JPS6055050B2 - Method for producing diacetoxybutene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diacetoxybutene from butadiene.

More specifically, the present invention relates to a method for producing diacetoxybutene from acetic acid, molecular acetic acid, and butadiene in a liquid phase using a solid catalyst.

It is known that 1,4-butanediol, whose demand has been increasing in recent years as an organic solvent and a raw material for synthetic resins, is synthesized by various methods. As a currently industrialized method, there is a known method of producing it using acetylene and formalin as raw materials by the Retzpe reaction, but this method has the drawbacks that the reaction process is complicated and the cost of raw materials is high.

Another known method is to use butadiene as an ophthalmologist to halogenate it, synthesize dihalogenated butene, hydrolyze it to produce butene diol, and then perform a hydrogenation reaction to synthesize butane diol. Like the Retuppe method, it has the drawbacks of a complicated process and high raw material costs. Currently, the most industrially important method is
In this method, butadiene is oxidized in one step in the presence of acetic acid to synthesize diacetoxybutene, which is then hydrolyzed with water to synthesize butanediol.

One-step synthesis methods for diacetoxybutene include gas phase method,
A liquid phase method has been proposed, but in the case of a gas phase method, there are problems such as the production of a large amount of by-products and the lifespan of the catalyst.
Among the liquid phase methods for synthesizing diacetoxybutene, there are cases in which the catalyst is uniformly dissolved in the reaction liquid and cases in which a heterogeneous catalyst is used. The former is industrially disadvantageous because the catalyst separation and recovery steps become extremely complicated, whereas the latter is more advantageous. Various methods have been proposed for the latter method using heterogeneous catalysts, but they have drawbacks such as low reaction rate, poor reaction selectivity, expensive catalysts, and short catalyst lifetimes. be. As a method of utilizing the latter heterogeneous catalyst, JP-A-49-11812 discloses a supported catalyst containing palladium and at least one of antimony, bismuth, selenium, and tellurium.

It has been shown that activated carbon treated with nitric acid is used as a catalyst carrier in this catalyst, and it has been reported that the activity deteriorates considerably in the absence of nitric acid treatment. Also, JP-A-50
In specification No. 140406, platinum and at least an element of group 5 or 6 of the periodic system (phosphorus, arsenic, blue lead, antimony, selenium, or tellurium as elements of group 5 and 6)
A catalyst containing . However, these catalysts have drawbacks such as relatively poor reaction rates and selectivities and high catalyst costs.

As a result of intensive studies to overcome the drawbacks of these conventional methods, the present inventors discovered that acetic acid, a molecular oxygen-containing gas, and butadiene were combined using a solid catalyst containing at least one of palladium, platinum, and rhodium and sulfur. After discovering that diacetoxybutene can be obtained in high yield by reacting with and in a liquid phase, he applied for a patent.

However, in this method, some by-products were produced in addition to the target product, so it was desired to develop a catalyst with even higher selectivity and activity.

As a result of various studies to overcome these drawbacks, the present inventors have found that by adding component X to these catalyst systems, the catalytic performance is dramatically improved, and that the previously reported catalysts, For example, compared to Pd-Te and Pd-S sowing, activated carbon is treated with nitric acid. High activity even without
This was accompanied by obtaining high selectivity results.

In addition, these binary catalysts containing Pd and one metal component do not show much activity, such as Pd-Sb (butadiene reaction rate 32.5%, diacetoxybutene ζ yield 12%).
, see Comparative Example 4 for details), a ternary catalyst containing sulfur, which is a feature of the present invention, such as Pd-S-Sb (butadiene reaction rate 95%, diacetoxybutene yield 90%, details see Example 3) The present invention was developed based on the knowledge that the catalyst showed excellent catalytic performance.

That is, the present invention is a method for producing diacetoxybutene by reacting acetic acid, molecular oxygen, and butadiene in a liquid phase using a solid catalyst containing a metal mainly consisting of palladium, sulfur, and at least one of the X components. It is.

The present invention will be explained in more detail below.

Alumina,
silica alumina, pumice, silica gel, synthetic zeolite,
Examples include activated carbon, among which silica gel and activated carbon are particularly excellent.

In particular, since activated carbon prepared from coal contains a small amount of sulfur, an active catalyst can be prepared by adding the noble metal and the X component without adding new sulfur. As a catalyst component, palladium alone or
Platinum and/or rhodium may coexist with palladium.

The amount of each coexisting is 10 mol or less per 1 mol of palladium. Palladium, platinum, rhodium and sulfur raw materials include, for example, palladium chloride, palladium nitrate, palladium acetate, chloroplatinic acid, platinum chloride (■), platinum chloride (■
), inorganic sulfur such as potassium chloroplatinate, rhodium chloride, rhodium nitrate, rhodium sulfate, elemental sulfur, thiourea, ammonium thiocyanate, sulfur monochloride, sulfur dichloride, phenyl sulfide, β-thiodiglycol, dimethyl disulfide Examples include organic sulfur such as sulfur, and inorganic and organic sulfur present in activated carbon. Furthermore, the X components used in the present invention, that is, periodic table 1, 4, 5, 6,
7,8, L as an element of the lanthanide and actinide groups
i, Na, K, Rb, Cs, Cu, Ag, Au, Sn,
Pb, Ti, Zr, P,, As, Sb, Bi, V, Nb
, Ta, Se, Te, Cr, MO, W, Mn, Re, F
Examples include e, CO, Ni, Ru, Ir, La, Ce, Th, and u.

Compounds of these elements are not particularly limited, but can be used in the form of oxides, hydroxides, chlorides, nitrates, sulfates, carboxylates, and the like.

The amount of palladium added to the carrier is 0.1 to 30% by weight.
is preferable, and most preferably 0.2 to 2% by heel weight.

If the amount added is less than 0.1% by weight, the reaction rate will be extremely slow, which will be economically disadvantageous. Furthermore, if the amount added is 3% or more, the amount of by-products produced tends to be large, which is undesirable. The amount of sulfur added to the carrier is 0.05
~10% by weight is preferred, most preferably 0.1~5%.
Call volume%.

If the amount of sulfur added is less than 0.05% by weight, the reaction rate will be extremely slow, which will be economically disadvantageous. Furthermore, if the amount added is 10% by weight or more, the amount of by-products increases, which is not preferable. The amount of component X added to the carrier is preferably 0.05 to 5% by weight, most preferably 0.1 to 3% by weight.

When the amount of the X component added is 0.05% by weight or less, the effect of the addition of the X component cannot be seen sufficiently. Moreover, if the amount added is 5% or more, the amount of by-products increases, which is not preferable. A method for preparing a catalyst is, for example, by dissolving sulfur or a sulfur compound in a suitable solvent, putting a carrier therein and slowly evaporating to dryness to first support sulfur on the carrier, and then adding a solution of the noble metal and component X. Then, it is evaporated to dryness in the same manner as before to support the noble metal and the X component.

On the contrary, by first supporting the precious metal and the X component,
Sulfur can also be added and supported later.

Further, when the sulfur compound, the noble metal compound, and the X component are dissolved at the same time, it is also possible to support them all at once.
Further, when sulfur is present in the carrier, the noble metal and the X component can be supported without adding a new sulfur compound.

After supporting sulfur, precious metals and X component, 150
It can be dried at ~300 DEG C. and then reduced by conventional methods, ie in a gas stream such as hydrogen or methanol saturated steam, or with a reducing agent such as hydrazine, NaBH, or formic acid.

The catalyst used in the present invention can be used in various shapes depending on the type of reactor.

For example, when using a slurry method, fine powder is preferable;
In the case of a fixed bed type, granular forms are preferred. The amount of catalyst used is preferably 0.2 to 3% by weight, most preferably 0.5 to 2% by weight based on the total amount of liquid. Catalyst amount is 0. If the amount is less than %, the reaction rate becomes very slow, which is industrially disadvantageous. In addition, when the amount of catalyst is 3% or more, there are many by-products. 3, which is not desirable.

The amount of acetic acid used is preferably 2 to 100 molar ratios, most preferably 5 to 50 molar times, relative to the raw material butadiene.

In this case, if the molar ratio is less than 2, the reaction rate becomes slow and at the same time the selectivity decreases significantly. Also, the molar ratio is 1
If the amount is 00 moles or more, separation of the target product after the reaction becomes uneconomical, which is industrially disadvantageous. The molecular oxygen used in the present invention may be pure oxygen or oxygen diluted with an inert gas, such as air.

The amount of oxygen used should be stoichiometric, that is, the amount of oxygen should be at least 0.5 times the mole of reacted butadiene. The oxygen concentration is not particularly limited, but may be within a range that does not fall within the explosive range in the gas phase.

The reaction temperature is preferably 30-200°C, most preferably 50-150°C. If the reaction temperature is lower than 30° C., the reaction rate becomes very slow, making it uneconomical. In addition, if the reaction temperature is higher than 200℃, 1,4
-Diacetoxy-cis-2-butene selectivity becomes very poor, which is not preferable. The reaction pressure is preferably normal pressure to 20 leakage pressure, most preferably normal pressure to 10 leakage pressure.

If the pressure is 20 leak pressure or more, it is unfavorable in terms of safety and economical efficiency of the device. As described above, the method of the present invention allows diacetoxybutene to be selectively obtained by reacting butadiene, acetic acid, and a molecular oxygen-containing gas in the presence of a catalyst, which is very useful industrially. It's advantageous. The present invention will be explained below with reference to Examples, but the present invention is limited by these Examples.
Ri5~! L) It's not a thing. In addition, the conversion rate of butadiene in the examples is the MOI% of reacted butadiene with respect to the raw material butadiene, and the yield of diacetoxybutenes is the MOI% of the produced diacetoxybutenes with respect to the raw material butadiene.
1% and selectivity to diacetoxybutenes indicate the yield of diacetoxybutenes relative to the conversion of butadiene, respectively.

Example 1 0.67g (5rr1m01) of sulfur chloride was dissolved in 20ml of carbon disulfide, and 5.0g of activated carbon containing 0.95% by weight of sulfur prepared from crystalline carbon was added thereto and soaked for 1 hour. After soaking, it was gradually evaporated to dryness on a hot water bath.

Next, this catalyst was mixed with 0.44 g of palladium chloride (2.5 rn
The mixture was poured into 20 ml of a monohydrochloric acid solution containing 0.075 g (0.2 rnmol) of lead acetate and slowly evaporated to dryness on a hot water bath.

The catalyst was then packed in a calcining tube and dried at 150°C for 3 hours in a nitrogen stream, then reduced at 200°C for 2 hours with a methanol/nitrogen mixture saturated at room temperature, and further reduced at 400°C for an hour. Ta.

0.1 g of this catalyst was placed in a glass sealed tube with an internal volume of 25 m1, and 4.2 g (70 n1 m01) of acetic acid was placed on top of it. The glass sealed tube was cooled in a dry ice methanol bath at -70°C, and the butadiene 0. .108g (2rr) M
After introducing oxygen, the gas phase of the glass sealed tube was replaced with pure oxygen, and then the tube was sealed with a burner. This reaction tube was heated to 85°C.
The mixture was allowed to react for 2 hours while rotating in a hot water bath. After generation, gas chromatography analysis showed that the conversion rate of butadiene was 85.0%, and the yield of diacetoxybutenes was 77.0%.
%, and the selectivity to diacetoxybutenes was 90.6%.

Example 2 0.67 g of sulfur chloride (5n1m0I) was dissolved in 20 ml of carbon disulfide, and 5.0 g of activated carbon containing 0.95% by weight of sulfur prepared from crystalline coal was added thereto and immersed for 1 hour. It was gradually evaporated to dryness on a water bath.

Next, this catalyst was mixed with 0.44 g of palladium chloride (2.5 n1
The mixture was poured into 20 ml of dihydrochloric acid solution containing m01) and gradually evaporated to dryness on a hot water bath.

After that, 0.044 g (0.2 n1 m
After being immersed in 20 ml of an ethanol solution containing 0.0 ml, the sample was gradually evaporated to dryness on a hot water bath.

Thereafter, the reaction was carried out in the same manner as in Example 1, and the conversion of butadiene was 90.0%, the yield of diacetoxybutenes was 81.5%, and the selectivity to diacetoxybutenes was 90.5%. It was hot.

Examples 3 to 10 Example 1 except that the following metal salts were used instead of lead acetate.
The catalyst was prepared and the reaction was carried out in exactly the same manner.

The results were as shown in the table below. However, in Example 3, 0.044 g of antimony trichloride (a). 2mm01), Example 4
is tellurium dioxide 0.032g (4). In Example 5, 0.044 g of ruthenium trichloride (0.2 mm
1), Example 6 is uranium nitrate 0.10g (0.2mm0
1), Example 7 uses 0.084 g (0.2 n1 m
01), Example 8 is manganese chloride 0.04g (0.2n
In Example 9, 0.088 g of cerous nitrate (
0.2mm01), Example 10 is niobium pentachloride 0.05
4g (0.2mm01) was used. Example 11 0.67 g (5n1 m01) of sulfur chloride was dissolved in 20 ml of acetone, and 5.0 g of activated carbon containing 0.95% by weight of sulfur prepared from Sekirei charcoal was added thereto, immersed for 1 hour, and then placed on a hot water bath. It was gradually evaporated to dryness.

Next, this catalyst was placed in 20 cc of water and allowed to stand for about 3 minutes to hydrolyze the adsorbed sulfur chloride, followed by evaporation to dryness on a hot water bath. Next, 0.072 g of tantalum pentachloride (
It was poured into an ethyl alcohol solution 20a1 containing 0.2 mm of water and gradually evaporated to dryness on a hot water bath.

Thereafter, 0.44 g of palladium chloride (0.
The mixture was poured into 20 ml of dihydrochloric acid solution containing 25 nm and 1 mol of water, and gradually evaporated to dryness on a hot water bath.

Thereafter, the reaction was carried out in the same manner as in Example 1, and the conversion of butadiene was 85.5%, the yield of diacetoxybutenes was 79.9%, and the selectivity to diacetoxybutenes was 93.5%. It was hot.

Comparative Example 1 A catalyst was prepared and the reaction was carried out in the same manner as in Example 1 except that no acetate was added. The conversion of butadiene was 60.0% and the yield of diacetoxybutenes was 52.8.
%, and the selectivity to diacetoxybutenes was 88.0%.

Comparative Example 2 0.44g of palladium chloride (2.5rnm
0I) and tellurium dioxide 0.063g (0.375r
Pour it into 20T1L1 of hydrochloric acid solution containing nm0 and approx.
After soaking for an hour, it was gradually evaporated to dryness on a hot water bath.

After that, the treatment was carried out in the same manner as in Example 1, and the reaction was carried out under the same conditions. The conversion of butadiene was 30.7%, the yield of diacetoxybutenes was 26.1%, and the selectivity to diacetoxybutene was 85.0. It was %. Comparative Example 3 The same method as in Comparative Example 2 was used except that coconut shell charcoal that had been heated and refluxed for 6 hours with a heel weight % aqueous solution of nitric acid was used. Yield of acetoxybutenes: 45.5%, selectivity to diacetoxybutenes: 87
．． It was 5%.

Comparative Example 4 Antimony trichloride 0.0 instead of tellurium dioxide
85g) (0.375n1m0) was carried out in the same manner as in Comparative Example 2, and the conversion of butadiene was 2% and 5%, the yield of diacetoxybutene was 12.0%, and the selectivity to diacetoxybutene was It was 42.1%.

Claims (1)

[Claims] 1 General formula Pd_1Pt_0_~_1_0Rh_0_~_1_0S
_0_・_0_5_～_1_0X_0_. ＿0＿5＿～
_1_0 (X is Pd, Sn, Ru, U, Au,
Butadiene, acetic acid, and an oxygen-containing gas are reacted in a liquid phase in the presence of a solid catalyst containing at least one component selected from Mn, Ce, Nb, and Ta (hereinafter referred to as component X). Characteristic method for producing diacetoxybutene. 2 Reaction temperature is 30-200℃, preferably 50-150℃
The method according to claim 1, wherein the temperature is .degree. 3 Reaction pressure is normal pressure to 200 atm, preferably normal pressure to 10
2. The method according to claim 1, wherein the pressure is atmospheric pressure. 4. The method according to claim 1, wherein the reaction is carried out in a molar ratio of acetic acid and butadiene of 2 to 100:1, preferably 5 to 50:1.