3. Steam Reforming of Methane
CH4 + H2O CO + 3H2 (Steam Reforming))
CO + H2O CO2 + H2 (water Gas Shift)
• Overall strongly endothermic
• Need to get large amounts of heat in
– narrow-bore steam reformer tubes
4. Steam Reforming of Heavier
Hydrocarbons
CnHm + nH2O nCO + (n+m/2)H2
Still endothermic
Easier than methane
More prone to carbon formation
5. Contents
Steam reforming reactions
Steam reforming catalysts
• catalyst activity
• catalyst development and testing
• importance of gas and htc
Equilibrium considerations
Carbon formation
Poisoning
Steam reformer modelling
Pre - and post reforming
6. Steam Reforming Catalyst
Steam reforming can be done without
catalyst, but needs very high temperatures
• partial oxidation
Modern steam reforming catalyst use
nickel on a ceramic support
• with or without promoters and stabilisers
• precious metals offer alternatives to Ni
Supports must be strong; inert; thermally
and chemically stable
Catalysts lower the temperature at which
steam reforming occurs at a high rate
7. Steam Reforming Catalyst Activity
Reaction highly endothermic
• may be limited by process of getting
heat in to reactant sites
Process may also be limited by diffusion
8. Activity Testing
Define some measure of reaction
• exit methane
Measure for a range of catalysts under
fixed conditions
• flow, temperature pressure, catalyst
10. Diffusion Processes
Molecular diffusion, Dm
• determined by rate at which molecules collide
with each other
• depends on pressure
• independent of pore radius
Knudsen diffusion, Dk
• determined by the rate at which molecules
collide with pore walls
• depends on pore radius
11. Check for Knudsen Diffusion
Mean free path of molecules must be greater
than pore radius for Knudsen diffusion to
dominate
• at 700oC (1290oF), mean free path is 100 Angstrom
Typical pore radius for steam reforming
catalyst is 150 - 1000 Angstrom
• Not Knudsen regime
12. Steam Reforming Catalyst Activity
Intrinsic activity (chemical reaction only)
Extrinsic activity (includes heat and mass
transfer effects)
Steam reforming dominated by extrinsic
effects
Influence of pressure significant
21. Steam Reformer Tubes
Need to get a lot of heat in
• narrow bore tubes
High temperatures and pressures
• tubes in creep region
• tubes will fail by rupture
• tube life very sensitive to temperature
23. Top Fired Reformer
Distance Down Tube m (ft)
TubeWallTemperature
DegC(DegF)
0 1 2 3 4 5 6 7 8 9 10 11 12
BASE CASE
BASE CASE WITH TWICE
SURFACE AREA
BASE CASE WITH TWICE
HEAT TRANSFER
840
800
760
720
(1544)
(1472)
(1400)
(6) (12) (18) (24) (30) (36)
Effect of Catalyst Design Variables on
Tube Wall Temperature
24. Tube Wall
Bulk Process
Gas Temp.
715oC (1319oF)
1200oC (2192oF)
830oC (1526oF)
775oC (1427oF)
Fluegas
Outside tube wall temperature
Inside tube wall temperature
Gas film
Temperature Profile
Top-fired reformer, 40% down
25. TemperatureDegC(DegF)
Tube Wall Temperature Limit
Poor stability
Good stability
Days on Line
0 1,000500100 200 300 400 600 700 800 900
925
(1697)
900
(1652)
875
(1607)
850
(1562)
Effect of Catalyst Stability on
Tube wall Temperature
31. Effect of Pressure
• Exit methane proportional to pressure squared
• lower exit methane at lower pressures
• overall plant economics dictate higher
pressures, typically 20 bar (300 psi)
CH4 + H2O CO + 3H2
F[CO ] F[H2]3 Kms Pt2
F[CH4] =
F[H2O]
32. Effect of Steam- to- Carbon Ratio
• Exit methane inversely proportional to steam
• lower methane requires more steam
• actual value depends on overall plant design
• s/c ratio typically 5-6 on older plants
• s/c ratio typically 3 on newer plants
CH4 + H2O CO + 3H2
F[CO ] F[H2]3 Kms Pt2
F[CH4] =
F[H2O]
33. • Exit methane proportional to Kms
• Kms approx inversely proportional to temperature
• lower methane requires higher temperatures
• limited by tube metallurgy
Effect of Temperature
CH4 + H2O CO + 3H2
F[CO ] F[H2]3 Kms Pt2
F[CH4] =
F[H2O]
35. Feedstock Refinery Off
Gas
Methane Butane Naphtha
C/H Ratio CH6 CH4 CH2.5 CH2.2
Exit Gas
CH4
CO
CO2
H2
6.67
8.14
4.45
80.74
5.35
12.18
9.12
73.35
4.29
14.17
12.36
69.16
4.01
14.73
13.77
67.49
All at exit temperature 850 Deg C (1562 Deg F)
Exit pressure 30 atas (435 psi)
Steam/carbon ratio 3.5
Effect of Feedstock
37. Approach to equilibrium
The system is not actually at equilibrium,
but close to it
A measure of catalyst performance is the
Approach to Equilibrium, ATEms
• ATEms = 0 when at equilibrium
• the bigger ATEms, the further from
equilibrium
38. Temperature oC (oF)
770 780 790 800 810 820
2
4
6
8
10
12
Methaneslip(%)
(1418) (1454)(1436) (1472) (1490)
Exit CH4
Approach to Equilibrium
(1508)
ATE
Equilibrium
Temp Gas Temp
39. 0 0.2 0.4 0.6 0.8 1
200
(392)
400
(752)
600
(1112)
800
(1472)
Fraction down tube
TemperatureoC(oF)
Gas Temp Eq'm Temp
Approach to equilibrium
40. Contents
Steam reforming reactions
Steam reforming catalysts
Equilibrium considerations
Carbon formation
• formation and removal reactions
• role of alkali
• range of catalysts
Poisoning
Steam reformer modelling
Pre-and post-reforming
43. Carbon Formation
CH4 C + 2H2 (Thermal Cracking)
CO + H2 C + H2O (CO Reduction)
2CO C + CO2 (CO disproportionation
“Boudouard”)
44. Carbon Formation
Direction of reaction determined by
process gas conditions
Generally, CO reduction and Boudouard
are carbon removing
Generally, cracking restricted to top half
of reformer
49. 800
100
10
1.0
0.1
0.6
0.5
0.4
0.3
550 600 650 700 750
Increasing
Potash
Content
1100 1200 1300 1400
(°F)
Carbon Formation - Effect of Alkali
Carbon Formation
Zone
Temperature (°C)
pH2
2
pCH4
No Carbon
Formation
50. Role of Alkali
Reduces likelihood that carbon will be
formed
Enables carbon to be removed readily
Incorporation into support must be done
correctly
• Release rate not too fast/slow
• Effect on activity
53. Feedstock Natural Gas
Reforming
Non-
alkalised
Associated
Gas Ref
Lightly
alkalised
Dual Feedstock
Reforming
Moderately
alkalised
Naphtha
Reforming
Heavily
alkalised
Non-alkalised Low alkali Moderate alkali High alkali
Naphtha 3.0-3.5
Light Naphtha 6.0-8.0 3.0-4.0 2.5-3.0
Butane 4.0-5.0 2.5-3.5 2.0-3.0
Propane, LPG 3.0-4.0 2.5-3.0 2.0-2.5
Refinery Gas 6.0-10.0 3.0-4.0 2.0-3.0 2.0-2.5
Associated
Gas 5.0-7.0 2.0-3.0 2.0-2.5
Natural Gas 2.5-4.0 1.5-2.0 1.0-2.0
Pre-reformed
Gas 2.0-3.0 1.0-2.0 1.0-2.0
Typical Steam Ratios for Catalyst/
Feedstock Combinations
54. Alternatives to Alkali
• Precious metals can also be used instead
of Ni as the catalyst
– Significant higher activity and hydrogenation
activity yields lower carbon formation rates
– Platinum, Ruthenium …etc
– Effective “ultra”-purification essential
• Lanthanum used in addition to Ni
– Helps also with the removal of carbon
• Magnesium/Ni
– Also suppresses carbon formation rates
– However, magnesium not stable with steam
56. Sulfur Poisoning
Most common poison
Severe levels (.5ppm) can lead to rapid
catalyst deactivation
“Normal” levels (20-30ppbv) leads to very
slow deactivation
Sulfur equilibrium depends on
temperature
58. Sulfur Poisoning
Complex; some disagreement in literature,
particularly at low levels
Low level Sulfur will lead to increased twt
with time
Other deactivation mechanisms also
operate
59. Sulfur Poisoning - Precious Metals
Reforming
• Precious metals require ultra-low poison
levels
– Typically <5 ppbv
– Use specialised purifcation absorbent
downstream of ZnO
• Typical S slip 1-2 ppbv
60. Catalyst Sintering
Initial rapid sintering
Slower subsequent sintering
Temperature dependent
Both Ni crystallites and support sinter
71. Pre-reforming
Low temperature adiabatic steam
reforming
Wide range of feedstocks
Requires highly active, high nickel
catalyst
Exo/endothermic, depending on feedstock
Converts all heavy hydrocarbons to
methane
72. Temperature
475 deg C
(890 deg F)
410 deg C
(770 deg F)
0 10050
NG Pre-reformer
Temperature Profile
Percentage Down Bed
73. 450 Deg C
(842 Deg F)
500 Deg C
(932 Deg
F)
Percentage Down Bed
Temperature
Naphtha Pre-reforming temperature
Profile
75. Post-reforming
Heat exchange type of steam reformer
Uses steam reformer exit gas as heating
medium for fresh feed
Compact design
• small footprint
Uses conventional catalyst
No extra fuel firing needed
• no increase in Nox emissions
Typically allows 25 % increase in rate