AGENDA
Background
ProcessOverview
HigherValueProducts
WaterandEmissions
Storage
Safety
AMMONIATRAINING
CITYOFGRANDFORKS,ND
KRISTINECLARK &
MICHAEL GOFF
WHYDOWENEEDSYNTHETICNITROGEN
FERTILIZER?
AMMONIA
OVERVIEW
Nitrogenisavitalnutrientfor
plants
Populationgrowthhurtfood
supply
Naturalfertilizerreserves
weredepleted
BackgroundandHistory
Economics
PlantInformation
Nitrogenintheatmosphereis
instable,unreactiveform
WHYDOWENEEDSYNTHETICNITROGEN
FERTILIZER?
EARLYAMMONIAHISTORY
1909 FritzHaberfixednitrogeninairinalabexperiment
1913 CarlBosch,BASF,developedindustrialscaleprocess
WaterGasShift
IronAmmoniaCatalyst
1921 Casale designedtheirfirstammoniaconverter
1928 Uhdes firstammoniaplant100t/d
1943 Kellogglicensesitsfirstammoniaplant
1960s Haldor Topsoe pioneersradialflowconverters
1963 Kelloggpioneersfirstcentrifugalcompressors
1966 CFBraunfirstPurifierTM NH3plantonline
1970s Kelloggstandardizesthe1000t/dplant
1971 Kelloggsfirsthorizontalconverter
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8/27/2014
AMMONIACONVERTER
(OPPAU/LUDWIGSHAFEN1913)
RECENTHISTORY
1980s Kelloggdevelopslowenergydesign
1990s Casale axialradialconverterdesign
1990s MergerofBraunPurifier&Kelloggconventionaldesign
1990s Prereformer Revamps
2000s HTI,KBR,&Uhde developlargecapacitydesigns
2010s GasHeatedReformerRevamps
AMMONIAPRODUCTIONBYGLOBALREGION
AMMONIAENDUSES
Fertilizer 80%
Metalsprocessing,explosives,
plastics,cleaningagentsand
otherindustries.
IndustrialRefrigeration
WHEREAMMONIAISPRODUCEDAND
CONSUMED
10
AERIALVIEWOFLIMA,OH
11
12
8/27/2014
ROUGHPRODUCTIONECONOMICS
PLANTINFORMATION
Mainproductioncostisthefeedstock,whichis
naturalgas.
Numberofemployeesvaries,between100250
Ammoniaproductionresponsiblefor~17%ofthe
energyusedinthechemical/petrochemicalsector
Operations
Maintenance
Engineering
About2732MMBtu ofnaturalgasisrequiredto
produce1tonofammonia.
Footprint
RightnowAmmoniaissellingforabout$710perton
inthemidwest,and$450pertonontheGulfCoast.
Ammonia&Urea:1000x700
Offsites
At$710/tonpriceand$4/MMBtu gas,profitis
~$500/ton.
13
AMMONIAPRODUCTIONCOST
AMMONIACOSTVS NATURALGASCOST
Feedstock
Naturalgasandcoalaretheprimaryfeedstocks
forammoniaproduction
Naturalgascostis75%ofammoniaproduction
costexcludingcapitalcost
Coalcostis62%ofammoniaproductioncost
excludingcapitalcost
CapitalCost
Naturalgasbasedplantcapitalcostis47%of
ammoniaproductioncost
Coalgasificationbasedplantcapitalcostis66%
ofammoniaproductioncost
excludescapitalcost
Thepriceofnaturalgasisakeymetricinthenitrogenbusiness:
a$1perMMBtuincreaseaddsaround$33tothecostof
manufacturingoneshorttonofammonia.
15
AMMONIAANDUREAPRODUCTIONCOSTSBY
GLOBALREGION
16
AMMONIADEMANDANDCAPACITYOVERTIME
Chinaaccountsforthelargestshareofprojectednewcapacity.
Butwithrisingdomesticenergycostsandthepotentialfor
closuresofinefficientcapacity,itisunlikelytosignificantly
increaseitsnitrogenexports.
UkraineandWesternEuropesetfloorpriceforammoniaandurea.
17
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8/27/2014
AMMONIATRADEGLOBALPROFILE
NATURALGASANDAMMONIAPRICE
COMPARISON
Nitrogenpresentsgoodopportunitytoupgradenaturalgas.
20
UREATRADEGLOBALPROFILE
FERTILIZERWORLDOUTLOOK20142018
INTERNATIONALFERTILIZERINDUSTRYASSOCIATION(IFA)
Nearly200fertilizerprojectsplanned,$110Bininvestments
Projected146mtpy (30%)increaseinglobalfertilizer
productcapacity
Ammonia
Projected30%increaseinindustrialnitrogendemand
15.5%supplyincreasefrom153mtpy to176mtpy
9.1%demandincreasefrom148mtpy to161mtpy
Urea
Chinahasperiodicallybeentheworld'slargestureaexporter,although
itsannualvolumesfluctuatewithchangesingovernmentexportpolicies.
UnitedStatesureaimportsaveraged17,000stpd in2011.
60newureaplantsprojected(25inChina)
14.8%supplyincreasefrom188mtpy to216mtpy.
12.6%demandincreasefrom180mtpy to203mtpy
22
21
NITROGENFERTILIZERPRICESSINCE2000
US$/ShortTon
AnhydrousNH3
Nsolutions
AmmoniumNitrate
UAN
PROJECTEDNATURALGASPRICES
AmmoniumSulfate
900
800
700
600
500
400
300
200
100
0
'00
'01
'02
'03
'04
'05
'06
'07
'08
'09
'10
'11
'12
'13
Source:USDAEconomicResearchService
Lastupdated:July12,2013
Changesinfertilizerpricegenerallyreflectthoseseenforammonia.
23
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8/27/2014
AMMONIAPRODUCTION
Natural
Gas
PROCESSOVERVIEW
Fuel
Gas
Comb
Air
Process
Air
Feed
Sulfur
Removal
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
25
Warm
NH3
Cold
NH3
26
REFORMING
AMMONIAPLANT
Natural
Gas
Fuel
Gas
Comb
Air
Process
Air
Feed
Sulfur
Removal
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
Warm
NH3
Cold
NH3
28
STEAMREFORMINGCHEMISTRY
STEAMREFORMINGCHEMISTRY
ReformingConvertshydrocarbons(CxHy)toSyngas(H2+CO)
Steammethanereformingequilibriumfavoredby:
Lowerpressure
Highertemperature
Highsteamtocarbonratio
CH4 +H20
Ni
CnH(2n+2)+nH20
Ni
CO+3H2
highlyendothermic
nCO+(2n+1)H2
highlyendothermic
ShiftconvertsCOtoH2(nocatalystneededabove1500F)
CO+H2O
CO2 +H2
COshifttoH2 equilibriumfavoredby:
Lowertemperature
Highsteamtocarbonratio
mildlyexothermic
Requiresheatinput
Desulfurizedfeedgas+MPsteampreheatedto9001200F
Hotcombustiongasprovidesheatintocatalysttubesinprimary
reformer
Steammethanereformingreactionsareslowerthan
COshift
SteamtoDryGasRatiotypically3.0to3.2preventsClaydown
29
SteammethanereformingandCOshiftreactions
arereversible
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REFORMING
REFORMING
REFORMING
REFORMING
REFORMING
REFORMING
8/27/2014
SECONDARYREFORMER
SECONDARYREFORMER
Natural
Gas
Fuel
Gas
Comb
Air
Process
Air
Oxidation
Feed
Sulfur
Removal
Primary
Reformer
Oxidationprovidesheatforreforming
HP
Steam
Secondary
Reformer
Oxidationaddsnitrogeninstoichiometric rationeededforNH3
MPSteam
StackGas
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
WaterGasShift
CO2
Removal
Methanation
Condensate
Stripping
ShiftconvertsCOtoH2
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
CO+H2O
H2
MPSteam
PurgeGas
Warm
NH3
Cold
NH3
37
REFORMING
REFORMING
38
REFORMING
SHIFT
Natural
Gas
Fuel
Gas
Comb
Air
Process
Air
Feed
Sulfur
Removal
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
Warm
NH3
Cold
NH3
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8/27/2014
SHIFTREACTION
ShiftReactionEquilibriumConstantvs.
Temperature,DegF
CO+H2O
CO+H2O
FeCr
HighTemp
CuZn
LowTemp
EquilibriumConstant,K
WaterGasShift
ShiftconvertsCOtoH2
CO2 +H2 exothermic(goingtoCO2)
CO2 +H2
exothermic(goingtoCO2)
K=[p(CO2)*p(H2)]/[p(CO)*p(H2O)]
Where:p()isthepartialpressureofthegas
Inatmospheres(abs).
100
10
1
400
500
600
700
800
900
1000
Temperature,DegF
43
44
CO2 REMOVAL
SHIFTS
Feed
Sulfur
Removal
Natural
Gas
Fuel
Gas
Comb
Air
Process
Air
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
Warm
NH3
Cold
NH3
46
CO2 REMOVAL
METHODSOFCO2 REMOVAL
AftershiftingofCOtoCO2 (previousstep)topurify
thesyn gas.
Solidbedquickcyclemolsieveunits
Anyoxidepoisonssynthesiscatalyst(CO,CO2,
water,oxygen)
ScrubbingProcesses:
WontproducepureCO2 streamforurea
1.
2.
Highpercentageremovaldesiredtominimize
methanationlosses(nextstep)
Physicalsolvents
Chemicalsolvents
IfmakingUrea,CO2 neededasafeedstream
47
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PHYSICALSOLVENTS
CHEMICALSOLVENTS
Usesgassolubilitypropertiesunderpressurefor
absorptionandreductioninpressuretorelease
dissolvedgases
StrongalkalinesolventslikeMEAdontreallyrequire
highgastreatingpressures:
Highregenerationheatrequirement
Moderatecirculationrates
Takesfairlyhighpressureforabsorption
Somewhatweakeralkalinesolventslikeactivated
potassiumcarbonate,andactivatedMDEArequire
highergastreatingpressures:
Requireslargecirculationvolumes
Adequateforbulkremovalonly wontproducea
highpuritysyngas
Lowregenerationheatrequirements
Somewhathighercirculationrates
Examplesarewater,FluorSolvent,Selexol,Rectisol
49
BENFIELD
50
METHANATION
Natural
Gas
Fuel
Gas
Comb
Air
Process
Air
Feed
Sulfur
Removal
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
51
Natural
Gas
RequiredtoremoveresidualCOandCO2fromsyn gas
COpoisonsammoniasynthesiscatalyst
CO2 reactswithNH3 toformsolidcarbamate
NH2CO2NH4
Theeasiestandmosteconomicalmethodtoremove
residualCOandCO2 istoreactwithhydrogentomake
methane
Ni
Ni
52
SYNGAS COMPRESSION
METHANATION
CO+3H2
CO2 +4H2
Fuel
Gas
Comb
Air
Process
Air
Feed
Sulfur
Removal
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
CH4 +H2O
CH4 +2H2O
Warm
NH3
Cold
NH3
exothermic
exothermic
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
53
Warm
NH3
Cold
NH3
54
8/27/2014
AMMONIASYNTHESIS
SYN GASCOMPRESSOR
Feed
Sulfur
Removal
Natural
Gas
Fuel
Gas
Comb
Air
Process
Air
Primary
Reformer
MPSteam
StackGas
HP
Steam
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
Warm
NH3
Cold
NH3
56
AMMONIAISHARDTOMAKE
AMMONIASYNTHESIS
HaberBoschAmmoniaSynthesis
Thermodynamic
equilibriumofsynthesis
reaction
1.5H2 +0.5N2 =NH3
limitsconversion
ofH2 andN2 toNH3
TypicalOperatingEnvelope
57
RELATIVESYNTHESISREACTIONRATE
58
1,000TPDKELLOGGCONVERTER
Outlet
Outlet
CDismaximum
reactionratecurve
#1
#1
#2
#3
#2
#4
Inlet
59
OriginalAxialFlow
4BedQuench
Inlet
RetrofitRadialFlow
Topsoe S200
60
10
8/27/2014
QUENCHCONVERTERTEMPERATURE
PROFILE
RADIALFLOWWITHINTERBED HEAT
EXCHANGETEMPERATUREPROFILE
Quench
causesdilution
Heatexchange
causesno
dilutionfrom
quenching
Bed#2
Bed#1
Bed#3
Bed#1
Bed#2
61
CASALE ISOTHERMALCONVERTER
62
BENEFITSOFHIGHERCONVERSION
Lessrecyclegasflow
Lowersyn gascompressorhorsepower
Higherammoniadewpoint inconvertereffluent
Refrigerationdutyshiftstohighertemperatures
Lowerrefrigerationcompressorhorsepower
Betterplantefficiency
Debottleneckssyn loopinexistingplants
Higherammoniaproduction
Radialflow converters were a major
improvement in plant performance
63
AMMONIACONVERTERS
64
AMMONIACONVERTERS
11
8/27/2014
AMMONIACONVERTER
AMMONIACONVERTER
USERECYCLELOOPTOMAKEAMMONIA
AMMONIACONVERTER
Lowammoniaconcentration(<25mole%)inreactor
outletmeanslotsofunreactedgas
Recycleunreactedgasfromreactorbacktoreactor
inloop,afterseparatingproductammonia
Recycleconcentratesinerts (methane,argon)in
reactor
Mustpurgesomeunreactedgasfromsynthesisloop
tolimitbuildupofinerts
Maintaincirculatinggasat3:1H:Nratioforhighest
conversiontoammonia
70
LOOPINERTS
AMMONIASYN LOOP
Inerts methaneandargondontparticipatein
synthesis,takeupspace
Syngas ispurgedfromlooptolimitbuildupofinerts
Purgedsyn gasisalossofunconvertedH2 andN2
Needmoremakeupgastoreplacepurgedgasto
maintainproductionrate
Thereisabalancebetweenbenefitofloweringloop
inerts versuscostoflostH2andN2inpurgegas
Typicalconverterinletis815mole%methane+
argon
71
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8/27/2014
HYDROGENRECOVERY
AMMONIASYN LOOP
Feed
Sulfur
Removal
Natural
Gas
Fuel
Gas
Primary
Reformer
Comb
Air
MPSteam
StackGas
HP
Steam
Process
Air
Secondary
Reformer
HP
BFW
HP
Steam
HP
BFW
HT/LT
Shift
Conversion
HighTemp
Syngas
Cooling
MPSteam
Stripped
Condensate
CO2
CO2
Removal
Methanation
Condensate
Stripping
HP
HP
Steam BFW
Syngas
Comp
Ammonia
Synthesis
Hydrogen
Recovery
Ammonia
Refrigeration
H2
MPSteam
PurgeGas
Warm
NH3
Cold
NH3
74
HYDROGENRECOVERY
HIGHERVALUE
PRODUCTS
ProcessestorecoverH2fromhighpressuresyn
looppurgegas
Membraneseparation
Cryogenicseparation
Urea
DieselExhaustFluid
AmmoniumNitrate
UreaAmmoniumNitrate
AmmoniumThiosulfuate
AmmoniumPolyphosphate
RelativelypureH2 isrecoveredandreturnedtoloop
makeupgas
N2,CH4,Ar arerejectedandsenttoprimary
reformerfuel
Lessprocessfeednaturalgasisneededwithpurge
gasrecovery,improvesenergyefficiency
Watch out for helium when present, it is
concentrated in loop by purge gas recovery
75
AMMONIAPRODUCTS
76
AMMONIAUSESANDTOPWORLDPRODUCERS
Top10worldproducersaccountfor19%oftotalcapacity
77
78
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8/27/2014
UREASYNTHESIS
UREAUSES
Ureaismadefromammoniaandcarbondioxideathigh
pressure(2000psig)andhightemperature(350to400F).
Fertilizer(~90%)
Granules
Ureaammoniumnitrateaqueoussolution
Ureaisformedinatwostepreaction
2NH3+CO2NH2COONH4(ammoniumcarbamate)
NH2COONH4H2O+NH2CONH2(urea)
Plywood
Ureaformaldehyde
Ureamelamineformaldehyde
Ureasynthesisisexothermic.Theureasynthesisreactor
iscooledbygeneratinglowpressuresteamincoilsinside
thereactor.
SelectiveCatalyticReduction(SCR)ofNOx Emissions
Powergenerationfluegas
Dieselengineexhaustgas
RawureafromthereactorcontainsunreactedNH3and
CO2andammoniumcarbamate.Asthepressureis
reducedandheatappliedtheNH2COONH4decomposes
toNH3andCO2.Theammoniaandcarbondioxideare
recycled.
Explosives
Ureanitrate
79
UREASYNTHESISWITHCO2STRIPPING
80
MillionsofGallonsperYear
UREADEMANDFORDIESELEXHAUSTFLUID
AlldieselenginesmanufacturedintheUnitedStatesmustcomplywithUSEPASCRmandatesby2016.
USureaconsumptionforDEFisforecasttobemorethan1billiongallonsperyearby2020.
81
82
COKEGASIFICATIONTOUANPLANT
UREAAMMONIUMNITRATE(UAN)
UANisacommonlyusedfertilizerintheUSMidwestfor
corn.
PhysicalandChemicalCharacteristicsofUANSolutions
Grade,%N:
28
30
Ammoniumnitrate(%):
40
42
32
45
Urea(%):
30
33
35
Water(%):
30
25
20
Specificgravityat16C:
1.283
1.303
1.320
Saltouttemperature(C):
18
10
83
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8/27/2014
ADDITIONALHIGHERVALUEPRODUCTS
EMISSIONSAND
WASTEWATER
AmmoniumThiosulfate
Excellentsourceofsulfurforplantnutrition
12%N,26%S
AmmoniumPolyphosphate
10%N,34%Phosphate
AmmoniaProcessEmissions
UreaProcessEmissions
WaterSupply
WasteWater
85
AMMONIAPLANTEMISSIONS
86
PRIMARYREFORMEREMISSIONS
TypicalCombustionProducts
NitrogenOxides(NOx)
CarbonMonoxide(CO)
CarbonDioxide(CO2)
Methane(CH4)
NitrousOxide(N2O)
VolatileOrganicCompounds
(VOCs)
SulfurDioxideandParticulate
Matter(TraceAmounts)
87
88
CO2REMOVAL
CONDENSATESTRIPPING
CO2mustberemovedfromprocessgas
Processcondensatecontainsthefollowing:
Nonmethane OrganicCompounds
CarbonDioxide
Ammonia
Emissions
CarbonMonoxide
MEA/Piperazine (activator)
VOCs
Ammonia
Mediumpressuresteamusedtostripprocess
condensate
89
90
15
8/27/2014
OTHERPRODUCTEMISSIONS
WATEROVERVIEW
Urea
Thepurposeofwater/wastewatertreatmentis:
Ammonia
Particulatematter
AmmoniumNitrate
Ammonia
Nitricacid
Particulatematter
Toprovideforefficient,costeffectiveproduction
Toprotect/preservecapitalinvestment
Tomakeefficientuseofwaterresources
Tomeetregulatoryrequirements
NitricAcid
Nitricoxide
Nitrogendioxide
91
92
AMMONIAPLANTWATERMASSBALANCE
Chemicals
Reverse
Makeup Osmosis
Water
Makeup
Water
Softener
Ion
Exchange
CoolingTower
Chemicals
Losses
Boilers
Ammonia
Process
MAKEUPWATER
RiverWater
CityWater
WellWater
Evaporation Wastewater
Chemicals
Solids
93
94
PRETREATMENT
PRETREATMENT
Waterpretreatmentistheprocessofpreparingthe
plantrawwatersupplyfordirectuseorfurther
treatment
Softening
Softening Precipitationprocessusedtoreducescaling
constituentsprimarilyduetohardness
Softeningalsoreducessilicalevels
Softeningisinducedprincipallybytheadditionoflime
andsodaash
Consequently,thelevelofpretreatmentvaries
accordingtotherawwatersupplyandplantusage
95
96
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March2013
March2013
PRETREATMENT
HIGHPURITYTREATMENT
Filtration
ReverseOsmosis
Removalofsuspendedsolidsbyflowthrough
filtrationmedia
Generallyusedasapolishingstepfollowing
pretreatmentorastandaloneprocess
Filtermediamaterialandgradecanbespecifiedto
accomplishspecifictasks
IonExchange
97
March2013
March2013
HIGHPURITYTREATMENT
COOLINGTOWERCHEMISTRY
ReverseOsmosis
Analysis
(a)
Specific
Conductance
pH
Calcium
Silica
Chloride
Total Alkalinity
(b)
(c)
(d)
Frequency
Continuous
TBD
Continuous
Shift
Shift
Shift
Shift
8.0 8.5
400 ppm
100 ppm
180 ppm
150 ppm
Iron
Free Chlorine
Shift
3 ppm
10 minutes following 0.3 0.5 ppm
chlorination
Total Chlorine
March2013
March2013
COOLINGTOWERCHEMISTRY
BOILERCHEMISTRY
ChemicalFeeds
BoilerFeedwater
TotalHardness
DissolvedO2
Acid
Scale/CorrosionInhibitor
Oxidant ChlorineGasorBleach
BiSulfite(ifrequired)
NonDetect
0.007mg/lO2
BoilerWater
SpecificConductivity
Silica
150S/cm
2mg/lSiO2
102
17
8/27/2014
March2013
WASTEWATER
WASTEWATER
TREATMENT
PriorityPollutants
Collectionpondsusedtocollect
wastewaterandseparateoils
pH
CoolingTowerBlowdown
ProcessSewers
SuspendedSolids
Chlorine
Nutrients
Temperature
TotalDissolvedSolids
103
104
March2013
SITEAERIALVIEW
WASTEWATER
TREATMENT
Recyclesupply
Plantdrains
Filterbackwash
Boilerblowdown
ROrejectwater
Storagearearunoff
CoolingTowers
Recycleusers
CoolingTowers
BoilerMakeup
105
106
NH3STORAGE
STORAGEAND
TRANSPORTATION
NH3StorageandHandlingregulatedby:
29CFR1910.111 StorageandHandlingof
AnhydrousAmmonia
StorageSystems
StorageCapacity
TransportationMethods
29CFR1910.119 ProcessSafetyManagementof
HighlyHazardousMaterials
ANSIK61.1 SafetyRequirementsfortheStorage
andHandlingofAnhydrousAmmonia
107
108
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8/27/2014
PROCESSFLOWDIAGRAM
PROCESSFLOWDIAGRAMKEY
COMPONENTS
ColdAmmoniaStorageTanks
TransferPumps
AmmoniaShelland
TubeHeaters
WarmAmmoniaStorage
Bullets
WarmAmmoniaTransfer
Pumps
Trucks/Railcars
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COLDAMMONIASTORAGETANKS
STORAGETANK
CONSTRUCTIONTYPES
Pressurizedvesselspracticalto~300tonsNH3
FullyRefrigeratedorSemiRefrigerated
SingleContainment
126to170ft diameter
DoubleContainment
60to105ft high
FullContainment
1530,000tonscapacity(6to12milliongallons)
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REFRIGERATEDTANKS
112
AMMONIATRANSPORTBYTRUCK
Heatleaksinfromenvironment
Refrigerationrequiredforatmosphericstorage
Componentsincludecompressor,intercooler,
condenser,andreceiver
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AMMONIATRUCKTRANSPORT
SAFEGUARDS
AMMONIATRANSPORTBYRAIL
Twosetsofinternal
closingvalves
Emergencyshutoff
Minimumtwosafety
reliefvalves
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EXISTINGAMMONIARAILCARFLEET
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AMMONIAPIPELINES
MagellanAmmoniaPipeline
NumberofCarsinService:~6,000
AverageAgeofFleet(est.):25years
MaximumAllowableServiceLife:40years
1,100miles
20terminalsTexastoMinnesota
DeliveryCapacity:900,000tons/yr
528,000tonsStorage
Kaneb Pipeline
2,000miles
24terminals,LouisianatoNebraska&Indiana
DeliveryCapacity:2milliontons/yr
1milliontonsStorage
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USAMMONIAINFRASTRUCTURE
REFRIGERATEDBARGES
ExistingAmmoniaBargeFleet
2,500tonCapacity
Ageofcurrentfleet:~40years
31BargesinService
MississippiRiverSystem
InterCoastalWaterway
PacificNorthwest
P
I
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AmmoniaPlants
StorageTanks
ImportTerminals
Kaneb Pipeline
MagellanPipeline
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SAFETYCLASSIFICATIONS
SAFETY
DOT:HazardousMaterial
OSHA:HazardousMaterial
EPA:ExtremelyHazardousSubstance
AmmoniaProperties
Exposure
Response
Leaks
Fire
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AMMONIAEXPOSURE
AMMONIAPROPERTIESANDLEAK
RESPONSECONSIDERATIONS
Skin Irritations
Burns, blisters
Upper
Flammable
Limit
Lower
Flammable
Limit
Immediate
Death
Colorlessliquid,
pungentodor
Death in
minutes
BoilingPoint28F
PEL
IDLH
(OSHA)
Z-List
Runny eyes
& nose
Vaporatatmospheric
conditions
Watersoluble
30,000 150,000
15 %
3%
280,000
28 %
10,000 PPM
1%
5000 PPM
.5%
700 PPM
STEL
Liquidunderpressure
Immediate
eye injury
140 PPM
50 PPM
35 PPM
300 PPM
25 PPM
2-5 PPM
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RELEASEPHASES
OSHARESPONSELEVELS
Vapor
(tracegas)
FirstResponder
Initialresponse
Defensiveresponse
Containment
Vapor
DenseGas
Aerosol
Liquid
HazardousMaterialsTechnician
AerosolStream
DenseGas
Moreaggressive,offensiverole
Purposeofstoppingrelease
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ENVIRONMENTALIMPACTSOFRELEASE
AMMONIAFIREHAZARDS
NH3:SmallFlammabilityRange,1528%
Runoff
Keepoutofdrainsandwaterways
SyngasishighlyflammablebecauseofitsH2
content
Watercanbeusedtosprayonvapors,butmustbe
trapped.
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AMMONIAFIRERESPONSE
FIREPROTECTIONANDSAFEGUARDS
MSDSRecommendations
NFPA72Standards
Extinguishwithwaterordrychemical
spray
NFPAFireRating
Flammability:1
HealthHazard:3
Reactivity:0
FireMonitoringandAlarms
UV/IRFlameDetectors
SmokeAlarms
LELGasDetectors
FireSuppression
ProtectEquipment
ContainFire
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130
www.bv.com
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