06 haldor topsoe
TRANSCRIPT
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Steam Reforming Technology User Conference
5-7 March 2007
Bo Hartvigsen, Sales Manager, Haldor Topsoe
A/S
Challenges in Steam ReformingChallenges in Steam Reforming
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Challenges in Steam ReformingChallenges in Steam Reforming
Agenda:
1. Carbon formation
2. Poisoning of catalyst (sulphur)
3. Sintering of catalyst
4. Loading
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Carbon FormationCarbon Formation
C2H6 2 CO + 5 H2
2 C + 3 H2
Carbon
+H2O
Reforming
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CARBON FORMATIONCARBON FORMATION
• Catalytic cracking
(on Ni crystals)• Thermal cracking
(on hot surfaces)
Two types of carbon formation:
Carbon whiskers, physical
damage of catalyst
Hot bands, NO physical
damage of catalyst
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PyrolyticPyrolytic carbon (thermal cracking)carbon (thermal cracking)
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Catalyst deactivation and Catalyst deactivation and
carbon formationcarbon formation
0
2
4
6
8
10
12
14
0
Ste
am
to h
igher
hydro
carb
on radio
1 2 3 4 5m from inlet
Critical
Carbon formation from higher hydrocarbons
Actual (high activity) Actual (low activity)
Carbon formation
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Formation of hot bandsFormation of hot bands
CnHm CnHm
High
activity
Low
activity
CnH
m
CnH
m
CnHmCnHm
Cn H
m
Cn H
mCn H
m
CnHmCn H
m
850°C
500°C
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Hot Bands in top fired reformerHot Bands in top fired reformer
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Hot spots in a sideHot spots in a side--fired reformerfired reformer
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Reformer design Reformer design
Radiant Wall
Topsøe
Selas
Terrace Wall
Foster Wheeler
Top Fired
MW Kellogg
KTI
UHDE
Bottom Fired
Chemico
Girdler
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Risk for carbon formation is higher in a top fired reformerRisk for carbon formation is higher in a top fired reformer
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HowHow to to PreventPrevent CarbonCarbon FormationFormation
1. High activity: reform higher hydrocarbons
at low temperatures
2. Use less acidic carrier
3. Promote with alkali
4. (Prereforming)
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0
400 500 600 700
Catalyst Temperature
Relative Activity
Impact of Alkali Impact of Alkali
Alkali lower catalyst activity, especially at low temperatures
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SulphurSulphur PoisoningPoisoning
Sulphur blocks the Nickel surface area
Nisurface + H2S ↔ S-Nisurface + H2
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Temperature dependenceTemperature dependence
0.4
0.6
0.8
1
500 550 600 650 700 750 800 850 900
Temperature, °C
ppbv=10
ppbv=50
ppbv=100
Sulphur Coverage
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Dynamics of poisoningDynamics of poisoning
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 20 40 60 80 100
Tube Length, %
Year 1
Year 2
Year 3
Equilibrium
Sulphur Coverage
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DesorptionDesorption of of sulphursulphur
0.0
0.2
0.4
0.6
0.8
1.0
1 10 100 1000 10000
Time, hr
Sulphur Coverage
700 °°°°C 800 °°°°C
S-Nisurface + H2 ↔ Nisurface + H2S
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SulphurSulphur RegenerationRegeneration
Steam SV : 4000 and T(exit): 800
900
920
940
960
980
1000
0 2 4 6 8 10Time
0
100
200
300
400
PPM SO2
TWT's
BeforeAfter
Temperat ure °° °°C
SO2
S-Nisurface + H2O → NiO + H2S
H2S + 2 H2O → SO2 + 2 H2
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Regeneration for CarbonRegeneration for Carbon
Steam SV : 4000 and T(exit): 800
0
2
4
6
8 9 10 11 12
Time
%
O2
CO2
C + O2 → CO2
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SinteringSintering
• Decreased C tolerance
• Decreased S tolerance
• Decreased activity
Fresh
Fresh Used
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Sintering of Nickel SurfaceSintering of Nickel Surface(Ceramic Reforming Catalyst)(Ceramic Reforming Catalyst)
1
0
0.2
0.4
0.6
0.8
1.0
10 100 1000
Time/hours
RelativeNiarea
aftersinter ings/s0
550°C
700°C
800°C
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Triple DeckerTriple Decker
700
750
800
850
900
0 2 4 6 8 10
Distance from Inlet, m
Temperature
TWT
Catalyst
Sulphur Carbon Sintering
RK-211 RK-201 R-67-7H
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Properties of Topsoe Reforming CatalystProperties of Topsoe Reforming Catalyst
R-67-7H : Carrier: MgAl2O4 (spinel)
Ni content: 14 %
RK-201: Carrier: CaAl2O4 + MgAl2O4
Ni content: 12 %
K content: 0.4 %
RK211: As RK-201 except :
Doped with noble metal
Prereduced
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Reformer loading techniquesReformer loading techniques
• Sock loading
• Unidense™
• SpiraLoad™
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SpiraLoadSpiraLoad loadingloading tubetube
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The The SpiraLoadSpiraLoad™™ techniquetechnique
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Comparison of reformer loading Comparison of reformer loading
techniquestechniques
Time pr. tube, min
Tubes unloaded, %
Manpower
Automised
Sock loading
30-40
~ 2
Demanding
Low
Unidense™
15-20
~ 2
Normal
Low
SpiraLoad™
15-20
0.01
Normal
High
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END END
CHALLENGES IN STEAM REFORMINGCHALLENGES IN STEAM REFORMING
QUESTIONS?