pox and sour shift catalyst applications
DESCRIPTION
(POx) Partial Oxidation and Sour Shift Catalyst Applications Coal Technology Gasification Products From Coal Power Conventional combustion Integrated Gasification Combined Cycle (IGCC) Ammonia Methanol Hydrogen FT Liquids Substitute Natural Gas (SNG)TRANSCRIPT
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VULCAN Systems Technology (POx) Partial Oxidation and Sour
Shift Catalyst Applications
A Business Unit of GBH Enterprises, Ltd.
Gerard B. Hawkins Managing Director
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Coal
An expanding market for catalysts and
absorbents
A Business Unit of GBH Enterprises, Ltd.
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Worldwide Energy Use
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A Business Unit of GBH Enterprises, Ltd.
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Wyoming Low-S Coal Mountain
80 ft wall of coal seam, Powder Rive basin = 40% of US Coal used today; 100yr supply
A Business Unit of GBH Enterprises, Ltd.
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Products from Coal
• Power • Conventional combustion • Integrated Gasification Combined Cycle (IGCC)
• Ammonia • Methanol • Hydrogen • FT Liquids • Substitute Natural Gas (SNG)
A Business Unit of GBH Enterprises, Ltd.
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Gasification applications
Power - IGCC
Air Sep
Gasifier Gas Cleaning
Sulfur Removal
Power Turbine
Air
Coal
Sulfur Flue Gas
Power
A Business Unit of GBH Enterprises, Ltd.
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Gasification for Power - IGCC
Demo units – 300 MW USD 300 million
A Business Unit of GBH Enterprises, Ltd.
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Gasification applications
Power with CO2 Sequestration
Air Sep
Gasifier Sour Shift
Acid Gas Removal
Power Turbine
Air
Coal
Sulfur + CO2
Flue Gas
Power
A Business Unit of GBH Enterprises, Ltd.
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Coal to Chemicals
Synthesis Gas
Air Sep
Gasifier Sour Shift
Acid Gas Removal
Air
Coal
Sulfur + CO2
Methanol
FT
Ammonia
Hydrogen
A Business Unit of GBH Enterprises, Ltd.
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Regional variations • China – methanol, ammonia fuels
• USA - SNG
• India - fuels
• Australia - ?
• Europe – biomass gasification
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• A fossil fuel with low H/C composition – Means that added H2 needed to utilize it – Energy density is low – More CO2/KW of energy produced than other fossil
fuels • Many impurities that should be removed
– Hg, S-oxides, NOx, ash, heavy metals, Se, As – US gets 52% of its electricity from coal
• Contributes to 60% of total SO2, 33% of Hg, 25% of NOx, and >33% of CO2 emissions
– China gets >90% of its electricity from coal • Will China widely adopt emission controls?
• CO2 does not have a clear cost-effect link – China will be the biggest emitter of CO2 in 2025
• Will China adopt CO2 emission controls?
Issues with Coal
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VULCAN Systems Capability
Sour shift • Catalyst supplier for this duty • Many years of successful experience
Purification
• Flexibility to adapt absorbent to specific requirements for COS / H2S, Mercury, Arsenic
Methanol technology
• Catalyst supplier
SNG technology
A Business Unit of GBH Enterprises, Ltd.
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Gasification applications
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Feedstocks
• Coal – China, USA
• In situ coal – Australia
• Tar sands - Alberta
• Heavy oil – not economic
• Biomass – future opportunity
A Business Unit of GBH Enterprises, Ltd.
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Gasification applications
Synthesis Gas
Air Sep
Gasifier Sour Shift
Acid Gas Removal
Air Sulfur + CO2
Methanol
FT
Ammonia
Hydrogen
A Business Unit of GBH Enterprises, Ltd.
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Gasification Technology Suppliers • GE / Texaco • Shell • ConocoPhillips • Siemens (Future Energy) • Choren • Lurgi • Advantica • Chinese
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Air Separation Technology Suppliers • Praxair • Air Products • Linde • Air Liquide
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Acid Gas Removal Technology Suppliers • Linde (Rectisol) • Lurgi (Rectisol) • UOP (Selexol) • BASF (MDEA)
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Technology Suppliers
E-Gas
Slag
Raw gas
Coke
Slurry
Quenchwater
Krupp-Uhde/Shell
Raw gas
HRSG
Burner
Slag
Coolingscreen
Burner
SlagRaw gas
Burner
Raw gasSlag
Refractorylining
FUTURE ENERGY Texaco Conoco Phillips/
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Technology Suppliers
FUTURE ENERGY GmbH Chevron Texaco Shell / Krupp-Uhde Conoco Phillips / E-Gas
Cooling screen Cooling wall Shell / Prenflow Shell
Feed fuel coal, ash containing materials
oil,
ash free materials coal oil coal oil coal, residues
Fuel feeding system pneumatic, slurry slurry pneumatic slurry (50 – 70 % coal)
Fuel ash content > 1% < 1 %
Slag molten, granulated molten, granulated molten, granulated molten, granulated
Pressure up to 80 bar up to 80 bar up to 40 bar up to 80 bar up to 40 bar
Capacity up to 500 MW up to 500 MW up to 500 MW
Reactor lining cooling screen cooling wall (refr. lining) refractory lining partial cooling
screen refractory lining refractory lining
Relining interval 10 years 5 years 1 – 2 years 5 years 5 years 5 years
Reactor heat loss 1 – 5 % low medium low low low
Quench / gas cooling total quench radiant heat exchanger
total or partial qu. radiant heat exchanger
total quench/radiant heat exch. (dependent on feedstock)
integr. radiant HE and pre-cooling
by syngas
total or partial qu. external radiant heat exchanger
pre-quench (2nd gas. stage) on coal slurry (900 - 1000 °C)
Start-up time 1 hour 3 days 3 days 3 days 3 days
Availability (single gasifier) 90 - 95 % 95 % 85 % 95 % 70 – 80 % 95 % 70 % Carbon conversion rate > 99 % > 99 % > 84 % > 99 % > 94 %
Cold gas efficiency 78 - 83 % 83.5 % 70.5 % 83 % 83.5 % 84.0 %
Reference plants (number) 5 plants 130 licenses / 72 plants 85 plants 1 plant
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Gasification for Ammonia / Methanol Chinese project using Shell technology
A Business Unit of GBH Enterprises, Ltd.
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A Business Unit of GBH Enterprises, Ltd.
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GSP gasifier building at Schwarze Pumpe
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Technology Suppliers Choren…
• Biomass to FT diesel
• Part-owned by Shell
• Building demo plant
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Choren demonstration plant in Freiberg
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Technology Suppliers Lurgi…
• Long history
• Alberta hydrogen project
• European research efforts
A Business Unit of GBH Enterprises, Ltd.
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High pressure test gasifier at Freiberg
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Use of VULCAN Sour Shift System
Increases hydrogen production
Produce syngas suitable for ammonia or methanol production
Produce syngas for methanation to SNG
Converts COS to H2S
Converts HCN to NH3
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Partial Oxidation Process
Oil or Coal
Condensate
Oxygen
Quench Chamber
Soot Scrubber
Sour Shift Beds
Syngas Product
Gasifier
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Catalyst Impact on Shift System Design
VIG SGS-201/202/203 operates over a wide range of steam ratios
VIG SGS-201/202/203 achieves maximum CO conversion, as determined by reaction equilibrium
VIG SGS-201/202/203 resists the possibility of methanation
VIG SGS-201/202/203 operates with a wide range of sulfur in the feed
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Dew point flexibility
VIG SGS-201/202/203 is active enough to operate within + 30-50 deg C of the gas dew point and give high CO conversion
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Sulfur & Shift Equilibrium
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Metal-S + H2O Metal Oxide
+ H2S
Sulfur Tolerant Shift Catalyst
Sulfur Requirement/Catalyst Hydrolysis
-Catalyst to remain Sulfided for Maximum activity
- Steam/Sulfur ratio and temperature critical
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Steam Requirement
VIG SGS-201 /202/203 can operate at low steam ratio without risk of methanation: CO + H2O CO2 + H2
CO + 3H2 CH4 + H20
Likely to require a steam : CO ratio of 2.0
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Effect of Trace components
COS - converted to H2S (COS hydrolysis) Metal carbonyls - decomposed and
deposited as sulfides (FeS/NiS) Nitrogen compounds - HCN almost
completely removed Halogens - catalyst not affected at typical
concentrations C, dust - deposited on catalyst
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Catalyst Attributes
high mechanical strength to resist external fouling, water impingement
resist deposit build-up stability to withstand high steam partial pressure at
high temperature high activity - low CO, close approach to shift
equilibrium operation close to dew point - occasional wetting low pressure drop - minimum pressure drop
increase
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Robustness/Regenerability
Maximum physical robustness
Can be regenerated if Carbon/Coke like polymer formation
Partial activity recovery
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Operating Experience
Long lives • Upstream bed : 2 - 5 years • Downstream bed : 3 - 7 years
Operating Temperature • Normal : 200 - 500 deg C • Excursions up to 550 deg C
Operating Pressures • Experience with wide pressure range • Up to 80 bar • Tested successfully up to 100 bar • Can tolerate high steam partial pressure ~ 50 bar
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Resistance to Fouling
SHIFT CATALYST
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Trap for Deposits and contamination
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Catalyst Developments
Improved activity variants - smaller
reactors, higher CO conversion
Lower pressure drop - optimization of particle size/shape
Manufacturing at new locations
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Catalyst Developments - Geometry
Particle size / shape optimisation
scope to lower initial pressure drop and rate of pressure drop increase
potentially some small impact on activity
options for radial flow configurations
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Catalyst Developments - VIG SGS-201/202/203
- High activity sour gas shift catalyst - CoO/MoO3 on MgO/Al2O3 support
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Catalyst Developments - VIG SGS-201/202/203
Higher external surface area to trap poisons good resistance to impurities including
heavy metals (Pb, Hg, As) and soot Higher voidage
lower pressure drop High thermal resistance & high mechanical
strength slow rate of PD increase
Optimized loading with VIG SGS-202, VIG SGS-203 and AST Support to suit requirements
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Conclusion – Sour shift
Requirement for POX increasing in response to several factors
Potential for successful integration of Sour Shift application with gasification technology
Opportunities to build on success of VIG SGS-201/202/203 with developments to meet particular client needs
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Conclusions
GBH Enterprises have a leading position in supplying technology, catalysts and absorbents for gasification applications
• Full capability for sour shift, purification and methanol synthesis
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