POx and Sour Shift Catalyst Applications

VULCAN Systems Technology
(POx) Partial Oxidation and Sour
Shift Catalyst Applications
A Business Unit of GBH Enterprises, Ltd.
Gerard B. Hawkins
Managing Director

Coal
An expanding market
for catalysts and
absorbents

Worldwide Energy Use

Wyoming Low-S Coal Mountain
80 ft wall of coal seam, Powder Rive basin = 40% of US Coal used today; 100yr supply

Products from Coal
• Power
• Conventional combustion
• Integrated Gasification Combined Cycle (IGCC)
• Ammonia
• Methanol
• Hydrogen
• FT Liquids
• Substitute Natural Gas (SNG)

Gasification applications
Power - IGCC
Air
Sep
Gasifier
Gas
Cleaning
Sulfur
Removal
Power
Turbine
Air
Coal
Sulfur
Flue
Gas
Power

Gasification for Power - IGCC
Demo units – 300 MW
USD 300 million

Power with CO2 Sequestration
Air
Sep
Gasifier
Sour
Shift
Acid Gas
Removal
Power
Turbine
Air
Coal
Sulfur +
CO2
Flue
Gas
Power

Coal to Chemicals
Synthesis Gas
Air
Sep
Gasifier
Sour
Shift
Acid Gas
Removal
Air
Coal
Sulfur + CO2
Methanol
FT
Ammonia
Hydrogen

Regional variations
• China – methanol, ammonia fuels
• USA - SNG
• India - fuels
• Australia - ?
• Europe – biomass gasification

• 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

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

Feedstocks
• Coal – China, USA
• In situ coal – Australia
• Tar sands - Alberta
• Heavy oil – not economic
• Biomass – future opportunity

Synthesis Gas
Air
Sep
Gasifier
Sour
Shift
Acid Gas
Removal
Air
Sulfur + CO2
Methanol
FT
Ammonia
Hydrogen

Gasification Technology Suppliers
• GE / Texaco
• Shell
• ConocoPhillips
• Siemens (Future Energy)
• Choren
• Lurgi
• Advantica
• Chinese

Air Separation Technology Suppliers
• Praxair
• Air Products
• Linde
• Air Liquide

Acid Gas Removal Technology Suppliers
• Linde (Rectisol)
• Lurgi (Rectisol)
• UOP (Selexol)
• BASF (MDEA)

Technology Suppliers
E-Gas
Slag
Raw gas
Coke
Slurry
Quench
water
Krupp-Uhde/Shell
Raw gas
HRSG
Burner
Slag
Cooling
screen
Burner
Slag
Raw gas
Burner
Raw gas
Slag
Refractory
lining
FUTURE ENERGY Texaco Conoco Phillips/

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 (2
nd
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

Gasification for Ammonia / Methanol
Chinese project using Shell technology

GSP gasifier building at Schwarze Pumpe

Choren…
• Biomass to FT diesel
• Part-owned by Shell
• Building demo plant

Choren demonstration plant in Freiberg

Lurgi…
• Long history
• Alberta hydrogen project
• European research efforts

High pressure test gasifier at Freiberg

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

Partial Oxidation Process
Oil or
Coal
Condensate
Oxygen
Quench
Chamber
Soot
Scrubber
Sour
Shift Beds
Syngas Product
Gasifier

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

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

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

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

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
A Business Unit of GBH Enterprises, Ltd.www.gbhenterprises.com

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

Robustness/Regenerability
 Maximum physical robustness
 Can be regenerated if Carbon/Coke like
polymer formation
 Partial activity recovery

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

Resistance to Fouling
SHIFT
CATALYST
Trap for Deposits
and contamination

Catalyst Developments
 Improved activity variants - smaller
reactors, higher CO conversion
 Lower pressure drop - optimization of
particle size/shape
 Manufacturing at new locations

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

Catalyst Developments - VIG SGS-
201/202/203
- High activity sour gas shift catalyst
- CoO/MoO3 on MgO/Al2O3 support

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

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

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

POx and Sour Shift Catalyst Applications

POx and Sour Shift Catalyst Applications

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