Theory and Operation of

Secondary Reformers
By:
Gerard B. Hawkins
Managing Director, CEO
Introduction
Purpose
Key to good performance
Problem Areas
Catalysts, heat shields and plant up-rates
Burner Guns
Development of High Intensity Ring
Burner
Case Studies
Conclusions
Secondary Reformer Purpose
Reduce methane slip to very low
levels
Around 0.3-0.5 % mol dry
For ammonia plants provide feed
point for nitrogen required for
ammonia synthesis
And thereby Ensure optimal H/N ratio
Generate heat for transfer for HP
steam in Waste Heat Boiler
Typical Reforming Configuration
Steam
Secondary
Reformer
Steam
Steam + Gas
Steam
Reformer
Air / Oxygen
500C
780C
450C
1200C
950C
10% CH
4
0.5% CH
4
Secondary Reformer Mechanical
Details
Refractory lined pressure shell
Fixed Catalyst bed in lower region
Combustion section in upper region
Water jackets to keep shell cool
Catalyst supported on brick arch
Keys to Good Performance
Three key
components
Burner Design
Mixing Volume
Catalyst
All must be designed
correctly to maximize
performance
Air/Oxygen
Steam Reformer
Effluent
To Waste
Heat Boiler
Keys to Good Performance
Again three key
components
Burner Design
Mixing Volume
Catalyst - VSG-
Z201/202/203
Since using O
2
as
oxidant, flame
temperature is
higher
Failures are much
faster
780C
540`C
2500C
1500C
1100-1200C
975C
1500C
1100-1200C
1300C
Note: Oxygen - Methanol Plant Design
Secondary Reformer Operation
Burner determines mixing performance
Air injected at high velocity
Forces mixing of air and process gas
Combusts only 20% of process gas
Must also mix in other 80%
Should achieve a uniform mixture
Catalyst bed can affect flow patterns
Secondary Reformer Combustion
Gas feed very hot > 630
o
C
Gas feed contains hydrogen
Gas ignites automatically
Autoignition >615
o
C
No need for spark or pilot
Must maintain gas above 615
o
C
Secondary Reforming Reactions
CH
4
+ 2CO = CO
2
+ 2H
2
O
2H
2
+ O
2
= 2H
2
O Exothermic - gives out
heat
Flame 2500
o
C mixed gas 1500
o
C
Steam reforming
CH
4
+ H
2
O = 3H
2
+ CO Endothermic - cools
down gas
Water gas shift
CO + H
2
O = CO
2
+ H
2
Slightly exothermic
Key Components: Catalyst
Problems
Catalyst can
Exhibit poor activity
Unlikely
Break up in service
Usually linked to a plant upset
Suffer physical blockage
Alumina vaporization
Become overheated and fuse
Causes increased pressure drop and gas mal-
distribution
Key Components: Catalyst Activity
Catalyst is exposed to very high
temperatures
Therefore nickel sinters
However once sintered it is very stable
Since catalyst operates at high temperature
it is difficult to poison
Poisons will not stick
For ammonia plants will pass through to
HTS and then LTS
For methanol plants will pass through to
methanol synthesis loop
Key Components: Catalyst Activity
VULCAN Series range of
catalysts VSG-Z201/202/203
Size - Mini and Standard plus
Elephant
Use as a heat shield
Shape
5-Hole
Quadralobe
Quadralobe has +20% more
activity than 4-hole
Well proven catalysts that are
high stable and strong
Long lives
Key Components: Catalyst Appearance
White - loss of nickel
Coated in white - alumina vaporization
Glazed or blue - very high temperatures
Pink crystals - synthetic ruby formation
Cause by high temperatures
A mixture of refractory and transition
metals
Key Components: Mixing Performance
Good mixing is absolutely essential
Poor mixing in mixing zone gives high approach
and high methane slip
Poor mixing can be due to
Poor burner design
Insufficient mixing volume
Burner gun failure
Root cause can be checked with CFD but will not
detect burner gun failure
Key Components: Burner Gun
If burner gun fails then can lead to
Wall refractory damage
Loss of vessel containment
Poor mixing can lead to zones of high
temperature
Leads to high rate of catalyst sintering
Reduction in catalyst activity
Increase in approach to equilibrium (ATE)
Poor mixing can lead to high flow zones
Movement/damage of target tiles or catalyst
bed
Increased ATE
Key Components: Burner Guns
Standard Ammonia secondary burners have
Small number of large holes
Give poor mixing at high rates
High risk of overheating bed
Methane slip rises rapidly at high rates
Burner can be plant limit
Key Components: Burner Guns
For methanol plants remember that
oxidant used in oxygen
Gives higher flame temperatures
If jet impinges on refractory then
refractory will be damaged much more
quickly
Vessel will fail rapidly
As oxidant flow is lower than for an
ammonia plant use a different design of
burner
Key Components
High Intensity Ring Burner
The high intensity burner differs from the
standard burners
Large number of small holes: Small flames
High degree of mixing: Short mixing distance
Oxidant fed evenly into process gas: Good
Mixing
Insensitive to rate increases
Used in ICI Ammonia plants
Effect of Operational Changes
Air Rate
Name Units Base
Case
Increased Air
Rate
Plant Rate % 100 100
Ai r Rate % 100 105
Exit Pressure Bara 39 39
Steam to Carbon to Primary n/a 2.88 2.88
Outlet Temperature C 1000 1026
Methane Slip mol % 0.41 0.41
H/N Ratio n/a 3.00 2.86
Approach to Equilibrium C 14.2 45.1

Effect of Operational Changes
Pressure
Name Units Base
Case
Increased
Exit Pressure
Plant Rate % 100 100
Ai r Rate % 100 100
Exit Pressure Bara 39 40
Steam to Carbon to Primary n/a 2.88 2.88
Outlet Temperature C 1000 1000
Methane Slip mol % 0.41 0.41
H/N Ratio n/a 3.00 3.00
Approach to Equilibrium C 14.2 11.3

Effect of Operational Changes
Steam to Carbon Ratio
Name Units Base
Case
Decreased
Steam to Carbon
Plant Rate % 100 100
Ai r Rate % 100 100
Exit Pressure Bara 39 39
Steam to Carbon to Primary n/a 2.88 2.78
Outlet Temperature C 1000 1002
Methane Slip mol % 0.41 0.41
H/N Ratio n/a 3.00 3.00
Approach to Equilibrium C 14.2 12.2

Key Components: Effect of Poor
Mixing
Poor mixing can be illustrates by assuming
a secondary reformer with a high zone of
high air flow and a zone with low flow
Name
Temperature
Methane slip
Approach
Poor
Units Too
much air
Too little
air
o
C 1034 902
Mol % 0.13 1.89
o
C 10 10
Mixed
971
0.9
53
Good
957
0.62
10
Key Components: Catalytic Heat Shield
Bed has to be protected
against disturbances
Conventional target tiles or
alumina lumps used
Even these can be moved
No longer required: can
replace with active catalyst
Additional activity improves
reforming performance
Use VULCAN Series AST
Advanced Support Technology
Large (35mm) 4-hole shape
Key Components
Use of CFD for Secondary Reformers
CFD modelling very good for secondary
reformers
BUT time consuming and expensive
Building up a library of case studies
VULCAN Series Catalysts VSG-Z201/202/203
has extensive experience with CFD for
secondary reformers
Troubleshooting problems
Designing burner guns
Validation of modifications
Optimization of catalyst quantity
Catalyst
Bed
Air
gun
Recirculation
zones
Case Study 1:
Insufficient Mixing Volume
1200 C 1400 C 1500 C 1600 - 2100 C
Air
Gun
Catalyst
Bed
<1200 C 1400 C
Case Study 1:
Insufficient Mixing Volume
Case Study 2 Burner Guns
In this case, secondary operated well up to 1450 mtpd
At rates above this, methane slip rose rapidly
Limiting further plant rate increases
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
1100 1200 1300 1400 1500 1600 1700
Pl ant rate, mtpd
M
e
t
h
a
n
e

s
l
i
p
Catalyst
Bed
Recirculation
Zone
Burner
Rings
1200 C 1300 C 1400 C 1500 C 1600 - 2100 C
Catalyst
Bed
Burner
Rings
<1200 C
Case Study 2:
High Intensity Ring Burner
Secondary Catalyst Conclusions
All three components must be designed
correctly
If there are problems then can change catalyst
type to high activity catalyst VULCAN Series
VSG-Z201/202/203 5-hole or Quadralobe
Can achieve large reduction volumes
Allows increase in mixing space
VSG-Z201/202/203 catalysts are well proven,
stable and reliable
Good mixing above the catalyst bed is essential
Poor mixing gives high methane slip
Mixing performance critically depends upon
burner
Secondary Reforming Conclusions
CFD useful for
Troubleshooting
Design, modifications and optimization
VULCAN Series Catalysts can offer this service
GBHE Catalyst Process Technology can
recommend the appropriate burner type
Eliminates problems caused by poor mixing
Optimum burner type opposite plant configuration
But still needs designing correctly
Continued process of improvement to design
Contact your GBHE Catalysts representative for
details