C2PT Catalyst Process Technology

By Gerard B Hawkins
Managing Director
Steam Reforming Catalysis :
◦ Chemical reactions
◦ Catalyst shape design
◦ Catalyst chemistry
◦ Carbon formation and removal
The conversion of hydrocarbons to a mixture of
CO, CO2 and H2
Two reactions: Reforming and Shift
Steam Reforming (very endothermic)
CH4 + H2O CO + 3H2
CnH2n+2 + nH2O nCO + (2n + 1)H2

Water gas shift (slightly exothermic)

CO + H2O CO2 + H2
Overall the reaction is highly endothermic
 Both reforming and shift reactions are
reversible
 Rate of shift is fast compared to reforming
 Methane conversion favored by:
– low pressure
– high temperature
– high steam to carbon ratio
 Steam + Gas
500°C Air / Oxygen

450°C
Steam
Reformer
Secondary
Reformer
Steam
1200°C

Steam

780°C 950°C
10% CH4 0.5% CH4
 The primary reformer is a heat exchanger

 Its function is to heat up process gas

 Catalyst and reaction in the tubes

 Combustion on the shell side

 Dominant heat transfer by radiation

 900

800 gas temp

700
temperature (°C)

600

500 ATE
Eq temp
400

300

200
0 0.2 0.4 0.6 0.8 1
fraction down tube
 Nickel on a ceramic support

 Three key factors in catalyst design:

– geometric surface area
– heat transfer from tube to gas
– pressure drop

 Also of concern:
– packing in the tube
– breakage characteristics
 Top Fired Reformer
860
840
tube wall temperature (°C)

820
800
780
760
740
base case
720 base case with twice GSA
700 base case with twice heat transfer
680
660
0 0.2 0.4 0.6 0.8 1
fraction down tube
 Gas film
1200°C
Fluegas
Outside tube wall
temperature 830°C

Inside tube wall

temperature 775°C

Bulk Process
Tube Gas Temp.
Wall 715°C
 Need to minimize thickness of gas film at tube
wall
 Smaller catalyst particles improve heat transfer
from wall to bulk gas and reduce tube
temperatures
 Smaller particles increase pressure drop
 Catalyst shape should be optimized for high
heat transfer with low pressure drop
 The traditional catalyst shape is a ring
 Smaller rings give high activity and heat
transfer but higher pressure drop
 Optimized catalysts offer high surface
area and heat transfer with low PD
 Important that shape also provides good
packing and breakage characteristics
1 2 3 4

1 2 3 4
Relative
Pressure Drop 1 0.9 0.9 0.8
Relative HTC 1 1.3 1.1 1.0
Voidage 0.49 0.6 0.58 0.59
Design of catalyst shape is a complex
optimization of:

– Higher surface area (needed for activity -

diffusion control)
– Higher heat transfer (needed for cooler
reformer tubes)
– Lower pressure drop (efficiency consideration)

Need also to consider breakage

characteristics and loading
pattern inside the reformer tube
Catalyst loading
can be improved
using various
dense loading
techniques
 Carbon formation is totally unwanted
 Causes catalyst breakage and
deactivation
 Leads to overheating of the tubes
 In extreme cases carbon formation
causes a pressure drop increase
 Carbon Formation and
Prevention
Reformer tube appearance - Carbon laydown

Hot Band Giraffe Hot Tube

Necking
 Cracking
– CH4 C + 2H2
– C2H6 2C + 3H2 etc

 Boudouard
– C + CO2 2CO

 Gasification
– C + H2O CO + H2
 Under normal conditions carbon
gasification by steam and CO2 is favored
(gasification rate > C formation rate)
 Problems of carbon formation occur when:
– steam to carbon ratio is too low
– catalyst is not active enough
– higher hydrocarbons are present
– tube walls are too hot
– catalyst has poor heat transfer characteristics
 Use of a potash doped catalyst reduces
probability of carbon formation
Methods of preventing carbon formation:

– Use more active catalyst

– Use better heat transfer catalyst
– Reduce level of higher hydrocarbons
– Increase the steam ratio
– Use VSG-Z102 (3-7) -hole tailored catalysts
catalyst (potash-promoted)
 Alkali greatly accelerates carbon removal
 Addition of potash to the catalyst support
reduces carbon formation in two ways:
a increases the basicity of the support
b promotes carbon gasification
OH -
C + H2O CO + H2

 Potash is mobile on the catalyst surface

 Potash doped catalyst is only needed in
the top half of the reformer tube
 Increasing the content of alkali (potash)

– Higher heat flux possible for light feeds

– Heavier hydrocarbons can be steam reformed
– Lower steam to carbon ratios
– Faster carbon removal during steaming
 920OC
(1688OF) Alkalised Non-Alkalised
Catalyst Catalyst

Carbon Forming Ring Catalyst

Region

820OC Optimised Shape

(1508OF) (4-hole Catalyst)

Inside Tube Wall

Temperature

720O C
(1328O F)
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Top Fraction Down Tube Bottom
For light feeds and LPG etc using lightly
alkalised catalyst VSG-Z101
– Potash is chemically locked into catalyst
support
– Potash required only in the top 30-50% of the
reformer tube

– Catalyst life influenced by

 Poisoning VSG-Z101
 Ni Sintering
 Process upsets etc
VSG-Z102
wt% of potash
VSG-Z102
3
Fresh
2.5 1 year
2 years
2 4 years
6 years
1.5

1 VSG-Z102

0.5

0
1.2m 3m 5m 6m 9m
Catalyst samples at various depths down
reformer tube
Requirements :
◦ High and stable activity
◦ Low pressure drop
◦ Good heat transfer
◦ High resistance to carbon
◦ High strength
◦ Robust formulation/simple operation

Best achieved with VSG-Z101 (3-7) -hole

tailored catalysts