JPH02174740A - Production of aldehyde - Google Patents

Abstract

PURPOSE:To readily, industrially and advantageously obtain the subject compound in high selectivity and yield by hydroformylating a terminal olefin as a raw material with CO and H2 using a specific catalyst system excellent in activity and stability. CONSTITUTION:A terminal olefin, such as ethylene, is reacted with CO and H2 in the presence of a catalyst system consisting of a rhodium compound, such as a compound expressed by formula I, a rhenium compound, such as a compound expressed by formula II and, as necessary, at least one selected from phosphorus compounds expressed by formula IV (R<1> to R<3> are alkyl, aryl, alkyloxy or aryloxy), such as a compound expressed by formula III, and phosphorus compounds expressed by formula VI, such as a compound expressed by formula V, in a solvent, such as tetradecane, to carry out hydroformylation and afford the objective compound, such as propanal, useful as a raw material, intermediate, etc., in organic synthesis. The above-mentioned catalyst is preferably used in an amount so as to provide 0.1-100 atomic ratio of Re to Rh or >=1 atomic ratio of P to Rh.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an improvement in a method for producing aldehydes using terminal olefins as raw materials. More specifically, the present invention provides an industrially advantageous method of hydroformylating terminal olefins with carbon monoxide and hydrogen in a liquid or gas phase using a catalyst system steeped in activity. The present invention relates to a method for manufacturing.

Conventional Technology Aldehydes are extremely important compounds as raw materials and intermediates in organic synthesis, and the conventional method for producing them is to react olefins with carbon monoxide and hydrogen in the presence of a catalyst to convert the olefins into hydroformyl. A manufacturing method is known.

Catalysts for the hydroformylation of olefins include, for example, carbonyl compounds of cobalt or rhodium, and organometallic complexes of cobalt or rhodium in which a portion of the carbonyl group of these compounds is substituted with a basic compound such as alkyl or arylphosphine. A liquid-phase homogeneous catalyst is known, and a process for producing aldehydes and alcohols from orenes, carbon monoxide, and hydrogen using this catalyst has already been developed. See Lectures, Volume 7, Page 86 (published by Maruzen, 1985)].

However, in the hydroformylation process using a liquid-phase homogeneous catalyst using rhodium carbonyl compounds or organometallic complexes, although the liquid-phase homogeneous catalyst has excellent hydroformylation activity and selectivity, it is not suitable for industrial use. In order to produce a relatively high proportion of a linear aldehyde that is useful and desirable for rhodium metal, it is necessary to add the basic compound in large excess to rhodium metal. However, although rhodium carbonyl catalysts provide high activity, there are problems such as the production of a large amount of undesirable hydrogenation by-products.

In addition, a method using three elements consisting of a rhodium compound, a phosphine compound, and a rhenium compound is also known in the hydroformation of internal olefins (Japanese Unexamined Patent Application Publication No. 1983-1972).
-16418 Publication, Comparative Example 1), this method cannot be said to be particularly advantageous compared to the three elements consisting of a rhodium compound and a phosphine compound, and cannot be said to be a sufficient method for industrial use. .

On the other hand, a method for producing aldehydes using a heterogeneous rhodium catalyst has been proposed in order to omit the complicated steps associated with separation and recovery of catalyst metal in a process using a liquid-phase homogeneous rhodium catalyst (Belgium Patent No. 721,686). This method has the disadvantage that the activity and selectivity of the heterogeneous rhodium catalyst is lower than that of the liquid-phase homogeneous rhodium catalyst.

Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional catalysts in the hydroformylation of olefins, and uses a highly active and highly selective catalyst to hydroformylate terminal olefins, carbon monoxide, and hydrogen. The purpose of this invention was to provide a method for producing aldehydes in high yield and industrially advantageously.

Means for Solving the Problems As a result of extensive research into hydroformylation catalysts for terminal olefins that have high activity and selectivity, the present inventors have found that rhodium compounds, rhenium compounds, and, in some cases, further specific phosphorus compounds. It has been discovered that the above object can be achieved by using a catalyst system consisting of a combination of the following, and based on this knowledge, the present invention has been completed.

That is, the present invention provides (A) a rhodium compound and '(B
) A catalyst consisting of a rhenium compound, or the above-mentioned (A) component, (B) component and (C) general formula (in the formula, R1, 2! and R3 are each an alkyl group,
At least one phosphorus compound selected from among the phosphorus compounds represented by (aryl group, alkyloxy group, or aryloxy group, which may be the same or different)
The present invention provides a method for producing aldehydes, which comprises reacting a terminal olefin with carbon monoxide and hydrogen in the presence of a catalyst comprising a species.

The present invention will be explained in detail below.

In the method of the present invention, a combination of the above-mentioned (A) component and (B) component, or a combination of (A) component, CB) component, and (C) component is used as the catalyst. It can be used both in phase and gas phase.

Component (A) of the catalyst used in the method of the present invention, that is, a rhodium compound, includes, for example, rhodium metal, oxides, inorganic salts such as halogen salts, nitrates, carbonates, acetates, oxalates, acetylacetate salts, etc. rhodium salts or chelate compounds of organic salts, as well as rhodium compounds and rhodium metal complexes such as amine complexes, metal alkoxide compounds, alkyl metal compounds, and carbonyl compounds, among which rhodium carbonyl compounds and rhodium metal complexes are used. is suitable. Examples of the rhodium metal complex include RhCl2 (Phs
P)3, RhH(COXPhxP)s, RhC(1(C
Examples include OXPbsP)x, Rhot(phsp)scQ, and the like. In the present invention, these rhodium compounds as component (A) may be used alone or in combination with
You may use combinations of more than one species.

Further, as the rhenium compound of component (B), for example, rhenium metal, oxides, rogen salts, acetates, carbonyl compounds, etc. can be used, and among these, rhenium carbonyl compounds are preferred. In the present invention, these rhenium compounds as component (B) may be used alone or in combination of two or more.

These rhenium compounds increase the hydroformylation activity of the catalyst and are particularly effective in stabilizing the catalyst.

As the catalyst in the method of the present invention, a combination of the above-mentioned components (A) and (B) may be used, or a combination of components (A) and (B) may further include component (C). A combination may also be used.

The (C) component has a general formula and a general formula (R1, R2 and R3 in the formula have the same meanings as above)
At least one selected from the phosphorus compounds represented by
Seeds are used. R1, R1 and R3 in the above general formulas (1) and (n) are each an alkyl group, an aryl group, an alkyloxy group or an aryloxy group,
These may be the same or different from each other, but from the viewpoint of ease of acquisition, R1, R1 and R1
are preferably used.

Examples of such phosphorus compounds include (C3HT)3
P, (CaHs)sP, (CsH,,),P, (
C18,)3P.

(CH3CaH1)IP, (Ca)1.0)sP, (
C2H60)IPO1(CJtO)sPo.

(CaHsO)sPo, (CaHs)sPo, (C
H3C@H,0)3PO and the like are preferred.

One type of these phosphorus compounds may be used, or two or more types may be used in combination. These phosphorus compounds are particularly effective in increasing the selectivity of linear aldehydes.

In the present invention, the above-mentioned (A) component in the catalyst and (
B) component means that the atomic ratio of rhenium to rhodium is
It is usually used in a ratio of 0.1-100, preferably 0.5-50. In addition, the phosphorus compound of component (C) is
It is preferable to use component (A) in such a proportion that the atomic ratio of phosphorus to rhodium is 1 or more.

In the method of the present invention, the catalyst may be in the form of a liquid-phase homogeneous catalyst, a liquid-phase heterogeneous catalyst, or a gas-phase solid supported catalyst;
It can also be used. When carrying out the method of the present invention in a liquid phase reaction, after reacting the terminal olefin, -carbon oxide and hydrogen with the catalyst in the liquid phase, the aldehyde produced is separated in a separator and the liquid phase catalyst is recovered. Alternatively, the terminal olefin, carbon oxide, and hydrogen may be added to the liquid phase catalyst, and the aldehyde may be removed from the reaction system as a gaseous product and recovered.

The solvents used in such liquid phase reactions need to be chemically inert under the reaction conditions and include, for example, aliphatic saturated carbonized solvents such as decane, tridecane, tetradecane, hexadecane, etc. Examples include hydrogen, aromatic hydrocarbons such as benzene, toluene, and methylnaphthalene, and esters such as dioctyl benzoate, ethinophthalate, triphenyl dimethinophosphate, tricresyl phosphate, and triphenyl phosphite. can. These solvents may be used alone or in combination of two or more.

In addition, when carrying out the present invention in a gas phase reaction, the above-mentioned (A) component and (B) component, or (A
) component, component (B), and component (C) are supported, and it is advantageous to carry out the reaction by loading this solid supported catalyst into, for example, a fixed bed flow reactor or a fluidized bed reactor. It is.

The porous support carrier has a specific surface area of 10 to 1000.
m"/1? and a pore diameter of 6 Å or more is preferable,
For example, silica-based supports such as silica, silicate, silica gel, molecular sheep, diatomaceous earth, porous carbon supports such as activated carbon, carbon fiber, carbon beads, and carbon black, alumina, magnesia, tita, nia, zinc oxide, etc. Examples include metal oxide carriers. The shape of these carriers is not particularly limited, and any shape such as powder, pellet, bead, or block shape can be used.

There are no particular restrictions on the method of supporting catalyst components on these carriers, and methods commonly used to support catalyst components on carriers may be used, such as preparing a mixed solution in which catalyst components are simultaneously dissolved in the same solvent, and applying the catalyst components to the carrier. A method of simultaneously supporting each catalyst component on a carrier, a method of sequentially supporting each catalyst component on a carrier, a method of supporting each catalyst component sequentially or stepwise while carrying out treatments such as reduction and heat treatment as necessary, etc. can be used. can. Examples of the solvent used in such a supporting treatment include water, methanol, ethanol, tetrahydrofuran, dioxane, acetone, hexane, benzene, toluene, methylene chloride, and chloroform.

In the method of the present invention, the terminal olefin used as a raw material component is an olefin in which a double bond is formed between a terminal carbon atom and its adjacent carbon atom, such as ethylene, propylene, - Linear or branched monoolefins or diolefins having 2 to 12 carbon atoms such as -butene, isoprene, butadiene, l-hexene, -octene, -decene, etc., styrene, α-methylstyrene, vinyltoluene, Examples include aromatic olefins such as vinyl xylene and vinyl ethylbenzene.

There are no particular restrictions on the ratio of these terminal olefins to carbon monoxide and hydrogen, but usually the molar ratio of olefin to carbon oxide is 1:10 to 10:l and the molar ratio of -carbon oxide:hydrogen is 1= It is desirable to use it in a ratio of 10 to 10:J.

In addition, the desired aldehyde can be produced with high selectivity and high yield even if the reaction is carried out at normal pressure, but in order to increase the specific activity per rhodium atom, it is preferable to carry out the reaction under pressure. The reaction pressure is 350 kg/cr
s”・G or less, preferably 8 to 300 kg/c112
・G range is desirable. On the other hand, the reaction temperature is usually 50~
The temperature is selected from 250°C, preferably from 80 to 200°C. If this temperature is less than 50°C, the reaction rate is too slow to be practical, and if it exceeds 250°C, many by-products will be produced.
There is a tendency for the selectivity of aldehydes to decrease.

Effects of the Invention According to the method of the present invention, aldehydes can be industrially produced in high yield and high selectivity by using a specific catalyst system with excellent activity and stability in the hydroformylation reaction of terminal olefins with carbon oxide and hydrogen. It can be manufactured advantageously.

Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.

Example! Tetrarhodium dodecacarbonyl [Rt, (co)+z
18.411g (1,12X 10-n++ao l
), rhenium carbonyl [Rez(Co)tol 29
．． After putting 411 g, (4-51X 10-" mmol) and 5.0 g of solvent notetradecane into a continuous reactor, a mixed gas of ethylene carbon dioxide:hydrogen molar ratio = 1:2:2 was continuously fed. 40 atm (gauge pressure), 1
Continuous reactions were carried out at 20°C. What is the mixed gas feed rate? ,
It was 5Q/h. The reaction products were continuously taken out from the reactor in gaseous form along with unreacted gas, and oxygen-containing products such as aldehydes were collected by dissolving them in water, and qualitatively and quantitatively analyzed by gas chromatography. On the other hand, for gaseous products, the reaction gas was directly collected and quantified by gas chromatography analysis.

After the reaction reached a steady state, the reaction results from 19 hours to 20 hours were an ethylene conversion rate of 23.9% and a propanal selectivity of 98.9%.

On the other hand, when rhenium carbonyl is not added in the above reaction, the ethylene conversion rate is 3.0% and the propanal selectivity is 85.
It was 6%.

Although the same reaction as above was carried out using rhenium carbonyl 29.41119, the catalyst activity was extremely low and the ethylene conversion rate was 1% or less.

Example 2 Rhodium chloride [RhCl3.3H2010, 480 g (
1,8211111101) was dissolved in a methanol solution, and activated carbon (Shikinichi Yakuhin Kogyo Co., Ltd.) was degassed by firing in advance at 300°C for 2 hours under high vacuum. 4.19 (10+w)
ff) was added and soaked. Next, methanol was distilled off to dryness using a rotary evaporator, and the mixture was further dried under vacuum.

After that, this was filled into a Pyrex reaction tube and heated at 450° under hydrogen gas (200 mQ/min) at normal pressure.
Rh/AC catalyst was prepared by reduction with C for 4 hours.

Then, rhenium carbonyl [Rat(Co)+o]0
．． The above Rh/AC catalyst 5+i (l) was added and immersed in an acetone solution in which 294 g (0.45 mmol) was dissolved. After removing acetone by the same treatment as above, reduction was carried out in the same manner under hydrogen gas aeration. and Re/
Prepare Rh/AC catalyst.

After putting 0.5 mQ1) of this Re/Rh/AC catalyst and 0.236 g (0.9 mmol) of liphenylphosphine and 5.09 g (0.9 mmol) of tetradecane as a solvent into a continuous reactor,
A mixed gas having a propylene carbon oxide:hydrogen molar ratio of 1:2:2 was introduced, and a continuous reaction was carried out at 8 atmospheres (gauge pressure) and 120°C. The feeding rate of the mixed gas was 7.5 Q/h. The reaction products were continuously taken out from the reactor in gaseous form along with unreacted gas, and oxygen-containing products such as aldehydes were collected by dissolving them in water, and qualitatively and quantitatively analyzed by gas chromatography. On the other hand, for gaseous products, the reaction gas was directly collected and quantified by gas chromatography analysis. After the reaction reaches steady state,
The reaction results from 15 to 16 hours were: propylene conversion rate 13.3%, aldehyde selectivity 98.5%, n-
The butanal/me-butanal ratio was 3.6.

Note that Rh/AC is used instead of Re/Rh/AC catalyst.
Hydroformylation of propylene was carried out in the same manner as above except that 0.5raQ catalyst was used. The reaction results for the Rh/AC catalyst were a propylene conversion of 9.6%, an aldehyde selectivity of 98.0%, and an n-butanal/me-butanal ratio of 3.7.

Example 3 Tetrarhodium dodecacarbonyl [Rh+(Co)+z
116.8 mg (2,25X 10-” mmol), rhenium carbonyl [Rex(CO)+ol 29.4 m
9 (4,51X 10-” mmol), l-hexene 1.09 (11,9 mmol) and solvent benzene 5
．． Put Og into a 30tQ autoclave and mix it with a mixed gas of carbon monoxide and hydrogen (Co/H2 molar ratio -1) at room temperature.
Introduced 50 atm (gauge pressure) and heated to 110 atm while stirring.
The reaction was carried out at ℃ for 1 hour. After the reaction, the gas components and liquid phase components in the autoclave were analyzed by gas chromatography and NMH.
Qualitative and quantitative analysis was performed. As a result, the conversion rate of 1 to hexene was 82.1%, and the yield of generated aldehyde was 80.7%. Furthermore, what is the distribution of the aldehyde produced? - 47% by weight of heptanal, 40% by weight of 2-methylhexanal, 2
- 13% by weight of ethylpentanal.

In addition, when rhenium carbonyl is not added in the above reaction, the 1-hexene conversion rate is 77.0%, and the aldehyde yield is 74%.
．． It was 1%. The distribution of aldehydes produced was similar to the above results.

Example 4 Tetrarhodium dodecacarbonyl [Rt, (co)+a
l16.8mg (2,25x 10-”mmol),
Rhenium carbonyl ERe2CCO)r. 158.7m
g (9,OX 10−2 mmol), triphenylphosphine oxyto 250.5+n9(0,90mmol+
), I-hexene 1.0g (11.9mmol) and benzene 5.0g were placed in a 30wrQ autoclave,
A mixed gas of carbon monoxide and hydrogen (CO/H2 molar ratio -1) was introduced at 50 atmospheres (gauge pressure) at room temperature, and the mixture was reacted for 1 hour with stirring at 120°C. After the reaction, the gas components and liquid phase components in the autoclave were qualitatively and quantitatively analyzed by gas chromatography and NMH. As a result, l-
Hexene conversion rate 96.4%, yield of generated aldehyde 95%
It was 2%. The distribution of aldehydes produced was 38% by weight of l-heptanal, 45% by weight of 2-methylhexanal,
The content of 2-ethylpentanal was 17% by weight. In addition, when rhenium carbonyl is not added in the above reaction,
l-hexene conversion rate 91.0%, produced aldehyde yield 8
It was 9.7%. The distribution of the aldehydes produced was 41% by weight of l-heptanal, 43% by weight of 2-methylhexanal, and 16% by weight of 2-ethylpentanal.

Example 5 Tetrarhodium dodecacarbonyl [Rh4(co)+2
116.811g (2,25X 10-”mmol)
, and = 17 A force/L, Bonyl [Rea(Co)t
ol 29.4mg (4,51X 10-”+oio+
), tributylphos 7(n182.1m9 (0.9m
mol) and the solvent tetradecane5. After putting h into a continuous reactor, ethylene carbon dihydrogen oxide-1:2:2
40 atmospheres (gauge pressure),
Continuous reactions were carried out at 120°C. The feeding rate of the mixed gas was 7.5 Q/h. The reaction products were continuously taken out from the reactor in gaseous form along with unreacted gas, and oxygen-containing products such as aldehydes were collected by dissolving them in water, and qualitatively and quantitatively analyzed by gas chromatography.

On the other hand, for gaseous products, the reaction gas was directly collected and quantified by gas chromatography analysis.

After the reaction reached a steady state, the reaction results from 26 hours to 27 hours were an ethylene conversion rate of 43.8% and a propanal selectivity of 96.6%.

Example 6 Re/Rh/AC catalyst sail 5mQ prepared in Example 2
, triphenylphosphine 0.236g (0.9m
After putting 5.0 g of tetradecane (mol) and solvent into a continuous reactor, ethylene dicarbonate:hydrogen-1:2:
A mixed gas of 2 and 40 atmospheres (gauge pressure) and 120
Continuous reactions were carried out at °C. Mixed gas feeding speed is 7.5Q
/h. The reaction products were mixed with unreacted gas and continuously taken out from the reactor in gaseous form, and oxygen-containing products such as aldehydes were collected by dissolving them in water, and qualitatively and quantitatively analyzed by gas chromatography. On the other hand, for gaseous products, the reaction gas was directly collected and quantified using a gas chromatography analysis group. After the reaction reached a steady state, the reaction results from 40 to 41 hours were ethylene conversion of 44.5% and propanal selectivity of 99.1.
%Met.

Note that hydroformylation of ethylene was performed in the same manner as above except that Rh/AC catalysts Q and 5+Q prepared in Example 2 were used instead of the Re/Rh/AC catalyst.

The reaction results using the Rh/AC catalyst were an ethylene conversion rate of 31.7% and a propanal selectivity of 98.9%.

Example 7 Tetrarhodium dodecacarbonyl [Rh, (Co)tx
]8.4m+19 (1,12X 10-”11111
01), rhenium carbonyl [Rez(CO)+o1
29.4u (4,51X 10-”mmol), triphenylphosphine 236.1u (0.9mn+ol)
After putting 5.0 g of tetradecane and the solvent into a continuous reactor, a mixed gas of ethylene carbon oxide: hydrogen-1; 2:2 was continuously fed to react at 40 atm (gauge pressure) and 120 atm.
Continuous reactions were carried out at 'O. The mixed gas feeding speed is 7.5
It was Q/h. The reaction products were continuously taken out from the reactor in gaseous form along with unreacted gas, and oxygen-containing products such as aldehydes were collected by dissolving them in water, and qualitatively and quantitatively analyzed by gas chromatography. On the other hand, for gaseous products, the reaction gas was directly collected and quantified by gas chromatography analysis. After the reaction reaches steady state,
The reaction results from 42 hours to 43 hours were an ethylene conversion rate of 31.0% and a propanal selectivity of 99.1%.

Example 8 Hydridocarbonyl tris(triphenylphosphine)
Rhodium (RhH-CO・(Ph3P)3)4.6m9
(5,0X10-'mmol), rhenium carbonyl (
Rea(co)to)17.289 (26,4X 1
After putting 39% of tetradecane (0-'mmol) and solvent into a continuous reactor, 1-1% of ethylene dihydrogen oxide
The reaction was carried out under the same conditions as in Example 7 by continuously feeding a 72:2 mixed gas.

The reaction product was continuously taken out from the reactor in gaseous form along with unreacted gas, and oxygen-containing bioacids such as aldehydes were collected by dissolving them in water, and qualitatively and quantitatively analyzed by gas chromatography. In addition, for gaseous products, the reaction gas was directly collected and quantified by gas chromatography analysis.

The amount of propionaldehyde produced by hydroformylation of ethylene using this catalyst is 21 to 20% after the start of the reaction.
In 22 hours it is 1880111g/hr and 30-
At 31 hours, it was 1652+++g/hr.

On the other hand, the amount of propylene aldehyde produced when rhenium carbonyl is not added in the above reaction is 983 mg/hr 21 to 22 hours after the start of the reaction, and 30-
At 31 hours, it was 420 mg/hr.

These results show that the hydroformylation activity of the catalyst can be greatly improved by adding a rhenium compound.

Example 9 Hydridocarbonyl tris(triphenylphosphine)
Rhodium (RhH-Co ・(PbsP)x) 4-6
mg (5-OX 10-3 mmol), triphenylphosphine (Pbsp) 11.8 m9 (45, OX 10
-'mmol), ram carbonyl CRe2(Co
) to) 81.6 mg (125 mmol) and 3 g of tetradecane as a solvent were placed in a continuous reactor, and Example 6
Hydroformylation of ethylene was carried out in the same manner.

The amount of propionaldehyde produced was 44-45% after the start of the reaction.
In hours, it was 1876 mg/hr, and in hours 118-119 it was 1557 mg/hr.

On the other hand, in the above reaction, the amount of propionaldehyde produced using a catalyst without rhenium carbonyl added was 1779 mg/h 43 to 44 hours after the start of the reaction, and 1
It was 611 mg/hr for 15 to 116 hours.

These results show that the addition of the rhenium compound significantly improves the catalyst performance and stabilizes the hydroformylation activity of the catalyst over a long period of time.

Claims (1)

[Claims] 1. A method for producing an aldehyde, which comprises reacting a terminal olefin with carbon monoxide and hydrogen in the presence of a catalyst consisting of (A) a rhodium compound and (B) a rhenium compound. 2 (A) rhodium compound, (B) rhenium compound, and (C) general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1, R^2 in the formula and R^3 are each an alkyl group, an aryl group, an alkyloxy group, or an aryloxy group, and they may be the same or different. at least 1
1. A process for producing aldehydes, which comprises reacting a terminal olefin with carbon monoxide and hydrogen in the presence of a catalyst consisting of a species.