JP7174947B2 - Solid catalyst and method for producing butadiene - Google Patents

Description

The present invention relates to a solid catalyst and a method for producing butadiene using the same.

Conventionally, 1,3-butadiene (hereinafter also abbreviated as "butadiene") has been used as a raw material for synthetic rubbers such as butadiene rubber (BR) and styrene-butadiene rubber (SBR) as a monomer. It is obtained as a by-product during the thermal decomposition of ethylene crackers (naphtha crackers) to produce ethylene and propylene.
However, the production amount of butadiene is decreasing due to the recent shift to light feed of raw materials.
Therefore, as a petrochemical alternative raw material, a process of fermenting biomass (corn and sugarcane) to produce butadiene via butanediol, butanol, butene or ethanol is being studied.

Here, as a method for producing butadiene from ethanol by a one-step method, for example, Non-Patent Document 1 describes a catalyst in which Zr and Zn are supported on silica, and a catalyst in which Cu, Zr and Zn are supported on silica. It is disclosed that contacting ethanol with a catalyst such as a catalyst increases the conversion of ethanol and increases the selectivity of butadiene in the product.

Further, in Patent Document 1, (A) component: a metal selected from the group consisting of Groups 11 and 10, and (B) component: selected from the group consisting of Group 12 and Group 3 lanthanides A step of producing butadiene from ethanol or a mixture of ethanol and acetaldehyde in the presence of a solid catalyst comprising a metal and (C) a metal selected from Group 4 supported on a carrier. A manufacturing method is disclosed ([Claim 1]).

Further, Patent Document 2 discloses a process for producing 1,3-butadiene using a supported catalyst comprising lanthanum, zirconium and zinc, wherein the carrier comprises silica. ([Claim 1]).

JP 2016-023141 A Japanese Patent Publication No. 2016-518395

Matthew D. Jones et. al, “Investigations into the conversion of ethanol into 1,3-butadiene”, Catalysis Science & Technology, 2011, 1, 267-272

The present inventors examined the solid catalysts used in the butadiene production methods described in Patent Documents 1 and 2 and Non-Patent Document 1, and found that depending on the combination of metals to be supported, the ethanol conversion rate and butadiene Since one or both of the selectivities are lowered, it has been clarified that there is room for improvement in improving the yield of butadiene.

Therefore, an object of the present invention is to provide a solid catalyst capable of increasing both the conversion rate of ethanol and the selectivity of butadiene and improving the yield of butadiene, and a method for producing butadiene using the same. .

As a result of intensive studies by the present inventors to achieve the above object, the metal (A) selected from Group 12, the metal (B) selected from Group 4, Group 2, scandium, Using a solid catalyst supporting at least one metal (C) selected from the group consisting of cerium, neodymium, gadolinium, group 6, group 7, group 9, palladium, and group 13 The present inventors have found that the conversion rate of ethanol and the selectivity of butadiene are both increased, and the yield of butadiene is improved, thereby completing the present invention.
That is, the inventors have found that the above problems can be solved by the following configuration.

[1] A solid catalyst comprising metal (A), metal (B) and metal (C) supported on a carrier,
The metal (A) is a metal selected from Group 12,
The metal (B) is a metal selected from Group 4,
The metal (C) is at least one metal selected from the group consisting of Group 2, scandium, cerium, neodymium, gadolinium, Group 6, Group 7, Group 9, palladium, and Group 13. is a solid catalyst.
[2] The solid catalyst according to [1], wherein the metal (A) is zinc and the metal (B) is zirconium.
[3] The metal (C) is at least one metal selected from the group consisting of Groups 2, 6, 7, 9, and 13, [1] or The solid catalyst according to [2].
[4] The content of the metal (A) is 0.5 to 50% by mass relative to the mass of the carrier, and the content of the metal (B) is 0.5 relative to the mass of the carrier. to 50% by mass, and the content of the metal (C) is 0.05 to 5% by mass with respect to the mass of the support.
[5] The solid catalyst according to any one of [1] to [4], wherein the carrier is silica.
[6] The solid catalyst according to [5], wherein the silica has an average pore diameter in the range of 3 to 15 nm.
[7] A method for producing butadiene, wherein butadiene is obtained from ethanol or a mixture of ethanol and acetaldehyde in the presence of a catalyst, comprising:
A method for producing butadiene, wherein the catalyst is the solid catalyst according to any one of [1] to [6].

ADVANTAGE OF THE INVENTION According to this invention, the conversion rate of ethanol and the selectivity of butadiene can both be made high, and the solid catalyst which can improve the yield of butadiene, and the manufacturing method of butadiene using the same can be provided.

The solid catalyst of the present invention and the method for producing butadiene of the present invention are described below.
In this specification, the numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
In addition, "butadiene" as used herein means "1,3-butadiene".

[Solid catalyst]
The solid catalyst of the present invention is a solid catalyst in which metal (A), metal (B) and metal (C) are supported on a carrier.
Here, the metal (A) is a metal selected from Group 12, the metal (B) is a metal selected from Group 4, the metal (C) is a metal selected from Group 2, at least one metal selected from the group consisting of scandium, cerium, neodymium, gadolinium, Groups 6, 7, 9, palladium, and Group 13;
In the present invention, the metal (A), metal (B) and metal (C) may be present on the carrier as metals or compounds such as metal oxides.

[Carrier]
The carrier used for the solid catalyst of the present invention is not particularly limited as long as it can support the metal (A), metal (B) and metal (C) described below, and specific examples thereof include silica, alumina, magnesia and the like.
Among these, silica is preferred because it provides higher ethanol conversion and butadiene selectivity.

In the present invention, silica having an average pore diameter in the range of 3 to 15 nm is preferably used as the carrier because the selectivity of butadiene is higher, and silica having an average pore diameter in the range of more than 3 nm and 10 nm or less is used. is more preferred.
Here, the "average pore size" refers to the pore size showing the peak value of the pore size distribution curve determined from the nitrogen adsorption isotherm by the BJH method or the DFT method.

[Metal (A)]
The metal (A) that the solid catalyst of the present invention has is a metal selected from Group 12.
Specific examples of Group 12 metals include zinc (Zn), cadmium (Cd), and mercury (Hg).
Of these, zinc is preferred because it provides higher ethanol conversion and butadiene selectivity.

Although the raw material of the metal (A) is not particularly limited, examples thereof include nitrates, acetates, and hydrates thereof of metals selected from Group 12. Specific examples include Zn(NO ₃ ) ₂ , Zn(NO ₃ ) _{2.6H 2 O, Zn(OCOCH 3 ) 2 and the like} .

The content of the metal (A) is preferably 0.1 to 50% by mass, more preferably 0.1 to 40% by mass, and 0.2 to It is more preferably 30% by mass.
Here, the "contents" of metal (A), metal (B) and metal (C) to be described later can be measured by, for example, ICP or fluorescent X-rays.

[Metal (B)]
The metal (B) that the solid catalyst of the present invention has is a metal selected from Group 4.
Specific examples of Group 4 metals include titanium (Ti), zirconium (Zr), and hafnium (Hf).
Of these, zirconium is preferred because it provides higher ethanol conversion and butadiene selectivity.

Although the raw material of the metal (B) is not particularly limited, examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 4, and hydrates thereof. Specifically, ZrO(NO ₃ ) ₂ , ZrO(NO ₃ ) _{2.2H 2 O, ZrO(OCOCH 3 ) 2 and the like} can be mentioned.

The content of the metal (B) is preferably 0.1 to 50% by mass, more preferably 0.1 to 40% by mass, and 0.2 to It is more preferably 30% by mass.

[Metal (C)]
The metal (C) of the solid catalyst of the present invention is selected from the group consisting of group 2, scandium, cerium, neodymium, gadolinium, group 6, group 7, group 9, palladium, and group 13. at least one metal that

<Second group>
Specific examples of Group 2 metals include beryllium (Ba), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).
Among these, magnesium, calcium, and barium are preferred because the ethanol conversion rate and butadiene selectivity are higher.
Group 2 metal raw materials are not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 2, and hydrates thereof. Specific examples include magnesium nitrate hexahydrate, calcium nitrate tetrahydrate, and barium nitrate.

<Scandium>
The metal source of scandium (Sc) is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 3, and hydrates thereof. Specific examples include scandium nitrate pentahydrate.

<Cerium>
The metal source of cerium (Ce) is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 3 lanthanides, and hydrates thereof. Specific examples include cerium (III) nitrate hexahydrate.
<Neodymium>
The metal source of neodymium (Nd) is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 3 lanthanides, and hydrates thereof. Specific examples include neodymium (III) nitrate hexahydrate.
<Gadolinium>
The metal source of gadolinium (Gd) is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 3 lanthanides, and hydrates thereof. Specific examples include gadolinium nitrate hexahydrate.

<6th family>
Specific examples of Group 6 metals include chromium (Cr), molybdenum (Mo), and tungsten (W).
Of these, chromium is preferred because it provides higher ethanol conversion and butadiene selectivity.
The Group 6 metal raw material is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 6, and hydrates thereof. Specific examples include chromium (III) nitrate nonahydrate and scheelite.

<Group 7>
Specific examples of Group 7 metals include manganese (Mn), technetium (Tc), and rhenium (Re).
Among these, manganese is preferable because it provides a higher ethanol conversion rate and butadiene selectivity, has a low raw material cost, and is easily available.
The Group 7 metal raw material is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 7, and hydrates thereof. Specific examples include manganese nitrate hexahydrate.

<Group 9>
Specific examples of Group 9 metals include cobalt (Co), rhodium (Rh), and iridium (Ir).
Of these, cobalt is preferred because it provides higher ethanol conversion and butadiene selectivity.
Group 9 metal raw materials are not particularly limited, but include, for example, nitrates, oxynitrates, acetates, oxyacetates, chlorides, and hydrates thereof of metals selected from Group 9. Specific examples include cobalt nitrate hexahydrate, iridium chloride hydrate, and rhodium chloride trihydrate.

<Palladium>
The metal raw material for palladium (Pd) is not particularly limited, but examples thereof include palladium nitrate, oxynitrate, acetate, oxyacetate, and hydrates thereof. Specific examples include palladium nitrate and palladium chloride.

<13th Family>
Specific examples of Group 13 metals include aluminum (Al), gallium (Ga), and indium (In).
Of these, gallium is preferred because it provides higher ethanol conversion and butadiene selectivity.
The Group 13 metal raw material is not particularly limited, but examples thereof include nitrates, oxynitrates, acetates, oxyacetates of metals selected from Group 13, and hydrates thereof. Specific examples include aluminum nitrate nonahydrate, gallium nitrate hydrate, and indium nitrate trihydrate.

In the present invention, since the conversion of ethanol and the selectivity of butadiene are higher, the metal (C) is selected from the group 2, 6, 7, 9 and 13 preferably at least one metal selected from the group consisting of

The content of the metal (C) is preferably 0.1 to 50% by mass, more preferably 0.1 to 40% by mass, more preferably 0.2 to 50% by mass, relative to the mass of the support. It is more preferably 30% by mass.
The mass ratio of the metal (C) to the total mass of the metal (A) and the metal (B) [C/(A+B)] improves the catalyst life and the butadiene selectivity. It is preferably 1/9 to 5/1, more preferably 2/8 to 5/2.

[Method for preparing solid catalyst]
The method for preparing the solid catalyst of the present invention is not particularly limited, and known methods such as an impregnation method and a sol-gel method can be employed. Among these methods, the impregnation method is preferred because the obtained solid catalyst has high activity and selectivity and is simple.
As the impregnation method, for example, a known technique such as a spraying method, a coating method, a pore filling method, or a selective adsorption method can be employed. Specifically, the metal nitrate, acetate, etc., which are the raw materials for the metal (A), metal (B), and metal (C) described above are dissolved in water, and the obtained aqueous solution is impregnated into the support described above, After that, a method of drying the carrier can be mentioned. The drying method and drying time are not particularly limited, but drying under reduced pressure at 60 to 80° C. is preferable. Moreover, it is preferable to bake at a temperature of 200 to 600° C. after drying.
In addition to the preparation method described above, for example, after mixing the nitrate, acetate, etc. of the metal that is the raw material of the metal (A), metal (B), and metal (C) described above, heating, concentration, hydrothermal A method of applying a treatment such as synthesis, followed by drying and firing may also be used.
In addition, the prepared catalyst may be subjected to molding, sizing, etc., if necessary, before use.

[Method for producing butadiene]
The method for producing butadiene of the present invention (hereinafter also abbreviated as "the production method of the present invention") comprises producing butadiene from ethanol or a mixture of ethanol and acetaldehyde in the presence of the solid catalyst of the present invention. The method.

〔material〕
In the production method of the present invention, ethanol or a mixture of ethanol and acetaldehyde is used as a starting material for the target product, butadiene.
Also, the raw material may be appropriately diluted and brought into contact with the solid catalyst.
Specific examples of the medium for diluting the raw material (hereinafter also referred to as "dilution medium") include inert gases such as nitrogen, argon, and helium.
In addition, the raw material may contain ethanol, acetaldehyde, impurities other than the dilution medium, and the like.

In the production method of the present invention, when a mixture of ethanol and acetaldehyde is used as a raw material, the mass ratio of ethanol and acetaldehyde (ethanol:acetaldehyde) is not particularly limited, but for example, 19:1 to A range of 1:9 is preferred, and a range of 16:4 to 2:8 is more preferred.

[Reaction conditions, etc.]
The production method of the present invention can be carried out in a known reaction format, and may be a flow system, a batch system, or the like, but from the viewpoint of productivity, it is preferably carried out in a flow system.
In addition, the production method of the present invention may be carried out in a gas phase or a liquid phase, but from the viewpoint of applying a high reaction temperature and improving the conversion rate of the raw material, it is preferable to carry out under gas phase conditions. preferable.
In addition, if desired, the catalyst may be reduced before the start of the reaction. For example, after the catalyst is reduced at 200 to 500° C. in a hydrogen stream, it is brought into contact with the raw material to carry out a butadiene production step. good too.

Examples of methods for bringing the raw material into contact with the solid catalyst include a suspended bed method, a fluidized bed method, and a fixed bed method. Further, the present invention may be carried out by either a vapor phase method or a liquid phase method, but the vapor phase method is preferably used.

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

The reaction temperature is preferably 260 to 500°C, more preferably 300 to 480°C.
The reaction pressure can be appropriately set in a wide range from normal pressure to high pressure, but is preferably set to 1.0 MPa or less from the viewpoint of production efficiency, apparatus configuration, and the like.

The contact time between the raw material and the solid catalyst can be controlled by adjusting the feed rate of the raw material, and the weight hourly space velocity (WHSV) per unit catalyst is 1.0 to 40 g-raw material/g-cat·h. It is preferably 2.0 to 20 g-raw material/g-cat·h.

After completion of the reaction, the reaction product is separated into light gas, C4 fraction, heavy fraction, water, ethanol, acetaldehyde, etc. by separation means such as distillation, extraction, membrane separation, or a combination of these separation means. It can be refined.

The present invention will be described in further detail based on examples below. The materials, amounts used, proportions, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below.

[Example 1]
Ca(NO ₃ ) 2.4H ₂ O (Ca salt) 0.021 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.183 g, and ZrO ₍ NO ₃ ) _{2.2H 2} O ₍ Zr Aqueous solution 1 was prepared by dissolving 0.108 g of salt) in 1 ml of water.
The prepared aqueous solution 1 is impregnated with silica (trade name: CARiACT G-6, average pore size: 6 nm, manufactured by Fuji Silysia Co., Ltd.), dried at 110 ° C. for 4 hours, and further baked at 500 ° C. for 4 hours. Thus, a solid catalyst 1 in which Ca, Zn and Zr are supported on silica was prepared.
Table 1 below shows the average pore diameter and half width of the carrier, and the type and amount of metal to be supported.

0.3 g of the obtained solid catalyst 1 is packed in a fixed bed flow reactor, N ₂ gas is flowed at 5 to 15 ml / min, and ethanol (EtOH) is added at a rate of 0.03 ml / min. It was added to the _two gas streams, and allowed to flow under the conditions of a reaction temperature of 425° C., atmospheric pressure, and a weight hourly space velocity (WHSV) of 4.7 g-raw material/g-cat·h. Table 1 below shows raw materials, reaction temperatures and weight hourly space velocities (WHSV).
The reaction was carried out for 2 hours, and the resulting product was analyzed using a gas chromatograph (manufactured by Shimadzu Corporation).
In addition, the conversion of raw material, butadiene (BD) selectivity, BD yield, and BD productivity were calculated according to the following formulas. These results are shown in Table 1 below.
Raw material conversion rate = (raw material input amount - unreacted raw material distillation amount) / (raw material input amount) x 100 (%)
BD selectivity = (amount of butadiene produced) / (amount of raw material input - amount of unreacted raw material distilled) x 100 (C-mol%)
BD yield = (conversion rate of raw material) × (BD selectivity) ÷ 100 (C-mol%)
BD productivity = (mass of butadiene produced per hour) / (mass of catalyst used) (g-BD/g-cat h)

[Example 2]
Instead of aqueous solution 1, 0.032 g of Mg(NO ₃ ) 2.6H ₂ O (Mg raw material), 0.183 g of Zn(NO ₃ ) _{2.6H 2} O (Zn salt), and ZrO ₍ NO ₃ ) ₂ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 2 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 3]
Instead of aqueous solution 1, 0.009 g of Ba(NO ₃ ) ₂ (Ba raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO ₍ NO ₃ ) _{2.2H 2} O In the same manner as in Example 1, except that aqueous solution 3 in which 0.108 g of (Zr salt) was dissolved in 1 ml of water was used, conversion of raw material, butadiene (BD) selectivity, BD yield, and BD Productivity was calculated. These results are shown in Table 1 below.

[Example 4]
Instead of aqueous solution 1, 0.022 g of Sc(NO ₃ ) ₂ (Sc raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO ₍ NO ₃ ) _{2.2H 2} O In the same manner as in Example 1, except that an aqueous solution 4 in which 0.108 g of (Zr salt) was dissolved in 1 ml of water was used. Productivity was calculated. These results are shown in Table 1 below.

[Example 5]
0.013 g of Nd(NO ₃ ) _{3.6H 2} O (Nd raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO(NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 5 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 6]
0.012 g of Gd(NO ₃ ) _{3.6H 2} O (Gd raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO(NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 6 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 7]
0.012 g of Ce(NO ₃ ) _{3.6H 2} O (Ce raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO(NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 7 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 8]
0.026 g of Cr(NO ₃ ) _{3.9H 2} O (Cr raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO(NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 8 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 9]
Instead of aqueous solution 1, 0.016 g of Mn(NO ₃ ) 2.6H ₂ O (Mn raw material), 0.183 g of Zn(NO ₃ ) _{2.6H 2} O (Zn salt), and ZrO ₍ NO ₃ ) ₂ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 9 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 10]
0.018 g of Co(NO ₃ ) 2.6H ₂ O (Co raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO ₍ NO ₃ ) ₂ instead of the aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that an aqueous solution 10 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Example 11]
0.009 g of Pd(NO ₃ ) ₂ (Pd raw material), 0.183 g of Zn(NO ₃ ) 2.6H ₂ O (Zn salt), and ZrO(NO ₃ ) _{2.2H 2} O instead of aqueous solution ₁ In the same manner as in Example 1, except that an aqueous solution 11 in which 0.108 g (Zr salt) was dissolved in 1 ml of water was used. Productivity was calculated. These results are shown in Table 1 below.

[Example 12]
Ga(NO ₃ ) 2.nH ₂ O (Ga raw material) 0.014 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.183 g, and ZrO ₍ NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution 12 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Comparative Example 1]
Cu(NO ₃ ) 2.3H ₂ O (Cu raw material) 0.015 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.183 g, and ZrO ₍ NO ₃ ) ₂ instead of aqueous solution ₁ - By the same method as in Example 1, except that an aqueous solution C1 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used, and the reaction temperature was changed to the temperature (400°C) shown in Table 1 below. , feedstock conversion, butadiene (BD) selectivity, BD yield, and BD productivity were calculated. These results are shown in Table 1 below.

[Comparative Example 2]
Ni(NO ₃ ) 2.3H ₂ O (Ni raw material) 0.019 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.183 g, and ZrO ₍ NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that an aqueous solution C2 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Comparative Example 3]
Cu(NO ₃ ) 2.3H ₂ O (Cu raw material) 0.015 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.183 g, and ZrO ₍ NO ₃ ) ₂ instead of aqueous solution ₁ · Conversion rate of raw material, butadiene (BD) selectivity, BD yield in the same manner as in Example 1 except that aqueous solution C3 in which 0.108 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water was used. , and BD productivity was calculated. These results are shown in Table 1 below.

[Comparative Example 4]
AgNO ₃ (Ag raw material) 0.007 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.183 g, and ZrO(NO ₃ ) _{2.2H 2} O (Zr salt) instead of aqueous solution ₁ The conversion rate of raw materials, butadiene (BD) selectivity, BD yield, and BD productivity were calculated in the same manner as in Example 1, except that an aqueous solution C4 in which 0.108 g was dissolved in 1 ml of water was used. did. These results are shown in Table 1 below.

[Comparative Example 5]
Cu(NO ₃ ) 2.3H ₂ O (Cu raw material) 0.0088 g, Zn(NO ₃ ) 2.6H ₂ O (Zn salt) 0.050 g, and ZrO ₍ NO ₃ ) ₂ instead of aqueous solution ₁ Using an aqueous solution C5 in which 0.105 g of 2H ₂ O (Zr salt) was dissolved in 1 ml of water, instead of silica (trade name: CARiACT G-6, manufactured by Fuji Silysia Co., Ltd., average pore size: 6 nm), silica (manufactured by Sigma-Aldrich, trade name: Davisil Grade 636, average pore size: 6 nm), and the reaction temperature was changed to the temperature shown in Table 1 below (400 ° C.). Raw material conversion, butadiene (BD) selectivity, BD yield, and BD productivity were calculated. These results are shown in Table 1 below.

From the results shown in Table 1, metal (A) selected from Group 12, metal (B) selected from Group 4, Group 2, Group 3, Group 3 lanthanoids, Group 6, When using a solid catalyst supporting a metal (C) selected from the group consisting of Groups 7, 9, palladium, and Group 13, both ethanol conversion and butadiene selectivity are It was found that the yield of butadiene was improved (Examples 1 to 12).

Claims (4)

A solid catalyst for use in the reaction of butadiene from ethanol or a mixture of ethanol and acetaldehyde, comprising:
A solid catalyst comprising metal (A), metal (B) and metal (C) supported on a carrier,
the metal (A) is zinc ,
The metal (B) is zirconium ,
The metal (C) is any metal selected from the group consisting of Ca, Mg, Ba, Sc, Nd, Gd, Ce, Cr, Mn, Co and Ga ,
The content of the metal (A) is 0.5 to 30% by mass with respect to the mass of the support,
The content of the metal (B) is 0.5 to 30% by mass with respect to the mass of the support,
The content of the metal (C) is 0.05 to 5% by mass with respect to the mass of the support, which is less than the content of either the metal (A) or the metal (B). , solid catalyst. 2. The solid catalyst according to claim 1 , wherein said support is silica. 3. The solid catalyst according to claim 2 , wherein the silica has an average pore size in the range of 3-15 nm. A process for the production of butadiene, wherein butadiene is obtained from ethanol or a mixture of ethanol and acetaldehyde in the presence of a catalyst, comprising:
A method for producing butadiene, wherein the catalyst is the solid catalyst according to any one of claims 1 to 3 .