# US 5,705,673 A · Continuous process for the preparation of phenyl methyl carbonate > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,705,673 A - Document ID: US5705673A - Status: Granted - Kind: A - Application number: 08/768,811 - Filed: 1996-12-18 - Granted: 1998-01-06 - Earliest claimed: 1996-01-16 - Assignees: Enichem S.p.A. - Inventors: Franco Rivetti; Renato Paludetto; Ugo Romano - Web page: https://patentgrep.com/patent/US5705673A ## CPC - B01D 3/009: {in combination with chemical reactions} - C07C 68/06: from organic carbonates - Y02P 20/10: Process efficiency - Y02P 20/582: Recycling of unreacted starting or intermediate materials - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract The present invention relates to a continuous process for the preparation of phenyl methyl carbonate. The process is carried out in a first distillation column consisting of a lower reactive section and an upper rectification section and a second rectification column. The reactive section of the first column has a practically constant thermal profile at the optimum temperature for the reaction, and that with the use of the second column a circulation of dimethyl carbonate is created between the top and bottom of the first column which allows an advantageous excess of dimethylcarbonate to be fed to the bottom of the first column. ## Claims ### Claim 1 A continuous process for the preparation of phenyl methyl carbonate starting from phenol, dimethyl carbonate and a transesterification catalyst, which comprises: (a) carrying out the process in a first distillation column consisting of a lower reactive section and an upper rectification section and in a second rectification column; (b) feeding to the top of the reaction section of the first column a stream (I) containing phenol and optionally dimethylcarbonate in a ratio equal to or higher than 60/40 by weight and all of the catalyst; feeding to the bottom of the reactive section of the same column a stream (II), comprising a stream or part of a stream (III) extracted from the bottom of the second column, containing dimethylcarbonate and optionally phenol in a ratio equal to or higher than 80/20 by weight; the streams (I) and (II) being fed in such a quantity that the ratio between the total moles of dimethylcarbonate and phenol fed ranges from 2:1 and 10:1; feeding to the top of the rectification section of the first column a stream (IV) which consists of the reflux of the column, having the composition of a stream (v) taken from the top of the column itself and fed to the second column, in such a quantity that the weight ratio of the reflexed liquid (stream IV) to the distillate (stream V) is within the range of 0.2-0.8; c) extracting from the bottom of the reactive section of the first column a stream (VI) essentially containing all the non-reacted phenol, phenyl methyl carbonate and any possible diphenylcarbonate produced, the transesterification catalyst and a fraction of the dimethyl carbonate fed so that the molar ratio in this stream between the dimethylcarbonate and the phenol is between 0.5 and 5; extracting from the top of the rectification section of the first column, a stream V, essentially containing dimethylcarbonate and all or basically all of the methanol produced by the reaction; d) feeding to an intermediate section of the second column a stream (V) extracted from the top of the first column; e) extracting from the top of the second column a stream (VII) containing all or practically all of the methanol fed to the second column and dimethyl carbonate in a ratio of more than 50% by weight; extracting from the bottom of the second column a stream (III) essentially consisting of the remaining dimethylcarbonate; f) recycling said stream III or part of it to the bottom of the first column. ### Claim 2 (depends on 1) The process according to claim 1, wherein the feed to the intermediate section of the second column consists of a stream (IX) taken from the top of the first column and the feed to the top of the rectification section of the first column of a stream (VIII) which forms the reflux of the column and is separated from stream (III), streams (VIII) and (IX) being fed in such a quantity that the weight ratio between the refluxed liquid (stream VIII) and the distillate (streams IX-VIII) is within the range of 0.2-0.8. ### Claim 3 (depends on 1, 2) The process according to claim 1 or 2, wherein the reactive distillation section of the first column comprises at least 3 theoretical distillation steps and the rectification section comprises at least 3 theoretical distillation steps. ### Claim 4 (depends on 1) The process according to claim 1, wherein stream (V) or stream (IX) contains phenol at a concentration of less than 2% by weight. ### Claim 5 (depends on 1) The process according to claim 1, wherein the concentration of methanol in stream (V) or in stream (IX) ranges from 1 to 5% by weight. ### Claim 6 (depends on 1) The process according to claim 1, wherein the operating pressure of the first column, measured at the top of the column, ranges from 3 to 10 absolute bars. ### Claim 7 (depends on 1) The process according to claim 1, wherein the temperature measured at the top of the first column ranges from 100.degree. and 210.degree. C. and the temperature at the bottom of the reactive section ranges from 250.degree. and 150.degree. C. ### Claim 8 (depends on 1) The process according to claim 1, wherein the difference between the temperature of the bottom and the temperature of the feeding zone of stream (I) is not higher than 20.degree. C. ### Claim 9 (depends on 1) The process according to claim 1, wherein the second column contains at least 10 theoretical distillation steps and is fed in such a way that the theoretical steps present above and below the feeding are arranged in a ratio ranging from 1/3 to 3/1. ### Claim 10 (depends on 1) The process according to claim 1, wherein the second column operates at a pressure, measured at the top, ranging from 1 to 10 absolute bars and a temperatures at the top and bottom ranging from 65.degree. and 135.degree. C. and from 90.degree. to 180.degree. C. respectively. ### Claim 11 (depends on 1) The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst based on alkoxides and aryl oxides of titanium and said catalyst is present in a molar quantity ranging from 0.1 to 10% with respect to the total phenol fed. ### Claim 12 (depends on 1) The process according to claim 1, wherein stream (VI) or part of it, extracted from the bottom of the reactive section of the first column is subjected to adiabatic flash by pressure reduction in a flash chamber and the vaporized stream thus obtained, extracted from the top of the flash chamber, is fed to the bottom of the reactive section of the first column to form, together with stream (III) or part of it and optionally fresh dimethyl carbonate, stream (II). ### Claim 13 (depends on 12) The process according to claim 12, wherein the flash chamber operates at atmospheric pressure and the flash temperature ranges from 130.degree. and 170.degree. C. ### Claim 14 (depends on 12) The process according to claim 12, wherein the vaporized stream taken from the top of the flash chamber is in a quantity equal to a fraction by weight of the feeding of the chamber itself ranging from 20 to 40%. ### Claim 15 (depends on 12) The process according to claim 12, wherein the stream taken from the top of the flash chamber contains dimethyl carbonate and phenol in a ratio equal to or higher that 80/20 by weight. ### Claim 16 (depends on 12) The process according to claim 12, wherein the stream taken from the bottom of the flash chamber contains a ratio phenol/dimethylcarbonate higher than that present in the stream fed, as well as most of the product formed and all of the catalyst. ### Claim 17 (depends on 1) The process according to claim 1, wherein the molar ratio of dimethylcarbonate to phenol of streams (I) and (II) ranges from 3:1 to 6:1, and wherein the molar ratio of dimethylcarbonate to phenol in step (c) ranges from 1 to 5. ### Claim 18 (depends on 2) The process according to claim 2, wherein the weight ratio of refluxed liquid to distillate ranges from 0.2 to 0.8. ### Claim 19 (depends on 3) The process according to claim 3, wherein the number of distillation steps ranges from 5 to 25. ### Claim 20 (depends on 6) The process according to claim 6, wherein said operating pressure ranges from 4 to 8 absolute bars. ### Claim 21 (depends on 7) The process according to claim 7, wherein the respective top and bottom temperatures range from 140.degree. to 180.degree. C. and 220.degree. to 180.degree. C. respectively. ### Claim 22 (depends on 9) The process according to claim 9, wherein the number of theoretical distillation steps ranges from 20 to 50 and wherein said ratio of distillation steps ranges from 1/1 to 1/3. ### Claim 23 (depends on 11) The process according to claim 11, wherein said catalyst is titanium tetraphenate, and the molar amount of said catalyst ranges from 0.2 to 2%.