GB2106893A - Process for the production of isobutyric acid anhydride - Google Patents

Abstract

In a process for the production of isobutyric acid anhydride in which propylene is initially carbonylated in the presence of a substantial molar excess of liquid anhydrous hydrogen fluoride to provide a reaction mixture of isobutyroyl fluoride and unreacted hydrogen fluoride, following distillation of the reaction mixture to recover a recycle stream of hydrogen fluoride, the isobutyroyl fluoride residue is partially hydrolyzed in the presence of a hydrogen fluoride acceptor resulting in a hydrolysis product consisting essentially of isobutyroyl fluoride, isobutyric acid anhydride and a hydrogen fluoride complex of said acceptor, and following removal of the solid complex, the hydrolysis product is fractionally distilled to yield an overhead fraction of isobutyroyl fluoride for reuse in the hydrolysis reaction.

Description

SPECIFICATION Process for the production of isobutyric acid anhydride This invention relates to a process for the production of a lower carboxylic acid anhydride from the corresponding mono-acyl fluoride.

It is known that olefins react readily with carbon monoxide at low temperatures and under moderately high pressure in the presence of a strong acidic medium, typically representative of which include anhydrous hydrogen fluoride, concentrated sulfuric acid and anhydrous clhorosulfonic acid. The postulated carbonylation mechanism involved is conventiona;ly referred to as the Koch reaction and is exemplified in U.S. Patent 2,831,877. The foremost problem faced in any commercial implementation of the Koch reaction in the production of a lower carboxylic acid resides in the difficulty experienced in recovering the acid catalyst in the form suitable for recycling.

Komatsu et al in Bull, Jap. Pet, Inst., 16 124-131 (1974) address this recovery aspect as such specifically applies to the Koch reaction employing a lower olefin. A procedure is accordingly outlined therein for the recovery of HF following preparation of pivalic acid in accordance with the Koch reaction. Essentially the procedure involves hydrolyzing the carbonylation reaction mixture with an equimolar mixture of hydrogen fluoride and water (54% aqueous HF) and distilling to recover anhydrous HF. Thereupon the residue in the form of an equimolar HF complex of pivalic acid is hydrolyzed using a minimum amount of water to provide two layers; the top layer being carboxylic acid product and the other being recyclable 54% aqueous HF.

Unfortunately, this method is not applicable in a like process for preparing isobutyric acid insofar as the said carboxylic acid is soluble in 50% aqueous HF. The only way to effect phase separation is to dilute the carboxylic acid solution with a substantial amount of water. The net result is that a mole of HF per mole of the carboxylic acid product is effectively non-recoverable for use in the process.

In accordance with the invention, there is provided an integral process for the production of isobutyric acid anhydride comprising the steps: (1) carbonylating propylene in the presence of a substantial excess of liquid anhydrous hydrogen fluoride to effect the formation of isobutyroyl fluoride: (2) fractionating the carbonylation reaction mixture to provide unreacted anhydrous hydrogen fluoride for recycle and isobutyroyl fluoride;; (3) partially hydrolyzing the isobutyroyl fluoride at a temperature between 0 and 1 00 C in the presence of a hydrogen fluoride acceptor and from 0.05 to 0.5 mole of water per mole of the isobutyroyl fluoride whereby the water is used to extinction in the hydrolysis reaction thereby providing an equilibrium hydrolysis reaction mixture including a liquid phase consisting essentially of isobutyroyl fluoride and isobutyric acid anhydride; and (4) fractionally distilling said liquid phase of the hydrolysis reaction mixture to provide an overhead fraction of isobutyroyl fluoride for recycle to said hydrolysis step (3) and an isobutyric acid an hydride product fraction.

In a further aspect of the invention, the spent accpetor is regenerated to provide anhydrous HF and acceptor for recycle.

The accompanying drawing is a flow diagram schematic illustrating the production of isobutryic acid anhydride via the carbonylation of propylene in the presence of anhydrous HF wherein the method of the present invention is implemented for the internal cyclical reuse of the anhydrous HF.

Although the present invention represents but a certain aspect of an overall process for producing isobutyric acid anhydride, much of which is prior art, a detailed description of the invention must necessarily be given in context of the contemplated overall processing scheme.

Reference is accordingly had to the accompanying drawing which first depicts a carbonylation reactor 1 wherein anhydrous hydrogen fluoride, a petroleum grade propylene and carbon monoxide are reacted to produce isobutyroyl fluoride with essentially 100% selectivity. In this connection mention will be made of the operating conditions determined to be optimum in a particular reactor design. These conditions may or may not be optimum for a different design.

However, the determination of such conditions for any particular design is within the province of a skilled worker.

The carbonylation reaction is carried out at a pressure of 340 atmospheres provided by the carbon monoxide feed stream (11) and a temperature of about 30"C. The propylene feed stream (10) is combined with the anhydrous HF stream (12) to provide a mole ratio ofl :1 5, respectively, within the carbonylation reactor. The residence time within the reactor is 30 minutes. The reactor effluent stream (13) is passed through adiabatic expansion valves (not shown) into the receiver or primary flash tank 2 within the pressure is 20 atmospheres.

The off-fuel gas stream (14) from the receiver 2 is passed through scrubber3 whereas the condensate composed mainly of isobutyroyl fluoride and liquid HF as stream (16) is introduced into the HF distillation still 4. The overhead HF fraction along with make-up HF constitutes the main HF reactor feed stream (12). The isobutyroyl fluoride residue from the HF distillation still 4 is introduced into the hydrolyzer 5 as the principal feed (18) thereto. Water is introduced into the hydrolyzer which is shown emanating from the off-fuel gas scrubber 3 as stream (19). The third feed to the hydrolyzer is the HF acceptor which in this particular exemplication is sodium fluoride as represented by stream (24).

The hydrolysis is carried out at a temperature between about 0 and 1 00 C. and more preferably from 0 to 40"C. in the presence of from 0.05 to 0.5 mole of water per mole of the isobutyroyl fluoride present in the hydrolysis reaction mixture and more preferably from 0.2 to 0.4 mole on the same basis. It is essential that the water be used to extinction in the course of the hydrolysis reaction. The resultant hydrolysis reaction product is an equilibrium mixture of isobutyric acid an hydride, isobutyroyl fluoride and the complexed sodium fluoride. A further feature of this invention is that of maintaining an appropriate amount of isobutyroyl fluoride in the equilibrium mixture which importantly serves as a solvent for the isobutyric acid anhydride.

Upon recovery of the complexed sodium fluoride by filtration as shown or by other suitable means; e.g., centrifugation, the homogeneous phase as stream (20) is introduced into the product fractional distillation column 6. The overhead fraction of isobutyroyl fluoride from column 6 is recycled to the hydrolyzer 5 and a product fraction of isobutyric acid an hydride is recovered as identified by stream (21).

While the above description refers to the use of sodium fluoride as the hydrogen fluoride acceptor, a variety of other compounds are applicable for this purpose. In the context of this invention an acceptor is broadly any compound which will accept a proton but at the same time will not competively react with either isobutyroyl fluoride or isobutyric acid anhydride. The preferred acceptors are the alkali metal fluorides, particularly sodium fluoride exemplified herein.

These salts are attractive because they readily complex with HF and are easily regenerated via a heat treatment with concurrent release of anhydrous HF. Activated carbon represents another suitable acceptor capable of being regenerated by heat. Tertiary amines, basic ion exchange resins as well as alkali metal oxides are capable of serving as acceptors. However, regeneration of the latter acceptors is not as facile as in the case of the indicated preferred acceptors.

Reverting to the accompanying drawing in connection with this discussion, the complexed sodium fluoride is shown as stream (22) from filter 7to the HF regenerator 8. In this instance the regenerator takes the form of a simple kiln. The generated HF is shown as stream (23) which is combined with stream (1 7) from HF DISTILLATION 4 for recycle to the carbonylation reactor 1 along with make-up HF. The regenerated sodium fluoride (24) is accordingly recycled to the hydrolyzer 5.

Example I In order to illustrate the best mode contemplated for practicing the present invention, the detailed description presented above is supplemented herein by providing the compositional data of the various process streams outlined in the drawing. This data is given on the basis of a unit designed to produce about 100 Ib. moles of isobutyric acid anhydride per hour.

Accordingly, the flow rates (1 b. moles/hr) of the various streams are tabularly listed in the following Table 1.

TABLE I STREAM FLOW RATES IN PRODUCTION OF ISOBUTYRIC ANHDRIDE (LB.MOLES/HR) STREAM NO. 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 PROPYLENE 22.0 6.6 6.5 6.3 .1 23.1 .2 .2 PROPANE 94.3 94.3 94.0 90.0 .3 .3 .3 .3 CARBON MONOXIDE 242.0 28.6 27.7 27.3 .9 .9 .4 .4 HYDROGEN FLUORIDE 3300 3086.5 10 Tr 3076.5 3000(-) 10 18.4 128.4 Tr 229.1 ISOBUTYRL FLUORIDE 202.7 202.7 5 200.7 Equil.

ISOBUTYRIC ACID Equil. 98.0 ISOBUTYRIC ANHYDRIDE WATER 5.2 101.4 HEAVY FLUORIDES 10.7 10.7 .7 10 SODIUM FLUORIDE 229.1 NaHF2 COMPLEX 229.1

Claims (6)

1. An integral process for the production of isobutyric acid anhydride comprising the steps: (1) carbonylating propylene in the presence of a substantial excess of liquid anhydrous hydrogen fluoride to effect the formation of isobutyroyl fluoride; (2) fractionating the carbonylation reaction mixture to provide unreacted anhydrous hydrogen fluoride for recycle and isobutyroyl fluoride; (3) partially hydrolyzing the isobutyroyl fluoride at a temperature between about 0 and 1 00 C.

in the presence of a hydrogen fluoride acceptor and from 0.05 to 0.5 mole of water per mole of the isobutyroyl fluoride whereby the water is used to extinction in the hydrolysis reaction thereby providing an equilibrium hyrolysis reaction mixture including a liquid phase consisting essentially of isobutyroyl fluoride and isobutyric acid anhydride; and (4) fractionally distilling said liquid phase of the hydrolysis reaction mixture to provide an overhead fraction of isobutyroyl fluoride for recycle to said hydrolysis step (3) and an isobutyric acid anhydride product fraction.

2. A process according to Claim 1 wherein said hydrolysis step (3) is effected at a temperature between 0 and 40"C. and in the presence of from 0.2 to 0.4 mole of water per mole of isobutyroyl fluoride.

3. A process according to Claim 2 wherein said hydrogen fluoride acceptor is an alkali metal fluoride.

4. A process according to Claim 3 wherein said acceptor is sodium fluoride.

5. A process according to Claim 3 or 4 wherein the hydrogen fluoride complexed acceptor is recovered from the hydrolysis reaction mixture of step (3) and heated to provide recycle anhydrous hydrogen fluoride and regenerated acceptor for reuse in the hydrolysis step (3).

6. A process for the production of isobutyric acid anhydride substantially as described herein and in accordance with the Example.