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Kautz, K.; Kirsch, H.; Laufhiitte, D. W. Spurenelementgehalte in Steinkohlen und den daraus entstehenden Reingassauben. VGB Kraftwerkstech. 1975,55 (lo), 672-6. Knbzinger, H. Benetzung im festen Zustand-Ein neuer Weg zur Herstellung uon oxidischen TrEigerkatalysatoren; Dechema: Frankfurt, June 1,1990. Linnros, B. The Crystal Structure of LiMo02Asz0,. Acta Chem. Scand. 1970,24, 3711-22. Pertlik, F. Structure Refinement of Cubic Asz03(Arsenolithe) with Single-Crystal Data. Czech. J. Phys. 1978, B B , 170-6.
Rademacher, J.; Borgmann, D.; Hopfengiirtner, D.; Wedler, G.; Hums, E.; Spitznagel, G. W. X-Ray Photoelectron Spectroscopic (XPS) Study of DeNO, Catalysts after Exposure to Slag Tap Furnace Flue Gas. Appl. Catal. 1992, in press. Russell, A. S.; Stokes, Jr., J. J. Surface Area in Dehydrocyclization Catalysis. Ind. Eng. Chem. 1946, 38, 1071-4.
Received for review May 13, 1991 Revised manuscript received August 1, 1991 Accepted October 14,1991
Intrinsic and Global Reaction Rate of Methanol Dehydration over 7-A1203Pellets
Gorazd BerEiEt and Janez Levec*J
Department of Catalysis and Chemical Reaction Engineering, Boris KidriE Institute of Chemistry, and Department of Chemical Engineering, University of Ljubljana, 61 000 Ljubljana, Slovenia, Yugoslavia
Dehydration of methanol on y-Al,O, was studied in a differential fixed-bed reactor at a pressure of 146 kPa in a temperature range of 290-360 "C. A kinetic equation which describes a Langmuir-Hinshelwood surface controlled reaction with dissociative adsorption of methanol was found to fit the experimental results quite well. Coefficients in the equation follow the Arrhenius and the van't Hoff relation. The calculated value for the activation energy was found to be 143.7 kJ/mol, while calculated values for the heat of adsorption of methanol and water were 70.5 and 42.1 kJ/mol, respectively. The measured global reaction rates for 3-mm catalyst particles were compared to those calculated by means of intrinsic kinetics and transport processes within the particles. A reasonable agreement was found when the effective diffusion coefficients for reaction components were calculated using a parallel-pore model assuming that only Knudsen diffusion is important.
Introduction Catalytic dehydration of methanol over an acidic catalyst (e.g. y-A1203) offers a potential process for dimethyl ether (DME) production, which is used as an alternative to freon spray propellants. In the MTG process, as has been described by Chang et al. (1978),the first reactor performs such a reaction. The open literature provides no information on kinetic equations which can be used successfully in designing a commercial reactor. From the patent literature (Woodhouse, 1935; Brake, 1986) it can be concluded that reaction takes place on pure y-alumina and on y-alumina slightly modified with phosphates or titanates, in a temperature range of 250-400 "C and pressures up to 1043 kPa. The kinetics of methanol dehydration on acidic catalysts has been studied extensively resulting in different kinetic equations. A summary of the published equations is presented in Table I. Most of the equations, i.e. eqs 4-9, have been derived from the experiments conducted in conditions not found in an industrial reactor. The experiments were mainly performed with mixtures of methanol, water, and nitrogen at low vapor pressures. Since water produced during the reaction considerably retards the reaction rate, the derived rate equations have, more or less, a semiempirical character and are not suitable for the industrial reactor design, where reaction takes place at high conversion levels. The outlet component concentrations correspond to the equilibrium values. However, the rate equations (1)-(3) in Table I, which were derived for an acidic ion exchange resin as a catalyst and are based on the Langmuir-Hinshelwood (L-H) or the Eley-Rideal (E-R) mechanism, can be used for design purposes after a reversible term is introduced into the driving-force term. The aim of this work was to determine an intrinsic rate equation which can be used to model the global reaction
Table I. Summary of the Published Rate Equations ref eauation
Kallo and Knozinger, 1967
+ k2Cw +
Sinicyna et al., 1986; kKM2CM2 Gates and -rM = (1 + KMCM K w C W ) ~ Johanson, 1971 Figueras et al., 1971 kKMCM'I2 -rM = 1 + KMCM1/' KwCw
~KMCM (7)' (1 + K M C M ) ~ Schmitz, 1978 -rM kl + kzCM Wb Rubio et al., 1980 -rM = klCM1lz kzCwl/z (9Y 'Acidic ion exchange resin as catalyst. bAlumina or silica-alumina as catalyst.
Than et al., 1972
rates in a pilot-plant reactor where 3-mm catalyst particles were used. In order to calculate the global reaction rate the effectiveness factor must be known. Since the intrinsic kinetic equation is highly nonlinear the effectiveness factor can be calculated only numerically.
* University of Ljubljana.
KidriE Institute of Chemistry.
Experimental Section Catalyst. A Bayer SAS 350 -pAl,O, catalyst support in the form of 3-mm spheres was employed as a catalyst. In order to avoid the intraparticle resistances, spheres were
o a a a - ~ a s ~ ~ ~ ~ ~ ~ s ~ ~ -0i 1992~ $ o ~ . oChemical Society o ~ American o / o
In fact. As an inert gas nitrogen was used. the produced water strongly retarded the reaction rate.20 0. Eng. and from 0 to 50 mol % for water.cWcE/K) (1+ 2(KMCM)l/' KWcW)4 + (10) The adsorption term for DME in the denominator of eq 10 was neglected since the DME adsorption constant was too small compared to the adsorption constants of methanol and water (Gates and Johanson. This indicates that the dehydration reaction undergoes dissociative adsorption of methanol on the catalyst surface.d. column packed with Porapak T (100/120 mesh). A database of more than 400 points was obtained.4 g.5. and 0.2 and 2. 1992 S u p e r f i c i a l velocity. The reaction rates were calculated on the basis of the measured conversions. Experiments showed that within the particles of 0. what is implied is that the driving-force term is mainly determined by the concentration of methanol in the feed and does not depend practically on the methanol conversion.d.30 in the differential reactor.17 mm. The oven temperature was 110 "C for the first 17. Analysis. the L-H concept. In the derivation of rate equations for the dehydration of methanol. 1969) can be calculated when an adiabatic operation of the differential reactor is assumed. Chem. was applied..00 0. increasing at a rate of 40 "C/min until 130 "C was reached. the L-H model can be represented in the following form (BerEiE. the concentrations of produced dimethyl ether were low. which all assume the reaction is irreversible. Vol.87mm 55wCHsOH E L \ t < I 10. It was estimated that at the experimental conditions the reversible term might change the value of the driving-force term not more than 0. the equation gives the smallest values for least squares residuals. Reactor. c m / s > JZ 50. The detector was a thermal conductivity detector (TCD) set in the low position.0. dependent on the outlet conversion and inlet concentration of methanol. The pressure was kept constant at 146 kPa. In order to achieve the desired conversions. nitrogen flow was controlled by means of an MKS 246 flow controller. Methanol was evaporated in a specially designed evaporator that consisted of a 5-m long SS coiled tube (1/4-in. mm Figure 1.1%).17 mm in size the intraparticle resistances are negligible. the coefficients in the equation must follow the Arrhenius and van't Hoff relation. The reversible term in eq 10 has negligible effect on the value of driving force. Since the reactor was not operated adiabatically. The observed temperature rise.50 T=360"C T=340°C. The inlet temperature was adjusted 90 that the mean temperature in the differential reactor was kept constant for all experiments. The GC conditions were as follows: a 230-cm X l/s-in. With the assumption that the surface reaction is a controlling step and that the dissociative adsorption of methanol on the surface of yA1203is taking place.87. Since the rates of dehydration with pure methanol or methanol-water mixtures were measured in the differential reactor. 31. 1971). respectively. The reversible term of the driving-force term (eq 10) consists of three factors: concentrations of water and DME.00 250.5% in a worst case (typically less than 0. At measured conversions. Res. The maximum systematic error (Massaldi and Maymo.). Three different particle sizes were used 0. Since the following inequality applies CM2>> CwCD/K. The inlet concentrations of reactants were varied between 15 and 90 mol % for methanol. the true error was even smaller. 1990). 1 . The analysis was performed by means of a HP 5890 GC connected to the reactor outlet. The duration of the analysis was 25 min. and the mass of catalyst in the differential reactor. the mass of the catalyst was varied between 0.00 200. The reactor was operated free of interparticle heat and mass resistances (Figure 1). The mole fraction of water was varied from 0 to 0. 4. dP=0. The temperatures of the evaporator and reactor oven were controlled by microprocessor-based controllers and were kept within *0. It is evident that in almost all rate equations for dehydration the reaction rate is proportional to the square root of the methanol concentration. The experiments were carried out in a differential reactor (8-mm i. while the mole fraction of DME formed during the reaction course was always in the order of a few hundredths (since methanol conversion is low).00 150.varied from 0 to 3 "C.g 8 LE 0. The published rate equations for dehydration of methanol to DME over alumina and acidic ion exchange resins are listed in Table I. In this way we simulated the conditions which are found at high methanol conversions in a commercial reactor. which has been further developed by Yang and Hougen (1950).3 "C. and the equation should be applicable for predicting behavior of an integral reactor. due the reaction progress Results and Discussion Intrinsic Rate Equation.5 min. The following criteria were used to distinguish between the kinetic equations shown in Table I: the obtained constants should be positive numbers. The carrier gas He (the flow rate through the column was 18 mL/min and through the reference 25 mL/min).00 1 ' 1 1 ' 1 1 1 ' 1 1 1 ' 1 1 1 ' 1 ' " ' 1 ' " 1 ' 1 1 1 1 ' 1 " 1 ' 1 1 100. On the other hand. the calculated systematic error was about 3%. 2-15%. 0. Determination of experimental conditions where external and internal transport resistances could be neglected. The estimated error for the rate was within &7% (BerEiE. A gas sample (0. The reactant outlet-gas compositions were determined by the calibration curve for each component. 1990): -rM = k&M2(CM2 . In that case the reversible term along the reactor length increases and consequently reduces the driving-force term. therefore this equation can be compared to those listed in Table I. No. and the equilibrium constant which takes values from about 7 to 11 (at conditions employed here).10 E L .) in a temperature range of 290-360 "C. 0. The total inlet volumetric flow rate was kept constant a t 65. Methanol or a methanol-water mixture was fed into the reactor by means of a Beckman 114M solvent delivery module.1036 Ind.37.3 cm3/s.00 1 = . this term is important when equations are used for the modeling of an integrally operated industrial or pilot reactor (where Cw = CDand at the reactor outlet Cw > CM). .25 mL) was injected into the GC through a sampling valve which was kept at 110 "C. crushed and sieved.00 Particle size. 0. inlet flow rates of methanol.1 ! I Fo.00 3.
6SEL003 ' 9 Equations 1-10 were compared to the experimental results for each temperature. Arrhenius plots for constants obtained by nonlinear regression for rate eqs 1.6 1086.3 429.4 3 23 186 14 468 13371 722. From Figure 2 it can be 1 /T Figure 2.9 290.690 0. varying starting values of parameters for a few orders of magnitude have not influenced the results.2 221.5 25.2 386.6" 289-418 silica-alumina Schmitz.7 11.Ind. thus m X I 2 Y= -X2X. Small differences are obtained by neglecting the reversible term in the case of eq 3.5 25.9 360 1 33.034* 0.6 283. 3. applying the Marquardt nonlinear regression method (Duggleby.1992 1037 Table 11. kmol(kg/h) KM.386 "Values marked with an asterisk indicate that only data for an inlet mixture of MeOH-N2 were used.1 551. Summary of Published Values for Activation Energy and Heat of Adsorption for Methanol and Water on Various Catalysts E.1 10..1 480.3 463.0 453. we cannot distinguish between the L-H mechanism and the E-R mechanism for dehydration of methanol on yA1203.0 226.019' 0.639 0.7 30.2 54.2c 290-360 alumina Figure 3 143.5 243. .909 0.621 3 0. Furthermore.64EL003 V " 3 ~~~*~~ 1 .0 4. Value obtained from slope In (-rM) v8 1/T.6 78.0 3 31 753 23 193 23 263 422.4 449. 1967 66.006* 0. 31.4 447.4 360.585 1.380 5. Since.5 301. "C catalyst ref 108. 1972 123.6 34.0 299. Value obtained by nonlinear regression for selected equation.4 10. With respect to the optimization algorithms.250b 1.4 1077.558 0.1 305. Coefficients B and D have the same values as is evident from Table III. 1987). Chem. an additional test was necessary. The equations which do not include the term of water concentration were tested only with the data obtained by the methanol-nitrogen inlet mixture.1 286.3 7. 1.5 10 73.7 305.002*b 0.1 25.407 0.6 479.4 307. 10 31.307 1. Experiments were carried out with mixtures of MeOH-N2 only. Res.452 5 3.8 50.7 355.1 15.02tjb 10 0.6 52.565 5.9 33.7792 0.9 150-225 silica-alumina Bakshi and Gavalas.2 1333.2 414.6 111-150 ion exchange resin Than et al.1 884.2 425. Optimum Parameter Set for Tested Equations Obtained with Nonlinear Regression (NLR) and Starting Values of Parameters Obtained with Linear (LR) and Robust Regressions (RR) k. when calculated values of the ac- Table 111.6 455. ma/kmol T.037* 0.623 6 0.670 0.2 221./K) (1 + 2 ( B x 1 ) ' / 2 + DX&4 (11) In the case of eq 3.m3/kmol Kw.7 320-360 alumina eq 3 a Value obtained by linear regression of initial rate data.9* 125."C eq NLR LR RR NLR LR RR NLR LR RR 320 1 5.0 10 11. in the beginning. Residuals Obtained with Nonlinear Regression of Dehydration Rate Equations with Our Experimental Results" residuals at given T ("C) 290 "C 340 "C 320 O C 360 "C eq 0. kJ/mol HM. concluded that the constants obtained for eqs 3 and 10 agree reasonably well with the Arrhenius and van't Hoff equation and can therefore be considered as the most favorable rate expressions. all nonlinear iteration procedures require approximate values of parameters. coefficient A is equal to the product of coefficients A and B obtained for eq 10.56E-003 L o ~~~~ 1 .013b 5..2 1346. 1984).1b 67.3" 160-195 alumina Kallo and Knininger.P 300-350 alumina Rubio et al.9 . eqs 3 and 10 are nondistinguishable.179 O.013* 8 0.024* 0.9 37.3 293. Convergence was fast and independent of starting approximations of parameters in almost all equations.we obtained values of parameters which were subsequently used as starting values of parameters in the Marquardt minimization algorithm.499 2 0.021b 1 0.0 Table IV.023* 7 0.3 290.3.4 6..17gb 6.0 40. and 10 have the smallest and almost equal sums of least squares. some of the equations have to be transformed into linear forms. With the use of a linear and robust linear regression (Rousseeuw and Leroy. Reaction rates were calculated with the mean concentrations of components in the differential reactor. Results are summarized in Table 11.567 0.5 20.5 41.9 384.4 220. From this table it is evident that eqs 1. kJ/mol T.1 340 1 13.026b 0.9 3 12 167 1 957 1 13415 1000.5 79..6 61. Therefore.972 0.862 4 7.6 224.kJ/mol Hw. 4.60EL003 ' I I I I I 1.0 Than et al.0 418.004b 1. 1978 120. 1972 This Work 117.. and 10.9 362. 1975 114. 1980 138.1 25. Proportional weights were used.8 298. since they represent the same target function. No.2b 127. On the basis of statistical criteria alone.0031 0. Vol.1 320-360 alumina eq 10 75.3 358.015* 9 0.021* 0.5 269. Eng.021* b 0.4 359.7b 70.816 1.
31.607 +m ' ' ' ' ' ' 1. In eqs 14 and 15. A value of the effective thermal conductivity coefficient was predicted on the basis of literature data and correlations and was found to be 2. The approach taken in that algorithm converts a boundary value problem with ordinary differential equations (ODES)into an initial value problem with partial differential equations (PDEs) by adding an appropriate transient term to the differential equations describing the material and energy balances.72E-003 I 8 ' I 8 r ' ' 1 '7' k 1.1/K Figure 3. These particles are less reactive. For more complex rate equations. Hg porosimetry) 2.1 1 Figure 4. Thus.1992 + \ 'I r \ I I u - 6 0 0 . Res. because they exhibit intraparticle mass. The solution obtained at that point is also a solution to the original problem. 1986). Sensitivity of Numerically Calculated Effectiveness Factor on Parameter Variation variation of produced change parameter parameter. The obtained set of PDEs is then integrated. Eng..1038 Ind. From the results of the sensitivity analysis presented in Table V. analytical solutions are given in terms of the Thiele modules (Froment and Bischoff. % in calculated 7. Physical Properties of Catalyst Particles (3-mm Granules of Bayer SAS 350 yA1208) surface area (BET) 247 m2/g surface area (a > 100 8. where some data of the measured physical properties of the catalyst particles are summarized. 4. M s and heat as transport within a spherical particle are governed by dr2 + . The global reaction rate is calculated from the intrinsic rate equation and effectiveness factor by the following equation -RM = q(-rM) (12) where the effectiveness factor is defined as (l/WJ(-rd 7 = (-rM) IS dV (13) In fact. The comparison between the experimentally determined reaction rates and those calculated for the same reaction conditions by eq 10 is illustrated in Figure 4. it an be assumed that for the reaction under the investigated conditions the Knudsen diffusion prevails . From Table VI.01 4% I / I I 0. % Ae +goo. to the steady state. In the case of the nonisothermal conditions within a catalyst particle. Vol.2846 g/cm3 bulk density (Hg porosimetry) particle density (He picnometer) 3. according to initial conditions. it is obvious that the effective diffusion coefficients for components should be predicted more accurately than the coefficient of effective heat conductivity.80E-003 I I I I 1/T . The catalyst particles which are used in commerical fixed-bed reactors are usually greater than those used in the kinetic rate equation determining experiments. the effectiveness factor must be calculated numerically. Comparison between experimentally measured and calculated intrinsic reaction rates with eq 10. =i4 f10 -rM PP *lo 74 n L I W I 10 . -90 -0. eq 10 seems to give more realistic predictions than eq 3.and heat-transfer resistances.268 g/cm3 particle porosity 0.1. 1979). a generalized approach or a numerical computation can be applied.01 Measured r a t e 0. as can be seen from Figure 1. - & A\ \ 8 Concentration of CHIOH In Inlet (volr) mixture CHIOH-N2 0 CHIOH 1% ( u L u 3 M CHIOH Onnno 45% CHIOH &&Ab UIW 60% CHIOH 75% CHIOH -90% CHIOH Table V. To solve the set of eqs 14-17. tivation energies are compared to the data found in the literature (Table IV) and to the results of the initial rate measurements (Figure 3). For the power-law rate expressions. it can be concluded that the majority of the total surface arises from the pores with a diameter under 100 A.24 m2/g 1. Chem.5 De f20 f8 f10 F8 d.- C U Q) + 0 J u 0 0 0. ferential equations describing mass and heat transfer within a catalyst particle must be solved. the algorithm proposed by Riggs (1988) was used. +1. using a mathematical package LSODE (Hindmarsh. two parameters appear which describe i) the transport of heat (Aeff) and mass (Deff for a particular component in a catalyst particle. No. 2 dCi ] = ppyirv (14) L atr=O 0.I 1 S7E-003 Table VI.7 X kJ/(s m K). to calculate the effectiveness factor a set of dif- atr=R T = Ts. Ci = Cis (17) A n analytical solution of the above system is possible only when iosthermal conditions within a particle are maintained. Global Reaction Rate. The reaction rate measured for such particles is called the global reaction rate. Determination of apparent activation energy from initial rate measurements.65E-003 ' I I I ' ' 1 I ''' '' 1.1 : .r dr with boundary conditions c d2C.
372 0.282 0.268 0.229 340 15.236 0.2 15 10 0."C dp = 0. It is also evident that the global reaction rate can be successfully predicted with the proposed intrinsic rate equation and the numerical procedure for the effectiveness factor calculation.1 0. or 10 predicts the effectiveness factor quite reasonable.: $ 5401.323 9. can be predicted if it is assumed that a parallel pore model with an experimentally measured porosity and a value of 4 for the tortuosity factor is used.6 60 10 0.413 0.2 45 40 0. Res. .0 12.3. Chem.1 bar 0" = 5. within a factor of 2.196 0. I . 31.469 0.(3 mm)/-r~(0.40 F 0. Equations 3 and 10 provide the temperature dependency of the activation energy and heat of adsorption according to the Arrhenius and van't Hoff relation.243 0. comparison between experimentally measured temperature and concentration profiles in an integral adiabatic fixed-bed pilot reactor is shown (BerEiE.5 45 20 0. Comparison between the Experimentally Determined and Numerically Calculated Effectiveness Factors inlet composition" conversion VulC b eq 1 eq 3 eq 10 mol % CH30H mol % H20 T. in the catalyst particles. Nomenclature c i = pore diameter. calculations on a trial and error basis were performed until the value which provided a good agreement between the measured and calculated reaction rates for 3-mm catalyst particles was obtained. it is further concluded that eq 10 represents the kinetic behavior of the dehydration reaction more realistically and is appropriate for modeling purposes.394 320 7.327 0. From that figure it is obvious that neglecting the reversible term in a rate equation leads to the wrong predictions.256 0.1992 1039 Table VII.9 11. 0. .1 45 30 0.1 Measured rate Figure 5.349 340 6.1 0.394 0. 4. No. I I .17 mm dp = 3 mm qexpt 12. either one of eq 1.218 6. I I I .415 340 4. Vol.32 kg/h dl = 0. I I . .8 0. Acknowledgment We acknowledge support from the Research Council of Slovenia under Grant No..290 0. effective diffusivity can be estimated using a parallel pre model: Deffi= dit/^ (18) According to Satterfield (1970).3. the agreement between the measured and calculated reaction rates was fairly good.5 9.8 30 10 0. Axial coordinate.206 10.8 10. m Figure 6. When a value of 3 was taken for the tortuosity factor in calculating the effective Knudsen diffusion coefficient and the numerical procedure for calculating the effectiveness factor.258 0.303 340 4.194 0. effective diffusivity. On the basis of the criteria applied.292 0. 1991) that a one-dimensional pseudohomogeneous model can be successfully used for modeling of an industrial reactor.421 5.277 0. it was shown (BerEiE and Levec. .290 0.P = 2.356 0.430 0. and 10 when they are used for interpretation of the results obtained in a differential reactor. As one can conclude from the results in Table W. I . as demonstrated by the use of eq 1 or 3.30 0. In Table VI1 some values are given for the calculated end experimentally determined effectiveness factor at different temperatures and compositions of reaction mixtures entering the differential reactor.9 45 0 0.~l. Comparison between experimentally measured temperature and concentration profiles in an adiabatic pilot reactor and those predicted by a pseudohomogeneous model.449 340 3.17mm)llT.10 0.304 0. I .415 0. Eng.bqexpt= [-R.00 4 1 1 1 1 1 1 I I 0. I .205 0.255 0. 1\ .15 K c . For operating conditions as specified in Figure 6. Assuming different values of this factor.236 0.275 340 9. A comparison of the calculated and experimental measured global rates in a differential reactor is shown in Figure 5.6 75 10 "Mole percent of CH30H and H20 in N2.217 340 7. 6' T = 30C 4' T = 30C T = 3200C T = 20C 9' 690 Y 665OPERATING CONDITIONS TI = 551.2 45 10 0. I I I I I .0 14.370 0.8 45 10 0.294 0.Ind.277 340 11. .275 0.312 340 4. Comparison between experimentally measured global reaction rates for 3-mm catalyst particles and those calculated numerically.302 0.6 45 10 0.00 . I .7 0.__ I I . C2-0541-104 and Nafta Lendava for making it possible to run a pilot reactor at their facilities for more than 2 months.01 0.379 0.216 0. 1990).3 7. The effective diffusivities for components can be effectively predicted using a parallel pore model and assuming the Knudsen diffusion mechanism.078 rn Q) 615- 5 640: / E : 2 590565 - .1 360 10. I 0.20 0.O. For materials like yAl. In Figure 6. -. Conclusions From the results discussed above it is obvious that there exist no significant differences among eqs 1.
Chim. Rubio.. J. An Introduction to Numerical Methods for Chemical Engineers. Chem. N. Solving Ordinary Differential Equations on an IBM-PC Using LSODE. Deshydration du Methanol Sur Silice-Alumine. Uniuersidad Nacional de San Luis.494-500.T. C. J. Eng.-Tech.. Lungmuir-Hinshelwood Kinetics of the Dehydration of Methanol Catalyzed by Cation Exchange Resin. L. Effects of Nonseparable Kinetics in Alcohol Dehydration over Poisoned Silica-Alumina. kg/h Subscripts D = dimethyl ether i = component i (H20.17. J. Figueras. G. K. Alvarez. G. M. D.. S. Collect. Nohl. Deu. F.p 185. Chang. Chem. 1935.CH30H. Kem. R. LLNL Tentacle Magazine. m3 x i = mole fraction of component i X = conversion.. M..O. A . Texas Tech University Press: Lubbock. m3/kmol P = pressure. Drus. 1967. IV. Chem. K TI= reactor inlet temperature (Figure 6).746504355. Dehydration of Methanol over yA1208. M. H. Bischoff. 1978. The two main technologies used commercially for obtaining methyl chloride are hydrochlorination of methanol and chlorination of methane./h) K = equilibrium constant. Commun. Becerra. N. Moskovskaja. Daniel E. J. Process Des. kJ/mol ks = rate constant of surface reaction. Sinicyna. 67-56-1. dimensionless @JM = = tortuosity. Reactor Model for the Catalytic Gas-Phase Dehydration of Methanol to Dimethyl Ether (DME). CA. B. H. M. N. D. Castro Luna.21.No. Gavalas. Determination of Mechanism of Catalyzed Gaseous Reactions. LLNL Livermore. KlusaEek. Eng.. after a catalyst screening and a study of operative conditions.1155-1163.. Methyl chloride is used as an intermediate in the obtainment of chlorinated bypro- 0888-5885/92/2631-1040$03. Au.. dimensionless 4 Greek Letters c = catalyst particle porosity.. N. Rousseeuw. P. mz/s E..113-119. I. g/cm3 T m K) component i.37. A.(CH3)20. p 42. Adolfo E.785. 1986. 1991 Accepted November 1.1040 Ind.-Ing.31. Czech. Argentina The intrinsic kinetics of the catalytic hydrochlorination of methanol to methyl chloride on yAl. Trujillo. 1972. Regression Analysis of Nonlinear Arrhenius Plots: An Empirical Model and a Computer Program. Satterfield. dimensionless Ki = adsorption constant of component i.D. Knozinger. Ind. P. W. V. Kinetika Degidratacii Metanola do Dimetilovogo Efira na SVK Ceolite. G.676-680. Chemical Reactor Analysis and Design. Katal. 1971. Levec.447-455. Res. Kuo. April 1986.S.255-260. Eng. Beranek. H. m Di = diffusivity of component i. mol/(g. Cumakova. G. 115-10-6. dimensionless 9 = effectiveness factor. K... Comput. 1987. 61-68. H. A. F. Zur Dehydratisierung von Alkoholen an Aliminiumoksid. Vestn. bar r = radial coordinate. Patent 2. 1992. AIChE J .. kJ/mol AH = reaction enthalpy. and Marta I. Quim. Duggleby.I. Yang. D. F. MA. DME. A.. Trambouze. Hindmarsh. kJ/(mol K) = concentration of component i. Kinet. BerEiE. A. K V = particle volume. 1991 Kinetics of the Catalytic Hydrochlorination of Methanol to Methyl Chloride Albert0 M. B. m dT = reactor diameter (Figure 6). Chem.) M = methanol S = conditions at catalysts surface v = per volume W = water 0 = initial conditions Registry No.4 . Than. Stationary Catalytic Kinetics via Surface Concentrations from Transient Data. Slou. Faraday SOC. 1988. J. John Wiley & Sons: New York. C. -pAlz03. L.67. D. Jacob. Massaldi. 1991. F.981-983. A large number of detailed reaction mechanisms was considered... Eng. Press: Cambridge. John Wiley & Sons: New York.. Robust Regression and Outlier Detection. (Madrid) 1980.. Trans. G. Methanol Dehydration. W. Froment.46. AIChE J. mol/(g. 1344-28-1. 1984./h) Hi= heat of adsorption of component i . Woodhouse.014. B. Error in Handling Finite Conversion Reactor Data by the Differential Method. 6.1986. kJ/mol T = temperature. The University of Ljubljana. Schneider. A. was determined from experiments in a tubular reactor in the temperature range of 513-593 K and at atmospheric pressure. Setinek. m2/s Deff = effective diffusivity of component i. Dehydration of Methanol and tert-Butyl Alcohol on Silica-Alumina. San Luis. J. Chem.1160-1162. A strategy of model discrimination and parameter estimation led to a Hougen-Watson type model with statistically significant and thermodynamically consistent parameters. R. 1040-1045 BerEiE. Lang. m R = particle radius. K. dimensionless methanol mass flow rate (Figure 6). D. 1982. Mourgues.. A.S. 1960. 1990.. Process Studies on the Conversion of Methanol to Gasoline. MeOH. Kinetics of Gas-Phase Dehydration of Methanol on a Sulphonated Ion Exchanger. D = constants in eq 11.. L. 25 de Mayo 384. J. B o g .. Gates. Kinetics of Reaction and Mathematical Model of an Industrial Reactor..17. 1969. L. Received for review May 7.595. Patent 4. Brake. 14. G.39.. Maymo. Castillo. dimensionless c = specific heat of component i. kJ/(s ~ ui = stoichiometric coefficient of pp = particle density.38. Hougen. K. Ponzi* Facultad de Ingenieria y Administracion. N. Ing. R. U. 5730 Villa Mercedes. 1970..408.1523-1528. Literature Cited Bakshi. Biol. Sci. mol/(g. U. K. 1975.p 406.12. D./h) -RM = global reaction rate. Ph. C. Riggs. Deshidratacion Catalitica de Metanol en Fase Vapor. H. C. m -rM = reaction rate. 146-157. 0. C. S. Dissertation. Catal. C. Diaz. TX. Johanson. Kinetics and Adsorption on Acid Catalysts. Mass Transfer in Heterogeneous Catalysis. 1971. A. D. Schmitz.27.253-270. R. dimensionless CB = catalyst bed porosity (Figure 6). 1979. Med.3878-3884. C. Kallo. dimensionless A r = effective heat conductivity of catalyst particle. Phys. J. Leroy. Y. 0.14.00/0 1992 American Chemical Society 0 . INTEQUI-CONICET..37. L.Vol. 1978. Ardissone. = activation energy. kmol/m3 dp = particle diameter..
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