Title of the invention: Method for producing modified aluminosilicate, method for producing modified aluminosilicate and aromatic dihydroxy compound using the same.
Technical field
[0001]
　The present invention relates to a method for producing a modified aluminosilicate, a modified aluminosilicate, and a method for producing an aromatic dihydroxy compound using the modified aluminosilicate.
Background technology
[0002]
　Aromatic dihydroxy compounds are important as various organic synthetic intermediates or raw materials, and are used in the fields of reducing agents, rubber drugs, dyes, pharmaceuticals, pesticides, polymerization inhibitors, oxidation inhibitors and the like.
　The aromatic dihydroxy compound obtained by reacting phenols with hydrogen peroxide is, for example, hydroquinone or catechol, and the production ratio of hydroquinone and catechol differs depending on the production method. In recent years, from the demand balance between hydroquinone and catechol, a method for producing hydroquinone with high selectivity has been desired.
[0003]
　A method of using titanosilicate, which is one of the crystalline porous silicates, as a catalyst for reacting phenols with hydrogen peroxide to produce an aromatic dihydroxy compound has been disclosed (for example, Patent Document 1, Patent Document 1, Patent Document 2). Further, Patent Document 3 discloses a titanosilicate obtained by treating an acid-treated aluminosilicate with a vapor phase titanium chloride or titanium alkoxide.
[0004]
　Further, Patent Document 4 is obtained by mixing aluminosilicate mold raw material, an aluminum source, a titanium source, a silicon source, an iodide, and water to prepare a gel, heating the gel to crystallize it, and then firing the gel. Discloses a method for producing titanosilicate.
Prior art literature
Patent documents
[0005]
Patent Document 1: Japanese Patent Application Laid-Open No. 425409
Patent Document 2: International Patent Publication
No. 2015/041137 Japanese Patent Document 3: Japanese Patent Application Laid-Open No. 2008-050186
Patent Document 4: Japanese Patent Application Laid-Open No. 2017-057626
Outline of the invention
Problems to be solved by the invention
[0006]
　In Patent Document 3, since the vapor phase titanium tetrachloride is used, it is highly corrosive and easily leaks, so that there is a problem in industrial production. For example, it is considered that corrosiveness and leakage can be improved by devising the material of the device, but there is a concern that the device becomes expensive and the fixed cost increases.
　In Patent Document 4, a template raw material for aluminosilicate and a titanium source or the like are mixed with water to directly synthesize titanosilicate, and in the presence of this titanosilicate, phenol and hydrogen peroxide are reacted. .. In this reaction result, the yield of hydroquinone seemed to be insufficient from the viewpoint of commercialization.
[0007]
　An object of the present invention is to provide a method for producing a modified aluminosilicate, which can highly selectively produce hydroquinones by reacting phenols with hydrogen peroxide under industrially advantageous conditions. Another object of the present invention is to provide a catalyst capable of highly selectively producing hydroquinones by reacting phenols with hydrogen peroxide under industrially advantageous conditions, and a method for producing an aromatic dihydroxy compound using the catalyst. There is.
Means to solve problems
[0008]
　As a result of investigating the above problems, the present inventors have fired an acid-treated aluminosilicate, preferably an acid-treated crystalline porous aluminosilicate under specific conditions, and then, 4 in the periodic table. A liquid containing one or more elements selected from Group 5 and Group 5 elements, for example, a liquid phase titanium source is brought into contact with each other, and further dried and calcined to produce a modified aluminosilicate capable of highly selectively producing hydroquinones. He found what he could do and came to complete the first invention. Further, the aromatic dihydroxy compound (for example, hydroquinones) is increased by reacting phenols with hydrogen peroxide in the presence of a specific aluminosilicate having a specific ultraviolet-visible spectrum, preferably a crystalline porous aluminosilicate. They found that they could be selectively produced, and completed the second invention.
[0009]
　That is, the present invention includes the matters described in the following [1] to [16].
[1] A first step of treating ammonium silicate with an acid, a second step of primary firing the processed product obtained in the first step at 550 ° C to 850 ° C, and a fired product obtained in the second step. And a liquid containing one or more elements selected from the group consisting of Group 4 and Group 5 elements in the periodic table, followed by a third step of drying and secondary firing. How to make a silicate.
[2] The method for producing a modified aluminosilicate according to [1], wherein the aluminosilicate is a crystalline porous aluminosilicate.
[3] The method for producing a modified aluminosilicate according to [1], wherein the liquid containing the element is a liquid containing one or more elements selected from the group consisting of Group 4 elements.
[4] The method for producing a modified aluminosilicate according to [1], wherein the liquid containing the element is a liquid containing titanium.
[5] Production of the modified aluminosilicate according to [4], wherein the liquid containing titanium is at least one selected from the group consisting of titanium tetrachloride, an aqueous solution of titanium tetrachloride, an aqueous solution of titanium trichloride, and an aqueous solution of titanium sulfate. Method.
[6] The method for producing a modified aluminosilicate according to [2], wherein the crystalline porous aluminosilicate has an MSE skeleton.
[7] The method for producing a modified aluminosilicate according to [6], wherein the crystalline porous aluminosilicate having an MSE skeleton is one or more selected from the group consisting of UZM-35, MCM-68 and YNU-3.
[8] A modified alumino containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements in the periodic table, and exhibiting an absorbance (A [300]) at 300 nm in the ultraviolet-visible spectrum of 1.0 or more. Silicate.
[9] The ratio (A [300] / A [210]) of the absorbance (A [300]) at 300 nm of the ultraviolet-visible spectrum to the absorbance (A [210]) at 210 nm of the ultraviolet-visible spectrum is 0.5 or more. The modified aluminosilicate according to [8].
[10] The modified aluminosilicate according to [8], which has crystallinity and porosity.
[11] The modified aluminosilicate according to [10], which has an MSE skeleton.
[12] The modified aluminosilicate according to [8], wherein the element is one or more elements selected from Group 4 elements.
[13] The modified aluminosilicate according to [8], wherein the element is titanium.
[14] The modified aluminosilicate according to [13], wherein the molar ratio of silicon to titanium ([Si] / [Ti]) is in the range of 0.1 to 100.
[15] A catalyst for producing an aromatic dihydroxy compound containing the modified aluminosilicate according to [8].
[16] A method for producing an aromatic dihydroxy compound, which comprises a step of reacting phenols with hydrogen peroxide in the presence of the catalyst for producing an aromatic dihydroxy compound according to [15].
The invention's effect
[0010]
　According to the method for producing modified aluminosilicate of the first invention, a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table with less risk of leakage, for example, a liquid phase. It has become possible to produce modified aluminosilicates using titanium sources, which has industrial significance. Further, by using the modified aluminosilicate produced by the above production method, an aromatic dihydroxy compound such as hydroquinone can be highly selectively produced by reacting phenols with hydrogen peroxide.
　According to the aluminosilicate of the second invention and the method for producing an aromatic dihydroxy compound using the aluminosilicate as a catalyst, an aromatic dihydroxy compound (for example, hydroquinone) is highly selectively produced by the reaction of phenols and hydrogen peroxide. be able to.
A brief description of the drawing
[0011]
FIG. 1 is a graph showing the absorbance of crystalline porous aluminotitanosilicate. The horizontal axis shows the wavelength (nm), and the vertical axis shows the absorbance.
[Fig. 2] Fig. 2 is a chart showing the results of X-ray diffraction measurement of aluminotitanosilicate of Example 1 and Patent Document 3.
Mode for carrying out the invention
[0012]
Hereinafter, embodiments according to the present invention will be described in detail.

First, the first invention, modification considered to replace a part of aluminum of aluminosilicate with one or more elements selected from Group 4 and Group 5 elements of the periodic table. A method for producing an aluminosilicate will be described. Here, it is preferable that the aluminosilicate used as a raw material does not contain the elements of Group 4 and Group 5, or even if they are contained, the effect of the present invention is not affected. Examples of the Group 4 element include titanium, zirconium, and hafnium. Examples of the Group 5 element include vanadium and the like. Among these elements, Group 4 elements are preferable, titanium, zirconium, and hafnium are more preferable, and titanium is even more preferable. The above-mentioned elements may be used alone or in combination of two or more.
[0013]
(First step) In
　the first step, the aluminosilicate is treated with an acid. The aluminosilicate is preferably crystalline, preferably porous, and more preferably crystalline porous. Hereinafter, the crystalline and porous aluminosilicate is simply referred to as a crystalline porous aluminosilicate. Crystallinity can be determined from a known diffraction pattern by X-ray measurement. The crystalline aluminosilicate preferably has the following structure.
　As the aluminosilicate, preferably, a SiO 4 tetrahedron in which oxygen is arranged at four vertices centered on silicon and an AlO 4 tetrahedron in which aluminum is arranged instead of silicon in the center are regularly three-dimensionally bonded. It is a porous crystal having at least a part of the formed portion. More specifically, zeolite can be mentioned as the crystalline porous aluminosilicate.
[0014]
　The crystalline aluminosilicate preferably used in the present invention is not particularly limited as long as it has the above structure, but in the structure code of the International Zeolite Association, it has an MSE-type structure (hereinafter referred to as the present specification). A crystalline porous aluminosilicate having (referred to as “MSE skeleton”) is preferable, and UZM-35, MCM-68, YNU-3 and the like are particularly preferable.
　In the method for producing a modified aluminosilicate of the present invention, it can be considered that a specific element is introduced mainly on the solid surface of the raw material aluminosilicate, so that the crystallinity of the raw material aluminosilicate is , Almost can be considered to be maintained in the modified aluminosilicate of the final product.
[0015]
　The crystalline porous aluminosilicate having the MSE skeleton has a three-dimensional pore structure having a 10-membered ring structure consisting of 10 tetrahedral units and a 12-membered ring structure consisting of 12 tetrahedral units. Has. Since the pores have the 12-membered ring structure, it is considered that the substrate can be easily diffused into the pores and high catalytic activity can be obtained. In addition, since there are no large cavities inside the pores, it is considered to exhibit para-position selectivity in the oxidation reaction of phenol.
[0016]
　The crystalline porous aluminosilicate having an MSE skeleton can be a commercially available product or can be produced by a conventionally known method.
　For example, UZM-35 is heated by adding dimethyldipropylammonium hydroxide, which is an organic structure regulating agent, an alkali source and a silicon source, and stirring the mixture. Further, it can be produced by a method of adding seed crystals and FAU-type zeolite to a raw material and heating the mixture.
[0017]
　The use of seed crystals promotes crystal growth during synthesis. The amount of the seed crystal added is preferably 1 to 40% by weight, preferably 2 to 30% by weight in the charged silicon source. Further, the FAU-type zeolite is added as a silicon source and an aluminum source, and the addition amount is preferably 5 to 50% by weight, more preferably 8 to 40% by weight.
[0018]
　Here, the seed crystal is not particularly limited as long as it is a crystalline porous aluminosilicate, but a material having the same crystal structure as the modified aluminosilicate which is a product can be particularly preferably used. Specifically, the crystalline porous aluminotitanosilicate when one or more elements selected from the Group 4 and Group 5 elements of the periodic table, which is a preferred embodiment of the modified aluminosilicate of the present invention, is titanium. When having an MSE skeleton, a material having a UZM-35, MCM-68 or YNU-3 structure can be preferably used as a seed crystal.
[0019]
　Further, regarding the crystallinity of the seed crystal, a substance having a low crystallinity can be used. The crystallinity of the seed crystal is not particularly limited, but is preferably 30 to 90%. Here, the crystallinity is obtained from the integrated intensity ratio of X-ray structural diffraction, and is expressed as a relative ratio of the integrated intensity when the crystalline porous aluminosilicate is set to 100.
[0020]
　MCM-68 is, for example, a mixture of a silicon source, an aluminum source, and an alkali source, and N, N, N', N'-tetraethylbicyclo [2,2,2] octa-7-, which are organic structure regulators. It can be produced by adding En-2,3: 5,6-dipyrrolidinium diiodide, stirring well, and heating.
[0021]
　YNU-3 is added, for example, to a mixture of N, N, N', N'-tetraethylbicyclo [2,2,2] octa-7-en-2,3: 5,6-dipyrrolidinium diiodide and an alkali source, and MCM. It can be produced by a method of adding −68 seed crystals, stirring, adding FAU-type zeolite to the mixture, and heating.
[0022]
　Examples of the silicon source include silica, colloidal silica, sodium silicate, wet silica, and dry silica. These silicon sources can be used alone or in combination of two or more.
[0023]
　As the aluminum source, for example, a water-soluble aluminum compound can be used. Examples of the water-soluble aluminum compound include aluminum hydroxide, sodium aluminate, aluminum nitrate, aluminum sulfate and the like. These aluminum sources can be used alone or in combination of two or more.
[0024]
　As the alkali source, for example, a hydroxide containing an alkali metal can be used. Examples of the hydroxide containing an alkali metal include sodium hydroxide and potassium hydroxide. These alkaline sources can be used alone or in combination of two or more.
[0025]
　Examples of the acid used in the first step include inorganic acids, organic acids and mixtures thereof, and specific examples thereof include nitric acid, hydrochloric acid, sulfuric acid, citric acid, oxalic acid and mixtures thereof. Can be mentioned. Among these, acids containing elements selected from Group 15 and Group 16 elements of the periodic table are preferable, and nitric acid is particularly preferable. The concentration of the acid is not particularly limited, but is preferably 5% by weight to 80% by weight, more preferably 40% by weight to 80% by weight. When this acid is used as an aqueous solution, the amount used is preferably 10 to 100 parts by weight, more preferably 20 to 100 parts by weight, based on 1 part by weight of the crystalline porous aluminosilicate.
[0026]
　The temperature condition for treating with the acid is preferably 50 ° C to 170 ° C, more preferably 130 ° C to 170 ° C. The time for treating with acid is preferably 5 hours to 48 hours, more preferably 12 hours to 36 hours. A more preferred lower limit of time is 18 hours. This acid treatment removes some of the aluminum from the aluminosilicate. It is presumed that mainly the aluminum on the surface of the aluminosilicate is removed. It is presumed that the treatment at a relatively high temperature for a long time as described above makes it easier to form a structure advantageous for introducing the Group 4 element and the Group 5 element in the firing step in the second step described later. Will be done.
[0027]
(Second step) In
　the second step, the primary firing of the processed product with the acid obtained in the first step is performed. The method of firing is not particularly limited, and examples thereof include a method of firing using an electric furnace, a gas furnace, or the like. As the firing conditions, it is preferable to heat in the atmosphere for 0.1 to 20 hours. The firing temperature is 550 ° C to 850 ° C, more preferably 600 ° C to 800 ° C. It is presumed that the primary firing in this relatively high temperature environment will provide an environment favorable for the formation of modified aluminosilicates, which contains Group 4 elements and Group 5 elements represented by titanium species, in a highly active state. Will be done.
[0028]
　Before firing the treated product with the acid, it is preferable to filter the treated product with Nutche or the like to separate the acid (aqueous solution) used, and then wash the filtered product with water and dry it. It is preferable that the cleaning step is performed while maintaining a wet state without drying. The drying method is not particularly limited, but it is preferable to dry uniformly and quickly. For example, an external heating method such as hot air drying or superheated steam drying, or an electromagnetic wave heating method such as microwave heating drying or high frequency dielectric heating drying. Can be used.
[0029]
(Third step) In
　the third step, the primary fired product obtained in the second step and a liquid containing one or more elements selected from Group 4 and Group 5 elements in the periodic table are used as element sources. Contact is performed in a liquid phase state, and drying and secondary firing are performed. Hereinafter, an embodiment used as a liquid containing titanium (a titanium source of a liquid phase), which is the most preferable embodiment, will be described as a representative example.
　The titanium source of the liquid phase is a titanium-containing liquid. Examples of the titanium-containing liquid include a liquid titanium compound itself, an aqueous solution of the titanium compound, and the like. Of these, a titanium compound that is substantially acidic in a liquid state is preferable.
　Examples of the liquid titanium compound include titanium tetrachloride (TiCl 4 ) and tert-butoxy titanium tetrachloride, and among them, titanium tetrachloride is preferable. Examples of the aqueous solution of the titanium compound include an aqueous solution of titanium tetrachloride, an aqueous solution of titanium trichloride (TiCl 3 ), and a titanium sulfate (Ti (SO 4 ) 2 ). ) Aqueous solution, potassium hexafluorotitate aqueous solution and the like, and among them, titanium tetrachloride aqueous solution, titanium trichloride aqueous solution and titanium sulfate aqueous solution are preferable. In the present invention, the catalytic activity described later can be exhibited even when a less reactive titanium source such as titanium trichloride or titanium sulfate is used in addition to titanium tetrachloride. In addition, these titanium-containing liquids can be used alone or in combination of two or more. As the titanium-containing liquid, a commercially available product can be used, or a solid titanium compound diluted with water to a desired concentration and appropriately prepared can be used. Compared to the gas phase titanium source, the liquid phase titanium source (liquid containing titanium) is less likely to leak, and the problem of corrosion to manufacturing machines and analytical instruments is also improved, so industrial manufacturing is carried out. It will be easier.
[0030]
　The conditions for adding the titanium source to the primary fired product are not particularly limited, but it is preferable that titanium is supported on the crystalline porous aluminosilicate, for example, a condition in which a part of aluminum can be replaced with titanium. For example, when the liquid titanium compound itself is used, it is preferable to add 5 to 300 parts by weight, and more preferably 20 to 250 parts by weight, of the liquid titanium compound per 1 g of the primary fired product. When an aqueous solution of the titanium compound is used, it is preferable to add 1 to 10 parts by weight of the aqueous solution of the titanium compound, and more preferably 1 to 7 parts by weight, per 1 part by weight of the primary fired product. The concentration of the aqueous solution varies depending on the compound used, but is, for example, 10 to 70% by weight, preferably 15 to 60% by weight.
　As for the amount of the titanium compound in the aqueous solution, the preferable lower limit value per 1 g of the primary fired product is 0.1 g, more preferably 0.2 g, still more preferably 0.3 g, and particularly preferably 0.5 g. On the other hand, the preferable upper limit value is 10 g, more preferably 5 g, and further preferably 3 g.
[0031]
　When the titanium source is added, if the total addition amount is within the range of the addition amount, the titanium source may be added at once, or the third step may be repeated and added in a plurality of times. For example, a titanium source may be added to the primary fired product, and the titanium source may be added again to the fired product obtained by drying and secondary firing described later to perform drying and secondary firing. When the titanium source is added, hydrogen chloride is generated by the reaction between the moisture in the air and the titanium compound, so it is preferable to add it in a nitrogen atmosphere.
[0032]
　After the primary fired product and the added titanium source are well mixed, the mixture is heat-treated or sufficiently dried by the same method as the drying method in the second step, and then the secondary fired product is performed. The temperature in the heat treatment and drying steps is not particularly limited, but for example, in order to effectively introduce titanium into aluminosilicate, the temperature is preferably in the range of 20 to 150 ° C. A more preferable lower limit value is 30 ° C., more preferably 40 ° C., and particularly preferably 50 ° C. On the other hand, a more preferable upper limit value is 140 ° C., more preferably 120 ° C., and particularly preferably 100 ° C. The time required for the above step is not particularly limited, but is preferably 0.1 to 24 hours. A more preferable lower limit is 0.3 hours, more preferably 0.4 hours, and particularly preferably 0.5 hours. On the other hand, a more preferable upper limit value is 12 hours, more preferably 6 hours. The method for secondary firing is not particularly limited, and for example, firing can be performed using an electric furnace, a gas furnace, or the like. The firing conditions are 400 ° C. or higher and 800 ° C. or lower for 0.1 to 20 hours in the atmosphere. By this step, it is possible to obtain a crystalline porous aluminosilicate in which a part of aluminum in the crystalline porous aluminosilicate is considered to be replaced with titanium.
[0033]
　Before performing the above drying step, the mixture of the titanium source and the primary calcined product is heated to preliminarily remove water, the mixture is filtered to remove impurities, and the cleaning operation is performed with an organic solvent. It may be fired.
　The above manufacturing conditions can be applied mutatis mutandis to the case where an element other than titanium is used.
[0034]
　Examples of compounds containing Group 4 elements of the periodic table that can be used in place of the titanium source include zirconium tetrachloride, tetraalkoxyzirconium, hafnium tetrachloride, tetraalkoxyhafnium, zirconium sulfate and the like, if necessary. It can be liquefied and used in combination with water, alcohol, ether and the like. Examples thereof include aqueous solutions of these compounds and solutions of alcohols, ethers and the like. In addition, as Group 5 elements of the periodic table that can be used in place of the titanium source, vanadium pentachloride, vanadium sulfate, vanadyl trichloride and its alkoxy substituents are also used as necessary, such as water, alcohol and ether. Can be used in combination with liquefaction. For example, those aqueous solutions and solutions such as alcohol and ether can be mentioned.
[0035]
　Like the raw material aluminosilicate, the modified aluminosilicate of the present invention preferably has crystalline property and is preferably porous. Crystallinity may be considered to be the same as the description of aluminosilicate as a raw material.
　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 / g. The lower limit of the specific surface area is more preferably 100 m 2 / g, still more preferably 150 m 2 / g. On the other hand, the upper limit of the specific surface area is more preferably 800 m 2 / g, still more preferably 600 m 2 / g.
　The above specific surface area value is a known calculation method based on the BET theory by creating a BET plot from the measurement results using a known nitrogen adsorption / desorption measuring device method (for example, BELSORP-max manufactured by Microtrac BEL). Can be determined by.
　The preferred pore volume range of the modified aluminosilicate of the present invention is 0.1 to 0.5 cm 3 / g, more preferably 0.2 to 0.4 cm 3 / g.
[0036]

　Next, in the ultraviolet-visible absorption spectrum measurement, which is the second invention of the present invention, a modified aluminosilicate characterized by absorption in a specific wavelength region will be described.
[0037]
　The modified aluminosilicate in the present invention contains an element selected from the group consisting of Group 4 elements and Group 5 elements in the periodic table, and exhibits an absorbance (A [300]) of 1.0 or more at 300 nm in the ultraviolet-visible spectrum. The description of specific examples and preferred examples of the elements selected from the Group 4 and Group 5 elements contained in the modified aluminosilicate of the present invention is the same as the method for producing the modified aluminosilicate of the first invention.
[0038]
　The modified aluminosilicate of the present invention preferably has crystallinity and porosity. The modified aluminosilicate having crystallinity and porosity preferably has an MSE skeleton. Crystallinity and porosity are the same as those described in the first invention.
　The modified aluminosilicate of the present invention is preferably a crystalline porous aluminosilicate obtained by a method such as replacing a part of aluminum contained in the crystalline porous aluminosilicate having crystalline and porous properties with titanium.
[0039]
　In the above-mentioned crystalline porous aluminosilicate, a SiO 4 tetrahedron in which oxygen is arranged at four apexes centered on silicon and an AlO 4 tetrahedron in which aluminum is arranged instead of silicon in the center are regularly three-dimensional. It is a porous crystal having at least a bonded portion, and is typically a type of zeolite containing aluminosilicate. The modified aluminosilicate having crystalline and porous properties preferably contains aluminum in the crystalline porous aluminosilicate skeleton and one or more elements selected from the group consisting of Group 4 elements and Group 5 elements in the periodic table. Is obtained by a method in which a part of aluminum in the crystalline porous aluminosilicate skeleton is replaced with one or more elements selected from the group consisting of Group 4 elements and Group 5 elements in the periodic table. For example, when one or more elements selected from the group consisting of Group 4 elements and Group 5 elements in the periodic table is titanium, the modified aluminosilicate of the crystalline porous material is a crystalline porous aluminotitanosilicate. The crystalline porous aluminum notitanosilicate contains aluminum and titanium in the aluminosilicate skeleton, and is preferably obtained by a method such as replacing a part of aluminum in the skeleton with titanium.
[0040]
　The content of Group 4 elements and Group 5 elements contained in the modified aluminosilicate of the present invention is not particularly limited. For example, when titanium is contained as one or more elements selected from the group consisting of Group 4 elements 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 100, more preferably in the range of 0.5 to 50, further preferably in the range of 1 to 30, and preferably in the range of 2 to 30. Most preferred.
　When a compound such as TiCl 3 that is easily crystallized by itself is used, the element may be introduced into the aluminosilicate surface in a cluster form or a crystal form. In this case, the apparent element content may increase, so the [Si] / [Ti] ratio tends to be a small value. The range of the [Si] / [Ti] ratio in such a case is preferably 0.5 to 30. A more preferable lower limit value is 1, and even more preferably 1.2. On the other hand, a more preferable upper limit value is 20, and even more preferably 15.
[0041]
　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, preferably in the range of 10 to 10000. It is more preferably in the range of 100 to 1000.
[0042]
　When A [300] is less than 1.0, the selectivity of the aromatic dihydroxy compound tends to be relatively low when the aromatic dihydroxy compound is produced by the reaction of phenols and hydrogen peroxide. The method for measuring the absorbance is not particularly limited, and the result may be the result of measurement by either the transmission method or the reflection method. When measuring by the reflection method, the reflected light may include diffusely reflected light and the like in addition to the specularly reflected light, but for convenience, all of them are assumed to be specularly reflected light.
[0043]
　Although the detailed mechanism is unknown, the present inventors speculate as follows (hereinafter, the crystalline porous aluminotitanosilicate in which the element selected from the above groups 4 and 5 is titanium). Explained as an example).
　It is presumed that aluminum and titanium are present on the skeleton surface of the crystalline porous aluminum notitanosilicate. Further, it is considered that these are preferably present mainly inside the recesses such as the pores of the crystalline porous aluminum notitanosilicate. Here, for example, it is considered that it contains only titanium that is produced by a method using high-temperature gaseous titanium tetrachloride as described in Patent Document 3 and is completely incorporated as a skeleton of a crystal structure without defects. In such an embodiment, it is presumed that the absorbance of the ultraviolet-visible spectrum near 300 nm is unlikely to be 1.0 or more. In other words, it is presumed that the crystalline porous aluminotitanosilicate that satisfies the requirements of the present invention contains many titaniums that are incompletely incorporated into the basic skeletal structure and have an unstable structure. Such titanium species greatly contribute to the formation reaction of aromatic dihydroxy compounds, and when the oxidation reaction of phenols with hydrogen peroxide proceeds, the instability of them causes 1,2 hydroxy, which is considered to be disadvantageous in terms of three-dimensional structure. It is presumed that the production of a compound (eg, catechol) and the production of benzoquinone, which is a more advanced form of the reaction, are suppressed, and that type 1 and 4 aromatic dihydroxy compounds can be produced with high selectivity.
[0044]
　From the viewpoint of further enhancing the selectivity of the aromatic dihydroxy compound, the preferable lower limit value of A [300] of the modified aluminosilicate is 1.5, more preferably 1.8. On the other hand, the setting of the upper limit value of A [300] has no essential meaning, but the preferable upper limit value is 15, and more preferably 10. Further, A [300] is 0.2 or less in the usual crystalline porous aluminum notitanosilicate.
[0045]
　The ratio of A [300] to the absorbance (A [210]) at 210 nm in the ultraviolet-visible spectrum (A [300] / A [210]) is preferably 0.5 or more, preferably 0.6 or more. It is more preferable, and 0.8 or more is most preferable. For example, when titanium is contained in the skeleton of the crystal structure without defects, A [210] is relatively higher than A [300], so that ordinary crystalline porous aluminum notitanosilicate usually contains A [300]. ] / A [210] is 0.1 or less. The upper limit of A [300] / A [210] has no particular meaning, but is preferably 1.5 and more preferably 1.0.
[0046]
　The modified aluminosilicate in the present invention is not particularly limited as long as it has the above-mentioned structure and further has the above-mentioned ultraviolet-visible spectral characteristics, but it has an MSE-type structure in the structural code of the International Zeolite Association. Crystalline porous aluminosilicates having (hereinafter referred to as “MSE skeleton” in the present specification) are preferable, and crystalline porous aluminosilicates having UZM-35, MCM-68, and YNU-3 structures are more preferable.
[0047]
　The crystalline porous aluminosilicate having the MSE skeleton has a three-dimensional pore structure having a 10-membered ring structure consisting of 10 tetrahedral units and a 12-membered ring structure consisting of 12 tetrahedral units. Has. Since the pores have the 12-membered ring structure, it is considered that the substrate can be easily diffused into the pores and high catalytic activity can be obtained. In addition, since there are no large cavities inside the pores, it is considered to exhibit para-position selectivity in the oxidation reaction of phenol.
[0048]
　The crystalline porous aluminosilicate having an MSE skeleton is preferably obtained by a method such as replacing the aluminum of the crystalline porous aluminosilicate having an MSE skeleton with an element selected from Group 4 and Group 5 of the periodic table. The element is preferably a Group 4 element, and particularly preferably titanium. The crystalline porous aluminosilicate having an MSE skeleton is the same as in the first invention.
[0049]
　Examples of the method for obtaining the modified aluminosilicate of the present invention include the method for producing the modified aluminosilicate of the first invention.
[0050]
(Method for Producing Aromatic Dihydroxy Compound) In
　the presence of the modified aluminosilicate obtained by the above-mentioned production method of the first invention or the modified aluminosilicate of the second invention, phenols and hydrogen peroxide are reacted to produce an aromatic dihydroxy compound. A method for producing a group dihydroxy compound will be described. The modified aluminosilicate of the second invention can be used without particular limitation as long as its ultraviolet-visible spectrum has an absorbance at 300 nm (A [300]) of 1.0 or more, and is preferably crystalline porous. It is a crystalline porous aluminosilicate obtained by a method such as replacing a part of aluminum contained in aluminosilicate with an element selected from Group 4 and Group 5 of the periodic table. The element is preferably a Group 4 element, and particularly preferably titanium.
[0051]
　The phenols used in the present invention mean unsubstituted phenol and substituted phenol. Here, examples of the substituted phenol include 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 and a hexyl group, or an alkylphenol substituted with a cycloalkyl group. Can be mentioned.
[0052]
　Examples of phenols include phenol, 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2-ethylphenol, 3-isopropylphenol, 2-butylphenol, 2- Cyclohexylphenol and the like can be mentioned, with phenol being preferred. When the phenols have substituents at both the 2- and 6-positions, the product is only a hydroquinone derivative.
[0053]
　Examples of the aromatic dihydroxy compound as a reaction product include hydroquinones (substituted or unsubstituted hydroquinone), catechols (substituted or unsubstituted catechol), and specific examples thereof include hydroquinone and catechol. , 2-Methylhydroquinone, 3-methylcatechol, 4-methylcatechol, 3-methylhydroquinone, 1,4-dimethylhydroquinone, 1,4-dimethylcatechol, 3,5-dimethylcatechol, 2,3-dimethylhydroquinone, 2, , 3-Dimethyl catechol and the like.
[0054]
　The modified aluminosilicate obtained in the present invention is used as a catalyst in producing an aromatic dihydroxy compound. As a catalyst filling method, various methods such as a fixed bed, a fluidized bed, a suspension bed, and a shelf fixed bed are adopted, and any method may be used. Further, the above-mentioned catalyst may be used as it is, or may be molded and used according to the catalyst filling method. As a method for molding a catalyst, extrusion molding, tableting molding, rolling granulation, spray granulation and the like are common. When the catalyst is used in the fixed floor method, extrusion molding or tableting molding is preferable. In the case of the suspension bed method, spray granulation is preferable. After spray granulation, drying or firing may be performed. 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. When it is 0.1 μm or more, it is preferable because it is easy to handle such as filtration of the catalyst, and when it is 1000 μm or less, it is preferable because the catalyst performance is good and the strength is strong.
[0055]
　The amount of the catalyst used is preferably 0.1 to 0.1 to the total mass of the reaction solution (the total mass of the liquid components in the reaction system and does not include the mass of the fixed components such as the catalyst). It is in the range of 30% by mass, more preferably 0.4 to 20% by mass. When it is 0.1% by mass or more, the reaction is completed in a short time and the productivity is improved, which is preferable. When it is 30% by mass or less, it is preferable because the amount of separated and recovered catalyst is small.
　When the modified aluminosilicate obtained by the production method of the first invention of the present invention or the modified aluminosilicate of the second invention is used as a catalyst of the aromatic dihydroxy compound production method, it can be combined with other components. For example, the siloxane compound described in Patent Document 1 and the specific alcohol compound described in Patent Document 2 can be mentioned. It is preferable to use such a component in a ratio such that the mass of the reaction solution is 5 to 90% by mass. More preferably, it is 8 to 90% by mass.
[0056]
　Further, hydrogen peroxide is preferably 0.01 or more and 1 or less in molar ratio with respect to phenols. The concentration of hydrogen peroxide used is not particularly limited, but a normal 30% aqueous solution may be used, or a higher concentration hydrogen peroxide solution may be used as it is or diluted with an inert solvent in the reaction system. May be used. Examples of the solvent used for dilution include alcohols and water. Hydrogen peroxide may be added all at once or gradually over time.
[0057]
　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 proceeds at temperatures other than this range, the above range is preferable from the viewpoint of improving productivity. The reaction pressure is not particularly limited.
[0058]
　The reaction method is not particularly limited, and the reaction may be carried out by any of a batch method, a semi-batch method, and a continuous method. In the case of continuous type, the reaction may be carried out in a suspension bed type uniform mixing tank, a fixed bed flow type plug flow type, or a plurality of reactors in series and / or in parallel. You may connect. The number of reactors is preferably 1 to 4 from the viewpoint of equipment cost. When a plurality of reactors are used, hydrogen peroxide may be added to them in a divided manner.
[0059]
　In order to obtain an aromatic dihydroxy compound from the reaction solution, the reaction solution or the separation solution containing the dihydroxy compound after separating the catalyst may be subjected to a purification treatment such as removing unreacted components and by-products. The purification treatment is preferably performed on this separation solution containing the aromatic dihydroxy compound after the catalyst has been separated.
[0060]
　The purification treatment method is not particularly limited, and specific examples thereof include oil-water separation, extraction, distillation, crystallization, and a combination thereof. The method and procedure of the purification treatment are not particularly limited, but for example, the separation solution containing the aromatic dihydroxy compound after separating the reaction solution and the catalyst can be purified by the following method.
[0061]
　When the reaction solution is separated into two phases, an oil phase and an aqueous phase, oil-water separation is possible. The oil-water separation removes the aqueous phase having a low dihydroxy compound content and recovers the oil phase. In this case, the separated aqueous phase may be extracted or distilled to recover the aromatic dihydroxy compound, or part or all of it may be used again in the reaction. Further, the catalyst separated in the catalyst separation step or the dried catalyst can be dispersed in the separated aqueous phase and supplied to the reactor. On the other hand, it is desirable that the oil phase is further refined by extraction, distillation, crystallization and the like.
[0062]
　Solvents such as 1-butanol, toluene, isopropyl ether and methyl isobutyl ketone are used for extraction. By combining the extraction and the oil-water separation, the oil-water separation can be efficiently performed. It is preferable that the extraction solvent is separated and recovered by a distillation column, recycled and used.
[0063]
　Distillation may be carried out on the reaction solution immediately after the catalyst separation, or may be carried out on the oil phase and the aqueous phase after the oil-water separation. Further, the extract may be distilled.
　When distilling the reaction solution immediately after the separation of the catalyst, it is preferable to first separate the light boiling components such as water and alcohols. Water and alcohols may be separated in separate distillation columns or in one distillation column.
[0064]
　After separating water and alcohols by the oil-water separation, extraction, distillation operation and the like described above, phenols may be recovered by the next distillation operation and used again in the reaction. If the recovered phenols contain water that cannot be completely separated, isopropyl ether or toluene can be added and removed by azeotropic distillation.
[0065]
　This azeotropic distillation can also be performed on water before recovery of phenols or liquid after separation of alcohols. The separated water may be used again for the reaction or may be used as wastewater. If the recovered phenols contain impurities such as reaction by-products other than water, they can be further separated by a distillation operation. If the impurity is a reaction by-product, benzoquinones, it can be resupplied to the reactor along with the phenols.
[0066]
　After the separation of the phenols, the components that are higher in boiling than the aromatic dihydroxy compound can be removed by distillation, and the hydroquinones and catechols can be separated by the following distillation operation. Further, the high boiling component, hydroquinones and catechols can be separated by one distillation operation by extracting the hydroquinones from the middle stage of the distillation column.
　Impurities can be removed from the obtained hydroquinones and catechols by distillation or crystallization, if necessary, to increase the purity.
　When, for example, phenol and hydrogen peroxide are reacted in the presence of the modified aluminosilicate according to the present invention, hydroquinone tends to be produced in a high yield. In addition, hydroquinone tends to be produced at a higher selectivity than catechol and benzoquinone. Therefore, it can be said that the modified aluminosilicate according to the present invention has high industrial value.
Example
[0067]
　Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
　(Preparation of UZM-35)
　UZM-35 having an MSE skeleton was prepared by the following method.
　First, 15.8 g of a 4.8 mmol / g NaOH aqueous solution, 15.9 g of a 4.7 mmol / g KOH aqueous solution, 31.5 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 55 g of colloidal silica (product name: LUDOX (registered trademark) AS-40 (manufactured by Sigma Aldrich) was placed in a container and stirred at 60 ° C. to obtain a gel-like substance.
[0068]
　Next, 10.2 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to 1.49 g of UZM-35 seed crystals and mixed with the obtained gel-like substance, and then the mixture was mixed. Was placed in an autoclave and heated at 160 ° C. for 68 hours. The cooled mixture was filtered, washed with water, air-dried for 1 day, and then calcined at 500 ° C. for 10 hours to obtain UZM-35.
　As the titanium tetrachloride, titanium tetrachloride aqueous solution, titanium trichloride aqueous solution, and titanium sulfate aqueous solution, commercially available reagents from the following manufacturers were used.
　Titanium tetrachloride: Kishida Chemical Co., Ltd.
　Titanium tetrachloride aqueous solution: Fuji Film Wako Pure
　Chemical Co., Ltd. Titanium trichloride aqueous solution: Kanto Chemical Co., Inc.
　Titanium sulfate aqueous solution: Kanto Chemical Co., Inc.
[0069]
(Example 1)
(Dealumination treatment of UZM-35 ) After adding
　3 g of UZM-35 prepared above and 120 g of 60% nitric acid to a container and mixing, the mixture is placed in an autoclave and heated at 148 ° C. for 24 hours. did. The cooled mixture was filtered, washed with water, air-dried for 1 day, and then first fired at 600 ° C. for 2 hours to desorb a part of aluminum in UZM-35 (hereinafter, "dealuminum-UZM-"). 35 ") was obtained.
[0070]
(Preparation of Ti-UZM-35 catalyst)
　Under a nitrogen atmosphere, 2 g of the dealuminum -UZM-35 obtained above was placed in a glass container, and 173 g (100 ml) of titanium tetrachloride was added thereto and mixed. , 120 ° C. for 1 hour. The cooled mixture was filtered, washed with toluene and hexane, and then degassed and dried. Then, secondary firing was performed at 600 ° C. for 2 hours, and a crystalline porous aluminum notitanosilicate (hereinafter, “Ti-UZM-35 catalyst”), which is considered to have been partially replaced with titanium in the aluminum of the dealuminum-UZM-35, was subjected to secondary firing. ") Was obtained. As a result of measurement by the nitrogen adsorption / desorption method described later, the specific surface area was 260 m 2 / g.
[0071]
(Example 2)
　1 g of dealuminum-UZM-35 prepared above was placed in a container and vacuum degassed at 60 ° C. for 1 hour using an evaporator. To this, 5 g of a 50% aqueous solution of titanium tetrachloride was added, and the mixture was degassed and dried at 70 ° C. for 1 hour. The dried product was secondarily calcined at 600 ° C. for 2 hours to obtain the Ti-UZM-35 catalyst of Example 2.
[0072]
(Example 3) Preparation was carried out under the same conditions as in Example 2 except that the 50% titanium tetrachloride aqueous solution was changed to a 20% titanium trichloride aqueous solution to obtain the Ti-UZM-35 catalyst of Example 3. It was.
[0073]
(Example 4)
　Preparation was carried out under the same conditions as in Example 2 except that the 50% titanium tetrachloride aqueous solution was changed to a 30% titanium sulfate aqueous solution to obtain the Ti-UZM-35 catalyst of Example 4. ..
[0074]
(Example 5)
　The Ti-UZM-35 of Example 5 was prepared under the same conditions as in Example 3 except that the primary firing temperature when preparing the dealuminum-UZM-35 was changed to 700 ° C. Obtained a catalyst.
[0075]
(Example 6)
　The Ti-UZM-35 of Example 6 was prepared under the same conditions as in Example 3 except that the primary firing temperature when preparing the dealuminum-UZM-35 was changed to 800 ° C. Obtained a catalyst.
[0076]
(Example 7)
　The Ti-UZM-35 catalyst of Example 7 was obtained by making preparations under the same conditions as in Example 3 except that the amount of 20% titanium trichloride aqueous solution used was 3 g. As a result of measurement by the nitrogen adsorption / desorption method, the specific surface area was 240 m 2 / g.
[0077]
(Example 8) The
　preparation was carried out under the same conditions as in Example 3 except that the amount of the 20% aqueous titanium trichloride solution used was 7 g, to obtain the Ti-UZM-35 catalyst of Example 8.
[0078]
(Example 9)
　1 g of the Ti-UZM-35 catalyst obtained in Example 3 was placed in a container and vacuum degassed at 60 ° C. for 1 hour using an evaporator. To this, 5 g of a 20% aqueous solution of titanium trichloride was added, and the mixture was degassed and dried at 70 ° C. for 1 hour. The dried product was secondarily calcined at 600 ° C. for 2 hours to obtain the Ti-UZM-35 catalyst of Example 9.
[0079]
(Example 10)
　The Ti-UZM-35 catalyst of Example 10 was obtained by preparing under the same conditions as in Example 3 except that the amount of the 20% aqueous titanium trichloride solution used was 1 g.
[0080]
(Comparative Example 1)
　Preparation was carried out under the same conditions as in Example 1 except that the primary firing temperature was 120 ° C., and the catalyst of Comparative Example 1 was obtained.
[0081]
(Comparative Example 2)
　The Ti-UZM-35 catalyst of Comparative Example 2 was prepared under the same conditions as in Example 3 except that the primary firing was not performed (naturally dried (air-dried) at 20 ° C.). Obtained.
[0082]
(Comparative Example 3) The
　preparation was carried out under the same conditions as in Example 3 except that the primary firing temperature was 400 ° C. to obtain the Ti-UZM-35 catalyst of Comparative Example 3.
[0083]
(Comparative Example 4)
　Preparation was performed under the same conditions as in Example 3 except that the primary firing temperature was set to 500 ° C. to obtain the Ti-UZM-35 catalyst of Comparative Example 4.
[0084]
(Comparative Example 5) The
　preparation was carried out under the same conditions as in Example 3 except that the primary firing temperature when preparing the dealuminum-UZM-35 was changed to 900 ° C. However, as a result of XRD measurement, the crystal structure of UZM-35 was broken, so that the desired Ti-UZM-35 catalyst could not be obtained.
[0085]
(Comparative Example 6) A
　catalyst was prepared by the same method as in Example 1 described in Patent Document 3.
[0086]
(Comparative Example 7) A
　catalyst was prepared by the same method as in Example 1 described in Patent Document 4.
[0087]
(Reference Example)
　1 g of dealuminum-UZM-35 prepared in Example 1 was placed in a container and vacuum degassed at 60 ° C. for 1 hour using an evaporator. To this, 1 g of a 20% aqueous solution of titanium trichloride was added, and the mixture was heat-treated at 160 ° C. for 4 hours. After cooling and filtering the heat-treated product, secondary firing was performed at 600 ° C. for 2 hours to obtain a Ti-UZM-35 catalyst as a reference example.
[0088]
(Evaluation of Performance of Each Catalyst
　) Hydroquinone (HQ) produced by reacting phenol with hydrogen peroxide in the presence of each catalyst obtained in Examples 1 to 10, Comparative Examples 1 to 4 and Reference Example 1. , Catechol (CA), and benzoquinone (BQ) were measured by the measuring method described later. From the obtained results, the hydroquinone yield (HQ yield) (%), hydroquinone / catechol ratio (HQ / CA ratio), benzoquinone yield (BQ yield) (%), and hydroquinone / benzoquinone ratio (%) are calculated from the following formulas. HQ / BQ ratio) was calculated. The results are shown in Table 1.
[0089]
　Hydroquinone yield (%) = (number of moles of hydroquinone produced) / (number of moles of hydrogen peroxide) x 100
　Hydrogen peroxide is partially decomposed into water and oxygen during the reaction process, so hydrogen peroxide utilization efficiency Is defined as follows.
　Hydrogen peroxide utilization efficiency = [(Mole number of hydroquinone produced) + (Mole number of catechol produced) + (Mole number of benzoquinone produced)] / Number of moles of hydrogen peroxide Using the
　above formula, the hydroquinone yield Can also be expressed by the following equation.
　Hydroquinone yield (%) = (hydrogen utilization efficiency) x (number of moles of hydroquinone produced) / [(number of moles of hydroquinone produced) + (number of moles of catechol produced) + (number of moles of benzoquinone produced) )] × 100
　Hydroquinone / catechol ratio = (number of moles of hydroquinone produced) / (number of moles of catechol produced)
　Hydroquinone / benzoquinone ratio = (number of moles of hydroquinone produced) / (number of moles of benzoquinone produced)
　benzoquinone yield Rate (%) = (number of moles of produced benzoquinone) / (number of moles of hydroquinone) × 100 Using the
　above-mentioned “hydroquinone utilization efficiency”, it can also be defined as follows.
　Benzoquinone yield (%) = (hydrogen peroxide utilization efficiency) x (number of moles of benzoquinone produced) / [(number of moles of hydroquinone produced) + (number of moles of catechol produced) + (number of moles of benzoquinone produced) )] × 100
[0090]
[Table 1]

(* In the table, the amount of titanium source added indicates the amount added to 1 g of dealuminum-UZM-35.) From
　Table 1, before adding the liquid phase titanium source, the temperature was 550 to 850 ° C. It can be seen that when the primary firing is carried out in the range, preferably in the range of 600 ° C to 800 ° C, the yield of hydroquinone is improved and the selectivity of hydroquinone is increased.
[0091]
(Evaluation of Physical Properties of Each Catalyst)
　0.1 g of each catalyst obtained in Examples 1 to 4, Comparative Examples 6 and 7, and Reference Example was placed in a cell, and an ultraviolet-visible analyzer (Shimadzu Corporation) was placed in the range of 200 to 800 nm. , UV-2550), and the absorbance at 210 nm and 300 nm was measured. Further, the amounts of Si and Ti were measured by an ICP emission spectroscopic analyzer (Agilent Technology, 720-ES), and the Si / Ti molar ratio was calculated. The results are shown in FIG. 1 and Table 1.
[0092]
(Measurement method) In
　a flask having an internal volume of 50 ml equipped with a cooler, a thermometer, a feed pump, and a magnetic stirrer chip, 0.2 g of each catalyst, 4.2 g of phenol, 3.0 g of t-butyl alcohol, 6.0 g of water was charged and heated to 50 ° C. in a hot water bath while stirring with a stirrer. Here, 0.5 g of 34% hydrogen peroxide was added dropwise from the feed pump over 10 minutes and held as it was for 60 minutes. After cooling the reaction solution, the catalyst was filtered off, a part of the reaction solution was taken, and the product was quantified by gas chromatography.
[0093]
　The analysis 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, temperature rise temperature 10 ° C / min, 280 Temperature up to ° C.
　Injection port; 280 ° C.
　Detector temperature; 280 ° C.
　carrier-gas; Helium
　flow rate; 80 ml / min
[0094]
　The specific surface area of ​​the Ti-UZM-35 catalyst was measured by the BET method using a nitrogen adsorption / desorption method measuring device (BELSORP-max manufactured by Nippon Bell Co., Ltd.).
[0095]
　This application is an application claiming priority based on Japanese application No. 2018-97032 and Japanese application No. 2018-097033 filed on May 21, 2018, and the specification and claims of the application. The contents described in the above are incorporated in this application.
The scope of the claims
[Claim 1]
　The first step of treating the alkylate with an acid,
　the second step of primary firing the processed product obtained in the first step at 550 ° C. to 850 ° C., the second step of primary firing the
　product obtained in the second step, and the period. Production of modified aluminosilicate, including a third step of contacting with a liquid containing one or more elements selected from the group consisting of Group 4 and Group 5 elements of the Periodic Table, followed by drying and secondary firing. Method.
[Claim 2]
　The method for producing a modified aluminosilicate according to claim 1, wherein the aluminosilicate is a crystalline porous aluminosilicate.
[Claim 3]
　The method for producing a modified aluminosilicate according to claim 1, wherein the liquid containing the element is a liquid containing one or more elements selected from the group consisting of Group 4 elements.
[Claim 4]
　The method for producing a modified aluminosilicate according to claim 1, wherein the liquid containing the element is a liquid containing titanium.
[Claim 5]
　The method for producing modified aluminosilicate according to claim 4, wherein the liquid containing titanium is at least one selected from the group consisting of titanium tetrachloride, an aqueous solution of titanium tetrachloride, an aqueous solution of titanium trichloride, and an aqueous solution of titanium sulfate.
[Claim 6]
　The method for producing a modified aluminosilicate according to claim 2, wherein the crystalline porous aluminosilicate has an MSE skeleton.
[Claim 7]
　The method for producing a modified aluminosilicate according to claim 6, wherein the crystalline porous aluminosilicate having an MSE skeleton is one or more selected from the group consisting of UZM-35, MCM-68 and YNU-3.
[Claim 8]
　A modified aluminosilicate containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, and exhibiting an absorbance (A [300]) at 300 nm in the ultraviolet-visible spectrum of 1.0 or more.
[Claim 9]
　Claim 8 that the ratio (A [300] / A [210]) of the absorbance (A [300]) of 300 nm of the ultraviolet-visible spectrum to the absorbance (A [210]) of 210 nm of the ultraviolet-visible spectrum is 0.5 or more. Modified aluminosilicate as described in.
[Claim 10]
　The modified aluminosilicate according to claim 8, which has crystallinity and porosity.
[Claim 11]
　The modified aluminosilicate according to claim 10, which has an MSE skeleton.
[Claim 12]
　The modified aluminosilicate according to claim 8, wherein the element is one or more elements selected from Group 4 elements.
[Claim 13]
　The modified aluminosilicate according to claim 8, wherein the element is titanium.
[Claim 14]
The modified aluminosilicate according to claim 13, wherein the molar ratio of silicon to titanium ([Si] / [Ti]) is in the range of 0.1 to 100.
[Claim 15]
　A catalyst for producing an aromatic dihydroxy compound containing the modified aluminosilicate according to claim 8.
[Claim 16]
　A method for producing an aromatic dihydroxy compound, which comprises a step of reacting phenols with hydrogen peroxide in the presence of the catalyst for producing an aromatic hydroxy compound according to claim 15.