Catalyst, method for producing a catalyst, method for producing an unsaturated compound, and method for producing an epoxy compound

Abstract

To provide a layered double basic salt capable of being used as a catalyst in a stationary floor reactor.SOLUTION: There is provided a catalyst containing: a stationary basis compound containing as different bivalent metal elements, M1 and M2; and a carrier. In an X-ray diffraction pattern of the catalyst using CuKα ray, there are a peak P1 in which, 2θ is d1° and peak strength is I1, and a peak P2 in which 2θ is (d1×2±0.2)° and peak strength is I2, and 3≤d1≤10 is satisfied, I1 / I2 is 1 or greater, a total content of M1 and M2 in the catalyst is 10-45 mass% by carrying the stationary basis compound to the carrier.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a catalyst, a method for producing a catalyst, a method for producing an unsaturated compound, and a method for producing an epoxy compound. [Background technology]

[0002] Layered compounds, such as clay minerals, hydroxyapatite, and hydrotalcite, are used in a variety of applications including fillers, catalysts, adsorbents, cosmetics, pharmaceuticals, ceramics, and civil engineering materials. Layered compounds form ion pairs in and between layers, and numerous catalytic reactions have been developed that take advantage of their unique properties. In particular, layered compounds with cations in the layers and anions between the layers exhibit solid basicity and are therefore used as basic catalysts (Non-Patent Literature 1).

[0003] As layered compounds exhibiting solid basicity, compounds called layered double hydroxides, in which divalent and trivalent metal hydroxides form a layered structure, have been widely studied (Non-Patent Literature 2). However, in layered double hydroxides, the areas that function as basic catalysts are limited to the solid surface or the edges of the layers. Therefore, in order to make them function more effectively as basic catalysts, methods using solid basic compounds (hereinafter also referred to as layered bibasic salts) in which two or more divalent metal hydroxides are combined to form a layered structure are being investigated (Non-Patent Documents 3 and 4). Layered bibasic salts are expected to be used as solid basic catalysts that can effectively utilize the basic sites within the layers.

[0004] Non-patent document 1 describes a method for synthesizing layered dibasic salts. Non-patent document 2 describes an epoxidation reaction of cyclic enones using layered dibasic salts as catalysts. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Nagendrappa, G., “Organic synthesis using clay and clay-supported catalysts,” Applied Clay Science, August 2011, Vol. 53, No. 2, pp. 106-138. [Non-Patent Document 2] Fan, G., et al., “Catalytic applications of layered double hydroxides: recent advances and perspectives,” Chemical Society Reviews, October 21, 2014, Vol. 43, pp. 7040-7066. [Non-Patent Document 3] Yamanaka, S., et al., “New anion exchangeable layered mixed basic salt, Ni1-xZn2x(OH)2(OCOCH3)2x·nH2O,” Materials Research Society Symposium Proceedings, 1995, Vol. 371, pp. 131-142. [Non-Patent Document 4] Hara, T. and others, “Epoxidation of cyclic enones with hydrogen peroxide catalysed by alkylcarboxylate-intercalated Ni-Zn mixed basic salts”, Catalysis Science & Technology, 2015, Vol. 5, p. 578-583 [Overview of the project] [Problems that the invention aims to solve]

[0006] For layered dibasic salts to be industrially utilized, they must be catalysts that can be used in fixed-bed reactors capable of continuous product production. However, until now, the use of layered dibasic salts as catalysts in fixed-bed reactors has not been investigated. When layered dibasic salts are used as catalysts in fixed-bed reactors, the layered dibasic salts swell by incorporating solvent between layers, increasing the pressure loss in the fixed-bed reactor. As a result, problems arise such as an increase in the energy required to supply raw materials and blockage of the reactor's flow path, preventing liquid flow. Thus, it has become clear that conventional layered dibasic salts have challenges for industrial use.

[0007] This invention has been made in view of the above circumstances, and aims to provide a catalyst that can reduce pressure loss when used as a catalyst in a fixed-bed reactor, a method for producing the catalyst, a method for producing an unsaturated compound, and a method for producing an epoxy compound. [Means for solving the problem]

[0008] The inventors of this invention conducted extensive research to achieve the above objective and discovered that this objective can be achieved by using a layered bibasic salt supported on a carrier at a specific concentration, thus completing the present invention. In other words, the present invention includes the following embodiments.

[0009] [1] A catalyst comprising a solid basic compound containing M1 and M2 which are different divalent metal elements, and a support, In the X-ray diffraction pattern of the catalyst using CuKα radiation, Peak P1 has 2θ = d1° and peak intensity I1, Peak P2 is a peak with 2θ of (d1 × 2 ± 0.2)° and peak intensity I2. It has, Satisfying 3 ≤ d1 ≤ 10, I1 / I2 is 1 or greater, A catalyst in which the solid basic compound is supported on the carrier such that the total content of M1 and M2 in the catalyst is 10 to 45% by weight. [2] The catalyst according to [1], wherein the solid basic compound has a composition represented by the following formula (I). [M1 1-x M2 2x (OH)2][A n- 2x / n·yH₂O] (I) In formula (I), M1 and M2 represent different divalent metal elements, and A n- represents an n-valent anion. Also, x satisfies 0 < x < 1, y represents a positive real number, and n represents a natural number. [3] The catalyst according to [1] or [2], wherein the carrier is a metal oxide. [4] The catalyst according to [3], wherein the metal oxide is at least one selected from the group consisting of silicon oxide and aluminum oxide. [5] The catalyst according to any one of [1] to [4], wherein M1 and M2 are metal elements of Group 6 to Group 12 in the fourth period of the periodic table. [6] The catalyst according to any one of [1] to [5], wherein M1 and M2 are nickel, zinc or copper. [7] A method for producing a catalyst according to any one of [1] to [6], comprising a step of producing the solid basic compound by hydrothermal synthesis in the presence of the carrier. [8] A method for producing an unsaturated compound, comprising a step of producing an unsaturated compound in the presence of the catalyst according to any one of [1] to [6]. [9] The method for producing an unsaturated compound according to [8], wherein the catalyst is filled in a fixed-bed reactor.

[10] A method for producing an epoxy compound, comprising a step of producing an epoxy compound in the presence of the catalyst according to any one of [1] to [6].

[11] The method for producing an epoxy compound according to

[10] , wherein the catalyst is filled in a fixed-bed reactor.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a catalyst capable of reducing the pressure loss when used as a catalyst in a fixed-bed reactor, a method for producing the catalyst, a method for producing an unsaturated compound, and a method for producing an epoxy compound.

Embodiments for Carrying Out the Invention

[0011] The embodiments of the present invention will be described in detail below. The following description of the constituent elements is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the gist of the invention.

[0012] [catalyst] A catalyst according to an embodiment of the present invention (hereinafter also referred to as "the catalyst of this embodiment") comprises a solid basic compound containing M1 and M2, which are different divalent metal elements, and a support. The catalyst of this embodiment has, in the X-ray diffraction pattern of the catalyst using CuKα rays, a peak P1 where 2θ is d1° and peak intensity I1, and a peak P2 where 2θ is (d1×2±0.2)° and peak intensity I2. Here, d1 satisfies 3≦d1≦10, and I1 and I2 satisfy I1 / I2≧1. In the X-ray diffraction pattern of the catalyst of this embodiment, peaks P1 and P2 are peaks originating from the solid basic compound. When peaks P1 and P2 satisfy the specified 2θ and peak intensity, the solid basic compound functions effectively as a basic catalyst.

[0013] d1 is a value derived from the interlayer distance of the solid basic compound. An increase in d1 indicates a decrease in the interlayer distance, and a decrease in d1 indicates an increase in the interlayer distance. When d1 satisfies 3 ≤ d1 ≤ 10, it means that the interlayer distance is such that the substrate is easily incorporated between the layers and the basic sites within the layers interact effectively with the substrate. It is preferable that the lower limit of d1 is 5 or greater. Furthermore, I1 / I2 represents the intensity ratio of peak P1 to peak P2. I1 / I2 is 1 or greater, preferably 3 or greater, and more preferably 5 or greater.

[0014] The X-ray diffraction pattern of the catalyst in this embodiment is obtained by measuring the catalyst in powder form. The measurement conditions are as follows: source: CuKα rays (λ=1.5418Å), tube voltage: 40kV, tube current: 15mA, longitudinal limiting slit: 10.0mm, divergence slit: 0.625deg, scattering prevention slit: 13.0mm, and light receiving slit: 13.0mm, and the image is monochromatized using a NiKβ filter. The measurement can be performed using a Rigaku Corporation product name: MiniFlex600 or similar. The obtained data should be processed by removing Kα2 rays using X-ray diffraction equipment data acquisition software such as Rigaku Corporation product name: MiniFlex Guidance.

[0015] The X-ray diffraction pattern satisfied by the catalyst of this embodiment is determined by the type and content of the divalent metal element in the solid basic compound, the type of support, and the anion contained between the layers (A in formula (I)). n- By adjusting the above as appropriate, the desired range can be achieved.

[0016] Furthermore, in this embodiment, the catalyst is supported on a carrier such that the total content of M1 and M2 in the catalyst is 10 to 45% by weight. When the combined content of M1 and M2 is 10% by weight or more, it functions effectively as a solid basic catalyst. Furthermore, when the combined content of M1 and M2 is 45% by weight or less, a sufficient effect of suppressing catalyst swelling can be obtained. The lower limit of the combined content of M1 and M2 in the catalyst of this embodiment is preferably 15% by mass or more, and more preferably 20% by mass or more. Furthermore, the upper limit of the combined content of M1 and M2 in the catalyst of this embodiment is preferably 40% by weight or less.

[0017] The total content of M1 and M2 can be calculated by analyzing the catalyst using atomic absorption spectrometry as follows. First, 0.01 g of catalyst is accurately weighed into a 500 mL volumetric flask, and 1 mL of concentrated hydrochloric acid is added and allowed to stand for at least 8 hours to dissolve the catalyst. Then, pure water is added to adjust the volume to 500 mL, and measurements are taken using an atomic absorption spectrophotometer with measurement wavelengths of Ni 232.0 nm and Zn 213.9 nm. An instrument such as the Thermo Elemental SOLAAR AA series S4 can be used.

[0018] Furthermore, in the catalyst of this embodiment, the fact that the solid basic compound is supported on the support can be confirmed, for example, using a scanning electron microscope (SEM). When the solid basic compound is supported on the support, a substance with a particle size different from that of the support is observed on the surface of the support in the catalyst. SEM measurement of the catalyst can be performed using an instrument such as the JEOL JSM-6510 after the catalyst has been coated with Pt. Pt coating can be performed using an instrument such as the JEOL JFC-1600.

[0019] <Solid basic compounds> The solid basic compound in the catalyst of this embodiment contains M1 and M2, which are different divalent metal elements, and as described above, it has peaks P1 and P2 in the X-ray diffraction pattern. As for the divalent metallic elements M1 and M2, from the viewpoint of stably forming a layered structure, they are preferably metallic elements from groups 6 to 12 of period 4 of the periodic table (https: / / pubchem.ncbi.nlm.nih.gov / periodic-table / ), and more preferably nickel, zinc, or copper. Examples of metallic elements in Groups 6 through 12 of Period 4 of the Periodic Table include chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

[0020] Furthermore, the solid basic compound in the present invention preferably has a composition represented by the following formula (I). [M1 1-x M2 2x (OH)2][A n- 2x / n ·yH2O] (I) In formula (I), M1 and M2 represent divalent metal elements different from each other, and A n- represents an n-valent anion. Also, x satisfies 0 < x < 1, y represents a positive real number, and n represents a natural number.

[0021] A, which is an n-valent anion n- can adjust the interlayer distance in the solid basic compound according to its size. Depending on the interlayer distance, the ease of incorporation of the solid basic compound into the substrate varies. Therefore, by appropriately selecting A n- according to the reaction to be applied, the solid basic compound can function effectively as a catalyst. n- As A, from the perspective of easy availability, it is preferably an anion or oxoanion of a Group 17 element, carboxylic acids, dicarboxylic acids, or a metal complex having a negative charge. F - , Cl - , Br - , I - , CO3 2- , SO4 2- , PO4 2- , ClO4 2- , RCOO - (R = C m H 2m+1 , provided that 0 ≤ m < 20), R’2(COO)2 2- (R’ = C i HT 2i+1 , provided that 0 ≤ i < 20) is more preferable. In addition, examples of Group 17 elements include halogen elements such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). <000015​It is preferable that x is between 0.05 and 0.45. When x is 0.05 or higher, the solid basic compound functions effectively as a solid basic catalyst. When x is 0.45 or lower, the layered structure can be stably formed. It is more preferable that the lower limit of x be 0.1 or higher, and even more preferable that it be 0.15 or higher. It is also more preferable that the lower limit of x be 0.4 or lower, and even more preferable that it be 0.35 or lower. The values ​​of y and n are not particularly limited, but generally y is in the range of 0 to 10 and n is in the range of 1 to 4.

[0023] <carrier> The support is not particularly limited as long as it is a chemically stable compound, but a metal oxide is preferred. This allows for efficient support because the acid sites on the surface of the support interact electrostatically with the solid basic compound. The metal oxide is preferably at least one selected from the group consisting of silicon oxide and aluminum oxide.

[0024] [Method for manufacturing catalysts] The catalyst manufacturing method of this embodiment preferably includes a step of producing the solid basic compound by hydrothermal synthesis in the presence of the support (hereinafter also referred to as the hydrothermal synthesis step). This allows the solid basic compound to be uniformly layered on the support.

[0025] <Hydrothermal synthesis process> In the hydrothermal synthesis process, the raw material compounds M1 and M2, the support, and the solvent are heated in a sealed reaction vessel to produce a solid basic compound supported on the support.

[0026] (M1 and M2 starting compounds) Examples of raw material compounds for M1 and M2 include carboxylates, oxides, hydroxides, chlorides, bromides, iodides, sulfides, carbonates, phosphates, nitrates, and sulfates of M1 and M2. Among these, carboxylates, oxides, and hydroxides are preferred from the viewpoint of easy catalyst synthesis. Furthermore, carboxylates are more preferred from the viewpoint of controlling the interlayer distance of the layered structure. The raw material compounds for M1 and M2 are preferably used so that the total concentration of M1 and M2 is 0.01 to 10 mol / L. A concentration of 0.01 mol / L ensures a stable crystal structure of the solid basic compound produced. A concentration of 10 mol / L or less ensures easy solubility in the solvent. The lower limit of the concentration is more preferably 0.1 mol / L or higher, and even more preferably 0.5 mol / L or higher. The upper limit of the concentration is more preferably 5 mol / L, and even more preferably 2.5 mol / L or lower.

[0027] (carrier) The above-mentioned compounds can be used as the carrier. Specifically, silica, alumina, and diatomaceous earth such as Celite can be used. (solvent) Water is usually used as the solvent, but an organic solvent may be used in combination with water if necessary. The organic solvent is not particularly limited as long as it is commonly used in organic synthesis reactions, and examples include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, diethyl ether and dibutyl ether; and amides such as N,N-dimethylformamide and N,N-dimethylacetamide.

[0028] (Reaction vessel) For the reaction vessel, for example, glass, stainless steel (SUS), iron, or other metals can be used. Among these, from the viewpoint of corrosion resistance, it is preferable to use a reaction vessel made of stainless steel (SUS) or a metal with a Teflon coating on the inside.

[0029] (Heating conditions) The heating temperature is preferably between 100 and 250°C. A heating temperature of 100°C or higher stabilizes the crystal structure of the solid basic compound produced. Furthermore, a heating temperature of 250°C or lower suppresses the decomposition of the solid basic compound and the support. The lower limit of the heating temperature is more preferably 120°C or higher, and even more preferably 140°C or higher. Furthermore, the upper limit of the heating temperature is more preferably 240°C or lower, and even more preferably 220°C or lower. A solid basic compound supported on a carrier can be produced by holding it at the aforementioned heating temperature for typically 0.5 to 168 hours, preferably 1 to 24 hours. The holding time can be appropriately adjusted depending on the content of M1 and M2, the heating temperature, the type of solvent, etc.

[0030] <Recovery and washing of solid basic compounds> The solid basic compound obtained by the hydrothermal synthesis process is recovered as a solid by means of filtration or other means. The recovered solid can be used as a catalyst, or it may be used after being washed with a solvent. This makes it possible to remove extraneous components that are not included in the crystal structure of the solid basic compound. The solvent used for washing is preferably water, or alcohols such as methanol, ethanol, octanol, or dodecanol, with water being more preferable. The washing method can be a method of adding the solvent to the catalyst and filtering, or a Soxhlet extraction method, and from the viewpoint of efficiently using the solvent, Soxhlet extraction is preferred.

[0031] [Methods for producing unsaturated compounds and epoxy compounds] The catalyst of this embodiment functions effectively as a solid basic catalyst and can be used in reactions such as Henry reactions, Aza-Henry reactions, Michael addition, epoxidation reactions, aldol reactions, Robinson cyclization reactions, and benzoin condensation, making it suitable for use in the production of unsaturated compounds and epoxy compounds.

[0032] <Method for producing unsaturated compounds> In another embodiment of the present invention, the production of an unsaturated compound proceeds by reacting a substrate to be attacked by nucleophilic attack with a substrate acting as a nucleophile in the presence of the catalyst described above. Examples of substrates to be attacked by nucleophilic attack include carbonyl compounds, imine compounds, and nitrile compounds. Examples of substrates acting as nucleophiles include carbonyl compounds, imine compounds, alcohol compounds, nitro compounds, and nitrile compounds.

[0033] Here, the term "carbonyl compound" refers to a broad definition of carbonyl compounds, encompassing not only those having only one carbonyl group (C=O double bond) but also organic compounds having two or more carbonyl groups. Carbonyl compounds can be any of the following: carbonyl compounds with two or more carbon atoms, unsaturated carbonyl compounds, cyclic carbonyl compounds, or aromatic carbonyl compounds. Examples include acetaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl vinyl ketone, 2-methylacetoethyl acetate, 2-methylacetoacetate methyl, cyclohexanone, cyclohexenone, benzophenone, acetophenone, and acetaldehyde.

[0034] Furthermore, the term "imine compound" is not limited to compounds having only one carbonyl group (C=N double bond), but also includes organic compounds having two or more imine groups, representing a broad definition of imine compounds. Imine compounds may be imine compounds with two or more carbon atoms, unsaturated imine compounds, cyclic imine compounds, or aromatic imine compounds, and may also have substituents. Examples of imine compounds include N-methylideneaniline, N-ethylideneaniline, N-propyrideneaniline, N-butylideneaniline, cyclohexaneimine, N-cyclohexylideneaniline, benzylidene, benzophenoneimine, methylphenylimine, phenylimine, N-benzylidenemethylamine, and benzylideneaniline.

[0035] The alcohol compound may be any of the following: an alcohol compound having one or more carbon atoms, an unsaturated alcohol compound, a cyclic alcohol compound, or a phenolic compound, and may also have substituents. Examples of alcohol compounds include methanol, ethanol, propanol, butanol, octanol, dodecanol, cyclohexanol, allyl alcohol, and phenol.

[0036] The nitro compound may be any of the following: a nitro compound having one or more carbon atoms, an unsaturated nitro compound, a cyclic nitro compound, or an aromatic nitro compound, and may also have substituents. An example of a nitro compound is nitromethane. The nitrile compound may be any of the following: a nitrile compound having two or more carbon atoms, an unsaturated nitrile compound, a cyclic nitrile compound, or an aromatic nitrile compound, and may also have substituents. Examples of nitrile compounds include acetonitrile, acrylonitrile, benzonitrile, and adiponitrile.

[0037] The unsaturated compound according to this embodiment may be produced without a solvent, or, if necessary, a solvent that does not adversely affect the reaction may be used. The solvent is not particularly limited, but specifically, examples include water; alcohols such as methanol, ethanol, octanol, and dodecanol; ethers such as tetrahydrofuran, dioxane, and tetraethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and acetophenone; aromatic compounds such as benzene, toluene, and trifluorotoluene; nitrogen-containing compounds and sulfur-containing compounds such as acetonitrile, dimethylformamide, dimethylacetamide, pyridine, and dimethyl sulfoxide; esters such as ethyl acetate and butyl acetate; and hydrocarbons such as hexane, cyclohexane, and decalin. Water, dimethylformamide, or hexane are preferred. These solvents may be used individually or in combination of two or more.

[0038] The reaction temperature for producing the unsaturated compound according to this embodiment is preferably 10°C to 150°C. A reaction temperature of 10°C or higher allows for the production of the unsaturated compound in a short reaction time. Furthermore, a reaction temperature of 150°C or lower reduces the amount of by-products, improves the yield of the unsaturated compound, and suppresses catalyst degradation. The lower limit of the reaction temperature is more preferably 30°C or higher. The upper limit of the reaction temperature is more preferably 130°C or lower, and even more preferably 110°C or lower.

[0039] <Method for producing epoxy compounds> In another embodiment of the present invention, the production of an epoxy compound proceeds using an olefin compound and an oxidizing agent as substrates in the presence of the above-mentioned catalyst. Here, the term "olefin compound" refers to a broad definition of olefin compounds, encompassing not only those with only one double bond, but also organic compounds with two double bonds. Olefin compounds may be terminal olefins, internal olefins, or cyclic olefins with two or more carbon atoms, and may also have substituents. Examples of olefin compounds include ethylene, propylene, 1-butene, 2-butene, 1-hexene, 2-ethyl-1-hexene, 1-octene, 1-nonene, 1-decene, propylene trimmer, propylene tetramer, butene dimer, buten trimmer, cyclohexene, cyclooctene, butadiene, pentadiene, hexadiene, octadiene, decadiene, limonene, methyl vinyl ketone, and cyclohexenone. For example, oxygen or peroxides can be used as oxidizing agents.

[0040] The epoxy compound according to this embodiment may be produced without a solvent, or, if necessary, a solvent that does not adversely affect the reaction may be used. The solvent is not limited to, but specifically includes: water; aromatic compounds such as benzene, toluene, and trifluorotoluene; nitrogen-containing compounds and sulfur-containing compounds such as acetonitrile, dimethylformamide, dimethylacetamide, pyridine, and dimethyl sulfoxide; esters such as ethyl acetate and butyl acetate; and other hydrocarbons such as hexane, cyclohexane, and decalin. Water, dimethylformamide, or hexane are preferred. These solvents may be used individually or in combination of two or more.

[0041] The reaction temperature for producing the epoxy compound according to this embodiment is preferably 10°C to 100°C. A reaction temperature of 10°C or higher allows for the production of the epoxy compound in a short reaction time. Furthermore, a reaction temperature of 100°C or lower reduces the amount of by-products, improves the yield of the epoxy compound, and suppresses catalyst degradation. The lower limit of the reaction temperature is more preferably 20°C or higher. The upper limit of the reaction temperature is more preferably 90°C or lower, and even more preferably 70°C or lower.

[0042] <Manufacturing using a fixed-bed reactor> The catalyst of this embodiment can be used in batch reactors, fluidized bed reactors, or fixed bed reactors, but from the viewpoint of continuous production of the product, it is particularly preferable to use it packed into a fixed bed reactor.

[0043] When the catalyst of this embodiment is used by filling a fixed-bed reactor, it is preferable to flow the raw materials so that the residence time calculated from the empty volume of the catalyst layer is 0.01 to 2 hours. A residence time of 0.01 hours or more allows for a sufficient reduction in pressure loss during the reaction. Furthermore, a residence time of 2 hours or less improves the amount of product produced per unit time. A lower limit of 0.05 hours is more preferable for the residence time. Furthermore, an upper limit of 1 hour or less is more preferable, and 0.5 hours or less is even more preferable.

[0044] Fixed-bed reactors can be made of glass, stainless steel (SUS), iron, or other metals. Of these, glass or stainless steel (SUS) reactors are preferred from the viewpoint of corrosion resistance and energy transfer efficiency. [Examples]

[0045] The embodiments of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0046] [Measurement of the total content of M1 and M2] The total content of M1 and M2 in the catalyst was calculated by analyzing the catalyst using atomic absorption spectrometry. First, 0.01 g of catalyst was accurately weighed into a 500 mL volumetric flask, and 1 mL of concentrated hydrochloric acid was added and allowed to stand for at least 8 hours to dissolve the catalyst. Then, pure water was added to adjust the volume to 500 mL, and the content of M1 and M2 was calculated by measuring with an atomic absorption spectrophotometer. The instrument used was a Thermo Elemental SOLAAR AA series S4, and the measurement wavelengths were Ni 232.0 nm and Zn 213.9 nm. Furthermore, when solid material is recovered by means of filtration or other methods, some metal components will dissolve into the filtrate. Therefore, the content rate calculated from the raw material charge ratio and the content rate calculated by performing the above-mentioned analysis on the obtained catalyst will not necessarily match.

[0047] [Measurement of X-ray diffraction patterns] The X-ray diffraction pattern of the catalyst was measured using a Rigaku Corporation "Mififlex 600" X-ray diffractometer with the catalyst in powder form. The measurement conditions were: source: CuKα rays (λ=1.5418Å), tube voltage: 40kV, tube current: 15mA, longitudinal limiting slit: 10.0mm, divergence slit: 0.625deg, scattering prevention slit: 13.0mm, and light receiving slit: 13.0mm. Monochromatic analysis was performed using a NiKβ filter. The obtained data was processed to remove Kα2 rays using X-ray diffractometer data acquisition software such as Rigaku Corporation's "MiniFlex Guidance".

[0048] [SEM measurement] SEM measurements of the catalyst were performed using a JEOL JSM-6510 after the catalyst was coated with Pt. The Pt coating was performed using a JEOL JFC-1600.

[0049] [Measurement of pressure loss] The pressure drop was measured using the following method. First, catalyst and 5 mL of ethanol were added to a flask, and the resulting dispersion solution was packed into a stainless steel column (φ6 mm × 150 mm) connected to a stainless steel packer. The catalyst was added so that the amount of solid basic compound in the catalyst was 0.5 g. Next, an HPLC pump (Shimadzu Corporation, LC-20AT) was used to pass ethanol through the column at a liquid pressure of 15 MPa for 10 minutes. Then, the HPLC flow pressure was measured when the flow rate of the HPLC pump was set to 1 mL / min, 0.5 mL / min, and 0.1 mL / min.

[0050] [Analysis of the product] The unsaturated and epoxy compounds produced were analyzed using gas chromatography (instrument: Shimadzu GC-2010, column: Restek Rtx-5MS capillary column, column length: 30 m, inner diameter: 0.25 mm, film thickness: 0.25 μm) or liquid chromatography (instrument: Shimadzu LC-20 series, detector: Shimadzu LC-20A, column: Nacalai Tesque COSMOSIL Packed Column 5C18-MS-II, column length: 100 mm, inner diameter: 4.6 mm, temperature: 40 °C, developing solvent: CH3CN:H2O=1:1, flow rate: 1 mL / min). The yields of the unsaturated and epoxy compounds were determined from the results of gas chromatography or liquid chromatography.

[0051] <Example 1> 11.67 g of Ni(AcO)2·4H2O (Wako Pure Chemical Industries Special Grade) and 5.07 g of Zn(AcO)2·2H2O (Wako Pure Chemical Industries Special Grade) were dissolved in 70 mL of distilled water. The resulting aqueous solution, along with 1.0 g of Celite (registered trademark, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a support, was sealed in a stainless steel autoclave with a Teflon (registered trademark) coating inside, and heated for 200°C. o Hydrothermal synthesis was carried out by holding the mixture in C for 24 hours to obtain a suspension containing solid basic compounds with Ni and Zn as M1 and M2, respectively. The obtained suspension was then filtered by suction to recover the solid basic compounds, which were used as a catalyst. SEM observation of the obtained catalyst confirmed that the solid basic compound was supported on the support. The XRD diffraction pattern of the catalyst and the total content of M1 and M2 are shown in Table 1, and the composition ratio and pressure drop of the solid basic compound are shown in Table 2.

[0052] Next, using the obtained catalyst, nitrodiphenylethylene and ethyl-2-acetyl-2-methyl-5-oxohexanoate were produced as unsaturated compounds, and 2,3-epoxycyclohexane-1-one was produced as an epoxy compound, as described below.

[0053] (Production of nitrodiphenylethylene using a batch reactor) The reaction was carried out by adding 0.1 g of catalyst, 1 mmol of benzophenone imine, and 2 mL of nitromethane to a flask and holding at 90°C for 24 hours. The yield of nitrodiphenylethylene obtained is shown in Table 3.

[0054] (Production of nitrodiphenylethylene using a fixed-bed reactor) The catalyst and 5 mL of ethanol were added to a flask, and the resulting dispersion solution was packed into a stainless steel column (φ6 mm × 150 mm) connected to a stainless steel packer. The catalyst was added so that the amount of solid basic compound in the catalyst was 0.5 g. Next, using an HPLC pump (Shimadzu Corporation, LC-20AT), ethanol was passed through the column at a pressure of 15 MPa for 10 minutes. Subsequently, nitromethane was passed through the column at a pressure of 15 MPa for 10 minutes. After that, a stainless steel tube packed with catalyst was kept warm at 90°C, and the reaction was carried out by passing a benzophenone imine nitromethane solution (0.3 mol / L, flow rate 0.1 mL / min) through it. The flow pressure at this time was 0.1 MPa, and no blockage of the stainless steel tube due to catalyst swelling was observed. After confirming by HPLC that the outlet composition was constant regardless of time, quantitative analysis of the separated outlet solution was performed by HPLC, and nitrodiphenylethylene was obtained in a yield of 12%.

[0055] (Production of ethyl-2-acetyl-2-methyl-5-oxohexanoate using a batch reactor) The reaction was carried out by adding 0.1 g of catalyst, 1 mmol of 2-methylacetoethyl acetate, 1.5 mmol of methyl vinyl ketone, and 5 mL of n-hexane to a flask and holding at 50°C for 6 hours. The yield of the obtained ethyl-2-acetyl-2-methyl-5-oxohexanoate is shown in Table 3.

[0056] (Production of 2,3-epoxycyclohexane-1-one using a batch reactor) 0.05 g of catalyst, 0.5 mmol of cyclohexenone, 2 mL of dimethylformamide, and 2.0 mmol of 30% aqueous hydrogen peroxide were added to a flask, and the reaction was carried out by holding at 60°C for 1 hour. The yields of the obtained 2,3-epoxycyclohexane-1-one are shown in Table 3.

[0057] <Examples 2-3> The catalyst was obtained in the same manner as in Example 1, except that the amount of Celite used was changed as shown in Table 1. SEM observation of the obtained catalyst confirmed that the solid basic compound was supported on the support. Table 1 shows the XRD diffraction pattern of the catalyst and the total content of M1 and M2, while Table 2 shows the composition ratio of the solid basic compound and the pressure drop, respectively.

[0058] <Examples 4-6> The solid basic compound was recovered in the same manner as in Example 1, except that Carriact Q-3 (Fuji Silysia Chemical Co., Ltd.) was used as the support and the amount used was changed as shown in Table 1. The obtained solid basic compound was Soxhlet washed with pure water using cylindrical filter paper for 12 hours to obtain a catalyst. SEM observation of the obtained catalyst confirmed that the solid basic compound was supported on the support. Table 1 shows the XRD diffraction pattern of the catalyst and the total content of M1 and M2, while Table 2 shows the composition ratio of the solid basic compound and the pressure drop, respectively.

[0059] Next, using the catalyst obtained in Example 6, nitrodiphenylethylene, ethyl-2-acetyl-2-methyl-5-oxohexanoate, and 2,3-epoxycyclohexane-1-one were produced in a batch reactor using the same method as in Example 1. The yields of nitrodiphenylethylene, ethyl-2-acetyl-2-methyl-5-oxohexanoate, and 2,3-epoxycyclohexane-1-one are shown in Table 3.

[0060] <Comparative Example 1> A solid was obtained in the same manner as in Example 1, except that Celite was not used. The obtained solid was washed with pure water using cylindrical filter paper for 12 hours using a Soxhlet wash to obtain a catalyst. SEM observation of the obtained catalyst confirmed that the solid basic compound was not supported on the carrier. Table 1 shows the XRD diffraction pattern of the catalyst and the total content of M1 and M2, while Table 2 shows the composition ratio of the solid basic compound and the pressure drop, respectively.

[0061] <Comparative Example 2> A catalyst was prepared by physically mixing 0.5 g of catalyst obtained by the same method as in Comparative Example 1 with 0.5 g of Celite as a support. SEM observation of the obtained catalyst confirmed that the solid basic compound was not supported on the carrier. Table 1 shows the XRD diffraction pattern of the catalyst and the total content of M1 and M2, while Table 2 shows the composition ratio of the solid basic compound and the pressure drop, respectively.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065] <Catalyst Manufacturing Examples 1-5> Except for using Alu-C (Nippon Aerosil Co., Ltd.) as a support and changing the amount used as shown in Table 1, the solid basic compound was recovered in the same manner as in Example 1 to obtain the catalyst. SEM observation of the obtained catalyst confirmed that the solid basic compound was supported on the support. The XRD diffraction pattern of the catalyst and the total content of M1 and M2 are shown in Table 4, and the composition ratio of the solid basic compound is shown in Table 5.

[0066] [Table 4]

[0067] [Table 5]

[0068] As shown in Tables 1 and 2, in Examples 1 to 6, low pressure drop values ​​were obtained by using catalysts that could support solid basic compounds having a specified XRD pattern on a carrier such that the M1 and M2 content was 10 to 45% by mass. Furthermore, as shown in Table 3, unsaturated compounds and epoxy compounds could be produced in good yield using these catalysts. In addition, as described in Example 1, "Production of Nitrodiphenylethylene using a Fixed-Bed Reactor," no reactor blockage due to catalyst swelling was observed even when a fixed-bed reactor was used.

[0069] On the other hand, as shown in Tables 1 and 2, Comparative Example 1, which used a catalyst manufactured without a support, showed a very high pressure drop exceeding 66 MPa. Also, as shown in Tables 1 and 2, Comparative Example 2, which included a support but used a catalyst formed by physically mixing a solid basic compound and the support, also showed a high pressure drop compared to Examples 1 to 6.

[0070] As shown in Tables 4 and 5, catalysts were produced in catalyst production examples 1 to 5 in which solid basic compounds having a specified XRD pattern were supported on a carrier such that the total content of M1 and M2 was 10 to 45% by mass.

Claims

1. A catalyst comprising a solid basic compound, which is a layered bibasic salt containing M1 and M2, which are different divalent metal elements, and an interlayer anion, and a support, In the X-ray diffraction pattern of the catalyst using CuKα rays, Peak P1 has 2θ d1° and peak intensity I1, Peak P2 is a peak with 2θ of (d1 × 2 ± 0.2)° and peak intensity I2. It has, Satisfying 3 ≤ d1 ≤ 10, I1 / I2 is 1 or greater, The aforementioned M1 and M2 are metallic elements from Group 6 to Group 12 of Period 4 of the Periodic Table. The anion is an anion or oxoanion of a group 17 element, carboxylic acids, dicarboxylic acids, or a negatively charged metal complex. The carrier is a metal oxide, A solid basic catalyst in which the solid basic compound is supported on the carrier such that the total content of M1 and M2 in the catalyst is 10 to 45% by weight.

2. The solid basic catalyst according to claim 1, wherein the solid basic compound has a composition represented by the following formula (I). [M1 １－ｘ M2 ２ｘ (OH) ２ ][A ｎ－ ２ｘ／ｎ ・yH ２ O] (I) In formula (I), M1 and M2 represent different divalent metallic elements from groups 6 to 12 of period 4 of the periodic table, and A ｎ－ The symbol represents an n-valence anion. Also, x satisfies 0 < x < 1, y is a positive real number, and n is a natural number.

3. The solid basic catalyst according to claim 1 or 2, wherein the metal oxide is at least one selected from the group consisting of silicon oxide and aluminum oxide.

4. The solid basic catalyst according to any one of claims 1 to 3, wherein M1 and M2 are nickel, zinc, or copper.

5. A method for producing a solid basic catalyst according to any one of claims 1 to 4, comprising the step of producing the solid basic compound by hydrothermal synthesis in the presence of the support.

6. A method for producing an unsaturated compound, comprising the step of producing an unsaturated compound in the presence of a solid basic catalyst according to any one of claims 1 to 4.

7. The method for producing an unsaturated compound according to claim 6, wherein the solid basic catalyst is packed into a fixed-bed reactor.

8. A method for producing an epoxy compound, comprising the step of producing an epoxy compound in the presence of a solid basic catalyst according to any one of claims 1 to 4.

9. The method for producing an epoxy compound according to claim 8, wherein the solid basic catalyst is packed into a fixed-bed reactor.

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