VAPORIZATION AND CONDENSATION 443

Basis: 100 molea of oil vapor .

In order to reduce the boiling point from ll70 to 340°F, the vaporization must be
. -
conducted at 490 mm pressure (Fig 5 27). Enough steam to reduce the partial
pressure in the gas phase to 490 mm will be used [see Eq. (16-8) ].
S (760 - 490)
100 490
or
S
—
=
55 moles
55 X 18 = 990 lb
If the pressure in the tower were 10 psig,

~ 760 + 760 -,
1 277 mm

s-- -
\Z 49° 100 = 158-6 molea or 2 860
27
\
~
» lb

Equilibrium Data, The so-called “ equilibrium constant ” designated

as K is not a constant in the ordinary sense because it is a function or Lhe
kind of material and the amounts and kinds of other materials that are
present, of the temperature, and of the pressure.2 It is merely the ratio
.
of y to x However, there are particular situations in which the ratios
can be estimated with some accuracy. In general, Raoult’ s law [Eqs.
(15-1 and (15-2)] may be employed for the normal paraffin hydrocarbons
^
if the pressure is below 60 psi. 8 As the pressure approaches the critical
pressure of the system, the deviation becomes great. This is indicated
in Pig. 15-2 for the high-boiling hydrocarbons or petroleum fractions 4 con¬
tained in mixtures of 82.9 API butane-free naphtha (only pentanes,
hexanes, and heptanes) and a 40.6 API furnace distillate having an ini¬
tial boiling point of 181°F but a 10 per cent point of 366°F. The dotted
lines indicate the K values of ep-ch of the cuts when no other cuts are
present. Note that Pig. 15-2 is only for a temperature of 660°F. The
point of convergency shown on such a diagram applies only to the par ¬
ticular set of components (or fractions) studied in plotting the diagram.
If only two (or a particular range) of the fractions (or hydrocarbons) are
involved , they will form their own point of convergency, which is depend¬
ent on their particular critical point or critical behavior. The point of
convergency is reasonably well defined in the case of complex high-boiling
mixtures such as these studied in Fig. 15-2, but for natural-gas-crude-oil
mixtures the situation is vitally dependent on the composition because
the properties of such gases as methane, ethane, and propane differ greatly
Sage, Hicks, and 'Lacey, Tentative Equilibrium Constanta for Light Hydrocar¬
1

.
bons, API Meeting, Wichita, Kans., June, 1938; also Ref Nai. Gaso. Mfr.t July, 1938,
p. 350.
3 Brown and Souders, Oil Gas May 26, 1932, p , 41.
* White and Brown, Phase Equilibria at High Temperatures, Ind . Eng. Chem. 34, ,
1162 (1942).
444 PETROLEUM REFINERY ENGINEERING

\ X X

XX \
Temparatur* 660 F .
\ X X V X

\ V \ v
X
\ V
X NX
» fANX
X X V

X X X X
^\ X
A
X
X d' a *
\
\
X
\
\
X
V
\
y>XT
T IT \ x
V
H* 1.0 X &'o
j
X
i r
X
V X
«t-
$ >
X: X

nm 0,5 N x
X N
X
X
X 'JO X
E X \
<Te N X
X*
i3 02 -
o' X y X
X X
X X
X x X*
X
X y
/ X
X

0.1
\ X X .

Xs.
N
V
X X
. y^
\
X V
X V
N
\ ^ !
o Mixture A \ X
0.05
•A Mixture B
Vapor pressure
X I

Butane at 300° F.
Estimated Ideal K 's X X
X

0.02
10 20 50 100 200 500
Pressure, Ib./ sq. In. abs .
Fia 16-2. Equilibrium constants ( or ratios ) at 6806F for the components contained in
.

two complex mixtures plotted as a function of pressure . (White and Brown, Ind .
Eng . Chem . )
from one another. If the point of convergence (Fig . 15-2) can be deter¬
mined for a particular mixture, then the pattern of the equilibrium ratio
diagram can be approximated with fair accuracy. The convergence pres¬
sure is a known point, and the equilibrium ratios at low pressure where
Raoult’8 Law is applicable constitute a series of lines. Accordingly,
attention is centering on methods of determining or estimating the con -
juim-cL |
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446 PETROLEUM REFINERY ENGINEERING

TABLE 15-2, EQUILIBRIUM CONSTANTS POR ETHANTI

-
At 100 F for lass- At 160*F for less -
At 220“ F for less-
volatile constituents volatile constituents volatile constituents -
For a 200-moleeular weight solvent
less volatile constituent at these
of these molecular of these molecular of these molecular
Pressure, weights0 weights* weights*
temperatures ®
psia

100 200 300 100 200 300 100 200 300 280“ F 340°F 400°F 460T

14.7 37.1 38.7 41.3 56 . S 63.7 56.9 75.6 77.2 73.7 « 2.0 103.0 113.0 122.0
2d . 0 27.3 28.5 30.3 41.6 42.5 41.9 55.6 56.9 54.2 67.6 76.0 83.0 90.0
40.0 13.8 14.4 15.3 20.9 21.4 21.1 27.8 28.6 27.3 34.0 88.2 42.0 46.0
00.0 6.2 8.7 10.8 14.0 14.3 14.2 18.6 19.3 18.4 22.9 26.0 28.8 31 0
100.0 5.6 5.9 6.3 8.5 8.7 8.7 11.2 11.7 11.2 14.0 16.0 17.9 10.3

150.0 3.84 8.99 4.26 6.73 6.90 6.00 7.56 7.88 7.67 0.50 10.9 12.2 13.4
200.0 2.93 8.08 3.28 4.35 4.49 4.52 5.72 6.04 5.90 7.25 8.40 0.40 10.8
300.0 2.05 2.13 2.37 2.96 3.09 3.15 3.89 4.13 4.13 5.05 5.90 8.60 7.2
400.0 1.61 l . flfl 1.79 2.30 2 41 2 , 46 2.96 3.22 3.23 3.95 4.60 6.20 5.75
500.0 1.35 1.38 1.50 1.90 2.00 2.07 2.42 2.68 2.71 3.30 8.80 4.30 4 80

750.0 1.04 1.04 1.16 1.35 1.46 1.56 1.70 1.93 2.02 2.36 2.80 3.15 3.50
1 , 000.0 0.63 1.06 1.09 1.22 1.38 1.35 1.69 1.69 1.91 2.24 2.63 2.77
3, 000.0 0.74 0.03 0.83 0.07 0.04 1.0«

- -
The k® volatile constituent has a viscoflity gruvjty constant of 0.82. Data from Bag*, Hicks, and L&ccy , Tentative
Equilibrium Constanta for light Hydrocarbons, API Meeting, Wichita, K&ns., June, 193&.
. .
* For temperatures above 22iyF, 0 G. Brown , Pet Enfr ., April, 1043 , .

Source Symbol Mixture

Koy o Ethane ond Butone
Soge, Hicks, Lacey A Methane ond Butane
Webber Natural gas, Butone and Absorption oil
1.0 i

1
I v
\
A
s

0.1
/00 1,000 10,000
Pressure, PS1A
FIG. 15-3. Equilibrium ratios of n-butane at 100 °F in mixtures with ethane, methane , ,

and with natural g &a in absorption oil. { Pci . Refiner . )

l
 /000
0
,
s=
v /
7
6
s t
f
1 -*- 1 71 f
/
2 (
L
?
’
/ T
ft Characterization factor
/0.5
/ It.5

ns
4 l
I l
\
12.5
!
J
f
\\ K s
^ v \ i
s
5T
too \ \ \

\
V

J
1I m
s

-
Nl
8
S
8
7
6
MS s:
§§ V
\
\
1
t!VW
l\\\
\\\
INSU
iass
5
s \ ! 6» Q
5
4
\ \
>

iss: %
\ ll S® KJOO'
m
T
z

to
\
&o \
S
o o:
ed £!S9i
|M!
900°F

in!
"<\ \ V V
e x 80O°F
H IASI
7
Hr :vi
6

I 2 3 4
\
5 6 7 B Q Q)
'
\ s.
7 ? 4 S 6 78
X
OJ
X x
J 4 5 6 7 8!Q
101
7 3 4 5 6 7 8 IQ

Equilibrium vaporization constant

FIG . 15- 5. Equilibrium ratios for petroleum fractions that boil at 600°F. ( Phillips Pel Co ) . .
448 PETROLEUM REFINERY ENGINEERING

vergence pressure, M by correlation of the dozens of systems that have

been Btudied experimentally .
The general effect of the kind of mixture on the equilibrium constants
-
of methane and ethane is indicated in Tables 15 1 and 16-2, wherein less
volatile constituents ranging from 60 to 300 molecular weight are con ¬

-
sidered. Examination of Fig. 15 2 also shows clearly that the equilibrium
-
constants of the low volatility components of a mixture are also affected
by the kind of more volatile materials associated with them. Likewise,
.
Fig 15-3 shows the effect of methane, ethane, and the normal compo¬
nents of natural gas on the equilibrium ratios of normal butane.6 The
dashed line indicates the ratios obtained from Raoult’s law.
Inasmuch as experimental values of equilibrium ratios for all systems
will not be complete for many years, a folded nomographic7 chart (Fig.
-
15-4) is offered as an approximation . Tables 15 1 and 15-2 are more
accurate than Fig. 15-4 for methane and ethane, and in general the K
values of Fig. 15-4 are not accurate at pressures approaching the conver -
gency pressure of the system, especially if the component is far removed
in boiling point from the main boiling range of the mixture. Finally,
.
Fig 15-5 is an indication 8 of the effect of Characterization Factor on the
equilibrium ratios of high-hoiling hydrocarbons. Thus, in the lowest
temperature ranges, ratios based on the vapor pressures of Figs. 5-25 to
-
5 27 may be used, but at pressures approaching the convergence pressure,
-
ratios similar to those of Fig, 15 5 are necessary.
For precise equilibrium ratios it is necessary to resort to elaborate sets
of curves or tabulations. Ratios for the lighter hydrocarbons are avail¬
able in the NGAA Equilibrium Data Book , ® or the Equilibrium Constant
.
and Fugacity Charts of the M , W Kellogg Co.10 Information on higher -
boiling oils is scant.
Example 16 -3. Equilibrium Relations at High Pressures. Example 15-1 will be
repeated using the actual equilibrium constants rather than assuming that Raoult’s
law is valid .
-
The composition of a butane pentane mixture that boils at 180°F will not be 46 per
cent butane (which was used in Example 15-1 ) because this composition and Fig. 15-1
6
Lenoir et al ., Vapor-Liquid Equilibrium Ratios (2 parts), Pet . Refiner , October,
p. 121, and December, p. 115, 1953.
* Winn, F. W . , Equilibrium K's by Nomograph, Pel . Refiner , June, 1954, p. 131 .
7 Miller and Barley , Correlation of Vapor-Liquid Equilibria . . . , Ind . Eng .

Ckem ., 36, 1018 (1944) .

* Poettmann and Mayland , Equilibrium Constants for . . . Fractions of Varying
Characterisation Factor , Pet . Refiner*, July , 1949, p. 101.
fl Natural Gasoline Association of America, Kennedy Bldg ., Tulsa,
Okla., 1955.
Basic equations of the vapor-liquid ratios have been computed , and punch cards for
use with computation machines are available.
10 Technical Data Bock , over 320 charts. New York , i 960.
 VAPORIZATION AND CONDENSATION 449
were based on the assumption that Raoult’s law was valid . The composition of the
mixture that boils at 180°F can be found from the following expression , which is the
same aa Eq. (16-2) but stated in terms of K B :
1 - Kt
Xl
Kt - Kt
Equilibrium constants can be obtained from Fig. 16-4 hy connecting temperature
(180°F) on the left with the compound point to locate a reference point at the right .
The reference point is then connected with the pressure ( 100 psig ) , which is also on the
left scale or line, and if a are read on the center scale . Accordingly,
Ki for butane = 1.43
Ki for pentane = 0.56
lif -TsS °-i ' 05
“d ** = 0495
2/ , = KiZi = 0.605 =
1.43 X 0.723
Vi - K &t =» 0.56 X 0.495 - 0.277
Note that neither the liquid nor the vapor composition is the same as in Example 15- 1 .

.
Equilibrium Relations for Complex Mixtures The relationships of
-
Eqs. (15-3) and (15 5) may be applied in the same manner as in Exam¬
- -
ple 15 1 or 15 3 to the solution of problems that involve complex mix ¬
-
tures, except that trial and-error methods must be used . The percentage
vaporized at a given temperature can be computed , aiid the composition
of the residue liquid and vapor can also be determined .
Consider 100 moles of a feedstock called F consisting of Fu Fi Fif etc., }

moles of the different components designated by the subscripts 1, 2, 3,

etc. By equilibrium vaporization of this mixture, by heating to a given
temperature at a fixed pressure, 7 moles of gas is produced which con¬
tains Ki, 72, 7S, etc., moles of the several components. A liquid residue,
h moles, is left behind , and it also consists of Lh L2, La , etc., moles of
the several components that constitute the feed .
By a material balance:

Feedstock F = Fx + + F 3 4- •

Vapor 7 = 7! + 7i + 7a + * *

Residue liquid L = L\ + Li + L3 + * *

The mole fraction of each component may be expressed as

Fi F2 7a U etc.
F F T V
Furthermore, for the total material or for any component, material bal¬
ance equations of this nature may be written
F =L +7 Fi = In + 7i and Fn «* Ln + Vn
450 PETROLEUM REFINERY ENGINEERING

Henry's law applied to any component is

v ~ K' r and
T " k’ T
or V\ — V% — etc.
Substituting ( F — V ) for L, for each component,
Vr = KX ( FX - Vd j; etc.>

Solving for Vi and simplifying

v^ jnjwi Kr^ '

Since the sum of volumes or moles is the total moles . of vapor,

K Fl _ KiF* . . . a 5-91
( L / V ') + iCi
L L
» etc
elC- -7
V
( L/ V ) + K2 ^ ( L/ V ) + K %
“

A similar statement assuming Raoult’s law but stated for the liquid resi¬
due is as follows:

+ r + P ,( V / L) + X P PWM ' ' ‘ L (15_ 10)

•r + Pi( V / L )
In this equation x refers to the total pressure, and Ph P 2 etc., to the j

vapor pressure of each component. The feed F may be totally a liquid ,

a vapor, or a mixture of liquid and vapor.
In solving these equations it is necessary to assume a value of L (or V) ;
and by substituting this value, a value of L can be computed . If the com ¬

puted value is not the same as the assumed value, other assumptions must
be made until finally the assumption checks the computed value. By
solving the equation for several temperatures, an equilibrium-flash-vapor¬
.
ization (E.F.V ) curve may be drawn , but such curves are usually not so
accurate as the empirical curves described on pages 112 to 119 unless
precise equilibrium ratios for the system are available. The partition
between liquid and vapor will occur at or near the component whose
vapor pressure ia equal to the pressure of the system (or K => 1.0) .
Graphical methods11 of conducting the trial and-error solution are use¬-
ful if numerous computations must be made, but they are of little assist¬
ance in occasional computations.
Example 15-4 Equilibrium Vaporization of Complex Mixtures. A wild gasoline
’

contains 16 per cent CH » , 10 per cent CtHa, 30 per cent CaH » , 5 per cent 1C4 H 10, 10 per
cent C 4 HK>, 15 per cent C8 Hu, and 15 per cent C#Hu and heavier materials. Vapori ¬
zation is conducted at 232 psia and at a temperature of 100*F . What ia the compoai-
n Nelson, W . L., Oil Gas J . , June 22, 1937, p. 63 ; Scheibel , E. G . , Pet. Refiner , July,
1948, p. 136; Reilly, P. M., Pet . Refiner , July, 1951, p. 132; and Wilson, C. L . , Pet .
Refiner , June, 1952, p. 131.
1
 VAPORIZATION AND CONDENSATION 451
tion of the residue gasoline and of the gas that is vaporized ? Basis; 100 moles (or
100 volumes) of gas.
-
Since Eq. (15 10) , which assumes Raoult’s law, is the more complicated, this equa/
tion will be used. Note, however, that Baoult's law is not valid at these conditions
and that more exact results would be obtained by using Eq. (16-0).
Inasmuch as the vapor pressures of C|Ha and CiHa are 194 and 750 psi, respectively,
and the vaporization pressure is 232, the split will occur between these components, or
the amount of vapor will be something larger than 25 per cent Assume L = 70 (see .
-
Table 15 3, column 5) .
For L = 70,
V _ 100 70
= L 0.429 —
70
Solving for L», as an example [Eq, (15-10)],

—
vapor pressure of C»Ha 194 psi
Pi
30 X 232
—
- ,
* “ * + P ( V / L) “ 232 + 194 X 0.429 '

The values of Li , Lit Lt , etc., are computed in a tabulated form in Table 15 3. -

TABLE 15 3 -
‘
(1) (2) (3) (4) (5) (6) (7) (8)

Material
Value

moles
Value
of F’ s, of P's,
psi
P's * (5) +r
(4)
-
(6) (2) - (7)
L’s, moles F's, moles

CH « 15 4 ,100 3 , 480 1, 755.0 1,987.0 1.75 13.25

CSH 8 . : 10 750 2 , 320 321.0 553.0 4.2 5.8
C, H 8 30 194 6 , 950 83.1 315.1 22.0 8.0
iCiH,, 5 78 1, 160 33.4 265.4 4.38 0.62
C *Hio 10 56 2 , 320 24.0 256.0 9.06 0.94
CIHIJ 16 19 3 , 480 8.1 240.1 14.5 0.50
C « Hh + 15 4 3, 480 1.7 233.7 14.9 0.10
Total 70.79 29.21

Table 15-3 shows that the assumption of 30 moles vaporized was not exactly correct
but the check was close (29.21). About 29 per cent will be vaporized at 100°F.
The mole composition of the equilibrium vapor and liquid may be computed by
dividing the moles of each component by the total moles;

Component Residue liquid Vapor

CH 4 2.47 45.37
CjH ( 5.93 19.85
C*H* 31.08 27.39
fC+Hu . 6.18 2.12
C 4 H19 12.80 3.22
CjHii 20.49 1.71
C >EH -P 21.05 0.34
Total 100.0 100.0
452 PETROLEUM REFINERY ENGINEERING

.
Experimental Vaporization Curves When such complex materials as
gasoline and petroleum fractions are dealt with, the application of the
aforementioned equilibrium laws is cumbersome. Furthermore, the com ¬
ponent analyses of these heavy oils cannot be easily obtained ; and even if
such analyses are avaifafie , accurate vapor-pressure or equilibrium data
for the compounds or fractions contained in them are not always avail¬
able. At present most equilibrium relations are obtained by determin ¬
ing experimental flash-vaporization curves or by computing such curves
from the empirical relationships discussed in Chap. 4. Empirical flash
-
curves can be estimated from true boiling-point or ASTM curves, and
with less accuracy from Hempel or Saybolt distillation curves.
.
Vaporization in the Critical Region Insufficient information is avail¬
able for determining the exact behavior of mixtures at temperatures and
pressures in the critical region , but the general situation is understood.
-
Lines A and B in Fig. 15-6 indicate the vapor pressure lines of two hydro¬
carbons ( A and B ) that compose a mixture, and line C may be considered
to represent another hydrocarbon that exhibits properties that in most
—
respects represent the properties of the mixture or better, line C repre
sents the molal average vapor pressure of the mixture and the molal
¬

average or pseudo critical temperature and pressure of the mixture. Such

critical points are indicated aa a, b, and c, respectively .
The volume of gaseous mixtures may be computed for any condition
that is not close to the envelope in the diagram, from the pressure-vol ¬
ume-temperature relations of the hypothetical material C using the
pseudo critical point designated as c (Example 5-5) . Lines of constant
volume are indicated on the diagram.
The density of the fluid under various conditions is indicated on Fig.
15-6 by the blackness or whiteness of each part of the single-phase area.
Thus, highly compressed liquids or vapors are shown as dark areas in the
left and upper part of the diagram, and the density graduates smoothly
-
to the low-pressure high temperature area in the lower right corner, which
we refer to as a typical or ideal gas region. Note that it is possible by
compressing a liquid , heating it, and reducing the pressure to convert a
liquid into a gas without conducting vaporization . The common process
of distillation is indicated midway on the diagram as a horizontal line or
constant-pressure process in which the liquid is heated , vaporization
occurs throughout a range of temperature, and finally the vapor may be
superheated. In a similar manner, a constant temperature expansion
-
(or compression) of a dense fluid is indicated as a vertical line midway on
the diagram. In such a process, liquid is produced upon partial expan ¬
sion, but the liquid vaporizes again upon further reduction of pressure
so that nothing but a pure gas phase remains after expansion . This sit¬
uation has been encountered commercially as retrograde condensation
, .