Catschool 1: Prereforming catalysts

Pia Elholm, Product manager for prereforming catalysts

Outline
• History
• Use of prereforming technology
• Topsøe prereforming catalysts
• Handling and installation of prereforming catalysts
• Evaluation and operational precautions
• Summary
• Quiz
Topsøe prereforming catalyst changes in operation
worldwide

100

90
80
No. of references

70

60
50

40
30

20
10

0
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012
Year
 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

 GTL/MeOH frontend with ATR

H2O Recycle O2

Feed H2O

H2

Feed Pre-
purification reformer
ATR
 Ammonia plant

Desulphurisation Reforming Shift

Prereforming
Process steam

Natural gas

Process air
Fuel
Stack

Purge gas

CO2-
removal

Ammonia Process
product Ammonia synthesis Methanation cond.
Benefits of prereforming technology

• Feedstock flexibility – Natural gas, naphtha, butane, LPG, Off-gas or

mixed
• Optimize steam to carbon ratio:
• Down to 1.6 with naphtha feedstock
• Down to 0.52 with light natural gas
• All higher hydrocarbons will be converted - Exit gas is H2, CO, CO2 and
CH4
• In new plants:
• In large capacity new plants savings can be made on the tubular reformer
• In revamp situations:
• Plant load can be increased if part of revamp
• Energy consumption can be lowered by reheat of the prereformer exit gas in
connection with a plant revamp
Catalyst characteristics

• AR-401 • RKNGR
• Suitable for reforming of natural gas, • Suitable for reforming of heavy
LPG and naphtha hydrocarbon feedstocks
• High activity • High resistance towards carbon
• Resistance towards sintering formation
• High resistance to carbon formation at • Resistance towards sintering
low steam to carbon
• Pre-reduced for easy start-up
• Unique ability to tolerate condensing
steam
• Pre-reduced for easy start-up

Catalyst AR-401 RKNGR

Carrier MgAl2O4 MgO/Al2O3
Nickel, wt% >30 >20
Shapes 7-hole 11×6 and cylinders 4.5×4.5
Prereformer

Inert material Alumina

Shape Sphere
Diameter, inch ½

Alumina balls
Diameter, inch 1
Al2O3, wt % >99
SiO2, wt % <0.2
AR-401 or RKNGR

Alumina balls
Benefits of prereforming catalysts

• Protection of downstream equipment and catalysts:

• Lower tube skin temperatures in the tubular reformer, resulting in a longer
lifetime of the tubes compared to operation without prereforming catalyst
• Installation of standard reforming catalyst in tubular reformer
• Risk of carbon formation in the tubular reformer can be excluded
• Extended lifetime of the catalyst in the tubular reformer
• Longer lifetime of MTS and LTS catalysts
Handling of Topsøe prereforming catalysts

• Installation
• All Topsøe prereforming catalysts are skin-passivated securing easy
handling
• Hose loading
• Avoid “chimney” effect
• Unloading
• The prereforming catalyst is pyrophoric due to chemisorbed H2
• Unloading from bottom dump chute to drums with lids in order to minimize
ingress of air
• Avoid “chimney” effect
Loading of catalyst
Loading of catalyst
Loading of catalyst
Loading of catalyst
Evaluation of prereforming catalysts

• Follow DP across reactor

• Visual monitoring of performance
with Z90 plot
• Measure slip of HHC

T
T
T
Temperature

Naphtha
T

LPG

Natural gas

0 Bed depth, % 100

Poisoning

Temperature
0 Bed depth, % 100
Z90, %

Age
 Calculation of Z90 in a naphtha based plant

495
T90
TExit
490
DT90
DT
485
Temperature (°C)

480
TMin

475

Z90
470
0 20 40 60 80 100
Height of bed, %
 Calculation of Z90 in a natural gas based plant

520

TInlet
500

480
Temperature (°C)

460 TExit
T9
0
440
0 20 Z9040 60 80 100
Height of bed, %
 Graphical deactivation plot -
the Z90 method

80

60

40

20
Z90, %

0
0 20 40 60
Age, months
 Graphical deactivation plot -
the Z90 method

80

60
Z70, %

40

20

0
0 10 20 30 40 50
Age, months
Significant change in Z90 plot

100

80

60

40
Z90, %

20

0
0 20 40 60 80 100
Age, months
Operational precautions

• Prevent poisoning from

• Sulphur
• Alkali
• Silica
• Prevent carbon formation
• Prevent oxidation
Prevent sulphur poisoning

Feed TK-250

H2

Hydro- Conversion of organic sulphur

genation R-SH + H2 → H2S + RH

Sulphur Absorption of inorganic sulphur

absorption ZnO + H2S ↔ ZnS + H2O

HTZ-5
Sulfur trap

Feed

H2
ST- 101

Hydro- Sulfur Sulfur

genation absorption absorption
Sulfur
trap

• Application • Properties
• CO2 or H2O in the feed • Pick-up of any H2S and organic
sulfur
• CO2 + H2 ↔ CO + H2O
• Cu-based
• ZnS + H2O ↔ ZnO + H2S
• Fluctuating sulfur levels
Boiler feed water requirements

Requirement Unit Specification

Generel Colourless, clear, free from nondisolved matter
pH value at 25ºC 9-10
Conductivity at 25ºC mS/cm < 0.2
Oxygen (O2) mg/kg < 0.1
Iron, total (Fe) mg/kg < 0.02
Copper, total (Cu) mg/kg < 0.003
Silicic acid mg/kg < 0.02
Sodium (Na) mg/kg < 0.01
Chlorine (Cl) mg/kg < 0.1
Sulphur (as SO42-) mg/kg < 0.2
KMnO4 consumption mg/kg <3
Mn(VII) -> Mn(II) as KMnO4
Oil, grease mg/kg <1
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
 Catalytic carbon formation

• During start up:

- Dry hydrocarbons during nitrogen recycle
Leaking valves on feed line:
- Valves (always) leak!
- Use double block and bleed (or blind)
Hydrocarbons from DES section:
- NG: Purge system properly: < 0.05 – 0.2 %
- Heavy feeds: Never include DES section in
nitrogen loop

• During operation:
- Complete loss of steam
- Operation at very low steam to carbon ratio
Oxidation of un-poisoned catalyst

Consequences of oxidation of un-

poisoned catalyst
• Loss of activity
• Increased sintering
• Very low degree of re-reduction at
operating conditions

Special risk during start-up/shut-down/trip

Oxidation of sulfur poisoned catalyst

 If the catalyst is oxidized Initial poisoning of top layer Oxidation of sulfur poisoned
some of the sulfur picked catalyst
up on the catalyst in the top
will be released
 This sulfur will be picked up
by the catalyst further down
in the bed
 The overall catalyst activity
will decrease when the
sulfur is distributed to a
larger part of the bed
Trouble-shooting

• Z90 deactivation rate increases, consider

• Poisoning
• Gum formation
• Increase in DP is measured, consider
• Whisker carbon formation
• Hydration
• Deposition of foreign material
• Milling
• Other considerations
• Steam quality
• Changes in feedstock
• Plant layout
• Catalyst quality
• Quality of inert materials
Summary

• Topsøe prereforming catalysts are high activity nickel catalysts on stable carrier
materials with excellent carbon resistance

• Topsøe prereforming catalysts are well-referenced for a all types of feedstock

• Loading and start-up is simple due to the prereduced, but skinpassivated

catalysts

• 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