(Chemical Engineering and Procesing 103 (206) 37-45 Contents lists available at ScioncoDirect Chemical Engineering and Processing: Process Intensification journal homepage: www. elsevier.comilocate/cep ELSEVIER Computer simulation of biodiesel production by hydro-esterification ® G.D. Machado®, T-L de Souza”, D.A.G. Aranda‘, FLP, Pessoa‘, M. Castier®, V.F. Cabral”, L. Cardozo-Filho” “unersiadeTcnlia Federal do Barn, Departament de genre Quin, Bras Unversidde Estadual de Marna, Departamento de Engenana Quins, Bra “Uinersiade Feder oR de oni, Depots de Engenharia Quimica. Braz “chem ngnerng Poa, Tse A Univer at Qatar str ever Reese 1 Jay 2015 ‘Accepted 4 October 2015 The conventional production method ofbiodieselby transestenificaionintwo stages chemiealreaction and product separation, has several disadvantages. Compared tot biodiesel production by hydre-esterifiction from fatty matter has many advantages but available tecnology sllrequires distinct steps for eacton and separation. This work presents computational simulations ofa multi-step process of soybean oil biodiesel production by hydro-esteification, The hydrolysis step uses packed bed reactor and the esterification step lutlizes a reactive stllation column. Reactive distilation combines the reaction and sepatationstepsinthe same piece of equipment. Several chemical processes employ this intensification technique but its application to eserifiation processes is recent. The simulation results show that the methodology used is Rows Bociese Reactive dition Hyére-estetetion ‘consistent and sensitivity analyses suggest that conversions close to 99% ae possible. 1 2015 Elsevier BY. All rights reserve. 1. Introduction ‘The main route for the industrial production of biodiesel uses the transesterification of refined oils by alkaline catalysts, such as sodium and potassium alkoxides, because the process is relatively simple and achieves conversions above 95% [27,24]. However, this route has problems, mainly in the purification step, that cause income losses and waste generation. To tackle this problem, several research groups worldwide have proposed the use of heteroge- neous catalysis. mainly in methanolic reactions (26). Significant attention has been devoted to the development of efficient catalysts that result im better conversion rates and reduced saponification problems. In this context, it is worth mentioning the use of inorganic heterogeneous catalysts, insoluble in the reaction medium and easily recyclable [4] ‘The use of heterogeneous catalysts can potentially reduce the cost of biodiesel production, making it competitive against fossil, ‘diesel They facilitate the purification of monoesters, reuse of the solid catalyst. minimize waste generation, decrease reaction time, yield higher conversions, and allow the use of low quality raw materials, thereby reducing costs. On the other hand, heteroge- neous catalysis processes require more severe reaction conditions, Corresponding autor mal eddreser:vfesbrl@vembs vcsbralho icon (VE. Cabra np fo rg0.1016) cep. 201510015 0255-2701)0 2015 elsewer BV. Al rights reserve such as high temperatures, so that the reaction rate is competitive with that of homogeneous processes (13,5,34] Hydro-esterification consists of a step of vegetable oil hydrolysis, followed by esterification of the fatty acids produced. Tr has several advantages, such as the ability to function with materials of high acidity and humidity. In the first stage, all triacylglycerices are converted to fatty acids on the action of water, In the second stage, the formed fatty acids are esterified using methanol or ethanol. Both steps can be accelerated by acid catalysts and become more attractive when coupled to the use of heterogeneous catalysts, eliminating soap formation, reducing the ‘number of separation units, enabling catalyst reuse, and producing high purity, salt-tree glycerin [3] The great advantage of hydro-esterifcation compared to transesterification is that the free fatty acid is reactant in the same reaction, thus not being a limitation in terms of specification of raw material [252712]. This makes it possible to use raw ‘material of high acidity, stich as macaiba (acrocomia aculeata) ol ‘with difficulties associated to harvesting and fruit processing, and of very high acidity (above 30mg KOH/g), without the need for pretreatment of the feeding oil via a neutralization reaction. Similar constraints of algal biodiesel include humidity and high acidity of algae oil (9) On the other hand, hydrolysis processes of raw materials are known and well established, with current operation on industrial scale. Moreover, the esterification step of fatty acids still has a number of technical challenges regarding the operation mode8 6D. Macha ea Chemo Engineering and Processing 12 (2018) 37-45 Gs c F TF F om Se Fig Schematic of ferential mass element W in a PRR. (adapted ro [4 (batch or continuous). Thus, opens up opportunity to use reactive distillation column (RDC) technology in the esterification step, Reactive distillation is a hybrid operation that combines physical sepatation and chemical reaction in the same piece of equipment [30], Thus, the use of RDCs increases productivity and selectivity, reduces energy use. eliminates the need for solvents: in other ‘words, it leads to process intensification [22], Some publications, such as those of 20) 16), and |29], show the use ofthis technology for the esterification of fatty acids to esters as biodiesel Several process simulation studies about fatty acid esterifica- tion in reactive distillation columns have appeared in the literature, However, none of them considers a bydro-esterification process that uses a PBR reactor combined with a RDC to perform the hydrolysis and esterification reactions, respectively. In chose studies, the fatty material contains different types of fatty acids: however, few studies take this variety into account [10]. Most of them consider only a single fatty acid [28,32.5,23.21,18 19.22] due to the difficulty in obtaining experimental data, kinetic param- eters, and thermodynamic properties for the different fatty acids found in raw materials. Only one simulation work that involves a mixture of fatty acids can be found in the literature | 10], However, the authors assumed a homogeneous catalyzed system where chemical equilibrium is attained on each reactive tray. This work presents computer simulations of a continuous multi-stage process for the production of biodiesel by hydro- esterification from fatty organic acids (a mixture similar to soybean oil) and ethanol. The hydrolysis reaction is performed in a packed bed reactor (PBR), while the esterification step is conducted in a RDC: a pseudo-homogenous kinetic model had been used in these steps. In both cases, sensitivity analyses of design parameters and operating conditions are performed in order to optimize the operation of each step. 2. Methodology 21. Hydrolysis Te choice ofthe tubular reactor for the hydrolysis steps based fon the fact that this reaction is conducted at high pressure and temperature, which can cause thermal degradation of the Fra, oven (HP) (1 Xn) (Op — Ka) — ko-sexP He) (Bc — Ka) (> — Ka) ‘components if the residence time in the reactor is large. A mass balance is performed in a differential catalyst mass element dW, for ‘component A, involved in one single reaction over the total mass of catalyst, W. Isothermal conditions and constant pressure along the PBR reactor ate considered in this work, The tubular reactor ean be described as in Fig. 1 Based on Fig. 1, a mass balance for component A can be performed by the following equation: Fa (Fa + OFy) =r a where Fy is the input molar stream of A, F,+ dF is output molar stream of A and 1',dW is the consumption/generation rate of A by ‘The mass balance can be rewritten in terms ofthe conversion of component A, X, leading to Fa = Fao(1 ~Xa) Q ‘where Fao is the molar inlet stream of compound A in the PBR reactor and Xp i the conversion of component A, Written in terms ‘of conversion, the differential mass balance for component A is: @) js integrated form is the design equation of a tubular reactor: w "fae oa 4 In this work, a pseudo-homogeneous model is used to express the chemical reaction rate as a function of reactants concen- trations. Eq. (5) shows this model, which considers a chemical reaction between two teactants forming two products (aA + BRescC + dD). Pa = KiCaCe = kee 6 ‘where C, and Cp are the molar concentrations of components A and, B, respectively, Cc and Cy are the molar concentrations of ‘components Cane D. respectively ky and K_ are reaction constants, of the direct and reverse reactions, given by the Arrhenius Eq. (5): Ey) mr) & keero( 6 ‘where Tis the temperature, Ris the universal gas constant, kis the pre-exponential factor and Ey is the activation energy of reaction The concentration of ll species in the reaction canbe writen 2s «function of volumetric flow rate (Vo), molar stream of the species (Fe). conversion of component A (Xa) and their stoichiometric coefficients as follows: 7 a where 2, ‘The design equation of PBR, for the particular reaction considered, is obtained by combining Eq. (5)-(7) into Eq. (4) &, 6)GD, Machado eo Cheri Engneering an Processing 103 (2016) 2-45 29 Fg. 2, Configuration of sae jin eatve ation corm 1) Im order to obtain the catalyst mass, Eq. (8) is numerically, integrated, resulting in a composition profile of each component ‘within the equipment by specifying the conversion of component AA, Xq, and the reactor feed flow, for known kinetic constants in function of temperature. The integration step (dXa) used was 0.01 22. Esterifcation ‘The modeling of the esterification step is based on consider= ations of 8), (1 and [29] for RDC simulations. The scheme of the ‘generic plate adopted in this work is shown in Fig. 2: For this configuration, the model equations for the distillation column are formulated as follows. Eq, (9) gives the mass balance of i component in stage jas a residual function ff Fig = (+ Vm + (2+ Yay why» Svat) °) where (K+ 1)nl isthe molar flow of the compound: in the liquid leaving the stage jl isthe flow rate of the compound iin the liguid sidestream, i the flow rate ofthe compound fin the liquid reaching the next stage. (Z; + 1)rl, is the molar flow of the ‘compound iin the vapor leaving the stage isthe molar low of the compound tin the vapor sidestrear, and ithe molar ow ofthe ‘compound iin the vapor reaching the next stage. In this equation vigisthe stoichiometric coefficient of component iin reaction, is the extent of reaction and nr represents the number of independent chemical reactions. Assuring that the streams of liquid and vapor that leave each stage ae in equilibrium, the equations defining this condition are described by another residue function, f', based onthe isofugacity oh n(n) — Inf) <0 29) In Fg. (10), the fugacity coefficients ofeach component in the vapor phase are assumed to be equal to 1, andthe Poynting factor correction is neglected. , and xf) are the mole fractions of compound iin the vapor and igi streams, respectively leaving the stage isthe pressure of stage). isthe vapor pressute of component in stage, isthe atvitycoeficient of component in the liquid steam leaving the stage). Theexpression ofthe reaction ratets also expressed bya residue (Fis) function given by Ba, (11) where VF denotes the molar volume ofan ideal liquid solution in stage j, key isthe kinetic constant of reaction k in stage j. ue represents the kinetic order of component jn reaction The energy balance, expressed by a residue function, fs SPATS DHE (HE, HHL +g +Q,) =0 (12) where (Rj + 1)Ff and (Z; + 1)HHf are the total enthalpies of the vapor and liquid streams leaving the stage j, Hf, and H|_, are the total enthalpies of the vapor and liquid streams entering stage Hr, isthe tral enthalpy ofthe fed stream and Qs the heat supplied or withdrawn of each stage) ‘An additional equation is used to specify the behavior of the condenser and rebole. based on a variable Ey which isthe rato between the total molar flow of vapor and liquid leaving the stage ‘This definition of E, can be written as a residue function, £7. specified by Eq. (13): FF Ge Em, BH 11 Ano (13) here values of £) 40 and y=0 are used in the extremes of the coluron. In this way, partial reboiler and a total condenser are Considered inal cases, The value of is calculated forthe internal stages of the cokumn (from 2 to N-1) ‘Addltional details about the solution method are available in the work of [1]. 2.3. Thermodynamic modeling and computational implementation The Dortmund UNIFAC excess Gibbs free energy model 15] is, used to describe the non-ideal liquid phase behavior. The ‘mathematical formulation was implemented using the program- ‘ming language FORTRAN 77. Expressions of residue functions, the Jacobian matrix and the activity coefficient models were generated using the Thermath program |7|. The technique used is similar to that used by [1] and [25]. Property model parameters from DIPPR Database Project 801 for pure compounds were used in the simulations [11] 2.4, Reaction conditions and alcohol used The kinetic data used considered the conditions under which they were obtained experimentally. The hydrolysis and esterifica- tion reactions were conducted experimentally at 260°C and 200°C, respectively [33], Thus, we consider these temperatures in the first step (hydrolysis) and in the second step (esterification). and the average temperature in the reactive sector of the distillation column is very close tothe experimental esterification temperature. As for the alcohol used, the choice of ethanol in the transesterification reaction (conventional process) has shown disadvantages. Compared to methanol, ethanol's higher water content can accelerate unwanted reactions in the conventional process. The hydro-esterification process studied here does not hhave such disadvantage because water is produced in the esterification reaction 3 Results 3.1 Hydrolysis The hydrolysis of soybean oll with water, producing hydrolyzed and glycerol takes place according to the following stoichiometry’ Soybean oil(1)+3.Water(2)= 3.Hydrolyzed(3) + Glycerol(4) (14)2 6D. Macha ea Chemvol Engineering and Processing 12 (2018) 7-45 Varnes Speen Tato iwateisovbean ol) 15690 (dineet]242 Gove) 404218) Due to the difficulty in representing the main components that comprise the soybean oil mixture and the lack of experimental data for these molecules, the phisieal properties of soybean oil properties are assumed to be identical to those of triolein in this hydrolysis step. The molar composition of fatty acids in the hydrolyzed soybean oil is 58.2% linoleic acid, 25.1% oleic aid, and 16.7% palmitic acid. To account for that, the hydrolyzed soybean oil is modeled as a pseudo-component that represents a mixture with, that composition. The considerations regarding the thermody- ‘namic properties of this pseudo-component are those used by [2°] The hydrolysis reaction is considered reversible. The rate model used is the pseudo-homogeneous with dependence of the molar concentrations of the reactants in the same way of Eq, (5) The kinetic data of the hydrolysis reaction are from [33] who used niobium oxide as catalyst. The specifications of the reactor and the reaction rate constants for this catalyst ate given in Table 1 Fig. 3 displays the liquid phase mole fractions along. the simulated PBR. The soybean oil fed to the reactor is almost completely consumed with 80 g mass catalyst, while excess water in the feed stream leaves the reactor with 40% molar composition in the output stream. This excess humidity can be removed by flashing in subsequent operations. The hydrolyzed soybean oil and glycerol generated in the chemical reaction form two phases that are essentially immiscible at mild temperatures. Thus, these products can be separated by decantation of centrifugation, Fig, 4 shows the liquid phase mole composition surface of soybean ol at the reactor output for several values of catalyst mass ona Liqula Phase mole Fraction (from 0 to 50 g) as function ofthe feed flow (a) and feed molar ratio ‘of water/soybean oll (b), respectively. From Fig 4(2), the minimum flow provides the best conversion, results, From 100 mol/min, there isa sharp drop of the soybean oil conversion with increasing feed flow rate. From the feeding molar ratio, Fig. 4(b), the smaller value of this variable represents to the process a lower processing cost in terms of raw materials. The stoichiometty of the hydrolysis reaction analyzed between water ‘and soybean oil is 3:1. Fora value twice ofthis ratio, the conversion ‘curve has almost stable value. As a way to avoid costly excess water recirculation, it was decided to consider a molar ratio close to 6:1, ‘more specifically 57:1. Industrial conditions at SCS (Ponta Grossa/ PR-Brazil) reported 16:1 molar ratio, which generated a 99.6% ‘conversion in this work. 2.2. Esteifcation ‘The esterification of hydrolyzed soybean oil with ethanol forming a mixture of esters of biodiesel and water takes place according to the following stoichiometry: Hydrolyzed(1)+ Ethanol(2)=Biodiesel(3)+Water(4) as) here “biodiesel” refers to the group of esters formed regardless of purity specifications for commercialization. In this work, as in the ‘ase of the hydrolyzed material, biodiesel is considered 2 pseudo- ‘component that represents a mixture of fatty acid esters with the following molar composition: 58.2% of ethyl linoleate, 25.1% ethyl oleate and 167% of ethyl palmitate. We follow the same Soybean oi —Water —Hysroiyzed —sHeor0! =e 0 8 © © © wi Fig. Ligue phate moe fractions within the simile POR6D. Machado eo chemical Engineering and Processing 105 (2015) 7-45 a ‘poe sou see tn » seed tow (elie) ‘ato Fig. 4, Suracecompostion of aybean i) nthe lg phare a fanesion fee fw eate by the maz fatal (W (8 an surface composition a function a fed sola rato. considerations used by [29] to calculate the thermodynamic properties of this pseudo-component. Inthe simulations performed here, we use the Antoine equation to calculate the vapor pressure: Inp(bar) = Ara as) To obtain the A,B, and € parameters of hydrolyze soybean oi and biodiesel, we generated pseudo vapor pressure dat at selected temperatures using the following equation PE xh an) where fi the mole fraction of component i in the pseudo- component, Fis the vapor pressute of component i calculated ata fiver temperature, and ne is the mmber of components considered in each pseudo-component. In these calculations, we used temperatures between 340 and 500K. The vapor pressure of each pure component (P.) was calculated using an extended ‘Antoine equation: ites) A phe +B "ihe 2 presents the printed a (8) fr ch pte cogent sired te pcs copie gered soybean oil and biodiesel), The parameters in Eq. (18) for pure Singonents wee one tn NST (Nara Ist Std tn Teg) dace [and IPR Os Institute for Physical Properties) database | 11\. us) Table 3 presents the Antoine parameters obtained for the hydrolyzed soybean oil and biodiesel. It also presents parameters used for water and ethanol. The parameters for ethanol and water can be used for temperature ranges of (364.80-513.91) K and (379.00-573,00) k, respectively. ‘The molar volume and heat capacity in liquid phase of hydrolyzed soybean oil and biodiesel were also calculated by the weighted average of the properties of the pure components considered in each pseudo-component. Table 3 shows the values of these properties used in the simulations. The value in the liquid phase of the heat capacity and molar volume were obtained for the temperatures of 450K and 298K, respectively, from the NIST (National institute of Standards and Technology) [51] and DIPPR (Design Insticute for Physical Properties) databases [11] The rate constants of Eq (5) were fitted from the experimental kinetic data of [33] who studied esterification of hydrolyzed soybean oil using the same niobium oxide catalyst employed for the soybean oi hydrolysis. ‘The simulated column has 20 stages: 1 partial reboiler, 18 adiabatic plates (12 of them reactive), and 1 total condenser, All specifications of the RDC ate shown in Table 4. Fig. 5 shows the liquid phase mole fraction profile to the components of the esterification reaction along the RDC 5 shows that the desired product, biodiesel, is removed from the bottom of the column with considerable purity (95.89%) Excluding the amount of ethanol in the bottom stream (which may be separated by a flash process). the purity of the biodiesel produced reaches 99%, This is due to the use of high heat duty in the reboiler. According to [25], the eboiler temperature can exceed 260°C. This high temperature could degrade the biodiesel formed land removed in the bottom stream, Tabte2 Tare Txtended avons ea = 7 ‘component i = ny z ange ove Tunas a6 atar ary 2a 5 ereney lec acid 02.45 19053 pera 2 38633-85000 Palme sd m9 ans oae8 6 Sase-00415 Bote Ta Hnoiate 106867 Ts510 7508-18 6 ai820-778 xl leate io6 085 =143923 a 5 25167-77210 Ex paratate 13.986, 2153526 ise 5 as7is-79840Tiqud mel volume pig Aavene equation parameters ext) ime) Ke Trobe’ 312005 05853 11a6) svaaaa —taa207 Bodies! 347508 ois 1139) soa 78 607 en b2 e255 19804 bie 4 Speccations forthe RDC and estenfation reaction, Variables Speakers Frese TA sages Towbar Stage nombre do Feta Condenser ao ieacive secon Nobium oe (NBO) stages 677 Gault S00 per stage ed Trenare Towzber (uverabres) 1219 mal ate eicion Areas Preeponential ior 1615 [@ueeh/O2 (eve) 3.3, Reboiler heat duty sensitivity analysis In order to obtain the optimum operating parameters, the influence of the heat duty on the reboiler was studied. Fix. 6(a) displays 2 temperature surface and Fig. 6(b) exhibits mole composition surface of biodiesel along the RDC as function of the reboiler heat duty. Fig. 7 shows the conversion of hydrolyzed soybean oil inthis sensitivity analysis, Fig. 6(a) shows a remarkable change in temperature. At the lower limit, with minimum heat duty on reboiler, the temperature {in the column bottom is approximately 290.9 K, When the upper Column Top 20 Stage Column Bottom 040 020 030 040 050 060 070 080 0.90 GD. Machado ea Chemo Engineering and Processing 12 (2018) 7-45 limit, 153.3 kWhjton fatty esters (biodiesel is used, the tempera ture reaches around 590K Such temperature can promote ‘thermal degradation of biodiesel and also increase the cost of the RDC operation, as mote energy is required. In addition, as Fig. 7 shows, the increased heat duty in the reboiler increased conversion by only about 1.88. Therefore, from the viewpoint of conversion, it is not recommend to ty to gain efficiency by increasing the heat load, According to [29], seting the reboiler off and using thermal ‘energy in the feed stream can reduce energy consumption and avoid exposure of the bottom product to elevated temperatures. 3.4. Hydrolyzed feed temperature sensitivity analysis As stated previously, the thermal effect on the reboiler can be unfavorable to the stability ofthe produced biodiesel. In order to ‘minimize this effect, a sensitivity analysis using the hydrolyzed (fatty acids) feed temperature as an independent variable was made, with values in the range between 380 and 533K. In such analysis, the energy supplied to the process by the reboiler was ‘kept minimal (about 22 kWhjton biodiesel produced), not zero for computer code convergence issues Considering Fig 8(a), it can be seen that the temperature of the hydrolyzed feed stream has a strong influence on the temperature profile along the column, The biodiesel liquid phase mole fraction profile of Fig. 8(b) differs substantially from the profile displayed in Fig, 6(b). Fig. 9 shows considerable increase in the hydrolyzed ‘conversion, showing that this variable is very important to the RDC performance. As the hydrolyzed saybean oil conversion exhibits a ‘wider range in Fig, 9 (~-$5-99%), increasing the feed temperature ‘of hyérolyzed soybean seems to be a better optimization strategy than increasing the reboiler heat transfer rate. Besides, in this procedure, with minimum thermal load in the reboiler, temper atures in the range 364-424K are found in the bottom product. ‘Such condition is not so extreme when compared with the full use of the reboile, as shown in the previous analysis, 35. The combined hydro-estrification process Fig. 10 shows a global process that combines the hydrolysis and, esterification reactions. Hyelrolysis occurs in a PBR reactor and esterification is performed in a RDC. —Hydrolyzed Ethanol —Biodiese! —Water 1.00 Liquid phase mole fraction6D. Machado eo chemical Engineering and Processing 105 (2015) 7-45 2 foe se ; 3 cont - i a cao ; 3 i Fig 6, Temperature surface 2) and biodiesel molar composition (long the KDC = 590.1K g 57° rs 5 + 3 z § ns 3 E no 2 wns 139094 oo 0000S) Reboiler heat duty (kWh/ton) Fig 7 fet ofthe eboie heat duty onthe hyolee conversion tn Hg, 10, the term "MIX" represents the mixing of reactants esterification process. It also shows that the recycles of ethanol before the PBR The cerm "SEP" identifies separation processes. and water allow the recovery of up to 20% of the ethanol fed into ‘Table $ shows the main and recovery flows of the hydro- the RDC and 98.5% of the water required in the PBR. : ok commento seas pie ce “ee at dra Feed Hydrated Feed “Tempertaret) rampeatre() ig. § Temperature surface (sand biadieslcompostion (slang the RDC6D. Machado ea Chemical Eng jnecing and Procesing 105 (208) 37-85. 00 a & 90.0 2 85.0 & & 20 3 a Hydrolyzed feed temperature (K) Water a + waterwoey —_af ir —@ UL water “or eal ——" # uv od ge Ethanol Hydrolysis Step ef) enna r aun seams (gla yéroized 3.7264 00260 odie = : : ‘40584 Recovery steams kin) Moreover, although soybean ol is used as raw material, this combined of hydro-esterification process can use any low cost feedstock with considerable humidity and fatty acids amounts, since they are both usable in the process and do not hinder the chemical reactions PEF -4 siosiese Esterifeation Step 4. Conclusions ‘This work presented computer simulations of a combined hydro-esterfieation process for biodiesel production in which the hydrolysis of soybean oil occurs in a tubular reactor and esterification of faty acids (hydrolyzed) takes place in a reactive distillation column. In both steps, the main fatty acids present in the soybean oil composition were considered. A pseudo-homoge- neous kinetic model based on experimental heterogeneous catalysis data was used, The simulations were performed with a validated non-commercial computational code, adopted in previ- ‘ous works of the group. The focus was on the calculation of ‘material flows; detailed analysss of the energy balance ané of the process economics are planned extensions of this work. In the hydrolysis step, when a minimum input flaw of soybean, oil is used (30mol/min, in this paper), the sensitivity analysis showed that a feed ratio of 5.7:1 (mole of water per mole of soybean oil) can lead to high conversions ‘An observed benefit of the combined process is that the water produced in the esterification step in the reactive distillation column can be recovered in the hydrolysis reaction in the reactor PBR. in previous step, together with the water fed in excess therein6D. Machado eo chemical Engineering and Processing 105 (2015) 7-45 * For the esterification step, increasing the feed temperature of hydrolyzed soybean is mote suitable than increasing the heat transfer rate in the reboiler. This strategy leads to mild temper atures inthe bottom product (364~424K) and thereby avoids the ‘exposure of biodiesel to high temperatures atthe column's bottom. ‘The results of sensitivity analyses showed operating conditions ‘optimized for conversions above 99% Regarding the specifications, ‘even ignoring the SEPIII separation process in Fig, 10, the produced biodiesel has purity of 98.3% on mass ester content, which is higher than cuttent international requirements of 96.5% for biodiesel, Acknowledgments ‘The authors thank CNPq (grant 168154/2014.5), FAPER). Fundacdo Araucéria and CAPES (grant BEX 6328)12-1) for nancial support. References In] ne Alradigu, ne. caster, Modeling and simulation of reactive distillation “alu using compute alga, Com. Che. Eng 29 (2005) 1875-1664 [b] DAG Aranda DA. Gangales, 5 Peres, ALD Ramos, CAR. De Mela, OAC ‘Ansnes NC Parada, CA Tat These a anim xi. and elite ‘aaa for esterieation reactions. | Phys Org Chem. 22 (2003) 709716, hp fx do. org10302pocis20. 1s] EF alti Hoja 0. Opal TE Madhur, D0. {heat BlomassBrenergy 91 (2016) 275"297 dot lrg 1010 biombioe 2019 1.08, Is] NeBaneheo, ED Kusumaningtyas, .Gozzelino, Reactive distillation i the stud flnd Eg. Cherm 20 2014) 4242-4288 [61 | Boumay B, Cassnve, B DelfrCHlon, A Chedorge New heterogeneous process for bediesel production: a way tolmprove the quality tnd the vale ofthe crude jena produce by biodiesel plants, Cas Today [71 Mecaster, Astamatic implementation ofthermedynamie modes using ‘computer slgeara, Comp. Cher. Eng 23 (1998) 1229-1285 [a] Eien. KS. Huss ME Malone, ME Dehery Comp. Chem. Eng 24 (2000 19 ct Conca 0 cancion ofa i, Beco. 167 [10] & Corso-vagat, FO. Harorosmio, 5, Hermander JG, Serovlhernander a. Cano-roigez, Thermally coupled cstilauon sequences: stacy sate Simulation the esesiaton of ay organ sls, chem Eng Process. 62 11] Dippr Databave Project S01-Fll version, 201, [2] MUD sero Rfeser Penge FSantaceratia. Heterogeneous aa Diocese procucion, Energy Fels 222008) 207-217 (15) Wis Fata LM Carvalo, 8 Mont jis, £C Vera AM. Constantin, Siva DAG Aranda Anas do 2 Congress Brablevode Cade Agta dos es Bras 2003, [14] Hs Fogler Element of Chemical feacson Enginering 3th Ein, Prentice Hal ook company Newt Jersey, 2002p. 40 ts) cog} a Sher nied UNA adel. een prt fer 32 (195) 178-19), [16] EL Gomez-asro,v Rice-ramisez. 6. Seovi-hernancez,. Hernan, Feasiiyseuay o «therally coupled veactvedsllation proces or odise! redaction, cher: Eng Press 49 (2010) 252-268, de px [n8] RM Ignata. AA Kiss Optimal devin, namic snaconzal of reactive DWC for biodiese production, Chem. Eng Res Des. 31 (2013) 1601767. [09] Adv kiss Hestanegrated reste dtlation proces for synthe of 57 120) & Kiss, Novel proces fr biadese 39 reactive abrorption Sep Fi Teche 2000) 280 dor hip lende or] 10 1016) seppur 2008 08 008, [at] Aa Kiss, Separatve racers for ineeateé production of bioethanel and Biosiese, Comp. Chean Eng 24 2010) 812-820 fay iy 8 Bld ated une sin poe lta Ina] RA fire JG Segoiaeranden ide, £Y Miranda-raings Hernandez Reacve DWC leading the way te OIE and ertane Ful 95 (2012), [24] Li, Layla ete Production of bodes! rom hidvoeterifacdo of cate i ‘doy. 230 I Thess (Maver these in Chemical and iochemiel Procestesi~Fstla de Quimica Universidade ederal do Rede ane. io de Janet ean 2007 [as] Eater eralSyatessebiogesl via accra nd Eng Chem. Res. 44 126} 6. Lourinho, P. Brite, Advanced biodiesel production technologies: novel dotorgn0 107 e11s7-onLb335-«. ' (m7) EMH Sanna Bois! rion: eve, Saeour Teo 70 [aa CD Macada, DAG, Aan Manteca | Cadre {elas Ind Eng hers. Re.50 (201) 10176-10184 dav tp colo ian et02329y [29] GD. Machida, FUP. Pessoa M Caster, DAG. Aranda VE. Cabral L Cadre. Fi. Bagiesi prediction by eseriiaion af Braid sasbean wih ‘thanol in eactve eeilon coloring simon stir ind Ene Cher, fes'52 (2015) 51-9465 do: ped org/10.1021 4008054 [bo] MF Aalone, ner ener Reactive dstlton ind Eng Chem Res. 39(2000) [1] Nist Chemistry WebBook. MST Standard Reference Database Number 69. 00s. [32] Emota, Ac Dimian A ik Fatty acid ericson by eave itl Part 1 equllbeumsed design, Chem ng Se 562003) 3188-3174 [p3] LLL Rocha, ALD Rasos. NR Assos! ho, NC Futlade, CA Tate DA. Aranda Froeucton of bidse by a wo-stegmabitm axe eialyod Fpl and estecneation Let Org Chem. 72010) 971 tp jc coiote Dba Cet Marne | Al egreé Ddel paductn: 4