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Challenges in Steam Reforming

Steam Reforming Technology User Conference


5-7 March 2007
Bo Hartvigsen, Sales Manager, Haldor Topsoe
A/S
Challenges in Steam Reforming
Agenda:
1. Carbon formation
2. Poisoning of catalyst (sulphur)
3. Sintering of catalyst
4. Loading
Carbon Formation

+H2O
C2H6 2 CO + 5 H2
Reforming

2 C + 3 H2
Carbon
CARBON FORMATION
Two types of carbon formation:

• Catalytic cracking • Thermal cracking


(on Ni crystals) (on hot surfaces)

Carbon whiskers, physical Hot bands, NO physical


damage of catalyst damage of catalyst
Pyrolytic carbon (thermal cracking)
Catalyst deactivation and
carbon formation
Carbon formation from higher hydrocarbons

Actual (high activity) Actual (low activity)


14
Critical
12
hydrocarbon radio
Steam to higher

10
8
Carbon formation
6
4
2
0
0 1 2 3 4 5
m from inlet
Formation of hot bands
CnHm CnHm

C 500°C C
nH nH
m m

C nH m
C nH m
C nH m C nH m

C nH m
Cn
Hm
C nH m

850°C
High Low
activity activity
Hot Bands in top fired reformer
Hot spots in a side-fired reformer
Reformer design

Radiant Wall Top Fired Bottom Fired Terrace Wall


Topsøe MW Kellogg Chemico Foster Wheeler
Selas KTI Girdler
UHDE
Risk for carbon formation is higher in a top fired reformer
How to Prevent Carbon Formation

1. High activity: reform higher hydrocarbons


at low temperatures

2. Use less acidic carrier

3. Promote with alkali

4. (Prereforming)
Impact of Alkali
Alkali lower catalyst activity, especially at low temperatures

Relative Activity

0
400 500 600 700
Catalyst Temperature
Sulphur Poisoning

Sulphur blocks the Nickel surface area

Nisurface + H2S ↔ S-Nisurface + H2


Temperature dependence

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
Dynamics of poisoning

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, %
Desorption of sulphur
S-Nisurface + H2 ↔ Nisurface + H2S

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
Sulphur Regeneration
S-Nisurface + H2O → NiO + H2S
H2S + 2 H2O → SO2 + 2 H2

Steam SV : 4000 and T(exit): 800


1000 TWT's 400
Temperature °C

980 300

PPM SO2
Before
960 After
200
940
920 SO2 100
900 0
0 2 4 6 8 10
Time
Regeneration for Carbon
C + O2 → CO2

Steam SV : 4000 and T(exit): 800


6
O2
4 CO2
%
2

0
8 9 10 11 12
Time
Sintering

• Decreased C tolerance
• Decreased S tolerance
• Decreased activity
Fresh Used

Fresh
Sintering of Nickel Surface
(Ceramic Reforming Catalyst)

1.0
after sinteri ng s/s0
Relative N i area

0.8 550°C

0.6
700°C
0.4

0.2
800°C
0
1 10 100 1000
Time/hours
Triple Decker

900 Sulphur Carbon Sintering

850
Temperature

TWT
800 Catalyst

750
RK-211 RK-201 R-67-7H

700
0 2 4 6 8 10
Distance from Inlet, m
Properties 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
Reformer loading techniques
• Sock loading
• Unidense™
• SpiraLoad™
SpiraLoad loading tube
The SpiraLoad™ technique
Comparison of reformer loading
techniques

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


END
CHALLENGES IN STEAM REFORMING

QUESTIONS?