JP2018171587A - Catalyst and process for production of 1,3-butadiene from ethanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst that makes it possible to produce 1,3-butadiene efficiently under practical operation conditions, and a method for producing the 1,3-butadiene with the catalyst.SOLUTION: A hydroxy group and an oxo group on a surface of a material containing elements (A) of groups 4 and 5 in a periodic table and silicon dioxide as a support component are subjected to a reaction with a silicon compound having a hydrolyzable group, for substitution with an -O-Si group, to produce a catalyst. The catalyst is used to produce, from a raw material containing ethanol, 1,3-butadiene.SELECTED DRAWING: None

Description

  The present invention 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 lost its competitiveness with the completion of butadiene extractive distillation technology from C4 fraction obtained from naphtha crackers. Currently not used except. However, in recent years, there are concerns about the expansion of the global butadiene supply-demand gap accompanying the growth in the number of automobiles, especially in Asia, and the lightening of cracker raw materials.

In the ETB process, there is a one-stage method (Lebedev method) in which ethanol is converted to butadiene in one stage, and a two-stage method (Ostromislensky method) in which ethanol is first dehydrogenated to synthesize acetaldehyde and butadiene is synthesized from ethanol and acetaldehyde. .
-One-step method 2 CH 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 Groups 4 and 5 of the periodic table are supported on silica is known. Ta ₂ O ₅ / SiO ₂ catalyst has long been known as a 1,3-butadiene synthesis catalyst (Patent Document 1, Non-Patent Documents 1 and 2). However, the butadiene selectivity at that time could not be said to be sufficiently high in the 60% range.

In recent years, a catalyst in which Ta is supported on mesoporous silica (Non-patent Document 3), Ta / SBA-15 in which Ta is supported on zeolite (Non-patent Document 4), and TaBEA in which Ta is inserted into a zeolite framework (Non-patent Document 5) Has been reported as a 1,3-butadiene synthesis catalyst. In addition, ZrO ₂ / SiO ₂ catalyst and HfO ₂ / SiO ₂ catalyst have also been known as 1,3-butadiene synthesis catalysts for a long time (Non-patent Document 2), and in recent years, they carry a metal having dehydrogenating ability. As a one-stage catalyst, Ag—ZrO ₂ —CeO ₂ —SiO ₂ (Patent Document 2), ZnZrSiO ₂ , CuZnZrSiO ₂ (Non-Patent Document 6), CuHfZnSiO ₂ (Non-Patent Document 7), and the like have been reported.

U.S. Pat.No. 2524848 Japanese Patent No. 5586572

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 more efficiently producing 1,3-butadiene under practical operating conditions and a method for producing 1,3-butadiene using the catalyst.

Under such circumstances, the present inventors diligently studied to solve the above-mentioned problems, and as a result, the present invention has been completed with the following configuration.
[1] Reaction of Group 4 and Group 5 element (A) in the periodic table with a silicon compound containing silicon dioxide as a carrier component and having at least part of its surface hydroxyl group and oxo group having a hydrolyzable group A 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol, wherein the catalyst is substituted with a —O—Si group.
[2] The molar ratio of silicon to element (A) in the silicon compound having a hydrolyzable group (silicon [mol] in the silicon compound having a hydrolyzable group / element (A) [mol]) is 0.1. The catalyst for producing 1,3-butadiene according to [1], wherein
[3] The 1,3-butadiene production catalyst according to [1] or [2], wherein the density of the element (A) on the silicon dioxide is in the range of 1 to 50 / nm ² .
[4] The 1,3-butadiene production catalyst according to any one of [1] to [3], wherein the element (A) is at least one selected from zirconium, hafnium and tantalum.
[5] Chemical shift value of ²⁹ Si-NMR: signal intensity at a chemical shift value: −105 ppm when the signal intensity at the maximum value near −111 ppm is 1, is 0.55 or more. 1,3-butadiene production catalyst according to any one of [1] to [4].
[6] Using the 1,3-butadiene production catalyst according to any one of [1] to [5], the reaction temperature is 300 ° C. or higher and 450 ° C. or lower, and the partial pressure of ethanol and acetaldehyde is 0.1-1. A method for producing 1,3-butadiene, which is characterized by being 0 MPaA and a weight space velocity in the range 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 a raw material gas containing ethanol.

The ²⁹ Si-MAS-NMR spectrum of the 1, 3- butadiene manufacturing catalyst prepared by the Example and the comparative example is 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 Group 4 and Group 5 elements (A) and silicon dioxide as a support component. A hydroxyl group (—OH) and an oxo group (═O) derived from a hydroxide or oxide of silicon or element (A) are present on the catalyst surface. In the present invention, at least one of the surface hydroxyl group and the oxo group is present. The moiety is substituted with a —O—Si group by reacting with a silicon compound having a hydrolyzable group. All hydroxyl groups and oxo groups may be substituted, or a part thereof may be substituted.

  Examples of the element (A) include titanium, zirconium, hafnium, vanadium, niobium, tantalum and the like, and the element (A) is at least 1 selected from zirconium, hafnium, and tantalum in terms of improving 1,3-butadiene selectivity. Preferably it is a seed.

  These elements (A) are fixed to silicon dioxide as a support in the state of metal, oxide, hydroxide, salt or 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 for fixing the element (A) to silicon dioxide, a chloride salt, nitrate, sulfate, phosphate, or alkoxide containing the element (A) is dissolved in water or an organic solvent, and a silicon dioxide powder or molded product is obtained. It can be prepared by impregnating a carrier comprising the above, followed by heating, drying and firing. As the impregnation method, a known method can be employed, and examples thereof include a spray method, a coating method, a pore filling method, and a selective adsorption method using an (water) solution containing the element (A). Further, a chloride salt, nitrate, sulfate, phosphate, alkoxide, etc. containing the element (A) may be dissolved in the dispersion of the silicon dioxide powder of the carrier. Furthermore, it can be prepared by vaporizing a chloride salt or alkoxide containing the element (A) and adsorbing it on the surface of the silicon dioxide support, followed by drying and baking.

  Moreover, after mixing an element (A) and the precursor of silicon dioxide, it can also prepare by performing processing, such as heating, concentration, and hydrothermal synthesis, and drying and baking. Examples of the precursor of the element (A) include alkoxides, chloride salts, nitrates, sulfates, phosphates, and metal oxide sols. Further, as a precursor of the silicon dioxide support, an organic silicon compound such as alkoxide, polysiloxane and polysilazane, an organic silicate such as silicate, silica sol and the like 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. The silicon compound having a hydrolyzable group is a compound in which 1 to 4 hydrolyzable groups are bonded to a silicon atom. Examples of hydrolyzable groups include hydrogen, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. The silicon compound having a hydrolyzable group is represented, for example, by the following formula (1).
SiY _n R _(4-n) (1)

  In formula, Y is a hydrolyzable group each independently, R is a C1-C20 substituted or unsubstituted hydrocarbon group. n is an integer of 1 to 4. The substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms is not particularly limited. For example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or 6 to 20 carbon atoms. An aryl group, a C7-20 aralkyl group, etc. are mentioned. In addition, when two or more Y or R couple | bond together, these may mutually be same or different. Furthermore, the silicon compound having a hydrolyzable group may be a partial polycondensate in which at least a part is polycondensed.

  The treatment may be performed 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. The treatment may be performed by vaporizing the silicon compound and adsorbing the element (A) onto the surface of the substance immobilized on silicon dioxide. By these treatments, the surface hydroxyl group of the substance in which the element (A) is immobilized on silicon dioxide, or the oxo group on the element (A) when the element (A) is a Group 5 metal of the periodic table, It is considered that a condensation reaction occurs with a hydrolyzable group of the above, and an —O—Si bond is formed on or around the element (A).

In recent years, it has become clear that the coordination state of metals in zeolite affects Lewis acidity and reactivity. In the zeolite into which Sn is introduced (SnBEA), it is clear that there are two types of active sites (-Si-O-) ₃ Sn-OH and Sn (-Si-O-) ₄ . (-Si-O-) ₃ Sn-OH has a stronger Lewis acid and has been reported to contribute to the adamantane oxidation reaction with hydrogen peroxide (Journal of Catalysis, vol. 234, pp. 111 (2005)). Similarly, in the zeolite into which Zr is introduced (ZrBEA), of the two types of active sites, (-Si-O-) ₃ Zr-OH has a stronger Lewis acid. It has been reported that there is a correlation between the reaction rate of butadiene synthesis 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 that an active metal is present in silicon dioxide is the same as the previous report, and the coordination state around the active metal (the —OH group). Or -OSi group) is expected to greatly contribute to the Lewis acidity and reactivity of the catalyst. Therefore, it is considered that the activity / selectivity of the catalyst is changed by generating -O-Si bond on or near the element (A).

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

  The molar ratio of silicon and 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, A range of 0.1 to 100 is preferred. If the molar ratio of silicon to 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 the silicon dioxide is not particularly limited, but a range of 1 to 50 / nm ² is preferable. If the density of the element (A) is too low, the production rate of 1,3-butadiene per unit volume of the catalyst becomes slow. When the density of the element (A) is too high, 1,3-butadiene selectivity decreases due to the progress of side reactions.

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

[Method for producing 1,3-butadiene]
The method for producing 1,3-butadiene according to 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 include ethanol derived from biomass such as sugar cane and corn, ethanol derived from petroleum, coal, or natural gas. In addition, if ethanol derived from biomass is used, it can contribute to greenhouse gas reduction.

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

  As acetaldehyde, one produced by dehydrogenation of ethanol can be used. In the dehydrogenation reaction of ethanol, for example, a known copper catalyst or silver catalyst disclosed in JP-A Nos. 2005-342675 and 2011-000532 is used. Specifically, Cu-based materials, metals of group 8 of the periodic table of elements such as Ni, Pd, and Pt can be suitably used, and those containing Cu are more preferable. For example, Cu alone or a material containing a two-component metal obtained by adding a transition metal element such as Cr, Co, Ni, Fe, or Mn to this can be used, and a material containing Cu and Ni is preferably used. Further, those containing three or more metal components are also preferably used. Further, those in which these are further supported on silicon dioxide, aluminum oxide, titanium oxide, zeolite or the like can be used.

The reaction conditions are not particularly limited, and the reaction is usually carried out in a range of about 200 to 300 ° C. under conditions that produce a predetermined amount of acetaldehyde.
As such a manufacturing method, a known method such as a batch method, a semi-batch method, or a continuous method can be adopted. When the continuous method is adopted, large-scale synthesis is possible, the operation workload is light, and the unreacted raw material can be reused in the reaction system to improve the raw material ethanol usage rate to an extremely high level. Therefore, it is preferable to employ a continuous system that can separate and recover 1,3-butadiene simply and efficiently.

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

  When performing the reaction 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 an inert gas and supplied to the reactor.

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

  The reaction temperature is, for example, about 300 ° C. or more and 450 ° C. or less, preferably 320 to 380 ° C. If the temperature is too high, the 1,3-butadiene selectivity decreases. On the other hand, if the temperature is too low, the butadiene production rate is not sufficient.

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

The contact time between the raw material and the catalyst can be controlled by adjusting the feed 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 is preferred. If WHSV is too low, the reactor size increases, which is not preferable from the viewpoint of equipment costs. On the other hand, if WHSV is too high, the butadiene yield decreases.

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

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples at all.
<Catalyst preparation>
Preparation Example 1
0.3 g of tantalum ethoxide (99.98%, manufactured by Sigma-Aldrich) is dissolved in 100 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), NIPGEL CX-200 (manufactured by Tosoh Silica Co., Ltd., specific surface area of 392 m) ^{2 /} g) After 10.0 g was added and stirred for 2 hours, ethanol was evaporated using an evaporator. After drying at 120 ° C., the catalyst 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 wt%) catalyst. This catalyst is expressed 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 support SiO ₂ was 14.9 atoms / 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 stirred for 2 hours, and then the ethanol was evaporated using an evaporator. After drying at 120 ° C., the catalyst 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 wt%) catalyst. This catalyst is expressed 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 support SiO ₂ was 2.8 atoms / nm ² .

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

Preparation Example 4
After dissolving 0.27 g of hafnium chloride in 50.0 ml of distilled water, adding 10.0 g of NIPGEL CX-200 and stirring for 30 minutes, the water was evaporated using an evaporator. After drying at 120 ° C., the catalyst was calcined at 500 ° C. under air flow to obtain a HfO ₂ / SiO ₂ (HfO ₂ loading amount 1.7% by weight) catalyst. This catalyst is expressed as HfO ₂ (1.7) / SiO ₂ . The specific surface area of this catalyst was 350 m ² / g, and the Zr atom density on the support SiO ₂ was 14.3 atoms / 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. Thereafter, the catalyst was recovered by centrifugation, dried at 120 ° C., and then calcined at 500 ° C. under air flow. The catalyst thus obtained is represented 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
12.5 g of ethyl silicate (manufactured by Wako Pure Chemical Industries, Ltd.), 12.5 ml of ethanol, 1.1 g of distilled water, 0.55 g of nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and stirred while stirring. Reflux for 3 hours at ° C. 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. Thereafter, the catalyst was recovered by centrifugation, dried at 120 ° C., and then calcined at 500 ° C. under air flow. The catalyst thus obtained is expressed 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 and the temperature was raised to 60 ° C. with stirring and held for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. in a stream of air. The catalyst thus obtained is represented 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
15 ml of NH ₃ water (pH = 10.0) is added to 3.0 g of ZrO ₂ (1.0) / SiO ₂ obtained in Preparation Example 3, and 0.083 g of 3-aminopropyltriethoxysilane is added dropwise thereto. The temperature was raised to 60 ° C. with stirring and held for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120 ° C., and calcined at 500 ° C. in a stream of air. The catalyst thus obtained is expressed 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) is added, and 0.083 g of 3-aminopropyltriethoxysilane is added dropwise thereto. The temperature was raised to 60 ° C. with stirring and held for 4 hours. Thereafter, the catalyst was recovered by centrifugation, dried at 120 ° C., and then calcined at 500 ° C. under air flow. The catalyst thus obtained is expressed as Si—HfO ₂ (1.7) / SiO ₂ . The specific surface area of this catalyst was 307 m ² / g.

Comparative Examples 1-4, Examples 1-5
<Reaction test>
0.63 g of the catalyst described in Table 1 was charged into a fixed bed flow type reactor, and an 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 gas composition at the outlet of the reactor was determined by gas chromatography.
Conversion and selectivity were determined by the following formulas.

The Ta ₂ O ₅ (1.6) / SiO _{2 of} Comparative Example 1 has a 1,3-butadiene selectivity of 66.2 C-mol% and a 1,3-butadiene yield of 32.3 C-mol%. In Si—Ta ₂ O ₅ (1.6) / SiO _{2 of} Example 1, 1,3-butadiene selectivity was 79.9 C-mol%, 1,3-butadiene yield was 39.5 C-mol%, Example 2 Si (TEOS) -Ta ₂ O ₅ (1.6) / SiO ₂ has a 1,3-butadiene selectivity of 73.4 C-mol%, a 1,3-butadiene yield of 36.8 C-mol%, and silicon. The 1,3-butadiene selectivity and the 1,3-butadiene yield were improved by the treatment with the contained material. The conversion was hardly changed by the treatment.

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

Similarly, even in ZrO ₂ (1.0) / SiO ₂ , the 1,3-butadiene yield was 32.3 C-mol% to 37.3% in Example 4 by treatment with a compound containing silicon compared to Comparative Example 3. In 4C-mol%, the 1,3-butadiene selectivity 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 1,3-butadiene yield increased from 37.0 C-mol% to 39.1 C-mol%. Butadiene selectivity was improved from 64.1 C-mol% to 68.0 C-mol% (Comparative Example 3, Example 5).

^<29 Si-MAS-NMR measurement>
²⁹ Si-MAS-NMR measurement was carried out under the following conditions.
Apparatus: VNMRS-600 manufactured by Agilent
Pulse program: Single pulse Sample rotation speed: 6 kHz
Repeat time: 100 sec
Pulse width: 90 °
Integration count: 512 times Adjusted to -34.44 ppm using polydimethylsiloxane (PDMS) as 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 (near -91 ppm), Q3 (near -101 ppm), and Q4 (near -111 ppm) were detected. The signal intensity at a chemical shift value of −105 ppm when the signal intensity at the maximum value near the chemical shift value of −111 ppm is 1 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 (near -91 ppm), Q3 (near -101 ppm), and Q4 (near -111 ppm) were detected. The signal intensity at a chemical shift value of −105 ppm when the signal intensity at the maximum value near the chemical shift value of −111 ppm was 1 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 (near -91 ppm), Q3 (near -101 ppm), and Q4 (near -111 ppm) were detected. The signal intensity at a chemical shift value of −105 ppm when the signal intensity at the maximum value near the chemical shift value of −111 ppm was 1 was 0.58.

Claims (6)

  By reacting with a silicon compound containing a group 4 element and a group 5 element (A) in the periodic table and silicon dioxide as a carrier component, at least part of the surface hydroxyl groups and oxo groups of which are hydrolyzable groups, A 1,3-butadiene production catalyst for producing 1,3-butadiene from a raw material containing ethanol, which is substituted with an O-Si group.   The molar ratio of silicon and element (A) in the silicon compound having a hydrolyzable group (silicon [mol] / element (A) [mol] in the silicon compound having a hydrolyzable group) is 0.1 to 100 The 1,3-butadiene production catalyst according to claim 1, wherein the catalyst is a production catalyst. Wherein the density of the element (A) on the silicon dioxide is in the range of 1-50 / nm ^2, according to claim 1 or 2 1,3-butadiene production catalyst.   The 1,3-butadiene production catalyst according to any one of claims 1 to 3, wherein the element (A) is at least one selected from zirconium, hafnium and tantalum. ²⁹ Si-NMR chemical shift value: signal intensity at chemical shift value: -105 ppm is 0.55 or more when the signal intensity at the maximum value near -111 ppm is set to 1. The 1,3-butadiene production catalyst according to any one of 1 to 4.   Using the 1,3-butadiene production catalyst according to any one of claims 1 to 5, the reaction temperature is 300 ° C to 450 ° C, the partial pressure of ethanol and acetaldehyde is 0.1-1.0 MPaA, weight A method for producing 1,3-butadiene, wherein the space velocity is in the range of 0.1 to 30 g / g-cat · h.

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