Worldwide Pollution

Control Association
Michigan Coal to Gas Seminar
J une 5-6, 2012
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SCR/CO Catalyst Considerations
Ken Jeffers
WPCA/Gulf Power
Coal to Gas Conversion Seminar
Detroit, FL
June 5-6, 2012
Topics
Regulatory Drivers for Controlling Emissions NO
x
, CO
SCR Catalyst for NO
x
control
CO oxidation catalyst
Regulatory Drivers - NO
x
Control
NO
2
is 1 of 6 criteria pollutants
Respiratory irritant, contributes to low-level ozone formation
Regulated per EPA NAAQS
MATS, Amendments to NSPS: NO
x
emission limit 0.7 lb/MWh
Further controls necessary per CSAPR which requires:
23 states to reduce SO
2
and NO
x
to help downwind states attain 2006
24-hour and/or 1997 annual PM
2.5
NAAQS
20 states to reduce Ozone Season NO
x
to help downwind areas attain
1997 8-hour Ozone NAAQS
CSAPR States
Regulatory Drivers - CO Control
CO is 1 of 6 criteria pollutants
Majority of CO emissions come from mobile sources
CO displaces oxygen to the heart and brain
Contributes to low-level Ozone formation
CO + 2O
2
CO
2
+ O
3
NAAQS for CO
8-hour average: </= 9 ppmv
1-hour average: </=35 ppmv
Fossil Fuel Air Emissions Comparison
(lb/MMBTU of Energy Input)
Pollutant Natural Gas Oil Coal
Carbon Dioxide 120 160 200
Carbon Monoxide 0.040 (?) 0.03 0.20
Nitrogen Oxides 0.35 0.40 0.40
Sulfur Dioxide 0.001 1.0 2.5
Particulates 0.007 0.08 2.7
Mercury 0.000 0.007 x 10
-3
0.016 x 10
-3
SCR Catalyst for NO
x
Control
SCR Configuration with Coal-fired Boilers
High Dust
Source: The Babcock and Wilcox Company www.babcock.com/products
SCR Configuration with Coal-fired Boilers
Low Dust
Air
Preheater
Hot-Side ESP
SCR Catalyst Types
Plate
Honeycomb Corrugated
Plate-type Catalyst
Composition
Stainless steel expanded mesh
substrate, coated with ceramic
material
TiO
2
, V-oxide/W-oxide/Mo-oxide
Notches formed into plates provide
separation
Inserted in element boxes with
variable spacing: 60 to 90 plates
Variable plate height up to 700 mm
Advantages
Ideal for high dust configurations
Plugging, erosion resistance
Low pressure loss
Honeycomb Catalyst
Composition
Homogeneously extruded ceramic with
square-opening cell structure
TiO
2
, V-oxide/W-oxide
Variable block height up to 1300 mm
Pitch: 2.1 mm 9.2 mm
Advantages
Ideal for low/no-dust applications
High active surface area per unit volume
pitch pitch
pitch pitch
Pitch = center to center distance from one plate/wall to the next
Catalyst Pitch and Structure
Plate-Type Structure
Flexible plates
Rectangular openings
Pitch: 5 to 7 mm
Honeycomb Structure
Rigid structure
Square openings
Pitch: 2.1 to 9.2 mm
Pitch Selection by Application
Application Plate Pitch Honeycomb Pitch
Natural Gas, Diesel -
2.1 mm (70 x 70 cell)
3.7 mm (40 x 40 cell)
Tail-End, Low-dust 5.0 5.6 mm
3.7 mm (40 x 40 cell)
6.7 mm (22 x 22 cell)
Fuel Oil 5.0 5.6 mm
4.9 mm (30 x 30 cell)
6.4 mm (23 x 23 cell)
Bituminous Coal 5.6 6.0 mm
6.7 mm (22 x 22 cell)
8.2 mm (18 x 18 cell)
PRB Coal 5.6 7.0 mm
8.2 mm (18 x 18 cell)
9.2 mm (16 x 16 cell)
Lignite 6.0 7.0 mm ? (no US examples)
Catalyst Modules for Utility SCRs
Catalyst elements arranged in steel frames
Plate 2 levels of 8 element boxes
Honeycomb 72 monoliths
Standardized cross-section
Possible to interchange catalyst types within
reactor
Module height varies with catalyst height
Suitable Operating Conditions
Flue Gas Temperature: 600 800 F
Flue gas linear flow velocity: 5.0 6.0 m/s
Thorough NH
3
-NO
x
mixing: 5% RMS (required for >85% deNOx with
low NH
3
slip)
For flue gas with particulate matter, need
Popcorn ash/LPA screens upstream of SCR reactor
Soot-blowers or sonic horns at catalyst layers
Means to keep catalyst dry and frost-free during outage periods
SCR Catalyst Deactivation
R
e
l
a
t
i
v
e

A
c
t
i
v
i
t
y
/
P
o
t
e
n
t
i
a
l
Operating Time
NG
Bituminous Coal
PRB Coal
Biomass
Masking:
Macroscopic blockage
of catalyst surface
by cemented fly ash
Plugging:
Microsopic blockage of
pore system
by small fly ash particles
Poisoning:
Deactivation of active
sites by chemical attack
Catalyst Surface
Pore
System
Small Fly Ash Particles
Catalyst Surface
Pore
System
Cemented Fly Ash
Catalyst Surface
Pore
System
Active Sites
Catalyst Deactivation Mechanisms
Advantages with Gas-firing
Catalyst Selection For Coal . . .
Large pitch to avoid ash plugging
Minimized SO
2
-SO
3
oxidation
Frequent replacement every 2 years
For Natural Gas firing . . .
Much slower catalyst deactivation longer catalyst life
Fewer catalyst replacements
No fly ash plugging
No Sulfur no ABS, can tolerate higher NH
3
slip
Possible reduced NO
x
reduction requirements
If 100% gas, can use higher cell density catalyst reduced volume
requirement
Sizing Examples
Base Bit Coal
Case
NG equal NO
x
load
NG reduced
NO
x
load
NO
x
in 300 ppmvd 300 ppmvd 240 ppmvd
NO
x
out 40 ppmvd 40 ppmvd 40 ppmvd
NO
x
Reduction 87% 87% 83%
NH
3
slip 2 ppmvd 2 ppmvd 5 ppmvd
Rel P0 1.00 0.83 0.77
Catalyst Pitch 5.6 mm plate 3.7 mm HC 3.7 mm HC
Relative Volume 1.00 0.26 0.21
Pressure drop 1.7 iwg 1.9 iwg 1.5 iwg
Catalyst Options for Coal to Gas Conversion
For Units already having SCR with coal-fired catalyst
Conversion to 100% Gas firing is OK
Remove portion of coal-fired catalyst for reuse in other coal units
Replace all coal-fired catalyst with gas-fired catalyst
If coal will be backup fuel or co-fired, gas-specific catalyst is not suitable
Fly ash plugging
High SO
2
SO
3
oxidation
If SCR required on unit after conversion
Conversion to 100% Gas firing install gas-fired catalyst
Conversion to Gas with Coal backup or co-firing gas and coal need catalyst
suitable for coal-firing.
CO Oxidation Catalyst
Oxidizes CO and VOCs to CO
2
Stainless steel foil or ceramic
honeycomb substrate, high surface
area alumina washcoat, Platinum
Group Metals (PGM) embedded in
washcoat
Blocks with 25 cpsi 400 cpsi
Standard block is 24 x 24, 200 cpsi
metal foil for gas turbine applications
Variable block cross-section possible
Metal foil depths of 1.5 5 inches
Catalyst conversion efficiency depends on catalyst durability, reactant
residence time and the active surface area of the catalyst
Catalyst activity maximized by dispersing the active metals throughout
the high surface-area washcoat on the substrate media
Substrate
Washcoat
Active Sites
Catalyst Conversion Efficiency
Catalyst Light-Off Temperature range at
which conversion occurs
CO Oxidation Catalyst Performance
Fuels Suitable for NG or ULSD
CO Reduction
50 - 95+% Range
80 - 90% Typical
VOC Reduction
0 70% Range
0 50% Typical
Pressure Drop
1.0 iwg Typical
Performance Guarantee Period
3 years or 5 years Typical
Oxidation Catalyst Placement
CCGT HRSG Example
Oxidation Catalyst Placement in a Boiler
Source: The Babcock and Wilcox Company www.babcock.com/products
Possible CO catalyst
location upstream from
NH
3
injection for SCR
Catalyst Deactivation Mechanisms
Thermal deactivation: (typically irreversible) Occurs above 1200 F
Failure of substrate material
Sintering of active catalytic species
Sintering of support
Reaction of catalyst materials
Catastrophic thermal event
Poisoning: (typically reversible)
Chemical (selective) contamination of active sites
Physical (non-selective) contamination
masking, fouling, plugging of cells/pores, washcoat attrition
Catalyst Deactivators (Poisons)
Heavy and Base Metals:
- Lead (Pb) - Iron (Fe)
- Arsenic (As) - Chrome (Cr)
- Zinc (Zn) - Phosphorous (P)
- Copper (Cu) - Silicon (Si)
- Sulfur (S) - Nickel (Ni)
- Mercury (Hg) - Antimony (Sb)
- Tin (Sn)
High Molecular Weight Organic Material
Dust and Particulates
CO Catalyst NOT SUITABLE FOR COAL-FIRED APPLICATIONS
Selective (Chemical) Poisoning
Example Sulfur can react directly with active site and degrade
performance.
Pt + S PtS alloy
Alloy has low activity
(For certain poisons it
is possible to reactivate
the catalyst by thermal
treatment)
Catalyst Regeneration or Cleaning Options
Thermal
Elevating Temperature
Oxidizes organic material
Physical
Vacuuming or Compressed Air Blowing
Removes dust and debris
Chemical (including DI Water)
Washing
Removes masking agents
Restores surface area
Reduces poison concentration
CO Catalyst Options if required after Coal to Gas
Conversion
Suitable for units converted to 100% Gas firing
Not suitable for coal firing (or fuels containing particulate and Sulfur)
Back-up fuel or co-firing
Suitable for low S fuel oil / ULSD / Light oil (?) used as back-up fuel.
Firing should be limited Typically < 500 hours per year
Not suitable for HFO
Summary Points
Gas-firing has many advantages for SCR
Slower deactivation longer lifetime
Low/No Sulfur No ABS, higher NH
3
slip tolerable
No fly ash/particulate plugging
May result in Lower NO
x
load, lower deNOx requirement
Low pitch, high cell density catalyst elements lower volume
requirement as compared to coal applications
Catalyst sized for natural gas not suitable for coal-firing
CO Oxidation catalyst suitable for gas-firing and low/no sulfur fuels
High rates of CO oxidation are possible
CO Oxidation catalyst is not suitable for coal-firing or fuels with
ash/particulate
Thank You!
Ken Jeffers
Sr. Applications Engineer
ken.jeffers@jmusa.com
678 341 7523