CHAPTER 2

ANALYSIS OF DISTILLATION COLUMNS

The major emphasis of this book is the use of rigorous steady-state and dynamic simulation for the design and control of distillation columns. However, several simple approximate methods provide signicant insight into how the various design and operating parameters impact separation. Some of these methods employ graphical techniques that give visual pictures of the effects of parameters. Although some of the methods are limited to binary systems, the relationships can be extended to multicomponent systems.

2.1

DESIGN DEGREES OF FREEDOM

The design of a distillation column involves many parameters: product compositions, product owrates, operating pressure, total number of trays, feed tray location, reux ratio, reboiler heat input, condenser heat removal, column diameter, and column height. Not all of these variables are independent, so a degrees of freedom analysis is useful in pinning down exactly how many independent variables can (and must) be specied to completely dene the system. A rigorous degrees-of-freedom analysis involves counting the number of variables in the system and subtracting the number of equations that describe the system. For a multicomponent, multistage column this can involve hundreds, if not thousands, of variables and equations. Any error in counting is grossly amplied because we are taking the difference between two very large numbers. A simple intuitive approach is used below. The normal situation in distillation design is that the feed conditions are given: owrate F [moles per hour (mol/h)], composition zj (mole fraction component j), temperature TF and pressure PF. The desired compositions of the product streams are also typically known. We consider a two-product column, so the normal specications are to set the heavy-key impurity in the distillate xD,HK and the light-key impurity in the bottoms xB,LK.
Distillation Design and Control Using AspenTM Simulation, By William L. Luyben Copyright # 2006 John Wiley & Sons, Inc.

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ANALYSIS OF DISTILLATION COLUMNS

The design problem is to establish the operating pressure P, the total number of trays NT, and the feed tray location NF that produces the desired product purities. All other parameters are then xed. Therefore, the number of design degrees of freedom is 5: xD,HK, xB,LK, P, NT, and NF. So if the desired product purities and the pressure are given, there are 2 degrees of freedom. Just to emphasis this point, the ve variables that could be specied might be the distillate owrate D, reux ratio RR R/D, P, NT, and NF. In this case the product compositions cannot be specied but depend on the distillate owrate and reux ratio selected. The steps in the design procedure will be illustrated in subsequent chapters. Our purpose in this chapter is to discuss some of the ways to establish reasonable values of some of the parameters such as the number of stages or the reux ratio.

2.2

BINARY MC CABE THIELE METHOD

The McCabe Thiele method is a graphical approach that shows very nicely in pictorial form the effects of VLE, reux ratio, and number of trays. It is limited to binary systems, but the effects of parameters can be extended to multicomponent systems. The basic effects can be summarized: 1. The easier the separation, the fewer trays required and the lower the required reux ratio (lower energy consumption). 2. The higher the desired product purities, the more trays required. But the required reux ratio does not increase signicantly as product purities increase. 3. There is an engineering tradeoff between the number of trays and the reux ratio. An innite number of columns can be designed that produce exactly the same products but have different heights, different diameters, and different energy consumptions. Selecting the optimum column involves issues of both steady-state economics and dynamic controllability. 4. Minimum values of the number of trays (Nmin) and of the reux ratio (RRmin) are required for a given separation. All of these items can be visually demonstrated using the McCabe Thiele method. The distillation column considered is shown in Figure 2.1 with the various ows and composition indicated. We assume that the feed molar owrate F and composition z are given. If the product compositions are specied, the molar owrates of the two products D and B can be immediately calculated from the overall total molar balance and the overall component balance on the light component: F DB zF DxD BxB   z xB DF xD xB

For the moment let us assume that the pressure has been specied, so the VLE is xed. Let us also assume that the reux ratio has been specied, so the reux owrate can be calculated

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BINARY MC CABE THIELE METHOD

29

Condenser Liquid Reflux, R NT Rectifying Section LR VR Reflux Drum

NF Feed F, z, q VS 2 1 Reboiler Energy Distillate D, xD LS

Stripping Section

Bottoms B, xB

Figure 2.1

McCabe Thiele method: distillation column.

R (RR)(D). The equimolal overow assumption is usually made in the McCabeThiele method. The liquid and vapor owrates are assumed to be constant in a given section of the column. For example, the liquid owrate in the rectifying section LR is equal to the reux owrate R. From an overall balance around the top of the column, the vapor owrate in the rectifying section VR is equal to the reux plus the distillate (VR R D). This method uses an xy diagram whose coordinates are the mole fraction of the light component in the liquid x and the mole fraction of the light component in the vapor phase y. The VLE curve is plotted for the selected pressure. The 458 line is plotted. The specied product compositions xD and xB are located on the 458 line, as shown in Figure 2.2.

VLE

xD

xB x

Figure 2.2 McCabe Thiele method: locate products and VLE.

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ANALYSIS OF DISTILLATION COLUMNS

VLE

xD y ROL

Slope =

LR VR

R R+D

RR 1 + RR

xB x

Figure 2.3 McCabe Thiele method: draw operating lines.

2.2.1

Operating Lines

Next the rectifying operating line (ROL) is drawn. This is a straight line with a slope equal to the ratio of the liquid and vapor owrates in the rectifying section: Slope ROL LR R RR VR R D 1 RR

The line intersects the 458 line at the distillate composition xD, so it is easy to construct (see Fig. 2.3). The proof of this construction can be derived by looking at the top of the column, as shown in Figure 2.4.
D, xD Cut above Tray n

Overall Balance: VR = LR + D R, xD Component Balance: VR yn = LR xn+1 + D xD yn = (LR/VR) xn+1 + (D xD/VR) y = m x+b Slope = m = LR/VR Intercept on 45 line (x = y) Xint = (LR/VR) xint + D xD/VR (VR LR) xint = D xD D xint = D xD Xint = XD

LR, xn+1

VR, yn

Figure 2.4

ROL construction.

2.2

BINARY MC CABE THIELE METHOD

31

The liquid and vapor owrates in the stripping section (LS and VS) can be calculated if the thermal condition of the feed is known. Since the temperature, pressure, and composition of the feed are given, the fraction of the feed that is liquid can be calculated from an isothermal ash calculation. This fraction is dened as the variable q. Knowing q, we can calculate the liquid and vapor owrates in the stripping section. If the feed is saturated liquid, q is 1; if the feed is saturated vapor, q is 0: q LS LR F

) LS qF LR
V S LS B The stripping operating line (SOL) can be drawn. It is a straight line with slope LS/VS that interects the 458 line at the bottoms composition xB. The proof of this construction can be derived by looking at the bottom of the column, as shown in Figure 2.5. Figure 2.6 shows the two operating lines. 2.2.2 q Line

There is a relationship between the intersection point of the two operating lines and feed conditions. As shown in Figure 2.7, a straight line can be drawn from the location of the feed composition z on the 458 line to this intersection point. As we will prove below, the slope of this line is only a function of the thermal condition of the feed, which is dened in the parameter q. The slope is 2q/(1 2 q), which makes the construction of the McCabe Thiele diagram very simple: 1. Locate the three compositions on the 458 line (z, xD, xB). 2. Draw the ROL from the xD point with a slope of RR/(1 RR).
Cut above Tray n

LS, xn+1

VS, yn

Total Molar Balance: LS = VS + B Component Balance: LS xn+1 = B xB + VS yn yn = (LS/VS) xn+1 (B xB/VS) y = m x+b

LS, x1

VS, yB

Slope = m = LS/VS Intercept on 45 line (x = y)

Q
B, xB

Xint = = (LS/VS) xint B xB/VS (VS LS) xint = - B xB B xint = B xB Xint = XB

Figure 2.5

SOL construction.

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ANALYSIS OF DISTILLATION COLUMNS

VLE

xD

ROL

SOL

xB x

Figure 2.6

Operating lines.

3. Draw the q line from the z point with a slope of 2q/(1 2 q). 4. Draw the SOL from the xB point to the intersection of the q line and the ROL. The equations of the rectifying and stripping operating lines are given below in terms of the point of intersection of the two lines at yint and xint:   LR DxD ROL: yint xint VR VR   LS BxB SOL: yint xint VS VS
q-Line VLE

xD

ROL y z

SOL xB x

Figure 2.7

q line.

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BINARY MC CABE THIELE METHOD

33

Subtracting the two equations gives (VR VS )yint (LR LS )xint (DxD BxB ) The last term on the right is just Fz. Using the denition of q leads to (VR VS ) (1 q)F (LR LS ) qF Substituting these relationships into the previous equation gives (1 q)Fyint qFxint Fz     q z yint xint 1q 1q This is the equation of a straight line with slope 2q/(1 2 q). The q line is vertical for saturated liquid feed (q 1), and it is horizontal for saturated vapor feed (q 0). On the 458 line, xint is equal to yint. We can dene this as x45: (1 q)x45 qx45 z x45 z Thus the q line intersects the 458 line at the feed composition z.

2.2.3

Stepping off Trays

The number of trays is determined by moving vertically from the xB point on the 458 line to the VLE line. This is the composition of the vapor yB leaving the partial reboiler. Then we move horizontally over to the SOL. This step represents the partial reboiler. The value of x on the SOL is the composition of liquid x1 leaving tray 1 (if we are numbering from the bottom of the column up). This stepping is repeated, moving vertically to y1 and horizontally to x2. Stepping continues until we cross the intersection of the operating lines. This is the feed tray. Then the horizontal line is extended to the ROL. Continuing to step until the xD value is crossed gives the total number of trays. A numerical example is given below.

2.2.4

Effect of Parameters

We know enough now about the McCabe Thiele diagram to make several observations, which can be applied to any distillation system, not just a binary separation: 1. The farther the VLE curve is from the 458 line, the smaller the slope of the rectifying operation line. This means a smaller reux ratio and therefore lower energy consumption. A fat VLE curve corresponds to large relative volatilities and an easy separation. 2. The easier the separation, the fewer trays is takes to make a given separation. 3. The higher the product purities, the more trays it takes to make a given separation.

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ANALYSIS OF DISTILLATION COLUMNS

VLE

xD

y z

Operating lines at total reflux

xB

Figure 2.8

Minimum number of trays.

4. Increasing product purities does not have a signicant effect on the required reux ratio. 5. Increasing the liquid to vapor ratio in a section of a column increases the separation that occurs in that section. These effects apply to all types of separations and distillation columns.
Pinch Condition, N

xD

y z VLE ROL at minimum reflux ratio

xB x

Figure 2.9

Minimum reux ratio.

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BINARY MC CABE THIELE METHOD

35

2.2.5

Limiting Conditions

Before we go through a specic example, we need to discuss some of the limiting conditions. The minimum number of trays for a specied separation corresponds to total reux operation. If the column is run under total reux conditions, the distillate owrate is zero. Therefore the reux ratio is innite, and the slope of the operating lines is unity. This is the 458 line. Thus the minimum number of trays can be determined by simply stepping up between the 458 line and the VLE curve (see Fig. 2.8). The minimum reux ratio for a specied separation corresponds to having an innite number of trays. This usually occurs when the operating lines and the q line intersect exactly on the VLE curve. This is a pinch condition. It would take an innite number of trays to move past this point. This is illustrated in Figure 2.9. The minimum reux ratio is calculated from the slope of this limiting operating line.

2.2.6

Numerical Example using DISTIL

To illustrate this method on a numerical example, consider the separation of benzene and toluene. The column operates at atmospheric pressure. The feed is 100 kmol/h of saturated liquid (q 1) with composition z 0.40 mole fraction (mf) benzene. The desired product compositions are xD 0.95 and xB 0.05. The owrates of the two products are    z xB 0:40 0:05 DF 100 38:9 kmol=h 0:95 0:05 xD xB B F D 100 38:9 61:1 kmol=h The software DISTIL can perform the McCabe Thiele analysis in a very convenient way. Start the program and use the Fluid Package Manager to dene uids property package and the components using the method described in Chapter 1. We use the Wilson uids property method for the benzene/toluene system. Select the Separation Manager and Graphical Column Design on the top toolbar. The window shown at the top of Figure 2.10 opens with the Setup page tab selected, on which the uid package and components are selected. Clicking Options under the Setup column on the left opens the window shown at the bottom of Figure 2.10, on which the pressure is specied. Clicking the Conguration page tab opens the window shown at the top of Figure 2.11. We want a standard two-product column, so there is nothing to specify on this window. Clicking the Spec Entry page tab opens the window given at the bottom of Figure 2.11. This view is used to specify the feed conditions and the bottoms and distillate specication. First click the Feed button and give the feed composition (0.40 mf benzene) and the feed thermal condition (q 1). Under the Internal Flow Specications, we set a preliminary value of the reux ratio to be 2. This will be changed later after the program calculates the minimum reux ratio for us. Clicking the Distillate button opens the window shown at the top of Figure 2.12, on which the distillate purity (0.95 mf benzene) is specied. Clicking the Bottoms button opens the window shown at the bottom of Figure 2.12, on which the bottoms impurity (0.05 mf benzene) is specied. Now the yellow message at the bottom of the window tells us that the program is Ready to Calculate. 

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ANALYSIS OF DISTILLATION COLUMNS

Figure 2.10

Selecting uid package and pressure.

Click Calculate to the right of the message. The message window turns green and says Calculations OK, as shown at the top of Figure 2.13. Note that the minimum reux ratio has been calculated (RRmin 1.489). The reux ratio that has been specied is 2, which gives a ratio of the actual reux ratio to the minimum of 2/1.489 1.34. The economic optimization of a distillation column is discussed in Chapter 4. Typical values of the RR to RRmin ratio are around 1.2, so our initial guess is a little high. Clicking the Summary page tab gives the window shown at the bottom of Figure 2.13. The DISTIL program uses the stage numbering convention of starting at the top. The reux drum is stage 0, and the partial reboiler is the last stage. For the specied reux ratio and product purities, 13 stages plus a partial reboiler are required, with the feed

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BINARY MC CABE THIELE METHOD

37

Figure 2.11

Selecting conguration, feed conditions, and reux ratio.

fed on stage 7. If the reux ratio is reduced to 1.2 RRmin [RR (1.2)(1.389) 1.67] and the calculations are redone, the number of stages increases to 17 with feed introduced on stage 9. Various types of plots can be generated by clicking the Plots page tab and selecting one of the three types of plots listed under Plot Generation. Figure 2.14 gives the McCabe Thiele xy diagram with the operating lines, the q line, the VLE curve, and the stages stepped off. Some of the features of this plot can be modied by right-clicking the plot and selecting Chart Control. Figure 2.15 gives the temperature prole and the benzene liquid and vapor mole fraction on all stages.

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ANALYSIS OF DISTILLATION COLUMNS

Figure 2.12

Specifying distillate and bottoms.

The DISTIL program can also be used to design columns in ternary systems, as we illustrate later in this chapter.

2.3

APPROXIMATE MULTICOMPONENT METHODS

Many years before the availability of computers for rigorous analysis, several simple approximate methods were developed for analyzing multicomponent systems. These methods are still quite useful for getting quick estimates of the size of a column

2.3

APPROXIMATE MULTICOMPONENT METHODS

39

Figure 2.13

Summary of calculated results.

(number of trays) and the energy consumption (reux ratios and the corresponding vapor boilup and reboiler heat input). 2.3.1 Fenske Equation for Minimum Number of Trays

The minimum number of trays corresponds to total reux operation (an innite reux ratio). The Fenske equation relates the compositions at the two ends of a column to the number of stages in the column under this limiting condition: h  i xD,LK log xD,HK xB,HK xB,LK log (aLK,HK )

Nmin 1

where Nmin is the minimum number of stages, xD,LK is the mole fraction of the light-key

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ANALYSIS OF DISTILLATION COLUMNS

Figure 2.14

xy diagram.

component at the top of the column, xD,HK is the mole fraction of the heavy-key component at the top of the column, xB,HK is the mole fraction of the heavy-key component at the bottom of the column, xB,LK is the mole fraction of the light-key component at the bottom of the column, and aLK,HK is the relative volatility between the LK and HK components.

Figure 2.15

Temperature and composition proles.

2.4

ANALYSIS OF TERNARY SYSTEMS USING DISTIL

41

This equation is applicable to multicomponent systems, but it assumes a constant relative volatility between the two components considered. An example of the use of the Fenske equation is given in Chapter 4. Results of this approximate method will be compared with the results found from rigorous simulation. 2.3.2 Underwood Equations for Minimum Reux Ratio

The Underwood equations can be used to calculate the minimum reux ratio in a multicomponent system if the relative volatilities of the components are constant. There are two equations:
NC X a jz j 1q a u j1 j NC X a j xDj 1 RRmin a u j1 j

The feed composition zj (mole fractions j 1, NC ), the desired distillate composition xDj ( j 1, NC ), and the feed thermal condition q are specied. The relative volatilities aj ( j 1, NC ) of the multicomponent mixture are known. The rst equation contains one unknown parameter u. However, expanding the summation of NC terms and multiplying through by all the denominator terms (aj 2 u) give a polynomial in u whose order is NC; therefore there are NC roots of this polynomial. One of these roots lies between the two relative volatility values aLK and aHK. This is found using some iterative solution method. It is substituted into the second equation, which can then be solved explicitly for the minimum reux ratio. An example of the use of the Underwood equations is given in Chapter 4. The results of this approximate method will be compared with the results found from rigorous simulation. 2.4 ANALYSIS OF TERNARY SYSTEMS USING DISTIL

The graphical column design feature of DISTIL can also be used for ternary systems. As an example, consider a column operating at 4 atm with a feed that is 30 mol% n-butane, 30 mol% n-pentane, and 40 mol% n-hexane. The Unifac uids package is set up, the components are specied and the pressure is set (see the top of Fig. 2.16). The feed composition is specied on the Spec Entry page tap, and a reux ratio of 2 is specied, as shown in the lower picture in Figure 2.16. Three compositions of the two product streams can be specied (see Fig. 2.17). We set the C4 in the bottoms at 1 mol% and the C5 in the distillate at 1 mol%. The remaining specication is the small amount of C6 in the distillate (0.001 mol%). The required column conguration (number of stages and feed tray) are given on the Summary page tab, shown in Figure 2.18.

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ANALYSIS OF DISTILLATION COLUMNS

Figure 2.16

Ternary analysis using DISTIL; setting feed and reux ratio.

Detailed results are plotted on the ternary diagram given in Figure 2.19. The feed, distillate, and bottoms points have been labeled. They lie on a straight line (the heavy dashed line), as required by the overall component balances. The liquid compositions on all the trays in the stripping and rectifying trays are shown. Residue curves are added by clicking any point on the diagram. Note that a residue curve passes through (or near) the bottoms and distillate point, so the specied product compositions should yield a feasible design. Composition proles (Fig. 2.20) and temperature proles can also be plotted.

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ANALYSIS OF TERNARY SYSTEMS USING DISTIL

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Figure 2.17

Specifying distillate and bottoms composition.

Figure 2.18

Column conguration.

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ANALYSIS OF DISTILLATION COLUMNS

Figure 2.19

Ternary plot.

Figure 2.20

Composition proles.

The value of these graphical ternary diagrams will be demonstrated more thoroughly in Chapter 5.

2.5

CONCLUSION

Several methods for analyzing distillation columns have been presented in this chapter. Graphical methods provide valuable insight into how various parameters affect separations in distillation.