Catalyst for decomposing bisphenol compounds and method for producing the same, as well as method for decomposing bisphenol compounds and method for producing bisphenol A.

Abstract

The purpose of the present invention is to provide a catalyst which is for decomposing a bisphenol compound and which, when decomposing a bisphenol compound, does not corrode facilities, can collect phenols or phenols and isopropenylphenols at high yield, and has suppressed elution (leaching) of metal components. This catalyst for decomposing a bisphenol compound contains a composite oxide containing magnesium and aluminum and is used to decompose bisphenol compounds such as bisphenol A, bisphenol C, and bisphenol F.

Description

[Technical Field]

[0001] The present invention relates to a catalyst for decomposing bisphenol compounds, a method for producing the catalyst, a method for decomposing bisphenol compounds, and a method for producing bisphenol A. This application claims priority based on Japanese Patent Application No. 2022-204524, filed in Japan on December 21, 2022, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Bisphenol compounds such as 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "bisphenol A"), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (hereinafter referred to as "bisphenol C"), and bis(4-hydroxyphenyl)methane (hereinafter referred to as "bisphenol F") are used in a wide range of applications, including as raw materials for polycarbonates, polyesters, epoxy resins, resin additives, adhesives, color developers for thermal paper, antioxidants, and polymerization inhibitors.

[0003] Bisphenol compounds are industrially produced by the reaction (condensation reaction) of ketones or aldehydes with phenols in the presence of an acidic catalyst. For example, bisphenol A is produced by reacting acetone with excess phenol in the presence of an acidic catalyst (Patent Document 1).

[0004] In this method, the bisphenol compound is obtained as a phenol solution, which is then distilled to remove low-boiling fractions and excess phenols, and then sent to a crystallization step where it is cooled and the bisphenol compound / phenol crystal adduct is separated. On the other hand, in the crystallization process, a mother liquor is obtained containing a phenol solution with by-products such as bisphenol compounds and their isomers, as well as a very small amount of colored impurities. If this mother liquor is recycled and reused directly in the bisphenol compound production process, the by-products and colored impurities will accumulate, making it necessary to remove these by-products and impurities. Therefore, when recycling the mother liquor into the bisphenol compound production process, a technique is known in which at least a portion of the mother liquor is separated and heated in the presence of a base catalyst to decompose the bisphenol compounds contained in the mother liquor and obtain an active ingredient, after which the obtained active ingredient is recovered and reused in the bisphenol compound production process. Known techniques for decomposing bisphenol compounds include techniques in which the active ingredients are phenols and isopropenylphenols, and techniques in which the active ingredients are phenols and ketones or aldehydes.

[0005] In the aforementioned decomposition step, the catalyst used for decomposing the bisphenol compound is required to decompose the bisphenol compound with high selectivity and recover the above-mentioned active ingredients in high yield. Furthermore, if metal components leach from the catalyst during the decomposition reaction, accumulating or adhering to the equipment, or causing blockages, it would require considerable effort to disassemble, clean, or replace the equipment, making it economically disadvantageous. In other words, there is a need for a bisphenol compound decomposition catalyst that suppresses the leaching of metal components.

[0006] As a technique for decomposing bisphenol compounds into phenols and isopropenylphenols, for example, Patent Document 2 discloses a method of decomposing bisphenol A by adding an aqueous solution of an alkaline substance such as an alkali metal hydroxide or alkaline earth metal hydroxide to a mother liquor containing bisphenol A and its isomers obtained in a crystallization step. Furthermore, Patent Document 3 discloses a method in which a mixture containing bisphenol and impurities produced as by-products in the bisphenol manufacturing process is cleaved in a cleavage device, the cleavage product is supplied in vapor form to a distillation column, and the bisphenol is decomposed into isopropenylphenol and phenol and recovered while being distilled at a specific reflux ratio.

[0007] As a technique for decomposing bisphenol compounds into phenols and ketones or aldehydes, for example, Patent Document 4 discloses a method of adding an aqueous ammonia solution, an alkali metal hydroxide or an alkaline earth metal hydroxide as a hydroxyl ion source to a feedstock stream containing bisphenol A and its isomers to decompose bisphenol A into phenol and acetone and recover them.

[0008] In addition, in the methods disclosed in Patent Documents 2 to 4 described above, a homogeneous base catalyst in which a base catalyst, which is a basic compound, is dissolved in the reaction solution is used. However, Patent Document 5 discloses a technique using synthetic zeolite, which is a solid acid catalyst, as a heterogeneous acid catalyst.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document ③

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0010] However, in the methods disclosed in Patent Documents 2 to 4, since a homogeneous base catalyst, that is, a base catalyst which is a basic compound, is dissolved in the reaction solution and used, the equipment may be corroded, and the base catalyst may precipitate as a salt and accumulate in the equipment or block the inside of the equipment. In addition, since it is difficult to separate the homogeneous base catalyst from the process liquid, waste containing a basic compound is generated, which requires a great deal of labor for its treatment and is also economically extremely disadvantageous. In particular, in the methods disclosed in Patent Document 2 and Patent Document 3, since the generation of by-products cannot be sufficiently suppressed, there is a problem that the recovery rate of phenol is low. In addition, in the method disclosed in Patent Document 4, although the recovery rate of phenol is relatively high, since a homogeneous base catalyst is used at a high concentration, a large amount of waste liquid containing a basic compound is generated, and there is a problem that a great deal of labor is required for its treatment.

[0011] In addition, the solid acid catalyst disclosed in Patent Document 5 has a problem that the yield of the target product is low. Further, there is a problem that it is necessary to replace the catalyst with a decreased catalytic activity with a new catalyst, and a great deal of labor is required for its treatment.

[0012] An object of the present invention is to provide a catalyst for decomposing a bisphenol compound that solves the above-described problems of the prior art and can recover phenols or phenols and isopropenylphenols in a high yield without corroding equipment when decomposing the bisphenol compound. Another object of the present invention is to provide a catalyst for decomposing a bisphenol compound in which elution (leaching) of a metal component from the catalyst is suppressed during the decomposition reaction. Furthermore, an object of the present invention is to provide a method for decomposing a bisphenol compound and a method for producing bisphenol A that solve the above-described problems of the prior art and can recover phenols or phenols and isopropenylphenols in a high yield without corroding equipment when decomposing the bisphenol compound. Note that in this specification, problems that can be solved by each embodiment of the present invention may be explicitly or implicitly disclosed.

Means for Solving the Problems

[0013] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific solid oxide catalyst, and have completed the present invention.

[0014] This invention was achieved based on the above findings, and its gist is as follows. [1] A catalyst for the decomposition of bisphenol compounds, comprising a complex oxide containing magnesium and aluminum, and used for the decomposition of bisphenol compounds represented by the following formula (1).

[0015] [ka]

[0016] [In equation (1), R 1 ~R 6 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, an alkoxy group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, or an amino group. [2] The catalyst for decomposing bisphenol compounds according to [1], wherein the molar ratio of magnesium to aluminum in the composite oxide, Mg / Al, is 1.0 or more and 10.0 or less. [3] The catalyst for decomposing bisphenol compounds according to [1] or [2], wherein the composite oxide is a calcined product of a double hydroxide containing magnesium and aluminum. [4] In X-ray diffraction measurements using CuKα rays, no diffraction peaks are observed that are caused by double hydroxides containing magnesium and aluminum, as described in [3]. [5] The catalyst for decomposing bisphenol compounds according to any one of [1] to [4], wherein the composite oxide is a calcined product of Mg-Al type hydrosaltite. [6] The catalyst for decomposing bisphenol compounds as described in [5], wherein no diffraction peaks attributable to Mg-Al type hydrosaltite are observed in X-ray diffraction measurements using CuKα rays. [7] In X-ray diffraction measurements using CuKα rays, no diffraction peaks are observed in the diffraction angle range 2θ = 10° to 30°, as described in [5], for the decomposition of bisphenol compounds. A method for producing a catalyst for decomposing bisphenol compounds as described in any of [8][1] to [7], comprising the following steps (1) to (3). Step (1): A process in which a compound containing aluminum atoms, a compound containing magnesium atoms, water, and one or more compounds containing at least one selected from cobalt, chromium, zinc, cerium, copper, zirconium, and nickel as an optional component, carbonates, and hydroxides are mixed, and then hydrothermally synthesized to obtain a double hydroxide containing magnesium and aluminum. Step (2): A step of filtering the obtained double hydroxide. Step (3): A step in which the filtered double hydroxide is calcined to obtain a composite oxide containing magnesium and aluminum. [9] A method for producing a catalyst for decomposing bisphenol compounds according to [8], wherein the compound containing an aluminum atom is aluminum nitrate and the compound containing a magnesium atom is magnesium nitrate.

[10] A method for producing a catalyst for decomposing bisphenol compounds according to [8] or [9], wherein the carbonate is an alkali metal carbonate or an alkaline earth metal carbonate, and the hydroxide is an alkali metal hydroxide or an alkaline earth metal hydroxide.

[11] A method for decomposing a bisphenol compound represented by the following formula (1) in the presence of a catalyst, A method for decomposing a bisphenol compound, wherein the catalyst comprises a composite oxide containing magnesium and aluminum.

[0017] [ka]

[0018] [In equation (1), R 1 ~R 6 These are, independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, an alkoxy group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, and an amino group.

[12] The decomposition method according to

[11] , wherein the composite oxide is a composite oxide in which the molar ratio of magnesium to aluminum Mg / Al is 1.0 or more and 10.0 or less.

[13] The decomposition method according to

[11] or

[12] , wherein the composite oxide is a calcined product of a double hydroxide containing magnesium and aluminum.

[14] The decomposition method according to any one of

[11] to

[13] , wherein the composite oxide is a calcined product of Mg-Al type hydrosaltite.

[15] The decomposition method according to any one of

[11] to

[14] , wherein the decomposition comprises alkaline decomposition of bisphenol A as the bisphenol compound to produce phenol and 4-isopropenylphenol. A method for producing bisphenol A, comprising obtaining phenol and 4-isopropenylphenol by the decomposition method described in

[16]

[15] , and then contacting the obtained phenol and 4-isopropenylphenol with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A.

[17] A method for producing bisphenol A, comprising carrying out the following steps (A) to (D) in order. Step (A): A reaction step in which acetone and phenol are condensed in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A. Step (B): A crystallization solid-liquid separation step in which crystals consisting of bisphenol A and phenol are generated from a reaction solution containing bisphenol A by crystallization, and the crystals are separated from the mother liquor. Step (C): An alkaline decomposition step in which the bisphenol A contained in the mother liquor obtained in step (B) is decomposed by the decomposition method described in

[15] to recover phenol and 4-isopropenylphenol, and Recombination reaction step: The recovered phenol and recovered 4-isopropenylphenol are contacted with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A. Process (D): A circulation process in which the reaction solution obtained in process (C) is circulated upstream from process (B).

[18] The decomposition method according to any one of

[11] to

[14] , wherein the decomposition comprises hydrolyzing bisphenol A as the bisphenol compound to produce phenol and acetone. A method for producing bisphenol A, comprising obtaining phenol and acetone by the decomposition method described in

[19]

[18] , and then contacting the obtained phenol and acetone with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A.

[20] A method for producing bisphenol A, comprising carrying out the following steps (A) to (D) in order. Step (A): A reaction step in which acetone and phenol are condensed in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A. Step (B): A crystallization solid-liquid separation step in which crystals consisting of bisphenol A and phenol are generated from a reaction solution containing bisphenol A by crystallization, and the crystals are separated from the mother liquor. Step (C): A hydrolysis step in which the bisphenol A contained in the mother liquor obtained in step (B) is decomposed by the decomposition method described in

[18] to recover phenol and acetone. Process (D): A circulation process in which the phenol and acetone recovered in process (C) are circulated upstream from process (B). [Effects of the Invention]

[0019] According to the present invention, since a basic compound is not dissolved and used as a base catalyst when decomposing bisphenol compounds, a catalyst for decomposing bisphenol compounds can be provided that allows for the recovery of phenols, or phenols and isopropenylphenols, in high yield without corroding the equipment. Furthermore, according to the present invention, a catalyst for decomposing bisphenol compounds can be provided in which the elution (leaching) of metal components is further suppressed. Furthermore, according to the present invention, since a basic compound is not dissolved and used as a catalyst when decomposing the bisphenol compound, it is possible to provide a method for decomposing bisphenol compounds and a method for producing bisphenol A that can recover phenols, or phenols and isopropenylphenols, in high yield without corroding the equipment. [Brief explanation of the drawing]

[0020] [Figure 1] (a) The Mg:Al=3:1 (molar ratio) double hydroxide obtained in Production Example 1 before calcination, and (b) the powder X-ray diffraction pattern of the hydrotalcite calcined product (1) obtained in Production Example 1 after calcination. [Modes for carrying out the invention]

[0021] The embodiments of the present invention will be described in detail below. The following embodiments are examples (representative examples) of embodiments of the present invention, and the present invention is not limited thereto. Furthermore, the present invention can be implemented with any modifications without departing from its spirit. Unless otherwise specified, numerical ranges expressed using "~" in this specification and the claims mean a range that includes the numbers before and after "~" as the lower and upper limits, respectively. For example, "A~B" means A or greater and B or less.

[0022] The bisphenol compound decomposition catalyst of the present invention is a catalyst used for the decomposition of bisphenol compounds represented by the following formula (1).

[0023] [ka]

[0024] In equation (1), R 1 ~R 6 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have substituents, an alkoxy group having 1 to 12 carbon atoms which may have substituents, an aryl group having 6 to 12 carbon atoms which may have substituents, or an amino group.

[0025] Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, i-propyl group, i-butyl group, t-butyl group, s-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. Examples of alkoxy groups having 1 to 12 carbon atoms include the methoxy group, ethoxy group, and butoxy group. Examples of aryl groups having 6 to 12 carbon atoms include the phenyl group and the naphthyl group.

[0026] R 1 ~R 6 Examples of substituents that the alkyl group, alkoxy group, or aryl group may have include alkyl groups having 1 to 4 carbon atoms, halogen atoms, and aryl groups. If a bisphenol compound has substituents, the number of substituents may be one or two or more. If it has two or more substituents, the substituents may be the same or different.

[0027] Specific examples of bisphenol compounds represented by formula (1) include, for example, bisphenol A, bisphenol C, and bisphenol F.

[0028] (Catalyst for the decomposition of bisphenol compounds) The catalyst for decomposing bisphenol compounds of the present invention comprises a composite oxide containing magnesium and aluminum. One embodiment of the composite oxide in the present invention is a calcined product of a double hydroxide containing magnesium and aluminum. Specifically, a calcined product of Mg-Al type hydrosaltite can be mentioned.

[0029] In this embodiment, it is preferable that the bisphenol compound decomposition catalyst does not show diffraction peaks caused by magnesium and aluminum-containing double hydroxides in X-ray diffraction measurements using CuKα rays. Specifically, it is preferable that no diffraction peaks are observed in the powder X-ray diffraction pattern due to the magnesium and aluminum-containing double hydroxide before the calcination treatment. Here, "no diffraction peaks are observed" means, for example, that the integral intensity relative to the maximum integral intensity in the range of 2θ = 10° to 30° (the sum of the integral intensities of peaks existing in the range of 2θ = 10° to 30°) does not have diffraction peaks of 5.0% or more, preferably 3.0% or more.

[0030] In the bisphenol compound decomposition catalyst of this embodiment, the absence of diffraction peaks caused by double hydroxides containing magnesium and aluminum characterizes the bisphenol compound decomposition catalyst as a calcined product of double hydroxides containing magnesium and aluminum, thereby improving the effects of the present invention as described above.

[0031] In this embodiment, it is preferable that the bisphenol compound decomposition catalyst does not show diffraction peaks caused by Mg-Al type hydrosaltite in X-ray diffraction measurements using CuKα rays. Specifically, it is preferable that no diffraction peaks originating from Mg-Al type hydrosaltite before the calcination treatment are observed in the powder X-ray diffraction pattern. Here, "no diffraction peaks observed" means, for example, that there are no diffraction peaks where the integrated intensity relative to the maximum integrated intensity in the range of 2θ = 10° to 30° (the sum of the integrated intensities of peaks existing in the range of 2θ = 10° to 30°) is 5.0% or more, preferably 3.0% or more.

[0032] In the bisphenol compound decomposition catalyst of this embodiment, the absence of diffraction peaks attributable to Mg-Al type hydrosaltite characterizes the bisphenol compound decomposition catalyst as a calcined product of Mg-Al type hydrosaltite, thereby further enhancing the effects of the present invention as described above.

[0033] In this embodiment, it is preferable that no diffraction peaks are observed within the diffraction angle range 2θ = 10° to 30° in X-ray diffraction measurements using CuKα rays. Specifically, in the powder X-ray diffraction pattern, it is preferable that, for example, no diffraction peaks are observed within the diffraction angle range 2θ = 10° to 30°. Here, "no diffraction peaks are observed" means, for example, that there are no diffraction peaks where the integrated intensity relative to the maximum integrated intensity within the range 2θ = 10° to 30° (the sum of the integrated intensities of peaks located within the range 2θ = 10° to 30°) is 5.0% or more, preferably 3.0% or more.

[0034] In the bisphenol compound decomposition catalyst of this embodiment, the absence of diffraction peaks within the diffraction angle range 2θ = 10° to 30° characterizes the bisphenol compound decomposition catalyst as a calcined product of Mg-Al type hydrosaltite, which can further enhance the effects of the present invention as described above.

[0035] Another embodiment of the composite oxide in the present invention is a composite oxide containing magnesium and aluminum, obtained by coprecipitation from a solution containing magnesium and aluminum, followed by calcining the coprecipitation. Specifically, the coprecipitates include mixtures of magnesium hydroxide and aluminum hydroxide, and double hydroxides containing magnesium and aluminum. Among these, double hydroxides containing magnesium and aluminum are preferred.

[0036] In this invention, a double hydroxide refers to a hydroxide having two or more different cations. As the double hydroxide, a layered double hydroxide having a structure in which metal hydroxide layers and layers composed of anions and interlayer water are alternately stacked is preferred.

[0037] The above-mentioned layered double hydroxide is a conventionally well-known layered double hydroxide, which is generally represented by the following general formula (2), and has a crystal structure in which the regular octahedral basic layer of the hydroxide and the intermediate layer composed of anions and interlayer water are alternately stacked, and the crystal flakes exhibit a leaf-like or scaly shape. [M 2+ 1-x M 3+ x (OH)2][A n- x / n ·mH2O] ···(2) However, in formula (2), M 2+ represents divalent metal ions such as Mg, Mn, Fe, Co, Ni, Cu, Zn, etc., and M 3+ represents trivalent metal ions such as Al, Cr, Fe, Co, In, etc. The regular octahedral layer of the hydroxide, which is the basic skeleton, has a positive charge as a result of substituting part of the divalent metal ions with trivalent metal ions, and in order to compensate for this charge, anions are incorporated into the interlayer to maintain electrical neutrality. The anion A n- in the intermediate layer is an n-valent anion such as Cl - , NO3 - , CO3 2- , COO - , etc., and can be exchanged depending on the type. x corresponds to the molar ratio of M 3+ / (M 2+ +M 3+ ), and m is a positive number.

[0038] The layered double hydroxide may be either a synthetic product or a natural product, and examples include hydrotalcite, hydrocalumite, pyroaurite, etc. Among the layered double hydroxides, hydrotalcite is particularly preferred. Compounds having functional groups such as hydroxyl groups, amino groups, carboxyl groups, and silanol groups may be coordinated to the above-mentioned layered double hydroxide.

[0039] In the catalyst for decomposing bisphenol compounds of the present invention, among the above-mentioned layered double hydroxides, Mg-Al-based layered double hydroxides such as hydrotalcite are preferred, and Mg-Al type hydrotalcite is more preferred. The structure of the Mg-Al layered double hydroxide is Mg in formula (2) above. 2+ Part of Al 3+ Replaced by CO3 between the layers 2- It is characterized by having [this feature]. Examples of hydrotalcite include those composed of magnesium, aluminum, and carbonic acid. Specifically, Mg6Al2(OH) 16 It is represented as CO3·4H2O.

[0040] Commercially available hydrotalcite products include Mg4Al2(OH) 12 CO3·3H2O (manufactured by Sakai Chemical Industry Co., Ltd., "STABIACE HT-1"), Mg 3.5 Zn 0.5 Al2(OH) 12 CO3·3H2O (manufactured by Sakai Chemical Industry Co., Ltd., STABIACE HT-7), Mg 4.5 Al2(OH) 13 Products containing zinc, ruthenium, etc., such as CO3·3.5H2O (manufactured by Sakai Chemical Industry Co., Ltd., "STABIACE HT-P"), Mg, Al, and CO3-based products (manufactured by Toagosei Co., Ltd., "IXE 700F") can be used.

[0041] The lower limit of the molar ratio Mg / Al of magnesium to aluminum in the composite oxide is preferably 1.0 or higher, more preferably 1.5 or higher, and even more preferably 2.0 or higher, in order to introduce a sufficient amount of basic sites, such as basic functional groups, into the resulting bisphenol compound decomposition catalyst. The upper limit of the molar ratio Mg / Al is preferably 10.0 or lower, more preferably 7.0 or lower, and even more preferably 5.0 or lower, in order to maintain good catalytic activity of the resulting bisphenol compound decomposition catalyst. The preferred lower and upper limits of the molar ratio Mg / Al can be arbitrarily combined.

[0042] (Method for producing a catalyst for decomposing bisphenol compounds) An example of a method for producing the bisphenol compound decomposition catalyst of the present invention is a method comprising the following steps (1) to (3). Step (1): A process in which a compound containing aluminum atoms (hereinafter referred to as "Al-containing raw material compound"), a compound containing magnesium atoms (hereinafter referred to as "Mg-containing raw material compound"), water, and one or more of the following as optional components: a compound containing at least one selected from cobalt, chromium, zinc, cerium, copper, zirconium, and nickel (hereinafter referred to as "third metal-containing raw material compound"), a carbonate (hereinafter referred to as "other carbonate"), and a hydroxide (hereinafter referred to as "other hydroxide") are mixed, and then hydrothermally synthesized to obtain a double hydroxide containing magnesium and aluminum. Step (2): A step of filtering the obtained double hydroxide. Step (3): A step in which the filtered double hydroxide is calcined to obtain a composite oxide containing magnesium and aluminum.

[0043] Examples of Al-containing raw material compounds used in step (1) include carboxylates, oxides, hydroxides, chlorides, bromides, iodides, sulfides, carbonates, phosphates, nitrates, and sulfates containing aluminum atoms. Among these, aluminum nitrate (Al(NO3)3) is preferred because of its good solubility in water during catalyst preparation. The Al-containing raw material compounds used may be one type or two or more types.

[0044] Examples of Mg-containing raw material compounds include carboxylates, oxides, hydroxides, chlorides, bromides, iodides, sulfides, carbonates, phosphates, nitrates, and sulfates containing magnesium atoms. Among these, magnesium nitrate (Mg(NO3)2) is preferred because of its good solubility in water during catalyst preparation. The Mg-containing raw material compounds used may be one type or two or more types.

[0045] Examples of triangular metal-containing raw material compounds that can be used as optional components include carboxylates, oxides, hydroxides, chlorides, bromides, iodides, sulfides, carbonates, phosphates, nitrates, and sulfates containing at least one triangular metal selected from cobalt, chromium, zinc, cerium, copper, zirconium, and nickel. Among these, nitrates such as Co(NO3)2, Cr(NO3)3, Zn(NO3)2, Ce(NO3)3, Cu(NO3)2, Ni(NO3)2, and Zn(NO3)2, and chlorides such as ZrOCl2 are preferred because they have good solubility in water during catalyst preparation. The triangular metal-containing raw material compounds used may be one or two or more.

[0046] Other carbonates that can be used as optional components are carbonates that do not contain Al, Mg, or third metals, and alkali metal carbonates or alkaline earth metal carbonates are preferred, with alkali metal carbonates being more preferred. Specific examples of alkali metal carbonates include, for example, Na2CO3 and K2CO3. The other carbonates used may be one type or two or more types.

[0047] Other hydroxides that can be used as optional components are hydroxides that do not contain Al, Mg, or third metals, and alkali metal hydroxides or alkaline earth metal hydroxides are preferred, with alkali metal hydroxides being more preferred. Specific examples of alkali metal hydroxides include, for example, NaOH and KOH. The other hydroxides used may be one type or two or more types.

[0048] While there are no particular limitations on the pH of the reaction solution during hydrothermal synthesis, it is usually considered to be within the range of pH 8.5 to 12.5, from the viewpoint of enabling the complex oxide to form a hydrosaltite structure and precipitate the complex oxide in sufficient yield.

[0049] The lower limit of the heating temperature in hydrothermal synthesis is not particularly limited, but it is preferably 60°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher, as this promotes efficient crystal growth. The upper limit of the heating temperature is not particularly limited, but it is preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower, from the viewpoint of suppressing the generation of impurities and by-products. The preferred lower and upper limits of the heating temperature can be arbitrarily combined.

[0050] The lower limit of the heating time in hydrothermal synthesis is not particularly limited, but it is preferably 10 hours or more, more preferably 11 hours or more, and even more preferably 12 hours or more, as this allows sufficient crystal precipitation from the liquid. The upper limit of the heating time is not particularly limited, but from an economic standpoint, it is preferably 24 hours or less, more preferably 20 hours or less, and even more preferably 16 hours or less. The preferred lower and upper limits of the heating time can be arbitrarily combined.

[0051] In step (2), the double hydroxide obtained in step (1) is filtered to recover the double hydroxide containing magnesium and aluminum. The recovered double hydroxide may be washed with water. An example of a washing method is to add water to the double hydroxide and then filter it.

[0052] For the calcination of the double hydroxide in step (3), a known calcination method can be used. The lower limit of the firing temperature is not particularly limited, but it is preferably 500°C or higher, more preferably 510°C or higher, and even more preferably 580°C or higher, as this allows for sufficient conversion to oxides and a sufficient reduction of carbonate ions. The upper limit of the firing temperature is not particularly limited, but it is preferably 800°C or lower, more preferably 760°C or lower, and even more preferably 720°C or lower, from the viewpoint of ensuring a sufficient specific surface area of ​​the composite oxide obtained by firing the double hydroxide. The preferred lower and upper limits of the firing temperature can be arbitrarily combined.

[0053] The bisphenol compound decomposition catalyst of the present invention, as described above, can decompose bisphenol compounds without corroding the equipment, recover phenols, or phenols and isopropenylphenols, in high yield, and suppress the elution (leaching) of metal components.

[0054] (Method for decomposing bisphenol compounds) The decomposition of bisphenol compounds using the bisphenol compound decomposition catalyst of the present invention can be carried out using known methods other than employing the bisphenol compound decomposition catalyst of the present invention. For example, in the production of bisphenol compounds, when the bisphenol compound produced from the raw material is recovered by crystallization and the mother liquor is recycled and reused in the bisphenol compound production reaction, the bisphenol compound can be decomposed by adding the bisphenol compound decomposition catalyst of the present invention to at least a portion of the mother liquor.

[0055] One method for decomposing bisphenol compounds is to heat the bisphenol compound in the presence of the bisphenol compound decomposition catalyst of the present invention. This yields phenols, or phenols and isopropenylphenols, as decomposition products of the bisphenol compound. As a specific example, one can illustrate a method of supplying the mother liquor and the bisphenol compound decomposition catalyst of the present invention to a distillation column and performing distillation. The mother liquor may be concentrated beforehand before the decomposition reaction.

[0056] [Method for decomposing bisphenol compounds] The present invention relates to a method for decomposing a bisphenol compound, wherein the present invention relates to a method for decomposing a bisphenol compound represented by the following formula (1) in the presence of a catalyst, wherein the catalyst comprises a composite oxide containing magnesium and aluminum. As the catalyst, the bisphenol compound decomposition catalyst of the present invention described above can be used.

[0057] [ka]

[0058] [In equation (1), R 1 ~R 6 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, an alkoxy group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, or an amino group.

[0059] Specific embodiments of the bisphenol compound decomposition method of the present invention include the bisphenol compound decomposition method (1) and the bisphenol compound decomposition method (2) described later.

[0060] [Method for decomposing bisphenol compounds (1)] One embodiment of the present invention's method for decomposing bisphenol compounds is a method (1) for decomposing bisphenol compounds, wherein the decomposition comprises alkaline decomposition of bisphenol A as a bisphenol compound to produce phenol and 4-isopropenylphenol.

[0061] The alkaline decomposition of bisphenol A is carried out in the presence of the bisphenol compound decomposition catalyst of the present invention, for example, under reduced pressure of 300 Torr or less at 150-260°C. To improve the yield, bubbling may be performed by continuously supplying an inert gas to the bottom of the reactor. The method of supplying the reaction material to the reactor may be continuous or intermittent, but continuous supply is preferred.

[0062] In the method for decomposing bisphenol compounds (1), the lower limit of the amount of catalyst added during the decomposition of bisphenol A is not particularly limited, but since the decomposition of bisphenol A is good, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the reaction solution containing bisphenol A subjected to this decomposition reaction. On the other hand, the upper limit of the amount of catalyst added is not particularly limited, but since side reactions are suppressed, it is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. The preferred lower and upper limits of the amount of catalyst added can be arbitrarily combined.

[0063] In the method for decomposing bisphenol compounds (1), the lower limit of the reaction temperature in the decomposition reaction of bisphenol A is not particularly limited, but since the decomposition of bisphenol A is good, it is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. On the other hand, the upper limit of the reaction temperature is not particularly limited, but since side reactions are suppressed, it is preferably 300°C or lower, more preferably 270°C or lower, and even more preferably 250°C or lower. The preferred lower and upper limits of the reaction temperature can be arbitrarily combined.

[0064] In the method for decomposing bisphenol compounds (1), the lower limit of the reaction time is not particularly limited, but it is preferably 0.1 hours or more, more preferably 0.5 hours or more, and even more preferably 1 hour or more, as this allows the decomposition reaction of the bisphenol compound to proceed sufficiently. On the other hand, the upper limit of the reaction time is not particularly limited, but it is preferably 5 hours or less, more preferably 3 hours or less, and even more preferably 2 hours or less, from the viewpoint of allowing the decomposition reaction of the bisphenol compound to proceed sufficiently and maintaining good economic efficiency. The preferred lower and upper limits of the reaction time can be arbitrarily combined.

[0065] [Method for producing bisphenol A (1-1)] A first embodiment of the method for producing bisphenol A of the present invention is a method for producing bisphenol A (1-1), which involves obtaining phenol and 4-isopropenylphenol from bisphenol A using the above-described method for decomposing bisphenol compounds (1) of the present invention, and then contacting the obtained phenol and 4-isopropenylphenol with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A. The alkaline decomposition of bisphenol A using the method for decomposing bisphenol compounds (1) in the method for producing bisphenol A (1-1) is as described above.

[0066] The acidic catalyst used in the recombination reaction is not particularly limited and includes, for example, mineral acids such as hydrochloric acid and sulfuric acid, strongly acidic cation exchange resins, and solid acids such as polysiloxanes. Among these, strongly acidic cation exchange resins are preferred from the viewpoint of suppressing corrosion of the apparatus, ensuring separation of the catalyst after the reaction, and ensuring catalytic activity. As a strongly acidic cation exchange resin, for example, a gel-type cation exchange resin having a sulfone group can be used. Specifically, examples include "Diaion" from Mitsubishi Chemical Corporation, and "Amberlite" and "Amberlist" from Rohm & Haas. The acidic catalyst used for the recombination of phenol and 4-isopropenylphenol may be one type or two or more types.

[0067] The lower limit of the reaction temperature for the recombination of phenol and 4-isopropenylphenol is not particularly limited, but it is preferably 40°C or higher, and more preferably 50°C or higher, as this facilitates sufficient recombination reaction. On the other hand, the upper limit of the recombination reaction temperature is not particularly limited, but it is preferably 130°C or lower, and more preferably 100°C or lower, as this suppresses side reactions. The preferred lower and upper limits of the reaction temperature can be arbitrarily combined.

[0068] The lower limit of the reaction time for the recombination of phenol and 4-isopropenylphenol is not particularly limited, but it is preferably 5 minutes or more, and more preferably 15 minutes or more, as this allows the recombination reaction to proceed sufficiently. On the other hand, the upper limit of the recombination reaction time is not particularly limited, but it is preferably 200 minutes or less, and more preferably 120 minutes or less, from the viewpoint of allowing the recombination reaction to proceed sufficiently and maintaining good economic efficiency. The preferred lower and upper limits of the reaction time can be arbitrarily combined.

[0069] When using a strongly acidic cation exchange resin to carry out the recombination reaction between phenol and 4-isopropenylphenol, the water content in the reaction solution is preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, as this facilitates the recombination reaction to proceed sufficiently.

[0070] [Method for producing bisphenol A (1-2)] A second embodiment of the present invention's method for producing bisphenol A is a method for producing bisphenol A (1-2) that includes performing the following steps (A) to (D) in order. Step (A): A reaction step in which acetone and phenol are condensed in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A. Step (B): A crystallization solid-liquid separation step in which crystals consisting of bisphenol A and phenol are generated from a reaction solution containing bisphenol A by crystallization, and the crystals are separated from the mother liquor. Step (C): An alkaline decomposition step in which the bisphenol A contained in the mother liquor obtained in step (B) is decomposed using the bisphenol compound decomposition method (1) to recover phenol and 4-isopropenylphenol, and Recombination reaction step: The recovered phenol and recovered 4-isopropenylphenol are contacted with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A. Process (D): A circulation process in which the reaction solution obtained in process (C) is circulated upstream from process (B).

[0071] In step (A), for example, acetone is condensed with phenol in a stoichiometrically excess amount relative to acetone in the presence of an acidic catalyst. The lower limit of the molar ratio of phenol to acetone (phenol / acetone) is preferably 3 or higher, and more preferably 5 or higher. The upper limit of the molar ratio (phenol / acetone) is preferably 30 or lower, and more preferably 20 or lower. The preferred lower and upper limits of the molar ratio (phenol / acetone) can be arbitrarily combined.

[0072] Any industrially available acetone can be used without particular restrictions. However, if the acetone used in the reaction contains alcohols such as methanol, it may reduce the activity of the acidic catalyst; therefore, it is preferable to remove the alcohols before use in such cases. While commercially available phenols may be used, it is preferable to use phenols that have been purified by contacting them with an acidic catalyst such as an acidic ion exchange resin to remove impurities, followed by distillation.

[0073] The acidic catalyst used in step (A) is not particularly limited, and for example, the same catalyst as the one exemplified as the acidic catalyst used in the recombination reaction in the method for producing bisphenol A (1-1) can be used as an example. From the viewpoint of suppressing corrosion of the apparatus, the separability of the catalyst after the reaction, and catalytic activity, a strongly acidic cation exchange resin is preferred.

[0074] In the condensation reaction of step (A), a sulfur-containing compound may be added during the reaction as a co-catalyst, or the sulfur-containing compound may be supported on an acidic catalyst, in order to improve the selectivity and conversion rate. A preferred example is the use of a strongly acidic cation exchange resin partially modified with a sulfur-containing amine compound such as 2-aminoethanethiol or 2-(4-pyridyl)ethanethiol. In the case of a sulfonic acid type strongly acidic ion exchange resin, the degree of modification with the sulfur-containing amine compound is preferably 2 to 60 mol%, more preferably 5 to 30 mol%, and even more preferably 10 to 20 mol% relative to the sulfonic acid group.

[0075] The reaction conditions for the condensation of phenol and acetone are not particularly limited, but for example, the reaction temperature can be 50-100°C and the reaction pressure can be atmospheric pressure to 600 kPa (absolute pressure). The condensation reaction between phenol and acetone can be carried out, for example, using a fixed-bed flow system. In this case, the liquid space velocity of the raw material mixture supplied to the reactor can be, for example, 0.2 to 50 / h.

[0076] The crystallization apparatus used in step (B) is not particularly limited, and known continuous crystallization apparatuses such as a crystallization apparatus with a cooling method using a jacket or internal coil, an external circulation cooling type crystallization apparatus, or a jacket type crystallization apparatus can be used. A classification device may be provided inside or outside the crystallization apparatus for the purpose of controlling the shape and size of the crystals.

[0077] The crystallization temperature is preferably 45°C to 60°C, and more preferably 45°C to 55°C. The residence time of the reaction solution containing bisphenol A in the crystallizer is preferably 1 to 10 hours, and more preferably 2 to 4 hours. Crystallization may be carried out in a single stage or in multiple stages.

[0078] The solid-liquid separation apparatus for separating crystals composed of bisphenol A and phenol from the mother liquor is not particularly limited and includes, for example, a horizontal belt filter, a rotary vacuum filter, a rotary pressure filter, a centrifugal filtration separator, a centrifugal sedimentation separator, and a hybrid type of centrifuge (screen ball decanter) thereof.

[0079] In step (C), the bisphenol A contained in the mother liquor obtained in step (B) is subjected to alkaline decomposition using the bisphenol compound decomposition method (1), after which phenol and 4-isopropenylphenol are recovered and a recombination reaction is carried out. Step (C) can be carried out in the same manner as the method for producing bisphenol A (1-1).

[0080] In step (D), the reaction solution obtained in step (C) is returned to an upstream point from step (B) and circulated. In step (D), the reaction solution obtained in step (C) may be added to the reaction solution in step (A) to carry out a condensation reaction, or it may be added to the reaction solution after step (A) and before step (B).

[0081] In the manufacturing method (1-2) of the present invention, a distillation step is provided after step (B) and before step (C), in which the mother liquor obtained in step (B) or the mother liquor processed product obtained by processing the mother liquor is distilled using a known distillation method and a known distillation column, and the bisphenol A contained in the high-boiling point composition extracted from the bottom of the distillation column is decomposed in step (C) using the bisphenol compound decomposition method (1).

[0082] [Method for decomposing bisphenol compounds (2)] Another embodiment of the method for decomposing a bisphenol compound according to the present invention is a method for decomposing a bisphenol compound (2), wherein the decomposition comprises hydrolyzing bisphenol A as the bisphenol compound to produce phenol and acetone.

[0083] The hydrolysis of bisphenol A can be carried out by contacting bisphenol A with water in the presence of the bisphenol compound decomposition catalyst of the present invention.

[0084] The amount of water used for the hydrolysis of bisphenol A is not particularly limited, but the weight ratio of water to bisphenol A (water / bisphenol A) is preferably 1:1 to 20:1, and more preferably 2:1 to 10:1.

[0085] In the method for decomposing bisphenol compounds (2), the lower limit of the amount of catalyst added during the decomposition of bisphenol A is not particularly limited, but since the decomposition of bisphenol A is good, it is preferably 0.001 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the reaction solution containing bisphenol A subjected to this decomposition reaction. On the other hand, the upper limit of the amount of catalyst added is not particularly limited, but since side reactions are suppressed, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less. The preferred lower and upper limits of the amount of catalyst added can be arbitrarily combined.

[0086] In the method for decomposing bisphenol compounds (2), the lower limit of the reaction temperature in the decomposition reaction of the bisphenol compound is not particularly limited, but since the decomposition of the bisphenol compound is good, it is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. On the other hand, the upper limit of the reaction temperature is not particularly limited, but since side reactions are suppressed, it is preferably 300°C or lower, more preferably 270°C or lower, and even more preferably 250°C or lower. The preferred lower and upper limits of the reaction temperature can be arbitrarily combined.

[0087] In the method for decomposing bisphenol compounds (2), the lower limit of the reaction time is not particularly limited, but it is preferably 0.1 hours or more, more preferably 1 hour or more, and even more preferably 4 hours or more, as this allows the decomposition reaction of the bisphenol compound to proceed sufficiently. On the other hand, the upper limit of the reaction time is not particularly limited, but it is preferably 150 hours or less, more preferably 100 hours or less, and even more preferably 80 hours or less, from the viewpoint of allowing the decomposition reaction of the bisphenol compound to proceed sufficiently and maintaining good economic efficiency. The preferred lower and upper limits of the reaction time can be arbitrarily combined.

[0088] [Method for producing bisphenol A (2-1)] A third embodiment of the method for producing bisphenol A according to the present invention is a method for producing bisphenol A (2-1), which involves obtaining phenol and acetone from bisphenol A using the method for decomposing bisphenol compounds according to the present invention (2) described above, then condensing the obtained phenol and acetone in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A, and then reusing the obtained reaction solution containing bisphenol A in the reaction step. The hydrolysis of bisphenol A using the method for decomposing bisphenol compounds (2) in the method for producing bisphenol A (2-1) is as described above.

[0089] Acetone can be recovered by neutralizing the reaction solution after hydrolysis and then distilling it. Alternatively, phenol can be recovered by solvent extraction of the phenol remaining in the reaction solution that did not evaporate, and then distilling the organic phase containing phenol. For solvent extraction of phenol, ethers such as tert-butyl methyl ether, tert-amyl ethyl ether, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and acetate esters of propyl acetate, butyl acetate, pentyl acetate, and hexyl acetate can be used.

[0090] The reaction conditions for the condensation of phenol and acetone are not particularly limited, and for example, the same conditions as those exemplified as step (A) in the method for producing bisphenol A (1-2) can be used.

[0091] [Method for producing bisphenol A (2-2)] A fourth embodiment of the present invention's method for producing bisphenol A is a method for producing bisphenol A (2-2) that includes performing the following steps (A) to (D) in order. Step (A): A reaction step in which acetone and phenol are condensed in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A. Step (B): A crystallization solid-liquid separation step in which crystals consisting of bisphenol A and phenol are generated from a reaction solution containing bisphenol A by crystallization, and the crystals are separated from the mother liquor. Step (C): A hydrolysis step in which the bisphenol A contained in the mother liquor obtained in step (B) is decomposed using the bisphenol compound decomposition method (2) to recover phenol and acetone, and Process (D): A circulation process in which the phenol and acetone recovered in process (C) are circulated upstream from process (B).

[0092] Steps (A) and (B) in the method for producing bisphenol A (2-2) can be carried out in the same manner as steps (A) and (B) in the method for producing bisphenol A (1-2). In step (C), the bisphenol A contained in the mother liquor obtained in step (B) is hydrolyzed using the bisphenol compound decomposition method (2), and then phenol and acetone are recovered. Step (C) can be carried out in the same manner as the method for producing bisphenol A (2-1).

[0093] In step (D), the phenol and acetone obtained in step (C) are returned to an upstream point from step (B) and circulated. In step (D), the phenol and acetone obtained in step (C) may be added to the reaction solution of step (A) to carry out the condensation reaction, or they may be added to the reaction solution after step (A) and before step (B).

[0094] In the manufacturing method (2-2) of the present invention, a distillation step is provided after step (B) and before step (C), in which the mother liquor obtained in step (B) or the mother liquor processed product obtained by processing the mother liquor is distilled using a known distillation method and a known distillation column, and the bisphenol A contained in the high-boiling point composition extracted from the bottom of the distillation column is decomposed in step (C) using the bisphenol compound decomposition method (2).

[0095] Furthermore, in the manufacturing method (2-2) of the present invention, a recombination reaction step is provided after step (C) and before step (D), in which the phenol and acetone recovered in step (C) are brought into contact with an acidic catalyst to recombine and obtain a reaction solution containing bisphenol A. The reaction solution containing bisphenol A obtained in the recombination reaction step can be circulated upstream from step (B) in step (D) as "phenol and acetone recovered in step (C)" or together with "phenol and acetone recovered in step (C)". [Examples]

[0096] The present invention will be described more specifically below with reference to experimental examples that replace the embodiments, but the present invention is not limited to these experimental examples.

[0097] The compounds used in the experimental example are as follows: Mg(NO3)2·6H2O (manufactured by Sigma-Aldrich) Al(NO3)3·9H2O (manufactured by Sigma-Aldrich) Na2CO3 (manufactured by Sigma-Aldrich) NaOH (manufactured by Sigma-Aldrich) Bisphenol A: 2,2'-bis(4-hydroxyphenyl)propane (manufactured by Mitsubishi Chemical Corporation) MgO: Magnesium oxide (manufactured by Sigma-Aldrich)

[0098] [Manufacturing Example 1] (Synthesis of hydrotalcite calcined product (1)) 23.1 g of Mg(NO3)2·6H2O as the Mg source and 11.3 g of Al(NO3)3·9H2O as the Al source were completely dissolved in 100 mL of deionized water to form Solution A. 15.9 g of Na2CO3 and 9.0 g of NaOH were completely dissolved in 300 mL of deionized water to form Solution B. Solution B was vigorously stirred while Solution A was slowly added dropwise from a dropping funnel to obtain a precipitate. After confirming that the precipitate had formed, the resulting mixed solution (pH=10) with the precipitate formed was transferred to an autoclave and hydrothermally treated at 90°C for 12 hours. After the hydrothermal treatment, the white precipitate, Mg-Al type hydrotalcite, was filtered and washed with deionized water until the waste liquid had a pH of 7. The washed precipitate was then dried overnight at 60°C to obtain a double hydroxide with a molar ratio of Mg:Al=3:1. The obtained double hydroxide was calcined in a calcination furnace according to the following calcination condition A, and the resulting calcined product was designated as hydrotalcite calcined product (1).

[0099] Figure 1(a) shows the powder X-ray diffraction pattern of the Mg:Al=3:1 (molar ratio) double hydroxide before calcination, and Figure 1(b) shows the powder X-ray diffraction pattern of the hydrotalcite calcined product (1) after calcination. In powder X-ray diffraction measurements, a sample ground into powder was analyzed using a solid powder X-ray diffractometer (Bruker D8 ADVANCE) with CuKα as the radiation source, in the range of 2θ = 1.5 to 80°, to obtain a powder X-ray diffraction pattern.

[0100] (Firing conditions A) Under a nitrogen atmosphere, the temperature inside the firing furnace was increased from 25°C to 200°C at a heating rate of 2°C / min and held at 200°C for 2 hours. Next, the furnace temperature was increased from 200°C to 700°C at a heating rate of 2°C / min and held at 700°C for 4 hours. After that, the furnace temperature was cooled from 700°C to room temperature.

[0101] [Manufacturing Example 2] (Synthesis of hydrotalcite calcined product (2)) In the preparation of solution A in Production Example 1, a double hydroxide with a molar ratio of Mg:Al:Co = 3:1:0.05 was obtained in the same manner as in Production Example 1, except that 0.44 g of Co(NO3)2·6H2O was added as a Co source and completely dissolved. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions A described above, and the resulting calcined product was designated as hydrotalcite calcined product (2).

[0102] [Manufacturing Example 3] (Synthesis of hydrotalcite calcined product (3)) Except for changing the amount of Mg(NO3)2·6H2O added in Production Example 1 to 15.4g, a double hydroxide with a molar ratio of Mg:Al=2:1 was obtained in the same manner as in Production Example 1. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions A described above, and the resulting calcined product was designated as hydrotalcite calcined product (3).

[0103] [Manufacturing Example 4] (Synthesis of hydrotalcite calcined product (4)) Except for changing the amount of Mg(NO3)2·6H2O added in Production Example 1 to 30.8g, a double hydroxide with a molar ratio of Mg:Al=4:1 was obtained in the same manner as in Production Example 1. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions A described above, and the resulting calcined product was designated as hydrotalcite calcined product (4).

[0104] [Manufacturing Example 5] (Synthesis of hydrotalcite calcined product (5)) Except for changing the amount of Mg(NO3)2·6H2O added in Production Example 1 to 38.5g, a double hydroxide with a molar ratio of Mg:Al=5:1 was obtained in the same manner as in Production Example 1. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions A described above, and the resulting calcined product was designated as hydrotalcite calcined product (5).

[0105] [Manufacturing Example 6] (Synthesis of hydrotalcite calcined product (6)) Except for adding 0.60 g of Cr(NO3)3·9H2O as a Cr source instead of Co(NO3)2·6H2O as in Production Example 2, a double hydroxide with Mg:Al:Cr=3:1:0.05 (molar ratio) was obtained in the same manner as in Production Example 2. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions B below, and the resulting calcined product was designated as hydrotalcite calcined product (6).

[0106] (Firing conditions B) Under a nitrogen atmosphere, the temperature inside the firing furnace was increased from 25°C to 200°C at a rate of 2°C / min and held at 200°C for 2 hours. Next, the furnace temperature was increased from 200°C to 600°C at a rate of 2°C / min and held at 600°C for 4 hours. After that, the furnace temperature was cooled from 600°C to room temperature.

[0107] [Manufacturing Example 7] (Synthesis of hydrotalcite calcined product (7)) Except for adding 0.45 g of Zn(NO3)2·6H2O as a Zn source instead of Co(NO3)2·6H2O as in Production Example 2, a double hydroxide with a molar ratio of Mg:Al:Zr = 3:1:0.05 was obtained in the same manner as in Production Example 2. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a hydrotalcite calcined product (7).

[0108] [Manufacturing Example 8] (Synthesis of hydrotalcite calcined product (8)) Except for adding 0.49 g of Ce(NO3)3·6H2O as a Ce source instead of Co(NO3)2·6H2O as in Production Example 2, a double hydroxide with a molar ratio of Mg:Al:Ce=3:1:0.05 was obtained in the same manner as in Production Example 2. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a hydrotalcite calcined product (8).

[0109] [Manufacturing Example 9] (Synthesis of hydrotalcite calcined product (9)) A double hydroxide with a molar ratio of Mg:Al:Cu = 3:1:0.05 was obtained in the same manner as in Production Example 2, except that 0.28 g of Cu(NO3)2 was added as a Cu source instead of Co(NO3)2·6H2O. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a hydrotalcite calcined product (9).

[0110] [Manufacturing Example 10] (Synthesis of hydrotalcite calcined product (10)) Except for adding 0.48 g of ZrOCl2·8H2O as a Zr source instead of Co(NO3)2·6H2O as in Production Example 2, a double hydroxide with a molar ratio of Mg:Al:Zr = 3:1:0.05 was obtained in the same manner as in Production Example 2. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a hydrotalcite calcined product (10).

[0111] [Manufacturing Example 11] (Synthesis of hydrotalcite calcined product (11)) Except for adding 0.44 g of Ni(NO3)2·6H2O as a Ni source instead of Co(NO3)2·6H2O as in Production Example 2, a double hydroxide with a molar ratio of Mg:Al:Ni=3:1:0.05 was obtained in the same manner as in Production Example 2. The obtained double hydroxide was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a hydrotalcite calcined product (11).

[0112] [Manufacturing Example 12] (Synthesis of solid base calcined product (12)) A composition with a molar ratio of Mg:Ce=3:1 was obtained in the same manner as in Production Example 1, except that 9.8 g of Ce(NO3)3·6H2O was added as a Ce source instead of Al(NO3)3·9H2O in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (12).

[0113] [Manufacturing Example 13] (Synthesis of solid base calcined product (13)) A composition with a molar ratio of Mg:Ce = 3:1 was obtained in the same manner as in Production Example 1, except that 8.9 g of Zn(NO3)2·6H2O was added as a Zn source instead of Al(NO3)3·9H2O in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (13).

[0114] [Manufacturing Example 14] (Synthesis of solid base calcined product (14)) A composition with a molar ratio of Mg:Zr = 1.7:1 was obtained in the same manner as in Production Example 1, except that the amount of Mg(NO3)2·6H2O added was changed to 13.1g, and 9.7g of ZrOCl2·8H2O was added as a Zr source instead of Al(NO3)3·9H2O. The resulting calcined product was designated as a solid base calcined product (14).

[0115] [Manufacturing Example 15] (Synthesis of solid base calcined product (15)) A composition with a molar ratio of Mg:La = 3:1 was obtained in the same manner as in Production Example 1, except that 13.0 g of La(NO3)3·6H2O was added as the La source instead of Al(NO3)3·9H2O in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (15).

[0116] [Manufacturing Example 16] (Synthesis of solid base calcined product (16)) A composition with a molar ratio of Mg:Ti = 3:1 was obtained in the same manner as in Production Example 1, except that 17.6 g of Titanium(IV) bis(ammonium lactato) dihydroxide solution (50 wt% aqueous solution) was added as a Ti source instead of Al(NO3)3·9H2O as in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (16).

[0117] [Manufacturing Example 17] (Synthesis of solid base calcined product (17)) A composition with a molar ratio of Mg:Ga=3:1 was obtained in the same manner as in Production Example 1, except that 7.7g of Ga(NO3)3 was added as a Ga source instead of Al(NO3)3·9H2O in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (17).

[0118] [Manufacturing Example 18] (Synthesis of solid base calcined product (18)) A composition with a molar ratio of Mg:Fe=3:1 was obtained in the same manner as in Production Example 1, except that 12.1 g of Fe(NO3)3·9H2O was added as the Fe source instead of Al(NO3)3·9H2O in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (18).

[0119] [Manufacturing Example 19] (Synthesis of solid base calcined product (19)) A composition with a molar ratio of Mg:Cr = 3:1 was obtained in the same manner as in Production Example 1, except that 12.0 g of Cr(NO3)3·9H2O was added as a Cr source instead of Al(NO3)3·9H2O in Production Example 1. The obtained composition was calcined in a calcination furnace according to the calcination conditions B described above, and the resulting calcined product was designated as a solid base calcined product (19).

[0120] [Manufacturing Example 20] (Synthesis of solid base calcined product (20)) A composition with a molar ratio of Mg:In=3:1 was obtained in the same manner as in Production Example 1, except that 9.0 g of In(NO3)3 was added as an In source instead of Al(NO3)3·9H2O. The obtained composition was calcined in a calcination furnace according to the calcination conditions A described above, and the resulting calcined product was designated as a solid base calcined product (20).

[0121] [Manufacturing Example 21] (Synthesis of solid base calcined product (21)) 3.0 g of Ca(NO3)2·4H2O as a Ca source, 10.8 g of La(NO3)3·6H2O as a La source, 1.2 g of citric acid, and 5 mL of water were stirred at 80°C and completely dissolved to obtain a solution. Excess water was removed from the obtained solution by distillation under reduced pressure at 80°C to obtain a gel-like composition with a Ca:Ln ratio of 1:2 (molar ratio). The obtained gel-like composition was calcined in a calcination furnace according to the calcination conditions C below, and the resulting calcined product was designated as a solid base calcined product (21).

[0122] (Firing condition C) Under a nitrogen atmosphere, the temperature inside the firing furnace was increased from 25°C to 200°C at a heating rate of 2°C / min and held at 200°C for 2 hours. Next, the furnace temperature was increased from 200°C to 650°C at a heating rate of 2°C / min and held at 650°C for 4 hours. After that, the furnace temperature was cooled from 650°C to room temperature.

[0123] [Manufacturing Example 22] (Synthesis of solid base calcined product (22)) Except for changing the amount of Ca(NO3)2·4H2O added to 3.5g in Production Example 21, changing the amount of citric acid used to 1.9g, and adding 8.9g of Zn(NO3)2·6H2O as a Zn source instead of La(NO3)3·6H2O, a gel-like composition with a Ca:Zn ratio of 1:2 (molar ratio) was obtained in the same manner as in Production Example 21. The obtained gel-like composition was calcined in a calcination furnace according to the calcination conditions C described above, and the resulting calcined product was designated as a solid base calcined product (22).

[0124] [Manufacturing Example 23] (Synthesis of porous magnesium oxide (23)) 0.4 g of magnesium oxide was mixed with 16 mL of water in an autoclave, and then hydrothermally treated at 160°C for 24 hours to obtain porous Mg(OH)2. The porous Mg(OH)2 recovered by filtration was calcined in a calcination furnace according to the calcination conditions D below, and the resulting calcined product was designated as porous magnesium oxide (23).

[0125] (Firing condition D) Under a nitrogen atmosphere, the temperature inside the firing furnace was increased from 25°C to 200°C at a rate of 2°C / min and held at 200°C for 2 hours. Next, the furnace temperature was increased from 200°C to 500°C at a rate of 2°C / min and held at 650°C for 4 hours. After that, the furnace temperature was cooled from 500°C to room temperature.

[0126] [Example 1] (Hydrolysis test of bisphenol A) 37.5 g of water, 11.0 g of bisphenol A, and 1.5 g of the hydrotalcite calcined product (1) were placed in a 100 mL autoclave equipped with a thermometer and pressure gauge. After purging the inside of the autoclave with nitrogen, the autoclave was sealed airtight. The autoclave was placed in an electric furnace set to 230°C, and after the internal temperature of the autoclave reached 230°C, the reaction was allowed to proceed for 72 hours while maintaining that temperature. After that, the autoclave was removed from the electric furnace and immersed in a basin of ice water for 1 hour. Then the autoclave was opened to obtain a mixture of reaction solution and catalyst. The catalyst was removed from the mixture by centrifugation, and the reaction solution was separated into two layers: an upper layer (aqueous phase) and a lower layer (organic phase).

[0127] The resulting reaction solution was analyzed using a high-performance liquid chromatography (HCL) analyzer to determine the composition of the raw material bisphenol A (BPA), the target product of the hydrolysis reaction (phenol, PHL), the by-product 4-isopropenylphenol (IPP), the 2,4-hydroxy isomer of bisphenol A (2,4-BPA), trisphenol (Tris), and other impurities. Other impurities include BPA decomposition products or altered products, IPP cyclized dimers, 4-isopropylphenol, hydroxyphenylchroman, and the like.

[0128] Furthermore, the conversion rate of BPA, the recovery rate of PHL, and the selectivity of PHL, IPP, 2,4-BPA, Tris, and other impurities were calculated using the sum of the content of the starting materials and each product in the reaction solution, which was obtained by summing the content of the starting materials and each product in the upper and lower layers calculated from the peak areas of high-performance liquid chromatography. The evaluation results are shown in Table 1. In Table 1, "Catalyst amount (%)" refers to the percentage of the catalyst (mass%) relative to 100% of the total mass of water, bisphenol A, and catalyst.

[0129] The conversion rate of BPA, the yield of PHL, and the selectivity of PHL, IPP, 2,4-BPA, Tris, and other impurities were calculated from the following measurements obtained by high-performance liquid chromatography (HPCL) under the following measurement conditions using the following formula. (HPLC measurement conditions) 50 μL of the resulting reaction solution was diluted with 30 mL of a 1 / 3 (volume ratio) mixture of acetonitrile and deionized water. The resulting diluted solution was then passed through a syringe with a filter pore size of 0.22 μm to remove particles and other foreign matter, and this was used as the measurement sample. Equipment: Agilent 1100 series (manufactured by Agilent) Method: Gradient method Eluent composition: Solution A: Acetonitrile Solution B: 0.1 vol% aqueous acetic acid solution Solution C: Methanol During the analysis time from 0 to 20 minutes, the ratio of solution A:solution B:solution C was maintained at 52:48:0 (volume ratio, the same applies below). During the 20-30 minute analysis period, the eluent composition was gradually changed to A:B:C = 75:25:0. For the 30-40 minute analysis period, the ratio of solution A:solution B:solution C was maintained at 75:25:0. During the 40-41 minute analysis, the eluent composition was gradually changed to A:B:C = 0:0:100. The ratio of solution A:solution B:solution C was maintained at 0:0:100 during the analysis period from 41 to 54 minutes. During the analysis time of 54-55 minutes, the ratio of solution A:solution B:solution C was gradually changed to 40:60:0. For the analysis time of 55 to 65 minutes, the ratio of solution A:solution B:solution C was maintained at 40:60:0. Column: ZORBAX StableBond 300SB-C18 (product name, manufactured by Agilent, column size: 4.6mm x 250mm, particle size: 5μm) Sample injection volume: 5 μL Eluent flow rate: 0.2 mL / min Analysis temperature: 40℃

[0130] (Calculation formula) BPA conversion rate (%) = [(Weight of added BPA - Weight of unreacted BPA) / (Weight of added BPA)] × 100 PHL selectivity (%) = [Weight of PHL produced / (Total weight of compounds containing benzene rings in the reaction solution - Weight of BPA in the reaction solution)] × 100 PHL yield (%) = [(BPA conversion rate (%) × PHL selectivity (%)] / 100

[0131] In the above formula, "weight of generated PHL" was replaced with "weight of generated IPP," "weight of generated 2,4-BPA," "weight of generated Tris," and "sum of weights of other impurities," respectively, to calculate the selectivity of IPP, BPA, 2,4-BPA, Tris, and other impurities.

[0132] (Leaching test) For the catalysts used in the examples and comparative examples, the elution rate was measured using the following procedure as an indicator of the elution properties of the catalyst components. A lower elution rate indicates that the catalyst components are less likely to elute from the catalyst. The reaction solution was diluted as needed, and the metal elements (magnesium or calcium) eluted into the solution were quantified by inductively coupled plasma atomic emission spectrometry (ICP-OES). An Avio 200 (PerkinElmer) was used as the analyzer for the ICP-OES method. Calibration curves were prepared by diluting 1000 ppm standard samples (Inorganic Ventures) of each metal element. (Calculation formula) Dissolution rate (%) = (weight of metal elements in the reaction solution) / (weight of metal elements in the catalyst) × 100

[0133] [Example 2] In Example 1, the hydrolysis test for bisphenol A was performed under the same conditions as in Example 1, except that the reaction time was changed from 72 hours to 4 hours. The evaluation was performed using the same method as in Example 1, and the results are shown in Table 1.

[0134] [Examples 3 and 15-21, Comparative Examples 1-13] The hydrolysis test for bisphenol A was performed under the same conditions as in Example 1, except that the hydrotalcite calcined product (1) in Example 2 was replaced with the catalysts listed in Tables 1 and 2. The evaluation was performed using the same method as in Example 2, and the results are shown in Tables 1 and 2.

[0135] [Table 1]

[0136] [Table 2]

[0137] As shown in Tables 1 and 2, in Examples 1-3 and 15-21, the conversion rate of BPA was high, and the yield and selectivity of the target product, PHL, were also high. On the other hand, the total selectivity of the by-products, IPP, 2,4-BPA, Tris, and other impurities was low. In particular, the dissolution rates in the dissolution test were low in Examples 1 and 2. In Comparative Examples 1-11, the conversion rate of BPA was low, and the yield and selectivity of the target product, PHL, were also low. Furthermore, the combined selectivity of the by-products, IPP, 2,4-BPA, Tris, and other impurities was high. In Comparative Example 12, the conversion rate of BPA was low, and the yield and selectivity of the target product, PHL, were also low. Furthermore, the combined selectivity of the by-products, IPP, 2,4-BPA, Tris, and other impurities was high. In addition, the elution rate in the elution test was high. In Comparative Example 13, the conversion rate of BPA was high, and the yield and selectivity of the target product PHL were also high, but the dissolution rate in the dissolution test was high.

[0138] [Reference Experiment Example 1] According to the method described in Japanese Patent Publication No. 2005-97568, a reaction step was performed in which an excess amount of phenol and acetone were condensed in the presence of a strongly acidic cation exchange resin catalyst; a concentration step was performed in which low-boiling point components and phenol were separated from the obtained reaction mixture to prepare a crystallization raw material containing concentrated bisphenol A; and a crystallization-solid-liquid separation step was performed in which a slurry containing an adduct of bisphenol A and phenol was formed from the obtained crystallization raw material, and the obtained slurry was separated into an adduct of bisphenol A and phenol and a mother liquor. The composition of the mother liquor separated in the crystallization-solid-liquid separation step was analyzed by high-performance liquid chromatography and was as follows. Note that the composition of the mother liquor was calculated with the total mass of the target product and by-products described above as 100%, and the small amount of water contained in the mother liquor was not considered. (Composition of mother liquor) Phenol: 80.2% by mass IPP: 0.0% by mass Bisphenol A: 8.8% by mass 2,4'-BPA: 2.5% by mass Tris: 0.7% by mass Other impurities: 7.8% by mass

[0139] [Example 4] (Decomposition test of the mother liquor obtained in the crystallization-solid-liquid separation process) 60 g of the mother liquor obtained in Reference Experiment Example 1 and 1.8 g of the hydrotalcite calcined product (1) were added to a 100 mL glass flask. A distillation apparatus was assembled by connecting a distillation tube, receiver, and vacuum piping to the glass flask. The decomposition reaction of the mother liquor was then carried out under reactive distillation conditions according to the following procedure 1 to 5. Procedure 1: Using a vacuum pump, the pressure inside the apparatus was reduced to 160 Torr through the vacuum piping, and the glass flask was held in an oil bath at 160°C for 1 hour while maintaining the pressure inside the reaction distillation apparatus. Step 2: After raising the oil bath temperature to 180°C, the pressure inside the apparatus was reduced to 15 Torr and maintained for 15 minutes while keeping the oil bath temperature and the pressure inside the reaction distillation apparatus constant. Step 3: The oil bath temperature was raised to 230°C and maintained for 1 hour while keeping the oil bath temperature and the pressure inside the reaction distillation apparatus constant. Step 4: Remove the glass flask from the oil bath and keep it at room temperature, then use nitrogen to return the pressure inside the reaction distillation apparatus to atmospheric pressure. Procedure 5: After the distillate in the receiver of the reaction distillation apparatus and the bottom liquid in the glass flask were cooled to approximately 100°C, samples for high-performance liquid chromatography analysis were taken from the distillate and the bottom liquid.

[0140] Steps 1 and 2 are intended to distill the PHL originally present in the mother liquor into the receiver via the distillation tube, while the decomposition reaction of the mother liquor mainly proceeds in the process of step 3.

[0141] After the reaction distillation, the distillate in the receiver of the reaction distillation apparatus and the bottom liquid in the glass flask were analyzed using a high-performance liquid chromatography apparatus to determine the composition of bisphenol A (BPA), the target products of the decomposition reaction, PHL and IPP, by-products such as BPA, 2,4-BPA, Tris, and other impurities in the reaction solution. Other impurities include BPA decomposition products or altered products, IPP cyclized dimers, 4-isopropylphenol, hydroxyphenylchroman, and the like. Furthermore, in the mother liquor decomposition test, BPA that was not decomposed may be present in the distillate and / or the bottom liquid. Since such BPA is an undesirable residue, it was treated as a by-product.

[0142] Furthermore, using the content of the starting materials and each product in the reaction solution calculated from the peak area of ​​high-performance liquid chromatography, the conversion rate of BPA, the total yield of PHL and IPP, and the respective content percentages of PHL and IPP (the target products of the decomposition reaction), as well as the content percentages of BPA, 2,4-BPA, Tris, and other impurities (by-products), were calculated. The evaluation results are shown in Table 3.

[0143] The conversion rate of BPA and the total yield of PHL and IPP mentioned above were calculated using the following formula from measurements taken by high-performance liquid chromatography (HPCL) under the following measurement conditions. (HPLC measurement conditions) 50 μL of the resulting reaction solution was diluted with 30 mL of a 1 / 3 (volume ratio) mixture of acetonitrile and deionized water. The resulting diluted solution was then passed through a syringe with a filter pore size of 0.22 μm to remove particles and other foreign matter, and this was used as the measurement sample. Equipment: Agilent 1100 series (manufactured by Agilent) Method: Gradient method Eluent composition: Solution A: Acetonitrile Solution B: 0.1 vol% aqueous acetic acid solution Solution C: Methanol During the analysis time from 0 to 20 minutes, the ratio of solution A:solution B:solution C was maintained at 52:48:0 (volume ratio, the same applies below). During the 20-30 minute analysis period, the eluent composition was gradually changed to A:B:C = 75:25:0. For the 30-40 minute analysis period, the ratio of solution A:solution B:solution C was maintained at 75:25:0. During the 40-41 minute analysis, the eluent composition was gradually changed to A:B:C = 0:0:100. The ratio of solution A:solution B:solution C was maintained at 0:0:100 during the analysis period from 41 to 54 minutes. During the analysis time of 54-55 minutes, the ratio of solution A:solution B:solution C was gradually changed to 40:60:0. For the analysis time of 55 to 65 minutes, the ratio of solution A:solution B:solution C was maintained at 40:60:0. Column: ZORBAX StableBond 300SB-C18 (product name, manufactured by Agilent, column size: 4.6mm x 250mm, particle size: 5μm) Sample injection volume: 5 μL Eluent flow rate: 0.2 mL / min Analysis temperature: 40℃

[0144] (Calculation formula) BPA conversion rate (%) = [(Weight of BPA in the prepared mother liquor - Weight of unreacted BPA) / (Weight of BPA in the prepared mother liquor)] × 100

[0145] Total yield of PHL and IPP (%) = [(Total weight of PHL and IPP after reaction distillation - Weight of PHL in the charged mother liquor) / (Weight of the charged mother liquor - Weight of PHL in the charged mother liquor)] × 100 In the mother liquor decomposition test, when calculating the total yield of PHL and IPP, the mother liquor already contains PHL, and its influence must be removed. Therefore, the weight of PHL already present in the mother liquor was subtracted from both the numerator and denominator of the above yield calculation formula.

[0146] The respective content percentages of PHL, IPP, BPA, 2,4-BPA, Tris, and other impurities were calculated by determining the content of each product in the reaction solution from the peak area of ​​the chromatograph measured by high-performance liquid chromatography (HPCL) under the above measurement conditions, and then dividing this by the total weight of the reaction solution.

[0147] [Examples 5-8, Comparative Examples 12-14] The mother liquor decomposition test was performed under the same conditions as in Example 4, except that the hydrotalcite calcined product (1) in Example 4 was replaced with the catalyst shown in Table 3. The evaluation was performed in the same manner as in Example 1, and the obtained evaluation results are shown in Table 3.

[0148] [Table 3]

[0149] As shown in Table 3, in Examples 4-8, the conversion rate of BPA was high, and the total yield and total selectivity of the target products PHL and IPP were also high. On the other hand, the total selectivity of the by-products BPA, 2,4-BPA, Tris, and other impurities was low. In Comparative Examples 12-14, the conversion rate of BPA was low, and the total yield of the target products, PHL and IPP, was also low. The total selectivity of the by-products, BPA, 2,4-BPA, Tris, and other impurities was high. In particular, the total selectivity of the target products, PHL and IPP, was low in Comparative Examples 13-14.

[0150] Although the present invention has been described above with reference to specific embodiments, each embodiment is presented as an example and does not limit the scope of the present invention. Each embodiment described herein can be modified in various ways without departing from the spirit of the invention and can be combined with features described in other embodiments to the extent that is feasible.

Claims

1. A catalyst for decomposing a bisphenol compound represented by the following formula (1), wherein the metal is a composite oxide of only two metals, magnesium and aluminum, or a composite oxide containing magnesium and aluminum and at least one selected from cobalt, chromium, zinc, cerium, copper, zirconium, and nickel, and the molar ratio of magnesium to aluminum in the composite oxide, Mg / Al, is 1.0 or more and 10.0 or less. 【Chemistry 1】 [In equation (1), R １ ~R ６ Each of these is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, an alkoxy group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, or an amino group.

2. A method for producing a catalyst for decomposing bisphenol compounds according to claim 1, comprising the following steps (1) to (3). Step (1): A process to obtain a double hydroxide containing magnesium and aluminum by mixing water with at least two compounds, one containing an aluminum atom and the other containing a magnesium atom, or a compound containing an aluminum atom, one containing a magnesium atom, and at least one selected from cobalt, chromium, zinc, cerium, copper, zirconium, and nickel, and then performing hydrothermal synthesis. Step (2): A step of filtering the obtained double hydroxide. Step (3): A step in which the filtered double hydroxide is calcined to obtain a composite oxide containing magnesium and aluminum.

3. A method for producing a catalyst for decomposing bisphenol compounds according to claim 2, wherein the compound containing an aluminum atom is aluminum nitrate, and the compound containing a magnesium atom is magnesium nitrate.

4. The method for producing a catalyst for decomposing bisphenol compounds according to claim 2, wherein in step (1), one or more selected from carbonates and hydroxides are further mixed, the carbonate being an alkali metal carbonate or an alkaline earth metal carbonate, and the hydroxide being an alkali metal hydroxide or an alkaline earth metal hydroxide.

5. A method for decomposing a bisphenol compound represented by the following formula (1) in the presence of a catalyst, A method for decomposing a bisphenol compound, wherein the catalyst comprises a composite oxide in which the metals are only two types, magnesium and aluminum, or a composite oxide containing magnesium and aluminum, and also containing at least one selected from cobalt, chromium, zinc, cerium, copper, zirconium, and nickel, and the molar ratio of magnesium to aluminum in the composite oxide, Mg / Al, is 1.0 or more and 10.0 or less. 【Chemistry 2】 [In equation (1), R １ ~R ６ These are, independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms that may have substituents, an alkoxy group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, and an amino group.

6. The decomposition method according to claim 5, wherein the composite oxide is a calcined product of a double hydroxide containing magnesium and aluminum.

7. The decomposition method according to claim 5 or 6, wherein the decomposition comprises alkaline decomposition of bisphenol A as the bisphenol compound to produce phenol and 4-isopropenylphenol.

8. A method for producing bisphenol A, comprising obtaining phenol and 4-isopropenylphenol by the decomposition method described in claim 7, and then contacting the obtained phenol and 4-isopropenylphenol with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A.

9. A method for producing bisphenol A, comprising performing the following steps (A) to (D) in order. Step (A): A reaction step in which acetone and phenol are condensed in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A. Step (B): A crystallization solid-liquid separation step in which crystals consisting of bisphenol A and phenol are generated from a reaction solution containing bisphenol A by crystallization, and the crystals are separated from the mother liquor. Step (C): An alkaline decomposition step in which the bisphenol A contained in the mother liquor obtained in step (B) is decomposed by the decomposition method described in claim 7 to recover phenol and 4-isopropenylphenol, and Recombination reaction step: The recovered phenol and recovered 4-isopropenylphenol are contacted with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A. Process (D): A circulation process in which the reaction solution obtained in process (C) is circulated upstream from process (B).

10. The decomposition method according to claim 5 or 6, wherein the decomposition comprises hydrolyzing bisphenol A as the bisphenol compound to produce phenol and acetone.

11. A method for producing bisphenol A, comprising obtaining phenol and acetone by the decomposition method described in claim 10, and then contacting the obtained phenol and acetone with an acidic catalyst to recombine them and obtain a reaction solution containing bisphenol A.

12. A method for producing bisphenol A, comprising performing the following steps (A) to (D) in order. Step (A): A reaction step in which acetone and phenol are condensed in the presence of an acidic catalyst to obtain a reaction solution containing bisphenol A. Step (B): A crystallization solid-liquid separation step in which crystals consisting of bisphenol A and phenol are generated from a reaction solution containing bisphenol A by crystallization, and the crystals are separated from the mother liquor. Step (C): A hydrolysis step in which the bisphenol A contained in the mother liquor obtained in step (B) is decomposed by the decomposition method described in claim 10 to recover phenol and acetone. Process (D): A circulation process in which the phenol and acetone recovered in process (C) are circulated upstream from process (B).

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