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8/27/2014

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

Worldwide ammonia production is about 143 million tons.

WHEREAMMONIAISPRODUCEDAND
CONSUMED

10

AERIALVIEWOFLIMA,OH

11

Plant is located in populated area and


close to city

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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.

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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.

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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

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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

xCH4 +yCO +zO2

CO2

(x+y)CO2 +2xH2O exothermic

WaterGasShift
CO2
Removal

Methanation

Condensate
Stripping

ShiftconvertsCOtoH2

HP
HP
Steam BFW

Syngas
Comp

Ammonia
Synthesis

Hydrogen
Recovery

Ammonia
Refrigeration

CO+H2O

CO2 +H2 exothermic(goingtoCO2)

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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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

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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

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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

N2 +3H2 Fe(reducedmagnetite) 2NH3


exothermic
Clariant (Sud Chemie)AmoMax wustite basedcatalyst
developedinChinastartingin1986.Firstcommercialcharge
installedin2003.Producesmoreammoniathanmagnetite.

TypicalOperatingEnvelope

57

RELATIVESYNTHESISREACTIONRATE

Ammonia synthesis equilibrium is favored by


low temperature and high pressure

58

1,000TPDKELLOGGCONVERTER
Outlet

Outlet

CDismaximum
reactionratecurve
#1

#1

#2

#3
#2
#4
Inlet

1.5 H2 + 0.5 N2 = NH3

59

OriginalAxialFlow
4BedQuench

Inlet

RetrofitRadialFlow
Topsoe S200

60

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8/27/2014

QUENCHCONVERTERTEMPERATURE
PROFILE

RADIALFLOWWITHINTERBED HEAT
EXCHANGETEMPERATUREPROFILE

Quench
causesdilution

Heatexchange
causesno
dilutionfrom
quenching

Bed#2
Bed#1

Bed#3

Bed sequence follows maximum rate curve

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

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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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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)

Source: US EPA: AP42 Section 5.2

87

88

CO2REMOVAL

CONDENSATESTRIPPING

CO2mustberemovedfromprocessgas

Processcondensatecontainsthefollowing:
Nonmethane OrganicCompounds
CarbonDioxide
Ammonia

Emissions

CarbonMonoxide
MEA/Piperazine (activator)
VOCs
Ammonia

CO2 is often used onsite to make urea.

Mediumpressuresteamusedtostripprocess
condensate

89

90

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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

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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

10 minutes following 0.5 1.0 ppm


chlorination
100

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

Limits from ASME Consensus on Operating Practices


for the Control of Feedwater and Boiler Water
Chemistry in Modern Industrial Boilers for
1,500 psi Drum Operating Pressure.
101

102

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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

18

8/27/2014

PROCESSFLOWDIAGRAM

PROCESSFLOWDIAGRAMKEY
COMPONENTS
ColdAmmoniaStorageTanks
TransferPumps
AmmoniaShelland
TubeHeaters
WarmAmmoniaStorage
Bullets
WarmAmmoniaTransfer
Pumps
Trucks/Railcars

110

109

COLDAMMONIASTORAGETANKS
STORAGETANK
CONSTRUCTIONTYPES

Pressurizedvesselspracticalto~300tonsNH3
FullyRefrigeratedorSemiRefrigerated

SingleContainment

126to170ft diameter

DoubleContainment

60to105ft high

FullContainment

1530,000tonscapacity(6to12milliongallons)

111

REFRIGERATEDTANKS

112

AMMONIATRANSPORTBYTRUCK

Heatleaksinfromenvironment
Refrigerationrequiredforatmosphericstorage
Componentsincludecompressor,intercooler,
condenser,andreceiver

113

114

19

8/27/2014

AMMONIATRUCKTRANSPORT
SAFEGUARDS

AMMONIATRANSPORTBYRAIL

Twosetsofinternal
closingvalves
Emergencyshutoff

Minimumtwosafety
reliefvalves

115

EXISTINGAMMONIARAILCARFLEET

116

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

117

118

USAMMONIAINFRASTRUCTURE

REFRIGERATEDBARGES
ExistingAmmoniaBargeFleet
2,500tonCapacity
Ageofcurrentfleet:~40years
31BargesinService
MississippiRiverSystem
InterCoastalWaterway
PacificNorthwest

P
I

119

AmmoniaPlants
StorageTanks
ImportTerminals
Kaneb Pipeline
MagellanPipeline
120

20

8/27/2014

SAFETYCLASSIFICATIONS

SAFETY

DOT:HazardousMaterial
OSHA:HazardousMaterial
EPA:ExtremelyHazardousSubstance

AmmoniaProperties
Exposure
Response
Leaks
Fire

121

122

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

REL TLV- TWA


Detectable
Odor

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

123

Ammonia vapors are hazardous, causing respiratory


distress and injury.

124

RELEASEPHASES

OSHARESPONSELEVELS

Vapor
(tracegas)

FirstResponder
Initialresponse
Defensiveresponse
Containment

Vapor

DenseGas
Aerosol
Liquid

HazardousMaterialsTechnician

AerosolStream
DenseGas

Moreaggressive,offensiverole
Purposeofstoppingrelease

125

Release phases depend on wind/weather


conditions and amount of release

126

21

8/27/2014

ENVIRONMENTALIMPACTSOFRELEASE

AMMONIAFIREHAZARDS
NH3:SmallFlammabilityRange,1528%

Runoff
Keepoutofdrainsandwaterways

SyngasishighlyflammablebecauseofitsH2
content

Watercanbeusedtosprayonvapors,butmustbe
trapped.

A little NH3 will drastically affect water pH

127

128

AMMONIAFIRERESPONSE

FIREPROTECTIONANDSAFEGUARDS

MSDSRecommendations

NFPA72Standards

Extinguishwithwaterordrychemical
spray
NFPAFireRating
Flammability:1
HealthHazard:3
Reactivity:0

FireMonitoringandAlarms
UV/IRFlameDetectors
SmokeAlarms
LELGasDetectors

FireSuppression
ProtectEquipment
ContainFire

129

130

www.bv.com
131

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