ammonia systems for scr - worldwide pollution control ...wpca.info/pdf/presentations/5) ammonia...
TRANSCRIPT
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Ammonia Supply Systems
for SCRWPCA/Duke NOx Seminar
June 7, 2005
Dr. Norman C. Foster
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Copyright 2005 Chemithon Enterprises
Why is Ammonia Required?
Ammonia (NH3) is the Reducing Agent for NOx
2 NH3 + 2 NOx + ½ O2 2 N2 + 3 H2O
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Copyright 2005 Chemithon Enterprises
N0x Control Using Ammonia
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Copyright 2005 Chemithon Enterprises
NH3 Injection System Example
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Copyright 2005 Chemithon Enterprises
Typical Ammonia Requirements
100‐5000 lb/h of Ammonia
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Copyright 2005 Chemithon Enterprises
Sources of Ammonia
Anhydrous Ammonia
Aqueous Ammonia
Urea
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia Properties
Molecular Weight ‐ 17.03
Vapor is 40% lighter than air
Flammable within narrow range 16‐25% in air
High heat of vaporizationUsed as refrigerantApproximately 588 btu/lb NH3
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Copyright 2005 Chemithon Enterprises
Characteristics of Anhydrous AmmoniaLiquid when Compressed or Cooled
Stored as a Liquid under pressure
1 Ft3 of Liquid produces 865 Ft3 of 100% pure NH3 Gas
1 Ft3 of Liquid must be diluted with 2,900,000 Ft3 air to reduce concentration below 300 ppm
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Anhydrous Ammonia Vapor Pressure
0
50
100
150
200
250
300
350
-50 0 50 100 150TEMPERATURE °F
PSIG
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Copyright 2005 Chemithon Enterprises
Effect of Pressure
When liquid anhydrous NH3 is released from storage pressure it cools
A drop from 200 psig (100oF) to atmospheric pressure cools ammonia to –28oF.
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia Hazards
EPA Regulated Toxic Substance40 CFR Parts 9 and 68
Requires storage at 250 psig or Refrigeration
OSHA poisonous gas list
Hazards in Transportation and Storage
Single tanker truck spill ‐ 20 acre lethal area
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia Regulatory Requirements
Transport, Handling & Incident Reporting: 49CFR 171‐180
Protection of Employees: 29CFR 1910, OSHA & DOL
Incident Reporting: 49 CFR 1904
Environmental Releases: 40 CFR 1‐799, FWPCA 1972, CWA 1977, CWA 1978, TSCA 1976, CERCLA 1980, SARA 1986
Emergency Planning and Community Right to Know: EPCRA 1986
Storage Tanks & Vessels: ANSI K61.1, ASME SEC VIII, Div 1
Process Piping: ANSI B31.3
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Ammonia Exposure LimitsLeast perceptible odor 5 ppmReadily detectable odor 20 – 50 ppmNo health impairment for prolonged exposure 50 – 100 ppmGeneral discomfort; no lasting health effect for shortexposure
150-200 ppm
Severe irritation; no lasting health effect for shortexposure
400 – 700 ppm
Dangerous less than ½ hour exposure may be fatal 2000- 3000 ppmRapidly fatal 5000- 10000 ppmImmediately fatal Over – 10000 ppm
From “Anhydrous Ammonia – Pamphlet G-2 Seventh Edition, Compressed GasInstitute
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Copyright 2005 Chemithon Enterprises
Uncontrolled Ammonia Releases
Ammonia Liquid refrigerates and forms lethal fog of Water/NH3
Typical Water/NH3 Cloud is white but may be invisible
Water/NH3 Clouds Move Unpredictably with Air Movement
Water/NH3 Clouds are heavier than air
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Copyright 2005 Chemithon Enterprises
Responding to an NH3 Release
Get out of the Area
Notify Emergency Response Staff
Isolate Ammonia Supply
Fog area with water spray
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia System
AmmoniaUn-Loading
AmmoniaStorage
AmmoniaPumping
AmmoniaVaporization
AmmoniaDilution
AmmoniaInjection
Safety Spray System
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia System Process
Ammonia is received by Tank TruckUnloaded using Unloading Bulkhead andUnloading Compressor System to Storage
Ammonia is pumped or flows by pressure fromstorage to the vaporizers
The operating vaporizer evaporates ammoniaAmmonia vapor is piped to NH3 metering/Dilution Air Skids
Ammonia is metered based on demand from SCR
Ammonia is metered into air and supplied to the Ammonia Injection Grid just upstream of the SCR.
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Copyright 2005 Chemithon Enterprises
Anhydrous NH3 System Unit Operations
• Safety Systems
• N2 Supply System
• Unloading Bulkhead
• Unloading Compressor System (optional)
• Ammonia Storage Tanks
• Ammonia Pumping System
• Ammonia Vaporizers
• Ammonia Metering and Dilution Air Systems
• Plant / Instrument Air Supply System
• Control System
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia Safety Systems
NH3 Sensor/Fog Water Areas
•NH3 Storage Tank Area
•Equipment Room
•Unloading Area
•Ammonia Metering Dilution Air Skids (3)
Safety Equipment
•Emergency Stops (E-Stops)
•Safety Shower Eyewash Stations
•NH3 Sensors
•Local Alarm Panels w/ Flashing Beacon & Horn
•Fog Water Systems
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Copyright 2005 Chemithon Enterprises
Emergency Spray System
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Copyright 2005 Chemithon Enterprises
Nitrogen Purge System
Why nitrogen (N2) Purge
•Used to purge
unloading arm connections.
•Eliminates NH3 from
connections.
•Eliminates O2 and H2O from
entering the system.
Equipment
•N2 cylinder rack
•Pressure reducing valve & pressure relief valve
•Pressure gauge and switch to alarm is low pressure supply.
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Copyright 2005 Chemithon Enterprises
Ammonia Unloading Bulkhead
•Equipment•Two Unloading Arms: Vapor & Liquid
•Automated liquid line valve, Emergency vapor line valve.
•Liquid line flow switch & vapor line pressure transmitter
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Copyright 2005 Chemithon Enterprises
Ammonia Storage Tanks
Equipment•Ammonia Storage Tanks, Rated 265 to 300 Psig
•Level, Pressure, and Liq. Temperature Transmitters
•Level Switch, Pressure safety valve manifold
•Piping system to select fill and supply tank.
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Copyright 2005 Chemithon Enterprises
NH3 Loading and Storage
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Copyright 2005 Chemithon Enterprises
Ammonia Pumping Systems
Equipment• Two Side Channel Pumps, one operates, one as inline spare
• Pressure Transmitter,
• Piping and automatic valves to select supply tank
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Copyright 2005 Chemithon Enterprises
NH3 Pumping
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia Tank
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Copyright 2005 Chemithon Enterprises
Anhydrous Ammonia Vaporizers
Equipment•Vaporizers may use either Steam, Electricity or Hot Water
•Two Vaporizers, one operates, one as inline spare
•NH3 Pressure, NH3 and Outlet water Temperature Transmitters,
•Piping and automatic valves to select vaporizer
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Copyright 2005 Chemithon Enterprises
NH3 Vaporizing
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Copyright 2005 Chemithon Enterprises
Anhydrous Storage Tank and Vaporizer Skid
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Copyright 2005 Chemithon Enterprises
Vaporizer Skid Control Panels
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Copyright 2005 Chemithon Enterprises
Liquid Ammonia Piping
•Do not block in piping system and components when full of liquidammonia. Thermal expansion of liquid ammonia will cause extremely high pressures. Ball
valves for
anhydrous
ammonia have
vented balls.
•Hydrostatic relief
valves on
piping system
prevent over
pressurizing.
Liq. NH3 Volume vs Temperature
2.55
2.6
2.65
2.7
2.75
2.8
2.85
2.9
-100.00 -50.00 0.00 50.00 100.00 150.00
Temperature (F)
Volu
me
(Ft^
3/10
0Lbs
)
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Copyright 2005 Chemithon Enterprises
Ammonia Metering & Dilution Air System
Equipment• Two dilution air blowers, one operates, one as inline spare
• NH3 and Air: Flow, Pressure & Temperature Transmitters
• Piping and automatic valves to isolate NH3 vapor and to select the operating blower
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Copyright 2005 Chemithon Enterprises
Ammonia Metering & Dilution
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Copyright 2005 Chemithon Enterprises
Dilution Air System
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Copyright 2005 Chemithon Enterprises
Aqueous Ammonia
EPA Regulated Toxic Substance
High energy costs to evaporate water588 BTU/ lb NH31000 BTU/ lb WaterAdditional heat required to prevent condensation
Concentration must be less than 20%
Transporting and Evaporating water
Higher Ammonia costs
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Copyright 2005 Chemithon Enterprises
Aqueous Ammonia System
Similar to Anhydrous Ammonia
Lower Pressure Storage Tanks
Fewer Safety Requirements
Uses much more energy to evaporate Water
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Copyright 2005 Chemithon Enterprises
Energy Required to Evaporate NH3
Ammonia Concentration
lbs NH3
Lbs Water/ lb NH3
BTU/lb NH3
Anhydrous NH3
1 0 588
28% NH3 1 2.57 3,159
19.5% NH3 1 4.13 4,716
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Copyright 2005 Chemithon Enterprises
Aqueous Ammonia Storage Vessel
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Copyright 2005 Chemithon Enterprises
Pump Skid
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Copyright 2005 Chemithon Enterprises
Urea
Safe non toxic stable material
Primary active component in fertilizer
Readily available
Delivered costs per pound of ammonia less than aqueous ammonia
Typical delivered costs about 1.5 to 2 times anhydrous per pound of ammonia
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Copyright 2005 Chemithon Enterprises
Chemithon SafeDeNOx®Urea‐to‐Ammonia Process
ScrubberSystem
Ammoniato
Process
Urea
SafeDeNOx® ReactorSystem
SafeDeNOx®ReactorSystem
Steam
UreaFeed
System
UreaStorageSystem
UreaFeed
System
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Copyright 2005 Chemithon Enterprises
Dry Urea Storage & Unloading
UREAFROM
TRUCK
DRY AIRTO
TRUCK
AIRDRYER
SILO
UREATO
SUPPLYSYSTEM
SILO SILO SILO
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Copyright 2005 Chemithon Enterprises
Dry Urea Storage
Truck can deliver up to 35 tons per load
Rail can deliver up to 100 tons per load
1,100 pounds of ammonia per ton of urea
Most economical form to store urea
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Copyright 2005 Chemithon Enterprises
Dry Urea Storage Benefits
Lower operating cost ‐ no heated tanks
Lower delivered cost
No spill containment required
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Copyright 2005 Chemithon Enterprises
Batch Urea Dissolving & Storage
UREADISSOLVING
TANK
STEAM
CONDENSATE
STEAM
CONDENSATE
RECYCLEH.E.
FE
FIC
CONDENSATE
RECYCLEPUMP
FEFI
UREATO
REACTOR
UREA FEEDPUMP
SC
FE
FIC
MAIN STORAGETANK
UREAFROM
TRUCK
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Copyright 2005 Chemithon Enterprises
Continuous Urea Dissolving Step
Can be continuous or batch
Requires density control
Mixing tanks are needed
Requires DI water service and storage
Best choice for smaller systems
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Copyright 2005 Chemithon Enterprises
Continuous Urea Dissolving System
UREADISSOLVER
STEAM
CONDENSATE
STEAM
CONDENSATE
UREAFROM
STORAGE
UREATO
REACTORUREAPUMP
FE
FICSC
CONDENSATE
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Copyright 2005 Chemithon Enterprises
Urea Melter System
UREAMELTER
STEAM
CONDENSATE
STEAM
CONDENSATE
UREAFROM
STORAGE
UREATO
REACTORUREAPUMP
FE
FICSC
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Copyright 2005 Chemithon Enterprises
Urea Melter System
No de‐ionized water needed
Urea melts at 271°F (133°C)
Molten urea has a low viscosity and is easily pumped
Similar to sulfurChemithon has over 40 years of experience in melting and handling sulfur
![Page 51: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/51.jpg)
Copyright 2005 Chemithon Enterprises
SafeDeNOx® Reactor System
UREAREACTOR
CONDENSATE
UREAFROMFEED
PUMPS
AMMONIAPRODUCT
FE
FIC
FE
FIC
STEAM
STEAM
FE STEAMCONDENSATE
FIC
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Copyright 2005 Chemithon Enterprises
SafeDeNOx®Process Reactions
Urea Decomposition(NH2)2CO +3H2O →CO2↑ + 2NH4OH urea water carbon ammonium
dioxide hydroxide
Neutralization of MAP2NH4OH + 2NH4H2PO4 →2(NH4)2HPO4 +2H20
“MAP” “DAP”
Decomposition of DAP2(NH4)2HPO4 →2NH4H2PO4 + 2NH3↑
“DAP” “MAP” ammoniavapor
![Page 53: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/53.jpg)
Copyright 2005 Chemithon Enterprises
SafeDeNOx®Overall Reaction
At equilibrium all three reactions occur simultaneously
Overall reaction(NH2)2CO + H2O → CO2↑ + 2NH3↑
urea water carbon ammoniadioxide vapor
![Page 54: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/54.jpg)
Copyright 2005 Chemithon Enterprises
SafeDeNOx® Catalyst Information
Mixture of Mono Ammonia di‐hydrogen Phosphate (MAP) and Di‐Ammonia hydrogen Phosphate (DAP) (excess)
It is a white, water‐soluble crystal, easy to add through the feed system.
3,300 lbs (1,500 kg) of catalyst for 1,400 lb/hr (635 kg/hr) reactor
![Page 55: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/55.jpg)
Copyright 2005 Chemithon Enterprises
SafeDeNOx®Reactor System
Uses self‐regenerating catalyst to accelerate the reaction
Mono‐ammonium phosphate (MAP)
Catalyst allows near stoichiometric levelsminimizes energy requirementsApproximately 3,500 BTU’s/lb (1,945 kcal/kg) NH3
![Page 56: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/56.jpg)
Copyright 2005 Chemithon Enterprises
SafeDeNOx® Response Rate
0
50
100
150
200
250
300
350
400
0 5 10 15 20 25 30
Time (minutes)
50%
Ure
a so
lutio
n Fe
ed R
ate
(lbs/
hr)
Ammonia FlowAmmonia Set PointUrea feed rate
90% Response rate within 5 MinutesFor a 55% change in demand.
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Copyright 2005 Chemithon Enterprises
SafeDeNOx® Response Rate
0
50
100
150
200
250
300
350
400
0 20 40 60 80 100 120 140 160
Time (min.)
Flow
rat
e (U
rea
lbs/
hr)
AmmoniaSet PointUrea Feed Rate
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Copyright 2005 Chemithon Enterprises
SafeDeNOx® Benefits
Responds quickly to changes in ammonia demand
Self‐regenerating catalyst significantly reduces urea residence time
Constant ammonia concentration (minimizes slip)
![Page 59: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/59.jpg)
Copyright 2005 Chemithon Enterprises
Startup of First Commercial System Reliability ‐ 98% Average
Plant Karn 1 & 2 Availability
92
94
96
98
100
June July August September
Perc
ent A
vaila
bilit
y
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Copyright 2005 Chemithon Enterprises
800 lb/hr (360 kg/hr) SafeDeNOx®System
![Page 61: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/61.jpg)
Copyright 2005 Chemithon Enterprises
Urea Storage and Handling
![Page 62: Ammonia Systems for SCR - Worldwide Pollution Control ...wpca.info/pdf/presentations/5) Ammonia Supply Systems for SCR.pdf · OSHA poisonous gas list ... Unloading Compressor System](https://reader031.vdocuments.net/reader031/viewer/2022030420/5aa6e1b67f8b9aee748b5178/html5/thumbnails/62.jpg)
Copyright 2005 Chemithon Enterprises
Urea Feeders & Melter
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Copyright 2005 Chemithon Enterprises
Thank you
Questions