Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-08-06
2001-09-11
Solola, Taofiq A. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S508000, C549S509000
Reexamination Certificate
active
06288245
ABSTRACT:
DESCRIPTION
The present invention relates to a process for the production of tetrahydrofuran and gammabutyrolactone, particularly to a process starting from maleic, succinic anhydride or fumaric acid esters, by vapour phase hydrogenation in two subsequent stages, the former on a copper based catalyst, the latter on an acid silica rich silica-alumina type catalyst.
Tetrahydrofuran is a solvent used extensively in organic chemistry, and on the industrial scale it is in high demand for the production of natural and synthetic resins Gamma-butyrolactone is on the other hand among the other things a useful solvent for acrylate and styrene polymers.
It is known from the prior art that there exist several methodologies that can be employed for the production of Tetrahydrofuran (THF) and Gammabutyrolactone (GBL).
THF is produced starting from butanediol (BDO), by a process involving dehydration GBL too is produced starting from BDO by a process involving dehydrogenation. The production of THF and GBL starting from BDO is particularly costly because of the relatively high costs inherent with BDO, whose production involves rather complex processes.
According to a method which is widely utilised by industry, BDO is produced allowing acetylene to react with formaldehyde, with concomitant formation of butynediol which subsequently undergoes hydrogenation to form BDO.
Mitsubishi Chemical Industries of Japan has developed a process for the production of BDO starting from Butadiene.
The synthetic strategy comprises butadiene acetoxylation to 1,4-diacetoxy-2-butene, which is subsequently hydrogenated and hydrolized to BDO.
General Electric Corporation patented a process for the production of BDO starting from propylene. The synthetic pathway in this case includes conversion of propylene to allyl acetate, subsequently converted to 4-acetoxybutanol which forms BDO after hydrolysis.
Special attention has been devoted to the development of processes in which butane is utilised as starting material, through the formation of a maleic anhydride intermediate.
Several processes have been proposed for the production of THF, GBL or BDO starting from maleic anhydride, its esters or similar esters like succinic and/or fumaric acid esters.
U.S. Pat. Nos. 4,584,419 and 4,751,334 assigned to Davy McKee Ltd. describe processes for the production of BDO by hydrogenation of carboxylic acid esters that contain 4 Carbon atoms (typically ethyl maleate).
In International Patent WO 86/07358, this too assigned to Davy McKee Ltd, an account is given for a process where GBL is produced starting from maleic anhydride or the homologous dicarboxylic acid esters, by hydrogenation carried out in the vapour phase and in two subsequent stages on a chromite type catalyst.
In EP No. 322 140 in the name of Standard Oil Company, a process for the production of THF and GBL is given, starting from maleic or succinic anhydride, by a single stage hydrogenation on a catalyst made up of a copper, zinc and aluminium based mixture.
The aim of the present invention is to propose a process for the production of THF and GBL in varying proportions, starting from maleic anhydride and/or succinic acid and/or fumaric acid esters, all of these obtained allowing the acids or anhydrides thereof to react with an alcohol containing from 1 to 4 Carbon atoms.
According to the present invention the process is based on the production of tetrahydrofuran and gammabutyrolactone, by vapour phase selective hydrogenation of maleic anhydride, succinic anhydride and/or fumaric acid esters, characterised by the fact that the hydrogenation takes place in two subsequent stages, of which the former takes place on a copper based catalyst, and the latter on an acidic silica-alumina type catalyst that is rich in silica.
These and other features will be more readily apparent from the following description of a preferred not limiting embodiment of the invention with reference to the accompanying drawing in which a scheme of the production process is shown.
In the process object of the present invention the ester, after being completely vapourised by a hydrogen rich stream, is fed to a reactor characterised by two distinct reaction stages. The first stage contains a copper based heterogeneous hydrogenation catalyst, with a preference given to copper-zinc oxide or stabilised copper chromite type catalysts.
The subsequent reaction stage contains an acidic silica enriched silica-alumina type heterogeneous catalyst.
To allow the reaction to take place in the vapour phase, the reaction mixture must be very rich in hydrogen.
The hydrogen to ester molar ratio ranges between 100 and 600:1, preferably between 200 and 400:1.
Pressure and temperature as well as catalyst contact times in each reaction stage may be optimised depending on the choice of the GBL:THF product ratio. Such ratio may be varied within a wide range, that is GBL:THF ratios that go from 70:30 to 40:60.
The average operating pressure ranges between 3 and 40 bars, preferably from 15 to 25 bars
In both reaction stages, temperatures range between 180 and 280° C., and typically between 200 and 250° C.
Overall Liquid Hourly Space Velocity ranges between 0.1 and 0.5 hr
−1
.
The space velocity with which the gaseous mixture goes on the catalyst (gaseous space velocity on the catalyst) in the second reaction stage results to be 1.5 to 10 times higher than that on the catalyst of the first reaction stage.
A cooling between the first and second reaction stage can be carried out in a heat exchanger or more simply by mixing the cold hydrogen mixture to the effluent in the first reaction stage.
REFERENCES:
patent: 4105674 (1978-08-01), De Thomas et al.
patent: 8607358 (1986-12-01), None
patent: 0322140 (1989-06-01), None
patent: 9743234 (1997-11-01), None
Miya et al., Prepr. Div. Pet. Chem., Am. Chem. Soc. 18(1) pp. 187-192, 1973.
Pantochim S.A.
Solola Taofiq A.
Stevens Davis Miller & Mosher LLP
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