Catschool 1 provides an overview of prereforming catalyst technology. Prereforming converts higher hydrocarbons in refinery and chemical plant feedstocks to hydrogen and carbon monoxide before the main reforming reactor. This improves the flexibility and efficiency of the downstream processes. Topsøe supplies two prereforming catalysts, AR-401 for natural gas and naphtha feeds, and RKNGR for heavier feeds. Proper handling, installation, and operation are required to prevent poisoning, carbon formation, and oxidation that could decrease catalyst lifetime.
Catschool 1 provides an overview of prereforming catalyst technology. Prereforming converts higher hydrocarbons in refinery and chemical plant feedstocks to hydrogen and carbon monoxide before the main reforming reactor. This improves the flexibility and efficiency of the downstream processes. Topsøe supplies two prereforming catalysts, AR-401 for natural gas and naphtha feeds, and RKNGR for heavier feeds. Proper handling, installation, and operation are required to prevent poisoning, carbon formation, and oxidation that could decrease catalyst lifetime.
Catschool 1 provides an overview of prereforming catalyst technology. Prereforming converts higher hydrocarbons in refinery and chemical plant feedstocks to hydrogen and carbon monoxide before the main reforming reactor. This improves the flexibility and efficiency of the downstream processes. Topsøe supplies two prereforming catalysts, AR-401 for natural gas and naphtha feeds, and RKNGR for heavier feeds. Proper handling, installation, and operation are required to prevent poisoning, carbon formation, and oxidation that could decrease catalyst lifetime.
Catschool 1 provides an overview of prereforming catalyst technology. Prereforming converts higher hydrocarbons in refinery and chemical plant feedstocks to hydrogen and carbon monoxide before the main reforming reactor. This improves the flexibility and efficiency of the downstream processes. Topsøe supplies two prereforming catalysts, AR-401 for natural gas and naphtha feeds, and RKNGR for heavier feeds. Proper handling, installation, and operation are required to prevent poisoning, carbon formation, and oxidation that could decrease catalyst lifetime.
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
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
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
• 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
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
