Chemical Product and Process Modeling

Volume 4, Issue 5 2009 Article 12

WCCE8 2009

Mathematical Model of a Falling Film Reactor for Methyl Ester Sulfonation
Jesús Alfonso Torres Ortega, Universidad de La Salle Giovanni Morales Medina, Universidad Industrial de Santander Oscar Yesid Suárez Palacios, Universidad Nacional de Colombia Francisco José Sánchez Castellanos, Universidad Nacional de Colombia

Recommended Citation: Torres Ortega, Jesús Alfonso; Morales Medina, Giovanni; Suárez Palacios, Oscar Yesid; and Sánchez Castellanos, Francisco José (2009) "Mathematical Model of a Falling Film Reactor for Methyl Ester Sulfonation," Chemical Product and Process Modeling: Vol. 4 : Iss. 5, Article 12. Available at: http://www.bepress.com/cppm/vol4/iss5/12 DOI: 10.2202/1934-2659.1393 ©2009 Berkeley Electronic Press. All rights reserved.

Mathematical Model of a Falling Film Reactor for Methyl Ester Sulfonation
Jesús Alfonso Torres Ortega, Giovanni Morales Medina, Oscar Yesid Suárez Palacios, and Francisco José Sánchez Castellanos

Abstract
Methyl ester sulfonation with sulfur trioxide derived from oleum is possible under special conditions on a pilot plant scale. Quantum chemical calculations were used to study the relative stability between intermediates in the proposed mechanism. In this report an analysis of a mathematical model for a falling film sulfonation reactor is presented. It aims to estimate the temperature and conversion profiles of the thin film. The model treats the heat released and the trioxide sulfur dissolution assuming that the film theory is applicable. The temperature and concentration gradients can exist across the film during the chemical reaction. The equations were solved using finite differences. The most important data obtained by the mathematical model for a subsequent correlation with the properties of the reagents and product are the conversion, the density and viscosity of the sulfonic product. The results indicate an increase in the axial temperature of the liquid film and the conversion from the top reactor in accordance with the experimental results. It considers that at the upper section of the reactor the reaction is controlled by means of mass transfer due to gas phase turbulence. A mild conversion on the reactor bottom means that the liquid phase controls the mass transfer due to the amounts of sulfur trioxide transferred into the film which produces changes in the film composition. KEYWORDS: modelling, film reactor, sulfonation, methyl stearate, sulfur trioxide Author Notes: We gratefully acknowledge Prof. Federico Ignacio Talens Alesson from University of Nottingham (England). During this study the authors were beneficiaries of a doctoral grant from COLCIENCIAS (Departamento Administrativo de Ciencia, Tecnología e Innovación).

2 0. Figure 9 should appear as follows: 80 70 Active matter percentage 60 50 40 30 20 10 0 0.5 0.7 Lenght.1 0.Erratum Page 11.0 0.4 0. m Active matter reactor Mater active model .3 0.6 0.

2008b).. The characterization of anionic surfactants was applied on the sulfonated product. 1975. Unsulfonated matter was measured by extraction with petroleum ether. 1978. it is considered of special interest for the current research. applied to SO3– absorption on the methyl esters mixture. Published by The Berkeley Electronic Press. diffusion. Methyl esters sulfonate (MES) has a wide range of application and important biological properties. 2001. mainly the kinetics for ageing (stabilization/digestion). The content of active matter or active ingredient was determined using a two-phase titration technique with Hyamine 1622 as a titrant and methylene blue as an indicator. Post-sulfonic reactions have been extensively studied. 2007). This paper presents a review of events that occur downstream in a FFR: convection. Roberts. Roberts et al. de Groot. That SO3 group would be especially active and therefore capable of sulfonating directly another methyl ester molecule in an alpha position (Stein and Baumann. 2007. 2009 1 . 1991. momentum and heat balances are developed herein. the third reaction stage is considerably slower than the previous one. bleaching and neutralization stages (Kapur et al. followed by evaporation and weighing of dry residue and finally the total acidity was determined with the potentiometric titration (Ahmad et al. 2008). Some physicochemical properties are listed in Table 1. Lim and Ahmad. 1998)... 2001).: Mathematical Model of Falling Film Reactor Introduction Falling film reactor (FFR) is widely used for exothermic gas–liquid reactions such as sulfonation. Therefore. the process inside the FFR has not been well understood. Roberts. Here. The results from the mathematical model were validated using physicochemical properties of the reactants and product. it is an interesting class of anionic surfactant (Ahmad et al. The chemistry of the methyl ester sulfonation is complex and is not yet fully elucidated. Reaction scheme of methyl ester sulfonation At the beginning of the reaction. Phenomenological descriptions of mass. the SO3 is absorbed by the liquid and an irreversible reaction occurs. reaction and the hydrodynamic process. However. but may be summarized in Figure 1.Torres Ortega et al. where an SO3 group is liberated (on ageing). The composition of SO3 as a sulfonation agent derived from oleum was determined empirically by absorbing on a sulfuric acid solution (Torres et al. The mathematical modeling relates several process variables with the conversion expressed as molar fraction of the sulfonated product. In this case a mixture of methyl esters (ME) composed mainly of methyl palmitate and methyl stearate is used (Torres et al. 2005)....

6 < x < 1: + 0. N/m Methyl ester viscosity.88 Torres et al.003 (11) + 0..31–0..25: −8 e (8) (9) μG = 1.031 × 10 1000μ 2 / 3 L Gas conductivity.003 Talens and Gutiérrez (1995)1 μ L = 3.bepress.7 × 10 1 2 −10 e 4850 TL +5. kg/ms (10) 4850 TL +1.66TL −11 TL DMES-ME = 3.1393 2 .3 Davis et al. m /s 2 Reid et al.288 × 10 μ 2 / 3 L (1) (2) (3) (4) (5) Method Torres et al. Art. (2005) Talens and Gutiérrez (1995)1 Diffusivity. (1979) de Groot (1991) (7) 5700 TL + 5. Iss. (1987)3 Some at nitrogen Davis et al..com/cppm/vol4/iss5/12 DOI: 10. 5.7 × 10 −10 e c) 0.86 x μ L = 2.6: Viscosity of the film.72 × 10 −7 e b) 0. J/kmolK Liquid conductivity. kg/ms Gas viscosity. J/msK Heat capacity of liquid.12 × 10 μ 2 / 3 L −11 TL DME-MES = 6. kg/m3 Correlation ρME = 881. (1979) Same methodology used by Broström (1975).010x cG = 29.25 < x ≤ 0.300 + 101. J/msK kw = 16. Parameter ME density kg/m3 Film density.Chemical Product and Process Modeling. (2005) Talens and Gutiérrez (1995)1 Some at nitrogen μ MES = 1. J/msK Surface tension. (1987)2 TL −10 DSO3= 2. The diffusivities are estimated of a modified form of equation Wilke and Chang (1955) and Hiss and Cussler (1973).. kg/ms Methyl ester sulfonic viscosity. Concentration dependence of binary liquid diffusion coefficient may be estimated through of equation Vignes (Vignes.36 × 10 a) 0< x ≤ 0.6 TL (6) Davis et al. Vol.046 μME = 8 × 10 e −6 1949. they measured diffusion coefficients and report that D~µ–2/3. (1979) Reid et al. 12 Table 1. 1966). kg/ms kG = 0. The correlations used for the falling film reactor calculations. J/kmolK Heat capacity of gas mix.9×10-5 2980 TL +3. 3 Calculated for each segment by the method of group contributions (Aspen Engineering SuiteTM V11.2202/1934-2659. http://www.82 kL = 0..22 x Wall thermal conductivity.1).035 x μ L = 3.8214TL ρL = 980 + 192x – 0.276 σ = 0.0279 cL = 507. 4 [2009].

here the spontaneity is favored because of negative value of enthalpy. −14350 (12) Published by The Berkeley Electronic Press. The B3LYP functional and 631G(d) basis set were used for calculating frequencies and geometries. 2003). Thus.Torres Ortega et al.14 × 1019 e T m3/kmol The activation energy is 30377 J/mol (Torres et al. the intermediates in the sulfonation and over-sulfonation steps were found to have the same relative stability. According to the results of the thermodynamic ground. Mechanism proposed for methyl ester sulfonation The reactivity of the ME due to its aliphatic chains is less than the aromatic compounds. Calculations were carried out in the Gaussian 03W program (Frisch et al.. 2001. RCH2CO2CH3 + SO3 Methyl ester k1 R – CH2 – C – O – CH3 O SO3– + (a) The first stage: sulfonation (very fast) R – CH2 – C – O – CH3 SO3– Intermediate I O + k2 k’2 R – CH = C – O – CH3 O SO3H Intermediate II k3 + SO3 R – CH – C – O – CH3 SO3H O SO3– Intermediate III + (b) The second and third stage: over-sulfonation (even faster than the first) O R – CH – C – O – CH3 SO3 SO3H O Intermediate III – + 353K Ageing R – CH – C – O – CH3 + SO3 SO3H α-sulfo methyl ester acid (c) The ageing stage Figure 1. these reactions are highly exothermic: 150 – 170 kJ/mol. the reaction kinetics in the reactor (FFR) was determined using the following rate law: r = −kCSO3 CME . This fact disregards the inclusion of these intermediates into the kinetic model and allows the use of a second order equation for the reaction progress. 2002). 2008a). The intermediate III is very stable according to the Gibbs diagram (ΔG < 0) as shown in Figure 2(b). using the Density Functional Theory (Young. including 25 kJ/mol of the absorption heat of gaseous SO3 (Roberts. The formation of intermediates is relatively fast. Cramer.: Mathematical Model of Falling Film Reactor Thermodynamics of the stable compounds for the reaction of methyl ester sulfonation was studied between methyl stearate and SO3. k = 1. 2004). 2009 3 . That is in agreement with the results showed in Figure 2(a).

Vol. T Water inlet Atmosphere Desiccan Falling Film Reactor SO3 storage tank Store of Oleum Water inlet Heating circuit Column of absorption Analysis Exhaust gases Water outlet P H2SO4 T NaOH Humidity remover Heating Circuit Ageing reactor Water inlet Water outlet Treatment of gases Nitrogen Figure 3. 12 515. 4 [2009].2202/1934-2659.15 Reaction Reaction (a) Heat of reaction. ΔH (b) Gibbs energy.1393 4 .bepress. The SO3 vapor was generated through distillation from oleum and diluted to the desired concentration with nitrogen before entering in FFR (Moretti and Adami.65 ΔG (kJ/mol) –158. Art. ΔG Figure 2. 2002). Iss.com/cppm/vol4/iss5/12 DOI: 10.91 –449.03 ΔH (kJ/mol) –116. Experimental setup for methyl ester sulfonation using FFR http://www.69 –470.Chemical Product and Process Modeling.63 119. 5. Analysis T SO3 and dry air (N2) P Methyl esters Water outlet Water Methyl esters storage Liquid feed Mass flow controller Heater Heater Dry Air Analysis Desiccan Air Filter Oleum H2SO4 P . Thermodynamic for the initial reaction between ME and SO3 at the B3LYP/6-31G(d) level The experimental apparatus utilized is presented in Figure 3.

Neutralization chemistry Mathematical model Previous models for FFR have been proposed by several authors for the tridecylbenzene and dodecylbenzene sulfonation (Johnson and Crynes. All of them with ½ inch inner diameter. 1999 and Akanksha et al. 1996. 0. Talens. 1979.. 2007).40 and 0. O O R– CH – C – O – CH3 SO3H + NaOH R–CH–C–O–CH3 + H2O SO3Na α-sulfo methyl ester acid (α-MES) sulfo methyl ester monosodium salt (Φ-MES) Figure 4. In the reactor the feedstock is injected upper section and the organic liquid is distributed as a thin film on the inner wall of the reactor tube. Davis et al. For industrial or commercial level the whole sulfonation process includes the neutralization stage to form the sulfo methyl ester monosodium salt as final product (Figure 4). Liquid organic entrance Sulfonate agent SO3/N2 into tube core SO3 conducted by nitrogen Metallic wall Jacket tube Jacket tube Organic liquid film (Methyl ester) Figure 5.. 2009 5 . Schematic view of the monotubular falling film reactor The principal assumptions made in our mathematical model are: Steady-state system. Some of their assumptions are questionable as they consider that the reaction occurs at the gas–liquid interface and SO3 chemisorptions and velocity profiles are assumed laminar.75 meters. Rectangular coordinate system.. Dabir et al.. Gutiérrez et al. 1974. 1988.: Mathematical Model of Falling Film Reactor Experiments were performed in three film reactors with different lengths: 0.Torres Ortega et al.25. Published by The Berkeley Electronic Press. Here the SO3/N2 stream occupies the core of the tube (Figure 5).

5. The equations are explained below according to the mass. The model predicts conversions. Art. Another portion of the reaction heat is transferred into the moving gas stream and raises the temperature of the gas phase. 12 The liquid film is symmetric in regards to the reactor axis. The SO3 radial diffuses from the core of the tube to the liquid–gas interface. The model proposed in this paper is appropriate for turbulent flows and considers effects of wavy film flow by using eddy diffusivity parameter. since degradation of the products may occur under certain conditions. The liquid reactant (ME) and the product (MES) are non-volatile at working temperatures. momentum and heat transfer. SO3 solubility in the liquid reactant and in the reaction product is ideal according to Henry’s law. Vol. which induces a change in the composition. The mono-sulfonation of methyl esters produces mainly MES. The reaction occurs in the film thickness with rapid changes of composition. 4 [2009].bepress. gas–liquid interface temperature along the reactor length and it is applicable to any falling film reactor. The model simulates the variations in physical http://www. Effects of interfacial drag at the gas–liquid interface and the gas–phase heat and mass transfer resistance have been also considered.2202/1934-2659. Knowledge of temperature distribution along the reactor is important for product quality control. No access of liquid droplets into the gas core. neither access of gas bubbles into the liquid film. 2004). A mild conversion on the bottom reactor means that the liquid phase controls the mass transfer due to the high amount of SO3 transferred into the film. Strong changes in conversion on upper reactor region due to the turbulence of the gas are enough to transport fresh liquid to the interface (Knaggs. In these equations the turbulent diffusivity for mass transfer with chemical reaction was considered. The rate is limited by the SO3 that can be supplied to the liquid interface. The liquid film and the gas mixture circulate simultaneously as a turbulent flow. A third portion of the reaction heat is transferred through the liquid film into the wall. The reaction heat must be removed to prevent degradation of the product into three statements: A portion of the reaction heat raises the temperature of the liquid film. The film thickness is small compared to the column radius.Chemical Product and Process Modeling. Hence the gas phase is entirely controlling the resistance to mass transfer.1393 6 .com/cppm/vol4/iss5/12 DOI: 10. Condensation and evaporation do not occur on the surface of the liquid film. Iss. Fully developed thin film (entrance and exit effects to reactor are neglected).

two-dimensional flow may be written in terms of the eddy diffusivity as: vz vz ∂C SO3 ∂z = ∂ ∂y ∂C SO3 ⎡ ⎢ D SO3 + DT ∂y ⎢ ⎣ ( ) ⎤ ⎥ − kC SO3 C ME ⎥ ⎦ 0≤y≤δ 0≤y≤δ (13) (14) ∂C ME ⎤ ∂C ME ∂ ⎡ = ⎢(D ME + DT ) ⎥ − kC SO3 C ME ∂y ⎣ ∂y ⎦ ∂z Gutiérrez et al. we consider a system in which a liquid (initially free of the absorbing species at z = 0) falls into the surface of a vertical and impermeable wall under the influence of gravity and gas mixture with y varies from y = 0 (at the wall surface) to y = δ (at the liquid free surface). methyl ester sulfonic acid (MES) and sulfur trioxide (SO3).Torres Ortega et al.5⎨1 + 0. Equations for turbulent diffusivity and turbulent viscosity in the liquid phase were suggested by Yih and Liu (1983).: Mathematical Model of Falling Film Reactor properties with temperature and predicts conversion and temperature of the liquid in the axial and transversal directions. Mass balance on finite volume includes the boundary conditions at the solid wall and gas/liquid interface As shown in Figure 6.64 y +2 × 1− e ⎬ ⎥ ⎪ ν τw ⎢ ⎪ ⎣ ⎦ ⎭ ⎩ 0.5 + 0. τ/τw = 1 – (τL/(τG + τL))3(y+/δ+) Published by The Berkeley Electronic Press. The differential equation for diffusion in fully developed. The mathematical model equations are: Liquid / Gas interface y Tube wall Liquid film SO3 (G) N2 (G) z=0 Tube core z −D ∂C ∂y z z+Δz y y+Δy Liquid phase Gas phase y=0 ∂CME =0 ∂y ∂C SO3 =0 ∂y y=δ ∂CSO3 ∂y = kG i CSO3 − mCSO3 DSO3 z=L y = d/2 ∂C SO3 ∂y =0 ( ) * k G PSO3 ∂C ME =0 ∂y D ME RT Figure 6.5 (15) (16) where. Here.5 ⎤ ⎫ ⎡ νT τ ⎢ ⎪ + A ⎥ ⎪ = −0. 2 ⎧ − y + (τ / τ w )0. three components are considered in the liquid phase: methyl ester (ME). Then two microscopic balances are sufficient to determine the concentration profiles. (1988) reported that due to the high Schmidt number and wavy film flow. 2009 7 . DT cannot be neglected.

186. For non–volatility liquids such as methyl stearate the vapor pressure is zero at working temperatures.5 + DT 1 − e ( − y (τ / τ w ) / B Where B+ is given by Habib and Na (1974) as: 5 B + = Sc −0. Art. 12 with A+ = 25.5 ∑i =1 Ci' (log Sc) i −1 (18) ( 3 3 ) kG = 0. C’1 = 34. The Henry constant m.2202/1934-2659. 5.8Sc −0. 1984) ⎛τ u=⎜ G ⎜ρ ⎝ G ⎞2 ⎟ ⎟ ⎠ 1 (20) (21) Where the turbulent velocity is defined as: The axial liquid velocity vz.5 + vT 1 − e ( − y (τ / τ w ) / A ) (17) ScT = = + 0.bepress. can be derived from the momentum equation after neglecting the pressure gradient and axial terms (see Figure 7). 4 [2009]. Boundary conditions at the solid wall and gas/liquid interface by momentum balance http://www. v = 0 Tube core vz du/dy = 0 y=δ vi u y = d/2 z=L y=0 Figure 7. At the interface. Vol. it is assumed that Henry’s and Raoult laws are applicable to determine the SO3 solubility.com/cppm/vol4/iss5/12 DOI: 10. C’3 = 33.96.97. C’2 = 28.704 u (McCready and Hanratty.1.Chemical Product and Process Modeling.1393 8 . vz = ρLg μL ⎡ y2 ⎤ τG y ⎢ yδ − ⎥+ 2 ⎥ μL ⎢ ⎣ ⎦ Liquid / Gas interface Gas phase SO3 (G) N2 (G) (22) Tube wall Liquid phase y z Liquid film z=0 y = 0. Iss. C’4 = 6.33.95. C’5 = –1. is determined from the SO3 vapor pressure: G G i (19) N SO = kG C SO − mCSO 3 Equations for turbulent diffusivity in the liquid phase follow the Cebeci’s modification of the van Driest model and were modified in this paper to include the effect of shear variable: + 0.

flow parameters can be introduced and adjusted to minimize the deviation from a data set (Talens.704 . The initial value of the film thickness δ can be obtained from: ⎛ 3Γμ ⎞ 3 δ =⎜ ⎜ gρ ⎟ ⎟ ⎝ L⎠ 1 (27) Later the δ value can be calculated by iteration through equation 24. 1999): Γ= ρ L g 3 τ Gδ 2 δ − 3μ L 2μ L (24) (25) (26) τ G = C f ρGu 2 ⎧ ⎫ ⎛ (ϕδ ) / d 1 13 ⎞⎪ ⎪ (ϕδ ) / d 5.93. μL (23) Calculation of τG based on the relations proposed by Riazi and Faghri (1986) shows that gas flow is turbulent. Consequently the SO3 is absorbed at the gas/liquid interface. Ln(φ) = 3. For relative high gas flow rates where the shear force predominates over the gravitational force.175 ms–1. an amount of heat is released and in this case an energy balance is required: vz ∂ρcT ∂ =− ∂z ∂y ⎡ ∂T ⎤ ⎢− k L ∂y ⎥ + (ΔH ) kC SO3 C ME ⎣ ⎦ (28) Equation 28 requires appropriate boundary conditions (Figure 8): 1 1 1 (29) = + d ex U k w d lm hw d ex d in The heat transport equations follow the Prandtl analogy and are equivalent to that used for mass transfer: Numerical scheme The model developed has the following sequence: the film thickness is determined by iteration with the mass flow per unit perimeter. Thereby in most cases for FFR interfacial drag effects cannot be neglected. the diffusivity and the reactant mass balance are calculated.8Sc − 0. For film sulfonation.59 – 5. 2009 9 . else Ln(φ) = 20. hG = 0.7 + Re ⎟⎬ ⎟⎪ ReG Cf ⎪ 3. On the basis SO3 concentrations.02 Log ⎜ = −4 Log ⎨ − 2 ⎜ 3.55 viL – 0. Then the turbulent viscosity.7 G ⎠⎭ ⎝ ⎩ If viL < 0.14 viL. the profile of MES concentrations is estimated. the linear velocity distribution is: vz = τG y .Torres Ortega et al.: Mathematical Model of Falling Film Reactor The flow profile of the liquid falling and gas is predominantly turbulent. In exothermic reactions. u (30) Published by The Berkeley Electronic Press.

(1988).Chemical Product and Process Modeling. The proposed model is a special case for exothermic gas absorption. Iss. This set of equations is numerically solved using the linearization of finite differences by Laasonen implicit forms for first and second order derivates. http://www. However they are adjusted for the next segment according to the output temperatures from each previous segment. Then the overall conversion in the segment is now estimated and the energy balance is solved.2202/1934-2659.com/cppm/vol4/iss5/12 DOI: 10. By an iteration process. 12 Liquid – Gas interface Tube wall y z Tw1 Liquid film TL1 Q Ti1 SO3 (G) N2 (G) z=0 Q TL2 Ti2 Tw2 y Liquid phase y+Δy Gas phase y=0 kL ∂T = U T y =0 − Tw ∂y ( ) y=δ − kL ∂T = hG T y =δ − TG ∂y ( ) z=L y = d/2 Figure 8. Mass and heat transfer coefficients in the gas phase are calculated using empirical equations proposed by McCready and Hanratty (1984) and Gutiérrez et al. and the mole fraction of SO3 in the gas phase and the temperature of the reactor jacket. This study uses the film theory to evaluate the consequences of intense heat effects during absorption and chemical reaction. Microscopic mass and energy balances are calculated using solving equations in partial derivatives for the liquid phase. the discrepancy is reduced to a certain value. Vol. 5. To ensure convergence of the system the transformation of the equations proposed by Agrawal and Peckoever (1980) was chosen following the same development by Talens (1999). The physical properties as well as the radial heat and mass transfer rates are assumed constant in each segment. The linear stability problem associated with a vertical liquid flowing under the action of gravity has been solved in terms of a numerical solution of the OrrSommerfeld equation. The crucial variables for the process are: the length and diameter of the FFR. The concentration values are corrected to determine the velocity profile and film thickness before making the calculations for the next stage. the flow of liquid reactant. Art. 4 [2009].1393 Tube core 10 . Sketch of the symbols used for heat balance on the segment That provides the new profile of SO3 concentrations.bepress. the molar ratio between SO3 and organic liquid.

80 70 Active matter percentage 60 50 40 30 20 10 0 0. 2009 11 . It also may be suitable for the design and operation of industrial falling film reactors. Later the resistance occurs in the liquid phase. It confirms that mass transfer is initially controlled by the resistance in the gas phase. % v/v Methyl esters inlet temperature.6 0.2 Lenght.4 0.2 0. K Reactor 3–7 313 – 343 343 – 353 1 – 1.1 0.Torres Ortega et al. the percentage of SO3 in the gaseous mixture.5 0. Base conditions used in the methyl ester sulfonation.3 0. Conditions SO3 in nitrogen (gaseous sulfonate mixture). m 0. K SO3/N2 inlet temperature.0 0. The operating conditions are listed in Table 2. An example of longitudinal conversion profile for ME sulfonation Table 2.7 0. An example of the longitudinal profile on the degree of sulfonation expressed as percentage of active matter is presented in Figure 9. reagents inlet temperatures and jack temperature. A fast conversion at the top of the reactor (linked with gas phase control) and slow conversion at the bottom (linked with liquid phase control) was observed.6 0. The progress of the reaction is decisive for the sulfonation degree expressed as the amount of active matter.3 0.0 0.2 313 – 333 Published by The Berkeley Electronic Press.5 0.: Mathematical Model of Falling Film Reactor Results This mathematical model allows one to calculate the longitudinal profiles of temperatures for any column height. K SO3/methyl esters mole ratio Wall temperature.7 Active matter reactor Mater active model Active matter reactor Active matter model Figure 9.1 0. For ME sulfonation several experiments were conducted varying different process factors: the mole ratio between methyl ester and SO3. The model was constructed to predict the sharp increase during the conversion that takes place in the first stage inside the FFR.4 0.

Liquid temperature profiles along the reactor Figure 11 presents the conversion profile in the film reactor at the same previous conditions.Chemical Product and Process Modeling. the temperature decreases while the viscosity increases. Viscosity presents variations as the result of an abrupt change in composition and release of energy in the initial part of the http://www. reactor %SO3=7.2202/1934-2659. Art. 4 [2009]. reactor %SO3=3. %SO3=3 mole ratio=1. model %SO3=3. model %SO3=7. The raise of SO3/ME mole ratio or the SO3 percentage in the sulfonate stream produces a temperature increase at the entrance of the reactor which results in a decrease of the film viscosity.1393 12 . 5. As observed. an increase of the liquid temperature according to the excess of SO3 in the gas flow occurs.4 0.1. the correlation between the values predicted by the model and those obtained experimentally is excellent with variations under 10%.1. 12 Figure 10 shows model results for different variations between SO3 in the gas mixture with the liquid interface temperature versus the reactor length. This can be explained due to late effects in the reactor.2 0. Conversions in the reactor are lower than those calculated by the model for the 25 cm reactor.6 %SO3=7 mole ratio=1. m 0. The temperature of the reagents is controlled to avoid undesirable effects which could reduce the selectivity. %SO3=3 mole ratio=1. purity and yield of the main product. The inlet temperatures for methyl ester are invariant (the mixture at 343 K and the wall temperature at 333 K).0 0. Temperature. K K 348 343 338 333 0. %SO3=7 mole ratio=1.4 Lenght. The jump conversion occurs in the top of the reactor and the temperature rises considerably reducing the viscosity of the liquid. for 40 and 75 cm reactors.1. 358 353 Temperature. Vol. Later. By contrast.com/cppm/vol4/iss5/12 DOI: 10.6 0.0 0. Figure 10.1.2 0.bepress. Iss.

6 0. The estimated density of the sulfonic product downstream of the reactor is similar to the determined by that experimental result (Figure 12).0016 0.8 0.1.0 0. 2009 13 .4 Lenght.0002 Film density model Film density Film density reactor Film viscosity model Film viscosity Film viscosity reactor Figure 12. reactor %SO3=3.2 0.001 0.0008 0.0004 0.Torres Ortega et al. kg/m3 950 950 900 900 850 850 800 800 750 750 0 0.7 0.1 0. model %SO3=3 %SO3=7 %SO3=7.2 0.0 0.5 0.10 0.0012 0. Density and viscosity calculated along the reactor Published by The Berkeley Electronic Press.2 0.0012 0.7 0. Kg/m3 Film density.0014 0.1 0.001 0.4 0.60 0.0008 0.4 0. these situations improve the SO3 absorption on the thin film. kg/ms Film viscosity. mole ratio=1.: Mathematical Model of Falling Film Reactor reactor which produces an increment in the temperature of this area.3 0.6 0. Consequently the interfacial velocity increases and the film thickness decreases (due to turbulent gas phase). mole ratio=1.1. 1000 1000 Film density. Conversion profiles calculated along the reactor At the end of the reactor.0006 0. Finally.0014 0.6 0. model %SO3=3. 1 0. mole ratio=1. This confirms that the model includes the presence of SO3 absorbed by the film. mole ratio=1.1 0.1 0 0.7 Conversion percentage %SO3=7 %SO3=7.3 0. there is a small jump in the conversion due to kinetic effects that achieve importance for the consumption of reactants. Kg/ms 0. m Film viscosity.7 0.0002 0.5 0.6 0. reactor %SO3=3 Figure 11.3 0.1.70 Length.30 0.1.5 0.40 0.0016 0.4 0.0004 0.5 0.3 0.50 0.20 0.0006 0. m 0.2 0.0 0.9 0.

atm = Prandtl number cμ/k. J/m s K. dimensionless = Temperature. kmol of SO3/m3 of gas/kmol of SO3/m3 of liquid = Pressure. Reaction rate constant. The stability of the intermediate species was verified experimentally as predicted with the Density Functional Theory B3LYP and the 6-31G(d) basis set. Considering that the liquid film and gas phase are turbulent. The first is characterized by an abrupt increase in conversion in which the controlling step initially depends on the gas phase. ReL = 4Г/μ. J/m2 s K = Thermal conductivity. The profiles of temperature. the viscosity fluid and the film thickness increase. kmol/m3 = Heat capacity.1393 .bepress. K 14 http://www. The model predicts two distinct transfer areas. m3/kmol s = Reactor length. Vol. This fact suggests that the methodology here proposed can be used to predict conversions in any film reactor. The mathematical model proposed agreed with the trend of the experimental results. elsewhere the film velocity decreases. 4 [2009]. J/mol = Aliphatic chain = Reynolds number. ReG = ρu(d – 2δ)/μ. However it can also occur inside the liquid. m = Henry constant. dimensionless = Heat of reaction. m = Acceleration of gravity.com/cppm/vol4/iss5/12 DOI: 10. m/s2 = Heat transfer coefficient. In the second area. viscosity and conversion are consistent with the experimental results and satisfy the conditions to minimize the mathematical mistakes made due to the usage of numerical solutions.Chemical Product and Process Modeling. Art. then the liquid phase becomes the controlling stage with a mild increase of conversion. 5. we conclude that mainly the reaction can occur at the interface gas/liquid. Nomenclature C c Cf D DT d g h k L m P Pr Q R Re Sc T = Concentration. density. m2/s = Turbulent diffusivity. 12 Conclusions An analysis of the reaction mechanism to methyl ester sulfonation was performed using modern techniques of simulation and molecular modeling.2202/1934-2659. J/kmol K = Friction factor = Diffusivity. Iss. m2/s = Reactor diameter. = Schmidt number μ/DρL.

10(1): 15-34. Modeling of sulphonation of tridecylbenzene in a falling film reactor. Oils and Related Materials. Pant K... Abd Aziz H. Abd Murad Z. m = Dimensionless film thickness. 46: 1332-1344..Torres Ortega et al. Srivastava V. m2/s = Film thickness. kg/m s = Liquid density.K.. Samsi J. m/s = Conversion expressed as molar fraction of the acid. Ahmad S. Palm based sulphonated methyl esters and soap. Beyond Biodiesel. 19: 171-178. Published by The Berkeley Electronic Press. Peckoever R. 2007.. Akanksha.S. 18: 216-220.K. Ismail Z. Ahmad S. kg/m3 = Interfacial shear stress. m/s = Transversal coordinate (from wall toward the liquid free surface) = Non-dimensional distance to the wall: y(τwgρ)½/μ = Axial coordinate Greek Symbols Γ δ δ+ φ μ ρ τ = Volumetric flow rate of the liquid per unit wetted perimeter. International News on Fats. N/m2 Subscripts ex G i in L lm w = Exterior = In gas phase = In the interface = Interior = In the liquid phase = Logarithmic mean = In the wall References Agrawal A. 1980. 2007... Mathematical and Computer Modelling. Siwayanan P. Methyl Esters as the Route for the production of Surfactants Feedstock.K. Journal of Oil Palm Research. δu/ ν = Roughness enhancement factor. Computer Physics Communications. J/m2 s K = Turbulence characteristic velocity of gas. dimensionless = Axial velocity of liquid film. 2009 15 . 1998. Seng Soi H.. Nonuniform grid generation for boundarylayer problems.: Mathematical Model of Falling Film Reactor U u x v y y+ z = Global heat transfer coefficient. dimensionless = Liquid viscosity.

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