Vous êtes sur la page 1sur 28

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

C2H6

+H2O

2 CO + 5 H2
Reforming
2 C + 3 H2
Carbon

CARBON FORMATION
Two types of carbon formation:
Catalytic cracking
(on Ni crystals)

Carbon whiskers, physical


damage of catalyst

Thermal cracking
(on hot surfaces)

Hot bands, NO physical


damage of catalyst

Pyrolytic carbon (thermal cracking)

Catalyst deactivation and


carbon formation
Carbon formation from higher hydrocarbons
Actual (high activity)

Steam to higher
hydrocarbon radio

14

Actual (low activity)


Critical

12
10
8
Carbon formation

6
4
2
0

2
3
m from inlet

Formation of hot bands


CnHm
C

nH
m

C nH m

500C

C nH m

nH
m

CnHm

C nH m

Hm
Cn
C nH m

C nH m

C nH m

850C
High
activity

Low
activity

Hot Bands in top fired reformer

Hot spots in a side-fired reformer

Reformer design

Radiant Wall

Top Fired

Bottom Fired

Terrace Wall

Topse

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

Relative Activity

Alkali lower catalyst activity, especially at low temperatures

0
400

500

600

Catalyst Temperature

700

Sulphur Poisoning

Sulphur blocks the Nickel surface area


Nisurface + H2S S-Nisurface + H2

Temperature dependence
Sulphur Coverage
1

0.8

ppbv=10
ppbv=50
ppbv=100

0.6

0.4
500 550 600 650 700 750 800 850 900
Temperature, C

Dynamics of poisoning
Sulphur Coverage
Year 1
Year 2
Year 3
Equilibrium

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

20

40

60

Tube Length, %

80

100

Desorption of sulphur
S-Nisurface + H2 Nisurface + H2S
Sulphur Coverage
1.0
0.8
0.6
0.4
0.2
0.0
1

10

700 C

100
Time, hr

1000

800 C

10000

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

Steam SV : 4000 and T(exit): 800


400

TWT's

980

300

Before
After

960

200

940
920

100

SO2

900

0
0

6
Time

10

PPM SO2

Temperature C

1000

Regeneration for Carbon


C + O2 CO2

Steam SV : 4000 and T(exit): 800


6
O2
CO2

4
%
2
0
8

10
Time

11

12

Sintering
Decreased C tolerance
Decreased S tolerance
Decreased activity
Used

Fresh

Fresh

Sintering of Nickel Surface


Relative N i area
after sinteri ng s/s0

(Ceramic Reforming Catalyst)


1.0

550C

0.8
0.6

700C
0.4
0.2

800C
0
1

10

100

Time/hours

1000

Triple Decker

Temperature

900

Sintering

Carbon

Sulphur

850
TWT
Catalyst

800
750
RK-211

RK-201

R-67-7H

700
0

Distance from Inlet, m

10

Properties of Topsoe Reforming Catalyst

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

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?