Startup of a PFR:

Consider the reaction A
B, occurring isothermally in a PFR. The startup of PFR is modeled as
follows. First we assume that a steady flow of the fluid is established, but the reaction hasn’t
started yet. Then suddenly we start the reaction (e.g. by suddenly increasing the temperature or
by introducing a small quantity of homogenous catalyst in the incoming stream).

If we consider a small volume ∆V, we can write the mass balance as

∂C
FA V + ( rA ) ∆V = FA V +∆V + A ∆V
∂t

Taking the limit when ∆V goes to zero, we get

∂FA ∂C A
+ = rA
∂V ∂t

This is a partial differential equation (pde), with two independent variables (t and V) and two
dependent variables (FA and CA). The dependent variables are related by the equation FA = Q ×
CA. If Q is a constant (e.g. steady flow, liquid phase reaction, or steady flow in gas phase with no
change in number of moles and without any pressure drop), then this equation can be simplified
to be one in a single dependent variable.

The initial conditions are

FA V =0 = FA−in and C A t =0 = C A−in

If there is a significant pressure drop, then, even without the reaction, the flow rate will be a
function of position (volume). Therefore, the concentration will be a function of volume, even
under steady flow condition without any reaction. Then the initial condition for concentration
will be C A t =0 = C A (V ) . The initial condition for FA will remain the same as before.

Depending on the order of reaction, this pde may be linear or nonlinear.

If there are multiple species, similar equations can be written for each species and the
corresponding initial conditions can also be written.

We will need to use a pde solver (Matlab, Mathematica, Comsol,…) or write our own code in
any programming language, to solve this.

If we do not assume that the operation is isothermal, then we need to write the heat balance
equation. Note that the temperature can change, and hence the rate constant will vary with
position and with time. Similarly, the volumetric flow rate (if the fluid is gas) will change with
respect to location and time. We will normally use ideal gas law to relate the flow rate to
pressure (which can change due to pressure drop), number of moles (which can change due to
reaction) and the temperature (which can change due to heat of reaction and heating/cooling
coils).
The heat balance is written as
 A ∂T
∑ FC
i
i T + ( − rA )( ∆V )( −∆H ) = ∑ FC
p −i
i
i p − iT +U
VPFR
( ∆V )(T − Tc ) + ∑ ( ∆V ) Ci C p −i
i ∂t
V V +∆V

This can be written as

  ∂T ∂T
( −rA )( −∆H ) =  ∑ FC i p −i  + Ua (T − Tc ) + ∑ Ci C p −i where ‘a’ is the area of heat
 i  ∂V i ∂t
exchanger per unit volume of the PFR
  ∂T ∂T
i.e.  ∑ FCi p −i  + ∑ Ci C p −i = ( −rA )( −∆H ) − Ua (T − Tc )
 i  ∂V i ∂t

Here we have assumed that the cooling fluid is available at a constant temperature Tc.

We assume that initially the fluid is coming in at a particular temperature and it remains the same
throughout the reactor. Then suddenly we start the reaction (e.g. by introducing a homogenous
catalyst). The reaction starts. The coolant supply also starts suddenly.
The initial conditions are
T @ V=0 is Tin and
T @ t=0 is also Tin.

Instead, if we assume that initially the temperature is Tinit and suddenly we make the temperature
of the fluid at inlet as a different number Tin. More realistically, we will be ramping up the
temperature of the feed over a time and hence Tin will be a function of time. Then accordingly
the initial conditions will also change.

Solving these pde’s is beyond the scope of this course.