Producing Petrochemicals from Alberta Oil Sands

Andrzej Krzywicki – NOVA Chemicals Corporation Vadodara, July 3, 2007
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Outline of Presentation
Introduction Project Objectives NOVA Heavy Oil Cracking

(NHC) Process
Aromatic Ring Cleavage (ARORINCLE) Process Conclusions
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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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Alberta, Canada

Athabasca Syncrude
Peace River Fort McMurray

Peace River Wabasca Cold Lake
Edmonton Calgary

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/Technologies
Technologies for Residue Upgrading
Carbon Rejection Processes Hydrogen Addition Processes Separation Processes

Catalytic Cracking

Non-Catalytic Cracking

Fixed Bed Hydroprocessing

Ebullating Bed Hydrocracking

Slurry Phase Hydrocracking

Solvent Deasphalting

FCCU Reduced Crude Cracking PetroFCC DCC, CPP 7

Thermal Cracking/ Visbreacking Fluid Coking/ Flexicoking

RDS/VRDS

H-Oil

CANMET

Rose (Kellogg)

Unicracking/ HDS Residfining

LC-Fining

VEBA Combi Demex Cracking (UOP) Hydrovisbreacking EST, (HC)3

Delayed Coking

NOVA Chemicals
5th largest producer of ethylene and 5th largest producer of polyethylene in North America Major feedstocks: E/P/B & Naphtha for our ethylene plants and benzene for styrenics Our Joffre-Alberta site: largest ethylene production complex in the world Corunna cracker – a flexicracker Styrenics – 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 Complex
Hydrogen Methane Ethylene Offgases

Ethylene Plant
Pyrolysis Gasoline

Propylene C4’s

Off-gas and/or VGO Supplier

Olefins

Paraffins

Aromatics Ring Cleavage

Crude BTX

Gasoline

Hydrotreated HVGO

NHC Unit
Cycle Oil

Aromatics Saturation

Hydrogen

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Slurry Oil

NOVA Heavy Oil Cracking Process
NHC 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 oils Cycle oils are rich in aromatic compounds FCC 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 FEED i-C4 n-C4 RM Factor HVGO 0.54 0.39 1.38 NHC-2 HVGO 0.24 0.33 0.72 NHC-3 HVGO 0.83 0.64 1.3 NHC-4 HVGO 0.49 0.42 1.17

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Feedstock and Catalyst Effects
Base Feed Type Temp (oC) Ethylene Propylene Butylene Total Light olefins (wt.%) HAGO 660 12.31 19.35 9.0 40.66 NHC-5 HAGO 660 11.67 22.25 12.03 45.95 Base HVGO 660 6.96 10.72 5.86 23.54 NHC-6 HVGO 660 9.22 16.10 9.45 34.77

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NHC versus Steam Cracking
Steam Cracking Feed Type Temp (oC) Ethylene Propylene Butylene Total Light olefins (wt.%)
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Steam NHC-5 Cracking HAGO 660 11.67 22.25 12.03 45.95 HVGO 760 15.60 11.85 5.99 33.44

NHC-6 HVGO 660 9.22 16.10 9.45 34.77

HAGO 800 18.80 11.64 6.01 36.45

NHC Unit Results
Yield (wt.%) Olefins Gasoline LCO Coke
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LVGO 38.9 23.4 18.9 2.3

HVGO 32.1 22.0 20.1 5.7

Advanced Catalytic Pyrolysis
(Yield examples in wt.% from published data)

Process
Feed Source Feed Type Temp. (oC) Ethylene Propylene Butadiene Total Olefins
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SC
Daqing AGO 800 26.60 13.75 4.39 44.75

CPP
Daqing AR 640 20.37 18.23 0.40 39.00

Petro FCC
N.A VGO N.A 6.00 22.00 14.00 42.00

NHC
HAGO 660 11.67 22.25 12.03 45.95

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

LCO H2

Ni/Mo

H2

Pd/Zeolite

Paraffins BTX

≈130 kg H2 per 1 t LCO ≈100 kg H2 per 1 t hydrogenated LCO
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Depending on operating severity

Heteroatoms Removal in the First Step of ARORINCLE Technology
Heteroatoms Sulfur [ppm] Nitrogen [ppm] Feed 2800 867 Product 50 14

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ARORINCLE Mass Balance
1. Step: HDS, HDN, HDA Catalyst T [°C] P [psi] LHSV [h-1] Total light paraffins Total liquid saturates <C12 Total liquid saturates >C12 Total Aromatics
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2. Step: Ring Cleavage Pd / zeolite 395 900 0.2 Feed Product 0 41.2 30.8 57.2 42.8 22.7 5.3

NiW – NiMo 410 1000 0.5 Feed Product 0 4.2

46.2 53.8

54.8 41.0

ARORINCLE Mass Balance
1. Step: HDS, HDN, HAD Feed Benzene Toluene Xylenes Ethyl-Benzene C9-Aromatics C10-Aromatics Monoaromatics Diaromatics Polyaromatics Product 2. Step: Ring Cleavage Feed Product 0.3 0.4 0.8 0.1 2.9 0.8

27.6 11.6 14.6

30.2 7.6 3.3

31.5 7.9 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
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Path Forward

Thank You

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