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Flash drums are one of the simplest unit operations in a chemical plant, both in terms of its operation and our ability to accurat
feed stream containing both vapour and liquid components is split into a vapour stream and a liquid stream according to the te
flash drum. As a result, we can use the concepts of mass balances and vapour-liquid equilibrium together to predict the vapou
composition of the vapour and liquid outlet streams.
The equations used for flash drum analysis are not really new; they are merely restated and rearranged versions of VLE and m
before. The central parameter used in a flash calculation is the equilibrium ratio K i, defined as:
¿ where yi is the mole fraction of component "i" in the gas phase, P is the total pressure, x i is the mole fra
yi γ i Pi and Pi* is the vapour pressure of component "i" at the specified temperature (calculated via Antoine's e
K i= = Fi accounts for the gas-phase non-ideality and gi (the liquid activity coefficient) accounts for the liquid-p
xi Φi P
As in the VLE spreadsheet, we assume Fi = 1 (ie. no gas-phase non-ideality, a generally good assump
This equation is simply a rearranged version of the modified Raoult's Law expression we have already seen on the VLE sprea
a partitioning coefficient giving some indication of the "lightness" of component "i" (ie. how likely component "i" is to partition in
We can also write a mole balance for this process since the total amount of component "i" in the inlet stream must equal the su
streams:
L+V =1 zi =x i L+ y i V zi =x i ( 1−V )+ y i V
where zi is the overall mole fraction of component "i" (considering both phases), L is the molar fraction of liquid an
relation to the total molar flow).
These VLE and mole balance equations can be combined to arrive at the flash equations:
zi K i zi
y i= x i=
1+V ( K i −1) 1+ V ( K i−1 )
Solving a flash problem is thus a problem of finding an appropriate value for V which results in both the vapour phase and liqu
Most commonly, this iterative procedure is conducted using the function F, which is defined as:
zi zi K i
F=∑ x i− ∑ y i =∑ +∑
i i i 1+V ( K i−1 ) i 1+V ( K i −1)
z1 ( K 1−1) z ( K −1 )
or, for a two-component system as analyzed in this spreadsheet: F= + 2 2
1+ V ( K 1 −1) 1+V ( K 2 −1 )
Convergence in this case is achieved as Sxi and Syi both approach 1, or as F approaches zero.
z 1 ( K 1 −1)2 z 2 ( K 2 −1 )2
Furthermore, this function is easily differentiated:
dF
dV
=−
[ 2
+
[ 1+V ( K 1 −1 )] [ 1+V ( K 2 −1 ) ]
2
]
dF/dV is always negative, meaning that F vs. V is a monotonic and Newton's method can be used to provide fast iterative conv
This can be done by estimating the next guess value of V with Newton's equation:
F (V k )
V k +1 =V k − where k is the iteration number
F ' (V k )
Two main problems arise when doing VLE calculations. First, on this spreadsheet, you are asked to select both a temperature
This set of T and P values may or may not result in a vapour-liquid equilibrium being established with the components you ch
only one phase exists at the entered (T,P) values, not only does the iterative solution procedure break down but is there no po
to check for VLE, the bubble pressure (upper limit of VLE) and dew pressure (lower limit of VLE) must first be calculated at the
the pressure you chose must lie within the PDP<P(chosen)<PBP range in which VLE is established. After doing this calculation
must then either (a) change the pressure such that it lies between the dew and bubble pressures or (b) change the temperatur
pressures, iterating as necessary until the fixed chosen pressure lies between the dew and bubble pressures.
Second, for non-ideal systems, we cannot immediately calculate the activity coefficients gi required for estimation of Ki since a
(including the Wilson equation used here) require knowledge of the liquid phase mole fractions. If we just guess the liquid pha
coefficients to 1 (as we did to start the iterations in the non-ideal dew and bubble point calculations), we may effectively force t
region of the non-ideal system. This is particularly true if strong non-ideal behaviour occurs in the component set chosen. If th
iterative method) are unable to converge to a real root for V and the problem is unsolvable. A similar problem (although not qu
procedure) occurs in estimating the vapour fraction V to use in the first iteration. We can get semi-empirical estimates of these
pressure P to the dew and bubble pressures of the component set at given (T,P) conditions:
Here, gi,dew is the converged activity coefficient from the dew pressure calculation and gi,bubble is the converged activity coeffi
This approach is similar to you drawing a tie-line on a phase diagram to estimate the vapour and liquid fractions and equilibriu
are the mathematical equivalent of the tie line approach which provide essentially weighted average estimates of the activity c
on how close the experimental pressure is to the bubble and dew pressures respectively. These guesses are surprisingly goo
very important to immediately consider the non-ideal behaviour of the liquid in the first iteration (ie. immediately satisfying P DP<
This spreadsheet will allow you to perform flash calculations on a variety of two-component systems assuming both ideal and
Cells with a red triangle in the upper right-hand corner have comments which will give you more information about what the va
the cell means or how to select a value for that variable.
nd rearranged versions of VLE and mass balance equations you have used
d as:
s the total pressure, x i is the mole fraction of component "i" in the liquid phase,
mperature (calculated via Antoine's equation).
coefficient) accounts for the liquid-phase non-ideality
on-ideality, a generally good assumption).
in the inlet stream must equal the sum of component "i" flowrates in the outlet
1−V )+ y i V
s), L is the molar fraction of liquid and V is the molar fraction of vapour (both in
ts in both the vapour phase and liquid phase mole fractions summing to 1.
1 ( K 1−1) z 2 ( K 2 −1 )
+
V ( K 1 −1) 1+V ( K 2 −1 )
z 2 ( K 2 −1 )2
+V ( K 2 −1 ) ]
2
]
be used to provide fast iterative convergence to the appropriate V value.
e asked to select both a temperature and a pressure for a given component set.
blished with the components you chose at the composition you chose; indeed, if
edure break down but is there no point doing a flash calculation at all! In order
f VLE) must first be calculated at the chosen temperature. For VLE to occur,
blished. After doing this calculation (set up for you on the spreadsheets), you
ssures or (b) change the temperature and re-calculate the dew and bubble
d bubble pressures.
required for estimation of Ki since all the liquid phase activity correlations
ions. If we just guess the liquid phase mole fractions or initially set the activity
culations), we may effectively force the iterations to initiate outside of the VLE
s in the component set chosen. If this occurs, Newton's method (or any other
. A similar problem (although not quite as damaging to the calculation
get semi-empirical estimates of these values from the proximity of the total
s:
P−P DP
=
P BP− PDP
ubble is the converged activity coefficient from the bubble pressure calculation.
ur and liquid fractions and equilibrium phase compositions. These equations
d average estimates of the activity coefficients and vapour phase fraction based
These guesses are surprisingly good (as you will see in the iterations) and are
ation (ie. immediately satisfying P DP<P<PBP).
Pressure P 1245 mm Hg
Temperature T 348 K
Gas Constant R 1.987 cal/mol K
ANTOINE'S COEFFICIENT
Component 1
Number Component 1 Component 2 A B C
1 Acetone Chloroform 7.11714 1210.595 229.664
2 Acetone Methanol 7.11714 1210.595 229.664
3 Acetone Water 7.11714 1210.595 229.664
4 Carbon tetrachloride Benzene 6.84083 1177.91 220.576
5 Chloroform Methanol 6.95465 1170.966 226.232
6 Ethanol Benzene 8.1122 1592.864 226.184
7 Ethanol Water 8.1122 1592.864 226.184
8 Ethyl acetate Ethanol 7.10179 1244.951 217.881
9 n-Hexane Ethanol 6.91058 1189.64 226.28
10 Methanol Benzene 8.08097 1582.271 239.726
11 Methanol Ethyl acetate 8.08097 1582.271 239.726
12 Methanol Water 8.08097 1582.271 239.726
13 Benzene Toluene 6.90565 1211.033 220.79
14 Methyl acetate Methanol 7.06524 1157.63 219.726
15 1-Propanol Water 8.37895 1788.02 227.438
16 2-Propanol Water 8.87829 2010.32 252.636
17 Tetrahydrofuran Water 6.99515 1202.29 226.254
18 Water Acetic Acid 8.07131 1730.63 233.426
19 Water 1-Butanol 8.07131 1730.63 233.426
20 Water Formic Acid 8.07131 1730.63 233.426
Component 1: Acetone
Component 2: Methanol
z1 0.5 Acetone
z2 0.5 Methanol
Antoine's Equation Coefficients for Acetone Antoine's Equation Coefficients for Methanol
A= 7.11714 B
A= 8.08097
B
B= 1210.595 ¿
P =10
( A− T −C ) B= 1582.271 ¿ ( A− T −C )
C= 229.664 C= 239.726 P =10
Conditions
Total Pressure 1245.000 mm Hg
Temperature 348.000 K
PDP 1241.723 mm Hg If PDP < P(chosen) < PBP --> Proceed with flash calculation
P(chosen) 1245 mm Hg Otherwise, return to Parameters page to (a) change the pressure to lie within
this range (immediately proceed to the flash calculation after selecting an
PBP 1255.260 mm Hg appropriate P) OR (b) change the temperature and recalcuate BUBBLE P and
DEW P
yi Pi z1 ( K 1−1) z ( K −1 ) z 1 ( K 1 −1)2 z 2 ( K 2 −1 )2
K i=
xi
=
PTOTAL
¿
(1)
F= + 2 2
1+ V ( K 1 −1) 1+V ( K 2 −1 )
=0
(2) dF
dV
=−
[ 2
+
[1+V ( K 1 −1 )] [ 1+V ( K 2 −1 ) ]
2
] (3)
F (V k)
Newton's Method Procedure: Adjust guess for iteration k+1 using equation V k +1 =V k − (4)
F ' (V k)
Newton's method is practically very useful in this case since the function dF/dV is easy to compute and is always negative, meaning that the F vs. V relationship is
monotonic and Newton's method rapidly converges on a solution. Also, unlike using a Goal Seek approach, Newton's method is completely automated on a
spreadsheet. Interestingly, Goal Seek is very poor at solving this problem since F has small values which are very sensitive to the value of V. Goal Seek (at least
in its default configuration) settles for "convergence criteria" for F which are not accurate enough to get good, converged solutions for V.
The variables highlighted in pink are the variables typically of interest in a flash equation solution.
** Keep in mind that depending on how non-ideal the system is, your choice of pressure that satisfies the condition P DP<P(chosen)<PBP for the
ideal case may not satisfy that same condition with the liquid-phase non-ideality factored in. Thus, it is highly likely you will have to change the
pressure of your system (according to the non-ideal P DP and PBP calculations) to perform the non-ideal flash calculation.
NON-IDEAL FLASH CALCULATION
Antoine's Equation Coefficients for Acetone Antoine's Equation Coefficients for Methanol
A= 7.11714 B
A= 8.08097
B
B= 1210.595 ¿
P =10
( A−
T −C ) B= 1582.271
P ¿ =10
( A− T −C )
C= 229.664 C= 239.726
Conditions
Total Pressure 1245.000 mm Hg
Temperature 348.000 K
L12 0.648998012213781
L21 0.826282194782044
g1 1.14351971777267
g2 1.16152434442555 Bubble P Equation: PBP =x 1 γ 1 P1 ( T )+ x 2 γ 2 P2 ( T )
¿ ¿
PBP 1445.541 mm Hg
y1 0.548
y2 0.452
PDP 1241.723
Sxi 1.0000
x1 0.448
x2 y 1 P DP y P
0.552 Dew P Equation:
∑ x i= γ + 2 DP =1
L12 0.648998012213781 1 P1 ¿ (T ) γ 2 P2 (T )
¿
L21 0.826282194782044
g1 (estimate) 1.17945765269759
g2 (estimate) 1.12958763314687
As with the DEW T calculation, continue iterations until both TDP and the two activity coefficients converge. You must perform GoalSeek
iterations on each Sxi box to converge to the answer.
Subsequent Iterations:
The following parameters are automatically entered if you complete all 8 iterations:
After 8 iterations, the converged dew point pressure is: 1429.593 mm Hg
After 8 iterations, x1 (converged) 0.433
After 8 iterations, g1 (converged) 1.191
After 8 iterations, g2 (converged) 1.121
PDP 1429.593 mm Hg If PDP < P(chosen) < PBP --> Proceed with flash calculation
Otherwise, return to Parameters page to (a) change the pressure to lie within
P(chosen) 1245.000 mm Hg
this range (immediately proceed to the flash calculation after selecting an
PBP 1445.541 mm Hg appropriate P) OR (b) change the temperature and recalcuate BUBBLE P and
DEW P
Iteration #1 Iteration #2 Iteration #3 Iteration #4 Iteration #5 Iteration #6 Iteration #7 Iteration #8 Iteration #9 Iteration #10
V(predicted) 12.5748162253436 23.954690446846 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
g1 1.73713893776665 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
g2 0.653915075487819 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
K1 1.93333244895894 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
K2 0.590838949114329 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
F 0.085994602395029 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
dF/dV -0.007556726965623 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
V* 23.954690446846 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
L -22.954690446846 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
x1 0.021406226478994 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
x2 -0.056809619595797 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
Sxi -0.035403393116803 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
y1 0.041385352261604 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
y2 -0.033565335941566 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
Syi 0.007820016320038 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
g1* Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
g2* Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502 Err:502
Again, the variables highlighted in pink are typically the variables of interest when doing a flash calculation.