Department of Energy

Politecnico di Milano
Via Lambruschini 4 – 20156 MILANO 
 

Exercises of Fundamentals of Chemical Processes

Exercise 5
Estimation of the heat supply Q required by the First Stage of a Reformer

In the first stage of the reforming process, synthesis gas is prepared starting from natural gas. The process
can be summarized with the following two reactions:

CH4 + H2O ↔ CO + 3 H2 (1)

CO +H2O ↔ CO2 + H2 (2)

The second reaction (2) is the Water Gas Shift. The first reaction is the Reforming of methane with steam
(steam reforming). This reaction is highly endothermic and the necessary heat is supplied via exchange at the
reactor walls. In a typical process, the feed gases (composition given in the Table) enter the reactor at 550°C
and exit at 800°C. Assuming that the process reaches the thermodynamic equilibrium, estimate the
composition of the outlet gas stream, and find the amount of heat Q to be supplied.

Data:
Stream 1: P = 30 atm T = 550°C
Stream 2: P = 30 atm T = 800°C
Hypothesis: Both the reactions reach the thermodynamic equilibrium
Ideal mixture of ideal gases

Species Flow Rate (Nm3/h)

CH4 22486
H 2O 94015
Solution

The problem asks for the estimation of the heat supply Q and of the composition of the outlet gas stream. For
each species, the material balance is written by applying the extent of reaction method: in this case, two
reactions are required, the steam reforming and the WGS. Therefore, it is possible to define the extent of
reactions λ1 and λ2. 100 mol/h inlet CH4 are chosen as the basis for the material balances. The flow rates of
the outlet gas stream are expressed as a function of λ1 and λ2:

NR
niout  niin  i , j   j
j 1

Species nin (mol/h) nout (mol/h)

CH4 100 100 - 1
H 2O 418.1 418.1 - 1 - 2
CO 0 1 - 2
H2 0 31 + 2
CO2 0 2
Total 518.1 518.1 + 21

The amount of H2O in the inlet feed is calculated as follows:

94015
n H 2O  100  418.1 mol/h
22486

To estimate the extent of the reactions, two equations must be written, knowing that the steam reforming
reaction and the WGS reaction reach the thermodynamic equilibrium. The following expressions are given for
the estimation of the G0R(T):

G R0 ,SR T   53717  60.25  T cal/mol 600 K < T < 1500 K

G R0 ,WGS T   8514  7.71  T cal/mol 600 K < T < 1500 K

At TOUT equal to 800°C, the values of the G0R are:

GR0 , SR 1073K   10931.2

GR0 ,WGS 1073K   241.2

These values lead to:

keqSR 1073K   169.50
keqWGS 1073K   1.12

Given the assumption of ideal gases, the equilibrium condition for the steam reforming reaction leads to the
following equation (Eq. 1):

P  y P  y   P       ntot 
3 3 3 3
NC NC i
out out out
yCO  yHout2 out
nCO  nHout2 out
ntot out

  Pi  P y  
i CO H2
k SR 2
 P 
2
 
eq
1 1 P  y P  y 
i out
CH 4
out
H 2O
out
yCH 4
 yHout2O out
nCH 4
 nHout2O out
ntot  ntot
out

 1  2    3 1  2 
3
P2
 
 518.1  2 1  100  1    418.1  1  2 
2

 1  2    31  2 
3
900
  169.50
 518.1  2 1  100  1    418.1  1  2 
2

In the case of the WGS reaction, the equation (Eq. 2) is:

WGS
k eq
NC
  Pi i   P  y i  

NC i P  y  P  y   y
out
CO2
out
H2
out
CO2  y Hout2

out
nCO  n Hout2 ntot

out
 ntot
out

P  y  P  y  y
2

1 1
out
CO
out
H 2O
out
CO  y Hout2O out
nCO  n Hout2O ntot
out
 ntot
out

2  3 1   2 

1  2   418.1  1  2 

2  3 1  2 
 1.12
1  2   418.1  1  2 

Equation 1 and 2 lead to the following solving system:

 169.50
 1  2    3 1  2   900  100  1    418.1  1  2    518.1  2 " 
3 2



  3     1.12      418.1    
 2  1 2  1 2  1 2


Where: 0 < λ1 ≤ 100 and 0 < λ2 ≤ λ1

To solve the system, an iterative procedure can be followed. Different solving strategies are possible. For
instance, it is possible to solve Equation 2 as a function of λ2, once a value is assigned to λ1. A quadratic
equation is obtained. The equation has two roots, only one of which has a physical meaning:

 3  1  468.272    3  1  468.272   0.48   468.272  1  1.12  12 

2

2 
0.24
A first attempt value is assigned to λ1, and λ2 is determined. With this value of λ2, a new value of λ1 is
determined from the first equation. Different numerical methods can be applied in this case, for instance the
bisection or the Newton method. With this value of λ1, a second new value is obtained for λ1. The iterative
procedure is repeated until the values converge to stable values. The final solving values are:

1  75.03
2  41.88

The composition of the outlet gas stream is:

Species nout (mol/h) % dry vol. % total vol.

CH4 24.97 6.80 3.74
CO 33.16 9.04 4.96
H2 266.96 72.75 39.95
CO2 41.87 11.41 6.27
H 2O 301.20 - 45.08
Total 668.17 100.00 100.00

It is important to note that the partial pressure of the reacting species contemporarily satisfy the equilibrium
conditions of both the reactions that are included in the system. It would have been incorrect to solve the
equilibrium composition for one reaction, and then determine the equilibrium composition for the other
reaction. The enthalpy balance is used to calculate the heat to be supplied to the reactor:

 
H IN n IN , TIN   H OUT nOUT , TOUT   Q  0

The reference state assumes the elementary species at TREF equal to 298.15 K and PREF equal to 1 atm. For
each species in the system, the specific molar enthalpy at temperature T is:

T
hi T   H F0 ,i  298K    C P ,i  dT
298 K

The enthalpy of a gas mixture is calculated as the sum of the product between the molar specific enthalpy
and the molar flow rate of each species in the mixture.

NC
H i T    ni  hi (T )
i

The following polynomial form is used for the calculation of the specific heats, taken for the thermodynamic
property database:

C P ,i (T)  ai  bi  T  ci  T 2  di  T 3
 T T
bi c d
 C P ,i dT    a  b T  c T 
 di  T 3  dT  ai  T  298      
 T 2  2982  i  T 3  2983  i  T 4  2984 
2
i i i
298 K 298 K
2 3 4

Knowing the molar flow rates of the gas streams at the inlet and at the outlet of the reactor, the enthalpy of
the gas mixtures are calculated once the coefficients for the specific heats are known:

 NC
 b c d 
H IN  nIN , TIN    niin   a i  (Tin  298)  i  (Tin2  298 2 )  i  (Tin3  298 3 )  i  (Tin4  298 4 ) 
i 1  2 3 4 

 NC
 b c d 
H OUT  nOUT , TOUT    niout   a i  (Tout  298)  i  (Tout
2
 298 2 )  i  (Tout
3
 298 3 )  i  (Tout
4
 298 4 ) 
i 1  2 3 4 

The required values are taken from the thermodynamic property database (J/mol/K):

H0F(298K)
Species a b x 103 c x 106 d x 109
[J/mol]
H2 0.000 27.14 9.274 -1.381 7.645
H 2O -2.420e+5 32.24 1.924 1.055 -3.596
CO -1.106e+5 30.87 -12.85 2.789 -12.72
CO2 -3.938e+5 19.80 73.44 -5.602 17.15
CH4 -7.490e+4 19.25 52.13 1.197 -11.32

By substituting these values and those of the molar flow rates in the solving equation, one obtains:


H IN n IN , TIN   1.5405  10 4  823.15  298.15  3.0087  823.15 2  298.15 2   
  
 1.8693  10 3  823.15 3  298.15 3  6.5888  10 7  823.15 4  298.15 4  1.0867  10 8 

H IN n IN , TIN   9.8117  10 7 J/h


H OUT nOUT , TOUT   1.9290  10 4  1073.15  298.15  3.5029  1073.15 2  298.15 2   
4
 
 5.4366  10  1073.15  298.15  2.4286  10  1073.15  298.15  9.4917  10 7
3 3 7
 4 4


H OUT nOUT , TOUT   7.6583  10 7 J/h

On a basis of 100 mol/h, the heat supply results:

J
Q  2.1534 107
h
In the case of 22486 Nm3/h incoming methane, the heat supply is:

 7 J h 22486 Nm3 h J
Q  2.1534 10   3
 2.160 1011  60.01MW
h 100mol 22.414 10 Nm mol
3
h