Journées Annuelles du PétroleLes 10 et 11 octobre 2007

Paris - Palais des Congrès, Porte Maillot

Hydrocarbures, la maîtrise du futur

Alternative Olefin Feedstocks –Refinery Links

Colin BowenV.P. Olefins

Business DevelopmentShaw Stone & Webster, Inc.

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Alternative Olefin Feedstocks – Refinery Links

• Conventional Olefin Feedstocks – Economic Trends• Current Regional Feedstock Economics• Alternative Feedstocks – Yesterday, Today, Tomorrow• Ethylene Sources, Trends• Propylene Sources, Trends• Catalytic Olefins – Technology Basis

– Integration Opportunities– Revamp Opportunities– Contaminant Removal– Relative Economics

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Feedstock & Energy Economic Drivers

Crude Oil$/bbl

Crude Oil$/MMbtu

Natural Gas$/MMbtu

1970 ~6.5 ~1.2 ~0.2

1980 ~25 ~4.6 ~1.61988 ~16 – 38 ~2.9 – 7.0 ~1.5 – 2.0

3Q2007 ~78 ~14 ~7 Standard Ratios:

Crude Costs $78/bbl ≡ $585/MT ≡ $14/MMbtuEthane Production Cost ~ $1/MMbtu above Natural Gas CostNaphtha ~ 120 – 130% Crude Oil CostHVGO ~ 85 – 95% Crude Oil CostAGO ~ 125 – 135% Crude Oil Cost

www.eia.doe.gov

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Relative Ethylene Production Economics

Basis: Steam Cracker ~600 kta Ethylene, 95% Operating Rate

Unit rates derived from CMAI Data, 2006

ETHANE NAPHTHA GAS OIL

$/tC2H4 $/t C2H4 $/t C2H4

Feedstock Cost 653 1892 2669Co-Product Credits 190 1490 2175Net Feedstock Cost 463 402 494Utilities, Cat/Chem 174 240 266Fixed Operating Costs 51 64 67Total Production Costs (+Admin) 696 716 838Ethylene Revenue (-Distribution) 1016 1016 1016Cash Margin 320 300 178

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Alternative Ethylene Technologies - Yesterday

• Direct Contact with High Temp Reactants• Inert Circulating Solids• Methane Routes – Oxidative/ Dehydrochlorination• Promoted Pyrolysis Developments

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Previous TechnologiesDirect Contact Thermal Processes

• Combustion Gas(UCC-ACR, Rockwell)

• Shift Reaction Gas(Dow - PCC, Ube, Toyo)

• Plasma(Huels, McGill Univ.)

• Shock Wave(Washington Univ., Nova)

Customized Recovery Flowschemes, Contaminant Concerns

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Previous TechnologiesInert Circulating Solids Demo Units

Thermal Regenerative Cracking(Quick Contact QC)

K-K ProcessCirculating Coke Particles

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Promoted Pyrolysis – Anticipated Advantages

• Combination co-cracking (S&W Duo-cracking)• Hydro-pyrolysis

– Pierrefitte-Audy, IFP, Rockwell• In-situ pre-gasification and pyrolysis

– Veba / Linde

Disappointed Demonstrations

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Alternative Olefin Feedstocks - Today

• Conventional pyrolysis, lower cost feedstocks– HCR– HAGO– GTL– HNGL

• LNG derived E / P / B feedstocks• HOFCC / DCC Catalytic Cracking

– HVGO– LSWR

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Alternative Olefin Feedstocks – Tomorrow

• Methane/Syn-gas/MeOH/MTO or MTP• Methane / syn-gas / Fischer-Tropsch• Coal / similar syn-gas technologies• Bio-routes via ethanol• VGO/ATB – next generation Catalytic Olefins (CPP)• Catalytic Naphtha Cracking• Refinery Off Gas Olefins• Bitumen-derived light feedstocks• Heavy olefin co-products (OCP)

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Global Ethylene Production & Predictions

2007 Production ~ 115 MMTA (Capacity ~ 125 MMTA)

2012 Production ~ 160 MMTA

2012 % Production from Ethane ~ 43%

• Mid East Project Incentives

• US Ethane vs Naphtha Cost Advantage

Naphtha54%

Others2%

Ethane28%

Propane7%

Butane4%

Gas Oil5%

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Global Propylene Production & Predictions

Pyrolysis64% Others

6%

FCC Units30%

2007 Production ~ 70 MMTA

2012 Production ~ 92 MMTA

Δ Production from Pyrolysis ~ 8 MMTA

Δ Production from FCC linked units ~12 MMTA

Δ Production from Alternative Routes ~ 2 MMTA

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Current FCC Capacities / Productions

Global FCC Operating Capacity ~ 16 MMBPD~ 770 MMTA

Typical light olefin yields ~ 3 - 4% wt C3H6

~ 0.7 – 1.2 % wt C2H4

Current FCC derived C3H6 ~ 28 MMTAApprox 2/3 FCC C3H6 as polymer gradeApprox 1/3 FCC C3H6 as refinery grade (+C3H8)C3H6 yield can be increased by ZSM-5 catalyst

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ZSM-5 Catalyst for FCC Applications

• ZSM-5 Zeolite catalysts convert gasoline fraction to lighter products, principally LPG.

• Potential C3H6 yield could increase to ~10% wt• FCC converter and recovery sections are correspondingly impacted• Related factors: Reaction temp, Convsn, Feedstock Adjustment• Economic incentives are linked to:

Δ Cost : propylene, propane, C4+ vs gasolineΔ Cost : catalystΔ Cost : unit capacity and potential design modificationsΔ Cost : propylene polymer grade vs refining grade productionΔ Cost : product transfer or freight costs

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Refinery Off Gas Opportunities

• Refinery Off Gas (ROG) primary source is FCC• FCC derived C2H4 is ~ 0.7 – 1.2% wt• Hence potential ROG C2H4 is up to 7 MMTA (but actual

rate is less than 1 MMTA)• ROG collection and ethylene recovery is advantageous

where refinery / petrochemical units are adjacent• ROG recovery units in several such USGC sites

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Refineries and Steam Crackers - USGC

Refineries

Black

Steam Crackers

Yellow

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Dedicated FCC Light Olefins Production

• Current Deep Catalytic Cracking (DCC) can increase both propylene & ethylene yields further (still 4:1 ratio)

4

8

20

FCC

FCCZSM-5

DCC(HOFCC)

C3H6Wt%

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DCC Technology Features• Secondary Cracking of Naphtha to produce

olefins

• Utilizes Well Proven FCC Components from S&W/Axens FCC Process

• No Separate Additive/Diluent

• High Pentasil Content

• Catalyst is Competitively Priced

• Utilizes Extensive S&W Experience in Polymer Grade C3

= and C2= Production Including

Contaminant Removals

• High Yields of C3/C4 Olefins and LPG

• Well Proven Process - Number of commercial units are operating

• Suitable for Integrating with Steam Crackers

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Catalytic Olefin Typical Yields

CPP (next generation) can increase ethylene product ratio.

10 20 30

C3H6

CPP

C2H4

FCCRFCC

DCC-2DCC-1

5

10

20

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Ethylene (wt%) vs Throughput

(25°API Feed)

0

200

400

600

800

1000

1200

0 10 20 30 40 50 60 70 80 90 100

Unit Throughput (1000's BPD)

Ethy

lene

Pro

duct

(100

0's

MT/

Y) Example: @ 50 MBPD Throughput,1 wt% Ethylene = 25,000 MT/Y4 wt% Ethylene = 99,000 MT/Y18 wt% Ethylene = 446,000 MT/Y

1 wt%

20

22

5

18

3

1 wt%

5

CPPCPP

DCCDCCFCCFCC

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Propylene (wt%) vs Throughput

(25°API Feed)

0

200

400

600

800

1000

0 10 20 30 40 50 60 70 80 90 100

Unit Throughput (1000's BPD)

Pro

pyle

ne P

rodu

ct (1

000'

s M

T/Y)

4 wt%

20

16

12

8

Example: @ 50 MBPD Throughput,4 w t% Propylene = 99,000 MT/Y12 w t% Propylene = 297,000 MT/Y20 w t% Propylene = 495,000 MT/Y

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DCC 1 and DCC 1 and CPPCPP

DCC 2DCC 2

FCCFCCAdditivesAdditives

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• High matrix activity for primary cracking of heavy feeds• Modified mesopore zeolite with pentasil structure for

secondary cracking of primary gasoline range product• Good isomerization performance • Low hydrogen transfer reaction• Good abrasion resistance

A series of DCC catalysts is formulated by RIPP and manufactured by Qilu Petrochemical Company

DCC catalysts are designed to possess the following characteristics:

DCC Catalyst Features

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TYPE I TYPE I TYPE IITYPE IIROT, °C 540-575 505-540

Cat/Oil, (wt / wt) 9-15 7-11

Dilution Steam Rate, wt% of Feed 20-30 10-15

Type of Cracking Riser & Bed Riser

Catalyst TypePentasil Zeolite Content High Medium

Comparison of DCC Type I and II Operating Conditions

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Process DCC Type I DCC Type II FCCMaterial Balance,wt%C2 Minus 11.9 3.6 3.5C3 & C4 LPG 42.2 34.5 17.6Naphtha 26.6 41.0 54.8LCO 6.6 9.8 10.2DO 6.1 5.8 9.3Coke 6.0 4.3 4.3Loss 0.6 1.0 0.3

Total 100.0 100.0 100.0Propylene 21.0 14.3 4.9Butylene 14.3 14.7 8.1

Feed: Waxy Chinese VGO, Pilot Plant Data

Product Yields for DCC Type I and II Operation

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No Location Feedstock Kt/a

Startup date

DCC type Feedstock

1 Jinan, PRC 150 1994 I & II VGO+DAO

2 Anqing, PRC 500 1995 I VGO+CGO

3 Daqing, PRC 120 1995 I VGO+ATB

4 TPI, Thailand 750 1997 I VGO+WAX+ ATB

5 Jingmen, PRC 800 1998 II VGO+VTB

6 Shengyang, PRC 400 1998 I VGO+VTB

7 Jinzhou, PRC 300 1999 I & II ATB

8 Lanxing, PRC 500 2005 I ATB

9 PetroRabigh, KSA 4600 2008 I HTVGO

10 JSC Tanneco Nishnekamsk FSU 800 2009 I HTVGO

Licensed DCC Units

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DCC Units – In Progress

Location Feedrate Propylene Status/ DCC Typekta kta Startup

PetroRabigh, KSA 4600 950 2008 I

Nishnekamsk, FSU 1100 225 2009 I

Several Prospective DCC Projects under Evaluation

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DCC - Thai Petrochemical Industries (1997)

Feedrate 18 MBPDPropylene 150 KTA

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TPI DCC Yields (1998 Test Data)

Feedstock Hydrotreated Arabian Light VGOPlus 6.5% DAO and 11% Wax

Catalyst CRP-1Reactor Temp,°C 565Yields, w%

C2 Minus 11.6C3+C4 41.5C5+ Naphtha 35.7RON 98.5MON 85.3

Olefin Yields, w%Ethylene 5.3Propylene 18.5Butylenes 13.3

In which Isobutylene 5.9

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DCC Process Benefits

• DCC is Commercially Proven and Enables the Refiner to Move Into Higher Value Niche Petrochemical Markets

• Refining/Petrochemical Integration Provides a very Attractive Return on Capital

• Low Cost Feedstocks Coupled with Flexibility to Compete in both Fuels & Petrochemicals is

Essential for Long-term Competitiveness

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CPP Key Elements

• FCC type reactor/regenerator scheme

• Dual function type catalyst– Acid sites, carbenium ions, C3

- C4- production

– Free radical initiators, C2- C3

- production

• 600–650 °C (1100-1200 °F) cracking temp

• Relatively high cat:oil ratio (15-20)

• Relatively high stm:oil ratio (0.3 – 0.5)

• Flexible propylene:ethylene ratio (0.5 – 1.0)

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CPP Performance Characteristics• Higher Severity Cracking of Heavy Oil

• Secondary Cracking of Naphtha

• Recycle Cracking of Low Value Co-Products

• Flexible Operating ModesMaximum Ethylene

Maximum Propylene

Maximum Total Olefins

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DCC/CPP Product Yields (wt%)DCC CPP

Feed Paraffinic VGO + ATB Paraffinic VGO + ATBASTM °F 650 – 1300 650 - 1300

C2 & Lighter 12 41C3 / C4 42 25C5 - 400 °F 27 12LCO / HCO 12 13

C2 4 24C3 23 15C4 17 7

---

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Shenyang Paraffin-Wax Chemical Co., LtdCPP Commercial Prototype 2008

Earlier DCC-2 Unit, First Commercial CPP Unit

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CPP Pyrolysis Gas Purification and Separation Project

CPP Gas

REFRIG

CONTAMREMOVAL

HOTFRAC

DCCCONVERTER

&FRACTIONATOR

R/CFNCE

COMP

COLD FRAC

Dry Gas

Fuel Gas

Ethylene

Propylene

C6+

C4/C5

Propane Ethane

Propane

Fuel Oil

CPP Naphtha

C5-

C6+

CPPCONVERTER

& FRACTIONATOR

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CPP Recovery Design Principles• CG compression, 4 stages• Amine / NaOH acid gas removal• Front end DeC3, As/Hg removal• De-Oxo, drier, COS/RSH chemi-sorption• Conventional cryogenic fractionation• C3 stripper / rectifier / hot water belt• C2, C3, C4, C5 recycle cracking

Optimally Combined Steam Cracker / ROG Configuration

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CPP Advantages & Potential

• Low cost feedstock

• High quality C5+ aromatic naphtha

• Flexible P:E ratio

• Recycle cracking of low value co-products

• Low cost fuel (ie. self produced coke)

• Integrate with existing ethylene unit

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O2 ThiophenesNOx DisulfidesH2S MeOHCO2 PropanolH2O MercuryCOS AsH3CS2 PH3NH3 OxygenatesHCN Acetylenes RSH Dienes

Typical Contaminants in ROGTypical Contaminants in ROG

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ROG TreatmentsContaminant Treatment Method

CO2 & H2S Amine and caustic washes

Oxygen Most dangerous, removed by hydrogenation

NOx Dangerous in the presence of O2, removed by hydrogenation

NH3 Formed by NOx hydrogenation and removed by adsorption

COS Removed by MEA and also by adsorption

RSH Removed by adsorption

AsH3 Removed by hydrogenation catalyst and finally by adsorption

Hg Removed by HgSiv3, sulfur / iodine impregnated charcoal, or sulfided metals

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Typical ROG Treatment

ROGFrom Refinery

Treated ROG To Ethylene Plant

Amine Wash

DeOxo Feed / Effluent Cross

Exchanger

DeOxoSteam Heater

DeOxoReactor

Reactor Effluent Cooler

Dryer Feed Drum

Dryer / Mercury

Removal Beds

RSH/COS Removal

Beds

Arsine Removal

Bed

NaOHWash

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Recent ROG Recovery Unit

DeOxo Reactor< 1 ppm mol O2

< 0.1 ppm mol NOx< 0.5% C2H4 loss

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• Catalytic Pyrolysis Process (CPP) for max ethylene• Deep Catalytic Cracking (DCC) for max propylene• Yields increased by catalytic recycling of C4/C5 cut• Integration / conversion opportunities

Catalytic Olefins Production - Summary

Low Cost Alternative Route to Light Olefins

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Relative Ethylene Production EconomicsBasis: ~600 kta Ethylene, 95% Operating Rate

Unit rates derived from CMAI Data, 2006

NAPHTHACRACKER

GAS OILCRACKER

HVGO/CPPMAX C2

- CASE

$/t C2H4 $/t C2H4 $/t C2H4

Feedstock Cost 1892 2669 2162Co-Product Credits 1490 2175 2345Net Feedstock Cost 402 494 (183)Utilities, Cat/Chem 240 266 135Fixed Operating Costs 64 67 64Total Production Costs (+Admin) 716 838 16Ethylene Revenue (-Distribution) 1016 1016 1016Cash Margin 300 178 1000

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Olefin Industry Challenges• Higher Feedstock / Energy Costs• Find Alternative Feedstocks• Improved Efficiencies• Tighter Environmental Limits• Optimum Upstream / Downstream Integration

Key to All Successful Solutions

TECHNOLOGY