JPS59176233A - Production of diacetoxybutene - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful for the synthesis of butanediol, etc., in high yield and selectivity, in one step, by reacting butadiene with acetic acid and an O2-containing gas in a liquid phase in the presence of a solid catalyst such as Pd-S-Sb catalyst having excellent catalyst performance. CONSTITUTION:The objective compound is prepared by reacting butadiene with acetic acid and an O2-contaning gas at 20-200 deg.C under normal pressure -200atm in the presence of a solid catalyst having the composition of formula I , formula II or formula III (X is one or more elements selected from the I , IV, V, VI, VII and VIII groups, lanthanide group and actinide group of the periodic table), e.g. Pd-S-Te, etc. The catalyst can be prepared e.g. by dissolving S or an S compound in a solvent, adding a carrier to the solution, evaporating the mixture slowly to dryness to carry the S on the carrier, adding a solution of a noble metal and the component X, evaporating the product slowly to dryness to support the noble metal and the component X on the carrier, drying at 150-300 deg.C, and reducing in the stream of H2, etc.

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 oxygen, 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 raw material for synthetic resins, is synthesized by various methods.

As a currently industrialized method, there is known a method of producing it using acetylene and formalin as raw materials through the Reppe reaction, but this method has the drawbacks of complicated reaction steps and high raw material costs. Also, using butadiene as a raw material, it is halogenated to synthesize dihalokenated butene, which is hydrolyzed to produce butynediol, and further (
A method of synthesizing butanediol by carrying out this hydrogenation reaction is also known, but this method, like the Reppe method, has the drawbacks of complicated steps and high raw material costs.

The method that is currently considered most important industrially is the one-step oxidation of butadiene in the presence of acetic acid to synthesize diacetoxybutene, which is then hydrolyzed with water to synthesize butanediol.

A gas phase method and a liquid phase method have been proposed as one-step synthesis methods for diacetoxybutene, but in the case of the gas phase method, there are problems such as production of many by-products and catalyst life. Among the methods for synthesizing diacetoxybutene by the enemy phase method, there are cases in which the catalyst is uniformly dissolved in the reaction solution, 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 using the latter heterogeneous catalyst system have been proposed, but they have drawbacks such as low reaction rate, poor reaction selectivity, expensive catalysts, and short catalyst lifetimes. be.

As a method using the latter heterogeneous catalyst, JP-A-49
-11812 specifies palladium, antimony,
A supported catalyst containing at least one of bismuth, selenium and tellurium is shown. 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 is considerably reduced in the absence of nitric acid treatment. Furthermore, in JP-A-50-140406, platinum and at least periodic group 5 or 6
Catalysts containing Group 5 and Group 6 elements (phosphorus, arsenic, pyrochloride, antimony, selenium or tellurium as elements of Groups 5 and 6) are indicated.

However, these catalysts have drawbacks such as relatively poor reactivity and selectivity, and the equivalence of the catalysts.

In order to overcome these drawbacks of the conventional methods, the present inventors conducted intensive studies and found that using a solid catalyst containing at least -:heavy of palladium, platinum, and rhodium and sulfur, -C acetic acid and molecular I learned that diacetoxybutene can be obtained in high yield by reacting oxygen-containing gas and butadiene in a liquid phase.
f L.

However, in this method, some by-products are produced in addition to the target product, so it is 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, Pd-8b, etc., activated carbon can be highly activated without being treated with nitric acid.
It was found that high selectivity results were obtained.

In addition, these catalysts do not show much activity in binary systems containing Pd and one metal component, such as Pd-5b (butadiene reaction rate 32.5%, diacetoxybutene yield 12%).
%, see Comparative Example 4 for details), but using a ternary catalyst containing sulfur, which is a feature of the present invention, for example, Pd-5-5b (butadiene reaction rate 95%, diacetoxybutene yield 90%, details in implementation) The present invention was achieved by finding that the catalyst (see Example 8) exhibits excellent catalytic performance.

That is, the present invention involves reacting acetic acid, molecular oxygen, and butadiene in a liquid phase using a solid catalyst containing a small amount of palladium, platinum, and rhodium, sulfur, and at least one of the X components to form diacetoxybutene. This is a method of manufacturing.

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, activated carbon prepared from coal contains some sulfur, so it is not necessary to add new sulfur (an active catalyst is prepared by adding the noble metal and the X component.

Palladium, platinum, rhodium and sulfur raw materials used as catalyst components are, for example, palladium chloride, palladium nitrate, palladium acetate, chloroplatinic acid, platinum chloride (river,
Platinum chloride (IVI, potassium chloroplatinate, rhodium chloride, rhodium nitrate, rhodium sulfate, elemental sulfur, thiourea, ammonium thiocyanate, inorganic sulfur such as -sulfur chloride, sulfur dichloride, phenyl sulfide, β-thiodiglycol) , organic sulfur such as dimethyl disulfide, and inorganic and organic sulfur present in activated carbon.

Furthermore, the X component used in the present invention, that is, periodic table 1.
4.5.6.7.8. Sakaki, Na, Rb, Cs, Cu as lanthanide and acti Lλ nide group elements
,Ag.

Au, Sn, Pb, Ti, Zr, P, As
, Sb, Bi, V, Nb, 'ra, Se, T
e.

Cr, Mo, W, Mn, Re, Fe, C:o
, Ni, Ru, lr, La, Ce, Th
, U, etc.

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 at least one noble metal selected from palladium, platinum and rhodium added to the carrier is preferably 0.1 to 30% by weight, most preferably 0.2 to 20% by weight.

If the amount added is less than 0.1% by weight or 16%, the reaction rate will be extremely slow and this will be economically disadvantageous. Furthermore, if the amount added is 3% or more, there is an undesirable tendency to produce a large amount of by-products.

The amount of sulfur added to the carrier is 0.05 to 100% by weight.
is preferable, and most preferably 0.1 to 5.0%.

When the amount of sulfur added is less than 0.05% by weight (this causes the reaction rate to be extremely slow, which is economically disadvantageous), and when the amount of sulfur added is more than 100% by weight, by-products are produced. Too many, which is not desirable.

The amount of component X added to the carrier is preferably 0.05 to 30% by weight, most preferably 0.1 to 30% by weight.

If the amount of the X component added is 0.05 F or less, the effect of the addition of the X component will not be sufficient. Also, the amount added is 50
If it exceeds % by weight, the amount of by-products increases, which is not preferable.

The method for preparing the catalyst is, for example, by dissolving sulfur or a sulfur compound in a suitable solvent, placing a carrier therein and slowly evaporating it to dryness to first support the sulfur on the carrier, and then adding a solution of the elbow 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, first the precious metal and the X component are supported,
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
Dry at ~300°C and then reduce in a conventional method, i.e., in a gas stream such as hydrogen or methanol saturated steam, in an oven.
This can be reduced with a reducing agent such as hydrazine, NaBH4, 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-only method, fine powder is preferable.
In the case of a fixed bed type, granular forms are preferred.

The slide used by 4M1 is the total amount (0.2~3゜ city i)
1t% is preferred, most preferably Q, 5-2°;
I:%. If the amount of catalyst) is less than 0.2% by weight or 11%, the reaction rate becomes extremely slow, which is industrially disadvantageous. Also, if the catalytic amount is 30% by weight or more of 'F+, it is not preferable because by-products will increase.

The amount of acetic acid used is preferably 2 to 100 times the mole of butadiene as a starting material, and the amount of acetic acid used is preferably 5 to 50 times the amount by mole. When this molar ratio is 2 or more, the reaction rate becomes slow and the selectivity is likely to decrease by 1. Furthermore, if the molar ratio is 100 times or more, it becomes uneconomical to separate the target product after the reaction, which is disadvantageous for industrial applications.

The P-type 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 based on chemical theory [ie, the amount of oxygen should be at least 0.5 mole relative to the 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. Also, if the reaction temperature is higher than 200°C, 1.
This is not preferred because the selectivity of 4-diacetoxy-cis-2-butene becomes unreasonably low.

The reaction pressure is preferably from normal pressure to 200 atm, most preferably from normal pressure to 100 atm. If the pressure is 200 atmospheres or more, it is unfavorable in terms of safety and economical efficiency of the apparatus.

As stated 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 advantageous industrially. It is. The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, the conversion rate of butadiene in the examples is based on the raw material butadiene (
The mo of reacted butadiene is 1%, the yield of diacetoxybutenes is mo1% of the generated diacetoxybutenes relative to the raw material butadiene, and the selectivity to diacetoxybutenes is the yield of diacetoxybutenes relative to the butadiene conversion rate. Each is shown below.

Example 1 Sulfur chloride 0.67? (5 mmol) in 20 ml of carbon disulfide, and in this, 5.02 ml of activated carbon containing 0.95% sulfur (prepared from this sweet charcoal) was added.
It was slowly evaporated to dryness on a time-soaked rewarming bath.

This catalyst was then mixed with the salt rHybaradium0.44y(2,5
mmol) and lead acetate 0.075 ';' (Q, 2
mmol) in 20 ml of 5N-hydrochloric acid solution containing
It was gradually evaporated to dryness on a water bath.

Thereafter, this catalyst was packed in a calcining tube, dried at 150°C for 3 hours in a nitrogen stream, saturated at room temperature, reduced at 200°C for 2 hours in a methanol/nitrogen mixture, and further heated to 400°C for 1 hour. Let me give you time back.

0.11 of this catalyst was placed in a glass sealed tube with an internal volume of 25 ml, and acetic acid 4,2r (70 mmol) was placed on top of it, and the glass sealed tube was cooled in a dry ice methanol bath at -70°C. Butadiene 0.108 f (2 dishes o
1), and then the gas phase of the glass sealed tube was replaced with pure oxygen, and then the tube was sealed with a burner.

The reaction tube was allowed to react for 2 hours while rotating in a water bath at 85°C.

The product liquid was analyzed by gas chromatography, and the conversion rate of butadiene was 85.0%, the yield of diacetoxybutenes was 77.0%, and the selectivity to diacetoxybutenes was 90.6.
%Met.

Example 2 20.67 t (5 mmol) of sulfur chloride was added. ml
Dissolved in carbon disulfide, and put activated carbon 5.09 prepared from charcoal and containing 0.95% by weight of sulfur into this and soaked for 1 hour.Afterwards, gradually evaporated to dryness in a hot water bath. I let it happen.

Next, this catalyst was mixed with palladium chloride 0°442 (245me
20 ml of a 5N hydrochloric acid solution containing 100 ml of water was added to the mixture, and the mixture was gradually evaporated to dryness on a hot water bath.

After that, stans chloride WO,044? (0.2mm
After soaking in 20 ml of ethanol solution containing 100 ml of ethanol, the mixture was gradually dried on a hot water bath.

Thereafter, the reaction was carried out in the same manner as in Example 1, and the butadiene conversion rate was 90. c%, the yield of diacetoxybutenes was 81.5%, and the selectivity to diacetoxybutenes was 90.5%.

Example A catalyst was prepared and the reaction was carried out in exactly the same manner as in Example 1, except that the following metal salts were used in place of lead acetate. The results were as shown in the table below.

However, in Example 3, antimony trichloride 0.0441 (0
,2m+nol), Example 4 is tellurium dioxide 0.08
2? (0,2m+no l), Example 5 is ruthenium trichloride 0.044 F (0,2r blood o1), and Example 6 is uranium nitrate 0.10? (0,2m+no
l), Example 7 is chloroauric acid 0.0841 (02m+
no l ), Example 8 had manganese chloride of 0.04!
CO, 2 strokes o1), Example 9 is cerium nitrate 0.0
88 f (0.2 plates o1), and Example 10 used niobium pentachloride 0.054 f (0.2 m+nol).

＼ Example 11 Dissolve 0.671 (5 mmol) of salt r sulfur in 20 ml of acetone, and add 5.0' activated carbon containing 0.95% by weight of sulfur split from clear sweet charcoal. After soaking for 1 hour, the mixture was gradually evaporated to dryness on a hot water bath.

Next E The catalyst was placed in 2 Occ of water and left to stand for about 30 minutes to hydrolyze the adsorbed sulfur chloride, and then evaporated to dryness on a hot water bath.

Next Nico's catalyst is tantalum pentachloride 0.0721 (0.2m
The mixture was poured into 20 ml of an ethyl alcohol solution containing mol) and gradually evaporated to dryness on a hot water bath.

Thereafter, this catalyst was added to 20 ml of a 5N hydrochloric acid solution containing 0.449 (2.5 mmol) of palladium chloride, and gradually evaporated to dryness on a hot water bath.

Thereafter, the reaction was carried out in the same manner as in Example 1. The conversion rate of butadiene was 85.5%, the yield of diacetoxybutenes was 79.9%, and the selection rate for diacetoxybutenes was 93.5%. Met.

Comparative Example 1 A catalyst was prepared and the reaction was carried out in exactly the same manner as in Example 1 except that lead acid was not added. The conversion rate of butadiene was 60.0%, and the yield of diacetoxybutenes was 52%.
8%, and the selectivity to diacetoxybutenes was 88.0%.

Comparative Example 2 Coconut charcoal 51 containing almost no sulfur and not treated with nitric acid was mixed with palladium chloride 0.44? (2.5m
mol) Oyo(j Tellurium dioxide 0.063 Y (0
, 175 mmol) in a 5N-hydrochloric acid solution containing 20 gt
After soaking in the water for about 1 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.
．． 7%, yield of diacetoxybutenes 26.1%.

The selectivity to diacetquin butene was 85.0%.

Comparative Example 3 Coconut charcoal that had been heated and refluxed in a 15t4:% nitric acid aqueous solution for 6 hours was used and the same method as in Comparative Example 2 was performed, except for T. The conversion rate of butadiene was 52.0%, and the The yield of acetoxybutenes was 45.5%, and the selectivity to diacetoxybutenes was 87.5%.

Comparative Example 4 Antimony trichloride 0,0859 instead of tellurium dioxide
(0,375 mtmO1) was used in the same manner as in Comparative Example 2, except for the following: -) The conversion of butadiene was 28.5%, the yield of diacetoxybutene was 12.0%, and the yield of diacetoxybutene was 12.0%. The selectivity rate was 42.1%.

Claims (1)

[Claims] l) - General formula % Formula % (1) (2) () (hereinafter referred to as X component)
A method for producing diacetoxybutene, which comprises reacting butadiene, acetic acid, and oxygen-containing gas in a liquid phase in the presence of a solid catalyst having the composition shown below. 2) Reaction i'f+u degree is 30-200℃, preferably 50
15. The method of claim 1, wherein the temperature is 150<0>C. 3) Reaction pressure is normal pressure to 200 atm, preferably normal pressure to 10 atm.
2. The method according to claim 1, wherein the pressure is 0 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. 5) The amount of at least one of palladium, platinum and rhodium supported on the carrier is 0.001 to 30% by weight, preferably 0.2 to 20% by weight, and sulfur is 0.05 to 100% by weight.
Weight wing, preferably 0.1 to 50% by weight, X component is 0,
2. A method according to claim 1, wherein the weight is between 0.05 and 50% by weight, preferably between 0.1 and 30% by weight.