Answer scheme for miniproject Sem 1 session 1920

The miniproject assessment is an open-ended problem to help the students learn further CRE1 lessons
in the textbook and acquire solution skill in a group. Nonetheless, the solution in this scheme is just a
suggestion and guideline to lecturers to mark their work. Other possible methods can be applied as
far as they are correct and appropriate.

Task 1

The reactions are


k1 and K1
CO + 2H 2  
 CH3OH


k2 and K 2
CO + H 2 O   CO 2 + H 2

k3
CH 3OH   CH 2 O + H 2

The multiple reaction is complex. Thus, the selectivity is as follows,

 C 
k1  CCO CH2 2  M 
r  K1 
S r1  1  (1)
r2  r3 r2  r3  C C 
k 2  CCO CH 2O  CO 2 H 2   k3CM
 K2 
It is difficult to deduce how reactant concentrations and reaction temperature can affect the
selectivity in Equation 1. The ratio of rate constant favours high reaction temperature as the desired
reaction has the highest activation energy. However, the main reaction is reversible and release heat
(or exothermic) as can be seen from the Vant Hoff equation of the equilibrium constant. Therefore,
an optimum temperature should be determined.

Mole balance of PFR (or batch reactor) can be calculated to delineate the effects.

Algorithm

Mole balance of species in PFR is expressed according to the rate constant unit i.e. mol/s:

dFi
 ri where i is for all reacting species. The initial molar flow rate of carbon monoxide and
dV
hydrogen are backwardly calculated from 40,000 tonnes per annum of AA at 8000 hr/yr for initial
guest.

Net rate laws:

 C 
r1  k1  CCO CH2 2  M 
 K1 
 C C 
r2  k2  CCO CH 2O  CO 2 H 2 
 K2 
r3  k3CM

ri   i rj where j is the reaction of which the stoichiometric coefficients and  is stoichiometric
coefficient are taken for a particular species
   Eaj 
k j  Aj exp   where T = 330 K (isothermal low temperature)
 RT 
Stoichiometry
F   T0  P0 P
Ci  CT 0  i  y   where CT 0  , FT  FCO  FH 2  FM  FCO 2  FW  FF and y 
 FT  T  RT P0
Analysis
r1
Instantaneous selectivity, S r2 
r2  r3 r2  r3
FAA
Overall selectivity, S 
FCO 2  FCH 2 O
rM
Instantaneous yield based on carbon monoxide, Y 

 rCO
FM
Overall yield based on ethylene oxide, Y 
FCO 0  FCO
The Polymath file is attached and the graphical example of all flows of species is shown in Figure 1.

Figure 1. Result of Graph

Instantaneous selectivity is generally used to determine optimum feed condition of the reactor and
reactor scheme. Selectivities of the desired product against the undesired products from 2-side
reaction are shown in Figure 2 for 4 temperatures of isothermal PFR at the lowest pressure i.e. 1 atm.
All selectivities are low except 380 K as at this pressure 400 K the mole balance calculation is not
possible. However, the volume for 380 K is too low and the conversion is far below than unity (1). The
conversion is not shown here but students can plot the selectivity against it using data from the table
of the ODE solver result.

At 80 atm, interesting trend lines are shown by different reaction temperatures. High instantaneous
is shown by low T i.e. 305 K at 99.36 % conversion for 2 m3 PFR. At 300 K the selectivity does not
achieve maximum value due to limitation of PFR length. The optimum reaction temperature is around
305 K for 80 atm pressure. If the pressure is reduced, this value will be higher. In the textbook, the
optimum reaction is above 310 K for 16 atm.
At 160 atm, the instantaneous selectivity is even higher. Unfortunately, the maximum conversion is
getting lower due to insufficient length of the reactor. 93.8 % conversion (not shown in the graph) is
obtained by 310 K for 2-m3 PFR.

From three graphs in Figure 2, the instantaneous selectivity is high when the pressure is high. The
reaction temperature inversely corresponds with reactor pressure. The optimum reaction
temperature will be high if the pressure is low. Therefore, students can generally say pressure must
be high and reaction temperature must be low but not to lead to low conversion. It seems that
enthalpy of reaction affects the exothermic reversible reaction of the desired reaction more than
activation energy of the reaction.

Instantaneous Selectivity at Various Instantaneous Selectivity at Various

Reaction Temperature of Isothermal Reaction Temperatures of
1.00E+03 PFR under 1 atm Isothermal PFR under 80 atm
300 K
305 K
8.00E+02 300 K
3 310 K
350 K 315 K
6.00E+02 2.5 320 K
380 K 325 K
2
350 K
4.00E+02 318.5
S

1.5
1
S

2.00E+02
0.5
0.00E+00 0
0 500 1000 1500 2000 0 500 1000 1500 2000
-0.5
-2.00E+02
-1
V Vpfr

Instantaneous Selectivity at Various Reaction Temperatures

of Isothermal PFR under 160 atm
25
300 K
20 305 K
310 K
15
315 K
10
S

0
0 500 1000 1500 2000
-5
Vpfr

Figure 2 Selectivity of methanol for various temperature at 3 reactor pressures

Next, the given ratio of feed, i.e. H2:CO:CO2:H2O = 7:3:3:2, is used in the abovementioned graphs
or figures. Water is involved in the second reaction consuming the desired product to form the
undesired products of carbon monoxide and hydrogen. Therefore, this water should not be fed.
Hydrogen is excess according to the stoichiometry of the first reaction to suppress the formation of
products in the second reaction based on the Le Chaterliar principle. Similarly, the carbon dioxide
feed will help reverse the second reaction based on the same principle. It is perfect, if the desired
product of methanol can be removed continuously by using a separation technology so that the third
reaction can be minimized.

Instantaneous Selectivity for 160 Overall Yield for 160 atm and 310 K
9 atm and 310 K 1.2
1
7
No water 0.8
5 0.6

Ỹ
With water No water
S

3 0.4
with water
0.2
1
0
-1 0 500 1000 1500 2000 0 500 1000 1500 2000
Vpfr Vpfr

Figure 3 Instantaneous Selectivity and Overall Yield under two feed ratio conditions

Finally, the reactor scheme is probably as shown in Figure 4.

Fco0, Fh20 Fco,Fh2, Fm,

and Fco20 Fco2 and Ff