Reforming Process PDF

ChE 201 Washington State University
Chemical Process Principles and Calculations Voiland School of Chemical Engineering

and Bioengineering
Fall, 2009 Richard L. Zollars

Problem 9.37, Felder and Rousseau

Hydrogen is produced in the steam reforming of propane:

( ) ( ) ( ) ( ) g H g CO v O H g H C
2 2 8 3
7 3 3 + +

The water-gas shift reaction also takes place in the reactor, leading to the formation of additional
hydrogen:

( ) ( ) ( ) ( ) g H g CO v O H g CO
2 2 2
+ +

The reaction is carried out over a nickel catalyst in the tubes of a shell-and-tube reactor. The
feed to the reactor contains steam and propane in a 6:1 molar ratio at 125C, and the products
emerge at 800C. The excess steam in the feed assures essentially complete consumption of the
propane. Heat is added to the reaction mixture by passing a hot gas over the outside of the tubes
that contain the catalyst. The gas is fed at 4.94 m
3
/mol C
3
H
8
, entering the unit at 1400C and
1 atm and leaving at 900C. The unit may be considered adiabatic.

Calculate the molar composition of the product gas, assuming that the heat capacity of the
heating gas is 0.040 kJ /(molC).

SOLUTION

Since we are bring asked to find a composition we can select a basis. Lets pick one mole of
propane entering the reactor. Thus there are 6 moles of H
2
O entering the reactor. Since the heat
capacity of the heating gas is on a molar basis we also need the molar flow rate of the heating
gas. Using the ideal gas law you get

( )
( )
mol
K
K mol
atm L
m
L
m atm
RT
PV
n 98 . 35
15 . 1673 08206 . 0
1000
94 . 4 1
3
3
=
|
.
|
\
|
= =

The inlet/outlet table would look like

n
in

in
H

n
out

out
H
.

C
3
H
8
1
1
H
0 -
H
2
O (v) 6
2
H
n
1

4
H
CO (g) - n
2

5
H
CO
2
(g) - n
3

6 .
H
H
2
(g) - n
4

7
H
Heating Gas 35.98
3
H
35.98
8
H

We need to select reference states. Lets use the elements (C, H
2
, and O
2
) at 25C and the
heating oil at 900C as the reference states. Then

| |
( ) ( ) ( )
( )
mol
kJ
H
H
dT T T T H
dT C H H
H C p
o
f
39 . 95 415 . 8 8 . 103
25 125
4
10 71 . 31
25 125
3
10 11 . 13
25 125
2
10 59 . 22
25 125 068032 . 0 8 . 103
10 71 . 31 10 11 . 13 10 59 . 22 068032 . 0 8 . 103

1
4 4
12
3 3
8
2 2
5
1
125
25
3 12 2 8 5
1
125
25
8 3 , 1
= + =
+ + =
+ + + =
+ =

}
}

For the remaining compounds you can use the enthalpy data in Table B.8. Thus

mol
kJ
dT C H H
mol
kJ
dT C H H
mol
kJ
dT C H H
v CO p
o
f
v O H p
o
f
v O H p
o
f
39 . 86 13 . 24 52 . 110

78 . 212 05 . 29 83 . 241

43 . 238 40 . 3 83 . 241

125
25
) ( , 5
800
25
) ( 2 , 4
125
25
) ( 2 , 2
= + = + =
= + = + =
= + = + =
}
}
}

mol
kJ
dT C H H
mol
kJ
dT C H H
g H p
o
f
g CO p
o
f
85 . 22 85 . 22 0

14 . 356 36 . 37 5 . 393

800
25
) ( 2 , 7
125
25
) ( 2 , 6
= + = + =
= + = + =
}
}

To get
3
H use the heat capacity data given in the problem statement.

( )
mol
kJ
dT C H
gas Heating p
20 900 1400 040 . 0
1400
900
, 3
= = =
}

Thus the input/output table becomes

n
in

in
H

n
out

out
H
.

C
3
H
8
1 -95.39 0 -
H
2
O (v) 6 -238.43 n
1
-212.78
CO (g) - n
2
-86.39
CO
2
(g) - n
3
-356.14
H
2
(g) - n
4
22.85
Heating Gas 35.98 20 35.98 0

For the overall system the energy balance would give

( ) ( )
( ) ( ) ( ) ( ) ( ) ( ) ( )
37 . 806 85 . 22 14 . 356 39 . 86 78 . 212
85 . 22 14 . 356 39 . 86 78 . 212 20 98 . 35 43 . 238 6 39 . 95 1

0
4 3 2 1
4 3 2 1
= + +
+ + + = + +
=
= A

n n n n
n n n n
H n H n
H
out
i i
in
i i

This gives one equation in our four unknowns. The other three equations can be derived from
balance on C, H and O. These are, respectively,

( )
3 2 1
4 1
3 2
2 6 :
2 2 20 8 2 6 :
3 :
n n n O
n n H
n n C
+ + =
+ = = +
+ =

This gives the equations, in matrix form, as

(
(
(
(
=
(
(
(
(
(
(
(
(
37 . 806
6
20
3
85 . 22 14 . 356 39 . 86 78 . 212
0 2 1 1
2 0 0 2
0 1 1 0
4
3
2
1
n
n
n
n

Solving this gives

02 . 9
02 . 2
983 . 0
983 . 0
4
3
2
1
=
=
=
=
n
n
n
n

Thus there is a total of 0.983 +0.983 +2.02 +9.02 =13.01 moles in the stream leaving the
reactor. The composition would be y
H2O
=0.0756, y
CO
=0.0756, y
CO2
=0.155, y
H2
=0.694.

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ChE 201 Washington State University

Chemical Process Principles and Calculations Voiland School of Chemical Engineering

H use the heat capacity data given in the problem statement.

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