RECYCLING CATALYST IN PREPARATION OF DIMETHYLFORMAMIDE FROM DIMETHYLAMINE AND CARBON MONOXIDE

Abstract: Dimethylformamide is produced by reacting dimethyla­ mine with carbon monoxide in the presence of sodium or other alkali metal methylate catalyst, the procedure being such that the reaction mass always contains dimethylamine in an amount of at least 0.1 wt % in excess of the stoichiometric requirements of the reaction. The effect of this is to enable the catalyst containing reaction mass to be subjected to subsequent distillation without substantial loss of dimethylformamide or of catalyst and this renders un­ necessary the costly pre-distillative catalyst removal usual in prior art processes.

Description: This invention relates to a method for preparing dimethylformamide (DMF) from dimethylamine (DMA) and carbon monoxide, using an alkali metal methylate as a catalyst. It is more particularly directed to an improvement in that process which permits the catalyst to be recycled and reused. DMF is a commodity in the chemical industry, widely used as a solvent and as a reaction medium in the preparation of dyes. One method for preparing DMF on a commercial scale is that in which DMA and carbon monoxide are catalytically reacted, using an alkali metal methylate as the catalyst. This produces crude DMF, which must be refined to be commercially acceptable. Before this is done, it is customary to remove the catalyst because its presence in the refining train together with water causes decomposition of the DMF product into DMA and formic acid, for obvious reasons an undesirable thing. This removal is ordinarily done by adding water to the reaction mass just before it is fed to the refining train. This converts the catalyst to an alkali metal formate precipitate, as shown by the following equations: where X is an alkali metal. As can be seen for equation (2), this producedure exacts an economic penalty because some of the product DMF is consumed. This yield loss can amount to as much as 2%, by weight. Furthermore, once the catalyst is so removed, it is lost and cannot be reused, which is another expense. To this must be added the additional cost of physically removing the alkal metal formate precipitate from the reaction mass. It has now been found that the catalyst removal step is not necessary and that the catalyst can be preserved, recycled and reused if an excess of at least 0.1%, by weight, over the stoichiometric amount of DMA is present in the reaction mass at all times. According to the present invention there is provided a process for the preparation of dimethylformamide which process comprises reacting dimethylamine with carbon monoxide in the presence of an alkali metal methylate as catalyst, characterised in that the reaction is effected with dimethylamine continuously present in the reaction mass in an amount of at least 0.1%, by weight, in an excess of the stoichiometric amount, and in that the reaction mass is subjected after formation of the dimethylformamide to distillative refining to separate a dimethylformamide raffinate for recovery as product from a catalyst-containing residue which is recycled to subsequent dimethylamine-carbon monoxide reaction. The reaction is conveniently effected in a reaction medium comprising dimethylformamide. The catalyst is preferably sodium methylate. The reaction is generally effected at a temperature of from 20°C to 160°C, preferably 60°C to 130°C. The reaction is in general effected at a pressure of from 40 to 220 psig (276 to 1517 kPa), reaction pressures in the range from 90 to 200 psig (620 to 1379 kPa) being preferred. The reaction is carried out preferably in the presence of less than 0.02 wt % water on the basis of the reaction mass. The following more detailed description illustrates the process of the invention by way of example. The DMA-carbon monoxide reaction is run by first charging a suitable reaction vessel with DMF. To this is added 0.25-2%, by weight of the DMF of an alkali metal methylate catalyst and, as mentioned earlier, this is preferably sodium methylate. The catalyst is added as a 0.5-10%, by weight, solution in methanol. To this catalyst-DMF mixture is then added 5-25%, by weight of the mixture, of DMA. The resulting reaction mass is then continuously stirred and its temperature is brought to and held at 20-160°C, preferably 60-130°C. The reactor is then pressurized to 276-1517 kPa gauge (40-220 psig), preferably 620-1379 kPa gauge (90-200 psig) with carbon monoxide. The reaction is allowed to continue until the DMA concentration in the reaction mass is no less than about 0.1%, by weight, as determined by periodic sampling and analysis by titrating with acid. The DMA can be present in the reaction mass in an amount greater than that just stated, but this confers no additional benefit and places a burden on the process because the excess DMA must be removed in a later stage. The reaction mass is then cooled to ambient temperature and the reaction vessel depressurized. The DMF produced by the DMA-carbon monoxide reaction is then separated from the reaction mass by distillation and is passed to a conventional refining train. The remainder of the reaction mass containing the catalyst, after replenishment of the DMA consumed in the reaction and the methanol lost in the distillation step, can be reused in another identical reaction. For maximum efficiency, about 5-10%, by weight, of the catalyst should be replaced after each cycle because of the slight but inevitable loss in the DMF separation step and the loss due to the usual presence of small amounts of water and carbon dioxide in the reaction mass. The DMA-carbon monoxide reaction can also be run continuously as shown, for example, in US Patent 2,866,822. Briefly, according to that process, DMA and a solution of methylate catalyst is methanol and introduced into a vertical reaction column at its top. The DMA and catalyst solution flow downwardly through the column, which has been pre-filled with DMA Carbon monoxide is introduced at the bottom of the column and flows upwardly, or countercurrent to the flow of DMA and catalyst solution. Product DMF is removed from the bottom of the column. The amounts of DMA and carbon monoxide fed into the reactor are regulated so that an excess of at least 0.1%, by weight, over the stoichiometric amount of DMA is present in the reaction zone at all times. This can easily be arranged by feeding the DMA and carbon monoxide at such rates that at least 0.1%, by weight, of DMA is continuously present in the reactor effluent. After the DMF product has been removed from the effluent by distillation, the DMF and catalyst which remain can, after replenishment as in the batch mode, be recycled to the top of the reactor. For the process of the invention to function at maximum efficiency, it is highly desirable that the reaction mass contain no more than about 0.02-0.03%, by weight, of water. The following is a specific Example intended to illustrate the invention, all parts mentioned in the Example being on a weight basis. A reactor was charged with 140 parts of DMF, a solution of 1.8 parts of sodium methylate in 38.2 parts of methanol and 11 parts of DMA. The reactor was sealed and the contents heated to and held at 105°C, with continuous stirring. The vessel was then pressurized with carbon monoxide (1379 kPa gauge, 200 psig). These conditions were held for 40 minutes at which time the DMA content of the reaction mass was about 0.1%. The reactor contents were then cooled to ambient temperature, the pressure released and the reactor opened. Sixteen parts of DMF and 38 parts of methanol were then distilled off at 155°F (about 68°C) and atmospheric pressure. To the remainder, which contained 1.7 parts of catalyst, were added another 11 parts of DMA and 38 parts of methanol. The reaction was then repeated with substantially the same result.

Claims: 1. A process for the preparation of dimethylformamide which process comprises reacting dimethylamine with carbon monoxide in the presence of an alkali metal methylate as catalyst, characterised in that the reaction is effected with dimethylamine continuously present in the reaction mass in an amount of at least 0.1%, by weight, in an excess of the stoichiometric amount, and in that the reaction mass is subjected after formation of the dimethylformamide to distillative refining to separate a dimethylformamide raffinate for recovery as product from a catalyst-containing residue which is recycled to subsequent dimethylamine-carbon monoxide reaction. 2. A process as claimed in claim 1 wherein the reaction is carried out in a reaction medium comprising dimethylformamide. 3. A process as claimed in claims 1 or 2 wherein the catalyst is sodium methylate. 4. A process as claimed in any preceding claim wherein the reaction is carried out at a temperature of from 20°C to 160°C. 5. A process as claimed in any preceding claim wherein the reaction is carried out at a pressure of from 40 to 220 psi (276 to 1517 kPa). 6. A process as claimed in any preceding claim wherein the reaction is carried out in the presence of not more than 0.02% water weight of the reaction mass. 7. A process according to claim 3 wherein the catalyst-containing residue which is recycled to subsequent dimetylamine carbone monoxide reaction is supplemented by added fresh catalyst in an amount of from 5% to 10% by weight.

Inventors: BELLIS, HAROLD EDWARD
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1981
Main classification: C07C233
IPC codes: C07B61, C07C67, C07C233, B01J31, C07C231