2) Dintses, AL, Came Read deed. Si, U8.R. 2,153 (1933) 13} Dinusee, A. Lipo Rin 95104 (1939), i De Frost, A. Vin'J Cem. Chom. USSR. 3 147 1933). o Dixon, W. J., Massey, F. J., Jr., “Introduction to Statistical ‘anaes Nase il, Now York, 1ST copies, 3) Sit, 1G, “Ea L, Boman 5 ‘strfeld CN, Inn Ewo, Chew Protas Dston Daven i ise, Beh he sen oy 8 Dinter, A. iy Bros, A.V. I. Plyr Chem: U'S.8.8. 290 (1936) 11) Kasunsky, B, Plate, A, F, Ber 67,1023 (1954. Konovaiov, 'D. Sy Migotina, "EN, Zk rill, Khim 26, 352 (1953). (13) "Kichler, Ly Trans, Faraday Se. 95,874 (1939). 14) Levenpiel’Q,"Chetmiesl Reaction Engineéxng," Wiley, few York 1962 13) Malinowski, M, 5. Stoyanovikays, Ya. 1, J. Appl. Chem CREE Te 580) i a continuous flow reactor. ‘approximate empirical relation: W ‘The reaction of toluene to form benzer Jo 21 pas few years there has been much incre i using the large supply of petrochemical toluene as a raw material for chemical synthesis rather than asa fuel. At elevated tem- peratures, tokiene will react with hydrogen to produce benzene and methane as the main products, cH ‘Yy m—(J+on Dee-0 Processes (or both the thermal and catalytic demethylation of toluene have appeared in the recent literature (3,-). Silsby and Sawyer (7) have proposed a reaction mechanism and presented some kinetic data on the thermal demethylation Feaction. Several other articles on the thermal demethylation reaction (/. 5. 8) have also appeared. However, few pert nent data of use o the chemical engineer have been published. This study was undertaken to obtain kinetic and engineering data on the thermal demethylation reaction, Of particular terest was the determination of the yield of benzene as a function of temperature, residence time, and the hydrogen toluene ratio ofthe feed. Some of the problems of commercial application were investigated by determining the effects of in the toluene and hydrogen feed streams, \ Present athens, Denne Rese tileron Cl 254 1AEC *ROCESS DESIGN AND DEVELOPMENT unaffected by thiophene, pyridine, or carbon monoxide. (09) Ma HB Eabuns B Me Smith JO, Sater, rsty and Reding Se Me. Reta, ed Vol I, Wiley, New York, in press Me (17 Bese, oN, Morton J My oe me lm, Se 3, 3190 (18) Raton, R, OH Gar J. 39, Feb. 13, p. 49; Feb, 20, . 45, Gout. (0 Sehiltee, C. Ry Wasermann, Gy, Z. Ektoaton, 47, 774 sai). (20), Sherwood, T. K., Reid, R. C., “The Proper Liquids,” MeGraw-Hill, New York, 1988. iy Steacic, E. W.R., "Atomic and Free Radical Reactions," 122, Reinhold, New York, 1984 (22) Sundgrén, A. tan. Ofte Nat Combustibler Lipids $44 (1920), (23) Tilieheev, M. Diy Za. Prd. Kim. 12,755 (1939) Receives for review July 25, 1963 Accerrep November 4, 1963 Work etrmed wer he deo of Mater Gana, Dze- torate Sf Advanced Systems Teshnology, Weight Air Development Bivsion, Wright-Patterson Air Force Bases Obie, on Centart AP 35057) 8103. of Gates and THERMAL DEMETHYLATION OF TOLUENE ©. C. ZIMMERMAN! AND ROBERT VORK, Come Univesity, tata, N.Y. The thermel demethylation of toluene at 700° to 950° C. and otmospheric pressure has been studied in @ The reaction was found to be first-order with respect to toluene and half-order ith respect to hydrogen. The rate constants for the decomposition of tol ‘are identical within experimental error and have valves in units of (moles/liter)~"* (sec.)~! of k, = 3.5 X 10! exp (—50,900/R7) and ky = 3.0 X 10! exp (—$0,900/RT]. The yield of by-products follows the 1.0 X 10" 6/b exp (—51,000/811, where W products, weight per cent of feed, b = hydrogen-tolvene ratio, ond # = actual gas residence time, seconds. is increased by the presence of large amounts of m-heptone, but is cond formation of benzene the yield of by- ‘A possible reaction mechanism is diseussed. Experimental Reactor System. ‘The flow eeacor is shown schematically in Figure 1 the ‘main part of the reaction system was a Vaporizer, a preheater anda reactor, The porter comined ff0 feet of inch stainless ste tubing Immersed in maton Sait bath. The vaporized ‘olene, after ming wth hydrogen, passed into the preheater tbe made of 1 esto Vyeortwbing Formed into a eat The picheater scion vas designed ob rapid heat crarser and s shor residence ine, Theceaete, fr iouher, section was uo constructed of Vyeor glass thing and provided the required. residence tine. for’ conversion tora place, The reator section was 2¢ inches tong and had olurae of 2.25 ler Temperature was measured with Bee there-Aluriel thermocouples lasted at intervals ina the reaction chamber. Rendence time in the reactor was varied byehanging the reactant feed rate, “The reaction produet vas quenched ina shor, double-pipe heat exchanger which was cotled with ceulatng eld water The reacdon peoduct pated through the annular space Be tween the thermocouple fad protection tube and the inner wall of the condenser. "The condenser effing, inthe forea ofa dense aromatic fog, was shen pase through a glas woo! Sesto separate the gas and Higuid. "The gus was then passed through cold wap (acstone and dry tee) where addlonal Tguld product condensed: “Toluene was fed into the reaction system by a metering pump. and the hvdrogen flow was regulated by means ol § Enlibated rotamecer. The liquid product from the seacor was determined by veighing the titer collection flak and cold trap after each CScous prndices were meer by a wettest meter prior © being vented row thare, f: Toma pliers Reaction Temperature and Volume. During the course ‘of each run the temperatures of the five thermocouples in the feactor were measured and recorded at regular intervals tosraly the maniac emperatre vaviaon among the {Pesan "The average of the poise readings of the pper tour thermocouples was used’ ab the correct reaction teimperature “The portion of the reactor which included the upper four thermocouples had a volume of 173 liters and comprised 78% ofthe total reactor volume In the lower portion of the reactor the temperature rapidly dropped until the exit temperature was abut 300° ©. below ths veaction temperature. The lower section of the reactor had a volume of 800 ma. or 22% ofthe total reactor volume. "The contribution which tis lower section made to the reaction was calculated by the method of equivalent reactor Jolume as outlined by Hougen and Watson (2). An activa: on energy of 30 keal. per gramemole was sanimed. for the Ealeulations. ‘The S00-mi. section was found to be equivatent {2 220 220 ml, at the temperature of the reaction. The Contribution of the preheater section, with a nominal volume F120 ml, was caleated tn the same manner and found to be fquivalent 1030 ++ 10 ml “The reactor volume used for calculation purposes was equal to the volume ofthe upper section plus the equivalent volumes of the lower section and the preheater. Thus, the reactor Solume was 2000 + 30 ml. forall uns "Analysis. Analysis of the liquid product was made by gas~ liquid chromatography. using a Zemetcr Type A. column (Gisodeey! phthalate on diatomaceous earch). "Analyses were conducted at 125° and 130" C. for each sample of liquid product. No analysis ofthe prodhict gas was made. Feod Materials ‘Toluene Mallinckrodt Chemieal Co. analytical ‘eagent grace, 993% purity by cei igrade, guaranteed purly 93.5% a apenas ino oe pint 98-99" G.);_ practical grade Foheprane 80%, mettivteyeloherane 1% noheptanes 9%, toluene Ie led into Experimental Runs, The experiments were di four main pacts: 1. Aeron ofrune with a large exces of hydrogen in which the’ tuene Bow rate and. (enpersure were Said: The inkl hydrogen toluene rato wat kept greater than #0 2. Avene of rant simiar to the fs seit where scat sively larger portions ofthe hydrogen were replaced by ito. gen.” For theve experiments the total gaeohuene rao Wat Spproximately 10. Pere erie of runs where the hydrogenoluene ratio wae varied, but no nitrogen was added. ie Alef rato deermine the effet of sch impurities as carbon monoxide, thiophene, pyridine, analyial grade Beptane, and practical grade wheptane Operating Conditions. The range of experimental oper- ating conditions is shown in Table I. For the series of runs with a large excess of toluene, the temperature varied from 692° to 949° C. and the residence lime from 1.3 t04.7 seconds. Tablo I. Operating Conditions Ws) Toluene Residence Tene Feet Atle "Fine Se pate ain St Minimum = 692 Aim, OMS Miumm 30) Aw 53S vemes | =e i RE Sage he Gc Ney pep Figure 1. Diagram of apparatus When nitrogen was added as a diluent, the hydragen- toluene ratio varied from 0.11 to 3.73. ‘Temperature varied from 714° to 859° G., and residence time from 1.8 to 5.0 seconds, In che series of runs without nitrogen, the hydrogen-toluene ratio varied feom 0.76 to 1.38. Temperature varied from 755° 10 863° C., and residence time from 2:4 to 4.4 seconds, ‘The compositions of the feed streams used t6 determine the effects of various impurities are found in Table II. The hydrogen-oluene ratio yaried from 1.2 to 4.3, temperature varied from 725° to 859° C., and residence time varied from 25 to 5.8 seconds, Reaction Kinetics, ‘The kinetic model of Silsby and ‘Sawyer (7) was found to ft the data best. This model the reaction mechanism Het 2H a He + GuHACH, ~ Odi: ++ CH, @ CHa: + Hy + Cully +H 6) Assuming that Reaction 1 is at equilibrium leads to kinetic equations of the form, _ dlescH} a/FY 1 (CaALACHs) (FE and dlCatl @,/F) ‘Theoretically, the rates of toluene decomposition and benzene formation are equal “The reaction rate constants were evaluated in the following manner. From the analysis of the liquid product, bath the conversion of toluene and the yield of benzene were computed These values, along with the temperature, pressure, feed rate, and the ratio of the reactants, were used to ealeulate the rate constants, using the equation = fy (CaHACH) [Hf 6:00 x 108 sé yor by = £2210 pergypys [* — Foe crons a Table. Feed Comporition For Rune 62 to 62 Tae Fe, “stg Fe, sled Capen, A et, ie i 4.65 prise ure hydrogen 9% thiophene Pure hydrogen 1.89 SMOPMEST pre neptane Rare Ryarebes 28% practical grade n-heptane Pare foluene e Pore hyerogen 8:5-20%, carbon monoxide VoL 2 NO.3 sULY 1964 255T T ewe, 822°C * Toluene. conversion % 8 0 1 . % T ; HeTOL @ario =5:1 0 « Toluene Conversion % 8 » v 2 3 4 5 Ye sec Etsecs) Figure 2. Effect of hydrogen-tolvene ratio on conversion ‘The experimental results are shown in Figures 2 through 6. Figure 2 shows the effect of hydrogen-oluene ratio on the conversion at a fixed temperature. Figure 3 shows the effect ff temperature on the conversion at 4 fixed hydrogen ratio. Figures 4 and 5 are standard Archenius plots showing the temperature relationships of the rate constants. ‘The reaetion ale conttants may be expressed by the equations, 3.53 100" exp (~$0,900/R7) o by = 3.0 X 109 exp (~50,900/R7) o ‘These equations are valid from 700° ro 950° C. and at hydro- gen-toluene ratios above 0.2. Above 850° C., the observed fate of formation of benzene will be slightly lower than pre dicted by Equation 5 ifthe hydrogen-toluene rato is less than 15 boeequse of increased by-proditet formation. ‘The benzene sing showed good stability under the reaction conditions. Carbon formation was low, and the liquid prod- uct recovered was 95% of the liquid feed or better, except under the most exteme conditions. Carbon was observabie on the reactor filter and inthe product only when the reaction temperature was above B50® C. and che hydrogen-toluene ratio was less than 1.5 0 By-Products. Three types of by-products were observed alkylated benzenes. diphenyl, and condensed ring structures. By-product yields varied fom negligible amount to more than S.weight % of the feed. Generally, by-product yields ex- ceeded 0.5 weight % of the feed only when the temperature vas above 850° C., the hydrogen-toluene ratio was less than 2 to 1. oF the conversion was greater than 30%, When the colvene catia, and the conversion temperature, the hyeroge Simultaneously exceeded these limits, the by-product forma sion was 2 weight “yof the eed or greater, 256 IMEC PROCESS DESIGN AND DEVELOPMENT Xe isec E isees) Figure 3, Effect of temperature on conversion of tolvene. ‘The yield of by-products follows the approximate empirical relation, Wo 10x 10 op (-sia00a) In Figure 6 the data are plowed from which Equation 6 was determined. Effect of Feed Composition. The demethylation reaction was unalfected by thiophene, pyridine, or carbon monoxide. However, the addition of mheptane to the toluene feed pro- duced a marked increase in both the demethylation reaction rate and the yield of by-products. The heptane also thermally cracked and formed low boiling compounds which were not recovered in the liquid product. The inerease in the reaction rate ean be seen in Figures 4 and 5, where the runs with hep= tane are also plotted, The activation energy calculated from the runs with heptane is 35 keal. per mole, Discussion The toluene decomposition and benzene formation rates shown in Equations 4 and 5 differ by about 15% forall values, of temperature, This difference is largely due to errors in the ‘material balance and not to the formation of by-products ‘Statistical analysis of the data shows that pre-exponential factors differ by less than one standard deviation, With confidence limits of 95%, the pre-exponential factors lie between 1.8 X 10! and 6.6 X 10! for toluene and 1.7 X 10" and 5.4 X 10! for benzene, The selective yield of benzene was 95% or better for the thermal demethylation. The actual yield of by-products found in the reaction product was generally less than 19 of the feed. Examination of Figuee 6 shows that the yield of by products ccaches 1" only above 840° C, if the hydrogen- toluene ratio and the eesidence time in the reactor are equal.He/Toluane ratio 2 4 tot erTolvene fot < 4 tot Nilogen edded os divert arden ment yeaaen icine or thiophene the feed toluene Toluene eontained 2001. % enepiane. 388 UT (iol ¢KI7? Figure 4, Toluene decomposition rate constant ‘The kinetic model of Silsby and Sawyer is based on the assumption of hydrogen dissociation equilibrium, rom data taken from the literature (6) the dissociation constant of hydrogen between 900° and 1250 ° K. may be expressed by the equation, K = 3990 exp (—104,400/RT) KO 63 exp (—52,200/2T) ‘The activation energy of Reaction 2 may be calculated using the hydrogen equilibrium constant and the experimentally determined rate constant, Ey = 50,900 — $2,000 = =1300 eal ‘This negative activation energy indicates that hydrogen dis- sociation equilibrium may not be reached during the reaction. ‘The increate in the reaction rate constants for the runs with 20% heptane are significantly different from the toluene de- ‘composition and benzene formation rate constants. The data for the 20% heptane runs fall ouside the upper 95% confidence limits for both the toluene decomposition and benzene forma~ tion rate constants. ‘The increase in the reaction rate constant noticed in the runs with 20% heptane is probably caused by the increase in the free radical concentration brought on by the eracking of the heptane. The higher activation energy of $5,000 cal. is also more consistent with the assumption of hydrogen dissocia~ sn equilibrium, since this higher value predicts a postive activation energy for Rexction 2. [t would appear. then, tha the incr promoting huedrogen listo ical roncentration has the effect of vst we in free won equilibeivm. A & & 08 Sl os He/ Toluene ratio 2 4 101 He/Tolvere retio < 4 tol Nitrogen added os dient Garton moses a hyagen ko as OSC Mos UT (toy eK-? Figure 5. Benzene formation rate constont , We Vel of b7-procoeis 5 ol toed ‘ iaragon--touane neater i x , imseconds eet ‘0 os 04 os oz a 08 008 008, ‘ag as e0S~— SoS Ur aor ee Figure 6. By-product formation Yous NO3 suLy 1964 257which functions by promoting hydrogen dissociation is pre dicted to increase the demethylation reaction to the de Cobyerved in the runs with heptane, This difference is equiva- Tene toa change in the renction temperature of about 50° C. Conclusions Toluene reacts with hydrogen readily at elevated tempera- tures, producing benzene and methane fs the main products. ‘The reaction i clean and unaffected by carbon monoxide, thiophene, or pytidine. The aromatic nucleus is not hydro~ genated at temperatures up to 950° C. Carbon and by- product formation ate minor unless the reaction temperacure And conversion are high and the amount of excess hydrogen is small "The toluene decomposition and benzene formation reactions fare festorder with respect to toluene and half-order with eapect to hydrogen, Hydrogen reacis with toluene by means Of a chain mechanism invalving hydrogen atoms. The acti vation energy ealeulated for the reaction indicates that the hydrogen stom concentration may not reach its equilibrium value. [From the runs with heptane it may be concluded that hep= rane acts af a (ree radical catalyst and increases the hydrogen ftom concentration to its equilibrium value. At the same time fide reactions are increased owing to the reaction of roluene tnd benzene with the heprane, “The ultimate yield of benzene predicted for thermal de- methylation is greater than 95%. Since this yield is high, the lise of a catalyst may not be justified. The inerease in sclee- ivity required to compensate a modest catalyst cost might be very difficult to obtain in practice, However, the benefits of a somerchat lower reaction temperature resulting from the use of a catalyst might justify che catalyst cost Nomenclature 1 = cae constant, (moles/ftes)-(s,)“ fe = fouene feed sate, ra /ein TP & reaction emperacure, °K feacton prese, inches Hig absoluce ial vale of tec es = Riven of toluene or yield of benzene, mele per mote of feed ‘i 4, m= hydropertoluene ratio, moles/mote iv = ylle of by-products I. feed 1 5 Real gens tne reser 4c & equilbsium constane for doeiaion of yrogen, “ He = 2H nates Literature Cited (1), BeutsW. D., Popper Fy Silsby, Ree Jeph Cen. 7, 497-503 (4959. Q2) Foosen, O; Aq Watson, K. My “Chemical Process Prine tiple." Val 3p. 84, Wiley, New Vor, 1947 (2) Bsicorbon Bacar Parl. Refer 42, No, 3, 121-4 (1963). G) Gna Bn. Chem 34, 26-32 (February 1962) (3) Mawsi, H Ry Tobubisa, HL, Bhi Sop. Pare. ts. 1677? (Macc 1959}, (6)'Rossinis FD a, “Seleeted! Values of Physical and Therrma- ‘uynamie Properties of Hydrocarbons and » Related Com- pounce p. 242, Carnegie Press, Bitsburgh, 1953 Gf Bisby 101, Sawyer, EW Appl Chim. 6, 347-56 (1956). B Bichiva, &, Hashimoto, \,, Tominaga, FL, Masainune, 8 ‘Bull. Jap. Petal. Inst. Ly 73-7 (Starch 1959). Receiven for review Augost 9, 1963, Neceprus November 26, 1963, REACTIONS OF CARBON VAPOR WITH HYDROGEN AND WITH METHANE IN A HIGH INTENSITY ARC RAYMOND F BADDOUR AND JEAN L. BLANCHET! Massachets Inatiieof Tebnalogy, Cambri 39, Mar. Theoret 1 calculotions show that oppreciable acetylene concentrations can be obtained when carbon vapor reacts with hydrogen ond with methane ct temperatures between 3500° and 4500 °K, A reactor was, bull to study these systems in o high intensity ore power inputs for the carbon-methane system. ‘ecrnie ares have been used recently in a variety of eew devices to ereate high energy environments, ts pa ticular. plasma jets, law intensity ares, and high intensity ares have been wed extensively to produce temperatites in the ange of about 30° 19 20,000° K. Recently. a high intensity age reactor was used (2) t0 make The major product obtained Because of cearboa react ith, hydrogen was acetylene, 1p 1 18%) a0 Leatm. pressure, Timitations in design vf the original reactor, only the hetero igeieousrrgion, where earban exists in the solid pas. voll be he The present sues is Paatnngs editor Ua isd 1kEC PROCESS DESIGN AND DEVELOPMENT 19 @ consumable graphite anode as the source of carbon ‘The acetylene output was determined to be mostly dependent on the quench temperature and the 1 appears that high concentrations of acetylene might be obteir .d ot competitive composition of a hot gas mixture obtained by reaction of carbon and hydrogen oF carbon and methane in an are struck between two entbon electrodes, In contrast with the previous work, an attempt his been made to study the homogeneous region, where carbon exists in the facetylene yields, and alzo to help determine which important teompounds may be expeciee in the equilibrium gas at high as phase only, to determine Carbor-Hydrogen Reactions Reliable thermodsnamie eka for CoH compouneds ac te 1 1300 K, ave alinast nonexistent in the liter imate sheramalstsinie properties im the high eines eave eines shot anetsrements have noc been