Tubular reforming
Research I Technology I Catalysts
MRPL Phase-III Refinery Project, Hydrogen Generation Unit
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
Overall reaction is strongly endothermic
↓
Heat has to be transferred from outside
Operating conditions for tubular reformers
Typical Your plant
Inlet temperature : 450 - 650 ºC 600 - 650 ºC
Exit temperature : 750 - 950 ºC 915 ºC
Pressure: 20 - 45 kg/cm2 g 29.3 kg/cm2 g
Steam/carbon ratio: 1.6 - 7 mole/mole 2.5 mole/mole
Reforming catalysts
Catalyst R-67-7H
Shape Cylinder with 7
axial holes
Size, mm 20x18
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
Nickel content vs. reforming activity
Relative reforming activity
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
R67 - - - NiO: >15% MgAl2O4
R67R - - Red Ni: >10% MgAl2O4
NiO: >14% MgAl2O4
RK-201 - -
K: 0.3-0.6% CaAl2O4
Red Ni: >9% MgAl2O4
RK-211 K: 0.3-0.6% CaAl2O4
NiO: >12% MgAl2O4
RK-202 - -
K: 1.0-1.5% CaAl2O4
Red Ni: >9% MgAl2O4
RK-212 K: 1.0-.15% CaAl2O4
Catalyst operational challenges
Sulphur poisoning
Carbon formation
Sulphur poisoning
Nickel
terrace
Nickel
step
Nisurface + H2S ↔ S-Nisurface + H2
4
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
Catalytic carbon formation
During start up
– Dry hydrocarbons during nitrogen recycle
During operation
– Complete loss of steam
– Operation at very low steam to carbon ratio
5
Nucleation of whisker carbon
Bengaard et al. J. Catal. 209, 354 (2002)
Thermal cracking
Too low catalyst activity
Flame impingement
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
low Temperature High
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
Monitoring of primary reformer
Important for optimal plant operation
Tube wall temperature tells a lot about how reformer
performs
Never trust DCS data alone – remember visual
inspection of reformer
– Visual inspection may catch problems long before they can be
measured and seen in the DCS
Tube wall temperature (TWT)
Design TWT important for the tube life time
Typically designed for a lifetime of 100,000 hours
A 15-20°C higher temperature than design →
tube lifetime is lowered by 50%
A 30-40°C higher temperature reduce lifetime by 75%
A 100°C higher temperature can cause tube rupture very
fast
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
880 920 960 1000
Tube skin temperature, °C
Tube damage
Two types of tube damage:
Creep Very high temperature
When reaching ~5% increased When exposed to very high temperatures
diameter the tube may rupture. mechanical strength is lost.
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
Keep records of TWT’s
880
870
Temperature C
860
850
840
830 Vise excel regneark med t wall
820
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.
Keep TWT records, to follow the trend
Place the TWT in a spread sheet as above
After installing a new catalyst, TWT are at a minimum
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
740.0 30000 NG flow
20.11.00 8.6.01 25.12.01 13.7.02 29.1.03 17.8.03 4.3.04 20.9.04 8.4.05
Date of Data
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
Thank you for your attention
10
