Steam reforming catalyst theory

Asim Yadav
25 Mar 2015
Westin Hotel Gurgaon, India

Introduction
Steam reforming catalysts the chemistry
Reactive metals
Support materials
Carbon formation and its prevention

Steam reforming catalysts the engineering

Catalyst shape
Catalyst strength and breakage
Catalyst packing
Heat transfer, pressure drop and surface area

Steam reforming the basics

CH4 + H2O CO + 3H2

DH = +206 kJ/kmol
CO + H2O CO2 + H2
DH = -41 kJ/kmol
Can combine with methane steam reaction above to give
CH4 + 2H2O CO2 + 4H2
Reversible reactions, equilibrium limited
Overall endothermic large heat requirement
High temperature for high conversion

Low pressure for high conversion but size and cost increases
pressure

C2H6 + 2H2O 2CO + 5H2

C3H8 + 3H2O 3CO + 7H2
..
Irreversible reactions can go to completion
Reaction pathways more complex than shown
Carbon forming intermediates such as ethylene

Steam reforming more basics

Steam reforming reactions are very fast
Reaction occurs within the surface layer of the pellet
Surface layer can react the gas faster than it arrives

Diffusion of gas within the pellet is relatively slow

Boundary layer
Steam reforming pellets have a low porosity
Need to be strong due to high temperature and thermal
movement

Steam reforming catalyst activity is proportional to the

charged pellet area, not the charged weight

Steam reforming active metals

Many active metals promote carbon formation
Highest activity metals are very expensive
Nickel presents the optimum choice
Optimum
Carbon formation

Inactive

Costly

Catalyst support the basics

3 commercially available choices
Alpha alumina
Calcium aluminate
Magnesium aluminate spinel

Set of requirements placed on the support

Chemically stable
Physically stable
Not detract from catalysis (if possible enhance the catalysis)
Economic

Pros and cons for each support type

Other supports available for niche applications
Stabilized zirconia for demanding applications (autothermal
reforming)

Supports nickel spinel formation

Nickel can form spinel with alumina (NiAl2O4)

Propensity depends on ionic radii of support atoms

Ca2+
0.99 Angstrom
Ni2+
0.68 Angstrom
Mg2+
0.65 Angstrom
Al3+
0.50 Angstrom
Nickel and magnesium very similar size

Relatively easy for nickel to migrate into magnesium aluminate

spinel support at moderate temperatures
Results in catalyst deactivation

Nickel can only incorporate into alpha alumina or calcium

aluminate at very high temperatures
Typically seen in nipped tubes or after an over firing incident

Supports catalyst reduction

Nickel added to the catalyst as nickel oxide
Must be reduced in situ to metallic nickel
Nickel support interaction controls ease of reduction

Alpha alumina has +ve charged acidic sites

Low interaction of +ve charged Ni ions with support

Calcium aluminate has ve charged basic sites

Ratio of calcium : alumina = 0.5:1
Dissimilar ionic sizes
Moderate interaction of +ve charged Ni ions with support

Magnesium aluminate has ve charged basic sites

Ratio of magnesium : alumina = 1:1
Magnesium and nickel ions have similar spacing
High interaction of + ve charged Ni ions with support

Increasing
difficulty of
reduction

Supports reduction temperature

400

1000

1400

1200

500

1600

Temperature
(F)

Magnesium Aluminate

Calcium Aluminate

Alpha Alumina

800

600

700

800

900

Temperature
(C)

Supports - hydration
Hydrolysis reaction of oxides to hydroxides
Occurs during start up and shut down
Or during steaming for carbon / sulphur removal

Alpha alumina is thermodynamically stable

Calcium aluminate has a low Ca:alumina ratio
Calcium oxide is locked into the support
Not available for hydration

Magnesium aluminate has a high Mg:alumina ratio

Easier for free magnesia to be present

Manufacturing process can not eliminate free magnesia
MgO + H2O Mg(OH)2
Hydrolysis results in volume changes and weakening of the
support

Supports carbon formation

The support can have an impact on carbon formation
+ve charged acidic sites enhance carbon formation rates
Alpha alumina is an acidic support
Calcium and magnesium aluminates are basic

Test results
Support

Highly acidic Alpha

support
alumina

Magnesium
aluminate

Calcium
aluminate

Minimum
steam ratio

10.0

3.7

3.5

4.3

Carbon formation gas feed

Formed from hydrocarbon cracking

CH4 C(s) + 2H2

C2H6 2C(s) + 3H2

C3H8 3C(s) + 4H2

..
Removed by steam

C(s) + H2O CO + H2

Carbon formation hydrocarbon feed

From cracking or polymerization of olefin intermediates
CxHy

Carbon formation avoidance

Carbon formation will always occur to some extent

Balance of formation and removal reactions
If rate of removal exceeds rate of formation then OK
Need to slow the formation and speed up the removal
Addition of potash (alkali) is the most common method
This makes the support more basic and less prone to carbon
The potash hydrolyses releasing volatile potassium
hydroxide
Known carbon gasification promoter

Johnson Matthey pioneered the use of alkali in the 1960s

and has been successfully using it since

Carbon formation alkali

Test results
Support

Alpha
alumina

Magnesium
aluminate

Calcium
aluminate

Alkalised
calcium
aluminate

Minimum
steam ratio

4.3

3.7

3.5

1.5

The potash is formed into the support as a mineral

Aluminosilicates such as Kalsilite KAlSiO4

Slowly releases to maintain an active level

Minimizes effect on activity
Creates a long life before the potash is depleted

Carbon formation effect of alkali

Standard and alkalized catalysts tested
Subject to carbon formation then removal conditions
CO2 released during carbon removal measured
CO2 in exit gas (mol%)

12
10
8
6

alkalized
Non alkalized

4
2
0
300

500
700
Temperature (C)

900

Carbon formation experiment

Carbon removal experiment

Catalyst shape the basics

Catalyst shape is a compromise between
High activity (area)
High heat transfer

Low pressure drop

High strength
Good breakage

small pellets with multiple holes

medium pellets with multiple large holes
holes aligned in the radial direction
good pellet to tube wall contact
large pellets with multiple large holes
holes aligned in the axial direction
poor pellet to tube wall contact
limited number of small or no holes
thick ligaments / webs
simple shape without stressed areas

Catalyst shape more basics

Can not develop a one size fits all catalyst
Different sizes of the same optimized support shape

QUADRALOBE now available in 4

size options

For use in different severity reformers

For split charges in different parts of the reformer tube
Lowest pressure drop with KATALCOJM 57-4XQ

Catalyst range

Range of sizes

MQ Q GQ XQ

Catalyst shape breakage

Poor shapes

Good shape

Catalyst breakage stress analysis

Load

Load

Catalyst shape packing

Poor shape

Good shape

Catalyst shape heat transfer

Poor shapes

Good shape

Catalyst shape heat transfer

Packing model

Flow simulation

Heat transfer
correlations

Tube wall temperature

Conclusions
The chemistry of steam reforming catalysts is complex
The support can have a significant impact on the catalyst
performance
The choice of support material is an optimisation between activity,
catalyst reduction, carbon resistance, strength and cost

The engineering of steam reforming catalysts is complex

The shape of the pellet is a key factor in the catalyst performance
The choice of shape is an optimisation between activity, pressure
drop, heat transfer, strength and crushing characteristics

Johnson Matthey has the best range of

catalyst and shapes for all reformer designs and feeds
techniques for monitoring and optimising reformer performance

Thank you