JPH0811185B2 - Hydrogenation catalyst for γ-butyrolactone production - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a nickel-based catalyst used for producing γ-butyrolactone by maleic anhydride or succinic anhydride by a catalytic hydrogenation reaction in a liquid phase.

According to the present invention, the sequential reaction products of γ-butyrolactone such as tetrahydrofuran are suppressed and γ-butyrolactone is highly selective.
Butyrolactone can be produced.

γ-butyrolactone is, for example, 1,4-butanediol,
Very useful in industry as a raw material for pyrrolidones, or as an electrolyte solvent for lithium batteries, a developer used when printing a printed circuit board substrate with a photocurable resin, and an organic solvent for other chemicals. It is a substance.

(Prior Art) Many methods have been proposed for producing γ-butyrolactone (hereinafter abbreviated as GBL) by a liquid phase catalytic hydrogenation reaction of maleic anhydride and / or succinic anhydride in the presence of a hydrogenation catalyst. As using a nickel-based hydrogenation catalyst as, Belgium Patent No. 835269, US Patent No. 2772
Publications such as Nos. 291 to 3, Japanese Patent Publication No. 49-9463, Japanese Patent Publication No. 49-16423 and Japanese Patent Publication No. 49-35620 are known.

However, these methods are not sufficient in terms of activity of the catalyst or resistance to acid, and in order to make up for this point, they are carried out under high catalyst concentration or very high pressure. .

Japanese Examined Patent Publication No. 54-41560 has a high selectivity that enhances acid resistance and suppresses sequential reactions from GBL to tetrahydrofuran.
As a GBL production catalyst, a catalyst in which nickel, molybdenum, and barium or thallium are closely combined has been proposed. According to the patent specification, a catalyst in which nickel and molybdenum are combined is effective in improving the acid resistance and producing tetrahydrofuran, but by adding barium or thallium to it, GBL high selection is performed while maintaining the acid resistance. It is said that the catalyst has been reformed into a strong catalyst, that is, a catalyst suppressing the sequential reaction of GBL.

(Object of the Invention) The present invention has been accomplished with the intention of improving the catalyst of JP-B-54-41560 to a catalyst having higher selectivity.

(Specific Means for Achieving the Object) The present invention achieves higher GBL selectivity by suppressing the sequential reaction of GBL without impairing the catalytic activity. That is, the present invention relates to a catalyst for producing GBL in which nickel, molybdenum, barium and rhenium are intimately combined on a support.

(Effect) Addition of rhenium to nickel, molybdenum, and barium system does not impair the activity of the catalyst,
It was possible to suppress the formation of tetrahydrofuran and enhance the selectivity of gamma-butyrolactone.

(Catalyst) A catalyst is prepared by heating in a reducing atmosphere, a nickel compound that decomposes into metallic nickel, a molybdenum compound that decomposes into metallic molybdenum or molybdenum oxide in a reducing atmosphere, and barium metal in a reducing atmosphere. And a barium compound and a rhenium compound that decompose into rhenium metal or barium oxide and a rhenium oxide, are closely coalesced on a carrier, and the resulting aggregate is heated in a reducing atmosphere.

This method can be carried out according to various embodiments, but it is preferable to use a means including a solution impregnation process for intimately combining the four compounds. That is, it is desirable to introduce the compound itself to be combined or its precursor or derivative in the form of a solution, particularly an aqueous solution, onto the carrier. In such a case, a method of impregnating a carrier with respective solutions or mixed solutions of four compounds, a method of simultaneously precipitating these compounds from a solution with a precipitating agent, or any one of the four compounds or Either method can be used, such as first precipitating the two species and then impregnating the remaining other components.

Specifically, for example, a method of impregnating a nickel compound, a molybdenum compound, a barium compound and a rhenium compound in the form of a soluble salt from an aqueous solution onto a carrier,
After drying the nickel salt with a carrier formed by depositing a nickel component on the carrier by dropping a precipitant into the aqueous solution of the nickel compound in which the carrier is dispersed, a soluble molybdenum compound, a barium compound and a rhenium compound are added thereto. A method of impregnating in an aqueous solution state, a method of uniformly kneading a molybdenum compound, a barium compound and a rhenium compound in an aqueous solution state into a nickel salt cake formed from a nickel compound using a precipitating agent, and kneading and adhering this to a carrier are carried out. It is possible.

Examples of nickel compounds include nickel nitrate, nickel sulfate, nickel chloride, and various organic acid nickel.Precipitants such as ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium hydroxide, etc., molybdenum compounds such as ammonium molybdate, and barium compounds include nitric acid. Ammonium perrhenate is preferred as the barium and rhenium compound.

A nickel compound produced according to the above embodiment,
After sufficiently drying a mixture containing a molybdenum compound, a barium compound, a rhenium compound and a carrier at a temperature of 80 to 110 ° C, 350 to 800 ° C in a reducing atmosphere, preferably 400 to 600.
The catalyst of the present invention can be obtained by reducing for several hours or more in the temperature range of ° C.

As the carrier, silica / alumina / diatomaceous earth, alumina or the like is used, and silica / alumina is particularly preferable.

Regarding the composition of the catalyst for the present invention, the atomic ratio of molybdenum to nickel (Mo / Ni) is 0.01 to 0.20, the atomic ratio of barium or rhenium to nickel (Ba / Ni), (Re / Ni) is
It is in the range of 0.005 to 0.10. The carrier is used in a weight ratio of nickel to carrier (carrier / Ni) of 0.25 to 4.

(Hydrogenation reaction) The catalyst produced in this manner suppresses the sequential reaction of the formation of tetrahydrofuran from gamma-butyrolactone in the method of producing gamma-butyrolactone from maleic anhydride or succinic anhydride, and has a high gamma- Gives butyrolactone selectivity.

The reaction temperature is usually 180 to 300 ° C., and the reaction pressure depends on the amount of the catalyst used or the reaction mode, but a hydrogen pressure of 20 atm or higher is generally used.

The reaction mode may be either a batch system or a continuous system.
As the continuous system, both a suspension bed and a fixed bed are possible, but a preferred embodiment is that in the presence of a hydrogenation catalyst in the presence of a hydrogenation catalyst, when the reaction product is catalytically hydrogenated in a suspension bed, the reaction product is vapor phase together with excess hydrogen gas It is a method of taking out from the reaction zone.

Hereinafter, the present invention will be further described with reference to specific examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

The (specific example) Catalyst Preparation Example nitrate nickel _{(Ni (NO 3) 2 ·} 6H 2 O) 150g was dissolved in demineralized water 75 ml, this solution, ammonium bicarbonate (NH ₄ HCO ₃₎ 1
A solution of 25 g dissolved in 625 ml of demineralized water was added dropwise with stirring to obtain a precipitate of basic nickel carbonate.

The precipitate was separated and washed with water to remove ammonium nitrate to obtain a basic nickel carbonate cake. The cake had a nickel content of 15.3 wt%.

This cake 58.93g (9.0g as Ni), ammonium molybdate _{((NH 4) 6 Mo 7} O 24 · 4H 2 O) 2.03g, barium nitrate _{(Ba (NO 3) 2)} 1.20g, ammonium perrhenate (NH ₄
ReO ₄ ) 0.493g was added in the form of an aqueous solution, and after thoroughly kneading, powdered silica-alumina (alumina content 13wt%)
18.0 g was added.

The whole was kneaded and crushed, heated at about 90 ° C., evaporated to dryness, and the obtained powder was further dried at 100 to 110 ° C. overnight in a dryer.

Dissolve 15 g of this powder in a quartz tube heated in an electric furnace at 450 ° C for 2 hours under air flow. After cooling, switch to nitrogen gas and replace, then switch to hydrogen at 550 ° C under hydrogen flow. Reduction was carried out for 3 hours.

After cooling to 150 ° C., switching to a nitrogen stream, cooling to room temperature, mixing air with nitrogen in a pulse, and stabilizing at a temperature of 50 ° C. or less, a catalyst was prepared.

This catalyst had a composition of Mo / Ni (atomic ratio) = 0.075, Ba / Ni (atomic ratio) = 0.03, Re / Ni (atomic ratio) = 0.012, and carrier / Ni (weight ratio) = 2. .

Example-1 Using 1 g of the catalyst prepared in the catalyst preparation example, the internal volume was 100 ml.
40 g of succinic anhydride was subjected to a hydrogenation reaction at a reaction pressure of 100 kg / cm ² G and a reaction temperature of 260 ° C. for 2 hours in the electromagnetic stirring autoclave.

After the reaction was completed, it was rapidly cooled and the contents were analyzed, and the following results were obtained.

 Conversion rate 95.3%.

 The yield of γ-butyrolactone was 80.3% and the selectivity was 84.3%.

 The yield of tetrahydrofuran is 8.4% and 8.8%.

In addition, in the following examples and comparative examples, the effect of the present invention can be understood by changing the composition of the catalyst and the catalyst reduction temperature. Hereinafter, regarding the catalyst composition, for example, the catalyst of the catalyst preparation example is Ni-Mo-Ba-Re / silica-alumina = 1: 0.075: 0.03: 0.012.
Write as / 2 (550 ℃ reduction).

Comparative Example-1 The reaction was performed in the same manner as in Example-1 except that 1 g of a catalyst containing Ni-Mo-Ba / silica / alumina = 1: 0.075: 0.03 / 2 (550 ° C reduction) containing no rhenium was used as the catalyst. I went. The results are shown in Table 1.
Shown in

Example-2 As a catalyst, the composition is the same as that of the catalyst preparation example, but the catalyst reduction temperature is 450 ° C., that is, Ni-Mo-Ba-Re / silica-alumina = 1: 0.075: 0.03: 0.012 / 2 (450 ° C. Reduction) The reaction was performed in the same manner as in Example 1 except that 1 g of the catalyst was used. The results are shown in Table 1.

Comparative Example-2 The composition of the catalyst was the same as that of Comparative Example-1 (not containing Re), but the catalyst reduction temperature was 450 ° C.

Ni-Mo-Ba / Silica / Alumina = 1: 0.075: 0.03 / 2 (450 ℃
Reduction) The reaction was performed in the same manner as in Example 1 except that 1 g of the catalyst was used. The results are shown in Table 1.

Example-3 Except that Re / Ni (atomic ratio) was 0.03 as a catalyst,
Same as 2, ie Ni-Mo-Ba-Re / silica-alumina = 1: 0.
075: 0.03: 0.03 / 2 (450 ° C. reduction) The reaction was performed in the same manner as in Example-1 except that 1 g of the catalyst was used. The results are shown in Table 1.

Example-4 In Example-1, the reaction conditions were hydrogen pressure of 80 kg / cm ² G,
The reaction was carried out in the same manner as in Example-1 except that the reaction temperature was 240 ° C. The results are shown in Table 1.

Comparative Example-3 In Comparative Example-1, the reaction conditions were the same as in Example-4,
That is, the same reaction was performed except that the hydrogen pressure was 80 kg / cm ² G and the reaction temperature was 240 ° C. The results are shown in Table 1.

In addition, FIG. 1 is a plot of each experimental example with the conversion rate VS selectivity.

In this reaction, the GBL concentration increases as the conversion rate increases, so the sequential reaction of GBL increases.
It is understood that in the (addition catalyst system) group, the selectivity of tetrahydrofuran is lower than that of the comparative example (catalyst system without Re), and the sequential reaction of gamma-butyrolactone is suppressed to give a high selectivity of gamma-butyrolactone.

[Brief description of drawings]

FIG. 1 is a correlation diagram of the conversion rate and selectivity of gamma-butyrolactone and tetrahydrofuran.

Claims (1)

[Claims] 1. A hydrogenation catalyst for producing γ-butyrolactone from maleic anhydride or succinic anhydride, which is a close combination of nickel, molybdenum, barium and rhenium on a carrier.