© 2006 UOP LLC. All rights reserved.

Light Olefin TechnologiesLight Olefin Technologies

UOP 4638-01UOP 4867-01

Journées Annuelles du PétroleOctober 11, 2007

© 2007 UOP LLC. All rights reserved.

Bryan GloverUOP LLC

Bryan GloverUOP LLC

Light Olefin Technologies

•• Propane dehydrogenation to Propylene Propane dehydrogenation to Propylene -- OleflexOleflex processprocess

•• Olefin Conversion ProcessesOlefin Conversion Processes-- Metathesis Metathesis -- Olefin CrackingOlefin Cracking

•• Methanol to OlefinsMethanol to Olefins-- SAPOSAPO--34 and ZSM34 and ZSM--5 based systems5 based systems

•• High Severity FCC processesHigh Severity FCC processes-- PetroFCCPetroFCC

•• Naphtha cracker feed enrichmentNaphtha cracker feed enrichment-- MaxEneMaxEne Process for separation of normal Process for separation of normal

paraffinsparaffins from naphtha for increased from naphtha for increased naphtha cracker ethylene yieldnaphtha cracker ethylene yield

Alternatives to Thermal Cracking for the production Alternatives to Thermal Cracking for the production of light olefins:of light olefins:

UOP 4867-02

Relative Light Olefin Yields

0% 20% 40% 60% 80% 100%

Naphtha Cracking

Nap. Cracking + OC

FCC

PetroFCC + ARU +OC

Propane Dehydro

MTO

MTO + OC

Product Mix

Propylene Ethylene BTXButadiene Mixed C4s GasolineCycle 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 BTXButadiene Mixed C4s GasolineCycle Oil Slurry Oil Light Ends

Issues to ConsiderIssues to Consider•• Feed availability Feed availability

and priceand price•• Relative Relative CapexCapex•• Multi product slate Multi product slate

/ integration/ integration

UOP 4867-03

Propane Dehydrogenation

PropanePropaneCatalystCatalyst

--ΔΔTT

PropylenePropylene & & HydrogenHydrogen

CC33HH6 6 && HH22

•• OnOn--purpose production of propylene purpose production of propylene from propanefrom propane

•• Produces propylene and hydrogenProduces propylene and hydrogen•• Typically Pt or Cr based systemsTypically Pt or Cr based systems

CC33HH88

UOP 4867-04

Propane DehydrogenationThe Oleflex Process

1.2 MT Propane1.2 MT Propane

1.0 MT Propylene1.0 MT Propylene

VC + FC InputsVC + FC Inputs

UtilitiesUtilitiesCatalystCatalyst

ChemicalsChemicalsLabor, etc.Labor, etc.

High yield Pt based catalyst High yield Pt based catalyst

UOP 4867-05

CC33 LPGLPG

CC44++

Net GasNet Gas HH22CC22--

OleflexOleflex

PropylenePropylene

DepropanizerDepropanizer

Propane DehydrogenationThe Oleflex Process

PP--P SplitterP Splitter

SHP

DeethanizerDeethanizer

UOP 4867-06

Heater CellsHeater Cells

NetNetSeparatorSeparatorOff GasOff Gas

To SHPTo SHP

DryerDryer

TurboTurboExpanderExpander

FreshFresh& Recycle& Recycle

FeedFeed

HH22 RecycleRecycle

CCR

Rx EffluentRx EffluentCompressorCompressor

Regeneration Regeneration SectionSection

Reactor Reactor SectionSection

Product Recovery SectionProduct Recovery Section

Propane DehydrogenationThe Oleflex Process

UOP 4867-07

Olefin Conversion Processes

CatalystCatalyst

-- ΔΔTTOlefin CrackingOlefin Cracking

CC44 to Cto C88OlefinsOlefins

CC44HH88 to Cto C88HH1616

Ethylene &Ethylene &PropylenePropylene

CC22HH44 & C& C33HH66(plus by(plus by--products)products)

Two types: Metathesis & Olefin CrackingTwo types: Metathesis & Olefin Cracking

PropylenePropyleneCatalystCatalyst

Ethylene &Ethylene &22--ButeneButene

CC33HH66CC22HH44 & C& C44HH88 (plus by(plus by--products)products)

Metathesis

UOP 4867-08

Olefin CrackingTOTAL PETROCHEMICALS / UOP Olefin Cracking Process

LightLightOlefinOlefin

ProductProductOlefinicOlefinicCC44 -- CC88FeedFeed

CC66+ +

PurgePurge

RerunRerunColumnColumn

RecycleRecycle

SHPSHPOC OC

ReactorReactor

DepropanizerDepropanizerColumnColumn

CC44 & C& C55PurgePurge

UOP 4867-09

Coke

Olefin Cracking The Mechanism

•• CC44== do not crack directlydo not crack directly

•• In principle, it is possible to produce Propylene and In principle, it is possible to produce Propylene and higher olefins from Ethylenehigher olefins from Ethylene

-- Ethylene activation is facilitated in the presence of Ethylene activation is facilitated in the presence of higher olefinhigher olefin

CrackingCracking

Hydride Hydride transfertransfer

FeedOlefins

Oligomers

ProductOlefins

Aromatics &Paraffins/H2

UOP 4867-10

TOTAL PETROCHEMICALS / UOP Olefin Cracking Process

•• 80% to 90% overall conversion 80% to 90% overall conversion of higher olefins of higher olefins

•• High selectivity to light olefinsHigh selectivity to light olefins-- 3.5 to 4.0 propylene/ethylene 3.5 to 4.0 propylene/ethylene

product ratioproduct ratio•• Over 90% olefin purity in COver 90% olefin purity in C22 & C& C33

fractionsfractions-- Upgrading to polymer grade is simple Upgrading to polymer grade is simple

•• FixedFixed--bed technologybed technology-- Swing regeneration systemSwing regeneration system-- High LHSVHigh LHSV-- Low Rx pressure (between 1 and 5 bar)Low Rx pressure (between 1 and 5 bar)

•• Reactor inlet temperatures 500 to 600Reactor inlet temperatures 500 to 600°°CC•• No No diluentdiluent additionaddition

Ethene

Ethane

Propane

Propene

C4+C1-

Ethene

Ethane

Propane

Propene

C4+C1-

Olefin Cracking Olefin Cracking Light Olefin ProductLight Olefin Product

UOP 4867-11

Olefin Cracking Process Applications

RefineriesRefineries

FCCFCC

OlefinOlefinOlefin

Recovery

GasGasOilsOils FCC

GasolineGasolineCycle OilsCycle Oils

LightLightOlefinsOlefins

CC44--CC88

LPGLPG

CC22==CC33==

OlefinCracking

Fuel GasFuel Gas

Naphtha CrackersNaphtha Crackers

FurnaceFurnaceProductProduct

Recovery &Recovery &Furnace Product

Recovery &Purification

CC55/C/C66ParaffinParaffin--RichRich

CC44/C/C55

CC22==

CC33==

PygasPygas

LightLightOlefinsOlefins

OlefinCracking

NaphthaNaphtha

CC22==CC33==

MTO PlantsMTO Plants

MeOHMeOH

CC44++

MTO

LightLightOlefinsOlefins

CC44--CC55OlefinsOlefins

OlefinCracking

Olefin Cracking can be integrated with a variety Olefin Cracking can be integrated with a variety of other processesof other processes

UOP 4867-12

MethanolMethanol

Methanol to Olefins

MTOMTO Ethylene & Ethylene & PropylenePropylene

Natural GasNatural Gas

Synthesis Gas

Production

Gas to Olefins (GTO)Gas to Olefins (GTO)Gas to Olefins (GTO)

Methanol Synthesis

CoalCoal

Coal to Olefins (CTO)Coal to Olefins (CTO)UOP 4867-13

ZSMZSM--5 (MFI)5 (MFI)

10R

5.6 x 5.3

Medium pore size: 5.1 x 5.5Medium pore size: 5.1 x 5.5ÅÅ

10R

Mobil discovered ZSMMobil discovered ZSM--5 5 for methanol to gasoline for methanol to gasoline (MTG) and olefins during (MTG) and olefins during early 1970s early 1970s

MTG commercialized in MTG commercialized in New Zealand during mid New Zealand during mid 1980s.1980s.

Methanol to OlefinsZSM-5

UOP 4867-14

L. Smith et al, L. Smith et al, CatalCatal. . LettLett. 1996, 41, 13. 1996, 41, 13

SAPOSAPO--3434

8-ring

SilicoaluminoSilicoalumino--PhosphatesPhosphates(SAPO) discovered in the (SAPO) discovered in the early 1980s by scientists at early 1980s by scientists at Union Carbide (UCC)Union Carbide (UCC)SAPOSAPO--34 has high 34 has high selectivity for MTO selectivity for MTO reaction.reaction.MTO development MTO development transferred from UCC to transferred from UCC to UOP in 1988UOP in 1988

3.8A

Methanol to OlefinsSAPO-34

UOP 4867-15

Small PoreSmall PoreWeak Acid Weak Acid

SitesSites

Medium PoreMedium PoreStrong Acid Strong Acid

SitesSites

3.83.8 Ă Ă 5.55.5 Ă Ă

Methanol to OlefinsSAPO-34 Comparison to ZSM-5

UOP 4867-16

7070

6060

5050

4040

3030

2020

1010

00CC22

== CC33== CC44

== CC55++

% Y

ield

% Y

ield

Methanol to OlefinsOnce Through Yields SAPO-34 and ZSM-5

•• SAPOSAPO--34 has slightly higher 34 has slightly higher coke selectivitycoke selectivity

48487878Light OlefinsLight Olefins

42424747PropylenePropylene

663131EthyleneEthylene

ZSMZSM--5 5 TypeType

SAPOSAPO--34 34 TypeType

•• SAPOSAPO--34 produces more 34 produces more light olefinslight olefins

CC11--CC55ParaffinsParaffins

Coke+Coke+COCOxx

•• CC44+ olefin conversion could + olefin conversion could improve light olefin yieldsimprove light olefin yields

UOP 4867-17

Methanol to OlefinsYields with C4

+ Olefin Recycle

SAPOSAPO--34 34 TypeType

ZSMZSM--5 5 TypeType

EthyleneEthylene 2929 nilnil

PropylenePropylene 6060 6565

Light OlefinsLight Olefins 8989 6565

MeOHMeOHConsumption, Consumption, kg/kg Olefinkg/kg Olefin

2.62.6 3.53.5

Low methanol consumptionLow methanol consumption

•• CC44+ from SAPO almost entirely converted + from SAPO almost entirely converted •• CC44+ from ZSM+ from ZSM--5 higher in aromatics5 higher in aromatics

7070

6060

5050

4040

3030

2020

1010

00CC22

== CC33== CC44

== CC55++

% Y

ield

% Y

ield

CC11--CC55ParaffinsParaffins

Coke+Coke+COCOxx

UOP 4867-18

Methanol to OlefinsUOP/HYDRO MTO Process

RegenRegen gasgas

AirAir

MethanolMethanol

DME &Oxygen.

Recovery

WaterWater

ReactorReactor RegeneratorRegeneratorQuenchQuenchtowertower

Caustic Caustic washwash

Mixed CMixed C44

PropanePropane

EthaneEthane

Tail gasTail gas

EthyleneEthylene

PropylenePropylene

CC55++

DryerDryer

CC22HH22reactorreactor

DeDe--CC2 2 DeDe--CC11

CC22splittersplitter

CC33splittersplitterDeDe--CC33 DeDe--CC44

WaterWater

ScrubberScrubber

Fluidized bed reactor & regenerator with continuous Fluidized bed reactor & regenerator with continuous steady state operation and polymersteady state operation and polymer--grade ethylene grade ethylene and propylene productand propylene product

UOP 4867-19

Methanol to OlefinsC4

+ Olefin Conversion

•• Heavies can be converted Heavies can be converted using UOP/Total using UOP/Total Petrochemicals Olefin Petrochemicals Olefin Cracking Process (OCP)Cracking Process (OCP)

•• Zeolite based system is Zeolite based system is needed needed for heavies for heavies conversionconversion –– higher higher acidity, larger pore size.acidity, larger pore size.

CC22==

CC33==MeOHMeOH

CC44++

MTO

LightLightOlefinsOlefins

CC44--CC55OlefinsOlefins

OlefinCracking

UOP 4867-20

Methanol to OlefinsExpanded P/E Ratio of Advanced MTO

•• Increased propylene production thanks to:Increased propylene production thanks to:-- Catalyst improvementsCatalyst improvements-- Process optimizationProcess optimization

P/E up to 2.1 P/E up to 2.1 with high selectivitywith high selectivity

6060

7070

8080

9090

100100

0.80.8 1.01.0 1.21.2 1.41.4 1.61.6 1.81.8 2.02.0 2.22.2P/E Ratios P/E Ratios -- ProductsProducts

Ethy

lene

+ P

ropy

lene

, wt%

Et

hyle

ne +

Pro

pyle

ne, w

t%

(C B

asis

)(C

Bas

is)

UOP 4867-21

FCC Unit Design & Operating Envelopes

Prop

ylen

e Yi

eld,

wt

Prop

ylen

e Yi

eld,

wt -- %%

FFFF

Gasoline Gasoline + LPG+ LPG

MaximumMaximumPropylenePropylene

5

10

20

Maximum Maximum GasolineGasoline

Gas

olin

e Yi

eld,

wt

Gas

olin

e Yi

eld,

wt -- %%

FFFF

30

60

f (Rx T, PP, C/O, PT)

UOP 4867-22

PetroFCCPetroFCCTechnologyTechnology

RxCatRxCat™™TechnologyTechnology

EthyleneEthylene

PropylenePropylene

Mixed CMixed C44ssAromatic Aromatic naphthanaphtha

Cycle oilsCycle oils

High cat / oilHigh cat / oil–– RxCat technology:RxCat technology:–– DeDe--couples catalyst couples catalyst

circulation from heat circulation from heat balancebalance

Low partial pressureLow partial pressure–– Optimize Steam and Optimize Steam and

Operating PressureOperating Pressure

Optimized Catalyst Optimized Catalyst SelectionSelectionHigh TemperatureHigh TemperatureIncreased flexibilityIncreased flexibility

UOP 4867-23

The PetroFCCTM Process

Naphtha Cracker Feed EnrichmentThe MaxEne Process

•• Adsorptive separation system for extraction of Adsorptive separation system for extraction of normal normal paraffinsparaffins from naphthafrom naphtha

-- Full range naphtha (CFull range naphtha (C66 to Cto C1212))-- ExtractExtract

High recovery of normal High recovery of normal paraffinsparaffinsNormal paraffin purity up to 95% Normal paraffin purity up to 95% Liquid phase, low temperature and pressureLiquid phase, low temperature and pressureLow utilitiesLow utilities

-- RaffinateRaffinateSuperior catalytic reformer feedSuperior catalytic reformer feed

NaphthaCracker

CatalyticReformer

MaxEneUnitFull Range Naphtha

CC77--

CC77++

UOP 4867-24

Naphtha Cracker Feed EnrichmentThe MaxEne Process

Adsorptive separationAdsorptive separation•• The adsorbent has greater The adsorbent has greater

affinity for affinity for nn--paraffins paraffins Simulates a moving bedSimulates a moving bed

•• The process influent and The process influent and effluent points move, but effluent points move, but the actual mechanical the actual mechanical connections do notconnections do not

•• The solid adsorbent is in The solid adsorbent is in packed, nonpacked, non--moving bedsmoving beds

•• The liquid feed flows counterThe liquid feed flows counter--currently relative to the solidcurrently relative to the solid

RaffinateRaffinate

PumparoundPumparoundpumppump

AdsorbentAdsorbentchamberchamber ExtractExtract

columncolumn

RaffinateRaffinatecolumncolumn

Feed to Feed to reformerreformer

nn--ParaffinsParaffinsfeed to feed to steam steam

crackercrackerDesorbentDesorbent

NaphthaNaphtha

FeedFeed

ExtractExtract

Desorbent

Desorbent

11

22334455667788

RotaryRotaryvalvevalve

UOP 4867-25

The MaxEne Process EffectSingle-pass Steam Cracker Yields

Typical ComplexTypical Complex

Hydrog

en

Hydrog

enMeth

ane

Methan

eProp

ane

Propan

eButy

lene

Butylen

eBen

zene

Benzen

e

Pygas

Pygas

Ethane

Ethane

Propyle

ne

Propyle

neEthy

lene

Ethylen

e

Cra

cker

effl

uent

, wt

Cra

cker

effl

uent

, wt -- %%

4040

3030

2020

1010

00

With a With a MaxEneMaxEne UnitUnit

UOP 4867-26

Conclusions

•• New routes must be considered to meet future New routes must be considered to meet future ethylene and propylene demand ethylene and propylene demand

•• A range of economically attractive options are A range of economically attractive options are available to meet this demandavailable to meet this demand

•• Each producer must consider key selection factorsEach producer must consider key selection factors-- Feedstock availabilityFeedstock availability-- Desired product slateDesired product slate-- Integration with existing facilitiesIntegration with existing facilities

UOP 4867-27

UOP 4867-28