JPH083110A - Production of unsaturated glycol diester and catalyst to be used therefor - Google Patents

Abstract

PURPOSE:To obtain the subject compound in an industrially advantageous way by acyloxylating a conjugated diene compound by using a highly and sustainedly active catalyst carried on a solid carrier having special structure. CONSTITUTION:This unsaturated glycol diester is obtained by reaction between a conjugated diene (e.g. butadiene, isoprene), carboxylic acid (e.g. acetic acid, propionic acid, butyric acid) and molecular oxygen at 20-150 deg.C under a pressure of 5-100kg/cm<2> by using a catalyst (with both palladium and tellurium as active ingredients) carried on a solid carrier with the volume of the pores 5-50nm in radius accounting for >=80% (pref. >=90%) of the total volume of the pores 1.8-10000nm in radius. It is preferable that the specific surface area of the solid carrier be <200m<2>/g (esp. 30-190m<2>/g), the solid carrier being e.g. silica, alumina, titania, zeolite, silica-alumina. The level of the Pd in the catalyst stands at 0.5-10 (pref. 2-6)wt.% and the amount of the Te carried 0.15-0.5 gram atom per gram atom of the Pd.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a method for producing an unsaturated glycol diester by reacting a conjugated diene with a carboxylic acid and molecular oxygen in the presence of a solid catalyst having palladium and tellurium supported on a carrier, and a method for producing the unsaturated glycol diester. It relates to the catalyst used in the method.

[0002]

Unsaturated glycol diesters, for example 1,
4-Butenediodiol diester is an important intermediate compound of 1,4-butanediol and tetrahydrofuran, which are raw materials for engineering plastics and the like. Tetrahydrofuran itself is a high-performance solvent, and its polymer, polytetramethylene ether glycol, is important as a raw material for elastic fibers. Regarding the method for producing this butenediole diester, many proposals have hitherto been made, among which, using a solid catalyst in which palladium and tellurium are supported on activated carbon, butadiene is reacted with a carboxylic acid and molecular oxygen. Methods for producing butenediole diesters are well known.

Specifically, for example, a method of using a solid catalyst containing palladium and at least one of tellurium and selenium (JP-A-48-72090), palladium, and at least one of antimony and bismuth. , A method of using a solid catalyst containing at least one of tellurium and selenium (JP-A-48-96513), in order to improve the catalytic activity of these solid catalysts, the active carbon of the carrier used is pretreated with nitric acid. To use (Japanese Patent Laid-Open No. 49-11812),
A method has been proposed in which these solid catalysts are subjected to reduction treatment, then treated with a gas containing molecular oxygen at a temperature of 200 ° C. or higher, and further subjected to reduction treatment (Japanese Patent Publication No. 52-12686). .

However, although the above catalysts show high catalytic activity and selectivity, the elution of the supported metal from the catalyst,
There is a decrease in catalyst activity over time, and improvement thereof has been desired.
In order to prevent the catalyst activity from deteriorating with time, a method in which the amount of impurities such as vinylcyclohexene in butadiene or formic acid in acetic acid is limited, and a reaction is carried out in the presence of a polymerization inhibitor in the reaction system (Japanese Patent Publication No. -15491), a method of reacting elemental sulfur in the presence of a deterioration inhibitor (JP-A-52-51313), and the like have been proposed. Although the above-mentioned drawbacks of the solid catalyst are remedied considerably, they have not been said to be sufficient.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies on the influence of the catalyst carrier on the catalytic performance in order to solve the above-mentioned conventional problems. That is, the first object of the present invention is to industrially advantageously produce an unsaturated glycol diester by reacting a conjugated diene, a carboxylic acid and molecular oxygen in the presence of a catalyst having a high activity and a very low activity decrease. To provide a method. A second object of the present invention is to provide a catalyst useful in the above method.

[0006]

The first object of the present invention is to react an conjugated diene with a carboxylic acid and molecular oxygen in the presence of a solid catalyst carrying palladium and tellurium as active ingredients to form an unsaturated glycol. -In the method for producing ludiester, the pore radius of 5 as a carrier of the solid catalyst.
The volume occupied by pores in the range
This is achieved by using a solid support that is greater than 80% with respect to the total pore volume in the 10,000 nm range. The second object of the present invention is to provide a solid carrier in which the volume occupied by pores having a pore radius of 5 to 50 nm is 80% or more of the total pore volume having a pore radius of 1.8 to 10,000 nm. This is achieved by a conjugated diene acyloxylation catalyst in which palladium and tellurium are supported as active ingredients.

The catalyst used in the present invention is one in which palladium and tellurium, which are catalyst components, are supported on a solid support having the above-mentioned specific pore distribution. The pore volume in the present invention is measured using a mercury porosimeter. That is, the basic relational expression (1) of the pore radius and the pressure in the pore measuring method, Pr = −2ψ · cos θ ---- (1) [In the above formula (1), P is the pressure, r is the pore radius, ψ is the surface tension of mercury, θ is the contact angle between mercury and the sample]
It is the pore volume measured under the conditions of ψ = 480 dyne / cm and θ = 140 °. In the present invention, the ratio of the pore volume in the range of 5 to 50 nm in the radius of pores to the total pore volume in the range of 1.8 to 10,000 nm in the pore radius (r) measured by this method. A catalyst in which palladium and tellurium, which are catalyst components, are supported on a solid support whose content is 80% or more is used. More preferred of this requirement is that pores with pore radii in the range 5 to 50 nm are 85% of the total pore volume in the pore radii 1.8 to 10,000 nm.
As described above, it is more preferable to use a 90% solid carrier on which palladium and tellurium as catalyst components are supported. In the present invention, the ratio of the supported amount of palladium as a catalyst component and tellurium as another catalyst component is such that the amount of tellurium is in the range of 0.05 to 5 g atom relative to 1 g atom of palladium, and Is 0.15 to 4 g atom, more preferably 0.15
~ 0.5 g atom range.

Since an unsaturated glycol diester producing apparatus for reacting a conjugated diene with a carboxylic acid and molecular oxygen is usually continuously operated for half a year to one year, it is strongly required that the catalytic activity does not decrease during this period. . In order for the catalyst to have a small activity decrease, the catalyst components, palladium and tellurium, are highly dispersed as a metal or an alloy on the carrier, and the metal is coated as a by-product with a high boiling point for a long time. It is considered necessary not to be done. It is generally considered that the average particle diameter of palladium and tellurium on the catalyst used for the production of unsaturated glycol diester is several tens of angstroms (several nm).

The reason why the carrier having a specific pore distribution used in the present invention works well is considered to be as follows. That is, in a macropore having a pore diameter of more than 100 nm, the specific surface area becomes small, so that the supporting density of the active ingredient is lowered and the reaction efficiency of the catalyst is lowered. In addition, since micropores with a pore diameter of less than 10 nm are easily clogged by a high boiling point by-produced in the reaction or a polymer of a conjugated diene as a raw material, the catalyst metal supported in such micropores has a long catalytic activity. It means that the decline will be large.

Therefore, like the solid carrier used in the present invention, the pore radius is in the range of 5 to 50 nm (diameter is 10 to 100 nm),
By supporting the catalyst metal on the carrier having most of the pores, a catalyst having high activity and not deactivating for a long time can be obtained. The pore volume is not particularly limited, but normally, the pore volume of 0.8 cc / g or more is advantageous because the amount of palladium and tellurium supported can be increased. Further, the specific surface area of the solid support used in the present invention may satisfy the above-mentioned conditions of pores, preferably
Less than 200 m ² / g, more preferably 30 to 190 m ² / g
Is. A carrier having a specific surface area exceeding 200 m ² / g and having a too large specific surface area is not preferable because the micropores excessively increase.

The shape of the solid carrier used in the present invention is not particularly limited, and powdery, crushed, particulate, columnar and other shapes can be arbitrarily used, but it is industrially 2.0. With a size (maximum diameter) of ~ 6.0 mm, the packing density is
Those of 0.35 g / ml or more are preferably used. As such a solid carrier, those obtained by molding silica, alumina, titania, zeolite, silica-alumina or the like into a predetermined shape are used. In addition, activated carbon can also be used if it satisfies the above conditions.

In order to support the metal of the catalytically active component on the solid support, a conventionally well-known method for preparing a metal catalyst with a support can be appropriately used. For example,
A palladium compound and a tellurium compound are dissolved in an aqueous nitric acid solution, a solid carrier is immersed in the aqueous solution, and the carrier is impregnated or adsorbed with the metal component, and then the carrier carrying the catalyst component is separated by filtration. Is generally dried in air and reduced in a stream of hydrogen or an organic compound having a reducing power.

Examples of the palladium compound used for preparing the catalyst include palladium nitrate, palladium chloride, palladium acetate, palladium ammine complex and the like, but if necessary, metallic palladium can also be used. The concentration of palladium in the catalyst is generally in the range 0.5 to 10% by weight, more preferably 2 to 6% by weight. Below the lower limit of the above range, it is difficult to prepare a highly active catalyst. Further, when the concentration is higher than the upper limit of the above range, it is not preferable for the following reason. That is, in order to keep the tellurium and palladium in the catalyst at a suitable ratio (tellurium / palladium atomic ratio), it is necessary to keep the concentration of tellurium at a certain value or higher in accordance with the concentration of palladium in the impregnating solution. is there. However, since the solubility of tellurium is smaller than that of palladium, if the concentration of palladium becomes too high (the concentration exceeding the upper limit of the above range), it becomes impossible to secure the tellurium concentration corresponding thereto.

Next, as tellurium compounds used for preparing the catalyst, halogen compounds such as tellurium (II) and (IV) chlorides, oxides such as tellurium (IV) and (VI) oxides, and telluric acid (H
₆ TeO ₆ ), metallic tellurium, etc. can be used. The tellurium supported on the carrier is a supporting ratio of tellurium to palladium in the catalyst, and is usually selected from the range of 0.05 to 5 gram atom per 1 gram atom of palladium, more preferably 0.15 to 1 gram atom of palladium. 4 gram atom, more preferably 0.15 to 0.5 gram atom. When the ratio of tellurium is less than the lower limit of the above range, palladium is eluted from the catalyst into the reaction solution during use in the reaction, and when the ratio of tellurium exceeds the upper limit of the above range, tellurium is eluted. In either case, the catalyst activity is lowered and it cannot withstand continuous use for a long time.

The ratio of the aqueous solution to the total pore volume of the carrier when the carrier is added to the aqueous solution of the palladium compound and tellurium compound to impregnate or adsorb the carrier, that is, (total volume of aqueous solution used) / (carrier used) The total pore volume of) is 0.
It is preferable to select from the range of 8 or more, and particularly preferable range is the above volume ratio of 0.9 to 1.1. The volume ratio is 0.
When it is lower than 8, it is difficult to uniformly support palladium and tellurium. On the other hand, if the volume ratio exceeds 1.1, a considerable amount of the solution that remains without being adsorbed on the carrier is produced, and it is not preferable because the solution must be recovered.

Next, in order to dry the solid support impregnated with the palladium compound and tellurium compound, a fixed bed may be formed from this solid support, and heated nitrogen, air, hydrogen gas or the like may be passed through this. The gas flow rate used in this case is
The space velocity (SV) of the catalyst is usually selected in the range of 20 (l / l.hr) or more, more preferably 1000 to 8000.
The range is (l / l ・ hour). If the SV value is too low, the drying time becomes long, and if it is too high, the amount of gas used becomes large, which is uneconomical.

The amount of water in the gas used for drying is usually in the range of 2% by weight or less, more preferably 0.5% by weight or more.
If the water content in the dry gas becomes too high, the catalyst performance finally obtained will deteriorate. Also, the drying temperature is usually 40 ~
The temperature is selected within the range of 150 ° C., but it is preferable that a gas of 60 to 100 ° C. is circulated to pre-dry and then a gas of 140 to 150 ° C. is circulated to complete the drying. For the activation treatment of the dried catalyst, a method of alternately repeating a reduction treatment with a reducing gas such as hydrogen and an oxidation treatment with a mixed gas of oxygen and nitrogen, or a method of performing the reduction treatment with a reducing gas alone. Any of these can be used.

The conjugated diene, for example, butadiene, as a reaction raw material used when producing an unsaturated glycol diester using the above catalyst is not necessarily required to be pure, and an inert gas such as nitrogen gas or methane may be used. , Ethane,
It may contain a saturated hydrocarbon such as butane or an unsaturated hydrocarbon such as butene. As a conjugated diene,
In addition, alkyl group-substituted butadienes such as isoprene, 2,3-dimethylbutadiene and piperylene can be used.

Next, as the carboxylic acid as the other reaction raw material, a lower aliphatic monocarboxylic acid having 2 to 6 carbon atoms such as acetic acid, propionic acid and butyric acid is used. Is more preferable. Usually, the carboxylic acid also serves as the reaction medium, but an organic solvent inert to the reaction, such as saturated hydrocarbon or ester, may be used together. However, it is preferable that 50% by weight or more of the reaction medium is the starting carboxylic acid. The amount of the carboxylic acid used is preferably in the range of stoichiometric amount or more and 60 mol or less with respect to 1 mol of the conjugated diene.

The molecular oxygen used in the method of the present invention need not be pure oxygen, but may be oxygen diluted with an inert gas such as nitrogen, for example air. The amount of oxygen used is not limited and may be within a range such that the gas does not have an explosive composition in the reaction system.

The reaction of molecular oxygen, a conjugated diene and a carboxylic acid in the presence of a solid catalyst according to the method of the present invention can be carried out by a batch system or a continuous process, and the catalyst is a fixed bed system, a fluid bed system or a suspension system. It can be carried out by any method such as a tank system. The reaction is usually carried out at a temperature of 20 ° C. or higher, but in consideration of the reaction rate and the production of by-products, a suitable reaction temperature range is 50 to 120 ° C. The reaction pressure is preferably 5 to 100 kg / in consideration of the reaction rate and the cost of the reaction equipment.
It is cm ^2.

[0022]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following Examples and Comparative Examples, the volume of pores having a pore radius of 5 to 50 nm with respect to the catalyst carrier used is relative to the total pore volume of the pore radius of 1.8 to 10,000 nm. ratio,
That is, [(volume occupied by pores having pore radius in the range of 5 to 50 nm) / (total pore volume in pore radius of 1.8 to 10,000 nm) x 100] is abbreviated as A ratio (%). .

Example 1 A silica carrier having a particle diameter of 2.4 to 3.4 mm and an A ratio of 97% (S980G manufactured by Shell Chemical Co., pore volume 1.12 cc).
/ G, average pore radius 22.6 nm, specific surface area of carrier 67 m ² / g) 56g
Add 57 g of an aqueous palladium nitrate solution containing 10% by weight of palladium in terms of metal and 140 g of an aqueous solution obtained by dissolving 2.6 g of tellurium dioxide in 35% nitric acid, and hold at 30 ° C for 2 hours, and then for 5 hours. I let it cool. This was filtered to collect a silica carrier, and this carrier was further centrifuged and deliquored to obtain 136 g of a catalyst.

This catalyst has an inner diameter of 4.6 cm (effective area 16.6 c
It was housed in a Pyrex glass tube of m ² ), heated at 65 ° C. for 6 hours, then heated to 100 ° C. and kept for 2 hours to be dried. Then, after raising the temperature to 150 ° C, the temperature was raised at a rate of 50 ° C / hr while flowing hydrogen gas at a flow rate of 330 Nl / hr.
After being kept at 0 ° C. for 4 hours, it was cooled in a nitrogen stream to obtain 60 g of an activated catalyst. The catalyst contained 4.9% by weight palladium and 1.8% by weight tellurium.

Next, 4 g of this catalyst was charged into a stainless steel reaction tube having an inner diameter of 12 mm (effective area 1.005 cm ² ) and 0.12-mol of 1,3-butadiene and 2.5 mol / hour of acetic acid in a liquid phase. ,
Further, 96.4 Nl / hour of nitrogen containing 6% by volume of oxygen was supplied in the gas phase, and the reaction was continuously carried out for 3900 hours at a reaction pressure of 60 kg / cm ² and a reaction temperature of 80 ° C. After the start of the reaction, analyze the product solution after a lapse of a predetermined time, determine the amount of diacetoxybutene produced per hour for 1 g of catalyst, calculate the reaction rate constant (k), and determine the deactivation rate of the catalyst activity. It was Table 1 shows the results.

Example 2 As a catalyst carrier, a silica carrier (trade name CARIACT 15) manufactured by Fuji Devison Co., Ltd. having an A ratio of 99% (particle diameter 2.4 to 4.0 mm,
Diacetoxybutene was produced in the same manner as in Example 1 except that the pore volume was 0.91 cc / g, the average pore radius was 10.3 nm, and the carrier specific surface area was 170 m ² / g). The results are shown in Table 1.

Comparative Example 1 As a catalyst carrier, a silica carrier (trade name CARIACT10) manufactured by Fuji Devison Co. having an A ratio of 67% (particle diameter 2.4 to 4.0 mm,
Diacetoxybutene was produced in the same manner as in Example 1 except that the pore volume was 0.94 cc / g, the average pore radius was 5.8 nm, and the carrier specific surface area was 273 m ² / g). The results are shown in Table 1.

COMPARATIVE EXAMPLE 2 As a catalyst carrier, peated coal having an A ratio of 29% (Sorbonorit-2X, trade name, manufactured by Norit of the Netherlands) (diameter 2 m
m, cylindrical length 6 mm, pore volume 0.69 cc / g, average pore radius 460 nm, carrier specific surface area 1058 m ² / g)
To 60 g of water, add 60 g of water and 60 g of 60 wt% nitric acid aqueous solution,
Hold at ℃ for 3 hours. After cooling, remove the solution by filtration,
A nitric acid-treated activated carbon was obtained.

Next, 20 g of an aqueous solution of palladium nitrate containing 10% by weight of palladium in terms of metal in the activated carbon and 0.55 g of metal tellurium in 35% nitric acid were prepared as an aqueous solution 120.
g was added, and the mixture was kept at 30 ° C. for 3 hours and then allowed to cool for 5 hours. It was filtered to remove the solution, then dried under vacuum at 240 torr for up to 140 ° C for 8 hours to give 4.2% by weight palladium.
And palladium and tellurium-supported activated carbon (hereinafter referred to as supported catalyst) containing 0.78% by weight of tellurium were obtained. Of the above supported catalyst, 30 cc was filled in a glass tube made of Pyrex with an inner diameter of 2.5 cm (effective area 4.9 cm ² ) and methanol 8
Nitrogen containing vol.% Was flown at a flow rate of 39 Nl / hour, and the temperature was raised to 350 ° C at a rate of 50 ° C / hour.
After holding for 4 hours, it was left to cool to room temperature in a nitrogen stream.

Next, a nitrogen gas containing 2% by volume of oxygen is supplied at a flow rate of 39.
The temperature was raised to 300 ° C. and kept at this temperature for 10 hours while flowing at a flow rate of Nl / hour, and then cooled to room temperature in a nitrogen stream. Then, nitrogen gas containing 8% by volume of methanol was added to 39%.
Flowing at a flow rate of Nl / hour, the flow rate of
The temperature was raised to 0 ° C., the temperature was maintained for 15 hours, and then the mixture was allowed to cool to room temperature in a nitrogen stream. Next, nitrogen gas containing 2% by volume of oxygen was flown at a flow rate of 39 Nl / hour, the temperature was raised to 300 ° C. and maintained at this temperature for 4 hours, and then cooled to room temperature in a nitrogen stream.

Next, while flowing hydrogen gas at a flow rate of 39 Nl / hour, the temperature was raised to 350 ° C. at a rate of 50 ° C./hour, held at this temperature for 4 hours, and then released to room temperature in a nitrogen stream. Chilled Then, nitrogen containing 2% by volume of oxygen is added to the flow rate of 39 Nl.
While circulating at a flow rate of / hour, the temperature was raised to 300 ° C., the temperature was maintained for 15 hours, and then the temperature was cooled to room temperature in a nitrogen stream. Next, while flowing hydrogen gas at a flow rate of 39 Nl / hour, the temperature was raised to 350 ° C at a rate of 50 ° C / hour, and the temperature was raised to 4 ° C.
After holding for a period of time, it was cooled to room temperature in a nitrogen stream. The supported catalyst prepared by carrying out the activation treatment in which the above oxidation and reduction were repeated contained 4.7% by weight of palladium and 0.87% by weight of tellurium.

Next, 4 g of this catalyst was filled in a stainless reaction tube having an inner diameter of 12 mm (effective area 0.848 cm ² ) and 0.12-mol / hr of 1,3-butadiene and 2.5 mol / hr of acetic acid in a liquid phase. ,
Further, 96.4 Nl / hour of nitrogen containing 6% by volume of oxygen was supplied in a gas phase, and the reaction was continuously performed at a reaction pressure of 60 kg / cm ² and a reaction temperature of 80 ° C. for 3800 hours. After the start of the reaction, analyze the product solution after a lapse of a predetermined time, determine the amount of diacetoxybutene produced per hour for 1 g of catalyst, calculate the reaction rate constant (k), and determine the deactivation rate of the catalyst activity. It was Table 1 shows the results.

Comparative Example 3 As a catalyst carrier, crushed coconut husk charcoal having an A ratio of 24% (size 4 to 6 mesh, pore volume 0.35 cc / g, average pore radius 180 nm, carrier specific surface area 1020 m ² / g) Diacetoxybutene was produced in the same manner as in Comparative Example 2 except that The results are shown in Table 1.

[0034]

[Table 1]

The indications in Table 1 are as follows. Reaction time
(t) indicates the time after the start of the reaction, and the reaction rate constant at this time is k. The initial activity represents a reaction rate constant measured 10 hours after the start of the reaction, and is defined as k ₀ . The deactivation rate (%) is a value calculated by the formula [(k ₀ −k) / k ₀ ] × 100. The deactivation rate is calculated by the formula [1- (k / k ₀ )] / lo
It is a value based on g (t / 10). The specific surface area of the carrier (m ² / g) is
It was calculated from the amount of nitrogen adsorbed at the liquid nitrogen temperature by the BET method. The carrier pore volume (cc / g) is the total pore volume in which the pore radius measured using a mercury porosimeter is in the range of 1.8 nm to 10,000 nm. The carrier average pore radius (nm) is the value at which the value obtained by integrating the pore volumes at each pore radius is 1/2 of the total pore volume in the pore radius range of 1.8 nm to 10,000 nm. Pore radius.

Example 3 The catalyst after reacting for 8600 hours in Example 2 was taken out of the reactor, washed with toluene using a Soxhlet extractor for 8 hours, and dried under reduced pressure in a vacuum dryer at 150 ° C. for 6 hours. did. The weight (w) of this catalyst was measured, and the high boiling point adhesion rate (% by weight) was determined from the following equation. High boiling rate (wt%) = [(w / w ₀ ) −1] × 100 (W _{0 in the} above formula represents the catalyst weight before the reaction.) Next, the amount of nitrogen adsorbed at the liquid nitrogen temperature by the BET method. The carrier specific surface area (m ² / g) was determined from the above. Further mercury porosimetry
The carrier pore volume (cc / g) was determined by using a tester. Table 2 shows the above results.

Comparative Example 4 The catalyst after the reaction for 3800 hours in Comparative Example 2 was taken out of the reactor, and the high boiling adhesion rate, the specific surface area of the carrier and the pore volume of the carrier were measured by the same method as in Example 3. I asked. Table 2 shows the results.

[0038]

[Table 2]

[0039]

EFFECTS OF THE INVENTION By using a solid carrier having a special structure as a carrier for a catalyst containing palladium and tellurium as active ingredients, it is possible to obtain an acyloxylation catalyst having a high activity and a very small decrease in activity over time. Furthermore, a method for industrially advantageous acyloxylation of a conjugated diene compound was established by using the catalyst.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C07C 67/05 9546-4H // C07B 61/00 300 (72) Inventor Youji Iwasaka Yokkaichi, Mie Prefecture Tohomachi No. 1 Mitsubishi Chemical Co., Ltd. Yokkaichi Plant

Claims (10)

[Claims] 1. A method for producing an unsaturated glycol diester by reacting a conjugated diene with a carboxylic acid and molecular oxygen in the presence of a solid catalyst supporting palladium and tellurium as active ingredients, wherein the carrier for the solid catalyst is a carrier. As a solid carrier, the volume occupied by pores having a pore radius of 5 to 50 nm is 80% or more of the total pore volume having a pore radius of 1.8 to 10,000 nm. A method for producing an unsaturated glycol diester. 2. The method according to claim 1, wherein the amount of tellurium supported on the solid catalyst is 0.15 to 0.5 gram atom per 1 gram atom of palladium. 3. The conjugated diene is butadiene, isoprene,
3. The method according to claim 1 or 2, wherein the method is selected from alkyl-substituted butadiene. 4. The solid catalyst carrier has a pore radius of 5 to 50 n.
The volume occupied by pores in the range of m is 1.8 to 10,
The production method according to any one of claims 1 to 3, which is 90% or more of the total pore volume in the range of 000 nm. 5. The method according to claim 1, wherein the carboxylic acid is acetic acid, propionic acid or butyric acid. 6. The method according to claim 1, wherein the reaction is carried out at a reaction temperature of 20 to 150 ° C. 7. The production method according to claim 1, wherein the reaction is performed under a reaction pressure of 5 to 100 kg / cm ² . 8. The production method according to claim 1, wherein the solid support is selected from silica, alumina, titania, zeolite, and silica-alumina. 9. The method according to claim 1, wherein the solid support has a specific surface area of less than 200 m ² / g. 10. A solid support in which palladium having a volume of pores having a radius of 5 to 50 nm occupies 80% or more of the total volume of pores having a radius of 1.8 to 10,000 nm. A catalyst for acylation of a conjugated diene, which comprises tellurium as an active ingredient.