Method for producing modified aluminosilicate, method for producing catalyst containing modified aluminosilicate, method for producing aromatic polyhydroxide compound using said catalyst, and modified aluminosilicate

Abstract

Provided are: a production method for a modified aluminosilicate that makes it possible to highly selectively produce a hydroquinone via a reaction between a phenol and hydrogen peroxide, with industrially advantageous conditions; a production method for a catalyst that is for producing an aromatic dihydroxide compound and that includes the modified aluminosilicate; a production method for an aromatic dihydroxide compound that uses the catalyst; and a modified aluminosilicate.　A production method for an aluminosilicate according to the present invention comprises: a first step for preparing a liquid obtained by contact between a metal compound (AL) containing aluminum and oxygen and silica in the form of a sol containing water, and obtaining an aluminosilicate in which the molar ratio (HMR) between water and silica is in a specific range; a second step for treating, with acid, the aluminosilicate obtained in the first step; a third step for performing primary firing with respect to the treated product obtained in the second step; and a fourth step for bringing into contact the primary fired product obtained in the third step and a liquid containing one or more elements selected from the group consisting of group 4 elements and group 5 elements of the periodic table, and thereafter performing drying and secondary firing. The metal compound (AL) is preferably a zeolite. The first step preferably includes a step for removing the water.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a modified aluminosilicate, a method for producing a catalyst containing the modified aluminosilicate, a method for producing an aromatic dihydroxide compound using the catalyst, and the modified aluminosilicate. [Background technology]

[0002] Aromatic dihydroxide compounds are important as intermediates or raw materials for various organic synthesis, and are used in the fields of reducing agents, rubber chemicals, dyes, medicines, agricultural chemicals, polymerization inhibitors, oxidation inhibitors, and the like.

[0003] Aromatic dihydroxide compounds obtained by reacting phenols with hydrogen peroxide include, for example, hydroquinone and catechol, and the ratio of hydroquinone to catechol produced varies depending on the production method. In recent years, in order to balance the demand for hydroquinone and catechol, there has been a strong demand for a method for highly selectively producing hydroquinone in particular.

[0004] Methods have been disclosed in which titanosilicate, a type of crystalline porous silicate, is used as a catalyst to produce aromatic dihydroxide compounds by reacting phenols with hydrogen peroxide (e.g., Patent Documents 1 and 2). Patent Document 3 also discloses titanosilicate obtained by treating an acid-treated aluminosilicate with gaseous titanium chloride or titanium alkoxide.

[0005] Furthermore, Patent Document 4 discloses a method for producing titanosilicate, in which aluminosilicate template raw materials, an aluminum source, a titanium source, a silicon source, iodide, and water are mixed together to prepare a gel, which is then heated to crystallize and then calcined.

[0006] The present inventors have disclosed a method for producing an aluminotitanosilicate by contacting an aluminosilicate compound with a liquid titanium halide compound (Patent Document 5). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 4254009 [Patent Document 2] International Patent Publication No. 2015 / 041137 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-050186 [Patent Document 4] Japanese Patent Application Laid-Open No. 2017-057126 [Patent Document 5] International Patent Publication No. 2019 / 225549 Summary of the Invention [Problem to be solved by the invention]

[0008] It has been suggested that the aluminotitanosilicate obtained in Patent Document 5 can be an excellent catalyst for producing aromatic dihydroxide compounds. It has been disclosed that an aluminotitanosilicate containing a titanium source introduced using titanium tetrachloride can produce aromatic dihydroxide compounds with particularly high selectivity. Furthermore, according to the inventor's X-ray crystal structure analysis (X-ray diffraction (XRD) diagram), the aluminotitanosilicate is a compound that exhibits a maximum peak at 23 to 24°.

[0009] The inventors have found that solid lumps may occur in gel-like silica used as an intermediate raw material. From an industrial perspective, the presence of such solids may hinder stable and quantitative transfer of the contents when transferred to a reaction apparatus (e.g., an autoclave) for hydrothermal synthesis in the subsequent step, or may result in reduced reactivity in subsequent steps due to the solids. This may be disadvantageous from the perspective of stable production. While crushing the solids would essentially solve this problem, crushing may require specialized equipment, resulting in increased fixed costs and a slower production rate, making the manufacturing process more complicated for industrial production.

[0010] An object of the present invention is to provide a method for producing a modified aluminosilicate such as an aluminotitanosilicate, which can produce hydroquinones, preferably with higher selectivity and in higher yield, under conditions more industrially advantageous than conventional methods, for example, by reacting a phenol with hydrogen peroxide, etc. Another object of the present invention is to provide a catalyst that can stably produce hydroquinones with higher selectivity under more industrially advantageous conditions, for example, by reacting a phenol with hydrogen peroxide, etc., a method for producing an aromatic polyhydroxide compound using the catalyst, and a modified aluminosilicate. [Means for solving the problem]

[0011] The present inventors conducted research into the above-mentioned problems. They contacted a silicate source, such as silica in a sol state containing water, with an aluminum source, such as zeolite, in a sol state, and then controlled the water-to-silica molar ratio (H2O / SiO2) (hereinafter sometimes referred to as "HMR"). They found that the HMR value significantly affected the performance of the solid material. They also found that by controlling the HMR value within a specific range, it was possible to efficiently produce a suitable aluminosilicate from a sol state, which has better fluidity than a gel. They also found that this aluminosilicate could be converted into a modified aluminosilicate, such as an aluminotitanosilicate, which can produce hydroquinones with extremely high selectivity through an acid treatment step or a contact treatment step with a transition metal compound, such as a titanium compound, and thus completed the present invention.

[0012] That is, the present invention includes the following items [1] to

[10] . [1] A liquid is prepared by contacting water-containing sol-state silica with a metal compound (AL) containing aluminum and oxygen; a first step of obtaining an aluminosilicate having a molar ratio of water to silica (H2O / SiO2:HMR) in the liquid in the range of 0.1 to 8.0; a second step of treating the aluminosilicate obtained in the first step with an acid; a third step of primarily firing the treated product obtained in the second step at 550°C to 850°C; a fourth step of contacting the fired product obtained in the third step with a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, followed by drying and secondary firing. [2] The method for producing a modified aluminosilicate according to [1], wherein the HMR is in the range of 3.0 to 6.6. [3] The method for producing a modified aluminosilicate according to [1] or [2], wherein the metal compound (AL) containing aluminum and oxygen is a zeolite. [4] The method for producing a modified aluminosilicate according to any one of [1] to [3], wherein the first step comprises a step of removing a portion of the water. [5] The method for producing a modified aluminosilicate according to [1], wherein the first step comprises contacting a water-containing sol of silica with a zeolite to prepare a liquid, and then removing a portion of the water in the liquid to obtain an aluminosilicate having a molar ratio of water to silica (H2O / SiO2:HMR) in the range of 0.1 to 8.0. [6] A method for producing a catalyst for producing aromatic polyhydroxide compounds, which contains the modified aluminosilicate according to any one of [1] to [4]. [7] A method for producing a catalyst for producing aromatic polyhydroxide compounds, which contains the modified aluminosilicate according to [5]. [8] A method for producing an aromatic polyhydroxide compound, comprising a step of reacting an aromatic hydroxide with a hydroperoxide in the presence of the catalyst according to [6]. [9] A method for producing an aromatic polyhydroxide compound, comprising a step of reacting an aromatic hydroxide with a hydroperoxide in the presence of the catalyst according to [7].

[10] A modified aluminosilicate having a ratio (A

[0300] / A

[0210] ) of the absorbance at 300 nm in the ultraviolet-visible absorption spectrum (A

[0300] ) to the absorbance at 210 nm in the ultraviolet-visible absorption spectrum (A

[0210] ) of 0.045 or more and 0.070 or less. [Effects of the Invention]

[0013] One feature of the modified aluminosilicate production method is that it can efficiently produce industrially useful aluminosilicates, even when using sol-state silica obtained by heating aqueous gel-state silica. Thus, even when using sol-state silica containing water, by contacting it with an aluminum- and oxygen-containing metal compound (AL), typically a zeolite (aluminum-containing crystalline compound), which is an aluminum source, and then controlling the ratio of water to silica, which are part of the raw materials, within a specific range, it is possible to efficiently produce aluminosilicates suitable for the production of aluminotitanosilicates, as described below. Furthermore, the aluminosilicate preferably has a specific structure determined by an X-ray diffraction pattern. Furthermore, aluminotitanosilicates suitable for use as catalysts for the production of aromatic polyhydroxide compounds can be obtained by contacting the aluminosilicate with a liquid containing one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table, such as an aqueous solution of a titanium source, under mild conditions. Furthermore, such aluminotitanosilicates may exhibit ultraviolet-visible light spectra (UV-Vis) that meet specific requirements. Therefore, the present invention is industrially important. Furthermore, by using the modified aluminosilicate produced by the above-described production method, aromatic dihydroxide compounds, such as hydroquinone, can be produced with high selectivity, for example, by reacting phenols with hydrogen peroxide. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a chart showing the X-ray diffraction patterns of the aluminosilicates obtained in Examples 1 to 3 and Comparative Example 1. [Figure 2] FIG. 2 is a chart showing the X-ray diffraction patterns of the aluminosilicates obtained in Examples 4 to 8. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, an embodiment of the present invention will be described in detail. <Method for producing aluminosilicate> The method for producing a modified aluminosilicate of the present invention includes a first step of preparing a liquid by contacting water-containing sol-state silica with a metal compound (AL) containing aluminum and oxygen, preferably zeolite, to obtain an aluminosilicate having a water to silica molar ratio (HO / SiO:HMR) in the range of 0.1 to 8.0; a second step of treating the aluminosilicate obtained in the first step with an acid; a third step of primarily firing the aluminosilicate obtained in the second step at 550°C to 850°C; The method includes a fourth step of contacting the fired product obtained in the third step with a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, followed by drying and secondary firing.

[0016] [Sol-like silica] The water-containing sol-type silica used in the present invention (hereinafter, the water-containing sol-type silica will be simply referred to as "sol-type silica") can be any known type without any limitations. The sol-type silica can be obtained by contacting a nitrogen-containing compound such as a quaternary ammonium salt or a known alkali source with a silica source such as commercially available colloidal silica, and optionally heating or stirring the mixture.

[0017] Specific examples of the quaternary ammonium salt include salts containing an ammonium ion (cation) containing 4 moles of a substituent, such as a hydrocarbon group having 1 to 10 carbon atoms per mole of nitrogen atom, and an anion, such as a halo ion, such as a hydroxy ion, chloride ion, bromide ion, or iodide ion. The hydrocarbon group preferably contains 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. On the other hand, the anion is more preferably a hydroxy ion, bromide ion, or iodide ion, with a hydroxy ion being even more preferred. More specific examples of such quaternary ammonium salts include tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dimethyldipropylammonium hydroxide, tetrapropylammonium bromide, and bis-1,6-(tripropylammonium)hexamethylenediiodide. Dimethyldipropylammonium hydroxide is particularly preferred.

[0018] Such quaternary ammonium salts are sometimes called organic structure-directing agents, and may have the function of controlling the higher-order structure of silica or aluminosilicate.

[0019] In the present invention, the ratio of the silica to the quaternary ammonium salt, in terms of the silicon atom / nitrogen atom molar ratio, is preferably in the range of 1.5 to 10. The lower limit of this ratio is more preferably 1.7, even more preferably 1.9, and particularly preferably 2.0. On the other hand, the upper limit of this ratio is more preferably 9, even more preferably 8, and particularly preferably 7.

[0020] In the case of an embodiment in which seed crystals are not used, as described below, the silicon atom / nitrogen atom molar ratio may preferably be slightly higher than the above range, with the preferred lower limit being 2.5, more preferably 3.0, even more preferably 3.6, and particularly preferably 3.7.

[0021] In the present invention, the molar ratio of water to silica in the sol-state silica is preferably a value exceeding 8.0.

[0022] Preferred examples of the water include water contained in commercially available colloidal silica, water contained in an organic structure-directing agent or an alkali source described below, and pure water used in combination by additional addition, etc. Of course, other forms of water may be used as long as they are water.

[0023] The temperature during the production of the sol-state silica is preferably relatively high, preferably 40°C or higher, more preferably 50°C or higher, even more preferably 60°C or higher, and particularly preferably 70°C or higher. On the other hand, the upper limit of the temperature is preferably 100°C, more preferably 95°C, even more preferably 92°C, and particularly preferably 90°C.

[0024] Here, the present invention is characterized in that in the first step, a liquid is prepared by contacting sol-state silica with the metal compound (AL), and the molar ratio of water to silica (H2O / SiO2:HMR) is controlled within the range of 0.1 to 8.0. The control method preferably includes a step of removing a portion of the water in the liquid containing sol-state silica and the metal compound (AL).

[0025] The preferred lower limit of the HMR is 1.0, more preferably 2.0, even more preferably 3.0, and particularly preferably 3.6. On the other hand, the preferred upper limit of the HMR is 7.5, more preferably 7.0, even more preferably 6.6, particularly preferably 6.2, and especially preferably 5.8. If the HMR is too low, the resulting solid may not be sufficiently effective in the second step (e.g., partial removal of aluminum by acid treatment) and the third step (e.g., introduction of a transition metal by contact with a transition metal compound), which will be described later. If the HMR exceeds 8.0, an aluminosilicate having the preferred structure may not be obtained due to a decrease in the reaction rate, etc.

[0026] Industrially, various steps are carried out using multiple reactors, and it is preferable to transfer the contents between the reactors via piping. Therefore, it is preferable that various reactants are in a liquid phase such as a liquid, solution, or slurry, or in a particulate form with flowability. Conventionally, the method of Patent Document 5 uses gel-like silica as a raw material, but it would be preferable from the above-mentioned viewpoint if sol-like silica could be used as a silica raw material.

[0027] On the other hand, it was thought that the use of such silica might result in an insufficient reaction with the metal compound (AL), and that the effects of the structure-directing agent preferably used in combination and the effects of the seed crystals described below might not be obtained. However, in the present invention, the inventors have found that by setting the conditions such that the HMR at the stage of contacting the sol-state silica with the metal compound (AL) as described above satisfies a specific range, an aluminosilicate that is a suitable raw material for the catalyst described below can be obtained.

[0028] In the manufacturing method of the present invention for obtaining an aluminosilicate having a specific structure as described below, the shape and number of pores in the obtained aluminosilicate are likely to be affected by the HMR value, which in turn affects the state of the reaction and the properties of the product in the second and third steps described below. For this reason, the inventors believe that it is important to control the HMR value within the above-mentioned numerical range.

[0029] The effect of controlling HMR as described above is as described above, and may also have a significant effect on the second and third steps.

[0030] [1st process] The first step is to prepare a liquid by contacting sol-state silica, which is a silicon source, with the metal compound (AL), which is an aluminum source, to produce an aluminosilicate having an HMR in the range of 0.1 to 8.0. Examples of the metal compound (AL) include known metal oxides such as various aluminum oxides and aluminum-containing composite metal oxides. More specific preferred examples include aluminosilicates, and zeolites are particularly preferred. Preferred zeolites include FAU-type zeolites and MSE-type zeolites, with FAU-type zeolites being more preferred. This step preferably includes a step of contacting aluminosilicate crystals (A) having an MSE structure with sol-state silica in advance. Other examples include aluminum salts such as aluminum hydroxide, sodium aluminate, aluminum nitrate, and aluminum sulfate.

[0031] The aluminosilicate obtained in the first step and the aluminosilicate crystals (A) are preferably porous. Hereinafter, a crystalline and porous aluminosilicate will be simply referred to as a crystalline porous aluminosilicate.

[0032] The MSE-type aluminosilicate (A) can be considered as a crystal called a "seed crystal" when producing an aluminosilicate, which will be described later. The use of a crystal having such a structure can be advantageous in obtaining a modified aluminosilicate, which is a raw material for a catalyst suitable for producing an aromatic polyhydroxide compound, which will be described later. On the other hand, depending on the production conditions, it may be preferable not to use a seed crystal.

[0033] The seed crystal material used in the present invention is not particularly limited as long as it has the above-mentioned structure. However, as described above, crystalline porous aluminosilicates having an MSE type structure (hereinafter referred to as "MSE framework") in the structure code of the International Zeolite Association are preferred, and UZM-35, MCM-68, YNU-3, etc. are particularly preferred.

[0034] The crystalline porous aluminosilicate having the MSE framework has a region in which SiO4 tetrahedra, in which silicon is at the center and oxygen is located at the four vertices, and TiO4 tetrahedra, in which titanium is located in place of the central silicon, are regularly bonded three-dimensionally, and has a three-dimensional pore structure having a 10-membered ring structure consisting of 10 of the tetrahedral units and a 12-membered ring structure consisting of 12 of the tetrahedral units in any proportion.

[0035] The first step of the present invention can be carried out by, for example, contacting a known silicon source such as known colloidal silica with the metal compound (AL), preferably an aluminum source such as zeolite, a quaternary ammonium salt (preferably an organic structure-directing agent such as dimethyldipropylammonium hydroxide), and a known alkali source, stirring and heating the mixture. The silicon source, quaternary ammonium salt, and alkali source may include those derived from the sol.

[0036] A method using gelled silica as the silica source is known, but as mentioned above, gelled silica is solid, and from the viewpoint of, for example, reaction efficiency, it may be difficult to obtain the effects in the second and third steps described below.In addition, from the viewpoint of fluidity, there is a possibility of a decrease in productivity.

[0037] The present invention is characterized in that after contacting sol-state silica with the metal compound (AL), preferably an aluminum-containing compound such as zeolite, to obtain a contact product, the water-to-silica molar ratio (HMR) is within a specific range. As described above, the inventors have discovered that using an aluminosilicate obtained through such an HMR state can produce suitable modified aluminosilicates, such as the aluminotitanosilicates described below, and catalysts. Any known method can be used to achieve such an HMR range. For example, the contact product can be heated and depressurized to remove water. Another example is a method of removing water by contacting the contact product with a water-absorbing agent, more specifically, by passing the contact product through a fixed bed packed with a water-absorbing agent. Among these methods, heating, depressurizing, and a combination of both are preferred. In the present invention, the first step preferably includes a step of removing a portion of the water in the liquid.

[0038] The HMR value can be determined using any known water content measurement method, or can be calculated from data related to the material balance during the reaction process.

[0039] By providing a process in which the HMR is within a specific range under specific conditions as described above, it is possible to efficiently produce modified aluminosilicates such as aluminotitanosilicate and aluminosilicates suitable as raw materials for catalysts.

[0040] To achieve the HMR range as described above, the temperature at the stage of contacting the sol-state silica with the metal compound (AL), preferably zeolite, is preferably the same as the preferred temperature range during the production of the sol-state silica, that is, preferably 40° C. or higher, more preferably 50° C. or higher, even more preferably 60° C. or higher, and particularly preferably 70° C. or higher. On the other hand, the preferred upper limit of the temperature is 100° C., more preferably 95° C., even more preferably 92° C., and particularly preferably 90° C.

[0041] Next, the contact product of the sol-like silica, the metal compound (AL), preferably the zeolite, preferably the seed crystals, and the structure-directing agent is preferably heated to 140 to 175°C and maintained at this temperature for 10 to 150 hours. The lower limit of the temperature is more preferably 145°C, even more preferably 148°C. The lower limit may also be 155°C, more preferably 157°C, even more preferably 159°C, and particularly preferably 160°C. On the other hand, the upper limit of the temperature is more preferably 170°C, even more preferably 168°C, and particularly preferably 165°C. The above conditions are preferable for producing aluminosilicates, which are suitable raw materials for modified aluminosilicates such as aluminotitanosilicates and catalysts, as described below. For example, the above conditions tend to be preferable from the viewpoint of increasing the selectivity of the compounds produced, as disclosed in the Examples. The above temperature range is applicable whether or not the seed crystals are used.

[0042] The lower limit of the time is preferably 15 hours, more preferably 20 hours. The upper limit is preferably 140 hours, more preferably 130 hours. In some cases, the time is preferably 68 hours, more preferably 65 hours, and even more preferably 60 hours.

[0043] In the present invention, for example, in an embodiment using the seed crystals, the heat treatment may be preferably performed at a relatively low temperature. The low temperature preferably refers to a temperature of 140°C or higher and lower than 160°C. The preferred lower limit of the temperature is 145°C, and the preferred upper limit is 157°C, more preferably 155°C. The preferred lower limit of the heat treatment time is 10 hours, more preferably 20 hours, even more preferably 23 hours, particularly preferably 30 hours, and especially preferably 35 hours. Depending on the stirring efficiency and mixing efficiency of the components, which depend on the stirring conditions and the shape of the container, a longer time may be preferable; for example, the lower limit is 40 hours, more preferably 45 hours, even more preferably 50 hours, particularly preferably 55 hours, and especially preferably 60 hours. The preferred upper limit of the treatment time is 140 hours, more preferably 130 hours. In the case of an embodiment using such seed crystals, heating at a low temperature may be advantageous in some cases for obtaining a modified aluminosilicate that satisfies the parameters of the ultraviolet light absorption intensity in a specific range as described below (for example, that shows an excellent tendency in terms of reaction yield).

[0044] In such a case, the HMR value is preferably 4.0 to 7.5. The lower limit is more preferably 4.5, even more preferably 5.0, particularly preferably 5.5, and especially preferably 5.7. On the other hand, the upper limit is more preferably 7.0, even more preferably 6.8.

[0045] In the present invention, for example, in an embodiment in which seed crystals are not used, the heat treatment may be preferably performed at a relatively low temperature for a long period of time. The low temperature preferably refers to a temperature of 140°C or higher and lower than 165°C. The preferred lower limit of the temperature is 145°C, the preferred upper limit is 160°C, and more preferably 155°C. The preferred long period of time preferably refers to a period of 40 hours or higher and 150 hours or lower. The preferred lower limit of the time is 50 hours, more preferably 60 hours, even more preferably 70 hours, particularly preferably 80 hours, and especially preferably 85 hours, while the preferred upper limit is 140 hours, more preferably 130 hours. In such an embodiment in which seed crystals are not used, heating at a low temperature for a relatively long period of time may be advantageous in obtaining a modified aluminosilicate that satisfies the parameters of the ultraviolet light absorption intensity in a specific range (e.g., that shows an excellent tendency in terms of reaction yield) as described below.

[0046] In such a case, the HMR value is preferably 3.0 to 6.0. The lower limit is more preferably 3.5, and even more preferably 4.0. On the other hand, the upper limit is more preferably 5.8, and even more preferably 5.6.

[0047] When the first step is carried out under the above conditions (for example, with an emphasis on the reaction yield), it tends to be easier to produce a modified aluminosilicate with an [A300] / [A210] ratio within a specific range, as described below. The reason for this tendency is currently unknown, but the present inventors speculate as follows.

[0048] Under the above conditions, the aluminosilicate crystallizes from a highly flexible sol state at a relatively low temperature, i.e., in a relatively mild environment, which is thought to facilitate the formation of fine crystals. However, because the reaction occurs in a liquid phase at a relatively low temperature, trace amounts of imperfect crystals may coexist. For this reason, the inventors believe that the above method is likely to form a morphology in which the [A300] / [A210] ratio, described below, satisfies a specific range (0.045 to 0.070).

[0049] On the other hand, in the case of using seed crystals, conditions where the HMR is relatively high (large amount of water) are preferred compared to the case of not using seed crystals. This is expected to be because the crystallization by the seed crystals tends to be promoted, and therefore, in the case of using seed crystals, conditions where the HMR is relatively high, which is thought to further increase the degree of freedom of the silica component in the sol, are considered to be preferable.

[0050] When the MSE-type aluminosilicate is used as a so-called seed crystal in the first step of the present invention, even if the sol-state silica is contained, the effect of promoting crystal growth during aluminosilicate synthesis is preferably exhibited by setting the HMR value within the above-mentioned specific range. Furthermore, since the sol-state silica is used in the first step of the production method of the present invention, at least initially, the silica and the metal compound (AL), preferably zeolite, are brought into contact with a relatively large amount of water derived from the sol-state silica. This water has the effect of promoting the reaction with components such as the metal compound (AL), preferably zeolite. Furthermore, by controlling the HMR to satisfy the above-mentioned range, the effect of promoting crystal growth may also be exhibited.

[0051] When the seed crystals are used, the amount thereof is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, of the silica as the silicon source. The metal compound (AL), preferably zeolite, as the aluminum source also functions as the silicon source, and the amount thereof is preferably 5 to 50% by weight, more preferably 8 to 40% by weight, of the silica.

[0052] The aluminosilicate obtained in this manner preferably has, in XRD measurement, the highest peak (β) in the 17.5 to 35° region, in the region of 20° or more and less than 22.5°, and the peak intensity ratio of peak (β) to the highest peak (γ) in the 25 to 27° region is preferably in the range of 1.60 to 5.0. The lower limit of this peak intensity ratio is more preferably 1.65, even more preferably 1.68, and particularly preferably 1.70. Meanwhile, the upper limit is preferably 4.5, more preferably 4.4.

[0053] Although the reason is unclear at this stage, when such an aluminosilicate is used, a suitable catalyst for an aromatic polyhydroxide compound can be obtained by using a method for introducing a titanium source, etc., as described below. Therefore, aluminosilicates having a structure having the diffraction pattern in XRD measurement as described above are part of the preferred embodiments of the present invention.

[0054] The aluminosilicate according to the present invention exhibits a crystalline structure, but its crystalline form is probably different from that of conventional aluminosilicates (especially from the peak intensity ratio of peak (β) to peak (γ)), ​​and it is speculated that it may have a slightly unstable structure or may contain an unstable structure. It is also speculated that such instability may lead to excellent performance as a catalyst for producing aromatic polyhydroxide compounds when it is converted into a modified aluminosilicate, as described below.

[0055] When an element selected from the group consisting of Groups 4 and 5 of the periodic table, which will be described later, is introduced into the calcined aluminosilicate obtained through the second and third steps, which will be described later, the site where the element is introduced can be considered to be mainly the solid surface of the calcined aluminosilicate, and therefore the crystal structure of the calcined aluminosilicate can be considered to be substantially the same before and after the introduction of the element.

[0056] Examples of raw materials for the sol-like silica include colloidal silica, sodium silicate, wet silica, dry silica, etc. These silicon sources can be used alone or in combination of two or more.

[0057] The metal compound (AL) serving as the aluminum source may be used in combination of two or more kinds. A preferred embodiment includes zeolite. As a component other than the zeolite, for example, a water-soluble aluminum compound can be used. Examples of the water-soluble aluminum compound include aluminum hydroxide, sodium aluminate, aluminum nitrate, and aluminum sulfate.

[0058] As the alkali source, for example, a hydroxide containing an alkali metal can be used. Examples of hydroxides containing an alkali metal include sodium hydroxide and potassium hydroxide. These alkali sources can be used alone or in combination of two or more.

[0059] As the organic structure-directing agent, known compounds such as N,N,N',N'-tetraethylbicyclo[2,2,2]oct-7-ene-2,3:5,6-dipyrrolidinium diiodide and N,N,N',N'-tetraethylbicyclo[2,2,2]oct-7-ene-2,3:5,6-dipyrrolidinium diiodide can be preferably used.

[0060] The aluminosilicate is preferably calcined before the second step described below. The calcination method is not particularly limited, and examples thereof include methods using an electric furnace, a gas furnace, etc. Calcination conditions are preferably heating in an air atmosphere for 0.1 to 20 hours. The calcination temperature is preferably 500 to 800°C, more preferably 550 to 750°C.

[0061] [Second process] The second step is a step of treating the aluminosilicate obtained in the first step with an acid, in other words, a step of contacting the aluminosilicate with an acid.

[0062] Examples of acids used in this step include inorganic acids, organic acids, and mixtures thereof. Specific examples include nitric acid, hydrochloric acid, sulfuric acid, citric acid, oxalic acid, and mixtures thereof. Among these, acids containing elements selected from Groups 15 and 16 of the periodic table are preferred, with nitric acid being particularly preferred. The concentration of the acid is not particularly limited, but is preferably 5% to 80% by weight, and more preferably 40% to 80% by weight. When using this acid as an aqueous solution, the amount used is preferably 1 to 100 parts by weight per part by weight of the aluminosilicate. A more preferred lower limit is 2 parts by weight, even more preferably 3 parts by weight, and particularly preferably 5 parts by weight. Meanwhile, a more preferred upper limit is 80 parts by weight, even more preferably 70 parts by weight, particularly preferably 60 parts by weight, and especially preferably 50 parts by weight.

[0063] The temperature conditions for contacting the aluminosilicate with the acid are preferably 50°C to 170°C, more preferably 130°C to 170°C. Furthermore, the time for the acid treatment is preferably 5 hours to 48 hours, more preferably 12 hours to 36 hours. An even more preferable lower limit of the time is 18 hours. It is believed that this contact with the acid removes a portion of the aluminum from the aluminosilicate. It is presumed that the aluminum removed is primarily from the surface of the aluminosilicate. It is presumed that selecting the above-mentioned relatively high temperature and long treatment time conditions facilitates the formation of a structure advantageous for the introduction of the Group 4 and Group 5 elements during the calcination treatment in the third step described below.

[0064] [3rd step] In the third step, the treated product obtained in the second step, i.e., the aluminosilicate contacted with acid, is subjected to primary calcination. The calcination method is not particularly limited, and examples include methods using an electric furnace, a gas furnace, etc. The calcination conditions are preferably heating in an air atmosphere for 0.1 to 20 hours. The calcination temperature is 550°C to 850°C, more preferably 600°C to 800°C. It is presumed that primary calcination in this relatively high-temperature environment provides an environment favorable for the formation of the so-called modified aluminosilicate obtained in the fourth step, which contains, in a highly active state, elements of Groups 4 and 5 of the periodic table, typified by titanium species.

[0065] Before calcining the aluminosilicate that has been contacted with the acid, it is preferable to filter the treated product using a funnel or the like to separate the acid (aqueous solution) used, and then wash and dry the solid portion (filtered product). The washing step is preferably carried out while maintaining the product in a wet state without drying it before washing. The method of drying after washing is not particularly limited, but uniform and rapid drying is preferable. For example, external heating methods such as hot air drying and superheated steam drying, and electromagnetic heating methods such as microwave heating drying and high-frequency dielectric heating drying can be used.

[0066] [4th step] In the fourth step, the calcined product obtained in the third step (hereinafter also referred to as the "primary calcined product") is brought into contact in a liquid phase with a liquid containing one or more elements selected from Group 4 and Group 5 elements of the periodic table as an element source, followed by drying and secondary calcination. Examples of Group 4 and Group 5 elements of the periodic table include titanium, zirconium, hafnium, and vanadium. Titanium, zirconium, and vanadium are preferred, with titanium being particularly preferred. Suitable compounds containing these elements include halides, alkoxides, and inorganic acid salts of the respective elements. More preferred halides include chlorides, and more preferred alkoxides include those containing an alkoxy group having 1 to 6 carbon atoms. More preferred alkoxides include ethoxide, butoxide (n-butoxide, i-butoxide, s-butoxide, t-butoxide), sulfates, and the like. Two or more of these compounds may be used in combination.

[0067] Hereinafter, an embodiment in which titanium, which is the most preferred embodiment among the Group 4 and 5 elements of the periodic table, is used as a liquid containing titanium (liquid-phase titanium source) will be described as a representative example.

[0068] The liquid-phase titanium source is a liquid containing titanium. Examples of the titanium-containing liquid include a liquid titanium compound itself and an aqueous solution of a titanium compound. Among these, a titanium compound that is substantially acidic in a liquid state is preferred.

[0069] Examples of liquid titanium compounds include titanium tetrachloride (TiCl4) and tedrabbutoxytitanium, with titanium tetrachloride being preferred. Examples of aqueous solutions of titanium compounds include aqueous titanium tetrachloride solutions, aqueous titanium trichloride (TiCl3) solutions, aqueous titanium sulfate (Ti(SO4)2) solutions, and aqueous potassium hexafluorotitanate solutions, with titanium tetrachloride solutions, titanium trichloride solutions, and titanium sulfate solutions being preferred. In the present invention, even when titanium sources other than titanium tetrachloride, such as titanium trichloride and titanium sulfate, which are less reactive than titanium tetrachloride, are used, the catalytic activity described below can be exhibited.

[0070] The titanium-containing liquids can be used alone or in combination of two or more. Commercially available titanium-containing liquids can be used, or liquids prepared by diluting a solid titanium compound with water to a desired concentration can be used. Compared to gaseous titanium sources, liquid-phase titanium sources (titanium-containing liquids) are less likely to leak and are less susceptible to corrosion problems on manufacturing machinery, analytical equipment, etc., and are therefore expected to facilitate industrial production.

[0071] The conditions for contacting the primary calcined product with the titanium source are not particularly limited, but this contact introduces titanium into the primary calcined product of the aluminosilicate. This titanium introduction is thought to occur by introducing titanium into the position of the aluminum that was supposedly removed in the second step, or by a reaction in which some of the aluminum in the aluminosilicate is replaced with titanium. Specific conditions for this step include, for example, when using a liquid titanium compound, adding 5 to 300 parts by weight, and more preferably 20 to 250 parts by weight, of the liquid titanium compound per part by weight of the primary calcined product. When using an aqueous solution of a titanium compound, adding 1 to 10 parts by weight, and more preferably 1 to 7 parts by weight, of the aqueous solution of the titanium compound per part by weight of the primary calcined product. The concentration of the aqueous solution varies depending on the compound used, but is, for example, 10 to 70% by weight, and preferably 15 to 60% by weight.

[0072] The amount of titanium compound in the aqueous solution is preferably 0.1 g, more preferably 0.2 g, even more preferably 0.3 g, and particularly preferably 0.5 g per gram of the primary fired product, and is preferably 10 g, more preferably 5 g, and even more preferably 3 g per gram of the primary fired product.

[0073] The contact of the titanium source with the primarily calcined aluminosilicate may be carried out once, or each component may be added in multiple batches, as long as the weight ratio is within the range of the addition amount. For example, the titanium source may be added to the primarily calcined product, followed by drying and secondary calcination as described below, to obtain a calcined product, to which the titanium source may be added again, followed by drying and secondary calcination. When the titanium source is added, it is preferable to carry out the addition in a nitrogen atmosphere, since hydrogen chloride is generated by the reaction between moisture in the air and the titanium compound.

[0074] More specifically, preferred methods include contacting the primary calcined product with a titanium source, thoroughly mixing the mixture, and then heating the mixture; or thoroughly drying the mixture using a method similar to that described in the third step, followed by secondary calcination. The temperature for the heating and drying treatments is not particularly limited, but a range of 20 to 150°C is preferred to effectively incorporate titanium into the primary calcined product. A more preferred lower limit is 30°C, even more preferably 40°C, and particularly preferably 50°C. A more preferred upper limit is 140°C, even more preferably 120°C, and particularly preferably 100°C. The time required for the above steps is also not particularly limited, but is preferably 0.1 to 24 hours. A more preferred lower limit is 0.3 hours, even more preferably 0.4 hours, and particularly preferably 0.5 hours. A more preferred upper limit is 12 hours, even more preferably 6 hours. The method for secondary calcination is not particularly limited, and calcination can be performed using, for example, an electric furnace, a gas furnace, or the like. The firing conditions are preferably 400°C or higher and 850°C or lower for 0.1 to 20 hours in an air atmosphere. The lower limit of the firing temperature is more preferably 500°C, even more preferably 550°C, and particularly preferably 600°C. On the other hand, the upper limit is more preferably 800°C, even more preferably 750°C, and particularly preferably 700°C.

[0075] The temperatures during the primary and secondary firings can be selected independently, and it may be preferable that the temperature during the secondary firing is higher than the temperature during the primary firing.

[0076] This fourth step makes it possible to obtain, for example, a crystalline porous aluminotitanosilicate, which is a preferred embodiment of the modified aluminosilicate of the present invention, in which a portion of the aluminum in the crystalline porous aluminosilicate is thought to have been substituted with titanium.

[0077] Before carrying out the drying treatment, the mixture of the titanium source and the primary calcined product may be heated to preliminarily remove water, the mixture may be filtered to remove impurities, and the mixture may be washed with an organic solvent, followed by drying and secondary calcination. The above-mentioned manufacturing conditions can be applied mutatis mutandis to the case where an element other than titanium is used.

[0078] Examples of compounds containing a Group 4 element of the periodic table that can be used in place of the titanium source include zirconium tetrachloride, tetraalkoxyzirconium, hafnium tetrachloride, tetraalkoxyhafnium, and zirconium sulfate, which can be liquefied by combining with water, alcohol, ether, or the like, as needed. Examples include aqueous solutions of these compounds, and solutions of alcohol, ether, and the like. Examples of compounds containing a Group 5 element of the periodic table that can be used in place of the titanium source include vanadium pentachloride, vanadium sulfate, vanadium trichloride, and alkoxy-substituted vanadium compounds thereof, which can be liquefied by combining with water, alcohol, ether, and the like, as needed. Examples include aqueous solutions of these compounds, and solutions of alcohol, ether, and the like.

[0079] [Modified aluminosilicate] The modified aluminosilicate obtained in the fourth step is preferably a crystalline porous aluminosilicate having crystallinity and porosity, similar to the raw material aluminosilicate obtained in the first step, more preferably a crystalline porous aluminosilicate having an MSE skeleton, even more preferably a crystalline porous aluminosilicate having a UZM-35, MCM-68, or YNU-3 structure, and particularly preferably a crystalline porous aluminotitanosilicate. The term "crystallinity" can be considered to have the same meaning as that described for the raw material aluminosilicate.

[0080] The crystalline porous aluminosilicate is a porous crystalline substance having at least a portion where SiO4 tetrahedra, in which oxygen is located at the four vertices around silicon, and AlO4 tetrahedra, in which aluminum is located in place of the central silicon, are regularly three-dimensionally bonded, and can be said to be a type of zeolite containing aluminosilicate. The crystalline and porous modified aluminosilicate, for example, contains aluminum and one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table in the crystalline porous aluminosilicate framework, and is preferably obtained by a method in which part of the aluminum in the crystalline porous aluminosilicate framework is replaced with one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table. In a more preferred example, when one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table are titanium, the crystalline porous modified aluminosilicate becomes a crystalline porous aluminotitanosilicate, which contains aluminum and titanium in the aluminosilicate framework and is preferably obtained by a method in which part of the aluminum in the framework is replaced with titanium.

[0081] The crystalline porous aluminosilicate with the MSE framework has a three-dimensional pore structure with a random ratio of 10-membered ring structures consisting of 10 tetrahedral units and 12-membered ring structures consisting of 12 tetrahedral units. The presence of pores with the 12-membered ring structure facilitates the diffusion of substrates into the pores, making it easier to achieve high catalytic activity. Furthermore, the absence of large cavities within the pores is thought to be one factor contributing to the para-selectivity observed in the oxidation of phenol.

[0082] It is well known that porous compounds have a large specific surface area. The modified aluminosilicate of the present invention has a specific surface area of ​​preferably 50 to 1000 m 2 The lower limit of the specific surface area is more preferably 100 m 2 / g, more preferably 150m 2On the other hand, the upper limit of the specific surface area is more preferably 800 m 2 / g, more preferably 600m 2 / g.

[0083] The value of the specific surface area can be determined by a known calculation method based on the BET theory by creating a BET plot from the measurement results using a known nitrogen adsorption / desorption measurement device (e.g., Microtrac BELSORP-max manufactured by BEL). The preferred range of pore volume of the modified aluminosilicate of the present invention is 0.1 to 0.5 cm 3 / g, more preferably 0.15 to 0.4 cm 3 / g.

[0084] There are no particular restrictions on the contents of Group 4 and Group 5 elements contained in the modified aluminosilicate of the present invention. For example, when titanium is contained as one or more elements selected from the group consisting of Group 4 and Group 5 elements contained in the modified aluminosilicate, the molar ratio of silicon to titanium ([Si] / [Ti]) is preferably in the range of 0.1 to 400, more preferably in the range of 50 to 300, even more preferably in the range of 100 to 280, and most preferably in the range of 150 to 260.

[0085] When a compound that easily crystallizes itself, such as TiCl3, is used, the element may be introduced to the aluminosilicate surface in the form of clusters or crystals. In this case, the apparent element content may increase, and the [Si] / [Ti] ratio tends to be small. In such cases, the [Si] / [Ti] ratio range is preferably 0.5 to 30. The lower limit is more preferably 1, and even more preferably 1.2. On the other hand, the upper limit is more preferably 20, and even more preferably 15.

[0086] The aluminum content of the modified aluminosilicate of the present invention is not particularly limited, but the molar ratio of silicon to aluminum ([Si] / [Al]) is preferably in the range of 5 to 100,000, even more preferably in the range of 10 to 10,000, and even more preferably in the range of 15 to 1,000.

[0087] The modified aluminosilicate of the present invention is preferably characterized by absorption in a specific wavelength region in ultraviolet-visible absorption spectrum measurement.

[0088] The modified aluminosilicate of the present invention preferably contains an element selected from the group consisting of Group 4 and Group 5 elements of the periodic table, and typically has an absorbance at 300 nm in the ultraviolet-visible absorption spectrum (A

[0300] ) of 1.0 or more. Specific examples and preferred examples of the element selected from Group 4 and Group 5 elements contained in the modified aluminosilicate of the present invention are the same as those described in the "Fourth Step" section above.

[0089] Furthermore, when the modified aluminosilicate satisfies the preferred XRD requirements in a tetravalent or pentavalent form, or when a tetravalent or pentavalent compound of an element selected from the group consisting of Group 4 and Group 5 elements of the periodic table is used in Step 4, the A

[0300] preferably has a value of more than 0.20 (hereinafter also referred to as "Specific Requirement 0"). Furthermore, when the specific requirement described below (A

[0300] / A

[0210] of 0.045 or more and 0.070 or less: hereinafter also referred to as "Specific Requirement 1") is satisfied, the A

[0300] is preferably 0.07 to 0.20, and more preferably 0.07 to 0.15, and in some cases, a range of 0.07 to 0.10 is particularly preferred.

[0090] When the A

[0300] is less than 1.0, or less than 0.20 when the specific requirement 0 is satisfied, or even less than 0.07 when the specific requirement 1 is satisfied, the selectivity of aromatic dihydroxide compounds tends to be relatively low when producing aromatic dihydroxide compounds by reacting phenols with hydrogen peroxide. There are no particular limitations on the method for measuring absorbance, and either a transmission method or a reflection method may be used. When measuring by a reflection method, reflected light may include diffuse reflected light in addition to specular reflected light, but for convenience, calculations are performed assuming that all light is specular reflected light.

[0091] Although the detailed mechanism is unknown, the inventors speculate as follows (hereinafter, the modified aluminosilicate will be described using, as an example, a crystalline porous aluminotitanosilicate in which the element selected from Groups 4 and 5 is titanium).

[0092] It is believed that aluminum and titanium are present on the surface of the crystalline porous aluminotitanosilicate framework. Furthermore, it is believed that these are preferably present mainly inside recesses such as pores in the crystalline porous aluminotitanosilicate. Here, for example, in the case of an embodiment in which titanium is produced using a high-temperature gaseous titanium tetrachloride method as described in Patent Document 3 and is considered to contain only titanium completely and defect-freely incorporated into the framework of the crystalline structure, it is believed that the absorbance near 300 nm in the ultraviolet-visible absorption spectrum is 1.0 or more, or unlikely to exceed 0.2, the specific requirement 0. Within this range, it is believed that a small amount of unstable titanium is present. In other words, it is believed that a crystalline porous aluminotitanosilicate that satisfies the requirements of the present invention contains a large amount of titanium that is incompletely incorporated into its basic framework, resulting in an unstable structure. It is presumed that such titanium species significantly contribute to the reaction of forming aromatic dihydroxide compounds, and that when the oxidation reaction of phenols with hydrogen peroxide proceeds, their instability suppresses the production of 1,2-hydroxide compounds (e.g., catechol), which are considered to be unfavorable in terms of their steric structure, and the further production of benzoquinone, which is the reaction's advanced form, thereby enabling the highly selective production of 1,4-type aromatic dihydroxide compounds.

[0093] From the viewpoint of further enhancing the selectivity for aromatic dihydroxide compounds, the preferred lower limit of A

[0300] of the modified aluminosilicate is 1.5, more preferably 1.8. Furthermore, when the specific requirement is 0, the more preferred lower limit of A

[0300] is 0.08, even more preferably 0.25, and particularly preferably 0.30. On the other hand, although there is no essential meaning in setting the upper limit of A

[0300] , the preferred upper limit is 15, more preferably 10. Furthermore, A

[0300] is 0.2 or less for ordinary highly crystalline porous aluminotitanosilicates.

[0094] Furthermore, the ratio (A

[0300] / A

[0210] ) of A

[0300] to the absorbance at 210 nm (A

[0210] ) of the ultraviolet-visible absorption spectrum of the modified aluminosilicate is more preferably 0.5 or more, even more preferably 0.6 or more, and particularly preferably 0.8 or more. When the specific requirement 0 is met, the "A

[0300] / A

[0210] " is preferably a value exceeding 0.10. A more preferred lower limit is 0.11. On the other hand, for example, when the "A

[0300] " is a small value less than 0.20, the "A

[0300] / A

[0210] " may preferably be in the range of 0.045 to 0.070. For example, when titanium is incorporated without defects into the framework of the crystal structure, the "A

[0210] " becomes relatively high compared to the "A

[0300] ", and therefore, it is difficult to obtain a normal crystalline porous aluminosilicate. In luminotitanosilicates, the A

[0300] / A

[0210] ratio generally tends to be 0.1 or less, but when it is 0.045 or more, a small amount of titanium with a special unstable structure is contained, and it is thought that this titanium may exhibit an activating effect either alone or by influencing other titanium. Such unstable titanium, which may be present in small amounts, has high reactivity and structural selectivity, and is thought to exhibit favorable performance such as high activity, high yield, and relatively high regioselectivity in the production of hydroquinone, etc., as described below. Although there is no particular significance to the upper limit of the A

[0300] / A

[0210] ratio, it is more preferably 1.5, and even more preferably 1.0. When it is considered that slightly unstable titanium as described above is present, the upper limit is preferably 0.070.

[0095] The ultraviolet-visible absorption spectrum can be measured by a conventional method, for example, the following method. "A 0.1g sample of solid aluminosilicate is placed in a cell with a 10mm optical path length, and the wavelength range of 200-800nm ​​is measured using a Shimadzu UV-2550 UV-Visible Spectrophotometer." It is preferable that the solid aluminosilicate sample be thoroughly dried before use.

[0096] The modified aluminosilicate obtained by the production method of the present invention can be used as a catalyst for producing an aromatic polyhydroxide compound, which is one embodiment of the present invention.

[0097] <Method of producing aromatic polyhydroxide compound> One embodiment of the present invention is a method for producing an aromatic polyhydroxide compound, comprising a step of reacting an aromatic hydroxide with a hydroperoxide in the presence of a catalyst for producing an aromatic polyhydroxide compound, the catalyst comprising the modified aluminosilicate.

[0098] Examples of aromatic hydroxides include phenols, which will be described later, as well as compounds having a structure in which one hydroxy group is bonded to a phenyl skeleton, such as hydroxynaphthalene and its derivatives, hydroxyanthracene and its derivatives, and hydroxyfluorene and its derivatives. Phenols are preferred.

[0099] Examples of hydroperoxides include hydrogen peroxide and compounds in which one hydrogen atom of hydrogen peroxide is substituted with an aliphatic or aromatic hydrocarbon group, a heteroatom-containing hydrocarbon group, etc., such as butyl hydroperoxide and cumene hydroperoxide. Hydrogen peroxide is preferred, and more specifically, aqueous hydrogen peroxide is a preferred embodiment.

[0100] The method for producing an aromatic polyhydroxide will be described below using a method for producing an aromatic dihydroxide compound as an example. For example, when a phenol is reacted with hydrogen peroxide in the presence of the modified aluminosilicate of the present invention, an aromatic dihydroxide compound can be produced with high selectivity.

[0101] The phenols refer to unsubstituted phenols and substituted phenols, including alkylphenols substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a butyl group, or a hexyl group, or a cycloalkyl group.

[0102] Examples of phenols include phenol, 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2-ethylphenol, 3-isopropylphenol, 2-butylphenol, and 2-cyclohexylphenol, and among these, phenol is preferred. When phenols have substituents at both the 2- and 6-positions, the product is only a hydroquinone derivative.

[0103] Examples of aromatic dihydroxide compounds that are reaction products include hydroquinones (substituted or unsubstituted hydroquinones) and catechols (substituted or unsubstituted catechol), and specific examples thereof include hydroquinone, catechol, 2-methylhydroquinone, 3-methylcatechol, 4-methylcatechol, 3-methylhydroquinone, 1,4-dimethylhydroquinone, 1,4-dimethylcatechol, 3,5-dimethylcatechol, 2,3-dimethylhydroquinone, and 2,3-dimethylcatechol.

[0104] The modified aluminosilicate obtained by the present invention is used as a catalyst for producing an aromatic dihydroxide compound. Various methods, such as a fixed bed, a fluidized bed, a suspension bed, and a tray-type fixed bed, can be used as the catalyst packing method, and any of these methods is acceptable. The catalyst may be used as is, or may be molded according to the catalyst packing method. Common methods for molding the catalyst include extrusion molding, tableting, tumbling granulation, and spray granulation. When using the catalyst in a fixed bed system, extrusion molding or tableting is preferred. When using a suspension bed system, spray granulation is preferred. Drying and calcination may be performed after spray granulation. The average particle size of the spray-granulated catalyst is preferably in the range of 0.1 μm to 1000 μm, more preferably 5 μm to 100 μm. A particle size of 0.1 μm or more is preferred because it allows for easy handling, such as filtration of the catalyst, while a particle size of 1000 μm or less is preferred because it provides good catalyst performance and high strength.

[0105] The amount of the catalyst used is preferably 0.1 to 30% by mass, more preferably 0.4 to 20% by mass, based on the total mass of the reaction solution (the total mass of liquid components in the reaction system, excluding the mass of fixed components such as the catalyst). An amount of 0.1% by mass or more is preferred because the reaction is completed in a short time and productivity is improved. An amount of 30% by mass or less is preferred because the amount of catalyst separated and recovered is small.

[0106] When the modified aluminosilicate of the present invention is used as a catalyst in a method for producing an aromatic dihydroxide compound, it can be combined with other components. Examples include the siloxane compounds described in Patent Document 1 and the specific alcohol compounds described in Patent Document 2. Such components are preferably used in an amount that accounts for 5 to 90% by mass of the reaction liquid, more preferably 8 to 90% by mass.

[0107] The molar ratio of hydrogen peroxide to phenols is preferably 0.01 or more and 1 or less. The concentration of hydrogen peroxide used is not particularly limited, but a typical aqueous solution of 30% may be used, or a more concentrated aqueous solution of hydrogen peroxide may be used as is or diluted with a solvent that is inert to the reaction system. Examples of solvents used for dilution include alcohols and water. Hydrogen peroxide may be added all at once or gradually over time.

[0108] The reaction temperature is preferably in the range of 30° C. to 130° C., more preferably in the range of 40° C. to 100° C. Although the reaction will proceed at temperatures outside this range, the above range is preferred from the viewpoint of improving productivity. The reaction pressure is not particularly limited.

[0109] The reaction method is not particularly limited, and the reaction may be carried out in any of batch, semi-batch, and continuous modes. When carried out continuously, the reaction may be carried out in a suspension bed homogeneous mixing tank, or in a fixed bed flow plug flow format, or multiple reactors may be connected in series and / or parallel. From the viewpoint of equipment costs, it is preferable to have 1 to 4 reactors. When multiple reactors are used, hydrogen peroxide may be added to them in divided portions.

[0110] In order to obtain the aromatic dihydroxide compound from the reaction solution, the reaction solution or the separated solution containing the dihydroxide compound after separating the catalyst may be subjected to a purification treatment such as removal of unreacted components and by-products. The purification treatment is preferably performed on the separated solution containing the aromatic dihydroxide compound after separating the catalyst.

[0111] The purification method is not particularly limited, and specific examples include oil-water separation, extraction, distillation, crystallization, a combination of these, etc. The purification method, procedure, etc. are not particularly limited, but the separated liquid containing the aromatic dihydroxide compound after separating the reaction liquid and the catalyst can be purified, for example, by the following method.

[0112] When the reaction liquid separates into two phases, an oil phase and an aqueous phase, oil-water separation is possible. By oil-water separation, the aqueous phase, which has a low content of dihydroxide compounds, is removed and the oil phase is recovered. In this case, the separated aqueous phase may be subjected to extraction, distillation, etc. to recover the aromatic dihydroxide compounds, or a portion or all of it may be reused in the reaction. Alternatively, the catalyst separated in the catalyst separation step or a dried catalyst may be dispersed in the separated aqueous phase and supplied to the reactor. On the other hand, it is desirable to further purify the oil phase by extraction, distillation, crystallization, etc.

[0113] For extraction, solvents such as 1-butanol, toluene, isopropyl ether, and methyl isobutyl ketone are used. Combining extraction with oil-water separation allows for efficient oil-water separation. The extraction solvent is preferably separated and recovered using a distillation column and recycled for reuse.

[0114] Distillation may be performed on the reaction solution immediately after catalyst separation, or on the oil and aqueous phases after oil-aqueous separation. The extract may also be distilled. When distilling the reaction solution immediately after catalyst separation, it is preferable to first separate low-boiling components such as water or alcohols. Water and alcohols may be separated in separate distillation columns, or they may be separated in a single distillation column.

[0115] After separating water and alcohols by the above-mentioned oil-water separation, extraction, distillation, etc., the phenols may be recovered by a subsequent distillation operation and reused in the reaction. If the recovered phenols contain water that has not been completely separated, it can be removed by azeotropic distillation using isopropyl ether or toluene.

[0116] This azeotropic distillation can also be performed on water before recovering phenols and on the liquid after separating alcohols. The separated water can be reused in the reaction or can be treated as wastewater. When the recovered phenols contain impurities such as reaction by-products other than water, they can be further separated by distillation. When the impurities are reaction by-products such as benzoquinones, they can be fed back to the reactor together with the phenols.

[0117] After separating the phenols, components with higher boiling points than the aromatic dihydroxide compounds are removed by distillation, and the hydroquinones and catechols can be separated by a subsequent distillation operation. Alternatively, the high boiling points, hydroquinones, and catechols can be separated in a single distillation operation by withdrawing the hydroquinones from the middle of the distillation column. The purity of the obtained hydroquinones and catechols can be increased by removing impurities by distillation, crystallization, etc., if necessary.

[0118] When, for example, phenol and hydrogen peroxide are reacted in the presence of the modified aluminosilicate of the present invention, hydroquinone tends to be produced in a high yield. Furthermore, hydroquinone tends to be produced with a high selectivity compared to catechol, benzoquinone, and the like. For this reason, the modified aluminosilicate of the present invention can be said to have high industrial value. It is also possible to produce aromatic polyhydroxide compounds under conditions similar to those used in the production method of aromatic dihydroxide compounds described above. [Example]

[0119] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0120] [XRD measurement method] X-ray diffraction of the sample crystal was measured by a conventional method, except for the following conditions. X-ray diffraction equipment: Rigaku Corporation, model: MultiFlex ·X-ray source: CuKα Output: 40kV / 40mA Divergence slit: 1° Scattering slit: 1° Receiving slit: 0.30 mm 2θ:3~50°

[0121] [Method for measuring ultraviolet-visible absorption spectra] A 0.1 g sample of solid aluminosilicate was placed in a cell with an optical path length of 10 mm, and measurements were taken in the wavelength range of 200 to 800 nm using a Shimadzu UV-2550 ultraviolet-visible spectrophotometer in the usual manner, to determine the absorption intensities at wavelengths of 300 nm and 210 nm.

[0122] [Example 1] [Preparation of Crystal (A1)] Crystals (A1) having an MSE skeleton were prepared by the following method. First, 7.90 g of (8 mol / L) NaOH aqueous solution, 8.18 g of (8 mol / L) KOH aqueous solution, 20.46 g of 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 33.82 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO2 content: 40 wt%)) were placed in a container and stirred at 80°C to obtain a sol-like substance. The stirring time was then adjusted so that the HMR value was 3.20. At this point, the raw materials had solidified.

[0123] Next, 6.91 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained lumps and mixed using a mortar. The mixture was then placed in an autoclave and heated at 160°C for 68 hours. The cooled mixture was filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (A1). The highest diffraction peak measured by XRD was observed at 21.66°.

[0124] [Step 1: Preparation of aluminosilicate] Next, 7.81 g of an 8 mol / L NaOH aqueous solution, 8.09 g of an 8 mol / L KOH aqueous solution, 24.36 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 36.13 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO content: 40 wt%)) were placed in a container and stirred at 80 °C to obtain a sol-like substance, to which 0.79 g of the crystals (A1) and 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.00. The contents were heated at 165 °C for 40 hours using the same autoclave as above. The cooled mixture was then filtered, washed with water, and vacuum-dried at 70 °C for 2 hours to obtain crystals (1-0).

[0125] The highest peak in the 17.5 to 35° region measured by XRD of the crystal (1-0) was observed at 21.6°, and the intensity ratio to the highest peak observed at 25.78° in the 25.0 to 27.0° region was 1.73. The XRD chart is shown in Figure 1. The crystal (1-0) was calcined at 550°C for 10 hours to obtain a crystal (1-1).

[0126] [Second step: contact with acid, third step: primary calcination] 2 g of the prepared crystal (1-1) and 80 g of 65% nitric acid were mixed in a container, and the mixture was then placed in an autoclave and heated at 148°C for 24 hours. The cooled mixture was filtered, washed with water, air-dried for one day, and then primarily calcined at 600°C for two hours to obtain crystal (1-2).

[0127] [Fourth step: contact with titanium compound, secondary calcination] 1 g of the prepared crystal (1-2) and 5 g of a titanium tetrachloride aqueous solution with a Ti concentration of 16% were placed in a container and heated and stirred in an oil bath at 40°C for 1 hour. Water was then added, and the mixture was filtered and washed. The dried product was then subjected to secondary firing at 650°C for 2 hours to obtain a crystalline porous aluminotitanosilicate (crystal (1-3)).

[0128] [Example 2] [Preparation of Crystal (A2)] Crystals (A2) having an MSE framework were prepared by the following method. First, 15.60 g of (8 mol / L) NaOH aqueous solution, 16.22 g of (8 mol / L) KOH aqueous solution, 40.60 g of 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 67.20 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO2 content: 40 wt%)) were placed in a container and stirred at 80°C to obtain a sol-like substance. The stirring time was then adjusted so that the HMR value was 3.50. At this point, the raw materials had solidified.

[0129] Next, 13.56 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained lumps and mixed using a mortar. The mixture was then placed in an autoclave and heated at 165°C for 40 hours. The cooled mixture was filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (A2). The highest diffraction peak measured by XRD was observed at 21.60°.

[0130] [Step 1: Preparation of aluminosilicate] Next, 7.78 g of an 8 mol / L NaOH aqueous solution, 8.17 g of an 8 mol / L KOH aqueous solution, 24.34 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 35.33 g of colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich (SiO content: 40% by mass)) were placed in a container and stirred at 80°C to obtain a sol-like substance, to which 0.79 g of the crystals (A2) and 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.80. The mixture was then placed in an autoclave and heated at 160°C for 37 hours. The cooled mixture was then filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (2-0).

[0131] The highest peak in the 17.5 to 35° region measured by XRD of the crystal (2-0) was observed at 21.6°, and the intensity ratio to the highest peak in the 25.0 to 27.0° region, observed at 26.08, was 4.30. The XRD chart is shown in Figure 1. The crystal (2-0) was calcined at 550° C. for 10 hours to obtain a crystal (2-1).

[0132] [Second step: contact with acid, third step: primary calcination] Crystal (2-2) was obtained in the same manner as in Example 1, except that Crystal (2-1) was used instead of Crystal (1-1).

[0133] [Fourth step: contact with titanium compound, secondary calcination] A crystal (2-3) was obtained in the same manner as in Example 1, except that the crystal (2-2) was used instead of the crystal (1-2).

[0134] [Example 3] [Preparation of Crystal (A3)] Crystals (A3) having an MSE framework were prepared by the following method. First, 15.62 g of an 8 mol / L NaOH aqueous solution, 16.22 g of an 8 mol / L KOH aqueous solution, 40.60 g of a 40 wt % dimethyldipropylammonium hydroxide aqueous solution, and 67.20 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO content: 40 mass%)) were placed in a container and stirred at 80°C to obtain a sol-like substance.

[0135] Next, 13.56 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained sol-like substance and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.00. The mixture was then placed in an autoclave and heated at 165°C for 40 hours. The cooled mixture was filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (A3). The highest diffraction peak measured by XRD was observed at 21.66°.

[0136] [Step 1: Preparation of aluminosilicate] Next, 7.81 g of an 8 mol / L NaOH aqueous solution, 8.14 g of an 8 mol / L KOH aqueous solution, 24.39 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 36.14 g of colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich (SiO content: 40% by mass)) were placed in a container and stirred at 80°C to obtain a sol-like substance, to which 0.79 g of the crystals (A3) and 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. The stirring time was adjusted so that the HMR value at this stage was 5.50. The mixture was then placed in an autoclave and heated at 160°C for 50 hours. The cooled mixture was then filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (3-0).

[0137] The highest peak in the 17.5 to 35° region measured by XRD of the crystal (3-0) was observed at 21.64°, and the intensity ratio to the highest peak in the 25.0 to 27.0° region, observed at 26.14°, was 4.125. The XRD chart is shown in Figure 1. The crystal (3-0) was calcined at 550° C. for 10 hours to obtain a crystal (3-1).

[0138] [Second step: contact with acid, third step: primary calcination] Crystal (3-2) was obtained in the same manner as in Example 1, except that Crystal (3-1) was used instead of Crystal (1-1).

[0139] [Fourth step: contact with titanium compound, secondary calcination] A crystal (3-3) was obtained in the same manner as in Example 1, except that the crystal (3-2) was used instead of the crystal (1-2).

[0140] [Comparative Example] [Preparation of Crystal (A-c1)] Crystals (A-c1) were obtained in the same manner as in the preparation of Crystals (A1) in Example 1.

[0141] [Preparation of aluminosilicate] Next, 7.81 g of an 8 mol / L NaOH aqueous solution, 8.11 g of an 8 mol / L KOH aqueous solution, 20.30 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 32.68 g of colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich (SiO content: 40 wt%)) were placed in a container and stirred at 80°C. Stirring was continued for a longer period than in Example 1, resulting in dehydration to an HMR of 3.50. At this point, the mixture was in a solidified, lumpy state, and it was determined that pulverization was necessary for reaction with zeolite or the like in the next step. Therefore, 0.79 g of the crystals (A-c1) and 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added to the raw material mixture, pulverized in a mortar, and thoroughly mixed. The mixture was then placed in an autoclave and heated at 160°C for 55 hours. Thereafter, the cooled mixture was filtered, washed with water, and vacuum dried at 70°C for 2 hours to obtain crystals (C1-0).

[0142] The highest peak in the 17.5 to 35° region measured by XRD of the crystal (C1-0) was observed at 21.58°, and the intensity ratio to the highest peak in the 25.0 to 27.0° region, observed at 25.72°, was 1.54. The XRD chart is shown in Figure 1. The crystal (C1-0) was calcined at 550° C. for 10 hours to obtain a crystal (C1-1).

[0143] [Contact with acid, primary baking] Crystal (C1-2) was obtained in the same manner as in Example 1, except that Crystal (C1-1) was used instead of Crystal (1-1).

[0144] [Contact with titanium compound, secondary firing] Crystal (C1-3) was obtained in the same manner as in Example 1, except that Crystal (C1-2) was used instead of Crystal (1-2).

[0145] [Example 4] [Step 1: Preparation of aluminosilicate] 7.81 g of an 8 mol / L NaOH aqueous solution, 8.09 g of an 8 mol / L KOH aqueous solution, 20.3 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 31.8 g of colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich (SiO content: 40% by mass)) were placed in a container and stirred at 80°C to obtain a sol-like substance, to which 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.00. The contents were heated at 165°C for 40 hours using the same autoclave as above. The cooled mixture was then filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (4-0).

[0146] The highest peak in the 17.5 to 35° region measured by XRD of the crystal (4-0) was observed at 21.6°, and the intensity ratio to the highest peak observed at 25.78° in the 25.0 to 27.0° region was 4.39. The XRD chart is shown in Figure 2. The crystal (4-0) was calcined at 550°C for 10 hours to obtain a crystal (4-1).

[0147] [Second step: contact with acid, third step: primary calcination] 2 g of the prepared crystal (4-1) and 80 g of 65% nitric acid were mixed in a container, and the mixture was then placed in an autoclave and heated at 148°C for 24 hours. The cooled mixture was filtered, washed with water, air-dried for one day, and then primarily calcined at 600°C for two hours to obtain crystal (4-2).

[0148] [Fourth step: contact with titanium compound, secondary calcination] 1 g of the prepared crystal (4-2) and 5 g of a titanium tetrachloride aqueous solution with a Ti concentration of 16% were placed in a container and heated and stirred at 40°C for 1 hour using an oil bath. Water was then added, the mixture was filtered, washed, and the dried product was subjected to secondary calcination at 650°C for 2 hours to obtain a crystalline porous aluminotitanosilicate (crystal (4-3)). The A

[0300] of the crystal (4-3) was 0.755, the A

[0210] was 2.873, and the A

[0300] / A

[0210] ratio was 0.246.

[0149] [Example 5] Crystal (5-0), Crystal (5-1), Crystal (5-2), and crystalline porous aluminotitanosilicate (Crystal (5-3)) were obtained in the same manner as in Example 4, except that in the first step, 31.94 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO content: 40% by mass)) was used, the stirring time was adjusted so that the HMR value was 5.00, and the contents were heated at 150°C using an autoclave for 100 hours. The XRD chart of Crystal (5-0) is shown in Figure 2. The A

[0300] of Crystal (5-3) was 0.083, the A

[0210] was 1.676, and the A

[0300] / A

[0210] value was 0.050.

[0150] [Example 6] Crystal (6-0), Crystal (6-1), Crystal (6-2), and crystalline porous aluminotitanosilicate (Crystal (6-3)) were obtained in the same manner as in Example 4, except that in the first step, 31.8 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO content: 40% by mass)) was used, the stirring time was adjusted so that the HMR value was 5.00, and the contents were heated at 150°C for 120 hours using an autoclave. The XRD chart of Crystal (6-0) is shown in Figure 2. The A

[0300] of Crystal (6-3) was 0.131, the A

[0210] was 1.975, and the A

[0300] / A

[0210] value was 0.066.

[0151] [Example 7] [Preparation of Crystal (A7)] Crystals (A7) having an MSE framework were prepared by the following method. First, 15.62 g of an 8 mol / L NaOH aqueous solution, 16.24 g of an 8 mol / L KOH aqueous solution, 40.60 g of a 40 wt % dimethyldipropylammonium hydroxide aqueous solution, and 67.23 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO content: 40 mass%)) were placed in a container and stirred at 80°C to obtain a sol-like substance.

[0152] Next, 13.56 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained sol-like substance and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.00. The mixture was then placed in an autoclave and heated at 165°C for 40 hours. The cooled mixture was filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (A7). The highest diffraction peak measured by XRD was observed at 21.58°.

[0153] [Step 1: Preparation of aluminosilicate] Next, 7.82 g of an 8 mol / L NaOH aqueous solution, 8.17 g of an 8 mol / L KOH aqueous solution, 24.36 g of a 40 wt % dimethyldipropylammonium hydroxide aqueous solution, and 35.38 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich (SiO content: 40 mass%)) were placed in a container and stirred at 80°C to obtain a sol-like substance, to which 0.79 g of the crystals (A7) and 6.79 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed.

[0154] The stirring time was adjusted so that the HMR value at this stage was 6.50. The mixture was then placed in an autoclave and heated at 150°C for 68 hours. The cooled mixture was then filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (7-0).

[0155] The highest peak in the 17.5 to 35° region measured by XRD of the above crystal (7-0) was observed at 21.58°, and the intensity ratio to the highest peak observed at 26.08° in the 25.0 to 27.0° region was 4.490. The XRD chart is shown in Figure 2. The above crystal (7-0) was calcined at 550°C for 10 hours to obtain crystal (7-1).

[0156] [Second step: contact with acid, third step: primary calcination] Crystal (7-2) was obtained in the same manner as in Example 1, except that Crystal (7-1) was used instead of Crystal (1-1).

[0157] [Fourth step: contact with titanium compound, secondary calcination] A crystal (7-3) was obtained in the same manner as in Example 1, except that the crystal (7-2) was used instead of the crystal (1-2). The A

[0300] of the crystal (7-3) was 0.102, the A

[0210] was 2.215, and the value of A

[0300] / A

[0210] was 0.046.

[0158] [Example 8] [Step 1: Preparation of aluminosilicate] 7.81 g of an 8 mol / L NaOH aqueous solution, 8.11 g of an 8 mol / L KOH aqueous solution, 20.35 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 33.57 g of colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich (SiO content: 40% by mass)) were placed in a container and stirred at 80°C to obtain a sol-like substance. 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was then added and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.00. The contents were heated at 150°C for 90 hours using the same autoclave as above. The cooled mixture was then filtered, washed with water, and vacuum-dried at 70°C for 2 hours to obtain crystals (8-0).

[0159] The highest peak in the 17.5 to 35° region measured by XRD of the above crystal (8-0) was observed at 21.64°, and the intensity ratio to the highest peak observed at 25.76° in the 25.0 to 27.0° region was 3.54. The XRD chart is shown in Figure 2. The above crystal (8-0) was calcined at 550°C for 10 hours to obtain crystal (8-1).

[0160] [Second step: contact with acid, third step: primary calcination] Crystal (8-2) was obtained in the same manner as in Example 4, except that Crystal (8-1) was used instead of Crystal (4-1).

[0161] [Fourth step: contact with titanium compound, secondary calcination] A crystal (8-3) was obtained in the same manner as in Example 5, except that the crystal (8-2) was used instead of the crystal (4-2). The A

[0300] of the crystal (8-3) was 0.086, the A

[0210] was 1.682, and the value of A

[0300] / A

[0210] was 0.051.

[0162] [Evaluation of catalytic performance] The performance of the crystalline porous aluminotitanosilicates of Examples 1 to 8 and Comparative Example 1 as catalysts for producing hydroquinone was evaluated below. The results are summarized in Tables 1 and 2. In the tables, HQ represents hydroquinone and CL represents catechol. The measurement methods and calculation formulas for each value are shown below.

[0163] [Measurement method] A 50 ml flask equipped with a condenser, thermometer, feed pump, and magnetic stirrer tip was charged with 0.2 g of each catalyst, 4.2 g of phenol, 3.0 g of t-butyl alcohol, and 6.0 g of water, and heated to 50°C in a water bath while stirring with a stirrer. 0.5 g of 34% hydrogen peroxide was added dropwise from the feed pump over 10 minutes, and the mixture was maintained for 60 minutes. After cooling the reaction solution, the catalyst was filtered off, and a portion of the reaction solution was taken and the product was quantified by gas chromatography.

[0164] The analytical conditions for gas chromatography are as follows. Detector: Hydrogen flame ion detector Column: DB-5 (Agilent J&W), inner diameter 0.25 mm, length 60 m, film thickness 0.25 μm Column temperature: 50°C for 10 minutes, then increase the temperature at 10°C / min to 280°C ·Inlet; 280℃ Detector temperature: 280℃ Carrier gas: Helium ·Flow rate; 80ml / min

[0165] (Calculation formula)

[0166] The hydroquinone yield is determined by calculation according to the following formula. Hydroquinone yield (%) = (hydrogen peroxide utilization efficiency) × (moles of hydroquinone produced) / (moles of hydroquinone produced) + (moles of catechol produced) × 100

[0167] Hydroquinone / catechol ratio = (moles of hydroquinone produced) / (moles of catechol produced)

[0168] [Table 1]

[0169] [Table 2]

[0170] Tables 1 and 2 show that the aluminotitanosilicate prepared by the method for producing a modified aluminosilicate satisfying the requirement [1] of the present invention exhibits a high hydroquinone yield and high hydroquinone selectivity. Furthermore, since sol-like silica can be used during the process, the modified aluminosilicate can be produced by an industrially advantageous method.

[0171] Furthermore, it is found that the use of modified aluminosilicates exhibiting a specific [A300] / [A210] range results in a very high HQ yield.

Claims

1. A liquid is prepared by contacting water-containing sol-state silica with a metal compound (AL) containing aluminum and oxygen; The molar ratio of water to silica in the liquid (H 2 O / SiO 2 a first step of obtaining an aluminosilicate having a % HMR (Hydroxymethylsilane) in the range of 0.1 to 8.0; a second step of treating the aluminosilicate obtained in the first step with an acid; a third step of primarily firing the treated product obtained in the second step at 550°C to 850°C; a fourth step of contacting the fired product obtained in the third step with a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, followed by drying and secondary firing.

2. 2. The method for producing a modified aluminosilicate according to claim 1, wherein the HMR is in the range of 3.0 to 6.

6.

3. 2. The method for producing a modified aluminosilicate according to claim 1, wherein the metal compound (AL) containing aluminum and oxygen is a zeolite.

4. 2. The method for producing a modified aluminosilicate according to claim 1, further comprising the step of removing a portion of the water in the first step.

5. The first step comprises preparing a liquid in which a water-containing sol of silica is brought into contact with a zeolite, and then A part of the water in the liquid is removed to obtain a water to silica molar ratio (H 2 O / SiO 2 2. The method for producing a modified aluminosilicate according to claim 1, wherein an aluminosilicate having a % HMR (Hydrogen-Reducing Ratio) is obtained in the range of 0.1 to 8.

0.

6. A method for producing a catalyst for producing aromatic polyhydroxide compounds, which comprises the modified aluminosilicate according to claim 1.

7. A method for producing a catalyst for producing aromatic polyhydroxide compounds, which contains the modified aluminosilicate according to claim 5.

8. A method for producing an aromatic polyhydroxide compound, comprising the step of reacting an aromatic hydroxide with a hydroperoxide in the presence of the catalyst according to claim 6.

9. A method for producing an aromatic polyhydroxide compound, comprising the step of reacting an aromatic hydroxide with a hydroperoxide in the presence of the catalyst according to claim 7.

10. A modified aluminosilicate having a ratio (A[300] / A[210]) of the absorbance at 300 nm (A[300]) in the ultraviolet-visible absorption spectrum to the absorbance at 210 nm (A[210]) in the ultraviolet-visible absorption spectrum, measured by filling 0.1 g of the sample into a cell with an optical path length of 10 mm, of 0.045 or more and 0.070 or less.

11. The modified aluminosilicate according to claim 10, which is measured using a UV-2550 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation.

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