JP2021010873A - Catalyst for hydroformylation reaction using carbon dioxide as raw material - Google Patents

Abstract

To provide a catalyst with which alcohols and aldehydes can efficiently be produced by conducting a hydrogenation reaction of carbon dioxide, successively conducting a hydroformylation reaction of an organic compound having an unsaturated carbon bond in a homogeneous liquid phase, and easily separating and purifying products.SOLUTION: A catalyst composition has a metal compound c and an object to be supported being a salt having a melting point of 250°C or less on outer and inner surfaces of a porous solid particle a, in which when there is only one kind of the metal compound, the metal compound is a ruthenium carbonyl complex compound, and when there are two kinds of the metal compounds, one of them is a ruthenium carbonyl complex compound, and the other is one out of an iridium carbonyl complex compound, a rhodium carbonyl complex compound, and a cobalt carbonyl complex compound. The catalyst composition is used in a reaction for producing alcohols and aldehydes by conducting hydroformylation of an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen performed at a temperature of the melting point of the salt or higher.SELECTED DRAWING: Figure 1

Description

The present invention relates to a catalyst composition for producing alcohols and aldehydes, and a method for producing alcohols and aldehydes.

Carbon monoxide is one of the important raw materials in the chemical industry. For example, the hydroformylation reaction (oxo reaction) uses carbon monoxide as one of the raw materials. This reaction produces more than 10 million tons of chemicals annually. However, due to the high toxicity of carbon monoxide, only a limited number of companies can implement processes that utilize carbon monoxide. Therefore, it has been studied to produce a carbon monoxide raw material on-site using hydrogenation of carbon dioxide, which is extremely less toxic than carbon monoxide and is easy to handle as a carbon source, and supply it to the next reaction. It's coming.

As a method for producing carbon monoxide by hydrogenation of carbon dioxide, a method using various metals, metal oxides, metal sulfides and the like as a catalyst is known, and patent applications and patent applications using such a catalyst are available. There are many reports. Specific examples include an example in which copper / zinc oxide is used as a catalyst in Non-Patent Document 1 and an example in which iron oxide is used as a catalyst in Non-Patent Document 2. Reactions using these catalysts usually require a high temperature of about 250 to 500 ° C.

On the other hand, the hydroformylation reaction is generally carried out at a temperature of 250 ° C. or lower, and in the method using various metals, metal oxides, metal sulfides and the like as catalysts, a carbon monoxide raw material is produced onsite. However, it is difficult to construct a manufacturing process to supply to the next hydroformylation reaction.

In the method for producing carbon monoxide by hydrogenation of carbon dioxide, the gold / titanium oxide catalyst produced by the precipitation precipitation method has a reaction of about 4 compared with the copper / zinc oxide / aluminum oxide catalyst at a low temperature of about 100 ° C. It has been reported that it accelerates twice (Non-Patent Document 3).

In these methods, the hydrogenation reaction is carried out in an air-solid heterogeneous system because the catalysts are all in a solid state under the reaction conditions.

The hydrogenation reaction in the above-mentioned non-uniform system is carried out by supporting a catalyst such as a metal, a metal oxide, or a metal sulfide on a carrier, but the reaction for producing carbon monoxide by hydrogenation of carbon dioxide is carried out. It is an endothermic reaction, and the endothermic reaction in a non-uniform air-staining system has a problem that it is difficult to control the temperature of the reactor, and when the temperature of the catalyst surface is lowered due to heat absorption, the reaction rate is reduced.

Therefore, the present inventors have considered that the hydrogenation reaction of carbon dioxide is carried out by a liquid phase uniform system reaction. Specifically, a patent application was filed for a carbon dioxide catalytic hydrogenation method for producing carbon monoxide by hydrogenating carbon dioxide in the presence of a homogeneous liquid-phase reaction catalyst consisting of a combination of a ruthenium carbonyl complex and a chlorine compound. (See Patent Document 1).

In addition, the present inventors hydrogenated carbon dioxide in the presence of a homogeneous liquid phase reaction catalyst composed of a combination of a ruthenium complex and a chlorine compound, which are active in both hydrogenation of carbon dioxide and hydroformylation, and further. , An organic compound having an unsaturated carbon bond is hydroformylated to produce alcohols and / or aldehydes, and a patent application has been filed for a method for producing aldehydes (see Patent Document 2).

Furthermore, the present inventors have considered combining the homogeneous liquid phase reaction catalyst with a hydroformylation catalyst to carry out a hydroformylation reaction of an organic compound having an unsaturated carbon bond using carbon dioxide and hydrogen as reaction reagents. Specifically, carbon dioxide is hydrogenated in the presence of a homogeneous liquid phase reaction catalyst composed of a combination of a ruthenium complex, a cobalt complex, and a chlorine compound, and an organic compound having an unsaturated carbon bond is hydroformylated. An international patent application has been filed for alcohols and methods for producing aldehydes and alcohols (see Patent Document 3).

Japanese Unexamined Patent Publication No. 7-157304 JP 2001-233795 International Publication No. 2009/041192 (WO2009 / 041192)

S.Fujita, M.Usui, N.Takezawa, J.Catal., 134,220 (1992). M.-D.Lee, J.-F.Lee, C.-S.Chang, J.Chem.Engineer, J., 23,130 (1990). H.Sakurai, A.Ueda, T.Kobayashi, M.Haruta, Chem.Commun., 271 (1997).

The method for catalytic hydrogenation of carbon dioxide described in Patent Document 1 and the method for hydroformylation of an organic compound having an unsaturated carbon bond using carbon dioxide and hydrogen as reaction reagents described in Patent Documents 2 and 3 are homogeneous systems. Since it is carried out in the liquid phase, temperature control is easy. Furthermore, since a homogeneous liquid-phase reaction catalyst composed of a combination of a ruthenium carbonyl complex and a chlorine compound is used, the hydrogenation reaction of carbon dioxide proceeds smoothly even under relatively low temperature conditions of around 160 ° C. It is effective.

However, since all of the above methods are carried out in a homogeneous liquid phase system, the advantage of ease of separation and purification of the product when a conventional heterogeneous catalyst is used is impaired. Another problem is pollution of the produced gas by the organic solvent used.

Under the above background, in the present invention, the hydrogenation reaction of carbon dioxide and the subsequent hydroformylation reaction of the organic compound having an unsaturated carbon bond are carried out in a homogeneous liquid phase, and the reaction is not carried out after the reaction. A catalyst capable of easily separating and purifying the product as in a homogeneous system, thereby efficiently producing alcohols and / or aldehydes, and alcohols using the catalyst, and / Or an object of the present invention is to provide a method for producing aldehydes.

Specifically, the present application provides the following inventions.
<1> A catalyst composition comprising a metal compound on at least a part of the outer surface and the inner surface of the porous solid particles and a carrier of salts having a melting point of 250 ° C. or lower.
When the metal compound is one kind, the metal compound is a ruthenium carbonyl complex compound.
When there are two types of the metal compound, one of them is a ruthenium carbonyl complex compound, and the other type used in combination with this is an iridium carbonyl complex compound having at least one carbonyl ligand, rhodium carbonyl. It is one of a complex compound and a cobalt carbonyl complex compound.
Moreover, the catalyst is a catalyst used in a reaction for producing alcohols and / or aldehydes by hydroformylating an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen, which is carried out at a temperature equal to or higher than the melting point of the salts. , The catalyst composition.
<2> When the metal compound is one kind, the metal compound is a ruthenium carbonyl complex compound having a nucleus of three or more ruthenium atoms.
The catalyst composition according to <1>, wherein when there are two types of the metal compound, one of them is a ruthenium carbonyl complex compound having a nucleus of one or more ruthenium atoms.
<3> The ruthenium carbonyl complex compound having a nucleus of three or more ruthenium atoms is one of Ru ₃ (CO) ₁₂ , H ₂ Ru ₄ (CO) ₁₂ , and H ₂ Ru ₆ (CO) ₁₈ . The catalyst composition according to <2>.
<4> The ruthenium carbonyl complex compounds having one or more ruthenium atom nuclei are Ru ₃ (CO) ₁₂ , H ₂ Ru ₄ (CO) ₁₂ , H ₂ Ru ₆ (CO) ₁₈ , [RuCl ₂ (CO) ₃ ] is one of _2, and the catalyst composition <5> when the metal compound is a two ruthenium carbonyl complex compound having a nucleus of one or more of ruthenium atoms according to <2>, and this The catalyst composition according to any one of <2> to <4>, wherein the mass ratio of the other metal compound used in combination is in the range of 1: 0.1 to 10.
<6> The catalyst composition according to any one of <1> to <5>, wherein the mass ratio of the one or two kinds of metal compounds and salts is in the range of 0.01: 5 to 0.1. ..
<7> The catalyst according to any one of <1> to <6>, wherein the porous solid particles are at least one kind of particles selected from the group consisting of silica, alumina, zeolite, titania, and carbon. Composition.
<8> The anion components of the salts are halide ion, acetate anion, trifluoroacetate anion, methanesulfonate anion, trifluoromethanesulfonate anion, bistrifluoromethanesulfonylamide anide, tetrafluoroborate anion, hexafluorophosphonate anion, and dicyano. The catalyst composition according to any one of <1> to <7>, which comprises at least one anion selected from the group consisting of amide anions.
<9> The anion component of the salts contains at least one anion selected from the group consisting of a halide ion, an acetate anion, a trifluoroacetate anion, a tetrafluoroborate anion, and a hexafluorophosphonate anion. <8> The catalyst composition according to.
<10> At least one selected from the group in which the cation component of the salts consists of an imidazolium cation, an ammonium cation, a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a sulfonium cation, a morpholinium cation, and a phosphonium cation. The catalyst composition according to any one of <1> to <9>, which is a cation.
<11> The catalyst composition according to any one of <1> to <10>, wherein the porous solid particles have a specific surface area of 80 m ² / g or more.
<12> The catalyst composition according to any one of <1> to <11>, wherein the porous solid particles have an average particle diameter in the range of 0.1 to 1000 μm.
<13> In the presence of the catalyst composition according to any one of <1> to <12>, it has an unsaturated carbon bond due to carbon dioxide and hydrogen at a temperature of 250 ° C. or lower and higher than the melting point of the salts. A method for producing alcohols and / or aldehydes, which hydroformylates an organic compound to produce alcohols and / or aldehydes.
<14> The method according to <13>, wherein the reaction is carried out in the absence of a solvent.
<15> The method according to <13> or <14>, wherein the reaction is carried out at a temperature of 80 ° C. or higher.

By using the catalyst composition of the present invention, carbon dioxide is used in a method for producing alcohols and / or aldehydes, which is usually carried out by hydroformylating an organic compound having an unsaturated carbon bond with carbon monoxide and hydrogen. Can be used as an alternative to carbon monoxide.
According to the catalyst composition of the present invention, the reaction of hydroformylating an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen to produce alcohols and / or aldehydes is a contact reaction of a gas-heterogeneous system. The alcohols and / or aldehydes produced can be easily separated and recovered from the reaction system.
Further, according to the contact reaction of the air-solid heterogeneous system by the catalyst composition of the present invention, the organic compound having an unsaturated carbon bond is hydroformylated with carbon dioxide and hydrogen to produce alcohols and / or aldehydes. In the reaction, alcohols and / or aldehydes can be produced in high yields comparable to or better than the contact reaction of a liquid phase homogeneous system.

It is a schematic explanatory drawing of the state in the pore of the catalyst composition (catalyst-supporting porous solid particle) of this invention. In the figure, a is a porous solid particle, b is a pore, and c is a metal compound and salts.

<Catalyst composition>
The present invention is a catalyst composition having one or two kinds of metal compounds and a carrier of salts having a melting point of 250 ° C. or less on at least a part of the outer surface and the inner surface of the porous solid particles. At least one of the metal compounds is a ruthenium carbonyl complex compound.
It is known that a ruthenium carbonyl complex compound having a nucleus of a ruthenium atom has a catalytic activity for producing carbon monoxide by catalytic hydrogenation of carbon dioxide (Patent Document 1). In addition to this, it is known that the ruthenium carbonyl complex compound has catalytic activity for hydroformylating an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen to produce alcohols and / or aldehydes. (Patent Document 2).
Therefore, when the catalyst composition contains one kind of metal compound, a ruthenium carbonyl complex compound is used.
On the other hand, when the catalyst composition contains two kinds of metal compounds, a ruthenium carbonyl complex compound can be used as one of them, and unsaturated carbon due to carbon monoxide and hydrogen is used as another kind in combination. Any metal compound having a catalytic activity of hydroformylating an organic compound having a bond to produce alcohols and / or aldehydes can be used.
Such metal compounds having catalytic activity for hydroformylating an organic compound having an unsaturated carbon bond with carbon monoxide and hydrogen to produce alcohols and / or aldehydes include, in addition to the ruthenium carbonyl complex compound, at least. Iridium carbonyl complex compounds, rhodium carbonyl complex compounds, cobalt carbonyl complex compounds and the like having one carbonyl ligand are known.
The catalyst composition of the present invention is used in a reaction carried out at a temperature equal to or higher than the melting point of the salts to hydroformylate an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen to produce alcohols and / or aldehydes. It is a catalyst to be used.

The catalyst composition of the present invention uses porous solid particles as a carrier, and has the above-mentioned metal compound and salts having a melting point of 250 ° C. or lower on at least a part of the outer surface and the inner surface thereof.

The porous solid particles are solid particles made of a substance substantially inactive with respect to the carrier, and are not particularly limited as long as they are porous. The porous solid particles can be, for example, at least one particle selected from the group consisting of silica, alumina, zeolite, titania, or carbon.

The porosity (porous) of the porous solid particles is appropriately determined from the viewpoint of considering the performance of the catalyst and securing a space for supporting the carrier. For example, from the viewpoint that a specific surface area of 80 m ² / g or more secures a space for supporting the carrier and an area of the surface on which the carrier is supported to provide a catalyst having good performance. preferable. The specific surface area of the porous solid particles is preferably 100 m ² / g or more, more preferably 150 m ² / g or more, and further preferably 200 m ² / g or more. On the other hand, if the specific surface area becomes large and the inner diameter of the pores becomes too small, it tends to be difficult to secure a space for supporting the carrier. In consideration of this point, the upper limit of the specific surface area of the porous solid particles is, for example, preferably 1000 m ² / g or less, preferably 800 m ² / g or less, and more preferably 600 m ² / g or less. However, it is not intended to be limited to these numerical ranges, and can be appropriately determined in consideration of the type of carrier and the amount of carrier.

The particle size of the porous solid particles can be appropriately determined in consideration of the reaction system to be used, the structure of the reaction apparatus, and the like. The particle size of the porous solid particles can be, for example, an average particle size in the range of 0.1 to 1000 μm. However, it is not intended to exclude that the size is less than or greater than this range. Further, the porous solid particles may be particulate matter, but may be a molded product (for example, honeycomb shape or the like) in addition to the particulate matter.

A metal compound and salts having a melting point of 250 ° C. or lower are supported on at least a part of the outer surface and the inner surface of the porous solid particles. As long as the metal compound and salts are supported on at least a part of the inner surface of the porous solid particles, the metal compounds and salts may not be supported on the outer surface. Preferably, the metal compound and salts are supported on at least a part of the inner surface and at least a part of the outer surface of the porous solid particles.
The catalyst composition of the present invention is used in a reaction of hydroformylating an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen to produce alcohols and / or aldehydes, and this reaction is above the melting point of the salts. It is carried out at a temperature of 250 ° C. or lower, preferably 250 ° C. or lower. In this reaction, the salts having a melting point of 250 ° C. or lower exhibit a liquid phase when the temperature reaches the melting point or higher, that is, they become molten salts. The metal compound contained in these salts functions as a catalyst. However, although salts exhibit a liquid phase in the reaction, they are easily separated from reaction products and the like because they are supported on porous solid particles. The melting point of the salt can be appropriately determined in consideration of the type of the metal compound used, the temperature condition of the carbon monoxide formation reaction, the type of the porous solid particles, and the like.

The salts are salts having a melting point of 250 ° C. or lower. At least a portion of the salt, the anion component is halide ion (a fluoride ion (F ^-), chloride ion (Cl ^-), bromide ion (Br ^-), and, iodide ion (I ^-)), acetate Salts that are anions selected from the group consisting of anions, trifluoroacetate anions, methanesulfonate anions, trifluoromethanesulfonate anions, bistrifluoromethanesulfonylamide anions, tetrafluoroborate anions, hexafluorophosphonate anions, dicyanoamide anions and the like. .. Preferably, it is a halide ion, an acetate anion, a trifluoroacetate anion, a tetrafluoroborate anion, or a hexafluorophosphonate anion. More preferably, it is a chloride ion. The salt is not limited to the above structure as long as it is a salt that is in a liquid state below the reaction temperature.

The cation component of the salt is, for example, at least one cation selected from the group consisting of imidazolium cation, ammonium cation, pyridinium cation, pyrrolidinium cation, piperidinium cation, sulfonium cation, morpholinium cation, and phosphonium cation. Can be.

Salts having a melting point of 250 ° C. or lower and composed of anionic and cationic components as described above are sometimes called ionic liquids or ionic liquids, and there are many commercially available products.

Specific examples of salts whose cation component is an imidazolium cation include the following compounds. However, these compounds are merely examples, and are not intended to be limited to these compounds.
1-Methyl-3-butylimidazolium chloride ([C ₄ mim] Cl) (melting point 68.8 ° C),
1-Methyl-3-butylimidazolium trifluoromethanesulfonate ([C ₄ mim] [TfO]) (melting point 16.4 ° C),
1-Methyl-3-butylimidazolium hexafluorophosphate ([C ₄ mim] PF ₆ ) (melting point 10.4 ° C.),
1-Methyl-3-butylimidazolium tetrafluoroborate ([C ₄ mim] BF ₄ ) (melting point -17 ° C),
1-Methyl-3-butylimidazolium acetate ([C ₄ mim] [AcO]) (melting point -20 ° C),
1-Methyl-3-butylimidazolium bistrifluoromethanesulfonylamide ([C ₄ mim] [TFSA]) (melting point-4.9 ° C.).
1-Methyl-3-butylimidazolium dicyanoamide ([C ₄ mim] [DCA]) (melting point -6 ° C),
1-Methyl-3-butylimidazolium thiocyanate ([C ₄ mim] [SCN]) (melting point-28.6 ° C),
1-Methyl-3-butylimidazolium methanesulfonate ([C ₄ mim] [MSA]) (melting point 72 ° C)

In addition to the above, examples of salts whose cation component is an imidazolium cation include the following. However, these compounds are merely examples, and are not intended to be limited to these compounds.
1-Methyl-3-methylimidazolium chloride ([C ₁ mim] Cl) (melting point 147 ° C.),
1-Methyl-3-ethylimidazolium chloride ([C ₂ mim] Cl) (melting point 82 ° C),
1-Methyl-3-pentylimidazolium chloride ([C ₅ mim] Cl) (melting point 75 ° C.),
1-Methyl-3-hexylimidazolium chloride ([C ₆ mim] Cl) (melting point -70 ° C),
1-Methyl-3-octylimidazolium chloride ([C ₈ mim] Cl) (melting point 12.3 ° C),
1-Methyl-3-decylimidazolium chloride ([C ₁₀ mim] Cl) (melting point 38 ° C),
1,2-Dimethyl-3-butylimidazolium chloride ([C ₄ dim] Cl) (melting point 99 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is an ammonium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
Butyltrimethylammonium bis (trifluoromethanesulfonyl) imide ([N ₁₁₁₄ ] [TFSA]) (melting point 17 ° C),
_{Tetraoctylammonium} bromide ([N ₄₄₄₄ ] Br) (melting point 103 ° C),
Tetrabutylammonium bis (trifluoromethanesulfonyl) imide ([N ₄₄₄₄ ] [TFSA]) (melting point 113 ° C),
Diethylmethyl (2-methoxyethyl) methylammonium bis (trifluoromethanesulfonyl) imide ([Deme] [TFSA]) (melting point -91 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is a pyridinium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
1-Butyl-4-methylpyridinium chloride ([4m-Pyri ₄ ] Cl) (melting point 160 ° C),
1-Butyl-4-methylpyridinium hexafluorophosphate ([4m-Pyri ₄ ] PF ₆ ) (melting point 42 ° C.),
1-Butyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide ([4m-Pyri ₄ ] [TFSA]) (melting point 10 ° C),
1-Butyl-4-methylpyridinium tetrafluoroborate ([4m-Pyri ₄ ] BF ₄ ) (melting point -30 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is a pyrrolidinium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
1-Butyl-1-methylpyrrolidinium chloride ([Pyro ₁₄ ] Cl) (melting point 198 ° C),
1-Butyl-1-methylpyrrolidinium bromide ([Pyro ₁₄ ] Cl) (melting point 216 ° C),
1-Butyl-1-methylpyrrolidinium bistrifluoromethanesulfonate ([Pyro ₁₄ ] [TfO]) (melting point 4 ° C),
1-Butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) amide ([Pyro ₁₄ ] [TFSA]) (melting point -18 ° C),
1-Butyl-1-methylpyrrolidinium bistetrafluoroborate ([Pyro ₁₄ ] [TfO]) (melting point 155 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is a piperidinium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
1-Butyl-1-methylpiperidinium bromide ([Pype ₁₄ ] Br) (melting point 230 ° C.),
1-Butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) amide ([Pype ₁₄ ] [TFSA]) (melting point -6 ° C),
1-Methyl-1-propylpiperidinium bis (fluoromethanesulfonyl) amide ([Pype ₁₃ ] [FSA]) (melting point -9 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is a sulfonium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
Trimethylsulfonium iodide ([S ₁₁₁ ] I) (melting point = 200 ° C),
Tributylsulfonium iodide ([S ₁₁₁ ] I) (melting point = 93 ° C),
Triethylsulfonium bis (trifluoromethanesulfonyl) amide ([S ₂₂₂ ] [TFSA]) (melting point = -17.6 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is a morphonium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
4-Ethyl-4-methylmorphonium bromide (melting point = 177 ° C)

The following compounds can be mentioned as typical examples of salts whose cation component is a phosphonium cation. However, these compounds are merely examples, and are not intended to be limited to these compounds.
Tetra-n-octylphosphonium bromide ([P ₈₈₈₈ ] Br) (melting point = 42 ° C),
Tetra-n-octylphosphonium tetrafluoroborate ([P ₈₈₈₈ ] BF ₄ ) (melting point = 155 ° C),
Tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) amide ([P _{444 (12)} ] [TFSA]) (melting point = 9.5 ° C),
Triethyldodecylphosphonium bis (trifluoromethanesulfonyl) amide ([P _{222 (12)} ] [TFSA]) (melting point = 13 ° C)

The ruthenium carbonyl complex compound has Ru (CO) ₅ and Ru ₃ (CO) ₁₂ having CO as a ligand, as well as CO and halogen, hydrogen, phosphine and the like as ligands, for example, [ It can be RuX ₂ (CO) ₃ ] ₂ , Ru ₄ X ₄ (CO) ₁₂ , Ru ₄ H ₄ (CO) ₁₂ , Ru (CO) ₂ (PPh ₃ ) ₃ , and so on. Here, X is a halogen and PPh ₃ is triphenylphosphine.
Of these, Ru ₃ (CO) ₁₂ , Ru ₄ X ₄ (CO) ₁₂ , and Ru ₄ H ₄ (CO) ₁₂ correspond to ruthenium carbonyl complex compounds having three or more ruthenium atom nuclei, and carbon dioxide. It has both catalytic activity to produce carbon monoxide by catalytic hydrogenation of and hydroformylation of an organic compound having an unsaturated carbon bond with carbon monoxide and hydrogen to produce alcohols and / or aldehydes. ..
Of these, Ru ₃ (CO) ₁₂ is particularly preferred.
On the other hand, Ru (CO) ₅ , [RuX ₂ (CO) ₃ ] ₂ , and Ru (CO) ₂ (PPh ₃ ) ₃ correspond to ruthenium carbonyl complex compounds having a ruthenium atom nucleus of 1 or 2, and are carbon dioxide. It has catalytic activity to produce carbon monoxide by catalytic hydrogenation of carbon. They also have catalytic activity that hydroformylates organic compounds with unsaturated carbon bonds with carbon monoxide and hydrogen to produce alcohols and / or aldehydes. Its activity is lower than that of a ruthenium carbonyl complex compound having a nucleus of three or more ruthenium atoms, but this can be supplemented if necessary by using a combined metal compound described later in combination.
Commercially available products of these ruthenium compounds are available, and they can also be prepared according to known methods.

The combined metal compound may be any compound having a catalytic activity of hydroformylating an organic compound having an unsaturated carbon bond with carbon monoxide and hydrogen to produce alcohols and / or aldehydes, for example, in the molecule. Examples thereof include a cobalt complex having a carbonyl ligand, a rhodium complex, an iridium complex, and a ruthenium carbonyl complex having a nucleus of three or more ruthenium atoms.
Such combined metal compounds include, for example, Co ₂ (CO) ₈ , Rh ₄ (CO) ₁₂ , and Ru ₃ (CO) ₁₂ having CO as a ligand, as well as halogen, hydrogen, phosphine, and CO. Those using acetylacetone as a ligand, for example, Ir ₄ (CO) ₁₂ , Ir (acac) (CO) ₂ , Rh (acac) (CO) ₂ , Ir (CO) (PR ₃ ) ₃ , Rh (CO) ) (PR ₃ ) _3, Co (CO) (PR ₃ ) _3, etc. Here, R is an arbitrary alkyl group or phenyl group, and acac is acetylacetone.

When there are two types of the metal compound, the mass ratio of the ruthenium carbonyl complex compound and the other metal compound used in combination thereof can be appropriately determined depending on the type of these compounds and the type of the carrier. For example, 1: 0. It is in the range of 1-10. This ratio is preferably in the range of 1: 0.1 to 5, more preferably in the range of 1: 0.1 to 2.

The mass ratio of the one or two types of metal compound and salt can be appropriately determined depending on the type of metal compound and salt and the type of carrier, and is, for example, in the range of 0.01: 5 to 0.1. This ratio is preferably in the range of 0.01: 2 to 0.1, more preferably in the range of 0.01: 1 to 0.1.

The amount of the salts supported is preferably, for example, 1 to 50% by volume, more preferably 5 to 20% by volume, based on the pore volume of the porous solid particles. However, it can be appropriately adjusted depending on the type of porous solid particles and the type of metal compound.

The amount of the one or two kinds of metal compounds used can be appropriately determined in consideration of the amount of the salts supported, the performance that the catalyst composition should have, and the like, and is, for example, 0 with respect to the mass of the porous solid particles. It can be in the range of .01 to 10% by mass. It is preferably in the range of 0.05 to 2% by mass.

In addition, when the amount of the metal compound and salts supported on the inner surface of the porous solid particles is too large and the pores of the porous solid particles are filled, the surface on which the metal compounds and salts are supported can be secured. Therefore, it is not possible to secure a reaction field with a sufficient surface area. As shown in FIG. 1, in the pores b of the porous solid particles a, the metal compound and the salts c are supported on the surface of the pores, and the amount of the metal compound and the salts supported fills all of the pores. It is appropriate that the amount is not so large that the pores are still present. For example, in the case of porous solid particles having a specific surface area of 500 m ² / g, the specific surface area after supporting the metal compound and salts is, for example, in the range of 100 to 490 m ² / g, preferably 200 to 470 m. range of ² / g, and more preferably can range 300~450m ² / g. However, this range is merely an example, and can be appropriately determined in consideration of the obtained catalytic activity depending on the type of porous solid particles (material and structure of pores) and the types of metal compounds and salts.

<Preparation method of catalyst composition>
The catalyst composition is prepared by immersing the porous solid particles in a solution in which a metal compound and salts are dissolved, allowing the solution to enter the porosity of the porous solid particles, and then removing only the solvent. The target metal compound and salts can be supported on the inner surface and the outer surface. The solution in which the metal compound and salts are dissolved can be prepared by dissolving in a solvent capable of dissolving the metal compound and salts. Examples of the solvent include methylene chloride, chloroform and the like.

The concentration of the metal compound and the salt in the solution in which the metal compound and the salt are dissolved can be appropriately determined in consideration of a desired carrying amount of the metal compound and the salt, the type of solvent (solubility), and the like.

<Manufacturing method of alcohols or aldehydes>
The present invention hydroformylates an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen at a temperature of 250 ° C. or lower and above the melting point of salts contained in the catalyst composition in the presence of the catalyst composition of the present invention. The present invention relates to a method for producing alcohols and / or aldehydes, which are converted to produce alcohols and / or aldehydes.

The volume ratio of carbon dioxide to hydrogen (carbon dioxide: hydrogen) can be arbitrarily selected from 1: 0.1 to 100. Preferably, it is 1: 0.1 to 10. Further, the volume ratio of the organic compound having an unsaturated carbon bond to hydrogen can be arbitrarily selected from the ratio of the organic compound having an unsaturated carbon bond to hydrogen from 0.01 to 0.5. It is preferably 0.05 to 0.3. The total pressure of carbon dioxide, hydrogen, and an organic compound having an unsaturated carbon bond at the time of the reaction is about 0.1 to 40 MPa, preferably 2 to 20 MPa. When the pressure is too low, the reaction rate is slow, while when the pressure is too high, it is disadvantageous in terms of the pressure resistance structure of the device such as the reaction vessel.

The production method of the present invention can be carried out by either a batch method or a continuous method. When carbon monoxide is mass-produced in a large-scale device and subjected to a subsequent hydroformylation reaction, it is preferably a continuous type, in which case the powder, granules and / or molded product of the catalyst composition of the present invention is filled. At a predetermined reaction temperature, carbon dioxide and hydrogen as raw materials and an organic compound having an unsaturated carbon bond are supplied to the reaction vessel. Depending on the conditions, the reaction product may contain unreacted carbon dioxide and / or hydrogen. In that case, carbon dioxide is separated from carbon monoxide by a chemical adsorption method using a base such as amine and synthesized. It can be used as a gas (carbon monoxide / hydrogen mixed gas).

The reaction temperature is 250 ° C. or lower and higher than the melting point of the salts contained in the catalyst composition, and can be appropriately determined in consideration of the type and reactivity of the salts contained in the catalyst composition. The reaction temperature is, for example, 80 to 250 ° C, preferably 120 to 200 ° C. When the reaction temperature is too low, the reaction is difficult to proceed, and when the temperature exceeds 250 ° C., the catalyst may be decomposed and ruthenium metal may be precipitated. Therefore, the temperature is preferably 250 ° C. or lower.

The reaction in the production method of the present invention is carried out in the absence of a solvent. The solvent may be an inorganic solvent or an organic solvent, and is not used in the method for producing carbon monoxide of the present invention.

Among the reactions in the production method of the present invention, hydrogenation of carbon dioxide is an equilibrium reaction, and the reaction temperature, the partial pressure of carbon dioxide and hydrogen used as a raw material, and the reaction time (maintain to the equilibrium state or bring it to the equilibrium state). The conversion rate to carbon monoxide changes depending on whether the reaction is terminated before it is reached).

By using the method of the present invention for producing alcohols and / or aldehydes by hydroformylating an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen, carbon dioxide is used in the hydroformylation reaction of the organic compound having an unsaturated carbon bond. Carbon can be used as an alternative to carbon monoxide. That is, the carbon dioxide remaining in the reaction product of carbon dioxide hydrogenation can be used as it is for reaction hydroformylation without being separated from carbon monoxide (see, for example, Catalysis Today 115 (2006) 70-72).

Hereinafter, the present invention will be described in more detail based on examples. However, the examples are examples of the present invention, and the present invention is not intended to be limited to the examples.

[Example 1]
Silica gel (WakosilC) is added to a solution obtained by dissolving 50.0 mg of Ru ₃ (CO) ₁₂ in 15 mL of methylene chloride and further adding 1600 mg of 1-methyl-3-hexyl midazolium chloride ([C ₆ mim] Cl). −200 Specific surface area: 475 m ² / g ± 25 m ² / g) was added in an amount of 10.0 g, and the mixture was stirred and methylene chloride was distilled off under reduced pressure to obtain catalyst-supported silica gel fine particles.

After 1.0 g of the catalyst-supported silica gel fine particles were placed in an autoclave having an internal volume of 45 mL, carbon dioxide, hydrogen, and propylene gas were press-fitted to 40 atm, 20 atm, and 5 atm (total pressure 65 atm), respectively. The reaction was carried out for 10 hours while maintaining the temperature at 170 ° C. After completion of the reaction, the obtained product was quantitatively analyzed by gas chromatography.

[Example 2]
The reaction was carried out under the same conditions as in Example 1 except that 1-methyl-3-butylimidazolium chloride ([C ₄ mim] Cl) was used instead of 1-methyl-3-hexylimidazolium chloride.

[Example 3]
The reaction was carried out under the same conditions as in Example 2 except that 1-methyl-3-ethylimidazolium chloride ([C ₂ mim] Cl) was used instead of 1-methyl-3-hexylimidazolium chloride.

[Example 4]
The reaction was carried out under the same conditions as in Example 3 except that the reaction temperature was 150 ° C.

[Example 5]
The reaction was carried out under the same conditions as in Example 3 except that the reaction temperature was 190 ° C.

[Example 6]
The reaction was carried out under the same conditions as in Example 1 except that 1-butyl-1-methylpyrrolidinium chloride ([P ₁₄ ] Cl) was used instead of 1-methyl-3-hexylimidazolium chloride.

[Example 7]
The reaction was carried out under the same conditions as in Example 1 except that 1-butyl-3-methylpyridinium chloride ([3-mPyri ₄ ] Cl) was used instead of 1-methyl-3-hexylimidazolium chloride.

[Example 8]
The reaction was carried out in the same manner as in Example 3 except that 60 mg of [RuCl ₂ (CO) ₃ ] ₂ was used instead of Ru ₃ (CO) ₁₂ .

[Example 9]
The reaction was carried out under the same conditions as in Example 3 except that 60.0 mg of [RuCl ₂ (CO) ₃ ] ₂ and 40.0 mg of Co ₂ (CO) ₈ were used instead of Ru ₃ (CO) ₁₂ .

[Example 10]
The reaction was carried out under the same conditions as in Example 3 except that [RuCl ₂ (CO) ₃ ] ₂ was used at 60.0 mg and Rh (acac) (CO) ₂ was used at 60.0 mg instead of Ru ₃ (CO) _12. It was.

[Reference example 1]
In an autoclave with an internal volume of 45 mL, 6.25 mg of Ru ₃ (CO) ₁₂ and 200 mg of 1-methyl-3-ethylimidazolium chloride as a reaction solvent were placed, followed by carbon dioxide, hydrogen, and propylene gas at 40 atm and 20 atm, respectively. After press-fitting to atmospheric pressure and 5 atm (total pressure 65 atm), the reaction was carried out for 10 hours while maintaining the temperature at 170 ° C. After completion of the reaction, the obtained product was quantitatively analyzed by gas chromatography.

[Reference example 2]
The reaction was carried out in the same manner as in Example 3 except that 40 mg of Co ₂ (CO) ₈ was used instead of Ru ₃ (CO) ₁₂ .

[Reference example 3]
The reaction was carried out in the same manner as in Example 3 except that 60 mg of Rh (acac) (CO) ₂ was used instead of Ru ₃ (CO) ₁₂ .

The results are shown in Table 1.

The sources of the reagents used in the above Examples and Reference Examples are as follows.
(1) Wakosil C-200 (Fuji Film Wako Pure Chemical Industries, Ltd.)
(2) Methylene chloride (Kanto Chemical Co., Inc.)
(3) Ru ₃ (CO) ₁₂ (Fuji Film Wako Pure Chemical Industries, Ltd.)
(4) [RuCl ₂ (CO) ₃ ] ₂ (STREM CHEMICALS)
(5) Co (CO) ₈ (Kishida Chemical Co., Ltd.)
(6) Rh (acac) (CO) ₂ (STREM CHEMICALS)
(7) [C ₆ mim] Cl (Tokyo Chemical Industry Co., Ltd.)
(8) [C ₄ mim] Cl (Tokyo Chemical Industry Co., Ltd.)
(9) [C ₂ mim] Cl (Tokyo Chemical Industry Co., Ltd.)
(10) [P ₁₄ ] Cl (Tokyo Chemical Industry Co., Ltd.)
(11) [3-mPyri ₄ ] Cl (Tokyo Chemical Industry Co., Ltd.)

As is apparent from the comparison of Examples 1-7 and Reference Example 1 using the same ruthenium complex compound, the method of the present invention is comparable to or higher than the reaction of a homogeneous liquid phase system. Gives the product yield. In particular, when [C ₂ mim] Cl was used as a salt (Example 3), the total hydroformylation product yield (butanol + butyraldehyde) was 60% or more.

Further, as is clear from Examples 9 and 10 and Reference Examples 2 and 3, Co (CO) ₈ and Rh (acac) (CO) ₂ are due to carbon dioxide and hydrogen even when used alone. Hydroformylation does not occur, but it is used in combination with [RuCl ₂ (CO) ₃ ] ₂ and Co (CO) ₈ or [RuCl ₂ (CO) ₃ ] ₂ and Rh (acac) (CO) _2. By doing so, a hydroformylated product could be obtained in a yield comparable to that of Example 3.

The present invention is useful in the technical fields related to alcohols made from carbon dioxide and methods for producing aldehydes.

Claims (15)

A catalyst composition comprising a metal compound on at least a part of the outer surface and the inner surface of the porous solid particles and a carrier of salts having a melting point of 250 ° C. or lower.
When the metal compound is one kind, the metal compound is a ruthenium carbonyl complex compound.
When there are two types of the metal compound, one of them is a ruthenium carbonyl complex compound, and the other type used in combination with this is an iridium carbonyl complex compound having at least one carbonyl ligand, rhodium carbonyl. It is one of a complex compound and a cobalt carbonyl complex compound.
Moreover, the catalyst is a catalyst used in a reaction for producing alcohols and / or aldehydes by hydroformylating an organic compound having an unsaturated carbon bond with carbon dioxide and hydrogen, which is carried out at a temperature equal to or higher than the melting point of the salts. , The catalyst composition. When the metal compound is one kind, the metal compound is a ruthenium carbonyl complex compound having a nucleus of three or more ruthenium atoms.
The catalyst composition according to claim 1, wherein when there are two types of the metal compound, one of them is a ruthenium carbonyl complex compound having a nucleus of one or more ruthenium atoms. 2. The ruthenium carbonyl complex compound having a nucleus of three or more ruthenium atoms is one of Ru ₃ (CO) ₁₂ , H ₂ Ru ₄ (CO) ₁₂ , and H ₂ Ru ₆ (CO) _18. The catalyst composition according to. The ruthenium carbonyl complex compounds having one or more ruthenium atom nuclei are Ru ₃ (CO) ₁₂ , H ₂ Ru ₄ (CO) ₁₂ , H ₂ Ru ₆ (CO) ₁₈ , [RuCl ₂ (CO) ₃ ] ₂ . The catalyst composition according to claim 2, which is one of them. When there are two types of the metal compound, the mass ratio of the ruthenium carbonyl complex compound having one or more ruthenium atom nuclei to the other metal compound used in combination therewith is in the range of 1: 0.1 to 10. The catalyst composition according to any one of claims 2 to 4. The catalyst composition according to any one of claims 1 to 5, wherein the mass ratio of the one or two kinds of metal compounds and salts is in the range of 0.01: 5 to 0.1. The catalyst composition according to any one of claims 1 to 6, wherein the porous solid particles are at least one kind of particles selected from the group consisting of silica, alumina, zeolite, titania, and carbon. The anion components of the salts are from halide ions, acetate anions, trifluoroacetate anions, methanesulfonate anions, trifluoromethanesulfonate anions, bistrifluoromethanesulfonylamide anions, tetrafluoroborate anions, hexafluorophosphonate anions, and dicyanoamide anions. The catalyst composition according to any one of claims 1 to 7, which comprises at least one anion selected from the group consisting of. 8. The anion component of the salts comprises at least one anion selected from the group consisting of halide ions, acetate anions, trifluoroacetate anions, tetrafluoroborate anions, and hexafluorophosphonate anions. Catalyst composition. The cation component of the salts is at least one cation selected from the group consisting of imidazolium cation, ammonium cation, pyridinium cation, pyrrolidinium cation, piperidinium cation, sulfonium cation, morpholinium cation, and phosphonium cation. , The catalyst composition according to any one of claims 1 to 9. The catalyst composition according to any one of claims 1 to 10, wherein the porous solid particles have a specific surface area of 80 m ² / g or more. The catalyst composition according to any one of claims 1 to 11, wherein the porous solid particles have an average particle diameter in the range of 0.1 to 1000 μm. In the presence of the catalyst composition according to any one of claims 1 to 12, an organic compound having an unsaturated carbon bond is hydroformylated with carbon dioxide and hydrogen at a temperature of 250 ° C. or lower and higher than the melting point of the salts. A method for producing alcohols and / or aldehydes, which produces alcohols and / or aldehydes. 13. The method of claim 13, wherein the reaction is carried out in the absence of a solvent. 13. The method of claim 13 or 14, wherein the reaction is carried out at a temperature of 80 ° C. or higher.

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