JPS6024084B2 - Method for producing oxygenated compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an oxygen-containing compound by reacting a gas mixture containing carbon monoxide and hydrogen in the presence of a catalyst.

More specifically, the group mainly consists of rhodium, nickel, and titanium, tantalum, niobium, chromium, cobalt, or rhenium (hereinafter abbreviated as promoter metals) (hereinafter abbreviated as metal-averse metals). ) in the presence of a catalyst composed of one or more components selected from
The present invention relates to a method for producing an oxygen-containing compound containing ethyl alcohol as a main component by reacting the mixed gas. The target oxygen-containing compound in the method of the present invention is:
Refers to alcohols, aldehydes, fatty acids and their esters, etc.

More specifically, the target substance in the present invention has 2 carbon atoms.
oxygenated compounds, namely ethyl alcohol, acetaldehyde, acetic acid and their 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. Oxygenated compounds, particularly oxygenated compounds such as ethyl alcohol, have traditionally been produced by petrochemical methods using naphtha as a raw material.
However, due to the recent rise in the price of crude oil, the manufacturing price has increased significantly, creating the need to switch raw materials. on the other hand,
Various methods have been studied for producing oxygen-containing compounds from a mixed gas of carbon monoxide and hydrogen, which is abundant and available at low cost.

That is, a method for selectively producing an oxygen-containing compound having 2 carbon atoms by reacting a mixed gas with rhodium as a main component in the presence of a catalyst consisting of a metal or a metal acid compound such as titanium, zirconium, tungsten, or manganese. It is publicly known.
However, this method also produces a large amount of 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 improved methods have been proposed for the purpose of producing oxygen-containing compounds with high yield and high selectivity (for example, JP-A-56-7727, 56-8333, 8334-90).
No. 028, etc.), but at present, all these methods still have drawbacks such as yield and selectivity.

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 have conducted extensive studies with the aim of providing a new method to replace the conventional method.

The result is a gas containing carbon monoxide and hydrogen. ) Oxygen-containing compounds containing ethyl alcohol as a main component can be produced with high yield and high selectivity by reacting in the presence of a catalyst composed of at least one component selected from the group of active catalyst metals. They discovered this and completed the present invention. The catalyst provided by the present invention is usually used supported on a carrier such as silica.
Therefore, the present invention also provides a practical catalyst for synthesizing an oxygen-containing compound containing ethanol as a main component from a mixed gas. Furthermore, the present inventors reacted a mixed gas in the presence of a catalyst containing rhodium and nickel as main components and supporting silicates or oxides of one or more promoter metals to produce ethanol as a main component. The present invention was completed after discovering the possibility of producing the oxygen-containing compound as a component in high yield and high selectivity.

Among the constituent components of the catalyst used in the present invention, nickel has been known as a catalyst that selectively produces lower hydrocarbons such as methane over carbon monoxide and hydrogen in high yield.

However, there is no known method for producing oxygen-containing compounds in high yield and high selectivity by reacting a mixed gas of carbon monoxide and hydrogen in the presence of a catalyst containing nickel. However, the present inventors discovered 'Erhodium.' } When nickel coexists with one or more metals selected from cocatalyst metals, the amount of hydrocarbons created is surprisingly reduced, and the main component of oxygen-containing compounds whose main component is ethyl alcohol is They found that the amount of growth increased. In addition, when nickel is not allowed to coexist with rhodium and each of the promoter metal components, in other words, if a catalyst consisting of nickel alone or other promoters is used, high selectivity as claimed in the method of the present invention can be achieved. It was discovered that it could not become a highly active catalyst. The method of the present invention will be explained in detail below.

As mentioned above, the catalyst used in the method of the present invention has one or more components selected from rhodium, nickel, and a metal promoter as a main component.

Substantially, a catalyst is used in which the components (a) to (o) above are dispersed on a carrier, as is usually done with noble metal catalysts. In this case, the catalyst is composed of one or more components selected from the group consisting of rhodium, nickel, and cocatalyst metals, and a carrier. The catalyst used in the process of the invention can be prepared using conventional noble metal methods.

For example, it can be prepared by an impregnation method, an immersion method, an ion exchange method, a mutual method, a mud sickle method, etc. Raw material compounds for catalyst preparation of the various components constituting the catalyst, rhodium, nickel, and promoter metal group, include oxides, chlorides,
Inorganic salts such as nitrates and carbonates, organic salts or chelates such as acetates, oxalates, acetylacetonate salts, dimethylglyoxime salts, ethylenediamine acetate, carbonyl compounds, cyclobentajenyl compounds, ammine chains, metals Compounds commonly used in preparing noble metal catalysts, such as alkoxide compounds and alkyl metal compounds, can be used.

The method for preparing the catalyst will be explained below by taking the impregnation method as an example. Dissolve the metal compound in the first half in a solvent such as water, methyl alcohol/ethyl alcohol, tetrahydrofuran, dioxane/n-hexane, benzene, toluene, etc., add a carrier to the solution, immerse it, remove the solvent, dry it, and remove it as necessary. If so, a treatment such as heating is performed to support the metal compound on the carrier.

As a special method, 'rhodium, nickel'
A method in which a mixed solution is prepared by simultaneously dissolving raw material compounds containing one or more components selected from the group of promoter metals in the same solvent, and the mixture is then simultaneously applied to one loss body, and each component is sequentially dissolved. Various techniques can be used, such as a method in which the components are supported on a carrier, or a method in which each component is supported sequentially or stepwise while performing treatments such as reduction and heat treatment as necessary. Other preparation methods, such as a method in which a metal is supported by ion exchange using an ion exchange chamber on a carrier, a method in which a catalyst is prepared by a co-pillar method, etc., can also be employed as a method for preparing the catalyst used in the method of the present invention.

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

In order to carry out the reduction, 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 20°C.
The reduction treatment is carried out at a temperature of 0°C to 600°C. At this time, hydrogen reduction may be carried out while raising the temperature gradually or stepwise from a low temperature in order to sufficiently disperse each component of the catalyst. Further, the reduction can also be carried out chemically 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 m/h and a pore diameter of 10 A or more.

Specific examples include silica, silicates of various promoter metals (e.g., titanium silicate, etc.), silica gel, alumina, activated carbon, oxides of promoter metals (e.g., zirconium oxide, titanium oxide, magnesia, etc.), and molecule. Examples include lar sheep and diatoms, but silica-based raccoon bodies are preferred. Furthermore, a silicate of a promoter metal used as a component of the catalyst or an oxide of a promoter metal can also be used as a carrier.

In this case, a catalyst having good activity can be obtained without adding one or more promoter metal components.

In other words, the promoter metal can be used in the form of a support as an oxide or a silicate. That is, an oxygen-containing compound containing ethanol as a main component can be obtained in high yield and high selectivity from a mixed gas using a catalyst in which rhodium and nickel are supported on a silicate or oxide of a cocatalyst metal.

The method for preparing the catalyst in this case is the same as the method for preparing the catalyst composed of {rhodium, nickel, {〇} co-catalyst metals, and a carrier. Damaged by acid salts or oxides.

In either case, the concentration and composition ratio of each component in the catalyst can be varied within a wide range. The ratio of W rhodium to one carrier is 0.00 by weight considering the specific surface area of the carrier.
01 to 0.5, preferably 0.001 to 0.3. The ratio of rhodium to nickel is nickel/rhodium in an atomic ratio of 0.001 to 5, preferably 0.01 to 2. Further, the ratio of nickel to one or more metals selected from the 'low promoter metal group is such that the atomic ratio of nickel/promoter metal is 0.005 to 10.0, preferably 0.0.
It ranges from 1 to 1. In addition, the ratio of rhodium promoter metal is 0.00 in atomic ratio of rhodium/promoter metal.
It ranges from 1 to 10, preferably from 0.01 to 5. When the promoter metal is used in the form of a carrier, that is, when rhodium and nickel are supported on a silicate or oxide carrier of the promoter metal and used as a catalyst, the ratio of rhodium to carrier, rhodium nickel, nickel, etc. The ratios of rhodium/promoter metal and rhodium/promoter metal may be the same as above.

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 purify the unreacted raw material gas, which can then be recycled and reused. Further, the present invention can also be applied to a fluidized bed type reactor. That is, the reaction can 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 carrying out 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 the main component in high yield and high selectivity. selected.

Although the target compound can be produced with high selectivity and high yield even under normal pressure (ie, OK9' gauge), the reaction can be carried out under increased pressure in order to increase the space-time yield. Therefore, the reaction pressure is from okg' to 350 kg/gauge, preferably from ok9/average gauge to 250 kg'. The reaction temperature is 15 to 45℃, preferably 18 to 350℃.
It is qo.

When the reaction temperature is high, the amount of hydrocarbons created increases, so it is necessary to increase the feed rate of the raw material. Therefore, the space velocity (raw material gas feed rate/catalyst volume) is in the standard state (0
It is appropriately selected from the range of 1 blood-1 to 1 "h-1" based on the relationship between the reaction pressure, reaction temperature, and raw material gas composition. The composition of the raw material gas is mainly a gas containing carbon monoxide and hydrogen, and if it is in a gaseous state under an inert gas such as nitrogen, argon, helium, or methane or under reaction conditions, hydrocarbons and It may contain carbon dioxide gas or water.

The mixing ratio of carbon monoxide and hydrogen is 0.1 to 2 CO/day.
10 preferably 0.25 to 5 (volume ratio). The present invention will be explained in more detail below with reference to Examples.

Example 1 Preparation of rhodium nickel titanium/silica catalyst Rhodium chloride (RhC13, 9 days 20) 1.2 evenings (4
．． 56 mol), nickel chloride (NiC12, mother L
O) 0.2 paper (1.0 skin mol), titanium tetrachloride (
TIC14) Silica gel (Davison NO. 57,
Manufactured by Davison, the same applies below) 10 evenings 280q0
The mixture was baked and degassed under vacuum for 2 hours, and added as a carrier and immersed.

Next, the solvent of this solution was removed using a rotary evaporator, dried, and further dried under vacuum to form a mixed gas of hydrogen and helium (ratio/He=40/20/min).
The temperature was raised stepwise under aeration of 200 mm, and finally hydrogen reduction was carried out at 40 pi for 3 hours, for a total of 16 hours, and an activation treatment was carried out. [Explanation] The catalyst obtained in the above reaction section using a catalyst was charged into a reaction tube (Pyrex glass 200 x 40 mm) of a normal pressure flow reactor,
Mixed gas of hydrogen, carbon monoxide, and helium CO/day 2/
Send the kite at a speed of 20/40/min.
The reaction was carried out.

Organic compounds with high boiling points in the product are dissolved in water and collected,
Hydrocarbons were directly analyzed by gas chromatography to determine the distribution of products.

The results are shown in Table-1. Example 2 Preparation of rhodium-nickel-tantalum silica catalyst Rhodium chloride (RhC13, Group 20) 1.2 nights (4.
56w mol), nickel chloride (NiC12/mother LO
) 0.2 lactate (1.0 mol), tantalum pentachloride (
Rhodium nickel was treated in the same manner as in Example 1 except that 60% of ethyl alcohol (99.5%) was dissolved using 3.40 mol of TaCl (9.5 mol).
A tantalum/silica catalyst was prepared.

‘o} reaction The reaction was carried out in the same manner as in Example 1 using the same apparatus.

The results are shown in Table-1. Example 3 Preparation of 10dium-nickel niobium silica catalyst 1.2 mols of rhodium chloride (4.56 mol), 0.23 mols of nickel chloride (1.0 mol), niobium pentachloride Example 1 except that (N ratio 15) 2,54 molar (9.4 mol) was dissolved in 60 mol of ethyl alcohol.
A rhodium-nickel niobo-silica catalyst was prepared in the same manner as above.

Ta’01 reaction A similar reaction was carried out using the same apparatus as in Example 1.

The results are shown in Table-1. Comparative Example 1 Preparation of rhodium-titanium/silica catalyst o Rhodium chloride (RhC13/Pan 20) 1.2 nights (4.56 m
mol), titanium tetrachloride (TIC14) 1.78 mol (
Prepare an ethyl alcohol solution of 9.4 mmol),
A catalyst was prepared in the same manner as in Example 1.

[o' Reaction was carried out using the same apparatus and method as in Reaction Example 1, and the products were analyzed and compared. The results are in Table-1
Shown below. Comparative Examples 2 to 4 A rhodium-zirconium silica catalyst, a rhodium-tantalum/silica catalyst, and a rhodium niobium silica catalyst were prepared in the same manner as in Comparative Example 1, and comparative experiments were conducted in the same manner.

Table - I Table - 1 Reaction conditions Reaction pressure: 0.5k9' ground gauge Raw material composition; Carbon monoxide: Hydrogen: Helium = 1:2:1 (
Capacity ratio) Space velocity: 19 ml Catalyst amount: 25' RhC13 20: 1.2 mol (4.56 mol)
Explanation of abbreviations (same in the table below) *1) Carbon monoxide reaction rate Number of moles of carbon monoxide consumed and reacted *11) Number of moles of carbon monoxide input × 100 (*) (*2 ) Oxygenated compound selectivity = MeOH, AcH, EtOH, ratio O
Total selection rate (%) on Et, P day, and B day (*3)
MeCH: Methyl alcohol (*4) AcH: Acetaldehyde *5) EtOH: Ethyl alcohol (*6) A
cOEt; ethyl acetate (*7) n-P H; Normanpropanol (*8)
Price OH: Noryangbuta/-ru (*9) C2-C4
:C2 day 4, C2 is C3 day 6, C3 day 8, Mr. C4, C
4 days, o*10) Selectivity Number of moles of carbon monoxide converted into a specific substance XI.

〇 (register) Number of moles of carbon monoxide (consumed) *11) (
*11) MeOH, AcH, EtOH, AcOEt,
n-P[] day, n-Bu○ day “C2-C4 and C02
Number of moles of carbon monoxide consumed to produce
6 mmol), 1.78 titanium tetrachloride (TIC14)
2 (9.4 mmol) and nickel chloride (NiC12
・Vary the mother LO) between 0 kite mole and 5.0 skin mol, prepare a solution of dissolved ethyl alcohol,
In addition, silica gel (D
avison #57) was added and treated in the same manner as in Example 1 to prepare a catalyst.

Next, a reaction was carried out using the same apparatus and method as in Example 1.
The results are shown in Table-2. Examples 11-16 Rhodium chloride (RhC13/Group 20) 1.2 evenings (4.5
6 wmol), nickel chloride (NiC12/mother LO) 0
．． 236 Yu (1.0 skin mol) and titanium chloride TIC
14 was varied between 4.56 Mmol and 14.10 mol and dissolved in ethanol to prepare a mixed solution.

Thereafter, the same treatment as in Example 1 was carried out to prepare a catalyst. Next, the same apparatus and method as in Example 1 were used. The results are shown in Table-3. ■ Satoshi ■■ ○ Kunzo b word ■■ Yuki○ 8 Kaorugo→・Jinbuna Q Go- Turtle and Thunder ■■ Satoshi Misaki■■ ○ no Sanhiro○ 〇【 Z .

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Example 17 {I' Preparation of rhodium nickel rhenium-titanium/silica catalyst Rhodium chloride (RhC13, 3 days 20) 1.
2 (4.56 mol), nickel chloride (NiCl)
2. Mother LO) 0.238 m (1.0 skin mol), rhenium pentachloride 0.367 m (1.0 skin mol), titanium tetrachloride (TIC14) 1.78 m (9.4 m mol)
was made into an ethanol solution, and 100 g of silica gel (Davison #57) treated in the same manner as in Example 1 was added to support it.

Hydrogen reduction was performed and activated in the same manner as in Example 1. 'A catalyst activity test was conducted using the same equipment and method as in Low Reaction Example 1.

The results are shown in Table-4. Example 18 Preparation of rhodium-nickel-chromium silica catalyst Rhodium chloride (R
hC13・Hoso20) 1.2 evenings (4.56 mol),
Nickel chloride (NiC12/mother LO) 0.2 porosity (1.
0 mol), chromium chloride (C13·SLO)2.
49 mol (9.5 skin mol), silica gel (Davis
On #57) A catalyst was prepared in the same manner as in Example 1 from 10 o'clock onwards.

An apparatus similar to that of Example 1 using the catalyst prepared by the 'low reaction';
The activity of the catalyst was investigated by the method.

The results are shown in Table-4. Example 19 Preparation of Rhodium Nickel-Cobalt Titanium/Silica Catalyst Rhodium chloride (RhC13, Group 20) 1.2 hours (4.56 mol), nickel chloride (NiC12,
Mother LO) 0.2 Madara (1.0 mol), cobalt chloride (C and l2.4 are also 0) 0.2*Yu (1.0 mol)
), titanium tetrachloride (TIC14) 1.78 mol (9.4 mol), silica gel (Davison #57) 10
In the evening, the listed catalyst was prepared in the same manner as in Example 1.

'.

} Using the catalyst prepared in reaction 'i', the activity of the catalyst was examined using the same apparatus and method as in Example 1.

The results are shown in Table-4. Table 1 4 (2) The reaction conditions described in the table are the same as those in Table-2.

Claims (1)

[Claims] 1. (a) rhodium, nickel, and (b) titanium, tantalum, niobium, chromium, cobalt, or rhenium (
At least one member selected from the group consisting of (hereinafter abbreviated as promoter metals) (hereinafter abbreviated as promoter metal group)
A method for producing an oxygen-containing compound containing ethyl alcohol as a main component by reacting a mixed gas containing carbon monoxide and hydrogen in the presence of a catalyst composed of the following components. 2. Claim 1, wherein the catalyst is supported on a carrier selected from silica, silica gel, alumina, activated carbon, molecular sieve, diatomaceous earth, nickel, or a promoter metal silicate, or an oxide of a promoter metal. Method described.