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Producing Petrochemicals from Alberta Oil Sands
Andrzej Krzywicki – NOVA Chemicals CorporationVadodara, July 3, 2007
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Outline of Presentation
Introduction Project ObjectivesNOVA Heavy Oil Cracking (NHC) ProcessAromatic Ring Cleavage
(ARORINCLE) ProcessConclusions
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Oil Sands production in Alberta is projected to increase from about 1MM b/d to about 3 MM b/d in
the next 10 years (Source: CAPP 2005)
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EdmontonEdmonton
CalgaryCalgary
Peace RiverPeace RiverFort Fort
McMurrayMcMurray
Athabasca Athabasca
Peace RiverPeace RiverWabascaWabasca
ColdColdLakeLake
SyncrudeSyncrude
Alberta, Canada
Adapted from AERI
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Facts on Alberta/Canada(Source: Alberta Finance 2004)
Oil Sands Reserves: 315 billion bbls of oil in place – probable estimate and 177 billion bbls recoverable with current economics and technology. 2nd in the World to Saudi Arabia in oil reserves.
• Canada is world’s 3rd largest Natural Gas producer• Canada is world’s 9th largest crude oil producer (moving up
quickly due to oil sands)• 500,000 direct jobs in the oil industry• $35 billion capital investment• $20 billion in payment to federal and provincial governments• #1 private sector investor in Canada
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Proven World Oil Reserves(Source: Oil and Gas Journal, Dec. 2004)
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Upgrading Processes/TechnologiesTechnologies for
Residue Upgrading
Carbon RejectionProcesses
CatalyticCracking
Non-CatalyticCracking
FCCU
Reduced CrudeCracking
PetroFCC
DCC, CPP
Thermal Cracking/Visbreacking
Fluid Coking/Flexicoking
Delayed Coking
Fixed BedHydroprocessing
Ebullating BedHydrocracking
Slurry PhaseHydrocracking
SolventDeasphalting
RDS/VRDS
Unicracking/HDS
Residfining
H-Oil
LC-Fining
CANMET
VEBACombi CrackingHydrovisbreacking
EST, (HC)3
Rose (Kellogg)
Demex(UOP)
Hydrogen AdditionProcesses
SeparationProcesses
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NOVA Chemicals
5th largest producer of ethyleneand 5th largest producer of polyethylene in North AmericaMajor feedstocks: E/P/B & Naphtha for our ethylene plants and benzene for styrenicsOur Joffre-Alberta site: largest ethylene production complex in the worldCorunna cracker – a flexicrackerStyrenics – Performance products and JV with INEOS
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Objectives of the Project“Add value to bitumen in Alberta.”
Convert heavy gas oils and aromatic compounds derived from Alberta bitumen into competitively advantaged petrochemical feedstock
– Develop catalyst and process to convert heavy gas oils (oil sands derived) to olefins, gasoline and cycle oils (aromatic rich)
– Develop catalyst and process technology to convert aromatic rich fractions in heavy oils (oil sands derived) to paraffins (feed to steam cracker) and BTX
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Block Flow Diagram of New ComplexHydrogen
Slurry Oil
Off-gas and/or VGO Supplier
Offgases Ethylene Plant
NHC Unit
Methane
Ethylene
Propylene
C4’s
Olefins
Aromatics Saturation
Aromatics Ring
Cleavage
Pyrolysis Gasoline
Hydrotreated HVGO
Paraffins Crude BTX
Gasoline
HydrogenCycle Oil
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NOVA Heavy Oil Cracking ProcessNHC Technology
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NOVA Heavy Oil Cracking (NHC) Process
Proliferation of oil sands development in Alberta will imply abundance of heavy oils.Cheapest of the oils (except residue) is Vacuum Gas Oil (VGO)Goal: Transform VGO into petrochemical feedstock (ethylene, propylene), gasoline and cycle oilsCycle oils are rich in aromatic compoundsFCC type units are used by others for cracking heavy oils provided that the proper catalyst is available (UOP –PetroFCC, SINOPEC – DCC, CPP)The catalyst for cracking oil sands derived heavy oils to petrochemical feedstock not commercially available now.
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Mechanism of Catalytic Pyrolysis for Heavy Oils
• Free radical mechanism = more n-C4s
• Carbonium ion mechanism = more i-C4s
• The ratio RM of i-C4 yield to n-C4 yield = relative extent of occurrence of the two mechanisms in catalytic pyrolysis processes
• Higher RM value for a given catalyst versus another catalyst indicates predominance of carbonium ion mechanism for that catalyst over free radical mech.
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RM factor of some prepared catalysts
NHC-1 NHC-2 NHC-3 NHC-4
FEED HVGO HVGO HVGO HVGO
i-C4 0.54 0.24 0.83 0.49n-C4 0.39 0.33 0.64 0.42
RMFactor
1.38 0.72 1.3 1.17
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Feedstock and Catalyst Effects
Base NHC-5 Base NHC-6
Feed Type HAGO HAGO HVGO HVGO
Temp (oC) 660 660 660 660
Ethylene 12.31 11.67 6.96 9.22
Propylene 19.35 22.25 10.72 16.10
Butylene 9.0 12.03 5.86 9.45
Total Light olefins (wt.%) 40.66 45.95 23.54 34.77
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NHC versus Steam Cracking
SteamCracking
NHC-5Steam
CrackingNHC-6
Feed Type HAGO HAGO HVGO HVGOTemp (oC) 800 660 760 660Ethylene 18.80 11.67 15.60 9.22Propylene 11.64 22.25 11.85 16.10Butylene 6.01 12.03 5.99 9.45Total Light olefins (wt.%)
36.45 45.95 33.44 34.77
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NHC Unit Results
Yield (wt.%) LVGO HVGOOlefins 38.9 32.1
Gasoline 23.4 22.0
LCO 18.9 20.1
Coke 2.3 5.7
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Advanced Catalytic Pyrolysis(Yield examples in wt.% from published data)
Process SC CPP PetroFCC NHC
Feed Source Daqing Daqing N.A -
Feed Type AGO AR VGO HAGO
Temp. (oC) 800 640 N.A 660
Ethylene 26.60 20.37 6.00 11.67
Propylene 13.75 18.23 22.00 22.25
Butadiene 4.39 0.40 14.00 12.03
Total Olefins 44.75 39.00 42.00 45.95
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NHC Technology Summary
- Olefin yield improvement over steam cracking was achieved using FCC platform
- Olefin yield depends on feed characteristics- Over 50 catalysts and modifications thereof
were synthesized and produced- Over 100 runs were carried out in the
confined fluid bed reactor (MAT unit) to optimize catalysts
- Best catalysts were run in the 2kg/hr Technical Scale Unit.
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AROmatic RINg CLEavage Process
ARORINCLE Technology
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ARORINCLE Process
• Aromatics-rich stream converted to paraffins and BTX. Two step process
• Step 1: Aromatic Rings Saturation on standard commercial catalysts (HDA, HDN and HDS)
• Step 2: Saturated aromatic rings opened & cleaved on proprietary zeolite based catalyst
• Standard hydrotreating process equipment used
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Developing Ring Opening/Cleavage Technology
ARORINCLE
Ni/MoLCO
H2Pd/Zeolite
H2
ParaffinsBTX
Depending on operating
severity
≈130 kg H2 per 1 t LCO≈100 kg H2 per 1 t hydrogenated LCO
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Heteroatoms Removal in the First Step of ARORINCLE
Technology
Heteroatoms Feed ProductSulfur [ppm] 2800 50
Nitrogen [ppm] 867 14
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ARORINCLE Mass Balance
1. Step: HDS, HDN, HDA
2. Step: Ring Cleavage
Catalyst NiW – NiMo Pd / zeoliteT [°C] 410 395P [psi] 1000 900LHSV [h-1] 0.5 0.2
Feed Product Feed ProductTotal light paraffins 0 4.2 0 41.2Total liquid saturates <C12
30.8
Total liquid saturates >C12
46.2 54.8 57.2 22.7
Total Aromatics 53.8 41.0 42.8 5.3
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ARORINCLE Mass Balance
1. Step: HDS, HDN, HAD
2. Step: Ring Cleavage
Feed Product Feed ProductBenzene 0.3Toluene 0.4Xylenes 0.8Ethyl-Benzene 0.1C9-Aromatics 2.9C10-Aromatics 0.8
Monoaromatics 27.6 30.2 31.5Diaromatics 11.6 7.6 7.9Polyaromatics 14.6 3.3 3.4
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ARORINCLE Results
Production of paraffin-rich stream over a Ring Cleavage catalyst has been demonstrated
Layers of commercial catalysts chosen for the 1st step
Zeolite based catalysts chosen for the second step
Acquired great understanding of both steps of ARORINCLE technology
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Conclusions
It is possible to convert gas oil fractions from crude oil or oil sands processing into petrochemicals and petrochemical feedstocks
Two different catalytic steps were developed using different technology platforms
– NHC technology - FCC platform
– ARORINCLE technology - hydrotreating (trickle-bed reactor) platform
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Acknowledgement Collaborative effort:
NOVA Chemicals Project Team: Michel Berghmans, John Henderson, Andrzej Krzywicki, James Lee, Mike Oballa, Vasily Simanzhenkov, Sunny Wong, Eric Kelusky, Graeme Flint
University of Stuttgart
China University of Petroleum
University of Calgary
Alberta Energy Research Institute
Path Forward
Thank You
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