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Topsøe prereforming catalysts

MRPL Phase-III Refinery Project, Hydrogen Generation Unit

Outline

 Topsøe prereforming technology and catalysts for


operational flexibility

 Operational precautions

 Evaluation of prereforming catalysts

Benefits of prereforming
 Feedstock flexibility
– Naphtha
– Butane
– LPG
– LNG / Off-gas
 All higher hydrocarbons will be converted
– H2, CO, CH4
 Can operate on low S/C to save energy
 Long lifetime of primary reformer catalyst
– No risk of carbon formation
– No risk of sulphur poisoning
 Longer lifetime of MTS catalyst
Hydrogen plant
H2O

Hydrocarbon
feed

Steam reforming
Hydrogenation

temperature
Pre-reforming
absorption

Medium
Sulphur

shift
Off gas

H2

Pressure swing absorption

CnHm + nH2O → nCO + (n+m/2)H2

CO + H2O ↔ H2 + CO2

CO + 3H2 ↔ CH4 + H2O

Prereformer

1” Alumina balls
½” Alumina balls

RKNGR, 4.3x4.3

1” Alumina balls

Prereforming catalyst and inert material


Catalyst RKNGR
Shape Cylinder
Diameter, mm 4.0-4.5
Height, mm 3.9-4.5
Reduced Ni, wt % >20
Al2O3 + MgO, wt % Balance

Inert material Alumina


Shape Sphere
Diameter, inch ½
Diameter, inch 1
Al2O3, wt % >99
SiO2, wt % <0.2
Structure of Ni crystallite

Terrace site Ni(111),


0.20nm

Ni(200),
Step site 0.18nm

1mbar H2 at 500°C

Nature 427, 426 (2004)

Resistance to sintering

H2, 600°C

Topsøe prereforming catalysts

Catalyst AR-401 RKNGR


Feed NG/LPG/ROG Naphtha
Carrier MgAl2O4 MgO/Al2O3
Nickel, wt% >30 >20
Shapes 7-hole 11×6 and cylinders 4.5×4.5
Topsøe prereforming catalyst references
worldwide
80

70

60
No. of references

50

40

30

20

10

0
1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009
Year

Typical installation H2O (optional)

Tubular
reformer

Prereformer

Waste heat channel

Feed

Steam

Operational precautions
 Prevent sulphur poisoning
 Prevent carbon formation
 Prevent oxidation
 Operate above hydration limit
Prevent sulphur poisoning

H2
Chlorine Chlorine
Absorption Absorption
HTG-1 HTG-1

Hydro-
genation Sulphur Sulphur
TK-250 Absorption Absorption
HTZ-3 HTZ-3

RSH + H2 → H2S + RH H2S + ZnO ↔ H2O + ZnS

Sulphur poisoning

Nisurface + H2S ↔ S-Nisurface + H2

Prevent carbon formation


Whisker carbon formation depressed by:
 Lower temperatures
 High steam/carbon ratios
 High H2 recycle

Gum formation depressed by:


 High temperatures
 High steam/carbon ratios
 High H2 recycle
Keep prereforming catalyst reduced
Special risk during start-up/shut-down/trip
1. If the catalyst is oxidized some of the sulphur picked up
on the catalyst in the top will be released
2. This sulphur will be picked up by the catalyst further
down in the bed
3. The overall catalyst activity will decrease when the
sulphur is distributed to a larger part of the bed

Operate above hydration limit


Equilibrium Steam Pressure for
MgO + H2O ↔ Mg(OH)2

Log(PH O ) = -4676/T - 1.54 log(T) + 12.57


2

– P = partial steam pressure (atm)


H2O

– Tiiii = temperature (K)

Operation of Topsøe prereforming catalysts


 Simple loading in adiabatic reactor
 Prereduced catalysts for easy
start-up
 Visual monitoring of performance
with Z90 plot
 Measure slip of HHC
 Follow ∆P across reactor
Temperature

Naphtha
T

LPG

Natural gas

0 Bed depth, % 100


Prereformer evaluation

 Check pressure drop across the prereformer


– Evaluate the trend
 Deactivation rate evaluation
– Use Z90 method
 Remaining catalyst life time estimation
– Based on Z90 plot

 The Z90 method gives a quick warning if sulphur leakage


from the desulfurization section should increase

Natural gas based plant – evolution in profiles


520

500
Temperature, °C

0 Days
137 Days
480 601 Days
1115 Days
T90
460 Z90

440
0 20 40 60 80 100
Bed height, %

Natural gas based plant – temperature profile

540
TInlet

520
Temperature (°C)

500

480 TExit
T90

460
0 20 Z90 40 60 80 100
Height of bed, %
Natural gas based plant – evaluation with Z90
80

60
Z90, %

40

20

0
0 20 40 60
Age, months

Temperature profiles in a naphtha prereformer


using RKNGR
500

490
1 9 13 22
Temperature (°C)

480

470

460
1 Time on-stream (months)
450

440
0.0 0.2 0.4 0.6 0.8 1.0
Relative distance in catalyst bed

Temperature profile for the prereformer in a


naphtha based plant
495
T90
TExit
490
∆T90
Temperature (°C)

∆T
485

480
TMin

475

Z90
470
0 20 40 60 80 100
Naphtha based plant – evaluation with Z90
80

60
Z90, %

40

20

0
0 20 40 60

Summary
 Topsøe prereforming catalysts are high activity nickel
catalysts with excellent carbon resistance
 Stable carrier material limits sintering
 Deactivation is diminished by avoiding poisoning of the
catalyst – caution against sulphur poisoning is essential
 Following the development in temperature profiles with
Z90 plot enables actions against poisoning

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