JPS6049614B2 - Method for producing alcohol having 1 to 4 carbon atoms - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an alcohol having 1 to 4 carbon atoms by catalytically reacting carbon monoxide and hydrogen in the presence of a catalyst consisting of iridium and iron.

As a method for producing alcohols from carbon monoxide and hydrogen, a catalyst in which iridium is supported on silica is reported in Journal of Catalysis, 52, 157-168, (1
978) and JP-A-54-41291 discloses a catalyst in which iridium clusters are supported on zinc oxide.

However, the former catalyst has low activity and the yield of alcohol is extremely low despite harsh reaction conditions. The latter has drawbacks such as difficulty in synthesizing metal carbonyl clusters as a raw material, and the need for an inert gas atmosphere during catalyst preparation and handling since the clusters decompose in air, so neither is practical. isn't it. The present inventor solved the above drawbacks and investigated iridium-based catalysts that have excellent activity and selectivity. As a result, the inventor discovered that the activity can be dramatically improved by adding iron as a co-catalyst, resulting in the present invention. did. That is, the present invention is a method for producing an alcohol having 1 to 4 carbon atoms by catalytically reacting carbon monoxide and hydrogen in the presence of a catalyst consisting of iridium and iron. The raw material compounds used to prepare the catalyst of the present invention include inorganic compounds such as oxides, chlorides, bromides, nitrates, and carbonates of each of the above elements, acetates, oxalates, acetylacetonate salts, and dimethylglyoxime. Compounds commonly used in preparing noble metal catalysts are widely used, such as salts, organic salts such as ethylenediaminetetraacetate, other chelate compounds, carbonyl compounds, cyclopentadiene compounds, ammine complexes, metal alkoxides, and al-Yal metal compounds. I can do it.

These catalyst components are used after being dispersed on a carrier by an impregnation method, a dipping method, an ion exchange method, a coprecipitation method, a kneading method, or the like.
As the carrier, a wide variety of carriers known as ordinary carriers can be used, but those having a specific surface area of 10 to 1,000 dia and a pore diameter of 108 or more are particularly preferred.

Specific examples of these include silica, silicates of various metals such as titanium and zirconium, molecular sieves, diatoms, silica gel, alumina, activated carbon, and periodic table
There are oxides of group metals, and silica is particularly preferred.
Although the concentration and composition ratio of each component in the catalyst can be varied over a wide range,
．． 001 to 0.5 (weight ratio), preferably 0.01 to 0
．． Support within the range of 3.

The addition ratio of iron to iridium is in the range of 0.01 to 10 (atomic ratio), preferably 0.05 to 5. It is desirable that this ratio be small when it is desired to increase the proportion of methanol in the alcohol, and high when it is desired to reduce the proportion of methanol in the alcohol. To support the catalyst component on a carrier, dissolve the above metal compound in a solvent such as water, methanol, ethanol, tetrahydrofuran, dioxane, n-hexane, benzene, etc., add the carrier to the solution, impregnate the catalyst component, and distill the solution. The support can be carried out by an impregnation method, etc. in which the resin is removed and dried.

Further, upon loading, each raw material compound may be dissolved in a different solvent and each component may be sequentially supported on the carrier, or a plurality of raw material compounds may be dissolved in the same solvent and supported simultaneously. Furthermore, a method may be used in which each component is supported sequentially or stepwise while carrying out treatments such as reduction and heat treatment as necessary. The catalyst prepared by such means is usually subjected to a reduction treatment to be activated and then subjected to a reaction.

Reduction is carried out in the presence of a gas containing hydrogen, carbon monoxide, etc.
Generally, the treatment is carried out at a temperature of 00°C or higher, preferably about 200 to 600°C, and the reduction is carried out while gradually or stepwise raising the temperature from a low temperature to ensure sufficient dispersion of each component of the catalyst. It is desirable to do so. In addition, reduction can also be carried out using a reducing agent such as hydrazine, a borohydride compound, or an aluminum hydride compound. As a reaction condition when carrying out the reaction of the present invention, the reaction temperature is 15
The temperature is 0 to 450C, preferably 200 to 3500C.

When the temperature is higher than 450°C, the amount of hydrocarbon by-products increases. The reaction pressure may be normal pressure, but in order to increase the space-time yield, it is preferable to carry out the reaction under pressure.
cIG1 is preferably 10 to 250k91cT1G. The space velocity is appropriately selected from the range of 1σ to 1σHr−1 depending on the reaction temperature and raw material gas composition. As the raw material gas, a gas containing carbon monoxide and hydrogen in a CO/H2 ratio of 0.1 to 101, preferably 0.25 to 5 (volume ratio) can be used,
It may also contain other gases that are inert to the reaction, such as nitrogen, argon, hydrocarbons, carbon dioxide, and water.

Also, if you want to increase the proportion of methanol in alcohol, it is preferable to increase the reaction pressure and space velocity and lower the CO/11 ratio. It is preferable to increase the /H2 ratio. The reaction method can be carried out by a fixed bed flow reaction, a fluidized bed reaction, or a liquid phase homogeneous reaction in which a catalyst is dispersed in a solvent.

According to the present invention, an alcohol having 1 to 4 carbon atoms can be produced in good yield from carbon monoxide and hydrogen.

Example 1 Iridium chloride 2.28rrLm01 and ferric chloride 0
．． 2281rrLm01 was dissolved in 99.5% ethyl alcohol, and 10
Add 25 ml (10 y) of -24 mesh silica gel.

Next, the ethyl alcohol was distilled off using a rotary evaporator, dried to dryness, and after drying under sufficient vacuum, hydrogen and helium. The temperature was raised stepwise while flowing a mixed gas of H2/He (H2/He=3/1), and finally the temperature was raised to 400°C for 6 hours, totaling 1C.
The catalyst was prepared by hydrogen reduction during i11. The catalyst 5T111 thus obtained was placed in a reactor (14φ×460
Tm), re-reduced with hydrogen for 1 hour, and then supplying a mixed gas of hydrogen and carbon monoxide (CO/H2=1/2),
Pressure 20k91CT1G1 Temperature 205℃, space velocity 60
The reaction was carried out under conditions of 00 hr-1. The results are shown in Table 1. Examples 2 to 5 Table 1 shows the results of reaction under the same conditions as in Example 1 while changing the amounts of iridium chloride and ferric chloride as shown in Table 1.

Examples 6-7 Iridium chloride 2.287T1. m01 and ferric chloride 1.

37nLm01 was used, and the hydrogen reduction treatment was carried out stepwise with a mixed gas of hydrogen and nitrogen (H2/N2=2/1), and finally at 4002C for 5 hours, except for the same example. A catalyst was prepared in the same manner as in Example 1.

10ml of this catalyst is mixed with 10~24 mesh silica gel 3
It was diluted with 0mt, filled into a reaction tube of 18φ x 1100mm, and heated at a temperature of 3000C for 2 hours with a mixed gas of hydrogen and nitrogen (H
After re-reduction with 2/N2=2/1), a mixed gas of hydrogen and carbon monoxide (CO/H2=1/2) was supplied, and the pressure was 50k9.
1C! The reaction was carried out at 1G1 temperature of 275°C (Example 6)
. The reaction was also carried out under the same conditions with the CO/H2 ratio changed to 1/1 (Example 7). The results are shown in Table 1. Example 8
~9 A catalyst was prepared in the same manner as in Example 6 except that the amounts of iridium chloride and ferric chloride were changed as shown in Table 1,
A reaction was carried out in the same manner as in Example 6 using 10 ml of the solution.

The results are shown in Table 1. Example 10 Iridium chloride and ferric chloride in the amounts shown in Table 1 were added to 1
A catalyst was prepared in the same manner as in Example 6 except that it was supported on 0 to 24 mesh alumina, and 10 ml of the catalyst was reacted in the same manner as in Example 6. Table 1 shows the results.

In addition to this, dimethyl ether has a selectivity of 16.6% (S
TY8.9qlk9-Catlhr). Comparative Example 1 A reaction was carried out in the same manner as in Example 1 using 10 ml of a catalyst containing only 2.287 TLm01 of iridium chloride at a space velocity of 180011 r1.

The results are shown in Table 1. Comparative Example 2 Using only 2.28rrL, m01 of ferric chloride as a catalyst, the hydrogen reduction treatment temperature was finally 500°C for 6 hours.
The reaction was carried out in the same manner as in Example 6, except that a total of 2C was used.

Claims (1)

[Claims] 1 Carbon monoxide and hydrogen are subjected to a catalytic reaction in the presence of a catalyst consisting of iridium and iron.
4. Method for producing alcohol.