Вы находитесь на странице: 1из 29

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)

3
Alberta, Canada

Athabasca
Syncrude
Peace River
Fort
McMurray
Peace River
Wabasca
Cold
Lake
Edmonton

Calgary

Adapted from AERI

4
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

5
Proven World Oil Reserves
(Source: Oil and Gas Journal, Dec. 2004)

6
Upgrading Processes/Technologies
Technologies for
Residue Upgrading
Carbon Rejection Hydrogen Addition Separation
Processes Processes Processes

Catalytic Non-Catalytic Fixed Bed Ebullating Bed Slurry Phase Solvent


Cracking Cracking Hydroprocessing Hydrocracking Hydrocracking Deasphalting

FCCU Thermal Cracking/ RDS/VRDS H-Oil CANMET Rose


Visbreacking (Kellogg)
Reduced Crude VEBA
Cracking Fluid Coking/ Unicracking/ LC-Fining Combi Demex
Flexicoking HDS Cracking (UOP)
PetroFCC Hydrovisbreacking

DCC, CPP Delayed Coking Residfining EST, (HC)3

7
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 Propylene


Plant
C4’s

Pyrolysis Gasoline
Off-gas
and/or
VGO Olefins Paraffins Crude
Supplier Aromatics BTX
Ring
Cleavage
Gasoline

Hydrotreated
HVGO NHC
Unit Aromatics
Saturation Hydrogen
Cycle
Oil
Slurry Oil
10
NOVA Heavy Oil Cracking
Process
NHC Technology

11
NOVA Heavy Oil Cracking
(NHC) Process
¾ Proliferation of oil sands development in Alberta will imply
abundance of heavy oils.
¾ Cheapest of the oils (except residue) is Vacuum Gas Oil
(VGO)
¾ Goal: Transform VGO into petrochemical feedstock
(ethylene, propylene), gasoline and cycle oils
¾ Cycle oils are rich in aromatic compounds
¾ FCC type units are used by others for cracking heavy oils
provided that the proper catalyst is available (UOP –
PetroFCC, SINOPEC – DCC, CPP)
¾ 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 NHC-2 NHC-3 NHC-4

FEED 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 1.38 0.72 1.3 1.17


Factor

14
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
40.66 45.95 23.54 34.77
olefins (wt.%)

15
NHC versus Steam Cracking
Steam Steam
NHC-5 NHC-6
Cracking Cracking
Feed Type HAGO HAGO HVGO HVGO
Temp (oC) 800 660 760 660
Ethylene 18.80 11.67 15.60 9.22
Propylene 11.64 22.25 11.85 16.10
Butylene 6.01 12.03 5.99 9.45
Total Light
olefins 36.45 45.95 33.44 34.77
(wt.%)

16
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

17
Advanced Catalytic Pyrolysis
(Yield examples in wt.% from published data)

Petro
Process SC CPP NHC
FCC
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

18
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.

19
AROmatic RINg CLEavage
Process
ARORINCLE Technology

20
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 Paraffins
Ni/Mo Pd/Zeolite
H2 H2 BTX

≈130 kg H2 per 1 t LCO Depending


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

22
Heteroatoms Removal in the
First Step of ARORINCLE
Technology

Heteroatoms Feed Product


Sulfur [ppm] 2800 50
Nitrogen [ppm] 867 14

23
ARORINCLE Mass Balance
1. Step: HDS, HDN, 2. Step: Ring
HDA Cleavage
Catalyst NiW – NiMo Pd / zeolite
T [°C] 410 395
P [psi] 1000 900
LHSV [h-1] 0.5 0.2
Feed Product Feed Product
Total light paraffins 0 4.2 0 41.2
Total liquid saturates 30.8
<C12
Total liquid saturates 46.2 54.8 57.2 22.7
>C12
Total Aromatics 53.8 41.0 42.8 5.3

24
ARORINCLE Mass Balance

1. Step: HDS, HDN, 2. Step: Ring


HAD Cleavage
Feed Product Feed Product
Benzene 0.3
Toluene 0.4
Xylenes 0.8
Ethyl-Benzene 0.1
C9-Aromatics 2.9
C10-Aromatics 0.8
Monoaromatics 27.6 30.2 31.5
Diaromatics 11.6 7.6 7.9
Polyaromatics 14.6 3.3 3.4

25
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

29