JPS61109785A - Production of lactone - Google Patents

Abstract

PURPOSE:The hydrogenation of a dicarboxylic acid and/or its anhydride is conducted in the presence of a catalyst containing palladium, copper and chromium as essential components to enable industrially advantageous and high-yield production of the titled compound for hours with increased and stabilized catalyst activity. CONSTITUTION:When a dicarboxylic acid and/or its anhydride such as maleic acid or its anhydride is hydrogenated into a lactone, preferably gamma-butyarolactone, a catalyst containing, as essential components, Pd, Cu and Cr, is used. The amount of hydrogen used is 10-1,000 times the molar amount of the dicarboxylic acid and/or its anhydride. The composition of the catalyst has 1/10-10, preferably 1/2-2 Cu/Cr atomic ratio, 1/2,000-1/20, preferably 1/1,500-1/50 Pd/Cr atomic ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for synthesizing lactones by hydrogenation of dicarboxylic acids and/or their anhydrides. More specifically, the present invention relates to a method for industrially advantageous synthesis of lactones by hydrogenating dicarboxylic acids and/or their anhydrides in the presence of a specific catalyst.

[Conventional technology]

Methods for producing dichtones by hydrogenating dicarboxylic acids and/or their anhydrides have been studied for a long time, and various catalysts have been proposed so far. For example, 08 P
206 JK is a compound selected from maleic anhydride, conolilic anhydride, and esters of maleic acid, succinic acid, and fumaric acid.

A method for producing r-butyro2chtone by subjecting it to gas phase hydrogenation in the presence of a copper chromite catalyst is described. However, this method has disadvantages in that the selectivity of the target product tends to be problematic and the catalyst life is short. As an improvement of such a copper chromite catalyst, for example, in Tokko Sho Dako/71/Za, succinic anhydride or maleic anhydride is hydrogenated in the gas phase in the presence of a copper-chromium-manganese oxide shaped catalyst. The production of γ-butyrolactone is described. The patent states that the presence of manganese as an improvement to the copper chromite catalyst increases the selectivity of hydrogenation ability and suppresses the hydrogenolysis reaction that occurs in parallel.
Although the yield is increased, even in this method, the selectivity and yield of the target product cannot be said to be sufficient.

On the other hand, Tokkosho, S"!-! No. 1102/, describes the use of a mixture of elemental steel and elemental palladium as a carrier as a hydrogenation catalyst for producing r-butyrolactone from maleic anhydride, succinic anhydride or a mixture thereof. Catalysts containing specified proportions of copper are described, which are much more active than copper alone or various mixtures with chromium and/or zinc, materials conventionally used to promote the activity of copper. However, there is a problem with the catalyst life, and when used for a long time, the conversion rate of the raw material in particular decreases significantly, and the yield of the target product decreases.

[Problem that the invention seeks to solve]

That is, when these conventionally known catalysts are used to hydrogenate dicarboxylic acids and/or their anhydrides to produce lactones, the reaction results are poor although side reactions are suppressed by controlling the heat of reaction, etc. In addition, if the reaction is carried out over a long period of time, the yield of the target product decreases due to deterioration of the activity of the catalyst.

The present invention solves this problem and hydrogenates dicarboxylic acids and/or their anhydrides in the presence of a specific catalyst with excellent activity stability, thereby achieving industrial advantage over a long period of time in high yields. The present invention provides a method for producing target lactones.

[Means for solving problems]

The gist of the present invention is a method for producing lactones by hydrogenating dicarboxylic acids and/or their anhydrides, which comprises hydrogenating lactones in the presence of a catalyst containing palladium, copper and chromium as essential components. It consists in the manufacturing method.

The present invention will be explained in more detail below.

The catalyst used in the present invention is not particularly limited as long as it contains palladium, copper, and chromium as essential components, but it is usually prepared by reducing a mixture of a copper-chromium complex oxide and palladium. This is what was obtained. Especially A
dk1nm catalyst (J, Am Ch@w, Soc,
! A combination of copper chromite catalyst known as rll, //3K (/qjyu) or its precursor compound and palladium is preferred.

Copper-chromium catalysts are usually prepared using the Natta method (Cata
lymls, Vol, l, P, JGq, /9
! ! ! ) The copper-chromium complex oxide of the present invention has a compositional formula of CuO.CuCr104 or CuCr40.
A composite oxide represented by 4 is preferred. When producing a copper-chromium catalyst, it is also possible to preferably include MnO@.

On the other hand, copper-chromium of various compositions can be obtained as copper-chromium composite oxides by the reaction of hydroxide steel or oxidized steel with chromic acid (edited by the Catalyst Society of Japan, Catalyst Engineering Course Vol. 6 p, gq-p, toq). Composite oxides can also be used. In some cases, chromium oxide or metal chromium may be further added to the copper-chromium composite oxide and fired at a temperature of about 30°C to 30°C to obtain a suitable copper chromite crystal, at least a part of which is converted into copper chromite crystals. The composition can also be obtained.

There are various methods for supporting palladium on a copper-chromium complex oxide, and although there are no particular limitations, the copper-chromium complex oxide is usually supported on a copper-chromium complex oxide by palladium nitrate, palladium chloride, or palladium formate. This is done by impregnating it in a solution of soluble salts such as. In some cases, palladium may be added as a soluble salt when producing a copper-chromium complex oxide.

The catalyst containing palladium, copper and chromium of the present invention is
Furthermore, as a co-catalyst, it may contain promoter components normally added to copper-based hydrogenation catalysts, such as zinc, cadmium, beryllium, nickel, cobalt, cerium, zirconium, strontium, barium, sodium, potassium, etc. These may be added when producing the copper-chromium complex oxide, or may be supported simultaneously when supporting palladium. As the co-catalyst, nickel and cobalt are particularly preferred in consideration of improving the stability of catalyst activity.

When using nickel or cobalt as a co-catalyst, the Ni or Co content is θ~0. rwt%N
It is used in the range of i/Cr or Co/Cr from Q to l/6θ.

Although the catalyst of the present invention does not particularly require the use of a carrier, it may be added for the purpose of controlling hot spots by dispersing reaction heat, improving catalyst moldability, and mechanical strength. Examples of the carrier include silica-based carriers such as silica, calcium silicate, and diatomaceous earth, glass, alumina, titanium oxide, zirconia oxide, and pumice.
! ; It is about Owt%. Although the carrier can be added at any stage, it is usually added during the production of the copper-chromium composite oxide, or
This is carried out when palladium is supported on a copper-chromium complex oxide.

A catalyst containing palladium, copper and chromium prepared according to the above embodiments was prepared in air/! After drying at about rOC for around 1 hour, dry under air circulation for 3jO~ttoo.
Calcination is carried out at ℃ for φ hours. Further, preliminary reduction was carried out at 1 soc for about 3 hours using nitrogen gas containing a small amount of hydrogen, about io%, and after the end of the heat generation, reduction was carried out at 2 IOC for about 2 hours, and further 1 soc.
The catalyst used in the present invention can be obtained by reducing the catalyst with a 00% water-accumulated gas for about 1 hour. It is presumed that the catalyst of the present invention thus obtained is one in which metallic palladium and metallic steel in an alloy state are dispersed in chromium oxide.

The final composition of the catalyst of the present invention is Co/Cr-// in atomic ratio
10~10, Pd/Cr −//2000~//2
Preferably in the range of 0 Cu/Cr −//Co ~ Co Pd
/Cr 1111///! 00~//! It is in the range of 0.

In the present invention, using such a catalyst, dicarboxylic acid and/or
Alternatively, lactones are produced by hydrogenating the anhydride. The lactone is preferably γ-butyrolactone.

The dicarboxylic acids and their anhydrides, which are the raw materials for this reaction, are saturated or unsaturated aliphatic dibasic acids and their anhydrides, and the dicarboxylic acids include maleic acid, citraconic acid,
Conolic acid etc. and dicarboxylic acid anhydride include
Maleic anhydride, citraconic anhydride, phosphoric anhydride, etc. may be mentioned.From the viewpoint of the structural stability of the obtained lactone, it is preferable that the straight chain containing carbonyl carbon has from K to S carbon atoms. Further, as the raw material compounds, unsaturated dicarboxylic acids, saturated dicarboxylic acids as their hydrides, unsaturated dicarboxylic anhydrides, and saturated dicarboxylic anhydrides as their hydrides may be used individually or in combination.

Preferred are five-membered dicarboxylic acid anhydrides, with maleic anhydride and conolilic anhydride being particularly preferred.

In the hydrogenation reaction, the proportion of hydrogen used is io'ytoo relative to the dicarboxylic acid and/or its anhydride.

It is twice the mole. In addition to hydrogen, the reaction gas may contain components inert to the reaction, such as methane, ethane, nitrogen, argon, carbon dioxide, etc., and can also be recycled. However, the amount of impurities in hydrogen is preferably 50 wt % or less, preferably /j vt % or less.

When an unsaturated dicarboxylic acid or its anhydride is used as a raw material for an unexploded hydrogenation reaction, the compound contains a carbonyl group and an ethylenically unsaturated bond site, and the catalyst of the present invention has high activity and high Due to its selectivity, hydrogenation of carbonyl groups and ethylenically unsaturated bond sites can be carried out in substantially a single step.

The hydrogenation reaction of the present invention is carried out in a low pressure gas phase or a high pressure liquid phase, and a low pressure gas phase reaction is particularly preferred. During the reaction, the raw material compound is dissolved in the target lactone as necessary and subjected to the reaction.

When performing a low pressure gas phase reaction, the reaction temperature is l! θ〜3
The temperature is about 30°C, preferably from IGO to COTC. The reaction pressure is about 1 atm to 1Q atm.

In addition, when using circulating gas as the reaction gas, since it may contain a small amount of carbon monoxide, all or at least a portion of the circulating gas should be methanized by a known method to suppress deterioration of the catalyst. It's good to do that.

In addition, when performing a high-pressure liquid phase reaction, the reaction temperature is 200~200℃.
The reaction pressure is about 100-tSO atm.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
Unless it exceeds the gist of the present invention, commercially available copper chromite catalyst (JGC N-2038D, CuO1ljvt%
, Cr20g, 4! l vt% content, and Mno! ,
BaOt - Contains a small amount, 200 mesh powder) RiO?
is impregnated with an aqueous solution of palladium nitrate with a Pd concentration / 00 fit, and an aqueous solution in which l- is mixed and dissolved in water / JO-,
After stirring this slurry for about an hour, t! Evaporated to dryness on QC. The obtained powder was made into 71111φX with a tablet molding machine.
Pelletize into 3111L L, under air circulation, yso
It was baked at ℃ for 3 hours.

A copper chromite catalyst containing 0.3 wt% palladium as a metal component was obtained (catalyst 1). The composition of catalyst 1 is shown in Table 1.

Catalyst production example Commercially available steel chromite catalyst (8 volatile chemical N-20 CoD, CuO
Jri, j vt%, Cr103 j 6. ! rwt%
, further containing a small amount of BaO1Mn01.5103 and Nano) 5 g mφ tO
It was baked for 3 hours at c. 0.0 as a metal component! wt
A copper chromite catalyst containing % palladium was obtained (catalyst co). Using a similar preparation method, palladium was added to 0. /wt% and 0.3vt% copper chromite catalyst was obtained (Catalyst J
, da). The compositions of Catalysts 2 to 1 are shown in Table 1.

Catalyst Production Example J The N-CoO used in Catalyst Production Example J was pulverized and sieved into a powder (100 mesh pass powder) 100? , Pd
Palladium nitrate aqueous solution with concentration/00 fit: 1.
Impregnation in an aqueous solution of Otut mixed and dissolved in water/El, -,
This slurry was stirred for about 1 hour and then baked for 3 hours.

A copper chromite catalyst containing 0.1 vt% palladium as a metal component was obtained (catalyst S).

Also, three boxes of powder obtained after the above evaporation to dryness? In contrast, glass powder 7. After adding gff and mixing well, the particles were compressed into tablets in the same manner as in Catalyst Production Example 1.
Calcined at 0° C. for 3 hours (catalyst 6).

catalyst! The composition of -4 is shown in Table 1.

Catalyst Production Example Tei Commercial Copper Chromite Catalyst (JGC Chemical N-CO0JBD) RiO? , a palladium nitrate aqueous solution of pa @ degree to o fit, /ld and nickel nitrate Ni (NOs)t.
6H, Oo, iRida 1 (o, ooot, mole) was simultaneously mixed and dissolved in water tSOd and impregnated in an aqueous solution, and this slurry was molded and air circulated. Calcined in OC for 3 hours (catalyst 7
). The composition of the catalyst is shown in Table 1.

Catalyst Production Example S The N-CO02D used in Catalyst Production Example S was crushed and sieved to form a powder (100 mesh pass powder) SO? Pdl
Palladium nitrate aqueous solution at l11 degrees/00 f-/l Sd and cobalt nitrate Co (NOI)t ・A Hl
O0-74c1jf (0,00J solu) water 9lmK
The slurry was impregnated with a mixed and dissolved aqueous solution, stirred for about 1 hour, and calcined in Jsoc for 3 hours (catalyst j). The composition of catalyst g is shown in Table 1.

Example 1 The catalyst listed in Table 1 was placed in a stainless steel reactor with an inner diameter of 1. was filled, and glass beads (Jmφ) were filled thereon to form an evaporation layer. Preliminary reduction was carried out for 3 hours until almost all the hydrogen was present, then the temperature was raised to xroc and maintained for 2 hours, and the hydrogen concentration was further increased to 100%, the temperature was raised to JOOC and reduction was carried out for λ time.

Dissolve anhydrous amber #t (hereinafter abbreviated as SAM) in cambutyrolactone and make amber/74! vt/vt
A solution was prepared, and this solution was sent to the evaporation layer at the top of the reactor using a liquid feed pump, followed by a hydrogen gas flow, and led to the catalyst layer to perform a hydrogenation reaction. The reaction conditions are as follows: raw material supply rate is 9.
J f/Hr, i.e. succinic anhydride 0.10; 1-S
AM/ f −Cm Lm /Hr, HtZSAH
'(molar ratio) -50, total pressure θkt/cIItG.

Incidentally, the catalyst beam ■φXJ■L pellets were divided into //G and used for the reaction. The product was collected by water-cooled condensation, and the waste gas was led to a trap at dry ice temperature for complete collection. Both collected liquids were analyzed by Karl Fischer method (moisture) and gas chromatography method. The gas phase was analyzed using a gas chromatograph equipped with a methanator. On the other hand, high-boiling substances are extracted by distilling a certain amount of the collected liquid under reduced pressure, distilling off low-boiling substances, and then extracting the remaining liquid by adding water-chloroform. The amount of quantifiable substances was determined by the Fisher method, and the unbalanced components were determined as high-boiling substances. Table 1 shows the reaction results when each catalyst listed in Table 1 was used.

Example 1 A gas phase hydrogenation reaction of succinic anhydride (catalyst 1) was carried out under the reaction conditions of Example 1, and changes over time in the reaction results were investigated. The results are shown in Table 3.

Table 3 Compared to the initial stage, stable results were shown even after 9 hours to 9 g hours.

Comparative example! In order to clarify the difference between the method of the present invention and the known method, a gas phase hydrogenation reaction of succinic anhydride was carried out under the same reaction conditions as in Example 1 using a commercially available steel-chromite catalyst (8 Volatile Chemical Co., Ltd., N-202D). We investigated its changes over time. The results are shown in Table DA.

table The catalytic activity was clearly inferior to that of the catalyst of the present invention.

Comparative Example: In order to clarify the difference between the method of the present invention and the known method, copper
Palladium-magnesium silicate catalyst (Tokuko Sho st
, -rt, oat) was used to perform a gas phase hydrogenation reaction of succinic anhydride under the same reaction conditions as in Example 1, and the change over time was investigated. The results are shown in Table 5. Incidentally, this catalyst contains Cu/wt% and Pd2O, 3vt% as metal components.

Table 5 Although this catalyst exhibited relatively high activity at the initial stage of the reaction, deterioration of the catalyst over time was observed, and a decrease in the conversion rate of the raw material and the selectivity of γ-butyrolactone was observed with long-term use.

Comparative Example 3 (manufactured by Mallinckrodt, K-10JTu) was used, a solution of succinic anhydride dissolved in gamma-butyrolactone of 0/t Owt/vt was used as the reaction raw material, and the reaction conditions were such that the raw material supply rate was O, OS ? -8AVy--
CatV'Hr, By'SAM (molar ratio) -g
o.

A gas phase hydrogenation reaction was carried out in the same manner as in Example 1 except that the total pressure was Okg/crda and the reaction temperature was 265°C. As a result, the conversion rate of succinic anhydride was 91% and the selectivity of gamma-butyrolactone was 61%. , which was significantly inferior to the method of the present invention.

Example 3 J, (
Copper chromite catalyst containing 7vt% palladium (N-λ
(7,7SD) was prepared. This catalyst is 9? After being reduced by the hydrogen reduction method of Example 1, the internal volume was 100-
Coated in a stainless steel vertical stirring autoclave.
% of succinic anhydride-gammabutyrolactone solution 301% and reacted in the liquid phase for several hours at a hydrogen partial pressure of 100 kg/cda and a reaction temperature of 200 C. The results are shown in Table 6.

Table 4 [Effects of the Invention] According to the present invention, when hydrogenating dicarboxylic acids and/or their anhydrides to produce lactones, it is possible to make the presence of a catalyst containing palladium, copper, and chromium as essential components. Particularly in low pressure gas phase hydrogenation, the desired product can be obtained with higher selectivity than conventional methods.

Refreshingly, since the catalyst has excellent activity stability, no reduction in conversion rate is observed even when used for a long period of time, and the target product can be obtained with high selectivity over a long period of time.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - 1 other person

Claims (3)

[Claims] (1) A method for producing lactones by hydrogenating a dicarboxylic acid and/or its anhydride, which is characterized by hydrogenating in the presence of a catalyst containing palladium, copper, and chromium as essential components. . (2) The atomic ratio of palladium, copper and chromium as catalyst components is Pd/Cr=1/2000 to 1/20, Cu/Cr=1
10. The manufacturing method according to claim 1, wherein the range is from /10 to 10. (3) The dicarboxylic acid and/or its anhydride is maleic anhydride and/or succinic anhydride, and the lactone is γ-
The manufacturing method according to claim 1, characterized in that it is butyrolactone.