About Nova Chemical Project

Producing Petrochemicals from Alberta Oil Sands

Andrzej Krzywicki – NOVA Chemicals Corporation Vadodara, July 3, 2007 1

Outline of Presentation ¾ Introduction ¾ Project Objectives ¾ NOVA Heavy Oil Cracking

(NHC) Process ¾ Aromatic Ring Cleavage

(ARORINCLE) Process ¾ Conclusions 2

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

Catalytic Cracking

Non-Catalytic Cracking

FCCU Reduced Crude Cracking

Hydrogen Addition Processes

Fixed Bed Hydroprocessing

Thermal Cracking/ Visbreacking

Ebullating Bed Hydrocracking

RDS/VRDS

Fluid Coking/ Flexicoking

Unicracking/ HDS

Delayed Coking

Residfining

PetroFCC DCC, CPP 7

Separation Processes

Slurry Phase Hydrocracking

H-Oil

LC-Fining

CANMET

Solvent Deasphalting

Rose (Kellogg)

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

NOVA Chemicals ¾ 5th largest producer of ethylene

and 5th largest producer of polyethylene in North America ¾ Major feedstocks: E/P/B & Naphtha for our

ethylene plants and benzene for styrenics ¾ Our Joffre-Alberta site: largest ethylene

production complex in the world ¾ Corunna cracker – a flexicracker ¾ Styrenics – Performance products and JV with INEOS 8

Objectives of the Project “Add value to bitumen in Alberta.” ¾ 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 9

Block Flow Diagram of New Complex Hydrogen Methane Ethylene Offgases

Ethylene Plant

Propylene C4’s Pyrolysis Gasoline

Off-gas and/or VGO Supplier

Olefins

Paraffins

Aromatics Ring Cleavage

Crude BTX

Gasoline

Hydrotreated HVGO

NHC Unit

Aromatics Saturation Cycle Oil

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Slurry Oil

Hydrogen

NOVA Heavy Oil Cracking Process NHC Technology

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NOVA Heavy Oil Cracking (NHC) Process ¾ Proliferation of oil sands development in Alberta will imply ¾ ¾ ¾ ¾

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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. 12

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. 13

RM factor of some prepared catalysts NHC-1 FEED

NHC-2

NHC-3

NHC-4

HVGO

HVGO

HVGO

HVGO

i-C4

0.54

0.24

0.83

0.49

n-C4

0.39

0.33

0.64

0.42

RM Factor

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

9.0

12.03

5.86

9.45

40.66

45.95

23.54

34.77

Butylene Total Light olefins (wt.%)

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NHC versus Steam Cracking Steam Cracking

Steam NHC-5 Cracking

NHC-6

Feed Type

HAGO

HAGO

HVGO

HVGO

Temp (oC) Ethylene Propylene Butylene Total Light olefins (wt.%)

800 18.80 11.64 6.01

660 11.67 22.25 12.03

760 15.60 11.85 5.99

660 9.22 16.10 9.45

36.45

45.95

33.44

34.77

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NHC Unit Results Yield (wt.%)

LVGO

HVGO

Olefins

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)

SC

CPP

Petro FCC

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

Process Feed Source

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NHC -

NHC Technology Summary - Olefin yield improvement over steam cracking -

-

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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.

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 21

Developing Ring Opening/ Cleavage Technology ARORINCLE

LCO H2

Ni/Mo

H2

Pd/Zeolite

≈130 kg H2 per 1 t LCO ≈100 kg H2 per 1 t hydrogenated LCO 22

Paraffins BTX

Depending on operating severity

Heteroatoms Removal in the First Step of ARORINCLE Technology Heteroatoms

Feed

Product

Sulfur [ppm]

2800

50

Nitrogen [ppm]

867

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 Aromatics 24

2. Step: Ring Cleavage

NiW – NiMo 410 1000 0.5 Feed Product 0 4.2

Pd / zeolite 395 900 0.2 Feed Product 0 41.2 30.8

46.2

54.8

57.2

22.7

53.8

41.0

42.8

5.3

ARORINCLE Mass Balance 1. Step: HDS, HDN, HAD Benzene Toluene Xylenes Ethyl-Benzene C9-Aromatics C10-Aromatics Monoaromatics Diaromatics Polyaromatics

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2. Step: Ring Cleavage

Feed

Product

Feed

27.6 11.6 14.6

30.2 7.6 3.3

31.5 7.9 3.4

Product 0.3 0.4 0.8 0.1 2.9 0.8

ARORINCLE Results ¾ Production of paraffin-rich stream over a Ring Cleavage catalyst has been demonstrated ¾ Layers of commercial catalysts chosen for the 1st step ¾Zeolite based catalysts chosen for the second step ¾ Acquired great understanding of both steps of ARORINCLE technology 26

Conclusions ¾ It is possible to convert gas oil fractions from

crude oil or oil sands processing into petrochemicals and petrochemical feedstocks ¾ Two different catalytic steps were developed

using different technology platforms – NHC technology - FCC platform – ARORINCLE technology - hydrotreating (trickle-bed reactor) platform 27

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 28

Path Forward

Thank You

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