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InaP-traIIIfcr .
INTRODUCTiON
In the design of a distillation column first the required number of ideal slage5 is detennined
lhen the concept of efficiency is used to decide how many real plates are required to achieve
the desired separation. Often this is done by distillation simulation program. Most
commercial simulator packages, however, deal with ideal plates and the user has to adjust the
number of ideal plates according 10 his idea of column efflciency. Some simulators allow the
user to define fixed plate effICiencies in input and program uses this given filed efficiency
value in calculations. Often the effICiencies are obtained from elperience or empirical
methods and the same effICiency is used 10 all components and plates of the column.
However, il has been shown experimentally that in multicomponent mixtures the Murphree
plate (tnoy) effICiencies may vary from plate to plate and evo:n from component to oomponent
in the NmC plate. Even in the "ideal mixtures, which have equal point efficiencies for all
components, have been shown to exhibil different plate effICiencies l . When the componenl
effICiencies differ, the same sepantion eannot be obtained using the concept of COI1SUIII
column etrlCiencies and thus il would be advantageow 10 include the plate effICiency
calculations into the simulation calculations of the column. If the individu.aJ componenl
effICiencies could be estimated during the simulation, the design of the column can be
improved by avoiding unnecessary over sizing and thus savings in the capital and opention
costs are obtained.
Two approaches are used to model vapor-liquid l1lI5S-transfer on distillation plate: the
equilibrium sla8e approach and the non-equilibrium stage approach. In the equilibrium stage
approICh the vapor-liquid I1lI5S transfer is modeled defining an equilibrium stage model in
H
497
G
,Ighted
a\!!nal
which the vapor and liquid phases leaving the plate are assumed to be in equilibrium with
each other. However real plates do not behave ideally and this non-ideal behavior is correclCd
by utilizing the concept of efficiency. In the non.equilibrium (ratebased) approach the actual
mass transfer is described in a direct way using mass transfer rates. The: scope of the non
equilibrium approach is outside of this paper. An ucellent review is given elsewberel .
The: simulaLion programs like Aspen Plus, ProSim and Hysim are often employed to
model distillation. Most of these programs utilize the equilibrium stage model and thus ideal
stages are used in the column model. As input the programs require the number of theoretical
plale$ in the column, and the location of feed and side draws are also given in terms of
theoretical plates. To the best of our knowledge none of the commercial simulaLion programs
is capable of handling multicomponent point and plate effICiency ealculations while solving
the simulaLion model of the column. 1be nonf\uilibrium simulators like the RatcflllC of
Aspen Plus' and the non--commercial ChemScp4. can calculate point efficiencies from the
results of non--equilibrium simulations, but the efficiencies are not used while solving the
model. 1be non--equilibrium models can be used in the backup calculations when estimating
the efficiencies. The non.equilibrium models, like the efficiency calculation models, employ
the concept of transfer unilS and thUll the reliability of the non--equilibrium models, as well as
the efftdency cakulation models, is considerably dependent on the reliability of the transfer
unit estimation.
Thc: amount of reponed multicomponent efficiencies of industrial scale distillation
columns available is limited. Multicomponent effICiencies of individual componenlS from
large-scale col umns are evcn less available than from the small scale or laboratory columns.
Also distillation efficiency CSlimation methods are often 1C!iled against experimental data from
binary systems. However almost all industrial scale dioUilJation operations are multicomponent
systems, performed often in large diameter columns. In the literature muhicomponent
effICiency estimation has been used for large scale columns by Biddulph and Ashton l , Ognisty
and Sakata6 and lime et
In this paper the multicomponent plate effICiency calculation model is presented and the
cak:ulated resullS are compared. against industrial data. The Murphree plate efficiencies of
individual componcnlS for industrial scale distillation column are determined. The calculated
efftcienciC5 are directly used in the simulation of the column and in the caiculaLion of the
column conoentration and temperalurc profiles and finally product compositions.
ae.
498
TABLE I
Plate detaBI for the MTBE rotuma
Welrleqth
1,1I9mm
600(700r'900 mm
39mm
0.348 m!
5 1 mm
2.02 m!
1,160 mm (side)
1,686 mm (center)
S67mm
0.18310. 113 m1hide)
O.366ItI.216 m!(ccnter)
600(700I900 mm
39mm
0.294 m1
31143 mm
1.85 1 m!
2 mm
2mm
................
CALCULATION OF EFFICIENCY
The caiculatiOfl model has been described in some detail previously" '. Briefly, it cOflsiders a
multicomponcnt mllS5 transfer model lind partial liquid miJlOing model 10 introduce the
backmiJlOin8 in the liquid phase. The calculation procedure consist of a sequence of stepS
which are repeated for all plale5 of the column. The gencnll outline of the developed plate
efficiency calculation model is ~nled in Table 2. The Murphree plate cfficiencies are
calculated from point errleiencies when the degree of miJlOin8 of phases in the plates have been
delen11.ined
MASS-TRANSFER MODEL
The mau transfer model utilizes number of transfer units (NlUs) correillioru to estimate the
binary NTUs for al l components. From these binary NTUs and collesponding compositions
the matrices of mUlticomponent NTUs can be calculated!. Then the mIlriJlO of overall number
of transfer units is calculated. According to the two-film theory of mass-transfer and
muiticomponent mass transfcr ~ the matrill of overall number of transfer units
INovJcan be calculated for lIOfl-ideal systems from the following equation:
(I)
where [Nv I and IN J are the matrices of multicomponent number of transfer units for vapor
lind liquid phase, respectively. [Pvl lind [I'd are the bootstrap matrices and IKJ is the
dilllonal mIlriJlO of equilibrium ratios of the first II - I values.
U QUID PHASE MIXING
In industrial scale colUmns the liquid on the plate is often OfIly partially miJlOed. The amount of
the liquid phase milling 0fI the plate is often described by the liquid Pcclet-number Pt. II can
be clkullted by IWO alternative approaches: from the number of perfectly mbed pooli or
from eddy diffusivily correillions. Porter el 11.11 have recently presented the mathematical
model for flow panerns on a sieve plate.
'"
TABLE 1
PUlCedure (or
!
cakulatiae
~t pblte
eftkiendes
m ecptIIibriaaa
.up
Step 1:
.....,
.....,
Step !Ii:
SWp7:
SWp9:
SWp 10:
Step 11:
(2)
The relationship between Peclct-number Pe and N can be ca1cuhued from the equation giVCfl
1
by Ashley and HaseIden ':
Pe::2N-2
(3)
Alternatively. the eddy diffusivity for valve plates can be cakulltcd from the comlation
Pop'led by Welch el a1. 11
(4)
'00
where QL i.I the volumetric liquid flow rate, W is the liquid flow path width and lid is the
clear liquid height on the: plate. The Peclet-number is defined by
where Z is the liquid flow path length and t L is the liquid phase residence time.
In this work the mixed pool madel LO was used in panialliquid mixing model. The model
gives the relation of the Murphree plate efficiency to the point efficiency:
(6)
The advantage of the mixed pool model is that the Murphree plate efficiencies can be
calculated in the whole liquid mixing range. The model (Eq. 6) reduces to the plug flow
model, when N -+ _ or Pe -+ _. Complete mixing occurs when N. I or Pe "" O.
SIMULATION PROGRAM
The pille effICiency calculation model has been inoorpora!ed within the non<011lmerciai
flow&hcct simulator package called A..OWBAT. The point and plate efflCiencics are
calculated during the simulation and the calculated efficiencics are used to compute the
component concentration profiles. The effICiency calculation sequence is repeated for tlICh
plait of the column until the mathematical model of the column is solved. The variabk
pamnetef relaxation method or the modified NewtonRapllson method can be used to solve
the model equations. The Newton-RapI\son method has been widely used to solve both the
equilibrium model and non-equilibrium model equations and it should preferably be used for
non-ideal mixturt5. In this work both methods converged. while the variabk parameter
relaxation method wu found to be tne:R robust. It also produced fUltSt computation times
The convergence depends on the liquid mixing model and the mixing comlations.
Becanse in this model the effICiencies can vary from component to component or from platt
to platt, the complete simulation of the column requires about three times tne:R computer
time compared to the simulations with constant efficiencics'. However, if the narure of the
system is very nonideal. the ideal stage model cannot describe the behavior of the system and
then the conversence is more difficult to obtain. The calculation times for solving the
simulation model of the MTBE column are given in Table 3. The system studied is so non
ideal tha the IXIIlvergellCt is more easily obtained using the efficiency calculation model. The
effICiency calculation takes more time because of many matrix calculation operations, but in
this case the sage modtl with effICiency calculation is faster than ideal s\.lit model which
have to take more iteration runs to get the model [0 convergence.
MODEL COMPARISON
The simulation model of the column wu specified by defining the thermodynamiC5 of the
system. the feed rate, the condition and composition of the fced, the column and platt
pme:tly. The Wilson liquid activity coefficient equation is used for liquid and SRK for
Yapor. The numbtB or transfer units for the liquid and vapor phases wert computed using the
~J-';ons of Chan and Fair L! . The method of OIan and Fair u.st5 the correlation of Bennet tC
."
1I.ll for the calculation of the clear liquid height on plates. The liquid phase diffusion
coefficients at infinite dilution were obtained using the Wilke-Chang l equation. lbc
simulations were perfonncd with liquid mi~ing cOlTClations (2) and (4) and the results were
compared to experimental data.
TABLE 3
81......1...... model
CPU time.
8.295
~~~~~I~20~%~'~'O~W~'~'~40~"~===~7~.4~8~'===
A comparison between predicted and measured top and bottom product mass fractions is
provided in Figure 2. lbc agreement between predicted and measured mass fraction s is
excellent for bottom product and for distillate product. lbc major di screpancy between the
plant data and the simulation resu lts is the concentration of normal -butane in the bottom
product which implies that the estimated plate efficiencies in the bottom section should be
,lightl), higher. In all. the a.c<.:UI'IOC:)' of predicled ma55 frac:lions is enough for design purposes.
lbc predicted liquid phase temperature profile through the column is shown in Figure 3
where the measured temperatures arc also shown. lbc comparison is fai rly good. l1!cre arc
small deviations between predicted and measured temperatures on plates 9 and 21. These
meISUred temperature readings, however. arc too low if they arc comparcd. 10 the other
measured values. lbc temperature profile should be decreased from the bottom of the column
10 the top.
The observed reboiler duty is 4.89 MW , while the s imulation model gives the value of
4.78 MW. The difference of duties is about 2.3 % which SO\Inds reasonable, because the real
column always has heat. losses and these arc nOi taken into consideration in the s imul ation
model. Also the accuracy of the enthalpy calculation in the simulation may cause dev iations.
FSTIMATED EFFICIENCIES
The predicted clear liquid heights, vapor and liquid residence times and liquid Peclet number
on the plates arc given in Figures 4 - 6 . The estimated point efficiencies arc shown in Figure 7.
11 CIIl noticed that the efficiencies arc 110( the same for each component. 1bc poinl efficiencies
vary between 40 90 %. It CIIl also be noticed that the point effICiencies of individual
compoacnts 00 not vary considerably from plate to plate through the column.
The Murphree plate efficiencies arc shown in Figure 8. The Murphree plate effICiencies
differ consideI1lbly from poinl efficiencies especiall), in the top section of the column.
However the efficiencies of the bottom section arc almost the same as the estimated point
effICiencies <in figure 7). 1bc onc-pass plates of the upper section have hi gtler platt!
eftkiencies than the two-pass plates while the point effICiencies of all plates arc almost equal.
In expcrimenlal wort. the plate efficiencies have sometimes been found 10 obtain unusual
values (less than 0 or more than 100 %) in plates with concentration maximum or min imum.
Such peak!; CIIl be found in the calculated point and plate effICiencies in Figures 7 and 8. lbc
high values of efficiencies exists when the denominator in the Murphree efficiency equation
S02
"".,.htoo ma~nal
will have very s mall value or when it goes to zero. This situation ex ists on plates where there
is a maximum in the concentration profile.
Plates of different design have different liquid n ow profiles and thus different plate
efficiencies. In the two-pass plates with shorter liqu id path lengths (.567 mm) the liquid phase
is almost totally mixed and one-pass plates with longer liquid path lengths (1,3.50 mm) tend to
have plug now. From Figure 6 can be noticed that the liquid Pedet number f(W the section
above the feed i~ about I I (one-pass plates) while the liquid Peclel number is about 2..5 for the
section below the feed (two-pass plates). This shows th at the liqu id phase: is partly mixed in
lhe upper section and almost compl etel y milled in the bottom section. According to the
results. the two-pass plates of Ihis column havc considerab ly lowe r Murphree plate
efficieoc ies than thc onepass platcs. Th is has also been found by Lockett (1986)" .
CONCLUSIONS
1be use of thc column sim ulator with the efficieocy calculation for the column design avoids
the cmpiricism and approximations of the conventional design methods. It permits the
simul ation of the distillation column with real platcs instead of theoretical plates. It also gives
morc precise information about thc hydraulics of phases (c.g. clcar liquid heights, re.!l idcllCC
times) and masHransfcr phcnomena (e.g. degree o f backm ix ing, point efficiencies, plate
effic iencies) on the plates. In this study the convergellCC of the simulat ion model was more
easi ly obl:ained for the Simulating model using efficicncies than for the ideal stage model. The
effic iency calculation model is an important tool f(W accurate simulation and design of plates
and distillation equipment and it can be the alternative choia: for thc non-t(juilibriu m stage
si mulators.
AC KNOWLEDGEMENT
One of the authors (J.K. li me) wishes to acknowledge the financial support of Neste Oy
Foundation for thi s work. 11Ic authOR would like to thank Neste Oy for the permission 10
prescnt these results. Special thanks to Ph.D. Kimmo Klemola for valuable comments.
NOMENCLATURE
D,
E_
Eo
'-
IKI
N
INLI
(N ov l
INvl
'03
bootstnlp matri~ for vapor phase,ratio of the slope of thc: equilibrium line to the slope of thc:
operating line,
REFERENCES
I.
2.
3.
4.
5.
6.
7.
8.
9.
10.
II.
12.
13.
14.
15.
16.
17.
"".
McNulty, K.J . and aumerjee, 5.0 .. 1992, Simulation of atmospheric crude towers
including I*ked bed pump-around wnc5 using I ratebased simulator. IClwmE
SympoJiwn Suitl No. 128. Distillation and Abscrptiotl: A329 A14I .
Taylor. R . Powers, M.F., Lao. M. and Arehole, A .. 1987. The development of a
nonequilibrium model for computer simulation of multicomponent distillation and
absorption operations, feMmE Symposiwn Suiu No. 104. Distillatiotl and Absorptioll:
83218329.
Taylor. R., Kooij man. H.A. and Woodman , M.R., 1992, Industrial applications of I
nonequilibrium model of distillation and absorption operations, IChcmE Symposiwn
SeritS No. 128. Distillation and Abscrptiotl: A415A427.
Ognisty. T .P and Sakata, M., 1987, Multicomponent diffusion: theory v. Industrial data,
~m. Eng. Prog. , 83 (3): 60-65.
nrne, I ., Aillamaa. J. and N)'5IfOm. L., 1995. Estimatin8 muhicomponent plate
efficiencies of I-butaneln-butane column. presented at thc: Annual AIChE Meetin8. Miami
Beach, PaperNo. 19d.
Aiuamaa, J., Estimating mullicomponent plate efficiencies in distillation, 1981 , Ktmio
Kcmi. 8: 295-317.
Drne, I., Klemola, K., Aittamal, 1. and NystrOm. L., 1996. CaJculllli n8 distillation
efficiencies of multicomponcnt j-butaneln-butane column. Clwm. Eng. Comm.
(submitted).
GauueaUJl. M .F. and O Connel. H.E .. 1955, Effect of length of liquid path on plate
efficiency, Cltem. Eng. Pros' .. 51: 232-237.
Welch, N.E., Dwbin. L.O. and Holland. C.O., 1964. Mixin8 on valve trays and in
do~ of a di5tillation column. MeIsE J., 10 (3): 373.
Chan. H. and Fair. lR., 19&4. Prediction of point effICiencies on sieve Inlys, lnd. Eng.
Chem. Proc. Des. De",., 23: 814-819. 820-827.
Bennet, O.l.. Agrawal. R. and Cook, P.l.. 1983. New pre$Su~ drop c:orrelation (or sieve
tray distillation columns, AIChE J. 29 (3): 434-442.
Wilke, C.R. and Chang. P .. 1955, Correlation of diffusion coefficients in dilute solutions,
MCIIE J., I : 264-270.
Lockett, MJ . 1986. Distilkltion Tr01 FlINiomcnlDu. Cambrid&e UniveBity Press.
Ashley, MJ. and Haselden, 0 .0 .. 1970. The calculation or plate effICiency under
conditions of finite midn, in both phases in multi plate columns. and the potential
advantage of parallel flow, C'hcm. Eng"" Sci. 25, \665.
Porter, K.E. , Yu, K.T . Chambers. 5., and Zhan8. M.Q., 1992. Aow patterns and
tcmpe,atu~ profiles on a 2.44 m diameler sieve tray, Chem. Eng. Rcr. Des .. 70 (AS), 489500.
so;
55.5 ' C
700 kP:
............
30.1 ' C
:.::=------o.j,!4.~5..Q .~.
........
-..........
....
MTBE
29.0w-%
1.34 w-%
32.! w-%
34.1 w-%
2.74 w-%
0.02 w-%
methanol 1.90w-%
46.5w-%
butenoa 48.2w-%
3.40w-%
MTBE
b""""',
1969.3
. . . . . .' .C.
....
1 86.3 C
MTBE
........
""""""'"
......
Fiaure 1.
0.296 feed
97.!w-%
O.OOw-%
O.34w-%
0.72w-%
1.18 w-%
s.s
G
.Ighted
a\!!nal
.-
100.00 r-----------------------~
[J [)Ide,.
10.00
1.00
0.10 )L_ _
~~
' .1
___
_ _.....J
100
10
Me 'nd~.. I'IIo1
Fiaure 2.
14'
-
,, '20
'-
r=
SimuIIIed
PI l uNd
110
I ..,
!
20
.'
10
15
20
PIIlI~(J
Fisure 3.
"
30
50.
'r---------------------,
j3
},
~
1
10
15
20
2S
30
Plate number I J
Figure 4.
10
r======\---l
..........
._
..... .. ".!'f!!:.roO-;:; .. -J
0.1
L...~~~~~
10
_ _ _ _~....J
15
20
2S
30
Plate number ( I
Fipre S.
5.,
.... '.,htoo ma~nal
12
_M _ _ _ _ M
____
00"\
WMctl II aI.
10
I
I
Gawu,UX I. 0'C0meI
,,
I--- _M -
10
15
- ---- - - -.
20
PIete number II
Figure 6.
"
30
r-------tt------,
10
lS
20
Plate number II
Figure 7.
"
30
Point effICiency profiles: I. MTBE. 2. methanol. J. wiler, . n-butane, !S. 11hexane, 6. i-butene. 7. l-butene, 8. tran.r-2-butcnc, 9. ci.r-2-bu1cne, 10. i-butanc.
'08
G
,Ighted
a\!!nal
2.5
n--;------j--------,
L
t
r
~
05
10
15
20
25
30
Plata number ( I
Figwe 8.
"'''''''.
5"