© 2006 UOP LLC. All rights reserved. Light Olefin Technologies Light Olefin Technologies UOP 4638-01 UOP 4867-01 Journées Annuelles du Pétrole October 11, 2007 © 2007 UOP LLC. All rights reserved. Bryan Glover UOP LLC Bryan Glover UOP LLC
© 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