Beruflich Dokumente
Kultur Dokumente
GENIE CHIMIQUE
VOL. 16 1961 Nos. 3 and 4
and
H. L. BAUNI
Humble Oil and Refining Company, Baytown, Texas, U.S.A.
Abstract-Proofs of the relationships between the temperature and composition of the feed
and those of the pinches are given for feeds having any one of five general thermal conditions.
In the applicationof these relationships a procedure for the calculation of the product distributions
at specified distillate and reflux rates is presented.
RBsum&L’auteur donne 3es preuves des relations existant entre la temp&rature et la com-
position de l’alimentation et celles des “ pinches ” pour des alimentations ayant l’une ou l’autre
des 5 conditions thermiques g&&ales.
Dans le cadre de l’application de ces relations, l’auteur prbsente un pro&d& pour le calcul
des distributions de produit et des taux de reflux pour un distillat dktermind.
THE RELATIONSHIPSwhich are proved herein apply authors solved the problem in which the separa-
at minimum reflux to distillation columns when the tions of two components are specified and the
keys are the most and least volatile components minimum reflux ratio (L,/D) required to effect the
of the mixture. These components are also for separation is determined. In the applications
convenience referred to as the lightest and presented the distillate rate, D, and the overhead
heaviest, respectively. The columns considered vapour rate, V,, (or L,) are specified and the
contain a single feed plate and two withdrawals, corresponding product distribution is determined,
the distillate and bottoms. provided the keys are the most and least volatile
The term “ pinch ” is used to denote the components of the mixture.
existence of a limit for the vapour and for the As discussed by GILLILAND [3], when two
liquid mole fractions as the number of plates is components other than the lightest and heaviest
increased without bound. Following the proofs are designated as the key components, the
a few applications are given. These applications rectifying pinch occurs infinite plates above the
represent a different approach than that taken by feed plate after all components less volatile than
SHIRAS et al. [l] and BACHELOR [2]. These the heavy key have been separated. The pinch
143
J. A. MCDONOUGH,C. D. HOLLANDand H. L. BAUNI
UNDERWOOD[5].
Feeds having any one of five general thermal
-____---_--- - ----
conditions are considered herein. The action r--- - ---1
I
assumed to occur at the feed plate for each type Vf+,= Vs cc= L, I
of feed is given by the following definitions. A f+Y, s 1
I I
I I
I I
r---'
I
I
I
I
i if_,= Lf_,+ F
I
FIG. 1. Conditions on the feed plate for bubble-point FIQ. 8. Conditions on the feed plate for a dew-point
liquid feeds. vapour feed.
144
Determination of the conditions at rrbimum reflux when the keys are the most and least volatile components
r___ ____-.__-__-___--- ---, then to enter the plate above the feed plate.
In the proofs which follow the equilibrium
,i
I
I Vf = v, f-l=Ls I
I .f,s I constants in Henry’s law are taken to be positive
I
I functions of temperature and pressure. Through-
I
out the pinches, the compositions are constant
for each component i. For the rectifying pinch
this is expressed as follows :
Lf_,=Lf_2+qfs q<O lim yji = yli and lim xj:3i= X,i
vr=vs t (I-q)F j+m j-too
FIG. 4. Conditions on the feed plate for a superheated Thus the temperatures are constant throughout
feed. each pinch. Since the enthalpies are functions of
the compositions and temperatures of the respec-
For dew point and superheated feeds it is assumed tive pinches it follows that the enthalpies as well
that the vapour upon entering the column mixes as the flow rates remain constant throughout
perfectly with the vapour rising from the feed each pinch.
plate and enters the plate above. (Equilibrium The relationships of the pinch compositions
between the mixed vapour and the liquid on the and temperatures with each other and with those
I of the feed are given in Table 1 for feeds having
I any one of the five thermal conditions. Except
I
I for a partially-vapourized feed, which is treated
I
I in a subsequent section, the relationships shown
I -I,r I in Table 1 are obtained in a similar manner to
Vff= v, Lf-,= L,
33
I
L--_- .__-- -------- ----. -- 1 that shown for a boiling-point liquid feed. For
F VF such a feed, Ufi = v/i and v,< = vii. Thus,
LF ----___------. y7i = y8i and since equilibrium exists at each
,____ --1 pinch, x,~ = x8:,iand T, = T,. For subcooled and
r----
VT = v, if-l = L$
I
superheated feeds the equality of the pinch
,S
compositions follows from the equilibrium rela-
tionships given in Table 2. The composition of
l the feed is related to those of the pinches by
I
I equation (3), which is based on the following
I material balance :
QVf tv, FXFi + Lr Xri + J’s yai = J’r Yri + Ls X.vi (1)
if_,=
Lf_,f’L,
Let the thermal condition of the feed be defined
in terms of Q as follows :
FIG. 5. Conditions on the feed plate for a partially
vapourized feed. L, = L, + qF, or V, - V, = (1 - q) F (2)
Ch. Engng. Sci. Vol. 16, Nos. 8 and 4. December, 1981.
_ .-
145
J. A. MCDONOUGH,C. D. HOLLAND and H. L. BAUNI
Table 1. Relationships necessary for the keys to be the most and least
volatile components of the feed
Thermal condition of
Ihe feed Relationships Inequrrlity
Boiling-point liquid Yli = Ysi, zTi = xti, XRi = xTi and T, = T, = T, ICI*-&*<;
Subcooled liquid Yri = Y& + = Q, T,, = T, and T, is given by IQ. [5] “l-Ke<(l +~+f
Partially vapourized yri = Ysi = YFi, si = xsi = xfiTi and T, = T, = TF K,-RK,<(l -+Q-!?j
Dew-point vapour Q = xai, Yri = yd, T, = T,, Xpi = y,i and TF = T,. = T, K,-Kc+ t r
*Where the components of the feed are numbered in the order of decreasing volatility ; the most volatile component
is denoted by “ 1” and the least volatile by “ c.”
bi _ (@fJdJ
--_I_ V& = vfi pi = “Li
Boiling-point liquid
di (vfi/bi) ’ di x ’ bi bi
Dew-point vapour
Superheated vapour
I
General pinch equations for a feed of any thermal condition
1
V-e= - ) & = Ati ‘!!i
di 1 - A,< di 0 di
146
Determination of the conditions at minimum reflux when the keys are the most and least volatile components
Once it has been shown that yri = ysi and L, zf-l i = Lr XJ-1, i + LEE XFi (9)
xri = x,i equations (1) and (2) may be combined
VT = vs + vl?, L, = L, + LF
to give the expression for the familiar q-line. (10)
XFi V 2 (YdKrJ 1
- 1
’ (T)= ii (5) _._t.= i-1
1
(1 - q) Kri + q - ’ (12)
vF
aiK,lxFi>l L
iK,s,Yl
i=l -- 7 _ i=l (20)
and since L,/Lp > 0, it is necessary that L,
l- xiKlizti
i-l
2 (Y~L) - 1 Usi
= vFi f1+ ( ‘r LF/‘Fq = v, vFi (26)
148
Determination of the conditions at minimum reflux when the keys are the most and least volatile components
Therefore, yti = Eli. By use of this result and of the pinches occur away from the feed plate.
equations (10) and (11) it follows that yTi = y,+ A system may be examined to determine whether
Hence, or not it is possible at the specified values of D
?/ri = Ysi - YFi (27) and V, for the keys to be the lightest and heaviest
components. Since the flow rates of all com-
Since TF = T, = T, division of each member of
ponents in the pinches are greater than zero it is
equation (27) by ~~~ yields
necessary that Ari and S, be less than unity.
x,i = xsi = XFi (23) The quantity A,i is largest when i = c, the heaviest
component, and S, is largest for i = 1, the
APPLICATIONS lightest component. These conditions and similar
In the following treatment of a system at ones for feeds of other thermal conditions lead
minimum reflux it is supposed that D, V,, the to the inequalities stated in Table 1. If the
thermal condition of the feed and the column inequality corresponding to a given feed condition
pressure are specified and that the keys are is satisfied for a given set of specifications a
designated as the most and least volatile com- solution is said to exist. It is to be observed that
ponents of the mixture. For this set of specifi- either the heaviest (or lightest) component
cations it is desired to find the product distribution ceases to be a key as it becomes completely
at infinite plates in both sections. Systems in separated in the limit as A,c (or S,,) approaches
which L/V remains constant throughout each unity.
section of the column and those where L/V may When the thermal condition of the feed is
vary in each section of the column are considered. either boiling-point liquid, dew-point vapour or
partially vapourized the product distribution is
Constant molal overjlows in each section calculated by use of the formulae given in Table 2,
When the specifications are as stated previously as illustrated by Example 1 of Table 3. For
the product distribution is readily obtained, systems with feeds having one of these thermal
provided it exists; that is a set of values for D and conditions a direct solution exists because the
VI may be specified such that it is impossible for temperature of the feed is equal to that of the
the keys to be the lightest and heaviest com- pinches.
ponents of the mixture. In which case one or both For the case of either a superheated or a
Solutifm
L s . = Km v= bi d.= FxFi
Ari = -.-L-
81 t
con&p. no. KFiV, 4 4 1 + bt/di
subcooled feed, the formulae given in Tables 1 tional procedure for the determination of the
and 2 are applicable, but some trial is involved product distribution at spetiified values of D and
since neither T, nor T, is known, only that VI follows closely that described for systems in
T, = T,. The value of T to be employed is the which the molal overflows remained constant
one for which p (T) = 0, equation (5). It is to be within each section of the column, except that the
observed that this T is a function of the thermal flow rates at the pinches are determined by use
condition of the feed alone and independent of of enthalpy and material balances.
V,., D and L,. However, in order for a solution to When the thermal condition of the feed is either
exist at the specific values of D and VI it is boiling-point liquid, dew-point vapour or partially
necessary for the appropriate inequality given in vapourized the following general procedure is
Table 1 to be satisfied at the T which gives recommended. On the basis of an assumed value
p (T) = 0. If the inequality is not satisfied it is for V,. which satisfies the appropriate inequality
impossible for the keys to be the lightest and of Table 1 b,/d, for each component is computed
heaviest components of the mixture. by use of the appropriate formula given in
In the solution of Example 2, Table 4, equation Table 2. Then by use of an over-all material
(5) was used to determine the temperature of the balance, equation (24), the product rates for each
pinches. The results obtained for Examples 1 component are calculated. After these have
and 2 were checked by use of the formulae stated been computed the compositions needed in the
by MURDOCH and HOLLAND [S]. In the application enthalpy balances are calculated. After the
of their formulae the values of b,/dg for components temperature (or temperatures) of the distillate
1 and 3 obtained for Examples 1 and 2 were taken and the top plate have been determined by
as the specifications. The corresponding values means of the appropriate equilibrium (bubble
of D and L,/D were then computed and found to point or dew point) and material balance calcula-
be in agreement with those specified for Examples tions the condenser duty is found by making an
1 and 2. enthalpy balance around the condenser. The
vapour and liquid rates at the rectifying pinch
Variable overJor.vs are calculated by means of enthalpy and material
For the case of variable overflows the calcula- balances around the condenser and the rectifying
Solution
150
Determination of the conditions at minimum reflux when the keys are the most and least volatile components
pinch. After these rates have been determined adjusting the computed value as required to
the flow rates at the stripping pinch are readily satisfy the inequality. The correct product
determined by use of the appropriate material distribution has been obtained when the assumed
balances. and calculated values of V, are in agreement. If
Instead of using the particular value of V, it is impossible to obtain agreement between these
(computed by means of enthalpy balances) for values and to satisfy the given inequality simul-
the next trial a better value to be employed is taneously a solution does not exist as discussed
the one given by interpolation (regula falsi), as in the preceding section.
described by SOKOLNIKOFF [7]. Before this In order to illustrate the use of the equations
value of V, may be used it is necessary to deter- for variable L/V prablems Example 3 shown in
mine whether or not it satisfies the appropriate Table 5 was solved by two different methods,
inequality of Table 1. If it does not the value of direct interation and interpolation. In the
V, to be assumed for the next trail is obtained by method of direct interation the assumed value of
1 55 54.499 ‘S H8 1’7.168039
2 54.499 54.352 i C4 HI, 9.501945
3 54.7058* 54.7060 n C4 % 7.361634
4 54.7058 54.7059** iC5 %z 3440505
n C5H12 2.527875
*For all trials after the second the assumed value was determined by interpolation.
Tin order to obtain this same accuracy by direct intertion thirteen additional trials were required.
cowkp. aI x lo2
I
a2x lo5 as x 10’
I a4 = 1PJ
Vr for the next trial was t a k e n equal to the one f e e d s L F ----F, and for d e w - p o i n t v a p o u r
calculated by the previous trial. As s h o w n in and s u p e r h e a t e d f e e d s L F ---- 0
p (T) = f u n c t i o n of t e m p e r a t u r e ; d e f i n e d by e q u a t i o n
Table 5 more rapid convergence is obtained by
(5)
use of interpolation. q ~ a m e a s u r e of t h e t h e r m a l c o n d i t i o n of t h e
Acknowledgments--The a s s i s t a n c e g i v e n by Mr. W. M. feed ; d e f i n e d by e q u a t i o n (2)
HARp and Dr. K. K. McMIIJ~IN of t h e H u m b l e Oil and Sji ~ s t r i p p i n g f a c t o r for c o m p o n e n t i and for p l a t e
R e f i n i n g C o m p a n y is a p p r e c i a t e d . The a u t h o r s a t the J
college wish to acknowledge t h e a d d i t i o n a l s u p p o r t g i v e n T ~ t e m p e r a t u r e in ° R
t o t h e m e i t h e r i n d i v i d u a l l y or collectively by t h e E. I. d u vii ~ m o l a l r a t e a t w h i c h c o m p o n e n t i in the
P o n t de N e m o u r s and C o m p a n y , the N a t i o n a l S c i e n c e v a p o u r s t a t e l e a v e s p l a t e j. vii ~ m o l a l r a t e
F o u n d a t i o n and the T e x a s E n g i n e e r i n g E x p e r i m e n t a t w h i c h c o m p o n e n t i in t h e v a p o u r s t a t e
S t a t i o n , and for t h e e n c o u r a g e m e n t g i v e n by Dr. E. C. e n t e r s p l a t e f -- 1
KLIPPLE of t h e college. VFi ~ m o l a l r a t e of flow of c o m p o n e n t i in the
v a p o u r p a r t of a p a r t i a l l y v a p o u r i z e d feed
NOTATIONS Vj ~ t o t a l m o l a l r a t e of flow of v a p o u r from p l a t e
j. Vy-----total m o l a l r a t e a t w h i c h v a p o u r
Aji = a b s o r p t i o n f a c t o r for p l a t e j and c o m p o n e n t
e n t e r s p l a t e f -- 1.
i. A t i = a b s o r p t i o n f a c t o r for c o m p o n e n t /
V F ~ m o l a l r a t e of flow of the v a p o u r p a r t of t h e
in t h e recitification p i n c h
f e e d . F o r b o i l i n g - p o i n t l i q u i d and s u b c o o l e d
bi ~ m o l a l w i t h d r a w a l rate of c o m p o n e n t i in t h e
f e e d s V F = 0, and for d e w - p o i n t v a p o u r and
bottom product
superheated feeds V F = F.
B = m o l a l w i t h d r a w a l r a t e of b o t t o m s
wFi ~ mole f r a c t i o n of c o m p o n e n t i in t h e l i q u i d
e ~ t o t a l n u m b e r of c o m p o n e n t s ; the l e a s t v o l a t i l e
p a r t of a p a r t i a l l y v a p o u r i z e d f e e d .
component
xji, ~ji = mole f r a c t i o n of c o m p o n e n t i in t h e l i q u i d
d i ~ m o l a l w i t h d r a w a l r a t e of c o m p o n e n t i in t h e
l e a v i n g p l a t e j and mole f r a c t i o n of c o m p o n e n t
distillate
i in t h e l i q u i d flowing o n t o p l a t e j + 1,
D ---- m o l a l w i t h d r a w a l r a t e of distillate
respectively
f = feed p l a t e
XDi mole f r a c t i o n of c o m p o n e n t i in t h e d i s t i l l a t e
~
F ~- m o l a l r a t e of flow of t h e e n t e r i n g feed
r e g a r d l e s s of s t a t e in w h i c h it is w i t h d r a w n
Kjl ~ the H e n r y - l a w c o n s t a n t (y = K x ) for com-
X~, i = t o t a l mole f r a c t i o n of c o m p o n e n t i in t h e t o t a l
p o n e n t i a t t h e t e m p e r a t u r e of p l a t e j. F o r
feed F , r e g a r d l e s s of s t a t e
the r e c t i f y i n g p i n c h j = r and for t h e s t r i p p i n g
YFI = mole f r a c t i o n of c o m p o n e n t i in t h e v a p o u r
pinch j = s p a r t of a p a r t i a l l y v a p o u r i z e d feed
lji .~ m o l a l r a t e a t w h i c h c o m p o n e n t i in t h e l i q u i d
Yji, Yji = mole f r a c t i o n of c o m p o n e n t i in t h e v a p o u r
s t a t e l e a v e s p l a t e j. ty-1, i = m o l a l r a t e of l e a v i n g p l a t e j and mole f r a c t i o n of com-
flow of c o m p o n e n t i in the l i q u i d s t a t e o n t o
p o n e n t i in t h e v a p o u r e n t e r i n g p l a t e j -- 1,
plate f. respectively
1Fi .~ m o l a l r a t e of flow of c o m p o n e n t i in the l i q u i d = relative volatility ;
p a r t of a p a r t i a l i y - v a p o u r i z e d feed
~i = g l / K b ,
Lj •ffi t o t a l m o l a l r a t e o f flow of l i q u i d from p l a t e j.
L f_1 = t o t a l m o l a l r a t e of flow of l i q u i d o n t o 1 ~ y i / ~ i ~ v a l u e of
where K b - ~ o:~xi i=l
t h e feed p l a t e
L p ~ m o l a l r a t e of flow of the l i q u i d p a r t of the i=1
f e e d . F o r b o i l i n g - p o i n t l i q u i d and s u b c o o l e d K for the base c o m p o n e n t
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[2] BACHELOR J. B. Petrol. Refin. 1957 3 6 161.
[8] GH~I~IX~ND E. R. lndnstr. Engng. Chem. 1940 3 2 1019.
[4] JENNY F. J. Trans. A m e r . I n s t . Chem. Engrs. 1989 3 5 641.
[5] UNDERWOOD A. J. V. Trans. I n s t . Chem. Engrs. 1932 10 112.
[6] MURDOCH P. G. and HOLLAND C. D. Chem. E n g r . Progr. 1952 4 8 287.
[7] SOKOLNIKOF~" I. S. and SOKOLNIKOFF E. S. Higher Mathematics for Engiheers and Physicists p. 101 M c G r a w H i l l .
N e w Y o r k 1941.
[8] LYSTER W, N., SULLIVAN S. L. Jr., BILLINGSLEY D. S. and HOLLAND C. D. Petrol. Refin. 1959 3 6 221o
[9] Equilibrium R a t i o Data Book. N a t u r a l G a s o l i n e A s s o c i a t i o n of A m e r i c a , T u l s a , O k l a h o m a 1957.
152