MASS CONSERVATION

CSTR
Consider the CSTR — the reaction is now exothermic and
heat is removed by a jacket containing a vaporizing
medium, so an energy balance is necessary.

Assumptions:
• vessel contents well mixed
• species A and B present in
dilute solution
• atmospheric pressure is
constant (e.g., P0‡ f (t))
• neglect shaft work of
impeller
• neglect heat interaction
with atmosphere
• otherwise, same as above
SYSTEM IN WHICH PRESSURE
AND VOLUME VARY
MOMENTUM BALANCE
EQUILIBRIUM SYSTEM —
FLASH DRUM
Derive an alternative model for the equilibrium flash vessel
in which separate species and energy balances are written
for both liquid and vapour phases. With reference to the
discussion of the index of differential algebraic equations :
(a) what are the mathematical properties of this model?
(b) what additional information does this model calculate?
(c) from a practical point of view, which of the two models
is appropriate for implementation in Speed Up?
Hint: it is useful to introduce variables in the balance
equations representing the flow of energy and each
chemical species between the two phases.
EQUILIBRIUM SYSTEM —
DISTILLATION TRAY
Consider the following abstraction of a distillation tower:

Each stage has the following regions of

material and energy accumulation:

having identified this decomposition, we can focus on modelling each

region in isolation.
Here, we will derive a model for the froth on the plate, which is
presumably designed to approach phase equilibrium as closely as
possible.
Note trays are numbered from the top of the column downwards.
 Froth on plate:

Control volume: the froth on the plate (e.g.,

encompassing both phases)

Assumptions:
• phases at phase equilibrium
• individual phases well mixed
• adiabatic
• both phases present at all times — e.g., model valid
while TBUBBLE ≤ T ≤ TDEW
• number of moles in vapour phase negligible in
comparison to liquid phase
• PV work terms in energy balance negligible
Multi-component
Distillation Column
 Modeling the unit:
We are interested in developing the
unsteady state model for the unit using the
flowing assumptions:

100% tray efficiency

Well mixed condenser drum and re-boiler.
Liquids are well mixed in each tray.
Notation: Negligible vapor holdups.
liquid-vapor thermal equilibrium

Li, Vi Liquid and vapor molar rates

Hi, hi Vapor and liquid specific
enthalpies
xi, yi Liquid and vapor molar
fractions
Mi Liquid holdup
q Liquid fraction of the feed
z Molar fractions of the feed
F Feed molar rate
 V n, yn
Vn, yn R, xd

stage n
(a)
Qc (b)

R, xd D, xd
Ln, xn Vn-1, yn-1

Li+1, xi+1 Vi, yi Lf+1, xf+1 Vf , yf

stage i stage f

(c) (d)

Li, xi Vi-1, yi-1 Lf, xf Vf-1, yf-1

L2, x2 V1, y1 V B, yB
Qr

stage 1
(f)
B, xB
(e)

L1, x1 VB, yB L1, x1

Stage n+1 (Condenser),
Total mass balance:

dM D V ( R D)
dt n (2.161)

Component balance:
d ( M D xD, j ) V yn,
n j ( R D) xD, j j 1, nc 1
dt (2.162)

Energy balance:

d (M h )
D D VH ( R D)hD Qc
n n (2.163)
dt
Note that R = Ln+1 and the subscript D denotes n+1
Stage n,
Total Mass balance:

dM n V V R L (2.164)
dt n 1 n n

Component balance:

d (M n xn, j )
Vn 1 yn 1, j Vn yn, j RxD, j Ln xn, j j 1, nc 1
dt (2.165)

Energy balance:

d ( M n hn ) V 1H VH Lh
n n 1 n n RhD n n
(2.166)
dt
Stage i,

Total Mass balance:

dM i V V L L (2.167)
dt i 1 i i 1 i
Component balance:

d ( M i xi, j ) V yi V yi, L x Lx
i 1 1, j i j i 1 i 1, j i i, j
j 1, nc 1 (2.168)
dt
Energy balance:

d ( M i hi ) V 1H VH L h Lh (2.169)
i i 1 i i i 1 i 1 i i
dt
 Stage f (Feed stage),

Total Mass balance:

dM f
Vf 1 (Vf (1 q) F ) Lf 1 (L f qF ) (2.170)
dt
Component balance:

d (M f x f , j )
Vf 1 y f 1, j (Vf y f , j (1 q)Fz j ) Lf 1 x f 1, j ( Lf x f , j
dt
qFz j ) (
2
.
1
7
1
)
j 1, nc 1

Energy balance:

d (M h )
f f (V H L h
Vf 1H f 1 f f (1 q)FH f ) f 1 f 1
(Lf hf qFh f ) (2.172)
dt
 Stage 1,

Total Mass balance:

dM 1
VB V1 L
2
L
1
(2.173)
dt
Component balance:

d ( M1 x1, j ) V yB, V y L x2, Lx

B j 1 1, j 2 j 1 1, j
j 1, nc 1 (2.174)
dt
Energy balance:

d ( M1h1 )
VB H B V1 H1 Lh
2 2
Lh
1 1 (2.175)
dt
Stage 0 (Re-boiler),
Total Mass balance:
dM B L
VB 1
B
dt (2.176)

Component balance:
M x
d( B B, j ) V yB, Lx
j 1 1, j
BxB, j j 1, nc 1
dt B (2.177)

Energy balance:

d ( M BhB ) Lh
VB H B 1 1
BhB Qr (2.178)
dt
Note that L0 = B and B denotes the subscript 0
Additional given relations:
Phase equilibrium: yj = f (xj, T,P)
Liquid holdup: Mi = f (Li)
Enthalpies: Hi = f (Ti, yi,j), hi = f (Ti, xi,j)
Vapor rates: Vi = f (P)
Degrees of freedom analysis Mi n
M B, M D 2
Li n
B,R,D 3
xi,j n(NC − 1)
xB,j,xD,j 2(NC − 1)
yi,j n(NC − 1)
Variables
yB,j NC − 1
hi n
h B, h D 2
Hi n
HB 1
Vi n
VB 1
Ti n
TD, TB 2
Equations: Total Mass n+2
Energy n+2
Component (n + 2)(NC − 1)
Equilibrium n(NC − 1)
Liquid holdup n
Enthalpies 2n+2
Vapor rate n
hB = h1 1
yB = xB (NC − 1)
Total 7+6n+2n(NC-1)+3(NC-1)
Constants: P, F, Z
Therefore; the degree of freedom is 4

To well define the model for solution we include four relations

imported from inclusion of four feedback control loops as follows:

Use B, and D to control the liquid level in the condenser drum and
in the re-boiler.
Use VB and R to control the end compositions i.e., xB, xD
 Simplified Model
One can further simplify the foregoing model by the
following assumptions:
a) Equi-molar flow rates, i.e. whenever one mole of liquid vaporizes
a tantamount of vapor condenses. This occur when the molar heat
of vaporization of all components are about the same.
This assumption leads to further idealization that implies constant
temperature over the entire column, thus neglecting the energy
balance.
In addition, the vapor rate through the column is constant and equal
to:
VB = V1 = V2 =… = Vn (2.179)
(b) Constant relative volatility, thus a simpler formula for the phase
equilibrium can be used:
yj = aj xj/(1+(aj − 1) xj) (2.180)
 Degrees of Freedom:
Variables:
Equations:
Mi, MB, MD n+2 Total Mass n+2

Li, B,R,D n +3 Component (n + 2)(nc − 1)

xi,xB,xD (n + 2)(nc − 1) Equilibrium n(nc − 1)

yj, yB (n + 1)(nc − 1) Liquid holdup n

V 1 yB = xB 1

Total 2 + 2n + (2n + 3)(nc − 1) Total 2+2n+(2n+3)(nc-1)

It is obvious that the degrees of freedom is still 4.

NON EQUILIBRIUM SYSTEM -
FLASH DRUM
Consider a model of a flash drum in which it cannot be assumed that the vapour and liquid
phases are in phase equilibrium:

The vessel can be abstracted as two well-mixed phases constrained within a fixed volume.
Material and energy fluxes exist between the phases:
NON EQUILIBRIUM SYSTEM - FLASH DRUM
Control volumes: control volume for gas phase and control
volume for liquid phase. Both will vary in size and shape as the
liquid level rises and falls.
Assumptions:
• individual phases are well-mixed.
• vessel adiabatic
• liquid feed stream well-mixed with the liquid phase
• both phases present at all times
• bulk flows into and out of vessel specified by user or
determined by upstream and downstream models
These assumptions are the simplest assumptions that can be
made. It is interesting to note that to assume anything else
would require a detailed knowledge of the internal
topology of the vessel and physico-chemical discontinuities (e.g.
the level of the feed pipe relative to that of the liquid level, the
area of heating coil/jacket immersed in the liquid phase, etc.).