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Abstract-Multicomponent distillation programs in general use are seldom capable of describing systems whose flow
patterns differ from the conventional counter-current. However, these programs may be extended to include
pumparounds or interphase mass transfer by algorithms which require neither additional internal iteration steps nor
repetitive solutions. For a pumparound, a recursive procedure is developed to use the conventional Thomas
Algorithm modified by an additional multiplier in the second step. To describe interphase mass transfer, the solution
to the set of material balance equations requires a recursive technique in which the definitions for the algorithm
alternate for successive stages. The use of recursional procedures is demonstrated on a multicomponent distillation
column simulation.
Scope-Multi-stage operations are widely used in the chemical and petroleum process industries to carry out
separations and achieve produce purity. Distillation is the most common of these but extraction and absorption
often are called upon when the components do not volatilize readily. These processes are designed for the most part
to operate with a counter-current flow pattern between the stages. The programs used to describe multi-stage
operations seldom provide for variations from counter-current flow either between the stages or within them.
However, the flow pattern is often varied by the use of pumparounds and it is often desirable to include explicitly the
intrastage cross flow in the computations. There is, therefore, a definite requirement for algorithms which may be
used to adapt multi-component programs to describe systems with non-conventional flow patterns.
The crux of the iterative computations which describe multi-stage operations lies in the solution of the set of
component-material balances. There is an effective algorithm for counter-current flow profiles and equilibrium
stages [6] since these cases may be described by a set of tridiagonal equations. A number of multi-stage descriptions
do not conform to the tri-diagonal configuration. Procedures are developed which may be used when off diagonal
elements are not adjacent to the conventional elements as well as procedures which are useful when additional
elements appear next to existing elements. The former case is illustrated by a pumparound in distillation, the latter by
interphase mass transfer computations for distillation or extraction stages.
The use of the existing Thomas Algorithm[6]for tri-diagonal configurations has been described by Friday & Smith
[5] for multi-stage operations. An improved modification has been suggested by Boston & Sullivan[2] and its
applicability in time-varying computations has been described by Waggoner & Holland[l3]. In this algorithm the
initial, interim, and solution elements are kept in vectors. No iteration is required to obtain a solution. An alternative
procedure involving matrix manipulation could become cumbersome, time consuming, or could consume excessive
core space for large multi-stage systems such as those encountered with super-fractionators.
The algorithms developed for non-conventional material balance configurations meet the criteria of vector
elements and direct solution. Their applicability is demonstrated as they are programmed to operate within the
structure of an on-line interactive multi-component distillation program.
NON-CONVENTIONAL
CONEIGIJEATtONS
FOR COMPONENT- PuMPAE0uND
MATEEIAL
BALANCE
COEEEICEh’T
MATEICES In many distillation and extraction operations a stream
For each component, the component-material balance is withdrawn from one stage of the column and then
equations must be solved simultaneously. When these returned to a different stage without a change in its
balances are written each around a single stage, the composition. In distillation heat is often added or with-
elements of the coefficient matrix take a tri-diagonal form drawn from this stream. The term most often used to
for standard configurations in distillation. This matrix describe the stream is “Pumparound”. The flow pattern
form is not changed if deviation from equilibrium is for a typical pumparound is illustrated by Fig. 2.
described in factor form[7, Chap. 141.When additions are
made to the standard flow profile or if deviation from Component material balance
equilibrium is described by interphase mass transfer, the If a liquid pumparound is withdrawn from stage s and
matrix format is altered. If a pumparound is used in returned to non-adjacent stage r without a change in
distillation, an element is added to the matrix in a location composition, the material balance for component i on
far removed from the diagonal. When interphase mass stage r may be written
transfer is included in multi-stage computations, addi-
tional elements are generated which appear adjacent to (L,-, - wr-1)x,-,.i - LJX, - KY, - VrYti+ v,+,Y,+,,i
the &i-diagonal elements.
Algorithms may be developed so that these non- + G,xsi+ F,,xfti= 0 (0
conventional cases may be solved as readily as the
conventional. The procedure for the off-diagonal element For equilibrium stages and for non-equilibrium stages
differs from that applicable to adjacent elements. A described by a component efficiency factor, the vapor
pumparound is used to illustrate the former and interph- phase composition is related to the liquid phase composi-
ase mass transfer the latter. tion by a multiplier.
CACE Vol. 1. No. I-D 49
50 R. C. WAGGONER and G. D. LOUD
Q,
pr=b, -:,fr_,
D
R
T=
No modification is required to account for the pump- tions and the energy balances contain enthalpy functions
around withdrawal but the bulk-material balance used to both of which are generally non-linear functions of temp-
calculate vapor boilup from the stage r + 1 may require erature (and may be non-linear in composition as well).
revision. The non-linearity of these functions requires that an
iterative procedure be used to determine the correct
V,,, = V, +L, - 15-1 -G,. (10) temperature profile. Many of the iterative programs for
multicomponent distillation follow the sequence illus-
Implementation trated in Fig. 1.
To include a pumparound withdrawn from stage s and 1. Initialize. Before the search for the column profiles is
returned to stage r, the following modifications to a begun, the data required is assembled and placed in
multicomponent distillation program are required. locations where it may be accessed during the iterative
1. From stage r to stage s - 1 the initial overflow profile computations. This information includes a description of
should be increased by the amount G moles. the feed to the column, the column operating specifica-
52 R. C. WAGGONER
and G. D. LOUD
Table 1.Statementof distillationcolumnoperations Chap. 41 is often selected for convergence. The Sum-
Rates method[5] has been found effective for absorbers.
Specifications The Theta multiplier[7] is often used to indicate con-
Thermodynamicdata 300psia vergence even when other correctors are applied to the
A total condenser temperature profile.
Distillaterate 328molh-’
4. Temperature profile. An improved temperature
Refluxrate 400molh-’
Number of stages-20 profile may be obtained from compositions determined in
step 2 or from step 3. Approximate dew point or bubble
Feeddescription point computations [7, Chap. IS] are often used to elimi-
Flow Bubble Dew nate the need for the internal iterative loop required to
rate point point obtain an exact temperature. The Sum-Rates method[5]
Stage Condition (mol h-‘) (“F) (“F) uses energy balance corrections to obtain improved
temperatures.
10 Bubble point 500 168 215 5. Bz&-flow profiles. When the composition profile is
liquid
used to obtain corrected temperatures they in turn may be
Component feed rates (mol h-‘) used to compute revised enthalpy values. These enthal-
C3H8 I-C4 N-C4 N-C5 pies are used in energy balances which, together with bulk
325 50 50 15 flow balances, may be oversensitive to small temperature
changes. The constant composition method [7, Chap. 51
avoids this problem. Steps 2-5 are repeated until the
Table 2. Distillation column operation described with equilibrium criterion for convergence has been met.
stages and without a pumparound To describe an operation which includes a pumparound,
the component material balance subroutine (MATBAL)
Temperature Liquid flow and the bulk flow profile subroutine (ENBAL) are re-
Stage (“PI (mol h-‘) placed with modified subroutines. The structure of
1 137.0 400.0
neither is changed. In MATBAL, an additional array is
2 138.7 394.8 defined to contain the elements generated by the pump-
3 140.6 389.3 around expressions (Eqs. 6 and 7). These equations are
4 142.8 383.6 programmed and placed within the loop which generates
5 145.1 377.8 the elements of the F and G vectors in the standard
6 147.5 371.7 subroutine. The programmed equation in the reverse loop
I 150.0 364.5 is revised to pick up the non-zero pumparound elements.
8 153.0 353.6 In ENBAL additional statements are added so that the
9 157.3 334.1 equations for the liquid overflow and vapor boilup are
IO 165.0 829.7
11 167.3 825.0
modified to include the effect of a returned pumparound,
12 171.1 819.0 (Eqs. 8 and 9). Logic is required so that these terms are
13 176.8 812.8 added only to the returning stage for liquid overflow and
14 184.7 808.5 to the stage below for vapor boilup. The effects of a pum-
15 194.5 808.5 paround on the separation described in Tables 1 and 2 are
16 205.5 812.4 shown for two pumparound rates in Table 3.
17 216.8 815.8
18 228.8 811.8 DEVIATION
FROM EQUILIBRIUM
19 243.2 796.8 In the design and operation of multi-stage mass transfer
20 262.3 172.0
units such as distillation towers and extractors, deviation
Product compositlons from equilibrium on the individual stages has a significant
Stage C3H8 I-C4 N-C4 N-C5 effect. This deviation is often large enough to reduce the
1 0.9764 0.0207 0.0027 0.0000 effectiveness of the unit to 5&70% of its theoretical
20 0.0275 0.2510 0.2853 0.4360 operation[lO]. Deviation from equilibrium should there-
fore be included in the simulations used to describe these
units. The factor procedure to describe deviation from the
tions, and the physical property data which are usually equilibrium is often used in distillation. It is exemplified
expressed as coefficients for the enthalpy and equilibrium by the Murphree Efficiency factor [9] and the vaporization
functions, This section generates an initial estimate for efficiency[7, Chap. 141.In extraction, deviation is often
the temperature and bulk-flow profiles. described by interphase mass transfer[l-4, 81. The two
2. Composition profiles. The composition of each com- procedures may be used to obtain equivalent results. An
ponent on each component on each stage is computed expression for the interphase mass transfer coefficient is
from the latest available temperature and bulk-flow obtained from the simultaneous solution of the vapor
profiles. Computations for each component are per- phase material balance and the definition of the Murphree
formed independently from those for all other compo- efficiency factor [9].
nents. Procedures such as the Thomas algorithm[6] are
often applied so that the elements used may be retained in
vector form. (11)
3.. Convergence. Although the compositions obtained in
step 2 may be used to improve the temperature profile, If values for mass transfer coefficients are obtained in this
procedures may be applied to correct it further to meet a way, they contain the approximation that the bulk vapor
process specification and/or to reduce the required rate does not change within the liquid and/or froth held on
number of iterations. The Theta method of Holland[7, the stage.
Solution of material balance equations 53
Pumparound
rate (mol h-‘) 80 450 80 450
Column profiles Temperature Temperature Liquid flow Liquid flow
Stage (“PI (“F) (mol b-‘) (mol hh’)
b, 0 4 XI ml
a* b* c2 0
, X2 m2
0 b, 0 4 Y2 m3
:: 0 b., C4 0 X3 m4
0 a5 b5 0 ds Y3 mS
For row k
k+, d&k+,
akzk-l + Zk - Zkil
-!!!$dk (26)
c,+,_!!h$dk &+I
The elements for the final two rows are obtained from the
ck+rmk - dkmk+,
= (17) following expressions.
-!!i.$dk ’
ck+l
For row k + 1
fu-3 = - VN/(VN-I+ KG,-,,UN-I(I + KN-JZN-a))
(27)
b,h+,
- -4
ak
+ h-t,&+, + ck+I -%dk)Zk+2 g2N-3=
FL:-IXFL~.,
V,+, f
+ Kc,-l,,U~-~K~-l.ig2~-4
KG,_,,~UN-I(I+ KN-~,if2N-d
(28)
h Implementation
= mk+,-2 mk. (18)
When deviation from equilibrium is described by in-
terphase mass transfer, the component-material balance is
The coefficients of these equations have a tri-diagonal the only computation which must be revised to implement
form in the variable zki so that the traditional algorithm (Eqs. 19-29). Values for X and g&are obtained from stage
may be used to obtain a solution. 1 to the bottom of the column. In addition to the variables
Values for f,, f*, g, and g,, are computed in terms of already available for distillation computations, values for
process variables. KG,?and for U must be stored. In many cases they may be
stored as a product in the array normally used for
(L*+Ko&K*i)V2 vaporization efficiency. After values for jk and & are
fl =- (L,(K&,)t V,) t V,W,ia2U2)K~i) (19) obtained for a particular component, the values of the
elements of the 2 vector may be obtained by the standard
F,xdG& - Fz%tiVz second step procedure of the Thomas algorithm. There are
A”= (L,(K,,U,+ V2)+ V,K,&K,i) (20)
two elements for each stage which may then be identified
-&JJ* as the composition variables for both phases.
’ = (Lg + K,&Kzi + Lj,) (21)
Xji= Z2jml,n (30)
FzLx~,, + La Yji= z*j j=l,N. (31)
g2 = (L, + K,$J,Kzi + L, f,’ (22)
The energy balance-bulk flow balance computations for
When these values are available a recursional operation the bulk flow profile need not be changed if the enthalpy
may be used to obtain succeeding values of X and gk. values are computed from the stored compositions.
gZj-3
= - FL~rr-r.i + K,,_,,u,-,Kk-,,i - 425
KorU,
, ,If*j_4
(24)
-(V,-,i-K,,,,U,-,)-[K,,_,,,U,-,Kj_,,, -#]f*j_d
Gl, I
Solution of material balance equations 55
2. J. F. Boston & S. L. Sullivan, Jr., Can. 1. Chem. Engng SO, 8. D. A. Jones & W. L. Wilkinson, Chem. Engng Sci. 28, 539
663 (1972). (1973).
3. S.-I. Cheng, International Conference on Solvent Extraction, 9. E. V. Murphree, Ind. Engng Chem. 17, 747 (1925).
Paper 80, The Hague (1971). 10. G. G. Pollock & A. I. Johnson, Can. J. Chem. Engng 48,711
4. I. J. Dunn & I. Ingham, Chem. Engng Sci. 27, 1751(1972). (1970).
5. J. R. Friday & B. D. Smith, MChE J. 10, (1964). 11. B. D. Smith, Design of Equilibrium Stage Processes, Chap. 16.
6. E. M. Grabbe, S. Ramo & D. E. Wooldridge, Handbook of McGraw-Hill, New York (1%3). _
Automatic Comoutation and Control. Vol. 1. D. 14. Wilev. 12. R. C. Waanoner. Solution of unsteadv state distillation urob-
New York (lS8i lems. Dis&tat&, director C. D. Holland, Texas A -& M
7. C. D. Holland, Multicomponent Distillation. Prentice-Hall, University, College Station, TX (1964).
Englewood Cliffs, N.J. (1%3). 13. R. C. Waggoner L C. D. Holland, AIChE J. 11, 112 (1%5).