SlideShare una empresa de Scribd logo
1 de 46
Descargar para leer sin conexión
Performance & Operation
Improvements using VULCAN Series
VSG-F101 High Temperature Shift
Catalysts
By:
Gerard B. Hawkins
Managing Director, CEO
Improvements in High Temperature
Shift Catalysts
 The high temperature shift duty
 introduction and theory
 HTS catalyst characteristics
 developments over time
 Typical HTS operational problems
 Improved catalysts
 VULCAN Series VSG-F101 Series
 Summary
Improvements in High Temperature
Shift Catalysts
 The high temperature shift duty
 Introduction and theory
 HTS catalyst characteristics
 Typical HTS operational problems
 Improved catalysts and loading regimes
 Summary
Introduction
What is the Shift Reaction ?
 Water gas shift reaction has two effects:
• generates hydrogen from carbon
monoxide & steam
• converts CO to CO2
CO + H2O <=> CO2 + H2
From Steam
Reformer
HTS LTS Methanation
LTS
(optional)
H2
Introduction
How to include a Shift Section ?
Liquid
CO2
Removal
PSAHTS
From Steam
Reformer
H2
Theory - Equilibrium
CO + H2O CO2 + H2 (+ heat)
• Reaction is reversible
• Forward reaction - moderately exothermic
– equilibrium at lower temperature favors
• more CO converted
• more H2 produced
• Cannot beat equilibrium !
Theory - Reaction Rate
 Reaction Rate depends on
• distance from equilibrium
 further from equilibrium =>
larger driving force
• catalyst formulation/activity
• operating temperature
 Catalyst enables reaction to proceed
 Higher temperature drives rate
Ideal catalyst promotes rate to achieve
equilibrium at low temperature
Improvements in High Temperature
Shift Catalysts
 The high temperature shift duty
 HTS catalyst characteristics
 developments over time
 Typical HTS operational problems
 Improved catalysts and loading regimes
 Summary
High Temperature Shift
Operating Conditions
 Inlet CO 8 - 15 % / outlet CO 2 - 4 %
(dry)
 Bulk of CO conversion > 75 %
 Typical inlet temp of 335 - 360OC (640 -
680OF)
• recent improvements down to 300oC
(575oF)
 Temperature rise 55 - 65OC (100 - 120OF)
 Typical lives 3 - 5 years
High Temperature Shift
Catalyst Issues
 Over-reduction at low steam/dry gas
ratio
 Cr6+ content
 Sulfur content
 Activity
 Strength
High Temperature Shift
Modern Catalyst Features
 Iron/chromium/copper oxides catalyst
• typical composition 87 % / 10 % / 3% (wt)
 Active phase is magnetite, Fe3O4
• supplied as haematite, Fe2O3
• requires reduction
 Activity supplemented by Cu
• helps avoid over reduction of Fe3O4
 Low Cr6+ and SO4
2-
• typically < 50 (Cr) & < 300 ppmw (S) or better
High Temperature Shift
Catalyst Features
 To overcome the catalyst issues
• Over-reduction
 copper promotion
• Cr6+ content and sulfur content
 production route
• High stable activity & high strength
 dispersion of iron oxide, Cr2O3 and Cu crystallites
 low hexavalent chromium
 copper promotion
 micro-structure, particularly iron oxide
 catalyst pellet size options
VULCAN Series VSG-F101 incorporates all the
required features
High Temperature Shift
Catalyst Structure - General
Small crystals of magnetite
high surface area => high activity
Good dispersion of Cr2O3 (Cr3+)
gives strength to resist breakage in process
upsets (eg wetting)
gives high thermal stability
prevents sintering of Cu and Fe3O4
slows activity loss & increases life
Good dispersion of Cu
small crystallites => high Cu surface area =>
high activity
slows Cu sintering
50-700 A pore
o
Chrome Oxide
Crystal
Iron Oxide Crystals
High Temperature Shift
Catalyst Structure
Cu Crystals
Amorphous Structure
(achieved in VSG-F101)
Microstructure of HTS Catalysts
Crystalline Structure
(Competitor)
HTS Catalyst - Addition of Copper
1. Activity
 Activity increase due to Cu addition
• much higher intrinsic activity than Fe3O4
• increases shift activity
 Benefits are
• at same SOR inlet temperature, maintain
equilibrium for longer - extend life
• achieve equilibrium at lower SOR inlet
temperature - lower CO slip, higher H2 make,
slower sintering (deactivation)
• for same SOR inlet temperature and life -
decrease catalyst volume
HTS Catalyst - Addition of Copper
1. Activity
 Cu issues - overcome by catalyst design
• Cu sinters rapidly at HTS operating
temperatures
• high Cu levels weaken catalyst structure
 => stabilize by the Fe3O4/Cr2O3 micro-
structure
• Pore diffusion controls overall reaction rate
 cannot achieve full benefit of Cu intrinsic
activity
 => optimize pore structure to maximize
benefit
HTS Catalyst - Addition of Copper
2. Over-reduction
 Fe3O4 => FeO => Fe
• causes increased Fischer-Tropsch activity
• C laydown (2CO <=> C + CO2)
 For over-reduction to occur
• need R ~ 1.5 or higher
• corresponds to S/C approx 2.8 in reformer
Reducing (CO)+ (H2)
Oxidising (CO2) + (H2O)
= Pc = R
HTS Catalyst - Addition of Copper
2. Over-reduction
 CO2/CO phase equilibrium
 Cu increases activity
• rapidly increases p[CO2]/decreases p[CO]
300 350 400 450 500 550
0.5
0.7
0.9
1.1
1.3
1.5
1.7
1.9
Temperature (oC)
P[CO2]/P[CO]
Fe
Fe3O4
HTS Catalyst - Addition of Copper
2. Over-reduction
 H2O/H2 phase equilibrium
• rarely close to boundary
• Cu tends towards lower temperature
operation
300 350 400 450 500 550
0.1
0.2
0.3
0.5
0.7
1
Temperature (oC)
P[H2O]/P[H2]
Fe
Fe3O4
FeO
High Temperature Shift
Chromium (VI) Issues
 Cr6+ content must be low
• Cr6+ can form during manufacture
 means less Cr2O3 so affects stability
• Cr6+ is a Category 1 carcinogen
• Cr6+ is water soluble
 can be washed out of catalyst into
condensate system (particularly during
start-ups)
 loss of catalyst strength
• upon reduction, Cr6+ gives an exotherm
 40OC (72OF) per 1%
 danger of over-temperature (catalyst;
vessel)
Low Cr6+ High Cr6+
High Temperature Shift
Chromium (VI) Issues
High Cr6+Low Cr6+
Boiling water testWater soak test
Low Cr6+ : typically < 10 ppmw
High Temperature Shift
Sulfur Removal Issue
 Sulfur source
• residual sulfate from metal salts used in
catalyst manufacture
 Sulfur problem during initial reduction
• liberate H2S during initial catalyst reduction
• poison for LTS catalyst or PSA absorbent
 vent exit gas to prevent poisoning
 if not, consumes up to 1 volume LTS catalyst
per 20 volumes HTS catalyst
• duration depends on catalyst sulfate level
• prolongs commissioning
High Temperature Shift
Sulfur Removal Issue
 Sulfur level
• depends on manufacturing route
 sulfate route (older) ~ 5000 ppmw
 nitrate route (newer) ~ 200 ppmw
 Effect of de-sulfiding on reduction time
• duration depends on catalyst type
 nitrate route: complete in ~4 hours
after process gas
 sulphate route: hold for 5 - 10 hours
extra
Improvements in High
Temperature Shift Catalysts
 The high temperature shift duty
 HTS catalyst characteristics
 Typical HTS operational problems
 Improved catalysts and loading
regimes
 Summary
HTS Operational Problems
Catalyst Start Up
 Exotherm on steam addition
• Temperature “spike” sometimes observed
 new HTS catalyst; all vendors
• often 100 oC (180 oF) and up to 250oC (450oF)
 Root cause analysis
• not understood for many years
• correlated with long hold on N2 flow at >> 200 oC
• catalyst surface becomes “super dry”
• steam re-hydrates surface (heat of hydration)
1st Steam
Introduced
0 20 40 60 80 100
250
300
350
400
450
500
600
700
800
Time, minutes
Temperature(°C)
Temperature(°F)
Inlet
Top
Mid
Bot
Exotherm on Steam
New HTS Catalyst
Large European Plant
HTS Operational Problems
Catalyst Start Up
 Exothermic Rehydration Case Study
• VSG-F101 Series installed
• subsequent performance unaffected
• demonstrates good catalyst thermal
stability
 Rehydration phenomenon
• avoid by controlling drying conditions
during start-up
HTS Operational Problems
Catalyst Start Up
 Exotherm due to H2 ingress
• passing valve allowed H2 entry
 before reduction started
 on hold at 200+ oC
• new VSG-F101 Series installed
• significant exotherm
• subsequent performance unaffected
 on line > 4 years
• demonstrates good catalyst thermal
stability
HTS Operational Problems
Upstream Boiler Leaks
 Boiler leaks
• relatively common
• more likely at high plant rates
 Effects
• possible catastrophic catalyst failure due
to thermal shock
• pressure drop increase due to
 boiler solids fouling of the catalyst
 catalyst breakage (droplet
impingement)
HTS Operational Problems
Upstream Boiler Leaks
 Boiler leak case study - background
• large new Syngas plant
• Vulcan Series catalysts throughout
 including VSG-F101
• observed increase in HTS pressure drop
• data consistency check indicated showed
high steam ratio in the shift section
• boiler leak suspected
HTS Operational Problems
Upstream Boiler Leaks
 Boiler leak case study - actions/outcome
• catalyst inspected
• boiler leak confirmed
• catalyst skimmed
• plant restarted at 100% rate with 40%
less HTS catalyst
 space velocity increased to 9000 h-1
• catalyst still achieved maximum
conversion
HTS Operational Problems
Unplanned Catalyst Oxidation
 Exothermic Catalyst Oxidation
• activated (reduced) catalysts
 reacts with air rapidly and exothermically
 catalyst oxidizes with possible thermal
damage
 Case Study from a large syngas plant
• air machine delivery valve failed
• huge HTS catalyst temperatures increase
 middle = 635oC (1175oF) and exit = 540oC
(1100oF)
• temperatures stayed high ~30 minutes
HTS Operational Problems
Unplanned Catalyst Oxidation
 Catalyst Oxidation Case Study - outcomes
• catalyst activity impaired
 flatter reaction profile
 CO slip has increased from < 3% to
>4%
• VSG-F101 remains operable
 capable of an acceptable
performance until a convenient
change is planned
 despite significant over-temperature
Improvements in High Temperature
Shift Catalysts
 The high temperature shift duty
 HTS catalyst characteristics
 Typical HTS operational problems
 Improved catalysts
 VSG-F101 Series
 Summary
VSG-F101 Series
Step change improvement for HTS
 Launched almost three years ago
 Reformulated catalyst
• similar bulk composition to previous grades
• modified iron oxide pore structure
 patented use of acicular iron oxide
 Increased activity by 20%
• reduced diffusion limitation
 Increased in-service strength +100%
VSG-F101 Series
Properties
 Composition
 Fe
 Ni
 Cu
 (+ Al2O3 )
 Form
 VSG-F101 9 mm (dia) x 5 mm pellets
 VSG-F101 5 mm (dia) x 8 mm spheres
 Charged bulk density
 0.8-1.1 kg/l (50-69 lb /ft3)
VSG-F101 Series
Improved HTS Catalyst
 Structural promoter
• Improves strength
 better able to withstand plant upsets such
as boiler leaks
 higher strength through life
• Modifies pore structure
 wider pore distribution
 allows easier diffusion through wide pores
to high surface area active sites in small
pores
 increases activity
Structural
promoter
Micrograph showing catalyst enlarged x140,000
VSG-F101 Series
Modified Microstructure
RadialCrushStrength
(Kg/cm)
VSG-F101 Competitor A Competitor B Competitor C
0
2
4
6
8
10
12
VSG-F101 Series Reduced Strength
Crush strength after 2
weeks operation
Months on Line
0
0
10
20
30
40
50
10 20 30
Start of Leak
Comp. A
VSG-F101
Limit
VSG-F101 Comparison
Boiler Leak
Months in Operation
CatalystActivity
2
3
4
5
6
7
8
9
10 20 30 400
Design for
VSG-F101
Expected for
VSG-F101
Measured
Activity
VSG-F101 in a
Large Syngas Plant in China
VSG-F101 Large Size for Low Pressure
Drop
 VSG-F101DG
• 14 mm dia x 5 mm height domed pellets
• pressure drop is 40 % lower than VSG-
F101
• larger pellet => stronger
 better resistance to plant upsets
• activity ~90 % that of VSG-F101 at 360 oC
 THUS exceeds that of VSG-F101
Improvements in High Temperature
Shift Catalysts
 The high temperature shift duty
 HTS catalyst characteristics
 Typical HTS operational problems
 Improved catalysts and loading regimes
 Summary
Summary
 Fundamentals of HTS Catalysis
 HTS catalysts have improved
• VULCAN Series VSG-F101
 Operational issues still affect HTS
catalysts
• start up exotherms; boiler leaks;
catalyst breakage; reoxidation
 Active and robust VSG-F101 Series
(HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev Overview

Más contenido relacionado

La actualidad más candente

La actualidad más candente (20)

Reduction and Start-Up of Steam Reforming Catalyst
Reduction and Start-Up of Steam Reforming CatalystReduction and Start-Up of Steam Reforming Catalyst
Reduction and Start-Up of Steam Reforming Catalyst
 
The Benefits and Disadvantages of Potash in Steam Reforming
The Benefits and Disadvantages of Potash in Steam ReformingThe Benefits and Disadvantages of Potash in Steam Reforming
The Benefits and Disadvantages of Potash in Steam Reforming
 
Shift Conversion Catalysts - Operating Manual
Shift Conversion Catalysts - Operating ManualShift Conversion Catalysts - Operating Manual
Shift Conversion Catalysts - Operating Manual
 
Ammonia CO2 Removal Systems
Ammonia CO2 Removal SystemsAmmonia CO2 Removal Systems
Ammonia CO2 Removal Systems
 
Steam Reforming - Types of Reformer Design
Steam Reforming - Types of Reformer DesignSteam Reforming - Types of Reformer Design
Steam Reforming - Types of Reformer Design
 
Feedstock Purfication in Hydrogen Plants
Feedstock Purfication in Hydrogen PlantsFeedstock Purfication in Hydrogen Plants
Feedstock Purfication in Hydrogen Plants
 
Benfield system
Benfield systemBenfield system
Benfield system
 
Steam Reforming - Carbon Formation
Steam Reforming - Carbon FormationSteam Reforming - Carbon Formation
Steam Reforming - Carbon Formation
 
Steam reforming - The Basics of Reforming
Steam reforming  - The Basics of ReformingSteam reforming  - The Basics of Reforming
Steam reforming - The Basics of Reforming
 
Steam Reforming - (ATM) Approach to Equilibrium
Steam Reforming - (ATM) Approach to EquilibriumSteam Reforming - (ATM) Approach to Equilibrium
Steam Reforming - (ATM) Approach to Equilibrium
 
Start Up Procedures for Primary Reforming Catalyst
Start Up Procedures for Primary Reforming CatalystStart Up Procedures for Primary Reforming Catalyst
Start Up Procedures for Primary Reforming Catalyst
 
Ammonia Formation over Steam Reforming Catalysts
Ammonia Formation over Steam Reforming CatalystsAmmonia Formation over Steam Reforming Catalysts
Ammonia Formation over Steam Reforming Catalysts
 
Secondary Reforming Burners
Secondary Reforming BurnersSecondary Reforming Burners
Secondary Reforming Burners
 
Water-Gas-Shift Reactor Loading & Unloading Considerations
Water-Gas-Shift Reactor Loading & Unloading ConsiderationsWater-Gas-Shift Reactor Loading & Unloading Considerations
Water-Gas-Shift Reactor Loading & Unloading Considerations
 
High Temperature Shift Catalyst Reduction Procedure
High Temperature Shift Catalyst Reduction ProcedureHigh Temperature Shift Catalyst Reduction Procedure
High Temperature Shift Catalyst Reduction Procedure
 
Steam Reforming - Tube Design
Steam Reforming - Tube DesignSteam Reforming - Tube Design
Steam Reforming - Tube Design
 
Secondary Reforming Flowsheets
Secondary Reforming FlowsheetsSecondary Reforming Flowsheets
Secondary Reforming Flowsheets
 
Ammonia Synthesis Flowsheet - Operator training
Ammonia Synthesis Flowsheet - Operator trainingAmmonia Synthesis Flowsheet - Operator training
Ammonia Synthesis Flowsheet - Operator training
 
Revamps for Ageing Methanol Plants
Revamps for Ageing Methanol PlantsRevamps for Ageing Methanol Plants
Revamps for Ageing Methanol Plants
 
Theory and Practice of Steam Reforming
Theory and Practice of Steam ReformingTheory and Practice of Steam Reforming
Theory and Practice of Steam Reforming
 

Destacado

Capital Projects Assessment [Infographic]
Capital Projects Assessment [Infographic]Capital Projects Assessment [Infographic]
Capital Projects Assessment [Infographic]
Gerard B. Hawkins
 

Destacado (14)

Capital Projects Assessment [Infographic]
Capital Projects Assessment [Infographic]Capital Projects Assessment [Infographic]
Capital Projects Assessment [Infographic]
 
Reformer Tube Metallurgy: Design Considerations; Failure Mechanisms; Inspecti...
Reformer Tube Metallurgy: Design Considerations; Failure Mechanisms; Inspecti...Reformer Tube Metallurgy: Design Considerations; Failure Mechanisms; Inspecti...
Reformer Tube Metallurgy: Design Considerations; Failure Mechanisms; Inspecti...
 
Hydrogen Plant Flowsheet - Effects of Low Steam Ratio
Hydrogen Plant Flowsheet - Effects of Low Steam RatioHydrogen Plant Flowsheet - Effects of Low Steam Ratio
Hydrogen Plant Flowsheet - Effects of Low Steam Ratio
 
Refinery Fluid Catalytic Cracking Unit Sales Market Overview, Size, Share And...
Refinery Fluid Catalytic Cracking Unit Sales Market Overview, Size, Share And...Refinery Fluid Catalytic Cracking Unit Sales Market Overview, Size, Share And...
Refinery Fluid Catalytic Cracking Unit Sales Market Overview, Size, Share And...
 
Methane Steam Reformer Re-tube Studies
Methane Steam Reformer Re-tube StudiesMethane Steam Reformer Re-tube Studies
Methane Steam Reformer Re-tube Studies
 
Catalyst Catastrophes in Syngas Production - I
Catalyst Catastrophes in Syngas Production - ICatalyst Catastrophes in Syngas Production - I
Catalyst Catastrophes in Syngas Production - I
 
Theory and Operation of Methanation Catalyst
Theory and Operation of Methanation CatalystTheory and Operation of Methanation Catalyst
Theory and Operation of Methanation Catalyst
 
Site Safety Awareness
Site Safety AwarenessSite Safety Awareness
Site Safety Awareness
 
Water Gas Shift & Hydrogen Purification Section Flowsheet
Water Gas Shift & Hydrogen Purification Section FlowsheetWater Gas Shift & Hydrogen Purification Section Flowsheet
Water Gas Shift & Hydrogen Purification Section Flowsheet
 
Steam Reforming - Poisons
Steam Reforming - PoisonsSteam Reforming - Poisons
Steam Reforming - Poisons
 
Gas Heated Reforming - An Overview
Gas Heated Reforming - An OverviewGas Heated Reforming - An Overview
Gas Heated Reforming - An Overview
 
Steam Reforming - Catalyst Loading
Steam Reforming - Catalyst LoadingSteam Reforming - Catalyst Loading
Steam Reforming - Catalyst Loading
 
Water Gas Shift Reactor Design
Water Gas Shift Reactor DesignWater Gas Shift Reactor Design
Water Gas Shift Reactor Design
 
Catalytic Reforming: Catalyst, Process Technology and Operations Overview
Catalytic Reforming:  Catalyst, Process Technology and Operations OverviewCatalytic Reforming:  Catalyst, Process Technology and Operations Overview
Catalytic Reforming: Catalyst, Process Technology and Operations Overview
 

Similar a (HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev Overview

Thermal Power Plants
Thermal Power PlantsThermal Power Plants
Thermal Power Plants
peeyush95
 
Hydrogen production in refinery
Hydrogen production in refineryHydrogen production in refinery
Hydrogen production in refinery
Anupam Basu
 
dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...
dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...
dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...
AJAYKUMAR801605
 

Similar a (HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev Overview (20)

Introduction To Syngas Plant Flowsheet Options
Introduction To Syngas Plant Flowsheet OptionsIntroduction To Syngas Plant Flowsheet Options
Introduction To Syngas Plant Flowsheet Options
 
(LTS) Low Temperature Shift Catalyst - Comprehensive Overview
(LTS) Low Temperature Shift Catalyst - Comprehensive Overview(LTS) Low Temperature Shift Catalyst - Comprehensive Overview
(LTS) Low Temperature Shift Catalyst - Comprehensive Overview
 
Chapter 6c -_ht_design_consideration_-_latest
Chapter 6c -_ht_design_consideration_-_latestChapter 6c -_ht_design_consideration_-_latest
Chapter 6c -_ht_design_consideration_-_latest
 
DEBOTTLENECKING METALLURGICAL AND SULPHUR-BURNING SULPHURIC ACID PLANTS: CAPA...
DEBOTTLENECKING METALLURGICAL AND SULPHUR-BURNING SULPHURIC ACID PLANTS: CAPA...DEBOTTLENECKING METALLURGICAL AND SULPHUR-BURNING SULPHURIC ACID PLANTS: CAPA...
DEBOTTLENECKING METALLURGICAL AND SULPHUR-BURNING SULPHURIC ACID PLANTS: CAPA...
 
HTS and LTS Reactors.pdf
HTS and LTS Reactors.pdfHTS and LTS Reactors.pdf
HTS and LTS Reactors.pdf
 
Hydrogen Plant - Normal Operations
Hydrogen Plant - Normal OperationsHydrogen Plant - Normal Operations
Hydrogen Plant - Normal Operations
 
Hydrocarbon Feed Purification for Ammonia Plants
Hydrocarbon Feed Purification for Ammonia PlantsHydrocarbon Feed Purification for Ammonia Plants
Hydrocarbon Feed Purification for Ammonia Plants
 
O&amp;m of boiler
O&amp;m of boilerO&amp;m of boiler
O&amp;m of boiler
 
Avoid syn gas catalyst mal operation
Avoid syn gas catalyst mal operationAvoid syn gas catalyst mal operation
Avoid syn gas catalyst mal operation
 
Key lessons to optimise ammonia plant
Key lessons to optimise ammonia plantKey lessons to optimise ammonia plant
Key lessons to optimise ammonia plant
 
Ammonia Plant - Methanation Operations
Ammonia Plant - Methanation OperationsAmmonia Plant - Methanation Operations
Ammonia Plant - Methanation Operations
 
Thermal Power Plants
Thermal Power PlantsThermal Power Plants
Thermal Power Plants
 
nitrogen_syngas_article_controlling_the_stresses_of-the_primary_reformer_may_...
nitrogen_syngas_article_controlling_the_stresses_of-the_primary_reformer_may_...nitrogen_syngas_article_controlling_the_stresses_of-the_primary_reformer_may_...
nitrogen_syngas_article_controlling_the_stresses_of-the_primary_reformer_may_...
 
AIChE 2018 improving catalytic reformer heaters using split flow technology rev2
AIChE 2018 improving catalytic reformer heaters using split flow technology rev2AIChE 2018 improving catalytic reformer heaters using split flow technology rev2
AIChE 2018 improving catalytic reformer heaters using split flow technology rev2
 
Principles of Pre-reforming Technology
Principles of Pre-reforming TechnologyPrinciples of Pre-reforming Technology
Principles of Pre-reforming Technology
 
Hydrogen production in refinery
Hydrogen production in refineryHydrogen production in refinery
Hydrogen production in refinery
 
Fischer tropsch
Fischer tropschFischer tropsch
Fischer tropsch
 
SRU Troubleshooting
SRU TroubleshootingSRU Troubleshooting
SRU Troubleshooting
 
dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...
dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...
dimpfolderssecondsemforrefiningmodulesslides11hydrogenproduction-091009115333...
 
Blast furnace process-Dry and wet coke in blast furnace
Blast furnace process-Dry and wet coke in blast furnaceBlast furnace process-Dry and wet coke in blast furnace
Blast furnace process-Dry and wet coke in blast furnace
 

Más de Gerard B. Hawkins

GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy Gases
GAS DISPERSION -  A Definitive Guide to Accidental Releases of Heavy GasesGAS DISPERSION -  A Definitive Guide to Accidental Releases of Heavy Gases
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy Gases
Gerard B. Hawkins
 
Theory of Carbon Formation in Steam Reforming
Theory of Carbon Formation in Steam Reforming Theory of Carbon Formation in Steam Reforming
Theory of Carbon Formation in Steam Reforming
Gerard B. Hawkins
 
Adiabatic Reactor Analysis for Methanol Synthesis Plant Note Book Series: P...
Adiabatic Reactor Analysis for Methanol Synthesis   Plant Note Book Series: P...Adiabatic Reactor Analysis for Methanol Synthesis   Plant Note Book Series: P...
Adiabatic Reactor Analysis for Methanol Synthesis Plant Note Book Series: P...
Gerard B. Hawkins
 
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
Gerard B. Hawkins
 
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...
Gerard B. Hawkins
 

Más de Gerard B. Hawkins (20)

Pressure Relief Systems Vol 2
Pressure Relief Systems   Vol 2Pressure Relief Systems   Vol 2
Pressure Relief Systems Vol 2
 
Pressure Relief Systems
Pressure Relief Systems Pressure Relief Systems
Pressure Relief Systems
 
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy Gases
GAS DISPERSION -  A Definitive Guide to Accidental Releases of Heavy GasesGAS DISPERSION -  A Definitive Guide to Accidental Releases of Heavy Gases
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy Gases
 
101 Things That Can Go Wrong on a Primary Reformer - Best Practices Guide
101 Things That Can Go Wrong on a Primary Reformer -  Best Practices Guide101 Things That Can Go Wrong on a Primary Reformer -  Best Practices Guide
101 Things That Can Go Wrong on a Primary Reformer - Best Practices Guide
 
El impacto en el rendimiento del catalizador por envenenamiento y ensuciamien...
El impacto en el rendimiento del catalizador por envenenamiento y ensuciamien...El impacto en el rendimiento del catalizador por envenenamiento y ensuciamien...
El impacto en el rendimiento del catalizador por envenenamiento y ensuciamien...
 
Theory of Carbon Formation in Steam Reforming
Theory of Carbon Formation in Steam Reforming Theory of Carbon Formation in Steam Reforming
Theory of Carbon Formation in Steam Reforming
 
Adiabatic Reactor Analysis for Methanol Synthesis Plant Note Book Series: P...
Adiabatic Reactor Analysis for Methanol Synthesis   Plant Note Book Series: P...Adiabatic Reactor Analysis for Methanol Synthesis   Plant Note Book Series: P...
Adiabatic Reactor Analysis for Methanol Synthesis Plant Note Book Series: P...
 
STEAMING PROCEDURE FOR VULCAN STEAM REFORMING CATALYSTS
STEAMING PROCEDURE FOR VULCAN STEAM REFORMING CATALYSTSSTEAMING PROCEDURE FOR VULCAN STEAM REFORMING CATALYSTS
STEAMING PROCEDURE FOR VULCAN STEAM REFORMING CATALYSTS
 
Calculation of an Ammonia Plant Energy Consumption:
Calculation of an Ammonia Plant Energy Consumption:  Calculation of an Ammonia Plant Energy Consumption:
Calculation of an Ammonia Plant Energy Consumption:
 
Calculation of Caloric Value and other Characteristic Data of Fuel Gas
Calculation of Caloric Value and other Characteristic Data of Fuel GasCalculation of Caloric Value and other Characteristic Data of Fuel Gas
Calculation of Caloric Value and other Characteristic Data of Fuel Gas
 
Pickling & Passivation
Pickling & PassivationPickling & Passivation
Pickling & Passivation
 
Piping and Vessels Flushing and Cleaning Procedure
Piping and Vessels Flushing and Cleaning ProcedurePiping and Vessels Flushing and Cleaning Procedure
Piping and Vessels Flushing and Cleaning Procedure
 
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
 
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...
 
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGA...
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGA...PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGA...
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGA...
 
Getting the Most Out of Your Refinery Hydrogen Plant
Getting the Most Out of Your Refinery Hydrogen PlantGetting the Most Out of Your Refinery Hydrogen Plant
Getting the Most Out of Your Refinery Hydrogen Plant
 
EMERGENCY ISOLATION OF CHEMICAL PLANTS
EMERGENCY ISOLATION OF CHEMICAL PLANTS EMERGENCY ISOLATION OF CHEMICAL PLANTS
EMERGENCY ISOLATION OF CHEMICAL PLANTS
 
PRACTICAL GUIDE TO DEVELOPING PROCESS FLOW DIAGRAMS AND PRELIMINARY ENGINEER...
PRACTICAL GUIDE TO DEVELOPING PROCESS FLOW DIAGRAMS AND  PRELIMINARY ENGINEER...PRACTICAL GUIDE TO DEVELOPING PROCESS FLOW DIAGRAMS AND  PRELIMINARY ENGINEER...
PRACTICAL GUIDE TO DEVELOPING PROCESS FLOW DIAGRAMS AND PRELIMINARY ENGINEER...
 
Purificación – Mecanismos de Reacción
Purificación – Mecanismos de Reacción Purificación – Mecanismos de Reacción
Purificación – Mecanismos de Reacción
 
Amine Gas Treating Unit - Best Practices - Troubleshooting Guide
Amine Gas Treating Unit  - Best Practices - Troubleshooting Guide Amine Gas Treating Unit  - Best Practices - Troubleshooting Guide
Amine Gas Treating Unit - Best Practices - Troubleshooting Guide
 

Último

Structuring Teams and Portfolios for Success
Structuring Teams and Portfolios for SuccessStructuring Teams and Portfolios for Success
Structuring Teams and Portfolios for Success
UXDXConf
 
Breaking Down the Flutterwave Scandal What You Need to Know.pdf
Breaking Down the Flutterwave Scandal What You Need to Know.pdfBreaking Down the Flutterwave Scandal What You Need to Know.pdf
Breaking Down the Flutterwave Scandal What You Need to Know.pdf
UK Journal
 
Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...
Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...
Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...
panagenda
 

Último (20)

AI presentation and introduction - Retrieval Augmented Generation RAG 101
AI presentation and introduction - Retrieval Augmented Generation RAG 101AI presentation and introduction - Retrieval Augmented Generation RAG 101
AI presentation and introduction - Retrieval Augmented Generation RAG 101
 
Extensible Python: Robustness through Addition - PyCon 2024
Extensible Python: Robustness through Addition - PyCon 2024Extensible Python: Robustness through Addition - PyCon 2024
Extensible Python: Robustness through Addition - PyCon 2024
 
Integrating Telephony Systems with Salesforce: Insights and Considerations, B...
Integrating Telephony Systems with Salesforce: Insights and Considerations, B...Integrating Telephony Systems with Salesforce: Insights and Considerations, B...
Integrating Telephony Systems with Salesforce: Insights and Considerations, B...
 
Easier, Faster, and More Powerful – Notes Document Properties Reimagined
Easier, Faster, and More Powerful – Notes Document Properties ReimaginedEasier, Faster, and More Powerful – Notes Document Properties Reimagined
Easier, Faster, and More Powerful – Notes Document Properties Reimagined
 
Continuing Bonds Through AI: A Hermeneutic Reflection on Thanabots
Continuing Bonds Through AI: A Hermeneutic Reflection on ThanabotsContinuing Bonds Through AI: A Hermeneutic Reflection on Thanabots
Continuing Bonds Through AI: A Hermeneutic Reflection on Thanabots
 
Oauth 2.0 Introduction and Flows with MuleSoft
Oauth 2.0 Introduction and Flows with MuleSoftOauth 2.0 Introduction and Flows with MuleSoft
Oauth 2.0 Introduction and Flows with MuleSoft
 
Structuring Teams and Portfolios for Success
Structuring Teams and Portfolios for SuccessStructuring Teams and Portfolios for Success
Structuring Teams and Portfolios for Success
 
Introduction to FDO and How It works Applications _ Richard at FIDO Alliance.pdf
Introduction to FDO and How It works Applications _ Richard at FIDO Alliance.pdfIntroduction to FDO and How It works Applications _ Richard at FIDO Alliance.pdf
Introduction to FDO and How It works Applications _ Richard at FIDO Alliance.pdf
 
Microsoft CSP Briefing Pre-Engagement - Questionnaire
Microsoft CSP Briefing Pre-Engagement - QuestionnaireMicrosoft CSP Briefing Pre-Engagement - Questionnaire
Microsoft CSP Briefing Pre-Engagement - Questionnaire
 
Powerful Start- the Key to Project Success, Barbara Laskowska
Powerful Start- the Key to Project Success, Barbara LaskowskaPowerful Start- the Key to Project Success, Barbara Laskowska
Powerful Start- the Key to Project Success, Barbara Laskowska
 
Long journey of Ruby Standard library at RubyKaigi 2024
Long journey of Ruby Standard library at RubyKaigi 2024Long journey of Ruby Standard library at RubyKaigi 2024
Long journey of Ruby Standard library at RubyKaigi 2024
 
ASRock Industrial FDO Solutions in Action for Industrial Edge AI _ Kenny at A...
ASRock Industrial FDO Solutions in Action for Industrial Edge AI _ Kenny at A...ASRock Industrial FDO Solutions in Action for Industrial Edge AI _ Kenny at A...
ASRock Industrial FDO Solutions in Action for Industrial Edge AI _ Kenny at A...
 
Google I/O Extended 2024 Warsaw
Google I/O Extended 2024 WarsawGoogle I/O Extended 2024 Warsaw
Google I/O Extended 2024 Warsaw
 
Syngulon - Selection technology May 2024.pdf
Syngulon - Selection technology May 2024.pdfSyngulon - Selection technology May 2024.pdf
Syngulon - Selection technology May 2024.pdf
 
Choosing the Right FDO Deployment Model for Your Application _ Geoffrey at In...
Choosing the Right FDO Deployment Model for Your Application _ Geoffrey at In...Choosing the Right FDO Deployment Model for Your Application _ Geoffrey at In...
Choosing the Right FDO Deployment Model for Your Application _ Geoffrey at In...
 
The Value of Certifying Products for FDO _ Paul at FIDO Alliance.pdf
The Value of Certifying Products for FDO _ Paul at FIDO Alliance.pdfThe Value of Certifying Products for FDO _ Paul at FIDO Alliance.pdf
The Value of Certifying Products for FDO _ Paul at FIDO Alliance.pdf
 
How Red Hat Uses FDO in Device Lifecycle _ Costin and Vitaliy at Red Hat.pdf
How Red Hat Uses FDO in Device Lifecycle _ Costin and Vitaliy at Red Hat.pdfHow Red Hat Uses FDO in Device Lifecycle _ Costin and Vitaliy at Red Hat.pdf
How Red Hat Uses FDO in Device Lifecycle _ Costin and Vitaliy at Red Hat.pdf
 
Overview of Hyperledger Foundation
Overview of Hyperledger FoundationOverview of Hyperledger Foundation
Overview of Hyperledger Foundation
 
Breaking Down the Flutterwave Scandal What You Need to Know.pdf
Breaking Down the Flutterwave Scandal What You Need to Know.pdfBreaking Down the Flutterwave Scandal What You Need to Know.pdf
Breaking Down the Flutterwave Scandal What You Need to Know.pdf
 
Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...
Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...
Easier, Faster, and More Powerful – Alles Neu macht der Mai -Wir durchleuchte...
 

(HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev Overview

  • 1. Performance & Operation Improvements using VULCAN Series VSG-F101 High Temperature Shift Catalysts By: Gerard B. Hawkins Managing Director, CEO
  • 2. Improvements in High Temperature Shift Catalysts  The high temperature shift duty  introduction and theory  HTS catalyst characteristics  developments over time  Typical HTS operational problems  Improved catalysts  VULCAN Series VSG-F101 Series  Summary
  • 3. Improvements in High Temperature Shift Catalysts  The high temperature shift duty  Introduction and theory  HTS catalyst characteristics  Typical HTS operational problems  Improved catalysts and loading regimes  Summary
  • 4. Introduction What is the Shift Reaction ?  Water gas shift reaction has two effects: • generates hydrogen from carbon monoxide & steam • converts CO to CO2 CO + H2O <=> CO2 + H2
  • 5. From Steam Reformer HTS LTS Methanation LTS (optional) H2 Introduction How to include a Shift Section ? Liquid CO2 Removal PSAHTS From Steam Reformer H2
  • 6. Theory - Equilibrium CO + H2O CO2 + H2 (+ heat) • Reaction is reversible • Forward reaction - moderately exothermic – equilibrium at lower temperature favors • more CO converted • more H2 produced • Cannot beat equilibrium !
  • 7. Theory - Reaction Rate  Reaction Rate depends on • distance from equilibrium  further from equilibrium => larger driving force • catalyst formulation/activity • operating temperature  Catalyst enables reaction to proceed  Higher temperature drives rate Ideal catalyst promotes rate to achieve equilibrium at low temperature
  • 8. Improvements in High Temperature Shift Catalysts  The high temperature shift duty  HTS catalyst characteristics  developments over time  Typical HTS operational problems  Improved catalysts and loading regimes  Summary
  • 9. High Temperature Shift Operating Conditions  Inlet CO 8 - 15 % / outlet CO 2 - 4 % (dry)  Bulk of CO conversion > 75 %  Typical inlet temp of 335 - 360OC (640 - 680OF) • recent improvements down to 300oC (575oF)  Temperature rise 55 - 65OC (100 - 120OF)  Typical lives 3 - 5 years
  • 10. High Temperature Shift Catalyst Issues  Over-reduction at low steam/dry gas ratio  Cr6+ content  Sulfur content  Activity  Strength
  • 11. High Temperature Shift Modern Catalyst Features  Iron/chromium/copper oxides catalyst • typical composition 87 % / 10 % / 3% (wt)  Active phase is magnetite, Fe3O4 • supplied as haematite, Fe2O3 • requires reduction  Activity supplemented by Cu • helps avoid over reduction of Fe3O4  Low Cr6+ and SO4 2- • typically < 50 (Cr) & < 300 ppmw (S) or better
  • 12. High Temperature Shift Catalyst Features  To overcome the catalyst issues • Over-reduction  copper promotion • Cr6+ content and sulfur content  production route • High stable activity & high strength  dispersion of iron oxide, Cr2O3 and Cu crystallites  low hexavalent chromium  copper promotion  micro-structure, particularly iron oxide  catalyst pellet size options VULCAN Series VSG-F101 incorporates all the required features
  • 13. High Temperature Shift Catalyst Structure - General Small crystals of magnetite high surface area => high activity Good dispersion of Cr2O3 (Cr3+) gives strength to resist breakage in process upsets (eg wetting) gives high thermal stability prevents sintering of Cu and Fe3O4 slows activity loss & increases life Good dispersion of Cu small crystallites => high Cu surface area => high activity slows Cu sintering
  • 14. 50-700 A pore o Chrome Oxide Crystal Iron Oxide Crystals High Temperature Shift Catalyst Structure Cu Crystals
  • 15. Amorphous Structure (achieved in VSG-F101) Microstructure of HTS Catalysts Crystalline Structure (Competitor)
  • 16. HTS Catalyst - Addition of Copper 1. Activity  Activity increase due to Cu addition • much higher intrinsic activity than Fe3O4 • increases shift activity  Benefits are • at same SOR inlet temperature, maintain equilibrium for longer - extend life • achieve equilibrium at lower SOR inlet temperature - lower CO slip, higher H2 make, slower sintering (deactivation) • for same SOR inlet temperature and life - decrease catalyst volume
  • 17. HTS Catalyst - Addition of Copper 1. Activity  Cu issues - overcome by catalyst design • Cu sinters rapidly at HTS operating temperatures • high Cu levels weaken catalyst structure  => stabilize by the Fe3O4/Cr2O3 micro- structure • Pore diffusion controls overall reaction rate  cannot achieve full benefit of Cu intrinsic activity  => optimize pore structure to maximize benefit
  • 18. HTS Catalyst - Addition of Copper 2. Over-reduction  Fe3O4 => FeO => Fe • causes increased Fischer-Tropsch activity • C laydown (2CO <=> C + CO2)  For over-reduction to occur • need R ~ 1.5 or higher • corresponds to S/C approx 2.8 in reformer Reducing (CO)+ (H2) Oxidising (CO2) + (H2O) = Pc = R
  • 19. HTS Catalyst - Addition of Copper 2. Over-reduction  CO2/CO phase equilibrium  Cu increases activity • rapidly increases p[CO2]/decreases p[CO] 300 350 400 450 500 550 0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 Temperature (oC) P[CO2]/P[CO] Fe Fe3O4
  • 20. HTS Catalyst - Addition of Copper 2. Over-reduction  H2O/H2 phase equilibrium • rarely close to boundary • Cu tends towards lower temperature operation 300 350 400 450 500 550 0.1 0.2 0.3 0.5 0.7 1 Temperature (oC) P[H2O]/P[H2] Fe Fe3O4 FeO
  • 21. High Temperature Shift Chromium (VI) Issues  Cr6+ content must be low • Cr6+ can form during manufacture  means less Cr2O3 so affects stability • Cr6+ is a Category 1 carcinogen • Cr6+ is water soluble  can be washed out of catalyst into condensate system (particularly during start-ups)  loss of catalyst strength • upon reduction, Cr6+ gives an exotherm  40OC (72OF) per 1%  danger of over-temperature (catalyst; vessel)
  • 22. Low Cr6+ High Cr6+ High Temperature Shift Chromium (VI) Issues High Cr6+Low Cr6+ Boiling water testWater soak test Low Cr6+ : typically < 10 ppmw
  • 23. High Temperature Shift Sulfur Removal Issue  Sulfur source • residual sulfate from metal salts used in catalyst manufacture  Sulfur problem during initial reduction • liberate H2S during initial catalyst reduction • poison for LTS catalyst or PSA absorbent  vent exit gas to prevent poisoning  if not, consumes up to 1 volume LTS catalyst per 20 volumes HTS catalyst • duration depends on catalyst sulfate level • prolongs commissioning
  • 24. High Temperature Shift Sulfur Removal Issue  Sulfur level • depends on manufacturing route  sulfate route (older) ~ 5000 ppmw  nitrate route (newer) ~ 200 ppmw  Effect of de-sulfiding on reduction time • duration depends on catalyst type  nitrate route: complete in ~4 hours after process gas  sulphate route: hold for 5 - 10 hours extra
  • 25. Improvements in High Temperature Shift Catalysts  The high temperature shift duty  HTS catalyst characteristics  Typical HTS operational problems  Improved catalysts and loading regimes  Summary
  • 26. HTS Operational Problems Catalyst Start Up  Exotherm on steam addition • Temperature “spike” sometimes observed  new HTS catalyst; all vendors • often 100 oC (180 oF) and up to 250oC (450oF)  Root cause analysis • not understood for many years • correlated with long hold on N2 flow at >> 200 oC • catalyst surface becomes “super dry” • steam re-hydrates surface (heat of hydration)
  • 27. 1st Steam Introduced 0 20 40 60 80 100 250 300 350 400 450 500 600 700 800 Time, minutes Temperature(°C) Temperature(°F) Inlet Top Mid Bot Exotherm on Steam New HTS Catalyst Large European Plant
  • 28. HTS Operational Problems Catalyst Start Up  Exothermic Rehydration Case Study • VSG-F101 Series installed • subsequent performance unaffected • demonstrates good catalyst thermal stability  Rehydration phenomenon • avoid by controlling drying conditions during start-up
  • 29. HTS Operational Problems Catalyst Start Up  Exotherm due to H2 ingress • passing valve allowed H2 entry  before reduction started  on hold at 200+ oC • new VSG-F101 Series installed • significant exotherm • subsequent performance unaffected  on line > 4 years • demonstrates good catalyst thermal stability
  • 30. HTS Operational Problems Upstream Boiler Leaks  Boiler leaks • relatively common • more likely at high plant rates  Effects • possible catastrophic catalyst failure due to thermal shock • pressure drop increase due to  boiler solids fouling of the catalyst  catalyst breakage (droplet impingement)
  • 31. HTS Operational Problems Upstream Boiler Leaks  Boiler leak case study - background • large new Syngas plant • Vulcan Series catalysts throughout  including VSG-F101 • observed increase in HTS pressure drop • data consistency check indicated showed high steam ratio in the shift section • boiler leak suspected
  • 32. HTS Operational Problems Upstream Boiler Leaks  Boiler leak case study - actions/outcome • catalyst inspected • boiler leak confirmed • catalyst skimmed • plant restarted at 100% rate with 40% less HTS catalyst  space velocity increased to 9000 h-1 • catalyst still achieved maximum conversion
  • 33. HTS Operational Problems Unplanned Catalyst Oxidation  Exothermic Catalyst Oxidation • activated (reduced) catalysts  reacts with air rapidly and exothermically  catalyst oxidizes with possible thermal damage  Case Study from a large syngas plant • air machine delivery valve failed • huge HTS catalyst temperatures increase  middle = 635oC (1175oF) and exit = 540oC (1100oF) • temperatures stayed high ~30 minutes
  • 34. HTS Operational Problems Unplanned Catalyst Oxidation  Catalyst Oxidation Case Study - outcomes • catalyst activity impaired  flatter reaction profile  CO slip has increased from < 3% to >4% • VSG-F101 remains operable  capable of an acceptable performance until a convenient change is planned  despite significant over-temperature
  • 35. Improvements in High Temperature Shift Catalysts  The high temperature shift duty  HTS catalyst characteristics  Typical HTS operational problems  Improved catalysts  VSG-F101 Series  Summary
  • 36. VSG-F101 Series Step change improvement for HTS  Launched almost three years ago  Reformulated catalyst • similar bulk composition to previous grades • modified iron oxide pore structure  patented use of acicular iron oxide  Increased activity by 20% • reduced diffusion limitation  Increased in-service strength +100%
  • 37. VSG-F101 Series Properties  Composition  Fe  Ni  Cu  (+ Al2O3 )  Form  VSG-F101 9 mm (dia) x 5 mm pellets  VSG-F101 5 mm (dia) x 8 mm spheres  Charged bulk density  0.8-1.1 kg/l (50-69 lb /ft3)
  • 38. VSG-F101 Series Improved HTS Catalyst  Structural promoter • Improves strength  better able to withstand plant upsets such as boiler leaks  higher strength through life • Modifies pore structure  wider pore distribution  allows easier diffusion through wide pores to high surface area active sites in small pores  increases activity
  • 39. Structural promoter Micrograph showing catalyst enlarged x140,000 VSG-F101 Series Modified Microstructure
  • 40. RadialCrushStrength (Kg/cm) VSG-F101 Competitor A Competitor B Competitor C 0 2 4 6 8 10 12 VSG-F101 Series Reduced Strength Crush strength after 2 weeks operation
  • 41. Months on Line 0 0 10 20 30 40 50 10 20 30 Start of Leak Comp. A VSG-F101 Limit VSG-F101 Comparison Boiler Leak
  • 42. Months in Operation CatalystActivity 2 3 4 5 6 7 8 9 10 20 30 400 Design for VSG-F101 Expected for VSG-F101 Measured Activity VSG-F101 in a Large Syngas Plant in China
  • 43. VSG-F101 Large Size for Low Pressure Drop  VSG-F101DG • 14 mm dia x 5 mm height domed pellets • pressure drop is 40 % lower than VSG- F101 • larger pellet => stronger  better resistance to plant upsets • activity ~90 % that of VSG-F101 at 360 oC  THUS exceeds that of VSG-F101
  • 44. Improvements in High Temperature Shift Catalysts  The high temperature shift duty  HTS catalyst characteristics  Typical HTS operational problems  Improved catalysts and loading regimes  Summary
  • 45. Summary  Fundamentals of HTS Catalysis  HTS catalysts have improved • VULCAN Series VSG-F101  Operational issues still affect HTS catalysts • start up exotherms; boiler leaks; catalyst breakage; reoxidation  Active and robust VSG-F101 Series