JPH0725795A - Vapor phase one-step production of 1,4-butanediol and gamma-butyrolactone - Google Patents

Abstract

PURPOSE: To provide a process for simultaneous preparation of 1,4-butanediol and γ-butylolactone in one step by using a highly safe catalyst.

CONSTITUTION: The gas-phase one-step process for preparation of 1,4-butanediol and γ-butylolactone is characterized by hydrogenating cracking reaction in gas-phase in one step starting from dialkyl maleate, dialkyl succinate or a mixture thereof in the presence of a copper or a copper compound as a catalyst in an atmosphere containing hydrogen at a temperature of 160 to 250°C and under a pressure of 20 to 70 kg/cm² adjusting the supplying rate of the starting material to be 0.05 to 3 hr^-1 and the mole ratio of the starting ratio/hydrogen to be 20 to 500.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a gas-phase one-step process for producing 1,4-butanediol and γ-butyrolactone. More specifically, it relates to a gas-phase one-step production method capable of simultaneously producing 1,4-butanediol and γ-butyrolactone, which can be suitably used for, for example, engineering plastics.

[0002]

2. Description of the Related Art 1,4-Butanediol is used as a monomer such as polybutylene terephthalate which is used as an engineering plastic.

Since engineering plastics using 1,4-butanediol as a monomer have excellent chemical resistance and heat resistance, they are widely used in electronic parts, printed circuits, automobile parts and the like. ing.

Since 1,4-butanediol also reacts with diisocyanate to form thermoplastic polyurethane or elastic polyurethane, it is used as a basic raw material for these polyurethanes.

In addition to these, 1,4-butanediol is also used as an intermediate for solvents such as γ-butyrolactone and tetrahydrofuran, and γ-butyrolactone is purified by dehydrogenation of the solvent to give tetrahydrofuran. It is used for purification.

Conventionally, as a method for producing 1,4-butanediol, a Reppe method using acetylene as a main raw material has been known. According to such a method, acetylene and formaldehyde are mixed with magnesium silicate or silicon dioxide. At a pressure of 15 psia and 66
1,4-Butanediol was produced by reacting at ˜90 ° C. to produce bitinediol and hydrogenating in the presence of nickel oxide, copper, and manganese catalyst using aluminum oxide as a carrier.

However, in the above method, since acetylene easily forms a polymer using copper as a catalyst, a reaction inhibitor must be added during the reaction, and the treatment of acetylene is difficult and the cost is high. There are problems such as the above, and methods for solving these problems are being studied.

Heretofore, as a new method, a method using butadiene, allyl alcohol or maleic anhydride as a raw material has been known.

For example, JP-A-53-68708 and JP-A-SHO
No. 52-133912 discloses that butadiene is used as a raw material and palladium-tellurium / activated carbon is used as a catalyst during a liquid phase or gas phase reaction to proceed an acetylene oxidation reaction with acetic acid at 80 to 106 ° C. at 20 to 60 atm. After that, a method of producing 1,4-butanediol through hydrogenation, hydrolysis, etc. is described. However, since acetic acid, which is highly corrosive, is used as a raw material in this method, there is a problem that the material of the reaction vessel must be made resistant to corrosion and the equipment cost increases.

Further, European Patent Application Publication No. 151822 (1985), European Patent Application No. 0018163 (1980),
JP-A-59-20238, JP-A-54-84508, JP-A-SHO
JP-A-53-68709, JP-A-52-78809, and the like, a reaction of adding carbon monoxide and hydrogen by using an organometallic rhodium as a catalyst after using epoxypropane as a raw material and isomerizing to make allyl alcohol. A method for further decomposing the product into 1,4-butanediol and isobutylene. However, such a method has a problem in that isobutylene must be refluxed during the process to reproduce allyl alcohol.

US Pat. No. 4,001,282 describes a method for producing .gamma.-butyrolactone by directly hydrogenating maleic anhydride, maleic acid or the like as a raw material. However, in such a method, since a metal such as copper-zinc is used as a catalyst, there is a problem that by-products such as butanedioic acid, propionic acid, butyric acid, and butyl alcohol are generated.

In addition to these, JP-A-63-313760,
JP-A-2-223627, JP-A-2-235880, JP-A
JP-A-2-233630 and JP-A-2-25434 disclose that maleic anhydride or butanedioic acid and γ-butyrolactone are directly hydrogenated at the same time to produce 1,4-butanediol and tetrahydrofuran. However, since copper-chromium or copper-zinc is used as a catalyst, not only by-products such as propionic acid are generated in the production process, but also the selectivity for 1,4-butanediol is high. There was a problem of badness.

Further, European Patent Application Publication No. 143,634 (1985) and International Publication No. 88/00937 (198)
8) and the like, maleic anhydride and an alcohol having 1 to 3 carbon atoms are subjected to an esterification reaction, and then copper-catalyzed
It is described that 1,4-butanediol is produced through a two-step or two-step or more hydrogenation reaction in the gas phase using chromium. Of these, European Patent Application Publication No.
Taking the method described in Japanese Patent No. 143,634 as an example, in this method, diethyl maleate is used as a raw material, 175 ° C in the presence of copper-chromium as a catalyst, a pressure of 42 bar, and a liquid supply rate LHSV: 0.34 hr. ^{-1 under} the conditions of hydrogen and maleic acid diester were reacted at a molar ratio of 359: 1, as a result of the reaction, diethyl succinate 95.5 mol% was produced, the diethyl succinate with a copper-chromium catalyst at 179 ℃, Liquid supply rate LHSV: Reacted under the condition of 0.16 to 0.53 hr ^-1 , 1,4
-Butanediol and γ-butyrolactone had formed. The polymerization rate in such a reaction is between 86.6 and 98.7 mol%, and the selectivity of 1,4-butanediol is 74.0-
80.1 mol%, γ-butyrolactone selectivity is 16.1-2
It was 1.4 mol%. According to such a method, not only is the use ratio of hydrogen high and the use of highly toxic metallic chromium as a catalyst, but also a two-step reaction results in high equipment cost and inconvenient operation. was there.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, in which 1,4-butanediol and γ-butyrolactone are produced by a one-step reaction using a highly safe catalyst. It is intended to provide a method that can be manufactured at the same time.

[0015]

That is, the present invention uses a maleic acid dialkyl ester, a succinic acid dialkyl ester or a mixture thereof as a raw material, and in the presence of copper or a copper compound as a catalyst, at a temperature of 160 to 250 ° C. and atmospheric pressure.
In a hydrogen-containing atmosphere having ²⁰ to 70 kg / cm ² , the feed rate of the raw material is adjusted to 0.05 to 3 hr ⁻¹ , and the molar ratio of the raw material and hydrogen (raw material / hydrogen) is adjusted to 20 to 500. The present invention relates to a gas-phase one-step production method of 1,4-butanediol and γ-butyrolactone, which comprises performing a gas-phase one-step hydrogenation cracking reaction.

[0016]

OPERATION AND EXAMPLES As described above, the gas-phase one-step production method of 1,4-butanediol and γ-butyrolactone according to the present invention uses a maleic acid dialkyl ester, a succinic acid dialkyl ester or a mixture thereof as a raw material and a catalyst. In the presence of copper or a copper compound as a temperature of 160-250
In a hydrogen-containing atmosphere having a temperature of 20 ° C. and atmospheric pressure of 20 to 70 kg / cm ² , the feed rate of the raw material is 0.05 to 3 hr ⁻¹ , and the molar ratio of the raw material and hydrogen (raw material / hydrogen) is 20 to 400. It is characterized in that the gas phase one-step hydrogenation cracking reaction is performed by adjusting to.

In the present invention, regardless of whether a maleic acid dialkyl ester or a succinic acid dialkyl ester is used as a raw material, 1,4-butanediol and γ- Butyrolactone can be obtained. That is, the present invention does not require the operation of a two-step reaction of hydrogenating maleic acid dialkyl ester to give succinic acid dialkyl ester, and further hydrogenating succinic acid dialkyl ester to give 1,4-butanediol. It is a method with excellent production efficiency.

Examples of the maleic acid dialkyl ester include maleic acid dialkyl ester obtained by reacting maleic acid with an alcohol having 1 to 4 carbon atoms. Examples of the alcohol having 1 to 4 carbon atoms include lower aliphatic alcohol having 1 to 4 carbon atoms. Representative examples of the maleic acid dialkyl ester include dimethyl maleate and diethyl maleate. The maleic acid dialkyl esters may be used alone or in combination of two or more.

The succinic acid dialkyl ester can be obtained, for example, by hydrogenating the maleic acid dialkyl ester, or by reacting succinic acid with an alcohol such as a lower aliphatic alcohol having 1 to 4 carbon atoms. Some of them are listed. Representative examples of the succinic acid dialkyl ester include dimethyl succinate and diethyl succinate. In addition, the said succinic acid dialkyl ester can be used individually or in mixture of 2 or more types.

The maleic acid dialkyl ester and the succinic acid dialkyl ester may be used alone or as a mixture.

In the present invention, copper or a copper compound is used as the catalyst.

As the catalyst, a carrier in which copper or a copper compound is supported can be used. Examples of the copper compound include copper oxide, copper nitrate, copper sulfate, and copper chloride. As the carrier, for example, the Ho value is −
Examples thereof include oxides between 3 and +3 and mixtures thereof.
Representative examples of the carrier include, for example, silicon oxide, zirconium oxide, titanium oxide and the like, which may be used alone or in admixture of two or more.

The content of copper in the catalyst is preferably 20 to 80% by weight, more preferably 45 to 65% by weight.
When the content of such copper is less than the above range,
When the selectivity of 1,4-butanediol is low, and when it is more than the above range, the catalyst tends to sinter, so that the activity tends to be lost.

In the present invention, in order to adjust the selectivity of 1,4-butanediol or γ-butyrolactone, alkali metals such as potassium and sodium, alkaline earth metals such as calcium and barium, zinc and manganese. , Palladium, nickel and their chlorides can be used as catalysts for property improvement.

The content of the property improving catalyst in the catalyst is preferably 0 to 10% by weight, more preferably 0 to 5% by weight. When the content of the property improving catalyst is more than the above range, the conversion rate tends to be low.

As the method for producing the catalyst, for example, a salt or oxide of silicon, zirconium or titanium is used.
As a catalyst carrier by precipitation method, coprecipitation method, copolishing method, etc.
Examples thereof include a method of supporting copper or a copper compound on the catalyst carrier by a precipitation method or an immersion method. As an example, for example, a 10 to 40 wt% aqueous solution of a copper salt is prepared, and the pH of the aqueous solution is adjusted to 7 to 11, particularly 8 to 10 by using aqueous ammonia, sodium carbonate, sodium hydrogen carbonate or the like. The catalyst can be obtained by adhering the aqueous solution to a carrier, immersing the carrier in the aqueous solution and then drying it, or by directly adhering copper to the carrier.

When the above-mentioned property improving catalyst is used,
The property-improving catalyst may be used as an aqueous solution of 5 to 20% by weight, for example, as described above, used by being mixed with an aqueous solution of copper salt.

The catalyst is used at 400 to 600 ° C. before use.
It is preferable to adjust the particle size to about 0.3 to 0.5 mm by subjecting to aeration baking and molding. In addition, the catalyst is preliminarily provided with suitable reducing conditions such as a ratio of hydrogen to nitrogen (volume ratio) of 1: 1 to 1:10, a heating temperature of 180 to 300 ° C., and an activation time of 4 to 24 hours. It is preferable to apply a hydrogen reduction treatment below.

In the present invention, the raw materials may be supplied by directly vaporizing them, or by mixing the raw materials and the solvent and then vaporizing them.

When a solvent is used, suitable solvents include alcohols, ketones and aldehydes. The amount of the solvent mixed is preferably 60 mol% or less based on the raw materials.

As a method of vaporizing the raw material, a method of causing hot hydrogen to be accompanied by saturated vapor of the raw material, or directly spraying the raw material in a mist state to vaporize in the hot hydrogen, and the temperature is set to an appropriate vaporization temperature, for example, 180 to Examples include a method of setting the temperature to 300 ° C.

If the feed rate of the raw material is too low, the yield will be low and it will be uneconomical, and if it is too high, the conversion will be incomplete, so 0.05 to 3 hr.
^-1 , preferably 0.1 to 3 hr ^-1 .

The reaction can be carried out in a fixed bed tube type reactor, and when the vaporized raw material is put into the reactor, it is immediately brought into contact with the catalyst and the reaction proceeds. A suitable reaction temperature is 16
The temperature is 0 to 250 ° C, preferably 170 to 200 ° C. When the reaction temperature is higher than the above range, the catalyst tends to sinter and the activity decreases, and when the reaction temperature is lower than the above range, the selectivity of 1,4-butanediol is low. Will be lower. The reaction pressure is 20 to 70 kg / c.
It is adjusted to be m ² , preferably 30 to 50 kg / cm ² . When the reaction pressure is higher than the above range, the equipment cost is high and the influence on the reaction is small, and when the reaction pressure is lower than the range, the obtained product is mainly γ-butyrolactone. It will be done.

When the value of the molar ratio of the raw material and hydrogen (raw material / hydrogen) is too small, the hydrogen in the circulating flow increases, and when it is too large, 1,
Since the selectivity of 4-butanediol is low, 20-500
, Preferably 20 to 400, more preferably 30 to 300.

A suitable space velocity of hydrogen is 1000 to 35.
000 hr ^-1, it is preferable that inter alia 1500~20000hr ^-1.

The injected hydrogen rapidly reacts with maleic acid dialkyl ester and succinic acid dialkyl ester to form 1,4-butanediol.
An inert gas may be mixed with hydrogen and supplied to prevent the formation of a polymer from butanediol.

Typical examples of the inert gas include nitrogen, argon, helium and methane.

Maleic acid dialkyl ester and succinic acid dialkyl ester which have not completely reacted, and γ-
Butyrolactone can be separated and reused for the reaction by refluxing.

Next, the gas phase one-step production method of 1,4-butanediol and γ-butyrolactone of the present invention will be described in more detail based on examples, but the present invention is limited to these examples. Not a thing.

Example The reaction was carried out inside a 3/8 inch stainless steel tube type reactor, and a fixed bed continuous reaction was adopted. After crushing the catalyst, 15 ml of catalyst granules that passed through a 20-30 mesh sieve
, The reaction conditions were set as in each experimental example, the products of the reaction were collected by cooling condensation, and then Shimadz
u GC-14A was analyzed by gas chromatography (Shimadzu Corporation). The analysis tube used is HP-F
30m x 0.53mm of FAP (cross-linked FFAP)
A FID detection measuring device was used with a x1.0 μm capillary glass tube.

The polymerization rate in each experimental example is expressed by the formula:

[0042]

[Equation 1]

The selectivity of 1,4-butanediol obtained by

[0044]

[Equation 2]

The selectivity of γ-butyrolactone obtained by the formula:

[0046]

[Equation 3]

The selectivity of the dialkyl succinate ester is calculated by the formula:

[0048]

[Equation 4]

It is obtained by

Experimental Example 1 196.85 g of copper nitrate was dissolved in 500 g of distilled water to obtain a copper nitrate aqueous solution. Separately, 100 g of silicon dioxide (BET
Surface area: 100 m ² / g) The powder is placed in a 1 liter glass flask, 200 ml of distilled water is added and stirred, and
The catalyst was obtained by heating to 50 ° C., slowly adding the copper nitrate aqueous solution obtained above, and adjusting the pH value to 8.

The obtained catalyst was subjected to aeration baking at 500 ° C. for 8 hours to form granules of 0.3 mm × 0.5 mm in a tablet making machine, and the granules passing through 20-30 mesh were put into a 15 ml reaction tube. Then, the mixture was reduced in a mixed gas of hydrogen: nitrogen = 1: 3 (molar ratio) at 180 ° C. for 8 hours.

[0052] Jichimeru maleate was injected into the vaporization zone by the high pressure pump at a rate of 0.5 hr ^-1, with mixing vaporized ester was injected into a vaporization zone hydrogen preheated to 220 ° C. at a rate of 9420hr ^-1, A bed contact reaction was carried out with the catalyst at 180 ° C and 42 atm.

The results of collecting and analyzing the products are shown in Table 1. The polymerization rate is 100 mol%, the 1,4-butanediol selectivity is 82.7 mol%, and the γ-butyrolactone selectivity is Was 10 mol%, which was superior in all respects to the case of using a commercially available copper-chromium or copper-zinc catalyst.

[0054] Experimental Example 2 hydrochloride zirconium _{(ZrOCl 2 · 8H 2 O)} 2.615
After adding kg to distilled water 10 liters and dissolving with stirring to obtain a zirconium aqueous solution, a 10% aqueous ammonia solution is slowly added dropwise to the zirconium aqueous solution with stirring to adjust the pH value to 10. A white precipitate (zirconium hydroxide) was obtained.

129.2 g of the obtained white precipitate was filtered, washed with water, then dried, and subjected to aeration baking at 550 ° C. for 4 hours to obtain zirconium oxide.

Next, in Experimental Example 1, silicon dioxide was used.
A catalyst of copper-zirconium oxide carrier was prepared in the same manner as in Experimental Example 1 except that 100 g of the zirconium oxide was used instead of 100 g.

A reaction was carried out in the same manner as in Experimental Example 1 using the obtained catalyst. The results are shown in Table 1.

Experimental Example 3 Titanium isopropyl acid [Ti (OC ₃ H ₇ ) ₄ ] 207.
After mixing 2 g and 151.9 g of tetrabutyl silicate, slowly add dropwise to a flask containing 500 ml of distilled water and stir, and adjust the pH value to 10 with 10% aqueous ammonia solution to generate a white precipitate. Let

After precipitation, filtration, washing with water and drying, 400
Aeration baking at 16 ° C. for 16 hours produced 100 g of a mixture of silicon dioxide and titanium dioxide.

Then, in the same manner as in Experimental Example 1, a copper-silicon dioxide-titanium dioxide carrier catalyst was prepared.

A reaction was carried out in the same manner as in Experimental Example 1 using the obtained catalyst. The results are shown in Table 1.

Experimental Example 4 Titanium isopropyl acid [Ti (OC ₃ H ₇ ) ₄ ] 3.63
Slowly add kg to a flask containing 10 liters of distilled water, stir, and inject 10% aqueous ammonia solution to adjust the pH value to 10 to generate a white precipitate.The white precipitate is filtered and washed with water. It was dried to obtain titanium hydroxide powder.

151.4 g of the obtained titanium hydroxide powder was added to 500
Aerated baking was performed at 6 ° C for 6 hours to obtain titanium dioxide.

Next, in Experimental Example 1, silicon dioxide was used.
A copper-titanium dioxide carrier catalyst was prepared in the same manner as in Experimental Example 1 except that 100 g of the titanium dioxide obtained above was used instead of 100 g and 208.3 g of an aqueous copper sulfate solution was slowly added dropwise.

Using the obtained catalyst, a reaction was carried out in the same manner as in Experimental Example 1. The results are shown in Table 1.

Experimental Example 5 75.7 g of the titanium hydroxide powder obtained in Experimental Example 4 and 64.5 g of the zirconium hydroxide powder obtained in Experimental Example 2 were mixed so as to have a uniform composition, and 150 ml of water was added. Then 4
The mixture of titanium dioxide and zirconium dioxide was obtained by polishing for an hour, evaporative drying and aeration baking at 550 ° C. for 10 hours.

Experimental Example 1 except that 102.1 g of the mixture of titanium dioxide and zirconium dioxide obtained above was used in place of 100 g of silicon dioxide in Experimental Example 1.
A copper-titanium dioxide / zirconium dioxide carrier catalyst was prepared in the same manner as in.

A reaction was carried out in the same manner as in Experimental Example 5 using the obtained catalyst. The results are shown in Table 1.

Comparative Example 1 Commercialized copper-chromium catalyst (copper content: 35% by weight,
Chromium content: 25% by weight) After crushing 50 g, put 15 ml that passed through 20-30 mesh into the reaction tube and in a mixed gas of hydrogen: nitrogen = 1: 3 (molar ratio) at 180 ° C for 8 hours. Reduced.

Dimethyl maleate was injected into the vaporizing zone by a high-pressure pump at a rate of 0.5 hr ^-1 , and was mixed and vaporized with hydrogen preheated to 220 ° C. Then, the reaction was allowed to proceed under exactly the same reaction conditions as in Experimental Example 1. It was The results are shown in Table 1.

Comparative Example 2 In Experimental Example 1, a copper-zinc catalyst commercialized as a catalyst (manufactured by Nissan Gardler, G-66B, copper oxide content:
30% by weight, zinc oxide content: 60% by weight)
The reaction was carried out in the same manner as in Experimental Example 1. The results are shown in Table 1.
Shown in.

[0072]

[Table 1]

As is clear from the results shown in Table 1,
In the case of using the catalyst obtained in Experimental Examples 1 to 5, as compared with the case of using the copper-chromium catalyst or the copper-zinc catalyst as in Comparative Examples 1 and 2 of the prior art, maleic acid dialkyl ester was used. It can be seen that hydrogenation cracking of succinic acid dialkyl ester is excellent.

When 1,4-butanediol and γ-butyrolactone were prepared with the specific catalyst of the present invention by the one-step hydrogenation cracking reaction as in Experimental Examples 1 to 5 of the present invention, While the selectivity of 1,4-butanediol is as high as 80 mol% or more,
When a conventional catalyst is used as in Comparative Examples 1 and 2,
Most of the product (about 60 mol%) remained in dimethyl succinate, and the selectivity of 1,4-butanediol was
It can be seen that it is lower than 30 mol%.

Experimental Example 6 In Experimental Example 1, copper nitrate 114.1 was used as the aqueous copper nitrate solution.
A catalyst was prepared in the same manner as in Experimental Example 1, except that an aqueous solution of copper nitrate in which 500 g of water was dissolved in 500 g of distilled water was used.

A reaction was performed in the same manner as in Experimental Example 1 using the obtained catalyst. As a result, the polymerization rate is 100 mol%,
The selectivity of 1,4-butanediol was 83.2 mol% and the selectivity of γ-butyrolactone was 15.2 mol%.

Experimental Example 7 In Experimental Example 1, copper nitrate 285.1 was used as the aqueous copper nitrate solution.
A catalyst was prepared in the same manner as in Experimental Example 1, except that an aqueous solution of copper nitrate in which 500 g of water was dissolved in 500 g of distilled water was used.

A reaction was carried out in the same manner as in Experimental Example 1 using the obtained catalyst. As a result, the polymerization rate is 100 mol%,
The selectivity of 1,4-butanediol was 91.2 mol% and the selectivity of γ-butyrolactone was 8.2 mol%.

Experimental Example 8 In Experimental Example 3, instead of the copper nitrate aqueous solution, copper carbonate 1
A catalyst was prepared in the same manner as in Experimental Example 3 except that an aqueous solution of copper carbonate in which 0.7 g was dissolved in 500 g of distilled water was used.

A reaction was carried out in the same manner as in Experimental Example 3 using the obtained catalyst. As a result, the polymerization rate is 100 mol%,
The selectivity of 1,4-butanediol was 84.2 mol% and the selectivity of γ-butyrolactone was 10.7 mol%.

Experimental Example 9 A catalyst was prepared in the same manner as in Experimental Example 1 except that 6 g of calcium chloride was added as a property-improving catalyst in Preparation of the catalyst.

A reaction was carried out in the same manner as in Experimental Example 1 using the obtained catalyst. The results are shown in Table 2.

Experimental Example 10 A catalyst was prepared in the same manner as in Experimental Example 4 except that 3 g of sodium nitrate was added as a property-improving catalyst when the catalyst was prepared in Experimental Example 4.

A reaction was carried out in the same manner as in Experimental Example 4 using the obtained catalyst. The results are shown in Table 2.

Experimental Example 11 Experimental Example 5 was repeated except that 15 g of nickel sulfate was added as a property improving catalyst when the catalyst was prepared.
A catalyst was prepared in the same manner as in.

A reaction was carried out in the same manner as in Experimental Example 5 using the obtained catalyst. The results are shown in Table 2.

Experimental Example 12 A catalyst was prepared in the same manner as in Experimental Example 1 except that 5 g of barium nitrate and 10 g of manganese nitrate were added as catalysts for improving the properties in Experimental Example 1.

A reaction was carried out in the same manner as in Experimental Example 1 using the obtained catalyst. The results are shown in Table 2.

Experimental Example 13 A catalyst was prepared in the same manner as in Experimental Example 2 except that 1 g of palladium nitrate was added as a property-improving catalyst when the catalyst was prepared in Experimental Example 2.

A reaction was carried out in the same manner as in Experimental Example 2 using the obtained catalyst. The results are shown in Table 2.

Experimental Example 14 A catalyst was prepared in the same manner as in Experimental Example 1 except that 7 g of zinc chloride was added as a property improving catalyst when the catalyst was prepared.

A reaction was performed in the same manner as in Experimental Example 1 using the obtained catalyst. The results are shown in Table 2.

Comparative Example 3 The same catalyst as used in Comparative Example 1 was prepared, and the catalyst was finely crushed and then passed through 100 mesh to obtain 20 g of 100 g.
After stirring in an aqueous solution containing 5 g of barium nitrate (5 g) and manganese nitrate (10 g), the mixture was stirred, allowed to stand for 10 hours, evaporated to dryness, and subjected to aeration baking at 500 ° C. for 6 hours.

Using the obtained catalyst, a reaction was carried out in the same manner as in Comparative Example 1. The results are shown in Table 2.

[0095]

[Table 2]

From the results shown in Table 2, when a metal such as an alkaline earth metal, palladium, zinc or nickel was used as the property improving catalyst, the selectivity of 1,4-butanediol was improved. Therefore, it is understood that the selectivity of γ-butyl lactone can be improved by using, for example, alkali metal, manganese, barium or the like.

Experimental Example 15 A reaction was carried out in the same manner as in Experimental Example 1 except that the supply ratio (molar ratio) of hydrogen and dimethyl maleate was changed to hydrogen: dimethyl maleate = 30: 1. As a result, the polymerization rate was 100 mol%, the 1,4-butanediol selectivity was 83.0 mol%, and the γ-butyrolactone selectivity was 5.2 mol%.
At mol%, dimethyl succinate was only 0.3 mol%.

Experimental Example 16 A reaction was carried out in the same manner as in Experimental Example 1 except that the feed ratio (molar ratio) of hydrogen to dimethyl maleate was changed to hydrogen: dimethyl maleate = 75: 1. As a result, the polymerization rate was 100 mol%, the 1,4-butanediol selectivity was 84.0 mol%, and the γ-butyrolactone selectivity was 7.1.
At mol%, dimethyl succinate was only 0.3 mol%.

Experimental Example 17 In Experimental Example 9, the supply ratio (molar ratio) of hydrogen and dimethyl maleate was hydrogen: dimethyl maleate = 300: 1.
The reaction was performed in the same manner as in Experimental Example 9 except that the above was changed.
As a result, the polymerization rate was 100 mol%, the 1,4-butanediol selectivity was 87.9 mol%, the γ-butyrolactone selectivity was 10.3 mol%, and the dimethyl succinate was only 1.2 mol%.

Experimental Example 18 Reaction was carried out in the same manner as in Experimental Example 1 except that the reduction condition of the catalyst was a hydrogen-to-nitrogen ratio (molar ratio) of 1:10 and reduction at 220 ° C. for 16 hours. Was done. As a result, the polymerization rate was 100 mol% and the selectivity of 1,4-butanediol was
83.2 mol%, γ-butyrolactone selectivity is 13.7 mol%
So, dimethyl succinate was only 1.7 mol%.

Experimental Example 19 The reaction was carried out in the same manner as in Experimental Example 1 except that diethyl maleate was used instead of dimethyl maleate. As a result, the polymerization rate was 100 mol%, the 1,4-butanediol selectivity was 80.3 mol%, the γ-butyrolactone selectivity was 14.7 mol%, and the amount of diethyl succinate was only 1.9 mol%.

Experimental Example 20 The reaction was carried out in the same manner as in Experimental Example 1 except that diethyl maleate was used instead of dimethyl maleate. As a result, the polymerization rate was 97.5 mol%, the selectivity of 1,4-butanediol was 75.3 mol%, the selectivity of γ-butyrolactone was 20.1 mol%, and the content of dimethyl succinate was only 3.3 mol%.

Experimental Example 21 A reaction was carried out in the same manner as in Experimental Example 1 except that the raw material supply rate was changed to 0.29 hr ⁻¹ . as a result,
The polymerization rate was 100 mol%, the selectivity of 1,4-butanediol was 84.7 mol%, the selectivity of γ-butyrolactone was 7.9 mol%, and dimethyl succinate was not generated.

Experimental Example 22 A reaction was performed in the same manner as in Experimental Example 3 except that the feeding rate of the esters was changed to 2.0 hr ⁻¹ . As a result, the polymerization rate was 100 mol%, the selectivity of 1,4-butanediol was 67.2 mol%, and the selectivity of γ-butyrolactone was 2 mol%.
At 2.0 mol%, dimethyl succinate was only 9.0 mol%.

Experimental Example 23 A reaction was carried out in the same manner as in Experimental Example 1 except that the reaction temperature was changed to 160 ° C. The results are shown in Table 3.

Experimental Example 24 The reaction was performed in the same manner as in Experimental Example 1 except that the reaction temperature was changed to 200 ° C. in Experimental Example 1. The results are shown in Table 3.

Experimental Example 25 The reaction was carried out in the same manner as in Experimental Example 1 except that the reaction atmospheric pressure was changed to 20 atm. The results are shown in Table 3.

Experimental Example 26 The reaction was carried out in the same manner as in Experimental Example 1 except that the reaction atmospheric pressure was changed to 10 atm. The results are shown in Table 3.

[0109]

[Table 3]

From the results shown in Table 3, according to Experimental Examples 23 to 26, 1,4-butanediol and γ-butyrolactone can be obtained in good yield, and the reaction such as pressure and temperature can be performed. It is understood that the selectivity of each compound produced can be adjusted by adjusting the conditions.

[0111]

EFFECTS OF THE INVENTION According to the gas-phase one-step manufacturing method of the present invention, 1,4 which can be suitably used for engineering plastics
-Butanediol and γ-butyrolactone can be produced simultaneously in a one-step reaction, and a catalyst having high activity and containing no toxic substance can be used, and alkali metal, alkaline earth metal, zinc nickel, manganese or palladium can be used. When the above is used as a property improving catalyst, the selectivity of 1,4-butanediol or γ-butyrolactone can be adjusted.

Further, the yield distribution of 1,4-butanediol and γ-butyrolactone can be adjusted only by changing the reaction temperature and the reaction pressure.

Therefore, the production method of the present invention is a method having an extremely high industrial utility value because it can easily realize the control of the equipment cost, the simplification of the operation, and the adjustment of the production amount.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (5)

[Claims] 1. A maleic acid dialkyl ester, a succinic acid dialkyl ester, or a mixture thereof is used as a raw material in the presence of copper or a copper compound as a catalyst at a temperature of 160 ° C.
In a hydrogen-containing atmosphere having a temperature of up to 250 ° C. and a pressure of 20 to 70 kg / cm ² , the feed rate of the raw material is 0.05 to 3 hr ⁻¹ and the molar ratio of the raw material and hydrogen (raw material / hydrogen) is 20 to 500. A method for producing 1,4-butanediol and γ-butyrolactone in a vapor phase in which the hydrogenation cracking reaction is carried out in a vapor phase in a single step. 2. The raw material is maleic acid dialkyl ester prepared by reacting maleic acid with an alcohol having 1 to 4 carbon atoms, succinic acid dialkyl ester prepared by hydrogenating maleic acid dialkyl ester, or a mixture thereof. Item 1,4-butanediol and γ-
Gas-phase one-step method for producing butyrolactone. 3. The 1,4-butanediol according to claim 1 or 2, wherein the catalyst is one in which at least one carrier selected from silicon oxide, zirconium oxide and titanium oxide is supported with copper or a copper compound. A gas-phase one-step method for producing γ-butyrolactone. 4. The catalyst is calcium, calcium chloride, zinc, zinc chloride, potassium, potassium chloride, sodium,
The 1,4-butanediol according to claim 1, 2 or 3, which contains at least one selected from sodium chloride, manganese, manganese chloride, palladium, barium, barium oxide, nickel and nickel chloride. A gas-phase one-step method for producing γ-butyrolactone. 5. The catalyst comprises 20 to 80% by weight of copper or a copper compound.
The gas-phase one-step production method of 1,4-butanediol and γ-butyrolactone according to claim 1, 2, 3 or 4, which is contained.