HYDROGENATION PROCESS

Abstract: A process for the hydrogenation of carboxylic acid derivatives such as carboxylic acid anhydrides or alkylidene dicarboxylates is provided. The catalyst used to effect the hydrogenation process comprises (1) a Group VIII metal catalyst e.g. ruthenium or rhodium, in the metallic state and (2) a strong acid promoter. The process is useful for hydrogenating acetic anhydride, propionic anhydride and ethylidene diacetate.

Description: HYDROGENATION PROCESS The present invention relates to the hydrogenation of carboxylic acids, carboxylic acid anhydrides, and alkylidine dicarboxylates. In particular the present invention relates to such a hydrogenation process carried out in the presence of a Group VIII metal catalyst. US 4,398,039 discloses a process for the vapour phase hydrogenation of carboxylic acids to yield the corresponding acid or its ester. The catalyst used is a mixed oxide based on ruthenium modified with (i) zinc and/or cadmium, (ii) cobalt and/or nickel and (iii) mixtures of iron, copper, rhodium, palladium, osmium, iridium and platinum. Our UK patent application No. 8328140 describes a process for the production of esters, e.g. ethyl acetate, by the hydrogenation of an acid anhydride, e.g. acetic anhydride, in the presence of a Group VIII metal, for example ruthenium. However, in this application the reaction is carried out in-the liquid phase and the Group VIII metal is present as a soluble inorganic or organometallic compound and not as the-metal itself. It has now been discovered that the hydrogenation of carboxylic acid anhydrides, alkylidene dicarboxylates or mixtures thereof can be effected using a Group VIII metal catalyst, where the Group VIII metal is present in the metallic state, and a strong acid promoter. Accordingly, the present invention provides a process for the hydrogenation of a feedstock comprising a carboxylic acid anhydride, an alkylidene dicarboxylate, or a mixture thereof which process comprises reacting the feedstock with hydrogen at elevated temperature and pressure in the presence of, as catalyst, (a) a Group VIII metal in the metallic state and (b) a strong acid promoter. The feedstock used in the hydrogenation process is suitably a carboxylic acid anhydride or an- -alkylidene dicarboxylate. Although in principle any such feedstock can be used, it is preferable to use a carboxylic acid anhydride derived from a C2-C10 carboxylic acid or an alkylidene dicarboxylate derived from a C2-ClO carboxylic acid and an alkylidene radical having less than 10 carbon atoms. Examples of preferred feedstocks include acetic anhydride, propionic anhydride, ethylidene diacetate and the like. The products of the hydrogenation depend on the feedstock used and to a certain extent on the Group VIII metal used as catalyst. When the feedstock used is a carboxylic acid anhydride the hydrogenation product can be one or more of an alcohol an ester of an alcohol and an alkylidene dicarboxylate while when an alkylidene dicarboxylate is used as feedstock an alcohol and/or an ester of an alcohol can be formed. The Group VIII metal used as the first component of the catalyst is preferably either ruthenium or rhodium and is present as the metal as to-a Solublce inorganic -coKmplexqof a higher oxidation state. It may be used supported or unsupported. When used unsupported the Group VIII metal is preferably added to the reaction mixture in a finely divided form for example ruthenium or rhodium black. Although the Group VIII metal may be added unsupported, it is in practice more convenient and preferable to support the Group VIII metal on an inert solid since this allows the dispersion of the Group VIII metal and hence the active surface area of the catalyst to be increased. By this means, a more efficient use is made of the Group VIII metal. The term inert solid is defined as a solid which (1) is not chemically or thermally degraded under the reaction conditions and (2) does not react with the feedstock in the absence of the Group VIII metal catalyst. Typical supports which may be used to advantage will be familiar to those skilled in the art and include, carbons, graphites, silicas, aluminas, zeolites, aluminosilicates, diatomaceous earths and clays. Of these carbons, graphites and aluminas are preferred supports. Methods of preparing such catalysts will also be familiar to the skilled man. A preferred method however is one in which the support is impregnated with a Group VIII metal salt or complex from aqueous solution, dried, and subsequently treated with hydrogen at elevated temperature to generate the Group VIII metal in the metallic state on the support. Conveniently, the supported catalyst is prepared so as to contain less than 25% by weight Group VIII metal. In addition to the GroupVIII metal, there is added a second catalyst component comprising a strong acid. Any strong acid which is stronger than acetic acid (i.e. its pKa at 25% is less than 4.75) and is chemically inert under the reaction conditions can be used as promoter. Thus the acid can be a strong mineral acid e.g. phosphoric acid, a fluorinated carboxylic acid, e.g. trifluoracetic acid or a sulphonic acid. Preferred sulphonic acids include methanesulphonic acid, trifluormethylsulphonic acid, benzenesulphonic acid and p-toluenesulphonic acid. It is also possible to use solid polymeric sulphonic acids, for example polyperfluorosulphonic acids such as those sold under the trade name Nation , admixed with the Group VIII metal catalyst or as a support for the Group VIII metal itself. The strong acid component is conveniently added in amounts up to-1OX by weight of the total reactor charge. The reaction is conveniently carried out at temperatures in excess of 500C, preferably in the range 75 to 2500C. It will be appreciated that for each feedstock the optimum reaction temperature will be different but in general it is desirable to carry out the process at the lowest temperature possible in order to minimise the formation of alkane byproducts. The hydrogen -gas used to effect the hydrogenation is conveniently fed to the reactor at superatmospheric pressure, preferably in the range 250 to 5,000 psi. It may contain impurities such as carbon monoxide, nitrogen and the inert gases e.g. helium. The hydrogenation process may be suitably carried out in either the liquid phase or the vapour phase. If carried out in the liquid phase, the Group VIII metal catalyst is suspended in the liquid feedstock and the promoter is either dissolved or suspended in the feedstock also An organic solvent which is inert under the reaction conditions can also be added if so desired although this is not essential if both the feedstock and its hydrogenation products are liquid at room temperature. As an alternative to carrying out the hydrogenation in the liquid phase, it is also possible to effect the hydrogenation by a vapour phase process wherein the reactants, in the vapour phase, and hydrogen are fed to a reactor containing a bed of the solid catalyst. In either case the process can be carried out batchwise or continuously. The present invention will now be illustrated by reference to the following Examples. Examples 1-3 - Comparative Test A and Comparative Test B Appropriate amounts of acetic anhydride, ruthenium on carbon (5% loading of reduced metal) and methane sulphonic acid were loaded into a corrosion resistant autoclave. The reactor was flushed several times with hydrogen gas, pressurised to 1500 psig with hydrogen and then heated with rapid stirring to the appropriate temperature. As soon as reaction was complete and gas uptake had stopped, the reactor was cooled and the products analysed by gas chromatography. The results and experimental conditions are summarised in Table 1. Table 1 EMI5.1 <tb> <SEP> Reactant <SEP> Catalyst <SEP> Product <SEP> (mmols) <tb> Example <SEP> T <SEP> t <SEP> (mmols) <SEP> (mmols) <tb> <SEP> ("C) <SEP> mins <tb> <SEP> Acetic <SEP> Ru <SEP> on <SEP> CH3S03H <SEP> Ethyl <SEP> Acetic <tb> <SEP> Anhydride <SEP> carbon <SEP> Acetate <SEP> Acid <tb> <SEP> 1 <SEP> 140 <SEP> 10 <SEP> 490 <SEP> 0.5 <SEP> 10.5 <SEP> 82 <SEP> 493 <tb> Test <SEP> A <SEP> 170 <SEP> 30 <SEP> 490 <SEP> 0.5 <SEP> - <SEP> <SEP> 5 <SEP> 50 <tb> Test <SEP> B <SEP> 170 <SEP> 30 <SEP> 490 <SEP> - <SEP> <SEP> 10.5 <SEP> 2 <SEP> 50 <tb> <SEP> 2 <SEP> 140 <SEP> 10 <SEP> 490 <SEP> 0.5 <SEP> 2.3 <SEP> i <SEP> 109 <SEP> 525 <tb> <SEP> 3 <SEP> 140 <SEP> 10 <SEP> 485 <SEP> 0.5 <SEP> 0.3 <SEP> 1 <SEP> 108 <SEP> 520 <tb> Example 4 This example demonstrates that trifluoroacetic acid can function as a promoter for the reduction of acetic anhydride. To a 300 ml autoclave was added 151.2 g acetic anhydride, ca 1.0 g trifluoroacetic acid and 6.08g of ruthenium metal on carbon in paste form containing ca 51% wt water (metal loading on dry powder 5% wt). The autoclave was flushed several times with hydrogen, then pressurised to 1500 psig with hydrogen, before being heated with rapid stirring. In this example, at a temperature of ca 90-100 C, a rapid reaction commenced, and the temperature rose rapidly to 155"C. The pressure was maintained at ca 1400* 200 psig until completion of the rapid reaction (time ca 0.8 hours). The autoclave was then cooled, and the product analysed by gas chromatography. It was found to contain 11.5% wt ethyl acetate, 0.7% wt ethylidene diacetate, and 51.1% wt acetic acid. Example 5 This example demonstrates that rhodium can also function as catalyst, and that using rhodium both carboxylic acid esters and alkylidene dicarboxylates can be obtained. To the autoclave of Example 6 was added 150.1 g acetic anhydride, 1.5g methanesulphonic acid, and 5.59 g rhodium metal on carbon in a paste form containing ca 50% water (metal loading on dry powder 5t wt). The autoclave was purged with hydrogen, then pressurised to 1420 psig with hydrogen, before being heated with rapid stirring. When the autoclave reached ca 1000C, a very rapid reaction began and the temperature rose rapidly to 1680C. During the reaction period the pressure was maintained at 1300 i 200 psig. After completion of the reaction (estimated time ca 0.75 hours) the autoclave was cooled and the product analysed by gas chromatography. The following composition was found: ethyl acetate 8.2% wt ethylidene diacetate 20.7% wt acetaldehyde -1.5% wt acetic acid 61.3% wt

Claims: Claims: 1. A process for the hydrogenation of a feedstock comprising a carboxylic acid anhydride, an alkylidene dicarboxylate or a mixture thereof which process comprises reacting the feedstock with hydrogen at elevated temperature and pressure in the presence of, as catalyst, (a) a Group VIII metal in the metallic state and (b) a strong acid promoter. 2. A process as claimed in claim 1 wherein the Group VIII metal is either ruthenium or rhodium. 3. A process as claimed in claim 1 wherein the strong acid promoter is an acid which is stronger than acetic acid. 4. A process as claimed in claim 3 wherein the strong acid promoter is a fluorinated carboxylic acid. 5. A process as claimed in claim 3 wherein the strong acid promoter is a sulphonic acid. 6. A process as claimed in claim 4 or claim 5 wherein the feedstock is acetic anhydride. 7. A process as claimed in claim 4 or claim 5 wherein the feedstock is propionic anhydride. 8. A process as claimed in claim 4 or claim 5 wherein the feedstock is ethylidene diacetate. 9. A process as claimed in claim 3 wherein the Group VIII metal is supported on an inert solid support. 10. A process as claimed in claim 9 wherein the inert solid support is a carbon or a graphite.

Inventors: WILLIAMS, PETER SEFTON
Applicants: BP CHEMICALS LIMITED
Application year: 1985
Main classification: C07C67
IPC codes: C07C51