United States Patent 1 Shamshoum et al. AQUA AAA A 1US005387732A, Patent Number: 5,387,732 Feb. 7, 1995 Date of Patent: il} 145] [54] START-UP PROCESS FOR IMPROVED SELECTIVITY IN TOLUENE. DISPROPORTIONATION Inventors: Eéwar S, Shamshoum; Ashim K. Ghosh, both of Houston; Thomas R. ‘Schuler, Galena Park, all of Tex. Fina Technology, Inc., Dallas, Tex. 40,764 ‘Mar. 31, 1993, 75] (73) i) [22] Assignee: Appl. No. Filed Related U.S. Application Data Continuation-in-part of Ser. No. 776 937, Oct. 15,1991, abandoned. Int. CLS... US. a. Field of Search . References Cited US. PATENT DOCUMENTS 3,667,973 7/1972. Mitshe etal 3,780,122 12/1973. Politzer etal. $665,258 5/1987 Butler et al. Primary Examiner—Asok Pal ‘Assistant Examiner—P. Achutamurthy ‘Attorney, Agent, or Firm—Betty M. Ellsworth; M. Norwood Cheairs 57] ABSTRACT A process is provided for the disproportionation of 2 [63] fs] [52] [58] [56] . COIC 3/62 385/475 585/475 02/70 ‘sasva7e 585/475 A H2/TOL MOLE RATIOI.IAT START OF FEED toluene feed stock that includes using an unconvention- ally low hydrogen to toluene mole ratio during reaction start-up, ie, until the production of non-aromatics be- gins to stabilize; thereafter the ratio is increased. Reduc- ing the hydrogen content at the beginning of the reac- tion substantially lessens any hydrogenation activity, thereby gaining optimum selectivities to benzene at a much sooner rate than that achieved using more con- ventional hydrogen to toluene ratios. The post start-up increase in hydrogen concentration following stabilized production of non-aromatics is generally believed to enhance the aging character of the catalyst, thereby preserving catalyst life. In practicing the invention, a reaction 2one is established loading a metal-modified ‘mordenite catalyst into the reaction zone. A toluene containing feed stock is continuously supplied to the reaction zone. Contemporaneous withthe introduction of the toluene, hydrogen gas is introduced into the reaction zone fo provide a hydrogen to toluene mole ratio of between 0.5 and 1.5. The feed stock contacts the catalyst forming a disproportionation product contain- ing benzene, xylene(s) and nonaromatic by-products. ‘The disproportionation product is continuously with- drawn and measured to determine its non-aromatic ‘content. When the non-aromatic content of the dispro- portionation product stabilizes, the amount of hydrogen supplied to the reaction zone is increased. 12 Claims, 4 Drawing Sheets —o— NONAROMATICS 8 H2/TOL MOLE RATIO CHANGED FROM LIT02.5 73S %1M. 28 TIME ON STREAM, DAYS H2/TOL MOLE RATIO CHANGED FROM 257045 —a— BENZENE 30 355,387,732 Sheet 1 of 4 Feb. 7, 1995 US. Patent ol SAVG ‘WV3YLS NO SWIL 2 9 Ss v @¢ Ollwy FION TOL/ZH -< at OllVe STOW TOL/ZH -2 SO OllWY STOW T0L/2H -1 Old ol sI 02 se WT% SEL5,387,732 Sheet 2 of 4 Feb. 7, 1995 USS. Patent ol SAvG ‘WV3ULS NO SIL 8 2 9 sg v @¢ OllwyY STOW 10L/2H -9 21 OllWY STOW 10L/ZH -S GO O1LWY STOW IOL/ZH -% 29l4 o— WT% SEL