JPS58150525A - Preparation of aliphatic alcohol - Google Patents

Abstract

PURPOSE:To improve the catalytic activity and make it possible to synthesize directly the aimed substance in obtaining an aliphatic alcohol from a mixture of carbon monoxide with hydrogen, by the presence of a rhenium compound as a catalyst and a halogen-containing compound as a cocatalyst. CONSTITUTION:A mixture of carbon monoxide with hydrogen is reacted in the presence of a rhenium compound as a catalyst and a halogen-containing compound as a cocatalyst at 150-450 deg.C, preferably 200-400 deg.C, to give the titled compound. The presence of nickel, palladium, platinum, etc. of Group VIII in the periodic table as a compound in the above-mentioned catalyst consisting of the rhenium compound and the halogen-containing compound further improves the yield of the titled compound. The concentration of the rhenium compound in the reaction system is within 0.001mol/l-1mol/l range, and the amount of the halogen-containing compound is preferably within (1/50)-(50/1) range expressed in terms of the molar ratio between the halogen-containing compound and the rhenium compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for the direct production of aliphatic alcohol chain pipes from a mixture of carbon monoxide and hydrogen (hereinafter abbreviated as synthesis gas) in the liquid phase. More specifically, the present invention relates to a novel method for producing lower aliphatic alcohols or polyhydric alcohols such as methanol, ethanol, and ethylene glycol.

Due to the difficulty of recycling the used catalyst, industrial realization is not expected.

The inventors of the present invention have intensively investigated the application of a catalyst tube containing rhenium, an element in group Ⅰ of the periodic table, to the above synthesis reaction, and have unexpectedly found that a certain type of compound can be used for rhenium compounds. By coexisting, aliphatic alcohols, especially methanol and ethylene glycol, can be obtained from synthesis gas II! In addition, the pipe heading, O which arrived at the present invention,
Regarding the catalytic activity of conventional rhenium compounds, D, R, ?
ahey ; J, Am, Oh@m, 8oc, mu),? /3t (/dill), there is some mention that a very small amount of methanol was produced from synthesis gas in the presence of a decaluponyldyrenium catalyst.

In the present invention, synthesis gas is reacted in the liquid phase in the presence of a catalyst consisting of a rhenium compound and a halogen-containing compound, or the presence of a catalyst consisting of a rhenium compound, a halogen-containing compound, and a compound of an element of group Ⅰ of the periodic table. The reaction below includes metals, binary compounds, salts, coordination compounds, etc.
Contains compounds in the form of tanks. Typical compounds include oxides, oxyacids and oxyacids, oxyhalides, nitrates, carbonates, halides, carboxylates, acetylacetonate salts, cyclopentagenyl compounds,
Examples include carbonyl compounds. These compounds are
It may be one having various ligands 1 containing oxygen, nitrogen, phosphorus elements, or the like.

Preferred specific examples of rhenium compounds include decaluponyldyrenium (Q), sodium pentacarbonylrhenium (-1), and hydridopentacarbonylrhenium (1).
, chloropentacarbonylrhenium (I), )licarponyl(1-cyclopentagenyl)rhenium (1),
In the case of rhenium hexafluoride (b), rhenium pentachloride (v), rhenium heptaoxide, -+ trioxide, ,', 1i4, it is usually used in the reaction in the form of being supported on a suitable carrier.

Furthermore, when a halogen-containing rhenium compound is used as a catalyst, significant activity 1 can be obtained even without the addition of a halogen-containing compound.

Specific examples of rhenium compounds containing all halogens include rhenium pentachloride, rhenium oxychloride, chloropentacarbonyl rhenium (1), and chlorotricarbonylbis(pyridine) rhenium.

In the method of the present invention, the activity of the catalyst can be significantly increased by coexisting a halogen-containing compound as a cocatalyst.The halogen-containing compound used contains inorganic and organic halides.In particular, halogenated Hydrogen, metal halides, onium halides, and alkyl halides are most commonly used; halides are listed in the periodic table [
It includes halides of all metals from Group 1 to Group 1. Among these, the first human race of the periodic table, the mansion! Preferred are metal halides of the Mu group and the Pth group, with specific examples of metal halides of Group V elements of the periodic table such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and phosphatide salts. Onium compounds are preferably used. Preferred specific examples are:
Bis(tritumenylphosphino)iminium chloride, bis(triphenylphosphino)iminium buclmide, bis(tritumenylphosphino)iminium l-cyto, tetran-situ, and halogen t/unit in the compound. Alkyl halides that generate hydrogen halide in the reaction system are preferred.

Specific examples of preferable alkylparites include those of nickel, palladium, platinum, rhodium, iridium, iron, ruthenium and osmium used in the method of the present invention in the catalyst consisting of a rhenium compound and a halogen-containing compound. Compounds of Group I elements of the periodic table include various forms of metals, binary compounds, salts, and coordination compounds, but include carboxylates, acetylacetonate salts, carbonyl compounds, and reactions. Compounds that can be converted into compounds by reaction in the system are preferred.

Specific examples of preferred compounds include acetates, acetylacetonate salts, halide salts, and dodecacarbonyl trichlorides of Group 1 elements of the periodic table, but are not particularly limited, but are preferred! The sections include water, ketones, alcohols, ethers, levonic acid, carboxylic anhydride, esters,
Lactones, 7mids, sulfones, sulfur oxides,
Aliphatic compounds are aromatic hydrocarbons, reaction i! solids and mixtures thereof that melt at temperatures below 50°C.

In the method of the present invention, f of the rhenium compound in the reaction system
ll*Id, 0.00/mol/4 ft l/I
L/mol/4 (D range.

The amount of the halogen-containing compound used is expressed as the ratio of the number of moles of the halogen-containing compound to the number of moles of the rhenium compound.
/ in the range of 〃 to 1000 //, preferably /
/Sθ to jθ//.

The amount of the compound of the Group 1 element of the periodic table to be added is the number of grams of gold atoms and the number of grams of rhenium atoms.

- The molar ratio of molar carbon to water volume is preferably in the range of ///θ to 10//. The degree of reaction source which may be present is preferably in the range of /jθ to 950°C,
More preferably, the temperature is Jθ or Daθθ°C, and it can be easily separated from the reaction solution by known separation operations (eg, i1' distillation, extraction, etc.). In the case of a heterogeneous catalyst, the catalyst used can be easily separated by, for example, filtration.In the case of a homogeneous catalyst, the residual liquid after separating the product may be used as is.Examples/~/3 and Comparisons Example: After purging the inside of a shaking type Hasteq C autoclave with an internal volume of 30 d with nitrogen, 0.7 mmol of decaluponyldyrenium, a predetermined amount of a halogen-containing compound as a cocatalyst, and N-methyl as a solvent. Pyrolidone 7!
; m , the contents were mixed well, and the autoclave was closed. Synthesis gas with a CO/H2 molar ratio of /// was injected into the autoclave through a trench with a CO/H2 molar ratio of θKp/cm2. 2 while shaking the autoclave? The reaction was carried out by heating at θ°C for 3 hours.

For comparison, the reaction was carried out in the same manner except that no halogen-containing compound was used.

Upon completion of the reaction, the autoclave was cooled to a temperature of about 100 ml, most of the gas was slowly released, and the reacted mixture was taken out through a normal pressure tube. A portion of the reaction mixture and released gas was collected and analyzed for the product by gas chromatography.

The results are shown in Table/. The "reaction pressure" column in the table indicates the maximum pressure reached in the old and old cases and the pressure at the end of the reaction.

In addition, in the table below, EGii ethylene glycol,
M.OH represents methanol and EtQH represents ethanol.

Table 7 * Bis(triphenylphosphino)iminium chloride** Bis(triphenylphosphino)iminium iodide** All experiments in Table 1 were repeated except that tetra-n-butylphosphonium bromide was used. 9. The results are shown in the table. a. Example 17~. 2j J[1 as decacarbonylsilenium θ, /Jmi υ
The experiment shown in Table 1 was repeated except for the run using a predetermined amount of a halogen-containing compound and a compound of an element of the periodic law **-group as a cocatalyst.The results are shown in Table JiC.

1! ! J Qin In these experiments, the reaction time is / J Hr・1
93-

Claims (1)

[Claims] (1) - A method for producing aliphatic alcohols, characterized by reacting a mixture of carbon oxide and hydrogen in the presence of a catalyst consisting of a rhenium compound and a halogen-containing compound (co) - A method for producing aliphatic alcohols, characterized by reacting a mixture of carbon oxide and hydrogen A method for producing aliphatic alcohols, which comprises reacting f*111 in the presence of a catalyst consisting of a rhenium compound, a hemagazine-containing compound, and a compound of group Ⅰ elements of the periodic table.