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J. D. Seader, Ernest J. Henley - Separation Process Principles 2nd Edition-Wiley (2005) - 376-395
J. D. Seader, Ernest J. Henley - Separation Process Principles 2nd Edition-Wiley (2005) - 376-395
9.1 FENSKE-UNDERWOOD-GILLILAND
METHOD
A n algorithm for the empirical Fenske-Underwood-Gilliland Number of Specifications
method, named after the authors of the three important steps Split of light key component 1
in the procedure, is shown in Figure 9.1 for a simple distilla- Split of heavy key component 1
tion column of the type shown in Figure 9.3. The column can Feed-stage location 1
be equipped with a partial or total condenser. From Reflux ratio (as multiple of 1
Table 5.4, the number of degrees of freedom with a total minimum-reflux ratio)
+ +
condenser is 2N C 9. In this case, the following vari- Reflux temperature
ables are generally specified with the partial reboiler counted Adiabatic reflux divider
as a theoretical stage: Pressure of total condenser
Pressure at reflux divider
Number of Specifications
Feed flow rate 1 Similar specifications can be written for columns with a
Feed mole fractions C- 1 partial condenser.
Feed temperature' 1
Feed pressure' 1
Adiabatic stages (excluding reboiler) N- 1 ' Feed temperature and pressure may correspond to known stream
Stage pressures (including reboiler) N conditions leaving the previous piece of equipment.
9.1 Fenske-Underwood-Gilliland Method 345
Start
Specified
Specify splits of
t w o key components
I Estimate splits
of nonkeey components I
Determine column pressure
and Of /
Bubble-pointldew-point calculations
Repeat only
i f estimated Adiabatic flash procedure
and calculated
I splits of 4
J
nbnkey
components Calculate m i n i m u m
differ considerably theoretical stages equation
1 Calculate splits
of nonkey components Fenske equation
Calculate m i n i m u m
reflux ratio
I Underwood equations
Calculate actual
theoretical stages Gilliland correlation
for specified reflux
ratio > m i n i m u m value
1 Calculate feed
stage location
1 Kirkbride equation
Calculate condenser
and reboiler duties
1 Energy-balance equations
Y
Exit
Figure 9.1 Algorithm for multicomponent
distillation by FUG method.
of n-butane in the isobutane recycle, and isobutane in the Figure 9.2 Separation specifications for alkylation-reactor
n-butane product, are specified, isobutane is the light key and effluent.
346 Chapter 9 Approximate Methods for Multicomponent, Multistage Separations
Table 9.1 Specificationsof Key Component Splits and Preliminary Estimation of Nonkey Component Splits for Alkylation
Reactor Effluent
Case 2, Debutanizer Case 3, Debutanizer
Case 1, Deisobutanizer Column First Column First
Column First, lbmol/h (iCs is HK), lbmolh (C6is HK), lbmoVh
Feed,
Component lbmolh Distillate Bottoms Distillate Bottoms Distillate Bottoms
c3 30.7 (30.7) (0) (30.7) (0) (30.7) (0)
iC4 380 368" 12b (380.0) (0) (380.0) (0)
nC4 473 25b 44ga 467a 6b 467a 6b
iCs 36 (0) (36) 13~ 23" (13) (23)
nCs 15 (0) (15) (1) (14) (1) (14)
c6 23 (0) (23) (0) (23) 0.01~ 22.99a
c7 39.1 (0) (39.1) (0) (39.1) (0) (39.1)
cs 272.2 (0) (272.2) (0) (272.2) (0) (272.2)
c
g 31.0 (0) (3 1.O) (0) (31.0) (0) (31.O)
1,300.0 423.7 876.3 891.7 408.3 891.71 408.29
n-butane is the heavy key. These two keys are adjacent in with preliminary estimates of the separation of nonkey
order of volatility. Because a fairly sharp separation between components shown in parentheses. This separation has
these two keys is indicated and the nonkey components are been treated by Bachelor [4]. Because nC4 and C8 comprise
not close in volatility to the butanes, as a preliminary estimate 82.2 mol% of the feed and differ widely in volatility, the
we can assume the separation of the nonkey components to temperature difference between distillate and bottoms is
be perfect. likely to be large. Furthermore, the light key split is rather
Alternatively, in Case 2, if the debutanizer is placed first sharp, but the heavy key split is not. As will be shown later,
in the sequence, specifications in Figure 9.2 require that this case provides a relatively severe test of the empirical
n-butane be selected as the light key. However, selection of design procedure discussed in this section.
the heavy key is uncertain because no recovery or purity is
specified for any component less volatile than n-butane.
Possible heavy-key components for the debutanizer are iC5,
nC5, or C6.The simplest procedure is to select iC5 so that the
two keys are again adjacent. C ' )
For example, suppose we specify that 13 lbmolh of iC5 Distillate
in the feed is allowed to appear in the distillate. Because the
A
7
Component Ibmollh
*
split of iC5 is then not sharp and nC5 is close in vola~ilityto iC4 (12)
iC5, it is probable that the quantity of nC5 in the distillate Feed -- Debutanizer
nC4
iC5
442
13
will not be negligible. A preliminary estimate of the distrib- Component Ibmollh
nC5 -(1)
utions of the nonkey components for Case 2 is given in iC4 12 (468)
nC4 (LK) 448
Table 9.1. Although iC4 may also distribute, a preliminary iC5 (HK) 36
estimate of zero is made for it in the bottoms. 4 15
C6 23
Finally, in Case 3, we select C6 as the heavy key for the c7 39.1
debutanizer at a specified rate of 0.01 lbmol/h in the distil- C8 272.2
Cs -31.0
late, as shown in Table 9. l. Now iC5 and nCs will distribute 876.3 Bottoms \
between the distillate and bottoms in amounts to be deter- Component Ibmollh
mined; as a preliminary estimate, we assume the same distri- nC4 6
bution as in Case 2. iC5 23
nC5 (14)
In practice, the deisobutanizer is usually placed first in the c6 (23)
sequence. In Table 9.1, the bottoms for Case 1 then becomes c7 (39.1)
C8 (272.2)
the feed to the debutanizer, for which, if nC4 and iC5 are C9 -(31.O)
selected as the key components, component-separation spec- (408.3)
ifications for the debutanizer are as indicated in Figure 9.3 Figure 9.3 Specifications for debutanizer.
9.1 Fenske-Underwood-Gilliland Method 347
EXAMPLE 9.1
Determine column operating pressures and type of condenser for
the debutanizer of Figure 9.3.
SOLUTION
Using the estimated distillate composition in Figure 9.3, we
compute the distillate bubble-point pressure at 120°F (48.9"C)
iteratively from (4-12) in a manner similar to Example 4.2. This
procedure gives 79 psia as the reflux-drum pressure. Thus, a total
condenser is indicated. Allowing a 2-psi condenser pressure Total reboiler
+
drop, column top pressure is (79 2) = 81 psia; and allowing a Figure 9.4 Distillation column operation at total reflux.
5-psi pressure drop through the column, the bottoms pressure is
(81 + 5 ) = 86 psia. Assume a feed-tray pressure midway between
the column top and bottom pressures or 83.5 psia. facilitate derivation of the Fenske equation, stages are num-
Bachelor [4]sets column pressure at 80 psia throughout. He ob- bered from the bottom up. All vapor leaving stage N is con-
tains a distillate temperature of 123°F. A bubble-point calculation densed and returned to stage N as reflux. All liquid leaving
for the bottoms composition at 80 psia gives 340°F. This tempera- stage 1 is vaporized and returned to stage 1 as boilup. For
ture is sufficiently low to prevent decomposition. steady-state operation within the column, heat input to the re-
Feed to the debutanizer is presumably bottoms from a deisobu- boiler and heat output from the condenser are made equal (as-
tanizer operating at a pressure of perhaps 100 psia or more. Results suming no heat losses). Then, by a material balance, vapor
of an adiabatic flash of this feed, by the procedure of Section 4.4, to
and liquid streams passing between any pair of stages have
80 psia are given by Bachelor [4]as follows.
equal flow rates and compositions, for example, V N - i = LN
Pound-Moles per Hour and y I , ~ - l= X , , N However, molar vapor and liquid flow
rates will change from stage to stage unless the assumption of
Component Vapor Feed Liquid Feed
constant molar overflow is valid.
iC4 3.3 8.7 Derivation of an exact equation for the minimum number
nC4 101.5 346.5 of equilibrium stages involves only the definition of the
iC5 4.6 31.4
K-value and the mole-fraction equality between stages. For
nCs 1.6 13.4 component i at stage 1 in Figure 9.4,
nC6 1.3 21.7
nC7 1.2 37.9 yi, 1 = Ki, lxi,1 (9-1)
nCs 3.2 269.0
nC9 - 0.2 -30.8 But for passing streams
116.9 759.4
Yi.1 = xi,^ (9-2)
The temperature of the ilashed feed is 180°F (82.2"C).From above,
the feed-mole-fraction vaporized is (116.91876.3)= 0.1334. Combining these two equations,
Similarly, for component j, The Fenske equation is quite reliable except when the rel-
ative volatility varies appreciably over the column, and/or
Yj,N = K ~ , KNj , ~ - l. . . K j , 2 K j , l ~ j , l (9-7) when the mixture forms nonideal liquid solutions. In those
Combining (9-6) and (9-7), we find that cases, if the Fenske equation is applied with (9-13), it should
be done with great caution, and should be followed by rigor-
2 = a N a N - 1 . . . a2al (9-8) ous calculations of the type in Chapter 10.
Y j ,N
or
(9-9)
For the debutanizer shown in Figure 9.3 and considered in Exam-
ple 9.1, estimate the minimum equilibrium stages by the Fenske
where ak = K l , k / K J , kthe
, relative volatility between com-
equation. Assume uniform operating pressure of 80 psia (552 kPa)
ponents i and j. Equation (9-9) relates the relative enrich- thmughout and utilize the ideal K-values given by Bachelor [41 as
ments of any two components i and j over a cascade of N the- plotted in Figure 9.5.
oretical stages
- to the stage relative volatilities between the
two components. Although (9-9) is exact, it is rarely used in
practice because the conditions of each stage must be known
SOLUTION
I
to compute the set of relative volatilities. However, if the rel-
ative volatility is assumed constant, (9-9) simplifies to
The two key components are n-butane and isopentane. Distillate
and bottoms conditions based on the estimated product distribu-
11
tions for nonkey components in Figure 9.3 are i
iC4
nC4 (LK)
, 10g{[(xi,~+l)/~i,l~[~j,l/(~j,~+l)]}
- iC5 (HK)
nun - (9-11)
log ai,j nC5
Equation (9-11) is extremely useful. It is referred to as nC6
the Fenske equation [5].When i = the light key (LK) and nC7
j = the heavy key (HK), the minimum number of equilib- ncs
rium stages is influenced by the nonkey components only by nC9
their effect (if any) on the value of the relative volatility
between the key components.
Equation (9-11) permits a rapid estimation of minimum
equilibrium stages. A more convenient form of (9-11) is ob-
tained by replacing the product of the mole-fraction ratios by
the equivalent product of mole-distribution ratios in terms of
component distillate and bottoms flow rates d and b, respec-
t i ~ e land
~ , by
~ replacing the relative volatility by a geomet-
ric mean of the top-stage and bottom-stage values. Thus,
From Figure 9.5, at 123"F, the assumed top-stage temperature is Based on N,,, = 8.88 stages from Example 9.2 and the above
geometric-mean relative volatilities, values of ( c Y ~ , ~ )are
? com-
( C I , C . + , ~=
C ~1.0310.495
)N = 2.08 puted relative to isopentane as tabulated below.
At 340°F, the assumed bottom-stage temperature is From (9-15), using the feed rate specifications in Figure 9.3 for
5, the distribution of nonkey iC4 is
(%c4,ic5)l= 5.2013.60 = 1.44
From (9-131,
a, = [(2.08)(1.44)]'/~= 1.73
Noting that (di/dj) = ( x D , / x ~ , )and (bi/bj) = (xBi/xBj),(9-12) Results of similar calculations for the other nonkey components are
becomes included in the following table.
log[(0.9445/0.0278)(0.0563/0.0147)]
Nmin= = 8.88 stages Component ( C W ~ , ~ C ~ ) { ~ ~ " di bi
log 1.73
-
SOLUTION
All nonkey relative volatilities are calculated relative to isopentane
using the K-values of Figure 9.5.
ai,iC5
Component 123OF 340°F Geometric Mean Figure 9.6 Location of pinch-point zones at minimum reflux:
iC4 2.81 1.60 2.12 (a) binary system; (b) binary system, nonideal conditions giving
nCs 0.737 0.819 0.777 point of tangency; (c) multicomponent system, all components
nC6 0.303 0.500 0.389 distributed (Class 1); (d) multicomponent system, not all LLK
nC7 0.123 0.278 0.185 and HHK distributing (Class 2); (e) multicomponent system, all
nCs 0.0454 0.167 0.0870 LLK, if any, distributing, but not all HHK distributing (Class 2).
nC9 0.0198 0.108 0.0463 (LLK = lighter than light key; HHK = heavier than heavy key.)
350 Chapter 9 Approximate Methods for Multicomponent, Mclltistage Separations
Similarly, for the stripping section, Underwood defined @' by With these two roots, (9-29) is written twice and solved
simultaneously to yield (R,),, and the unknown value of
x,c,,J. The solution must, of course, satisfy the condition
= 1.0.
where R k = L I , / B and the prime refers to conditions in the With the internal reflux ratio (R,),, known, the external
stripping-section pinch-point zone. In his derivation, Under- reflux ratio is computed by enthalpy balance with (9-23).
wood assumed that relative volatilities are constant in the This requires a knowledge of the rectifying-section pinch-
region between the two pinch-point zones and that (R,)- point compositions. Underwood [9]shows that
and (Rk),, are related by the assumption of constant molar
overflow in the region between the feed entry and the
rectifying-section pinch point and in the region between the
feed entry and the stripping-section pinch point. Hence, with yi,, given by (9-17). The value of 0 to be used in
(L',)min - (Lcolmin = q F (9-26) (9-30) is the root of (9-29) satisfying the inequality
With these two critical assumptions, Underwood showed
that at least one common root 0 (where 0 = @ = @') exists
where HNK refers to the heaviest nonkey component in the
between (9-24) and (9-25). distillate at minimum reflux. This root is equal to
Equation (9-24) is analogous to the following equation
L,/[V,(Kr),] in (9-27).With wide-boiling feeds, the ex-
derived from (9-19),and the relation ai,r = Ki / K r ,
ternal reflux can be significantly higher than the internal re-
flux. Bachelor [4]cites a case where the external reflux rate
is 55% greater than the internal reflux.
352 Chapter 9 Approximate Methods for Multicomponent, Multistage Separations
where, in this case, 0 is the root of (9-29) satisfying the nc; 0.0354 0.0362
inequality 1.OOOO
The q for the feed is assumed to be the mole fraction of liquid in
where HNK refers to the heaviest nonkey in the bottoms the flashed feed. From Example 9.1, q = 1 - 0.1334 = 0.8666.
Applying (9-28), we have
product at minimum reflux.
Because of their relative simplicity, the Underwood 2.43(0.0137) 1.93(0.5113) l.OO(0.0411)
minimum-reflux equations for Class 2 separations are widely 2.43 - 0 + 1.93-0 + 1.00-0
used, but too often without examining the possibility of non-
key distribution. In addition, the assumption is frequently
made that ( R , ) ~ , equals the external reflux ratio. When the
assumptions of constant relative volatility and constant molar
overflow in the regions between the two pinch-point zones Solving this equation by a bounded-Newton method for two roots 4
are not valid, values of the minimum-reflux ratio computed of 0 that satisfy !i
from the Underwood equations for Class 2 separations can
be appreciably in error because of the sensitivity of (9-28) to
the value of q, as will be shown in Example 9.5. When the
Underwood assumptions appear to be valid and a negative
minimum-refluxratio is computed, this may be interpreted to 0, = 1.04504 and O2 = 0.78014. Because distillate rates for nC4 !
mean that a rectifying section is not required to obtain the and iC5 are specified (442 and 13 Ibmoyh, respectively), the fol-
specified separation. The Underwood equations show that lowing form of (9-29) is preferred: I
EXAMPLE 9.5
Repeat Example 9.4 assuming a Class 2 separation and utilizing
the corresponding Underwood equations. Check the validity of the
Underwood assumptions. Also calculate the external reflux ratio.
Stripping pinch
173°F The temperature of the rectifying-section pinch point is obtained
from either a bubble-point temperature calculation on x i , , or a
Figure 9.8 Pinch-point region conditions for Example 9.5 from
dew-point temperature calculation on y i , , . The result is 126°F.
computations by Bachelor.
Similarly, the liquid-distillate temperature (bubble point) and the
[From J.B. Bachelor, Petroleum Refine6 36(6), 161-170 (1957).]
temperature of the vapor leaving the top stage (dew point) are both
computed to be approximately 123°F. Because rectifying-section
true value of 298 is the invalidity of the assumption of constant pinch-point temperature and distillate temperatures are very close,
molar overflow. Bachelor computed the pinch-point region flow it is expected that (R,),in and (R,,,ii,)e,te,,,,l will be almost iden-
rates and temperatures shown in Figure 9.8. The average tempera- tical. Bachelor [4] obtained a value of 292 Ibmolih for the external-
ture of the region between the two pinch regions is 152°F (66.7"C), reflux rate, compared to 298 lbmolih for the internal reflux rate.
which is appreciably lower than the flashed-feed temperature. The
relatively hot feed causes additional vaporization across the feed
zone. The effective value of q in the region between the pinch points Gilliland Correlation for Actual Reflux Ratio
is obtained from (7-18): and Theoretical Stages
To achieve a specified separation between two key compo-
nents, the reflux ratio and the number of theoretical stages
This is considerably lower than the value of 0.8666 for q based on must be greater than their minimum values. The actual reflux
the flashed-feed condition. On the other hand, the value of (YLK,HK ratio is generally established by economic considerations at
at 152°F (66.7"C) is not much different from the value at 180°F
some multiple of minimum reflux. The corresponding num-
(82.2"C). If this example is repeated using q equal to 0.685, the re-
ber of theoretical stages is then determined by suitable ana-
sulting value of (L,),;, is 287.3 lbmolh, which is only 3.6%
lower than the true value of 298. Unfortunately, in practice, this lytical or graphical methods or, as discussed in this section,
corrected procedure cannot be applied because the true value of q by an empirical equation. However, there is no reason why
cannot be readily determined. the number of theoretical stages cannot be specified as a
To compute the external-reflux ratio from (9-23), rectifying multiple of minimum stages and the corresponding actual re-
pinch-point compositions must be calculated from (9-30) and flux computed by the same empirical relationship. As shown
(9-17). The root of 0 to be used in (9-30) is obtained from the in Figure 9.9, from studies by Fair and Bolles [12], the opti-
version of (9-29) used above. Thus, mal value of RIR,, is approximately 1.05. However, near-
2.43(12) 1.93(442) l.OO(13) optimal conditions extend over a relatively broad range of
2.43-0+ '1.93-0
+- --
1.00-0 mainly larger values of RIR,,. In practice, superfractiona-
tors requiring a large number of stages are frequently
designed for a value of RIR,, of approximately 1.10, while
where 0.765 > 0 > 0. Solving, 0 = 0.5803. Liquid pinch-point separations requiring a small number of stages are designed
compositions are obtained from the following form of (9-30): for a value of RIR,, of approximately 1.50. For interme-
diate cases, a commonly used rule of thumb is R/Rmin equal
to 1.30.
The number of equilibrium stages required for the sepa-
with (L,),;, = 219.8 lbmolh. ration of a binary mixture assuming constant relative volatil-
For iC4, ity and Constant molar overflow depends on Zi,F, Xi,& x i , ~ q,
,
R, and a. From (9-ll), for a binary mixture, Nfi, depends
on x i , D , and a, while R, depends on Z ~ , RX ~ , D ,q, and a.
From a combination of (9-17) and (9-18), Accordingly, a number of investigators have assumed
empirical correlations of the form
354 Chapter 9 Approximate Methods for Multicomponent, Multistage Separations
-
3. Pressure: vacuum to 600 psig 6. Nmin:3.4 to 60.3
- -
The line drawn through the data represents the equation
developed by Molokanov et al. [17]:
- -
\
\ -40°F
- - (9-34)
\
-
\
4 -
where
X=
R - Rfin
R+1
This equation satisfies the end points (Y = 0, X = 1) and
0 I I I I I
1.0 1.1 1.2 1.3 1.4 1.5 (Y = 1, X = 0). At a value of R/R,, near the optimum
RIRmin of 1.3, Figure 9.10 predicts an optimal ratio for N/N,, of
Figure 9.9 Effect of reflux ratio on cost. approximatel$2. The value of N includes one stage for a par-
[From J.R. Fair and W.L. Bolles, Chem. Eng., 75(9), 156-178 (1968).] tial reboiler and one stage for a partial condenser, if any.
The Gilliland correlation is very useful for preliminary
exploration of design variables. Although it was never in-
Furthermore, they have assumed that such a correlation tended for final design, the Gilliland correlation was used,
might exist for nearly ideal multicomponent systems even before the applicability of digital computers, to design many
though additional feed composition variables and nonkey distillation columns for multicomponent separations without
relative volatilities also influence the value of R,,. benefit of accurate stage-by-stage calculations. In Fig-
The most successful and simplest empirical correlation of ure 9.11, a replot of the correlation in linear coordinates
this type is the one developed by Gilliland [13] and slightly shows that a small initial increase in R above R ~ causes
, a
modified in a later version by Robinson and Gilliland [14]. large decrease in N, but further changes in R have a much
The correlation is shown in Figure 9.10, where the three sets smaller effect on N. The knee in the curve of Figure 9.11 cor-
of data points, which are based on accurate calculations, are responds closely to the optimal value of R/R,, in Figure 9.9.
Robinson and Gilliland [14] state that a more accurate
correlation should utilize a parameter involving the feed con-
dition q. This effect is shown in Figure 9.12 using data points
for the sharp separation of benzene-toluene mixtures from
Guerreri [18]. The data, which cover feed conditions ranging
0.1 1 I
.01 0.1 1
R - Rmin Feed-Stage Location
R t 1
Implicit in the application of the Gilliland correlation is the
Figure 9.12 Effect of feed condition on Gilliland correlation.
specification that the theoretical stages be distributed opti-
[From G. Guerreri, Hydrocarbon Processing, 48(8), 137-142 (1969).]
mally between the rectifying and stripping sections. As sug-
gested by Brown and Martin [15],the optimal feed stage can
from subcooled liquid to superheated vapor (q equals 1.3 to be located by assuming that the ratio of stages above the feed
-0.7), show a trend toward decreasing theoretical-stage re- to stages below the feed is the same as the ratio determined
quirements with increasing feed vaporization. The Gilliland by simply applying the Fenske equation to the separate sec-
correlation appears to be conservative for feeds having low tions at total reflux conditions to give
values of q. Donne11 and Cooper [19]state that this effect of NR (N~)min
-
q is important only when the a between the key components NS (N~)min
is high or when the feed is low in volatile components.
A serious problem with the Gilliland correlation can occur
when stripping is much more important than rectification.
For example, Oliver [20] considers a fictitious binary case
with specifications of Z F = 0.05, x~ = 0.40, x~ = 0.001, Unfortunately, (9-35) is not reliable except for fairly sym-
q = 1, a = 5, R/ Rmi, = 1.20, and constant molar overflow. metrical feeds and separations.
By exact calculations, N = 15.7. From the Fenske equation, A reasonably good approximation of optimal feed-stage
Nin = 4.04. From the Underwood equation, R ~ =, 1.21. location can be made by employing the empirical equation
From (9-32)for the Gilliland correlation, N = 10.3. This is of Kirkbride [22]:
34% lower than the exact value. This limitation, which is
caused by ignoring boilup, is discussed further by Strangio
and Treybal [21],who present a more accurate, but far more
tedious, method for such cases. An extreme test of both these equations is provided by the
fictitious binary-mixture problem of Oliver [20]cited in the
previous section. Exact calculations by Oliver and calcula-
tions using (9-35) and (9-36)give the following results:
Use the Gilliland correlation to estimate the theoretical-stage Method NRINs
requirements for the debutanizer of Examples 9.1, 9.2, and 9.5 for
an external reflux of 379.6 lbmolk (30% greater than the exact Exact 0.08276
value of the minimum-reflux rate from Bachelor). Kirkbride (9-34) 0.1971
Fenske ratio (9-33) 0.6408
SOLUTION Although the result from the Kirkbride equation is not very
F~~~ the examples cited, values o f ~ , i , and [ ( R - R,~,)I(R + 111 satisfactory, the result from the Fenske ratio method is much
are obtained using a distillate rate from Example 9.5 of 469.56 worse.
lbmolrh. Thus, R = 379.61469.56 = 0.808. With N f i , = 8.88,
and
From (9-34), Use the Kirkbride equation to determine the feed-stage location for
N - Nmin - 1 - exp
-- [( + )
1 54.4(0.182) (0.182 - 1 )] the debutanizer of Example 9.1, assuming an equilibrium-stage
N+1 +
11 117.2(0.182) 0.182°.5 requirement of 18.27.
= 0.476
N=
+
8.88 0.476
= 17.85
SOLUTION
1 - 0.476 Assume that the product distribution computed in Example 9.3 for
N - 1 = 16.85 total-reflux conditions is a good approximation to the distillate and
356 Chapter 9 Approximate Methods for Multicomponent,Mu llistage Separations
-
to the number of equilibrium stages required. These approx-
imate procedures are called group methods because they
provide only an overall treatment of the stages in the cascade
without considering detailed changes in temperature, flow L ~ + l
Feed liquid
70°C (158°F)
+
A
Rich gas
rates, and composition in the individual stages. In this sec- 29 psia (200 kPa)
tion, single cascades used for absorption, stripping, and
liquid-liquid extraction are considered. so2 10.0
1,3-Butadiene (83) 8.0
Kremser [I] originated the group method. He derived 1.2-Butadiene (B2) 2.0
Butadiene sulfone (BS) -
100.0
overall species material balances for a multistage counter-
LNtl= 120.0
current absorber. Subsequent articles by Souders and Brown
[24] Horton and Franklin [25] and Edmister [26] improved - 1
30 psia (207 kPa)
the method. The Kremser equations are derived and applied V, Gas stripping agent
Pure N2 Stripped liquid
to absorption in Section 5.4. These equations are illustrated 70°C (158°F)
for strippers and extractors here. Another treatment by Smith <0.05 mol % SO,
and Brinkley [27] emphasizes liquid-liquid separations. <0.5 m o l % (83 + 82)
Figure 9.15 Specifications for stripper of Example 9.8.
Strippers
The vapor entering a stripper is often steam or an inert gas. given by
When the stripping agent contains none of the species in the
feed liquid, is not present in the entering liquid, and is not ab-
sorbed or condensed in the stripper, the only direction of mass
(
Pis = exp 17.30 -
T +459.67
where Pis is in pounds force per square inch and T is in degrees
transfer is from the liquid to the gas phase. Then, only values Fahrenheit. The liquid enthalpy of BS is
of the effective stripping factor, S, as defined by (5-51), are
needed to apply the group method via (5-49) and (5-50). The
equations for strippers are analogous to those for absorbers. where ( h L ) ~iss in British thermal units per pound-mole and T is in
For optimal stripping, temperatures should be high and degrees Fahrenheit.
pressures low. However, temperatures should not be so high The entering flow rate of the stripping agent Vo is not specified.
as to cause decomposition, and vacuum should be used only The minimum rate at infinite stages can be computed from (9-37),
provided that a key component is selected. Suppose we choose B2,
if necessary. The minimum stripping-agent flow rate, for a
which is the heaviest component to be stripped to a specified extent.
specified value of +s for a key component K corresponding
At 70°C, the vapor pressure of B2 is 90.4 psia. From Raoult's law
to an infinite number of stages, can be estimated from an at 30 psia total pressure,
equation obtained from (5-50) with N = CQ,
and 30 psia, L = LN+l = 120 lbmolth, and V = Vo equal to a Entering feed Extract
V N + ~ U. N
t
+ ~
1. I Raffinate
LN,[N
.
Figure 9.16 Countercurrent, liquid-liquid extraction cascade.
From Figure 5.9,
( $ s ) B ~ = 0.04
factol; E, is used, where
Thus,
The reciprocal of E is
This is considerably above the specification of 0.05. Therefore,
repeat the calculations with, say, ($s)B2 = 0.09 and continue to
repeat until the specified value of ($s)B2+B3 is obtained. In this
manner, calculations for various numbers of theoretical stages are The working equations for each component are
carried out with converged results as shown.
Fraction Not Stripped vi = V N + I @ U+lo(l -+E) (9-41)
1~ = 10 + V N +-~ 211 (9-42)
where
These results show that the specification on SO2 is also met for
all four values of N.
For the Kremser approximation, values of Ei and Uiin (9-39)
Liquid-Liquid Extraction and (9-40) are based on the feed and solvent at entering con-
ditions. However, in liquid-liquid extraction, values of V, L,
A schematic representation of a countercurrent extraction and KD may change considerably from stage to stage. There-
cascade is shown in Figure 9.16, with stages numbered from fore a better approximation is desirable. This is achieved,
the top down and solvent VN+1 entering at the bottom4 with reference to Figure 9.16, by the following relations due
The group method of calculation can be applied, with the to Horton and Franklin [25] and Edmister [26],which use
equations written by analogy to absorbers. In place of the average values of Ei and U, based on estimates of values of
K-value, the distribution coefficient is used: V, L, and KD at each end of the cascade. These equations are
applied in Example 9.9.
MC 40.2 -?
-2
0.8
FA 0.005
DMA 2.2 0.7
W 0.003
0.6
DMA 20 20
Fmm (9-44), (9-43), (9-41), and (9-42), we have
DMF 400 400
W 3,560 25 3,560 25 Pounds per Hour
MC - 0 9,973 88
- 9,885 Component +E +U Raffinate, llo Extract, vl
4,000 10,000 3,670 10,330
FA 0.9870 19.7 0.3
DMA 0.0 - 0.0 20.0
From (9-45) through (9-49), we have
DMF 0.000374 0.422 1.3 400.7
The calculated total flow rates Llo and V1 are almost exactly
equal to the assumed rates. Therefore, an additional iteration is not
necessary. The degree of extraction of DMF is very high. It would
be worthwhile to calculate additional cases with less solvent andlor
From (9-39), (9-40), (9-48), and (9-49). assuming a mass fraction of
fewer equilibrium stages.
0.09 for DMF in LI in order to obtain (KD)DMFfor stage 1, we have
I 360 Chapter 9 Approximate Methods for Multicomponent, Multistage Separations
SUMMARY
1. The Fenske-Underwood-Gilliland (FUG) method for simple 3. Estimates of the distribution of nonkey components and the
distillation of ideal and nearly ideal multicomponent mixtures feed-stage location can be made with the Fenske and Kirkbride
is useful for making preliminary estimates of stage and reflux equations, respectively.
requirements. 4. The Underwood equations are more restrictive than the Fenske
2. Based on a specified split of two key components in the feed equation and must be used with care and caution.
mixture, the theoretical Fenske equation is used to determine the 5. The Kremser group method can be applied to simple strippers
minimum number of equilibrium stages at total reflux. The theoret- and liquid-liquid extractors to make approximate estimates of
ical Underwood equations are used to determine the minimum- component recoveries for specified values of entering flow rates
reflux ratio for an infinite number of stages. The empirical Gilliland and number of equilibrium stages.
correlation relates the minimum stages and minimum reflux ratio to
the actual reflux ralio and the actual number of equilibrium stages.
I REFERENCES
I 1. KREMSER,
A,, Natl. Petroleum News, 22(21), 43-49 (1930). 16. VANWINKLE,
M., and W.G. TODD,Chem. Eng., 78(21), 136-148
I
2. EDMISTER,
W.C., AIChE J., 3, 165-171 (1957). (1971).
I
3. KOBE,K.A., and J.J. MCKETTA, JR., Eds, Advances in Petroleum 17. MOLOKANOV, Y.K., T.P. KORABLINA, N.I. MAZURINA,
and G.A.
Chemistry and Refining, Vol. 2, Interscience, New York, 315-355 (1959). NIKIFOROV,
Int. Chem. Eng., 12(2), 209-212 (1972).
I
4. BACHELOR,
J.B., Petroleum Refiner; 36(6), 161-170 (1957). 18. GUERRERI,
G., Hydrocarbon Processing, 48(8), 137-142 (1969).
I
I 5. FENSKE,
M.R., Ind. Eng. Chem., 24,482485 (1932). 19. DONNELL,
J.W., and C.M. COOPER,
Chem. Eng., 57, 121-124 (1950).
I
6. SHIRAS, R.N., D.N. HANSON, and C.H. GIBSON, Ind. Eng. Chem., 42, 20. OLIVER, E.D., Diffusional Separation Processes: Theory, Design, and
I / '
Evaluation, John Wiley and Sons, New York, pp. 104-105 (1966).
I 871-876 (1950).
7. UNDERWOOD, A.J.V., Trans. Inst. Chem. Eng., 10, 112-158 (1932). 21. STRANG103 and R.E. TREYBAL3 Ind. Process
Dev., 13,279-285 (1974).
8. GILLILAND,
E.R., Ind. Eng. Chem., 32,1101-1106 (1940).
22. KIRKBRIDE,
C.G., Petroleum Refiner; 23(9), 87-102 (1944).
9. UNDERWOOD,
A.J.V., J. Inst. Petrol., 32,6 14-626 (1946).
23. STUPIN, W.J., and F.J. LOCKHART, "The Distribution of Non-Key
lo. F,J.lD.N. HANSON) and C.J. KING,Ind. En&'. Chem.2 Process Components in Multicomponent Distillation," presented at the 61st Annual
Des. Dev., 11, 136-140 (1972). Meeting of the AIChE, Los Angeles, CA, December 1-5.1968.
11. TAVANA, M.3 and D.N. HANSON,
Ind. Eng. Chem.9 Process Des. Dev.8 24, SO~DERS,
M., and G.G. BROWN,
Ind. Eng. Chem., 24,519-522 (1932).
18,154-156 (1979).
25. HORTON,
G., and W.B. FRANKLIN,
Ind. Eng. Chem., 32, 1384-1388
12. FAIR,J.R., and W.L. BOLLES,
Chem. Eng., 75(9), 156-178 (1968). (1940).
13. Gilliland, E.R., Ind. Eng. Chem., 32, 1220-1223 (1940). 26. EDMISTER,
W.C., Ind. Eng. Chem., 35,837-839 (1943).
14. ROBINSON, C.S., and E.R. GILLILAND,Elements of Fractional Distilla- 27, SMITH,
B.D,,and W,K. BRINKLEY, AIChE J , , 6, 446-450 (1960).
tion, 4th ed., McGraw-Hill, New York, pp. 347-350 (1950).
15. BROWN,
G.G., and H.Z. MARTIN,
Trans. AIChE, 35,679-708 (1939).
EXERCISES
Section 9.1
kmollh
9.1 A mixture of propionic and n-butyric acids, which can be as-
sumed to form ideal solutions, is to be separated by distillation into
a distillate containing 95 mol% propionic acid and a bottoms prod- Sequence of
uct containing 98 mol% n-butyric acid. Determine the type of con-
denser to be used and estimate the distillation-column operating
pressure.
9.2 A sequence of two distillation columns is to be used to pro-
duce the products indicated in Figure 9.19. Establish the type of
condenser and an operating pressure for each column for: (a) The
direct sequence (C2/C3 separation first) and (b) The indirect
sequence (C3InCd separation first). Use K-values from Figures 2.8
and 2.9. Figure 9.19 Data for Exercise 9.2.
Exercises 361
krnollh
C, 20
C2 4.995 130 kPa
Benzene 5
>
D- krnollh krnollh
krnollh C2 0.005 Benzene 257
C, 20 - Benzene 485 Toluene 0.1
c2 5 - Toluene 0.5
Benzene
Toluene
500
100
Feed 165 kPa
- Vapor
krnollh
krnollh side stream
> Benzene 260 -.A- > Benzene 3
180 kPa Toluene 79.4
krnollh Toluene 80
Benzene 10 Biphenyl 5 Biphenyl 0.2
Toluene 99.5
Figure 9.20 Data for Exercise 9.3.
krnollh
> Toluene 0.5
Biphenyl 4.8
Figure 9.22 Data for Exercise 9.5.
a, average
Cornp. relative volatility
Cornp. krnollh
C, 160
C, 370
C2 240
9.10 Use the Underwood equations to estimate the minimum 9.17 The following feed mixture is to be separated by ordinary
external-reflux ratio for the separation by distillation of 30 mol% distillation at 120 psia so as to obtain 92.5 mol% of the nC4 in the
propane in propylene to obtain 99 mol% propylene and 98 mol% liquid distillate and 82.0 mol% of the iC5 in the bottoms.
propane, if the feed condition at a column operating pressure Component lbmolh
of 300 psia is: (a) Bubble-point liquid, (b) Fifty mole percent
vaporized, and (c) Dew-point vapor. Use K-values from Figures 2.8
and 2.9.
9.11 For the conditions of Exercise 9.7, compute the minimum-
external-reflux rate and the distribution of the nonkey components
at minimum reflux by the Underwood equation if the feed is a
bubble-point liquid at column pressure.
9.12 Calculate and plot the minimum-external-reflux ratio and (a) Estimate the minimum number of equilibrium stages required
the minimum number of equilibrium stages against percent product by applying the Fenske equation. Obtain K-values from Figures 2.8
purity for the separation by distillation of an equimolar bubble- and 2.9.
point liquid feed of isobutaneln-butane at 100 psia. The distillate is (b) Use the Fenske equation to determine the distribution of non-
to have the same iC4 purity as the bottoms is to have nC4 purity. key components between distillate and bottoms.
Consider percent purities from 90% to 99.99%. Discuss the signif- (c) Assuming that the feed is at its bubble point, use the Underwood
icance of the results. method to estimate the minimum-reflux ratio.
9.13 Use the Fenske-Underwood-Gilliland shortcut method to (d) Determine the number of theoretical stages required by the
determine the reflux ratio required to conduct the distillation oper- Gilliland correlation assuming L / D = 1.2(L/ D ) ~ , , a partial
ation indicated in Figure 9.25 if N I Nmin= 2.0, the average relative reboiler, and a total condenser.
volatility = 1.11, and the feed is at the bubble-point temperature at (e) Estimate the feed-stage location.
column feed-stage pressure. Assume that external reflux equals in-
9.18 Consider the separation by distillation of a chlorination
ternal reflux at the upper pinch zone. Assume a total condenser and
effluent to recover C2H5Cl.The feed is a bubble-point liquid at the
a partial reboiler.
column pressure of 240 psia with the following composition and
9.14 A feed consisting of 62 mol% para-dichlorobenzene in K-values for the column conditions:
ortho-dichlorobenzene is to be separated by distillation at near at-
mospheric pressure into a distillate containing 98 mol% para iso- Component Mole Fraction K
mer and bottoms containing 96 mol% ortho isomer. C2H4 0.05 5.1
If a total condenser and partial reboiler are used, q = 0.9, aver- HC1 0.05 3.8
age relative volatility = 1.154, and reflux/minimum reflux = 1.15, C2H6 0.10 3.4
use the Fenske-Underwood-Gilliland procedure to estimate the C2H5Cl 0.80 0.15
number of theoretical stages required.
Specifications are: (xD/xe) for C2H5C1= 0.01
9.15 Explain why the Gilliland correlation can give erroneous (xD/xe) for CzH6 = 75
results for cases where the ratio of rectifying to stripping stages is
Calculate the product distribution, the minimum theoretical
small.
stages, the minimum reflux, and the theoretical stages at 1.5 times
9.16 The hydrocarbon feed to a distillation column is a bubble- minimum L I D and locate the feed stage. The column is to have a
point liquid at 300 psia with the mole fraction composition, partial condenser and a partial reboiler.
C2 = 0.08, C3 = 0.15, nC4 = 0.20, nC5 = 0.27, nC6 = 0.20, and
9.19 One hundred kilogram-moles per hour of a three-component
nC7 = 0.10.
bubble-point mixture to be separated by distillation has the follow-
(a) For a sharp separation between nC4 and nC5, determine the col- ing composition:
umn pressure and type of condenser if condenser outlet tempera-
ture is 120°F. Component Mole Fraction Relative Volatility
(b) At total reflux, determine the separation for eight theoretical A 0.4 5
stages overall, specifying 0.01 mole fraction nC4 in the bottoms B 0.2 3
product. C 0.4 1
(c) Determine the for the in part (b). (a) For a distillate rate of 60 kmol/h, five theoretical stages, and
(d) Determine the number of theoretical stages at L I D = 1.5 total reflux, calculate the distillate and bottoms compositions by the
times minimum using the Gilliland correlation. Fenske equation.
(b) Using the separation in part (a) for components B and C, deter- 1
Distillate
-
krnollh
mine the minimum reflux and minimum boilup ratio by the Under-
wood equation.
Propylene 347.5 (c) For an operating reflux ratio of 1.2 times the minimum, deter-
mine the number of theoretical stages and the feed-stage location.
351.0
Bottoms
9.20 For the conditions of Exercise 9.6, determine the ratio of
Propane
- rectifying to stripping equilibrium stages by: (a) Fenske equation,
600 (b) Kirkbride equation, and (c) McCabe-Thiele diagram. Discuss
Figure 9.25 Data for Exercise 9.13. your results.
Exercises 363
~y
q
(a) Use the Fenske-Underwood-Gilliland method to estimate the
number of stages required for a reflux-to-minimum reflux ratio of
lbmollh
1.10. Estimate the feed stage location by the Kirkbride equation.
= Rich oil (b) From the results of part (a) for reflux, stages, and distillate rate,
C3 96 use the Edmister group method of Section 5.4 to predict the com-
nC4 52 positions of the distillate and bottoms. Compare the results with the
nC5 - 24
specifications.
*
2,000
Bubble-point I kmollh
--2 atm : lo ortho-xylene
kmolih
Cl 13.7 12 Ethylbenzene 100
C, 1 0 1 . 3 W 2 atm
Para-xylene 100 35 psia
C3 146.9
Superheated Meta-xylene 200
nC, 23.9
Ortho-xylene 100
1
- steam, 2 atm, 300°F
nC5 5.7 4
nCll 196.7
150°F
2 krnol/h
rneta-xylene
Figure 9.27 Data for Exercise 9.24. Figure 9.29 Data for Exercise 9.28.