JPS61246173A - Productionof gamma-butyrolactone - Google Patents

Abstract

PURPOSE:To obtain the aimed compound in high yield with a long catalyst life, by catalytically dehydrogenating 1,4-butanediol in the presence of a catalyst, e.g. copper-chromium-manganese based catalyst or copper-chromium-zinc based catalyst. CONSTITUTION:1,4-Butandiol is dehydrogenated in the presence of a copper- chromium-manganese based catalyst or copper-chromium-zinc based catalyst, preferably under conditions of preferably 200-250 deg.C under 0-5kg/cm<2>G pressure and 0.5-3hr<-1> weight hourly space velocity (WHSV) in the liquid or vapor phase to give gamma-butyrolactone particularly useful as a precursor for N- methylpyrrolidone in high yield using the above-mentioned catalyst with a long life. Preferably, the composition ratios of the respective component elements in the above-mentioned catalyst expressed in terms of the respective metals are set as follows; 30-60pts.wt. Cu, 70-40pts.wt. Cr., 3-20pts.wt. Mn based on 100pts.wt. total of Cu and Cr and 20-50pts.wt. Zn based on 100pts.wt. total of Cu and Cr.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention provides γ useful as a precursor of N-methylpyrrolidone.
- It relates to a method for producing butyrolactone, and more specifically, to a method for producing γ-butyrolactone in high yield.

[Technical background of the invention and its problems] γ-Butyrolactone is used as a solvent, an electrolytic sealing liquid for lithium batteries,
It is a compound useful as a lubricating oil refining solvent, and especially as a precursor of N-methylpyrrolidone.

This γ-butyrolactone is generally produced by catalytic dehydrogenation of 1,4-butanediol in the presence of a catalyst. Conventionally, a Cu-Cr catalyst is known as a dehydrogenation catalyst for 1,4-butanediol. However, when using this catalyst, the desired γ-
There were problems in that the yield of butyrolactone was low, and the life of the catalyst itself was short.

[Object of the Invention] The object of the present invention is to provide a method for producing γ-butyrolactone in a high yield while solving the conventional problems and having a long life of the catalyst used.

[Summary of the Invention] As a result of extensive research to achieve the above object, the present inventor has developed a Cu-Cr-Mn-based or Cu-Cr-based dehydrogenation catalyst in place of the conventional Cu-Cr-based catalyst. The present invention was completed based on the discovery that the use of a Zn-based catalyst improves the yield of γ-butyrolactone and that the catalyst itself has a long life.

That is, the method for producing γ-butyrolactone of the present invention includes:
It is characterized by dehydrogenating 1,4-butanediol in the presence of a copper-chromium-manganese catalyst or a copper-chromium-zinc catalyst.

First, as described above, the catalyst used in the present invention is one in which Mn or Zn is blended with Gu and Cr. These catalysts can be easily prepared by applying a conventional method using an oxide or salt of each metal as a starting material.

The composition ratio of each component element in the obtained catalyst is not particularly limited, but is preferably set as follows. That is, Cu and Cr each have a metal equivalent of 30
~60 parts by weight and 70 to 40 parts by weight, and this C
Mn or Zn to be mixed with u and Cr is set so that Mn is 3 to 20 parts by weight and Zn is 20 to 50 parts by weight, based on metal equivalents, for a total of 100 parts by weight of Cu and Cr. do.

The method of the present invention dehydrogenates 1,4-butanediol in the presence of the above-mentioned catalyst, and conventional methods can be applied thereto. Specifically, for example, 1,4-butanediol is preheated together with a diluent such as hydrogen, and then introduced into a reactor filled with the above catalyst to perform a dehydrogenation reaction, and then the resulting reaction product is After cooling, gas-liquid separation can be performed to produce the desired γ-butyrolactone.

In this manufacturing process, the reaction temperature is 150-300°C.
℃, preferably 200-250℃, pressure 0-10k
g/dG, preferably θ to 5 kg/cnG. The reaction may be carried out in either liquid phase or gas phase, and the weight hourly space velocity (wHsv) is 0.1-
It is set to 10 hr', preferably 0.5 to 3 hr-'.

[Examples of the invention] Examples 1 to 10 Comparative examples 1 to 3 (1) Preparation of catalysts CuCu-1Or-based catalysts A, B and Cu-Cr-Zn-based catalysts C, D, used in the method of the present invention, In addition, Cu-Cr catalyst E used in the conventional method was prepared as follows.

Dissolve 128.1 g of ammonium dichromate in 500 cc of distilled water, and add 1.5 g of 28% ammonia water to this solution.
Added 0cc. On the other hand, nitric acid ti4 (trihydrate) 241
．． 13g and manganese nitrate (hexahydrate) 28.7g
was dissolved in 500 cc of distilled water, and this nitrate solution was added dropwise to the above ammonium dichromate solution while stirring. The resulting precipitate was washed with water, dried, and pulverized.
It was fired at a temperature around 0.degree. C., and 3 to 5% of graphite was added thereto and formed into a predetermined shape. Prior to use, the catalyst thus obtained was reduced in a hydrogen stream at 180-200°C. Note that this catalyst is, for example, copper chromate (C
It is estimated that n is combined with uCr204) in some form, and the composition ratio of each component is Gu: Cr: Mn = 55: 45: 5.
It was 3.

15'' Ammonium dichromate, copper nitrate (trihydrate), and manganese nitrate (6 hydrate) were used in amounts of 12f1.
Catalyst B was prepared in exactly the same manner as Catalyst A above, except that the amounts were 1 g, 241.8 g, and 57.0 g.

The composition ratio of each component is Cu: Or: Mr+=55
:45:10.

83 g of ammonium dichromate was dissolved in 300 cc of distilled water, and 74 cc of 28% aqueous ammonia was added to this solution. On the other hand, 55 g of copper nitrate (trihydrate) and 87 g of zinc nitrate (hexahydrate) were dissolved in 400 cc of distilled water at about 70°C, and this citrate mixed solution was stirred into the ammonium dichromate solution. It dripped. The resulting precipitate was filtered, dried at about 110°C, and then calcined at a temperature around 350°C. Then, the obtained baked product was crushed for 10
Treated twice with 800 cc each of % acetic acid, distilled water volume 800 cc
After washing four times with 3 to 5% of graphite was added to this material and it was molded into a predetermined shape. The catalyst thus obtained was reduced at 200-210° C. in a hydrogen stream prior to use. Note that this catalyst is, for example, chromium 1% 2 copper (CuCr204
) and zinc chromate (ZnCr204), and the composition ratio of each component is Tecu: Or
: Zn=35:65:3s-t'.

The amounts of ammonium dichromate, copper nitrate (trihydrate) and zinc nitrate (hexahydrate) used were 63g and 5g, respectively.
Catalysts were prepared in exactly the same manner as Catalyst C above, except that the amounts were 5 g and 84 g. The composition ratio of each component is Cu:C
r: Zn=35=85: There were 45 teeth.

1 Grave J Dissolve 56.3 g of ammonium dichromate in 200 cc of distilled water, and add 48.4 g of 28% ammonia water to this solution.
Add 94 g of copper sulfate (pentahydrate) into this.
．． A solution prepared by dissolving 3 g in 300 cc of distilled water was added dropwise while stirring. The resulting precipitate was filtered, washed 2 to 3 times with 500 cc of warm water, and then dried. Then, after pulverizing, it was fired at 350 to 380°C. Copper oxide (approximately 23
%) was changed to copper chromate, and after drying and pulverizing, 3 to 5% graphite was added and molded into a predetermined shape. Prior to use, the catalyst thus obtained was heated at 180 to 200°C in a hydrogen stream.
It was returned in The composition ratio of each component in this catalyst was Cu:Cr=40:f30.

(2) Production of γ-butyrolactone 99% 1,4-butanediol (commercial product, first class reagent)
After preheating to about 200° C. with hydrogen (diluent) in a preheater, each sample was fed into a stainless steel reactor with an inner diameter of 10 mm at the feed rates shown in Table 1. This reactor has a first
Filled with 29g of each catalyst shown in the table, the reaction was carried out at normal pressure.
and at the indicated temperatures. Then, after cooling the obtained reaction product and performing gas-liquid separation,
The composition ratio (wt%) of the product was analyzed by gas chromatography. The results obtained are shown in Table 1.

Reference Example In order to evaluate the life of each of the above catalysts, a dehydrogenation reaction of 1,4-butanediol was carried out in the same manner as in the above example, and the change in the conversion rate of 1,4-butanediol with respect to the amount of oil passed was observed. The results are shown in Table 2. However, the reaction was conducted under the following conditions.

Catalyst loading amount 5.0g Reactivity
240°C 1,4-butanedio-)1H martyrdom 25 g/hr Hydrogen supply amount
8.3N! ;L/hrWH9V
5. Ohr' Table 2 [Effects of the Invention] As is clear from the above explanation, by applying the method of the present invention, γ-butyrolactone can be produced in a much higher yield than the conventional method. Since the life of the catalyst is long, its industrial value is extremely important, especially in the process of producing N-methylpyrrolidone.

Claims (1)

[Claims] A method for producing γ-butyrolactone, which comprises dehydrogenating 1,4-butanediol in the presence of a copper-chromium-manganese catalyst or a copper-chromium-zinc catalyst.