JPS6388044A - Hydrogenation catalyst for preparing gamma-butyrolactone - Google Patents

Abstract

PURPOSE:To enhance the slectivity of gamma-butyrolactone while suppressing the formation of tetrahydrofran without losing catalytic activity, by further adding rhenium to a nickel-molybdenum-barrium system. CONSTITUTION:A nickel compound decomposed to metal nickel under heating in a reductive atmosphere, a molybdenum compound decomposed to metal molybdenum or molybdenum oxide in the reductive atmosphere, a barium compound decomposed to metal barium or barium oxide in the reductive atmosphere and a rhenium compound decomposed to metal rhenium or rhenium oxide in the reductive atmosphere are tightly united on a carrier composed of silica.alumina. The generated aggregate is reduced in the temp. range of 350-800 deg.C for several hr in the reductive atmosphere to obtain the desired highly selective catalyst for preparing GBL.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a nickel-based catalyst used in producing r-butyrolactone from maleic anhydride or succinic anhydride through a liquid phase catalytic hydrogenation reaction.

According to the present invention, sequential reaction products of γ-butyrolactone such as tetrahydrofuran are suppressed, and γ-butyrolactone can be produced with high selectivity.

r-butyrolactone is, for example, 1,4-butanediol,
Extremely useful in industry as a raw material for pyrrolidones, an electrolyte solvent for lithium batteries, a developer used when printing circuits on printed wiring boards with photocurable resin, and an organic solvent for the adhesive. It is a substance.

(Prior Art) Many methods have been proposed for producing r-butyrolactone (hereinafter abbreviated as GBL) by a liquid phase catalytic hydrogenation reaction of maleic anhydride and/or co-phosphoric anhydride in the presence of a hydrogenation catalyst. Examples of using a nickel-based hydrogenation catalyst as a hydrogenation catalyst include Belgian Patent No. 835269, U.S. Patent No. 2772291-3, Japanese Patent Publication No. 49-9463,
Publications such as Japanese Patent Publication No. 49-16423 and Japanese Patent Publication No. 49-35620 are publicly known.

However, these methods are not sufficient in terms of catalyst activity or acid resistance, and to compensate for this,
It is carried out at high catalyst concentrations or at very high pressures.

Japanese Patent Publication No. 54-41560 discloses that G
A catalyst that closely combines nickel, molybdenum, and barium or thallium has been proposed as a highly selective GBL production catalyst that suppresses the sequential reaction of BL to tetrahydrofuran and the like. According to Patent Specification G, a catalyst combining nickel and molybdenum improves acid resistance and is effective in producing tetrahydrofuran, but by adding barium or thallium to it, GB can be produced while maintaining acid resistance.
It is said that it has been modified into a highly selective L catalyst, that is, a catalyst that suppresses the sequential reactions of GBL.

(Objective of the Invention) The present invention was achieved with the intention of improving the catalyst of Japanese Patent Publication No. 54-41560 to a catalyst with higher selectivity.

(Specific Means for Achieving the Object) The present invention achieves higher GBL selectivity by suppressing the sequential reactions of GBL without impairing the melting activity.

That is, the present invention relates to a catalyst for the production of GBL in which nickel, molybdenum, barium and rhenium are intimately combined on a support.

(Effect) By further adding rhenium to the nickel, molybdenum, and barium system, it was possible to suppress the production of tetrahydrofuran and increase the selectivity of gamma-butyrolactone without impairing the activity of the catalyst.

(Catalyst) The method for preparing the catalyst is to prepare a nickel compound that decomposes into metal nickel by heating in a reducing atmosphere, a molybdenum compound that decomposes into metal molybdenum or molybdenum oxide in a reducing atmosphere, and a barium metal compound in a reducing atmosphere. and rhenium metal or barium oxide, and a barium compound and a rhenium compound that decompose into rhenium oxide, are tightly combined on a carrier, and the resulting aggregate is heated in a reducing atmosphere.

Although this method can be carried out in various ways, it is preferable to use a means including a solution impregnation process to tightly combine the four types of compounds.

That is, it is desirable to introduce the compound to be combined or its precursor or derivative onto the carrier in the form of a solution, particularly an aqueous solution. In such cases, a method may be used in which the carrier is impregnated with individual solutions or a mixed solution of the four types of compounds, a method in which these compounds are simultaneously precipitated from the solution with a precipitant, or one or more of the four types of compounds is used. Any method can be used, such as a method in which the two types are first precipitated and then the remaining 9 other components are impregnated.

Specifically, for example, a method in which a nickel compound, a molybdenum compound, a barium compound, and a rhenium compound in the form of soluble salts are impregnated onto a carrier from an aqueous solution state, and a precipitant is dropped into an aqueous nickel compound solution in which a carrier is dispersed. After drying the supported nickel salt produced by depositing the nickel component on the carrier, the nickel salt is impregnated with soluble molybdenum compounds, barium compounds, and rhenium compounds in an aqueous solution state. Possible methods include a method in which a molybdenum compound, a barium compound, and a rhenium compound are uniformly kneaded in an aqueous solution state into a nickel salt cake, and the mixture is mixed and deposited on a carrier.

Nickel compounds include nickel nitrate, nickel sulfate,
Nickel chloride, various organic acid nickel, etc. Precipitating agents include ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium hydroxide, etc. Molybdenum compounds include ammonium molybdate, barium compounds include barium nitrate, and rhenium compounds include ammonium perrhenate. is preferred.

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

As the carrier, silica/alumina, diatomaceous earth, alumina, etc. are conveniently used, and silica/alumina is particularly preferred.

Regarding the composition of the catalyst for the present invention, the atomic ratio of molybdenum to nickel (Mo/Ni) is 0. O1~0.
20. Atomic ratio of barium or rhenium to nickel (Ba
/Ni), (Re/Ni) is 0.005 to 0.10
is within the range of Further, the amount of carrier used is such that the weight ratio to nickel (carrier A) is in the range of 0.25 to 4.

(Hydrogenation reaction) The catalyst produced in this manner suppresses the sequential reaction of producing tetrahydrofuran from gamma-butyrolactone in the process of producing gamma-butyrolactone from maleic anhydride or succinic anhydride, and produces high gamma-butyrolactone. Provides selectivity for specific lactones.

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

The reaction may be carried out either batchwise or continuously. As for continuous type, both suspended bed and fixed bed are possible.
A preferred embodiment is a method in which the raw material is catalytically hydrogenated in a suspended bed in the presence of a hydrogenation catalyst, and the reaction product is extracted from the reaction zone together with excess hydrogen gas in the vapor phase.

Hereinafter, the present invention will be further explained using specific examples, but the present invention is not limited to these examples unless the gist thereof is exceeded.

(Specific Examples) Catalyst Preparation Example Nickel nitrate (M (NO3)2.6H20) 150
t was dissolved in 75 d of demineralized water, and in this solution, 125 t of ammonium bicarbonate (NH4HCO3) was dissolved in 6 d of demineralized water.
A solution dissolved in nickel nickel carbonate was added dropwise under stirring to obtain a precipitate of basic nickel carbonate.

This precipitate was separated from F and washed with water to remove ammonium nitrate.
A basic nickel carbonate cake was obtained. The nickel content of this cake was 15.3 wt%.

This cake 58.9 s t (9.Or as Ni
), ammonium molybdate ((NH4)6M07
024.4) L! O) 2.03, barium nitrate A (B
a(NO3)z) 1.20 y and ammonium perrhenate A (NLReO4) 0.4932 in the form of aqueous solutions, and after thorough mixing, powdered silica
1 g of alumina (alumina content 13 wt%) and Of were added.

The whole is kneaded and crushed, heated at around 90℃, evaporated to dryness, and the obtained powder is further dried in a dryer at 100-110℃.
It was dried overnight.

This powder 15f was decomposed in a quartz tube heated in an electric furnace at 450°C under air flow for 2 hours, and after cooling, it was switched to nitrogen gas for substitution, then switched to hydrogen, and heated at 550°C under hydrogen flow. Reduction was performed for 3 hours.

After cooling to 150°C, the nitrogen flow was switched to, and after cooling to room temperature, air was mixed into the nitrogen in pulses to stabilize the temperature at 50°C or lower to prepare a catalyst.

This catalyst has a Mo/Ni (atomic ratio) of 0.075
, Ba/Ni (atomic ratio) -0.03, Re/Ni (atomic ratio) = 0.012, and carrier/N1 (weight ratio) -2.

Example-1 Using 1 ton of catalyst prepared in the catalyst preparation example, the internal volume was 100
A hydrogenation reaction was carried out on 40 f of succinic anhydride at a reaction pressure of 10 o#/4G and a reaction temperature of 260°C for 2 hours in a magnetically stirred 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%.

γ-Butyrolactone zero fold rate 79.6%, selectivity 8
3.5%.

8-4% of tetrahydrofuran, 8-8
%.

In addition, in the following examples and comparative examples, the composition of the catalyst and the catalyst reduction temperature are changed to help understand the effects of the present invention. In the following, regarding the catalyst composition, for example, the catalyst in the catalyst preparation example is Ni-Mo-Ba-Re/silica-alumina.
1 = 0.075: 0.03: 0.012/2 (550
℃ reduction).

Comparative Example-1 Ni-Mo-Ba containing no rhenium as a catalyst
/Silica/Alumina=1: 0.075: 0.03
/2 (550°C reduction) Example-1 except that catalyst 1 was used.
The reaction was carried out in the same manner. The results are shown in Table 1.

Example 2 The composition of the catalyst was the same as in the catalyst preparation example, but the catalyst reduction temperature was 450°C, that is, Ni-Mo-Ba-Re/Silica-Alumina-1: 0.075: 0.03:
0.012/2 (450℃ reduction) catalyst 1? The reaction was carried out in the same manner as in Example-1 except that . The results are shown in Table 1.

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

Ni-Mo-B87 silica alumina = 1:0.075
:0.03/2 (reduction at 450°C) The reaction was carried out in the same manner as in Example 1, except that catalyst 1f was used. The results are shown in Table 1.

Example-3 Same as Example-2 except that Re/Ni (atomic ratio) was Q, 03 as a catalyst, that is, Freeze-Mo-Ba-Re/
Silica self-alumina-1: 0.075: 0.03
: A reaction was carried out in the same manner as in Example-1 using a pond using 1 ton of 0.03/2 (450° C. reduction) catalyst. The results are shown in Table 1.

Example-4 In Example-1, the reaction conditions were hydrogen pressure of 80#/c! 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 was carried out in the same manner as in Example 4, except that the reaction conditions were the same as in Example 4, that is, hydrogen pressure go, 1/ctIc, and reaction temperature 240°C. The results are shown in Table 1.

(The following is a margin.) In addition, in FIG. 1, each experimental example is plotted as conversion rate vs. S selectivity.

This reaction increases the conversion rate and GBL! As the temperature increases, the sequential reaction of GBL increases, but as shown in Figure 1, the selectivity of tetrahydrofuran in the example group (Re-added catalyst system) is smaller than that of the comparative example (catalyst system without Re), and the gamma-
It is understood that the successive reactions of butyrolactone are suppressed and a high selectivity of gamma-butyrolactone is provided.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] A hydrogenation catalyst for producing γ-butyrolactone from maleic anhydride or succinic anhydride, characterized in that nickel, molybdenum, barium and rhenium are intimately combined on a support.