JPS6335532A - Method for producing isovaleraldehyde and/or isoamyl alcohol - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for perfume, etc., industrially advantageously without requiring complicated operation and device, by using methyl-t-butyl ether as a starting raw material and passing through a third process to convert methyl-t-butyl ether into isobutylene and methanol in the presence of a catalyst. CONSTITUTION:Methyl-t-butyl ether is used as a raw material and converted into isobutylene and methanol in the presence of a solid acid catalyst (e.g. silica or zinc oxide). The reaction temperature is 70-500 deg.C, preferably 100-400 deg.C and the pressure is preferably normal pressure-40atm. Then reaction is carried out in the presence of a metal and/or a metallic oxide at 150-450 deg.C, methanol is selectively converted into carbon monoxide and hydrogen, then converted carbon monoxide and hydrogen are reacted with isobutylene in the presence of an oxo synthesis catalyst preferably at 100-200 deg.C at 70-350atm. to give the aimed compound.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Applications> The present invention relates to a method for producing isoparealdehyde and/or isoamyl alcohol using methyl-t-butyl ether as a starting material.

<Conventional technology> Isoparealdehyde, isoamyl alcohol (hereinafter referred to as
Abbreviated as IVA and IAA, respectively. ) is an important compound as a raw material for perfumes, medicines, various solvents, etc., and it is well known that it can be obtained by extraction from natural oils.

It has also been proposed to
Publication No. 587).

<Problems to be solved by the invention> The method of extracting from natural oil has the disadvantage that the purity of the target product obtained is low, and furthermore, since the raw material is a natural product, the supply amount is greatly affected by weather etc. There were drawbacks.

On the other hand, when carrying out the oxo reaction method industrially, the raw material olefin is so-called spent BB (isobutylene, 1-butene,
(containing 2-butene, etc.) or isobutylene obtained by further purifying and separating the spent BB.

However, in the former case, the product is a mixture of isomers with similar physical properties, and in the latter case, the product is an isomer mixture with very similar physical properties, so I!
In the case of rI, there was a major drawback in that the energy of the latter was consumed.

Furthermore, in the conventional oxo method, so-called synthesis gas produced by partial oxidation or steam reforming of coal, oil, or natural gas is used as a carbon monoxide source and hydrogen source, and the synthesis gas production equipment is also limited. It has the disadvantage that it requires a separate service.

Means for Solving the Problems and Effects of the Invention> Under these circumstances, the present inventors have conducted intensive studies to develop a more industrially advantageous method for producing IVA and/or IAA. This method is based on a new route that is completely different from the conventional method by using methyl t-butyl ether as a starting material, and it solves all the above-mentioned drawbacks of the conventional method at once, and is extremely advantageous because each step is easy to implement industrially. They discovered a method and completed the present invention.

That is, the present invention consists of (1) converting methyl-t-butyl ether into isobutylene and methanol in the presence of a solid acid catalyst (first step);
, ■ The methanol is then converted to carbon monoxide and hydrogen in the presence of a metal catalyst and/or a metal oxide catalyst (
(1st step), (1) Thereafter, isobutylene, carbon monoxide, and hydrogen are reacted in the presence of an oxo synthesis catalyst (step (2)).
Alternatively, the present invention provides a method for producing IAA.

The present invention will be explained in detail below.

(1) Step of converting methyl-t-butyl ether into isobutylene and methanol (first step).

CH, QC (CHs)s-→(C mountain), CwC formula +C
Examples of catalysts used in the YamaOH main process include oxide catalysts such as silica, alumina, titania, zinc oxide, vanadium oxide, boron oxide, tin oxide, lanthanum oxide, and niobium oxide, aluminum phosphate, and zirconium phosphate. , phosphate catalysts such as titanium phosphate, zinc phosphate, boron phosphate, vanadium phosphate, nickel sulfate, zinc sulfate, aluminum sulfate, manganese sulfate, copper sulfate, strontium sulfate, magnesium sulfate, barium sulfate, iron sulfate , sulfate-based catalysts such as chromium sulfate, natural clay mineral-based catalysts such as acid clay, clarite, bentonite, kaolin, montmorillonite, A, X.

Can be mentioned.

These may be used in combination of two or more, or supported on a carrier, and are usually used in the reaction after being fired at a temperature of 300°C or higher.

There are no particular restrictions on the raw material methyl t-butyl ether, and gasoline machining materials that are easily available industrially can also be used. The feeding rate depends on the reaction temperature, reaction pressure, etc., but usually the superficial velocity (SV) is 1 x 10 to 1 x 10
The range is hr.

The reaction temperature is usually 70-500°C, preferably 100-500°C.
It is 400'C. The reaction pressure is not particularly limited, but is generally from normal pressure to 100 atm, preferably from normal pressure to 40 atm.

A mixture of methanol and isobutylene is thus produced from methyl t-butyl ether. Methanol and isobutylene are usually used as a mixture as a raw material for the next step, but after separating the two, methanol can be used as a raw material for the next step, and isobutylene can be used as a raw material for the next step.

■ Process of converting methanol into carbon monoxide and hydrogen (first step) CH, OH-1→CO+2 Catalysts used in the Yamamoto process include, for example, chromium, manganese, iron, cobalt, nickel, palladium, rhodium, and platinum. Examples include metals such as and oxide catalysts thereof. These may be a combination of two or more dishes,
It can also be used by being supported on a carrier such as silica, alumina, titania, magnesia, or the like.

When methanol is converted into carbon monoxide and hydrogen in the presence of isobutylene, it is important to selectively convert only methanol without changing isobutylene at all. In this case, the catalyst is copper zinc type, copper chromite type,
It is particularly preferable to use a composite oxide catalyst containing copper or zinc, such as zinc chromite, which can prevent hydrogenation of isobutylene and selectively convert methanol into carbon monoxide and hydrogen. can do.

In addition, when a mixture of methanol and isobutylene is used as a raw material, by filling the same reactor with the catalyst for step jII and the catalyst for step Carbon and hydrogen can also be produced all at once.

Further, in some cases, by additionally adding a small amount of methanol to the raw material obtained in the previous step, the raw material usage ratio in the next step, that is, the ratio of carbon monoxide and hydrogen to isobutylene, can be changed.

The reaction temperature in this step is usually 100 to 600''C, preferably 150 to 450''C. The raw material supply rate depends on the reaction temperature, reaction pressure, etc., but usually the SV is 1XIO3~IX
The reaction pressure is not particularly limited, but is usually from normal pressure to 100 atm, preferably from normal pressure to 40 atm.

Thus, methanol is converted to carbon monoxide and hydrogen, but if isobutylene is present, it is usually cooled and possibly compressed before being led to a gas-liquid separator to convert hydrogen and monoxide. It is separated into a carbon mixed gas (Co/H molar ratio of about 1/2) and corrugated isobutylene, each of which is used as a raw material for the next step.

■ A step of reacting isobutylene, carbon monoxide, and hydrogen (step ■).

H.

(CHs)zc=cH, +CO--→CCHa), CH
CH, CHll・.

(IVA) H Kenichi → (C Mountain), CHCH, C Xun 0H CIAA) As the catalyst in this step, compounds known as oxo synthesis catalysts such as cobalt compounds and rhodium compounds are used. Any of these may be used as long as it forms a carbonyl compound under the reaction conditions, and examples thereof include carbonyl compounds of cobalt and rhodium, as well as acetylacetone salts, carboxylates, carbonates, and halides. The amount used is usually I× per mole of isobutylene in terms of metal.
10 to txtor atoms.

When the above catalyst is used alone, IVA is normally obtained selectively, but when used in combination with octagrade phosphine,
IAA can also be produced all at once from isobutylene.

Examples of such 8th class phosphine include triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, triphenylphosphine, etc., and the amount used is usually in the amount per 11 atoms of the catalyst metal. 0.
It is 1 to 100 moles.

Further, when reacting a mixed gas of carbon monoxide and hydrogen with isobutylene, the mixed gas is pressurized to a predetermined pressure beforehand. -The ratio of carbon oxide to hydrogen may be used as it was obtained in the previous step (Co/H, molar ratio 172), but it can also be used in the range of usually 10/1 to 1/10. . This ratio can be adjusted by using an adsorbent or a separation membrane. Furthermore, the mixed gas used in the reaction can be used even if an inert gas such as methane, carbon dioxide, or nitrogen is present.

The reaction temperature in this step is usually 50-800°C, preferably 100-200°C, and the reaction pressure is usually 50-800°C.
The pressure is 500 atmospheres, preferably 70 to 850 atmospheres. The reaction time is not particularly limited, but is usually 0.1 to 10 hours.

In this step, a solvent is not particularly required, but aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, aldehydes, ketones, ethers, etc. may be used depending on the case. Moreover, the mixed gas of carbon monoxide and hydrogen used in excess can be mixed into the fresh mixed gas stream obtained in the previous step as a recycled stream after the reaction, and can be used effectively. This step can be carried out either batchwise or continuously.

In this way, IVA and/or IAA can be selectively obtained, and these can be easily purified and isolated industrially by distillation or the like, and highly pure products can be produced.

In addition, the obtained IVA was hydrogenated by a known method.
It is also possible to lead to A. At this time, the hydrogen gas used can be one separated from the mixed gas of carbon monoxide and hydrogen obtained in the first or second step using an adsorbent or a separation membrane. In this case, the IAA yield from the starting material methyl t-butyl ether is significantly increased,
This method is extremely advantageous industrially because the hydrogen produced from methyl t-butyl ether via methanol can be used effectively without waste.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 A reaction was carried out using a gas phase flow reactor equipped with a raw material feed pump, a preheater, a reactor, and a product collector.
.

Nickel sulfate as catalyst3. Of was used.

Methyl-t-butyl ether was fed at a rate of 10 y/hr, and the reaction was carried out at 297°C under normal pressure. The product was analyzed by gas chromatography and the following results were obtained.

The conversion rate of methyl-t-butyl ether was 99.5%, and the yields of isobutylene and methanol were almost quantitative based on the converted methyl-t-butyl ether.

(i-2) Using a gas phase flow reactor similar to that used in 1-1, 45 wt% of CuO, 45 wt% of ZnO, and C
The complex acid tanol containing r, O, and 79wt9/ were fed at a rate of 5.2 f/hrx s, tf/hrc molar ratio 1/1), and the reaction was carried out at 286°C under normal pressure, and the following results were obtained. I got it. The yield and conversion rate are shown based on the methanol fed.

The conversion rate of methanol was 99.8%, the yield of -carbon oxide was 97.1%, the yield of hydrogen was 189.6, and isobutylene was quantitatively recovered.

In a 50 ml stainless steel autoclave, add 5 ml of ethylbenzene and 1.3 ml of isobutylene obtained in the previous step.
1 and cobalt carbonyl (Co2(Co)s)
0.1 If-atom in terms of
) was injected under pressure up to 120 kq/d, and then reacted at 150°C for 2 hours.

The results obtained are shown in Table 1.

In Example 1-8, cobalt carbonyl was used as a catalyst in terms of Co, QJlIIg-atom and tri-n-butylphosphine 9.3 mmol, the mixed gas was pressurized to 60:9/c4, and the reaction temperature was 190°C. The reaction was carried out in the same manner as in Example 1-8. The results are shown in Table 1.

Example 8 CB-1) A reaction was carried out using a gas phase flow reactor equipped with a raw material feed pump, a preheater, two reactors connected in series, and a product collector.

In the first stage reactor, a silica-alumina catalyst calcined at 550°C in air was used. Of, the second stage reactor contains Cu
45 wt% O, 45 wt% ZnO, 1 Cr, 03
A, oy is filled with a composite oxide catalyst containing 0 wt%,
The reaction temperatures of the first and second stages were set to 147°C and 285°C, respectively.

The reaction was carried out by feeding methyl-t-butyl ether at a rate of 10 y/hr. The results obtained are shown below. yield,
The conversion rate was expressed based on the number of feed moles of methyl-1-butyl ether.

The conversion rate of methyl-t-butyl ether was 98.9%, -
The yield of carbon oxide is 98.7%, the yield of hydrogen is 187.1
%, methanol yield is 2.5%, methane yield is 0.
The yield of carbon dioxide was 1.5%, and the yield of isobutylene was 98.7%.

Using the product obtained above, rhodium carbonyl (Rh4(co), □) was added as a catalyst at 0.001 in terms of Rh.
The reaction was carried out in the same manner as in Example 1-8 except that 1-a atom was used and the reaction temperature was 180°C. The results obtained are shown in Table 1.

Table 1

Claims (1)

[Claims] Conversion of methyl-tert-butyl ether to isobutylene and methanol in the presence of a solid acid catalyst, then conversion of methanol to carbon monoxide and hydrogen in the presence of a metal catalyst and/or metal oxide catalyst, followed by oxo synthesis. A method for producing isopallelaldehyde and/or isoamyl alcohol, which comprises reacting isobutylene, carbon monoxide, and hydrogen in the presence of a catalyst.