, Pt12 (P(C6&)3)
Examples include 2-Sn12. Furthermore, the quaternary phosphonium halogen salt used in the method of the present invention has the general formula (1) (1) R2-? -R4×R3 (wherein R,, R2, R3 and R4 have 1 to 1 carbon atoms)
20 alkyl group, aryl group, alkaryl group or cycloalkyl group, and xe represents a halogen anion), for example,
n-heptyltriphenylphosphonium bromide, penzyltriphenylphosphonium bromide, tetraethylphosphonium bromide, tetraphenylphosphonium bromide, penzyltributylphosphonium bromide, mono-n-heptyltriphenylphosphonium chloride, penzyl chloride Triphenylphosphonium, tetraethylphosphonium chloride, tetra-n-butylphosphonium chloride, amyltriphenylphosphonium chloride, n-heptyltriphenylphosphonium iodide, penzyltriphenylphosphonium iodide,
Examples include tetraethylphosphonium iodide.

The liquid medium used in the method of the invention is a hydrocarbon solvent with a dielectric constant of 2.6 or less at room temperature.

Examples of such liquid media are saturated hydrocarbons such as heptane, octane, cyclohexane, decalin, and aromatic hydrocarbons such as benzene, toluene, xylene. These liquid media may be used alone or in combination of two or more.

Further, alcohols, esters, etc. generated during the reaction may be contained. In the method of the present invention, the reaction temperature is 8
The temperature is 0 to 300°C, preferably 170 to 250°C, and more preferably 210 to 230°C.

Further, the reaction pressure is usually 30 k9/gauge or higher, preferably 100 to 1000 k9/gauge. Furthermore, although the molar ratio of carbon monoxide and hydrogen used as synthesis raw materials is stoichiometrically 1:2, the reaction proceeds satisfactorily even at other molar ratios.

The molar ratio range is usually 1:10 to 10:1. The synthesis raw material gas can also be used even if it contains other components that are inert to the reaction, such as methane and nitrogen. Further, the concentration of the ruthenium compound and platinum compound used in the method of the present invention in the liquid medium is usually 0.1 to 1 part by weight per 100 parts by weight of the liquid medium as the sum of the weights converted to ruthenium atoms and platinum atoms.
The range is 0 parts by weight.

Further, the ratio of the ruthenium compound to the platinum compound used is in the range of 300:1 to 1:10 in terms of atomic ratio of ruthenium:platinum. Used in the method of the invention.

The amount of tin compound and/or lead compound is controlled by the relative amount to the ruthenium compound. If the amount of the tin compound and lead compound is too small, the effect of the addition will not be recognized, but if the amount is too large, the effect of the addition may be impaired. The preferred range of the amount added is 0.001 to 10 times the number of moles, more preferably 0.1 to 3 times the number of moles relative to the number of gram atoms of ruthenium in the ruthenium compound.

The amount of the phosphonium salt to be used is 0.01 to 10 moles, more preferably 1 to 60 times the number of gram atoms of ruthenium in the ruthenium compound.

The method of the present invention can be carried out in a batch, semi-continuous or continuous manner.

The ruthenium, platinum, tin and/or lead compounds, phosphonium salt and liquid medium may initially be added to the reactor batchwise or may be combined semi-continuously or continuously.

The product can be removed by a known method such as distillation or stripping, and if necessary, the catalyst etc. can be recycled to the reactor for use.

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples. Example 1 Triruthenium dodecacarbonyl [Ru3(CO),2]0 was placed in a stainless steel autoclave with an internal capacity of 50'.
．． 15 evening, platinum potassium chloride [K2PtC14] 0
．． 11 evenings, n-heptyltriphenylphosphonium bromide 3.1 evenings, stannous chloride [SnC12] 0.265
A mixed gas of carbon monoxide and hydrogen (CO:2 molar ratio 1:1) was charged at 290 ml of toluene at room temperature.
It was press-fitted to the kg/c cargo gauge.

The autoclave was heated under a rope rope, and when the internal temperature reached 220 qo, the temperature was maintained at a constant temperature for 3 hours to carry out the reaction. During this time, the autoclave internal pressure was 360-320k.
g/changed to negative gauge. Next, the heating of the autoclave was stopped, and after cooling to room temperature, the pressure was released, and the contents were taken out and analyzed by gas chromatography. The reaction solution is 2
The total of both phases is 3.36 mmol methanol, 5.89 mmol ethanol, 0.
53 mmol of propanol, 0.48 mmol of methyl acetate, 0.31 mmol of ethyl acetate, 1.05 mmol of acetic acid and very small amounts of methyl formate were detected. Examples 2 to 8 and Comparative Examples 1 to 3 In Example 1, a ruthenium compound, a platinum compound, a tin compound or a lead compound, a phosphonium salt, a reaction pressure,
The reaction was carried out by changing the amounts as shown in Table 1.

These results are shown in Table 1 together with Example 1. It's a female ship [Tokito Sabami] The delivery room is about to be a mizoreimizokidog.''・33-ll Ball Koichi" / Goyama Convex Success! '7K Lower/■ Hifube G Kol〇- Bulb surface incense paste N Bu00○ Examples 9 to 15 and Comparative Examples 4 to 5 In Example 1, a tin compound or a lead compound, a phosphonium salt, and a reaction pressure were used. The reaction was carried out by changing the reaction temperature and amount as shown in Table 2.

Note that the dielectric constant of tetralin, the solvent used in Comparative Examples 4 and 5, is 2.733.

Table 2 Note: In Table 2, each symbol represents the following compound: oRu
: Same as Table 1.

PtOZ2: Platinum chloride Pt-0. : Dichlorpis (tri-n-butylphosphine) platinum (Pt○mu2 (Bu3P)2) Pt"D
: Diiodopis (triphenylphosphine) Bratinum (Pt12(Ph3P)2) Pt-day : Diprompis (Triphenylphosphine) Bratinum (PtBr
2(Ph3P)2) TBOL: Tetra-n-butylphosphonium chloride BPOL: Penzyltriphenylphosphonium chloride HTI: n-heptyltriphenylphosphonium chloride TBBr: Tetra-n-butylphosphonium bromide NimuHTBr: Same Bu2Sn0 as in Table 1
M2: Di-n-butyltin dichloride SnBr4: Stannic bromide Sn12: Stannous tin chloride Sn○ M2: Same as Table 1 K Ph2Pb0 2: Diphenyl lead dichloride Et3Pb0 B: Triethyl lead chloride

Claims (1)

[Claims] 1 Carbon monoxide and hydrogen in a hydrocarbon solvent with a dielectric constant of 2.6 or less containing a ruthenium compound, a platinum halide, a tin halide and/or a lead halide, and a quaternary phosphonium halide. A method for producing ethanol, characterized by carrying out a catalytic reaction.