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Steam Reforming
Practical Operation
By Gerard B Hawkins
Managing Director, CEO
Contents
Reaction Chemistry
Typical Reformer Configurations
Catalyst Deactivation
Catalyst Loading
CO + H2O CO2 + H2
Radiative
heat flows
Heat Transfer - Side Fired / Terraced
Steam + Gas
500C
Steam
Reformer
Steam
1200C
Steam
870C
3% CH4
Reformer Firing Balancing
Burner problems
VSG-Z101
Tubes id : 95 mm
Loaded Length : 12.98 m
6.49m
Catalyst Types : 50% VSG-Z101
50% VSG-Z102
Loaded density : VSG-Z101 0.857 kg/l
VSG-Z102 0.828 kg/l
VSG-Z102
Catalyst
Support Grid
Ammonia Plant
Primary Reformer
Reforming involves heating the process gas
900 Gas T
800
Temperature (C)
700
600
500 ATE
400 Eqm. T
300
200
100
0
0 0.2 0.4 0.6 0.8 1
Fraction down tube
Primary Reformer Catalyst
Requirements
High and Stable Activity
High Strength
Also of concern:
Bulk Gas
Ni
Gas Fil
m Sites
H2O
CO
H2
CH4
Catalyst Support
Key Reaction Steps
1. Fast
Diffusion of the molecules in the bulk gas
phase
2. Slow
Diffusion of the molecules through the gas
film
3. Slow
Diffusion through catalyst pores
4. Fast
Absorption of the molecules onto the Ni
sites
5. Fast
Chemical reaction to produce CO2 and H2
Reaction Rate
Reaction rate controlled by film diffusion
Gas film
Fluegas T 1200C
860
Tube Wall Temperature (C)
840
820
800
780
760
Base case
740
Base case with twice GSA
720
Base case with twice heat transfer
700
680
660
0 0.2 0.4 0.6 0.8 1
Fraction Down Tube
Heat Transfer and Pressure Drop
1 2 3 4
1 2 3 4
Voidage 0.49 0.6 0.58 0.59
Relative PD 1 0.9 0.9 0.8
Relative HTC 1 1.3 1.1 1
Catalyst Design Criteria
Conclusions
Design of catalyst shape is a complex optimization of:
VULCAN
VSG-Z102
Catalyst Breakage
100
0 5 10 15 20
% Breakage
Breakage Characteristics is an
Important Consideration
Breakage Characteristics
Breakage Characteristics
Packing Characteristics
Void
Catalyst Support
Alpha Alumina
Calcium Aluminate
Some Strongest
bonding of bonding of
Ni 2+ ions Ni 2+ ions
Catalyst Support - Solid Solutions
NiO / Ni Heat
Fresh catalyst
High surface area
NiO / MgO NiAl2O4
Solid solution formed
Temperature (F)
Magnesium aluminate
spinel material usually
supplied pre-reduced
Temperature (C)
860
880
900
920
940
820
840
0
POWER OUTAGE
200
ICI RINGS
400
CATALYST CHANGE
AT 584 DAYS
0
SHAPE
REDUCED
COMP A
RATE 25%
CATALYST CHANGE
200 0
AT 258 DAYS
SHAPE
COMP B
CATALYST CHANGE
200 0
AT 280 DAYS
PD LIMIT RATE
200
REDUCED
COMP B
SHAPE 2 CATALYST CHANGE
0
AT 421 DAYS
DAYS ON LINE
200
400
600
ICI SHAPE
Tube Wall Temperature Stability
TWT
LIMIT
700
800
900
Carbon Formation and Prevention
Boudouard
2CO C + CO2
CO Reduction
CO + H2 C + H2O
Intermediates
(Olefins, Paraffins, Steam
Catalyzed
CH4, & H2) Reforming
Partial
Decomposition
H2O
CH4, H2, CO2
Hydrocarbon Polymerization
& CO
Feed
H2O
Thermal
Cracking Carbon
Carbon
Gasification
Effect of Carbon Formation
1. Physical poisoning
3. Hot tubes
- Carbon laydown on the inside of the tube
wall
- Lower catalyst activity
Carbon Formation and Prevention
Reformer tube appearance - Carbon laydown
C + H2O CO + H2
No Carbon
Formation
(pH2) 2 10
pCH4
0.1
550 600 650 700 750 800
Temperature (C )
Methane Cracking - Kinetic Limitation
100
No Carbon
Formation
(pH2) 2 10
pCH4
Carbon Formation
1.0 Zone
100
Fraction of
tube length
0.6
from top
0.5
10 No Carbon 0.4
(pH2) 2
Formation
pCH4
Carbon Formation
0.3 Zone
1.0
100
No Carbon 0.6
Formation 0.5
(pH2) 2 10 0.4
100
No Carbon 0.6
Formation 0.5
(pH2) 2 10 0.4
Increasing
pCH4 Potash
0.3 Content
1.0
Carbon
0.25
Formation Zone
0.1
550 600 650 700 750 800
O
Temperature C
Carbon Formation and Prevention
920C
Alkalised Non-Alkalised
Catalyst Catalyst
720C
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
Carbon Formation and Prevention
VSG-Z102
VSG-Z101
VSG-Z102
K2O-Al2O3-SiO2 CaO-Al2O3-SiO2
CO2 + H2
CaO-Al2O3 CaO-MgO-SiO2
MgO-Al2O3 K2CO3
H2O
Note:- MgO is chemically
locked into catalyst support
material 2KOH + CO2
Carbon Formation and Prevention
Potash promotion
Refinery Gas 6.0 10.0 3.0 4.0 2.0 3.0 2.0 2.5
2 major factors:
Poisoning by sulfur
Thermal sintering
Sulfur ex feedstock
Phosphate ex BFW
Metals ex BFW or liquid feed
Sulfur Poisoning
CH4
S S
S S
S Pellet
S Nickel
S
S
H 2O S S
Sulfur Poisoning
0.8
Activity
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1
Coverage
Sulfur Poisoning
sulfur poisoning
Poor performance of the desulfurization
system
Steaming Reforming Catalysts
3
Residual wt % of potash
2.5
VSG-Z102
2
1.5
Comp. A
1
0.5
Comp. B
0
500 550 600 650 700 750
Steaming Temperature C (equivalent to 1 year operation)
Steaming Reforming Catalysts
200 1.6
1.4
4.5
Methane slip (mol % dry)
4 HDS
Problem
3.5 Design
3
Catalyst
Steamed
2.5
0 5 10 15 20 25 30 35
Time on line (months)
Steaming Reforming Catalysts
Sulfur removal
300
sulfur (ppm wt)
Before Steaming
200 After Steaming
100
0
0 10 20
Distance Down Reformer Tube (m)
Steaming Reformer Catalyst
MgO in catalyst support must not be "free"
otherwise during steaming, the MgO will
hydrolyse
Exit Methane
Tube Wall Temperature (TWT)
Tube Appearance
Pressure Drop
Approach to Methane Steam Equilibrium
Reformer Catalyst Monitoring
Methane Slip
Approach to Equilibrium
Since PD (velocity) 2
100 2
Normalised PD = Measured PD
( % design
(
Approach to Equilibrium (ATE)
H2 68.0
N2 1.6 Reformer Exit
Temperature
CH4 9.6 (TWGS) = 796C
CO 10.2
CO2 10.6
Total 100.0 Dry
H2O 76.6
Total 176.6 Wet
pCH4 = 9.6 x 31.6 = 1.7178 ata
176.6
pCO . (pH2)3
= 1.7178 x 13.7065
1.8251 x (12.1676) 3
= 7.161 x 10-3
Handling on arrival
Storage
Charging
Storage in vessel before start-up
Storage
Maldistribution
10 C approach to equilibrium
Tube 1: 105% flow 850C Exit T
Tube 2: 95% flow 890C Exit T
Base Case Maldistribution Case
Tube 1 Tube 2
full
'Sock' or 'Unidense' method recommended
Charging Technique
Support grid
Catalyst Charging - Unidense Method
Benefits
Introduction
Start-up Procedures
Warm-up
Catalyst Reduction
Feed Introduction
Shut-down
Case Studies
Introduction
Steam reformer is complex
heat exchanger
chemical reaction over catalyst
combustion, leading to steam generation
NiO + H2 Ni + H2O
Introduction - Catalyst Reduction
500
Oxidising Conditions
300
200
Reducing Conditions
100
400 500 600 700 800
(752) (932) (1112) (1292) (1472)
Temperature C (F)
Introduction - Catalyst Reduction
Introduction
Start-up Procedure
Warm-up
Catalyst Reduction
Feed Introduction
Shut-down
Case studies
Start-Up Procedure - Warm Up
Purge plant of air with N2
(Care: must be free of hydrocarbons and carbon
oxides)
Heat reformer above condensation temperature
(min 30%)
Stop N circulation
2
reformer tubes
refractory linings
Steam Steam
Reformer
Cold Pipe-work
Start-Up Procedure - Warm Up
1,000,000
100,000
Tube Life ( hours )
10,000
30 bar 5 bar
1,000
100
10
1
800 900 1000 1100 1200
(1500) (1650) (1830) (2010) (2200)
Introduction
Start-up Procedure
Warm-up
Catalyst Reduction
Feed Introduction
Shut-down
Case studies
Start-Up Procedure - Catalyst Reduction
Higher hydrocarbons
Ammonia
Methanol
Catalyst Reduction with Hydrogen
Natural Gas
Purification issues
- Desulfurization
- Methanation of carbon oxides
Uncommon Procedure
Introduction
Start-up Procedure
Warm-up
Catalyst Reduction
Feed Introduction
Shut-down
Case studies
Start-Up Procedure - Feed Introduction
Introduction
Start-up Procedure
Warm-up
Catalyst Reduction
Feed Introduction
Shut-down
Case Studies
Shut-down
Reduce tube exit temperature to 750C
Introduction
Start-up Procedure
Warm-up
Catalyst Reduction
Feed Introduction
Shut-down
Case Studies
Case Studies - No 1
Ammonia Plant
increased
Tubes looked hot
No reduction in PD
Plant shutdown
CH4 C + 2H2
Tube life
Artificial limitation on plant rate
Effect of Tube Wall Temperature on
Tube Life
20
Tube Life (Years)
Design
10
+ 20C
5
2
1
0.5
0.2
Contact
- Surface Thermocouple
"Pseudo-contact
Non-contact
Disappearing Filament
Infra Red Optical Pyrometer
Laser Pyrometer
Surface Thermocouples
Easy to use
Inexpensive
Laser Pyrometer
BUT
- Limited access
- Awkward to use
Gold Cup Pyrometer
Gold Cup
Lance
Water To
Cooling Recorder
Accurate Temperature Measurement
e = emissivity
r = reflectance
= (1-e)
Accurate Temperature Measurement
- Calculate etube
Background Temperature Measurement
NORTH
a
1
A
a
2
Comparison of Infra-red Pyrometer and
Calculated Tube Wall Temperature
Measurements
950 1742
Uncorrected Pyrometer
900 1652
Temperature (C)
Temperature (F)
Corrected Pyrometer
850 Calculated 1562
800 1472
Top-fired reformer 2C
Side-fired reformer 16C
Classroom Exercise 2 - PROBLEM
pH2O . pCO
= 9.7766 x 0.9497
5.5221 x 2.0771
= 8.09 x 10-1
pCO . (pH2)3
= 0.4061 x 5.5221
2.0771 x (9.7766) 3
= 1.15 x 10-3