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Visualizing the

McCabe-Thiele Diagram

Paul M. Mathias Use this spreadsheet-based visualization

Fluor Corp.

and interactive analysis of the

McCabe-Thiele diagram to understand the

foundations of distillation engineering.

M

ore than 80 years ago, McCabe and Thiele such as composition pinches and unforgiving composition

developed a creative graphical solution tech- profiles (i.e., a steep peak in the composition profile of one

nique based on Lewis’s assumption of constant or more components in multicomponent distillation) —

molal overflow (CMO) for the rational design of distilla- until they are converged. For these reasons, textbooks on

tion columns (1). The McCabe-Thiele diagram enabled staged separations stress the visual approach and present

decades of effective design and operational analysis of the McCabe-Thiele diagram as an essential tool for under-

distillation columns, and has been used to teach several standing and analyzing cascaded operations. Experienced

generations of chemical engineers to design and trouble- process engineers often use McCabe-Thiele diagrams to

shoot distillation and other cascaded processes. understand or help debug simulation results (3). Yet some

Simplified methods such as McCabe-Thiele are rarely consider graphical techniques tools of the past, and as a

used today for detailed design. Modern tools are based result, the distillation column has become a black box and

on rigorous solution of the equations governing cascaded engineers’ understanding of distillation has suffered (4).

separations, and properly deal with multicomponent sys- Even though the construction of McCabe-Thiele dia-

tems, heat effects, chemical reactions and mass-transfer grams is straightforward, it is a tedious and error-prone

limitations (2). Commercially available software enables process. Hence, engineers rarely study the large number

simulation of entire chemical plants for the purposes of of cases needed to understand the interactions of the many

design, optimization and control — but it is important process variables. This article introduces a spreadsheet-based

to ensure the discriminating and competent use of these approach that readily produces McCabe-Thiele diagrams for

sophisticated tools. The McCabe-Thiele visual approach binary systems so that the interacting effect of process vari-

provides a powerful way to attain this judgment and ables can be visualized easily and interactively; the Excel file

competency. is provided as a supplement to the online version of this arti-

Software applications based on rigorous calculations cle (www.aiche.org/cep). Because it is based on the widely

do not explain how distillation really works and how the available Excel software and uses standard techniques, this

numerous process variables interact to yield a distilla- method is a useful advance over existing software tools that

tion column that is energy efficient, stable, and produces enable visualization of the McCabe-Thiele diagram.

products with the desired purities. If the design engi- Excel spreadsheets are increasingly used in chemical

neer specifies an impossible set of inputs, even the best engineering education and industrial practice (5). This

commercial software either crashes or returns vague and article demonstrates how Excel may be used for chemical

unhelpful messages (e.g., “Tray j dried up”). Engineers engineering computation and visualization. Through the

who have only performed simulations resort to arbitrary example presented in the sidebar, the article also demon-

and frantic changes in input variables to obtain a simula- strates how the McCabe-Thiele method, and, in particular,

tion with a feasible specification. In addition, rigorous, the spreadsheet application introduced here, answers typi-

computerized calculations do not reveal design problems cal design questions.

36 www.aiche.org/cep December 2009 CEP

org/cep 37 . respectively. The rectifying-section operating line is drawn using tion (feed tray and below).6 and to the specified q) 38. Q B molal-overflow (CMO) assumption applies. a distillation expert. The stages are counted from the top down. Figure 1 is a schematic diagram of a distillation col. has The vapor and liquid flows in the rectifying section (above answered question b. the first stage is at the top of the column where the b. The slope counted as the first equilibrium stage. Vapor-liquid QF equilibrium (VLE) data are provided for this binary (heat rate required N to change its QR Q system. The 10 equilibrium V stages include a partial reboiler. Assume that the constant. calculated values L L yj+1 = x j + ( . CMO approximation.aiche. or values from V V commercial software.V ) x D ^1 h The relationship between the reflux ratio (R = L/D) The approach and the liquid-to-vapor flow ratio (L/V) is: As far as possible. Analogous to Eq. the operating line for the strip- This function is used. this application uses Excel’s standard capabilities. If it is possible to move the feed inlet stage. including experimental data. the compositions refer to the more-volatile component. If the minimum number of stages exceeds 10. CEP December 2009 www. reflux. q-line is performed in Excel as follows: tifying section (above the feed tray) and the stripping sec. the separation is impossible.) According to the of the q-line is q/(q – 1). called Interp. q is usually referred to as the thermal state of stage 1 at the top of the column where the reflux enters. the feed. respectively.” starts from a point on the umn with a total condenser and a partial reboiler. Is the CMO approximation valid? reboiler. The column needs to be D reused to separate an acetone-ethanol binary mixture F0 1 at a pressure of 1 atm. or “q-line. with literature. would flows resulting from the CMO approximation lead to the you recommend that this be done? What is the optimum following component-balance equation (or operating line) feed location? How is the separation affected as the in the rectifying section: feed inlet is changed? e. respectively. Following the usual practice. How should the design be changed if the tray L L efficiency decreases below unity? y j + 1 = V x j + (1 . and the Nth stage is the partial reboiler. Q Example: The Problem Statement QC An existing distillation column consists of a total condenser and 10 equilibrium stages. it will have to be vapor) or greater than unity (subcooled liquid). The constant vapor and liquid d. mum number of stages needed at total reflux is less The equations resulting from the McCabe-Thiele than 10. 1. and N stages. The construction of the two operating lines and the and the vapor and liquid flows are constant in both the rec.9 kJ/mol. The feed line. which was V = 1+R ^2 h developed using Visual Basic for Applications (VBA) and is provided as part of the online version of the article. for example. to interpolate vapor. and assures you that the mini. This feature enables the spreadsheet application to accept x-y data from any source. The par. In the distillation is not. The feed is 20% vaporized and R (feed with q = 1) contains 50 kmol/h acetone and 50 kmol/h ethanol. x = y diagonal line where x = xF and has a slope based tial reboiler is an equilibrium stage. Your supervisor. the feed tray) are denoted as V and L. each stage is at phase equilibrium. c. but the total condenser on q or the liquid fraction of the feed. The exception is a function to L R perform data interpolation. The F desired distillate and bottoms compositions of acetone are 90 mole% and 3 mole%. S Figure 1. and the enthalpies of vaporization of acetone thermal state and ethanol may be assumed to be constant at 29. with the feed inlet on the fifth stage from the top. ping section is: pressure and x-y equilibrium data. The example distillation column has a total condenser. 1. Calculate the number of stages needed at total reflux enters. Note that q can be less than zero (superheated (Note that if a partial condenser is used. Calculate the reflux ratio needed to achieve the technique are available in textbooks on separations and desired separation. How does the reflux ratio change as the thermal state of the feed is varied? are only summarized here. Eqs. 1 and 2 and the specified values of xD and R. a partial a.1) x B ^3 h derived from a thermodynamic model.

q) 6 x F DH 1 + (1 . Q F = F (1 . In this way. VLE data for the acetone-ethanol system at 50°C. 0). Goal Seek or Evaluating binary separations Solver may be used to calculate the reflux ratio to obtain A spreadsheet is used to analyze the separation of the the liquid composition (xB) descending from tray 10.Reactions and Separations 2. The concept of Murphree efficiency pressure of the binary mixture is given by Eq.x j . The stripping-section operating line is the straight calculated from the vapor mole fraction.x D) DH 2 @ ^5 h The McCabe-Thiele diagram is constructed by “stepping off stages. the use of Murphree efficiencies requires from (xF. 8. y_Data.aiche. the McCabe. The is achieved on each stage. 71°C and 80°C (6. Since the pressure is low (about 2 bar or less). These data may be obtained from Thiele procedure may be made more realistic by relax. the entire McCabe-Thiele diagram can be computed and graphically represented using standard Excel charting QR = QC . which is obtained using state of the feed from the saturated-liquid state is: the function Interp: x1 = Interp (xD. acetone-ethanol mixture and other binary mixtures using (Solver seems to converge more reliably and accurately the McCabe-Thiele approach. x_Data. is the heat 101 points (x_Data. Standard Excel what-if analysis capability can be used to evaluate design results. In Eq. For the purpose of calculating equilibrium densing binary mixtures based on their (fixed) enthalp- compositions.) The McCabe-Thiele diagram is constructed by inter- As was first suggested by Murphree.org/cep December 2009 CEP . y_Data). xj* is the liquid mole fraction that is in equi. It is useful to estimate heat effects consistent with the section operating line and the q-line. x-y data have been entered as a table with ies of vaporization.x F) DH 2 @ ^6 h balance equation). For example. 9: 38 www.Q C = V 6 x D DH 1 + (1 . the total bottom will be reduced. The liquid composition condenser and reboiler duties is zero for a saturated-liquid descending from tray 1 is the mole fraction in equilibrium feed (q = 1). However. xB) to the intersection of the rectifying. This spacing of data points removal rate required to condense a vapor with flowrate V is expected to be adequate for accurate interpolation of and composition xD: the acetone-ethanol x-y diagram. switching to The reboiler duty (QR) is calculated from QC and QF: the stripping-section operating line at the feed tray. so x j . effects on the liquid fugacity may be neglected and the the decrease in liquid mole fraction from the distillate to the vapor phase can be treated as an ideal gas. xF) with a slope equal to q/(q – 1). The heat duty required to change the thermal with a vapor with composition xD. line from (xB. and the is equally applicable to the vapor or liquid phase. Note that if may be calculated from Eq. 4. a modification in the way that the liquid mole fraction is 3.QF ^7 h capability. than Goal Seek. The stepping off of stages continues over the entire column. For another system with an x-y diagram that has a more complex shape. QC.x j-1 the use of Excel for regression of phase-equilibrium data E ML = ^4 h x *j . and here vapor composition for the specified liquid composition it is convenient to apply it to the liquid phase. 7) have been used to regress the librium with the vapor ascending from tray j and xj is the parameters of the NRTL activity-coefficient model. CMO approximation. The q-line is constructed by drawing a straight line Eq. a variety of sources. which is the vapor The CMO approximation implies that the sum of the composition ascending from tray 1. The condenser duty. 4 is be applied. . Thus. Here. again using Interp. the vapor composition rising from tray 2 is calculated vap vap from the rectifying-section operating line (or component. x-y data may not always be available for the system of interest. more data vap vap points in the table may be needed.1 to generate the x-y data is demonstrated here. it is assumed that sensible The function Interp is useful in implementing the heat effects and heats of mixing are negligible and that operating lines and the q-lines even though all three are heat duties are only associated with evaporating and con- straight lines. Next. polation of x-y data. such as standard thermodynamic ing the approximation that vapor-liquid equilibrium models or commercial process-simulation software. pressure As the efficiency EML decreases to values less than unity. The Murphrey efficiency is advantage of this approach is that the source may be defined as: sophisticated models and databases that are difficult and time-consuming to program in Excel.” The starting point is (xD. xD). actual mole fraction of the liquid descending from tray j.

Today. and understanding to develop superior rigorous methods is available today in commercial software. as well as the judgment to diagnose and resolve which has completely replaced simplified methods for the operational problems. visualization benefits inherent in the simpli. 8) is equal to the stage pressure (constant at 1 atm or 101.176. it is tedious. infeasible separation sequences. and have been extended to “Perry’s Chemical Engineers’ Handbook” (21) states: multicomponent systems and pressure variations. eliminated the need for approximate solutions in are well worth the time and effort required to collect them. insight. the diagram can easily be constructed from a rigorous distil- fied procedures are in danger of being lost.128.aiche. improving thermodynamic properties (especially vapor-liquid equilib.e. implementation of the McCabe-Thiele graphical computerized calculations are often used as a black box. procedure does not require the CMO approximation. approach to design is equation based … Nevertheless. Any suitable activity-coefficient model may be used Using the NRTL model with Eqs.325 kPa).724358. the number of tower has been extended to multicomponent systems by Hengste- malfunctions is not declining (12). 8–12. In addition.org/cep 39 . which corresponds to have been estimated using the function Interp and infinite reflux ratio.33876. results of equation-based methods. The optimum values of the NRTL parameters P= P 1sat x 1 c1 + P 2sat x 2 c2 ^8 h (A12. Although Goal Seek may be used to solve this equa- GE G 21 x21 G 12 x12 tion. energy efficiency (18). the effect of various design variables. At each value of x. the temperature model has been chosen: must be found such that the total pressure (Eq. but most convenient for these purposes. such as composition pinches and unforgiving compo. B21 = 921. these rigorous. since a single Excel step generates the entire x-y table. the McCabe-Thiele diagram despite the huge progress in distillation. The x-y diagram is the sition profiles (15). are excellent diagrams are useful for quick approximations. since and the intuitive. Residue and explaining counter-intuitive observations in a multi-feed curve maps (RCMs) (14) provide visualization of feasible and distillation tower (20). When used in this manner. A12 = 0. since the calculation will have to be x 1 x 2 RT = x 1 + x 2 G 21 + x 2 + x 1 G 12 ^10h repeated 101 times.ax12) and G 21 / exp (.3. Visualiza- tion tools capture the fundamentals of distillation. Good plant data are difficult to obtain.” linear in reciprocal temperature. for interpreting troubleshooting tools because they uncover design prob. B12 and B21) have been determined using Solver to minimize the sum-squared error between the measured and calculated total pressures (i. A21 = –2. an x-y dia- to represent the liquid nonideality. B12 = –159. since they are the prime tool of the troubleshooter. design of distillation towers. rium) is crucial to producing correct designs (13). A comprehensive suite of powerful results. Kister noted that lation calculation. the vapor pressures of acetone and ethanol The total-reflux calculation. beginning in about 1951. beck. is useful because it determines the assuming that the logarithm of the vapor pressure is minimum number of stages needed for the target separa- CEP December 2009 www. designing steam-stripping systems (17)..ax21) ^11h minimize the sum-squared error by changing the 101 cells that contain the temperatures corresponding to the liquid compositions. and then use Solver to G 12 / exp (. Accurate calculation of (16). like McCabe-Thiele and Hengstebeck diagrams. multicomponent distillation profiles and RCMs. The latter methodology (provided with the x12 = A 12 + B 12 /T and x21 = A 21 + B 21 /T ^12h online article) is efficient in terms of human effort. McCabe-Thiele/Hengste- Experts recognize that an effective distillation design beck diagrams are highly effective as design and trouble- and analysis toolkit must have more than the capability for shooting tools for analyzing new energy-saving technologies rigorous. evaluating revamp improvements (19). computerized calculations. and here the NRTL gram is generated. A better approach is to calculate the sum-squared error of the difference between the calcu- lated pressures and 101. Such a equilibrium-stage distillation calculations and enabled more diverse and comprehensive toolkit gives engineers detailed rigorous simulations. A21. Graphical “With the widespread availability of computers. Barker’s method). Unfortunately. P The optimum values of the NRTL parameters are: y1 = ^9 h P 1sat x 1 c1 α = 0. The Role of the McCabe-Thiele Method in Distillation Engineering T he availability of digital computers and the intense development of solution algorithms. the preferred techniques. The equations for the resulting activity coefficients (γ1 and γ2) are available in standard references. At each Total reﬂux temperature. and for demonstrating lems.325 kPa. designs.

xB-error is the square of the difference between the desired and the diagonal (x = y) line. The McCabe-Thiele diagram for acetone-ethanol at 1 atm shows the input variables (design specifications) and key calculated tion.15 optimum feed location is fairly small. where QF is the heat load required to varying q and make the best design choice. its calculated q variations with rigorous results from the QR + QF is exactly equal to –QC.00 xB 0. since it does major operating cost).8 xD 0.5 6 8 Operating 0.0300 y = Mole Fraction of Acetone in Vapor 2 0.3 10 Feed Line 0. S Figure 3. it is possible to use a distil.6 2.7 Reflux Ratio 2.03.1 1.5 0. and negligible sensible 40 www.79 6 4.1 2. (Based on the Lewis CMO approximation. modify the thermal state of the feed from q = 1 (saturated This McCabe-Thiele method was tested by comparing liquid).9 and xB = 0. The value of this analysis is that not include any heat treatment of the feed.5 Feed Stage 5 xB Stage 10 0.9 1 S Figure 2.984 3 EML 1.83 5.75 the feed is summarized in Table 1 (using the optimum 1 1.) On this basis.2 0.7 0.89 6 4.83 the reflux ratio that gives the target bottom concentration.6 0. reflux ratio and the reboiler and condenser duties.6 0.44 6 2. The analysis demonstrates that the effect of an no pressure effects on the liquid fugacity.25 –5. the table the design engineer can easily understand the benefits of includes QR + QF.12 6 3.93 A study of the effect of varying the thermal state of 0. and the NRTL increase in q results in a decrease in capital costs (due to activity-coefficient model).03.8 0.aiche.2 2.53 4.7 0.2 Top 0. the desired Ratio Tray GJ/h GJ/h GJ/h reflux ratio is readily calculated using Solver to determine –0.39 is tray 6 rather than tray 5. xD = 0.07 –4. 0.9 1 XD xF 0. lation column with 10 stages for the desired separation.5 1 y = Mole Fraction of Acetone in Vapor 1 0. Solver is used to vary reflux ratio to drive xB-error to acetone-ethanol is presented as Figure 2.75 6 4.4 3 0.27 6 2. that between six and seven stages are needed to achieve Table 1.5.6 7 0. Figure 3 presents the reflux ratio needed to achieve q Reflux Optimum Q R.8 Operating 4 5 Line 5 0. GJ/h 4.8 q 0.68 xB = 0. It does not make the Lewis approximations (con- column diameter).03 QR.9 Bottom 2 0. as well as a decrease in operating stant molal overflow or constant heat of vaporization even costs (mainly a lower heating duty. Q R + Q F.1 x = Mole Fraction of Acetone in Liquid 0 0 0.9 E–23 0. The required reflux ratio decreases as the thermal state of the feed (q) increases.4 0.9 1 0. Thus.75 4. As shown in the figure.03.39 5. xB = 0.03.4 0. but the penalty for the non. Q C.3 0. uses the same thermodynamic model (ideal vapor phase. EML = 1.5 0.68 5. 0 2.1 0.Reactions and Separations 1 Design Specifications Calculated 0.8 0. but rigorously deals with heat a lower reflux ratio and column flows and hence a smaller effects.06 –5. which indicates a minimum value (effectively zero).4 2.15 5.3 0. Hence.90 QC. GJ/h –4.56 –4. Acetone-ethanol separation at 1 atm and total reflux requires x = Mole Fraction of Acetone in Liquid between six and seven stages to achieve xD = 0. At infinite reflux.09 and xB = 0.60 4.4 11 Line 7 XB 0. both operating lines reduce to variables.3 0. the desired separation. tray 6).65 –5.53 reboiler duty (QR) increases as q increases.1 0.025 0. The thermal state of the feed affects the xD = 0. and the 1. Figure 3 demonstrates that the optimum feed location 0. The Aspen Plus simulation heat load decreases as q increases.00 6 3. The reboiler duty in Table 1 is not the entire heat load.93 4.60 –4.60 feed location.8 1.1 0. The total-reflux diagram for calculated values of xB.org/cep December 2009 CEP . 0.88 –4. the total Aspen Plus process simulator.2 0.6 4 xB-error 8. xF = 0.9.0 (QR + QF) is the reboiler duty plus the heat required to raise Effect of q and comparison with rigorous calculation the feed from a saturated liquid to its feed thermal state.09 –5.54 6 2. which is usually the as the liquid composition changes.299 0.7 6 0.2 9 0 0.

g.8 Operating 3 diagram. the McCabe-Thiele 0.4 0.4 0.2 tray location on the required reboiler duty. S Figure 9.6 0. 39 (“The Role of the McCabe-Thiele Bottom 1 0. The liquid composition profiles obtained using the McCabe- Thiele techinique and rigorous calculations are similar.8 1 100 Rigorous: Solid lines q = Thermal Quality of Feed McCabe-Thiele: Dashed lines 75 0 2 4 6 8 10 S Figure 5.9 x = Mole Fraction of 3 from rigorous calculation 0. and hence provides a way to and rigorous calculations for the column flow profiles.4 10 7 Line 0.6 0. 6 Reboiler Duty. There is poor agreement between the Lewis approximations heat and heat of mixing).7 present-day value as a design and troubleshooting tool.7 Rigorous 2. S Figure 7.3 1. The required reflux ratio is a function of the thermal quality of the feed. Figures 4 and 5 indicate that the Lewis approxima. has excellent Line 4 0.1 0 0. and hence remains important for understanding the foundations of distillation engineering.8 Reflux Ratio Acetone in Liquid 2. Note that a 0.8 1 0 q = Thermal Quality of Feed 0 2 4 6 8 10 Tray Number S Figure 4. A nonoptimum feed tray location (such as tray 3 or 9) would McCabe-Thiele method captures the trends reasonably require a larger reboiler duty to achieve the target separation. 1 3.4 2 McCabe-Thiele McCabe-Thiele 0. S Figure 6.8 0.5 2.9 2 Method in Distillation Engineering”).7 0.2 0. without the CMO approximation.1 severely nonoptimum feed location (e.5 11 6 Operating Effect of feed location 0.aiche. GJ/h 5 200 4 Rigorous Vapor 175 3 Flow. The Lewis approximations 7 are in excellent agreement with the rigorous calculation 6 for the liquid composition profile (Figure 6). However.9 1 6) will require the reboiler duty to be doubled in order x = Mole Fraction of Acetone in Liquid to achieve the target separation.6 2. 0. tray 0 0 0.1 0. estimate the errors caused by the approximations.4 0.2 Rigorous 1. well.6 0.6 0.3 0. Figures 4 and 5 clearly demonstrate that the S Figure 8. rigorous calculations rather than shortcut meth- Feed Tray ods are used for detailed design of distillation columns. Figure 9 illustrates the pinch point that occurs when the feed point is too low.2 0.2 0. showing that the liquid mole fraction reaches an asymp- CEP December 2009 www.8 0.2 Error bars show ±10% variance 0. As discussed in y = Mole Fraction of Acetone in Vapor 1 the sidebar on p. GJ/h tions cause errors of about 10% in the reflux ratio and up 8 to 15% in the reboiler duty. such as Figure 10 provides further illustration of the pinch point.org/cep 41 . tray 9 vs. A pinch point occurs when a feed point is too low. The reboiler duty is a function of the thermal quality Tray Number of the feed. tray 9 rather than the optimum tray 6.2 0.6 5 Top 0.4 0.8 0. 9 Reboiler Duty. 3 3 4 5 6 7 8 9 Today.5 0.6 0.3 8 Figure 8 shows the effect of nonoptimum feed 9 Feed Line 0.. kmol/h 2 McCabe-Thiele 150 Error bars show ±15% 1 variance from rigorous calculation 125 Liquid 0 0 0. but poor 5 agreement with the rigorous calculation for the flow 4 profiles (Figure 7).

69 13. located feed stage.85 0.6 5 18. rectifying and stripping). The number of stages needed at total reflux is It should be emphasized that the Murphree efficiency between six and seven.80 3.03. Therefore.4 ing product purities.38 6 9. it is of reduced tray efficiency.6 xF = 0. compared a. When the feed point is too low (tray 9 rather than the opti- 0.4 EML Reflux Ratio Optimum Tray QR.05 S Figure 10. Since efficiencies vary from 15 one section to another.8 ratio and reboiler duty. 0.4 detrimental effect that occurs if the feed point is too high. with a required reflux ratio of 2.5. In not yield reliably accurate results.00 unity.9 if the feed location is lowered to tray 6.e. 0. But CMO does separation more difficult.07 0.9 Table 2. xB = 0.68 18. where the enthalpy of shows the negative effects that will occur for a poorly vaporization of ethanol is 32% higher than that of acetone.8 totic value of about 0. GJ/h McCabe-Thiele 0. d.95 2. Note also that the optimum feed location changes as Efficiency efficiency changes.aiche.9 Effect of reduced tray efﬁciency 0.0. and the addition of 0.3 5 22. q = 1.95 6 10. The existing feed location (tray 5) is only slightly Solution to the acetone-ethanol example problem suboptimal.88 6 5. it is best to apply the efficiency Reflux Ratio separately for each section (i. b. The reduced Murphree efficiency captures trends. The effects shown here are only is 2.41 6 4. the liquid composition reaches an asymptotic value. and the qualitatively applicable. The Murphree efficiency (EML) substantially decreases with a feed location when the reflux ratio is high. 0. 4) has been used to investigate the effect of tray efficiency. the desired separation is barely possible for EML = 0. preferable to operate the column at high values of q.67.Reactions and Separations 1 0. and thus serves as an aid to understand the effectively reduces the relative volatility.95 1.5 The Excel file can be used to further study the analogous 0. which makes the fundamentals of distillation engineering. The CMO approximation is especially useful because it e.2 Rigorous 0.7.68 6 12.80 0.65 0.1 0.73 6. The reflux ratio decreases with increasing q. higher reflux ratio.1 efficiency be defined as the ratio of the theoretical num- ber of stages to the actual number of stages to achieve 20 a particular separation (8).9.70 6 7.7 0.67 28.0.2 5 30.74 5. the available 10-stage col- is only a crude description of the performance of real umn is likely to be adequate for the desired separation.75 5. but useful to illustrate the effects required heat duty decreases as q increases. Table 2 and 5 Figure 11 show that the required reflux ratio and the resulting 0 reboiler duty increase substantially as EML decreases below 0.9 It is usually recommended that the sectional column 0.93 Tray Number 0.72 7.70 0. The Murphree efficiency (EML) affects the reflux x = Mole Fraction of 0.75 0.0 0. and hence the effect of varying EML should be c. Figure 8 approximation even for this case.70 10. and is not recommended fact. for detailed design calculations.3 1.0 more stages above the feed will have no effect on improv.81 5 15. xD = 0.42 0 0 2 4 6 8 10 0. Figure 12 presents the McCabe-Thiele diagram for the case where EML = 0.8 5 48..09 at tray 9. Thus. Constant molal overflow is a reasonably good with 1. trays. 0.org/cep December 2009 CEP . separation impossible.89 6 4. even at total reflux.71 8. The reflux ratio needed for the specified separation interpreted with caution. 10 The concept of Murphree efficiency (EML. requiring a higher reflux ratio. especially since software and further reduction in the efficiency will make the desired employing rigorous methods is widely available. The separation becomes far more difficult as EML 42 www.90 0.71 0. Eq. Acetone in Liquid 0.90 2.57 5 13.5 0. although the results are insensitive to the S Figure 11.83 mum tray 6).00 1.85 2.10 6 4.

G21 = terms in NRTL model (Eqs. The effective equilibrium curve (green) at the reduced = enthalpy of vaporization of efficiency of EML = 0. which CEP December 2009 www. The Excel file supplied online provides two R = gas constant additional examples of x-y diagrams for binary systems. B21 = temperature-dependence 0. γ1. The reader j = stage number is urged to perform another calculation by increasing xD R = reboiler slightly.org/cep 43 . 10) x = Mole Fraction of Acetone in Liquid G12. from 0.4 11 Operating (Eq.0.89 (EML = 1.5 6 Top parameters in NRTL model 0. R = reflux ratio The first example is representative of the benzene. ΔH2vap components 1 and 2.3 0.4 is required for the target separation. 10) system at 1 atm from the Aspen Plus process simulator. Hence.6.7 0. 4) 0 0.9 1 GE = excess Gibbs energy (Eq. GJ/h mixture. kPa Other binary separations q = liquid fraction or thermal state of the feed.8 0.3 10 B = bottom flowrate.2 8 D = distillate flowrate. 13) an exercise for the reader. sat.8 4 0.9). applied to 0.7 on the McCabe-Thiele diagram reveals that the ΔH1vap. D = distillate F = feed more stages are needed above the feed stage. The required reflux ratio almost doubles (to 10. kmol/h 9 EML = Murphree efficiency.84 (leaving xB unchanged at 0.aiche. 11) easily be studied. A21. 4) xa y = vapor mole fraction (of the more- y= ^14h volatile component) 1 + (a . kmol/h values of EML may cause pinch points that do not exist at P = pressure.4 0.01).x) volatile component) x* = liquid composition in equilibrium with y (Eq.y) / (1 . Note also that low section. kmol/h L = liquid flowrate in stripping decreases below unity (Figure 11).1) x Greek Letters The value of the simple constant-α system is that the α = nonrandomness parameter in effects of close-boiling and wide-boiling systems may NRTL model (Eq. T = temperature. 10 and 11) S Figure 12. saturated liquid ing the x-y table used here for the acetone-ethanol binary Q = heat rate.9 Bottom 2 Operating 3 Nomenclature 0. section. sat = vapor pressures of components P1 P2 1 and 2. kJ/mol required reflux ratio increases from 1. kPa higher efficiencies.7 Line 0.2). Detailed study of this system is left as α = relative volatility (Eq. kmol/h Feed Line 0. 2 = components 1 and 2 the optimum feed tray is low in the column because the B = bottom separation is very difficult at high ethanol concentrations C = condenser due to the formation of an azeotrope (at x ≈ 0. y = Mole Fraction of Acetone in Vapor 1 1 0. optimum feed L = liquid flowrate in rectifying location) to 10.6 5 A12. q = 1 corresponds to Other binary systems may easily be studied by replac.2 0. The McCabe-Thiele diagram indicates that (1) a reflux Subscripts ratio of 5.6 0. kmol/h y/x a/ ^13h x = liquid mole fraction (of the more- (1 . kmol/h V = vapor flowrate in stripping section.83 to 0.5 0. γ2 = activity coefficients of In the second example. and (2) 1.1 0. 12) 7 Line 0.1 0 the liquid compositions (Eq. K toluene system and assumes constant relative volatility. B12. α: V = vapor flowrate in rectifying section. x-y data from an external components 1 and 2 τ = interaction-energy parameter in source are used — x-y data for the ethanol-water binary NRTL model (Eq.

What and The ability to easily vary input specifications in the When. the McCabe-Thiele approach captures mercial Towers. systems. 28–39 (2003). 609 (Apr. Eng. W. tions and 75 presentations at technical conferences. “Perry’s Chemical Engineers’ California. 7. and Diisopropyl Ether.Reactions and Separations highlights the difficulty of achieving higher product purity in the vicinity of the azeotrope. Egloff.g. W. Eng. Kister. Phone: (949) 349-3595. Eng. Kister. Zygula. 920–923 by eliminating the poor approximations and thus become (1929). 30. tions for Ternary Systems. should this tool be extended to improve accuracy Ancient and Modern. Z.” J. “What Caused Tower Malfunctions in the Last very powerful for describing real distillation systems. NY the Indian Institute of Technology.” Comptes Rendus. “The B. 102 (44). E. pp. He earned a BTech from Handbook. Hoboken. 81A. 20. “Excess Thermodynamic Func- simulation as a design and troubleshooting tool.-J. 42–46 (1996). Engineering Data and Industrial & Engineering Chemistry Research. “Design of Separation Units tion fundamentals. He occasionally teaches chemical engineering courses at the Univ.” Chem. pp. L. pp.. The 50 Years?.. 56–61. applicable to more realistic distillation situations (e. Progress.” Topical Conference Proceedings. D..” Chem. effects. Excel spreadsheet and to visualize the effects on column 4. Irvine. Wankat. “Hydraulic Analysis is Key to Effective.-H. Eng. and they become better design (1996).. Progress.” Trans. S.. “Don’t Gamble With Physical Properties design requirements very well. “Sur la Rectificaton de l’alcool.” in “Distillation 2007. “Distillation Design. discriminating users of 6. 21. 103 (10). and previously worked on the ASPEN Project 19.. 2007). M.. etc. Eng. 6. of Florida. “Distillation Troubleshooting. Chem. Progress.” detailed methodologies. complex column configurations. spreadsheet method presented here is to produce engineers 14. He is a member of AIChE. 2. D. CA 92618. Irvine. and at Aspen Technology. be done with caution. 88–103 (1985).. Chem. H.. M. pp. W. Education. 16.. which Acetone-Ethanol-Water at 50°C. et al. NY (2001). “Effects of Design on Tray Efficiency in Com- author’s experience. M. Kister. (Before Computers) and A. kinetics. trends well and thus is a valid and useful teaching tool. et al. Houston. Green. 2007). L. J. NY (1992). pp. Seader. IChemE. MATHIAS is a technical director at Fluor Corp.aiche.” Ind. (May 2007). (2008). Doherty.” Ind. pp.. C. 22–26.” Topical Confer- ence Proceedings.)? Extensions should be limited and should 19 (2). H. F. Lowry. Z. and become discriminating users of sophisticated 15. et al. G. Z. D. “Can We Believe the Simulation Results?. In fact. Kister. Chem.” Oil & Gas Journal. AIChE Spring National Meeting. pp.. specializing in properties and process modeling. p. “A Design Review of Steam Stripping Col- McCabe-Thiele diagram. C. Malone. Burns.. H.. CEP umns for Wastewater Service. and C. the best use of the for Simulations. Perry. of Equilibrium-Stage Operations. As Kister noted. AIChE Spring National Meeting. Sorel. “the two can coexist” (4). Eng.. Hu. 9.. So. The visual approach Literature Cited clearly provides insight and understanding of the special 1. 97–105 a chemical technologist with more than 30 years of broad experience. Eng.. Eng. 99 (7). D. mass transfer limitations. 25. E. Thiele. p. He is Product Separation.” 8th ed... Ohe.. Progress.” Wiley. and has been a member of the editorial advisory boards of two journals: Chemical & Low-Cost Demethanizer Debottleneck.. 39–47 (2008). C. 35 (3).. Texas.” McGraw-Hill. 17. pp. T. Total-Pressure Data and GE for But how robust is the McCabe-Thiele approach. A. The understanding gained from ria for Mixtures of Ethanol. chemical reactions and 11. 109. Mathias@Fluor.. have good engineering Distillation Systems. 83–98 (1995). 18. “Energy-Saving Distillation Through Internal Heat it is good practice to benefit from both the accuracy and Exchange (HiDiC). and R.. Madras and a PhD from the Univ." Chem. Taylor. M.” Chem. Acetone. New York. (47 Discovery. New York.” the spreadsheet is a valuable first step in using a rigorous Fluid Phase Equilibria. Eng. “Isothermal Vapor-Liquid Equilib- commercial software. can it give results that will confuse or even mislead? In the 8.” in “Distillation 2007.org/cep December 2009 CEP . F. P. Thus. pp. p. Eng. pp. 52–58 (2002).com). PAUL M. H. judgment. both in chemical engineering. Love. 254–257 (1980). (2004). 5–26 (2003). Bellner. E-mail: Paul. 44 www.. Z. “Distillation Methods. C. M. Engineers are better able to grasp the Using Spreadsheets. and C. D. “Graphical Design of considerations required for the purification of a mixture Fractionating Columns. Houston. of 21. 5. He has 50 publica. multi-component 58. P. 168–171 (2001). Data. pp. “Real-World Modeling of Distillation. performance has significant value in teaching distilla. H. at Air Products and Chemicals. Education. 22–26. Education. is the foundation of this Excel application? In particular. Lee. and J. Fax: (949) 349-5058). M. “Teaching Separations: Why.. NJ (2006).” McGraw-Hill. 13–17. engineers and more competent. New York. that forms an azeotrope. 1128 (1889). 62–69 effects of various inputs. Chem. McCabe. and E. pp. S.” Chem. understanding gained by visualization of the venerable 17. 13 (Apr. H. R. “Rethink Column Internals for Improved (MIT). p. et al. Jr. Closing thoughts 3. Z. Kister. 104 (6). heat 10. and M. Sung. pp. “Conceptual Design of who understand the fundamentals. 605–611 (1925).. pp. McGraw-Hill. flexibility of rigorous calculations and the insight and TX.... Chaudhry. 97 (10). Rigorous modeling methods are 12. computer code based on these methods supports flexible 13.” Hydrocarbon Processing. Carlson.” Chem.

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