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Innovative Solutions for Optimizing Refining & Petrochemicals Synergies

Jean-Paul Margotin

Agenda

Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production
Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production

R&P synergies for aromatics

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Refining & Petrochemical Flow Exchanges


Refining Unsaturated ROG FCC C3 cut FCC C4-C5 cuts Coker C3-C4 cuts Saturated ROG Excess of C3, C4 SR Naphtha Cracked Naphtha CCR Reformate Gas Oil HC bleed VGO to SC or PetChem FCC Bases Gasoline PetChem Pool RFCC AR/VR Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011 to Aromatics to SC Purification Dehydrogenation H2, C4, Pygas HDT & Splitter Raffin. Pygas (Styrene) PS Polyethylene terephthalate PET 3 Steam Steam Cracker Cracker (C2=) PE, PVC (C3=) PP PRU Conversion to C3= (C3=) PP Technology Petrochemicals Petrochemicals Final Products

Aromatics Aromatics Complex Complex ParamaX ParamaX

Agenda

Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production
Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production

R&P synergies for aromatics

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Propylene Production Forecast by Source


2010 Production ~ 75 Million tons (Mt) Additional Propylene Production by Process Technology
20 18 16 14 12 10 8 6 4 2 0

Mt/y

From Refineries (DCC/RFCC/FCC) From Steam crackers On purpose production


Metathesis Olefins cracking MeOH to propylene C3 dehydrogenation
Source: Axens (2011)

Basis
2010 2011 2012 2013 2014 2015

Global Additional Demand 2010-2015: ~ 20 Mt Average annual growth rate: ~ 4.5%

Additional propylene production from refineries > 4 Mt


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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Propylene Production from Refinery


LPG Naphtha Resid

Steam Cracker Complex

C4-C5 cut

Olefins cracking
>8 wt% C2=

Olicrack
C4-C5 cut C4-C5 cut
C4-C5 Olefins Recovery
or

>30 wt% C3=

Coker

On-purpose C3= unit

FCC
VGO High Propylene FCC HS-FCC Resid Resid to Propylene

C3=
8 to 20 wt%

C3= FlexEne
or Gasoline /Distillate

Alternative Fuel units Fischer-Tropsch

C4-C5 cut
Unique integration With FCC for flexibility

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Comparative Yields HDT VGO Feed


Yields, wt %

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

High Propylene FCC Technology

Location: Al Jubail, Saudi Arabia

Source: Google Earth

HP FCC Technology
33,000 bpsd Start-up in 2013 >10%wt Propylene production LCN recycle before feed injection Feed: Deeply hydrotreated VGO 3 other recent similar units in Middle East
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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

HP FCC Technology

Riser separator RS Stripper / Packing Regenerator Bathtub catalyst distributor 540-560C C/O = 10 ZSM-5 content )crystal 40% (10-20% Feed LCN recycle
Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

High Severity Fluidized Catalytic Cracking HS-FCC


A worldwide cooperation Saudi Aramco (Saudi Arabia) JX (Japan) Shaw (United States) Axens (France)

Catalyst down flow

Regenerator

Feed injection Downflow reactor

HS-FCC Yields, wt.%


Catalyst / Product separator
Catalyst up flow

Ethylene = 4% Propylene = 20%

Stripper using structured packing

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Resid to Propylene FCC Technology

Ruwais refinery, Abu Dhabi Resid to Propylene Technology (R2P)



Source: Google Earth

127,000 bpsd R2R technology, >12 wt% Propylene PetroRiser recycling LCN Atm. Residue, API=21, CCR=4 to 6, S = 1.7 wt%
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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Resid to Propylene Process Scheme & Technology


Fuel Gas C3 C3 C4 C4 LPG LPG Treatment Treatment & & Separation Separation C3 C3 Splitter Splitter Propylene PG

Fractionator Fractionator & & Gas Recovery Gas Recovery

Propane Naphtha Naphtha Splitter Splitter Raw C4 HCN LCO Slurry/CLO FEED
660C 720-740C
550C C/O 8

590C C/O 12

R2R R2R R2R R2R Risers Risers & Risers & Risers& & Regenerators Regenerators Regenerators Regenerators LCN Recycle

R2R Unit

Main Riser Resid

PetroRiser LCN
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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Propylene Production from Refinery


LPG Naphtha Resid

Steam Cracker Complex

C4-C5 cut

>8wt% C2=

Olicrack
C4-C5 cut C4-C5 cut
C4-C5 Olefins Recovery
or

>30wt% C3=

Coker

On-purpose C3= unit

FCC
VGO High Propylene FCC HS-FCC Resid Resid to Propylene

C3=
8 to 20 wt%

C3= FlexEne
or Gasoline /Distillate

Alternative Fuel units Fischer-Tropsch

C4-C5 cut
Unique integration With FCC for flexibility

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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FlexEneTM - Flow Scheme


Polymer Grade Propylene Propane Gas Recovery Raffinate C4-C5 cut Gasoline Recycle Distillate Gasoline MF Pool

Sweetening SulfrexTM

PolynaphthaTM

Distillate

FCC Feed

Recycle Oligomers from Polynaphtha to FCC riser to maximize C3=

Or

Valorize Polynaphtha Gasoline or Distillate to Motor Fuel to adjust Gasoline/Diesel ratio


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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

FlexEne & Polynaphtha

FlexEne enables:
The addition of 3-6% wt. of propylene yield, over and above the effect of ZSM-5 The increase of the desired Motor Fuels by flexible recycle selection

Polynaphtha:
is an Oligomerization unit Using a solid acidic catalyst

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Petron Bataan Refinery

Location: Petron, Philippines

High Propylene FCC (HP FCC)


Source: Google Earth

34,000 bpsd 250 kt/y of Propylene FlexEneTM, Gasoline & Propylene mode Feed: VGO + Hydrotreated Coker Gasoil
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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Propylene Production from Refinery


LPG Naphtha Resid

Steam Cracker Complex

C4-C5 cut

>8 wt% C2=

Olicrack
C4-C5 cut C4-C5 cut
C4-C5 Olefins Recovery
or

>30 wt% C3=

Coker

On-purpose C3= unit

C3= / C2= ratio > 3 - 4

FCC
VGO High Propylene FCC HS-FCC Resid Resid to Propylene

C3=
8 to 20 wt%

C3= FlexEne
or Gasoline /Distillate

Alternative Fuel units Fischer-Tropsch

C4-C5 cut
Unique integration With FCC for flexibility

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Operability
Continuous Catalyst Regeneration is based on Axens CCR experience > 100 Octanizing & Aromizing references Iso-5 Process Flexible and easy to operate regenerator
Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Agenda

Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production
Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production

R&P synergies for aromatics

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Axens Technologies for Olefins Upgrading


Ethylene

C3=

Selective Selective Hydrogenation Hydrogenation


Maximum Butadiene

MAPD MAPD

Purification Purification Multibed Multibed Butadiene Extraction C4 C 4

Dimerization Dimerization AlphaButol AlphaButol

Oligomerization Oligomerization AlphaSelect/ -Select/ -Hexol AlphaHexol

1-Hexene Lin. - Olefins Propylene Butadiene 1-Butene Isobutane Isobutylene

C4

C4Acetylenes Acetylenes C4

Selective Selective Hydrogenation Hydrogenation


Maximum Butenes Selective Selective Hydrogenation Hydrogenation

Butadiene Butadiene

Etherification Etherification

Steam Cracker

Catacol Catacol

Hydrogenation Fractionation Fractionation Hydrogenation

MaxB=1 B=1 Max

SuperSuper-

2-Butenes

Dimerization Dimerization Dimersol Dimersol-X


Dehydro .

Octenes n-Butane MEK MTBE, ETBE Solvents TAME, TAEE Benzene Toluene C8 Aromatics to Aro. Complex

Hydrogenation Hydrogenation
Isomerization Isomerization

MaxB=2 B=2 Max

IB=Purification Purification IB=

Isopure Isopure

Hydration

Skeletal Skeletal

C4/C5

Olefins Olefins Hydrogenation Hydrogenation C2


LPG

C4 /C C 4/C55

Iso-5 Iso-5

C5=

C5Etherification Etherification C 5 Catacol Catacol


Advanced Advanced Pygas Pygas Upgrading Upgrading

Oligomerization Oligomerization Selectopol Selectopol Polynaphtha Polynaphtha

Hydrogenation Hydrogenation

Olefins Olefins

C5

APU APU

C6-C10 Selective Selective Pygas Hydrogenation Hydrogenation C5-C10

C6-C8 C9-C10

Pygas Pygas GHU1 GHU1

C6-C10

Hydrodesulfurization Hydrodesulfurization

Pygas Pygas GHU2 GHU2

Extraction Extraction Sulfolane Sulfolane Morphylane Morphylane Sulfur Sulfur Removal Removal OATS OATS

To Motor Gasoline Pool Condensates


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Removal of Arsenic & Mercury RAM II

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

AlphaHexol Key Features

Selective ethylene trimerization mechanism (Cr catalyst) Recently born process, similar to AlphaButol, strongly backed up by extensive industrial experience in homogeneous catalysis
Polymer grade 1-hexene suitable for LLDPE & HPDE Efficient ethylene feed use Catalyst Preparation Process simplicity and and Storage ease of operation Recycle Column Ethylene High flexibility Reactor Feed Mild operating temperature 1 3 and pressure Catalyst Liquid phase 2 Removal Carbon steel equipment Heavy Ends with spent Catalyst
Solvent Recycle Separation section 1-Hexene

C8+ Cut

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Agenda

Refining & Petrochemical (R&P) synergies: Flow exchanges R&P synergies for olefins production
Propylene (& Ethylene) production Olefins upgrading and alpha-olefins production

R&P synergies for aromatics

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Aromatic Complex Blocks Functions ParamaX Suite


HN
BT
T& NHd ation tion c a r F

FRN

ng: i m r 9+ efo A R / X R / CC B/ T o t a th Naph

A9+

T
BZ

ion t c a r xt BT E tionation ac & Fr

BZ

A8

ation l y k l sa 8A Tran to BZ/C 9+ A + l To


A8

BZ

PX

oop L s e n /BZ Xyle X P to C8A

Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Refinery with HCK, HP FCC + ParamaX


SR Naphtha

Aromatic Complex ParamaX


Naphtha H2

Benzene Paraxylene

CDU

Naphtha

Gasoline Toluene rich cut, A8+ Pool A9+, raffinate, light naphtha
Kero

HCK VDU
VGO Bleed

Gasoline

Diesel

HP FCC Delayed HCGO Coker


Refinery production 400,000 bbl/d

Propylene

LPG Coke Aromatics production Paraxylene: 700 kt/y (2.5% of 2009 PX world production) Benzene: 140 kt/y
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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Existing Refinery with Steam Cracker + ParamaX


Heavy Naphtha

Aromatic Complex ParamaX

Benzene Paraxylene

Gasoline Existing refinery


Kero Diesel Residue Pygas

H2 export

C2, LPG, raffinate Light Naphtha SC

Propylene Ethylene

Existing Refinery production 400,000 bbl/d

Aromatics production Paraxylene: 1,400 kt/y (5% of 2009 PX world production) Benzene: 650 kt/y
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Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

Conclusion Refining & Petrochemicals integration is achievable through:


Full range of innovative technologies from residue conversion to olefins / aromatics maximization Full range of associated services: consulting (configuration studies), tech service. Full range of products: catalysts & adsorbents
Petrofed, Leadership Seminar on Innovation in Oil & Gas Sector, October 19, 2011

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Innovative Solutions for Optimizing Refining & Petrochemicals Synergies

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