Gerard B.
Hawkins
Managing Director
Kp
Temperature
The aim of this presentation is to
Give an understanding of equilibrium
Methane Steam
Water Gas Shift
Explain what affects equilibrium
Explain concept of approach to equilibrium
There is an equilibrium effect
Limits the reaction rate
Point at which forward and reverse reactions are
equal
Defined by
[ ] [ ]
[ ] [ ] CO .P H P
O H .P CH P
Kp
3
2
2 4
=
Can rearrange into a more useful form
So now we can relate partial pressure of
methane to other parameters
But can simplify again to
This is the most useful form
[ ]
[ ] [ ]
O] P[H
CO .P H P
Kp CH P
2
3
2
4
=
[ ]
[ ] [ ]
O] [H
CO . H P
Kp CH
2
3
2
2
4
=
Equilibrium defined by
We can see therefore
Methane slip is proportional to Kp
Methane slip is proportional to P
Methane is inversely proportional to steam fraction
Reason why SC Ratio is high
So we can now determine cause and effect by
using this simple expression
[ ]
[ ] [ ]
O] [H
CO . H P
Kp CH
2
3
2
2
4
=
Kp is inversely proportional to temperature
Therefore to achieve a good equilibrium position
need to use a high temperature
Kp
Temperature
Water Gas Shift (WGS) is also equilibrium limited
Equilibrium defined by
Which can be rearranged to
P[CO
2
] P[H
2
]
Kp = ____________
P[CO] P[H
2
O]
[CO
2
] x [H
2
]
[CO] = _________
Kp x [H
2
O]
[CO] not dependant upon pressure
[CO] 1/[H
2
O]
Higher steam to carbon ratio gives lower CO content
Higher steam to carbon ratio gives higher CO
2
content
Kp is related to temperature
High exit temperature gives more CO and
conversely less CO
2
Water Gas Shift (WGS) is at equilibrium at exit
of the reformer
Reaches equilibrium very fast
Kp
Temperature
By using equation earlier can relate methane slip
to temperature
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472) (1490)
Temperature C (F)
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472)
(1490)
Temperature C (F)
Exit CH
4
Equilibrium
Temperature
Gas Exit
Temperature
ATE
Approach to Equilibrium (ATE) is therefore
defined by
ATE = Actual temperature - Equilibrium
temperature
ATE is 0F when gases at equilibrium
This never happens
Usually ATE in in range 5-20F
ATE rises as the catalyst ages
Can translate this graph to give
0 0.2 0.4 0.6 0.8 1
200
300
400
500
600
700
800
900
Fraction down tube
T
e
m
p
e
r
a
t
u
r
e
C
Gas Temp
Eq'm Temp
390
570
750
930
1110
1290
1470
1650
Can then superimpose the reaction path
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472) (1490)
Temperature C (F)
Equilibrium
Line
Reaction
Path
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472) (1490)
Temperature C (F)
ATE
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472) (1490)
Temperature C (F)
Equilibrium
Line
Increasing pressure
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472) (1490)
Temperature C (F)
Increasing
pressure
ATE
A reformer is essentially an equilibrium reactor
Low ATEs are achieved at the exit
Any change that affects the equilibrium position
will affect the performance of the catalyst/reformer
Will affect the approach
Will affect the methane slip
Raising the outlet pressure will
Increase kinetic rate which will reduce ATE
But equilibrium position is worse
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472)
(1490)
Temperature C (F)
Equilibrium
Line
Reaction
Path
Effect of
Raising Exit
Temperature
So raising the exit temperature
Reduces the methane slip
Tightens the approach to equilibrium
But
Will increase tube temperatures
May reduce tube wall margin
Classic trade off between maximizing production
but sacrificing tube life
Any increase in feed rate will
Increase exit temperature or methane slip
Depends on operating policy
Increase pressure drop
Increase ATE - lower residence time
Increase maximum tube wall temperatures
Hence reduce tube life
Increase fluegas flow
Increase temperature
Reduced contact time
Converse is also true
Reducing steam to carbon ratio
If methane slip is held constant will require an increase in
exit temperature
ATE will reduce
Maximum tube wall temperature will rise
If exit temperature is held constant will cause methane
slip to rise
ATE will increase
Pressure drop will be reduced
Converse is also true
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472) (1490)
Temperature C (F)
Cold
Zone
Hot
Zone
Actual
Operating Point
Effect of such a spread is
Tight approaches in both hot and cold zones
Methane slip is average of both zones
Temperature is average of both zones
Approach for mixed gas is high
Appears as if catalyst is not working well
From the above, there are conflicts as defined
below
Temperature Pressure
Steam to
Carbon
Kinetics
Equilibrium
Overall
Conflict ?
High
High
High
No
High
Low
?
Yes
Low
High
?
Yes
Pressure - defined by other issues
CAPEX of reformer
High pressure = thicker tubes
Size of synthesis gas compressor
High pressure reduces size of synthesis gas machine
But increases the size of the air compressor
Methane slip is increased
But secondary reduces the effect
Does represent an inefficiency
Classic balance between CAPEX and OPEX
Steam to Carbon - defined by other issues
Must raise HP steam for synthesis gas machine
Do get MP steam from extraction from turbine
Try to minimise capacity to reduce CAPEX - more steam
raising requires more coils/heat exchangers
HTS operation - over reduction
CO
2
removal - reboiler heat load
Metal dusting is a problem at low steam to carbon ratios
508
203
102
E
q
u
i
l
i
b
r
i
u
m
%
C
H
4
(
d
r
y
b
a
s
i
s
)
P
r
e
s
s
u
r
e
(
p
s
i
g
)
P
r
e
s
s
u
r
e
(
b
a
r
g
)
Steam
Ratio
2.0
3.0
4.0
5.0
35
14
7
1.0
2.0
5.0
10
20
50
Equilibrium exit CH
4
at these
conditions ?
P= 30bar (435psi)
T = 850C (1562F)
Steam/Carbon = 3.5
508
203
102
E
q
u
i
l
i
b
r
i
u
m
%
C
H
4
(
d
r
y
b
a
s
i
s
)
P
r
e
s
s
u
r
e
(
p
s
i
g
)
P
r
e
s
s
u
r
e
(
b
a
r
g
)
Steam
Ratio
2.0
3.0
4.0
5.0
35
14
7
Equilibrium CH
4
= ~5.6%
1.0
2.0
5.0
10
20
50
CH
4
slip is a function of
Catalyst activity
Reformer exit temperature
Reformer exit pressure
S:C Ratio
varies with operating conditions
Assessment of catalyst performance
CH
4
slip alone is not a good measure of performance
ATE is a better guide
will not change dramatically with operating conditions
Take inlet and exit gas samples for analysis
Measure steam reformer exit T & P
Measure reformer inlet steam and feed flows
Need to calculate reformer exit dry gas flow
all carbon in the feed ends up in the dry gas
hence we can calculate exit dry gas rate by carbon
balance
Need to calculate the reformer exit steam flowrate
can be done by Hydrogen balance across the
reformer
Can also do a balance on O
2
as a cross check
Calculate exit wet gas composition and then K
p
Calculate Equilibrium Temperature
Calculate Approach to Equilibrium
Assumes measured data is correct
In practise always errors in measured data
feed flow
feed analysis
steam flow
exit analysis
exit pressure
exit temperature
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472)
(1490)
Temperature C (F)
Exit CH
4
Equilibrium
Temperature
Gas Exit
Temperature
ATE
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472)
(1490)
Temperature C (F)
Exit CH
4
Gas Exit
Temperature
Pressure
770 780 790 800 810
4
6
8
10
12
M
e
t
h
a
n
e
s
l
i
p
(
%
)
(1418)
(1454) (1436) (1472)
(1490)
Temperature C (F)
Worst ATE
CH4
Gas Exit
Temperature
Actual ATE
Best ATE
Pressure
Need to do a consistency check on the data
Check data for a consistent H & M balance
GBHE VULCAN CERES H & M Balance reconciliation
WGS at reformer exit temperatures
At high temps, WGS reaction should be at Equilibrium
We can similarly calculate approach to WGS
equilibrium
Often WGS appears to not be at equilibrium
Suggests errors in exit analysis and exit T
Well
Use VULCAN CERES
Use VULCAN TP
3
Use VULCAN REFSIM
And most of all Think !
