JP2018202304A - Production method of zeolite catalyst - Google Patents

Abstract

To provide a novel method for conveniently producing a zeolite catalyst which has high catalytic activity, with which an oligosilane can be produced and with which an aromatic compound can be produced from methane.SOLUTION: A method for producing a zeolite catalyst includes a raw material preparation step (A) to prepare a composition which includes: a carrier including zeolite; a transition element compound including at least one transition element selected from a group consisting of molybdenum, tungsten, vanadium, niobium, and chromium and having solubility in water at 20°C of 0-30 mg/mL; and water, a heat treatment step (B) to heat treat the composition prepared in the raw material preparation step (A) in the presence of liquid water at 40°C or more, and a moisture removal step (C) to remove moisture in the product obtained in the heat treatment step (B) by heating.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a zeolite catalyst, and more particularly to a method for producing a zeolite catalyst that can be used in a method for dehydrocondensing hydrosilane to produce oligosilane or a method for producing an aromatic compound from methane.

  Zeolite, a kind of aluminosilicate, has fine pores of molecular size in the crystal structure, and can adsorb and desorb molecules corresponding to the size, and separate molecules of different sizes. It is used in a wide range of applications such as ion exchangers, various adsorbents and catalyst carriers.

  As an example to which a zeolite catalyst is applied, a reaction for producing an aromatic compound using a lower hydrocarbon as a raw material is known. Patent Document 1 discloses a zeolite made of metallosilicate carrying molybdenum.

  The present inventors have found that a zeolite catalyst containing a transition element in zeolite exhibits activity as a disilane production catalyst, and has developed a zeolite catalyst for oligosilane production (Patent Document 2).

As described in Patent Document 2, an impregnation method, an ion exchange method, and a sublimation method are known as methods for blending a transition element into zeolite.
When molybdenum (Mo) is supported on zeolite by a wet method such as an impregnation method, for example, as described in Non-Patent Document 1 and Patent Document 1, usually, water-soluble hexaammonium heptamolybdate is used. Use the prepared aqueous solution. In this case, since the size of hexammonium heptamolybdate, which is a polyacid, is larger than the pore diameter of zeolite, it cannot enter the pores. Also, in the impregnation, large aqueous molybdate ions cannot be directly cation exchanged with the cation exchange site of H-ZSM-5. Therefore, after impregnating the zeolite with an aqueous molybdenum solution and calcining at 400 ° C. or higher, hexaammonium heptamolybdate is converted to molybdenum oxide (MoO ₃ ) on the zeolite surface.
In addition, a method has been proposed in which molybdenum (Mo) is supported on zeolite by a dry method in which molybdenum oxide and zeolite powder are physically mixed and then calcined at a high temperature of 400 ° C. or higher (Non-patent Document 2).

JP 2010-125342 A International Publication No. 2016/027743

Catalysis Letters 35, 1995, 233. Journal of Physical Chemistry B, 1999, Vol.103, p.5787-5796.

According to the study by the present inventors, in order to use a zeolite impregnated with an aqueous solution of hexammonium heptamolybdate as an oligosilane production catalyst, after impregnation, the catalyst activity is not expressed unless it is calcined at a high temperature of about 400 ° C. or higher. I understood it. Moreover, after the molybdenum oxide and zeolite powder proposed in Non-Patent Document 2 are physically mixed, the zeolite carrying molybdenum (Mo) by a dry method of firing at a high temperature of 400 ° C. or higher is used for the production of oligosilane. As a result, although the catalytic activity was shown, the activity was lower than that of the zeolite catalyst by the wet method using the hexammonium hexamolybdate aqueous solution.
An object of the present invention is to provide a novel method for easily producing a zeolite catalyst having high catalytic activity capable of producing an oligosilane and capable of producing an aromatic compound from methane.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain at least one transition element selected from the group consisting of molybdenum, tungsten, vanadium, niobium, and chromium. The present invention has found that hydrosilane can be efficiently dehydrogenatively condensed by performing a reaction in the presence of a transition element-containing zeolite catalyst produced by a specific method using at least one kind of hardly soluble transition element compound. Was completed.
Embodiments of the present invention include the following.
[1] A carrier containing zeolite, a transition element compound having a solubility in water at 20 ° C. of 0 to 30 mg / mL containing at least one transition element selected from the group consisting of molybdenum, tungsten, vanadium, niobium and chromium And a raw material preparation step (A) for preparing a blend containing water, and a heat treatment step (B) for heat-treating the blend prepared in the raw material preparation step (A) to 40 ° C. or higher in the presence of liquid water. And a water removal step (C) in which the water content of the product obtained in the heat treatment step (B) is removed by heating.
[2] The zeolite catalyst according to [1], wherein the transition element compound has a solubility in water at 20 ° C. of less than 1 mg / mL, and the formulation of the raw material preparation step (A) further includes a dissolution aid. Manufacturing method.
[3] The method for producing a zeolite catalyst according to [1] or [2], wherein the heat treatment step (B) is performed at 85 ° C. or higher.
[4] The method for producing a zeolite catalyst according to any one of [1] to [3], wherein the heat treatment step (B) is performed in a closed system.
[5] The heat treatment step (B) is performed under conditions of less than 100 ° C. and atmospheric pressure to 20 atmospheres, or under conditions of 100 ° C. and more and the vapor pressure of water at the temperature to 20 atmospheres. The method for producing a zeolite catalyst according to any one of 1] to [4].
[6] The method for producing a zeolite catalyst according to any one of [1] to [5], wherein the heat treatment step (B) is performed for 10 minutes to 120 hours.
[7] The method for producing a zeolite catalyst according to any one of [1] to [6], wherein the transition element compound is molybdenum oxide.
[8] The method for producing a zeolite catalyst according to any one of [1] to [7], wherein the water removal step (C) is performed at 100 to 1000 ° C.
[9] A dehydrogenation coupling method including a step of performing a dehydrogenation reaction using the zeolite catalyst obtained by the production method according to any one of [1] to [8].
[10] A method for producing oligosilane, wherein the dehydrogenation coupling method according to [9] is dehydrogenation coupling of a silane compound.

According to one embodiment of the present invention, a transition element compound having a solubility in water at 20 ° C. of 0 to 30 mg / mL containing at least one transition element selected from the group consisting of molybdenum, tungsten, vanadium, niobium, and chromium As a raw material, a novel method for easily producing a zeolite catalyst having higher catalytic activity capable of producing an oligosilane by a wet method or producing an aromatic compound from methane is provided. In addition, this method exhibits high activity for hydrosilane and methane, and is suitable as a transition element composite solid acid catalyst, particularly as a catalyst for producing hydrosilanes and deriving oligosilanes, and for producing aromatic compounds from methane. A zeolite catalyst that can be used is provided.

It is a conceptual diagram of the reactor which can be used for the manufacturing method of oligosilane ((a): Batch reactor, (b): Continuous tank reactor, (c): Continuous tube reactor). It is a conceptual diagram showing the profile of reaction temperature. It is a conceptual diagram of the reactor used for the Example and the comparative example.

A first aspect of the present invention is a method for producing a zeolite catalyst, comprising at least one transition element selected from the group consisting of a support containing zeolite, molybdenum, tungsten, vanadium, niobium, and chromium at 20 ° C. The raw material preparation step (A) for preparing a transition element compound having a solubility in water of 0 to 30 mg / mL and a formulation containing water, and the formulation prepared in the raw material preparation step (A) are liquid water A heat treatment step (B) in which heat treatment is performed at 40 ° C. or higher in the presence, and a water removal step (C) in which moisture of the product obtained in the heat treatment step (B) is removed by heating. Features. Hereinafter, it may be described as a process (A), a process (B), and a process (C).
When molybdenum (Mo) is supported on zeolite by a wet method, an aqueous solution prepared using water-soluble hexaammonium heptamolybdate is usually used. As described above, according to the study by the present inventors, in order to use a zeolite impregnated with an aqueous solution of hexaammonium heptamolybdate as an oligosilane production catalyst, after impregnation, it must be calcined at a high temperature of about 400 ° C. or higher. Does not develop. This is because the polyammonium hexamolybdate hexamolybdate ion (Mo ₇ O ₂₄ ⁶⁻ ), which is larger than the pore diameter of zeolite, cannot enter the pores. This is probably because acid ions cannot be directly cation exchanged with the cation exchange sites of carrier zeolite such as H-ZSM-5. In the case of using an aqueous solution of hexaammonium heptamolybdate, after impregnating the zeolite with an aqueous molybdenum solution and calcining at about 400 ° C. or higher, the hexaammonium molybdate is converted to molybdenum oxide (MoO ₃ ) on the zeolite surface. It is considered that MoO ₃ moves into the zeolite pores due to surface physical diffusion and is compounded with the acid sites of the zeolite to exhibit catalytic activity.
On the other hand, surprisingly, the Mo-containing zeolite catalyst obtained by the method using the poorly soluble transition element compound according to one aspect of the present invention is subjected to a drying treatment without passing through a high-temperature firing step as described above. Only shows catalytic activity. Moreover, by baking at a high temperature, a catalyst having a higher catalytic activity is obtained, and a catalyst having a higher catalytic activity can be obtained than the impregnation method using hexammonium heptamolybdate as a Mo source. Even if it is hardly soluble in water such as molybdenum oxide (MoO ₃ ), a part of the molybdenum compound becomes small molybdate ion MoO ₄ ²⁻ etc. by the heat treatment step (B), and the pores of the zeolite It is considered that it is introduced into the inside and supported on zeolite. The same applies to tungsten oxide (WO ₃ ).
Hereinafter, each step will be described in detail.

<Raw material preparation process (A)>
The method for producing a zeolite catalyst which is an embodiment of the present invention includes a support containing zeolite as a first step, and at 20 ° C. containing at least one transition element selected from the group consisting of molybdenum, tungsten, vanadium, niobium, and chromium. The process of obtaining the compound containing the transition element compound whose solubility in water is 0-30 mg / mL, and water is included.

(Carrier containing zeolite)
The support used in the method for producing a zeolite catalyst which is one embodiment of the present invention is not particularly limited as long as it contains zeolite having pores having a minor axis of 0.43 nm or more and a major axis of 0.69 nm or less. Zeolite is preferable in terms of thermal stability, and the pore space of zeolite is considered to work as a reaction field for dehydrogenative condensation, and the pore size of “minor axis 0.43 nm or more and major axis 0.69 nm or less”. However, it is considered optimal for suppressing excessive polymerization and improving the selectivity of oligosilane.
Note that “zeolite having pores with a minor axis of 0.43 nm or more and a major axis of 0.69 nm or less” actually means only zeolites having “minor pores of 0.43 nm or more and major axis of 0.69 nm or less”. It is not intended to include zeolites whose “short diameter” and “long diameter” of pores theoretically calculated from the crystal structure satisfy the conditions described later. By the way, regarding the `` short diameter '' and `` long diameter '' of the pore, `` ATLAS OF ZEOLITE FRAMEWORK TYPES, Ch. Baerlocher, LBMcCusker and DH Olson, Sixth Revised Edition 2007, published on behalf of the structure Commission of the international Zeolite Association '' Can be helpful.
The minor axis of the zeolite is preferably 0.45 nm or more, particularly preferably 0.47 nm or more.
The major axis of the zeolite is preferably 0.65 nm or less, particularly preferably 0.60 nm or less.
In addition, when the pore diameter of zeolite is constant due to the circular cross-sectional structure of the pores, the pore diameter is considered to be “0.43 nm or more and 0.69 nm or less”.
In the case of a zeolite having plural kinds of pore diameters, the pore diameter of at least one kind of pores may be “0.43 nm or more and 0.69 nm or less”.

Specific examples of zeolites are the structural codes compiled by the International Zeolite Association, AFR, AFY, ATO, BEA, B
OG, BPH, CAN, CON, DFO, EON, EZT, GON, IMF, ISV, ITH, IWR, IWV, IWW, MEI, MEL, MFI, OBW, MOZ, MSE, MTT, MTW, NES, OFF, OSI, Zeolite corresponding to PON, SFF, SFG, STI, STF, TER, TON, TUN, USI, VET is preferred.
The structure code is ATO, BEA, BOG, CAN, IMF, ITH, IWR, IWW, MEL, MFI, OBW, MSE, MTW, NES, OSI, PON, SFF, SFG, STF, STI, TER, TON, Zeolite corresponding to TUN and VET is more preferable.
Zeolite whose structural code corresponds to BEA, MFI, or TON is particularly preferred.
As zeolites whose structural code corresponds to BEA, * Beta (beta), [B-Si-O]-* BEA, [Ga-Si-O]-* BEA, [Ti-Si-O]-* Examples include BEA, Al-rich beta, CIT-6, Tschernichite, pure silica beta (* indicates a polymorphic mixed crystal having three types of structures).
Zeolite whose structural code corresponds to MFI includes: * ZSM-5, [As-Si-O] -MFI, [Fe-Si-O] -MFI, [Ga-Si-O] -MFI, AMS- 1B, AZ-1, Bor-C, Boralite C, Encilite, FZ-1, LZ-105, Monoclinic H-ZSM-5, Mutanite, NU-4, NU-5, Siliconelite, TS-1, TSZ, TSZ- III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, organic-free ZSM-5 and the like.
Examples of the zeolite whose structural code corresponds to TON include * Theta-1, ISI-1, KZ-2, NU-10, ZSM-22, and the like.
Particularly preferred zeolites are ZSM-5, beta, ZSM-22.
The silica / alumina ratio (mole / mole ratio) is preferably 5 to 5000, more preferably 10 to 500, and particularly preferably 15 to 100.
As the carrier, a commercially available product may be obtained and used, or the carrier may be prepared and used by itself. Further, for example, it may be fired at 500 ° C. to be used as a proton type, or may be used as it is unfired.
Specific types of carriers include zeolite as described above, but include silica, alumina, titania, zirconia, activated carbon, aluminum phosphate, etc. in addition to the zeolite as long as the effects of the present invention are not impaired. Also good.
The size of the carrier can be applied as long as it can be filled in the reactor. Zeolite is originally in the form of powder, and the size of the primary particles is 3 to 20 μm, and the secondary particles are 0.01 mm to 0.5 mm. It is preferable to use it in the form of beads or pellets. The size of the beads and pellets in this case is not particularly limited, but it is preferable to use those formed to have a diameter of 0.15 mm to 4.8 mm.

(Transition element compound having a solubility in water at 20 ° C. of 0 to 30 mg / mL)
In the method for producing a zeolite catalyst of one embodiment of the present invention, the solubility in water at 20 ° C. containing at least one transition element selected from the group consisting of molybdenum, tungsten, vanadium, niobium, and chromium is 0 to 30 mg. A transition element compound that is / mL is used. The use of the above five transition elements is effective as a dehydrogenation coupling reaction catalyst such as a method for dehydrocondensing hydrosilane to produce oligosilane and a method for producing an aromatic compound from methane. The solubility of the transition element compound in water at 20 ° C. is preferably 0 to 20 mg / mL, more preferably 0 to 10 mg / mL. In addition, when using the transition element compound whose solubility with respect to water at 20 degreeC is 0, alkali components, such as ammonia, hydrogen peroxide, etc. are used together as a dissolution aid. In addition, when a transition element compound having a solubility in water at 20 ° C. of more than 0 and less than 1 mg / mL is used, it is preferable to use 1/10 mol or more and 10 mol or less of a dissolution aid with respect to 1 mol of the transition metal. .
Specifically, the transition element compounds having the above-described solubility include MoO ₃ (1 mg / mL) _, H ₂ MoO ₄ (1 mg / mL), CaMoO ₄ (0.05 mg / mL), BaMoO ₄ (0.06 mg). / ML), WO ₃ (0.004 mg / mL), H ₂ WO ₄ (0.004 mg / mL), V ₂ O ₅ (0.07 mg / mL) _, Ba ₂ CrO ₄ (0.003 mg / mL), Cr ₂ O ₃ (1 × 10 ⁻⁷ mg / mL), Nb ₂ O ₅ (0 mg / mL) (the numerical value in parentheses represents the solubility in water at 20 ° C.), one or two of these A combination of more than one species can be used. For the poorly soluble transition element compound, a commercially available product may be obtained, or synthesized and used. Among these, MoO ₃ and H ₂ WO ₄ are preferable, and MoO ₃ is particularly preferable. When using these transition element compounds, it is preferable to adjust a compounding quantity so that it may become 0.5 mass%-5 mass% as a transition element with respect to the zeolite catalyst obtained from a viewpoint of catalyst activity.
Although there is no restriction | limiting in particular in the shape of a transition element compound, It is preferable to use the powdery thing whose diameter is 0.01 micrometer-1 mm from a viewpoint melt | dissolved in water.

(container)
Although the container used for a raw material preparation process (A) is not specifically limited, From a viewpoint of productivity, what can be continuously used for a heat processing process (B) and a water | moisture-content removal process (C) is preferable, and the objective A suitable pressure-resistant container made of, for example, glass or stainless steel is suitably used.

In the raw material preparation step (A), for example, distilled water or ion-exchanged water having a mass about 30 to 100 times that of a hardly soluble transition element compound is put in a pressure vessel, and the whole vessel is used for the heat treatment step (B). Can do. The order in which the carrier containing zeolite, water, and the hardly soluble transition element compound are put in the container is not particularly limited. Before being subjected to the heat treatment step (B), each raw material may be mixed so as to be uniformly suspended, or a carrier containing zeolite, water, and a poorly soluble transition element compound are put into a container. You may use for a heat-processing process (B) as it is.
In a general impregnation method, an aqueous solution is prepared by dissolving a water-soluble compound in water, and then a carrier is impregnated in the aqueous solution. In the method for producing a zeolite catalyst which is one embodiment of the present invention, a hardly soluble transition element compound is used. Therefore, a carrier containing zeolite, water, and a hardly soluble transition element compound are charged into a container without preparing an aqueous solution. The heat treatment step (B) can be used as it is, and there is an advantage that it is simpler than the impregnation method including a step of preparing an aqueous solution by dissolving the compound in water. Note that an aqueous solution of a poorly soluble transition element compound may be prepared in advance, and a carrier may be put therein.

<Heat treatment step (B)>
The method for producing a zeolite catalyst which is an embodiment of the present invention includes a heat treatment step (B) in which the compound prepared in the raw material preparation step (A) is heat-treated at 40 ° C. or higher as the second step. In this process, since water exists as a liquid in the formulation, it is fluid. Here, fluidity means a level at which stirring at 1000 rpm is possible using a magnetic stirrer.
The heating temperature is preferably 60 ° C. or more, more preferably 85 ° C. or more, preferably less than 200 ° C., preferably 180 ° C. or less, and more preferably 150 ° C. or less.
As the compound used in the raw material preparation step (A) is less soluble in water, it is preferably carried out at a higher temperature. Specifically, it is performed under conditions of less than 100 ° C. and atmospheric pressure to 20 atmospheres, or 100 ° C. or more. It is preferably carried out under the conditions of the vapor pressure of water and 20 atm or less at that temperature, more preferably 85 to 200 ° C and more preferably atmospheric to 10 atm. It is more preferable to carry out under conditions of less than ° C. and 1.1 atm or more and 5 atm or less, and particularly preferably carried out under conditions of 100 ° C. or more and 150 ° C. or less and 1.2 to 3 atm. Needless to say, it is necessary to take appropriate measures such as using a closed system so that the temperature can be maintained. In this case, the closed system is also used to suppress the evaporation of water during processing and the entry of dust from the outside. It is preferable to carry out at
There is no particular limitation on the method of heating the container, and the container is placed on a hot plate set to a predetermined temperature, immersed in an oil bath or water bath set to a predetermined temperature, or inside the container in the heating device. Can be heated together with a mixing shaker. When heating in a pressurized atmosphere, a pressure-resistant autoclave can be used. In order to adjust the pressure, it is possible to pressurize with an inert gas such as air or nitrogen.
Further, when cooling the container, the container may be separated from the heating means and air cooled, or may be cooled by a forced cooling device such as a refrigerator or a freezer.
The heat treatment time is preferably from 10 minutes to 120 hours, more preferably from 1 hour to 48 hours, and even more preferably from 2 hours to 12 hours, from the viewpoint of efficiently impregnating the zeolite pores.
A zeolite catalyst having higher activity than conventional low temperature (room temperature) treatment or dry treatment is produced by performing a wet treatment using the sparingly soluble transition element compound of this embodiment, particularly a wet treatment at a temperature of 85 ° C. or higher. be able to.
In this heat treatment step (B), it is preferable to mix the transition element compound so that the transition element compound comes into contact with the support surface uniformly (supports the transition element). As the mixing means, known methods can be used as appropriate. For example, a magnetic stirrer may be put into the mixture prepared in the step (A), and the mixture may be stirred and mixed while heating the container on a hot plate. Further, for example, the preparation prepared in the step (A) may be mixed while being kept at a predetermined temperature in a sealed container.

<Moisture removal step (C)>
The method for producing a catalyst which is one embodiment of the present invention includes a moisture removal step (C) in which moisture is removed by heating from the product obtained in the heat treatment step (B) as a third step.
In this moisture removal step (C), drying is performed to remove moisture contained in the product obtained in the heat treatment step (B), and thereafter baking is performed as necessary. Drying and baking may be performed separately or may be performed continuously.
The drying and firing conditions in the moisture removal step will be described below.
The heating temperature during drying is usually a temperature at which moisture can be dried, but is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, preferably 400 ° C. or lower, more preferably 300 ° C. or lower. The heating time is preferably 30 minutes or more and 24 hours or less after reaching a predetermined temperature. More preferably, it is 1 hour or more and 12 hours or less. When heated within the predetermined temperature and predetermined time range, a catalyst having higher activity can be produced. There is no restriction | limiting in particular in the atmosphere at the time of drying, Although it can implement in any of an atmospheric condition and inert atmosphere, it is an atmospheric condition normally.
Even if the transition element compound that is hardly soluble in water is not highly water-soluble, for example, molybdenum oxide, a part of the molybdenum compound is a small molybdate ion MoO ₄ ² by the heat treatment step (B). ^It is considered that the catalyst activity is exhibited only by drying at 100 ° C. or more and 300 ° C. or less when introduced into the pores of the zeolite and supported by the zeolite.
Moreover, by baking, a catalyst having higher catalytic activity than that obtained by the impregnation method using hexaammonium heptamolybdate can be obtained.
The heating temperature in the case where drying also serves as baking or baking after drying is preferably 500 ° C. or higher, more preferably 600 ° C. or higher, further preferably 700 ° C. or higher, preferably 1000 ° C. or lower, more preferably 950. It is below ℃.
However, depending on the type of zeolite, the applicable temperature may vary. For example, the heating temperature when the support is ZSM-5 is preferably 700 ° C. or higher, more preferably 750 ° C. or higher, and further preferably 800 ° C. or higher. Preferably, it is 1050 degrees C or less, More preferably, it is 1000 degrees C or less, More preferably, it is 950 degrees C or less.
The heating temperature when the carrier is beta is preferably 500 ° C. or higher, more preferably 600 ° C. or higher, further preferably 700 ° C. or higher, preferably 1000 ° C. or lower, more preferably 900 ° C. or lower, still more preferably. Is 800 ° C. or lower.
The heating time is preferably 30 minutes or more and 24 hours or less after reaching a predetermined temperature, and more preferably 1 hour or more and 12 hours or less. A catalyst with higher activity can be manufactured as it is in the said range.
In addition, the atmosphere in which the firing is performed is usually an air atmosphere.

(Zeolite catalyst)
The catalyst obtained by the production method of the present invention is supported in the form of a metal or a metal oxide on the pore inner surface of a support containing zeolite, or Mo inside the support (support skeleton) by ion exchange or complexation. , W, Cr, Nb, or V is introduced, the state and composition of the transition element in the catalyst are not particularly limited. For example, you may carry | support in the state of a metal or a metal oxide on the surface (outer surface) of a support | carrier. Further, transition elements other than the above five types and typical elements may be supported on the surface (outer surface) or pores of the carrier.
The total content of transition elements in the catalyst (relative to the mass of the carrier containing typical elements and transition elements) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably Is 0.5% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. When it is within the above range, oligosilane can be produced more efficiently.

The zeolite catalyst obtained according to one embodiment of the present invention is preferably in the form of a molded body obtained by forming a powder into a spherical shape, a cylindrical shape (pellet shape), a ring shape, a honeycomb shape, or the like. In addition, you may use binders, such as an alumina and a clay compound, in order to shape | mold a powder. If the amount of binder used is too small, the strength of the molded product cannot be maintained, and if the amount of binder used is too large, the catalyst activity will be adversely affected. Therefore, the alumina content when alumina is used as the binder (alumina , Based on 100 parts by mass of the carrier (original powder form) that does not contain a transition element and a typical element) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more. The amount is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less. Within the above range, it is possible to suppress adverse effects on the catalyst activity while maintaining the carrier strength.
The zeolite catalyst obtained by one aspect of the present invention, that is, the disilane selectivity when the oligosilane is produced using the catalyst after passing through the water removal step (C), the zeolite before the raw material preparation step (A) It is possible to realize a selectivity of 1.1 times or more with respect to the disilane selectivity in the case where oligosilane is produced using. The disilane selectivity is preferably 1.2 times or more, more preferably 1.3 times or more.

(Dehydrogenation coupling method)
One embodiment of the present invention is a dehydrogenation coupling method including a step of performing a dehydrogenation reaction using a zeolite catalyst obtained by the above production method.
The zeolite catalyst obtained by the production method according to one embodiment of the present invention includes a dehydrogenation coupling method in which tetrahydrosilane (SiH ₄ , “silane”, also referred to as “monosilane”) is dehydrogenatively condensed to generate oligosilane, It has high activity as a catalyst for a dehydrogenation coupling method for producing an aromatic compound from methane.
The mechanism from methane to aromatics such as benzene is as follows. First, methane is dehydrogenated to produce ethylene, and cyclization and trimerization proceeds, or methylene intermediates dehydrogenated from methane are sequentially cyclized. It is thought that the reaction to benzene is in progress. Molybdenum-supported zeolite catalysts are particularly superior because molybdenum effectively acts as a catalyst for the highly stable methane dehydrogenation reaction, and the cyclization to a benzene ring is possible due to the acid point and shape selectivity of the zeolite. It is presumed that it is effectively promoted while suppressing coking.
Similarly, in the reaction from silane to oligosilane, molybdenum accelerates the reaction of dehydrogenation coupling of silane, and in this case, while suppressing the formation of solid polysilane by the acid point and shape selectivity of zeolite. It is assumed that silylene intermediates and the like dimerize without cyclization due to the difference in atomic radius, and react with disilane and further with trisilane.

(Manufacturing method of oligosilane)
As an example of the dehydrogenation coupling, the production of an oligosilane that dehydrocondenses hydrosilane will be described in detail below.
The reactor, operation procedure, reaction conditions, etc. used for the production of oligosilane are not particularly limited, and can be appropriately selected according to the purpose. Hereinafter, although a specific example is given and demonstrated about a reactor, an operation procedure, reaction conditions, etc., it is not limited to these content.
The reactor is a batch reactor as shown in FIG. 1 (a), a continuous tank reactor as shown in FIG. 1 (b), or a continuous tube reactor as shown in FIG. 1 (c). Any type of reactor may be used.

For example, when using a batch reactor, the operation procedure is to install the dried zeolite catalyst according to the present invention in the reactor, remove the air in the reactor using a vacuum pump, etc., and then remove tetrahydrosilane and the like. There is a method in which the reaction is started by charging and sealing, and raising the temperature in the reactor to the reaction temperature.
On the other hand, when using a continuous tank reactor or a continuous tube reactor, the dried zeolite catalyst according to the present invention is installed in the reactor, and the air in the reactor is removed using a vacuum pump or the like. And a method of starting the reaction by circulating hydrosilane or the like and raising the temperature in the reactor to the reaction temperature.

The reaction temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, further preferably 200 ° C. or higher, preferably 450 ° C. or lower, more preferably 400 ° C. or lower, and further preferably 350 ° C. or lower. When it is within the above range, oligosilane can be produced more efficiently. The reaction temperature is set constant during the reaction step as shown in FIG. 2 (a), and the reaction start temperature is set lower as shown in FIGS. 2 (b1) and (b2). Alternatively, the temperature may be raised during the reaction process, or as shown in FIGS. 2 (c1) and (c2), the reaction start temperature may be set higher and the temperature may be lowered during the reaction process (the reaction temperature rises). The temperature may be continuous as shown in Fig. 2 (b1) or stepwise as shown in Fig. 2 (b2). ) Or continuous as shown in FIG. 2 (c2). In particular, it is preferable to set the reaction start temperature to be low and raise the reaction temperature during the reaction step. By setting the reaction start temperature lower, deterioration of the zeolite and the like according to the present invention is suppressed, and oligosilane can be produced more efficiently. The reaction start temperature when raising the reaction temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 150 ° C. or higher, preferably 350 ° C. or lower, more preferably 300 ° C. or lower, even more preferably. Is 250 ° C. or lower.

In the reactor, a compound other than hydrosilane and the zeolite catalyst according to the present invention may be charged or passed. Examples of the compound other than hydrosilane and the zeolite catalyst according to the present invention include hydrogen gas, helium gas, nitrogen gas, argon gas, and other solid substances such as silica, titanium hydride, and the like that have almost no reactivity with hydrosilane. However, it is particularly preferable to carry out in the presence of hydrogen gas. In the presence of hydrogen gas, deterioration of zeolite and the like is suppressed, and oligosilane can be produced stably for a long time.
By dehydrogenative condensation of hydrosilane, disilane (Si ₂ H ₆ ) is generated as shown in the following reaction formula (i), and a part of the generated disilane is shown in the following reaction formula (ii). It is thought that it is decomposed into tetrahydrosilane (SiH ₄ ) and dihydrosilylene (SiH ₂ ). Further, the produced dihydrosilylene is polymerized to form solid polysilane (Si _n H _2n ) as shown in the following reaction formula (iii), and this polysilane is adsorbed on the surface of the zeolite, and the dehydrogenative condensation activity of hydrosilane. Therefore, the yield of oligosilane containing disilane is considered to decrease.
On the other hand, when hydrogen gas is present, tetrahydrosilane is produced from dihydrosilylene as shown in the following reaction formula (iv), and the production of polysilane is suppressed, so that oligosilane can be produced stably for a long time. It is considered a thing.
2SiH ₄ → Si ₂ H ₆ + H ₂ (i)
Si ₂ H ₆ → SiH ₄ + SiH ₂ (ii)
nSiH ₂ → (SiH ₂ ) _n (iii)
SiH ₂ + H ₂ → SiH ₄ (iv)
In addition, it is preferable that moisture is not contained in the reactor as much as possible. For example, it is preferable to sufficiently dry the zeolite and the reactor before the reaction.

The reaction pressure is preferably 0.1 MPa or more in absolute pressure, more preferably 0.15 MPa or more, further preferably 0.2 MPa or more, preferably 10 MPa or less, more preferably 5 MPa or less, and further preferably 1 MPa or less. . The partial pressure of tetrahydrosilane is preferably 0.0001 MPa or more, more preferably 0.0005 MPa or more, still more preferably 0.001 MPa or more, preferably 100 MPa or less, more preferably 50 MPa or less, and even more preferably 10 MPa. It is as follows. When it is within the above range, oligosilane can be produced more efficiently.
The partial pressure of hydrogen gas when the reaction step is performed in the presence of hydrogen gas is preferably 0.01 MPa or more, more preferably 0.03 MPa or more, further preferably 0.05 MPa or more, preferably 10 MPa or less, More preferably, it is 5 MPa or less, More preferably, it is 1 MPa or less. Within the above range, oligosilane can be produced stably for a long time.

When using a continuous tank reactor or continuous tube reactor, the flow rate of hydrosilane to be circulated is too low if the contact time with the catalyst is too short, and if it is too long, polysilane is likely to be produced. The time should be between 0.01 seconds and 30 minutes. In this case, with respect to 1.0 g of the zeolite catalyst according to the present invention, the flow rate of the tetrahydrosilane gas (volume converted amount in a standard state (0 ° C.-1 atm) of the tetrahydrosilane gas circulated for 1 minute) is preferably 0.01 mL / Min. Or more, more preferably 0.05 mL / min or more, further preferably 0.1 mL / min or more, preferably 1000 mL / min or less, more preferably 500 mL / min or less, and further preferably 100 mL / min or less. When it is within the above range, oligosilane can be produced more efficiently. In addition, even when the reaction is carried out batch-wise using an autoclave or the like, if the reaction is carried out over a long period of time, polysilane can be easily formed, and the reaction conversion rate becomes too low in a short time, so the reaction time is 1 minute to 1 hour, More preferably, it should be about 5 to 30 minutes.
When the reaction step is performed in the presence of hydrogen gas, the flow rate of the hydrogen gas to be circulated is the hydrogen gas flow rate (standard state of hydrogen gas circulated per minute (0) with respect to 1.0 g of the zeolite catalyst according to the present invention. The volume conversion amount at ° C-1 atm) is preferably 0.01 mL / min or more, more preferably 0.05 mL / min or more, further preferably 0.1 mL / min or more, preferably 100 mL / min or less, more Preferably it is 50 mL / min or less, More preferably, it is 10 mL / min or less. Within the above range, oligosilane can be produced stably for a long time.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.
In Examples and Comparative Examples, the catalyst was immobilized on a fixed bed in the reaction tube of the reaction apparatus shown in FIG. 3 and a reaction gas containing silanes was circulated. The generated gas was analyzed with a TCD detector using a gas chromatograph GC-17A manufactured by Shimadzu Corporation. Disilane correction and identification were performed using a known concentration of silane and disilane mixed gas as the standard gas. Further, when GC was not detected (below the detection limit), the yield was expressed as 0%. Qualitative analysis of disilane and the like was performed with MASS (mass spectrometer). Although the filter 10 of FIG. 3 is used for reaction gas sampling, in the examples, the reaction gas was directly introduced into the gas chromatograph for analysis without being particularly cooled and sampled. Since the reactor used for this evaluation is for testing and research purposes, it is equipped with an exclusion device 13 for discharging the product out of the system in a safe manner.

[Example 1] (MoO ₃ hot water impregnation method)
Content as Mo with respect to NH ₄ -ZSM-5 (product of Tosoh: product name 820NHA silica / alumina ratio: 23 powder) as a carrier 5.15 g, molybdenum oxide 0.078 g (total amount of catalyst (total amount of carrier and molybdenum oxide)) Was 1% by mass) and 7.4 g of distilled water were placed in a glass container and sealed (raw material preparation step (A)). The formulation prepared in step (A) was stirred on a hot plate at 110 ° C. at 1000 rpm for 2 hours. Then, remove the lid of the container and open it to the atmosphere (at this time, the liquid temperature is about 90 ° C.). While maintaining the hot plate temperature at 110 ° C., the mixture is heated and mixed with a magnetic stirrer to form a mud. At that time, stirring was not sufficiently performed, so the process was stopped (heat treatment step (B)). Further, it was dried at 110 ° C. in an air atmosphere for 2 hours by a dryer, and then calcined at 900 ° C. in an air atmosphere for 2 hours (moisture removal step (C)) to obtain a powdery solid product. .

Example 2 (MoO ₃ impregnation method 60 ° C.)
_NH 4 -ZSM-5 as a carrier (manufactured by Tosoh: Product name 820NHA silica / alumina ratio: 23 powdery) 10.07 g, content of the Mo for molybdenum oxide 0.153 g (total catalyst (total amount of carrier and molybdenum) Was 1% by mass) and 15.5 g of distilled water were placed in a glass container and sealed (raw material preparation step (A)). (A) 60 ° C. of the formulation prepared in the process
On a hot plate at 1000 rpm for 2 hours. Then, remove the lid of the container and open it to the atmosphere (at this time the liquid temperature is about 60 ° C.), raise the temperature of the hot plate to 110 ° C., stir with a magnetic stirrer, and mix by heating. At that time, stirring was not sufficiently performed, so the process was stopped (heat treatment step (B)). Further, it was dried at 110 ° C. in an air atmosphere for 2 hours with a dryer, and then fired at 900 ° C. in an air atmosphere for 2 hours (moisture removal step (C)) to obtain a powdery solid product.

Example 3 (MoO ₃ impregnation method 40 ° C.)
Content as Mo with respect to NH ₄ -ZSM-5 (product of Tosoh: product name 820NHA silica / alumina ratio: 23 powder) as a carrier, 10.03 g, molybdenum oxide 0.151 g (total amount of catalyst and the total amount of molybdenum oxide) Was 1% by mass), and 15.4 g of distilled water was put in a glass container and sealed (raw material preparation step (A)). The mixture was stirred at 1000 rpm on a 40 ° C. hot plate for 2 hours. Then, remove the lid of the container and open to the atmosphere (at this time the liquid temperature is about 40 ° C.), raise the temperature of the hot plate to 110 ° C., stir with a magnetic stirrer and mix with heat to form a mud. At that time, stirring was not sufficiently performed, so the process was stopped (heat treatment step (B)). Further, it was dried at 110 ° C. in an air atmosphere for 2 hours with a dryer, and then fired at 900 ° C. in an air atmosphere for 2 hours (moisture removal step (C)) to obtain a powdery solid product.

[Comparative Example 1] (Ammonium molybdate room temperature impregnation method powder: conventional method)
7 Ammonium molybdate tetrahydrate (solubility in water at 20 ° C .: 400 mg / mL) 0.37 g (content as Mo based on the whole catalyst (total amount of support and ammonium molybdate) is 1% by mass) and distilled water 20 g was put in a glass container and thoroughly mixed at room temperature (about 20 ° C.) to prepare an aqueous solution. This aqueous solution was added to 20.0 g of NH ₄ -ZSM-5 (product of Tosoh: product name: 820NHA silica / alumina ratio: 23 powder) as a carrier and impregnated with stirring at room temperature for 2 hours.
Thereafter, it was dried at 110 ° C. in an air atmosphere for 2 hours with a dryer, and then calcined at 900 ° C. in an air atmosphere for 2 hours to obtain a powdery solid product.

[Comparative Example 2] (Ammonium molybdate room temperature impregnation method pellet: conventional method)
Ammonium molybdate tetrahydrate 0.37 g (content as Mo with respect to the whole catalyst (total amount of carrier and ammonium molybdate) is 1% by mass) and 10 g of distilled water are placed in a glass container at room temperature (about 20 ° C. ) And mixed well to prepare an aqueous solution. This aqueous solution was added to 20.0 g of H-ZSM-5 (manufactured by Tosoh: product name 822HO3DA silica / alumina ratio: 23 pellets), and the container was sufficiently shaken at room temperature, and then impregnated for 2 hours without stirring. Thereafter, it was dried at 110 ° C. in an air atmosphere for 2 hours by a dryer, and then calcined at 900 ° C. in an air atmosphere for 2 hours to obtain a powdery solid product.

[Comparative Example 3] (MoO ₃ mixing method)
NH ₄ -ZSM-5 (product of Tosoh: product name 820 NHA silica / alumina ratio: 23 powder) 20.01 g, molybdenum oxide 0.30 g (total content of catalyst (total amount of support and molybdenum oxide) as Mo is 1 (Mass%) was mixed in powder form and ground in a mortar. Grind and mix until the color is uniform by visual inspection. Thereafter, it was dried at 110 ° C. in an air atmosphere for 2 hours by a dryer, and then calcined at 900 ° C. in an air atmosphere for 2 hours to obtain a powdery solid product.

[Comparative Example 4] (MoO ₃ room temperature impregnation method)
NH ₄ -ZSM-5 (manufactured by Tosoh: product name 820 NHA silica / alumina ratio: 23 powder) 10.05 g, molybdenum oxide 0.15 g (total amount of catalyst and molybdenum oxide) as Mo content is 1 (Mass%) was charged with 12.1 g of distilled water in a glass container and stirred at room temperature (about 20 ° C.) at 1000 rpm for 2 hours. Thereafter, it was dried in a vacuum dryer at room temperature until the fluidity disappeared. Further, drying was performed at 110 ° C. in an air atmosphere for 2 hours with a dryer, followed by firing at 900 ° C. in an air atmosphere for 2 hours to obtain a powdery solid product.

[Example 4] (H ₂ WO ₄ hot water impregnation ammonia water addition method)
NH ₄ —ZSM-5 (product name: 820NHA silica / alumina ratio: 23 powder) 5.0 g, distilled water 8.1 g, 1.05% ammonia water (commercially available ammonia water diluted with distilled water) 0.364 g (ammonia 0.225 mmol) was put in a glass container, sealed, and sufficiently dispersed by stirring at 1000 rpm. Next, the lid was opened, and 0.068 g of H ₂ WO ₄ (0.27 mmol: the content as W with respect to the whole catalyst (total amount of carrier and tungstic acid) was 1% by mass) was put in a glass container (raw material preparation step) (A)) After that, it was sealed again and stirred on a hot plate at 110 ° C. at 1000 rpm for 2 hours. Thereafter, the lid of the container was removed and the atmosphere was released (the liquid temperature at this time was about 90 ° C.) to maintain the temperature of the hot plate at 110 ° C. The mixture was stirred and heated with a magnetic stirrer, and when it became a mud, stirring was not sufficient, so it was stopped (heat treatment step (B)). After further drying at 110 ° C. for 2 hours with a dryer, firing was performed at 900 ° C. in an air atmosphere for 2 hours (moisture removal step (C)) to obtain a powdery solid product.

[Comparative Example 5] (Ammonium Tungstate Room Temperature Impregnation Method Powder: Conventional Method)
_{(NH 4) 10 W 12 O} 41 · 5H 2 O ( solubility in water at 20 ℃: 40mg / mL) 0.14g ( content of the W to the entire catalyst (total carrier and ammonium tungstate) 1 mass %) And 18 g of distilled water were placed in a glass container and thoroughly mixed while heating to about 70 ° C. to prepare an aqueous solution. _NH 4 -ZSM-5 The aqueous solution as a carrier (Tosoh Corporation: product name 820NHA silica / alumina ratio: 23 powdery) was added to 10.0 g, was impregnated with stirring at room temperature for 2 hours.
Then, after drying at 110 ° C. in a drier and an air atmosphere, firing was performed at 900 ° C. in an air atmosphere for 2 hours to obtain a powdery solid product.

[Example 5]
0.10 g of MoO ₃ hot water impregnated ZSM-5 prepared in Example 1 was put into a reaction tube, and the inside of the reaction tube was removed with a vacuum pump under reduced pressure, and then replaced with He gas. He gas was circulated at a rate of 20 mL / min, and the temperature was raised to 300 ° C. and then circulated for 1 hour. Thereafter, a mixed gas of 20 mol% Ar gas and 80 mol% silane gas was mixed at a gas mixer at 3 mL / min and hydrogen gas 1 mL / min, and was circulated. The reaction time (gas residence time in the reaction tube) was 3.4 seconds. After reaching a predetermined pressure (absolute pressure 0.3 MPa), the reaction gas composition after a predetermined time elapsed was analyzed by a gas chromatograph. The evaluation results are shown in Table 1.

[Example 6]
The reaction was conducted in the same manner as in Example 5 except that the catalyst prepared in Example 2 was used, and the reaction gas composition was analyzed. The evaluation results are shown in Table 2.

[Example 7]
The reaction was conducted in the same manner as in Example 5 except that the catalyst prepared in Example 3 was used, and the reaction gas composition was analyzed. The evaluation results are shown in Table 3.

[Comparative Example 6]
The reaction was conducted in the same manner as in Example 5 except that the catalyst prepared in Comparative Example 1 was used, and the reaction gas composition was analyzed. The evaluation results are shown in Table 4.

[Comparative Example 7]
The reaction was performed in the same manner as in Example 5 except that the catalyst prepared in Comparative Example 2 was used, and the reaction gas composition was analyzed. In addition, since the catalyst prepared in Comparative Example 2 was in the form of pellets and had a higher bulk density than the powdered catalyst, the reaction time (gas residence time in the reaction tube) was 2 seconds. The evaluation results are shown in Table 5.

[Comparative Example 8]
The reaction was conducted in the same manner as in Example 5 except that the catalyst prepared in Comparative Example 3 was used, and the reaction gas composition was analyzed. The evaluation results are shown in Table 6.

[Comparative Example 9]
The reaction was conducted in the same manner as in Example 5 except that the catalyst prepared in Comparative Example 4 was used, and the reaction gas composition was analyzed. Table 7 shows the evaluation results.

[Example 8] Life test 0.20 g of the MoO ₃ hot water impregnated ZSM-5 prepared in Example 1 was put in a reaction tube, and the inside of the reaction tube was removed with a vacuum pump under reduced pressure, and then replaced with He gas. He gas was circulated at a rate of 20 mL / min, and the temperature was raised to 300 ° C. and then circulated for 1 hour. Thereafter, the mixture was cooled to 220 ° C., and a mixed gas of 20% Ar gas and 80% silane gas was mixed with a gas mixer at 3 mL / min and hydrogen gas at 1 mL / min and circulated. The reaction time (gas residence time in the reaction tube) was 6.8 seconds. After reaching a predetermined pressure (absolute pressure 0.3 MPa), the reaction gas composition was analyzed with a gas chromatograph. The reaction was continued by changing the reaction temperature as shown in Table 8 so as to maintain a disilane yield of 10%.

[Comparative Example 10] Life test (comparison)
0.20 g of room temperature-impregnated ZSM-5 pellets of ammonium molybdate prepared in Comparative Example 2 was placed in a reaction tube, and the inside of the reaction tube was removed with a vacuum pump under reduced pressure, and then replaced with He gas. He gas was circulated at a rate of 20 mL / min, and the temperature was raised to 300 ° C. and then circulated for 1 hour. Thereafter, the mixture was cooled to 200 ° C., and a mixed gas of 20% Ar gas and 80% silane gas was mixed with a gas mixer at 3 mL / min and hydrogen gas at 1 mL / min and circulated. Since the catalyst prepared in Comparative Example 2 was in the form of pellets and had a higher bulk density than the powdered catalyst, the reaction time (gas residence time in the reaction tube) was 4 seconds. After reaching a predetermined pressure (absolute pressure 0.3 MPa), the reaction gas composition was analyzed with a gas chromatograph. The reaction was carried out by changing the conditions as shown in Table 9 so as to maintain a disilane yield of 8%.

By comparing Examples 5 to 7 and Comparative Examples 6 to 9, the disilane yield is most improved by using a catalyst prepared by mixing a poorly soluble Mo compound as a raw material in zeolite and hot water. I understand that.
By comparing Example 5, Example 6, Example 7, and Comparative Example 9, when preparing a catalyst by a wet method using a hardly soluble Mo compound as a raw material, the higher the temperature of the heat treatment step, the disilane yield. It can be seen that the rate is improved. In particular, there is a clear difference in disilane yield between Example 7 and Comparative Example 9, and it is found that it is preferable to heat in water at 40 ° C. or higher in one embodiment of the present invention.
By comparing Example 8 and Comparative Example 10, using a hardly soluble Mo compound and using a catalyst prepared by mixing in zeolite and hot water, the disilane yield is improved and the catalyst life is also increased. It turns out that it becomes long.

[Example 9]
0.10 g of H ₂ WO ₄ hot water-impregnated ZSM-5 prepared in Example 4 was put in a reaction tube, and the inside of the reaction tube was removed with a vacuum pump under reduced pressure, and then replaced with He gas. He gas was circulated at a rate of 20 mL / min, and the temperature was raised to 300 ° C. and then circulated for 1 hour. Thereafter, a mixed gas of 20 mol% Ar gas and 80 mol% silane gas was mixed at a gas mixer at 3 mL / min and hydrogen gas 1 mL / min, and was circulated. The reaction time (gas residence time in the reaction tube) was 3.4 seconds. After reaching a predetermined pressure (absolute pressure 0.3 MPa), the reaction gas composition was analyzed with a gas chromatograph. Table 10 shows the evaluation results.

[Comparative Example 11]
The reaction was conducted in the same manner as in Example 9 except that the catalyst prepared in Comparative Example 5 was used, and the reaction gas composition was analyzed. The evaluation results are shown in Table 11.

  By comparing Example 9 and Comparative Example 11 in which the same proportions of W and ammonia derived from the raw material were added to the zeolite, the poorly soluble W compound was used as a raw material, and a small amount of ammonia water was mixed in hot water. In particular, it can be seen that the disilane yield after 3 hours from the start of the reaction is improved, and the catalyst deterioration is suppressed.

  The catalyst obtained according to one embodiment of the present invention is very useful as a catalyst for dehydrogenative condensation of hydrosilane. The disilane obtained by the reaction using the catalyst obtained according to one embodiment of the present invention can be used as a production gas for semiconductor silicon, and improvement in yield and selectivity of disilane is expected to improve productivity in the semiconductor industry. it can.

1 Tetrahydrosilane gas (SiH ₄ ) cylinder (Ar 20% by volume mixed)
2 Hydrogen gas (H ₂ ) cylinder 3 Helium gas (He) cylinder 4 Emergency shutoff valve (Gas detection interlocking shutoff valve)
5 Pressure reducing valve 6 Mass flow controller (MFC)
7 Pressure gauge 8 Gas mixer 9 Reaction tube 10 Filter 11 Rotary pump 12 Gas chromatograph 13 Detoxifying device

Claims (10)

  A support containing zeolite, a transition element compound having a solubility in water at 20 ° C. of 0 to 30 mg / mL, containing at least one transition element selected from the group consisting of molybdenum, tungsten, vanadium, niobium, and chromium; and A raw material preparation step (A) for preparing a blend containing water, a heat treatment step (B) for heat-treating the blend prepared in the raw material preparation step (A) to 40 ° C. or higher in the presence of liquid water, And a moisture removal step (C) for removing moisture of the product obtained in the heat treatment step (B) by heating.   The method for producing a zeolite catalyst according to claim 1, wherein the transition element compound has a solubility in water at 20 ° C of less than 1 mg / mL, and the blend of the raw material preparation step (A) further contains a dissolution aid. .   The manufacturing method of the zeolite catalyst of Claim 1 or 2 which performs the said heat processing process (B) at 85 degreeC or more.   The manufacturing method of the zeolite catalyst as described in any one of Claims 1-3 which performs the said heat processing process (B) by a closed system.   The heat treatment step (B) is performed under a condition of less than 100 ° C and an atmospheric pressure of 20 atmospheres or less, or 100 ° C or more and a water vapor pressure of 20 ° C or less at that temperature. The method for producing a zeolite catalyst according to any one of 4.   The manufacturing method of the zeolite catalyst as described in any one of Claims 1-5 which performs the said heat processing process (B) for 10 minutes-120 hours.   The method for producing a zeolite catalyst according to any one of claims 1 to 6, wherein the transition element compound is molybdenum oxide.   The manufacturing method of the zeolite catalyst as described in any one of Claims 1-7 which performs the said water removal process (C) at 100-1000 degreeC.   The dehydrogenation coupling method including the step which performs a dehydrogenation reaction using the zeolite catalyst obtained by the manufacturing method as described in any one of Claims 1-8.   The method for producing oligosilane, wherein the dehydrogenation coupling method according to claim 9 is dehydrogenation coupling of a silane compound.