JP2015034151A - BUTADIENE SYNTHESIS METHOD FROM ETHANOL BY METAL-ADDED SiO2-MgO CATALYST PREPARED BY HYDROTHERMAL SYNTHESIS METHOD - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 1,3-butadiene obtaining 1,3-butadiene from ethanol by a simple and industrially advantageous method.SOLUTION: The method for producing 1,3-butadiene is characterized in that, while being heated, a raw material at least containing ethanol is contacted with a catalyst having a magnesium silicate structure obtained by a hydrothermal synthesis method to obtain 1,3-butadiene. As the elemental ratio between the magnesium and silicon composing the catalyst (molar ratio: the former/the latter), 0.7 to 2.0 is preferable. As the element composing the catalyst, in addition to the magnesium and the silicon, the incorporation of at least one kind selected from vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium and cerium is preferable.

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 characterized in that 1,3-butadiene is obtained by contacting a raw material containing at least ethanol under heating with a catalyst having a magnesium silicate structure obtained by a hydrothermal synthesis method. A method for producing 3-butadiene is provided.

  The present invention also provides the method for producing 1,3-butadiene as described above, wherein the element ratio (molar ratio: former / latter) of magnesium and silicon constituting the catalyst is 0.7 to 2.0.

  In addition to magnesium and silicon, the present invention also includes at least one element selected from vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, and cerium in addition to magnesium and silicon. A process for producing the aforementioned 1,3-butadiene containing

  In the present invention, the content (metal element equivalent amount) of at least one element selected from vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, and cerium is also a catalyst. The method for producing 1,3-butadiene is provided in an amount of 0.1 to 5.0% by weight based on the total amount.

  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.

It is a figure which shows the X-ray-diffraction result of catalyst (1)-(5) obtained by the preparation examples 1-5.

  In the method for producing 1,3-butadiene according to the present invention, 1,3-butadiene is obtained by bringing a raw material containing at least ethanol into contact with a catalyst having a magnesium silicate structure obtained by a hydrothermal synthesis method under heating. It is characterized by obtaining.

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

[catalyst]
The catalyst of the present invention is characterized by having a magnesium silicate structure. The magnesium silicate structure is a shape in which a brucite (Mg (OH) ₂ ) layer is sandwiched between silica (SiO ₂ ) layers, and each electrically neutral layer is formed by stacking several layers with weak van der Waals force Talc-like structure. Since the catalyst of the present invention has the above structure, magnesium, which is the active site of the positive reaction, is efficiently arranged on the contact surface with the reaction substrate, and there are almost no strong acid points and base points that promote side reactions. Thus, 1,3-butadiene can be selectively produced from ethanol. The magnesium silicate structure of the catalyst can be confirmed by X-ray diffraction.

  The element ratio (molar ratio: former / latter) of magnesium and silicon constituting the catalyst of the present invention is, for example, 0.7 to 2.0, preferably 0.8 to 1.5, and particularly preferably 0.9 to 1.2. If the Mg / Si element ratio exceeds the above range, the specific surface area of the catalyst tends to decrease and the ethanol conversion tends to decrease. On the other hand, when the Mg / Si element ratio is below the above range, the amount of acid sites on the catalyst increases, and the dehydration reaction (side reaction) from ethanol to ethylene tends to be promoted.

  Moreover, as an element which comprises the catalyst of this invention, you may contain 1 type, or 2 or more types of other elements besides magnesium and silicon. The catalyst of the present invention contains, as the other element, at least one selected from vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, and cerium. It is preferable in that 1,3-butadiene can be produced with a further excellent yield by improving the conversion rate of ethanol, particularly selected from cobalt, nickel, copper, zinc, gallium, silver, and indium. It is preferable to contain at least one kind in that 1,3-butadiene can be produced in a particularly excellent yield by improving the selectivity of 1,3-butadiene together with the conversion of ethanol.

  The content of other elements (amount in terms of metal element) is, for example, 0.1 to 5.0% by weight, preferably 0.5 to 5.0% by weight, particularly preferably in the total amount of catalyst (100% by weight). 1.0 to 5.0% by weight. When the content of other elements exceeds the above range, only a specific stage of the above-described reaction process is promoted too much, or side reaction is promoted, and the selectivity for 1,3-butadiene tends to decrease. is there.

  As the particle size of the catalyst of the present invention, for example, the particle size is 20 mesh (aperture: 0.85 mm) or more and 10 mesh (aperture: 2.0 mm) or less (that is, it passes through a 10 mesh sieve, 20 Size of particles remaining on the mesh screen).

  The catalyst of the present invention is synthesized by subjecting a magnesium compound and a silicon compound to hydrothermal synthesis. More specifically, it is synthesized by heating an acidic aqueous solution containing magnesium and silicon in a pressure vessel in the presence of a uniform precipitant.

  Examples of the magnesium compound include magnesium hydroxide, magnesium nitrate, and magnesium oxalate. These can be used alone or in combination of two or more.

  Examples of the silicon compound include silicic acid (for example, colloidal silica, fumed silica, etc.), tetraethyl orthosilicate, and the like. These can be used alone or in combination of two or more.

A catalyst containing the above-mentioned other elements in addition to magnesium and silicon as constituent elements can be produced by subjecting a compound containing other elements together with a magnesium compound and a silicon compound to hydrothermal synthesis.
For example, a catalyst containing cobalt as another element is a compound containing cobalt (eg, cobalt nitrate (II) hexahydrate, cobalt acetate (II) tetrahydrate, cobalt sulfate) together with a magnesium compound and a silicon compound. (II) heptahydrate etc.) can be produced by hydrothermal synthesis.
A catalyst containing nickel as another element is produced by subjecting a compound containing nickel (for example, nickel nitrate hexahydrate, nickel (II) sulfate, etc.) together with a magnesium compound and a silicon compound to hydrothermal synthesis. be able to.
The catalyst containing copper as another element is a hydrothermal treatment of a compound containing copper (for example, copper nitrate (II) trihydrate, copper sulfate (II) pentahydrate, etc.) together with a magnesium compound and a silicon compound. It can be manufactured by subjecting it to synthesis.
The catalyst containing zinc as another element is a hydrothermal synthesis of a compound containing zinc (eg, zinc nitrate hexahydrate, basic zinc carbonate, zinc sulfate heptahydrate, etc.) together with a magnesium compound and a silicon compound. It can manufacture by attaching | subjecting to.
A catalyst containing gallium as another element can be produced by hydrothermal synthesis of a compound containing gallium (eg, gallium nitrate hydrate, gallium hydroxide, etc.) together with a magnesium compound and a silicon compound. .
A catalyst containing silver as another element can be produced by subjecting a compound containing silver (for example, silver nitrate, silver sulfate, etc.) together with a magnesium compound and a silicon compound to hydrothermal synthesis.
A catalyst containing indium as another element can be produced by subjecting a compound containing indium (eg, indium nitrate) together with a magnesium compound and a silicon compound to hydrothermal synthesis.

  Examples of the uniform precipitant include urea and hexamine. These can be used alone or in combination of two or more.

  The amount of the uniform precipitant used is, for example, 1.2 mol or more, preferably 1.5 mol or more, per 1 mol of the magnesium compound. By using the uniform precipitant within the above range, the pH can be swung in a uniform state, and crystal nuclei can be generated uniformly.

  The hydrothermal synthesis of the magnesium compound and the silicon compound is preferably performed in the presence of an acidic aqueous solution (for example, nitric acid aqueous solution, sulfuric acid aqueous solution, etc.). About 1 to 3 times by weight, preferably 1 to 1.5 times by weight.

  The reaction temperature during the hydrothermal synthesis of the magnesium compound and silicon compound is, for example, 80 ° C. or higher, preferably 100 ° C. or higher. The pressure during the reaction is, for example, 0.3 MPa or more, preferably 0.5 MPa or more. The reaction time is, for example, 24 hours or longer, preferably 48 hours or longer.

  After completion of hydrothermal synthesis, for example, drying, firing (for example, heating at 120 to 200 ° C. for about 0.5 to 3.0 hours, and further heating at 450 to 600 ° C. for about 1 to 5 hours), pulverization, and the like are performed. Thus, the catalyst of the present invention can be produced.

[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, in particular, the use of biomass-derived ethanol is a greenhouse gas whose main cause of global warming is 1,3-butadiene, which is a raw material for synthetic rubber, which is important in many industrial fields. It is preferable at the point which can manufacture, suppressing the discharge amount.

  Moreover, it is preferable that the raw material of this invention contains acetaldehyde 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: latter) is, for example, about 9.9: 0.1 to 5: 5, preferably 9: 1 to 5: 5, particularly preferably 7: 3-5: 5. When the content of acetaldehyde exceeds the above range, unreacted aldehyde tends to be consumed by side reactions such as condensation and decomposition.

  The ratio of ethanol (in the case of containing acetaldehyde together with ethanol) in the raw material (100% by weight) of the present invention is, for example, 50% by weight or more, preferably 70 to 100% by weight, particularly preferably 85 to 100%. %.

[Method for producing 1,3-butadiene]
The method for producing 1,3-butadiene according to the present invention is a method for obtaining 1,3-butadiene from ethanol, wherein the raw material is brought into contact with the catalyst under heating.

  The degree of the heating is such that the temperature in the reaction system is, for example, 300 to 450 ° C., preferably 350 to 400 ° C. When the temperature in the reaction system is below the above range, sufficient catalytic activity cannot be obtained, the reaction rate tends to decrease, and the production efficiency tends to decrease. On the other hand, if the temperature in the reaction system exceeds the above range, the catalyst may be easily deteriorated.

  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.

  In the case of adopting the continuous type, the feed rate of the raw material to the catalyst (W / F [g · min / mL] = (catalyst weight) / (raw material feed rate)) is, for example, 0.001 to 0.1 g · min / mL, preferably 0.01 to 0.05 g · min / mL, particularly preferably 0.02 to 0.04 g · min / mL.

  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. Unreacted raw materials may be recovered and reused.

  The reaction pressure can be appropriately set within a wide range from reduced pressure to high pressure. From the viewpoint of production efficiency and apparatus configuration, it is preferable to set the pressure to 1 MPa (gauge pressure) or less.

  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.

  In the catalyst of the present invention, the catalytically active component is hardly eluted in the reaction solution, and even when the catalyst and the raw material are contacted by a suspension bed method or a fluidized bed method, physical reaction such as filtration or centrifugation from the reaction solution is performed. It can be easily recovered by a simple separation method.

  The catalyst of the present invention is circulated in a reactor, for example, at a temperature of 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 above, 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 the method for producing 1,3-butadiene of the present invention, 1,3-butadiene can be selectively produced, and the reaction is performed under the conditions of a reaction temperature of 350 ° C. and W / F = 0.03 g · min / mL. The selectivity for 1,3-butadiene 10 minutes after the start of the reaction is, for example, 20% or more, preferably 30% or more, particularly preferably 40% or more, and most preferably 45% or more. Further, the method for producing 1,3-butadiene of the present invention is excellent in the conversion rate of ethanol, and 10 minutes after the start of the reaction when the reaction is performed under the conditions of a reaction temperature of 350 ° C. and W / F = 0.03 g · min / mL. The subsequent ethanol conversion is, for example, 18% or more, preferably 25% 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 (Preparation of catalyst by hydrothermal synthesis method)
To 10 mL of 0.1 M nitric acid aqueous solution, 5.63 g (0.02 mol) of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.00 g of urea were added and stirred until dissolved.
To the obtained solution, 5 mL (0.02 mol) of tetraethyl orthosilicate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred until the solution became uniform.
The homogenized solution was transferred to a 100 mL pressure vessel and sealed, and then heated at 100 ° C. for 48 hours under self-pressure. The gel formed in the pressure vessel was recovered by filtration and dried at 60 ° C. for 2 days to obtain a white solid. This solid was pulverized and calcined at 170 ° C. for 1 hour and at 500 ° C. for 2 hours to obtain an oxide. The oxide was tableted and hardened, then crushed and classified with 10-20 mesh to obtain catalyst (1) (MgO—SiO ₂ : Mg / Si = 1).

Preparation Example 2 (Preparation of catalyst by coprecipitation method)
To 10 mL of 0.1 M nitric acid aqueous solution, 5.63 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred until dissolved.
To the resulting solution, 5 mL of tetraethyl orthosilicate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred until the solution became uniform.
To the homogenized solution, 5.7 mL of a 10% aqueous ammonia solution was added dropwise with stirring to form a gel. The obtained gel was collected by filtration and dried at 60 ° C. for 2 days to obtain a white solid.
This solid was pulverized and calcined at 170 ° C. for 1 hour and at 500 ° C. for 2 hours to obtain an oxide. This oxide was tableted and hardened, then crushed and classified with 10-20 mesh to obtain catalyst (2) (MgO—SiO ₂ : Mg / Si = 1).

Preparation Example 3 (Preparation of catalyst by impregnation method)
To 10 mL of 0.1 M nitric acid aqueous solution, 5.63 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred until dissolved.
1.32 g of fumed silica (trade name “Aerosil 380PE”, manufactured by Nippon Aerosil Co., Ltd.) was added to the obtained solution and evaporated to dryness while stirring on an 80 ° C. hot water bath to obtain a powder.
The obtained powder was calcined at 170 ° C. for 1 hour and at 500 ° C. for 2 hours to obtain an oxide. This oxide was tableted and hardened, then crushed and classified with 10-20 mesh to obtain catalyst (3) (MgO—SiO ₂ : Mg / Si = 1).

Preparation Example 4 (Preparation of catalyst by wet kneading method)
10 mL of 0.1 M nitric acid aqueous solution, pure water 20 mL, magnesium nitrate hexahydrate (made by Wako Pure Chemical Industries, Ltd.) 5.63 g, fumed silica (trade name “Aerosil 380PE”, manufactured by Nippon Aerosil Co., Ltd.) 1.32 g was added and kneaded with an auto mill for 4 hours.
The obtained sol was calcined at 170 ° C. for 1 hour and at 500 ° C. for 2 hours to obtain an oxide. This oxide was tableted and hardened, then crushed and classified with 10-20 mesh to obtain catalyst (4) (MgO—SiO ₂ : Mg / Si = 1).

Preparation Example 5 (Preparation of catalyst by physical mixing)
Magnesium oxide (manufactured by Nacalai Tesque Co., Ltd.) 0.89 g, fumed silica (trade name “Aerosil 380PE”, Nippon Aerosil Co., Ltd.) 1.32 g are mixed with an auto mill for 4 hours to obtain a mixed oxide powder. It was.
The obtained mixed oxide powder was tableted and hardened, then crushed and classified with 10-20 mesh to obtain catalyst (5) (MgO—SiO ₂ : Mg / Si = 1).

  X-ray diffraction was performed on the catalysts obtained in Preparation Examples 1 to 5. The results are shown in FIG. FIG. 1 shows that the magnesium silicate crystal phase is formed only on the catalyst (1) obtained by the hydrothermal synthesis method (the catalyst obtained in Preparation Example 1).

Preparation Example 6
A catalyst (6) (MgO—SiO ₂ : Mg / Si = 1.5) was obtained in the same manner as in Preparation Example 1, except that the amount of tetraethylorthosilicate used was changed to 3.3 mL (0.15 mol). .

Preparation Example 7
A catalyst (7) (MgO—SiO ₂ : Mg / Si = 2) was obtained in the same manner as in Preparation Example 1, except that the amount of tetraethylorthosilicate used was changed to 2.5 mL (0.01 mol).

Preparation Example 8
Catalyst (8) (V ₂ O ₅ —MgO—SiO ₂ ) was prepared in the same manner as in Preparation Example 1 except that 0.30 g of ammonium vanadate (manufactured by Wako Pure Chemical Industries, Ltd.) was used together with magnesium nitrate hexahydrate. : Mg / Si = 1, V: 5.0% by weight).

Preparation Example 9
Catalyst (9) (MnO-MgO) was prepared in the same manner as in Preparation Example 8, except that 0.51 g of manganese nitrate (II) pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. _{-SiO 2: Mg / Si = 1} , Mn: 5.0 wt%) was obtained.

Preparation Example 10
Catalyst (10) (Fe ₂ O) was prepared in the same manner as in Preparation Example 8 except that 0.91 g of iron (III) nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. ₃ -MgO—SiO ₂ : Mg / Si = 1, Fe: 5.0% by weight).

Preparation Example 11
Catalyst (11) (CoO-MgO) was prepared in the same manner as in Preparation Example 8, except that 0.30 g of cobalt nitrate (II) hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. _{-SiO 2: Mg / Si = 1} , Co: 2.5 wt%) was obtained.

Preparation Example 12
Catalyst (12) (NiO—MgO—SiO ₂ ) was prepared in the same manner as in Preparation Example 8, except that 0.57 g of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. : Hydrothermal, Mg / Si = 1, Ni: 5.0% by weight).

Preparation Example 13
Catalyst (13) (CuO-MgO) was prepared in the same manner as in Preparation Example 8 except that 0.44 g of copper (II) nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. _{-SiO 2: Mg / Si = 1} , Cu: 5.0 wt%) was obtained.

Preparation Example 14
Catalyst (14) (ZnO—MgO—SiO ₂ ) was prepared in the same manner as in Preparation Example 8, except that 0.21 g of zinc nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. : Mg / Si = 1, Zn: 2.5% by weight).

Preparation Example 15
Catalyst (15) (Ga ₂ O ₃ —MgO—) was prepared in the same manner as in Preparation Example 8 except that 0.71 g of gallium nitrate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. SiO ₂ : Mg / Si = 1, Ga: 5.0% by weight).

Preparation Example 16
Catalyst (16) (Nb ₂ O ₅ —MgO—SiO) was prepared in the same manner as in Preparation Example 8 except that 0.94 g of pentakis hydrogen niobium oxalate (manufactured by Mitsuwa Chemical Co., Ltd.) was used instead of ammonium vanadate. ₂ : Mg / Si = 1, Nb: 5.0% by weight).

Preparation Example 17
Catalyst (17) (Ag ₂ O—MgO—SiO ₂ : Mg /) was prepared in the same manner as in Preparation Example 8 except that 0.09 g of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. Si = 1, Ag: 2.5% by weight).

Preparation Example 18
Catalyst (18) (In ₂ O ₃ —MgO) was prepared in the same manner as in Preparation Example 8 except that 0.18 g of indium nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. _{-SiO 2: Mg / Si = 1} , In: 2.5 wt%) was obtained.

Preparation Example 19
Catalyst (19) (CeO ₂ —) was prepared in the same manner as in Preparation Example 8 except that 0.36 g of cerium (III) nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ammonium vanadate. MgO—SiO ₂ : Mg / Si = 1, Ce: 5.0% by weight).

Example 1 and Comparative Examples 1 to 4
The catalyst obtained in the preparation example was filled in a 6 mmφ SUS reaction tube connected to a fixed bed type gas-phase continuous flow reactor (reactor), and heated to 500 ° C. in an electric furnace under N ₂ flow of 100 mL / min. did.
After pretreatment for 1 hour, the electric furnace temperature was kept at 400 ° C., and 6.5% ethanol / N ₂ gas was passed through the reactor at a rate of W / F = 0.03 g · min · mL ^−1. Allowed to react. The reactor outlet gas was gas-liquid separated and then cooled by a cooler to recover the condensate.
The reactor outlet gas composition was analyzed for 10 minutes and 360 minutes after the start of the reaction using a gas chromatograph and a Karl Fischer moisture meter.
In Example 1, the catalyst obtained in Preparation Example 1, Comparative Example 1 in Preparation Example 2, Comparative Example 2 in Preparation Example 3, Comparative Example 3 in Preparation Example 4, and Comparative Example 4 in Catalyst 5 were used. The results are shown in Table 1 below.

Examples 2-4
The catalyst obtained in the preparation example was filled into a 6 mmφ SUS reaction tube connected to a fixed bed type gas-phase continuous flow reactor (reactor), and heated to 500 ° C. with an electric furnace under N ₂ flow of 100 mL / min. Heated.
After the pretreatment for 1 hour, the electric furnace temperature was maintained at 350 ° C., and 6.5% ethanol / N ₂ gas was passed through the reactor at a rate of W / F = 0.03 g · min · mL ^−1. And reacted. The reactor outlet gas was gas-liquid separated and then cooled by a cooler to recover the condensate.
In Example 2, the catalyst obtained in Preparation Example 1, Example 3 in Preparation Example 6 and Example 4 in Preparation Example 7 were used.
The gas composition at the outlet of the reactor 360 minutes after the start of the reaction was analyzed with a gas chromatograph and a Karl Fischer moisture meter. The results are shown in Table 2 below.

Examples 5-17
The catalyst obtained in the preparation example was filled into a 6 mmφ SUS reaction tube connected to a fixed bed type gas-phase continuous flow reactor (reactor), and heated to 500 ° C. with an electric furnace under N ₂ flow of 100 mL / min. Heated.
After the pretreatment for 1 hour, the electric furnace temperature was maintained at 350 ° C., and 6.5% ethanol / N ₂ gas was passed through the reactor at a rate of W / F = 0.03 g · min · mL ^−1. And reacted. The reactor outlet gas was gas-liquid separated and then cooled by a cooler to recover the condensate.
In addition, Example 5 is Preparation Example 1, Example 6 is Preparation Example 8, Example 7 is Preparation Example 9, Example 8 is Preparation Example 10, Example 9 is Preparation Example 11, Example 10 is Preparation Example 12, Example 11 is Preparation Example 13, Example 12 is Preparation Example 14, Example 13 is Preparation Example 15, Example 14 is Preparation Example 16, Example 15 is Preparation Example 17, Example 16 is Preparation Example 18, Example 17 used the catalyst obtained in Preparation Example 19.
The gas composition at the outlet of the reactor 10 minutes after the start of the reaction was analyzed with a gas chromatograph and a Karl Fischer moisture meter. The results are shown in Table 3 below.

Examples 18, 19 and Comparative Examples 5-7
The catalyst obtained in Preparation Example 1 was filled in a 6 mmφ SUS reaction tube connected to a fixed bed gas-phase continuous flow reactor (reactor), and 500 ° C. in an electric furnace under N ₂ flow of 100 mL / min. Heated to.
After the pretreatment for 1 hour, the electric furnace temperature was maintained at 350 ° C., and the substrate / N ₂ gas shown in the table was passed through the reactor at a rate of W / F = 0.03 g · min · mL ^−1. And reacted. 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 10 minutes after the start of the reaction was analyzed with a gas chromatograph and a Karl Fischer moisture meter. The results are shown in Table 4 below.

Claims (4)

  1. A process for producing 1,3-butadiene, characterized in that 1,3-butadiene is obtained by bringing a raw material containing at least ethanol under heating into contact with a catalyst having a magnesium silicate structure obtained by a hydrothermal synthesis method .   2. The method for producing 1,3-butadiene according to claim 1, wherein an element ratio (molar ratio: former / latter) of magnesium and silicon constituting the catalyst is 0.7 to 2.0.   The element constituting the catalyst contains at least one selected from vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, and cerium in addition to magnesium and silicon. Or the manufacturing method of 1, 3- butadiene of 2.   The content of the at least one element selected from vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, and cerium (amount in terms of metal element) is 0.1 to 0.1 of the total amount of the catalyst. The method for producing 1,3-butadiene according to claim 3, wherein the content is 5.0% by weight.

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