Академический Документы
Профессиональный Документы
Культура Документы
van
'
JOSEF
....................... ...... ............................. FRENKEL .
.,. ................................................ ............ _......... '
. onderwerp:
l.
r'
I I
I
L •
~
.I
rl
~J
Josef F'renkel
n Koornmarkt 9
Delft
n
n
r
u
l _
l.
"
. ,I
.j
l
l To strive, to seek, to find
Front "Ulysses"
by Alfred Lord Tennyson
l
n
l •
J -1-
List of contents
Topic
I. Summary 2
11. Conclusions and Recommendations 3
III. Introduc tion 4
IV. Theory and literature research 6
V. Calculational procedure 10
, ,
n
n
-2--
L
I. Summary
----------
r
l _ The problem was attacked by selecting, aftel' an extensive literature
study, the Wilson equation which seemed to be the most applicable
,, ~
~l
In order to check the whole calculational procedure of the Wilson constants
and the incorporation of the latter in a design of a distillation column,
it is suggested to apply it to a system for which the Vlilson constants
J are known in the literature.
1
n
n
u -3-
1. The Wilson constants for the binary system (a) DMA-water exhib ited
regular behaviour, while those for thc binary systems (b) },flvlA.-water
and(c) TMA-water exhibited some anomalies. The cause(s) of this
irregular behaviour may lie in one or more of the following factors:
(a) tbe occurrence of immiscibility;
(b) data over an insufficiently wide range;
(c) inaccuracies in the data.
l .
4. It is suggested to check the calculational procedure concerning the
r , Wilson ccnstants and the distillation column for a system, whose
L • Wilson parameters and distillation' s design are knovn from literature.
r '
5. It is suggested to develop a more efficient computer program for the
design of a distillation column for nonideal systems.
r 1
l
l
l
n
n
-4-
111. Introduction
1. General
n
, 1
-5-
,'
L
r'
l
methanol, and two weeks storage for all anhydrous products, complete
battery limits process plant, cost is $ 1.6 million based on current
labor and material costs in u.s. (valid for November 1973).
r~
i
l.
2. Extractive distillation and its application in this project.
MMA and DMA pass through the bottom of the column to uridergo further
n separation.
rl
r}
L ·-6-
f.(T,P,X)
.1 a. (T, P, x)
1
= 1
(Iv-1)
1n which:
.th
a. activity of the 1 component [dimensionless]
1
f. fugacity of the component 1n the given state [atm. ]
1
l f<?
1
fugacity of the component 1n a standard state [atm. ]
I .
r ,
I
LJ
-7-
r.
L~
r' ~.
l
= RT In f. + B(T)
l
(rV-2)
ln which:
r '
,
l _
th
~. - chemical potentialof the i component [cal/gmol]
l
r' O
R - Universal gas constant [cal/gmol K ]
= o = (Iv-4)
f.
l
f.
l
= al = x.l (rV-5)
n
r
r'
l ,
-8-
f '
L
I'
2.2. The activity coefficient y. is the ratio of the activity of 1
1
l~ te some conven ient measure of the concentration of i, which lS
usually taken to be the mole fraction:
f'
l _
al
y.
1
= x. (Iv-6)
1
ai x.
y.
1
= x. = x.1 = (IV-7)
1 1
O
K.
1
= y. K.
1 1
(Iv-8)
ln which:
K.1 equilibrium constant which equals Y/X [dimensionlessJ
pO/TI [dimensionless].
r ,
ln which:
l ,
, J
3. Estimation of multicomponent vapor liguid eguilibria
i
, J
3.1. As pointed out above, the core of the problem of describing a
real multicomponent system is to estimate the vapor-liquid
l
• J
equilibria. In most of the cases the required experimental data
are almost never available. In order to make the best possible
estimate with a minimum of experimental data it is efficient and
useful to express the problem in thermodynamic terms which would
consolidate the basis for a molecular model. Because the activity
coefficients are exactly defined thermodynamic quantities it is
possible in terms of them to describe real systems in equilibrium
under various conditions.
n
r
rl
-9-
r '
L
The us e ful thermodynamic concept for efficiently expressing the
E
nonideálity of a liquid mixtur e is the excess Gibbs energy g ,
which ",as originálly introduced by Scatchard (12). I t is defined
f'
l. as follows (3):
E
I
g = g(actual solution) g(ideal solutio~ at)
(IV-9)
l,
at T, Pand X same T, Pand X
r'
1n which:
E
g Excess Gibbs energy of the solution ~alJ
H'
By means of the function g'" it is possible to derive an expreSS 10n
for the activity coefficient Y for any component K in the system.
K
d . E
nTg )
(
= dOK T,P all n. (i;lK)
1
(IV-l0)
1n which:
~l
In Y
2 =
[ 1 2
+B-X-
A Xl
f (IV-J2)
~l
I ,
-10-
. '
ln 'lhich:
r~
L •
Note that Vli th systems for ,-,hich A=B. both the van Laa.r and
Margu.les equations further simplify to the common form:
In Yl = AX 2 (IV-15)
2
= AX 2 (IV-16)
1
,l in which:
J q.
1
a constant which Wohl called the effective molar
volume of the component.
n
r
l.
[
L...
-11-
q.X.
1 1
z.1 = n
(IV-18)
L q.X.
j=1 J J
L:Z. = (IV-19)
j J
3.3. The methods cited above have some inadequacies which must be kept
in mj:'1d while calculating the activity coefficients. The constants
which appear in these equations are a function of temperature and
pressure but are not dependent on the composition. Concerning the
pressure, the dependence is not great; at low and moderate pres s ures
it can be neglected. However, the temperature usually plays a role
ln determining the values of the constants. Only in one case is the
temperature effect on the constants zero. This occurs when the
solution is athermal, viz., I"hen the solution process of the com-
r 1
1
ponents occurs isothermically, isobarically and with ~H = O.
For practical applications it is assumed that the dependence of the
activity constants on temperature at a modest range of the latter
can be neglected.
n
n
, ,
-12-
r -
• J
~l
.1
:l
1
n
n "
1 ~
,
''l
r 1
-13-
L
4. The Wilson Equation
L
v.
l
Aji = (IV-21)
v. L
J
in which:
n
, I
results. If one parameter is greater than unity and the other one lS
less, than the deviations from ideality are not large.
n
n
--14-
I .
l g
E
= RT
n
L
i=l
x.lny .
l l
(IV-22 )
By i nt r oduci ng Wil son' s equat ion int o Equa tion IV- 22 , one get s :
g
E
= - RT
n [ n 1 (IV-23)
L x . ln L xJ' Al'J'J
. 1
l= l . 1
J=
X.
= -In [~ x. A .] + 1 - ~ l
n
(IV-24)
j=l J kJ i=l
L x. A •.
j=l J lJ
A12
A2l ] (rV- 2S)
lnYl = -ln(x l + A12x 2 ) + x 2 [Xl + A12 x 2 A21 x l + x 2
A
12 A2l ] (IV-26 )
lnY2 = -ln(x + A x ) - xl
2 21 l [Xl + A12x 2 A x + x
2l l 2
4.2. The Hilson e quat ion h as two rema r k able advantage s which make it
very useful for engineering applications. Firstly~it has a built-in
• 1
n components and for the individual binary systems. The relative simplicity
of the experimen~al determination of binary data as contrasted to multi-
n
-15-
L
from the binary to the multicomponent case requires no additional
assumptions.
( ,
l.
4.3. There are blO disadvantages of Hilson' s equation which must be
n
L T ••G.. X.
E n J1 J1 J
iL j~1
= I x. (IV-27)
RT 1 n
i=1
L GR,iXR,
R.=1
where
(g ..
J1 - g .. )
11
T ••
J1 = (g ..
Jl = g 1J
.. ) (rv-28)
RT
G..
J1
= exp( -ex ••
J1
T .. )
J1
(ex ..
J1
= ex 1J
.. ) (IV-29)
n
n
n
, ,
-16-
I '
V. Calculational Procedure
r'
1. General
l,
In order to design the distillation coluum it was necessary to
calculate some parameters concerning the pure component properti es and
the multicomponent system.
These parameters were calculated by means of computer programs which
are specified in the book "Computer Calculations for multicomponent
Vapor-Liquid Equil ibria" by Prausnitz, Eckert, Orye and O'Connell (19).
[ ,
The .des ign of the column lS base d on a computer program for nonideal
( , distillation. The latter appears in the book "Computation of Multistage
I , Separation Processes" by Hanson, Duffin and Somerville (20). Originally
the program was written with a subroutine based on the Margules equation
to calculate the activity coefficients. This subroutine was replaced by
another one based on the Wilson equation.
2. Calculation of Parameters
L 2
v = a + bT + CT (V-1)
~1
The constants are
L L L L
:1 c
(T -T ) (v -v ) - (v 3-v 1 ) (T -T )
3 1 2 1 2 1
= (v.,.2L
(T 2 _T 2 ) (T -T ) - (T 2 _T 2 )
~1
(T -T )
2 1 3 1 3 1 2 1
L' L 2 2
(v 2-v 1 ) - c(T 2-T 1)
"
n b =
T2 -T
1
n a = v L - bT 1 - cT 2
1 1 (V-3)
n
r
-17-
r'
r' Tl' T and T a re the temperatures at which the pure component liquid
2 3 L
L L L
molar volumes v l' v 2 and v 3 are avai l able.
( , A computer program for this purpose - VMOL - des cribed ln Appendix B.
L The data was taken from Gallant (21).
lnP~(atm. ) = (v-4)
l
r .
Cl' C , C4 and C are constants.
2 6
, )
B
lnP~(atm.) = A + ---- (V-5)
l
~l
n This form of equation was used in the design of the distillation column.
The equations for ~1A and DMA were taken froID the Handbook of Chemistry
and Physics (25).
n
n
r-,
I
( )
l ~
r '
-18-
l ,
The equat ion for TMA was taken from Felsing (23). The equation
for vlater was taken from Bijwaard (26).
The constants are listed in Table V-1.
Table V-1: Constants fOT the vapor pressure equation of MMA, TMA,
DMA and wate r.
r' L •
Component A B Range
0
C
{ ,
For mixtures of components i and j, the two parameters /tij and 1\ji
can be obtained from vapor-liquid equilibria data. In principle, on ly
one experiment al poi nt (X, Y, T or p) lS required, and sometimes it
is possible to obtain a good estimate of the parametersmerely from
azeotropic composition and boiling point. In general, however, it lS
n
I: X.dlny. = o (at constant Pand T) (v-6)
n i=1
l l
n composition.
r
( )
L~
-î9-
I •
L.
C •
the thlrd vl•rl
• ••
al coefflclent ,-cm 3/ gmol ) 2 ]
[ f
etc .
The distillat ion colliEr! for which the following progran has been
rl designed is that with a total condenser. It is taking into consi deration
the fact that the system is nonideal and the composition effect on the
equilibrium constants is here expre ssed by means of the activity
l) coefficients as follows:
(K)modifi ed = y(K)'d
l eaI
(v-8)
-2C-
I'
I
L~
A
InK = + B
r: (TOF) + 460
rl
I I The constants are listed ln Table" V-2 /j
l J
Table V-2: The equilibrium constant for ~ffi, TMA, DMA and water
Component A B
[1 IvIMA - 5859.4 9.805907
TMA. - 4983.9 7.823033
n DMA
Water
-6031.9
- 8585.1
9.537244
]0.568466
I,
-21-
r'
I
I
l .
l.
r ~1
r 1
\ J
f1
fl
-22-
r~
= a + (VI-l )
l.
The constants are listed in Talbe VI-l.
These values,like the rest of the values discussed in this chapter,
were calculated using proc edures descri be d in chapter V.
[:
Table Vl-l: Constants of MMA, TMA, DMA and Water ln the liquid
, '
molar eguation.
I
l .
. 3 o
f '
Component a[cm 3 /gmol] b[cm / grnol TK] c[cm 3 / gmol (T K)2]
l •
_4
MMA 5.537 * 101 -1.413 '* 101 3.830
* 10
4
TMA 7.964 * 101 -9. 633 3i 10 2 4.9 118 * 10
101 4
DMA 8.239 * 101 -2.155 * 5.800 ii 10
1 10- 2 4
Hater 2.288 * 10 -3.6 112 * 6.856 * 10
r'
I
2. Vapor pressure
r -,
The vapor pressure of the pure component as a function of temperature
l ,
is written as follows:
n Table VI-2: Constants of MMA, TMA, DMA and water ln the vapor
pressure equation
n I
n I
I
r
I
, 1
-23--
[: Tabl e VI - 2 : Constants of MMA, TMA, DMA and Water ln the vapor pressure
equation.
[: Compone nt C C C Range ° C
I
Cl 2 3 4
[:
2 4 -1 2
MMA 8 . 55 12* 10 - 2 . 995067*10 1. 859* 10 -1.420*1 0 80~ Î4 0
1 0
TMA 4 . 3780*10 -3.-(1 5630*10 3 8.818*lÖ 3 -5.821*10 60-i- 11fO
r' 1 4 -1 '1 . -"'-3
2
DHA )0 * 10 81 7 139
I
I 9 .4267*1 0 -3 . 333743*10 2 . 0 11*1 0 -
l.
r'
Water
.
7.0430* 10
1
-7.362690*10
3
I 6- . 950* 10-3 - 9 . 000*10 ° o .:;1 25
I
I, •
The Hilson constants vere calculated for the following binary systems :
(a) M.r-1A- water; (b) TJ"IA-water; (c) DMA-..rater . The ca lculation ..ras carried
, I
out at t emperatures between 70 to 140°C in int ervals of 10°C. The
l •
results are listed in Tabl es VI-3, VI-4 and VI-5.
,1
i ,I tOe A A
l' 12 21
r 1 70 5.4647 0.0000
80 4.9892
90 4.4315
f1 100 4.0338 (see Fig. 3)
110 3.6300
D 120 3.2716
,/
o
130
140
3.0000
2.7143 1
n
n
/
r
1
f 1
L~
-24-
tOe Á Á
12 21
70 0.0801 0.7502
80 0.0835 0.6623
90 0.0890 0.5628
(see Fig. 4,5)
100 0.0950 0.4702
110 0.0969 0.4114
120 0.1009 0.3474
130 0.0000 1.4387
l •
tOe Á Á
12 21
70 0.2418 1 .7253
80 0.2603 1 .5802
90 0.3560 1.2178
100 0.3031 1 .2854
110 0.3198 1 • 1520 (see E'ig. 6, 7)
rl
The characteristic ener~T differences (À .. -À .. ) and (À •. -À .. ) were
• lJ II lJ JJ
calculated for the binary systems mentioned above at temperatures between
fl o
70 to 140 e. The results are listed in Table VI-6.
o
fl
n
~
( ,
L -25-
r •
L.
Table VI - 6 : Energy coefficients of interaction ( À.. -À .. ) and (À . . -À .. )
lJ II J-J JJ
for the binary systems:
( a ) HMA-H ; (b) TMA-W; (c) DMA-W.
MMA-W 24520.
[1 130 TMA-W
- 1797.
27630. 1180.
DMA-W - 337. 1283.
n MMA-W - 1774. 24180.
n 140 TMA-W
DMA-IV - 314. 1381.
n Note: there was no data available for the binary systern Tr"IA,-W at 140°C.
n
, )
-26-
r '
3.2. Discussion
The scop e of this p aragraph is: (a) to discuss the method according
to whjch, the Hilson equation was applied to the various binaries
which compose the r:mlticor.'lponent syst.em under discussion ; (b) to
clarify some points c oncerning the computer progrrun (see Appendix C),
by means of .rhich the Hilson parruneters a r e obtained ; (c) to analyse
the values obtained for the paramet.ers ; (d) to disc u ss some other
methods for the calculation of the activity coefficients.
r '
the binary systems: (a) HHA-W, (b) TVlA-H, (e) DMA-H for vlhieh only
0
j , bubbl e -point behaviour was a vailable in the range 70 ~ T ~ 140 c and
a eoncentration rang e of 0.0 to ea. 40.0 mole-% of the resp ee tive
am1ne.
n routine LSQ was not deserib ed in the program, and therefore another
subroutine nruned oppm" replaced it. The latter has been used at the
T.H. Delft and gave good results for ealeulating the minimum sum of
n squares and thus finding the best fit between a eertain function and
given data.
n
L J
r
( ,
L ,
-27-
In the light of these r esults it was suspe cted that a mistake was
made vrhile punehing the program on eards. The listing .TaS ear efully
eheeked several times but no mistakes eould be found. The only two
reasons whieh might e ause the di sagreement in the results eould be
the following :
(a) subroutin e LSQ is more effieient 1n ealculating and minimizing
the sum of the squares .,hil e fitting a function to data in compari son
, ,
eoncerning the calculat ed Wilson constants , the system DM.4. ( 1 )-H( 2)
exhibited normal behaviour ln its variation of A and A with tempe-
12 21
ratur e . The rate of change of A and A is r egular and indee d the
12 21
r ,
parameters do not vary mueh over a modest range of temperatur e .
0
At 70 e A = 0.2418 and A = 1.725 3; at 140 0 e A has increased to
12 21 12
0 .3167; while A has decreased to 0.8599.
r- 21
I
I,
For the binary systems TMA(1)-H(2) and MHA. (1)-W(2), however, anomal ous
behaviour is found. For the former system the change in the values of
0 0
A and A with temperatur e from 70 to 120 e is normal. At 70 e,
12 21
A12 = .D.0801 and A21 = 0.7502; at 120 0 e A12 has incr eased to 0.1009
~l and A has decreased to 0.3474. This rate of change is regular. But at
0
21
130 e there is an abrupt change in the trend of the values of the
parameters. A decreases to 0.0 and A increases to 1.4387.
12 21
The constants of the binary system MMA(1)-W(2) vary too much in a small
n 0
range of t emperatur es ; e.g., at 70 e A = 5.4647, while at 90 e
A = 4.4135. A
12
0
n 12 21
0
tures 70 ~ T ~ 140 e and is equal to o.o.
Bearing in mind the fact that th e se constants are not supposed to vary
n
r 1
I
L~
-28-
I.
l~
The values obtained for the energy coefficients (1.. -1.. ) and
12 11
12-1.. 2 2) raised some questions , namely:
(1..
(a ) the tre nd in the values of (1.. -1.. ) and (1.. -1.. ) of the binary
12 11 12 22
system TMA (l )-H(2) suddenly rcverses in direction at 130 0 C (keep in
mind the abrupt change in A and A for this system mentioned above ).
12 21
Up to 130 o C, ( 1.. -1.. ,) lS 1n the order of a few hundreds cal. / gmol .
12 11
At 130°C , (1.. 12 -1.. 11 ) lS equal to 27630 .ca l. /gmol. This jump seems
strange;
(b) the r esults for the binary systems at 80 0 e are, for example:
cal. cal.
Component ( 1 ) ( 1..
12-",1) gmo l (1.. 12 -"22 ) gmol
TMA 509. 15 22 .
DMJI.
- 63. 687.
I
l J MMA - 1886 . 22888.
l ,
Note: water(W) l S no.(2).
Based on these resul ts the following statements can be "rri tt en , in
which r = energy of interaction in c al. /gmol. Recall the fact that
n and:
n (>..
. 12
-À )
22 ('l'MA-W)
À )
22 (DMA-W)
= 835. cal/gmol
n
n 7. r(D~ffi-W) > r(TMA-W)
L ) - = -21366. cal./gmol
l; ( À
12
-
'ë2 (THA-W)
(1..
12
À )
22 (MMA-I-l)
-29-
r '
I
I
L•
H
r ~
H - 0
1
1
TMA-I'l interact.ion
r ,
CH - N - CH
t., 3 3 .J
CH
3
r ï
?H3
I ' 1
2
TMA-TMA int e raction
CH
3
- n - eH 3
( , eH
3
- N- eH
3
l, IL CH
3 .....
Concerning the other statemen~ it lS difficult to say defineteiy whether
they are correct or not, since two opposing effects must be taken into
Because the writer, after much thought and consultation, could not
n explain the cause of all these ancmalous results obtained for the Hilson
parameters a letter was sent to Professor J.H. Prausnitz of the University
r '
L_
[: (d) various sets of parameters can be obtained for varlOUS sets of data;
(d) the parameters obtained depend on the reduction method of the data,
viz., the fit of vapor composition data, or the fit of total pressure
data.
[~
equation to this problem.
Concerning points, (c) and (d), the data used to calculate the parameters
[1- were taken from graphs published by Rohm and Haas Co. (28) and Gallant
(21). No tables were found with TI vs.T for the binary system under dis-
cussion. Because the data for TI appeared on a logarithmic scale it was
difficult to read it accurately • .On top of that the graphs of TI vs.T
i . -3'-
L_
Because of some unc ertain values of the Wilson constants it was decided
to try and calculate the activity coefficients for the multicomponent
system under discussion by means of the three suffix Margules equation.
Some methods are described in Hála ((2), p. 41), from which it i s
poss ibl e to calculate the constants A and B in the Margules equation
without a knol-Jledge of the equilibrium G-L composition of the binary
systems; only a knowledge of the bubble-point behaviour is required.
0
TI - y 2P 2X2
Y , =
0
(VI-3)
l , P,X,
0
TI - y,p,X,
Y2 = (vI-4)
0
P X
2 2
r'
I
l !
As X ~ '.0, Y ~ '.0 so that an apparent activity coefficient can be
2 2
calculated for component' by assuming Y = '.0. By plotting these
2
apparent activity coefficicnts on semilog paper vs.X, an extrapolation
may be made to find the terminal values of the activity coefficient s ,
whose logarithms are the constants in the Margules equation.
n But the data for the binary systems and the respective amines cover only
concentrations range up to approximately 40.0 mole-%. Therefore a tangent
r
!
-32-
to the curve at X = 1.0 could not be dravrn, and . thus the method could
not be applied.
Summing up, the values obtained for the Wilson parameters exhibit
different trends for the various binary systems under discussion. The
parameters cannot be rega.rded as reliaole until certain points viz.,
miscibility, range of data and its accuracy can be clarified. In any
The program v;as punched on cards and a test-run vTaS made wi th the example
which appeared in Hanson's book (20)~ however, no solution vas obtained.
I ' The program was checked several times and according to the writer, there
are two mistakes in it, namely:
(a) statement no. 23 is written as follows:
r 23 DO 24 J = 1,JC
it should be written:
n 23 DO 24 J=1,JD;
DO 26 J = 1,JC
DO 26 J = 1,JD
n
I '
Î
l _
- 33--
·~ i
I
r '
.
A I
MMA( 1 )-vl( 2 ) TMA (1)-H( 2 ) I DMA ( 1 )-Vl (2)
I
I
I
I iI
l 1\21
I
0.0000
I
0.53 110
I
1. 2279
i
I , Note: ln the cas e of the binary system TMA(1)-W( 2 ) the anomalous
r '
value s at 130 0 C we r e neglected in the calculation of the
I 1
avera ge.
n The reason for averaging of the parameters was that an actual column, which
separated TMA from the syst em under discussion by means of extractive
r ' -34-
I
I
l ,
r'
I Many trials were made vrith vanous reflux ratios (0.5 R .: 2.0 R) and
l.
various rates of extrac tive "Tater (0.75 F :. 1. 65 F in kgmol/hr).
Unfortunately, none provided an optimal desigr... All of them exhibited
an -anomalolB change of t emperatures along the column and an insuffic ient
[ : separatioll of TMA.
As for exampl e
( ,
SOLVENT PLUS
eorrOM PRODUCT
S
,,
F
1 = 142.8 kgmol/hr r 22 .4 kgmol/hr MMA
20.3 11
TMA
18.4 " DMA
r'
i \..81.6 " w
l ,
F
2 = 233.3 kgmol/hr W
l)
The column consists of 60 plates, and the feed lS introduced above the
50th plate. The extractive water is introduc ed above the 55 th plate.
[1 The reflux ratio is set equal to 1.0, thus R
L
=D = 1.0.
n (3 )
(4)
DMA
W
n
n
.------, ..--------, r- ~ , r- - '[ I
,.
"
l
en ~
BOTTCM P~ODUCT
p, «en CD I .
)-'.
en c+
en
~ (t) O.62077902E-01 (2) O.124825<J 13!: -C'1 ( 3)O .4~ ~SJ2 i2~- Ol ~ 4 ' O .8 J ~40160E na
c+ CD f-'
)-'. S c+
f-' en RE88ILEI\ VAPOR
f-'
Pl
c+
)-'~ ~
,0
H:l 0.22443ó28E ro O.225874 90F. nn () .2 :l6262tnE ;')11 :) • 2 G) 3 ',I ~ 12 E 00
0 J CD I
::s ><
~ Rf FLUX W
c+ V1
en >-j
,l .l H328154E rIJ I
J Pl O.15ó7C86oE-Ol Oo7~313231~ CO J.gFt':ÏC' ,)69[- Ol
() t::J ()
c+
~J
0
::sp, )-'.
TOP PROfJUC T
)-'. ~
<
CD
ei- O.15670866E-Ol O.7H:H32.31F 00 \~.11nL(H')41: 'I r) "I.13245CSb '}E-01
)-'. P,
0 )-'.
::s en
BorTOM PRODUCT RECOVERY rR~CTrGNS
en c+
)-'.
~ f-' O.0S57ó367E 00 O.21765nOOE 00 '1.d6C) CH4J::3 [ 00 Cl. C1 94:i'ltZ5E 00
CD f-'
>-j-
CD ~
)-'. TOP PRODUCT RECOVERY FRACTIONS
en o 0.14271677E-01 0.7~313226E 00 fl . LH 1 391'5 E >') (1 0 . 5341J~73E -02
"d ::s
CD
()
)-'.
o
H:l
H:l SUft'MATION OF R.EC I)VERY fRACTIUNS
~
)-'.
CD 0.lCOC0353E 01 O.lO(')782')E I)!. \I • l('\{) 0 1 5 1 6 E iJl l:" . :) j09U 2S5E ClJ
P,
-36-
The change and rate of change of the temperatures along the c olumn
r
l ,
are v ery strange, namely :
n would incorporate heat balance and would converge more quickly after a
small number of iterations. A basis for such a program can be found in
n
n
f '
L
-37-
l~
VII. Figures
, l~
I
--------------
I [:
[~
r
r
~
I [:
r ,
l.
, ~
I
,I .
[~
r
n
l 1
n
n
n
n
n
n
r
l.
:-l ==:J ==:J ==:J :=:J ==:J =:Jo .---,
...
~
J
..----,
J ,
r - !I ~
'---'
r----: r---'
L
CRUOE
CONVERTER PRODUCT ' NH) TMA MMA DMA
STORAGE COLUMN COL UMN ' COLUMN COL UMN
..,.
~
METHANOL
WATER
.. - ;; .~
H2+ CO
~COOling-
AMMONIA
..
~a ttr
~',
'- Î
-..) ~~ ...
.A.....
.... ~-
.,- ~
~
I
W
CD
I
, } ANHYOROUS
IL-----:-1....
to PRODUCTS
I
=J ''8 -1-
.! -~ç}",""",
WASTE
r . -39-
SOL V[ NT
[ FEEP--oI
SOLVENT PLUS
80TIOM PRODUCT
n
n
( 1
( .
I
L.
r
A .A /2
\
5.S· \
\\
5 .0
; __ __..,.__. _L __ --=-_ ._.:. __ .. __ .;-__ _ ....
~
~ I
r~.
t
i
f--- - r ..
: _. - I
1
L
r
n
n
n ,I . t ,
_o r'
n 1-'
I ,I
~
!
( ,
-41-
!'
l .
Fig . 4: Hilson constant 1\12 vs. T(co) for the binary system TMA( 1 )-vl( 2 )
___ i - - .- ..L _ •• _ _ ~ •. _
,
__ • • L ____ _
. ,
----- _ ._~
i
L ___ J
l_.l
r~
l .
n
n
n ,
! -
- • -
;
! -. ·- 1-
,
i
r I
, •• 0 .
r-- :
.- - 1---' -t·--·- ..-
i ;
r·-- :----· :· ---:··- Ij--'-'-' T ··_·_·1----··-
I 1
, 'I ' . ,
I
0 .00
70 ?D 90 Ic".) 11 :-;
( 1
I I
(
- _. _.;----- --.-,--., --
r ' ,
- j.
I
- "--- ----- --. - ,- ------
!
- .;
Fig. 5: 1,1ilson constant 1\21 vs. T[co], for the binary system TMA( 1 )-W(2)
r
A '2./
( ,
r '
! ,
1.5 I-_. __ _~. _____ j ._-~.- _. __ J.. ____ __ -- -- _ -:---_._---j.,------~. -_._- . -- ..
i : I .
. . I
L
r~
fl
n
n
, _·: .. ··t··.. ;·..·r... -
n f.
~ I
i .•. - -Ol
LJy~t----~i--~Ir---~I----TI--~Ir---TI----~I------~....
. I
L
L
[
Fig . 6 : \·;::..:....3on::onstant A
l 12
v s . T[ co ], for the binary system Dîv1A( 1 )-H( 2)
r:
i
f _..; ,··:- 1
n
n
D
i·
n I !
,. .
o ,ZO _
n r··
._ - " ... . . . ... .. .,-- - . -_ .••. r ..' I ... _. . ~ _. r . . .. 1
I
r· !
1 I
-tv I I I
!?("
I
Ho
I
H')
I
.. T [C")
70 ë-: I')') li') I~
f 1
I
LJ .,
I
( . -44 -
I
l.
L
r
[~ .
Fig . 7 : vlilson constant 1\2 1 v s T [ co ], for the binary system DMA( 1 )- W(2)
[:
r'
n
n
n
1.0
n I
j
I
--- .•
i
:
:
---- - --- t-
i
-···-----t-----
'
._-,--_... _- . i
lo() 11 0
r 1
l~
-45-
VIII. Nomenclature
L
A a constant ln the van Laar 2.nd t-1argules equation [dimensionl ess J
a activity [dimensionless J
p pressure [atm. J
[,
pr essure at standard state [atm. ]
r '
P<?1 vapor pressure of pur e compon ent 1 [atm. ]
n
ri
(
11
I
\
1-1
-46-
l
chemical potential [cal. / gmol ]
L 11
r
r
L
["
1~
[.
r .
1
r:
L
r
f:
lJ
~1
n
r
n
r
r'
I
(
-47-
, '
I
l .
n 23. Felsing, W.A. , Day, H.O.,J. Am. Chem. Soc. , 72, 1698 (1950).
24. Jordan, T . E. , "Vapor Pr es sure of Organic Compounds" Interscience
n
r
1
-48-
!'
L_
29 . Carlson, H. C., and Colburn , A. P ., lnd. Eng . Chem ., 34, 58 1 (1 9 42 ).
30. Renon, H., and Prausnitz, J.M., A.I.Ch.I. Journal~, 135 (1 968).
31. Naphthali, L . N., and Sandholm, D.P., A.I.Ch.E. Journal, 17, 148 (1 97 1).
r'
Il
( ,
l,
~
n
n
n
~
1
I 1
l,
-49-
l.
t: ~!?!?::~~~::::::
L
L
['
f'
e
L
L
!'
r'
r
r~
. J
n
n
n
fl
n
~
!" , .
:!
I
L ... -1-
Deviations in the ideality of the l iquid phase can be described making use
of the concept of " excess funct ion s ". The molar exce ss Gibbs energy , for
example , is defined as follows:
[.
E g ( actual soluti on ) g(ideal solution at)
g = at T, Pand X same T, Pand X
[.
This function is th e most u sefnl one fo r our purpose , because i t c an be
dire ctly r e lat ed to the activity coefficient by means of the rela ti on :
n
E
g = RT L x .lny.
l l
i=l
Th? excess Gibbs ener gy l S formed from two , parts the excess enthalpy and
the exc ess entropy :
E
r '
g =
E
v,T}}en molecules of unequal Slze are mixed, hOIvever, it lS better to set h
r1 equal to zero.
Solutions in which hE = 0, are temperature independent because mixing o~curs
I
l,
( , E
n 0.l
g = RT E x.ln
l i=1
l
x.
l
r- J.n ,.rhich :
ln "hich:
In order to obt ai n the i-lil son equation a binary solution of components 1 and
2 is, firstly, considered. If a central molecule of type 1 is considere d,
r: then the p robabi lity of finding a molecule of type 2 instead of type 1
around this c entral molecule is given by the relation:
x exp(- À /RT)
2 12
= (6)
x exp(- À ,1RT)
1 1
x exp(- À /RT)
1 12
n = x 2 exp(- À /RT)
2
n With the help of these definitions Wilson redefined the volume fractions of
the Flory-Huggins equation into what he called local volume fractions ~1 and
~2'
r
I
-3-
r '
L
x v exp (- À1/ RT)
1 1
[. ~1 = L L
(8)
x v exp(- À /RT) + x v exp(- À /RT)
1 1 1 2 2 12
[: and
L
x v exp(- À /RT)
2 2 2
~2 = L L
x 2Y 2 exp(- À2 /RT) + x 1v 1 exp( - 1. 1/RT)
If we define
L
v
2
A
12 = ~ exp[-(À 12-À
11
)/RT] ( 10)
v
1
and
L
v
A 1
21 = L
exp[-(À
12
-À
22
)/RT] ( 11 )
v
, ' 2
l,
E
L
RT
= ( 12)
E n n
IE-
RT
= LX. • ln ( LX. A. . ) ( 13)
n
i=1 l j=1 J lJ
ln which
n A. .
lJ
=
v.
~ exp[-(À .. -1. .. )/RT]
vi lJ I I
11 v.
A. . = ~ exp [- (À .. -À. . ) IRT]
n Jl vj Jl JJ
I .
n n x.A· ·
l l k
= ln[ L x.A .] + 1 - L ( 16)
l. j=l J kJ
i=l
n
L x.A ..
j=l J lJ
r'
L In the special case of a binary system one gets
r = ( 18)
[ :
[,
rl
II
l J
n
n
-1-
The program , by means of ,rhieh the constants in the liquid molar volume
equation are ealeulated is essentially sclf-explanatory . It ean be desc rib e d
[:
seh ematieally as fol l ows :
v 21'2 ; v3'l'2 I
v
Caleula~~l
~
v._-'-" --- J
Caleulat e b
---_.
'v
I
Caleulate a
Print result s
I ~
2
= a + bT + cT
n
n
n
n
.. --- ,.....
i ) .---. ,----, ~
r--; r--: r--- ~
,
~ ::-=;J ~. ] ~=:J c:::::J :==J
*\~ A TF ! V
c V,'.ID l
C
C
C lHI S PRO GR lIM CAlC ULAI t:S T H~ I) Ef'tN iJb~ CE lJF rHE PU I<. t:-CI)I'If'UNFI~r
C U QulU MOLIIR VOLUME UN THE TEI'IPERATURE
C TH! S OEPENDENCE HAS lH E HJlliJW IN(; t'Üf(N
C VN OL(CM* * 3/G MO l) = A + 8* 1 +C*T**2
1 011'1 EN S lOr. A ( 10) ,B ( lO ) ,C ( lO ) , T ( lO,3 ) ,V ( 10.3)
2 RE ,\ I) ( 5 • 1 ) l
3 ~O R~I AT( 1 2 )
4 DO 2 1=1, l
5 2 REAU (~,3)(V(I,J).J=l.3)
6 3 FOR i~A T( 3Fó .3)
7 DO 4 1= 1 • L
8 4 REAU ( 5 ,3)(T( I,J),J=1,3)
9 DO 5 !=1,l
10 C(I)=((T(!,3)-T(!,1)) * (V(!,2)-V(I,1))-(V(I,3)-V(!,1))*(T(),2)-T(),
11)) )/(((T(I, 2 )* * 2 - T(I,1) **2 ) * (T(I,3)-T( 1,11 11-( (T(I,3)**2-T(I,11**
22P(T(!,21-T(I,l))))
11 R ( 1 ) = ( ( V ( J ,2 )- V ( I ,1 ) ) -C ( I ) * ( T ( I , 2 ) ""2 - 1 ( 1 , 1 1 ,;,,;, 2 ) ) / ( T ( I ,2) - T ( I , 11 I
12 A (I)=V(I,l)-(fHI) * T(I,l))-(C(I)*T(I,U ~";'2 ) ·
13 5 CON TI NUE
14 6 WRlTE (ó,7)
15 7 F OR I'l AT(1H1,'VALUES OF A(I) , B (I) , C(I) , HILlli'tl 'In
ló ,oJRIT E(ó, 8 )
17 8 FOR"IAT (lH ,'VMOL(I)(CI~*"3 / GM() U A(I)" B(I)~'T + C(ll~' T * *2 '
lil)
18 \-JR ITE(6, 9 )
19 9 FORMAT(IHO,'NO.',T9,'A(ll',T24,'l\(ll',T40,'C(ll'l
20 WR ITE(ó,lOI(!,A(Il, B (ll,C(I),I=l,Ll
21 1 0 FORMATl1RO,I2,T9,OPF10.3,T25,lPEI0.3,T41,lPEI0.31
22 20 STOP
23 END
*DA TA
---
,. i
L-,
-1-
r'
l ,
[:
L
"
L
Compute matrix
etements
[~
[ , Sotve tor
C1 • C2 • C4
~
r'
l, Compute sum
square % error
r~
r~ Change C6
l.'
No
n
0 \
n
n lnpo( atm. ) = C
1
+
C
2
(ToK)
+ C (TOK) + C 1n(ToK}
4 6
(taken fro~ Prausnitz (19) pp. 75; detailed discussion and nomenclature
G' is given en p.p. 155)
r
----j ' __ J -------. .-------, ...--,
::=J ::=::J c:::J ~ ===:J :-J
.-------, .-------,
J
,......---.
:--l :---J ~ r---: ,...--, ~ ..------.
•.'
... ATd V
l 'IAI''VIT
l
(. fï, ...H:'"MI TC' llhTAHJ PAPfli'tf'TE, - ::, U~ ~lllif( r - " :'_ \M f' T~, VAP. P ~c,. f -, J ~~
l
1 Hl t ... ! II T ~ c ~l ,. Ol I A- Hit HAL" IJ I û- L I
<: OIMLi":>lUN Tn 1181, lUfiHIZI. TilJu), CP~flTllultPI1.001,
ifllL"rdlOOI,YCALllOOI, ti:Ll1001 ,I-CO(- STl1. n O). [ll(\FST(1(lOI
3 LAI-MAJ\ "C=
4 1 .... LAU 15,':, H![l = 9991 JO
5 UlhllN =
0.00001
ó lû~,",AT I1RA41
7 "t':'''' 15,10IN, rer'IT, I-(.I.,IT, .. U ('rlT, TrIX, PFJX, Ffl~"AX, IDUIT
U 10 ~u l,i1"T I IE,6F9.4,16X,<:A4)
4 If lid 9S<;,S°<l, 11
dl 11 ~ U! iiT::. = N
11 :>I"ut';,,,, = PIJIN~<: f~rMAX * •• 2
~2 f,EAU 15,201 Tl, Dl, T2, 02, T3. ';3
U 40 n",,'MAT I bF 12."1
J.4 vl "clGIéT / [11
l~ "Z "U(.HT / D2
lu V3 "êl(.HT / ~3
17 Tl Tl .. TH X
lb U T Z .. TI' IX
19 TJ T3" "-FIX
20 uO .;;0 1 1, ~I
LA. kEf,U 15,ZOI rl!), Pil)
22 TI -I) = (Til) .. TFIXI I 100.0
~J PI ij = i'II) / f'FIX
24 ~o C0 " T HWI::
.:.5 LAt 0 =
20 T::'"i'I C.O
21 T"::'ur·\ 0.0
~6 r::,;:, UI1 C.O
~9 14;:'u/·' 0.0
~O OU 40 J =
1, N
.:>1 l:"uM lSl;H .. TIJ)
>, ' )
... ~ T 2;:'U,-\ TZ SUM .. TlJI*.Z
j:; T ;,;:'ul-\ T?5L!1 .. TIJ)":;
.) 4 T4;:,U~i 145UM .. T( J )**4
,,5 40 l..UiI·IIIWE
3ó l..l>;:'Aï(ó) 0.0
j -r Jlf'::.AT -10.0
:: 0 S-i U t:" r = 1.OrnO
J'j .,vi\..>~P '" 1.Of"30
40 5~ L Af' = LM .. 1
'.1 1';:' u1'1 0.0
4.! Fi'::'ûll =0.0
4"
,.4
I T ,;:'0"
lJ0 55
C.C
J=l.N
45 n = IlJLU«PIJII - CPSAlioJ • ULûGITlJI!! • TIJ!
4ó PS0M PSUM.. PT
4'1 I-T~UM PTsur·, + PT. TIJ!
4tl !-T,SuM PT2SUH" PT * TIJI*.Z
49 55 l..01'11' lNUi..
')u d = I-~UM * T3 SU., - PTSurl * T2;,UM
,1 L~ = PTSlJM * T4SUM - ~lZ:>UH • T~SUM
:'2 All PUINTS * T?SUN - TSUM • T2SUM
53 Al, TSUM * T'SUM - T2SUM • T,SUM
54 A21 TSUM. T4SUM - T.!SUH • T3:>UM
~
*LJATA
, ,
-1-
r '
l,
Appendix D
-----------
The program by means of which' the Hil son constants ar e calculated can
be described schematically as follow s :
L -
fi.-Yi. )!'J,o(P OI exp (P V/R~ '
i,I) ,
:r:
r'
l,
Intermedia te
printoul
r
I New eslimate of Parameters '
( J mode by subroutine oPPc\f;
. . ._ _BR-P'UIm...·!ll
·.:., .'"'~
n Yes
D
o ,
i' F'gure 6·2. Schema tic diagram for program to fit Wilson parameters
-, ;
n
n (taken from Prausnitz (19) p.p.
is given on p.p. 162}
77; detailed discussion and nomenclature
.----., --------, ,----, ...-----, ,..-----, ,..----. ,..----. - r--
~---"J =--=:J ::::=:J ~ :==J ===:J ~_---.1
-' :--J . ~ ~ L
"
- ----- ---------------
r----; .-----, .------, ,----. --~---:-
~~ ~ ~ __ J ==:J c=J ~ _ . _ . ..J
j
~
:--l ~
~
r-----; r-----o
.------
~
~ ~
~
:--J ~ ==:J r==1 r=J r=J ~-:J 1- j j I I
•
CUNTINUAflUN UF PKUGRAM: ~llS
380 CONTINUE WILS 3~1
38 1 Rt: TUKI~ lolI LS 352
END WILS 353
C ~IL5 ]54
CVIRIAl WILS 355
SU~RUUTINE VIRIAl WILS 35&
C wILS 351
C SUbROUTINE FOR ÇALCUlATION OF SECONO VIRIAL COEFFICIENTS WILS 358
C WILS 359
lMPllllT kEAl*SIA-H,[-ll WilS 360
REAL*4 TITLE WILS 361
':OMMûi~ reKlT, PCR lT, VCR [T, OME GA. VII IJ, CVU lol. PSAT, CP SAT ,e AC TCD. GAMMA. lol I LS 302
1 X.SUMX,Y,SUMY,P,1,TOLO,PHI,B,8MIX,VMIX,lMIX,F,FREFER,HENRY, WILS 363
2 CHE I ~Ky,IILlI,jL,ClllIQL,O""EGAH,OIPCLE,i::rA,IIRATIO,RT,RRT, WILS 3(,4
) TITLE, N CUMP.NLI~HT,NACTCO,IOENT,NKEFER.NCRIT WilS 365
OOllk l~ 5 IU .'i TlTU1161, TCRITIlO,lOI, PCRlTllOtlOI, VCRITIIOI, WILS 366
LUHEGAIIUI, lUENTIIO,21, VUQII01, CVlHII10,31, PSATlI01, WILS 361
2CPSArllu,6I, CACTCOIIO,lO,3I, GAMMAIlOI, XIIOl, YIIOI, PHIIIOI, WILS 31>6
38110.101, F1101, fREFF.RIlOI, NREFERIIOl, HENRYII0,lOI, WILS 31>9
4CHE I'II\" 10, 10,21, VLIQUI0,l01, CIIU\JlIlU,lOt2I, llMEGAHtlOl, WILS 310
5ülPULE1101, ETAII01 WILS 311
P2VP~ITR,KOI = -5.237220 + DlOGIROI • 15.065607 + DlOGI~DI .( wILS 372
1-2.13j810 + OLOGIRDI * .252537)1) + 15.10~110 + OlOGIRDI * (-6.181WllS 313
, 24l7 + ,OLOGIROI * 12.283270 - DlOGIROI * .L6490741)1 I TR wILS 314
DJ ' 2U2 I = 1, NCllMP WilS 375
Ull 201 J e I, NCOMP WILS 376
TR = TITCRITII,JI WILS 317
' w = (OM EGAlIl 11 + OMEGAHIJII I 2.0 WILS 378
OSECVIK = IJ.1445 -10.330 + 10.1385 + 0.0121 I TRI I TRI I TR + 'W WILS 379
1* 10.073 + 10.46 -10.50 +10.091 + 0.0013 I TR •• 51 I TRI I TR) I TRwlLS 360
211 WILS 381
IF IDIPUlEll1 • OlPCLEIJl1 200, 200, 100 WILS 302
100 IF 10.95 - TRI ioo, 200, 125 WILS 383
125 RO 10.E04 * OIPOL[II) • DIPOlEIJI • PCRITII,J) I ITCRITII,JI WIL~ 384
1*.21 WIL S 335
l~ (KO - 4.UI 200, 2CO, 135 lol ILS 336
135 SECVIK = SECVIR + P2VPFITR,RD) WILS 30r
150 If I[UIl) + ETAIJ)) 200, 200, 175 WilS 388
115 ScCVI ~ = SECVIR - 0.5 * IETAll) + ETAIJl) *OEXPI6.ó • 10.7 - TRIl WILS J8~
200 Sll,JI = SECVIR • 82.057 • TCRITII,J) I PCRIT(I,J) WILS 390
B(J,lI = IH1,JI WILS 3'11
lOl CONTINUE WILS 392
202 CONTINUE WIL S 393
ReTURN WILS 394
END WILS 395
C WILS 3g6
CPHI~IX WilS 397
SUUROUTINE PHIMIX IMARKI WILS 398
C WILS 399
C SUURUUHNt: FOR CALCULATION OF VAPI:R P~tASE FUGAClTY COEFFICIENTS WILS 400
I
:--J'"
,----, ..----,
:=:J =:=J ==:J c:J [ .1 t=J :---J :---J I ~ ~
,-----,
j
r----' r~, r' ----:'"' r:::-:: I
l_
I)
I
l,
-1-
The method of mass balance used in the design of the column lS called
the method of successive flashes ( see Hanson ( 20 ) p.p. 12).
The unsteady state equation for any component i on any stage p of the
column "\wuld be
dy dx
Sv _.2. + S --12. = (v Y +L X )
p de Lp de P P P P
[: ln which:
L liquid flol-T[kgmol/hr]
= V K
p-1 p-1 p-1
X + L X
p+1 p+1
- X (V K +L )
P P P P
(2)
r'
I
Substituting the definition
l J
T = els lp
rî
or
[1 dT = (4)
n results in:
dx
n . -12.
dT = V K X
p-1 p-1 p-1
+ L X
p+1 p+1
- X (V K +L )
P P P P
n
I l
r'
I,
L ,
-2-
Defining
(6 )
s = ( V K +L )
P P P
dx
dT = ---"L (8)
À-Xp S
À
(X) exp(G~) + D [1 - exp(-~)J ( 10)
p r ~
where
~ = BAT ( 11 )
[1 V K X
À p-J p-J p-J + Lp+J Xp+1
= ( 12)
B V K + L
P P P
l _
-3-
r'
,
L.
This equation has the exact form of the flash equations and that lS
[:
[,
I
L ,
n
n
o
n
n
n
r
l •
11
l J
-1-
Appendix F
----------
[~
Set varlOUS counters to zero
V
Fin the X, Y and Y a rrays wi th
starting values
I-
I Calculate boil ing point f "
,; I Calculate plate composi tions 1
[: No
I Ca lculat e yl < ABS[ (SUNX (J)-1.0)-SUMERR ]~0 ] \/
,
rl ', 1[\
Yes
L
"
/
No
I ABS[(SUMY(J)-1.0)-SUMERRJ~0 J
\ Yes
rl
L /
No
I
ABS [(RFSUM-l .0 )-RFERR] <0
-
I
n
n
~ I"\ [
~ ] ,.----------, ..----.,
~
...----, ........----, ........----, r- r - ..... ......--
~ =--=:J J =::::J c=J =:==J J .
1" .-.rJu KIL ,I j ) , "u I IJ ( 1 \1 J ) t f,' LL IQ ( 1 ,~ ) , f U 1 V,ul ( 1.) I , F IJ .~L! J ( I ' ) I , r n l V ~ I' ( 1'1) , f Ij{ S 0
LIl .... LI.tl L 0 1 ,~ ' U VA P ( 1 (') ., lil trll ,11 ( 1 d ) tC ( I ) I , ._,,\11L ( L:.1, 1') J I, fC ( lOL I t 'i 1'''1 ( 1 n " ('i I
3L I , L .. " ( 1 ,).:) , T 51 1 J ) , RF il" Tl 1 0 I , Kr r [lP ( 1 J I ,Id- :.. U'1 ( 1) I , ,lflT" ( IC) , T Co r L> ( 10) !l1:; IJ
4 , .. JIJ A ( I J I , V;. i'Y ( 1 :J I ,C/,'!:' 1\ ( I ·) I ,~ 1 '; '1
Ctj,.I ,", I. , " L ,.X ,u c.-jy , S L '" ~ , :; U'~Y , rf' Mf' , V:,,'u,{ , ~u I i I, Fr: 1 L I 'J' n; 1 V bI', Fr: ,! L I ','; , f C I: I ~ 1')
l.cV IV, /-1 1 JL I ... , F J:J V"'I' , ~ , 0, C, CA ' IL , h .. t :)f' ,'I, [ .,r- , r s , o1f h ' ) T , ·H rIJP, ~ r <; \, ~ , Hl T P I. Ir, 11
2,TUI'I', wJ 'J X ,~ A "'Y,(~~:'A 111 5 12
c:~Ullr- (A'J,C,II~t:xD(A/(T+4(,C.OJ+Ll+'-"*l 1+ .. ,,0.)11 r [~ 13
100l KE'\il(5, j IL, M ,~L,ML,N 'liS 1"
J I' u 1~ '1 \ r ( :, 1 31 r. I 5 15
lUl>I':,\ L J t. jSU:>I C I'~ 10
i\l i. ul J ' '':~ J I~i:.ól: (I I ,SE IISr: (51 !'1 <; 17
22J Flold'i ,\ T ( ~ L "I I; I S ld
Jl = ooi +1-1 L t i 1.< +;1+ 1 US 11
Jl = J r + L 0 15 2C
J U= JL+ I CIS 21
J,11 1' ; JT-L IJ I') Z2
,{L ,\L'I ?, " ( Tt . ~ i' 1 J) ,J = I, J rJ j) 15 23
'. h J ... ,11\ T ( Ir l.i • ..: I Cl :; 2'.
"Lll l).I ·J, ·.) Iv,\ I' ·..JI( IJ I,J=l, J r. 1 111 5 25
KU\l } I~, !,ll.J(UIJI,J=I · ,J [) 1 DI, 20
H ï~ "iJ I ') , ·, I I ' : 11 lL I .~ ( I I, 1=1, L I U I'; L7
Ku\ ·. )I~, ':' II"' I IVAPIII,I=l,L) D I~ 2 ,J
),L .\l.l 1 ') . -, I (I ,J ': II J ( j I , [ =1 ,L I [; I'; iej
Rb\UI:., .. I(t li 2VA"'lll,!=I,L)
K[ 1. 1: 15 , 'T I 1i ,)j L ( " 1 I I , I = I, LI
.fiS
D( S
30
~ 1
RCÄJI~, ti (I I.. JV i,PI 11 '\=I,lI (;1') 32
d b ruK .'1 AIlL..: l u ....d . US jj
Ri.. AJ 1j , -':.:l I 1 " I I I , I = l,l I Ol S 34
KUw 1 j , 'IJ I I b i ( I , ( = I, L I [ I'i 1',
RlI. J ( :> , d ..J )( l. 1 11 , I = I, L I ~ IS j~
~[A D I5,~IF J llIS,fCl~,s.rC2l1s,F~2VAS.FUJlls,rC3VAS f) I 5 37
Kl I,u 1 J, ft! SJ n U\", RF[ P R , ~; PERR CIS Hl
,., " ITU f. , :>I PIS 31
j t-u Kh Al i '. 'hlll r,PUr f),qA FOR PRCli . NU. us [:'/'; PR O(IIAM '.)
DIS ',0
W" , I T [ 1 (.. , (.. ) l , H , ,., l,l~ 2 ,~; n IS ',1
(, fu KI1 ,\T (Ili,rll ,ü). cr CO ' H'CNFtn5 PLt.ftS [ ~ J S': CTI "J,j ~I PLATfS niS It 2
11 ,. Sl LII J. l ,.IJ. PlATr S IN Sf:I..TIU ii i~": "L"Tr, s UI SrCTIGI>l NII10 1; 1<; 43
.1, I~J, U", li?, 1':;)1 Cl') 44
~~ITtl o ,71~UILIS,fflVA S .FC2LIS,fU~"hS,fJJlIS,f0JVA~ nIS "5
7 rU H:-\.\T (:.i vIIUfLtLl fLtJIIS IN GHOJFil. Of l .J"i..JT EI-<Tf.,'U!'i0 Tij I-l(,HfST/JtH-O l) IS ',0
lM,ILL :; F [c " Ll",UILl 1-1<.~ lfS FEE,) VAl'lJK/(t'lb.tl,l21.'l11 C l') '.1
W~ J Tt I I" .J J I I' UI L 1;.. , 1 ) , FD 1 \I AP ( I ) • r f)~ II J liJ, r lllV /I r , r I, r 0 IL I Q I I I ,F n 3 VA C IS ',8
lf'llltl=i,Ll n is 49
(l FUK I1i.T 12jlliJ(.ul1f'û/ü~T fEEC AMtJUhTS/ '),H LGllf'~1 HEf) 015 'ja
~ ===:J , J ==:J ===:J
.....----, ~ ....--------.., .---,
_ -.J
~- j
....--------.., .---,
j
.---, r----'
1
A
"'\ 1 I L ( " , ) ) ( I. ( 1 I ,ü ( I ) , C ( I ), f = 1 • L I , I J ~ t.
'1 FIII\l1:,r (J"10 t;.lU Ill ClP IU:-1 cc/\;n',f:;.\ (~UIL!'liUU" (;[,~srM\f'; 1\ J I '; ~r,
1 L,,01LlHI(lUI1 Cl.'--IS TA I;TS (/(U'i.o,LlZ'). ,lIl L IS 'J u
\1KI 1db 01 0 ) S 0Mli{/(, P-F,R R , APF.Ht< IJl S ') 1
1<1 ( 9utioJC:F.k uR Ll/ilT eN SV-IMA TIu,' 1
f tJ",~"T t<l;{OR ll"'IT C/\ Ilbr:rVEIlY F r:IS 5d
l i\I\CT l v i SU ;" 1:t<P.C'< l IMIl 'l'j l:U[',b LL f'ul;n/[:2'). 'J,[3'.i.hr~(,.f!1 LI S 'j')
.. "iEl , 0111 ITEl"IPIJI,~~PCRIJI ,r;UIOIJI ,J=l,j f) IJJ5 ~c
11 rU ,, ",AT 1:;~rl0 T~ t~r rRA TURfC; VAf'ut< ~lC.;S lIr.UIC rLrI,S u s (, 1
1I1.>t.!J. il ll ni S 62
SU :>I, r,,=0. () u IS (:)
SU J~ r =0 . 0 ~ I S 6~
CH[C~=~.J OIS 65
I TU, .:. r = Cl [) I<; 66
IJL' 1 L 1= 1 , L f) 1') (, 7
1o:! T.> I 1 ) =Ft) 1 L 1.. I 1 ) H [ tv" P ( 1 ) H ;) 2 L (0. ( 1 I .. F J ~ VAI' ( I I +r f) J l I H I I • HU IJ M ( I I :) I S (, 8
SU;-u J L =hJ 1 Ll .lH-U':L I S+H13 L1 0; n 15 (, g
Su,·d" l'. = h H .... A'; t-F U2 v A5 +F i' 3VA S GIS 70
I1 ( --,IJ '1ruL) 13,LJ,17 '11; 71
13 11' ( :;c/ ',1 iJ -'1 I ~l,~l.t~ Cl:; n
14 J.J 1 ~ 1= 1, L C15 7J
15 vÄ PY I I I = I FJ1 "Ai> I I1 Hen AP Ii1 HUJV Ar I 1111 SUI'~FOV Cl I ~ 1 1,
T=ll --11' 111 L,; 1S lS
CAL L ij [,, 1'.1 ' -Ol\!' Y , T , ~ , tJ , C, L , 11 P OR f\ I IJl S n
LJG 1 ,'> l=l,L l) 1 5 77
1<.. JU lIJ ,« I ) = v.:Ir y ( II/ H L! lK (A I II , 1\ I I ) ,C I I1 , r 1 Cl'; B
~u T d lJ IJ 15 7')
17 Ir l"oJ1FOv) ld,lJ,21 • DIS 90
1J UU 1-1 f = l,L f) [) '31
1'J JU IU,\ I I 1-= 11 diL 1'.. ( I l+ F8.' L 1ç I ( IH C .3l1 '" ( I I1 /:) U,.., FCL Cl 1 5 _J 2
T=rL,1P Ill UIS il3
CALl il lJLlrr I\'/UIJX,T,A, fl ,C,L, p,fl ~"RI r:lS 34
UL; .!. \ J 1=1, L I)I5 ~5
20 VAI'Y(1)= .. ulcJ,,(III*cCLllKlhlll,01I),!.:III,TI L,;IS 0'>
Gû r.J 2:J niS 37
21 Vl' L~ I =1,L [) 1 5 ~ i:
UU 1 u " ( I ) = ( 1- u lU i,l I 1 I H [) l l I ç I I I q. IJ JU ,. I I I j I ~ U.'I f r; L D 15 J'l
2': ';;",'Y I 1)= I !',HIIAP I I) ~FC2VAP I rl .HJ.3VAPI III/SJ,'~FDII L,; I ~ 'JI':,
LJ ;1.) ':", J=l,JU f) IS 'H
lJu ~I l=l,L CIS n
GLNA(I,JI=JJIUXIII DI S 9.3
Gt: ;jyll,JI=VAf''I'III IJ I <; '1'1
24 ",\i1L , l, J ) = 1.0 UIS 15
C u IS 'J(>
(. C" U;ULIITld,1 Uf PL,\TE ColMPOSITTur~ IJ IS ') 7
C r 15 93
.!5 DG ':", 1=1,l IJl <; 0;,
OU 2. ,> J~l,JU IJ I '; 100
· ".. .-----, .-----, ~
~
:------J ::-l ==:J ::=J c=:J c=J :-=--J :------J :--l ~ r---'
LlJI+ I . 0,, - Lu C 15 1 27
l,l . •Y 'I , J) =0L1 j X (I,JI ~ f :.l K IJI 11 1 5 1 ~ fJ
2. J J = J-t IJl S 12'1
.it. I" " I, 11 = I vl: ,L( I I , 2 1.')1J J 0 ( 2 1 +F f) I LIl / ~ F M( 11 .. 1. Cl; -2 ) UI S 1i0
~') Gt:J. H .l,Ll =v L" X(I,lI +ECK llI !) I ~ IJl
I. PiÜ J' JlIl. r A, ·l ,J.J I~ T~ F(CG VE ~ Y F HACT 10 :15 SUI'!'l i\ T I l F IS ;) I S 1j 2
C Cl S 133
C [l I S I ~"
uu TP ; = '.). U C IS 1]')
T uP t' ,; ~· ) . U CI S 1 36
$ U I'.f- 0 =. ) • 0 015 13 7
tJu ,)0 l = l,L I) I S 133
Su .·\ F J"~ UI IFI ) + r s , 11 [) I S 1 3 ':1
T Ut'~ (I) =~UIJ (j O I ·(~~X II,jC) lJ I S 1',C
k t- T.J f' , I 1= T JI' P I I I / I S ( II C [ S Jltl
*
Uw T I' I I ) = "i U I J ( 1 I Gl ' JX CI, II !J I S 1 ', 2
Rh , u r I I1 = llu TP ( i 1 /l S I 11 IJ 1 S I ', 3
kt-':>U , H II =I\r r U P(II+ ~ F [l nr(l) , fJ I S 1'+"
ûLlT I' S= :j, lTP:' +uLlTt' (11 11 1 ~ 1ft 5
J u TlJPI' ::> = TUPl' ,,+. fOP ? ( iI 0 1<; I ',t
1)1) ,) 1 j = 1 , j U O l S 1 /,1
S U ;~,( IJl =v . a DI S I', S
SU.-\'( I J 1 = v. 0 C I S lft ':l
0 ,) J 1 1= i, L r: IS 15 C
.....
~
" ~ ] =:J =::J ::=J r------'
'------' ~ ] ::--=:J ~
.------, .----, .------,
j :-J
r-------.
l-: ~
[
bj
"ij
LJu u .1 l=l,L
\IJ ," I I = ~ C:
~M-: " I~'II ='; .\.'\L (I ,J)
.,x' I ,J I
111'; 2J5
CI S 23'>
f)IS 237
U .. lL ülJ b P f~ '~UI0).,GAMMA,T[ i~P(JI ,A,Ll,C,L,tiPr:flf11 r.152J'.1
64 Cu!;T L, UE [) IS 239
Tl ,'H) 'J Ll ) =Tfdl" Jel D 15 ':4'.l
(,U Tu 2'J C I5 2'01
[t,u nis 2',2
C UI'j 2 'tJ
C [1<; 2'<4
L :'U iJl("ClTI.I[ rul{ 110LCING P.ECllVEP.Y FI : ALTIIJ ~; UF t. C I I~PUIJf.ljJ IN lHE TGP DI 5 24~
C "i{uUUI.. I ,) 1 S 2',6
C PRLJvHi\ ' 1 4 IJ 1 S 2',7
C niS 2"~
C U IS 2', '1
SU i H(UUf"i~ I-.FI '~U Bfn,CtlECK,JTtJOI [IS 2:;0
<
~
~
:::----:J ==:J :=.J c=J C:J ==:J ::-J ---. - ._ --, .--------, ------------, .----,
~
.----, r----" r--~
3'::1, ~ ""I lJ':I, T~I IJ I , ; !_ r'~i' TI 101 , r,1 I'H'( 1 JI"II' JIJ '" t lI,. i) 11'1 IC), Ir,Fl'1 Ir) ", 1 ') • ,.. '.
't , .. JIJ l\ I t ,-,) , V ,H' Y 11 C ) ,G ,\ ' \I~ \ IlO) ,_ I ~ ~ I ) C)
CUm,U,j vl :O" (jun, ~ L ,~ ), '; L.~IY. TE Mf', \11, P<JI~, " u liJ, I' J 1 L [ ,J, F ,)[ 'I H , F r.7l H.;, • r r I (~ t? ~ '.1
1211 AI', FIU l l .. , fJJ VAl', A. R, C, GAHI.. FI; , SHI,I:: _ .1\, T S, RF lHl T, ilF TUI' ,RF SLM, lj/lTl' I1 1 ~ ol. ~ 7
L.TUf'r,wJI0A,~~f'Y,GA~~A IJ 1 S 2 t. 11
3 HJR ,\ , .. T 113,2rd.31 :1 1<; 2'J ')
IF '~;Uti ,':T) '),'t,5 lilS 2e:.
't Rt.;\J'~,j) ll.. l"kFrCC,RFI: I~R DIS ';/'1
Su , j~, T=~ J ei){ T + 1 • U Cl <; 2,r,z
AS::; l,j ', 7 Tu i.U :1 rJ! S 263
'j I1 'Ao"l"rTCl..-,lFTCf'IICC))-RFERR) 17,l7,o CI5 20 "
t.. .:;U TJ :'l:,'I, (7,'1,11,12) , :; I ') 261j
7 RF Tt'=hl- T 'Jt>1 [CCI [) IS 266
";U[ UI.=J 'J liJl JJ) Cl, 1.67
IF 1 ,' fTl..L-,;H d PIICC)) ,'.1,17,10 Ol S ;>(d
::l KI- T" ="
r TJ I' I 1 -: l..l DIS 2 (} '-j
0t::li'=-.1)*~u10'JJ) f) I, 270
t;.0I u.J = .. ,J{ IJl JiJ I ') IS 271
~UIU'JJ)=~UiJ'JUI+nELP DIS 272
... ~:.I.>;l '; TJ ;W ,'-' OIS n3
";L. T.J Ij DIS 27'0
'J 11- 1,, 1 TLL-,.f TJf'1 ICC)) '1,17,12 Cl'> 275
Il' IlfTP="rl u l'(Il..l..) rJ I 'j 2 (IJ
LJt ll'=.,. ') .IJ~ ' ,JILlll ) DIS 271
'J uILJ ,; = ,.ui :1I J.)) CIS 21<1
Ql' llJ I J Iq = jJ I'; , J C I .r: ELP [) I 'i 27<)
A, $';l"l. 11 T,j "IUM [lIS 2!jO
Gu Tu LJ hs 2'11
11 If IKrfd. - .': I' l,JPIICC)) 12,17,11 ij (S ?J2
lL SLUj'ï=(i,r Tl't'l ;-:CI'-U1P) 11 I;; U I I; (J';)-..ilJ IlIlJl IJl S .!JJ
ieU I LJ;j= ( I i : I TL..L -t{ F T L P ( I CC: ) ) I SL C Pl ) + ~u It) 'JU I i; IS 2\)lt
RI 11'=,:1-' Tdl'( IC ... ) I~ I 5 2~ ~
I./Uluu=IJJIII\ JJ) lJl'; ~%
.J'J IU( JiJl= ,jJ liJ II [IS 2:17
DE LI'=", ~ J1 cl( Ju) -.U I t;C DI S 2 (J e
,AS::;IG" u Tol ;,o,'1 nIS 2UfJ
I.> J, J l" J = 1 , J 1 Cl S ;")0
1't V hl'lJ~ IJ)=V~~u~IJ)+crlf' I) I <; 2 '11
oJJI :JI U="Llll. I U-lJHf' r; IS Z')2
Hl. TU '{i' j I, I S ,~ 'JJ
1~ FU,, ~\A T ":'dûPKUllLEI' ~(j;1 wild RFCJVeKY fl-:ACT [eN 11' 'mI:: CUMPr)NI:NT 1'1 [j (5 29 ,
1 TII L Tol t' f',',, :)UC T ~1Ol/3/tll j,r-CUIIERY FR ... l.. TI ON cr r:C:WC'HI\T 17,9,", 5 r.1<; 2"J5'
ZET AT F"."" [) 1 S 1.9(,
10 fuil"i.r l'tjrl01.lIlCl.llllfD RE:CCVEIlY I'RflCTlu;j uI' ct:'\I"J'lLtIT 12,)H= flj.IJ û I') l ' /7
11 JIS Z9i!
17 ~Rlrt'G,I))ILL,RfTCC I; IS L SS
wRI Tdo,[oIIC\,.,HF 'CPIICC) DIS J00
j l'"'l
:=::J ~----, ~ ~ ..-----. ,----., jOI\
.~
C
..:
_"'\ ,,:) ...... ;::)
:.J C" 0
r:''''''""''''
u C · _ - -t ~
...- ....- -1" ..:!" ..t' .~ .... ..:!" ..:
N ," ",
_ _------
::
.......
=:-:
~ :...:..=: ':...J u 2
r'
l
[ ,
[,
[1
U
...., ..-
+
c. ~-
..... c..
-,J
::l-J
'<VI
:r. ...
J-
'.I"'::
' '<
<::>
', J
,.,'"
:
~
j
'1") ' <
I ~
rl - .0
-~ ~ ...
-
11
j "-:>
• 'P
...... It ...., Z
~ ~~ ~ -:') U - -:) ~""
--.-<- .-
_ -:l..-<~~-::)
":JII':""" .....
~ H
~
~L.:.'?-::
::: -
tt :.:J: ..J
'. "l _ _ '.:J L'\ ; - .#'\ ....
~::> ..J 11 :::l.J.,,; '~
t- ..!) ~ W
Z
r 1
L..
-1-
l~
[:
A letter vrritten to professor J . M. Prausnitz of the Univers i ty
of California, Berkeley on the 28th of Mareh, 1974 .
['
[,
l:
I~
l J
fJ
rJ
n
f;
-1 -
I. Beschrijving van het vlo~i st of-dampevenw;'cht voor het systeem mono-, di-, trimethylamine en water.
2. Draaiklaar maken van een pregramma voor destillatie van niet-ideale multicomponentsy~te~p.n.
3. Ontwerp van een destillatiekolom voor extractieve destillatie van methylamines met water.
De bes?reking van het helder ge schreven verslag, dat laat zien dat een aanzienlijke hoevee!heid werk is verzet,
concentreerde zich op de mislukte poging de destillatieberekeniu 3 uit te voeren. Als resultaat van de bespreking
volgt hier eeu korte discus~ie van mogelijke oorzaken en een s amenvatting van suggesties voor voortzetting van
het werk.
I. Het destillatieprogramma bevat fouten. Dit is niet waarschijnlijk aangezien het testvoorbeeld goed draait.
2. De evenwichtsgegevens zijn niet correct. Dit lijkt wel waarschijnlijk, temeer daar het destillatie programma
vast loopt op abnormale temp '~rat"ren. Ervaringen van De Winter geven aan dat het dan meestal gaat om foutie-
ve evenwichtsgegevens.
2. I. De hier gebruikte Wi lson-vergelijking zou niet toepasbaar È.unnen zijn t. g.'~. IOOgelijka anomalieën van het
systeem, met name ontmenging van de vlo ei stoffa~e. Frenkel zag hierin een belangrijke mogelijke oorzaak,
mede gezien zijn correspondentie met prof. Prau~nitz, en er.kele vreemde uitkomsten van Wilsonconsr:anten.
Na uitvoerige discussie we,-d dit toch erg onwaarschijnlijk geacht. De P tot -'"r. diagr=cn van de binairen
aminè-water (resultaat voolbespr. dW-vdW) geven vloeiende lijnen die geenszins op ontcenging duiden. De
uit die gegevens voortkome"de Wilson-beschrijving van het multicoDFonentsysteem zal ook vloeiende lijnen
opleveren (Wilson ~ geen ontmenging en dergelijke anomalieën beschrijven.)
I. Nader onderzoek van de uitkom i ten van het programma dat Wilson-constanten berekent door met deze uitkorr5tcn
Ptot-~ diagramr.en te mak2u el deze te vergelijken met de inputdata • . Fouten t.g.v. 2.2. I. en 2.2.2. moete"
daarbij tevoorschijn komen, e',l ku.....,nen aanleiding zijn grondig in de programmatuur te duiken.
2. De destillatieberekening cont ' ~oleren door toepassing op een ~engsel met bekende Wilson-constanten (suggestie
verslag Freakel) • Dit is alle,m zinvol als te we., ,,-.i. g vertrOUwd kan worden op de bij het destillatieprogralr.'-'i
gevoegde testberekening.
3. De Renon-vergelijking toepass tln i.p.v. de Wilson-vergelijking (suggestie verslag Frenkel). Dit is sterk af te
raden - zie ook het vergelijk'md onderzoek van D.J. McCann, I.Chem.E.Sym?Series,no .15,pg 4:3 (1972). De Re"on--
vergelijking heeft per binair een parameter meer dan Wilson (dus 3 i.p.v. 2). Eet risico van een inaècqcate ~~
beschrijving is daardoor veel groter. Wel 1,an in principe ontmenging in de vloeistoffase beschreven worden.
Conclusie.
Een eventuele opvolger van Frer-.k" l heeft na een stevige inwerkperiode uitzicht op goede resultaten voor het ontw0rp
van een extractieve destillatie "an methylamines met water. Constr.lctÎt! en kritische beschouwing van !.~~~ dii!-
grammen voor het mengsel TI-'A-,.,., t c. r of TMA- (water+DMA+NI-'A), waarbij de laatste drie in een vaste verhouding gekczen
\Oordom, kan het inzicht in deze u:atérie vergroten en wel:icht zichtbaar maken of de gewenste scheiding op grond V.ln
de gebruikte gegevens realiseer;;. ar is.
Kvdw / 30-6-1974