Article pubs.acs.


Economic Optimum Design of the Heterogeneous Azeotropic Dehydration of Ethanol
William L. Luyben*,†

Department of Chemical Engineering, Lehigh University, Bethlehem, Pennsylvania 18015, United States ABSTRACT: Several processes are available for the important operation of dehydrating ethanol/water mixtures to concentrations above the azeotrope (90 mol %). Heterogeneous azeotropic distillation has been studied using several entrainers: benzene, cyclohexane, isooctane, ethylene glycol, etc. A pioneering paper by Ryan and Doherty [Ryan, P. J.; Doherty, M. F. Design optimization of ternary heterogeneous azeotropic distillation sequences. AIChE J. 1989, 35, 1592−1601.] explored several alternative process configurations and concluded that the three-column flowsheet with a preconcentrator (beer still), an azeotropic column, and a recovery column was the economic optimum. They used approximate ternary diagram methods. It appears that they arbitrarily assumed a beer still distillate composition with an ethanol concentration of about 88 mol %, which is quite close to the azeotropic composition of 90 mol %. Energy consumption in the beer still increases as its distillate composition gets closer to the azeotrope. On the other hand, energy consumption in the azeotropic-recovery column section of the process decreases as the feed to this section becomes richer in ethanol. It appears that this fundamental trade-off has not been studied in the literature. This paper examines quantitatively, using rigorous simulations, how this design parameter affects the energy and capital investment of the entire system. The focus is the distillate composition trade-off. The example used is the heterogeneous azeotropic distillation process, but the same issue applies in any of the other methods (such as extractive distillation) in which a preconcentrator column is used.

1. INTRODUCTION The production of high-purity ethanol from the ethanol−water mixture coming from batch fermenters in biorefineries is complicated by the occurrence of an azeotrope with a composition of 90 mol % ethanol at atmospheric pressure. Typical ethanol concentration in the fermenter broth is 5 mol % ethanol. The concentration needed for blending into gasoline is 99.5 mol % ethanol. One method for ethanol dehydration is heterogeneous azeotropic distillation, which has been used for many decades.1 A suitable light entrainer component (benzene, cyclohexane, isooctane, ethylene glycol, etc.) is added to modify the relative volatilities. The water is driven overhead with the entrainer, and a high-purity ethanol bottoms stream is produced in the azeotropic column. The overhead vapor is condensed and fed to a decanter. The organic phase is refluxed back to the column. The aqueous phase is fed to another column that produces a bottoms product of high-purity water and a distillate that is recycled back to the azeotropic column. A third column in the front end of the process is used to preconcentrate the lowconcentration stream from the fermenter up to a concentration closer to the azeotrope before feeding this into the azeotropic column. In addition to heterogeneous azeotropic distillation, several alternative methods are available for ethanol dehydration such as extractive distillation, adsorption, and pervaporation. A comprehensive review of the subject, including 302 references, has been presented by Vane.2 A recent paper3 by Kiss and Paul claims that the heterogeneous azeotropic distillation process is more economical than adsorptive drying because of the large amount of energy required to regenerate the adsorbent. A pioneering paper by Ryan and Doherty4 explored several alternative heterogeneous azeotropic configurations using
© 2012 American Chemical Society

benzene as the entrainer. They examined two-column and three-column flowsheets and concluded that the three-column flowsheet with a preconcentrator (beer still), an azeotropic column, and a recovery column was the economic optimum. They used approximate ternary diagram methods of analysis. Figure 6 in the Ryan−Doherty paper shows a binary feed composition to the azeotropic column of about 88 mol % ethanol. There is no discussion in the paper of the impact of this parameter on the optimum design. Fairly detailed information is given for the azeotropic column and the recovery column, but essentially nothing is provided about the beer still. The 88 mol % ethanol concentration is quite close to the azeotropic composition of 90 mol %. Energy consumption in the beer still could be reduced by designing for ethanol concentrations further away from the azeotropic composition. However, lower ethanol concentrations in the feed to the azeotropic column will increase energy consumption in the azeotropic column. Clearly there is an optimum beer still distillate composition. Other papers have also arbitrarily assumed beer still distillate compositions. For example, Martinez et al.5 specify a beer still feed flow rate of 45.36 kmol/h with 10 mol % ethanol. Then they set the beer still distillate flow rate at 5.41 kmol/h. With negligible losses of ethanol in the bottoms, the distillate composition is 4.536/5.41 = 0.838, which is about 6 mol %
Received: Revised: Accepted: Published:

August 4, 2012 November 19, 2012 November 21, 2012 November 21, 2012 | Ind. Eng. Chem. Res. 2012, 51, 16427−16432

050 380. It should be emphasized that this composition trade-off exists in any other process. so base pressure varies as the number of trays is changed.3582 0.821 1.1734 0.067 1. Reflux-drum temperature varies slightly with distillate composition. Eng.8045 26 13 2. which leads to columns that are significantly different than those given by Ryan and Doherty. 16428 3. OPTIMIZATION OF THE BEER STILL (PRECONCENTRATOR) Three different distillate compositions are considered.3062 0. respectively. Energy costs and column Table 1. Table 3.8100 0.823 1. The feed stage locations assumed in that study (using Aspen notation) were as follows: dx.6 0. using total annual cost (TAC) as the economic objective. Li and Bai6 select a 85 mol % distillate.996 1. In the next section we see what the effect is in the azeotropic and recovery columns.6898 0.8543 21 10 2. In 36 22 2.029 375. Base pressure affects the base temperature for a fixed composition. OPTIMIZATION OF THE AZEOTROPIC AND RECOVERY COLUMNS The beer still considered in the previous section can be optimized in isolation given a specified distillate composition.1878 0. As the beer still distillate composition is moved further from the Table 2.8381 2. Tables 2 and 3 give results for the 80 and 75 mol % cases.9966 46 39 3.050 376.852 and 0.1 psi per tray. energy TAC a Reflux-drum = 351.047 382.047 377.1916 0. azeotropic composition.1564 0.3318 0. 80. partial reboiler. A total condenser. Article diameters decrease as more stages are used. but the capital cost of the heat exchangers (condenser and reboiler) decrease.9 0. For all cases.7000 0.124 1.3 K.582 kW m−2 K−1.8160 0. No consideration of the steady-state economic optimum design was considered in that study. A similar flowsheet was used in a control study7 of these two columns.906 1. Aspen Plus UNIQUAC physical properties are used.6938 0.5099 0.1286 0. Table 1 gives results for the 85 mol % distillate composition case for a range of total stages.056 376. such as extractive distillation. 16427−16432 . and the number of stages in the recovery column is given as 30. energy and capital costs decrease.3532 0.8702 26 16 2.5 0.906 1. Res. In the Ryan−Doherty paper the number of stages in the azeotropic column is given as 36.2122 0. Overall heat-transfer coefficients in the condenser and reboiler are 0.302 1. The variables that are manipulated to achieve these two specifications are the distillate flow rate and the reflux ratio. Beer Still Optimization: 80 mol % Casea NT1 NF1opt QR1 QC1 ID1 TB1 capital (MW) (MW) (m) (K) (106 $) HX column total (106 $/y) (106 $/y) 21 13 3. The downstream columns do not affect the beer still since there is no recycle back to it.2590 0. Chem.5313 0.538 1. Cooling water inlet and outlet temperatures are assumed to be 305 and 315 K. The optimum feed tray location is determined for each selected number of total trays by finding the feed location that minimizes reboiler duty.7130 0.9872 energy TAC a Reflux-drum = 351.3 0. The feed of fermentation broth is assumed to be 1000 kmol/ h with a composition of 5 mol % ethanol and 95 mol % water.853 1. Beer Still Optimization: 85 mol % Casea NT1 NF1opt QR1 QC1 ID1 TB1 capital (MW) (MW) (m) (K) (106 $) HX column total (106 $/y) (106 $/y) 36 29 3.3 0. The 46-stage column has the minimum TAC for the 85 mol % case.3586 0. Beer Still Optimization: 75 mol % Casea NT1 NF1opt QR1 QC1 ID1 TB1 capital (MW) (MW) (m) (K) (106 $) HX column total (106 $/y) (106 $/y) 16 8 3.1797 0. It is clear that lower beer still distillate compositions reduce costs in the beer still.6 K.2409 0.1853 0.1728 0.1922 0.326 1.3 K in all cases.4 K.422 2.047 379.78 per GJ) is used since the base temperature is never greater than 382. The capital cost of the column vessel increases as more stages are used.4712 0.047 1.1755 0. However.030 377.3675 0. 2012. Low-pressure steam (433 K and $7. and 85 mol % ethanol. respectively. the other two columns must be optimized together because of the recycle of the recovery column distillate back to the azeotropic column and the recycle of the organic phase from the decanter back to the azeotropic column.538 1. Column vessel and heat-exchanger capital costs are given by the equations found in ref 7. An additional contribution of this paper is to demonstrate an effective homotopic method for converging the two recycle loops that occur in this very nonlinear system.8092 energy TAC a Reflux-drum = 351.538 1. each of the distillation columns is optimized in terms of the number of stages.5 0.996 1.7476 0.7525 0.4143 0. and theoretical trays are assumed.8 0.Industrial & Engineering Chemistry Research away from the azeotropic composition.3202 0.8396 0.1611 0.644 1.9860 56 48 3.084 379. that uses a preconcentrator.3 0. The purpose of this paper is to explore this interesting tradeoff. The two design specifications in the beer still are a bottoms ethanol concentration of 50 ppm (molar) and a distillate ethanol concentration that is set for the three cases: 75. 51.2037 0. Tray pressure drop is assumed to be 0. as does the optimum number of stages. which impacts the required reboiler heat-transfer area and resulting capital investment. the operating pressure is set at 1 atm in the reflux drum.853 1. and the optimum beer still configuration for each is determined.6 0.1021/ie3020878 | Ind.1729 0.

The flow rate of organic reflux dropped from 82.29 1.9 mol % water.227 0. The number of stages in the recovery column is fixed at 32.2 0.868 373.2 0.0 0.7643 374.280 1. Note that this is almost twice the number of stages recommended by Ryan and Doherty. A. Changing feed stage locations from Stage 15 and Stage 10 in the azeotropic column to Stage 12 and Stage 1 (top tray in the Aspen stripping Radf rac column) lowered the reboiler duty from 1.5773 0.026 mol % water in the bottoms.6745 22 3 62 60. giving an ethanol product with 99.7523 375.3079 0.5944 0.270 0.241 0.Industrial & Engineering Chemistry Research 1.597 to 1. The right three columns in Table 4 give results for the azeotropic column with varying number of stages. azeotropic column − 62 stages.56 atm.4468 0. The next issue is to find the economic optimum number of stages in each column. Eng.54 mol % ethanol.56 atm.8205 (106 $/y) Azeotropic and recovery columns: decanter − 322 K. The azeotropic column feed flow rate was adjusted from that used in the previous study (216 kmol/h) to correspond to the 1000 kmol/h of fermenter broth fed to the beer still used in the present study.1416 0.5775 32 4 62 60.255 1.597 MW and the reboiler duty in the recovery column is 0.7122 MW.3140 Recovery Column Optimization: 85 mol % Case.3079 0. Recycle of recovery column distillate (D3) was fed on Stage 10 of the azeotropic column.500 per year. 1. The organic phase from the decanter plus a very small benzene makeup was fed at the top of the azeotropic column.3381 52 20 62. Optimum Number of Stages.3918 0.5068 0. Azeotropic Column Optimization: 85 mol % Case.3218 0.91 1. NT2 = 62 NT3 NF3 NT2 organic reflux R2 QR2 QC2 ID2 TB3 QR3 capital azeotropic column recovery column energy azeotropic column recovery column TACa a 12 3 62 60. Adding more stages reduces the amount of organic reflux required to meet the specification.3228 0. 2. Note that the distillate of the recovery column (D3) is fed to the top of the azeotropic column in all cases. With a distillate composition of 85 mol % ethanol.70 1.4762 0. Table 6 summarizes the results using the previously found optimum designs of the beer still for each distillate composition (xD1) and finding the required organic reflux and reboiler duties in the other two columns for each value of xD1.7 kmol/h. Optimum Feed Locations. The separation is quite easy.456 MW.99 1.5 0.4236 0. The locations of the feeds were scaled up or down directly with the total number of stages using the results for the 32-stage columns. Table 5. Combining all three columns is considered in the next section. The organic reflux for this design is 82.56 atm.7170 62 24 60. and the heat duty in the overhead condenser is adjusted to give a very small flow rate of gas with the decanter temperature of 322 K and pressure of 0. which reduces energy consumption.1416 0. Then the number of stages in the recovery column is varied with the number of stages in the azeotropic column fixed at 62.4 0.7033 MW and lowered the organic reflux further to 68.doi.1 atm. which lowered its reboiler duty from 0.5773 (kmol/h) (MW) (MW) (m) (K) (MW) (106 $) (kmol/h) (MW) (MW) (m) (K) (MW) (106 $) 32 12 82.1986 (106 $/y) 0. 16427−16432 . this feed flow rate is 62. Chem. OPTIMIZATION OF THE ENTIRE PROCESS The optimum beer still designs with their associated capital and energy costs are now combined with the azeotropic and recovery column designs for the three values of beer still distillate composition.7523 379.1458 0. The aqueous phase was fed on Stage 11 of the 32-stage recovery column.89 kmol/h. 51.3248 0. which were not optimized in the original control study. A 62stage azeotropic column gives the minimum TAC of the twocolumn portion of the process.12 1.0 0.7122 0.98 1. The column labeled “base” in Table 4 gives the economic results for this base-case design.02 mol % benzene and 0. We assume that the optimum numbers of stages in the azeotropic and recovery columns do not change significantly as the beer still distillate composition varies over the range of 75 to 85 mol % ethanol.1).5771 0.255 1.7208 (106 $/y) Azeotropic and recovery columns: decanter − 322 K.7122 to 0.1396 0. the reboiler duty (QR2) in the azeotropic column is 1.7643 375.595 0.1 atm.242 0. (106 $/y) 0. The decanter is adiabatic. The first issue is to find the optimum feed locations. 0. Table 4. With this flow rate and with the number of trays and feed locations stated above.2 0.241 0. 3.255 1. 2 atm. 4.243 1. Table 5 shows that the optimum number of stages (12 is selected as the minimum practical number) is much smaller than recommended in the Ryan and Doherty design.70 to 69. Beer still distillate (D1) was fed on Stage 15 of a 32-stage azeotropic column. Remember that these results are for a 85 mol % ethanol beer still distillate. An Aspen Flash3 model is used for the decanter. These results are based on designing the azeotropic column for 0.4764 0.7443 376.91 1. 2012.86 kmol/h.255 1.7523 381. Note that the TAC of the two columns (not including the beer still) is $820.597 1. The design specification in the recovery column is a bottoms purity of 99. dx. B. azeotropic column − 2 atm. NT3 = 32 base NT2 NF2 organic reflux R2 QR2 QC2 ID2 TB2 QR3 capital azeotropic column recovery column energy azeotropic column recovery column TACa a Article Then the feed stage location in the recovery column was changed from Stage 11 to Stage 4. 0. 16429 4. recovery column − 32 stages.7158 72 28 60. so a small vapor stream is required. so the reflux ratio is set at a very small value (RR = 0. recovery column − 1. The two variables adjusted to achieve these specifications were organic reflux (R2) and bottoms flow rate (B2).44 kmol/h.1747 0.242 0. Res.1021/ie3020878 | Ind.3050 0.5692 0.

The energy and capital costs in the recovery column are less affected by the beer still distillate composition.34 8. This reduces reboiler duty in the azeotropic column (QR2).7130 0. NT3 = 12a xD1 D1 organic reflux R2 aqueous phase B3 D3 NT1 QR1 QR2 QR3 capital (mol % ethanol) (kmol/h) (kmol/h) (kmol/h) (kmol/h) (kmol/h) (MW) (MW) (MW) (106 $) beer still azeotropic column recovery column total (106 $/y) beer still azeotropic column recovery column total (106 $/y) 75 66. The net result of all these effects on the total energy cost is a minimum at a beer still composition of 80 mol % ethanol. The overhead energy TAC a Decanter − 322 K. Flowsheet of 80 mol % case. However.doi. So beer still capital and energy costs increase.3270 0.541 80 62. 1.56 atm. Figure 1 gives the flowsheet for this case with details of the equipment sizes.5826 0.1970 1. azeotropic column − 62 stages.1021/ie3020878 | Ind.76 60. recovery column − 12 stages.1416 1.60 72.1429 1.32 46 3.61 12. Overall Optimization: NT2 = 62.4764 0.44 65. 2 atm. The Ryan and Doherty flowsheet was stated as 8200 kJ/kg. The beer still distillate flow rate decreases slightly as distillate composition is increased and less organic reflux (R2) is required.1926 1.733 40.5771 0.3079 0. as does the optimum number of stages in the beer still (NT1).0454 0.11 16.906 1. Chem.1 atm.1799 1. Total annual cost also is minimized at 80 mol % ethanol. Figure 2 shows the ternary diagram at 2 atm.828 1. and operating conditions.0496 0. 16427−16432 .6938 0.5300 0. vapor from the azeotropic column is located in the narrow wedge at the bottom of the upper region. The recovery column distillate Figure 2. 0.450 0.1986 1. No Figure 1. Res.60 43. It should be noted that the total energy consumption in the proposed design is 7500 kJ per kg of ethanol product.5297 85 58. 2012.2655 stream conditions.86 60. which is recycled back to the azeotropic column. beer still − 1 atm. 51. while those costs in the azeotropic column decrease.1849 0.25 26 2. The bottoms of the azeotropic column is located at the ethanol corner.3318 0.Industrial & Engineering Chemistry Research Table 6.11 53. Eng. 16430 dx. Ternary diagram at 2 atm. The flow rate of the feed to the recovery column (Aqueous) decreases since less water needs to be removed from the bottom of the column (B3 decreases as xD1 increases).6605 Article (D3). Figure 3 gives the temperature and composition profiles in the azeotropic column.255 0.69 55.333 0.5699 0.326 1.4851 0.3559 0. the reboiler duty in the beer still (QR1) increases as distillate composition is increased.5099 0.36 43. decreases slightly.1398 1.51 21 2.3675 0.8160 0.1936 1. The net result of all these effects on the total capital cost is an increase with increasing beer still composition.

FLOWSHEET RECYCLE CONVERGENCE Recycle streams can present problems in process simulations.85 mol % benzene). One of the Aspen Design spec/ vary functions used in the azeotropic column manipulated the flow rate of the organic reflux (R2) to attain the specified composition of benzene in the bottoms (0. This reduces the required flow rate of the organic solvent from 65. The same basic approach was used for the organic recycle loop with some modification.71 kmol/h in the cyclohexane process. comparison of capital investment can be made since insufficient information was provided in their paper. Liquid composition profiles in azeotropic column.658 versus 1.903 81. the fraction of the stream split is slowly reduced getting closer and closer to no purge.85 mol % benzene 7. Chem. A.333 0. This method was directly and successfully applied to the recovery column distillate recycle loop.1021/ie3020878 | Ind. A small fraction of this total stream was purged off. and the composition of R2 is dx. both of which complicate the convergence of the flowsheet simulation. recovery column − 12 stages. a different approach was used.71 1. A fraction of the total stream (∼5%) is initially specified to be purged out of the process. 51. In the limit as the specified split fraction is made negligibly small. 16427−16432 .doi. the solution is the desired one. It was also necessary to make a guess of the composition of this stream. in the recycle of recovery column distillate back to the azeotropic column.5699 1.95 mol % cyclohexane versus 81.2 mol % impurity in the ethanol product stream is now cyclohexane. Eng.69 kmol/h in the benzene process to 51. 0. B. a temporary flow splitter is installed in the line with the loop closed. which proved quite effective and avoided the conversion to a dynamic simulation. azeotropic column − 62 stages. 5. To get around this problem. Figure The latter uses less total energy than the former (1. For example. The specifications are the same except that the 0.56 atm.Industrial & Engineering Chemistry Research Article Table 7. decanter − 322 K. So the flow rate of this stream could not be independently set.903 MW) in the reboilers of the azeotropic and recovery columns.94 mol % benzene). What remains is compared with the R2 flow rate (determined by the design spec/vary function) and the guessed composition of R2. Up to this point the only successful solution of the problem discussed in the literature7 for this process used the approach of converting the simulation into a dynamic one and then closing the recycle loops with a plantwide control structure in place to drive the process to the desired steady state. The method uses "homotopy” to slowly converge each recycle loop. 2012. a second flow splitter was inserted in the line after the organic phase from the decanter and the very small benzene makeup stream had been mixed. The simulation was easily converted to the different solvent. The number of stages and feed locations in the other two columns are kept the same as that used for benzene. the additional advantage over benzene of avoiding the problem of carcinogenic properties.95 mol % cyclohexane 2. The aqueous phase has a lower cyclohexane concentration than it does in the benzene case (2. Table 7 gives a comparison of the benzene and the cyclohexane processes. The beer still is not affected. Res. CYCLOHEXANE ENTRAINER Benzene has been used in the cases studied in the previous sections. This makes the closing of the loop less difficult because the numerical convergence algorithm does not have to find the solution where the process equations are perfectly balance so as to precisely match the feed streams fed into the system and all the other fixed variables.658 92. the same basic process configuration was examined with cyclohexane substituted for benzene. The process studied in this paper has two recycles and is very nonlinear. Of course. The organic phase has a higher cyclohexane concentration than it does in the benzene case (92. Comparison of Benzene and Cyclohexane Entrainer Processes (80 mol % Case)a benzene organic reflux R2 QR2 QR3 total organic phase aqueous phase a cyclohexane 51.2 mol % benzene).69 1. The fraction split is adjusted to make the two flow rates the same.137 0.82 mol % cyclohexane versus 7. The loop was not closed.5215 1. During the course of the present study.1 atm. To see the effect of entrainer choice. 1. 2 atm.83 mol % cyclohexane (kmol/h) (MW) (MW) (MW) (mol %) (mol %) 65.94 mol % benzene Beer still distillate composition −80 mol % ethanol. Once this initial solution is found. cyclohexane has 16431 6. Temperature profile in azeotropic column.

D. Prog. and the guessed and calculated compositions of R2 are identical. Article 7. REFERENCES (1) Black. 2012. 1989. Suszwalak. 2013. E-mail: WLL0@ Lehigh. Hernandez.. ■ ■ AUTHOR INFORMATION Corresponding Author *Phone: 610-758-4256.. Bai. 2012. 2012. (5) Martinez. (2) Vane. Chem. Purif. Wiley. Eng. M. A. Bioprod. 35. Notes The authors declare no competing financial interest. 2nd ed. 51. Technol.. (4) Ryan. (7) Luyben. Ind. 2012. 2723− 2729. 1592−1601. Eng. This paper demonstrates that the optimum is much lower (80 mol %) so that the capital and energy costs of the two sections of the process are economically balanced. I. S. Doherty.. 2. 86. Res. 2008. Distillation modeling of ethanol recovery and dehydration processes for ethanol and gasohol. Seqovia-Hernandez. J. L. The economic optimum flowsheet has been developed for the benzene entrainer system. Fax: A.Industrial & Engineering Chemistry Research adjusted with each iteration to match that calculated. G. Ryan and Doherty assume a composition (88 mol % ethanol) quite close to the azeotropic composition. 5847−5855. The composition of the distillate from the beer still is demonstrated to be a key design optimization variable. J. Biofuels. F. Design optimization of ternary heterogeneous azeotropic distillation sequences. Res. there is nothing purged. The threecolumn configuration proposed by Ryan and Doherty is used. CONCLUSION The main contribution of this paper is pointing out that an important design optimization variable has been neglected in many papers that explore heterogeneous azeotropic distillation for ethanol dehydration. L.. Biorefin. 51. Separation technologies for the recovery and dehydration of alcohols from fermentation broths. Enhanced bioethanol dehydration by extractive and azeotropic distillation in dividing-wall columns. Dehydration of bioethano by hybrid process liquid-liquid extraction/ extractive distillation. P. (3) Kiss. (6) Li. 70. 76 (9). A. Chem. Saucedo-Luna. 553−588. Res. Comez-Castro. Ind. M. AIChE J. A.1021/ie3020878 | Ind. J. Sep. 16432 dx. DOI: 10. Other authors select compositions around 85 mol %.1002/bbb. Eng.. New operation strategy for separation of ethanolwater by extractive distillation. Chem. The number of stages in the columns and the feed locations are adjusted to arrive at the most economical design in terms of total annual cost. C. J. When the loop has converged. 1980. 16427−16432 . F. G. 78. 51. W..doi.. P. Distillation Design and Control Using Aspen Simulation. Castro-Monteya. Eng. A.