JP6084963B2 - Method for producing 1,3-butadiene - Google Patents

Description

  The present invention relates to a novel 1,3-butadiene production method for producing 1,3-butadiene, which is a raw material of synthetic rubber important in many industrial fields including the automotive industry field and the electronic material field, from ethanol in one pass.

  Conventionally, 1,3-butadiene has been produced mainly by refining a C4 fraction produced as a by-product when ethylene is synthesized from petroleum (= naphtha cracking). However, in recent years, instead of chemical industrial raw materials obtained from petroleum, chemical industrial raw materials derived from biomass-derived raw materials have attracted attention. For example, biomass-derived bioethanol such as sugarcane and corn is converted into 1,3-butadiene. The technology to convert is anxious.

As a method for obtaining 1,3-butadiene using ethanol as a raw material, a method using MgO as a catalyst (Patent Document 1) and a method using a mixture of Al ₂ O ₃ and ZnO (mixing ratio: 60/40) Patent Document 1) and the like are known. However, the manufacturing technology is not as delicate and established as naphtha cracking, the catalyst is easily deteriorated by heat and is difficult to recycle, the cost is increased, the ethanol conversion efficiency is low, and the yield of 1,3-butadiene is low. However, it is difficult to find an advantage that can be opposed to a manufacturing method using chemical industrial raw materials obtained from petroleum, and the practical use is not progressing.

US Pat. No. 2,436,681

Journal of Catalyst 5: 152 (1967)

  Accordingly, an object of the present invention is to provide a method for producing 1,3-butadiene, which obtains 1,3-butadiene from ethanol by a simple and industrially advantageous method.

  As a result of intensive studies to solve the above problems, the present inventors have found that when ethanol is brought into contact with a specific catalyst in a heating environment, 1,3-butadiene can be obtained with extremely excellent selectivity. The present invention has been completed based on these findings.

That is, the present invention is a method for producing 1,3-butadiene, which obtains 1,3-butadiene from ethanol, wherein the following raw materials are brought into contact with the following catalyst under heating: A manufacturing method is provided.
Raw material: including ethanol Catalyst: Periodic Table 4-13 Group metal oxide (component A), magnesium oxide (component B), and a catalyst containing a binder component (component C) containing an inorganic oxide other than the above

  The present invention also provides the method for producing 1,3-butadiene as described above, wherein the inorganic oxide in component C is silicon dioxide.

  The present invention also provides the above-described method for producing 1,3-butadiene, wherein the raw material is contacted with a catalyst in the presence of hydrogen.

  The present invention also provides the method for producing 1,3-butadiene as described above, wherein Component C is zeolite.

The present invention also provides the above-mentioned method for producing 1,3-butadiene, wherein the zeolite is a zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 12 or more and a pore diameter of 10 mm or less.

  The present invention also provides the above-mentioned method for producing 1,3-butadiene using magnesium silicate as component B and component C.

  The present invention also provides the method for producing 1,3-butadiene as described above, wherein the magnesium silicate is magnesium phyllosilicate.

The present invention also provides the method for producing 1,3-butadiene, wherein the raw material is contacted with the following catalyst (A) and catalyst (B) in this order.
Catalyst (A): a catalyst containing a group 4-13 metal oxide (component A), magnesium oxide (component B), and a binder component (component C) containing an inorganic oxide other than those described above. Catalyst having a selectivity of acetaldehyde of 10% or more obtained when ethanol is brought into contact with the catalyst (temperature: 400 ° C., space velocity: 360 hr ⁻¹ ) Catalyst (B): Group 4-13 metals in the periodic table Catalyst (component A), magnesium oxide (component B), and a binder component (component C) containing an inorganic oxide other than the above, wherein ethanol is brought into contact with the catalyst (temperature: 400 ° C., space Catalyst having a selectivity of acetaldehyde of less than 10% and a selectivity of 1,3-butadiene of 45% or more at a rate of 360 hr ^-1 )

  According to the method for producing 1,3-butadiene according to the present invention, 1,3-butadiene can be selectively produced from ethanol by a simple method. In addition, the catalyst used in the present invention is hardly deteriorated by heat and can be used repeatedly. Therefore, the method for producing 1,3-butadiene according to the present invention is preferably used in a method for industrially producing 1,3-butadiene, which is an important raw material for synthetic rubber in many industrial fields, from ethanol. Can do.

The method for producing 1,3-butadiene according to the present invention is characterized in that the following raw materials are brought into contact with the following catalyst under heating.
Raw material: including ethanol Catalyst: Periodic Table 4-13 Group metal oxide (component A), magnesium oxide (component B), and a catalyst containing a binder component (component C) containing an inorganic oxide other than the above

The method for producing 1,3-butadiene of the present invention is considered to undergo the following reaction steps.

[material]
The raw material of the present invention contains at least ethanol. The ethanol is not particularly limited, and examples thereof include ethanol derived from biomass such as sugar cane and corn, ethanol derived from petroleum or natural gas, and the like. In the present invention, it is particularly preferable to use biomass-derived ethanol because it can greatly contribute to the reduction of greenhouse gases.

  The content of ethanol in the raw material (100 wt%) of the present invention is, for example, 50 wt% or more, preferably 70 to 100 wt%.

  The raw material of the present invention may contain acetaldehyde together with ethanol. By containing acetaldehyde together with ethanol, 1,3-butadiene can be obtained more selectively and with a high yield.

  When acetaldehyde is contained together with ethanol, the molar ratio of ethanol to acetaldehyde (the former: the latter) is, for example, about 95/5 to 50/50, preferably 90/10 to 60/40, particularly preferably 85/15 to 65 / 35, most preferably in the range of 80/20 to 70/30.

[catalyst]
The catalyst of this invention contains the binder component (component C) containing the oxide (component A) of a periodic table group 4-13 metal, magnesium oxide (component B), and inorganic oxides other than the above. The catalyst of the present invention is obtained by joining a metal oxide (component A) of groups 4 to 13 of the periodic table and magnesium oxide (component B) with a binder component (component C) containing an inorganic oxide other than the above. Catalyst.

  The Group 4-13 Group metal oxide (component A) acts as a co-catalyst and exhibits an effect of improving the selectivity of 1,3-butadiene. For example, the step (a) In the step (d), the side reaction of dehydrating ethanol to suppress ethylene and suppressing the side reaction of obtaining ethylene to promote the reaction of dehydrating ethanol to obtain acetaldehyde. O) has a function of promoting a reaction of selectively hydrogenating, byproduct of crotonaldehyde hydride of carbon-carbon double bond (for example, butyraldehyde, normal butanol, etc.), and condensation of crotonaldehyde Decomposition can be suppressed.

  Examples of the metals in groups 4 to 13 of the periodic table include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, zirconium, niobium, molybdenum, tantalum, tungsten, and silver. Can be mentioned.

  As the oxide (component A) of the metals of Groups 4 to 13 of the periodic table in the present invention, at least one selected from titanium, chromium, copper, zinc, gallium, zirconium, niobium, tantalum, and silver, among others. The metal oxides are preferred.

  The magnesium oxide (component B) is an active species in the catalytic reaction for obtaining 1,3-butadiene from ethanol.

The component C acts as a diluent for stabilizing fine particles of magnesium oxide (component B) which is an active species. As the inorganic oxide in component C, silicon dioxide is preferred. Therefore, in the present invention, it is preferable to use a binder component containing silicon dioxide as component C. Component C may further contain an oxide (for example, Al ₂ O ₃ or the like) of the metals in groups 4 to 13 of the periodic table.

The specific surface area of the component C (BET specific surface area), for example, 10 to 1000 m ² / g, preferably about 50~1000m ² / g, more preferably 100~1000m ² / g, particularly preferably 250~1000m ² / g Most preferably, it is 330 to 1000 m ² / g. When the specific surface area of Component C is below the above range, it tends to be difficult to stabilize the magnesium oxide (Component B) fine particles. Further, if the specific surface area of component C exceeds the above range, the pore diameter becomes extremely small, so that pore clogging due to carbon deposition is likely to occur, and the diffusion of the substrate to the active site is inhibited, so the deactivation rate is Tend to be faster.

  The shape of the component C is not particularly limited, and various shapes such as powders, lumps, layers, porous shapes, so-called honeycomb structures can be used.

  Examples of component C include colloidal silica (silica sol), silica gel, fumed silica, diatomaceous earth, mica, mesoporous silica (MCM-41), zeolite, and silicoaluminophosphate. These can be used alone or in admixture of two or more.

The zeolite is a general term for crystalline aluminosilicates, and includes A type, X type, Y type, mordenite type, ferrierite type, ZSM-5 type, β type and the like. Zeolite is represented by the following formula. In the formula, M ^{n +} represents a cation such as Na ⁺ , K ⁺ , Ca ²⁺ and H ⁺ . x represents a number of 2 or more, and y represents a number of 0 or more.
_{^{(M n +) 2 / n}} O · Al 2 O 3 · xSiO 2 · yH 2 O

The SiO ₂ / Al ₂ O ₃ molar ratio of zeolite is preferably 12 or more, particularly preferably 18 or more, and most preferably 300 or more. When the SiO ₂ / Al ₂ O ₃ molar ratio of zeolite is adjusted to the above range, it is preferable in that strong acid sites can be reduced and side reactions that generate ethylene by dehydrating ethanol can be suppressed. On the other hand, if the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite is out of the above range, the acid point increases and the amount of ethylene produced by ethanol dehydration tends to increase.

  Further, the pore diameter of zeolite is preferably 10 mm or less, particularly preferably 4 to 8 mm. Zeolite having a pore size in the above range can suppress the by-generation and diffusion of large molecules having 5 or more carbon atoms, and can further improve the selectivity of 1,3-butadiene.

In the present invention, as component C, for example, trade name “Snowtex 30” (colloidal silica, silicon dioxide content ratio: 30 wt%, specific surface area: 300 ± 100 m ² / g, manufactured by Nissan Chemical Industries, Ltd.), product Name “Snowtex XS” (colloidal silica, silicon dioxide content: 20% by weight, specific surface area: 800 ± 200 m ² / g, manufactured by Nissan Chemical Industries, Ltd.), trade name “Aerosil 380PE” (fumed silica, dioxide) Commercial products such as silicon content ratio: 99.9% by weight, specific surface area: 380 ± 30 m ² / g, manufactured by Nippon Aerosil Co., Ltd. may be used.

In the present invention, the component C may form a composite oxide (for example, magnesium silicate), an oxo acid salt, or the like together with the component B, and the composite oxide may have a layer structure ( For example, magnesium phyllosilicate). In the present invention, the trade name “Mizuka Life P-1” (MgO / SiO ₂ (weight ratio) = 35/65, specific surface area: 400 m ² / g, Mizusawa Chemical Co., Ltd.) You may use commercial items, such as a product made from Corporation | KK.

The content of each component in the catalyst (100% by weight) of the present invention (the total amount when two or more are contained) is preferably in the following range.
Component A content: for example 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 1 to 5% by weight
Component B content: for example 20 to 95% by weight, preferably 30 to 90% by weight, more preferably 50 to 90% by weight, particularly preferably 60 to 90% by weight, most preferably 75 to 85% by weight
Component C content: for example 5 to 80% by weight, preferably 10 to 70% by weight, particularly preferably 15 to 25% by weight

  If the component A content in the catalyst is below the above range, the effect of improving the 1,3-butadiene selectivity tends to be difficult to obtain. On the other hand, if the component A content exceeds the above range, it does not disperse well on the catalyst, but rather tends to lower the catalytic activity by closing the active sites.

  If the content of component B in the catalyst is below the above range, the active sites are decreased, and the butadiene yield tends to be greatly reduced. On the other hand, when the component B content exceeds the above range, the basicity of the catalyst increases and the n-butanol selectivity tends to increase.

  When the content of component C in the catalyst is below the above range, the specific surface area decreases due to aggregation of magnesium oxide (component B), and the ethanol conversion tends to decrease. On the other hand, when the component C content exceeds the above range, the acid point increases and the amount of ethylene produced by ethanol dehydration tends to increase.

The catalyst of the present invention may contain components other than the above components (for example, oxides of alkali metals such as Na ₂ O and K ₂ O). In particular, the catalyst of the present invention preferably contains an oxide of an alkali metal such as Na ₂ O or K ₂ O in that the selectivity of 1,3-butadiene can be further improved. The content of other components is about 0.01 to 1% by weight of the catalyst (100% by weight), preferably 0.05 to 0.5% by weight.

  In the method for producing 1,3-butadiene according to the present invention, one type of the catalyst may be used, or two or more types may be used in combination. Moreover, when using in combination of 2 or more types, you may perform a contact with a raw material and 2 or more types of catalysts in 1 step (that is, you may make it contact in the state which mixed 2 or more types of catalysts), It may be carried out in two or more stages (that is, two or more kinds of catalysts may be contacted separately).

  For example, when two types of catalysts are contacted in two stages, a catalyst to be contacted first (hereinafter sometimes referred to as “catalyst (A)”) and a catalyst to be contacted later (hereinafter referred to as “catalyst (B)”) Each of which has the following characteristics.

Catalyst (A): a catalyst containing a group 4-13 metal oxide (component A), magnesium oxide (component B), and a binder component (component C) containing an inorganic oxide other than those described above. Catalyst having an acetaldehyde selectivity of 10% or more (preferably 15% or more, particularly preferably 20% or more) obtained when ethanol is brought into contact with the catalyst (temperature: 400 ° C., space velocity: 360 hr ⁻¹ ) Catalyst (B): A catalyst containing a group 4-13 metal oxide (component A), magnesium oxide (component B), and a binder component (component C) containing an inorganic oxide other than those described above. ethanol contact with the catalyst (temperature: 400 ° C., space velocity: 360hr ^-1) acetaldehyde obtained when obtained by the selectivity is less than 10%, and 1,3-butadiene selectivity of 45% or more (Preferably 50% or more, particularly preferably 55% or more) as a catalyst

  Among the oxides of the metals of Groups 4 to 13 of the periodic table in the catalyst (A), among them, the oxides of metals of Groups 11 or 12 of the periodic table such as copper, zinc, silver, etc. This is preferable in that the reaction rate promoting action is excellent.

  In the catalyst (B), the Group 4-13 Group metal oxide includes, among others, a Group 4 or Group 5 metal oxide such as titanium, zirconium, niobium, and tantalum. (D) It is preferable at the point which is excellent in the reaction rate acceleration | stimulation effect | action.

As a use ratio of the catalyst (A) and the catalyst (B), at least one selected from the volume ratio, the contact time ratio, and the space velocity ratio of the catalyst (A) and the catalyst (B) is within the following range. Is preferred.
The volume ratio (the former / the latter) of the catalyst (A) and the catalyst (B) is, for example, about 1/9 to 1/1 (preferably 1/7 to 1/2, particularly preferably 1/5 to 1/3). The contact time ratio (the former / the latter) of the catalyst (A) and the catalyst (B) is, for example, about 1/9 to 1/1 (preferably 1/7 to 1/2, particularly preferably 1/5). Within a range of ˜1 / 3) The space velocity ratio (the former / the latter) of the catalyst (A) and the catalyst (B) is, for example, about 9/1 to 1/1 (preferably 7/1 to 2/1, particularly Preferably within the range of 5/1 to 3/1)

  If the volume ratio and / or contact time ratio of the catalyst (A) is too large, 1,3-butadiene can be produced with excellent selectivity immediately after the start of the reaction. The rate tends to decrease, and the by-product of the compound having 4 or more carbon atoms tends to increase. On the other hand, if the volume ratio and / or contact time ratio of the catalyst (B) is too large, the effect of promoting the rate-determining step reaction is difficult to obtain, and the ethanol conversion tends to decrease.

[Method for preparing catalyst]
Examples of the method for preparing the catalyst include a kneading method, an impregnation method, a vapor deposition method, and a supported complex decomposition method. In the present invention, it is preferable to employ a kneading method because a catalyst that produces 1,3-butadiene with excellent selectivity can be prepared with good reproducibility. In the kneading method, for example, a metal compound belonging to Groups 4 to 13 of the periodic table (for example, a copper compound, a zinc compound, a chromium compound, a silver compound, a titanium compound, a zirconium compound, a niobium compound, a tantalum compound) and a magnesium compound (for example, Magnesium hydroxide, magnesium nitrate, magnesium oxalate, etc.) and a binder component containing an inorganic oxide other than the above and a compound corresponding to the above other components (for example, sodium hydroxide, potassium hydroxide, etc.) as necessary. Then, it is suspended in a solvent (for example, water, acetone, alcohol, or a mixture thereof), kneaded using an auto mill or the like, dried, baked (heat treatment), and periodic groups 4 to 13 A catalyst containing a binder component containing a metal oxide, magnesium oxide and an inorganic oxide other than the above can be prepared.

  Examples of the copper compound include copper nitrate, copper sulfate, copper acetate, copper isopropoxide, and the like.

  Examples of the zinc compound include zinc nitrate, zinc sulfate, and bisacetylacetonato zinc.

  Examples of the chromium compound include chromium nitrate, chromium formate, and chromium sulfate.

  Examples of the silver compound include silver nitrate, silver nitrite, silver carbonate, and silver acetate.

  Examples of the titanium compound include titanium tetrachloride, titanium trichloride, titanium ammonium oxalate, titanium isopropoxide, and the like.

  Examples of the zirconium compound include zirconium oxynitrate, zirconium sulfate, zirconium carbonate, zirconium acetylacetonate and the like.

  Examples of the niobium compound include niobium oxalate and niobium ethoxide.

  Examples of the tantalum compound include tantalum ethoxide and tantalum chloride.

[Method for producing 1,3-butadiene]
The method for producing 1,3-butadiene according to the present invention is a method for producing 1,3-butadiene that obtains 1,3-butadiene from ethanol, and the raw material is heated under the above catalyst (groups 4 to 13 of the periodic table). A metal oxide (component A), magnesium oxide (component B), and a binder component (component C) containing an inorganic oxide other than the above are contacted.

  The method for producing 1,3-butadiene of the present invention can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system. When the batch system or the semi-batch system is employed, the usage rate of the raw material can be made extremely high. In addition, since the method for producing 1,3-butadiene according to the present invention uses the above catalyst, even if a continuous method is employed, ethanol as a raw material can be converted more efficiently than in the past, and unreacted raw material can be further converted. By reusing them in the reaction system, the usage rate of the raw material ethanol can be improved to a very 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. Further, the present invention may be either a gas phase method or a liquid phase method. In the present invention, in particular, the catalyst can be filled into the reaction tube to form a catalyst layer in that mass synthesis is possible, operation workload is light, and catalyst recovery and regeneration are simple. It is preferable to use a fixed bed gas phase continuous flow reaction apparatus that is made to flow as a gas and react in the gas phase.

  When the reaction is performed 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, carbon dioxide gas, etc. It may be appropriately diluted with an inert gas and supplied to the reactor.

  In the method for producing 1,3-butadiene according to the present invention, the selective hydrogenation reaction of crotonaldehyde to crotyl alcohol in the step (d) may be performed by bringing the raw material into contact with a catalyst in the presence of hydrogen. Is promoted and the condensation and decomposition of crotonaldehyde are suppressed, which is preferable in that the selectivity of 1,3-butadiene can be improved.

  The molar ratio of the raw material to be brought into contact with the catalyst and hydrogen [the former / the latter] is, for example, about 10/90 to 95/5, preferably 20/80 to 90/10, particularly preferably 30/70 to 70/30. .

  When the molar ratio of the raw material to be contacted with the catalyst and hydrogen [the former / the latter] is below the above range, the condensation and decomposition of crotonaldehyde is promoted, and when the above range is exceeded, the dehydrogenation reaction from ethanol to acetaldehyde is suppressed Since the dehydration reaction from ethanol to ethylene is promoted, the selectivity of 1,3-butadiene tends to decrease.

  As reaction temperature, it is about 300-500 degreeC, for example, Preferably it is 350-450 degreeC. If the reaction temperature is below the above range, sufficient catalytic activity may not be obtained, the reaction rate may decrease, and the production efficiency may decrease. On the other hand, if the reaction temperature exceeds the above range, the catalyst may be deteriorated.

  The reaction pressure can be appropriately set within a wide range from normal pressure to high pressure. From the viewpoint of production efficiency, device configuration, etc., it is preferable to set it to 1 MPa or less.

When the continuous method is adopted, the contact time between the raw material and the catalyst (when the catalyst is contacted in multiple stages, the sum of the contact times) is, for example, about 0.1 to 30 seconds, preferably 1 to 10 seconds. If the contact time is too short, ethanol does not convert to butadiene, and unreacted ethanol and acetaldehyde, crotonaldehyde, and the like as intermediates tend to increase at the reactor outlet. On the other hand, if the contact time with the catalyst becomes too long, condensation or polymerization of acetaldehyde, butadiene or the like proceeds and a large amount of high-boiling components tend to be generated. The contact time between the raw material and the catalyst can be controlled by adjusting the feed rate of the raw material. For example, the ethanol gas space velocity is 100 to 50000 hr ⁻¹ (preferably 200 to 10000 hr ⁻¹ , particularly preferably 300 to It is preferable to adjust within the range of 5000 hr ⁻¹ ).

  After completion of the reaction, the reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, and extraction, or a separation means that combines these.

  The catalyst of the present invention comprises a binder component (component C) containing an oxide of a metal of group 4 to 13 of the periodic table (component A), magnesium oxide (component B) as a catalytic active component, and an inorganic oxide other than the above. (In particular, since the component A and the component B have a structure in which the component B is joined by the component C), the catalytically active component is not easily eluted in the reaction solution even in the organic synthesis reaction, and the reaction solution is filtered, centrifuged, etc. It can be easily recovered by the physical separation method. Unreacted raw materials may be recovered and reused.

  In addition, the catalyst of the present invention allows air to flow in the reactor under heating at, for example, about 350 to 500 ° C., preferably 450 to 500 ° C., for example, for 1 to 24 hours, preferably 3 to 6 hours. By performing the treatment, the catalyst activity is recovered to 90% or more with respect to the unused catalyst, and can be reused.

  In the method for producing 1,3-butadiene according to the present invention, since the raw material containing ethanol is brought into contact with the catalyst under heating, 1,3-butadiene is excellent in ethanol conversion and excellent in selectivity. Can be manufactured.

  In particular, when ethanol is brought into contact with the catalyst (A) and the catalyst (B) in this order under heating, the catalyst (A) accelerates the acetaldehyde generation process, which is the rate-limiting step of the reaction, and further the catalyst (B). This promotes the reaction of obtaining crotyl alcohol from ethanol and crotonaldehyde, so that 1,3-butadiene can be produced with excellent ethanol conversion and excellent selectivity.

The method for producing 1,3-butadiene according to the present invention can selectively produce 1,3-butadiene, for example, after the start of the reaction when the reaction is carried out under conditions of a reaction temperature of 400 ° C. and a space velocity of 360 hr ^−1. The selectivity for 1,3-butadiene after 75 minutes is, for example, 45% or more, preferably 55% or more, particularly preferably 60% or more. In addition, the method for producing 1,3-butadiene of the present invention is excellent in the conversion rate of ethanol. For example, the conversion of ethanol 75 minutes after the start of the reaction at a reaction temperature of 400 ° C. and a space velocity of 360 hr ^−1. The rate is, for example, 25% or more, preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.

  Since the 1,3-butadiene production method of the present invention has a very high selectivity for 1,3-butadiene as described above, the ethanol usage rate is improved by reusing unreacted ethanol in the reaction system. 1,3-butadiene can be produced industrially efficiently.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Preparation Example 1
Magnesium hydroxide (manufactured by Kanto Chemical Co., Inc.) 24.1 g, colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, Ltd., specific surface area: 800 ± 200 m ^{2 /} g), 14.4 g, tantalum ethoxy 0.74 g of the slurry was suspended in water and kneaded in an auto mill for 4 hours to obtain a sol. The obtained sol was dried at 80 ° C. for 16 hours and then at 110 ° C. for 4 hours, then heated to 500 ° C. at 1 ° C./min and calcined at 500 ° C. for 2 hours to obtain a cake. The obtained cake was crushed and classified with 10-20 mesh to obtain catalyst (1) (Ta ₂ O ₅ / MgO / SiO ₂ (weight ratio) = 2/83/15).

Preparation Example 2
The catalyst (2) (Cr ₂ O ₃ / MgO / SiO ₂ (Cr) was prepared in the same manner as in Preparation Example 1 except that 1.92 g of chromium (III) nitrate nonahydrate was used instead of 0.74 g of tantalum ethoxide. Weight ratio) = 2/83/15).

Preparation Example 3
Catalyst (3) (ZrO ₂ / MgO / SiO ₂ (weight) was prepared in the same manner as in Preparation Example 1 except that 1.79 g of zirconium oxynitrate (IV) dihydrate was used instead of 0.74 g of tantalum ethoxide. Ratio) = 4/82/14).

Preparation Example 4
Catalyst (4) (CuO / MgO / SiO ₂ (weight ratio)) was prepared in the same manner as in Preparation Example 1 except that 2.49 g of copper (II) nitrate trihydrate was used instead of 0.74 g of tantalum ethoxide. = 4/82/14).

Preparation Example 5
Catalyst (5) (Nb ₂ O ₅ / MgO / SiO ₂ (weight ratio)) was prepared in the same manner as in Preparation Example 1 except that 1.62 g of niobium pentaoxalate (V) was used instead of 0.74 g of tantalum ethoxide. = 2/83/15).

Preparation Example 6
Catalyst (6) (TiO ₂ / MgO / SiO ₂ (weight ratio) = the same as in Preparation Example 1 except that 1.47 g of titanium (IV) ammonium oxalate was used instead of 0.74 g of tantalum ethoxide. 2/83/15) was obtained.

Preparation Example 7
Catalyst (7) (Ag ₂ O / MgO / SiO ₂ (weight ratio) = 1 / (similar to Preparation Example 1) except that 0.30 g of silver nitrate (I) was used instead of 0.74 g of tantalum ethoxide. 84/15).

Preparation Example 8
Catalyst (8) (ZnO / MgO / SiO ₂ (weight ratio)) was prepared in the same manner as in Preparation Example 1 except that 2.99 g of zinc nitrate (II) hexahydrate was used instead of 0.74 g of tantalum ethoxide. = 4/82/14).

Preparation Example 9
Catalyst (9) (Nb ₂ O ₅ / MgO / SiO ₂ (weight ratio) = 1/84/15 in the same manner as in Preparation Example 5, except that the amount of niobium pentaoxalate (V) used was changed to 0.81 g. )

Preparation Example 10
A catalyst (10) (MgO / SiO ₂ (weight ratio) = 85/15) was obtained in the same manner as in Preparation Example 1, except that tantalum ethoxide was not used.

Preparation Example 11
A powder obtained by immersing Sepiolite 19.67 g in an aqueous solution in which 1.72 g of manganese nitrate hexahydrate is dissolved, evaporating to dryness on a hot water bath at 80 ° C., and baking at 500 ° C. for 4 hours. Then, tableting, crushing, and classification with 10-20 mesh gave catalyst (11) (Mn / sepiolite) (Mn: 0.3 mmol / g-cat).

Preparation Example 12
The powder obtained by dipping 17.96 g of sepiolite in an aqueous solution in which 5.42 g of sodium vanadate is dissolved, evaporating to dryness on a hot water bath at 80 ° C., and baking for 4 hours at 500 ° C. Molding, crushing and classification with 10-20 mesh gave catalyst (12) (V / sepiolite) (V: 2 mmol / g-cat).

Preparation Example 13
17.35 g of magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd.), colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, Ltd., specific surface area: 800 ± 200 m ^{2 /} g), 39.25 g of water And kneaded in an auto mill for 4 hours to obtain a sol. The obtained sol was dried at 80 ° C. for 16 hours and then at 110 ° C. for 4 hours, then heated to 500 ° C. at 1 ° C./min and calcined at 500 ° C. for 2 hours to obtain a cake. The obtained cake was crushed and classified with 10-20 mesh to obtain catalyst (13) (MgO / SiO ₂ (weight ratio) = 60/40).

Preparation Example 14
Magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd.) 7.23 g, colloidal silica (trade name “Snowtex XS”, Nissan Chemical Industries, Ltd., specific surface area: 800 ± 200 m ^{2 /} g) 24.51 g, hydroxylated 0.028 g of sodium was suspended in water and kneaded in an auto mill for 4 hours to obtain a sol. The obtained sol was dried at 80 ° C. for 16 hours and then at 110 ° C. for 4 hours, then heated to 500 ° C. at 1 ° C./min and calcined at 500 ° C. for 2 hours to obtain a cake. The obtained cake was crushed and classified with 10-20 mesh to obtain catalyst (14) (Na ₂ O / MgO / SiO ₂ , Na: 0.1 wt%, Mg / Si (molar ratio) = 1/1). Got.

Preparation Example 15
Magnesium hydroxide (manufactured by Kanto Chemical Co., Inc.) 23.6 g, colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, Ltd., specific surface area: 800 ± 200 m ^{2 /} g), 14.1 g, zinc nitrate (II) 1.46 g of hexahydrate and 0.88 g of zirconium oxynitrate (IV) dihydrate were suspended in water and kneaded in an auto mill for 4 hours to obtain a sol. The obtained sol was dried at 80 ° C. for 16 hours and then at 120 ° C. for 4 hours, then heated to 500 ° C. at 1 ° C./min, and baked at 500 ° C. for 2 hours to obtain a cake. The obtained cake was crushed and classified into 10-20 mesh to obtain catalyst (15) (ZnO / ZrO ₂ / MgO / SiO ₂ (weight ratio) = 2/2/82/14).

Preparation Example 16
Magnesium hydroxide (manufactured by Kanto Chemical Co., Inc.) 17.0 g, colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, Ltd., specific surface area: 800 ± 200 m ^{2 /} g) 25.7 g, chromium nitrate 1.92 g of nonahydrate was suspended in water and kneaded in an auto mill for 4 hours to obtain a sol. The obtained sol was dried at 80 ° C. for 16 hours and then at 110 ° C. for 4 hours, then heated to 500 ° C. at 1 ° C./min and calcined at 500 ° C. for 2 hours to obtain a cake. The obtained cake was crushed and classified with 10-20 mesh to obtain catalyst (16) (Cr ₂ O ₃ / MgO / SiO ₂ (weight ratio) = 2/59/39).

Preparation Example 17
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), fumed silica (trade name “Aerosil 380PE”, manufactured by Nippon Aerosil Co., Ltd.) The catalyst (17) (Ta ₂ O ₅ / MgO / SiO ₂ (weight ratio) = 2/83/15) was obtained in the same manner as in Preparation Example 1 except that the specific surface area was 320 m ² / g. .

Preparation Example 18
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), Y-type zeolite (trade name “LZY-210”, JGC Universal Co., Ltd.) The catalyst (18) (Ta) was prepared in the same manner as in Preparation Example 1 except that SiO ₂ / AI ₂ O ₃ weight ratio: 12, specific surface area: 800 to 900 m ² / g, pore diameter: 8 to 10 mm was used. ₂ O ₅ / MgO / Y-type zeolite (weight ratio) = 2/83/15) was obtained.

Preparation Example 19
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), ZSM-5 type zeolite (trade name “MFI-40”, JGC Universal ( The catalyst (19) (Ta ₂ O) was prepared in the same manner as in Preparation Example 1, except that SiO ₂ / AI ₂ O ₃ weight ratio: 40, specific surface area: 400 m ² / g, pore size: 6 mm) was used. ₅ / MgO / ZSM-5 zeolite (weight ratio) = 2/83/15).

Preparation Example 20
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), ZSM-5 type zeolite (trade name “MFI-300”, JGC Universal ( The catalyst (20) (Ta ₂ O) was prepared in the same manner as in Preparation Example 1 except that SiO ₂ / AI ₂ O ₃ weight ratio: 300, specific surface area: 400 m ² / g, pore size: 6 mm) was used. ₅ / MgO / ZSM-5 zeolite (weight ratio) = 2/83/15).

Preparation Example 21
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), β-type zeolite (trade name “Beta”, manufactured by JGC Universal Co., Ltd., Catalyst (21) (Ta ₂ O ₅ / Ta) was prepared in the same manner as in Preparation Example 1 except that SiO ₂ / AI ₂ O ₃ weight ratio: 25, specific surface area: 650 m ² / g, and pore diameter: 6 to 8 mm were used. MgO / β-type zeolite (weight ratio) = 2/83/15) was obtained.

Preparation Example 22
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), β-type zeolite (trade name “H-BEA-150”, Clariant Catalyst ( Co., Ltd., SiO ₂ / AI ₂ O ₃ weight ratio: 184.6, specific surface area: 620 m ² / g, pore diameter: 6 to 8 mm), catalyst (22) (Ta ₂ O ₅ / MgO / β-type zeolite (weight ratio) = 2/83/15) was obtained.

Preparation Example 23
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), mordenite-type zeolite (trade name “LZM-8”, JGC Universal Co., Ltd.) The catalyst (23) (Ta ₂ O ₅ / Ta) was prepared in the same manner as in Preparation Example 1 except that the product, SiO ₂ / AI ₂ O ₃ weight ratio: 18, specific surface area: 480 m ² / g, pore diameter: 7 mm, was used. MgO / mordenite zeolite (weight ratio) = 2/83/15) was obtained.

Preparation Example 24
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), silicoaluminophosphate (trade name “SAPO-11”, JGC Universal ( Ltd.), SiO ₂ / AI ₂ O ₃ weight ratio: 0.154, specific surface area: 240 m ² / g, pore diameter: 6 Å) except for using in the same manner as in preparation example 1, the catalyst (24) (Ta ₂ O ₅ / MgO / silicoaluminophosphate (weight ratio) = 2/83/15) was obtained.

Preparation Example 25
Instead of colloidal silica (trade name “Snowtex XS”, manufactured by Nissan Chemical Industries, specific surface area: 800 ± 200 m ² / g), silicoaluminophosphate (trade name “SAPO-34”, JGC Universal ( The catalyst (25) (Ta) was prepared in the same manner as in Preparation Example 1 except that SiO ₂ / AI ₂ O ₃ weight ratio: 0.070, specific surface area: 750 m ² / g, pore size: 4 mm) was used. ₂ O ₅ / MgO / silicoaluminophosphate (weight ratio) = 2/83/15) was obtained.

Preparation Example 26
Magnesium phyllosilicate (trade name “Mizuka Life P-1”, manufactured by Mizusawa Chemical Industry Co., Ltd., MgO / SiO ₂ (weight ratio) = 35/65, specific surface area: 400 m ² / g), 9.8 g, zinc nitrate ( II) 0.62 g of hexahydrate was suspended in water and kneaded in an auto mill for 4 hours to obtain a sol. The obtained sol was dried at 80 ° C. for 16 hours and then at 110 ° C. for 4 hours, then heated to 500 ° C. at 1 ° C./min and calcined at 500 ° C. for 2 hours to obtain a cake. The obtained cake was crushed and classified with 10-20 mesh to obtain catalyst (26) (ZnO / MgO / SiO ₂ (weight ratio) = 2/34/64).

Preparation Example 27
The catalyst (27) was prepared in the same manner as in Preparation Example 26 except that 0.62 g of zinc (II) nitrate hexahydrate and 0.02 g of sodium nitrate were used instead of 0.62 g of zinc (II) nitrate hexahydrate. ) (Na ₂ O / ZnO / MgO / SiO ₂ (weight ratio) = 0.07 / 2/34/64).

Preparation Example 28
A catalyst (28) was prepared in the same manner as in Preparation Example 26 except that 0.62 g of zinc nitrate (II) hexahydrate and 0.02 g of potassium carbonate were used instead of 0.62 g of zinc nitrate (II) hexahydrate. ) (K ₂ O / ZnO / MgO / SiO ₂ (weight ratio) = 0.1 / 2/34/64).

Preparation Example 29
A catalyst (29) was prepared in the same manner as in Preparation Example 26 except that 0.62 g of zinc (II) nitrate hexahydrate and 1 g of silver nitrate (I) were used instead of 0.62 g of zinc nitrate (II) hexahydrate. ) (Ag ₂ O / ZnO / MgO / SiO ₂ (weight ratio) = 1/2/34/63).

Preparation Example 30
Preparation Example 26 except that 0.62 g of zinc (II) nitrate hexahydrate, 0.02 g of potassium carbonate and 0.38 g of tantalum ethoxide were used instead of 0.62 g of zinc (II) nitrate hexahydrate. Similarly, catalyst (30) (K ₂ O / Ta ₂ O ₅ / ZnO / MgO / SiO ₂ (weight ratio) = 0.1 / 2/2/34/62) was obtained.

Preparation Example 31
Preparation Example 26 except that 0.62 g of zinc (II) nitrate hexahydrate, 0.08 g of potassium carbonate, and 0.38 g of tantalum ethoxide were used instead of 0.62 g of zinc (II) nitrate hexahydrate. Similarly, catalyst (31) (K ₂ O / Ta ₂ O ₅ / ZnO / MgO / SiO ₂ (weight ratio) = 0.5 / 2/2/33/62) was obtained.

Preparation Example 32
In the same manner as in Preparation Example 26 except that 0.66 g of zinc (II) nitrate hexahydrate and 0.38 g of tantalum ethoxide were used instead of 0.62 g of zinc (II) nitrate hexahydrate, the catalyst ( 32) (Ta ₂ O ₅ / ZnO / MgO / SiO ₂ (weight ratio) = 2/2/34/62) was obtained.

Preparation Example 33
Preparation example except that zinc nitrate (II) hexahydrate 0.62 g was used instead of zinc nitrate (II) hexahydrate 0.62 g, silver nitrate (I) 0.02 g and tantalum ethoxide 0.38 g In the same manner as in No. 26, a catalyst (34) (Ag ₂ O / Ta ₂ O ₅ / ZnO / MgO / SiO ₂ (weight ratio) = 0.1 / 2/2/34/62) was obtained.

Preparation Example 34
A catalyst (34) was prepared in the same manner as in Preparation Example 26 except that 0.62 g of zinc (II) nitrate hexahydrate and 0.03 g of sodium nitrate were used instead of 0.62 g of zinc (II) nitrate hexahydrate. ) (Na ₂ O / ZnO / MgO / SiO ₂ (weight ratio) = 0.1 / 2/34/64).

Examples 1-11, Comparative Examples 1-5
The catalysts described in Tables 1 and 2 were filled into a 10 mmφ SUS reaction tube connected to a fixed bed type gas-phase continuous flow reactor (reactor), and 500 μm by an electric furnace under N ₂ flow of 100 mL / min. Heated to ° C.
After the pretreatment for 1 hour, the electric furnace temperature was maintained at the temperature described in the table, and about 90% ethanol / N ₂ gas was allowed to flow through the reactor at a rate of GHSV = 360 hr ⁻¹ for reaction. (Raw material catalyst contact time: 10 seconds). The reactor outlet gas was gas-liquid separated and then cooled by a cooler to recover the condensate.
The composition of the gas at the outlet of the reactor 60 to 75 minutes after the start of the reaction was analyzed with a gas chromatograph and a Karl Fischer moisture meter.
As the catalysts, Examples 1 to 8 are Preparation Examples 1 to 8, Example 9 is Preparation Example 2, Example 10 is Preparation Example 1, Example 11 is Preparation Example 9, and Comparative Examples 1 to 5 are Comparative Examples 1 to 5, respectively. The catalyst obtained in Preparation Examples 10-14 was used.

＊ＥｔＯＨ：エタノール

* EtOH: Ethanol

＊ＥｔＯＨ：エタノール

* EtOH: Ethanol

Example 12
1.5 mL of the catalyst (8) obtained in Preparation Example 8 (ZnO / MgO / SiO ₂ (weight ratio) = 4/82/14) and the catalyst (3) obtained in Preparation Example 3 (ZrO ₂ / MgO / SiO ₂ (weight ratio) = 4/82/14) 1.5 mL is connected to a 10 mmφ SUS reaction tube connected to a fixed-bed gas-phase continuous flow reactor (reactor). The mixture was charged in the order of 3) and heated to 500 ° C. with an electric furnace under N ₂ flow of 100 mL / min (catalyst (8): catalyst (3) (volume ratio) = 1: 1).
After the pretreatment for 1 hour, the electric furnace temperature was maintained at 400 ° C., and about 90% ethanol / N ₂ gas was passed through the reactor at a rate of GHSV = 360 hr ⁻¹ (feed catalyst contact time: 10 Seconds). The reactor outlet gas was gas-liquid separated and then cooled by a cooler to recover the condensate.
The composition of the gas at the outlet of the reactor 60 to 75 minutes after the start of the reaction was analyzed with a gas chromatograph and a Karl Fischer moisture meter.

Example 13
1.5 mL of the catalyst (8) obtained in Preparation Example 8 (ZnO / MgO / SiO ₂ (weight ratio) = 4/82/14) and the catalyst (3) obtained in Preparation Example 3 (ZrO ₂ / MgO / SiO ₂ (weight ratio) = 4/82/14) Example 12 except that 1.5 mL was thoroughly mixed and charged into a 10 mmφ SUS reaction tube connected to a fixed bed type gas phase continuous flow reactor. The same was done.

Example 14
The same procedure as in Example 12 was performed except that 3.0 mL of the catalyst (15) obtained in Preparation Example 15 was charged into a 10 mmφ SUS reaction tube connected to a fixed bed gas phase continuous flow reactor.

＊ＥｔＯＨ：エタノールThe above results are summarized in the following table.

* EtOH: Ethanol

Examples 15 and 16
Catalyst (8) obtained in Preparation Example 8 (ZnO / MgO / SiO ₂ (weight ratio) = 4/82/14), and Catalyst (3) obtained in Preparation Example 3 (ZrO ₂ / MgO / SiO ₂₎ The same procedure as in Example 12 was conducted except that the amount (weight ratio) = 4/82/14) was changed to the amount shown in Table 4.

After the pretreatment for 1 hour, the electric furnace temperature was maintained at 400 ° C., and about 90% ethanol / N ₂ gas was passed through the reactor at a rate of GHSV = 360 hr ⁻¹ , and 5 to 20 minutes after the start of the reaction. The gas composition at the outlet of the reactor was analyzed with a gas chromatograph and a Karl Fischer moisture meter. The results are summarized in Table 4 below.

＊ＥｔＯＨ：エタノール

* EtOH: Ethanol

In addition, after the pretreatment for 1 hour, the electric furnace temperature was maintained at 400 ° C., and about 90% ethanol / N ₂ gas was allowed to flow through the reactor at a rate of GHSV = 360 hr ⁻¹ , and 60 to 75 after the start of the reaction. The gas composition at the outlet of the reactor was analyzed with a gas chromatograph and a Karl Fischer moisture meter. The results are summarized in Table 5 below.

＊ＥｔＯＨ：エタノール

* EtOH: Ethanol

The catalyst (A) containing a metal oxide of Group 4-13 of the periodic table that promotes the process of producing acetaldehyde from ethanol, which is the rate-limiting step of the reaction, or the reaction that produces crotyl alcohol from ethanol and crotonaldehyde The catalyst (A) and the catalyst (B) are used in combination as compared with the case where the catalyst (B) containing an oxide of a metal of Group 4 to 13 of the periodic table is used alone, and ethanol is catalyzed. By contacting in the order of (A) -catalyst (B), the yield of 1,3-butadiene could be remarkably improved.
Moreover, when the volume ratio of the catalyst (A) and the catalyst (B) was adjusted to a specific range, 1,3-butadiene could be further selectively produced at a high yield.

Example 17
The catalyst (16) obtained in Preparation Example 16 (Cr ₂ O ₃ / MgO / SiO ₂ (weight ratio) = 2/59/39) was connected to a fixed bed gas phase continuous flow reactor (reactor). The reactor was filled in a 22.2 mmφ SUS reaction tube and heated in an electric furnace at 500 ° C. for 1 hour under N ₂ flow of 100 mL / min (pretreatment).
After performing the pretreatment, the temperature of the electric furnace was lowered to 400 ° C. and kept for 1 hour in a state where 26.7 mL / min of H ₂ was circulated. By starting to supply ethanol as a raw material at a rate of 130 mg / min, about 70% ethanol gas / 30% H ₂ gas was allowed to flow through the reactor at a rate of GHSV = 360 hr ⁻¹ and reacted (catalyst contact of raw material) Time: 10 seconds). The reactor outlet gas was gas-liquid separated and then cooled by a cooler to recover the condensate.
The gas composition at the outlet of the reactor 60 to 150 minutes after the start of the reaction was analyzed with a gas chromatograph and a Karl Fischer moisture meter.

Examples 18-26
Example 17 was repeated except that the catalyst and the charged composition were changed as shown in Table 6. Examples 18 and 19 are the catalyst (16) obtained in Preparation Example 16, Examples 20 to 24 are the catalyst (1) obtained in Preparation Example 1, and Examples 25 and 26 are obtained in Preparation Example 7. Catalyst (7) was used. The results are summarized in Table 6 below.

＊ＥｔＯＨ：エタノール

* EtOH: Ethanol

Examples 27-32
The reaction was conducted in the same manner as in Example 21 except that the reaction temperature and the catalyst contact time of the raw materials were changed as shown in Table 7. The results are summarized in Table 7 below.

Examples 33-36
Example 21 was repeated except that the feed composition and the catalyst contact time of the raw materials were changed as shown in Table 8. The results are summarized in Table 8 below.

＊ＥｔＯＨ：エタノール
ＡＤ：アセトアルデヒド

* EtOH: Ethanol AD: Acetaldehyde

Examples 37-42
The reaction was performed in the same manner as in Example 35 except that the reaction temperature and the catalyst contact time of the raw materials were changed as shown in Table 9. The results are summarized in Table 9 below.

Examples 43-51
Example 41 was repeated except that the catalyst was changed to the catalyst shown in Table 10. In Examples 43 to 51, the catalysts obtained in Preparation Examples 17 to 25 were used. The results are summarized in Table 10 below.

Examples 52, 53
Except having changed the preparation composition as described in Table 11, it carried out similarly to Example 41,46. The results are summarized in Table 11 below.

Example 54
10 mmφ SUS in which the catalyst (26) obtained in Preparation Example 26 (ZnO / MgO / SiO ₂ (weight ratio) = 2/34/64) was connected to a fixed-bed gas-phase continuous flow reactor (reactor). The reaction tube was filled and heated to 500 ° C. with an electric furnace under N ₂ flow of 100 mL / min.
After the pretreatment for 1 hour, the electric furnace temperature was maintained at the temperature indicated in the table, and 85% ethanol / 15% H ₂ gas was allowed to flow through the reactor at a rate of GHSV = 360 hr ⁻¹ for reaction. (Raw material catalyst contact time: 10 seconds).

Comparative Example 6
Instead of the catalyst (26) (ZnO / MgO / SiO ₂ (weight ratio) = 2/34/64) obtained in Preparation Example 26, magnesium phyllosilicate (trade name “Mizuka Life P-1”, Mizusawa Chemical Industries, Ltd.) Co., Ltd., specific surface area: 400m ² / g) the Philo magnesium silicate, which was granular (trade name "hydration life F-2GH", Mizusawa chemical industry Co., Ltd., MgO / SiO ₂ (weight ratio) = 35 / 65, specific surface area: 500 m ² / g).

The results are summarized in Table 12 below.

Examples 55-60
Example 54 was repeated except that the reaction temperature, the catalyst contact time of the raw materials, and the feed composition were changed as shown in Table 13. The results are summarized in Table 13 below.

＊ＥｔＯＨ：エタノール
ＡＤ：アセトアルデヒド

* EtOH: Ethanol AD: Acetaldehyde

Examples 61-70
The same procedure as in Example 59 was conducted, except that the catalyst and the charged composition were changed to those shown in Table 14. In Example 61, the catalyst obtained in Preparation Example 27 was used. In Examples 62 and 69, the catalyst obtained in Preparation Example 28 was used. In Example 63, the catalyst obtained in Preparation Example 29 was used. In Example 64, the catalyst obtained in Preparation Example 30 was used. In Examples 65 and 70, the catalyst obtained in Preparation Example 31 was used. In Example 66, the catalyst obtained in Preparation Example 32 was used. In Example 67, the catalyst obtained in Preparation Example 33 was used. In Example 68, the catalyst obtained in Preparation Example 34 was used. The results are summarized in Table 14 below.

＊ＥｔＯＨ：エタノール

* EtOH: Ethanol

Claims (8)

A method for producing 1,3-butadiene, wherein 1,3-butadiene is obtained from ethanol, wherein the following raw materials are brought into contact with the following catalyst under heating.
Raw material: containing ethanol Catalyst: Tantalum, chromium, copper, zinc, zirconium, niobium, titanium, silver and gallium oxide (component A), magnesium oxide (component B) and other than the above Containing a binder component (component C) containing an inorganic oxide of   The method for producing 1,3-butadiene according to claim 1, wherein the inorganic oxide in component C is silicon dioxide.   The method for producing 1,3-butadiene according to claim 1 or 2, wherein the raw material is brought into contact with the catalyst in the presence of hydrogen.   The method for producing 1,3-butadiene according to claim 1 or 3, wherein Component C is zeolite. The method for producing 1,3-butadiene according to claim 4, wherein the zeolite is a zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 12 or more and a pore diameter of 10 Å or less.   The method for producing 1,3-butadiene according to claim 1 or 3, wherein magnesium silicate is used as component B and component C.   The method for producing 1,3-butadiene according to claim 6, wherein the magnesium silicate is magnesium phyllosilicate. The method for producing 1,3-butadiene according to any one of claims 1 to 7, wherein the raw material is brought into contact with the following catalyst (A) and catalyst (B) in this order.
Catalyst (A): at least one metal oxide selected from tantalum, chromium, copper, zinc, zirconium, niobium, titanium, silver and gallium (component A), magnesium oxide (component B) and other inorganics A catalyst containing an oxide-containing binder component (component C), the selectivity of acetaldehyde obtained when ethanol is brought into contact with the catalyst (temperature: 400 ° C., space velocity: 360 hr ⁻¹ ) is 10% or more Catalyst (B): an oxide (component A) and magnesium oxide (component B) of at least one metal selected from tantalum, chromium, copper, zinc, zirconium, niobium, titanium, silver and gallium A catalyst containing a binder component (component C) containing an inorganic oxide other than the above, and contacting ethanol with the catalyst (temperature: 400 ° C., space velocity: 60 hr ^-1) selectivity for acetaldehyde obtained when allowed to is less than 10%, and the catalyst of 1,3-butadiene selectivity of 45% or more