Method for producing modified aluminosilicate, modified aluminosilicate, and method for producing aromatic polyhydroxide compound using the same

Abstract

The present invention provides a method for manufacturing a modified aluminosilicate in which a hydroquinone is highly selectively manufactured by a reaction between a phenol and hydrogen peroxide under industrially advantageous conditions, wherein the manufacturing method comprises: a second step for treating an aluminosilicate with an acid, the highest peak (B) in a region of 17.5-35° in XRD measurement being located in a region of from 20° to less than 22.5°, and the peak intensity ratio of the peak (B) relative to the highest peak (Y) in a region of 25-27° being in a range of 1.7-5.0; a third step for performing primary firing of the treatment product obtained in the second step; and a fourth step in which the primary fired product obtained in the third step, and a liquid containing one or more elements selected from the group consisting of elements in Group 4 and Group 5 of the Periodic Table, are brought into contact with each other, and drying and secondary firing are then performed.

Description

Technical Field

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

Background Art

[0002] Aromatic dihydroxide compounds are important as various organic synthesis intermediates or raw materials, and are used in fields such as reducing agents, rubber chemicals, dyes, pharmaceuticals, agricultural chemicals, polymerization inhibitors, and antioxidants.

[0003] Aromatic dihydroxide compounds obtained by reacting phenols with hydrogen peroxide are, for example, hydroquinone and catechol, and the production ratios of hydroquinone and catechol differ depending on the production method. In recent years, due to the demand balance between hydroquinone and catechol, a method for producing hydroquinone with high selectivity has been eagerly desired.

[0004] In order to produce an aromatic dihydroxide compound by reacting phenols with hydrogen peroxide, a method using titanosilicate, which is one of the crystalline porous silicates, as a catalyst has been disclosed (for example, Patent Document 1 and Patent Document 2). Further, Patent Document 3 discloses a titanosilicate obtained by treating an acid-treated aluminosilicate with titanium chloride or titanium alkoxide in the gas phase.

[0005] Further, Patent Document 4 discloses a method for producing a titanosilicate, which is obtained by mixing a template raw material of aluminosilicate, an aluminum source, a titanium source, a silicon source, an iodide, and water to prepare a gel, heating the gel for crystallization, and then firing the gel.

[0006] The present inventors have disclosed a method for producing an aluminotitanosilicate by bringing an aluminosilicate compound into contact with a liquid titanium halide compound. (Patent Document 5)

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0008] It is suggested that the aluminotitanosilicate obtained in Patent Document 5 above can be an excellent catalyst for producing aromatic dihydroxide compounds. Among them, it is disclosed that an aluminotitanosilicate into which a titanium source is introduced using titanium tetrachloride gives an aromatic dihydroxide compound with a particularly high selectivity. Further, according to the X-ray crystal structure analysis (X-ray diffraction (XRD) measurement) by the present inventor, the aluminotitanosilicate in the example of Patent Document 5 was a compound showing a maximum peak at 23 to 24°.

[0009] On the other hand, although it is disclosed that it is possible to produce an aromatic dihydroxide compound with a high selectivity even by a method using an aqueous solution of titanium trichloride or the like, which is a milder method for introducing a titanium source, it seems that it does not reach the method using the above titanium tetrachloride.

[0010] An object of the present invention is to provide a method for producing a modified aluminosilicate capable of highly selectively producing hydroquinones under industrially more advantageous conditions than conventional ones, for example, by reacting phenols with hydrogen peroxide or the like. Another object is to provide a catalyst capable of highly selectively producing hydroquinones under more industrially advantageous conditions, for example, by reacting phenols with hydrogen peroxide or the like, and a method for producing an aromatic polyhydroxide compound using the same catalyst.

Means for Solving the Problems

[0011] As a result of investigations into the above problems, the present inventors have found that when an aluminosilicate is produced by bringing an aluminosilicate showing a special diffraction pattern in XRD measurement, zeolite, and silica gel into contact with each other, a modified aluminosilicate such as an aluminotitanosilicate capable of producing hydroquinones with extremely high selectivity can be obtained even in a mode in which a titanium source is introduced using a trivalent transition metal compound such as an aqueous titanium trichloride solution. Further, in a mode using a tetravalent transition metal compound such as titanium tetrachloride, it has been found that a modified aluminosilicate such as a more highly performance aluminotitanosilicate can be obtained, and the present invention has been completed.

[0012] That is, the present invention includes the matters described in the following [1] to [8]. [1] A first step of obtaining an aluminosilicate (A-1') by bringing gel-like silica, zeolite, and a crystal (A) which is an aluminosilicate having the highest peak (α) at 22.5 to 25.0° in the range of 17.5 to 35° in XRD measurement into contact with each other; A second step of treating the aluminosilicate (A-1') obtained in the first step with an acid; A third step of subjecting the treated product obtained in the second step to primary firing at 550°C to 850°C; A method for producing a modified aluminosilicate, including a fourth step of bringing the fired product obtained in the third step into contact with a liquid containing one or more elements selected from the group consisting of elements of Group 4 and Group 5 of the periodic table, followed by drying and secondary firing. [2] The method for producing a modified aluminosilicate according to [1], wherein the crystal (A) in the first step is obtained by including a step of bringing gel-like silica and zeolite into contact with each other and treating them at 155 to 168°C for 30 to 40 hours. [3] In the XRD measurement in the range of 17.5 to 35°, having the highest peak (β) in the range of more than 20° and less than 22.5°, and the peak intensity ratio of the peak (β) to the highest peak (γ) in the range of 25 to 27° is in the range of 1.7 to 5.0, aluminosilicate (A-1). [4] The aluminosilicate (A-1) according to [3], wherein the peak intensity ratio is in the range of 1.7 to 4.0. [5] A catalyst for producing an aromatic polyhydroxide compound, comprising the modified aluminosilicate according to [1]. [6] A second step of treating the aluminosilicate (A-1) according to [3] with an acid, A third step of subjecting the treated product obtained in the second step to primary firing at 550°C to 850°C, A fourth step of contacting the fired product obtained in the third step with a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, and then performing drying and secondary firing, a method for producing a modified aluminosilicate. [7] A catalyst for producing an aromatic polyhydroxide compound, comprising the modified aluminosilicate according to [6]. [8] A method for producing an aromatic polyhydroxide compound, comprising a step of reacting an aromatic hydroxide and a hydroperoxide in the presence of the catalyst according to [5] or [7].

Advantages of the Invention

[0013] According to the method for producing the modified aluminosilicate, it is one feature to obtain an industrially useful modified aluminosilicate using an aluminosilicate having a specific crystal structure as a raw material. Such a modified aluminosilicate can be used as a catalyst suitable for the production of aromatic polyhydroxide compounds even when it is brought into contact with a liquid containing one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table, for example, an aqueous solution of a titanium source, under mild conditions. Thus, an aluminotitanosilicate can be obtained. Therefore, the present invention has important industrial significance. Further, by using the modified aluminosilicate produced by the above production method, for example, an aromatic dihydroxide compound such as hydroquinone can be highly selectively produced by reacting phenols with hydrogen peroxide.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0015] Hereinafter, embodiments of the present invention will be described in detail. <Method for Producing Modified Aluminosilicate Using Aluminosilicate (A-1’)> The method for producing the modified aluminosilicate of the present invention comprises gel-like silica and zeolite In the XRD measurement, in the range of 17.5 to 35°, a first step of obtaining an aluminosilicate (A-1') by bringing into contact a crystal (A) (hereinafter also simply referred to as "crystal (A)"), which is an aluminosilicate having the highest peak (α) at 22.5 to 25.0°, a second step of bringing the aluminosilicate (A-1') obtained in the first step into contact with an acid; a third step of subjecting the treated product obtained in the second step to primary firing at 550°C to 850°C; and a fourth step of performing drying and secondary firing after bringing the fired product obtained in the third step into contact with a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table.

[0016] 〔First step〕 The first step is a step of producing an aluminosilicate (A-1') by bringing crystal (A) into contact with gel-like silica as a silicon source and zeolite as an aluminum source.

[0017] First, crystal (A) used in the first step will be described. Here, it is preferable that crystal (A) does not contain Group 4 elements and Group 5 elements, or even if it contains them, the degree does not affect the effects of the present invention. Examples of the Group 4 elements include titanium, zirconium, hafnium, etc. Examples of the Group 5 element include vanadium, etc. Among these elements, Group 4 elements are preferable, titanium, zirconium, and hafnium are more preferable, and titanium is even more preferable. The above elements can be used alone or in combination of two or more.

[0018] Crystal (A) and the aluminosilicate are preferably porous. Hereinafter, a crystalline and porous aluminosilicate is simply referred to as a crystalline porous aluminosilicate.

[0019] Crystal (A) has a structure in which, in the range of 17.5 to 35° in XRD measurement, the highest peak (α) appears at 22.5 to 25.0°. The range of the angle showing the highest peak (α) has a preferable lower limit value of 22.7°, more preferably 23.0°, and even more preferably 23.3°. On the other hand, its preferable upper limit value is 24.7°, more preferably 24.5°.

[0020] Crystal (A) having a structure specified by such XRD measurement can be regarded as a so-called "seed crystal" when producing the aluminosilicate described later. By using crystal (A) having the above structure, an aluminosilicate, which is a raw material of a catalyst suitable for producing the aromatic polyhydroxide compound described later, can be obtained.

[0021] Crystal (A) preferably has a porous crystalline body having at least a part where SiO4 tetrahedrons with oxygen arranged at four vertices centered on silicon and AlO4 tetrahedrons with aluminum arranged instead of the central silicon are regularly three-dimensionally bonded.

[0022] Crystal (A) is not particularly limited as long as it has the above structure. In the structure code of the International Zeolite Association, a crystalline porous aluminosilicate having an MSE-type structure (hereinafter referred to as "MSE framework") is preferable, and UZM-35, MCM-68, YNU-3, etc. are particularly preferable.

[0023] The crystalline porous aluminosilicate having the above MSE framework has a three-dimensional pore structure having a 10-membered ring structure composed of 10 units of the above tetrahedrons and a 12-membered ring structure composed of 12 units of the above tetrahedrons.

[0024] The crystalline substance (A) can be obtained, for example, by bringing a known silicon source such as colloidal silica, an aluminum source such as zeolite, preferably an organic structure-directing agent such as dimethyldipropylammonium hydroxide, and a known alkali source into contact with each other, stirring, and heating. The colloidal silica can also be used in a sol state by previously setting the temperature to a high temperature such as 50°C to 100°C, which is a preferred method. At this time, the heating temperature range is 155 to 168°C, and it is preferable to maintain this temperature for 30 to 40 hours. A more preferable lower limit value of the temperature is 157°C, and even more preferably 158°C. On the other hand, a more preferable upper limit value is 167°C, and even more preferably 166°C.

[0025] By setting such a temperature range, there is a tendency to easily produce an aluminosilicate having a crystal structure that strongly diffracts at the specific angle. In addition, in the step of producing the crystalline substance (A), the temperature does not substantially exceed 168°C. (The term "substantially" means that, for example, in the above heating step, when controlling the temperature, it is allowed to exceed 168°C for about several minutes.)

[0026] Next, the aluminosilicate (A-1') will be described. The aluminosilicate (A-1') obtained in the first step of the present invention can generally be produced by the same method as the method for producing the crystalline substance (A). However, it is essential to bring the gel-like silica as the silicon source and the zeolite as the aluminum source into contact with each other in the presence of the crystalline substance (A). In addition, the heating temperature and time in the first step are arbitrary as long as they do not conflict with the object of the present invention. A preferable lower limit value of the temperature is 130°C, and more preferably 150°C. On the other hand, a preferable upper limit value is 700°C.

[0027] In addition, a preferable lower limit value of the time is 10 hours, and more preferably 20 hours. On the other hand, a preferable upper limit value is 100 hours, and more preferably 90 hours.

[0028] By using the crystal (A) as a so-called seed crystal, crystal growth during the synthesis of aluminosilicate (A-1') is promoted. The amount of the crystal (A) used is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, based on silica as the silicon source. Further, the zeolite as the aluminum source also functions as a silicon source, and the amount of its use is preferably 5 to 50% by weight, more preferably 8 to 40% by weight, based on silica.

[0029] The aluminosilicate (A-1') thus obtained preferably has the highest peak (β) in the region of 20° or more and less than 22.5° in the region of 17.5 to 35° in XRD measurement, and the peak intensity ratio of the peak (β) to the highest peak (γ) in the region of 25 to 27° is in the range of 1.7 to 5.0. The preferable lower limit value of the peak intensity ratio is 1.72, more preferably 1.8, particularly preferably 1.9. On the other hand, the preferable upper limit value is 4.5, more preferably 4.2, still more preferably 4.0, particularly preferably 3.5. Among these, the still more preferable upper limit value is 3.0, particularly preferably 2.5.

[0030] When using such an aluminosilicate (A-1’), although the reason is unclear at present, by using a method of introducing a titanium source or the like as described later, for example, a catalyst suitable for an aromatic polyhydroxide compound can be obtained. In addition, the aluminosilicate used in the second step described later has the highest peak (β) in the region of 20° or more and less than 22.5° in the region of 17.5 - 35° in XRD measurement, and if the peak intensity ratio of the peak (β) to the highest peak (γ) in the region of 25 - 27° is in the range of 1.7 - 5.0 as described above, preferably 1.7 - 4.5, more preferably 1.7 - 4.0, even if it is not the aluminosilicate (A-1’) obtained by the production method in the first step, a catalyst for an aromatic polyhydroxide compound having characteristics as described later can be obtained. The overall body with such a “specific requirement of having the highest peak (β) in the region of 17.5 - 35° in XRD measurement, in the region of 20° or more and less than 22.5°, and the peak intensity ratio to the highest peak (γ) in the region of 25 - 27° being in the range of 1.7 - 5.0” is defined as aluminosilicate (A-1) in the present invention, and will be described in detail later.

[0031] The aluminosilicate (A-1’) shows a crystal structure, but its crystal form is presumably different from that of conventional aluminosilicates, and may be a somewhat unstable structure (especially compared to the value of the intensity ratio of the peak (β) to the peak (γ)). It is also speculated that such instability may lead to excellent performance as a catalyst for producing aromatic polyhydroxide compounds when it becomes the modified aluminosilicate described later.

[0032] In addition, when introducing an element selected from the group consisting of Groups 4 and 5 of the periodic table described later in the present invention into the fired product of the aluminosilicate (A-1’) obtained through the second and third steps described later, the introduction site of the above element can be mainly considered as the surface of the solid of the fired product of the aluminosilicate (A-1’). Therefore, it can be considered that the crystal structure is almost the same before and after the introduction of the above element.

[0033] Examples of the raw materials for the gel-like silica include colloidal silica, sodium silicate, wet silica, dry silica, etc. These silicon sources can be used alone or in combination of two or more.

[0034] As the above aluminum source, components other than zeolite may be used in combination. 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, etc. These aluminum sources can be used alone or in combination of two or more.

[0035] As the above alkali source, for example, a hydroxide containing an alkali metal can be used. Examples of the hydroxide containing an alkali metal include sodium hydroxide, potassium hydroxide, etc. These alkali sources can be used alone or in combination of two or more.

[0036] As the above organic structure-directing agent, known compounds such as N,N,N’,N’-tetraethylbicyclo[2,2,2]oct-7-ene-2,3:5,6-dipyrrolidinium diiodide can be used.

[0037] It is preferable to calcine the aluminosilicate (A-1’) before the second step described later. The method of the above calcination is not particularly limited, and for example, a method of calcining using an electric furnace, a gas furnace, etc. can be mentioned. As the calcination conditions, it is preferable to heat for 0.1 hour to 20 hours in an air atmosphere. The calcination temperature is preferably 550°C to 850°C, and more preferably 600°C to 800°C.

[0038] 〔Second Step〕 The step of treating the aluminosilicate (A-1’) obtained in the first step with an acid, in other words, the step of bringing the aluminosilicate (A-1’) into contact with an acid is the second step. Examples of the acid used in this step include inorganic acids, organic acids, and mixtures thereof. Specific examples thereof include nitric acid, hydrochloric acid, sulfuric acid, citric acid, oxalic acid, and mixtures thereof. Among these, acids containing elements selected from Group 15 and Group 16 elements of the periodic table are preferred, and nitric acid is particularly preferred. The concentration of the acid is not particularly limited, but is preferably 5% by weight to 80% by weight, and more preferably 40% by weight to 80% by weight. When this acid is used as an aqueous solution, its usage amount is preferably 1 to 100 parts by weight with respect to 1 part by weight of the aluminosilicate (A-1'). A more preferable lower limit value is 2 parts by weight, still more preferably 3 parts by weight, and particularly preferably 5 parts by weight. The upper limit of the preferable range is 10 parts by weight, more preferably 20 parts by weight. On the other hand, a more preferable upper limit value is 70 parts by weight, still more preferably 50 parts by weight.

[0039] The temperature condition for bringing the aluminosilicate (A-1') into contact with the acid is preferably 50°C to 170°C, and more preferably 130°C to 170°C. The time for treatment with the acid is preferably 5 hours to 48 hours, and more preferably 12 hours to 36 hours. A further preferable lower limit of the time is 18 hours. It is considered that a part of aluminum is removed from the aluminosilicate by contact with this acid. It is presumed that mainly the aluminum on the surface of the aluminosilicate is removed. By selecting the conditions of relatively high temperature and long time as described above, it is presumed that it becomes easier to form a structure advantageous for the introduction of the Group 4 and Group 5 elements in the firing treatment in the third step described later.

[0040] 〔Third Step〕 In the third step, primary firing of the processed material obtained in the second step above, i.e., the aluminosilicate (A-1') contacted with an acid, is performed. The firing method is not particularly limited, and examples include firing using an electric furnace, a gas furnace, or the like. As the firing conditions, it is preferable to heat in an air atmosphere for 0.1 hour to 20 hours. The firing temperature is 550°C to 850°C, and more preferably 600°C to 800°C. It is presumed that the primary firing in this relatively high-temperature environment provides an environment favorable for the formation of the so-called modified aluminosilicate obtained in the fourth step, which contains Group 4 and Group 5 elements of the periodic table, with titanium species as a representative example, in a highly active state.

[0041] Before firing the aluminosilicate (A-1') contacted with the above acid, it is preferable to filter the processed material using a Nutsche or the like to separate the used acid (aqueous solution) and the like, and then wash and dry the solid part (filter cake). The washing step is preferably performed while maintaining a wet state without drying before washing. The drying method after water washing is not particularly limited, but it is preferable to dry uniformly and rapidly. For example, external heating methods such as hot air drying and superheated steam drying, or electromagnetic wave heating methods such as microwave heating drying and high-frequency dielectric heating drying can be used.

[0042] 〔Fourth step〕 In the fourth step, the fired product obtained in the above third step (hereinafter also referred to as "primary fired product") is brought into contact in a liquid phase with a liquid containing one or more elements selected from Group 4 and Group 5 elements of the periodic table as an element source, and then dried and secondarily fired. Examples of the Group 4 and Group 5 elements of the periodic table include titanium, zirconium, hafnium, vanadium, etc. Preferred elements are titanium, zirconium, and vanadium, and titanium is particularly preferred. Examples of compounds containing these elements include halides, alkoxides, and salts of inorganic acids of each element as suitable compounds. More preferably, as the halide, it is chloride, and as the alkoxide, it is in a form containing an alkoxy group having 1 to 6 carbon atoms. Even more preferred alkoxides include ethoxide, butoxide (n-butoxide, i-butoxide, s-butoxide, t-butoxide), sulfate, etc. These compounds may of course be used in combination of two or more.

[0043] Hereinafter, as a representative example, an embodiment using a liquid containing titanium (liquid-phase titanium source), which is the most preferred embodiment among Group 4 and Group 5 elements of the periodic table, will be described.

[0044] The liquid-phase titanium source is a liquid containing titanium. Examples of the liquid containing titanium include, for example, the liquid titanium compound itself or an aqueous solution of a titanium compound. Among them, it is a preferred embodiment that it is a titanium compound that substantially shows acidity in a liquid state.

[0045] Examples of the liquid titanium compound include, for example, titanium tetrachloride (TiCl4), tetrabutoxytitanium, etc. Among them, titanium tetrachloride is preferred. Examples of the aqueous solution of a titanium compound include, for example, an aqueous solution of titanium tetrachloride, an aqueous solution of titanium trichloride (TiCl3), titanium sulfate ( titanium, etc. Among them, titanium tetrachloride is preferred. Examples of the aqueous solution of a titanium compound include, for example, an aqueous solution of titanium tetrachloride, an aqueous solution of titanium trichloride (TiCl3), titanium sulfate ( Examples of the titanium-containing liquid include aqueous solutions of Ti(SO4)2 and potassium hexafluorotitanate. Among these, aqueous solutions of titanium tetrachloride, titanium trichloride, and titanium sulfate are preferred. In the present 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 below can be exhibited. In particular, there is a tendency to achieve catalytic activity that can obtain aromatic polyhydroxide compounds with high selectivity.

[0046] The above-mentioned titanium-containing liquid can be used alone or in combination of two or more. As the above-mentioned titanium-containing liquid, commercially available products can be used, or a product appropriately prepared by diluting a solid titanium compound with water to a desired concentration can also be used. Compared with a gas-phase titanium source, a liquid-phase titanium source (titanium-containing liquid) is less likely to leak, and the problem of corrosion of manufacturing machines, analytical instruments, etc. is also improved, so industrial production becomes easier to implement.

[0047] The conditions for contacting the above primary fired product with the titanium source are not particularly limited. By this contact, titanium is introduced into the primary fired product of the aluminosilicate. It is considered that this introduction of titanium occurs such that titanium is introduced at the position of aluminum that is considered to have been removed in the second step, or a reaction occurs in which part of the aluminum in the aluminosilicate (A-1') is replaced by titanium. As specific conditions for this step, for example, when using the liquid titanium compound itself, it is preferable to add 5 to 300 parts by weight, more preferably 20 to 250 parts by weight of the liquid titanium compound per 1 part by weight of the primary fired product. When using an aqueous solution of a titanium compound, it is preferable to add 1 to 10 parts by weight, more preferably 1 to 7 parts by weight of the aqueous solution of the titanium compound per 1 part by weight of the primary fired product. The concentration of the above aqueous solution varies depending on the compound used, but is, for example, 10 to 70% by weight, preferably 15 to 60% by weight.

[0048] The amount of the titanium compound in the aqueous solution, the preferable lower limit 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 is 10 g, more preferably 5 g, and still more preferably 3 g.

[0049] The contact between the above titanium source and the aluminosilicate (A-1') fired primarily may be carried out only once as long as the weight ratio used is within the above addition amount range, or each component may be used in multiple portions. For example, a titanium source may be added to the primary fired product, and then the titanium source may be added again to the fired product obtained by performing drying and secondary firing described later, followed by drying and secondary firing. When adding the above titanium source, since hydrogen chloride is generated by the reaction between moisture in the air and the titanium compound, it is preferably carried out under a nitrogen atmosphere.

[0050] As a more specific preferred method, after bringing the primary fired product into contact with the titanium source and thoroughly mixing them, the mixture may be heat-treated, or after sufficiently drying it by the same method as the drying method exemplified in the third step above, secondary firing may be performed. The temperature in the above heat treatment and drying treatment is not particularly limited. For example, in order to effectively introduce titanium into the primary fired product, a range of 20 to 150°C is preferred. A more preferred lower limit is 30°C, still more preferably 40°C, and particularly preferably 50°C. On the other hand, a more preferred upper limit is 140°C, still more preferably 120°C, and particularly preferably 100°C. There is no particular limitation on the time required for the above steps, but it is preferably 0.1 to 24 hours. A more preferred lower limit is 0.3 hours, still more preferably 0.4 hours, and particularly preferably 0.5 hours. On the other hand, a more preferred upper limit is 12 hours, still more preferably 6 hours. The method of secondary firing is not particularly limited, and for example, firing can be performed using an electric furnace, a gas furnace, or the like. As the firing conditions, in an air atmosphere, it is preferably carried out at 400°C or higher and 850°C or lower for 0.1 to 20 hours. A more preferred lower limit of the firing temperature is 500°C, still more preferably 550°C, and particularly preferably 600°C. On the other hand, a more preferred upper limit is 800°C, still more preferably 750°C, and particularly preferably 700°C.

[0051] The temperatures during the above primary firing and secondary firing can be independently selected. In some cases, it is preferably that the temperature during secondary firing is higher than the temperature during primary firing.

[0052] By the fourth step, for example, a crystalline porous aluminotitanosilicate, which is a preferred embodiment of the modified aluminosilicate of the present invention in which part of the aluminum in the crystalline porous aluminosilicate is considered to be substituted with titanium, can be obtained.

[0053] Before performing the above drying treatment, the mixture of the titanium source and the primary fired product may be heated to preliminarily remove moisture, the mixture may be filtered to remove impurities, and after performing a washing operation with an organic solvent, etc., drying and secondary firing may be performed. The above manufacturing conditions can also be applied mutatis mutandis to the case of using elements other than titanium.

[0054] Examples of compounds containing Group 4 elements of the periodic table that can be used in place of the above titanium source include zirconium tetrachloride, tetraalkoxyzirconium, hafnium tetrachloride, tetraalkoxyhafnium, zirconium sulfate, etc. These can be liquefied and used in combination with water, alcohol, ether, etc. as necessary. For example, aqueous solutions of these compounds, solutions in alcohol, ether, etc. can be mentioned. Further, as Group 5 elements of the periodic table that can be used in place of the above titanium source, vanadium pentachloride, vanadium sulfate, vanadyl trichloride and its alkoxy-substituted products, etc. can also be liquefied and used in combination with water, alcohol, ether, etc. as necessary. For example, their aqueous solutions, solutions in alcohol, ether, etc. can be mentioned.

[0055] 〔Modified aluminosilicate〕 The modified aluminosilicate obtained in the fourth step is preferably a crystalline porous aluminosilicate having crystallinity and porosity, similar to the aluminosilicate (A-1') obtained in the first step. A crystalline porous aluminosilicate having an MSE framework is more preferred, a crystalline porous aluminosilicate having a UZM-35, MCM-68, or YNU-3 structure is even more preferred, and a crystalline porous aluminotitanosilicate is particularly preferred. Crystallinity can be considered in the same manner as the description of crystal (A).

[0056] A crystalline porous aluminosilicate is a porous crystal having at least a part where a three-dimensional regular bond is formed between SiO4 tetrahedrons in which oxygen is arranged at four vertices around silicon and AlO4 tetrahedrons in which aluminum is arranged instead of the central silicon. Typically, it can be said to be a kind of zeolite containing aluminosilicate. A modified aluminosilicate having crystallinity and porosity contains, for example, aluminum and one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table in the above-mentioned crystalline porous aluminosilicate framework. Preferably, it is obtained by a method of replacing a part 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. As a more preferred example, when one or more elements selected from the group consisting of Group 4 and Group 5 elements of the periodic table are titanium, the crystalline porous modified aluminosilicate becomes a crystalline porous aluminotitanosilicate, and the crystalline porous aluminotitanosilicate contains aluminum and titanium in the aluminosilicate framework, and preferably is obtained by a method of replacing a part of the aluminum in the framework with titanium.

[0057] The crystalline porous aluminosilicate having the above MSE framework has a three-dimensional pore structure having a 10-membered ring structure composed of 10 units of the above tetrahedrons and a 12-membered ring structure composed of 12 units of the above tetrahedrons. Since it has pores with a 12-membered ring structure, it is considered that the diffusion into the pores of the substrate is facilitated and high catalytic activity is easily obtained. In addition, since there are no large cavities inside the pores, it is considered to be one of the factors that easily shows para-position selectivity in the oxidation reaction of phenol.

[0058] It is well known that porous compounds have a large specific surface area. The modified aluminosilicate of the present invention preferably has a specific surface area of 50 to 1000 m 2 / g. As the lower limit of its specific surface area, more preferably 100 m / g, even more preferably 150 m 2 / g, 2 / g. On the other hand, as the upper limit value of the specific surface area, more preferably 800 m 2 / g, still more preferably is 600 m 2 / g.

[0059] The above specific surface area value can be determined by a known calculation method based on the BET theory by creating a BET plot from the measurement results using a known nitrogen adsorption / desorption measurement device method (for example, BELSORP-max manufactured by Microtrac BEL).

[0060] The preferable 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.

[0061] There is no particular limitation on the content of Group 4 elements and Group 5 elements contained in the modified aluminosilicate of the present invention. For example, when titanium is included as one or more elements selected from the group consisting of Group 4 elements and Group 5 elements contained in the above 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, still more preferably in the range of 1 to 30, and most preferably in the range of 2 to 30.

[0062] When a compound that is easily crystallized by itself, such as TiCl3, is used, the element may be introduced in the form of clusters or crystals on the surface of the aluminosilicate In this case, since the apparent element content may increase, 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 still more preferably 1.2. On the other hand, a more preferable upper limit value is 20, and still more preferably 15.

[0063] 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, more preferably in the range of 10 to 10,000, and most preferably in the range of 100 to 1,000.

[0064] The modified aluminosilicate of the present invention preferably has characteristics in the absorption in a specific wavelength region in the ultraviolet-visible absorption spectrum measurement.

[0065] The modified aluminosilicate according to the present invention contains an element selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, and preferably shows an absorbance (A

[0300] ) of usually 1.0 or more at 300 nm in the ultraviolet-visible spectrum. Specific examples and preferred examples of the elements selected from Group 4 and Group 5 elements contained in the modified aluminosilicate of the present invention are the same as the content in the section of the above "Fourth Step".

[0066] Further, when the element selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table is contained in the modified aluminosilicate in a tetravalent or pentavalent form, or when a tetravalent or pentavalent compound of the element selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table is used in the fourth step, the A

[0300] is preferably a value exceeding 0.20.

[0067] When the A

[0300] is less than 1.0, or less than 0.20 in the specific case, the selectivity of the aromatic dihydroxide compound tends to be relatively low when producing the aromatic dihydroxide compound by the reaction of phenols and hydrogen peroxide. There is no particular limitation on the method for measuring the absorbance, and the result measured by either the transmission method or the reflection method may be used. When measuring by the reflection method, the reflected light may include diffuse reflected light etc. in addition to the specular reflected light, but it is calculated assuming that all are specular reflected light for convenience.

[0068] Although the detailed mechanism is unknown, the inventors presume as follows (hereinafter, as the modified aluminosilicate, a crystalline porous aluminotitanosilicate in which the element selected from Group 4 and Group 5 is titanium will be described as an example).

[0069] It is presumed that aluminum and titanium exist on the skeletal surface portion of the crystalline porous aluminotitanosilicate. Further, these are preferably considered to exist mainly inside concave portions such as pores of the crystalline porous aluminotitanosilicate. Here, for example, in the case of a mode that is produced by a method using gaseous titanium tetrachloride at a high temperature as described in Patent Document 3 and is considered to contain only titanium that is completely incorporated into the crystal structure of the skeleton without defects, the absorbance at around 300 nm in the ultraviolet-visible spectrum is presumed to be 1.0 or more, or in the above specific case, it is difficult to exceed 0.2. In other words, it is presumed that there are many titaniums that are incompletely incorporated into the basic skeletal structure of the crystalline porous aluminotitanosilicate satisfying the requirements of the present invention and have an unstable structure. Such titanium species greatly contribute to the aromatic dihydroxide compound formation reaction. When the oxidation reaction of phenols with hydrogen peroxide proceeds, due to its instability, the formation of a 1,2-hydroxide compound (e.g., catechol) that is considered to be sterically disadvantageous and the formation of benzoquinone, which is a further advanced form of the reaction, are suppressed, and it is estimated that a 1,4-type aromatic dihydroxide compound can be produced with high selectivity.

[0070] From the viewpoint of further enhancing the selectivity of the aromatic dihydroxide compound, the preferable lower limit value of A

[0300] of the modified aluminosilicate is 1.5, more preferably 1.8. Further, when the element selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table is tetravalent or pentavalent, the more preferable lower limit value of A

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

[0300] , the preferable upper limit value is 15, more preferably 10. Further, A

[0300] is 0.20 or less in a normal crystalline porous aluminotitanosilicate.

[0071] Furthermore, the ratio of A

[0300] to the absorbance (A

[0210] ) at 210 nm in the ultraviolet-visible spectrum of the modified aluminosilicate, i.e., A

[0300] / A

[0210] , is more preferably 0.5 or more, still more preferably 0.6 or more, and particularly preferably 0.8 or more. Also, when an element selected from the group consisting of Group 4 and Group 5 elements of the periodic table is contained in the aluminosilicate in a tetravalent or pentavalent state, or when a tetravalent or pentavalent compound is used in the fourth step, the value of the "A

[0300] / A

[0210] " is preferably greater than 0.10. A more preferable lower limit value is 0.11. For example, when titanium incorporated without defects in the crystal structure framework is included, A

[0210] becomes relatively high with respect to A

[0300] , so that in a normal crystalline porous aluminotitanosilicate, usually A

[0300] / A

[0210] is 0.10 or less. Although there is no particular meaning for the upper limit value of the above A

[0300] / A

[0210] , it is more preferably 1.5 and still more preferably 1.0.

[0072] Incidentally, the above ultraviolet-visible spectrum can be measured by a conventional method. For example, the following method can be mentioned. "A method of putting 0.1 g of a solid aluminosilicate sample into a cell with an optical path length of 10 millimeters and measuring the range of wavelengths from 200 to 800 nm using a UV-2550 type ultraviolet-visible analyzer manufactured by Shimadzu Corporation." Needless to say, it is preferable that the above solid aluminosilicate sample is used after being sufficiently dried.

[0073] <Aluminosilicate (A-1)> One embodiment of the present invention is an aluminosilicate (A-1) that, in the range of 17.5 to 35° in XRD measurement, has the highest peak (β) in the range of 20° or more and less than 22.5°, and the peak intensity ratio of the peak (β) to the highest peak (γ) in the range of 25 to 27° is in the range of 1.7 to 5.0. The preferable lower limit value of the peak intensity ratio is 1.72, more preferably 1.8, particularly preferably 1.9. On the other hand, the preferable upper limit value is 4.5, more preferably 4.2, still more preferably 4.0, particularly preferably 3.5, among which, still more preferably 3.0, particularly preferably 2.5.

[0074] The aluminosilicate (A-1) is a novel substance and can be considered as a crystal with a slightly unstable structure that satisfies the requirements for peak intensity in the XRD measurement. As described above, such characteristics will lead to the performance as the catalyst for producing the aromatic polyhydroxide compound.

[0075] The manufacturing method of the aluminosilicate (A-1’) described in the first step can be considered as one aspect of the manufacturing method of the aluminosilicate (A-1).

[0076] As another manufacturing method of the aluminosilicate (A-1), for example, even when using an aluminosilicate crystal (B) other than the crystal (A) as described above as a seed crystal, it can also be manufactured by changing specific conditions of the other first step. As a method of using a crystal other than such a crystal (A), for example, a method (Z method) of controlling the molar ratio of water to silica within a specific range using a sol-like silica containing water instead of the gel-like silica can be cited as an example. As another method, there is a method (G2 method) of using a specific gel-like silica containing water as the gel-like silica. The above-mentioned gel-like silica can be obtained by controlling the molar ratio of water to silica within a specific range. As described above, the molar ratio of water to silica may also be an important requirement for producing a modified aluminosilicate such as aluminotitanosilicate described later in the present invention.

[0077] Describing the above Z method in more detail, the sol-like silica containing water, zeolite, and preferably the above organic structure-directing agent and crystal (B) are brought into contact, preferably stirred and mixed, to prepare a sol with a temperature of 50°C to 100°C, and then the molar ratio of water to silica (HMR-Z) is adjusted within the range of 0.1 to 8.0 by methods such as evaporating water, and then a method of reacting in the range of 130°C to 700°C (so-called hydrothermal synthesis method) can be exemplified. Since the above method uses sol-like silica, it is expected to be advantageous not only in terms of fluidity, which is important from an industrial perspective, but also in terms of reactivity.

[0078] Describing the above G2 method in more detail. Solid matter may be generated during the preparation process of the gel-like silica. Even if such solid matter is generated, in the case of using the above crystal (A), there is a tendency that no major problem occurs, but when using the above crystal (B), the performance as a catalyst described later may be reduced. In addition, the generation of such solid matter may cause obstacles to the stable and quantitative transfer of the content from an industrial process perspective, and there may be risks such as a decrease in reactivity in subsequent processes due to the solid, so it may be disadvantageous from the perspective of stable production. Therefore, in the above G2 method, it is important to preferably reduce the generation of solid matter and use a gel-like silica containing a solid shape that does not hinder the reactivity in subsequent processes. In order to obtain such a suitable gel-like silica, it is preferable to adjust the molar ratio of water to silica (HMR-G2) of the gel-like silica within the range of 3.6 to 6.0. Other preferable conditions are the same as those described in the above first step. Within the above numerical range, even if solid matter is generated, it has excellent reactivity and the reaction proceeds sufficiently in the next step, etc., showing an advantageous tendency for obtaining a desired aluminosilicate (titanosilicate).

[0079] Preferable examples of the above crystal (B) include aluminosilicates having the highest peak in the region of 20° or more and less than 22.5° in the 17.5 to 35° region in XRD measurement.

[0080] <Method for producing modified aluminosilicate using aluminosilicate (A-1)> One embodiment of the present invention is a method for producing a modified aluminosilicate, comprising: a second step of treating an aluminosilicate (A-1) with an acid; a third step of subjecting the treated product obtained in the second step to a primary firing at 550°C to 850°C; and a fourth step of contacting the fired product obtained in the third step with a liquid containing one or more elements selected from the group consisting of Group 4 elements and Group 5 elements of the periodic table, followed by drying and secondary firing.

[0081] In this embodiment, the terms "step 2" to "step 4" and "modified aluminosilicate" are the same as those in the above <Method for producing modified aluminosilicate using aluminosilicate (A-1')>, in which aluminosilicate (A-1) is used instead of aluminosilicate (A-1'). The specific production method and preferred conditions are also the same as those in the above case where aluminosilicate (A-1') is used.

[0082] The modified aluminosilicate obtained by the production method of the present invention can be used as a catalyst for producing an aromatic polyhydroxide compound, which is one embodiment of the present invention, as described below.

[0083] <Method of producing aromatic polyhydroxide compound> One embodiment of the present invention is a method for producing an aromatic polyhydroxide compound, comprising a step of reacting an aromatic hydroxide with a hydroperoxide in the presence of a catalyst for producing an aromatic polyhydroxide compound, the catalyst containing the modified aluminosilicate.

[0084] Examples of aromatic hydroxides include phenols described below, as well as compounds having a structure in which one hydroxy group is bonded to a phenyl skeleton, such as hydroxynaphthalene and its derivatives, hydroxyanthracene and its derivatives, and hydroxyfluorene and its derivatives. Phenols are preferred.

[0085] Examples of the hydroperoxide include hydrogen peroxide and a compound in which one hydrogen of hydrogen peroxide is substituted with an aliphatic or aromatic hydrocarbon group, a heteroatom-containing hydrocarbon group, etc., for example, butyl hydroperoxide, cumene hydroperoxide, etc. Hydrogen peroxide is preferable, and more specifically, an aqueous hydrogen peroxide solution is a preferable embodiment.

[0086] Hereinafter, regarding the method for producing an aromatic polyhydroxide, a method for producing an aromatic dihydro Xide compound will be described as an example. In the presence of the modified aluminosilicate of the present invention, for example, when phenols and hydrogen peroxide are reacted, an aromatic dihydroxy compound can be produced with a high selectivity.

[0087] The above-mentioned phenols mean unsubstituted phenol and substituted phenol. Here, examples of the substituted phenol include an alkylphenol substituted with a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a butyl group, a hexyl group, or a cycloalkyl group.

[0088] Examples of the phenols include phenol, 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2-ethylphenol, 3-isopropylphenol, 2-butylphenol, 2-cyclohexylphenol, etc. Among them, phenol is preferable. When both the 2-position and the 6-position of the phenols have substituents, the product will be only a hydroquinone derivative.

[0089] Examples of the aromatic dihydroxide compound as the reaction product include hydroquinones (substituted or unsubstituted hydroquinone), catechols (substituted or unsubstituted catechol), etc. Specific examples thereof include hydroquinone, catechol, 2-methylhydroquinone, 3-methylcatechol, 4-methylcatechol, 3-methylhydroquinone, 1,4-dimethylhydroquinone, 1,4-dimethylcatechol, 3,5-dimethylcatechol, 2,3-dimethylhydroquinone, 2,3-dimethylcatechol, and the like.

[0090] The modified aluminosilicate obtained in the present invention is used as a catalyst in the production of an aromatic dihydroxide compound. As the catalyst filling method, various methods such as a fixed bed, a fluidized bed, a suspension bed, and a tray fixed bed can be adopted, and any method can be used without any problem. Further, the above catalyst may be used as it is, or may be molded according to the catalyst filling method and then used. As the catalyst molding method, extrusion molding, tableting molding, rolling granulation, spray granulation, etc. are common. When using the catalyst in a fixed bed method, extrusion molding or tableting molding is preferable. In the case of a suspension bed method, spray granulation is preferable. Drying or firing may be performed after spray granulation. The average particle size of the spray granulated catalyst is preferably in the range of 0.1 μm to 1000 μm, more preferably 5 μm to 100 μm. When it is 0.1 μm or more, it is preferable because handling such as filtration of the catalyst is easy, and when it is 1000 μm or less, it is preferable because the performance of the catalyst is good and the strength is strong.

[0091] The amount of the above catalyst used is preferably in the range of 0.1 to 30% by mass, more preferably 0.4 to 20% by mass, based on the total mass of the reaction solution (the total mass of the liquid components in the reaction system, excluding the mass of the fixed components such as the catalyst). When it is 0.1% by mass or more, the reaction is completed in a short time and the productivity is improved, so it is preferable. When it is 30% by mass or less, it is preferable in terms of the small amount of separation and recovery of the catalyst.

[0092] When the modified aluminosilicate of the present invention is used as a catalyst for the method for producing an aromatic dihydroxide compound, it can also 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. Such components are preferably used in a proportion such that they account for 5 to 90% by mass of the mass of the reaction solution. More preferably, it is 8 to 90% by mass.

[0093] In addition, hydrogen peroxide is preferably used in a molar ratio of 0.01 or more and 1 or less with respect to phenols. The concentration of hydrogen peroxide used is not particularly limited, but an ordinary 30% aqueous solution may be used, or a higher-concentration hydrogen peroxide solution may be used as it is or diluted with a solvent inert in the reaction system. Examples of the solvent used for dilution include alcohols and water. Hydrogen peroxide may be added all at once or gradually over time.

[0094] 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 proceeds even at temperatures outside this range, but the above range is preferred from the viewpoint of improving productivity. The reaction pressure is not particularly limited.

[0095] The method of the above reaction is not particularly limited, and the reaction may be carried out in any of a batch system, a semi-batch system, and a continuous system. When carried out in a continuous system, it may be carried out in a suspension-bed type homogeneous mixing tank, in a fixed-bed flow type plug flow format, or a plurality of reactors may be connected in series and / or in parallel. From the viewpoint of equipment cost, the number of reactors is preferably 1 to 4. When using a plurality of reactors, hydrogen peroxide may be added to them in portions.

[0096] In order to obtain an aromatic dihydroxide compound from the reaction solution, a purification treatment such as removing unreacted components and by-products may be performed on the reaction solution or the separation liquid containing the dihydroxide compound after separating the above catalyst. The purification treatment is preferably performed on this separation liquid containing the aromatic dihydroxide compound after separating the catalyst.

[0097] There are no particular restrictions on the purification method, and specifically, methods such as oil-water separation, extraction, distillation, crystallization, and combinations thereof can be mentioned. The purification method, procedure, etc. are not particularly limited. For example, the following method can be used to purify the separation liquid containing the aromatic dihydroxide compound after separating the reaction liquid and the above catalyst.

[0098] When the reaction liquid separates into two phases, an oil phase and a water phase, oil-water separation is possible. By oil-water separation, the water phase with a low dihydroxide compound content is removed, and the oil phase is recovered. In this case, the separated water phase may recover the aromatic dihydroxide compound by extraction or distillation, or part or all of it may be used in the reaction again. Also, the catalyst separated in the above catalyst separation step or the dried catalyst can be dispersed in the separated water phase and supplied to the reactor. On the other hand, it is desirable to further purify the oil phase by extraction, distillation, crystallization, etc.

[0099] For extraction, solvents such as 1-butanol, toluene, isopropyl ether, and methyl isobutyl ketone are used, for example. Combining extraction and oil-water separation enables efficient implementation of the above oil-water separation. The extraction solvent is preferably separated and recovered by a distillation column and recycled for use.

[0100] Distillation may be carried out on the reaction liquid immediately after catalyst separation, or on the oil phase and water phase after the above oil-water separation. Further, the extract may be distilled.

[0101] When distilling the reaction liquid 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 one distillation column.

[0102] After separating water and alcohols by the above-mentioned oil-water separation, extraction, distillation operations, etc., phenols can be recovered in the next distillation operation and used in the reaction again. If the recovered phenols contain water that cannot be completely separated, isopropyl ether or toluene can be added and removed by azeotropic distillation.

[0103] This azeotropic distillation can also be carried out on the liquid after separation of water or alcohols before recovery of phenols. The separated water may be reused in the reaction or may be used as wastewater. When the recovered phenols contain impurities such as reaction by-products other than water, they can be further separated by a distillation operation. When the impurities are benzoquinones as reaction by-products, they can be supplied to the reactor again together with the phenols.

[0104] After separation of the phenols, components having a higher boiling point than the aromatic dihydroxide compound are removed by distillation, and hydroquinones and catechols can be separated by the next distillation operation. Also, the high-boiling components, hydroquinones, and catechols can be separated by one distillation operation by withdrawing the hydroquinones from the middle stage of the distillation column.

[0105] The obtained hydroquinones and catechols can be purified by removing impurities by distillation or crystallization as necessary.

[0106] In the presence of the modified aluminosilicate according to the present invention, when, for example, phenol and hydrogen peroxide are reacted, hydroquinone tends to be produced in a high yield. Also, hydroquinone tends to be produced with a high selectivity as compared with catechol, benzoquinone, etc. Therefore, it can be said that the industrial value of the modified aluminosilicate according to the present invention is high. It is also possible to produce an aromatic polyhydroxide compound under the same conditions as the method for producing an aromatic dihydroxide compound as described above.

Example

[0107] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

[0108] [XRD measurement method] The X-ray diffraction phenomenon of the crystal as a sample was measured by a conventional method except for the following conditions. ·X-ray diffractometer: manufactured by Rigaku Corporation, model: MultiFlex was used. ·X-ray source: CuKα · Output: 40 kV / 40 mA · Divergence slit: 1° · Scattering slit: 1° · Receiving slit 0.30 mm · 2θ: 3 to 50°

[0109] [Example 1] [Preparation of Crystal (A1)] A crystal (A1) having an MSE framework was prepared by the following method. First, 15.8 g of an 8 mol / L NaOH aqueous solution, 15.9 g of an 8 mol / L 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) were placed in a container and stirred at 60 °C to obtain a gel-like substance.

[0110] Next, 10.2 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained gel-like substance and mixed. Then, the mixture was placed in an autoclave and heated at 160 °C for 34 hours. The cooled mixture was filtered and washed with water and vacuum dried at 70 °C for 2 hours to obtain crystal (A1). The highest diffraction peak measured by XRD was observed at 23.8°.

[0111] [First Step: Preparation of Aluminosilicate (A-1')] Next, 15.8 g of an 8 mol / L NaOH aqueous solution, 15.9 g of an 8 mol / L 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) were placed in a container and stirred at 60 °C to obtain a gel-like substance. 1.47 g of the above crystal (A1) and 10.2 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. Then, the mixture was placed in an autoclave and heated at 160 °C for 68 hours. The cooled mixture was filtered and washed with water and vacuum dried at 70 °C for 2 hours to obtain crystal (1-0).

[0112] The highest peak in the 17.5 - 35° region measured by XRD of the above crystal (1 - 0) was observed at 21.6°, and the intensity ratio to the peak observed at 26.1°, which was the highest peak in the 25.0 - 27.0° region, was 2.07. The above crystal (1 - 0) was calcined at 550°C for 10 hours to obtain crystal (1 - 1).

[0113] [Second Step: Contact with Acid, Third Step: Primary Calcination] 3 g of the crystal (1 - 1) prepared above and 120 g of 60% nitric acid were put into a container and mixed. Then, the mixture was put into an autoclave and heated at 148°C for 24 hours. The cooled mixture was filtered, washed with water, air - dried for one day, and then subjected to primary calcination at 600°C for 2 hours to obtain crystal (1 - 2).

[0114] [Fourth Step: Contact with Titanium Compound, Secondary Calcination] Under a nitrogen atmosphere, 2 g of the crystal (1 - 2) obtained above was put into a glass container, 100 ml of titanium tetrachloride was added thereto and mixed, and heat - treated at 120°C for 1 hour. The cooled mixture was filtered, washed with toluene and hexane, and then degassed and dried. Thereafter, secondary calcination was carried out at 600°C for 2 hours to obtain crystal (1 - 3), which is a crystalline porous aluminotitanosilicate.

[0115] [Example 2] 1 g of the crystal (1 - 2) prepared above was put into a container and vacuum - degassed at 60°C for 1 hour using an evaporator. 5 g of a 20% aqueous titanium trichloride solution was added thereto, and degassed and dried at 70°C for 1 hour. The dried product was subjected to secondary calcination at 600°C for 2 hours to obtain a crystalline porous aluminotitanosilicate (crystal (2 - 3)).

[0116] [Example 3] In the preparation process of crystal (A1), crystal (A3) was obtained in the same manner as in Example 1 except that it was put into an autoclave and heated at 165°C for 34 hours. The highest diffraction peak measured by XRD was observed at 23.8°.

[0117] Preparation was carried out under the same conditions as in Example 2 except that the above-mentioned crystal (A3) was used instead of crystal (A1), and crystals (3-0), (3-1), (3-2), and crystalline porous aluminotitanosilicate (crystal 3-3) were obtained.

[0118] The highest peak in the 17.5 - 35° region measured by XRD of crystal (3-0) was observed at 21.7°, and the intensity ratio to the peak observed at 25.8° was 2.04.

[0119] [Comparative Example 1] [Preparation of crystal (A-c1)] Crystal (A-c1) was obtained under the same conditions as in Example 1 except that the temperature and time during the preparation of crystal (A1) in Example 1 were set to the condition of heating at 160°C for 68 hours. The highest diffraction peak measured by XRD was observed at 21.6°.

[0120] Preparation was carried out under the same conditions as in Example 2 except that the above-mentioned crystal (A-c1) was used instead of crystal (A1), and crystals (C1-0), (C1-1), (C1-2), and crystalline porous aluminotitanosilicate (crystal C1-3) were obtained.

[0121] The highest peak in the 17.5 - 35° region measured by XRD of crystal (C1-0) was observed at 21.6°, and the intensity ratio to the peak observed at 26.0° was 1.35.

[0122] [Comparative Example 2] [Preparation of crystal (A-c2)] Crystal (A-c2) was obtained under the same conditions as in Example 1 except that the temperature and time during the preparation of crystal (A1) in Example 1 were set to the condition of heating at 160°C for 48 hours. The highest diffraction peak measured by XRD was observed at 22.46°.

[0123] Preparation was carried out under the same conditions as in Example 2 except that the above-mentioned crystal (A-c2) was used instead of crystal (A1), and crystals (C2-0), (C2-1), (C2-2), and crystalline porous aluminotitanosilicate (crystal C2-3) were obtained.

[0124] The highest peak in the range of 17.5 - 35° measured by XRD of crystal (C2-0) was observed at 21.7°, and the intensity ratio to the peak observed at 26.2° was 1.42.

[0125] [Comparative Example 3] [Preparation of crystal (A-c3)] Crystal (A-c3) was obtained under the same conditions as in Example 1, except that the temperature and time during the preparation of crystal (A1) in Example 1 were changed to heating at 170°C for 34 hours. The highest diffraction peak measured by XRD was observed at 22.3°.

[0126] Preparation was carried out under the same conditions as in Example 2, except that the above crystal (A-c3) was used instead of crystal (A1), and crystals (C3-0), (C3-1), (C3-2), and crystalline porous aluminotitanosilicate (crystal C3-3) were obtained.

[0127] The highest peak in the range of 17.5 - 35° measured by XRD of crystal (C3-0) was observed at 21.7°, and the intensity ratio to the peak observed at 25.8° was 1.66.

[0128] The XRD measurement results of the above crystals obtained in Examples 1 and 3 and Comparative Examples 1 - 3 are shown in Figure 1, and 2 to as shown.

[0129] [Performance evaluation as a catalyst] Hereinafter, the performance of the crystalline porous aluminotitanosilicates of Examples 1 - 3 and Comparative Examples 1 - 3 as a hydroquinone production catalyst was evaluated. The results are summarized in Table 1. In the table, HQ represents hydroquinone and CL represents catechol. The measurement method and the calculation formula for each value are shown below.

[0130] [Measurement method] Into a 50 ml volumetric flask equipped with a cooler, thermometer, feed pump, and magnetic stirrer chip, 0.2 g of each catalyst, 4.2 g of phenol, 3.0 g of t-butyl alcohol, and 6.0 g of water were charged, and the mixture was heated to 50 °C in a 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 for 60 minutes as it was. 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.

[0131] The analysis conditions for gas chromatography are as follows. · Detector; Flame ionization detector · Column; DB-5 (Agilent J&W), inner diameter 0.25 mm, length 60 m, film thickness 0.25 μm · Column temperature; Held at 50 °C for 10 minutes, heating rate 10 °C / min, heated to 280 °C · Injection port; 280 °C · Detector temperature; 280 °C · Carrier gas; Helium · Flow rate; 80 ml / min

[0132] (Calculation formula) Hydroquinone yield (%) = (number of moles of hydroquinone produced) / (number of moles of hydrogen peroxide) × 100

[0133] Using the above formula, the hydroquinone yield can also be expressed by the following formula. Hydroquinone yield (%) = (hydrogen peroxide utilization efficiency) × (number of moles of hydroquinone produced) / [(number of moles of hydroquinone produced) + (number of moles of catechol produced)] × 100

[0134] Hydroquinone / catechol ratio = (number of moles of hydroquinone produced) / (number of moles of catechol produced)

[0135]

Table 1

[0136] From Table 1, it can be seen that when using the aluminotitanosilicate prepared using crystal (A) that satisfies the provisions of Claim 1 of the present invention, both titanium tetrachloride and titanium trichloride aqueous solutions exhibit a high yield of hydroquinone and a high hydroquinone selectivity.

[0137] Examples 4 to 7 and Comparative Examples 4 to 5 below mainly correspond to examples of the production method of the modified aluminosilicate using the above aluminosilicate (A-1) and their comparative examples.

[0138] [Example 4] [Preparation of Crystal (A4)] Crystal (A4) having an MSE framework was prepared by the following method. First, 7.90 g of an 8 mol / L NaOH aqueous solution, 8.18 g of an 8 mol / L KOH aqueous solution, 20.46 g of a 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 33.82 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container and stirred at 80 °C to obtain a sol-like substance. Then, the stirring time was adjusted so that the HMR value became 3.20. At this time, the raw materials had solidified.

[0139] Next, 6.91 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained lump substance and mixed using a mortar. Then, the mixture was placed in an autoclave and heated at 160 °C for 68 hours. The cooled mixture was filtered and washed with water and vacuum dried at 70 °C for 2 hours to obtain crystal (A4). The highest diffraction Pi -peak measured by XRD was observed at 21.66°.

[0140] [Preparation of Aluminosilicate (A-1)] Next, 7.81 g of an 8 mol / L aqueous NaOH solution, 8.09 g of an 8 mol / L aqueous KOH solution, 24.36 g of a 40 wt% aqueous dimethyldipropylammonium hydroxide solution, and 36.13 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container, stirred at 80 °C to obtain a sol-like substance, and 0.79 g of the above crystal (A1) and 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. The stirring time was adjusted so that the HMR value at this stage was 4.00. The contents were heated at 165 °C for 40 hours using the autoclave. Thereafter, the cooled mixture was filtered, washed with water, and dried under vacuum at 70 °C for 2 hours to obtain crystals (4-0).

[0141] The highest peak in the 17.5 - 35° region measured by XRD of the above crystals (4-0) was observed at 21.6°, and the intensity ratio to the peak observed at 25.78°, which is the highest peak in the 25.0 - 27.0° region, was 1.73. The XRD chart is shown in Figure 3. The above crystals 4-0 were calcined at 550 °C for 10 hours to obtain crystals (4-1).

[0142] [Second step: Contact with an acid, Third step: Primary calcination) 2 g of the crystals (4-1) prepared above and 80 g of 65% nitric acid were placed in a container and mixed. Then, the mixture was placed in an autoclave and heated at 148 °C for 24 hours. The cooled mixture was filtered, washed with water, air-dried for 1 day, and then subjected to primary calcination at 600 °C for 2 hours to obtain crystals (4-2).

[0143] [Fourth step: Contact with a titanium compound, Secondary calcination) 1 g of the crystals (4-2) prepared above and 5 g of an aqueous titanium tetrachloride solution with a Ti concentration of 16% were placed in a container, and heated and stirred at 40 °C for 1 hour using an oil bath. Thereafter, water was added, filtered, further washed, and the dried product was subjected to secondary calcination at 650 °C for 2 hours to obtain crystalline porous aluminotitanosilicate (crystals (4-3)).

[0144] [Example 5] 〔Preparation of Crystal (A5)〕 A crystal (A5) having an MSE framework was prepared by the following method. First, 15.60 g of an 8 mol / L aqueous NaOH solution, 16.22 g of an 8 mol / L aqueous KOH solution, 40.60 g of a 40 wt% aqueous dimethyldipropylammonium hydroxide solution, and 67.20 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container and stirred at 80 °C to obtain a sol-like substance. Then, the stirring time was adjusted so that the HMR value became 3.50. At this time, the raw materials had solidified.

[0145] Next, 13.56 g of an FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained lump-like substance and mixed using a mortar. Then, the mixture was placed in an autoclave and heated at 165 °C for 40 hours. The cooled mixture was filtered and washed with water and dried in vacuo at 70 °C for 2 hours to obtain crystal (A5). The highest diffraction Pi - peak measured by XRD was observed at 21.60°.

[0146] 〔Preparation of Aluminosilicate (A-1)〕 Next, 7.78 g of an 8 mol / L aqueous NaOH solution, 8.17 g of an 8 mol / L aqueous KOH solution, 24.34 g of a 40 wt% aqueous dimethyldipropylammonium hydroxide solution, and 35.33 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container and stirred at 80 °C to obtain a sol-like substance, and 0.79 g of the above crystal (A2) and 6.78 g of an FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. The stirring time was adjusted so that the HMR value at this stage became 4.80. Then, the mixture was placed in an autoclave and heated at 160 °C for 37 hours. Then, the cooled mixture was filtered and washed with water and dried in vacuo at 70 °C for 2 hours to obtain crystal (5-0).

[0147] In the XRD of the above crystal (5-0), the highest peak in the region of 17.5 to 35° was observed at 21.6°, and the intensity ratio to the peak observed at 26.08 which was the highest peak in the region of 25.0 to 27.0° was 4.30. The XRD chart is shown in Figure 3. The above crystal (5-0) was calcined at 550°C for 10 hours to obtain crystal (5-1).

[0148] [Second Step: Contact with Acid, Third Step: Primary Calcination] Crystal (5-2) was obtained in the same manner as in Example 4 except that crystal (5-1) was used instead of crystal (4-1).

[0149] [Third Step: Contact with Titanium Compound, Secondary Calcination] Crystalline porous aluminotitanosilicate (crystal (5-3)) was obtained in the same manner as in Example 4 except that crystal (5-2) was used instead of crystal (4-2).

[0150] [Example 6] [Preparation of Crystal (A6)] Crystal (A6) having an MSE framework was prepared by the following method. First, 15.62 g of 8 mol / L NaOH aqueous solution, 16.22 g of 8 mol / L KOH aqueous solution, 40.60 g of 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 67.20 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container and stirred at 80°C to obtain a sol-like substance.

[0151] Next, 13.56 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) was added to the obtained sol-like substance and mixed. The stirring time was adjusted so that the HMR value at this stage became 4.00. Then, the mixture was placed in an autoclave and heated at 165°C for 40 hours. The cooled mixture was filtered and washed with water and vacuum dried at 70°C for 2 hours to obtain crystal (A6). The highest diffraction Pi - peak measured by XRD was observed at 21.66°.

[0152] 〔Preparation of Aluminosilicate (A-1)〕 Next, 7.81 g of an 8 mol / L aqueous NaOH solution, 8.14 g of an 8 mol / L aqueous KOH solution, 24.39 g of a 40 wt% aqueous dimethyldipropylammonium hydroxide solution, and 36.14 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich Co., LLC) were placed in a container, stirred at 80 °C to obtain a sol-like substance, and 0.79 g of the above crystal (A6) and 6.78 g of FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added and mixed. The stirring time was adjusted so that the HMR value at this stage was 5.50. Thereafter, the mixture was placed in an autoclave and heated at 160 °C for 50 hours. Thereafter, the cooled mixture was filtered and washed with water and dried under vacuum at 70 °C for 2 hours to obtain a crystal (6-0).

[0153] The highest peak in the 17.5 to 35° region measured by XRD of the above crystal (6-0) was observed at 21.64°, and the intensity ratio to the peak observed at 26.14, which is the highest peak in the 25.0 to 27.0° region, was 4.125. The XRD chart is shown in Figure 3. The above crystal (6-0) was calcined at 550 °C for 10 hours to obtain a crystal (6-1).

[0154] 〔Second Step: Contact with Acid, Third Step: Primary Calcination〕 A crystal (6-2) was obtained in the same manner as in Example 4 except that the crystal (6-1) was used instead of the crystal (4-1).

[0155] 〔Fourth Step: Contact with Titanium Compound, Secondary Calcination〕 A crystalline porous aluminotitanosilicate (crystal (6-3)) was obtained in the same manner as in Example 4 except that the crystal (6-2) was used instead of the crystal (4-2).

[0156] [Example 7] 〔First Step: Preparation of Aluminosilicate (A-1)〕 7.81 g of an 8 mol / L aqueous NaOH solution, 8.11 g of an 8 mol / L aqueous KOH solution, 24.36 g of a 40 wt% aqueous dimethyldipropylammonium hydroxide solution, and 36.08 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container and stirred at 60 °C to dehydrate until HMR = 4.0. The obtained silica compound was in a gel state containing a swollen solid, and it was judged that this could be used as it was in the next step.

[0157] To the solidified raw material mixture, 0.79 g of the crystal (A4) and 6.78 g of an FAU-type zeolite (product name: HSZ-HUA350, manufactured by Tosoh Corporation) were added. The mixture was placed in an autoclave and heated at 165 °C for 40 hours. The cooled mixture was filtered, washed with water, and vacuum dried at 70 °C for 2 hours to obtain a crystal (7-0).

[0158] The highest peak in the 17.5 - 35° region measured by XRD of the above crystal (7-0) was observed at 21.68°, and the intensity ratio to the peak observed at 26.18°, which is the highest peak in the 25.0 - 27.0° region, was 3.56. The XRD chart is shown in Figure 4. The above crystal (7-0) was calcined at 550 °C for 10 hours to obtain a crystal (7-1).

[0159] 〔Second step: Contact with an acid, Third step: Primary calcination〕 2 g of the crystal (7-1) prepared above and 80 g of 65% nitric acid were placed in a container and mixed. Then, the mixture was placed in an autoclave and heated at 148 °C for 24 hours. The cooled mixture was filtered, washed with water, air-dried for 1 day, and then subjected to primary calcination at 600 °C for 2 hours to obtain a crystal (7-2).

[0160] 〔Third step: Contact with a titanium compound, Secondary calcination〕 0.5 g of the crystal (7-2) prepared above was placed in a container and vacuum degassed at 60 °C for 1 hour using an evaporator. 2.5 g of a 20% aqueous titanium trichloride solution was added thereto, and it was degassed and dried at 70 °C for 6 hours. The dried product was subjected to secondary calcination at 600 °C for 2 hours to obtain a crystalline porous aluminotitanosilicate (crystal (7-3)).

[0161] [Comparative Example 4] [Preparation of Crystal (A-c4)] [Example 4 Crystal (A-c4) was obtained in the same manner as the preparation of crystal (A4).

[0162] [Preparation of Aluminosilicate] Next, 7.81 g of 8 mol / L aqueous NaOH solution, 8.11 g of 8 mol / L aqueous KOH solution, 20.30 g of 40 wt% dimethyldipropylammonium hydroxide aqueous solution, and 32.68 g of colloidal silica (product name: LUDOX (registered trademark) AS-40, manufactured by Sigma-Aldrich) were placed in a container, stirred at 80 °C, and further dehydrated to HMR = 3.50 by continuing stirring for a longer time than [Example 4]. At this point, the mixture was in a solidified lump state, and it was determined that grinding was necessary for reaction with zeolite etc. in the next step. Therefore, 0.79 g of the above crystal (A-c4) and 6.78 g of FAU zeolite were added to the raw material mixture, ground in a mortar, and thoroughly mixed. Then, the mixture was charged into an autoclave and heated at 160 °C for 55 hours. Thereafter, the cooled mixture was filtered and washed with water and vacuum dried at 70 °C for 2 hours to obtain crystal (C4-0).

[0163] The highest peak in the 17.5 - 35° region measured by XRD of the above crystal (C4-0) was observed at 21.58°, and the intensity ratio to the peak observed at 25.72 which is the highest peak in the 25.0 - 27.0° region was 1.54. The XRD charts are shown in Figures 3 and 4. The above crystal (C4-0) was calcined at 550 °C for 10 hours to obtain crystal (C4-1).

[0164] [Contact with Acid, Primary Calcination] Crystal (C4-2) was obtained in the same manner as the second and third steps of Example 4, except that crystal (C4-1) was used instead of crystal (4-1).

[0165] [Contact with Titanium Compound, Secondary Calcination] A crystalline porous aluminotitanosilicate (crystal (C4-3)) was obtained in the same manner as in the fourth step of Example 4, except that crystal (C4-2) was replaced with crystal (C4-2).

[0166] [Comparative Example 5] [Contact with Titanium Compound, Secondary Firing] 0.5 g of the crystal (C4-2) prepared above was placed in a container and degassed under vacuum at 60 °C for 1 hour using an evaporator. 2.5 g of a 20% aqueous titanium trichloride solution was added thereto, and the mixture was degassed and dried at 70 °C for 6 hours. The dried product was subjected to secondary firing at 600 °C for 2 hours to obtain a crystalline porous aluminotitanosilicate (crystal (C5-3)).

[0167] [Performance Evaluation as Catalyst] Hereinafter, the performance of the crystalline aluminotitanosilicates of Examples 4 to 7 and Comparative Examples 4 to 5 as catalysts for hydroquinone production was evaluated. The results are summarized in Table 2. In the table, HQ represents hydroquinone and CL represents catechol. The measurement method and the calculation formula for each value are the same as those in Examples 1 to 3 and Comparative Examples 1 to 3 above.

[0168]

Table 2

[0169] It can be seen from Tables 1 and 2 that the aluminotitanosilicate prepared by the method for producing a modified aluminosilicate of the present invention exhibits a high hydroquinone yield and a high hydroquinone selectivity.

Claims

1. A first step of obtaining an aluminosilicate (A-1') by bringing a gel-like silica, a zeolite, and a crystal (A) which is an aluminosilicate having the highest peak (α) at 22.5 to 25.0° in the range of 17.5 to 35° in XRD measurement into contact with each other; A second step of treating the aluminosilicate (A-1') obtained in the first step with an acid; A third step of subjecting the treated product obtained in the second step to primary firing at 550°C to 850°C; A method for producing a modified aluminosilicate, comprising: a fourth step of bringing the fired product obtained in the third step into contact 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.

2. The method for producing a modified aluminosilicate according to claim 1, wherein the crystal (A) in the first step is obtained by a step of bringing a gel-like silica and a zeolite into contact with each other and treating them at 155 to 168°C for 30 to 40 hours.

3. A method for producing a catalyst for producing an aromatic polyhydroxide compound, comprising a step of producing a modified aluminosilicate by the method according to claim 1.

4. A method for producing an aromatic polyhydroxide compound, comprising a step of producing a catalyst by the method according to claim 3 and reacting an aromatic hydroxide with a hydroperoxide in the presence of the catalyst.

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