KR102391319B1 - Method for producing disilane - Google Patents

Abstract

The present invention relates to a method for producing disilane. Specifically, related is a method for producing disilane capable of massively producing disilane from monosilane by using a catalyst. The method for producing disilane comprises: a step of removing air from a reactor provided with a catalyst layer, and raising temperature; a step of producing disilane through a dehydrogenation condensation reaction of monosilane; and a step of discharging the disilane.

Description

Method for producing disilane

The present invention relates to a method for producing disilane. Specifically, it relates to a method for producing disilane capable of mass-producing disilane from monosilane using a catalyst.

In general, a silane-based CVD (Chemical Vapor Deposition) process performed at a high temperature forms poly-silicon with large particles, which are gate electrodes or deep contact interconnects ( Inter Connect) application is very unfavorable.

Since disilane is easier to decompose than monosilane, it can be used as a raw material gas for manufacturing poly-silicon, silicon epitxial, or amorphous silicon.

In addition, disilane can be processed at a relatively low temperature and provides effective uniformity control and smooth thin film formation because it forms a homogeneous poly-silicon composed of smaller particles compared to monosilane. It is reported that the sensitivity to temperature is lower than that of monosilane, and the CVD deposition rate is 4 to 5 times faster. Accordingly, as the line width of the semiconductor process becomes thinner, the demand for disilane is increasing.

Moreover, disilane has the advantage that it can be used in existing processes without the need to modify the conventional monosilane-applied CVD deposition apparatus and delivery system.

However, the current price of disilane is high, being traded at a price more than 100 times per unit weight than the price of monosilane.

On the other hand, the conventional manufacturing process of disilane is a process of manufacturing disilane from monosilane using thermal decomposition or a catalytic reaction, and these processes have low yields or require high temperature and high pressure conditions. There is this.

Therefore, there is an urgent need to develop a method for manufacturing disilane having excellent manufacturing efficiency, in particular, a method for manufacturing high-efficiency disilane so that commercially high value-added disilane can be practically used in industry.

Republic of Korea Patent Publication No. 10-2019-0041512 Republic of Korea Patent Publication No. 10-2019-188344 Republic of Korea Patent Publication No. 10-1231370 Republic of Korea Patent Publication No. 10-1945215

Accordingly, an object of the present invention is to provide a method for producing disilane that enables industrial mass production of disilane at high efficiency and low cost by solving the problems in the conventional method for producing disilane.

The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

For the above purpose, the manufacturing method of the disilane of the present invention,

i) removing air and raising the temperature of a reactor having a catalyst layer therein;

ii) Using the catalyst of the catalyst layer in a range of 'volume of catalyst (cm ³ ) / flow rate per minute (ml/min.) of monosilane in the range of 0.01 to 1.5', disilane is produced by dehydrogenation condensation of monosilane to do; and

iii) discharging the generated disilane.

The step of removing air from the reactor in step i) is a step of removing the gas in the reactor using a vacuum pump after replacing the air in the reactor with an inert gas using an inert gas, and the temperature increase is to increase the temperature of the reactor. will be.

In addition, the reactor may include an inlet through which monosilane is introduced and an outlet through which the produced disilane is discharged.

In one embodiment of the present invention, the inert gas is helium (He), nitrogen (N2), or argon (Ar).

In one embodiment of the manufacturing method of the present invention, the elevated temperature may be 150 ℃ to 400 ℃.

In one embodiment of the manufacturing method of the present invention, a heating device may be included outside or inside the reactor to increase the temperature of the reactor in step i).

In an embodiment of the manufacturing method of the present invention, the method may further include pre-heating the monosilane in step i-1) between steps i) and ii), wherein the pre-heating temperature is 50° C. to 300° C. can be

In the ii) step of producing disilane by dehydrogenation condensation of monosilane, the pre-heated or non-pre-heated monosilane is introduced into the reactor, and disilane is produced by dehydrogenation condensation reaction using a dehydrogenation catalyst in the reactor In this step, the catalyst of the catalyst layer is used in the range of 'the ratio of the volume (cm ³ ) of the catalyst to the flow rate per minute (ml/min.) of monosilane (cm 3 ) is 0.01 to 1.5'.

In one embodiment of the manufacturing method of the present invention, the reaction temperature of step ii) may be 150 ℃ to 400 ℃.

In an embodiment of the manufacturing method of the present invention, the reactor outlet temperature to which the disilane produced among the reactor temperatures in step ii) is discharged may be the same as or higher than the reactor inlet temperature to which the monosilane is introduced.

In an embodiment of the manufacturing method of the present invention, the temperature of the outlet of the reactor in step ii) may be 20° C. to 100° C. higher than the temperature of the inlet.

In one embodiment of the method of the present invention, the pressure inside the reactor due to the inflow of the monosilane in step ii) may be 0.1 to 10 bar.

In one embodiment of the method of the present invention, the dehydrogenation condensation reaction time of the monosilane in step ii) may be 0.1 hours to 20 hours.

In an embodiment of the present invention, the monosilane is a compound having at least one silicon-hydrogen (Si-H) bond, and a substituent (atom) bonded to silicon is a hydrocarbon group having 1 to 6 carbon atoms (saturated hydrocarbon). group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, etc.) and the like. More specific examples of the monosilane compound include tetrahydromonosilane (SiH4), methyltrihydromonosilane, ethyltrihydromonosilane, phenyltrihydromonosilane, or dimethyldihydromonosilane. As the monosilane, a raw material monosilane may be selected according to the disilane to be manufactured, for example, the disilane having a specific substituent.

In one embodiment of the present invention, the dehydrogenation catalyst in step ii) may include at least one metal selected from the group consisting of an alkali metal of Group 1 and an alkaline earth metal of Group 2 of the periodic table.

In one embodiment of the present invention, the dehydrogenation catalyst of step ii) may include a carrier.

In one embodiment of the present invention, the dehydrogenation catalyst of step ii) may be one in which one or more metals selected from the group consisting of alkali metals of Group 1 and Group 2 of the periodic table are included on the surface or inside of the carrier, , The carrier may be at least one selected from the group consisting of silica, alumina, titania, zirconia, zeolite and activated carbon.

In an embodiment of the method of the present invention, the dehydrogenation catalyst of step ii) includes at least one metal selected from among metals consisting of alkali metals and alkaline earth metals, a carrier, and a Group 3 transition metal; Group 4 transition metals; Group 5 transition metals; Group 6 transition metals; Group 7 transition metal; Group 8 transition metals; Group 9 transition metal; Group 10 transition metals; and a Group 11 transition metal; may include one or more transition metals selected from the group consisting of.

The step iii) discharging the generated disilane is a step of discharging the disilane generated by the dehydrogenation condensation reaction of monosilane using the catalyst.

In one embodiment of the production method of the present invention, the temperature of the generated and discharged disilane may be the same as the reactor outlet temperature, or may be higher.

The method for producing disilane of the present invention has the advantage of enabling high-efficiency and low-cost disilane production as well as industrial mass production.

Hereinafter, with reference to a preferred embodiment of the present invention will be described so that those of ordinary skill in the art can easily implement it. In addition, in the description of the present invention, if it is determined that a detailed description of a related known function or a known configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

Since the present invention can apply various transformations and can have various embodiments, specific embodiments are illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention. In addition, throughout the specification, when a part "includes" a certain component, it means that other components may be further included, not excluding other components, unless otherwise stated.

Terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present invention, the terms include or have is intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features, number, step , it should be understood that it does not preclude in advance the possibility of the presence or addition of an operation, component, part, or combination thereof.

The manufacturing method of the disilane of the present invention is

i) removing air and raising the temperature of a reactor having a catalyst layer therein;

ii) Disilane is produced by dehydrogenation condensation reaction of monosilane using the catalyst of the catalyst layer in the range of 'volume of catalyst (cm ³ ) / flow rate per minute (ml/min.) of monosilane in the range of 0.01 to 1.5'. to do; and

iii) discharging the generated disilane.

The step of removing air from the reactor in step i) is a step of removing the gas in the reactor using a vacuum pump after replacing the air in the reactor with an inert gas using an inert gas, and the temperature increase is to increase the temperature of the reactor. will be.

The reactor may include an inlet through which monosilane is introduced and an outlet through which the produced disilane is discharged.

In one embodiment of the present invention, the inert gas is helium (He), nitrogen (N2), or argon (Ar).

In one embodiment of the manufacturing method of the present invention, the elevated temperature may be 150 °C to 400 °C, preferably 200 °C to 350 °C.

In an embodiment of the manufacturing method of the present invention, the temperature increase may be achieved by equipment inside the reactor or external equipment. The equipment may use a well-known equipment in the art.

In one embodiment of the manufacturing method of the present invention, a step of pre-heating the monosilane in step i-1) between steps i) and ii) may be further included, and the pre-heating temperature is 50° C. to 300° C. can be

The pre-heating of the monosilane may be performed by heating the monosilane by passing the monosilane after heating of a pre-heater installed before the reactor.

In the ii) step of producing disilane by dehydrogenation condensation of monosilane, the pre-heated or non-pre-heated monosilane is introduced into a preheated reactor and dihydrogenated by a dehydrogenation condensation reaction using a dehydrogenation catalyst in the reactor. This is a step of preparing silane, and the catalyst in the catalyst layer has a 'volume (cm3) ratio of the catalyst to the flow rate per minute (ml/min.) of monosilane' in the range of '0.01 to 1.5'.

In one embodiment of the manufacturing method of the present invention, the 'volume of catalyst (cm ³ )/ratio of flow rate per minute (ml/min.) of monosilane (ml/min.)' in step ii) is preferably '0.05 to 1.0'.

In one embodiment of the manufacturing method of the present invention, the internal pressure of the reactor due to the introduction of monosilane in step ii) may be 0.1 to 10 bar. Preferably it may be 0.5 to 7 bar. More preferably, it may be 1 to 5 bar.

In an embodiment of the present invention, the dehydrogenation condensation reaction temperature of monosilane in the reactor in step ii) may be 150 °C to 400 °C. Preferably, it may be 200 °C to 350 °C.

In an embodiment of the present invention, the temperature of the reactor outlet through which the disilane produced in step ii) is discharged may be the same as or higher than the temperature of the reactor inlet through which the monosilane is introduced.

In an embodiment of the method of the present invention, the temperature of the outlet of the reactor in step ii) may be 20° C. to 200° C. higher than the inlet temperature, preferably 30° C. to 100° C. higher.

In one embodiment of the method of the present invention, the dehydrogenation condensation reaction time of the monosilane in step ii) may be 0.1 hours to 20 hours. Preferably it may be 0.5 to 15 hours.

In an embodiment of the present invention, the monosilane is a compound having at least one silicon-hydrogen (Si-H) bond, and a substituent (atom) bonded to silicon is a hydrocarbon group having 1 to 6 carbon atoms (saturated hydrocarbon). group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, etc.) and the like. More specific examples of the monosilane compound include tetrahydromonosilane (SiH4), methyltrihydromonosilane, ethyltrihydromonosilane, phenyltrihydromonosilane, or dimethyldihydromonosilane. As the monosilane, a raw material monosilane may be selected according to the disilane to be manufactured, for example, the disilane having a specific substituent.

In one embodiment of the production method of the present invention, the preferred monosilane may be tetrahydromonosilane (SiH4).

In one embodiment of the present invention, the dehydrogenation catalyst in step ii) may include at least one metal selected from the group consisting of an alkali metal of Group 1 and an alkaline earth metal of Group 2 of the periodic table.

In an embodiment of the present invention, the alkali metals of Group 1 and Group 2 of the periodic table included in the dehydrogenation catalyst of step ii) may be Na, K, Mg, Ca, Rb, Cs and Ba. Preferably it may be Na, K, Ca, Rb, Cs, and Ba, More preferably, it may be Na, Rb, and Ba.

In one embodiment of the present invention, the dehydrogenation catalyst of step ii) may include a carrier.

In one embodiment of the present invention, the dehydrogenation catalyst of step ii) may be one in which one or more metals selected from the group consisting of alkali metals of Group 1 and Group 2 of the periodic table are included in the surface or inside of the carrier, , The carrier may be at least one selected from the group consisting of silica, alumina, titania, zirconia, zeolite and activated carbon.

In one embodiment of the preparation method of the present invention, the carrier included in the dehydrogenation catalyst of step ii) may be a zeolite.

In one embodiment of the manufacturing method of the present invention, the zeolite as a carrier included in the dehydrogenation catalyst of step ii) is a structural code databased by the International Zeolite Association, AFR, AFY, ATO, BEA, BOG, BPH, CAN, CON, DFO, EON, EZT, FAU , FER, GON, IMF, ISV, ITH, IWR, IWV, IWW, LTA, LTL, MEI, MEL, MFI, MOR, MWW, OBW, MOZ, MSE, Zeolites corresponding to MTT, MTW, NES, OFF OSI, PON, SFF, SFG, STI, STF, TER, TON, TUN, USI, and VET are preferred.

More preferred zeolite structure codes are ATO, BEA, BOG, CAN, IMF, ITH, IWR, IWW, MEL, MFI, OBW, MSE, MTW, NES, OSI, PON, SFF, SFG, STF, STI, TER, TON , TUN, and VET are the zeolite structures.

Particularly preferred structural codes are zeolite structural codes corresponding to BEA, MFI, and TON, and zeolites whose structural codes correspond to BEA are *Beta, [B-Si-O]-*BEA, [Ga-Si -O]-*BEA, [Ti-Si-O]-*BEA, Al-rich beta, CIT-6, Tschernichite, pure silica beta, etc. ).

Zeolites whose structural code corresponds to MFI are *ZSM-5, [As-Si-O]-MFI, [Fe-Si-O]-MFI, [Ga-Si-O]-MFI, AMS1B, AZ-1 , Bor-C, Boralite C, Encilite, FZ-1, LZ-105, Monoclinic H-ZSM-5, Mutinaite, NU-4, NU-5, Silicalite TS-1, TSZ, TSZ- III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, organic-free ZSM-5, etc.

Zeolites whose structural code corresponds to TON include Theta-1, ISI-1, KZ-2, NU-10, ZSM-22, and the like.

Among the BEA, MFI and TON, a particularly preferred zeolite has an MFI structure, and a more preferred zeolite is ZSM-5, Beta, or ZSM-22.

5-10000 are preferable, as for the silica/alumina ratio (mol/mol ratio) of the said zeolite, 10-2000 are more preferable, 20-1000 are especially preferable.

In one embodiment of the present invention, the dehydrogenation catalyst of step ii) includes at least one metal selected from among metals consisting of alkali metals and alkaline earth metals, a carrier, and a Group 3 transition metal; Group 4 transition metals; Group 5 transition metals; Group 6 transition metals; Group 7 transition metal; Group 8 transition metals; Group 9 transition metal; Group 10 transition metals; and a Group 11 transition metal; may include one or more transition metals selected from the group consisting of.

In an embodiment of the present invention, the Group 3 transition metal among the transition metals included in the dehydrogenation catalyst of step ii) is scandium (Sc), yttrium (Y), lanthanoid (La), samarium (Sm), and , Group 4 transition metals are titanium (Ti), zirconium (Zr), and hafnium (Hf), Group 5 transition metals are vanadium (V), niobium (Nb), and tantalum (Ta), and group 6 transition metals Silver is chromium (Cr), molybdenum (Mo), tungsten (W), Group 7 transition metals are manganese (Mn) and rhenium (Re), and Group 8 transition metals are iron (Fe), ruthenium (Ru), Osmium (Os), Group 9 transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir), and Group 10 transition metals are nickel (Ni), palladium (Pd), and platinum (Pt), The Group 11 transition metal may be copper (Cu), silver (Ag), or gold (Au).

In an embodiment of the present invention, a preferred transition metal among the transition metals included in the dehydrogenation catalyst of step ii) may be a Group 8 transition metal, a Group 9 transition metal, and/or a Group 10 transition metal.

In an embodiment of the present invention, a more preferable transition metal among the transition metals included in the dehydrogenation catalyst of step ii) may be Ni, Co, Ru, or a mixture thereof.

In one embodiment of the production method of the present invention, one or more metals selected from the group consisting of alkali metals of Group 1 and Group 2 of the periodic table included in the dehydrogenation catalyst of step ii) are 0.01 mass by mass relative to the support. % to 20% by mass or less, preferably 0.1 to 10% by mass or less. If it is in the said range, since a favorable reaction conversion rate can be ensured and the side reaction by excessive use can also be suppressed, disilane can be manufactured more efficiently.

In one embodiment of the production method of the present invention, the total content of the transition element included in the dehydrogenation catalyst of step ii) is 0.01 mass % to preferably 10 mass % or less with respect to the mass of the entire catalyst. If it is within the above range, oligosilane can be produced more efficiently

In one embodiment of the production method of the present invention, the catalyst has a conventional shape in the art, such as a spherical shape, a columnar shape (pellet shape), a ring shape, or a honeycomb shape, preferably a spherical shape.

In one embodiment of the present invention, the amount of the catalyst used in step ii) is 1 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 40 to 80 parts by weight. When the catalyst is used in less than 1 part by weight, the conversion rate of monosilane to disilane is lowered, and when the amount of catalyst used exceeds 100 parts by weight, economic feasibility is lowered in the entire process of the disilane manufacturing method due to the expensive catalyst.

In one embodiment of the production method of the present invention, the monosilane supplied in step ii) is supplied at 10 to 600 ml/min, preferably 50 to 600 ml/min, more preferably 100 to 500 ml/min am. In the case of supplying monosilane at 10 ml/min, the total amount of disilane produced is small, so it cannot be used industrially. There are disadvantages.

The amount of catalyst used in step ii) and the monosilane supplied in step ii) in an embodiment of the production method of the present invention are 'volume (cm ³ ) ratio of catalyst to flow rate per minute (ml/min.) of monosilane' It is used in the range of '0.01 to 1.5', and 1 part by weight of the catalyst is about 1.5 cm ³ .

The step iii) discharging the generated disilane is a step of discharging the disilane generated by the dehydrogenation condensation reaction of monosilane using the catalyst.

In one embodiment of the present invention, the temperature of the generated and discharged disilane may be the same as or higher than the temperature of monosilane introduced into the reactor.

According to the method for producing disilane including steps i) to iii) of the present invention as described above, the yield of disilane from monosilane is improved, and in particular, the STY (g/kgh) value is improved.

The STY (g/kgh) value represents the amount of disilane generated per hour compared to the amount of catalyst used as a public yield of disilane, and may be a standard for mass production. That is, when the STY has a large value, it means that the amount of disilane generated per hour relative to the amount of catalyst used increases, and therefore, if the STY value is large, it indicates that mass production is possible.

Hereinafter, the present invention will be described using specific examples.

The example relates to the production of disilane from monosilane using a reactor having a catalyst bed therein. The produced disilane was analyzed with a TCD (thermal conductivity type) detector using a gas chromatography 7890B manufactured by Agilent. The reactor was used by processing a 1-inch SUS tube (nominal diameter 19.4mm, thickness 1mm, length 680mm), and an electric heater was installed outside. A temperature sensor was installed in the catalyst bed portion of the reactor inlet, and a temperature sensor was installed in the catalyst bed portion of the outlet to measure the reactor temperature, the inlet temperature of monosilane, and the discharge temperature of disilane.

In addition, the pre-heater for pre-heating monosilane is the same as the reactor, except that the catalyst is not filled.

The following preparation examples relate to the preparation of the catalyst used in the method for preparing disilane of the present invention.

<Preparation Example 1: Preparation of Barium (Ba) Supported Zeolite Catalyst>

800 g of distilled water and 6 g of BaCl ₂ (1.5% in terms of Ba) were added to 200 g of Na-ZSM-5 (SiO ₂ /Al ₂ O ₃ =21), and the mixture was mixed at 80° C. for 6 hours. Thereafter, after drying at 100° C., it was calcined at 800° C. for 8 hours to obtain Ba-supported ZSM-5.

<Preparation Example 2: Preparation of Nickel (Ni)-Barium (Ba) Supported Zeolite Catalyst>

To 100 g of Ba-supported ZSM-5 prepared in Preparation Example 1, 400 g of distilled water and 20.6 g of NiCl ₂ .6H ₂ O (5% in terms of Ni) were added and mixed at 80° C. for 6 hours. Thereafter, after drying at 100°C, it was calcined at 800°C for 8 hours to obtain Ni/Ba-ZSM-5.

<Preparation Example 3: Preparation of Cobalt (Co)-Barium (Ba) Supported Zeolite Catalyst>

To 100 g of Ba-supported ZSM-5 prepared in Preparation Example 1, 400 g of distilled water and 20.6 g of CoCl ₂ ·6H ₂ O (5% in terms of Co) were added and mixed at 80° C. for 6 hours. Thereafter, after drying at 100°C, it was calcined at 800°C for 8 hours to obtain Co/Ba-ZSM-5.

<Preparation Example 4: Preparation of Nickel (Ni), Cobalt (Co)-Barium (Ba) Supported Zeolite Catalyst>

To 100 g of Ba-supported ZSM-5 prepared in Preparation Example 1, 400 g of distilled water, 10.3 g of NiCl ₂ .6H ₂ O (2.5% in terms of Ni), and 10.3 g of CoCl ₂ .6H ₂ O (2.5% in terms of Co) were added at 80° C. Mixed for 6 hours. Thereafter, after drying at 100°C, it was calcined at 800°C for 8 hours to obtain NiCo/Ba-ZSM-5.

<Preparation Example 5: Preparation of Nickel (Ni)-Sodium (Na) Supported Zeolite Catalyst>

400 g of distilled water and 20.6 g of NiCl ₂ ·6H ₂ O (5% in terms of Ni) were added to 100 g of Na-ZSM-5 (SiO ₂ /Al ₂ O ₃ =21) and mixed at 80° C. for 6 hours. Then, after drying at 100 degreeC, it baked at 800 degreeC for 8 hours, and obtained Ni/Na-ZSM-5.

<Preparation Example 6: Preparation of Cobalt (Co)-Sodium (Na) Supported Zeolite Catalyst>

400 g of distilled water and 20.6 g of CoCl ₂ ·6H ₂ O (5% in terms of Ni) were added to 100 g of Na-ZSM-5 (SiO ₂ /Al ₂ O ₃ =21), and the mixture was mixed at 80° C. for 6 hours. Thereafter, after drying at 100°C, it was calcined at 800°C for 8 hours to obtain Co/Na-ZSM-5.

<Preparation Example 7: Preparation of Nickel (Ni), Cobalt (Co)-Sodium (Na) Supported Zeolite Catalyst>

100 g of Na-ZSM-5 (SiO ₂ /Al ₂ O ₃ =21), 400 g of distilled water, 10.3 g of NiCl ₂ .6H ₂ O (2.5% in terms of Ni), 10.3g of CoCl ₂ .6H ₂ O (2.5% in terms of Co) was added and mixed at 80 °C for 6 hours. Thereafter, after drying at 100°C, it was calcined at 800°C for 8 hours to obtain NiCo/Na-ZSM-5.

<Preparation Example 8: Preparation of Ruthenium (Ru), Nickel (Ni), Cobalt (Co)-Barium (Ba) Supported Zeolite Catalyst>

To 100 g of NiCo/Ba-supported ZSM-5 prepared in Preparation Example 4, 200 g of distilled water and 1.0 g of RuCl ₃ ·6H ₂ O (0.5% in terms of Ru) were added and mixed at 80° C. for 6 hours. Thereafter, after drying at 100°C, it was calcined at 800°C for 8 hours to obtain RuNiCo/Ba-ZSM-5.

In the following examples, the yield and STY of disilane according to the flow rate per minute (ml/min.) of monosilane for each of the catalysts prepared in the preparation example were calculated, and the results are shown in Tables 1 to 12.

Example 1

65 g (about 100 cm ³ ) of the catalyst Ba-ZSM-5 prepared in Preparation Example 1 was installed in the reactor, the air in the reactor was substituted using helium gas, the gas in the reactor was removed using a vacuum pump, and the reactor was The temperature was raised to 280 °C. SiH ₄ was filled to a reactor pressure of 3 bar at a flow rate of 100 mL/min and then circulated. The yield of the produced disilane was analyzed by gas chromatography. The results are shown in Table 1. The test yield STY was calculated as the disilane yield/catalyst amount per hour (g/kgh).

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 13.1 62.1 8.1 60 9.4 2 15.4 60.4 9.3 60 10.8 3 16.5 59.2 9.8 60 11.4 4 16.8 58.0 9.8 60 11.4 5 16.4 58.9 9.6 60 11.1 6 15.0 59.8 9.0 60 10.4

Example 2

It was carried out in the same manner as in Example 1, except that SiH ₄ flowing into the reactor was pre-heated to 150° C. using a wire heater, and the results are shown in Table 2 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 23.9 50.6 12.1 60 14.7 2 21.8 50.4 11.0 60 12.8 3 19.6 51.4 10.1 60 11.7 4 18.1 52.7 9.5 60 11.0 5 17.3 53.4 9.2 60 10.7 6 17.0 54.1 9.2 60 10.7

Example 3

It was carried out in the same manner as in Example 2, except that SiH ₄ was injected into the reactor at a flow rate of 200 mL/min, and the results are shown in Table 3 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 19.3 59.7 11.5 30 26.8 2 21.4 56.4 12.1 30 28.0 3 22.1 55.2 12.2 30 28.3 4 21.7 54.8 11.9 30 27.6 5 20.3 54.8 11.1 30 25.9 6 19.5 55.1 10.8 30 24.9 7 19.1 55.3 10.6 30 24.6 8 19.0 55.8 10.6 30 24.5

Example 4

It was carried out in the same manner as in Example 2, except that SiH ₄ was injected into the reactor at a flow rate of 400 mL/min, and the results are shown in Table 4 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 20.6 55.1 11.3 15 52.6 2 20.0 54.5 10.9 15 50.7 3 18.8 54.6 10.3 15 47.7 4 17.1 55.8 9.5 15 44.3 5 16.1 57.0 9.2 15 42.6 6 15.5 57.6 8.9 15 41.4 7 15.1 58.5 8.8 15 41.0 8 14.7 59.1 8.7 15 40.3

Example 5

Using the catalyst prepared in Preparation Example 2, except for injecting SiH ₄ into the reactor at a flow rate of 400 mL/min, it was carried out in the same manner as in Example 2, the results are shown in Table 5 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 18.7 61.4 11.5 15 53.2 2 16.4 63.2 10.4 15 48.2 3 13.8 68.0 9.4 15 43.6 4 13.4 68.1 9.1 15 42.4 5 12.4 69.5 8.6 15 39.9 6 10.4 72.8 7.6 15 35.1 7 9.7 74.0 7.2 15 33.2 8 8.9 75.0 6.7 15 31.0

Example 6

Using the catalyst prepared in Preparation Example 3, except that SiH ₄ was injected into the reactor at a flow rate of 400 mL / min was carried out in the same manner as in Example 2, the results are shown in Table 6 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 11.0 72.8 8.0 15 37.1 2 10.5 75.4 7.9 15 36.8 3 9.1 74.2 6.7 15 31.2 4 8.7 75.1 6.5 15 30.4 5 7.8 74.6 5.8 15 27.1 6 7.5 75.4 5.6 15 26.2 7 7.2 76.2 5.5 15 25.4 8 6.9 76.9 5.3 15 24.5

Example 7

Using the catalyst prepared in Preparation Example 4, except that SiH ₄ was injected into the reactor at a flow rate of 400 mL / min was carried out in the same manner as in Example 2, the results are shown in Table 7 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 23.7 61.7 14.6 15 67.7 2 21.9 65.3 14.3 15 66.4 3 19.1 67.0 12.8 15 59.4 4 16.7 68.5 11.4 15 53.1 5 14.9 70.0 10.5 15 48.5 6 13.7 71.1 9.7 15 45.0 7 12.6 72.0 9.1 15 42.2 8 12.2 72.8 8.9 15 41.4

Example 8

The catalyst was used as a catalyst Na-ZSM-5 (Na 3wt%), and was carried out in the same manner as in Example 2, except that SiH ₄ was injected into the reactor at a flow rate of 400 mL/min, and the results are shown in Table 8 below. .

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 5.3 86.9 4.6 15 21.3 2 3.5 99.9 3.5 15 16.1 3 3.2 99.9 3.2 15 15.0 4 3.1 99.9 3.1 15 14.4 5 2.9 99.9 2.9 15 13.6 6 2.8 99.9 2.8 15 13.0 7 2.7 99.9 2.7 15 12.7 8 2.7 99.9 2.7 15 12.4

Example 9

Using the catalyst prepared in Preparation Example 5, and except that SiH ₄ was injected into the reactor at a flow rate of 400 mL / min was carried out in the same manner as in Example 2, the results are shown in Table 9 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 9.4 75.0 7.0 15 32.6 2 9.0 78.2 7.1 15 32.8 3 8.1 79.2 6.4 15 29.9 4 7.5 80.8 6.0 15 28.0 5 7.1 81.8 5.8 15 27.0 6 6.7 82.6 5.5 15 25.5 7 6.3 83.5 5.3 15 24.4 8 6.3 82.9 5.2 15 24.1

Example 10

Using the catalyst prepared in Preparation Example 6, except that SiH ₄ was injected into the reactor at a flow rate of 400 mL / min was carried out in the same manner as in Example 2, the results are shown in Table 10 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 12.0 72.5 8.7 15 40.3 2 11.2 73.9 8.3 15 38.4 3 10.6 74.7 7.9 15 36.6 4 10.0 75.4 7.6 15 35.1 5 9.5 76.2 7.2 15 33.6 6 8.9 76.9 6.8 15 31.8 7 8.6 77.4 6.7 15 30.8 8 7.8 76.6 6.0 15 27.8

Example 11

Using the catalyst prepared in Preparation Example 7, and except that SiH ₄ was injected into the reactor at a flow rate of 400 mL / min was carried out in the same manner as in Example 2, the results are shown in Table 11 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 12.9 73.9 9.5 15 44.2 2 12.1 76.0 9.2 15 42.7 3 11.0 76.3 8.4 15 38.8 4 9.8 78.7 7.7 15 35.9 5 9.7 79.4 7.7 15 35.7 6 9.2 80.4 7.4 15 34.2 7 8.6 81.2 7.0 15 32.6 8 8.5 82.2 7.0 15 32.3

Example 12

Using the catalyst prepared in Preparation Example 8, except that SiH ₄ was injected into the reactor at a flow rate of 400 mL / min was carried out in the same manner as in Example 2, the results are shown in Table 12 below.

Reaction Time
(hr) SiH ₄ Si ₂ H ₆ contact (residence)
time (seconds) STY
(g/kgh) Conversion (%) Selectivity (%) Yield (%) One 48.0 51.9 24.9 15 115.4 2 42.2 53.0 22.4 15 103.7 3 34.6 54.7 18.9 15 87.7 4 28.0 57.6 16.1 15 74.8 5 27.9 57.2 16.0 15 74.0 6 22.0 63.4 13.9 15 64.6 7 19.0 65.8 12.5 15 57.9 8 17.3 67.1 11.6 15 53.7

As shown in Tables 1 to 12, the STY (g/kg*?*h, disilane production amount/mass of catalyst per hour) value of the disilane according to the method for preparing the disilane of the present invention is from a minimum of 9.4 to a maximum of 115.4. This STY value is significantly higher than the STY value of Patent Document 4, which is a prior art. This seems to be due to the fact that the amount of catalyst used in the method for preparing disilane of the present invention compared to monosilane is smaller than that of the prior art.

As such, the present invention has the effect of showing a high STY value, which is an indicator of an increase in yield and mass production during the production of disilane, by using a catalyst amount compared to monosilane in a specific ratio, and this high STY indicates the possibility of mass production of disilane In addition, it has an economically advantageous advantage even in a large-scale production process by using less expensive catalyst.

As seen above, the manufacturing method of disilane of the present invention is a manufacturing method suitable for mass production of disilane, and has excellent industrial applicability.

The scope of the present invention is not limited to the above-described embodiments, but may be implemented in various types of embodiments within the scope of the appended claims. Without departing from the gist of the present invention claimed in the claims, it is considered to be within the scope of the claims of the present invention to various extents that can be modified by any person skilled in the art to which the invention pertains.

Claims (16)

i) removing air and raising the temperature of a reactor having a catalyst layer therein;
ii) Disilane is produced by dehydrogenation condensation reaction of monosilane using the catalyst of the catalyst layer in the range of 'volume of catalyst (cm ³ ) / flow rate per minute (ml/min.) of monosilane in the range of 0.01 to 1.5'. to do; and
iii) discharging the generated disilane; The method according to claim 1,
The temperature rise temperature of the temperature raising step is 150 ℃ to 400 ℃, characterized in that, the manufacturing method of disilane The method according to claim 1,
Between steps i) and ii), it may further include the step of pre-heating the monosilane in step i-1), wherein the pre-heating temperature is 50° C. to 300° C., the production of disilane Way The method according to claim 1,
Method for producing disilane, characterized in that the reactor outlet temperature to which the disilane is discharged among the temperature of the reactor in step ii) is the same as or higher than the reactor inlet temperature to which the monosilane is introduced The method according to claim 1,
Of the reactor in step ii), the reactor outlet temperature of the generated disilane is the same as the reactor inlet temperature into which the monosilane is introduced, or 20 to 100 °C higher, characterized in that the disilane Manufacturing method The method according to claim 1,
The reaction temperature of step ii) is 150°C to 400°C, and the reaction time is 0.1 hours to 20 hours, the method for producing disilane The method according to claim 1,
The reaction temperature of step ii) is 150° C. to 400° C., the reaction time is 0.1 hour to 20 hours, and the reactor pressure by the inflow of monosilane is 0.1 to 10 bar, the method for producing disilane The method according to claim 1,
The monosilane is a compound having at least one silicon-hydrogen (Si-H) bond, and a substituent bonded to silicon is a hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group is a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group. Method for producing disilane, characterized in that it is a hydrocarbon group The method according to claim 1,
The monosilane is tetrahydromonosilane (SiH4), methyltrihydromonosilane, ethyltrihydromonosilane, phenyltrihydromonosilane, or dimethyldihydromonosilane, characterized in that the method for producing disilane The method according to claim 1,
The catalyst is a method for producing disilane, characterized in that it comprises an alkali metal of Group 1 and/or an alkaline earth metal of Group 2 of the periodic table, and a carrier 11. The method of claim 10,
The method for producing disilane, characterized in that the carrier is at least one selected from the group consisting of silica, alumina, titania, zirconia, zeolite and activated carbon. 11. The method of claim 10,
The method for producing disilane, characterized in that the alkali metal of Group 1 and/or the alkaline earth metal of Group 2 of the periodic table is contained in an amount of 0.01% by mass to 50% by mass or less with respect to the carrier 11. The method of claim 10,
The catalyst is a Group 3 transition metal; Group 4 transition metals; Group 5 transition metals; Group 6 transition metals; Group 7 transition metal; Group 8 transition metals; Group 9 transition metal; Group 10 transition metals; and a group 11 transition metal; characterized in that it further contains one or more transition metals selected from the group consisting of, 14. The method of claim 13,
Method for producing disilane, characterized in that the amount of the transition metal used is 0.01% by mass to 10% by mass based on the mass of the total catalyst The method according to claim 1,
The catalyst is Ba-ZSM-5, Ni/Ba-ZSM-5, Co/Ba-ZSM-5, NiCo/Ba-ZSM-5, Na-ZSM-5, Ni/Na-ZSM-5, Co/Na -ZSM-5, NiCo/Na-ZSM-5, or RuNiCo/Ba-ZSM-5, characterized in that the method for producing disilane delete