JP6803289B2 - 1,3-Butadiene production catalysts and processes from ethanol - Google Patents

Description

It relates to a catalyst for producing 1,3-butadiene from ethanol.

Butadiene production from ethanol (ETB) is a technology with an industrial track record in the past, but it has lost its competitiveness due to the completion of the butadiene extraction distillation technology from the C4 distillate obtained from naphtha crackers, so some areas have been expanded. Except now it is not used. However, in recent years, there are concerns about the expansion of the global butadiene supply-demand gap due to the increase in the number of automobiles spread mainly in Asia and the lightening of cracker raw materials, and there is increasing interest in the ETB process that can produce butadiene separately.

The ETB process includes a one-step method (Lebedev method) in which ethanol is converted to butadiene in one step, and a two-step method (Ostromislensky method) in which ethanol is first dehydrogenated to synthesize acetaldehyde and then butadiene is synthesized from ethanol and acetaldehyde. ..
・ One-step method 2CH ₃ CH ₂ OH → CH ₂ = CH-CH = CH ₂ + 2H ₂ O + H ₂
・ Two-stage method CH ₃ CH ₂ OH → CH ₃ CHO + H ₂
CH ₃ CH ₂ OH + CH ₃ CHO → CH ₂ = CH-CH = CH ₂ + 2H ₂ O

As an ETB catalyst used in such a reaction, a catalyst in which elements of Group 4 and Group 5 of the Periodic Table are supported on silica is known. The Ta ₂ O ₅ / SiO ₂ catalyst has long been known as a 1,3-butadiene synthetic catalyst (Patent Document 1, Non-Patent Documents 1 and 2). However, the butadiene selectivity at that time was in the 60% range, which was not high enough.

In recent years, a catalyst supporting Ta on mesoporous silica (Non-Patent Document 3), Ta / SBA-15 supporting Ta on zeolite (Non-Patent Document 4), and TaBEA with Ta inserted in a zeolite skeleton (Non-Patent Document 5). Has been reported as a 1,3-butadiene synthesis catalyst. In addition, ZrO ₂ / SiO ₂ catalysts and HfO ₂ / SiO ₂ catalysts have long been known as 1,3-butadiene synthesis catalysts (Non-Patent Document 2), and in recent years, they carry a metal having dehydrogenation ability. as one step _{catalyst, Ag-ZrO 2 -CeO 2 -SiO} 2 ( Patent Document _2), ZnZrSiO 2 and CuZnZrSiO ₂ (non-patent Document 6), CuHfZnSiO ₂ (non-Patent Document 7) have been reported.

U.S. Pat. No. 2524848 Japanese Patent No. 5864572

Industrial and Engineering Chemistry, vol.39, pp.120 (1947) Industrial and Engineering Chemistry, vol.42, pp.359 (1950) Chemical Engineering Journal, vol.278, pp.217 (2015) Applied Catalysis B, vol. 150-151, pp.596 (2014) Catalysis Communication, vol. 77, pp.123 (2016) Catalysis Science and Technology, vol. 1, pp.267 (2011) ACS Catalysis, vol.5, pp.3393 (2015)

An object of the present invention is to provide a catalyst capable of producing 1,3-butadiene more efficiently under practical operating conditions, and a method for producing 1,3-butadiene using the catalyst.

[1] A silicon compound having a hydrolyzable group at least a part of surface hydroxyl groups and oxo groups of a substance containing the elements (A) of Group 4 and Group 5 of the periodic table and silicon dioxide as a carrier component. Obtained by substitution with -O-Si group by reaction
The substance is characterized in that the element (A) of Group 4 and Group 5 of the periodic table is supported on the surface of silicon dioxide which is a carrier component, and the element (A) is immobilized on the silicon dioxide. , A method for producing a 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol.
[2] The method for producing a 1,3-butadiene production catalyst according to [1], wherein the silicon compound having a hydrolyzable group is a monomer represented by the formula (1).
SiY _n R _(4-n) ・ ・ ・ (1)
In the formula, Y is an independently hydrolyzable group, R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 1 to 4.
[3] In the 1,3-butadiene production catalyst, at least a part of the surface hydroxyl group and the oxo group on the element (A) is reacted with the silicon compound having a hydrolyzable group to form an -O-Si group. The method for producing a 1,3-butadiene production catalyst according to [1] or [2], which is obtained by substituting with.
[4] The molar ratio of silicon to element (A) in a silicon compound having a hydrolyzable group (silicon [mol] / element (A) [mol] in a silicon compound having a hydrolyzable group) is 0.1. The 1,3-butadiene production catalyst of [1] to [3], which is characterized by being from 100 to 100.
[5] The method for producing a 1,3-butadiene production catalyst according to [1] to [4], wherein the density of the element (A) on silicon dioxide is in the range of 1 to 50 elements / nm ² .
[6] The method for producing a 1,3-butadiene production catalyst according to [1] to [5], wherein the element (A) is at least one selected from zirconium, hafnium and tantalum.
[7] ^{29 When} the signal intensity of the maximum value in the vicinity of the chemical shift value of Si-NMR: −111 ppm is set to 1, the signal intensity at the chemical shift value of −105 ppm is 0.55 or more. , [1] to [6], a method for producing a 1,3-butadiene production catalyst.
[1A] Elements (A) of Groups 4 and 5 of the Periodic Table and elements (A) of Groups 4 and 5 of the Periodic Table are contained on the surface of silicon dioxide as a carrier component. Is supported, the element (A) is immobilized on the silicon dioxide, and at least a part of the surface hydroxyl group and the oxo group on the element (A) are substituted with -O-Si group-( A) A 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol, which comprises an -O-Si group.
[2A] The elements (A) of Groups 4 and 5 of the Periodic Table and silicon dioxide as a carrier component are contained, and at least a part of the surface hydroxyl groups and oxo groups on the element (A) is -O-Si. Containing terminal- (A) -O-Si groups substituted with groups,
The terminal- (A) -O-Si group is characterized by having a structure in which a monomer of a silicon compound is bonded to the element (A), and 1,3-butadiene is produced from a raw material containing ethanol1. , 3-butadiene production catalyst.
[3A] The molar ratio of silicon to element (A) in a silicon compound having a hydrolyzable group (silicon [mol] / element (A) [mol] in a silicon compound having a hydrolyzable group) is 0.1. A 1,3-butadiene production catalyst of [1A] or [2A], characterized in that it is from to 100.
[4A] The 1,3-butadiene production catalyst of [1A] to [3A], wherein the density of the element (A) on silicon dioxide is in the range of 1 to 50 elements / nm ² .
[5A] The 1,3-butadiene production catalyst of [1A] to [4A], wherein the element (A) is at least one selected from zirconium, hafnium and tantalum.
[6A] ^{29 When} the signal intensity of the maximum value in the vicinity of the chemical shift value of Si-NMR: −111 ppm is set to 1, the signal intensity at the chemical shift value of −105 ppm is 0.55 or more. , [1A] to [5A] 1,3-butadiene production catalysts.
[7A] Using the 1,3-butadiene production catalysts of [1A] to [6A], a raw material containing acetaldehyde alone or together with ethanol has a reaction temperature of 300 ° C. or higher and 450 ° C. or lower, and the partial pressures of ethanol and acetaldehyde are high. A method for producing 1,3-butadiene, which comprises contacting with the catalyst in the range of 0.1-1.0 MPaA and a weight space rate of 0.1 to 30 g / g ^-cat · ^h .

According to the 1,3-butadiene production catalyst of the present invention and the production method using this catalyst, 1,3-butadiene can be produced more efficiently from the raw material gas containing ethanol.

The ²⁹ Si-MAS-NMR spectra of the 1,3-butadiene production catalysts prepared in Examples and Comparative Examples are shown.

Hereinafter, modes for carrying out the present invention will be described.
[1,3-butadiene production catalyst]
The catalyst used in the present invention contains the elements (A) of Groups 4 and 5 of the Periodic Table and silicon dioxide as a carrier component. Hydroxides (-OH) and oxo groups (= O) derived from hydroxides or oxides of silicon or element (A) are present on the surface of the catalyst, but in the present invention, at least one of the surface hydroxyl groups and oxo groups The moiety is replaced with an —O—Si group by reacting with a silicon compound having a hydrolyzable group. All hydroxyl groups and oxo groups may be substituted, or some of them may be substituted.

Examples of the element (A) include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. At least one element (A) is selected from zirconium, hafnium, and tantalum in terms of improving 1,3-butadiene selectivity. It is preferably a seed.

These elements (A) are fixed to silicon dioxide as a carrier in the state of metals, oxides, hydroxides, salts and the like. Examples of silicon dioxide include amorphous silica, silica sol, silica gel, colloidal silica and the like. Further, mesoporous silica such as MCM-41, FSM-16, SBA-15, and zeolite can also be used.

As a method of immobilizing the element (A) on silicon dioxide, a chloride salt, a nitrate, a sulfate, a phosphate, and an alkoxide containing the element (A) are dissolved in water or an organic solvent, and a powder or a molded product of silicon dioxide is dissolved. It can be prepared by impregnating a carrier made of the same material, heating, drying and firing. As the impregnation method, a known method can be adopted, and examples thereof include a spraying method, a coating method, a pore filling method, and a selective adsorption method for a (water) solution containing the element (A). Further, a chloride salt, a nitrate, a sulfate, a phosphate, an alkoxide or the like containing the element (A) may be dissolved in a dispersion of silicon dioxide powder of the carrier. Further, it can also be prepared by vaporizing a chloride salt or alkoxide containing the element (A), adsorbing it on the surface of a silicon dioxide carrier, and then drying and calcining it.

It can also be prepared by mixing the element (A) and the precursor of silicon dioxide, then subjecting them to treatments such as heating, concentration, and hydrothermal synthesis, and then drying and firing. Examples of the precursor of the element (A) include alkoxides, chloride salts, nitrates, sulfates, phosphates, metal oxide sol and the like. Further, as the precursor of the silicon dioxide carrier, an organic silicon compound such as alkoxide, polysiloxane, polysilazane, an organic silicate such as a silicate, and a silica sol can be used.

The catalyst in which the element (A) is immobilized on silicon dioxide is treated with a silicon compound having a hydrolyzable group. A silicon compound having a hydrolyzable group is one in which 1 to 4 hydrolyzable groups are bonded to a silicon atom. Examples of the hydrolyzable group include hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. A silicon compound having a hydrolyzable group is represented by, for example, the following formula (1).
SiY _n R _(4-n)・ ・ ・ (1)

In the formula, Y is an independently hydrolyzable group, and R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n is an integer of 1 to 4. The substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group, and an alkyl group having 6 to 20 carbon atoms. Examples thereof include an aryl group and an aralkyl group having 7 to 20 carbon atoms. When two or more Y or R are combined, they may be the same or different from each other. Further, the silicon compound having a hydrolyzable group may be a partially polycondensed product at least partially polycondensed.

The treatment may be carried out by dissolving a silicon compound having these hydrolyzable groups in water, an organic solvent or the like, and adding a substance in which the element (A) is immobilized on silicon dioxide, or the hydrolyzable group may be used. The silicon compound may be vaporized and the element (A) may be adsorbed on the surface of a substance immobilized on silicon dioxide for treatment. By these treatments, the surface hydroxyl group of the substance in which the element (A) is immobilized on silicon dioxide and the oxo group on the element (A) when the element (A) is a metal of Group 5 of the periodic table are silicon compounds. It is considered that the condensation reaction with the hydrolyzable group of the element (A) forms an −O—Si bond on or around the element (A).

In recent years, it has become clear that the coordination state of a metal in zeolite affects Lewis acidity and reactivity. It has been clarified that there are two types of active sites (-Si-O-) ₃ Sn-OH and Sn (-Si-O-) _{4 in the} Sn-introduced zeolite (SnBEA). It has been reported that (-Si-O-) ₃ Sn-OH has a stronger Lewis acid and contributes to the adamantane oxidation reaction by hydrogen peroxide (Journal of Catalyst, vol. 234, pp. 111 (2005)). Similarly, in the Zr-introduced zeolite (ZrBEA), (-Si-O-) ₃ Zr-OH of the two types of active sites has a stronger Lewis acid, and 1,3- from ethanol. It has been reported that there is a correlation between the butadiene synthesis reaction rate and the number of (-Si-O-) ₃ Zr-OH (ACS Catalysis, vol. 5, pp. 4833 (2015), Journal of Physical Chemistry, vol. 119, pp.17633 (2015)).

The catalyst described in the patent does not have a zeolite structure, but the state in which the active metal is present in silicon dioxide is the same as in the previous report, and the coordination state around the active metal (-OH group). , -OSi group) is expected to contribute significantly to the Lewis acidity and reactivity of the catalyst. Therefore, it is considered that the activity / selectivity of the catalyst is changed by forming an −O—Si bond on or near the element (A).

In the present invention, when the signal intensity of the maximum value near the chemical shift value of ²⁹ Si-NMR of the catalyst: -111 ppm is 1, the signal intensity at the chemical shift value of -105 ppm is 0.55 or more. preferable. A catalyst having such a signal intensity of a chemical shift value has high catalytic activity.

The molar ratio of silicon to the element (A) in the silicon compound having a hydrolyzable group (silicon [mol] / element (A) [mol] in the silicon compound having a hydrolyzable group) is not particularly limited. The range of 0.1 to 100 is preferable. If the molar ratio of silicon to the element (A) in the silicon compound having a hydrolyzable group is too low, the effect of the silicon compound treatment cannot be sufficiently obtained. If the molar ratio of silicon to the element (A) in the silicon compound having a hydrolyzable group is too high, it is considered that the silicon completely covers the element (A) and the catalytic activity may decrease.

The density of the element (A) on silicon dioxide is not particularly limited, but is preferably in the range of 1 to 50 elements / nm ² . If the density of the element (A) is too low, the 1,3-butadiene formation rate per catalyst unit volume will be slow. If the density of the element (A) is too high, the side reaction proceeds and the 1,3-butadiene selectivity decreases.

The catalyst may contain metals such as zinc, silver, copper, and gold, alkali metals, alkaline earth metals, lanthanoids, and the like, in addition to the element (A) and silicon dioxide.
The shape of the catalyst is not particularly limited, and known shapes such as granular, cylindrical, cylindrical, and honeycomb can be used.

[Method for producing 1,3-butadiene]
The method for producing 1,3-butadiene of the present invention is characterized in that a raw material containing at least ethanol is brought into contact with the catalyst under heating. The ethanol is not particularly limited, and examples thereof include ethanol derived from biomass such as sugar cane and corn, and ethanol derived from petroleum, coal, or natural gas. If ethanol derived from biomass is used, it can contribute to the reduction of greenhouse gases.

The raw material of the present invention may be ethanol alone, or may contain acetaldehyde together with ethanol.
When acetaldehyde is contained, the molar ratio of ethanol to acetaldehyde (EtOH: AcH) is in the range of 95: 5-40: 60, preferably 90: 10-50: 50, more preferably 85: 15-50: 50. is there.

As acetaldehyde, one produced by the dehydrogenation reaction of ethanol can be used. In the dehydrogenation reaction of ethanol, for example, known copper catalysts and silver catalysts disclosed in JP-A-2005-342675 and JP-A-2011-000532 are used. Specifically, Cu-based metals, metals of Group 8 of the Periodic Table of the Elements such as Ni, Pd, and Pt can be preferably used, and among them, those containing Cu are more preferable. For example, Cu alone or one containing a two-component metal to which a transition metal element such as Cr, Co, Ni, Fe, Mn is added can be mentioned, and one containing Cu and Ni is preferably used. Further, those containing a metal having three or more components are also preferably used. Further, those obtained by further supporting these on silicon dioxide, aluminum oxide, titanium oxide, zeolite or the like are also used.

The reaction conditions are not particularly limited, and the reaction is usually carried out in the range of about 200 to 300 ° C. under conditions such that a predetermined amount of acetaldehyde is produced.
As such a manufacturing method, well-known methods such as batch type, semi-batch type, continuous type and the like can be adopted. If the continuous method is adopted, mass synthesis is possible, the operating work load is light, and the ethanol usage rate of the raw material can be improved to an extremely high level by reusing the unreacted raw material in the reaction system. Therefore, it is preferable to adopt a continuous system that can easily and efficiently separate and recover 1,3-butadiene.

Examples of the method of bringing the raw material into contact with the catalyst include a suspension bed method, a fluidized bed method, a fixed bed method and the like. Further, the present invention may be either a gas phase method or a liquid phase method, but it is preferable to use the gas phase method.

When the reaction is carried out in the gas phase, the raw material gas (for example, ethanol gas, preferably a mixture of ethanol gas and acetaldehyde gas) may be supplied to the reactor without dilution, such as nitrogen, helium, argon, water vapor, etc. It may be appropriately diluted with the inert gas of the above and supplied to the reactor.

At the time of the reaction, acetaldehyde may be added to the raw material containing ethanol, and the molar ratio (EtOH: AcH) of ethanol and acetaldehyde (total amount after addition) may be the above ratio.

The reaction temperature is, for example, about 300 ° C. or higher and 450 ° C. or lower, preferably in the range of 320 to 380 ° C. If the temperature is too high, the 1,3-butadiene selectivity will decrease. On the other hand, if the temperature is too low, the butadiene formation rate is not sufficient.

The reaction pressure can be appropriately set in a wide range from normal pressure to high pressure, but the partial pressures of ethanol and acetaldehyde are preferably set to 0.1 to 1.0 MPaA from the viewpoint of production efficiency and device configuration.

The contact time between the raw material and the catalyst can be controlled by adjusting the supply rate of the raw material, and the weight space velocity (WHSV) per unit catalyst is 0.1 to 30 g- _{(EtOH + AcH)} · g _-cat. ^-1 · h ^-1 , preferably 0.5 to 20 g- _{(EtOH + AcH)} · g _-cat ^-1 · h ^-1 . If the WHSV is too low, the reactor size becomes large, which is not preferable in terms of equipment cost. On the other hand, if WHSV is too high, the butadiene yield will decrease.

After completion of the reaction, the reaction product is separated and purified into light gas, C4 fraction, heavy component, water, ethanol, acetaldehyde, etc. by, for example, separation means such as distillation and extraction, or a separation means combining these. Can be done.
In the present invention, 1,3-butadiene can be produced more efficiently using the catalyst described above, so that it has high industrial applicability.

[Example]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Catalyst preparation>
Preparation Example 1
0.3 g of tantalum ethoxydo (99.98%, manufactured by Sigma-Aldrich) was dissolved in 100 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and NIPGEL CX-200 (manufactured by Toso Silica Co., Ltd., specific surface area 392 m) was dissolved. ^{2 /} g) After 10.0 g was added and the mixture was stirred for 2 hours, ethanol was evaporated using an evaporator. After drying at 120 ° C., it was calcined at 500 ° C. under air flow to obtain a Ta ₂ O ₅ / SiO ₂ (Ta ₂ O ₅ supported amount: 1.6% by weight) catalyst. This catalyst is referred to as Ta ₂ O ₅ (1.6) / SiO ₂ . The specific surface area of this catalyst was 335 m ² / g, and the Ta atom density on the carrier SiO ₂ was 14.9 n / nm ² .

Preparation Example 2
0.06 g of tantalum ethoxide was dissolved in 100 ml of ethanol, 10.0 g of NIPGEL CX-200 was added, and the mixture was stirred for 2 hours, and then ethanol was evaporated using an evaporator. After drying at 120 ° C., it was calcined at 500 ° C. under air flow to obtain a Ta ₂ O ₅ / SiO ₂ (Ta ₂ O ₅ supported amount: 0.16% by weight) catalyst. This catalyst is referred to as Ta ₂ O ₅ (0.16) / SiO ₂ . The specific surface area of this catalyst was 357 m ² / g, and the Ta atom density on the carrier SiO ₂ was 2.8 cells / nm ² .

Preparation Example 3
0.22 g of zirconium oxynitrite dihydrate was dissolved in 50.0 ml of distilled water, 10.0 g of NIPGEL CX-200 was added, and the mixture was stirred for 30 minutes, and then the water was evaporated using an evaporator. After drying at 120 ° C., it was calcined at 500 ° C. under air flow to obtain a ZrO ₂ / SiO ₂ (ZrO ₂ supported amount: 1.0% by weight) catalyst. This catalyst is referred to as ZrO ₂ (1.0) / SiO ₂ . The specific surface area of this catalyst was 341 m ² / g, and the Zr atomic density on the carrier SiO ₂ was 14.7 n / nm ² .

Preparation Example 4
0.27 g of hafnium chloride was dissolved in 50.0 ml of distilled water, 10.0 g of NIPGEL CX-200 was added, and the mixture was stirred for 30 minutes, and then the water was evaporated using an evaporator. After drying at 120 ° C., it was calcined at 500 ° C. under air flow to obtain an HfO ₂ / SiO ₂ (HfO ₂ supported amount 1.7% by weight) catalyst. This catalyst is referred to as HfO ₂ (1.7) / SiO ₂ . The specific surface area of this catalyst was 350 m ² / g, and the Zr atomic density on the carrier SiO ₂ was 14.3 n / nm ² .

Preparation Example 5
To 3.0 g of Ta ₂ O ₅ (1.6) / SiO ₂ obtained in Preparation Example 1, 15 ml of NH ₃ water (pH = 10.0) was added, and 3-aminopropyltriethoxysilane (Shin-Etsu Chemical) was added thereto. 0.070 g (manufactured by Kogyo Co., Ltd.) was added dropwise, the temperature was raised to 60 ° C. with stirring, and the mixture was held for 4 hours. Then, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. under air flow. The catalyst thus obtained is referred to as Si-Ta ₂ O ₅ (1.6) / SiO ₂ . The specific surface area of this catalyst was 289 m ² / g.

Preparation Example 6
Ethyl silicate (manufactured by Wako Pure Chemical Industries, Ltd.) 12.5 g, ethanol 12.5 ml, distilled water 1.1 g, nitric acid 0.55 g (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed and stirred while stirring 76. The mixture was refluxed at ° C. for 3 hours. On the other hand, 0.3 g of tantalum ethoxide was dissolved in 100 ml of ethanol, 10.0 g of NIPGEL CX-200 was added, and the mixture was stirred at room temperature for 2 hours. These two solutions were mixed and refluxed at 76 ° C. for 5 hours. Then, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. under air flow. The catalyst thus obtained is referred to as Si (TEOS) -Ta ₂ O ₅ (1.6) / SiO ₂ . The specific surface area of this catalyst was 361 m ² / g.

Preparation Example 7
To 3.0 g of Ta ₂ O ₅ (0.16) / SiO ₂ obtained in Preparation Example 2, 15 ml of NH ₃ water (pH = 10.0) was added, and 0.026 g of 3-aminopropyltriethoxysilane was added thereto. Was added dropwise, the temperature was raised to 60 ° C. with stirring, and the mixture was held for 4 hours. Then, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. under air flow. The catalyst thus obtained is referred to as Si-Ta ₂ O ₅ (0.16) / SiO ₂ . The specific surface area of this catalyst was 314 m ² / g.

Preparation Example 8
To 3.0 g of ZrO ₂ (1.0) / SiO ₂ obtained in Preparation Example 3, 15 ml of NH ₃ water (pH = 10.0) was added, and 0.083 g of 3-aminopropyltriethoxysilane was added dropwise thereto. Then, the temperature was raised to 60 ° C. with stirring and maintained for 4 hours. Then, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. under air flow. The catalyst thus obtained is referred to as Si-ZrO ₂ (1.0) / SiO ₂ . The specific surface area of this catalyst was 305 m ² / g.

Preparation Example 9
To 3.0 g of HfO ₂ (1.7) / SiO ₂ obtained in Preparation Example 4, 15 ml of NH ₃ water (pH = 10.0) was added, and 0.083 g of 3-aminopropyltriethoxysilane was added dropwise thereto. Then, the temperature was raised to 60 ° C. with stirring and maintained for 4 hours. Then, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. under air flow. The catalyst thus obtained is referred to as Si-HfO ₂ (1.7) / SiO ₂ . The specific surface area of this catalyst was 307 m ² / g.

Comparative Examples 1 to 4, Examples 1 to 5
<Reaction test>
0.63 g of the catalyst shown in Table 1 was filled in a fixed bed flow reactor, and the experiment was conducted under the following reaction conditions.

While flowing nitrogen (6.8 Nml / min) through the reactor, the temperature was raised to 350 ° C. and the pressure was increased to 0.26 MPaG, and then ethanol (11.0 Nml / min), acetaldehyde (4.4 Nml / min) and nitrogen were used as raw material gases. (6.8 Nml / min) was mixed and supplied to the reactor (WHSV = 3.0 _{g-(EtOH + AcH)} · g _-cat ^-1 · h ^-1 ). The composition of the reactor outlet gas was determined by gas chromatography.
The conversion rate and selectivity were calculated by the following formulas.

In Comparative Example 1, Ta ₂ O ₅ (1.6) / SiO ₂ , the selectivity of 1,3-butadiene was 66.2 C-mol% and the yield of 1,3-butadiene was 32.3 C-mol%, whereas it was 32.3 C-mol%. In the case of Si-Ta ₂ O ₅ (1.6) / SiO _{2 of} Example 1, the selectivity of 1,3-butadiene was 79.9 C-mol%, the yield of 1,3-butadiene was 39.5 C-mol%, and that of Example 2. In Si (TEOS) -Ta ₂ O ₅ (1.6) / SiO ₂ , silicon has a selectivity of 73.4 C-mol% and a yield of 1,3-butadiene of 36.8 C-mol%. Treatment with a substance containing improved 1,3-butadiene selectivity and 1,3-butadiene yield. The conversion rate was almost unchanged by the treatment.

Even with Ta ₂ O ₅ (0.16) / SiO ₂ having a different amount of Ta carried, in Example 3 in which the treatment with a compound containing silicon was performed as compared with Comparative Example 2, the yield of 1,3-butadiene was 16.2 C. It was slightly improved from −mol% to 16.7C−mol%, and the 1,3-butadiene selectivity was improved from 66.3C−mol% to 71.7C−mol% (Comparative Example 2 and Example 3 respectively).

Similarly, in ZrO ₂ (1.0) / SiO ₂ , the yield of 1,3-butadiene was 32.3 C-mol% to 37. In Example 4 by treatment with a compound containing silicon as compared with Comparative Example 3. At 4C-mol%, the selectivity of 1,3-butadiene was improved from 67.5C-mol% to 77.3C-mol% (Comparative Example 3 and Example 4, respectively).

Comparing Comparative Example 4 and Example 5 with HfO ₂ (1.7) / SiO ₂ , the yield of 1,3-butadiene increased from 37.0 C-mol% to 39.1 C-mol%, 1,3-. The butadiene selectivity was improved from 64.1 C-mol% to 68.0 C-mol% (Comparative Example 3 and Example 5).

< ²⁹ Si-MAS-NMR measurement>
²⁹ Si-MAS-NMR measurement was carried out under the following conditions.
Equipment: Agilent's VNMRS-600
Pulse program: Single pulse sample rotation speed: 6 kHz
Repeat time: 100 sec
Pulse width: 90 °
Number of integrations: 512 times Adjusted to -34.44 ppm using polydimethylsiloxane (PDMS) as a secondary standard

Comparative Example 5
²⁹ Si-MAS-NMR of Ta ₂ O ₅ (1.6) / SiO ₂ obtained in Preparation Example 1 was measured. Signals attributed to Q2 (around -91 ppm), Q3 (around -101 ppm), and Q4 (around -111 ppm) were detected. When the signal intensity of the maximum value near the chemical shift value of −111 ppm was set to 1, the signal intensity at the chemical shift value of −105 ppm was 0.48.

Example 6
²⁹ Si-MAS-NMR of Si-Ta ₂ O ₅ (1.6) / SiO ₂ obtained in Preparation Example 6 was measured. Signals attributed to Q2 (around -91 ppm), Q3 (around -101 ppm), and Q4 (around -111 ppm) were detected. When the signal intensity of the maximum value near the chemical shift value of −111 ppm was set to 1, the signal intensity at the chemical shift value of −105 ppm was 0.68.

Example 7
²⁹ Si-MAS-NMR of Si (TEOS) -Ta ₂ O ₅ (1.6) / SiO ₂ obtained in Preparation Example 7 was measured. Signals attributed to Q2 (around -91 ppm), Q3 (around -101 ppm), and Q4 (around -111 ppm) were detected. When the signal intensity of the maximum value near the chemical shift value of −111 ppm was set to 1, the signal intensity at the chemical shift value of −105 ppm was 0.58.

Claims (7)

At least a part of the surface hydroxyl groups and oxo groups of a substance containing the elements (A) of Group 4 and Group 5 of the periodic table and silicon dioxide as a carrier component is reacted with a silicon compound having a hydrolyzable group. Obtained by substitution with an —O—Si group
The substance is characterized in that the element (A) of Group 4 and Group 5 of the periodic table is supported on the surface of silicon dioxide which is a carrier component, and the element (A) is immobilized on the silicon dioxide. , A method for producing a 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol. The method for producing a 1,3-butadiene production catalyst according to claim 1, wherein the silicon compound having a hydrolyzable group is a monomer composed of the formula (1).
SiY _n R _(4-n) ... (1)
In the formula, Y is an independently hydrolyzable group, R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. In the 1,3-butadiene production catalyst, at least a part of the surface hydroxyl group and the oxo group on the element (A) is replaced with an —O—Si group by a reaction with the silicon compound having a hydrolyzable group. The method for producing a 1,3-butadiene production catalyst according to claim 1 or 2, wherein the catalyst is obtained. The molar ratio of silicon to element (A) in a silicon compound having a hydrolyzable group (silicon [mol] / element (A) [mol] in a silicon compound having a hydrolyzable group) is 0.1 to 100. The method for producing a 1,3-butadiene production catalyst according to any one of claims 1 to 3, wherein the method is characterized by the above. The production of the 1,3-butadiene production catalyst according to any one of claims 1 to 4, wherein the density of the element (A) on silicon dioxide is in the range of 1 to 50 elements / nm ^2. Method. The method for producing a 1,3-butadiene production catalyst according to any one of claims 1 to 5, wherein the element (A) is at least one selected from zirconium, hafnium and tantalum. ²⁹ Si-NMR chemical shift value: When the signal intensity of the maximum value near −111 ppm is 1, the signal intensity at the chemical shift value: −105 ppm is 0.55 or more. The method for producing a 1,3-butadiene production catalyst according to any one of 1 to 6.

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