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Design of Reactive Distillations for Acetic Acid Esterification

Yeong-Tarng Tang, Yi-Wei Chen, Hsiao-Ping Huang, and Cheng-Ching Yu
Dept. of Chemical Engineering, National Taiwan University, Taipei 106-17, Taiwan

Shih-Bo Hung and Ming-Jer Lee
Dept. of Chemical Engineering, National Taiwan University of Sci. Tech., Taipei 106-07, Taiwan DOI 10.1002/aic.10519 Published online April 21, 2005 in Wiley InterScience (www.interscience.wiley.com).

The reactive distillation provides an attractive alternative for reaction/separation processes with reversible reactions, especially for etherification and esterification. The discrete nature of chemical species and the complexity of phase equilibria seem to cloud the picture in understanding reactive distillation. The esterifications of acetic acid with five different alcohols, ranging from C1 to C5, are studied. First, qualitative relationships between macroscopic process flowsheet and microscopic phase equilibria are established, and the process flowsheets are classified into type I, II, and III for these five systems. Next, a systematic design procedure is devised to optimize the design, based on the total annual cost (TAC) and dominant design variables are identified for different flowsheets. Once quantitative design is available, process characteristic are analyzed and potential problems in process operation are identified. Finally, the economic potentials of these three different flowsheets are explored and explanations are given. The results clearly indicate that it is possible to systemize the design of reactive distillation by qualitatively generating flowsheet from phase equilibria and by quantitatively completing the process flow diagram from a sequential design procedure. Moreover, some of the flowsheets presented in this work cannot be found elsewhere in the open literature. © 2005 American Institute of
Chemical Engineers AIChE J, 51: 1683–1699, 2005

Keywords: esterification, acetate, reactive distillation, process design

Introduction
Reactive distillation provides an attractive alternative for process intensification, especially for reaction/separation systems with reversible reactions. The literature in reactive distillation has grown rapidly in recent years and the books by Doherty and Malone1 and Sundmacher and Kienle2 give updated summaries in the field. Taylor and Krishna3 give an in-depth review on potential advantages and hardware configCorrespondence concerning this article should be addressed to C.- C. Yu at ccyu@ntu.edu.tw.

© 2005 American Institute of Chemical Engineers

urations. As pointed out by Doherty and Buzad,4 the concept of combining reaction and separation has long been recognized, but rarely put into commercial practice, not until the successful application for the production methyl acetate.5 Despite clear advantages of simultaneous reaction/separation,6 commercializing of reactive distillation processes is still quite limited for several reasons. An obvious one is mentioned in4 “There is almost always a conventional alternative to reactive distillation which is seductive because we have always done it this way”. The scenario remains more than a decade later. After the management and technical levels were convinced by the clear edge of reactive distillation, another reason is that the process flowsheets seem to change from case to case (for example,
Vol. 51, No. 6 1683

AIChE Journal

June 2005

at 363 K) changes from 1. Literature surveys indicate that most of these data have become available in the past five years13. IPAc and AmAc systems are described by the NRTL model while MeAc and BuAc systems are represented using the UNIQUAC model. Correct description of the existence of azeotropes and the ranking of azeotropic temperatures will lead to generating correct residue curve map (RCM). ethyl acetate. the models also Vol. the flowsheet configurations also vary8.from methyl acetate. First.000 kJ/kmol. n-butyl acetate (BuAc). these five quaternary systems also show complex phase behavior with the number of azeotropes (binary and ternary) varying from 2 to 6 with possible liquid phase splitting. to ethyl acetate. with normal boiling point ranges from 57 to 147°C.5. 51. we are interested in the solid-catalyzed reaction kinetics for an obvious reason that one can place the reactive zone in different sections of the reactive distillation columns.16. methyl acetate. respectively. Moreover. In this work.10. the seemingly casebased design approach and a great deal of process configurations (to choose from) add additional complexity to reactive distillation.6 to 16. design procedures are proposed for different process configuration to determine.11. sulfuric acid). No. iso-propyl acetate. and so on). qualitatively. activation energy of the forward reaction varies from 44. Esters are of great importance to chemical process industries. process characteristics of these five optimally designed reactive distillations are studied. butyl acetate.17 and Table 1 lists the reaction kinetics used in this study. Despite the fact that the kinetic experiments were performed by different groups with somewhat different type of catalysis.5 10 3. Then.20 Two important steps to validate model parameters are: (1) good prediction of azeotropes. with the component represented in terms of activity. The esterification reactions are studied in this work.19 The Aspen Plus built-in association parameters are used to compute fugacity coefficients. Next. The solid catalyst can be either 1684 June 2005 . butyl acetate. quantitatively. The reaction rates are expresses in the pseudohomogeneous model or Langmuir-Hinshelwood and. and the heat of reactions are almost negligible except for the methyl acetate and ethyl acetate systems. Table 2 lists the model parameters for these five quaternary systems where EtAc. Moreover.000 kJ/kmol to 70. the thermodynamic properties for these five quaternary systems are investigated. These cover the production of a range of important solvents. ethyl acetate (EtAc). A reasonable prediction of LL envelope can facilitate possible use of decanter which is often encountered in esterification reactive distillation systems. to butyl acetate and so on). Table 3 reveals that the model parameters give reasonably good description of existing experimental azeotropic data22 for all 5 systems.9. immobilized via structured packings such as Katapak-S (Sulzer Chemtech3.12. iso-propanol (IPOH).20. we observe certain degree of consistency in the kinetic data (Table 1). followed by the conclusion. ethyl acetate. the vapor phase nonideality considered is the dimerization of acetic acid as described by the Hayden-O’Conell second virial coefficient model. The equilibrium constant (Keq. Phase Equilibria To account for nonideal vapor-liquid equilibrium (VLE) and possible vapor-liquid-liquid equilibrium (VLLE) for these quaternary systems. In addition to its industrial importance. the tray numbers in each section of reactive distillation systems and design is optimized based on the total annual cost (TAC). isopropyl acetate (IPAc). In applying the reaction kinetics to a reactive distillation. it is assumed that the solid catalyst occupies 50% of the tray holdup volume and a catalyst density of 770 kg/m3 is used to convert the volume into catalyst-weight (mcat). A number of chemical systems have been studied in the literature using reactive distillation columns and among the 74 applications listed in Sundmacher and Kienle.11 as one went through the literature. 6 AIChE Journal Reaction Kinetics and Phase Equilibria Reaction kinetics The esterification of the acetic acid with different alcohols can be expressed in the following general form acid N alcohol k 1 acetate k1 water (1) The alcohols studied in this work include methanol (MeOH). Table 1 also shows that the methyl acetate system has the most favorable reaction kinetics catalyst an order of magnitude larger than the rest of the systems. ethanol (EtOH). Note that for the isopropyl acetate. Finally.73 10 4 to 2. Unlike the conventional distillation. The objective of this work is intended to provide possible generalization for the design of reactive distillation for esterification reactions with acetic acid. and amyl acetate. placing separators in the right sections. and esters are typically produced from the reactions of acid and alcohols under acidic condition.14. they are all catalyst-weight (mcat) based kinetics.8. such as Amberlyst 15 (Rohm and Hass) and Purolite CT179 (Purolite). in this work.8. We have not seen too many kinetics data on solid-catalyzed esterification reactions until recently.15. possible process flowsheets are generated based on the VLLE behaviors of these five systems. The solid catalysts used are acidic ion-exchange resin. consequently. It should be emphasized the quality of the model parameters (Table 2) is essential to generate correct process flowsheet.6 10 3 (mol H /kgcat) is assumed to convert the catalyst weight-based expression.21 This is also the reason why the NRTL and UNIQUAC models are preferred for activity coefficients.9.2 most common applications of reactive distillation are etherification and esterification reactions.11 Even for the same chemical production (for example. the [H ] concentration of 4. the NRTL18 model or UNIQUAC model is used for activity coefficients. n-butanol (BuOH). we explore the esterifications of acetic acid with different alcohols ranging from C1 to C5.10.7. In order to provide possible generalization to the design procedure. the forward rate constant (k1.10. and amyl acetate (AmAc). and.12) or simply placed inside the tray with certain type of replacement mechanism (Davy Process Technology). It is clear that this provides flexibility in process design as opposed to using homogeneous catalysis (for example. at 363 K) ranges from 1. and n-pentanol (amyl alcohol. AmOH) and corresponding products are methyl acetate (MeAc). generally. and (2) reasonable description of the liquid-liquid (LL) envelopes for VLLE systems. Because of the almost atmospheric pressure.

55 103 exp 105 exp 48300 RT [kmol/(kgcat s)] (iii) IPAc 66200 RT Langmuir-Hinshelwood/Hougen-Watson model 1 (Amberlyst 15) r mcat k1 aHAc aIPOH aIPAc aH 2O /Keq KHAc aHAc KIPOH aIPOH KIPAc aIPAc 10 5 exp 23.147.2533 exp 51740 RT 45280 RT k 1 C AmAc C H 2O ) 1. (i) Popken et al. the models predict three minimum boiling azeotropes and one minimum boiling ternary azeotrope (Figures 1B and 1C).32 10 4 10.7 k1 K eq 7.17 predict ternary azeotropes for 4 quaternary systems except the MeAc system (Table 3).76 [kmol/(kgcat s)] 69230 RT Pseudo-homogeneous model 1 (Purolite CT179) r k1 k 1. K IPOH 4. C i [kmol/m3]. x i [mole fraction].314 [kJ/kmol/K]. T [K].24 4.43 RT 0. Kinetic Equations for Five Esterification Systems System (i) MeAc Pseudo-homogeneous model (Amberlyst 15) r k1 k (ii) EtAc m cat (k 1 a HAc a MeOH 2.5079 8.0135 106 exp 106 exp k 1 BuAc H 2 O a a ) 2.78 10 4 3.1667 exp 2.667 [kmol/(kgcat s)] 0. r [kmol/s]. 6 1685 .49 10 3 16. K IPAc 3 1 KH 2O aH 2O 2 2.961 1. For the EtAc and IPAc quaternary systems. The BuAc quaternary system has three minimum boiling and one maximum boiling binary azeotropes and two Vol.13 (ii) Hangx et al. No.14 (iii) Gadewar et al.Table 1.6 10 Assumption: mol H /kgcat (iv) BuAc Pseudo-homogeneous model (Amberlyst 15) r k1 k (v) AmAc m cat (k 1 a HAc a BuOH 3. The phase equilibria results reveal that the MeAc quaternary system has two minimum boiling binary azeotropes as shown in Figure 1A and this is the only system without any AIChE Journal June 2005 ternary azeotrope.3856 1.81 68620.1976.2396. K H 2O 0.26 10 4 8. 51.15 (iv) Gangadwala ¨ et al.9 70660 RT [kmol/(kgcat s)] 742417 RT Quasi-homogeneous model 1 (Amberlyst 15) r k1 k m cat (k 1 C HAc C AmOH 31.11 (v) Lee et al. K HAc 0.6 [m6/(kmol kgcat s)] 1 *R 8.348 104 exp 106 exp k 49190 RT 1 MeAc H 2 O Kinetic Model (Catalyst) k 1 (T 363K) K eq (T 363K) a a ) 2.5 m cat (k 1 x HAc x EtOH k 1 EtAc H 2 O x x ) 4. m cat [kgcat].13 10 6 1.7.50 4.

186 422. BuAc.245 0.3000 1.279 515.41293 421.4000 IPOH(2) H2O(4) 20.71011 1.0869653 157. especially for the acid free ternary systems (Figure 1).3000 BuAc(3) H2O(4) 345.972 81.001167 0. It is important to notice that.0021609 0.29355 0.15) HAc(1) HAc(1) IPOH(2) IPAc(3) IPAc(3) H2O(4) 70.5 0.1453 2. qi xi i nc .38 62.848 98. nc nc j ij j ji j 1 j 1 k kj k 1 nc UNIQUAC model: ln i xi z q ln 2 i li xi xj lj j 1 qi 1 ln .315 74.3009 Gji xj nc xk ki Gkj xj Gij nc ij k 1 nc NRTL model: ln j 1 i nc j 1 .0346 390.12 326.55 0. ij aij ln i bij .018 0. qi xi i nc . T ij cij .83 0.43637 0.3643 IPAc(3) H2O(4) 415.8857 0. ij aij bij T cij T.3014 110.8886 723.00027235 0.0013309 0. j b ij (K) b ji (K) c ij nc ji a HAc(1) MeOH(2) 0.62672 HAc(1) AmOH(2) 316. Significant LL envelopes are also observed for these five quaternary systems.0030613 0.6904 41. the minimum temperature inside the composition space is the ternary minimum boiling azeotrope.3000 (iv) BuAc System—UNIQUAC (Venimadhavan et al.4746 AmOH(2) H2O(4) 100.806535 0.04 0.92 265.9763 3. AmAc systems.00024019 0.0060713 0. i Comp.1039255 0.42868 0.2000 (i) MeAc system—UNIQUAC (Popken et al.4 (v) AmAc System—NRTL (Chiang et al.8 320. i Comp.0070149 EtOH(2) H2O(4) 0. i Comp.9005536 0.97039 2.72476 62.0585 575.6447911 40.0603422 0.05742325 833.462808 0.96255662 0.34561 3. i Comp.817306 4.2987 144. j b ij (K) b ji (K) c ij Comp.68 219.003157 HAc(1) EtOH(2) 0 0 252.888 0. Gkj xk Gki xk k 1 k 1 Gkj xk k 1 Gij b exp ij ij . li z r 2 i ternary azeotropes (Figure 1D) and the AmAc system gives three minimum boiling binary azeotropes and two ternary azeotropes (Figure 1E).2000 nc 110. ri xi i nc . j a ij a ji b ij (K) b ji (K) c ij Comp.Table 2.1 1447.6521 0.482 225.051007 0.3293 609.8 178.193 358.478762 1373.5 0.000076741 0.7 265.098 232.00020133 EtAc(3) H2O(4) 2.289 1614.4756 0. 51. & 1686 June 2005 IPAc systems show type I LL envelopes while the BuAc & AmAc systems give type II envelopes as shown in Figure 1.0422748 0.96295 593.2980 MeAc(3) H2O(4) 0. Gii nc i i 1 and i ii 0. The MeAc.010143 0.32) HAc(1) HAc(1) EtOH(2) BuAc(3) BuAc(3) H2O(4) 150. j b ij (K) b ji (K) Comp.853826 1290. j a ij a ji b ij (K) b ji (K) c ij j (K 1) c ji j (K 1) Comp. 6 AIChE Journal . No.247 AmAc(3) H2O(4) 254.47 2221.21) HAc(1) HAc(1) AmOH(2) AmAc(3) AmAc(3) H2O(4) 37.26 65. i Comp.533 444.3000 1.227 292.5806744 424. That is relatively pure water can be recovered from the LL separation for 4 out of these 5 systems (except the MeAc system) and the separation (for achieving high purity water) becomes easier as the carbon number in the alcohol inVol.3 0.26) HAc(1) HAc(1) EtOH(2) EtAc(3) EtAc(3) H2O(4) 0 0 235. Activity Coefficient Models Parameters for Five Esterification Systems Comp.3048 HAc(1) BuOH(2) 66.13) ¨ 0.96532461 77.2997 191.943 214.287 0.464 4.1000 (ii) IPAc System—NRTL (Gadewar et al.3255 BuOH(2) H2O(4) 34. IPAc.53679 12. for EtAc.2 0.57 424.447 172. EtAc.3000 HAc(1) IPOH(2) 141.0023547 (ii) EtAc System—NRTL (Tang et al.1695 HAc(1) MeAc(3) HAc(1) H2O(4) EtOH(2) MeAc(3) MeOH(2) H2O(4) 3. rk xk k 1 k 1 qk xk k 1 qk xk qi ri 1 and z 10.8212 0.1162 0.514285 266. The tie lines slop into pure water node and it becomes more evident as the carbon number in the alcohol increases.

09°C (0. typically.58°C (0.1292.6108.24 but the purity level ( 80%) is far from the product specification and further purification is needed. 0. 0.8304) 95.2858) 70.21°C (0.2°C (0. Actually.4018) IPOH/IPAc 78.3131) 70.8488) 95. Azeotrope Data for Five Esterification Systems (i) MeAc MeOH/MeAc 53.96°C (0. Again. and possibly a decanter.18°C) azeotrope that may prevent obtaining high purity H2O if one is performing the separation along the EtOH-H2O edge. 0.538) EtOH/H2O 78. 0. configuration (with a little modification. this has important implications in the flowsheet development.5982.9016.1512.4016) 80.22°C (0.27) HAc/BuOH/BuAc 121.1667) HAc/AmOH 140. first proposed by Agreda et al.1069. 0. 0.18°C (0. 0.146.80°C (0.3885) IPAc/H2O 76.6°C (0. That is to device hybrid reactive distillation systems to produce commercial grade acetates.62°C (0. 0.2823.3423) HAc/BuOH 123.EtAc & IPAc Type I Flowsheet .1377. As will be shown later. Process Flowsheets In this section.1126. **Experimental data (Horsly22) in italics. 0.4572. we are separating HAc/MeAc with small amount of H2O.847) AmAc/H2O 94.54°C (0.1696. we also observe the Vol.90°C (0.1196) (ii) EtAc EtOH/EtAc/H2O 70.65°C (0.359.43°C (0.7°C (0.43°C).0984) 78. in particular. 6 1687 .8904. For methyl acetate system.2225.Table 3. It becomes obvious that the EtAc system has a much complicated phase behavior and. 0. On the other hands. 0. For EtAc system. 0. 0.3309) 82. 722) BuOH/H2O 92. it is possible to achieve high purity products at both ends with the type I flowsheet (Figure 2A). The azeotropes play little role in the separation sections except that the top product is a saddle (ultimately the RCM will end at the MeAc/H2O azeotrope.6869. If the reactive zone consumes all the acid. it was simulated by several researchers. we also have EtOH/H2O (78. 0.07°C (0. if we react away most of the alcohol toward the top section of the reactive zone. we are dealing with the separation of the H2O/ MeOH/MeAc. 0. The heavy product of the reaction. 0. an almost ternary system. Nevertheless.37°C (0. creases. 0.752) BuOH/BuAc 116. 51.166.7415) * Heteroazeotropes in boldface.7075) 89.0864.4019) 76. 0. 0. despite being a saddle in the RCM rotation.57°C (0.23°C (0. reactive section. at design stage.0963) (iii) IPAc IPOH/IPAc/H2O 74.85°C (0.4641) (v) AmAc AmOH/AmAc/H2O 94. This is exactly the methyl acetate process AIChE Journal June 2005 The boiling point temperature ranking may suggest that we can use the type I flowsheet for the EtAc production with the EtAc and H2O withdrawn the top and the bottom of the column. No. 0. the RCM in Figure 3A shows that it is possible to obtain relatively high purity MeAc. three distillation boundaries are found for the H2O/EtOH/ EtAc system (Figure 3B).754) BuAc/H2O 90.2377.8804.0488.5359. the ternary minimum boiling azeotrope lies inside the LL envelope and it moves further inside the LL zone as the carbon number increases. 0.3115) EtOH/EtAc 71. 0.2°C (0. 0. 0. For IPAc.7847. 0.4092. In analogy to the MeAc system.5428) 71. in the rectifying section.3085) EtAc/H2O 70. 3492) IPOH/H2O 80.206. attempts are made to generate flowsheet for high purity acetates using the combination of stripper.4°C (0. Figure 3A indicates that most of the composition space lead to a rather pure H2O in the bottom of the reactive distillation. and the light product MeAc is taken out from the top. the heavy reactant is fed from the top of the reactive section and the light reactant goes into the bottom part of the reactive zone.06°C (0. 0.9037.278. 56.73. 0.5789.2585.9°C (0.7 This process flowsheet can be understood from the boiling point (including azeotropes) temperatures ranking (Table 4).5°C (0.2°C (0.5 and studied by many others.5°C (0.81°C (0. 0. Moreover.5984. This will cause some problems in control and operation. 0.834) AmOH/H2O 95.2451.1°C (0.6508.1096) 56. 0.248.3531) 75.641) MeAc/H2O 56. the ternary minimum boiling azeotrope lies closely on the edge of LL envelope.6073.38°C (0. we are looking at the H2O/EtOH/EtAc ternary system for the stripping section. Indeed. rectifier. Type II Flowsheet . H2O is withdrawn from the bottoms. 0.2396.6875.81°C (0. Lee25 also shows that only one double-feed column (type-I flowsheet) cannot produce pure EtAc and further purification is needed. BuAc.5981.7549) 92.462. 0.71°C (0. in the stripping section.68°C (0.174°C (0. & AmAc systems. 0.6691. 0.135. 0. 0.2153) 116.23.111. 0.4°C (0. 0.822) 94.8°C (0.107.89°C (0.854) HAc/AmOH/AmAc 139. 0.4938. 0. 0.1.4182. 0. 0.6885.6593) 54°C (0.7177) 90. 0. 0. However.3407. the heavy reactant is the acid (HAc) and the light reactant is the alcohol (MeOH). 0.MeAc In reactive distillation.046.3125) (iv) BuAc BuOH/BuAc/H2O 90.

IPAc system is even more favorable with the type II flowsheet than the EtAc system for the reasons that it has a larger LL envelope with a minimum boiling ternary azeotrope (74. A decanter is placed to remove the heavy product H2O from the aqueous with the organic phase further processed to Figure 2. the information about isopropyl acetate synthesis with acetic acid in a reactive distillation process can hardly be found in the literature except for the VLE and kinetics data. part of the organic distillate is fed to a stripper by removing high purity IPAc from the bottoms and the top product of the stripper is recycled back to the decanter (Figures 2 and 3C). with the top recycled back to the decanter. 1688 June 2005 obtain high purity EtAc in a stripper (Figure 3B). Therefore.1.Figure 1. 51. Three possible flowsheets for these five esterification systems systems. Once the H2O is removed from the aqueous phase of the decanter. No.27 The RCM of IPAc system in Figure 3C clearly suggests that the type II process is an ideal candidate for the IPAc synthesis using a reactive distillation.26 which is denoted as type II process hereafter (Figure 2).22°C) located further inside the LL zone with tie lines mostly point to the high-purity H2O corner. we end up close to the ternary azeotrope at the top of the column between the EtAc/H2O (70. Figure 3B. note that the top products of both the reactive distillation (1st column in Figure 2) and the stripper (2nd column in Figure 2) all point toward the ternary Vol.37°C) binary azeotrope and the ternary azeotrope. Also. Note that the products of both the first column (reactive zone rectifier) and the second column (stripper) are all nodes (stable or unstable) and they possess much better operability as compared to the MeAc system.09°C) (Table 4 and Figure 1B). for example. In contrast to MeAc and EtAc synthesis. the azeotrope lies on the edge of the LL envelope with the tie lines slop toward relatively high purity H2O (Figure 1B). 6 AIChE Journal . Furthermore. ternary azeotrope EtOH/EtAc/H2O has the lowest temperature (70. Liquid-liquid envelopes and azettropic temperature and NBP temperatures of pure component. This is the basic process configuration presented by Burkett and Rossiter8 and Tang et al. when most of the acid is consumed in the reactive section.

RCM and LL envelope for combinations of ternary systems. It is interesting to see the gradual transition in the VLLE Vol.BuAc & AmAc The boiling point temperature rankings in Table 4 reveal that butyl acetate differs from the IPAc in that the acetate is the highest boiling component. No. the BuAc and IPAc systems also share a common characteristic: a minimum boiling ternary azeotrope exists in the acetate/alcohol/water ternary system and it locates inside the LL envelope as shown in Figure 1D.11.Figure 3. Unlike the type II flowsheet. The removal of water should be relatively easy with the significant LL envelope and the favorable RCM as a result of the ternary azeotrope (Figure 3D). It is also observed that amyl alcohol is the second highest boiling pure component. Moreover. azeotrope (an unstable node) while the bottom product of the stripper slops to a stable node (IPAc corner in Figure 3C). This naturally leads to the type III flowsheet by removing rather pure water from the top and heavy acetate from the bottoms. This is exactly the flowsheet proposed by several different research groups. 6 1689 . This immediately suggests a decanter should be placed in the column top by removing almost pure water from the aqueous phase.16. That is quite similar to a typical column with the reactive zone locates in the middle with a decanter to perform LL separation. 51. That implies that we can remove the acetate from the column base.28 The amyl acetate system also shows a similar VLLE characteristic with an even larger LL envelope for the acetate/ alcohol/water system as shown in Figure 1E. The larger LL zone suggests that the LL separation could be even easier for the AmAc system (as compared to the BuAc system). which is different from the BuAc system where the acid is the one. the heavy boiling acetate implies that we can totally recycle the AIChE Journal June 2005 organic phase back to the column and withdraw the acetate from the bottoms.10. the minimum boiling azeotrope between BuOH and H2O is a heterogeneous one (Figure 1D) and this leads to a type II LL envelope in the BuAc/BuOH/H2O ternary composition space. Figure 1D also reveals that the two-liquid zone in the ternary system constitutes more than 50% of the composition space. However. Type III Flowsheet . even from a hybrid reactive distillation. The scenario suggests the type III flowsheet for the BuAc as shown in Figure 2.

Figures 1 and 3) as the carbon number in the alcohols increases.Table 4. it seems that we can determine the type of flowsheet by simply examining the VLLE behavior.28 In theory the 1690 June 2005 equalmolar feed flow rates (FAcid FAlcohol) should be economically optimal. For the type II process.89°C HAc/AmOH 140. Nrxn. Typically. despite of seemingly different process configurations.02°C HAc 118.21°C BuAc 126. That is they all consist of three major elements: a reactive section.52°C H2 O 100. and FR.37°C EtOH/EtAc 71.09°C EtAc/H2O 70. despite having different process configurations.68°C BuAc/H2O 90.02°C HAc 118. a systematic design procedure can be devised for all three flowsheets. Place the heavy reactant feed (NFheavey) on the top of the Vol. defines the distribution of heat input (QR/QR.01°C HAc/BuOH/BuAc 121. Note that there is no product withdrawal from the bottoms of the RD column. Obvious design parameters are the number of rectifying tray (NR).71°C *Heteroazeotropes in boldface. That means the top product is withdraw from the aqueous phase and a total reflux for the organic phase. In a type I process. 51. Design procedure As pointed out earlier.54°C IPOH/H2O 80.53°C H2O 100. Set the reactants feed ratio to 1 initially (that is. In addition to the tray numbers.65°C MeAc/H2O 56. The third degree of freedom should be the aqueous reflux ratio. trays.31°C H2O 100.57°C IPOH/IPAc 78. Appendices A and B give the detailed step for computing the TAC. Once the column configuration is specified. 2. S) between the RD column and the stripper. it is also observed that.90°C AmOH/H2O 95. ranking of boiling points in Table 4) pass through some critical points. the aqueous reflux ratio has little effect on the product purity and we assume no reflux for the aqueous phase. and no aqueous reflux are used to define the flowsheet. Qualitatively. For a type III process. Steady State Design The total annual cost (TAC) of Douglas29. For the type III flowsheet. and a reactive section.05°C MeOH 64.02°C HAc 118.94°C BuOH/H2O 92. All the simulations are carried out using ASPEN PLUS with the RADFRAC module provided with FORTRAN subroutines for the reaction rates. FR FAcid/FAlcohol 1). For a system with a given production rate with product specifications.18°C EtOH 78.20°C EtOH/H2O 78. In this work.01°C (ii) EtAc EtOH/EtAc/H2O 70. the number of stripping trays (NS).58°C HAc/BuOH 123. two product specifications are given to define the simple one-feed-two-product column and typically reflux flow and heat input are used to meet the specification.68°C HAc/AmOH/AmAc 139. a stripper.62°C H2O 100. one product purity and no aqueous reflux are used to define the flowsheet.85°C BuOH 117.06°C IPOH 82. and catalyst. one product purity. these flowsheets all consist of a rectifier. but for the type II flowsheet. despite via discrete change between chemical species. we are left with two degrees of freedoms for type I & III processes and three degrees of freedoms for type II flowsheet. a rectifier.01°C (iv) BuAc BuOH/BuAc/H2O 90.02°C BuOH/BuAc 116. These observations will be examined carefully in the next section.01°C AmOH 137. and the capital cost covers the cost of the column. Fix a number of reactive trays (Nrxn). generally we adjust the heat duty to achieve desired product purity.71°C AmAc/H2O 94. Because the water content in the aqueous phase is primarily determined by the shape of the LL zone.20. 3. the design steps are 1. so the boilup rate is the sum of total feed and reflux flow and no degree of freedom left once the reflux flow is given. No. The TAC is defined as TAC operating cost capital cost payback year (2) where the operating cost includes the costs of steam. a payback year of 3 is used and the catalyst life of 3 months is also assumed.43°C MeAc 57. The organic reflux ratio. the organic reflux ratio. this degree of freedom is used to drive the acid purity level to an acceptable level.22°C IPAc/H2O 76.80°C H2O 100. 6 AIChE Journal .20.81°C EtAc 77. Finally. and a stripper with somewhat different arrangement. in a sense. the feed ratio (FR FAcid/FAlcohol) is also an important design variable. system (for example. NFAcid & NFAlcohol. It is even more interesting to find out the jumps between process flowsheets (Figure 2) as the VLLE characteristics (for example. NS.02°C HAc 118. Once the dominant design variables are identified.07°C AmAc 147.21 is used to evaluate different designs.01°C (iii) IPAc IPOH/IPAc/H2O 74. cooling water.01°C (v) AmAc AmOH/AmAc/H2O 94. heat exchangers. another set of important design parameters are the feed tray locations (NFAcid & NFAlcohol).68°C HAc 118. Ranking of Azeotropic Temperatures and Pure Component NBP Temperatures (i) MeAc MeOH/MeAc 53.35°C IPAc 88. and the number of reactive trays (Nrxn). Thus. potential design variables for these 3 flowsheets are: NR. these three flowsheets (Figure 2) share a common characteristic.

Note that these two trays lie inside the reactive zone (but not on the top and bottom).08 cm (Type III) is assumed for the reactive tray. Nrxn. the optimal feed tray for the heavy reactant (HAc) is the column base. despite with small difference in the TAC’s. therefore. and FR. Effects of design variables on TAC for the MeAc system. No. Nrxn. This is understandable because we have the largest catalyst holdup in the reboiler and this leads the same feed location for both Vol. NFheavy & NFlight.EtAc & IPAc The type II flowsheet differs from the type I in that the reactive zone extends to the column base of the first column (called RD column) and.MeAc For the MeAc system. Top graph of Figure 4 shows that NR & NS have little impact on the TAC. We also assume the feed ratio of the reactant can be changed and this lead to the following optimization variables: NR & NS. Change the reflux flow (R) and heat input (QR) (type I flowsheet) or organic reflux flow (R) and stripper heat input (QR. Go back to (2) and vary Nrxn until the TAC is minimized. For EtAc. the results (Figure 6) indicate that the number of trays in the rectifying section in the RD column (NR) is one of the dominant optimization variables while the NS shows little impact on the TAC once NR is fixed. As for the feed tray locations. Relatively. bottoms of the reactive section. despite showing a minimum as NS varies. The results indicate that the light reactant (MeOH) should be fed to tray 13 (counting the tray number from bottoms up) and the heavy reactant (HAc) should be introduced to tray 36. the column base holdup is taken to be 10 times of the tray holdup. In the work we assume the catalyst occupies 50% of the holdup volume in a reactive tray. S) (type II flowsheet) or heat input (QR) (type III flowsheet) until the product specification is met. the column diameter is sized using the short-cut method of Douglas29 and a weir height of 10. It is more practical to carry out the simulation sequentially. 7. 6. and NFheavy & NFlight. Guess the tray numbers in the rectifying section (NR) and the stripping section (NS). Optimal Design Type I . That is the catalyst weight is fixed once the column diameter is determined. 4. 8. Note that the top two graphs in Figure 6 are obtained by fixing the feeds to the top and AIChE Journal June 2005 Figure 4. Figure 2). Extensive experience on reactive distillation simulation indicates that the algorithm for the reactive distillation is much less robust as compared to typical distillation. Go back to (3) and find the feed locations (NFheavey & NFlight) until the TAC is minimized. Note that this profile is obtained by fixing the feeds to the top and bottom of the reactive section (for example. It seems strange to devise a sequential design procedure when it may have been done simultaneously. 51. Go back to (4) and change NR and NS until the TAC is minimized. a much larger holdup is expected in the bottom of the RD column (Figure 2). we assume an equalmolar feed rates (FR 1). In this work. Flat profiles are also observed as we change the number of reactive trays. Go back to (1) and change the feed ratio (FR) until the TAC is minimized (for type II flowsheet only). thus the dominant variables for optimization become: NR & NS.16 cm (Type I & II) or 5. The most dominant optimization variables are the feed tray locations as shown in Figure 4. variation of Nrxn results in a rather small change in the TAC. 6 1691 . 9.reactive zone and introduce the light reactant feed (NFlight) on the lowest tray of the reactive zone. Type II . 5.

another dominant variable for optimization is the feed ratio (FR) and result shows that a little alcohol excess is preferred because this facilitates the top of the RD column falls inside the LL envelope leaving trace amount of acid.98 and this implies some feedback control is necessary to maintain the feed ratio. Nrxn. the operating window for the feed ratio ranges from 0. top and bottoms of the reactive section. Numerical simulation results indicate that the minimum number of reactive trays needed to achieve the desired purity (mole fraction of acetate equal to 0. Effects of design variables on TAC for IPAc system. Optimized process flowsheets for these five esterification systems. and NFheavy & NFlight. Nrxn. we have the following optimization variables: NR & NS. The operating window for the feed ratio ranges from 0.BuAc & AmAc The type III flowsheet has been studied by several researchers.min 7). the minimum number of reactive trays needed to achieve the desired purity (mole fraction of acetate equal to 0.20. the top graph of Figure 8 shows that variations in NR and NS result in a rather small change in the TAC. Also note that. both reactant feeds should be introduces to the reboiler. Vol. Effects of design variables on TAC for the EtAc system.Figure 6. for the same specification. Again. reactants.946 to 0. The results also indicate a little alcohol excess is favorable to obtain as easier LL separation. we have the same optimization variables for the type II flowsheet. some feedback mechanism is needed to adjust the feed ratio. For the IPAc system. the number of trays in the rectifying section (NR) is one dominant variable for optimization. The reboiler duty in the RD column reveals this fact as shown in Figure 6. Note that the TAC’s are obtained by fixing the feeds to the top and bottoms of the reactive section.99 and acid purity less than 100 ppm) is 9 (that is.99 for the desired specification. Note that the top two graphs in Figure 7 are obtained by fixing the feeds to the 1692 June 2005 Figure 7.21 In theory.99 and acid purity less than 100 ppm) is 7 (that is. Surprisingly. Again. Type III . Again. Relatively. 51. For the IPAc process.962 to 0. as expected. The bottom graph in Figure 8 clearly shows that the feed locations are the most important optimiza- Figure 5. The other is the feed ratio (FR) as shown in Figure 7. No. changes in Nrxn result in a rather small variation in the TAC. For the BuAc system. 6 AIChE Journal . Nrxn. the results (Figure 7) reveal that NS has little impact on the TAC and.min 9).

Table 5 summarizes the optimal designs for these five systems and the flowsheets are given in Figure 5. designing the composition for the stripper and the rectifier.30 Figure 10A also shows the fraction of total conversion in the reactive zone (shaded area in Figure 10).5°C). the TAC’s are obtained by fixing the feeds to the top and bottoms of the reactive section. The scenario is quite similar to the interaction between reaction section and separation section in the design of recycle plant. the order of the normal boiling point temperature is: HAc (118°C) H2O(100°C) MeOH (64. for pure components. Effects of design variables on TAC for the BuAc system. The temperature profile in the MeAc reactive distillation column shows a nonmonotonic temperature distribution (Figure 10B). (2) NR and FR for the type II flowsheet. No. Again. Figure 9. The optimization results show an interesting fact that different flowsheets give rise to different dominant optimization variables. 51. The composition profile in Figure 10A indicates that we are primarily separating MeOH/H2O in the rectifying section. 6 1693 Figure 8. such as NR & NS and Nrxn. This clearly shows the advantage of the reactive distillation by reacting away the heaviest acid toward the bottom part of the reactive zone and consuming the lighter alcohol toward the upper part of the reactive zone. For the AmAc system. in a sense. This makes the separation easy by.tion variables as shown in Figure 8 where significant TAC is saved by simply varying the feed locations. This can be understood because we need to arrange the feeds such that optimal reactant and temperature profiles can be achieved in the reactive section. Process Characteristics Type I . They are: (1) NFheavy & NFlight for the type I flowsheet. Effects of design variables on TAC for the AmAc system. and (3) NFheavy & NFlight for the type III flowsheet.5°C) MeAc (57. The bottom graph in Figure 9 clearly indicates that. AIChE Journal June 2005 . The rest of reactive trays (especially toward the upper section of the reactive zone) seem to serve more for the separation purpose by consuming most of the MeOH to facilitate the separation in an almost MeOH free environment. the feed locations are the dominant optimization variables as compared to other variables. It reveals that 95% of the total conversion occurs in 10 reactive trays from the total of 34 reactive trays. top graph of Figure 9 shows that variations in NR and NS result in a rather small change in the TAC. The reasons come from reaction oriented thinking (as opposed to the separation oriented thinking) in the Vol.MeAc It is important to recall that the temperature ranking of the MeAc in Table 4 that. again.

00 49.00688 0.96129 0.82 3428. 2002).56 1388.00 50.01237 0. The composi1694 June 2005 tion profile in Figure 13 indicates that the reactive section generates necessary acetates followed by a rectifying section in which the composition of the heavy acid (HAc) is kept to a ppm level.99 92.88 130.f. and favorable reaction temperature.00643 0.98 50.06 57.) Water (m.71 833.53 29.95 0.) Alcohol (m.00 50.74 539.40 50.5E-6 0.41 1.85 373.28 850.07 16.34 0.00076 0.98000 0.94 48.f.84 197.82 57. It should be understandable that control a point near a saddle is not an easy task and reports on the difficulty can be found in the literature (Al-Arafaj and Luyben.98 1.26 8. Thus. of trays in stripping section (N S ) No.54 2195.02 0.02 1095.00556 0.0508 36.965 1051.44 511.01006 0.37 96.00019 0.1016 50 107.60 356.61 173. A straightforward separation is performed in the stripper as shown in the composition profile (Figure 13).11 7.30 48.78 57. this flowsheet should be less interacting from steady-state as well as dynamic points of view.03 38. which is further separated by the decanter and high purity H2O is removed from the aqueous as shown in Figure 11.63 21.24 168.00835 0.02337 0.562 482.aq Acid (m.62 170.02665 0. Figure 13 also reveals the 80% of the conversion occurs in the column base of the RD column as a result of large catalyst holdup.99117 0. 6 AIChE Journal .061 374.f. of trays in reactive section (N rxn ) No.30 50.80 289.90 1.99000 0.62 408. high reactant composition.06 129.06 399.92 111.20 50.00001 0.94 91.10 0. Steady-State Operating Condition and Total Annual Cost (TAC) for Reactive Distillation Designs of Five Esterification Systems System Column Configuration Total no. The temperature profile in the RD Vol.66 16.14 (ii) EtAc RD 20 11 9 0 10 0 0 48.58 506.15 227.63 28.EtAc & IPAc The type II flowsheet differs from the type I in that the two columns (RD column and the stripper) are separated by a decanter.8 2005.f.) Condenser duty (kW) Subcooling duty (kW) Reboiler duty (kW) Column diameter (m) Weir height (m) Decanter temperature (°C) Condenser heat transfer area (m2) Subcooling heat transfer area (m2) Reboiler heat transfer area (m2) Damkohler number (Da) ¨ Total capital cost ($1000) Column Column trays Heat exchangers Total operating cost ($1000/year) Catalyst cost Energy cost Wastewater treatment cost TAC ($1000/year) (50 kmol/hr) TAC ($1000/year) (52825 ton/year) (i) MeAc RD 39 3 34 1 4 37 36 13 50. The 3-D composition profile in Figure 11 reveals a potential problem for the operation of the MeAc column that the top product MeAc is a saddle and a further increase in the MeAc/ H2O azeotrope in the MeOH free composition space.42 1532.55 30.99000 10 8 1483.57 88.98990 10 8 2857. Figure 12 shows the nonmonotonic behavior in the acetate composition as we change the reflux flow rate while keeping the bottoms water purity at 98%.26 547.82 4523.55 8.Table 5.01533 0.45 0.) Acetate (m.925 1304.94 Stripper 10 9 (iii) IPAc RD 26 13 13 0 12 0 0 48.62 0.01670 0.470 753.68 1.f.00711 0.31 1. of trays in rectifying section (N R ) Reactive trays Acetic acid feed tray Alcohol feed tray Feed flow rate of acid (kmol/h) Feed flow rate of alcohol (kmol/h) Top product flow rate (kmol/hr) Bottom product flow rate (kmol/hr) X D or X D.00010 0.96500 0. and very high purity EtAc can be obtained and the purity level of the acid is the product stream depends on the amount of acid allowed in the overhead of the RD column.38 49.98000 1280.0508 50 27.00993 0. thus.00078 1860. while the top of the stripper is recycled back to the decanter.29 7.26 Stripper 8 7 (iv) BuAc RD 34 9 20 4 10 29 25 29 50.) Alcohol (m.f.23 0.88 730.77 621.01357 0. of trays including the reboiler No.31 67.00002 0.35 3085.f.89 0.55 617.56 97.14 659.53 13.35 49.54 482.89 1370.0508 50 57.0508 68.16 474.00 50.80 2.97 548.00289 0.) Water (m.86 1277.1016 40 157.00 50. Part of the organic phase is refluxed back to the RD column while the other part is fed to the stripper to purify EtAc in the left corner of the composition space (Figures 11 and 13).00 49.00763 10 8 0.00 50.54 4265.65 0.89 115. 51.20 (v) AmAc RD 37 12 22 2 13 34 30 34 50.78 323.46 feed arrangement and.79 327. deliberately driving the heavy reactant toward the top and light reactant to the bottom as shown in Figure 10.00221 0.71 1.97566 0. The overhead vapor is condensed and the condensate falls within the LL envelope.22 1035.00 64.) Acetate (m.1016 80.15 4.00004 0.10 1451.49 7.51 3473.99000 0.7 Type II .93 71.00 50.00005 1129.48 1. No.00087 0.61 2051.00912 0.f.92 461.88 0.03 0.08 1731.) XB Acid (m.35 854.72 29.

AIChE Journal June 2005 Figure 11. less reactive trays are required to react away the heavy reactant (as compared to the BuAc system). the acid is reacting away in the lower part of the reactive zone as shown in Figure 15A. the flowsheet changes from type I. Vol. The vapor and liquid composition profile in a 3-D plot (Figure 11) clearly shows the separation characteristic in the stripping section (along the BuOH/BuAc edge). Again. Because the AmAc has a larger LL envelope as compared to the BuAc system. again.For the AmAc system. Because of a large LL envelope. No. as well as in the LL envelope. the stripping section is performing separation between HAc/AmAc as shown in Figure 16A. The separation in the stripper is quite straightforward and high purity IPAc can be achieved with little difficulty. most of the conversion takes place in the column base of the RD column (Figure 14). the AmOH has the second highest NBP temperature (which is different from the ranking for the BuAc system). Composition profiles and material balance lines for these five esterification systems. However. Because we do not have stringent product specification on the alcohol. Results and Discussion The analyses of the esterification of the acetic acid with five alcohols ranging from MeOH to AmOH (C1 C5) are intended to gain insight for the design of reactive distillation by varying the chemical species discretely. we should consume most of the alcohol in the reactive zone. Figure 10. 51. Very similar composition profile is observed for the IPAc system and. The composition profile in the stripping section clearly shows that the stripper is performing BuOH/BuAc separation. majority portion of the reaction takes place in the upper section of the reactive zone where the two feeds are located. only two rectifying trays are required to drive the overhead condensate into the LL zone. Composition and temperature profiles for the MeAc system. only 4 rectifying trays are needed to drive the condensate of the top vapor into the LL zone. the acetic acid has the second highest normal boiling temperature (NBP) and. a small amount of AmOH is allowed to leave the reactive zone. therefore.BuAc & AmAc For the BuAc system. As the carbon number in the alcohol increases. column shows a monotonic behavior which was dominated by the acid profile. In theory. A nonmonotonic temperature profile is observed as a result of large boiling point temperature difference ( 20°C) between these two reactants. and then to type III (Figure 2). The material balance lines in Figure 11 shows how separation is achieved around the decanter. to type II. Figure 15B shows an almost monotonic temperature for the reason that these two reactants are close-boiling components with 1°C temperature difference in the NBP’s. Type III . Still. 6 1695 . Figure 11 shows a different characteristic in the stripping section where the composition distributed along the HAc/AmAc edge. It is also observed that significant conversion occurs in the upper section of the reactive zone where two feeds are located nearby. The concentration effects of these two reactants enhance the reaction in that region (Figure 15A). The determinant factors in the flowsheet selection are the ranking of the pure component/azeotrope temperatures (Table 4) and the size of the LL envelope (Figure 1).

99) are not feasible for the MeAc case. the acetic acid esterifications with five different alcohols. That implies the structure of the flowsheet can be determined once the VLLE data become available. 1696 June 2005 Figure 15. Vol. This can be understood because the reactants composition distribution is important for the kinetically controlled reactive distillation. The flowsheets may look different in the arrangement. The type III flowsheet. Figure 12. much smaller energy consumption is expected. the purity level difference will not lead to such significant reduction in the TAC. Finally. Another reason for the MeAc to have the lowest TAC is that the purity level of the acetate is 0. needs to boil up some acetate/alcohol along with H2O upward to get into the LL envelope and then recycles the organic phase totally back into the column. 51. The explanations for this are that the type II flowsheet boils up both products to the top of the RD column (Figure 2) and recycles an almost ternary azeotropic composition back to the decanter from the stripper. Conclusion In this work. No. XD. Composition and temperature profiles for the BuAc system. ranking from methanol to amyl alcohol (C1 to C5). Thus. The difference in the TAC’s between EtAc and IPAc comes from VLLE advantage of the IPAc system which has a large LL envelope (Figure 1). 6 AIChE Journal . this flowsheet is energy intensive with significant heattransfer areas. The reactive section also facilitates the separation by reacting away the heavy reactant toward the lower part of the reactive zone and by consuming most of the light reactant toward the upper part. despite not boiling up both products to the top.MeAc XB.Figure 14.H2O 0. Once the flowsheet structure is determined. One would expect larger energy consumption for this type of system (as compared to systems without a decanter). However. Again. followed by type III flowsheet (BuAc & AmAc) and the type I flowsheet is the most economical process. It is also observed that the function of the reactive zone goes beyond providing necessary conversion. therefore. a reactive zone. The reason for the difference is that higher purity levels at both ends (for example. Composition profile and fraction of reaction for the EtAc system. The nonmonotonic behavior in the acetate composition. the design can be carried out in a sequential manner by minimizing the TAC.99 the other four cases.98 (mole fraction) which is typically seen in the literature as compared to 0. they all include the following units: a stripping section. Composition profile and fraction of reaction for the IPAc system. and a rectifying section. Figure 13. the difference between BuAc and AmAc lies on the fact that the AmAc system has a larger LL envelope (Figure 1). the MeAc system (type I) only boils up components necessary to achieve desired product purity and. It is interesting to note that most of the dominant design variables are mostly associated with the feed: the feed tray locations (for type I & III) and the feed ratio (for type II). The TAC comparison in Figure 17 shows that the type II (EtAc & IPAc) flowsheet is the most expensive process.

The dominant design variables are also identified and they are: feed locations for the type I flowsheet. We also thank Y. S R r Ri Rtot k1 k-1 Keq mcat TAC XB XD XD. The results presented in this provide insight for the conceptual design of reactive distillation systems. AIChE Journal June 2005 Vol. Three process flowsheets. Then.using the reactive distillation are explored. TAC’S (based on 50 kmo1/h production rate) for five esterification systems. Two important factors in the flowsheet determination are: (1) the ranking of the pure component/azeotrope boiling point temperature. a systematic design procedure is devised to optimize the quantitative design based on the total annual cost (TAC). 6 1697 . No. are identified and they all lead to relatively pure products. Finally. the characteristics of the optimally designed reactive distillation for these three types of flowsheets are investigated explanations are given. Notation AmAc AmOH BuAc BuOH Da EtAc EtOH FAcid FAlcohol FR IPAc IPOH MeAc MeOH NFAcid NFAlcohol NFheavy NFlight NR Nrxn NS NT QC QR QR. the economic potential is ranked. org Amyl acetate Amyl alcohol (n-pentanol) n-butyl acetate n-butanol Damkohler number for the whole column ¨ ethyl acetate ethanol acid feed flow rate alcohol feed flow rate feed ratio isopropyl acetate isopropanol methyl acetate methanol acid feed location alcohol feed location heavy reactant feed location light reactant feed location number of trays in the rectifying section number of trays in the reactive section number of trays in the stripping section total number of trays condenser duty reboiler duty of the reactive distillation column reboiler duty of the stripper reflux flow rate reaction rate reaction on tray i total reaction in the column forward rate constant backward rate constant equilibrium constant for the esterification reaction catalyst-weight total annual cost liquid mole fraction in the bottom product liquid mole fraction in the distillate organic liquid mole fraction in the decanter Figure 16. 51. the qualitative relationship between phase equilibria and possible process flowsheets is established. Acknowledgment This work is supported by the Ministry of Economic Affairs under grant 92-EC-17-A-09-S1-019. II & III. and (2) the size and the location of the liquidliquid phase zone. and the explanation is Figure 17. and feed locations for the type III flowsheet. type I. the TAC’s of different flowsheets are compared. for providing wastewater treatment costs for TAC calculation. This sequential design procedure overcomes the fragility of the simulation algorithm even with the state-of-the-art process simulator for the reactive distillation. Composition and temperature profiles for the AmAc system. L. feed ratio and the number of trays in the rectifying section for the type II flowsheet. First. Liu and China Petrochemical Development Corp. given. Next.

isopropanol-isopropyl acetate-Water system at 760 mmHg. Wu HT. 6 AIChE Journal 1698 June 2005 . and the log-mean temperature driving force TC [K] depends on the dew points and bubble points for a total condenser.1999. Malone MF. Washington. Reactive Distillation by Design. Ind Eng Chem Res. n-Butyl acetate synthesis via reactive distillation: thermodynamic aspects. 51(9): 2203.67 10 8 2 MW V 1/ 2 DC m V1/ 2 (A3) where V [kmol/h] is the maximum vapor flow rate. 54:5205. 14:135. Kuo CL. 38:714.2000. 18. Trans IchemE. Doherty MF. AIChE J. Ind Eng Chem Res. Gangadwala J. Steinigeweg S. New York: McGraw-Hill. Malone MF. Komatsu H. Weinheim: Germany. Chem Eng Sci. Stein E. 35:3470. Ind Eng Chem Res. TAC calculation The equipment cost estimation follows the procedure of Douglas29 and specific equations of Elliott and Luyben. 25. Schoenmakers T.XD. 19. New York: McGraw-Hill. Appendix A. 2004. J Chem Eng Japan. 7. Popken T.2003. 48:800. KGaA. 116. Eng. Feasible region for a countercurrent cascade of vapor-liquid CSTRs. 43:136. 2001. Chem Eng Sci. Fluid Phase Equilib. A generalized method for predicting second virial coefficients. 12:147. Mahajani S. Materials of construction are stainless steel. Production of butyl acetate by catalytic distillation: Process design studies. Phase and reaction equilibria of the acetic acid29.1977. the overall heat-transfer coefficient UR is assumed 788. Process Des. Hanika J. Chiang SF.uk/intint/NonConf_Doc. Smejkal Q. Partin LR. Rossiter D.2003. Literature Cited 1. Markusse P.2002. Gadewar SB. (3) Column diameter (DC) 5. Conceptual Design of Distillation System. 10. Kwant G. Hayden JG. A new method of convergence for solving reacting distillation problems.2002. and simulation studies. Gotze L.2001.2002. 11.1999. and MW [kg/kmol] is the average molecular weight. 30. AIChE J.2004. Chem. Huang HP. 2000.. Venimadhavan G. 32.1973. 14. Yu CC. Chien I-L. 6. Douglas. the overall heat-transfer coefficient UC is assumed 473. Ind Eng Chem Res. Krishna R. Doherty MF. Mankar S. aq aqueous liquid mole fraction in the decanter 28. Cheng YC. Gorak A.. Gangadwala J. Lin HM. Tang YT. Technical Report to the European Commission.cpi. Quantitative comparison of reactive distillation with conventional multiunit reactor/column/recycle systems for different chemical equilibrium constants. Dynamic and control of an ethyl acetate reactive distillation column.asp. (2) Condenser heat-transfer area (AC) A C m2 QC UC TC (A2) where QC [W] is the condenser duty. Deliverable 22. 51.1990. 27. 17. Design alternatives for the amyl acetate process: Coupled reactor/column and reactive distillation.45 W/(m2*K). Kuo MZ. Ind Eng Chem Res. Intelligent Column Internals for Reactive Separations (INTINT). Gmehling J. Kenig EY. Chem. Huang SG. 42:2146. Proc. Advances in Chemistry Series No. and a M&S index of 1108. of Process Control and Instrumentation 2000: Glasgow. Ind. Wiley-VCH Verlag GmbH & Co.31 and Chiang et al.1999. Chem Eng Sci. Local compositions in thermodynamics excess functions for liquid mixtures. Ind Eng Chem Res. Doherty MF. Bebling B. 31. Burkett RJ. Kienle A. 55:5183. Reaction Kinetics of the Esterification of Ethanol and Acetic Acid Towards Ethyl Acetate.2003. Yu CC. AIChE J. Choosing the right control structure for industrial distillation columns. Prausnitz JM. Sundmacher K. Gmehling J.2002. American Chemical Society. Investigation of ethyl acetate reactive distillation process. Lee LS. Ind Eng Chem Res. Feasibility studies on quaternary reactive distillation systems. 16. Comparative control study of ideal and methyl acetate reactive distillation. Luyben WL.2000. J Chem Eng Japan. Vora N. Lee MJ. 43:2493. Doherty MF. J Chin Inst Chem Eng. 5.. Wong DSH. 86(2):40. Butylacetate vis reactive distillationmodelling and experiment. 22. A payback period of 3 years is assumed. 41:4632. pilot-plant experiments. O’Connell JP.1968. Reactive Distillation: Status and Future Directions. 42:4348. 41:5483. 30:117. Bader H. Yu CC. 12. Elliott TR. Taylor R. Luyben WL. 2. 4. Holland CD. Esterification of acetic acid with butanol in the presence of ion-exchange resins as catalysts. 26. Modelling Reactive Distillation.07 W/(m2*K). Chen YW. Lee JW. Kaymak DB. 3. 57:5039. Temperature control of heterogeneous reactive distillation: Butyl propionate and butyl acetate esterification.umist. Daoutidis P. 2001. 40:833. Conceptual Design of Chemical Process. 10:292.21 were used. A novel distillate policy for batch reactive distillation with application to the production of butyl acetate. 21. Kuo CL.1992. 41:3233.. 8. Yu CC. Res.2002. Kolena J.. 13. JM. Chem Eng Sci. 36:1352. Hung SB. A70:448. 2003. http://www. Azeotropic Data – III. Renon H. The capital and operating costs are calculated according to: (1) Column cost Vol. 23.1996. Stein E. (4) Column height (LC) LC m 0. Kienle A. Effects of process design on recycle dynamics and its implication to control structure selection. Malone MF. Ind Eng Chem Res.2003. Agreda VH.1996. Adrian T.2001. Heise WH.C.7315NT (A4) where NT is the total number of trays. High Purity Methyl Acetate via Reactive Distillation. Sensitivity of thermodynamic parameter to the design of heterogeneous reactive distillation: Amyl acetate esterification.. J Chin Inst Chem Eng. Ind Eng. 1988. Huang SG.1 is used in the calculation. 34:345. V [kg/m3] is the vapor density in the column. Mahajani S. Ind Eng Chem Res. Quantitative assessment of controllability during the design of a ternary system with two recycle streams. Reaction kinetics and chemical ¨ ¨ equilibrium of homogeneously and heterogeneously catalyzed acetic acid esterification with methanol and methyl acetate hydrolysis.1975. No. Hangx G. 2004. 9. Kienle A. D. 14:209. and the temperature driving force TR [K] in the reboiler depends on the steam. 56:6185. UK 38. Dev. 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29 280 FC (A7) Appendix B.424 2634.333 840.802 101.562 Item Mass flow rate (ton/year) NaOH Requirement (ton/year) NaOH Electricity H3PO3 Sludge incineration IPCC-COD IPCC-SS IPCC-water TAC ($1000/year) Unit Price Consumption AIChE Journal June 2005 Vol.35 0) 3. followed by a central WW processing unit in the industrial park (denoted as IPCC cost).463 2561.2941 ($/kg) 0.3854 0. First. where FC (Fd Fp)Fm (1.04 85.682 2716.0529 ($/kWhr) 0.73E-5 ($/kg) 5.594 7.753 8.92 0.080 784.306 808.476 791.24 777.0605 ($/kg) 0.9DC LC 2.327 144. $0. Table B1.813 136. The following table (Table B1) describes the on-site and IPCC costs. (4) Steam cost Steam cost $ year $CS QR 453.2 (kg/ton) 0.12 0.7162 (A10) Heat exchanger cost $ M & S 0.7DC LC FC 280 1 1.8 0.1 (kg/ton) 1000 (kg/ton) 578.03 0.018 2410.967 746. the WW is neutralized and processed in an on-site biological WW treatment facility.096 0.493 724.470 AmA Cost ($/year) 8138.114 844.116 2574. and the total operating cost is computed accordingly.533 832.744 793.7.070 140. 51.896 8.066 0.160 2418. Wastewater Treatment Cost MeAc Cost ($/year) 8164.853 7.8 1.675 2812.061 EtAc Cost ($/year) 8646. (6) Catalyst cost (assuming a catalyst life of 3 months) $ kg Catalyst cost $ catalyst loading kg 7.019 702.08 648.187 750. and revision received Oct.75 for the condenser.785 m3 kg (A6) Tray cost $ where FC Fs Ft Fm (3) Heat exchanger cost M&S 1.32 481.848 103.55 4.18 280 (5) Cooling water cost FC (A5) Cooling water cost $ $ Cooling water cost year year QC 30 8150 h year (A9) where FC FmFp (2) Tray cost 3.888 2486.551 704.67 1. 2004.0012 ($/kg) 0.198 7.75 for the reboiler and FC (Fd Fp)Fm (1 0) 3. Wastewater treatment TAC calculation The wastewater (WW) is treated in a two-stage structure.001 m3 3. 6 1699 . 2004.057 (kg/ton) 5.586 786.965 BuAc Cost ($/year) 8392.4817 ($/kg) 0.302 145.598 136. Manuscript received July 23.925 IPAc Cost ($/year) 8689.864 2642.8632 ($/kg) 9.404 815.59 kg V 8150 h year (A8) where Cs is the saturated steam price and is the latent heat of the steam which depends on the bottom temperature.941 2798.6 (kWhr/ton) 0.65 A 2. 21. No.710 837.350 (kg/ton) 0.Column cost $ M&S 1.