Professional Documents
Culture Documents
Agenda
Introduction –Reforming
Reforming catalyst
Catalyst operational challenges
Monitoring of a reformer
Primary reformer
1
Chemical reactions in a steam reformer
Reforming:
CH4 + H2O ↔ CO + 3 H2
CnHm + n H2O → n CO + (n + ½m) H2
ex. (C4H10 + 4 H2O → 4 CO + 9 H2)
Shift:
CO + H2O ↔ CO2 + H2
Reforming catalysts
Catalyst R-67-7H
Diameter, mm 19 – 20
Height, mm 15 - 18
NiO, wt % >15
MgAl2O4, wt % Balance
2
Reforming catalysts
Critical catalyst parameters
Large nickel surface
– Activity
– Poison capacity
Carrier thermal stability
Carbon resistance
Catalyst Shape:
– Pressure drop
– Crush strength
– Geometric surface area
– Heat transfer
Ni content
Sintering
Decreased activity
Decreased C tolerance
Decreased S tolerance
Fresh Used
Fresh
3
Topsøe reforming catalysts
Alkali Pre- Noble
Catalyst Metal content carrier
promoted reduced metal
Sulphur poisoning
Nickel
terrace
Nickel
step
4
Carbon formation
+H2O
C2H6 2 CO + 5 H2
Reforming
2 C + 3 H2
Carbon !
Carbon formation
Two types of carbon formation:
During operation
– Complete loss of steam
– Operation at very low steam to carbon ratio
5
Nucleation of whisker carbon
Thermal cracking
Too low catalyst activity
Flame impingement
10
8
Carbon formation
6
4
2
0
0 1 2 3 4 5
m from inlet
6
Formation of hot bands
CnHm CnHm
C
nH
500°C C
nH
m m
C nH m
C nH m
C nH m
C nH m
Cn
C nH m
Hm
C nH m
850°C
High Low
activity activity
7
Effect of TWT on tube life
100,000
Life time, hours
50,000
30,000
20,000
HK40 IN519 25/35 Nb HP-BST-M
Tube damage
Two types of tube damage:
Visual inspection
The most important inspection is visual
You can see differences down to 5-10°C
You can see single hot spots even if it is far away from
the peep hole
You should do visual inspection during the night
You cannot ”see” the real temperature of the tubes
Visual inspection must be combined with pyrometer
measurements
8
Measurement of tube wall temperatures
870
Temperature C
860
850
840
810
800
790
27
45
11
13
15
17
19
21
29
31
33
35
23
25
37
39
41
43
1
9
3
Tube No.
TWT record
average
920.0 60000
TWT
900.0
55000 max TWT
N a t u r a l G a s f lo w , N m 3 /h
880.0
T e m p e ra t u re ( °C )
860.0 50000
min TWT
840.0
45000
820.0 Design
800.0 40000 TWT
780.0 Toutlet
35000
760.0
9
What to watch out for in operation
Start-up
– Heating stagnant/circulation
– Introduction of steam/hydrogen/feed
Operation
– Increase in production (steam/feed/air)
– Maximum operating parameters
Shut-down
– Avoid overheating of tubes (Protection steam)
– Avoid oxidation of catalyst
10