Documente Academic
Documente Profesional
Documente Cultură
1
Attainable Region
Attainable region (AR) defines the achievable compositions that
may be obtained from a network of chemical reactors.
2
Attainable Region
The van de Vusse kinetics is:
k1 k3 k4
A B C , 2A D
k2
4
Attainable Region
Step 2: When the PFR trajectory bounds a convex region, this
constitutes a candidate AR. A convex region is one in which all
straight lines drawn from one point on the boundary to any
other point on the boundary lie wholly within the region or on
the boundary. If not, the region is nonconvex. When the rate
vectors, [dCA/dτ, dCB/dτ]T, at concentrations outside of
candidate AR do not point back into it, the current limits are the
boundary of AR and the procedure terminates.
In this example, , so
proceed to the next step.
5
Attainable Region
Step 3: The attainable region is expanded by linear arcs,
representing mixing between the PFR effluent and the feed. Note
that a linear arc connecting two points on a composition
trajectory is expressed by the equation: c* c1 (1 ) c2 ,where
c1 and c2 are vectors for two streams in the composition space,
c* is the composition of the mixed stream, and α is the fraction of
the stream with composition c1 in the mixed stream. The linear
arcs are then tested to ensure that no rate vectors positioned on
them point out of the AR. If there are such vectors, proceed to
the next step, or not return to step 2.
7
Attainable Region
Step 4: Since there are vectors pointing out of the convex hull, it
is possible that a CSTR trajectory enlarges the attainable
region. After placing the CSTR trajectory that extends the AR the
most, additional linear arcs that represent the mixing of streams
are placed to ensure that the AR remains convex.
9
Attainable Region
Since the union of the previous AR and the CSTR trajectory is
not convex, a linear arc, AGO, is augmented. This arc represents
a CSTR with a bypass stream.
10
Attainable Region
Step 5: A PFR trajectory is drawn from the position where the
mixing line meets the CSTR trajectory. If this PFR trajectory is
convex, it extends the previous AR to form an expanded
candidate AR. Then return to step 2. Otherwise, repeat the
procedure from step 3.
12
Example 7.4
Maleic anhydride,C4H2O3, is manufactured by the oxidation of
benzene with excess air over vanadium pentoxide catalyst:
9
Reaction 1 : C6 H 6 O 2 C 4 H 2 O 3 2CO 2 2H 2 O
2
Reaction 2 : C 4 H 2 O3 3O 2 4CO 2 H 2 O
15
Reaction 3 : C6 H 6 O 2 6CO 2 3H 2 O
2
Since air is supplied in excess, the reaction kinetics are approxi-
mated using first-order rate laws:
A
k1
P
k2
B, A
k3
C, r1 k1CA , r2 k2CP , r3 k3CA
12660 15000 10800
k1 4280 exp , k2 70100 exp , k3 26 exp
T ( K ) T ( K ) T ( K )
A is benzene, P is maleic anhydride, and B and C are byproducts
(CO2 and H2O). The ris have the units of m3/(kg catalyst.s).
13
Example 7.4
Given that the available feed stream contains benzene at a
concentration of 10 mol/m3, with a volumetric flow rate , v0, of
0.0025 m3/s (the feed is largely air), propose a network of
isothermal reactors to maximize the yield of maleic anhydride.
14
Influence of temperature on rate constants for
MA manufacture
15
Example 7.4: Solution
For this system, the attainable region is straight forward to
contract. This begins by tracing the composition space trajectory
for a packed-bed reactor (PBR), modeled as a PFR, which
depends on the solution of the molar balances:
dCA
v0 k1CA k3CA , CA0 10 mol/m 3
dW
dCP
v0 k1CA k 2CP , CP0 0, W kg of catalyst
dW
The next Figure represents solutions of these equations for
several operating temperatures. Since these trajectories are
convex, and rate vectors computed along their boundaries are
tangent to them, it is concluded that each trajectory bounds the
AR for its corresponding temperature.
16
Attainable regions for MA manufacture
17
Example 7.4: Solution
Evidently, a single PFR provides the maximum production of
maleic anhydride, with the desired space velocity being that
which brings the value of CP to its maximum value.
19
Example 7.4: Solution
The following Figure indicates that the yield (the ratio of the
desired product rate and feed rate) under these conditions is
61%, while the selectivity (the ratio of the desired product rate
and total product rate) is only about 10%.
20
Principle of Reaction Invariants
Because the attainable region depends on geometric construct-
ions, it is effectively limited to the analysis of systems involving
two independent species.
kmol k 2
4
PH 2 PCO 2
r2 3.5 PCH 4 PH 2O
2 (DEN) 2
kg cat h PH 2 K2
PH2O
DEN 1 K CO PCO K H2 PH2 K CH 4 PCH 4 K H 2O
PH 2
2.292 10 4 3
K1 (bar ) exp 20.52
2
7.195 ln T 2.949 10 T
T
1.760 10 4 3
K 2 (bar ) exp 32.63
2
8.207 ln T 2.835 10 T
T
24
Example 7.5: AR for Steam-Methane Reforming
Ei 1 1
ki ki ,Tr exp , i 1, 2
R T Tr
H j 1 1
K j K j ,Tr exp , j CO, H 2 , CH 4 , H 2 O
R T Tr
0 0 1 1 1
A [ A d | A i ] 2 2 0 4 0
0 1 2 0 1
4 1
1 nCH 4
n d A d A i n i 2 1
1 1 CO
n
26
Example 7.5: AR for Steam-Methane Reforming
Step 1: Begin by construction a trajectory for a PFR from the
feed point, continuing to the complete conversion of methane or
chemical equilibrium. Here, the PFR trajectory is computed by
solving the following equations:
dN CH 4 dN CO kmol
r1 r2 , r1 , N i
dW dW hr
The partial pressure of each components can be calculated by:
N H 2 4N CH 4 N CO
Ni N H O 2N CH N CO
Pi P, where 2 4
N total N N CH 4 N CO
CO 2
N total 2N CH 4
This leads to trajectory (1), which tracks the composition from
the feed point, A, to chemical equilibrium at point B.
27
Example 7.5: AR for Steam-Methane Reforming
28
Example 7.5: AR for Steam-Methane Reforming
30
Example 7.5: AR for Steam-Methane Reforming
Step 4: Since there are vectors pointing out of the convex hull, it
is possible that a CSTR trajectory enlarges the attainable
region. After placing the CSTR trajectory that extends the AR the
most, additional linear arcs that represent the mixing of streams
are placed to ensure that the AR remains convex.
32
Example 7.5: AR for Steam-Methane Reforming
Step 5: A PFR trajectory is drawn from the position where the
mixing line meets the CSTR trajectory. If this PFR trajectory is
convex, it extends the previous AR to form an expanded
candidate AR. Then return to step 2. Otherwise, repeat the
procedure from step 3.
34