Producing Petrochemicals from Alberta Oil Sands
Andrzej Andrzej Krzywicki Krzywicki – NOVA Chemical Chemicals s Corporatio Corporation n Vadodara, July 3, 2007
Outline of Presentation
Introduction Project Objectives NOVA Heavy Oil Cracking
(NHC) Process
Aromatic Ring Cleavage (ARORINCLE) Process Conclusions
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)
Alberta, Canada
Athabasca Syncrude Peace River Fort McMurray
Peace River Wabasca Cold Lake Edmonton Calgary
Adapted from AERI
Facts on Alberta/Canada (Source: Alberta Finance 2004)
Oil Sand Sands s Reserve Reserves: s: 315 315 billi billion on bbls bbls of oil oil in plac place e – pro probab bable le 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 in the oil industry $35 billion capital investment $20 $20 bil billilion on in payme ayment nt to fed federa eral and and prov provin inci cial al gove govern rnm ments ents #1 private sector investor in Canada
5
Proven World Oil Reserves (Source: Oil and Gas Journal, Dec. 2004)
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
Fluid Coking/ Flexicoking
Ebullating Bed Hydrocracking
RDS/VRDS
Unicracking/ HDS
PetroFCC DCC, CPP
Separation Processes
Slurry Phase Hydrocracking
H-Oil
CANMET
LC-Fining
VEBA Combi Cracking
Solvent Deasphalting
Hydrovisbreacking Delayed Coking
Residfining
EST, (HC)3
Rose (Kellogg) Demex (UOP)
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 Corunn Corunna a crac cracker ker – a flex flexicra icracke ckerr Styrenics – Performanc Performance e product products s and and JV JV with with Styrenics INEOS
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 Develop catalys catalystt and process process to convert convert heavy heavy gas oils (oil sands derived) to olefins, gasoline and cycle oils (aromatic rich) – Develop Develop cataly catalyst st and and process process technolog technology y to convert aromatic rich fractions in heavy oils (oil sands derived) to paraffins (feed to steam cracker) and BTX
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 Cycle Oil Slurry Oil
Aromatics Saturation
Hydrogen
NOVA Heavy Oil Cracking Process NHC Technology
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 – PetroF PetroFCC, CC, SINOPE SINOPEC C – DCC, CPP) The catalyst for cracking oil sands derived heavy oils to petrochemical feedstock not commercially available now.
Mechanism of Catalytic Pyrolysis for Heavy Oils • Free Free radi radica call mec mech hanis anism m = mo more n-C4 n-C4s s • Carb Carbo onium nium ion ion me mechan chanis ism m = mor more e i-C i-C4s 4s • 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.
RM factor of some prepared catalysts N HC - 1 FEED
N HC - 2
N HC - 3
NHC-4
HVGO
HVGO
HVGO
HVGO
i-C4
0.54
0 .2 4
0 .8 3
0.49
n-C4
0.39
0.33
0.64
0.42
RM Factor
1.38
0.72
1.3
1 .1 7
Feedstock and Catalyst Effects B ase
NHC-5
Base
N HC - 6
Feed Type
HAGO
HAGO
HVGO
HVGO
Temp (oC)
66 0
66 0
66 0
660
Ethylene
12.31
1 1 .6 7
6.96
9.22
Propylene
19.35
22.25
10.72
16.10
9.0
12.03
5.86
9 .4 5
40.66
45.95
23.54
34.77
Butylene Total Light olefins (wt.%)
15
NHC versus Steam Cracking Steam Cracking
Steam NHC-5 Cracking
NHC-6
Feed Type
HAGO
HAGO
HVGO
HVGO
Temp (oC)
800
660
760
660
Ethylene
1 8 .8 0
11.67
15.60
9 .2 2
Propylene
11.64
2 2 .2 5
11.85
16.10
6.01
12.03
5.99
9.45
36.45
45.95
33.44
34.77
Butylene Total Light olefins (wt.%)
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
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
NHC -
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.
AROmatic ARO matic RIN RINg g CLE CLEavage avage Process ARORINCLE Technology
ARORINCLE Process • Arom Aromat atic icss-ri rich ch stre stream am conv conver erte ted d to to par paraf affi fins ns and and BTX. Two step process • Step Step 1: Arom Aromat atic ic Ring Rings s Sat Satur urat atio ion n on on standard commercial catalysts (HDA, HDN and HDS) • Step Step 2: 2: Satu Satura rate ted d arom aromat atic ic rin rings gs ope opene ned d& cleaved on proprietary zeolite based catalyst • Stan Standa dard rd hydr hydrot otrea reati ting ng proc proces ess s equi equipm pmen entt used used
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
≈ ≈
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
ARORINCLE Mass Balance 1. Step: HDS, HDN, HDA Catalyst
2. Step: Ring Cleavage
NiW – NiMo
Pd / zeolite
T [°C]
41 0
395
P [psi]
1 0 00
9 00
0.5
0.2
LHSV [h-1] Total light paraffins
Feed
Product
Feed
Product
0
4.2
0
41.2
Total liquid saturates
30.8
Total liquid saturates >C12
46.2
54.8
57.2
22.7
Total Aromatics
53.8
4 1 .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
25
2. Step: Ring Cleavage
Feed
Product
Feed
2 7 .6 11.6 1 4 .6
30.2 7 .6 3 .3
3 1 .5 7.9 3.4
Product 0 .3 0 .4 0 .8 0 .1 2 .9 0 .8
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
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 tech techno nolo logy gy - FCC plat platfo form rm – AROR ARORIN INCL CLE E tech techno nolo logy gy - hydr hydrot otre reat atin ing g (trickle-bed reactor) platform
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
