Method for producing modified aluminosilicate and method for producing aromatic polyhydroxide compound

Abstract

Provided is a method that makes it possible to produce a modified aluminosilicate more efficiently than conventional methods.　This method for producing a modified aluminosilicate comprises: a first step for obtaining an aluminosilicate (A-1) by bringing a gel-like or sol-like silica, zeolite, and an ammonium salt represented by formula (1) into contact with each other; a second step for treating the aluminosilicate (A-1) obtained in the first step with an acid; and a third step for bringing the product obtained in the second step into contact with a compound including at least one element selected from the group consisting of group-4 elements and group-5 elements in the periodic table, and then drying and sintering the same. (In formula (1), C represents a carbon atom, N+ represents a nitrogen cation, X- represents a halogen anion or a hydroxy anion, R and R1 each independently represent a hydrogen atom or a hydrocarbon group optionally having a heteroatom, m1 and m2 each independently represent an integer of 0-5, n1 and n2 each independently represent an integer of 0-5, the sum of n1 and n2 is 1-10, and R and R1 which are present in a quantity of more than one can bind to each other to form a ring structure.)

Description

Method for producing modified aluminosilicate and method for producing aromatic polyhydroxy compounds

[0001] The present invention relates to a method for producing a modified aluminosilicate and a method for producing an aromatic polyhydroxy compound using the modified aluminosilicate.

[0002] Aromatic dihydroxy compounds are important as intermediates or starting materials in various organic synthesis processes and are used in fields such as reducing agents, rubber compounds, dyes, pharmaceuticals, agrochemicals, polymerization inhibitors, and oxidation inhibitors.

[0003] Aromatic dihydroxyd 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 manufacturing method. In recent years, due to the balance of demand for hydroquinone and catechol, there has been a strong desire for a method to produce hydroquinone with high selectivity.

[0004] A method has been disclosed for producing aromatic dihydroxyl compounds by reacting phenols with hydrogen peroxide, using titanosilicate, a type of crystalline porous silicate, as a catalyst (for example, Patent Documents 1 and 2). Patent Document 3 also discloses titanosilicate obtained by treating acid-treated aluminosilicate with gas-phase titanium chloride or titanium alkoxide.

[0005] Furthermore, Patent Document 4 discloses a method for producing titanosilicate, which is obtained by mixing aluminosilicate mold raw materials, an aluminum source, a titanium source, a silicon source, iodide, and water to prepare a gel, heating it to crystallize it, and then firing it.

[0006] The present inventors have disclosed a method for producing modified aluminosilicates such as aluminotitanosilicate by contacting an aluminosilicate compound with a liquid titanium halide compound. They have also disclosed a method for producing aromatic polyhydroxy compounds using the modified aluminosilicate (Patent Documents 5-7).

[0007] Japanese Patent No. 4254009, International Publication No. 2015 / 041137, Japanese Unexamined Patent Publication No. 2008-050186, Japanese Unexamined Patent Publication No. 2017-057126, International Publication No. 2019 / 225549, International Publication No. 2022 / 225050, International Publication No. 2023 / 204296

[0008] The aluminotitanosilicates obtained by the methods described in the above-mentioned Patent Documents 5 to 7 have been shown to be excellent catalysts for the production of aromatic dihydroxyl compounds. However, these examples disclose manufacturing methods that involve multiple manufacturing steps lasting 10 hours or more.

[0009] Furthermore, it has been disclosed that hydroquinone can be obtained in high yield and with high selectivity when phenol and hydrogen peroxide are reacted in the presence of aluminotitanosilicate. However, from the perspective of environmental impact and economic efficiency, there is a need to further increase the yield (reactivity) and selectivity. On the other hand, it is known that it tends to be difficult to further increase already high reactivity and selectivity.

[0010] The present invention aims to provide a method for producing modified aluminosilicates more efficiently than conventional methods. It also aims to provide a method for producing aromatic polyhydroxy compounds such as hydroquinone with higher reactivity and selectivity.

[0011] As a result of investigating the above-mentioned problems, the present inventors have found that by using a method that includes a specific quaternary ammonium salt as an essential component in the production process of aluminosilicate, which is the raw material for the modified aluminosilicate, it is possible to produce aluminosilicate in a shorter time than conventional methods, and as a result, the production efficiency of modified aluminosilicate can be increased. Furthermore, the inventors have found that by using a heteroatom-containing compound such as an alcohol in combination with a method for producing hydroquinone using, for example, phenol and hydrogen peroxide in the presence of the modified aluminosilicate, the yield and selectivity can be further increased, thus completing the present invention.

[0012] In other words, the present invention includes the following items [1] to

[11] : [1] A method for producing a modified aluminosilicate, comprising: a first step of contacting gel-like or sol-like silica, zeolite, and an ammonium salt represented by the following formula (1) to obtain an aluminosilicate (A-1); a second step of treating the aluminosilicate (A-1) obtained in the first step with an acid; and a third step of contacting the product obtained in the second step with a compound 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 calcination. (In the above formula (1), C is a carbon atom, N ＋ X is a nitrogen cation. － R and R represent halogen anions or hydroxy anions. １ Each of the following independently represents a hydrocarbon group which may contain a hydrogen atom or a heteroatom, m1 and m2 are each independently integers from 0 to 5, n1 and n2 are each independently integers from 0 to 5, the sum of n1 and n2 is from 1 to 10, and there are multiple R and R １ These can each bond with each other to form a ring structure.) [2] The X － The method for producing a modified aluminosilicate according to [1], wherein the iodine anion is present. [3] The method for producing a modified aluminosilicate according to [1] or [2], wherein the m1 and m2 are 0. [4] The R １The method for producing a modified aluminosilicate according to any one of [1] to [3], which comprises a ring structure in which the members are bonded to each other. [5] The method for producing a modified aluminosilicate according to any one of [1] to [4], wherein a compound containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table is brought into gaseous contact. [6] The method for producing a modified aluminosilicate according to any one of [1] to [5], wherein a compound containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table is brought into gaseous contact at 350 to 850 °C. [7] The method for producing a modified aluminosilicate according to any one of [1] to [6], wherein the element selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table is titanium. [8] A first step of obtaining an aluminosilicate (A-1) by bringing a gel-like or sol-like silica, a zeolite, and an ammonium salt represented by the following formula (1) into contact with each other, a second step of treating the aluminosilicate (A-1) obtained in the first step with an acid, and a third step of drying and firing after bringing the product obtained in the second step into contact with a compound containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table. A process for producing an aromatic polyhydroxy compound, which comprises a step of reacting an aromatic hydroxide and a hydroperoxide in the presence of a modified aluminosilicate obtained by the method including the steps. (In the above formula (1), C is a carbon atom, N ＋ is a nitrogen cation, X － represents a halogen anion or a hydroxy anion, R and R １ each independently represent a hydrocarbon group which may contain a hydrogen atom or a hetero atom, m1 and m2 are each independently an integer of 0 to 5, n1 and n2 are each independently an integer of 0 to 5, the sum of n1 and n2 is 1 to 10, and a plurality of R and R １ can be bonded to each other to form a ring structure.) [9] The method for producing an aromatic polyhydroxy compound according to [8], wherein the modified aluminosilicate contains a compound [AD] represented by the following formula (3). (In the above formula (3), R １１(wherein Q represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and Q is a substituent that includes a heteroatom and an atom selected from the group consisting of a hydrogen atom and a carbon atom.)

[10] The method for producing an aromatic polyhydroxy compound according to [9], wherein the compound [AD] is an alcohol.

[11] The method for producing an aromatic polyhydroxy compound according to [9] or

[10] , wherein the compound [AD] is an alcohol containing ethanol.

[0013] The present invention provides a method for producing modified aluminosilicates more efficiently than conventional methods. Furthermore, it provides a method for producing aromatic polyhydroxy compounds such as hydroquinone with higher reactivity and selectivity.

[0014] Embodiments of the present invention will be described in detail below. <Method for producing modified aluminosilicate> A method for producing modified aluminosilicate, which is one embodiment of the present invention (hereinafter also referred to as "the present production method 1"), includes: a first step of contacting gel-like or sol-like silica, zeolite, and an ammonium salt represented by the following formula (1) to obtain aluminosilicate (A-1); a second step of treating the aluminosilicate (A-1) obtained in the first step with acid; and a third step of contacting the product obtained in the second step with a compound 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 calcination.

[0015]

[0016] In the above formula (1), C is a carbon atom, N ＋ X is a nitrogen cation. － R and R represent halogen anions or hydroxy anions. １ Each of the following independently represents a hydrocarbon group which may contain a hydrogen atom or a heteroatom, m1 and m2 are each independently integers from 0 to 5, n1 and n2 are each independently integers from 0 to 5, the sum of n1 and n2 is from 1 to 10, and there are multiple R and R １ These elements can bond to each other to form a ring structure.

[0017] [First Step] The first step is a process of producing aluminosilicate (A-1) by contacting gel-like or sol-like silica with zeolite and an ammonium salt represented by the above formula (1).

[0018] [Zeolite] Zeolites are hydrated aluminosilicates containing alkali or alkaline earth metals, consisting of an anionic framework with regular channels (tubular pores) and cavities. A typical example of a zeolite is aluminosilicate.

[0019] Preferably, the zeolite used in the first step does not contain group 4 and group 5 elements, or if it does, it contains them to an extent that does not affect the effects of the present invention. Examples of group 4 elements include titanium, zirconium, and hafnium. Examples of group 5 elements include vanadium.

[0020] The zeolite is preferably composed of silicon with oxygen atoms arranged at four vertices. ４ A tetrahedron and an AlO2 with aluminum instead of silicon at the center. ４ It is a porous crystalline material having at least a portion of its structure where tetrahedra are regularly bonded in three dimensions.

[0021] The zeolite is not particularly limited as long as it preferably has the above structure, but aluminosilicate is more preferred, and crystalline and porous aluminosilicate having a FAU type structure (hereinafter also referred to as "FAU type skeleton") and crystalline and porous aluminosilicate having an MSE type structure (hereinafter also referred to as "MSE skeleton") in the framework code of the International Zeolite Association are even more preferred, with UZM-35, MCM-68, YNU-3, STZ-1 and the like being particularly preferred. Hereinafter, crystalline and porous aluminosilicate will simply be referred to as crystalline porous aluminosilicate.

[0022] The crystalline porous aluminosilicate having the above-mentioned MSE framework is said to have 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.

[0023] Zeolites can be used as an aluminum source, and among such zeolites, those having a FAU-type skeleton are a suitable example. Other components may also be used in combination as an aluminum source. For example, water-soluble aluminum compounds can be used. Examples of water-soluble aluminum compounds include aluminum hydroxide, sodium aluminate, aluminum nitrate, and aluminum sulfate. These aluminum sources can be used alone or in combination of two or more.

[0024] Zeolites that function as so-called seed crystals can also be used. Suitable seed crystals for this purpose include materials having the structure of UZM-35, MCM-68, YNU-3, or STZ-1.

[0025] The amount of zeolite used as seed crystal is preferably 1 to 40% by weight of silica, which is the silicon source described later, and more preferably 2 to 30% by weight. Furthermore, zeolite used as an aluminum source (e.g., FAU-type zeolite) also functions as a silicon source, and the amount used is preferably 5 to 50% by weight of silica, and more preferably 8 to 40% by weight.

[0026] [Ammonium Salt] The ammonium salt used in the first step is represented by the following formula (1).

[0027] In the above formula (1), C is a carbon atom, N ＋ X is a nitrogen cation. － R and R represent halogen anions or hydroxy anions. １ Each of the following independently represents a hydrocarbon group which may contain a hydrogen atom or a heteroatom, m1 and m2 are each independently integers from 0 to 5, n1 and n2 are each independently integers from 0 to 5, the sum of n1 and n2 is from 1 to 10, and there are multiple R and R １These elements can bond to each other to form a ring structure.

[0028] Examples of the above-mentioned halogen anions include chloride anions, bromine anions, iodine anions, and astatine anions. － The anion is preferably a bromine anion and an iodine anion, and more preferably an iodine anion.

[0029] R and R in equation (1) １ In this context, a hydrogen atom is represented as "H-" in a general structural formula and refers to a form that can form covalent bonds with atoms such as carbon. １ Specific examples of hydrocarbon groups in this context include substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms. Examples of such substituents include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and hydrocarbon groups having 6 to 20 carbon atoms with aryl groups. These may also contain heteroatoms that are atoms in groups 15 to 17 of the periodic table. R and R １ Preferably, it is a hydrocarbon group consisting only of carbon and hydrogen.

[0030] The hydrocarbon group described above is a monovalent hydrocarbon group having preferably 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 6, and especially preferably 2 to 6 carbon atoms. Specifically, examples of such hydrocarbon groups include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, such as substituted or unsubstituted aryl groups, substituted or unsubstituted cycloalkenyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, and phenyl group. Among these, n-butyl group, isobutyl group, hexyl group, octyl group, and phenyl group are preferred, and n-butyl group, isobutyl group, and phenyl group are more preferred.

[0031] The hydrocarbon group described above may be a hydrocarbon group containing heteroatoms such as nitrogen, oxygen, phosphorus, and halogen. The heteroatoms are preferably oxygen and nitrogen. The hydrocarbon group can be selected from known structures. More specifically, suitable examples include carboxylic acid ester groups, aldehyde groups, acetyl groups, carbonyl structure-containing groups such as oxycarbonylalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyloxy groups, substituted or unsubstituted cycloalkyloxy groups, substituted or unsubstituted cycloalkenyloxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryloxy groups, substituted or unsubstituted heteroaryloxy groups, and siloxy groups.

[0032] The multiple R and R mentioned above １ These can combine with each other to form a ring structure. The ring structure is preferably a 3-membered ring to an 8-membered ring, more preferably a 4-membered ring to an 8-membered ring, even more preferably a 5-membered ring to an 8-membered ring, particularly preferably a 5-membered ring to a 7-membered ring, and especially preferably a 5-membered ring or a 6-membered ring. The above ring structure is a configuration in which R members combine with each other to form a ring structure, or R １ It is preferable that the elements are joined together to form a ring structure.

[0033] In formula (1), n1 and n2 are preferably integers between 0 and 4, more preferably between 1 and 3. The sum of n1 and n2 is preferably between 1 and 8, more preferably between 2 and 8, even more preferably between 3 and 6, particularly preferably between 3 and 5, and especially preferably between 3 or 4.

[0034] In formula (1), m1 and m2 are preferably integers between 0 and 3, more preferably between 0 and 2. Particularly preferable is the configuration in which both m1 and m2 are 0. This configuration can be represented by the following structural formula (2).

[0035]

[0036] Each symbol in formula (2) above has the same meaning as each symbol in formula (1).

[0037] In the above equation (2), R １It is preferable that the elements bond to each other to form a cyclic structure, and it is more preferable that the cyclic structure contains a nitrogen atom (cation). It is even more preferable that the cyclic structure is a 4-membered ring to a 7-membered ring, particularly preferable that it is a 5-membered ring to a 7-membered ring, and especially preferable that it is a 5-membered ring or a 6-membered ring.

[0038] More specifically, examples of quaternary ammonium salts include compounds having a 6-membered ring and a 1,4-diamino type skeleton, as shown below.

[0039]

[0040]

[0041] In addition to the above, 1,3-diamino type compounds and 1,2-diamino type compounds are also specific examples. Furthermore, compounds with similar structures in cyclic skeletons other than six-membered rings are also specific examples.

[0042] Among the above, (iodide) 1,1'-(cyclohexane-trans-1,4-diyl)-bis-(1-piperidinium) is a preferred example.

[0043] Furthermore, compounds having the above-mentioned cyclic skeleton exist in various structural isomers, such as cis and trans isomers, and both structures, as well as mixtures thereof, are within the scope of the present invention. In some cases, the trans isomer may be preferred over the cis isomer.

[0044] The amount of quaternary ammonium salt used is preferably 1 mol% to 70 mol% per mole of silicon in silica. A more preferable lower limit is 5 mol%, even more preferably 10 mol%, and particularly preferably 12 mol%. On the other hand, a more preferable upper limit is 60 mol%, even more preferably 50 mol%, and particularly preferably 45 mol%.

[0045] Quaternary ammonium salts can generally be considered a type of component known as an organic structure modifier.

[0046] [Gel-like or Sol-like Silica] Examples of gel-like or sol-like silica used in the first step include known silicon-containing compounds such as colloidal silica, sodium silicate, wet silica, and dry silica. These gel-like or sol-like silica sources can be used alone or in combination of two or more. Among these, colloidal silica is a preferred example. Colloidal silica can also be used in a sol state by preheating it to a high temperature such as 50°C to 100°C.

[0047] [Production of Aluminosilicate (A-1)] Aluminosilicate (A-1) is obtained by contacting gel-like or sol-like silica with zeolite and a quaternary ammonium salt represented by the above formula (1). When contacting the materials, stirring and heating are desirable.

[0048] The temperature range of the reaction system during heating is preferably 135 to 170°C. The lower limit of the above temperature range is more preferably 140°C, and even more preferably 143°C. On the other hand, the upper limit of the above temperature range is more preferably 165°C, even more preferably 163°C, particularly preferably 160°C, and especially preferably 157°C.

[0049] The above temperature range tends to facilitate the aluminosilicate crystal formation reaction. Furthermore, it is preferable that the temperature does not exceed substantially 165°C during the crystal (A-1) production stage. "Substantially" means, for example, that when controlling the temperature during the heating process, a deviation of 5°C for a few minutes is permissible.

[0050] During the heating process described above, it is preferable to maintain the temperature within the above temperature range for 6 to 240 hours. The lower limit of the holding time is more preferably 10 hours, even more preferably 12 hours, and particularly preferably 24 hours. On the other hand, the upper limit of the holding time is more preferably 120 hours, even more preferably 90 hours, and particularly preferably 60 hours. Conventionally, the above process required the reaction to be carried out over a period of more than 10 days, but in the present invention, as described above, the desired aluminosilicate can be produced in a relatively short time.

[0051] This manufacturing method 1, by using the above-mentioned quaternary ammonium salt as an organic structure-controlling agent, tends to shorten the above-mentioned time compared to conventional methods. The reason for this effect is not yet clear, but the inventors have the following hypothesis.

[0052] The above-mentioned quaternary ammonium salt has a relatively rigid structure called an alicyclic skeleton (compared to linear or branched skeletons), and is therefore presumed to exhibit less structural displacement compared to quaternary ammonium salts with linear or branched structures. Because of this reduced structural displacement, the reaction environment when the silica and zeolite come into contact and react is relatively stable, which may facilitate the reaction and increase the crystallization rate. Furthermore, it is possible that the above-mentioned cyclic quaternary ammonium salt may exhibit an effect that further promotes crystallization through interaction with the zeolite.

[0053] The aluminosilicate (A-1) obtained in the first step has a high crystallization rate during manufacturing, which makes it easy to form relatively small crystals. As a result, it is possible that it has a higher-order structure that differs from conventional aluminosilicates, which tend to have a large specific surface area and / or a large number of OH groups on the surface.

[0054] Another preferred method for producing aluminosilicate (A-1) is, for example, a method in which the molar ratio of water to silica is controlled within a specific range using gel-like silica. Alternatively, a method in which the molar ratio of water to silica is controlled within a specific range using sol-like silica containing water instead of gel-like silica is also an example of a preferred method.

[0055] As mentioned above, the molar ratio of water to silica can also be an important requirement for producing modified aluminosilicates such as aluminotitanosilicate, which will be discussed later.

[0056] Using the aluminosilicate (A-1) produced in the first step, although the reason is currently unknown, a suitable catalyst for aromatic polyhydroxy compounds can be obtained, for example, by introducing elements from groups 4 and 5 of the periodic table, such as titanium, as described later.

[0057] Aluminosilicate (A-1) exhibits a crystalline structure, but its crystalline form is thought to contain many somewhat unstable crystals due to factors such as the action of the quaternary ammonium salt and the rapid crystallization rate. It is also thought that this instability, when it becomes a modified aluminosilicate as described later, may lead to its excellent performance as a catalyst for the production of aromatic polyhydroxyd compounds.

[0058] Furthermore, as will be described later, in the third step of introducing a group 4 or group 5 element of the periodic table, such as titanium, to the aluminosilicate (A-1), an unexpected tendency is observed: a modified aluminosilicate suitable as a catalyst for the production of aromatic polyhydroxy compounds can be produced whether the reaction is carried out under high temperature and gas phase conditions or low temperature and liquid phase conditions. It is thought that this tendency may be due to the somewhat unstable crystal structure mentioned above.

[0059] In the first step, other quaternary ammonium salts other than the quaternary ammonium salt represented by formula (1) above may be used in combination, to the extent that the objective of the present invention is not impaired. Specifically, other quaternary ammonium salts include N,N,N',N'-tetraethylbicyclo[2,2,2]octa-7-ene-2,3:5,6-dipyrrolidinium diodide (TEBOP) ２＋ (I － ) ２ It may be written as such.) Examples of well-known quaternary ammonium salts include ).

[0060] It is preferable to calcinate the aluminosilicate (A-1) before the second step described later. There are no particular restrictions on the calcination method, and examples include calcination using an electric furnace or a gas furnace. The calcination conditions are preferably heating in an air atmosphere for 0.1 to 20 hours. The calcination temperature is preferably 550°C to 850°C, and more preferably 600°C to 800°C. In addition to the above, a heat history may be added for the purpose of drying. In this case, it is preferable to dry under conditions such as 50 to 100°C for 5 to 10 hours.

[0061] [Second Step] The second step is to treat the aluminosilicate (A-1) obtained in the first step with acid, or in other words, to bring the aluminosilicate (A-1) into contact with acid.

[0062] Examples of acids used in the second step include inorganic acids, organic acids, and mixtures thereof. Specific examples of these 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 more preferred.

[0063] 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 this acid is used as an aqueous solution, the amount used is preferably 1 to 100 parts by weight per 1 part by weight of aluminosilicate (A-1). The lower limit of the above numerical range is more preferably 2 parts by weight, even more preferably 3 parts by weight, and particularly preferably 5 parts by weight. A more preferable lower limit is 10 parts by weight, and more preferably 20 parts by weight. On the other hand, the upper limit of the above numerical range is more preferably 70 parts by weight, and even more preferably 50 parts by weight.

[0064] The temperature conditions for contacting the aluminosilicate (A-1) with the acid are preferably 50°C to 170°C, more preferably 100°C to 170°C, and particularly preferably 130°C to 170°C.

[0065] The acid treatment time is preferably 5 to 48 hours, and more preferably 12 to 36 hours. A more preferable lower limit for the acid treatment time is 18 hours.

[0066] It is thought that contact with this acid removes some of the aluminum from the aluminosilicate. It is presumed that mainly the aluminum on the surface of the aluminosilicate is removed. By selecting relatively high temperatures and long durations as described above, it is presumed that a structure favorable for the introduction of one or more elements selected from the group consisting of Group 4 and Group 5 elements will be more easily formed during the calcination process in the third step described later.

[0067] The aluminosilicate (A-1) that has been in contact with the above-mentioned acid is preferably subjected to a washing process in which the treated material is filtered using a Nutche filter, filter paper, etc., to separate the acid (aqueous solution) used, and then the solid part (filtered material) is washed with water and dried. The above-mentioned filter paper is appropriately selected depending on the particle size of the product. For example, it is preferable to use fine-mesh filter paper such as #3, #6, #5C, and #4, which are commercially available standards. More preferably, #6, #5C, and #4 are used, and even more preferably, #5C and #4 filter paper are used.

[0068] Furthermore, if filtration is difficult, a washing method using centrifugal separation can be employed. It is preferable to carry out this washing process while keeping the material wet without drying it beforehand. There are no particular restrictions on the drying method after washing, but it is preferable to dry it uniformly and quickly. For example, external heating methods such as hot air drying and superheated steam drying, or electromagnetic heating methods such as microwave heating drying and high-frequency dielectric heating drying can be used. In addition, vacuum drying is also a suitable method. Of course, a method that combines vacuum drying with the above-mentioned heating drying method is also a suitable drying method.

[0069] Furthermore, it is preferable to calcine the processed material obtained in the second step above, i.e., the aluminosilicate (A-1) that has been in contact with the acid. There are no particular restrictions on the calcination method, and examples include calcination using an electric furnace or a gas furnace. As for the calcination conditions, it is preferable to heat in a dry stream of an inert gas such as argon or nitrogen or in an atmospheric environment for 0.1 to 20 hours, but a dry stream of an inert gas is more preferable. The calcination temperature is preferably in the range of 350°C to 850°C, more preferably 450°C to 750°C, and particularly preferably 550°C to 750°C. It is presumed that calcination in this relatively high-temperature environment can make the defective parts of the skeleton into a highly reactive state, and that an environment favorable for the formation of the modified aluminosilicate obtained in the third step, which contains group 4 and group 5 elements of the periodic table, with titanium being a representative example, can be obtained. Hereafter, calcination by this method may be called zero-order calcination, and the compound obtained by said zero-order calcination may be called zero-order calcined product.

[0070] [Third Step] In the third step, the product (or calcined product) obtained in the second step is brought into contact with a compound 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 calcination.

[0071] Examples of Group 4 and Group 5 elements in the periodic table include titanium, zirconium, hafnium, and vanadium. Of these, preferred elements are titanium, zirconium, and vanadium, with titanium being the most preferred element. Examples of compounds containing Group 4 and Group 5 elements include halides, alkoxides, or inorganic acid salts of each element. Preferred embodiments include chlorides as halides and embodiments containing alkoxides with 1 to 6 carbon atoms. Even more preferred embodiments include ethoxides, butoxides (n-butoxide, i-butoxide, s-butoxide, t-butoxide), and sulfates as alkoxides. Two or more of these compounds may be used in combination.

[0072] Below, we will describe, as representative examples, the most preferred embodiment of titanium-containing compounds (liquid-phase or gaseous (gas-phase) titanium sources) among the Group 4 and Group 5 elements of the periodic table.

[0073] In the embodiment using a liquid-phase titanium source, the liquid-phase titanium source is a titanium-containing liquid. Examples of titanium-containing liquids include liquid titanium compounds themselves or aqueous solutions of titanium compounds. In particular, a titanium compound that exhibits substantially acidity in its liquid state is preferred.

[0074] Examples of liquid titanium compounds include titanium tetrachloride (TiCl). ４ Examples of titanium compounds include tetrachloride, tetrachloride, and titanium tetrachloride, among which titanium tetrachloride is preferred. Examples of aqueous solutions of titanium compounds include aqueous solution of titanium tetrachloride and titanium trichloride (TiCl). ３ ) aqueous solution, titanium sulfate (Ti(SO) ４ ) ２ Examples include aqueous solutions of titanium dioxide, potassium hexafluorotianoate, and among these, aqueous solutions of titanium tetrachloride, titanium trichloride, and titanium sulfate are preferred. In this invention, even when a titanium source less reactive than titanium tetrachloride, such as titanium trichloride or titanium sulfate, is used in addition to titanium tetrachloride, the catalytic activity described later can be achieved. In particular, there is a tendency to achieve catalytic activity that yields aromatic polyhydroxyl compounds with high selectivity.

[0075] The titanium-containing liquids described above can be used alone or in combination of two or more. Commercially available titanium-containing liquids can be used, or solid titanium compounds can be diluted with water to the desired concentration and prepared as appropriate.

[0076] There are no particular restrictions on the conditions for contacting the product obtained in the second step with the titanium source. For example, when using the liquid titanium compound itself, 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 part by weight of the product from the second step. When using an aqueous solution of the titanium compound, it is preferable to add 1 to 10 parts by weight, and more preferably 1 to 7 parts by weight, of the aqueous solution of the titanium compound per 1 part by weight of the 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.

[0077] 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 product, with an upper limit of 10 g, more preferably 5 g, and even more preferably 3 g.

[0078] The contact between the titanium source and the product may be performed only once, or each component may be used in multiple steps, as long as the weight ratio used is within the above range. For example, the titanium source may be added to the product, and the resulting calcined product may be dried and calcined as described later. The titanium source may then be added again to the calcined product and dried and calcined again. When adding the titanium source, it is preferable to do so under a nitrogen atmosphere because hydrogen chloride is generated by the reaction of moisture in the air with the titanium compound.

[0079] A more specific preferred method involves contacting the above product with a titanium source, thoroughly mixing the mixture, then heating the mixture and / or thoroughly drying it in a manner similar to the drying method exemplified in the second step, followed by firing. There are no particular restrictions on the temperature during the above heating and drying processes. For example, to effectively introduce titanium into the above product, a relatively low temperature range of 20°C to less than 350°C (mainly for liquid reactions) is acceptable, but in the case of the present invention, a range of 350 to 850°C (mainly for gaseous reactions) is often preferred. The lower limit of the above range is more preferably 400°C, even more preferably 450°C, and particularly preferably 500°C. On the other hand, the upper limit of the above range is more preferably 750°C, even more preferably 700°C, and particularly preferably 650°C. There are no particular restrictions on the time required for the above process, but it is preferably 0.1 to 24 hours. The lower limit of the above range is more preferably 0.3 hours, even more preferably 0.4 hours, and particularly preferably 0.5 hours. On the other hand, the upper limit of the above range is more preferably 12 hours, and even more preferably 6 hours. There are no particular restrictions on the firing method, and firing can be carried out using, for example, an electric furnace or a gas furnace. The firing conditions are preferably in an atmospheric environment at 400 to 850°C for 0.1 to 20 hours. The lower limit of the firing temperature is more preferably 500°C, even more preferably 530°C, and particularly preferably 550°C. On the other hand, the upper limit of the firing temperature is more preferably 800°C, even more preferably 750°C, and particularly preferably 700°C.

[0080] Furthermore, the process may include a stage where the temperature falls within the above-mentioned range before the product is brought into contact with the titanium source. Such a stage can also be considered as the zero-order firing process.

[0081] The titanium compounds in the gaseous state described above often have relatively large molecular weights and are liquid compounds at room temperature and pressure. Therefore, when contacting the above product, it is preferable to use a gas stream that also contains so-called inert gases such as nitrogen or group 18 elements. In this case, hydrolysis of the titanium compound by water vapor may occur, so it is preferable to use a dry gas to prevent this. Other preferred embodiments, such as high-temperature firing conditions, are the same as those for the embodiments using the titanium compounds in the liquid state described above.

[0082] Before the drying process in the third step, it is preferable to pre-heat the mixture of the titanium source and the above product to remove moisture, filter the mixture to remove impurities, wash it with an organic solvent, and then dry and calcine it. The conditions for this calcination stage are preferably within the same range as those disclosed in the first calcination. It is presumed that calcination in this relatively high-temperature environment condenses any remaining small defect sites, thereby improving hydrophobicity and, consequently, catalytic activity.

[0083] The above manufacturing conditions can also be applied mutatis mutandis when using elements other than titanium.

[0084] Examples of compounds containing Group 4 elements of the periodic table that can be used as a substitute for the above-mentioned titanium source include zirconium tetrachloride, tetraalkoxyzirconium, hafnium tetrachloride, tetraalkoxyhafnium, zirconium sulfate, etc., liquefied with water, alcohol, ether, etc., as needed. Examples include aqueous solutions of these compounds or solutions with alcohol, ether, etc. Examples of Group 5 elements of the periodic table that can be used as a substitute for the above-mentioned titanium source include vanadium pentachloride, vanadium sulfate, vanadyl trichloride, and their alkoxy derivatives, liquefied with water, alcohol, ether, etc., as needed. Examples include aqueous solutions of these compounds or solutions with alcohol, ether, etc.

[0085] In the third step, for example, it is thought that some of the aluminum in the above-mentioned product of crystalline porous aluminosilicate is replaced with titanium, thus introducing titanium. This introduction of titanium is thought to occur in the position where the aluminum that was removed in the second step was introduced, or in a reaction in which some of the aluminum in the aluminosilicate (A-1) is replaced with titanium. As a result, a crystalline porous aluminotitanosilicate, which is a preferred form of modified aluminosilicate, can be obtained.

[0086] [Modified Aluminosilicate] The modified aluminosilicate obtained in the third step is preferably a crystalline porous aluminosilicate having crystalline and porous properties, similar to the aluminosilicate (A-1) 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, YNU-3, or STZ-1 structure, and particularly preferably a crystalline porous aluminotitanosilicate. Crystallinity is the same as described in the [Zeolite] section.

[0087] A 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 replacing a portion of the aluminum in the crystalline porous aluminosilicate framework with one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table. A more preferred example is when one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table are titanium, in which case the crystalline porous modified aluminosilicate becomes a crystalline porous aluminotitanosilicate, and this crystalline porous aluminotitanosilicate contains aluminum and titanium in the aluminosilicate framework, and is preferably obtained by replacing a portion of the aluminum in the framework with titanium.

[0088] The crystalline porous aluminosilicate having the above-described MSE framework 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. Because it has the 12-membered ring structure of pores, it is thought that the diffusion of the substrate into the pores is facilitated, making it easier to obtain high catalytic activity. Furthermore, because there are no large cavities inside the pores, it is thought that this is one of the factors that makes it easier to exhibit para-selectivity in the oxidation reaction of phenol.

[0089] It is well known that porous compounds have a large specific surface area. The modified aluminosilicate produced by this manufacturing method 1 has a specific surface area of ​​preferably 50 to 1000 m². ２ It is / g. The lower limit of its specific surface area is more preferably 100m ２ / g, more preferably 150m ２ It is / g. On the other hand, the upper limit of its specific surface area is more preferably 800 m ２ / g, more preferably 600m ２ It is / g.

[0090] The above specific surface area value can be determined by a known calculation method based on BET theory, by creating a BET plot from measurement results using a known nitrogen adsorption / desorption measurement device (for example, BELSORP-max manufactured by Microtrac BEL).

[0091] The preferred pore volume range for the above-mentioned modified aluminosilicate is 0.1 to 0.5 cm. ３ / g, more preferably 0.2 to 0.4 cm ３ It is / g.

[0092] There are no particular restrictions on the content of Group IV and Group V elements in the above-mentioned modified aluminosilicate. For example, if titanium is included as one or more elements selected from the group consisting of Group IV and Group V elements in the above-mentioned modified aluminosilicate, the molar ratio of silicon to titanium ([Si] / [Ti]) is preferably in the range of 1 to 500, more preferably in the range of 5 to 280, even more preferably in the range of 10 to 100, and particularly preferably in the range of 30 to 70.

[0093] There are no particular restrictions on the aluminum content of the above-mentioned modified aluminosilicate, but the molar ratio of silicon to aluminum ([Si] / [Al]) is preferably in the range of 5 to 100,000, more preferably in the range of 10 to 10,000, and particularly preferably in the range of 100 to 1,000.

[0094] The above-mentioned modified aluminosilicate can be used as a catalyst for the production of aromatic polyhydroxy compounds, as described later, according to one embodiment of the present invention.

[0095] <Method for Producing Aromatic Polyhydroxy Compounds> One embodiment of the present invention is a method for producing aromatic polyhydroxy compounds (hereinafter also referred to as "the present production method 2"), which includes a first step of contacting gel-like or sol-like silica, zeolite, and an ammonium salt represented by the following formula (1) to obtain an aluminosilicate (A-1); a second step of treating the aluminosilicate (A-1) obtained in the first step with acid; and a third step of contacting the compound obtained in the second step with a compound 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 calcination, and then reacting an aromatic hydroxide with a hydroperoxide in the presence of a modified aluminosilicate obtained by this method.

[0096] The significance of steps 1 through 3 in this manufacturing method 2 is the same as that of each step in this manufacturing method 1.

[0097] Examples of aromatic hydroxides include phenols (described later), hydroxynaphthalene and its derivatives, hydroxyanthracene and its derivatives, hydroxyfluorene and its derivatives, and other compounds whose structure mainly consists of one hydroxyl group attached to a phenyl skeleton. Phenols are preferred.

[0098] 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. Hydroperoxide is preferably hydrogen peroxide, and more preferably hydrogen peroxide solution.

[0099] The following describes manufacturing method 2 as an example of a method for producing aromatic dihydroxyl compounds. In the presence of the modified aluminosilicate obtained in steps 1 to 3 above, for example, by reacting phenols with hydrogen peroxide, aromatic dihydroxyl compounds can be produced with high selectivity.

[0100] The above-mentioned phenols refer to unsubstituted phenols and substituted phenols. Examples of substituted phenols include alkylphenols substituted with linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl groups, ethyl groups, isopropyl groups, butyl groups, and hexyl groups, or with cycloalkyl groups.

[0101] 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, with phenol being preferred. If the phenol has substituents at both the 2- and 6-positions, the product will be only a hydroquinone derivative.

[0102] Examples of aromatic dihydroxy compounds that are reaction products include hydroquinones (substituted or unsubstituted hydroquinones) and catechols (substituted or unsubstituted catechols). Specific examples of these 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.

[0103] The above-mentioned modified aluminosilicate is used as a catalyst in the production of aromatic dihydroxyl compounds. Various methods can be used for catalyst packing, such as fixed bed, fluidized bed, suspension bed, and shelf-type fixed bed, and any of these methods may be used. The catalyst may be used as is, or it may be molded to suit the catalyst packing method. Common methods for molding the catalyst include extrusion molding, tableting, rolling granulation, and spray granulation. When using the catalyst in a fixed bed system, extrusion molding or tableting is preferred. In the case of a suspension bed system, spray granulation is preferred. Drying or 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 in the range of 5 μm to 100 μm. A particle size of 0.1 μm or more is preferred because it makes handling such as catalyst filtration easier, and a particle size of 1000 μm or less is preferred because it provides good catalyst performance and strength.

[0104] The amount of catalyst used is preferably 0.1 to 30% by weight, more preferably 0.4 to 20% by weight, relative to the total weight of the reaction solution containing the aromatic hydroxide and hydroperoxide (the total weight of liquid components in the reaction system, excluding the weight of fixed components such as the catalyst). An amount of 0.1% by weight or more is preferable because the reaction is completed in a short time and productivity is improved. An amount of 30% by weight or less is preferable because the amount of catalyst separated and recovered is small.

[0105] When the above-mentioned modified aluminosilicate is used as a catalyst in the present manufacturing method 2, 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 used. Such components are preferably used in a proportion of 5 to 90% by weight of the reaction solution, and more preferably in a proportion of 8 to 90% by weight.

[0106] It is preferable that the amount of hydrogen peroxide relative to the phenols be 0.01 to 1 in molar ratio. The concentration of hydrogen peroxide used is not particularly limited; a typical 30% aqueous solution may be used, or a higher concentration of hydrogen peroxide solution may be used directly or diluted with an inert solvent in the reaction system. Examples of solvents used for dilution include alcohols and water. The hydrogen peroxide may be added all at once or gradually over time.

[0107] 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. The reaction will proceed at temperatures outside this range, but the above range is preferred from the viewpoint of improving productivity. The reaction pressure is not particularly limited.

[0108] The reaction method described above is not particularly limited and may be carried out in batch, semi-batch, or continuous configurations. In the case of a continuous configuration, it may be carried out in a suspension-bed homogeneous mixing tank, a fixed-bed plug-flow system, or multiple reactors connected in series and / or parallel. From the standpoint of equipment costs, it is preferable to use 1 to 4 reactors. Furthermore, when using multiple reactors, hydrogen peroxide may be added to them in divided portions.

[0109] To obtain an aromatic dihydroxyl compound from the reaction solution, the reaction solution or the separation solution containing the aromatic dihydroxyl compound after the catalyst has been separated may be subjected to purification treatment, such as removing unreacted components or by-products. The purification treatment is preferably performed on this separation solution containing the aromatic dihydroxyl compound after the catalyst has been separated.

[0110] There are no particular restrictions on the purification method, and specific examples include oil-water separation, extraction, distillation, crystallization, and combinations thereof. While there are no particular limitations on the purification method or procedure, for example, the separation liquid containing the aromatic dihydroxyl compound after separating the reaction solution and the catalyst can be purified by the following method.

[0111] When the reaction solution 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 aromatic dihydroxyl compounds, is removed, and the oil phase is recovered. In this case, the separated aqueous phase may be used again in the reaction, either to recover the aromatic dihydroxyl compounds by extraction or distillation, or some or all of it may be used again. Alternatively, the catalyst separated in the catalyst separation step or a dried catalyst can 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.

[0112] 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. It is preferable to separate, recover, and recycle the extraction solvent using a distillation column.

[0113] Distillation may be carried out on the reaction solution immediately after catalyst separation, or on the oil and aqueous phases after the oil-water separation described above. The extract may also be further distilled.

[0114] When distilling the reaction solution immediately after catalyst separation, it is preferable to first separate light-boiling components such as water and alcohols. Water and alcohols may be separated in separate distillation columns or in a single distillation column.

[0115] After separating water and alcohols through the above oil-water separation, extraction, and distillation operations, the phenols may be recovered in the next distillation operation and used again in the reaction. If the recovered phenols contain water that could not be separated, it can be removed by adding isopropyl ether or toluene and azeotropic distillation.

[0116] The above azeotropic distillation can also be performed on water before phenol recovery or on the liquid after alcohol separation. The separated water may be reused in the reaction or treated as wastewater. If the recovered phenols contain impurities other than water, such as reaction by-products, they can be further separated by distillation. If the impurities are benzoquinones, which are reaction by-products, they can be supplied back to the reactor along with the phenols.

[0117] After separating the phenols, components with higher boiling points than aromatic dihydroxy compounds can be removed by distillation, and hydroquinones and catechols can be separated by the next distillation operation. Alternatively, the high-boiling components, hydroquinones, and catechols can be separated in a single distillation operation by withdrawing the hydroquinones from the middle of the distillation column.

[0118] The obtained hydroquinones and catechols can be purified by removing impurities through distillation or crystallization, if necessary, to increase their purity.

[0119] When phenol and hydrogen peroxide are reacted in the presence of the above-mentioned modified aluminosilicate, hydroquinone tends to be produced in high yield. Furthermore, hydroquinone tends to be produced with higher selectivity compared to catechol and benzoquinone. For this reason, the above-mentioned modified aluminosilicate has high industrial value. It is also possible to produce aromatic polyhydroxy compounds under the same conditions as the above-mentioned method for producing aromatic dihydroxy compounds.

[0120] When producing the above-mentioned aromatic polyhydroxy compounds, preferably when reacting the modified aluminosilicate with a hydroperoxide, if the modified aluminosilicate contains the compound [AD] specified by the following formula (3), it may be possible to produce aromatic polyhydroxy compounds in high yield and with high selectivity for specific compounds such as hydroquinone.

[0121]

[0122] In the above formula (3), R １１ Q represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and Q represents a substituent containing a heteroatom and an atom selected from the group consisting of hydrogen and carbon atoms.

[0123] The above R １１Examples include aliphatic hydrocarbon groups that may have branched chains, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, and vinyl groups, and alicyclic hydrocarbon groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups. Among these, hydrocarbon groups with 1 to 2 carbon atoms are preferred, methyl, ethyl, and vinyl groups are more preferred, and ethyl groups are even more preferred.

[0124] The above Q is a substituent that includes a heteroatom such as nitrogen, oxygen, phosphorus, and halogen, and also includes an atom selected from the group consisting of hydrogen and carbon atoms. As the above Q, known functional groups can be given as preferred examples. Specifically, examples include carbonyl groups such as hydroxyl groups, amino groups, nitrile groups, and acetyl groups, and functional groups such as carboxyl groups, phosphoric acid groups, thiol groups, and sulfoxy groups. Among these, the above Q is preferably a hydroxyl group.

[0125] From the above viewpoint, examples of compound [AD] include alcohols such as methanol, ethanol, propanol, butanol and their various isomers, hexanol and its various isomers, nitrogen-containing compounds such as methylamine, ethylamine, and acetonitrile. Of these, compound [AD] is preferably an alcohol, more preferably methanol, ethanol, and even more preferably ethanol.

[0126] There are no particular restrictions on the amount of the optional compound [AD] used, but it is preferable to use it in a ratio of 0.1 to 20 moles per gram of the modified aluminosilicate. A more preferable lower limit is 0.5 moles, even more preferably 0.8 moles, and particularly preferably 1 mole. On the other hand, a more preferable upper limit is 10 moles, even more preferably 7 moles, and particularly preferably 5 moles.

[0127] The reason why using compound [AD] increases yield and selectivity is currently unknown. The inventors of this invention have proposed the following hypothesis.

[0128] The above-mentioned modified aluminosilicate may have a relatively large number of Si-OH structures on its outer surface due to reasons such as the rapid crystallization rate during its manufacturing process, resulting in small primary crystals. The presence of such OH groups increases the hydrophilicity of the particle's outer surface and generally reduces its affinity for highly hydrophobic organic substrates. Furthermore, the presence of such OH groups may lead to relatively strong interactions with the resulting aromatic polyhydroxy compounds, potentially causing these compounds to accumulate near the catalytic active site and hindering their access to the catalytic active site of aromatic hydroxy compounds, such as phenols, which are the raw materials for these compounds.

[0129] When the above-mentioned modified aluminosilicate contains compound [AD], compound [AD] is expected to have a relatively strong interaction with the surface OH groups of the modified aluminosilicate, making the surface of the modified aluminosilicate a relatively hydrophobic environment. As a result, aromatic polyhydroxy compounds are less likely to accumulate near the catalytic active site, and the relatively less polar starting aromatic hydroxy compounds can easily approach the catalytic active site, thus increasing the reaction rate.

[0130] On the other hand, the active sites on the outer surface (where the steric restriction effect is expected to be weak, likely resulting in low selectivity) readily react with compound [AD], potentially inactivating them or reducing their reactivity to a moderate level, thus increasing selectivity. This explains why relatively small (low number of carbon atoms) compounds [AD] are preferred.

[0131] From the above perspective, it is believed that if the above-mentioned modified aluminosilicate contains compound [AD], aromatic polyhydroxy compounds can be produced in high yield and with high selectivity.

[0132] From the above perspective, the method for producing modified aluminosilicate according to the present invention, and the method for producing aromatic polyhydroxy compounds using the modified aluminosilicate obtained by this method, have high industrial value.

[0133] [XRD Measurement Method] The X-ray diffraction phenomenon of the sample crystal was measured using a conventional method, except for the conditions listed below. • X-ray diffraction analyzer: Rigaku Corporation, Model: MultiFlex • X-ray source: CuKα • Output: 40kV / 20mA • Divergence slit: 1° • Scattering slit: 1° • Receiving slit: 0.30mm • 2θ: 2-52°

[0134] [Synthesis Example 1-1] Synthesis of 1,1'-(cyclohexane-trans-1,4-diyl)-bis-(1-piperidine) (hereinafter referred to as "CHDP") 5.716 grams (50.05 mmol) of trans-1,4-diaminocyclohexane were dissolved in 40 ml of distilled water in a 500 ml round-bottom flask. 8.99 grams (225 mmol) of NaOH were dissolved in 160 ml of distilled water and added to the above solution. 30 ml of distilled water was added to make a total of 230 ml of water, and then 25.50 grams (110.92 mmol) of 1,5-dibromopentane were added. The reaction vessel was immersed in an oil bath at 130°C and stirred under reflux for 18 hours. A white solid precipitated, and the entire reaction mixture including it was transferred to a separatory funnel using 100 ml of chloroform and water and separated. The aqueous layer was extracted with chloroform (100 ml x 2 times). The combined chloroform layer was washed with water (100 ml x 2 times) and saturated saline solution (100 ml x 1). The chloroform layer was dried with potassium carbonate and then filtered using filter paper (#2), and the filtrate was concentrated using a rotary evaporator. The residue (white solid) was subjected to benzene azeotrope (15 ml x 2 times), and 7.907 grams of white solid (CHDP) were obtained by vacuum drying (63.1%).

[0135] [Synthesis Example 1-1'] Synthesis of 1,1'-(cyclohexane-trans-1,4-diyl)-bis-(1-piperidine) 5.756 grams (50.4 mmol) of trans-1,4-diaminocyclohexane were dissolved in 40 ml of acetonitrile in a 500 ml round-bottom flask. 43.915 grams (317.8 mmol) of potassium carbonate and 120 ml of acetonitrile were added to the above solution. 25.097 grams (109.1 mmol) of 1,5-dibromopentane and 20 ml of acetonitrile were added to bring the total volume of acetonitrile to 180 ml. The reaction mixture was heated using an oil bath, and reflux was started after 15 minutes. The mixture was then stirred under reflux conditions for 17 hours. The reaction mixture was filtered using filter paper (#2), and the residue was thoroughly washed with chloroform (total 300 ml). The solvent was removed from the filtrate using a rotary evaporator, and the residue (white solid) was dissolved in 200 ml of chloroform. This solution was washed with water (100 ml x 2 times) and saturated saline solution (100 ml x 1 time). After drying the chloroform layer with potassium carbonate, the solution was filtered using filter paper (#2), and the filtrate was concentrated using a rotary evaporator. The residue (white solid) was subjected to azeotropic benzene treatment (20 ml x 2 times), and 10.229 grams of white solid (CHDP) were obtained by vacuum drying (81.0%).

[0136] The results of analyzing the white solids of synthesis examples 1-1 and 1-1' using the method described below are shown. Both compounds showed almost identical results.

[0137] [ １ [H NMR Measurement] Using an ECA-500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., the solvent was deuterated chloroform containing 0.03 wt% tetramethylsilane (TMS), and approximately 20 milligrams of the sample were dissolved in 0.7 milliliters of the solvent. The measurement temperature was room temperature, and the observed nucleus was １ The conditions were as follows: H (500 MHz), sequence was single pulse, 45° pulse, repetition time of 5.0 seconds or more, and integration count was 8 to 16 times or more. As a reference for chemical shift, the TMS proton was set to 0 ppm. １ Each resonance peak of H was assigned using a conventional method. The results are shown below.

[0138] 1 H NMR (CDCl3) δ: 1.23-1.31 (4H, m, N-CH2-CH2-CH2-), 1.42-1.43 (4H, m, N-CH(CHH-)2), 1.55-1.58 (8H, m, (-N(-CH2-CH2-)2, 1.89-1.94 (4H, m, N-CH(CHH-)2) 2.20-2.24 (2H, m, >CH-N<), 2.42-2.56 (8H, m, -CH2-N-CH2-)

[0139] [ １３ [C NMR Measurement] Using a JEOL Ltd. ECA-500 nuclear magnetic resonance spectrometer, approximately 20 milligrams of the sample were dissolved in 0.7 milliliters of deuterated chloroform. The measurement temperature was room temperature, and the observed nucleus was １３ The measurement conditions were as follows: C (125 MHz), single-pulse proton decoupling mode, pulse width 90°, repetition time 5.0 seconds or more, cumulative count 256 to 512 times or more, and observation range 25 to 225 ppm. As a reference for chemical shift, the central peak of the solvent-derived triplet signal was set at 77.0 ppm. (TMS) １３ This is equivalent to setting the peak of C to 0 ppm. １３ Each resonance peak of C was assigned using a conventional method. The results are shown below.

[0140] 13 C NMR (CDCl3) δ: 24.79 (N-CH2-CH2-CH2-), 26.39 (-N(CH2-CH2-)2), 27.52 (>N-CH(CH2-)2), 50.21 (-N(CH2-CH2-)2), 64.04 (>CH-N<)

[0141] [FT-IR Measurement] Measurements were taken at room temperature using a standard method with an FT / IR-6000 Fourier transform infrared spectrophotometer manufactured by JASCO Corporation. Approximately 1 milligram of powder was sandwiched between two 3 mm square KBr plates, and a single transparent KBr plate was created by compression molding and used for the measurement. The obtained spectra were analyzed according to the information provided. The results are shown below.

[0142] ​​IR (KBr, cm -1 ): 2932, 2854, 2793, 1445, 1394, 1378, 1349, 1320, 1306, 1291, 1271, 1259, 1195, 1161, 1148, 1119, 1105, 1064, 1035, 1020, 958, 918, 897, 878, 860, 849, 791, 666, 512, and 427.

[0143] [Synthesis Example 1-2] (Iodide) 1,1'-(cyclohexane-trans-1,4-diyl)-bis-(1-piperidinium) (hereinafter referred to as "CHDMP") ２＋ (I － ) ２ Synthesis of CHDP (as described above): 7.537 grams (30.10 mmol) of CHDP obtained by the method of Synthesis Example 1-1 above was dissolved in a 300 ml round-bottom flask in a mixed solvent of 45 ml methanol and 45 ml acetonitrile, and 17.33 grams (122.08 mmol) of methyl iodide was added at room temperature. The mixture was heated and stirred for 19 hours using an oil bath at 60°C. The condenser was removed, and the mixture was stirred at 70°C for 1 hour to remove the excess methyl iodide. After cooling, the solvent was removed using a rotary evaporator. 40 ml of benzene was added and then removed by distillation, and another 40 ml of benzene was added and removed by distillation. The residue was suspended in approximately 30 ml of acetone, filtered through a glass filter, and the solid on the filter was washed with approximately 70 ml of acetone. Further washing was done with benzene (10 ml x 2 times), and the mixture was dried under reduced pressure to obtain CHDP. ２＋ (I － ) ２ 15.106 grams (93.9%) were obtained as a white powder. The above white solid was analyzed by the following method.

[0144] [ １ [H NMR Measurement] Using an ECA-500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., deuterated methanol was used as the solvent, and approximately 7 milligrams of the sample were dissolved in 0.7 milliliters of solvent. The measurement temperature was 45°C, and the observed nucleus was １The conditions were: H (500 MHz), sequence: single pulse, 45° pulse, repetition time of 5.0 seconds or more, and number of integrations of 8 to 16 or more. As a criterion for chemical shift, the central peak of the signal originating from the solvent CH was set to 3.3 ppm (TMS). １ This is equivalent to setting the H peak to 0 ppm. １ Each resonance peak of H was assigned using a conventional method. The results are shown below.

[0145] 1 H NMR (CD3OD) δ: 1.69-1.75 (4H, m, N-CH2-CH2-CH2-), 1.88-1.96 (4H, m, N-CH(CHH-)2), 1.97-2.01 (8H, m, (-N(-CH2-CH2-)2), 2.42-2.43 (4H, m, N-CH(CHH-)2), 3.01 (6H, s, NCH3), 3.40-3.45 (4H, m, -CHH-N-CHH-), 3.52-3.57 (4H, m, -CHH-N-CHH-), 3.84-3.90 (2H, m, >CH-N<)

[0146] [ １ [H NMR Measurement] An ECA-500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. was used, with 0.1 wt% of 3-trimethylsilylpropionic-2,2,3,3-d solvent. ４ acid, sodium salt (TMSP-d ４ A heavy water solution containing ) was used, and approximately 15 milligrams of the sample were dissolved in 0.7 milliliters of the solvent. The measurement temperature was room temperature, and the observed nucleus was １ The conditions were: H (500 MHz), sequence: single pulse, 45° pulse, repetition time: 5.0 seconds or more, and number of integrations: 8 to 16 or more. TMSP-d was used as the criterion for chemical shift. ４ The proton concentration was set to 0 ppm. １ Each resonance peak of H was assigned using a conventional method. The results are shown below.

[0147] 1 ​​H NMR (D2O, 3-trimethylsilylpropionic-2,2,3,3-d4acid, sodium salt (TMSP-d4)) δ: 1.61-1.76 (4H, m, N-CH2-CH2-CH2-), 1.82-1.86 (4H, m, N-CH(CHH-)2), 1.89-1.94 (8H, m, (-N(-CH2-CH2-)2), 2.45-2.46 (4H, m, N-CH(CHH-)2), 2.96 (6H, s, NCH3), 3.37-3.42 (4H, m, -CHH-N-CHH-), 3.45-3.50 (4H, m, -CHH-N-CHH-), 3.60-3.65 (2H, m, >CH-N<)

[0148] [ １３ [C NMR Measurement] Using an ECA-500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., deuterated methanol was used as the solvent, and approximately 7 milligrams of the sample were dissolved in 0.7 milliliters of solvent. The measurement temperature was 45°C, and the observed nucleus was １３ The measurement conditions were as follows: C (125 MHz), single-pulse proton decoupling mode, pulse width 90°, repetition time 5.0 seconds or more, cumulative count 1024 to 1536 times or more, and observation range 25 to 225 ppm. As a reference for chemical shift, the central peak of the septuplicate signal originating from the solvent was set at 49.0 ppm (TMS). １３ This is equivalent to setting the peak of C to 0 ppm. １３ Each resonance peak of C was assigned using a conventional method. The measurement temperature was set to 45°C due to the low solubility of deuterated methanol. Using heavy water is more suitable, as described below. The results are shown below.

[0149] 13 C NMR (CD3OD) δ: 20.95 (-N(CH2-CH2-)2), 21.97 (N-CH2-CH2-CH2-), 24.65 (>N-CH(CH2-)2), 44.86 (-NCH3), 61.31 (-N(CH2-CH2-)2), 69,54 (>CH-N<)

[0150] [ １３ ​[C NMR Measurement] A JEOL Ltd. ECA-500 nuclear magnetic resonance spectrometer was used, with 0.1 wt% 3-trimethylsilylpropionic-2,2,3,3-d solvent. ４ acid, sodium salt (TMSP-d ４ A heavy water solution containing ) was used, and approximately 15 milligrams of the sample were dissolved in 0.7 milliliters of the solvent. The measurement temperature was room temperature, and the observed nucleus was １３ The measurement conditions are as follows: C (125 MHz), single-pulse proton decoupling mode, pulse width 90°, repetition time 5.0 seconds or more, cumulative count 256 to 512 times or more, and observation range 25 to 225 ppm. TMSP-d is used as the reference for chemical shift. ４ of １３ The peak of C was set to 0 ppm. １３ Each resonance peak of C was assigned using a conventional method. The results are shown below.

[0151] １3 C NMR (D2O, TMSP-d4) δ: 22.23 (-N(CH2-CH2-)2), 23.28 (N-CH2-CH2-CH2-), 26.06 (>N-CH(CH2-)2), 46.32 (-NCH3), 62.75 (-N(CH2-CH2-)2), 71.03 (>CH-N<)

[0152] [FT-IR Measurement] Measurements were taken at room temperature using a standard method with an FT / IR-6000 Fourier transform infrared spectrophotometer manufactured by JASCO Corporation. Approximately 1 milligram of powder was sandwiched between two 3 mm square KBr plates, and a single transparent KBr plate was created by compression molding and used for the measurement. The obtained spectra were analyzed according to the information provided. The results are shown below.

[0153] IR (KBr, cm -1 ): 3518, 3455, 3011, 2949, 2877, 1617, 1489, 1472, 1454, 1399, 1223, 1077, 1023, 978, 963, 934, 912, 878, 854, 824, 793, 757, and 576.

[0154] ​[Example 1] [First Step: Preparation of Aluminosilicate (A-1)] 1.50 grams of colloidal silica (product name: LUDOX (registered trademark) HS-40, manufactured by Sigma-Aldrich), 40 milliliters of distilled water, 78 milligrams of Al(OH) ３ was placed in a container and stirred for 10 minutes to obtain a gel-like substance. 620 milligrams of 6.02 mmol / gram - KOH aqueous solution was added, and it was further stirred for 30 minutes. Then 536 milligrams of CHDMP obtained by the method of Synthesis Example 1-2 above ２＋ (I － ) ２ was added and stirred for 4 hours. Then the mixture was put into an autoclave and heated at 160 °C for 42 hours. The cooled mixture was centrifuged, washed with water, and dried (drying conditions: 80 °C, 8 hours) to obtain crystals (1-0).

[0155] The highest peak in the 17.5 - 35° region measured by XRD of the above crystals (1-0) was observed at 21.76°, and the intensity ratio with the peak observed at 26.22°, which is the highest peak in the 25.0 - 27.0° region, was 3.08. The above crystals (1-0) were heated in a muffle furnace at a rate of 1 °C / min to 650 °C and calcined at that temperature for 10 hours to obtain crystals (1-1).

[0156] [Second Step: Contact and Treatment with Acid] 3 grams of the crystals (1-1) prepared above and 90 grams of 60% nitric acid were placed in a round-bottom flask with a Dimroth condenser, mixed, and then the flask was immersed in an oil bath at 130 °C and heated under reflux for 24 hours. The cooled mixture was centrifuged and washed with water (until the washing liquid became neutral), and air-dried at 30 - 40 °C overnight to obtain crystals (1-2).

[0157] [Third step: Contact with titanium compound, secondary calcination] Under argon flow, 0.5 grams of the crystals (1-2) obtained above were packed into a quartz glass tube with an inner diameter of 10 mm, and the temperature was raised to 500°C over 100 minutes while argon (30 ml / min) was flowed through it, and the tube was heat-treated at that temperature for 4 hours. Next, the temperature was raised to 600°C over 30 minutes. Separately, about 10 ml of titanium tetrachloride was placed in a glass bubbler container, and the titanium tetrachloride vapor generated by bubbling argon (30 ml / min) was brought into contact with the crystals (1-2) heated to 600°C as described above, at 600°C for 1 hour. After that, only an argon gas stream (30 ml / min) was flowed at 600°C for 1 hour, and the tube was allowed to cool under argon flow. The solid after treatment was collected, washed with water, and then degassed and dried. Subsequently, the temperature was raised to 650°C at a rate of 1°C / min in a muffle furnace, and firing was carried out at that temperature for 4 hours to obtain crystals (1-3) which are crystalline porous aluminotitanosilicate.

[0158] [Example 2] Ti-MSE_CHDMP [Step 1: Preparation of aluminosilicate (A-2)] 1.50 grams colloidal silica (product name: LUDOX® HS-40, manufactured by Sigma-Aldrich), 40 milliliters distilled water, 78 milligrams Al(OH) ３ The mixture was placed in a container and stirred for 10 minutes to obtain a gel-like substance. 620 milligrams of a 6.06 mmol / gram-KOH aqueous solution were added and stirred for a further 30 minutes. Then, 536 milligrams of the CHDMP obtained by the method described in Synthesis Example 1-2 above were added. ２＋ (I － ) ２ After adding and stirring for 4 hours, the mixture was placed in an autoclave and heated at 160°C for 42 hours. The cooled mixture was centrifuged, washed with water, and dried (drying conditions: 80°C, 8 hours) to obtain crystals (2-0).

[0159] In the above crystal (2-0), the highest peak in the 17.5–35° region measured by XRD was observed at 21.62°, and the intensity ratio of this peak to the highest peak in the 25.0–27.0° region, observed at 26.12°, was 3.01. The above crystal (2-0) was calcined at 650°C for 10 hours to obtain crystal (2-1).

[0160] [Second Step: Contact with Acid] 2 grams of the crystals (2-1) prepared above and 60 milliliters of 60% nitric acid were placed in a 200-milliliter round-bottom flask with a Dimroth condenser and mixed. Then, it was heated using an oil bath at 130 °C for 24 hours (the first acid treatment). After the cooled mixture was centrifuged, washed with water, and air-dried for 1 hour, the exact same operation as the first acid treatment was performed again. The cooled mixture was centrifuged, washed with water, and air-dried for 15 hours to obtain crystals (2-2).

[0161] [Third Step: Contact with Titanium Compound] Under an argon flow, 0.5 grams of the crystals (2-2) obtained above were packed into a quartz glass tube with an inner diameter of 10 mm. While flowing argon (30 milliliters / minute), the temperature was raised to 500 °C over 100 minutes and heat-treated at that temperature for 4 hours. Separately, about 10 milliliters of titanium tetrachloride was placed in a glass bubbler container, and the vapor of titanium tetrachloride generated by bubbling argon (30 milliliters / minute) was brought into contact with the crystals (2-2) heated to 600 °C as described above at 600 °C for 1 hour. Then, only an argon stream (30 milliliters / minute) was flowed at 600 °C for 1 hour, and it was allowed to cool under an argon flow. The treated solid was recovered, washed with water, and then degassed and dried. Thereafter, the temperature was raised to 650 °C at 1 °C / minute in a muffler furnace, and calcination was performed at that temperature for 4 hours to obtain crystals (2-3) which are crystalline porous aluminotitanosilicate.

[0162] [Comparative Example 1] In a conventional method for producing titanosilicate having MCM-68 as the basic framework, an MCM-68 particle sample ([Ti]-MCM-68cal) was prepared through the first to third steps. Specifically, it was prepared according to the following procedure.

[0163] [First Step] 15.01 grams of colloidal silica (Ludox AS40) and 20.0 grams of water were placed in a container with an internal volume of 180 milliliters and stirred for 10 minutes. Here, 0.780 grams of Al(OH) ３ and 6.23 grams of an aqueous KOH solution (8 mol / liter) were added and stirred for 30 minutes. Subsequently, TEBO ２＋ (I - ) ２5.583 grams of [the substance] and 20.3 grams of pure water were added and the mixture was stirred for 4 hours. The 125 ml Teflon® container containing the prepared gel was placed directly into a stainless steel autoclave and left to stand in an oven at 160°C for 16 days. The resulting product was filtered and washed with water, and then dried at room temperature to obtain 5.804 grams of crystals (C1-0).

[0164] The highest peak in the 17.5–35° range of the above crystal (C1-0), measured by XRD, was observed at 21.68°, and the intensity ratio of this peak to the highest peak in the 25.0–27.0° range, observed at 26.14°, was 3.11. The above crystal (C1-0) was calcined at 650°C for 10 hours to obtain crystal (C1-1).

[0165] [Steps 2-3] Preparation was carried out under the same conditions as in Example 1, except that the above crystal (C1-1) was used instead of crystal (1-1), to obtain crystal (C1-2) and crystalline porous aluminotitanosilicate (crystal C1-3).

[0166] [Evaluation of Catalyst Performance] The performance of the crystalline porous aluminotitanosilicates of Examples 1 and 2 and Comparative Example 1 as hydroquinone production catalysts was evaluated using the following three measurement methods. The results are summarized in Table 1. In the table, HQ represents hydroquinone and CL represents catechol. The measurement methods and calculation formulas for each value are shown below.

[0167] [Measurement Method 1] In a 35 ml glass pressure vessel, 20 ml each of the catalysts, 21.25 mmol of phenol, and 4.25 mmol of hydrogen peroxide (466 ml of 30 wt% hydrogen peroxide solution) were charged. In some cases, 42.5 mmol of ethanol was added as an additive. The mixture was heated for 60 minutes using a water bath preheated to 70°C, while stirring with a stirrer. After cooling the reaction mixture in an ice bath, the sulfolane (2 g, solvent that does not affect the main reaction for derivatization) and anisole (2.0 mmol, internal standard substance) catalysts were centrifuged. A portion of the supernatant (100 ml) was taken, and an excess amount of acetic anhydride (2 mmol) and potassium carbonate (300 ml) were added. The mixture was reacted at 35°C for 10 minutes to thoroughly acetylate the OH groups. After removing solids with a membrane filter, the resulting solution was quantitatively analyzed by gas chromatography. The unreacted hydrogen peroxide was quantified using iodine titration as follows. A solution of 0.2 grams of potassium iodide dissolved in 2.0 mol / liter hydrochloric acid was thoroughly mixed with 1.0 gram of the reaction solution, and the mixture was titrated with a 0.1 mol / liter aqueous solution of sodium thiosulfate. The endpoint was determined using a potentiometric automatic titrator AT-710 manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0168] [Measurement Method 2] The same conditions as in Measurement Method 1 were used, except that ethanol was not used.

[0169] [Measurement Method 3] The same conditions as in Measurement Method 2 were used, except that the water bath temperature was set to 100°C and the heating time was set to 10 minutes.

[0170] The analytical conditions for gas chromatography are as follows: • Detector: Flame ion detector • Column: DB-1 (Agilent J&W), inner diameter 0.25 mm, length 30 m, film thickness 1.0 μm • Column temperature: Held at 50°C for 10 minutes, heating rate 10°C / min, heating up to 280°C • Inlet: 280°C • Detector temperature: 280°C • Carrier gas: Helium • Flow rate: 80 ml / min

[0171] [Calculation formula] Total yield = ((moles of hydroquinone produced) + (moles of catechol produced) + (moles of benzoquinone produced)) / (moles of hydrogen peroxide introduced) × 100 Hydroquinone yield (%) = (moles of hydroquinone produced) / (moles of hydrogen peroxide introduced) × 100

[0172] Hydrogen peroxide conversion rate (%) = (Moles of hydrogen peroxide introduced - Moles of unreacted hydrogen peroxide) / (Moles of hydrogen peroxide introduced) Hydroquinone / catechol ratio = (Moles of hydroquinone produced) / (Moles of catechol produced)

[0173]

Claims

1. A method for producing a modified aluminosilicate, comprising: a first step of contacting gel-like or sol-like silica, zeolite, and an ammonium salt represented by the following formula (1) to obtain an aluminosilicate (A-1); a second step of treating the aluminosilicate (A-1) obtained in the first step with acid; and a third step of contacting the product obtained in the second step with a compound 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 calcination. (In the above formula (1), C is a carbon atom, N ＋ X is a nitrogen cation. － R and R represent halogen anions or hydroxy anions. １ Each of the following independently represents a hydrocarbon group which may contain a hydrogen atom or a heteroatom, m1 and m2 are each independently integers from 0 to 5, n1 and n2 are each independently integers from 0 to 5, the sum of n1 and n2 is from 1 to 10, and there are multiple R and R １ These elements can bond to each other to form a ring structure.

2. The aforementioned X － The method for producing a modified aluminosilicate according to claim 1, wherein the iodine anion is used.

3. The method for producing a modified aluminosilicate according to claim 1, wherein m1 and m2 are 0.

4. The aforementioned R １ A method for producing a modified aluminosilicate according to claim 1, comprising a ring structure formed by bonding of two or more elements.

5. A method for producing a modified aluminosilicate according to claim 1, comprising contacting a compound containing one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table in gaseous form.

6. A method for producing a modified aluminosilicate according to claim 1, comprising contacting a compound containing one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table in gaseous form at 350 to 850°C.

7. The method for producing a modified aluminosilicate according to claim 1, wherein the element selected from the group consisting of Group 4 and Group 5 elements of the periodic table is titanium.

8. A first step of obtaining an aluminosilicate (A-1) by contacting a gel-like or sol-like silica, a zeolite, and an ammonium salt represented by the following formula (1); a second step of treating the aluminosilicate (A-1) obtained in the first step with an acid; and a third step of drying and firing after contacting the product obtained in the second step with a compound containing one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table. A method for producing an aromatic polyhydroxy compound, which comprises a step of reacting an aromatic hydroxide and a hydroperoxide in the presence of a modified aluminosilicate obtained by the method. (In the above formula (1), C is a carbon atom, N ＋ is a nitrogen cation, X － represents a halogen anion or a hydroxy anion, R and R １ each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, m1 and m2 are each independently an integer of 0 to 5, n1 and n2 are each independently an integer of 0 to 5, the sum of n1 and n2 is 1 to 10, and a plurality of R and R １ may be bonded to each other to form a ring structure.) 9. The method for producing an aromatic polyhydroxy compound according to claim 8, wherein the modified aluminosilicate comprises a compound [AD] represented by the following formula (3). (In the above formula (3), R １１ (where Q represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and Q is a substituent containing a heteroatom and an atom selected from the group consisting of hydrogen and carbon atoms.) 10. The method for producing an aromatic polyhydroxy compound according to claim 9, wherein the compound [AD] is an alcohol.

11. The method for producing an aromatic polyhydroxy compound according to claim 9, wherein the compound [AD] is an alcohol containing ethanol.

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