JPS58162543A - Production of dimethyl ether - Google Patents

Abstract

PURPOSE:In the production of dimethyl ether from hydrogen and carbon monoxide, a catalyst containing copper, chromium and a metal of group VIII in the periodic table is used, thus giving the objective compound efficiently in high yield. CONSTITUTION:In the production of dimethyl ether from hydrogen and carbon monoxide, a catalyst containing copper, chromium and at least one selected from metals of group VIII in the periodic table, preferably iron, preferably addtionally at least one from metal of group IIA, is used to produce dimethyl ether through a customary process in markedly increased selectivity. Since this process gives dimethyl ether with one-stage reaction, the operations are simple and operability is good. This process forms 1-4C alcohols and hydrocarbons as well as dimethyl ether and is utilized advantageously in the field of synthetic chemical industry.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing dimethyl ether, and more specifically, a method for efficiently producing dimethyl ether by using a synthetic gas (mixed gas consisting of hydrogen and carbon monoxide) as a raw material and using a specific catalyst. Regarding.

Generally, methods for producing methanol from synthesis gas are widely known, and the catalysts used in these productions include copper-zinc type and zinc-chromium type.

Various types are known, such as copper-chromium type, copper-cobalt type, and rhodium type.

However, in all of the above conventional methods, methanol and other alcohols are mainly produced, and dimethyl ether is produced in small quantities as a by-product. It wasn't something.

The present inventors have conducted intensive research on particularly suitable catalysts in order to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method capable of producing dimethyl ether from synthesis gas with high selectivity. As a result, copper as a catalyst.

It was discovered that the objective could be achieved by using a catalyst containing chromium and a metal from group I of the periodic table, or a catalyst containing a metal from group A of the periodic table in addition to these metals. The present invention was completed based on this knowledge. That is, the present invention provides a method for producing dimethyl ether from hydrogen and carbon monoxide using a catalyst containing copper, chromium, and at least one metal of group Ⅰ of the periodic table (hereinafter referred to as "catalyst A"), or copper, chromium, Provided is a method for producing dimethyl ether, characterized in that it uses a catalyst (hereinafter referred to as 1 catalyst B) containing at least one metal of Group 1 of the Periodic Table and at least one metal of Group 1 IA of the Periodic Table. It is something.

The raw materials for the method of the present invention are a gas consisting of hydrogen and carbon monoxide or C, that is, a synthetic gas, and the ratio of hydrogen to carbon monoxide in this synthetic gas is usually 0.0 as H2/CO. ,
! ~S (molar ratio), preferably 0. s~3 (molar ratio).

The catalyst used in the method of the present invention is the above-mentioned catalyst A or catalyst B, but these two catalysts basically exhibit the same catalytic action. By adding Table IIA metals, its functionality is further enhanced.

Copper and chromium, which are the components of the above catalyst, may be used as simple metals, but they are usually used in the form of oxides or various salts such as sulfates, carbonates, nitrates, oxalates, acetates, and chlorides. It will be done.

Group II metals in the periodic table include iron, cobalt, nickel, rhodium, palladium, platinum, and other metals. Use a mixture of two or more types. The metal of group 1 of the periodic table is preferably iron or cobalt, and in particular, in the case of catalyst A, iron is most preferable. Although it is made of metal, the ratio of each metal component is not particularly limited and may be appropriately selected depending on the purpose and various conditions. However, usually copper nichrome: Group ■ metal - θ, / ~ θ1g: θ, / ~ 0, g: 0.0
/~θ-5 (indicates the atomic ratio. However, the sum of the ratios of each component is /
It is. ) should be within the range.

On the other hand, the catalyst B of the present invention contains the above-mentioned copper and chromium.

It contains metals of group 11A of the periodic table as well as metals of group 1 of the periodic table. Here, there are various metals of Group 1A, such as magnenium, calcium, strontium, and barium, and these are usually used alone or in a mixture of two or more in the form of oxides or salts.

Catalyst B of the present invention contains copper, chromium, and
The ratio of each component of group metals and group 11A metals of the periodic table is not particularly limited, but is usually copper nichrome: group Ⅰ metal: group 1IA metal -/~θ9g: 0, /~o, g: o
, θ/~θ, 3: 0.00/~θ4 (indicates the original r ratio. However, the sum of the ratios of each component is /).

In preparing catalyst A and catalyst B of the present invention,
Any known method may be used, for example, adding each component compound to a medium such as water, mixing and stirring, and then co-precipitating.
After sufficient drying, it is baked at 300 to Sθθ℃ for about λ hours, and further impregnated with other ingredients as necessary to give a powder with a temperature of 700 to 1
After drying at 5θ℃, tablet molding, then 200-300℃
The desired catalyst can be prepared by a method such as reduction in an atmosphere of hydrogen or carbon monoxide. Note that the atmosphere for reduction here is particularly preferably carbon oxide, and it may also be diluted with inert gas.

Various conditions can be used to produce dimethyl ether using catalyst A or catalyst B of the present invention prepared in this way and using synthesis gas as a raw material, but usually the reaction temperature is θ0 to 500°C, preferably 2 0~1Ioo℃,
Reaction pressure θ~so.

Atmospheric pressure, preferably 40-2θθ atmospheric pressure, and gas air velocity (GH8V) 300~/θ00θhr-',
Preferably it should be 1000 to gθθθhr-'.

According to the method of the present invention as described above, dimethyl ether can be obtained with significantly higher selectivity than the conventional synthetic method for producing dimethyl ether from a gas. Furthermore, since dimethyl ether can be obtained immediately through a single reaction, the operation is extremely simple and the workability is good. In addition, according to the method of the present invention, alcohols and hydrocarbons having a carbon number of 1 to 1 are co-produced together with dimethyl ether.

Therefore, the method of the present invention can be effectively used in the field of synthetic chemical industry.

Next, the present invention will be explained in more detail by -★ Examples.

[Catalyst preparation]

Preparation example/ Nitrate steel (trihydrate) 211.2t, chromium nitrate (q-hydrate)
Aqueous solution/2 containing lIO,011 was maintained at gθ°C, and to this was quickly added sodium carbonate (anhydrous>3./, aqueous solution/2 containing g ii', and kept at gOoC for 2 hours with vigorous stirring. Thereafter, the product was filtered, washed with water until sodium ions were removed, dried overnight, and calcined in air at 33θ°C for 2 hours.

Add graphite to the obtained powder and make 2■φX, 2fi
The mixture was compressed into a cylindrical tablet to obtain Catalyst I. The ratio of copper to chromium charged in this catalyst I is Ou : Cr-/
: / (atomic ratio).

Preparation example Copper nitrate (trihydrate) 23.0 ? , chromium nitrate (q-hydrate) 3 g,/f- and ferric nitrate (nase-hydrate)
3. G! Aqueous solution containing i'/! 32. Maintain the temperature at gθ℃ and add thorium carbonate (anhydrous) to it. 'l Aqueous solution containing F/,! ;, 1? was quickly added and kept at 30° C. for 2 hours with vigorous stirring. Hereinafter, the same operation as in Preparation Example/ was carried out to obtain Catalyst (2). The charge ratio of copper, chromium and iron in this catalyst ■ is Ou : (!r :Fe=
/ :/ :0, / (atomic ratio).

Preparation Example 3 Copper nitrate (trihydrate) 23.0 ? , chromium nitrate (q-hydrate salt) 3 g, / El and cobalt nitrate (filtrate salt) 21 g? An aqueous solution/1 containing sodium carbonate (anhydrous) was kept at gθ°C, and 7.5 p of an aqueous solution containing sodium carbonate (anhydrous) 3 /g fl- was quickly added thereto, and the mixture was kept at gθ°C for 2 hours with vigorous stirring. Thereafter, the product was filtered, washed with water until sodium ions were removed, dried overnight, and calcined in air at 35θ°C for 2 hours. Next, this calcined product was impregnated with magnesium acetate equivalent to /wt% as magnesium oxide, and after sufficiently drying, graphite was added and the product was compressed into a cylindrical shape of 2fiφ x 2mm to form a catalyst. It's a good deal. The charging ratio of copper, chromium, cobalt and gnesium in this catalyst ① is Ou
:Or:Co:Mg=/:/:0. /
: 0.04' (atomic ratio).

Preparation Example 3 In Preparation Example 3, instead of magnesium acetate, sulfur acetate equivalent to "strontium oxide/wt%" was added.
The same operation as in Preparation Example 3 was carried out except that trontium was used to obtain catalyst (2). The charging ratio of copper, chromium, cobalt and strontium in this catalyst ① is O
u : Or : Co : Sr =/ : / :
0. /: 0.0 /Otsu (atomic ratio).

Copper nitrate (trihydrate) as a preparation example, 23. Of, chromium nitrate (nase hydrate)
, J' g, i y- and ferric nitrate (nase hydrate)
3. Aqueous solution containing g fl-/! was maintained at gθ℃, and an aqueous solution containing sodium carbonate (anhydrous) 3/, g9-, S2 was quickly added thereto, and the mixture was heated to gθ℃ while stirring vigorously.
It was held for an hour. Thereafter, it was filtered, washed with water until sodium ions were removed, dried overnight, and calcined in air at 330° C. for 2 hours.

Subsequently, 7wt% of magnesium oxide was added to this fired product.
The catalyst was impregnated with magnesium acetate corresponding to the above amount and dried sufficiently, graphite was added thereto and the mixture was compressed into a cylindrical tablet having a diameter of 2 mm and a size of 2 mm to obtain a catalyst (2).

The ratio of copper, chromium, iron, and magnesium in this catalyst (■) is as follows: Ou: Or: Fe:
Mg-/ :/ :0.7 :0.0111C atomic ratio)
Met.

Comparative Examples/and Examples/~G The catalyst obtained in the above Preparation Examples/~S was filled in a reaction tube, and a reducing gas with a CO/N2 ratio of /9 was flowed under normal pressure at GH8V go o o o hr. The temperature was gradually raised while maintaining the temperature at 2'lθ°C for 73 hours. Thereafter, the synthesis as a raw material was switched to S (H2/CO ratio, 2), the pressure was increased to a predetermined pressure, and the reaction was carried out at a predetermined temperature.

Three gas chromatographs were directly connected to the reactor to analyze the reaction products. The results are shown in Table 1.

Claims (1)

[Scope of Claims] 1. Production of dimethylniter, characterized in that a catalyst containing copper, chromium, and at least one metal of Group I of the Periodic Table is used in producing dimethyl ether from hydrogen and carbon monoxide. Method. 2. The method according to claim 1, wherein the Group Ⅰ metal of the periodic table is iron. 3. In producing dimethyl ether from hydrogen/hydrogen and carbon monoxide, copper, chromium, at least one metal from group Ⅰ of the periodic table, and at least one metal from group B of the periodic table are used.
A method for producing dimethyl ether, characterized by using a catalyst containing a Group A metal.