On Purpose Propylene Production UOP

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




High-Severity FCCPetroFCCTM

Process


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


ProcessProcess

Olefin CrackingOlefin CrackingMTOMTO





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


ProcessProcess

Olefin CrackingOlefin Cracking

OleflexOleflexTMTM

ProcessProcess



==


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


ProcessProcess

MTOMTO

OleflexOleflexTMTM

ProcessProcess






==

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


OlefinCracking

NaphthaNaphtha

UOP 4399A-22

CC22==

CC33==

MTO PlantsMTO Plants

MeOHMeOH

CC44++

MTO


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..


MTO / GTOMTO / GTO MeOH

UOP 4399A-26

OnOn--Purpose Propylene TechnologiesPurpose Propylene TechnologiesSummarySummary


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


MTOMTOMonetize natural gas or Monetize natural gas or coalcoalHigh yields of CHigh yields of C33

== & C& C22==

Competitive with steam Competitive with steam crackingcracking


==

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

Documents

On Purpose Propylene Production UOP