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UOP 4288K-1
““OnOn--PurposePurpose”” PropylenePropyleneTechnology DevelopmentsTechnology Developments
Tim FoleyTim FoleyUOP LLCUOP LLC
©© 2005 UOP LLC. All rights reserved.2005 UOP LLC. All rights reserved.
““OnOn--PurposePurpose”” Propylene:Propylene:Propylene supply/demand Propylene supply/demand overviewoverviewAlternatives to steam cracking Alternatives to steam cracking for propylene productionfor propylene production
–– Refinery FCCRefinery FCC–– Propane DehydrogenationPropane Dehydrogenation–– Methanol to OlefinsMethanol to Olefins–– Olefin ConversionOlefin Conversion
Selection of a propylene Selection of a propylene processprocess
CC33HH66
UOP 4288K-2
CC33==/C/C22
== RatiosRatiosWorldwideWorldwide
DemandDemand
MT Propylene / MT EthyleneMT Propylene / MT Ethylene
0.590.59
0.620.62
20042004 20062006 20082008 20102010 20122012 20142014YearYear
Supply from steam crackers
Supply from steam crackers
~ 18
M M
TA
~ 18
M M
TA
0.36
0.400.40
0.350.35
0.450.45St
eam
Cra
cker
Pro
duct
ion
Stea
m C
rack
er P
rodu
ctio
n
0.540.54
0.640.64
Dem
and
Dem
and
UOP 4399A-4Data Source: CMAI 2005Data Source: CMAI 2005
Propylene Supply & DemandPropylene Supply & DemandPolymer Grade & Chemical GradePolymer Grade & Chemical Grade
Steam Steam CrackerCracker Refinery
OthersOthers
2004 Supply2004 Supply
DehydroDehydro
~ 67%~ 67%
6060
7070
8080
9090
100100
Mill
ion
MT
AM
illio
n M
TA
20042004 20062006 20082008 20102010 20122012 20142014YearYear
Current Capacity
Steam CrackersSteam CrackersSteam Crackers
RefineryRefineryRefineryTotal D
emand
Other On-Purpose
38%
38
%
UOP 4399A-2
Substantially more propylene will have to come from on-purpose technologies
Substantially more propylene will have Substantially more propylene will have to come from onto come from on--purpose technologiespurpose technologies
Source: CMAISource: CMAI
OnOn--Purpose Propylene TechnologiesPurpose Propylene Technologies
High-Severity FCCPetroFCCTM
Process
HighHigh--Severity FCCSeverity FCCPetroFCCPetroFCCTMTM
ProcessProcess
Olefin CrackingOlefin CrackingOlefin CrackingMTOMTOMTO
OleflexTM
ProcessOleflexOleflexTMTM
ProcessProcess
VGO, ATM ResidVGO, ATM Resid PropanePropane
Mixed CMixed C44== toto CC88
==Natural Gas, Coal, MethanolNatural Gas, Coal, Methanol
UOP 4399A-5
Olefin CrackingOlefin CrackingMTOMTO
OleflexTM
ProcessOleflexOleflexTMTM
ProcessProcess
PropanePropane
Mixed CMixed C44== toto CC88
==Natural Gas, Coal, MethanolNatural Gas, Coal, Methanol
OnOn--Purpose Propylene TechnologiesPurpose Propylene Technologies
High-Severity FCCPetroFCCTM
Process
HighHigh--Severity FCCSeverity FCCPetroFCCPetroFCCTMTM
ProcessProcess
VGO, ATM ResidVGO, ATM Resid
UOP 4399A-6
Propylene from RefineriesPropylene from Refineries
VGO
CrudeOil
CrudeCrudeColumnColumn
C4 and Lighter
Straight Run Gasoline
Kerosene
AGO
VacuumVacuumColumnColumn
Vacuum ResidueVacuum Residue
FCCFCC
PropylenePropylene
Fuel GasFuel Gas
LPGLPG
GasolineGasoline
DieselDiesel
Heavy Heavy Fuel OilFuel Oil
PRUPRU
DownstreamProcessing
UOP 4288K-4
Propylene from FCCPropylene from FCCPr
opyl
ene
Yie
ldPr
opyl
ene
Yie
ld
Unit Design and OperationUnit Design and Operation
Max. GasolineMax. Gasoline3 3 -- 5 wt%5 wt%
GasolineGasoline
Enhanced Enhanced PropylenePropylene5 5 –– 7 wt%7 wt%
CC33==
GasolineGasoline
HighHigh--Severity Severity FCCFCC
10 10 --16 wt%16 wt%
CC22==
CC33==
GasolineGasoline
PetroFCCPetroFCC20 + wt%20 + wt%
CC22==
CC33==
AromaticsAromatics
UOP 4399A-7
Increasing Propylene Production
High Severity FCCHigh Severity FCCA Flexible ProcessA Flexible Process
Steps to increase propyleneSteps to increase propyleneIncrease riser temperatureIncrease riser temperatureUse low HUse low H--transfer catalysttransfer catalystUse shape selective additiveUse shape selective additiveUse new reactor technologyUse new reactor technology
–– RxCatRxCatTMTM
Designed with the flexibility to operate in a propylene or gasoline mode
Designed with the flexibility to operate Designed with the flexibility to operate in a propylene or gasoline modein a propylene or gasoline mode
UOP 4399A-8
RxCatRxCatTTechnologyechnology
RxCat and PetroFCC Benefits:RxCat and PetroFCC Benefits:Enhanced catalytic crackingEnhanced catalytic cracking–– Increased propylene yieldIncreased propylene yieldReduced thermal crackingReduced thermal cracking–– Decreased dry gas yieldDecreased dry gas yieldCatalyst selection flexibilityCatalyst selection flexibility–– Choice of catalyst supplyChoice of catalyst supply–– Optimized for feedstock andOptimized for feedstock and
product objectivesproduct objectives
What is the PetroFCCWhat is the PetroFCC Process?Process?
UOP 4399A-11
NaphthaNaphtha
DistillateDistillateFuel OilFuel Oil
CokeCoke
53.5
14147755
28
9.59.5
5.55.555
CC44’’ss11
1914CC44
= =
Typical PetroFCC Process Yield, wtTypical PetroFCC Process Yield, wt--%%(VGO Feed)(VGO Feed)
Traditional FCCTraditional FCC PetroFCC ProcessPetroFCC Process Light OlefinsLight Olefins
CC33’’ss6.5
2422CC33
==
CC22--
9
6CC22==
3
18
AromaticsAromaticsBTXBTX
UOP 4399A-12
OCPOCPOlefin
Cracking
Is Integration an Objective? Is Integration an Objective?
Light gasesLight gasesEthyleneEthylenePropylenePropyleneMixed CMixed C44’’ss
Gas Con
AromaticAromaticNaphthaNaphtha
OlefinsRecovery
BenzeneBenzenepp--XyleneXyleneParexTM
ProcessParexTM
Process
TatorayTM
ProcessTatorayTM
Process
IsomarTM
ProcessIsomarTM
ProcessFractionation
ProcessFractionation
Process
SulfolaneTM ProcessSulfolaneTM Process
Gas OilGas Oil
Other FeedsOther Feeds
UOP 4399A-27
HighHigh--Severity FCCSeverity FCCPetroFCCPetroFCCTMTM
ProcessProcess
Olefin CrackingOlefin CrackingMTOMTO
VGO, ATM ResidVGO, ATM Resid
Mixed CMixed C44== toto CC88
==Natural Gas, Coal, MethanolNatural Gas, Coal, Methanol
OnOn--Purpose Propylene TechnologiesPurpose Propylene Technologies
OleflexOleflexTMTM
ProcessProcess
PropanePropane
UOP 4399A-13
What is Propane What is Propane Dehydrogenation (PDH)?Dehydrogenation (PDH)?
PropanePropaneCatalystCatalyst
−−ΔΔ TT
Propylene Propylene & Hydrogen& Hydrogen
CC33HH6 6 && HH22
OnOn--purpose production of propylene purpose production of propylene from propanefrom propaneProduces propylene and hydrogenProduces propylene and hydrogen
CC33HH88
UOP 4354J-12
CC33 Oleflex ProcessOleflex Process
P -P
Spl
itter
SHP
Dep
ropa
nize
r
Net GasNet Gas
PropanePropane
PropanePropaneFeedFeed
CC44++
Oleflex
CC2 2 --PropylenePropylene
HH22
Dee
than
izer
Six operating Six operating units with units with capacities ranging capacities ranging from 100,000 to from 100,000 to 350,000 MTA 350,000 MTA propylene propylene 1.25 M MTA 1.25 M MTA operating capacityoperating capacity40 plus plant 40 plus plant years of operating years of operating experienceexperienceLarger unit Larger unit capacities capacities in design in design
UOP 4399A-15
HighHigh--Severity FCCSeverity FCCPetroFCCPetroFCCTMTM
ProcessProcess
Olefin CrackingOlefin Cracking
OleflexOleflexTMTM
ProcessProcess
VGO, ATM ResidVGO, ATM Resid PropanePropane
Mixed CMixed C44== toto CC88
==
OnOn--Purpose Propylene TechnologiesPurpose Propylene Technologies
MTOMTO
Natural Gas, Coal, MethanolNatural Gas, Coal, Methanol
UOP 4399A-16
MethanolMethanol
What is MTO?What is MTO?
MTOMTO Ethylene & Ethylene & PropylenePropylene
Natural GasNatural Gas
Synthesis Gas
Production
Gas to Olefins (GTO)Gas to Olefins (GTO)
Methanol Synthesis
CoalCoal
Coal to Olefins (CTO)Coal to Olefins (CTO)UOP 4399A-17
UOP/HYDRO MTO ProcessUOP/HYDRO MTO Process
Regen GasRegen Gas
AirAir
MethanolMethanol
WaterWater
ReactorReactor RegeneratorRegeneratorQuenchQuenchTowerTower
OxygenateRecovery
WaterWater
Light Olefin
Recovery
High selectivity to light High selectivity to light olefinsolefins
–– Minimizes feedstock Minimizes feedstock costscosts
–– High value product mix High value product mix with little Cwith little C55
+ + coco--productproduct–– Little hydrogen & Little hydrogen &
methanemethane
Flexibility of CFlexibility of C22==/C/C33
= =
product ratios product ratios
Ethylene & Ethylene & PropylenePropylene
UOP 4399a-18
Why MTO?Why MTO?
0%0%
20%20%
60%60%
80%80%
100%100%
RO
IR
OI
1010 2020 3030 4040 5050Crude Oil Benchmark, $/BBLCrude Oil Benchmark, $/BBL
40%40%
Naphtha CrackerNaphtha Cracker
MTOMTO
MTO Advantage
MTO Advantage
UOP 4399A-19
Product values generally increase Product values generally increase with crude oil prices with crude oil prices Naphtha cracker feedstock prices Naphtha cracker feedstock prices are closely linked to crude oil are closely linked to crude oil pricesprices
–– High feedstock costs offset most High feedstock costs offset most of the economic benefits as of the economic benefits as product values increase product values increase
MTO feedstock is from dedicated MTO feedstock is from dedicated sources using cost advantaged sources using cost advantaged feedstockfeedstock
–– Fixed price not tied to crude oilFixed price not tied to crude oil–– Can support increased Can support increased
methanol prices when olefin methanol prices when olefin values are higher (high crude values are higher (high crude oil prices)oil prices)
MTO is competitive with steam MTO is competitive with steam crackers when crude oil is above $16 crackers when crude oil is above $16 per barrelper barrel
–– Huge advantage when crude oil Huge advantage when crude oil prices are highprices are high
HighHigh--Severity FCCSeverity FCCPetroFCCPetroFCCTMTM
ProcessProcess
MTOMTO
OleflexOleflexTMTM
ProcessProcess
VGO, ATM ResidVGO, ATM Resid PropanePropane
Natural Gas, Coal, MethanolNatural Gas, Coal, Methanol
OnOn--Purpose Propylene TechnologiesPurpose Propylene Technologies
Olefin CrackingOlefin Cracking
Mixed CMixed C44== toto CC88
==
UOP 4399A-20
What is Olefin Cracking?What is Olefin Cracking?
CatalystCatalyst
−−ΔΔ TTOlefin CrackingOlefin CrackingCC44 to Cto C88
OlefinsOlefinsCC44HH88 to Cto C88HH1616
Ethylene &Ethylene &PropylenePropyleneCC22HH44 & C& C33HH66
Production of propylene and ethylene Production of propylene and ethylene from Cfrom C44 to Cto C88 olefinsolefins
UOP 4399A-21
RefineriesRefineries
FCC
OlefinOlefin
Recovery
GasGasOilsOils FCC GasolineGasoline
Cycle OilsCycle Oils
LightLightOlefinsOlefins
CC44--CC88
LPGLPG
CC22==CC33==
OlefinCracking
ATOFINA/UOP Olefin Cracking Process ATOFINA/UOP Olefin Cracking Process ApplicationsApplications
Naphtha CrackersNaphtha Crackers
FurnaceProduct
Recovery &Furnace
ProductRecovery &Purification
CC55/C/C66ParaffinParaffin--RichRich
CC44/C/C55
CC22==
CC33==
Fuel GasFuel GasPygasPygas
LightLightOlefinsOlefins
OlefinCracking
NaphthaNaphtha
UOP 4399A-22
CC22==
CC33==
MTO PlantsMTO Plants
MeOHMeOH
CC44++
MTO
LightLightOlefinsOlefins
CC44--CC55OlefinsOlefins
OlefinCracking
Olefin Cracking can be integrated with a variety of processes
Olefin Cracking can be integrated Olefin Cracking can be integrated with a variety of processeswith a variety of processes
Selection of Propylene OptionsSelection of Propylene OptionsKey IssuesKey Issues
Feedstock Feedstock –– CostCost–– FlexibilityFlexibility
YieldsYields–– CoCo--products products –– IntegrationIntegration
CapacityCapacity–– IncrementalIncremental–– New complex New complex
CapitalCapital
UOP 4399A-23
What Products are Desired?What Products are Desired?
0% 20% 40% 60% 80% 100%
Naphtha Cracking
Nap. Cracking + OC
FCC
PetroFCC + ARU +OC
Propane Dehydro
MTO
MTO + OC
Product Mix
Propylene Ethylene BTX Butadiene Mixed C4s
Gasoline Cycle Oil Slurry Oil Light Ends
0% 20% 40% 60% 80% 100%
Naphtha Cracking
Nap. Cracking + OC
FCC
PetroFCC + ARU +OC
Propane Dehydro
MTO
MTO + OC
Product Mix
Propylene Ethylene BTX Butadiene Mixed C4s
Gasoline Cycle Oil Slurry Oil Light Ends
Issues to ConsiderIssues to ConsiderPropylene yieldPropylene yieldCoCo--productsproductsIntegrationIntegration
UOP 4399A-24
How Much Propylene Is Desired?How Much Propylene Is Desired?
IncrementalIncremental(<200 (<200 kMTAkMTA))
–– Revamp existing Revamp existing assetsassets
IntermediateIntermediate(100 (100 –– 300 300 kMTAkMTA))
–– Integrate new Integrate new units with units with existing assetsexisting assets
World scaleWorld scale(>250 (>250 kMTAkMTA))
–– New complexesNew complexes–– IntegrationIntegration00
100100
200200
300300
400400
500500
600600
Cracker FurnacesCracker FurnacesFCC revampFCC revampPRUPRUOleflexOleflex
RevampsRevamps
Naphtha CrackerNaphtha CrackerOleflexOleflexMTOMTOPetroFCCPetroFCCOlefin CrackingOlefin Cracking
Grass RootsGrass Roots
Prop
ylen
e C
apac
ity, k
MT
A
New UnitNew UnitIntegrationsIntegrations
Olefin CrackingOlefin CrackingMTOMTOHigh Severity FCCHigh Severity FCC
UOP 4399A-25
How Much Capital is Available?How Much Capital is Available?Low capitalLow capital(<$200 M)(<$200 M)
–– FCC PRUFCC PRU–– FCC RevampFCC Revamp–– OCOC
Intermediate capitalIntermediate capital(<$500 M)(<$500 M)
–– OleflexOleflex–– PetroFCCPetroFCC–– MTOMTO
Large capital Large capital (>$500 M)(>$500 M)
–– GTOGTO–– PetroFCC/ARU/OCPetroFCC/ARU/OC
Excludes Olefin Derivative UnitsExcludes Olefin Derivative Units
00 200200 400400 600600 800800 10001000Millions US$Millions US$
Naphtha CrackerNaphtha Cracker
FCC/PetroFCCFCC/PetroFCC BTX
FCC PRU Add.FCC PRU Add.
Propane Propane DehydroDehydro..
Olefin CrackingOlefin Cracking
MTO / GTOMTO / GTO MeOH
UOP 4399A-26
OnOn--Purpose Propylene TechnologiesPurpose Propylene TechnologiesSummarySummary
VGO, ATM ResidVGO, ATM Resid
HighHigh--Severity FCCSeverity FCC& PetroFCC Process& PetroFCC Process
Proximity to CProximity to C33== usersusers
CC33== & gasoline flexibility& gasoline flexibility
Refinery / PC integrationRefinery / PC integration
UOP 4399A-28
PropanePropane
OleflexOleflexTMTM ProcessProcessPropylene/Propane price Propylene/Propane price differentialdifferentialSimple backSimple back--integrationintegration
–– one feed one feed –– one productone product
Natural Gas, Coal, MethanolNatural Gas, Coal, Methanol
MTOMTOMonetize natural gas or Monetize natural gas or coalcoalHigh yields of CHigh yields of C33
== & C& C22==
Competitive with steam Competitive with steam crackingcracking
Mixed CMixed C44== toto CC88
==
Olefin CrackingOlefin CrackingFeedstock flexibilityFeedstock flexibilityIntegration flexibilityIntegration flexibility
Economic over a broad Economic over a broad range of Crange of C33
== / C/ C22= = pricesprices
ConclusionsConclusionsNew options must be New options must be considered to meet future considered to meet future propylene demand propylene demand Several options available for Several options available for increasing propyleneincreasing propyleneEach producer must consider Each producer must consider key selection factorskey selection factorsUOP can help!UOP can help!
UOP 4399A-29
UOP 4288K-27
Acknowledgments:Bipin Vora, Mark Houdek, Chuck Hemler, Bob James, Joe Gregor, Jim Andersen – UOPHenning R Nilsen, Steinar Kvisle – Norsk HydroWalter Vermieren – Total Petrochemicals