JPH11285625A - Catalytic separation membrane, catalytic reaction method ahd production of compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To recover a homogeneous catalyst having high performance but difficult to be recovered by forming a membrane from an inorg. membrane through which the catalyst, part or all of which is dissolved in a liq., is not passed. SOLUTION: An inorg. membrane used for this catalytic separation membrane may be any inorg. membrane if a catalyst, part or all of which is dissolved in a liq., is not passed through the membrane. An org. membrane cannot be used because it has inferior resistance to org. compd. performance, is swollen with an org. solvent and also has inferior separation performance. Since the purpose is to separate the catalyst used for an org. reaction, the inorg. membrane excellent in org. chemical resistance and without being swollen with an org. solvent must be used. The catalyst separation mechanism may be based on either of a size, an affinity or an other method. Though the mechanism is not clear at this point of time, the separation is preferably carried out by the size. The material of the inorg. membrane is not particularly limited if the catalyst can be separated but a molecular sieve membrane is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for efficiently performing a chemical reaction using a homogeneous catalyst which is difficult to separate from a product because it is dissolved in a liquid.

[0002]

2. Description of the Related Art In conventional industrial catalytic reaction methods, solid catalysts have been favorably used because the catalyst can be easily separated from a reaction substrate and a reaction product. In recent years, homogeneous catalysts having extremely high activity, selectivity, and the like, such as metal complex catalysts and heteropolyacid catalysts, have come to be known. However, since these homogeneous catalysts are dissolved in the reaction solution, the catalyst and the reaction substrate,
There is a disadvantage that separation from the reaction product is difficult. Also, these homogeneous catalysts are generally very expensive, and losing the catalyst during recovery of the catalyst significantly increases production costs. From such a viewpoint, many attempts have been made to immobilize these homogeneous catalysts.

[0003]

However, in general, when a homogeneous catalyst is immobilized, the degree of freedom of the catalyst is lost, so that the activity may be reduced or the original catalyst performance may not be exhibited. Further, even if immobilized, there is a problem that the catalyst component cannot be completely immobilized and the catalyst component elutes during the reaction. An object of the present invention is to provide a catalyst separation membrane capable of recovering such a high-performance but difficult-to-recover homogeneous catalyst, a catalyst reaction method using the same, and a method for producing a compound. .

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a film made of an inorganic material having resistance to organic chemicals can be used to prevent the product from passing through catalyst molecules. Succeeding in making a membrane that allows a part to pass through, led to the present invention.

That is, the present invention provides a catalyst separation membrane composed of an inorganic membrane that does not allow a part of or the whole of a catalyst dissolved in a liquid to pass through, and at least the following two steps (1): Liquid phase reaction step in which the catalyst molecules and the reaction substrate come into contact. (2) a catalyst separation step including an inorganic membrane that allows at least a part of the reaction product to pass without passing through the catalyst molecule; and a catalyst reaction method including: passing at least a part of the reaction product without passing through the catalyst molecule. This is a method for producing a compound, comprising contacting a catalyst separation membrane composed of an inorganic membrane with a reaction solution containing at least a part of a catalyst after or during the reaction.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic film of the present invention may be of any type as long as it does not allow a partially or wholly dissolved catalyst to pass through. However, it is essential to be an inorganic film. The organic film is
It has poor organic compound resistance, swells with organic solvents, has poor separation performance, and cannot be used. An object of the present invention is to separate a catalyst used for an organic reaction, and it is essential that the inorganic film has excellent organic chemical resistance and does not swell with an organic solvent.

In the present invention, the mechanism for separating the catalyst may be a method of separating by size, a method of separating by affinity, or another method. The mechanism is unknown at this time. Preferably they are separated by size. The material of the inorganic membrane is not particularly limited as long as it can separate the catalyst, but is preferably a molecular sieve membrane. Molecular sieves have a uniform pore size with a molecular size. The molecular size is a range of the size of a single molecule existing in the world, and generally means a range of about 3 to 20 angstroms. Examples of the molecular sieve include crystalline silicates, crystalline aluminosilicates, crystalline metallosilicates, crystalline aluminophosphates, crystalline metalloaluminophosphates, and other zeolites or zeolite analogs, MCM-41, F
A mesoporous material such as SM-16 can be used. There are no particular restrictions on the type of zeolite or zeolite analog such as crystalline silicate, crystalline aluminosilicate, crystalline metallosilicate, crystalline aluminophosphate, crystalline metalloaluminophosphate, and, for example, atlas of zeolite structure types (W M. Meyer, D. H. Olson, C. H. Veloture, Zeolites, 17 (1/2), 199
6) (Atlas of Zeolite Structure types (WM Meier,
DH Olson, Ch. Baerlocher, Zeolites, 17 (1/2), 19
96)). Of course, zeolites not listed here and zeolite-like substances are also included. These substances not only have pores of molecular size, but also easy to control properties such as hydrophilicity and hydrophobicity, and not only separate catalysts by size difference, but also by the difference in affinity with membrane. It is also possible to divide. The inorganic film of the present invention is not limited to a film containing zeolite or a zeolite analog as a main component as described above.For example, if the pore size can be controlled to the molecular size, the gap between the particles of the ceramic ultrafine particles can be increased. The used film may be used. However, it is difficult to obtain pores having a uniform molecular size with good reproducibility by utilizing the particle gap, and a zeolite or zeolite-like membrane is preferably used.

The form of the inorganic membrane is not particularly limited, but generally, the membrane for separating the catalyst is coated on a porous support having a larger pore diameter. Of course, a single film without coating may be used, but from the viewpoint of strength, it is preferable to coat the support. The thinner the film coated on the support, the larger the required amount of permeation of the required substance is, and thus, the preferable film is. The material of the porous support is not particularly limited, but is a metal or a metal oxide. From the viewpoint of heat resistance and chemical resistance, metal oxides are preferably used. The metal oxide is not particularly limited, but alumina, zirconia, silica, mullite and the like are preferably used. There is no particular limitation on the shape of the support, and those generally available on the market, such as a sphere, a plate, a tube, a monolith, and a honeycomb, can be used. Among them, a tube-shaped or monolith-shaped support is preferable in terms of both surface area and strength. The support may be directly coated with the catalyst separation membrane. However, in order to improve the coating performance, an intermediate layer may be provided on the support, and the catalyst separation membrane may be coated thereon. The intermediate layer is formed by, for example, coating particles having a relatively small particle diameter on a support and, if necessary, drying or firing. The intermediate layer has effects such as smoothing the surface of the support, reducing the pore diameter of the support, and improving the affinity with the catalyst separation membrane phase. The material of the intermediate layer is not particularly limited, either.
Any material may be used as long as it is inorganic. The intermediate layer and the catalyst separation membrane may be coated on either side of the support, or may be coated on both sides. The support is tubular, monolithic,
When it is in a honeycomb shape, it is preferable to be coated on the inside. In the case of coating on a spherical support, the entire outer surface can be coated with a catalyst separation membrane and used as microcapsules in which catalyst molecules are built, which is also within the scope of the present invention. The pore diameter of the porous support is not particularly limited, but is preferably 5 μm or less.
If it is larger than this, it becomes difficult to form a catalyst separation membrane layer. The pore size of the support is preferably small, but if too small, the permeation amount of the substance becomes too small, which is inappropriate. The preferred pore range is 0.01 to 3 μm, particularly preferably 0.05 to 1.0 μm.

The method for producing the catalyst separation membrane is not particularly limited. When the catalyst separation membrane is a molecular sieve membrane,
As a method for producing a molecular sieve film, a generally known method can be applied. For example, in the case of coating a molecular sieve film on a support, a method in which a support is put in a precursor gel for synthesizing a molecular sieve and subjected to hydrothermal treatment (eg, JP-A-63-291809), A method in which a support is coated in advance with molecular sieve seed crystals, and then the precursor gel is subjected to hydrothermal treatment (for example:
JP-A-7-109116), a method in which a precursor gel is coated on the surface of a support, dried, and then treated with steam (eg, JP-A-7-89714), or molecular sieve fine particles are directly coated. (Japanese Patent Publication No. 5-50331) can be applied.

The method for coating the support with the molecular sieve seed crystal, the molecular sieve precursor gel, and the molecular sieve fine particles is not particularly limited, and any known method can be applied. For example, after the support is immersed in the slurry, it is pulled up as it is, a coating method, a method in which one side of the support is brought into contact with the slurry and the pressure is reduced from the other side, and the slurry is pressed from one side of the support by applying pressure. A method is conceivable. The coating of the molecular sieve film may be performed twice or more. After the molecular sieve film is formed, a treatment such as washing with water, drying and baking may be added. Whether or not the molecular sieve film has been formed can be confirmed by using an X-ray diffractometer for a thin film. From the measurement result, the structure of the molecular sieve can be identified. Once the structure is known, the reference (Atlas of Zeolite Str
ucture types (WM Meier, DH Olson, Ch. Baerloc
her, Zeolites, 17 (1/2), 1996)) and the like, the pore size can be easily known. As used herein, the pore size of zeolite refers to the largest diameter of the opening, and from the above references, MFI zeolite has 5.6 Å, M
The OR zeolite has a thickness of 7.0 angstroms, and the LTA zeolite has a thickness of 4.1 angstroms. Of course, this membrane is a polycrystal of zeolite or zeolite analog and often contains pores in the interstices of the particles, not strictly only the pores contained in the crystals of zeolite or zeolite analog described above. . The pores that form in the interstices of the crystal are particularly problematic when practically larger than the pores in the crystal, but such pores can be reduced by post-treatment,
After the formation of the zeolite or zeolite-like membrane, post-treatment is applied to fill such unnecessary pores in the crystal gap, and it is preferably performed. An example of a subsequent treatment method is an organic compound having a size that does not enter the pores of the zeolite or the zeolite analog, but can enter the crystal gap of the zeolite or the zeolite analog, such as 1,3,5-triisopropylbenzene. Or the like, and then filling the crystal gap of zeolite or zeolite analog, and then calcining and carbonizing under a nitrogen stream to fill the holes in the crystal gap. Alternatively, the crystal gap may be filled with silicone rubber or the like.

The catalyst according to the present invention is one in which a part or the whole is dissolved in a liquid. What is generally referred to as a homogeneous catalyst is the catalyst referred to herein, but even if it is referred to as a solid catalyst, a substance which is partially dissolved in a liquid is included in the definition of the catalyst of the present invention. In the present invention, the inorganic membrane must not allow the dissolved catalyst to pass through. Whether or not to pass can be confirmed as follows. Dissolve 1 to 10% of the catalyst molecules in a solvent having a relatively small molecular size such as ethanol, contact the formed membrane at room temperature, reduce the pressure from the opposite side with a rotary pump, etc., and convert the permeated vapor or liquid at the temperature of liquid nitrogen. The trapped and collected liquid is analyzed to confirm the presence of catalyst molecules. As a method for confirming the presence of the catalyst molecule, an atomic absorption method or an ICP method (Inductively coupled pl
This is performed by confirming the presence of the metal contained in the catalyst by asma analysis). The permeation time is 20 hours for a 1 cm 2 membrane, and if the membrane area is doubled, the permeation time can be halved. Conducts a permeation experiment between the liquid containing the catalyst and the liquid without the catalyst, analyzes the total amount of metal in the permeated liquid, and detects the difference in the content of at least one metal among the metals contained in the catalyst. If it is within 0.01% of the liquid, it can be defined as not passing. Materials for the permeation experiments must be carefully selected. The material containing the metal contained in the catalyst is selected as little as possible. In addition to the confirmation by experiments, in the case of a membrane using a molecular sieve, the catalyst can be defined by the molecular size. The molecular size mentioned here is a molecular model assembled,
This is the diameter of the circle in which the diameter of the circle is the smallest among the cylinders that can contain the molecular model. The molecular model is assembled using a commercially available molecular model. If there is no commercially available model using a special element, a molecular model may be assembled on a computer.
When assembling on a computer, for example, it can be obtained as follows. If there is no crystal structure analysis data or no crystal structure analysis data, the determination is made based on the molecular structure created by the molecular design software Cerias2 (manufactured by MSI). The molecular structure when there is no crystal structure analysis data is created by using the MM (Molecular Mechanics) tool and MD (Molecular Dynamics) tool which are modules of the software. In the case where the number of atoms is 50 or less and the system does not impose much load on the CPU to create the molecular structure, the molecular structure created by the MM and MD tools is further converted to a molecular orbital calculation method (MOPAC6).
(QCPE # 455 registration) and Gaussian94 (G
aussian inc. Optimize the structure. M
The force field parameters used in M and MD tools are C
Universal F mounted on erius2
Calculate using the orce Field parameter.
As the charge parameter, the Qeq method of Cerius2 is used. When using the MM and MD tools, the force field parameters must first be set to the Universal Force Fie.
After setting the ld parameter, use the MD tool ADIAB in the default state except that the MD tool is set to calculate the Qep method every 50 steps.
Calculate ATIC method 5 times, then canonic
After calculating the al method five times, the MM tool may calculate it twice in the default state. As an initial structure used when creating a molecular structure using Cerus2, it is preferable to create an initial structure by using crystal data having a similar structure or the like. In the calculation using MOPAC, the entire structure is optimized by the MNDO method. In the calculation using Gaussian 94, the entire structure is optimized using 6-31G * as a basis function. The molecular size of the catalyst determined in this way is
It is also possible to predict whether or not permeation is possible depending on whether or not it is larger than the pore size of the molecular sieve.

Although the mechanism of catalyst separation is not clear, a method of separating the catalyst according to the degree of affinity between the inorganic membrane and the catalyst,
Either method may be used in which the difference is determined by the difference between the molecular size of the catalyst and the size of the pore size of the inorganic membrane. To completely separate the catalyst,
The molecular size of the catalyst is 1. the pore size of the molecular sieve membrane.
It is desirable that it be at least one time. If the size of the catalyst molecule is
Even if the size of the pores of the molecular sieve membrane is about the same as or slightly smaller, it is possible in some cases not to allow the catalyst to pass through, but there is a possibility that the pores of the molecular sieve membrane may be blocked with catalyst molecules. In this case, it is conceivable that the permeation of the reaction product is hindered, so that the size of the catalyst molecule is desirably 1.1 times or more the pore diameter of the molecular sieve membrane. The pore size of the molecular sieve membrane is the size of the pores of the molecular sieve forming the membrane. The definition of the molecular size of the catalyst is as described above. Further, the molecular weight of the reaction product to be passed through the membrane is preferably smaller than the molecular weight of the catalyst. The larger the difference in molecular weight is, the more preferable it is.
Above is particularly preferable.

Examples of the catalyst include a heteropoly acid and a metal complex. Examples of heteropolyacids include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, lyvanadomolybdic acid, lynnvanadotungstic acid, lintangstomolybdic acid, and categonstomolybdic acid, of course. It may be salt. Examples of metal complexes include Sharpless oxidation catalyst (Chemical Formula 1)

Embedded image Jacobson oxidation catalyst

Embedded image Asymmetric Lewis acid catalyst (Chemical formula 3)

Embedded image And the like.

Here, it is necessary to select an inorganic film according to the catalyst and reaction product used. As a criterion for selection of the inorganic membrane, it is most preferable to use an inorganic membrane having a pore size such that the molecular size of the catalyst> the pore size of the catalyst separation membrane> a part of the product, but is not limited thereto. .

The present invention also provides a catalytic reaction method including at least the following two steps. (1) A liquid phase reaction step in which a partially or wholly dissolved catalyst molecule is brought into contact with a reaction substrate. (2) A catalyst separation step using an inorganic membrane that allows at least a part of the reaction product to pass without passing through catalyst molecules.

In the catalyst reaction method of the present invention, the size of the catalyst is not particularly limited, but a catalyst separation step using an inorganic membrane that does not pass through catalyst molecules but allows at least a part of the reaction product to pass through is essential. .

Here, it is necessary to select an inorganic film according to the catalyst and the reaction product used. As a criterion for selection of the inorganic membrane, an inorganic membrane having a pore diameter such that the molecular size of the catalyst> the pore size of the catalyst separation membrane> the molecular size of a part of the product can be considered, but is not limited thereto. . Actually, it is confirmed that the catalyst does not pass by the above-mentioned method, and that a part of the reaction product passes. Whether or not the reaction product has passed can be confirmed in the same manner as in the case of the catalyst.
The solution containing the reaction product is brought into contact with the formed film at room temperature or with heating, and the pressure is reduced by a rotary pump or the like from the opposite side,
Trap the vapor or liquid that has permeated at liquid nitrogen temperature,
The collected liquid is analyzed by a general organic compound identification method such as gas chromatography or liquid chromatography to confirm the presence of product molecules. The higher the concentration of the reaction product, the better. The permeation time is 20 hours for a 1 cm 2 membrane, and if the membrane area is doubled, the permeation time can be halved.

The method for separating the catalyst through the inorganic membrane is not particularly limited, but generally at least a part of the product is
Driving force is required to permeate the membrane. As a method of applying the driving force, a method in which a reaction solution containing a catalyst is flowed while applying pressure,
A method of reducing the pressure on the opposite side of the membrane in contact with the reaction solution containing the catalyst is conceivable. The temperature at which the light is transmitted is not particularly limited, and the higher the temperature, the easier the light is transmitted.
However, if there is no problem with the permeation rate, it is preferable that the permeation is performed at the same temperature as the reaction temperature without wasting energy.

It is essential that the method of the present invention includes a liquid phase reaction step in which the reaction substrate is brought into contact with a partially or completely dissolved catalyst molecule. The liquid phase reaction in which the catalyst molecule and the reaction substrate come into contact with each other is not particularly limited, and examples thereof include a hydration reaction, a dehydration reaction, an ether cleavage reaction, a condensation reaction, an esterification reaction, and an ester decomposition reaction with a heteropolyacid catalyst. The alkylation, dealkylation reaction, acetalization, acylation, isomerization, disproportionation, dimerization, trimerization, cyclization, and oxidation reactions are referred to herein as partially or wholly dissolved catalyst molecules. This is a liquid phase reaction in which the reaction substrate comes into contact with the reaction substrate. Other,
Asymmetric synthesis using a metal complex catalyst is one of industrially useful compounds in the liquid phase reaction of the present invention. As an example of the reaction with the metal complex catalyst, there is an epoxidation reaction of allyl alcohol using tetraisopropoxy titanium and diethyl tartrate, which are well-known as Sharpless oxidation catalysts, as an asymmetric catalyst (Journal of American Chemical Society (J. Am. Chem. .Soc.), 102,5974 (1980)). Further, methacrolein is reacted with 2,3-dimethyl-1,3-butadiene using an asymmetric Lewis acid catalyst (monoacyloxytartaric acid and borane) to give (1R) -1,3,4-trimethyl-3-cyclohexene-1- There is an asymmetric Diels-Alder reaction that synthesizes carbaldehyde (Org. Synthesis. 72,86-94 (199
Five)). Further, a reaction for producing various optically active epoxides using a Jacobsen catalyst as shown below is also an example of the reaction of the present invention.

[0020]

Embedded image

[0021]

Embedded image

The present invention provides (1) a liquid phase reaction step in which a catalyst substrate in which at least a part or the whole is dissolved is brought into contact with a reaction substrate. (2) A catalytic reaction method including two steps of a catalyst separation step including an inorganic membrane that allows at least a part of a reaction product to pass without passing through catalyst molecules. , You can be together. That is, a method of separating at least a part of a product while performing a catalytic reaction may be used. One in which the catalyst molecule is microencapsulated inside the zeolite membrane is also within the scope of the present invention.

The substance permeating the membrane may be anything other than the catalyst, but it is essential that a part of the product permeates. When only necessary products pass through, it may be left as it is, but when two or more compounds pass through, it is necessary to provide a step of recovering the necessary compounds. A known method such as distillation, adsorption separation, or cryogenic separation can be used for the recovery. When a reaction substrate and / or a solvent are introduced in the recovery step and these are separated in the recovery step, the reaction may be returned to the liquid phase reaction step in which the reaction substrate comes in contact with a part or all of the dissolved catalyst molecules. .

The catalyst molecules that have not permeated the membrane may be returned to the liquid phase reaction step in which the partially or completely dissolved catalyst molecules come into contact with the reaction substrate. In order to recover the catalyst molecules that have not permeated the membrane, a compound unrelated to the reaction may be used, or a step of newly removing the added compound may be added.

FIG. 1 is a schematic diagram of the above method. In the figure, 1 is a reaction step, 2 is a catalyst separation step, 3
Is a recovery step.

The present invention relates to contacting a catalyst separation membrane composed of an inorganic membrane that allows at least a part of a reaction product to pass through without passing through catalyst molecules, and at least a part of a reaction solution after or during the reaction. Also provided are methods of making the characterized compounds.

In the present invention, a catalyst separation membrane composed of an inorganic membrane that allows at least a part of a reaction product to pass through without passing through catalyst molecules is essential.

The method of contacting the catalyst separation membrane with at least a part of the reaction solution containing the catalyst is not particularly limited.
A method of applying a pressure to the reaction solution containing the catalyst and a method of reducing the pressure on the opposite side of the film in contact with the reaction solution containing the catalyst can be considered.

The type of the reaction is not particularly limited, and a reaction applicable to the above-mentioned catalytic reaction method can be used.

Among the microcapsules containing the catalyst molecules in the space surrounded by the molecular sieve membrane, those in which the reaction solution comes into contact with the catalyst separation membrane are also within the scope of the present invention.

The material permeating the membrane may be anything other than the catalyst, but it is essential that a part of the product permeates. When only necessary products pass through, it may be left as it is, but when two or more compounds pass through, it is necessary to provide a step of recovering the necessary compounds. A known method such as distillation, adsorption separation, or cryogenic separation can be used for the recovery. When a reaction substrate and / or a solvent is introduced into the recovery step and separated in the recovery step, the reaction may be returned to the liquid phase reaction step in which the partially or wholly dissolved catalyst molecules come into contact with the reaction substrate.

The catalyst molecules that have not permeated the membrane may be returned to the liquid phase reaction step in which the partially or wholly dissolved catalyst molecules come into contact with the reaction substrate. In order to recover the catalyst molecules that have not permeated the membrane, a compound unrelated to the reaction may be used, or a step of newly removing the added compound may be added.

As a method for producing an optically active substance, the method of the present invention is most preferably used, but is not limited thereto.

[0034]

The present invention will be described below with reference to examples. (Preparation of Inorganic Membrane) Inorganic Membrane 1 Silicalite membrane is referred to (J. Membrane Sci.) 129
(1997), 77-82). Inorganic film 2 Mordenite film is referred to (Microporous Materials, 7 (199)
6), 299-308). Inorganic film 3 20 g of a 20% aqueous solution of tetrapropylammonium hydroxide (TPAOH) (Tokyo Kasei 20
0.28 g of NaOH (Katayama Chemical Reagent 1)
Grade) was added and stirred. 5 g of fumed silica (Aldrich) was added thereto and heated to 80 ° C. to obtain a transparent aqueous solution. Put this in a Teflon line autoclave,
After heating at 25 ° C. for 8 hours, fine particles of silicalite (about 80 nm) were obtained.

The silicalite fine particles (average particle size 80 n
m) 9% of 1% colloid is 1.4cm square and 3mm thick
Α-alumina porous ceramic plate (average particle size 100
(nm) was vacuum-absorbed from the opposite side to adhere to a porous ceramic plate, dried, and fired at 550 ° C. for 3 hours.
1 g of Ludox HS-30, 1 g of a 10% TPAOH aqueous solution and 1 g of water were placed on a ceramic plate coated with the silicalite fine particles.
After dropping 0.1 g of a mixture of 2.48 g and drying overnight at room temperature, 5
0.5 g of water was placed in a 0 ml autoclave and heated at 150 ° C. for 5 days under steam pressure. This is vacuum dried at room temperature for 2
After 4 hours, Ludox HS-30 1g, 10% TPAOH aqueous solution 1g
Then, 0.1 g of a mixed solution of water and 2.48 g of water was added dropwise, and the mixture was dried at room temperature overnight. Then, 0.5 g of water was put in a 50 ml autoclave and heated at 150 ° C. for 5 days under steam pressure. It was confirmed by X-ray diffraction and an electron microscope that the silicalite thin film was formed on a ceramic flat plate.

(Evaluation of Permeation of Membrane) Example 1 1 mol of ethanol, 1 mol of acetic acid and 0.01 mol of phosphomolybdic acid were added to a 200 ml flask, and the mixture was heated at 60 ° C. for 3 hours.
Allowed to react for hours. The reaction solution was brought into contact with the inorganic membrane 1 and the side not in contact with the inorganic membrane 1 was depressurized with a rotary pump, and the vapor permeating the membrane was trapped with liquid nitrogen. When the trapped liquid was analyzed, phosphorus and molybdenum were not detected. Ethyl acetate, ethanol,
The presence of water and acetic acid was confirmed by gas chromatography. The size of phosphomolybdic acid is 10 Å (Applied Catalysis A: General, 165 (1997),
219-226). Example 2 A 2 L flask was charged with titanium (IV) isopropoxide (Ti (iP
r) 4) 38.1 g and 1 L of dichloromethane were charged and stirred at -70 ° C. Then, with stirring, 33.1 g of diethyl L-tartrate and E
25 g of -2-hexen-1-ol was added. With further stirring, 184.5 ml (2.71 M) of a toluene solution of anhydrous tertiary butyl hydroperoxide was added. The cooling was stopped, the temperature of the reaction solution was raised to 0 ° C. with stirring, and the stirring was continued for about 2 hours. Next, the reaction solution was passed through an inorganic membrane 2 (pore diameter: about 7 angstroms). When analyzing the liquid that passed through the silicalite membrane, no titanium was detected at all,
(2S, 3S) -3-propyloxirane methanol was detected. (Synthesis Reference Organic Synthesis (Org. Synthesis). 63 (1984), 66-78) Example 3 1 mol of ethanol, 1 mol of acetic acid and 0.01 mol of phosphomolybdic acid were added to a 200 ml flask, and the mixture was heated at 60 ° C. 3
Allowed to react for hours. The reaction solution was brought into contact with the inorganic membrane 3 and the side not in contact with the inorganic membrane 3 was depressurized with a rotary pump, and vapor that had permeated the membrane with liquid nitrogen was trapped. Further, the membrane is washed with ethanol from the permeation side, mixed with the trapped liquid,
Upon analysis, phosphorus and molybdenum were not detected. Ethyl acetate, ethanol, water,
The presence of acetic acid was confirmed by gas chromatography. The permeated liquid was distilled, and ethanol and acetic acid fractions were collected. Further, the supply side of the membrane was washed with a mixed solution of ethanol and acetic acid, mixed with ethanol and acetic acid recovered by distillation, and reacted again. When the reaction solution was analyzed by gas chromatography, ethyl acetate was generated. Example 4 1 mol of propylene oxide and 0.55 mol of water were
The reaction was carried out at 25 ° C. for 12 hours in the presence of 0.2 mol% of (Salen) Co (III) (O ₂ CCH ₃ ) complex (Jacobsen's catalyst B described above). The reaction solution was brought into contact with the inorganic membrane 3 and the side not in contact with the inorganic membrane 3 was depressurized with a rotary pump, and vapor that had permeated the membrane with liquid nitrogen was trapped. Further, the membrane was washed with ethanol from the permeation side, mixed with the trapped liquid, and analyzed, but no Co was detected. The permeated liquid was distilled. At 34 ° C., low temperature components distilled out. The component was propylene oxide, the yield was 44%, and the optical yield was 98% ee. The residue was 1,2-propanediol with a yield of about 5
At 0%, the optical yield was 98% ee. Further, the supply side of the membrane was washed with a mixed solution of 1 mol of propylene oxide and 0.55 mol of water, and reacted again at 25 ° C. for 12 hours. As a result of performing the same operation, the same result was obtained.

[0037]

According to the present invention, a homogeneous catalyst, which has been difficult to recover and reuse in the past, can be used for the reaction as a homogeneous system, and the catalyst can be easily separated. A continuous reaction process using a catalyst is also possible.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one example of the reaction method of the present invention.

[Explanation of symbols]

 1 reaction step 2 catalyst separation step 3 recovery step

Claims (14)

[Claims] 1. A catalyst separation membrane comprising an inorganic membrane that does not allow a part of or the whole of a catalyst dissolved in a liquid to pass through. 2. The catalyst separation membrane according to claim 1, wherein the inorganic membrane is a molecular sieve membrane. 3. The catalyst separation membrane according to claim 1, wherein the catalyst is at least one selected from heteropolyacids and metal complex catalysts. 4. A catalytic reaction method comprising at least the following two steps. (1) A liquid phase reaction step in which a partially or wholly dissolved catalyst molecule is brought into contact with a reaction substrate. (2) A catalyst separation step using an inorganic membrane that allows at least a part of the reaction product to pass without passing through catalyst molecules. 5. The catalytic reaction method according to claim 4, wherein the inorganic film is a molecular sieve film. 6. The catalytic reaction method according to claim 4, wherein the catalyst is at least one selected from heteropolyacids and metal complex catalysts. 7. The catalytic reaction method according to claim 4, further comprising a step of recovering a required substance from the liquid passed through the inorganic membrane. 8. The method according to claim 4, wherein the catalyst molecules that have not passed through the inorganic membrane are returned to the liquid phase reaction step.
The catalytic reaction method described in the above item. 9. Contacting a catalyst separation membrane comprising an inorganic membrane, which allows at least a part of a reaction product to pass through without passing through catalyst molecules, and a reaction solution containing at least a part of the catalyst after or during the reaction A method for producing a compound, characterized in that: 10. The method for producing a compound according to claim 9, wherein the inorganic film is a molecular sieve film. 11. The method according to claim 9, wherein the catalyst is at least one selected from heteropolyacids and metal complex catalysts. 12. The method for producing a compound according to claim 9, wherein a required substance is recovered from the liquid having passed through the catalyst separation membrane. 13. The method according to claim 9, wherein the catalyst molecules that have not passed through the catalyst separation membrane are reused.
A method for producing the compound described in the above item. 14. The method for producing a compound according to any one of claims 9 to 13, wherein the compound is an optically active substance.