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ChallengesChallenges inin SteamSteam ReformingReforming Steam Reforming Technology User Conference 5-7 March 2007 Bo
ChallengesChallenges inin SteamSteam ReformingReforming
Steam Reforming Technology User Conference
5-7 March 2007
Bo Hartvigsen, Sales Manager, Haldor Topsoe
A/S
ChallengesChallenges inin SteamSteam ReformingReforming Agenda: 1. Carbon formation 2. Poisoning of catalyst (sulphur)
ChallengesChallenges inin SteamSteam ReformingReforming
Agenda:
1. Carbon formation
2. Poisoning of catalyst (sulphur)
3. Sintering of catalyst
4. Loading
CarbonCarbon FormationFormation +H2O C2H6 2 CO + 5 H2 Reforming 2 C + 3 H2
CarbonCarbon FormationFormation
+H2O
C2H6
2 CO
+
5 H2
Reforming
2 C
+ 3 H2
Carbon
CARBONCARBON FORMATIONFORMATION Two types of carbon formation: • Catalytic cracking (on Ni crystals) • Thermal
CARBONCARBON FORMATIONFORMATION
Two types of carbon formation:
• Catalytic cracking
(on Ni crystals)
• Thermal cracking
(on hot surfaces)
Carbon whiskers, physical
damage of catalyst
Hot bands, NO physical
damage of catalyst
PyrolyticPyrolytic carboncarbon (thermal(thermal cracking)cracking)
PyrolyticPyrolytic carboncarbon (thermal(thermal cracking)cracking)
CatalystCatalyst deactivationdeactivation andand carboncarbon formationformation Carbon formation from higher
CatalystCatalyst deactivationdeactivation andand
carboncarbon formationformation
Carbon formation from higher hydrocarbons
Actual (high activity)
Actual (low activity)
14
Critical
12
10
8
Carbon formation
6
4
2
0
0
1
2
3
4
5
m from inlet
Steam to higher
hydrocarbon radio
C H n m C H n m C H n m C H n
C H
n
m
C H
n
m
C H
n
m
C H
n
m
FormationFormation ofof hothot bandsbands
C H
n
m
C n H m
C n H m
C n H
m
500°C
C H
n
m
C H
n
m
C H
850°C
n
m
High
Low
activity
activity
HotHot BandsBands inin toptop firedfired reformerreformer
HotHot BandsBands inin toptop firedfired reformerreformer
HotHot spotsspots inin aa sideside--firedfired reformerreformer
HotHot spotsspots inin aa sideside--firedfired reformerreformer
ReformerReformer designdesign Radiant Wall Top Fired Bottom Fired Terrace Wall Topsøe MW Kellogg KTI UHDE
ReformerReformer designdesign
Radiant Wall
Top Fired
Bottom Fired
Terrace Wall
Topsøe
MW Kellogg
KTI
UHDE
Chemico
Foster Wheeler
Selas
Girdler
RiskRisk forfor carboncarbon formationformation isis higherhigher inin aa toptop firedfired reformerreformer
RiskRisk forfor carboncarbon formationformation isis higherhigher inin aa toptop firedfired reformerreformer
HowHow toto PreventPrevent CarbonCarbon FormationFormation 1. High activity: reform higher hydrocarbons at low
HowHow toto PreventPrevent CarbonCarbon FormationFormation
1. High activity: reform higher hydrocarbons
at low temperatures
2. Use less acidic carrier
3. Promote with alkali
4. (Prereforming)
ImpactImpact ofof AlkaliAlkali Alkali lower catalyst activity, especially at low temperatures 0 400 500 600
ImpactImpact ofof AlkaliAlkali
Alkali lower catalyst activity, especially at low temperatures
0
400
500
600
700
Catalyst Temperature
Relative Activity
SulphurSulphur PoisoningPoisoning Sulphur blocks the Nickel surface area ↔ Ni surface + H 2 S
SulphurSulphur PoisoningPoisoning
Sulphur blocks the Nickel surface area
Ni surface + H 2 S
S-Ni surface + H 2
TemperatureTemperature dependencedependence Sulphur Coverage 1 ppbv=10 ppbv=50 ppbv=100 0.8 0.6 0.4 500 550 600
TemperatureTemperature dependencedependence
Sulphur Coverage
1
ppbv=10
ppbv=50
ppbv=100
0.8
0.6
0.4
500 550
600 650 700
750 800 850
900
Temperature, °C
DynamicsDynamics ofof poisoningpoisoning Sulphur Coverage Year 1 1 Year 2 0.9 Year 3 0.8 Equilibrium
DynamicsDynamics ofof poisoningpoisoning
Sulphur Coverage
Year 1
1
Year 2
0.9
Year 3
0.8
Equilibrium
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
20
40
60
80
100
Tube Length, %
DesorptionDesorption ofof sulphursulphur ↔ S-Ni surface + H 2 Ni surface + H 2 S
DesorptionDesorption ofof sulphursulphur
S-Ni surface + H 2
Ni surface + H 2 S
Sulphur Coverage
1.0
0.8
0.6
0.4
0.2
0.0
1
10
100
1000
10000
Time, hr
700 °°°°C
800 °°°°C
PPM SO2 SulphurSulphur RegenerationRegeneration S-Ni surface + H 2 O → NiO + H 2
PPM SO2
SulphurSulphur RegenerationRegeneration
S-Ni surface + H 2 O → NiO + H 2 S
H 2 S + 2 H 2 O
SO 2 + 2 H 2
Steam SV : 4000 and T(exit): 800
1000
TWT's
400
980
300
Before
After
960
200
940
100
920
SO 2
900
0
0
2
4
6
8
10
Time
Temperature °°C°°
RegenerationRegeneration forfor CarbonCarbon C + O 2 → CO 2 Steam SV : 4000 and
RegenerationRegeneration forfor CarbonCarbon
C + O 2
→ CO 2
Steam SV : 4000 and T(exit): 800
6
O2
4
CO2
%
2
0
8
9
10
11
12
Time
SinteringSintering • Decreased C tolerance • Decreased S tolerance • Decreased activity Fresh Used Fresh
SinteringSintering
• Decreased C tolerance
• Decreased S tolerance
• Decreased activity
Fresh
Used
Fresh
SinteringSintering ofof NickelNickel SurfaceSurface (Ceramic(Ceramic ReformingReforming Catalyst)Catalyst) 1.0 550°C
SinteringSintering ofof NickelNickel SurfaceSurface
(Ceramic(Ceramic ReformingReforming Catalyst)Catalyst)
1.0
550°C
0.8
0.6
700°C
0.4
0.2
800°C
0
1
10
100
1000
Time/hours
R
Ne
i area
e r a s ti i n vel t ea rft
ing
s/s 0
TripleTriple DeckerDecker 900 Sulphur Carbon Sintering 850 TWT Catalyst 800 750 RK-211 RK-201 R-67-7H 700
TripleTriple DeckerDecker
900
Sulphur
Carbon
Sintering
850
TWT
Catalyst
800
750
RK-211
RK-201
R-67-7H
700
0
2
4
6
8
10
Distance from Inlet, m
Temperature
PropertiesProperties ofof TopsoeTopsoe ReformingReforming CatalystCatalyst R-67-7H : Carrier: Ni content: MgAl2O4
PropertiesProperties ofof TopsoeTopsoe ReformingReforming CatalystCatalyst
R-67-7H :
Carrier:
Ni content:
MgAl2O4 (spinel)
14 %
RK-201:
Carrier:
Ni content:
K content:
CaAl2O4 + MgAl2O4
12 %
0.4 %
RK211:
As RK-201 except :
Doped with noble metal
Prereduced
ReformerReformer loadingloading techniquestechniques • Sock loading • Unidense™ • SpiraLoad™
ReformerReformer loadingloading techniquestechniques
• Sock loading
• Unidense™
• SpiraLoad™
SpiraLoadSpiraLoad loadingloading tubetube
SpiraLoadSpiraLoad loadingloading tubetube
TheThe SpiraLoadSpiraLoad™™ techniquetechnique
TheThe SpiraLoadSpiraLoad™™ techniquetechnique
ComparisonComparison ofof reformerreformer loadingloading techniquestechniques Sock loading Unidense™ SpiraLoad™
ComparisonComparison ofof reformerreformer loadingloading
techniquestechniques
Sock loading
Unidense™
SpiraLoad™
Time pr. tube, min
30-40
15-20
15-20
Tubes unloaded, %
~ 2
~ 2
0.01
Manpower
Demanding
Normal
Normal
Automised
Low
Low
High
ENDEND CHALLENGESCHALLENGES ININ STEAMSTEAM REFORMINGREFORMING QUESTIONS?
ENDEND
CHALLENGESCHALLENGES ININ STEAMSTEAM REFORMINGREFORMING
QUESTIONS?