JPS6049618B2 - Method for producing oxygen-containing compounds containing ethyl alcohol as the main component - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing oxygen-containing compounds.

More specifically, when carbon monoxide and hydrogen are reacted in the presence of a rhodium catalyst to produce an oxygen-containing compound whose main component is ethyl alcohol, vanadium and (B) iron and iridium are used as promoter components. It relates to a method characterized in that it is used in combination with at least one kind. The oxygen-containing compounds targeted in the method of the present invention include alcohols, aldehydes, fatty acids, esters thereof, and the like.

More specifically, the target substance in the present invention has 2 carbon atoms.
oxygenated compounds, namely ethyl alcohol, acetaldehyde, acetic acid and its esters. More specifically, the object of the present invention is an oxygen-containing compound having 2 carbon atoms and containing ethyl alcohol as a main component. It has been produced by an acid-containing method using oxygen-containing compounds, especially ethyl alcohol. However, due to the rise in the price of crude oil in recent years, the manufacturing price has increased significantly, making it necessary to switch raw materials. On the other hand, various methods of producing oxygen-containing compounds from a mixed gas of carbon monoxide and hydrogen, which are abundant and available at low cost, have been studied.

That is, a method for selectively producing an oxygen-containing compound having 2 carbon atoms by reacting a mixed gas with rhodium as the main component in the presence of a catalyst consisting of a metal or metal oxide such as titanium, zirconium, tungsten, or manganese. It is publicly known.
However, this method also produces a large amount of by-product hydrocarbons, such as methane, and has a low selectivity for oxygen-containing compounds.

Furthermore, the amount of target compounds produced based on rhodium, which is an expensive precious metal, is still small, and the reality is that no technology has been developed that is economically or process-perfect.
Furthermore, various combinations with a large number of elements have been proposed for the purpose of producing the target compound with high yield and high selectivity (for example, Japanese Patent Application Laid-open Nos. 56-7727 and 56-8334).
(No. 56-83426, etc.), there are many cases in which the yield decreases depending on the combination of components, and there are also many that increase the yield but reduce selectivity. It's not easy.

As described above, no method has been provided for efficiently and economically producing an oxygen-containing compound containing ethyl alcohol as a main component from a gas containing carbon monoxide and hydrogen.

The present inventors aimed to improve the yield and selectivity per rhodium catalyst in a method for efficiently and economically producing an oxygen-containing compound containing ethyl alcohol as a main component from a gas containing carbon monoxide and hydrogen. As a result of intensive studies on combination tests of a large number of co-catalyst components, it was discovered that a catalyst in which rhodium is combined with vanadium and iron and/or iridium as a co-catalyst has a preferable yield and high selectivity. It was completed.

In addition, when producing an oxygen-containing compound having two carbon atoms from carbon monoxide and hydrogen, rhodium and iron (JP-A-51-80807
Although it is known to use a so-called binary catalyst that combines rhodium and vanadium (Japanese Patent Application Laid-open No. 57-6223), the so-called ternary or quaternary catalyst of the present invention described above is a combination of these known catalysts. Yield expected from binary catalyst results,
It was found that there were significant differences in selectivity, especially for ethyl alcohol, and a synergistic effect, so to speak. below,
The method of the present invention will be explained in more detail.

As described above, the catalyst of the present invention is a catalyst containing rhodium, bound vanadium as a co-catalyst, and (B) at least one of iron and iridium.

Although the state of each component element under the reaction conditions is not necessarily clear, the so-called active site that is the center of the reaction is a place where rhodium and (4) vanadium and at least one of (B) iron and iridium coexist. There are no restrictions on the form of the element, including the form of the precursor.
Although the catalyst component can be subjected to the reaction without a carrier, it is usually preferable to use it dispersed on a carrier. The catalyst used in the method of the present invention can be prepared according to conventional methods when using noble metals.

For example, it can be prepared by an impregnation method, a dipping method, an ion exchange method, a coprecipitation method, a kneading method, etc. Raw material compounds that can be used to prepare the catalyst from rhodium, batodium, iron, and iridium, which are the components that make up the catalyst, include inorganic salts such as oxides, chlorides, oxychlorides, nitrates, and carbonates, and acetates. , oxalates, acetylacetonate salts, dimethylglyoxime salts, ethylenediamine acetate salts, organic salts or chelate compounds, carbonyl compounds, cyclopentadienyl compounds, ammine complexes, metal alkoxide compounds, alkyl metal compounds, etc. Compounds that are used when doing so can be used. The method for preparing the catalyst will be explained below using the impregnation method as an example.

The above metal compound is dissolved in a single or mixed solvent such as water, methyl alcohol, ethyl alcohol, tetrahydrofuran, dioxane, n-hexane, benzene, toluene, etc., a carrier is added to the solution and immersed, and the solvent is distilled off.
Dry, heat, gas treatment, etc. if necessary.
A metal compound is supported on a carrier.

Supporting methods include preparing a mixed solution in which raw material compounds containing rhodium, vanadium, and iron or/and iridium components are dissolved simultaneously in the same solvent, and simultaneously supporting the solution on the carrier, and sequentially loading each component onto the carrier. Various techniques can be used, such as a method of supporting, or a method of supporting each component sequentially or stepwise while performing treatments such as reduction, heat treatment, and gas treatment as necessary.

Other preparation methods, such as a method in which metals are supported by ion exchange using the ion exchange ability of a carrier, and a method in which a catalyst is prepared by a coprecipitation method, are also adopted as methods for preparing the catalyst used in the method of the present invention. can.

The catalyst prepared by the above-mentioned method is usually activated by reduction treatment and then subjected to the reaction.

It is convenient and preferable to carry out the reduction using a hydrogen-containing gas at an elevated temperature. At this time, the reduction temperature is
The reduction treatment can be carried out at the temperature at which rhodium is reduced, that is, about 100'C, but preferably at 200'C.
The reduction treatment is carried out at a temperature of C to 600C. At this time, in order to sufficiently disperse each component of the catalyst,
Alternatively, hydrogen reduction may be performed while increasing the temperature in stages. It is also possible to perform chemical reduction using a reducing agent. For example, reduction treatment may be performed using carbon monoxide and water, or using a reducing agent such as hydrazine, a borohydride compound, or an aluminum hydride compound.

As the carrier used in the present invention, those commonly known as carriers can be used as long as they preferably have a specific surface area of 10 to 1000 rI1Iy1 and a pore diameter of 10 A or more.

Specific carriers include silica, various silicates, alumina, activated carbon, oxides of various metals (e.g. zirconium oxide, titanium oxide, magnesia, etc.), molecular sieves, diatomaceous earth, etc. A carrier system is preferred. The ratio of rhodium to the carrier is 0.001 to 0.000 by weight considering the specific surface area of the carrier. It is preferably 0.001 to 0.3.

The ratio of vanadium and rhodium is vanadium/rhodium (
(atomic ratio) is in the range of 0.001 to 1 ash, preferably 0.01 to 3. Furthermore, the ratio of iron to rhodium is iron/rhodium (atomic ratio) of 0.001 to 101, preferably 0.01 to 101.
3, and the ratio of iridium to rhodium (atomic ratio) is in the range of 0.01 to 3. The ratio of iron to vanadium is iron/vanadium (atomic ratio) in the range of 0.005 to 101, preferably 0.01 to 2, and the ratio of iridium to vanadium is iridium/vanadium (atomic ratio) of 0.005 to 101, preferably 0.01 to 2. It is in the range of 05-101, preferably 0.01-2. The method of the present invention can be applied, for example, to a fixed bed flow reactor.

That is, a reactor is filled with a catalyst, and a raw material gas is introduced to cause a reaction. It is also possible to separate the product and recycle and reuse the unreacted raw material gas. Further, the present invention can also be applied to a fluidized bed type reactor. That is, the reaction can also be carried out by bringing the raw material gas and the fluidized catalyst together. Furthermore, the present invention can also be applied to a liquid phase heterogeneous reaction in which a catalyst is dispersed in a solvent and a raw material gas is introduced to carry out the reaction.

The conditions adopted when implementing the method of the present invention are organic combinations of various reaction condition factors for the purpose of producing oxygen-containing compounds containing ethyl alcohol as a main component with high yield and high selectivity. selected.

Although the target compound can be produced with high selectivity and high yield even at normal pressure (ie, 0k9/Clt gauge), the reaction can be carried out under pressure in order to increase the space-time yield. Therefore, the reaction pressure is 0k9/C
d gauge ~ 350kg/CIL gauge preferably 0k9
The test is carried out under a pressure of 250 kg/d gauge to 250 kg/d gauge.
The reaction temperature is 150°C to 450°C, preferably 180°C to
The temperature is 350°C.

When the reaction temperature is high, the amount of hydrocarbon by-product increases, so it is necessary to increase the feed rate of the raw material. Therefore, the space velocity (raw material gas feed amount/catalyst capacity) is in the standard state (a)
It is appropriately selected from the range of 10h-1 to 1σh-1 (calculated at 1 atm) in relation to the reaction pressure, reaction temperature, and raw material gas composition. The composition of the raw material gas is a gas mainly containing carbon monoxide and hydrogen, and gases such as nitrogen, argon, helium, methane, etc., or hydrocarbons and dioxide if in a gaseous state under the reaction conditions. It may contain carbon, generated oxygen-containing compounds, and water.

The mixing ratio of carbon monoxide and hydrogen is CO/H2 (volume ratio) of 0.1 to 10. Preferably it is 0.25 to 5, and the total proportion of carbon monoxide and hydrogen in the raw material gas is 20 to 6 volume%,
Preferably it is 60-10% by volume. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 Rhodium chloride (RhCl3.31120) 1.20y1
Vanadium trichloride (VOCl3) 0.26y1 iron chloride (
FeCl2・4H20) 0.09f in methanol 30m
1 and 25 ml of silica gel (DAVIS
ON#57) was added and impregnated, and then the solvent was removed using a rotary evaporator.

This supported catalyst was packed into a Pyrex glass reaction tube,
The temperature was gradually raised from room temperature while flowing nitrogen-diluted hydrogen (H2:N2 = 40:40 ml/min) for 5 hours, and hydrogen reduction was carried out at 400°C for 5 hours to prepare a catalyst. Example 2 RhC13.3
H201.20y1■0C130.26y1 0.48q of iridium chloride (IrCl4.](1,0) was dissolved in 30ml of methanol, and 25ml of the silica gel described in Example 1 was added and impregnated. The catalyst was prepared by processing.

Example 3 IrCj4●H2OO. Example 1 was dissolved in a mixed solution of 20 mL of water and 10 mL of ethyl alcohol.
After adding and impregnating 25 ml of silica gel described in , the solvent was removed using a rotary evaporator.

This was filled into a Pyrex glass reaction tube, and air (2
00m1/min) at 150°C, 3 powders, 25
It was treated at 0°C for 1 full hour. This supported catalyst is RhCl3.3
FI201.20y1■0C130.79y. ．． FeC
1. - A catalyst was prepared by impregnating it with a solution in which 4H200.272q was dissolved in 30 ml of methanol, and then treating it in the same manner as in Example 1. Comparative Example 1 RhC13・3F1201.20y. ．． V0C130.
26 Da was dissolved in 30 ml of methanol, and 25 ml of the silica gel described in Example 1 was added thereto for impregnation, followed by treatment in the same manner as in Example 1 to prepare a catalyst.

Comparative Example 2 RhC13・3F1201.20y. ．． FeC12●4
H200.07y was dissolved in 30 mL of methanol, 25 ml of the silica gel described in Example 1 was added thereto for impregnation, and then treated in the same manner as in Example 1 to prepare a catalyst.

Comparative example 3 RhC13・mortar 1201.20f1. ．． IrC14・H
2Ol. 6lf was dissolved in 30 ml of methanol, 257n1 of the silica gel described in Example 1 was added thereto for impregnation, and the same procedure as in Example 1 was carried out to prepare a catalyst.

Activity test and results Outer diameter 8T! r! Inner diameter 18W$ with n thermocouple protection tube
10 mt of the above catalyst was diluted with 30 ml of the silica gel described in Example 1 and filled into a L titanium reaction tube.

Claims (1)

[Claims] 1. In a method for producing an oxygen-containing compound containing ethyl alcohol as a main component by reacting carbon monoxide and hydrogen in the presence of a rhodium catalyst, (A) is used as a co-catalyst component.
Vanadium and (B) at least one of iron and iridium
A manufacturing method characterized by the combined use of seeds.