Innovative Solutions for Optimizing Refining...

1

Innovative Solutions for

Optimizing Refining

& Petrochemicals Synergies

Jean-Paul Margotin

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

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


•PRU

•Conversion to C3=

•Purification

•Dehydrogenation

•to Aromatics

•to SC or PetChem FCC

•PetChem RFCC

Refining & Petrochemical Flow Exchanges

Aromatics Aromatics Complex

ParamaX

Refining Technology Petrochemicals Final Products

(C2=) PE, PVC

(C3

=) PP

…

(Styrene) PS

Polyethylene

terephthalate

PET …

H2, C4, Pygas

Pygas

Gasoline Pool Bases

Raffin.

•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

•AR/VR

Steam

Cracker

•HDT & Splitter

(C3=) PP

•to SC


Agenda


Flow exchanges






0

2

4

6

8

10

12

14

16

18

20

2010 2011 2012 2013 2014 2015

Source: Axens (2011)

2010 Production

~ 75 Million tons (Mt)

On purpose production • Metathesis

• Olefins cracking

• MeOH to propylene

• C3 dehydrogenation

From Refineries

(DCC/RFCC/FCC)

From Steam crackers

52%

36%

12%

• Global Additional Demand 2010-2015: ~ 20 Mt

Average annual growth rate: ~ 4.5%

• Additional propylene production

from refineries > 4 Mt

Additional Propylene Production

by Process Technology

Mt/y

Basis

Propylene Production Forecast by Source


Propylene Production from Refinery

Steam Cracker

Complex

Coker

FCC High Propylene FCC

HS-FCC

Resid to Propylene

Alternative Fuel

units

C4-C5

Olefins

Recovery

C4-C5 cut

C4-C5 cut

C4-C5 cut

C4-C5 cut

Olicrack™

FlexEne™

LPG

Naphtha

Resid

Resid

VGO

C3=

or

8 to 20 wt%

On-purpose C3= unit

Unique integration

With FCC for flexibility

C3=

Gasoline

/Distillate

or

>30 wt% C3=

>8 wt% C2=

Fischer-Tropsch

Olefins cracking


4%4%

11%

55%

6%

17%

1%1%

6%3%

9%

48%

11%

20%

1%2%

6%

5%

8%

33%

20%

22%

4%

2%

0%

20%

40%

60%

80%

100%

FCC High Propylene

FCC

HS-FCC

Fuel Gas

Ethylene

C3s + C4s

Propylene

Gasoline

LCO

Slurry

Coke

Yields, wt %

Comparative Yields – HDT VGO Feed


High Propylene FCC Technology

• 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

Location: Al Jubail, Saudi Arabia Source: Google Earth


HP FCC Technology

Regenerator

Stripper / Packing

Riser separator RS²

Feed

540-560°C

C/O = 10

ZSM-5 content

10-20% (40% crystal)

LCN recycle

Bathtub

catalyst

distributor


High Severity Fluidized Catalytic Cracking HS-FCC

Feed injection

Regenerator

Stripper using

structured packing

Catalyst / Product

separator

Downflow

reactor

Catalyst down flow

Catalyst up flow

HS-FCC Yields, wt.%

Ethylene = 4%

Propylene = 20%

A worldwide cooperation

Saudi Aramco (Saudi Arabia)

JX (Japan)

Shaw (United States)

Axens (France)


Resid to Propylene FCC Technology

• Resid to Propylene Technology (R2P)

• 127,000 bpsd

• R2R technology, >12 wt% Propylene

• PetroRiser recycling LCN

• Atm. Residue, API=21, CCR=4 to 6, S = 1.7 wt%

• Ruwais refinery, Abu Dhabi

Source: Google Earth


R2R Risers &

Regenerators

FEED

Propylene PG

LCO

Slurry/CLO

C3 C3 Splitter

Naphtha Splitter

Fuel Gas

LCN

Recycle

HCN

Raw C4

Propane

C3 C4 LPG Treatment

& Separation Fractionator & Gas Recovery

Resid to Propylene Process Scheme & Technology

R2R Risers &

Regenerators

R2R Risers &

Regenerators

Main Riser Resid

PetroRiser LCN

720-740°C

660°C

550°C C/O 8

590°C C/O 12

R2R Unit



Steam Cracker

Complex

Coker


HS-FCC

Resid to Propylene

Alternative Fuel

units

C4-C5

Olefins

Recovery

C4-C5 cut

C4-C5 cut

C4-C5 cut

C4-C5 cut

Olicrack™

FlexEne™

LPG

Naphtha

Resid

Resid

VGO

C3=

or

8 to 20 wt%

On-purpose C3= unit

Unique integration


C3=

Gasoline

/Distillate

or

>30wt% C3=

>8wt% C2=

Fischer-Tropsch


PolynaphthaTM Distillate

Gasoline Gasoline

Distillate

Polymer Grade Propylene

Propane Sweetening SulfrexTM

FlexEneTM - Flow Scheme

Raffinate

Gas Recovery

Recycle

FCC

Feed

C4-C5 cut

MF

Pool

Recycle Oligomers from

Polynaphtha to FCC riser

to maximize C3=

Valorize Polynaphtha

Gasoline or Distillate

to Motor Fuel to adjust

Gasoline/Diesel ratio

Or


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


Petron Bataan Refinery

• High Propylene FCC (HP FCC)

• 34,000 bpsd

• 250 kt/y of Propylene

• FlexEneTM, Gasoline & Propylene mode

• Feed: VGO + Hydrotreated Coker Gasoil

Location: Petron, Philippines

Source: Google Earth



Steam Cracker

Complex

Coker


HS-FCC

Resid to Propylene

Alternative Fuel

units

C4-C5

Olefins

Recovery

C4-C5 cut

C4-C5 cut

C4-C5 cut

C4-C5 cut

Olicrack™

FlexEne™

LPG

Naphtha

Resid

Resid

VGO

C3=

or

8 to 20 wt%

On-purpose C3= unit

Unique integration


C3=

Gasoline

/Distillate

or

>30 wt% C3=

>8 wt% C2=

Fischer-Tropsch

C3= / C2

= ratio > 3 - 4


Operability

Continuous Catalyst Regeneration

is based on

Axens CCR experience

> 100 Octanizing & Aromizing references

Iso-5 Process

Flexible and easy to operate regenerator


Agenda


Flow exchanges






Axens Technologies for Olefins Upgrading

MAPD Selective

Hydrogenation

MAPD Selective

Hydrogenation

C 3 =

C 4

Ethylene

Propylene

1 - Butene

MEK

Octenes

MTBE, ETBE

TAME, TAEE

C 5 - C 10

Pygas

Pygas Selective

Hydrogenation

GHU1

Pygas Selective

Hydrogenation

GHU1

C 5 Etherification

Catacol C 5 Etherification

Catacol

Pygas Hydrodesulfurization

GHU2

Pygas Hydrodesulfurization

GHU2

Dimerization

AlphaButol Dimerization

AlphaButol

Isobutane

Dehydro .

Dimerization

Dimersol Dimerization

Dimersol-X

C 6 - C 10

n - Butane

Lin. αααα - Olefins

C 4 /C 5 Olefins

Hydrogenation

C 4 /C 5 Olefins

Hydrogenation

C 5

Hydration

Ste

am

Cra

cke

r

Advanced Pygas

Upgrading

APU

Advanced Pygas

Upgrading

APU

C 2

LPG

C 6 - C 10

To Motor Gasoline Pool

C4 Acetylenes Selective

Hydrogenation

C4 Acetylenes Selective

Hydrogenation

Butadiene Maximum Butadiene

Max B=1 Hydrogenation


C 4 Etherification

Catacol

C 4

Etherification

Catacol

Butadiene Selective

Hydrogenation

Butadiene Selective

Hydrogenation

Maximum Butenes

2 - Butenes



IB= Purification

Isopure IB= Purification

Isopure

Isobutylene

C 5 =

Skeletal Isomerization

Iso - 5

Skeletal Isomerization

Iso - 5

C 9 - C 10

C 4 /C 5

Butadiene

Extraction

Benzene Toluene C 8 Aromatics to Aro . Complex

Oligomerization

α - Select/ α - Hexol

Oligomerization AlphaSelect/ AlphaHexol

C 6 - C 8 Extraction

Sulfolane

Morphylane

Extraction

Sulfolane

Morphylane

Super -

Fractionation Super -

Fractionation

Purification

Multibed Purification

Multibed

Oligomerization

Selectopol

Polynaphtha

Oligomerization

Selectopol

Polynaphtha

Olefins Hydrogenation

Olefins Hydrogenation

Solvents

Removal of

Arsenic & Mercury

RAM II

1 - Hexene

Condensates

Sulfur

Remov al

OATS

Sulfur

Remov al

OATS


C8+ Cut

Catalyst

Removal

Catalyst

Preparation

and Storage

Ethylene Feed

Reactor

Recycle

Column

Heavy Ends with spent Catalyst

Solvent Recycle

Separation

section

1-Hexene

1 3 4

2

C8+ Cut

Catalyst

Removal

Catalyst

Preparation

and Storage

Ethylene Feed

Reactor

Recycle

Column

Heavy Ends with spent Catalyst

Solvent Recycle

Separation

section

1-Hexene

1 3 4

2

3 C2H4

1-Hexene

LnM + LnM

M = Metal

Ln = Ligand

3 C2H4

1-Hexene

LnM + LnM

M = Metal

Ln = Ligand

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 • Process simplicity and

ease of operation

• High flexibility • Mild operating temperature

and pressure • Liquid phase

Carbon steel equipment


Agenda


Flow exchanges






Aromatic Complex Blocks Functions ParamaX Suite


Refinery with HCK, HP FCC + ParamaX

HP FCC

CDU

Benzene

Paraxylene SR Naphtha

Propylene

Naphtha

Bleed

HCGO

VGO

Kero

Coke

Aromatic Complex

ParamaX

Delayed Coker

HCK

VDU

Naphtha

LPG

Diesel

Aromatics production Refinery production

Benzene: 140 kt/y

Paraxylene: 700 kt/y (2.5% of 2009 PX world production) 400,000 bbl/d

Gasoline Pool

H2

Toluene rich cut, A8+

A9+, raffinate, light naphtha

Gasoline


SC

Ex

isti

ng

re

fin

ery

Existing Refinery with Steam Cracker + ParamaX

Benzene

Paraxylene Heavy Naphtha

Propylene

Aromatic Complex

ParamaX

Pygas

Light Naphtha

C2, LPG, raffinate

Ethylene

Aromatics production Existing Refinery production

Benzene: 650 kt/y

Paraxylene: 1,400 kt/y (5% of 2009 PX world production) 400,000 bbl/d

Kero

Diesel

Gasoline

Residue

H2 export


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

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Innovative Solutions for

Optimizing Refining

& Petrochemicals Synergies

Innovative Solutions for Optimizing Refining...

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