PROCESS FOR THE PRODUCTION OF METHYL FORMATE

Abstract: Methyl formate is prepared by reacting methanol with a hydrogen acceptor at elevated temperature in the presence of a platinum group metal catalyst. The hydrogen acceptor, which includes species such as aldehydes, ketones and olefins, undergoes hydrogenation during the process to produce a product which is preferably easy to separate from the other components of the reaction mixture. The process can be operated in either the liquid or vapour phase using a wide range of platinum group metal catalysts including simple salts, organic and organometallic complexes, and supported catalysts. The preferred platinum group metal is ruthenium.

Description: PROCESS FOR THE PRODUCTION OF METHYL FORMATE This invention relates to a process for the conversion of methanol to methyl formate, more particularly to a process operated in the gas or liquid phase using a homogeneous platinum group metal catalyst. Methyl formate is a useful organic chemical and can be used as an intermediate for the preparation of a wide range of other chemicals including formic acid itself and higher carboxylic acids such as acetic acid and propionic acid and their esters. The preparation of methyl formate from methanol is a commercially attractive proposition. Thus methanol is a readily available commodity chemical obtained from a variety of cheap hydrocarbon feedstocks, e.g. natural gas and synthesis gas. Methyl formate has been prepared previously by reaction of methanol and carbon monoxide and by reaction of methanol and carbon dioxide using Group VIII metal catalysts. A possible method of preparing methyl formate from methanol, without the need for coreactants, exists namely the reaction EMI1.1 in which a molecule of methanol is oxidatively dehydrogenated. In order to carry this reaction out it is necessary to have, in addition to methanol and a catalyst, a feedstock capable of accepting the hydrogen produced during the reaction. This hydrogen, acceptor feedstock is conveniently an organic molecule capable of A undergoing a hydrogenation reaction with the hydrogen, for examples an aldehyde, ketone or an olefin. J.,Organic Chemistry (1974) Volume 39 page 1622 discloses a process in which alcohols are oxidatively dehydrogenated to the corresponding aldehyde or ketone in the presence of RhH(PPh3)4 (Ph=phenyl) and, as hydrogen acceptor a cycloolefin. In this reference however all the alcohols were oxidatively dehydrogenated during the reaction with the exception of methanol which appeared substantially unreactive. It has now been found that methanol can be converted to methyl formate using a wide range of hydrogen acceptors and using a platinum group metal catalyst. Accordingly, the present invention provides a process for the preparation of methyl formate characterised in that methanol is reacted with a hydrogen acceptor at elevated temperature in the presence of a platinum group metal catalyst. As mentioned previously, the hydrogen acceptor is suitably an organic molecule capable of undergoing a hydrogenation reaction with the hydrogen denated by the methanol and includes species such as aldehydes, ketones and olefins. In the case of an aldehyde or a ketone, the hydrogenation product is the corresponding alcohol, while in the case of an olefin hydrogenation of the double bond occurs. Any aldehyde, ketone or olefin can be used in principle although it is preferable to choose a hydrogen acceptor whose hydrogenation product can be easily separated from the other reaction components. Suitably C1-C20, preferably C1-C10, aldehydes, ketones or olefins are used. Preferred hydrogen acceptors include, for example, cyclohexanone, methyl ethyl ketone, acetone and acetaldehyde. The conversion of methanol to methyl formate in the presence of a hydrogen acceptor is catalysed by a platinum group metal catalyst. By platinum group metal is meant a metal or metals selected from the group consisting-of ruthenium, rhodium palladium, osmium, iridium and platinum. Preferably the platinum group metal is ruthenium. The platinum group metal catalyst can be a simple salt or an inorganic or organometallic complex of the platinum group metal. Such complexes may contain ligands such a halide ions, amines, phosphines, arsines and stibines. In addition ligands able to 1T- bond to the metal, e.g. the cyclopentadienyl and pentamethyl cyclopentadienyl anions and benzene and its substituted derivatives can also be present. The complex of the platinum group metal can be cationic, anionic or neutral and can be prepared separately or generated in situ in the reaction mixture. In a preferred form, the catalyst is a phosphine or phosphite complex of the platinum group metal which can be formed in situ by reaction of a metal complex with a phosphine or phosphite. In this case the preferred platinum group metals are ruthenium. The phosphine or phosphite used can be a monodentate, bidentate or polydentate phosphine or phosphite. Preferred phosphines are trialkylphosphines e.g. tributylphosphine tridrylphosphines e.g. triphenylphosphine or phosphines having both alkyl or aryl groups attached to the phosphorus atom e.g. diphos, dppe and the like. Preferred phosphites are trialkylphosphites and triarylphosphites. When salts and complexes of the type described above are used it is preferable to operate the process as a liquid phase process with the catalyst soluble or partially soluble in the reaction mixture. As an alternative to a liquid phase process the reaction may be effected in the gaseous or vapour phase. In this mode of operation, the hydrogen acceptor, together with the methanol, are vapourised and passed over or through a bed of solid catalyst. Suitably, the solid catalyst comprises the platinium group metal supported on an inert carrier. The carrier can be inorganic, for example ametaloxide, silica, alumina, an aluminosilicate, clay or diatomaceous earth or organic for example polymers, such as polystyrene, polystyrene/divinylbenzene copolymers and fluorinated polymers. Various methods of supporting the platinum group metal, on the inert carrier are available and are familiar to the skilled man. Examples include impregnation, ion-exchange and coprecipitation methods7 A preferred method involves chemically binding a ligand to the inert carrier, for example a phosphine ligand, and then completing the bound phosphine ligand with a platinum group compound. The phosphine is bound to the carrier by means of one or more reactive groups attached to the phosphine. The solid catalyst can, of course aslo be used in association with a liquid phase mode of operation, although in this case the catalyst will be insoluble in the reaction medium. However, for both modes of operation it is preferable that the molar ratio of methanol to hydrogen acceptor is greater than 1:1 preferably 10:1. The reaction is suitably carried out at elevated temperature in the range 100-240"C although higher temperatures may be used if desired. Preferably the reaction temperature should be in the range 140-185"C. The reaction may be carried out at pressures up to 20 bars, preferably in the range 5-10 bars. When the reaction is carried out at superatmospheric pressure, the pressure may be generated by the autogenous pressure of one or more of the reactants at the temperature of reaction, or it may be generated by applying an overpressure of a suitable inert gas e.g. nitrogen, or a combination of both. The process as described can be carried out either batchwise or continuously. When the process is operated in the gas phase, continuous operation is preferred. The invention is illustrated by the following examples. Examples 1 to 8 Cyclohexanone (8 mmol) and methanol (195 mmol) and catalyst (0.08 mmol) were heated to 1500C in a Fisher-Porter tube. At the end of the reaction time recorded in Table 1 below, the contents were cooled and analysed by gas chromatography. In Examples 6-8 the ruthenium trichloride used was ruthenium chloride hydrate supplied by Johnson-Matthey. The catalysts therefore refer to one mole of ruthenium chloride hydrate and the appropriate number of moles of triphenyiphosphine. Examples 1 to 8 illustrate the following reaction using differerit catalysts and varying reaction times. EMI5.1 <tb> Cyclohexanone <SEP> + <SEP> methanol <SEP> =E <SEP> cyclohexanol <SEP> + <SEP> methyl <SEP> formate. <tb> TABLE 1 EMI5.2 <tb> <SEP> Reaction <SEP> Cyclohexanol <SEP> Methyl <SEP> formate <tb> <SEP> time <SEP> mmol <SEP> and <SEP> mmol <SEP> and <tb> Example <SEP> Catalyst <SEP> (hours) <SEP> moles <SEP> of <SEP> moles <SEP> of <tb> <SEP> product <SEP> per <SEP> product <SEP> per <tb> <SEP> mole <SEP> of <SEP> mole <SEP> of <tb> <SEP> catalyst <SEP> catalyst <tb> <SEP> ¯¯ <tb> <SEP> 1 <SEP> I(C5Me5Rh)2C14] <SEP> 19 <SEP> 1.1 <SEP> (14) <SEP> 1.3 <SEP> (16) <tb> <SEP> 2 <SEP> [(C5Me5Ir)2Cl4] <SEP> 18 <SEP> 1.2 <SEP> (15) <SEP> trace. <tb> <SEP> 3 <SEP> [(C6Me6Ru)2Cl4] <SEP> 18 <SEP> 0.5 <SEP> (6) <SEP> 1 <SEP> trace. <tb> <SEP> 4 <SEP> (Ph3P)3RuCl2 <SEP> 9.5 <SEP> 6.8 <SEP> (85) <SEP> 4.8 <SEP> (60) <tb> <SEP> 5 <SEP> (Ph3P)30sHBr(CO) <SEP> 18 <SEP> 1.0 <SEP> (12) <SEP> 2.8 <SEP> (35) <tb> <SEP> 6 <SEP> RuC13+1molePPh3 <SEP> 18 <SEP> 0.3 <SEP> (3) <SEP> 3.3 <SEP> (42) <tb> <SEP> 7 <SEP> RuCl3+2molesPPh3 <SEP> 18 <SEP> 0.3 <SEP> (4) <SEP> 3.6 <SEP> (45) <tb> <SEP> 8 <SEP> RuCl3+3molesPPh3 <SEP> 18 <SEP> 6.2 <SEP> (77) <SEP> 3.5 <SEP> (44) <tb> TABLE 2 EMI5.3 <SEP> - <SEP> &verbar; <SEP> - <SEP> t <tb> <SEP> Hydrogen <SEP> Methyl <tb> Example <SEP> Acceptor <SEP> Product <SEP> mmol <SEP> of <SEP> formate <tb> <SEP> product <SEP> and <SEP> mmol <SEP> and <tb> <SEP> moles/mole <SEP> moles/mole <tb> <SEP> catalyst <SEP> catalyst <tb> <SEP> 9 <SEP> cyclohexanone <SEP> cyclohexanol <SEP> 5.4 <SEP> (67) <SEP> 2.0 <SEP> (25) <tb> <SEP> 10 <SEP> PhCOMe <SEP> PhCHOHMe <SEP> 0.4 <SEP> (5) <SEP> 2.1 <SEP> (26) <tb> <SEP> 11 <SEP> MeCOEt <SEP> MeCHOHEt <SEP> 1.5 <SEP> (19) <SEP> 1.5 <SEP> (18) <tb> <SEP> 12 <SEP> PhCHO <SEP> PhCH20H <SEP> 1.4 <SEP> (17) <SEP> trace. <tb> <SEP> 13 <SEP> 4t-butyl- <SEP> 4-t <SEP> butyl- <SEP> 6.2 <SEP> (77) <SEP> 0.7 <SEP> (9) <tb> <SEP> cyclohexanone <SEP> cyclohexanol <tb> <SEP> (trans:cis=4:1) <tb> <SEP> 14 <SEP> Me2C=CHCOMe <SEP> Me2CHCH2COMe <SEP> 7.4 <SEP> (92) <SEP> 2.8 <SEP> (35) <tb> <SEP> 15 <SEP> cyclohexene <SEP> cyclohexane <SEP> 0.2 <SEP> (3) <SEP> trace. <tb> Examples 9 to 15 These examples illustrate the reaction of methanol as a hydrogen donor with various hydrogen acceptors using, as catalyst, (Ph3P)3RuCl2 which was the most active catalyst recorded in Table 1. The reaction may be summarised: methanol + hydrogen acceptor ¯iW product + methyl formate. In'the examples the hydrogen acceptor (8 mmol), methanol (200 mmol) and (Ph3P)3RuCl2 (0.08 mmol) were heated in a Fisher-Porter tube at 139 to 1480C for 18 hours. At the end of the reaction time the contents were cooled and analysed by gas chromatography. Example 16 Cyclohexanone (4.9 cm3, 48 mmol) methanol (55 cm3) and [(CsMesRh)2(0H)3]cl (0.3 g, 0.5 mmol) were heated in a stainless steel autoclave under nitrogen for 5 hours at 1500C and 60 bar. Analysis showed the presence of cyclohexanol (4.1 mmol; 8 mol/mol catalyst) and methyl formate (2.1 mmcl; 4 mol/mol catalyst). Example 17 Methylvinylketone (3.9 cm3, 48 mmol) methanol (56 cm3) and I(C5MeSRh)2(0H)3]C1 (0.3 g, 0.5 mmol) were heated in a stainless steel autoclave under nitrogen for 5 hours at 1500C and 60 bar. Analysis showed the presence of methylethylketone (butan-2-one) (25 mmol; 52 mol/mol) catalyst and methyl formate (12 mmcl; 25 mol/mol catalyst). Example 18 Example 18 illustrates that the process of the present invention may be carried out in the gas phase using a platinum group metal catalyst supported on an inert carrier. (a) Preparation of the Catalyst Davison 57 grade silica gel (mesh 30-60) wa functionalised by reaction with the phosphine (EtO)3SiCH2CH2PPh2). The functionalised silica (lOg. 0.8Z wt P) was treated with RuCl3 in 200 mls of refluxing ethanol. After ca 2 hours the mixture was cooled, the solid separated by filtration and the remaining solvent removed under vacuum. Care was later to exclude air all times during the preparation. The resulting catalyst was bottle-green. (b) Gas phase process 4g of the catalyst described in (a) was charged to a tubular glass reactor (0.5 cm id) contained in an oven and equipped with preheat section, liquid feed pump, gas feed system and product recovery section. Nitrogen (30 ml/min) and a 1:1 mixture of methanol and acetone (liquid feed equivalent to 15ml gas/min) were then paused over the catalyst. During this time the catalyst was maintained at 1800C. After ca 4 hours the feed was stopped and the recovered product analysed. The product contained 0.3% wt methyl formate and 0.9X wt % isopropanol as determined by G.C.

Claims: Claims: 1. A process for the preparation of methyl formate characterised in that methanol is reacted with a hydrogen acceptor at elevated temperature in the presence of a platinum group metal. 2. A process as claimed in claim 1 characterised in that the hydrogen acceptor is selected from the group consisting of aldehydes, ketones and olefins. 3. A process as claimed in claim 2 characterised in that the reaction is carried out in the liquid phase using a platinum group metal catalyst which is soluble in the reaction mixture. 4. A process as claimed in claim 3 characterised in that the platinum group metal catalyst is a simple salt, or an inorganic or organometallic complex of a metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum. 5. A process as claimed in claim 4 characterised in that the platinum group metal catalyst is a phosphine or phosphite complex of ruthenium. 6. A process as claimed in claim 5 characterised in that the phosphine or phosphite complex of ruthenium contains at least one ligand selected from the group which consists of trialkylphosphines, triarylphosphines, trialkylphosphites and triarylphosphites. 7. A process as claimed in claim 5 characterised in that the phosphine or phosphite complex is formed in situ from a ruthenium compound and a phosphine or phosphite. 8. A process as claimed in claim 1 characterised in that the reaction is carried out in the vapour phase in the presence of a of the platinum group catalyst. 9. A,process as claimed in claim 8 characterised in that the platinum group metal catalyst comprises a platinum group metal compound supported on an inert carrier. 10. A process as claimed in claim 9 characterised in that (i) the inert carrier is functionalised by chemically bonding a ligand to the inert carrier and (ii) a platinum group metal compound is subsequently complexed to the ligand. 11. A process as claimed in claim 8 characterised in that the platinum group metal catalyst is a ruthenium catalyst.

Inventors: MAITLIS, PETER MICHAEL, SMITH, THOMAS ASHLEY
Applicants: BP CHEMICALS LIMITED, THE UNIVERSITY OF SHEFFIELD
Application year: 1985
Main classification: C07C67
IPC codes: C07C67, C07C1, C07C69, B01J31, C07C27, C07C29, B01J27, B01J23, C07C5