3 gasoline pool cd

1

Gasoline PoolLatest Developments in Catalysts & Technology

Jacques Rault

2Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

• Clean Gasoline Challenge• FCC Gasoline and Light Cuts Processing

� Prime-G+� Etherification� Polynaphtha� Dimersol-G

• Light Naphtha Isomerization• Octanizing• Benfree

Agenda


• Clean Gasoline Challenge• FCC Gasoline and Light Cuts Processing



Agenda


Gasoline Specifications Chart

None

5-10

2.7

1.0

10

35

WWFCFourth

Category

Dir 98/702009

Euro V(Final Proposal)

Dir 98/702005

Euro IV

Dir 98/702000

Euro III

EN 228 1993

Euro II

NoneNoneNone0.013Lead, g/l max

60.0 / 70.0 (3)60.0 / 70.060.0 / 70.035 - 100RVP, kPa

1050(10) (1)150500Sulfur, ppm, max

2.7/3.7 (2)2.72.7-Oxygen, wt%, max

1.01.01.05.0Benzene, vol%, max

181818-Olefins , vol%, max

353542-Aromatics, vol%, max

(1) 2005 introduction of 10ppm sulphur – Fuel must be geographically available in an appropriately balanced manner(2) 3.7% by mass in “high biofuel petrol” (Methanol: 3% vol, Ethanol: 10% vol, Iso-propyl alcohol: 12% vol, Tert-butyl alcohol: 15% vol, Iso-butyl alcohol: 15% vol, ETBE: 22%vol, other oxygenates: 15%vol) (3) The legal vapor pressure limit remains at 60kPa for both gasoline grades and at 70kPa for Member States with arctic or severe weather conditions. However, blending ethanol in gasoline results in a non-linear change of the vapor pressure, and, as oil refiners do not currently produce low vapor pressure gasoline, the commission has introduced a permitted vapor pressure waiver that is directly linkedto the percentage of ethanol blended in gasoline (ranging from 0 vol% to 10 vol%).

Source: IFQC, WWFC


Gasoline Pool Constraints

Olefins

Aromatics

Benzene

OctaneRetention

SulfurOctanizing

Benfree

Light NaphthaIsomerization

Prime-G+

Etherification

Polynaphtha

Dimersol-G


Axens: a Key Technology Licensor

Reformulated Fuels

Complete Portfolio• All technos except

alky.• Straight run naphtha

reformulation • FCC effluents handling• Expertise for

upgrading naphtha from conversion

EuroV achievement

FCC or FCC or Resid FCC

R2R

CRUDEDIST.

C3

C4

Naphtha

Desulfurization

Prime- G+

Etherification

Catacol

Oligo.

Polynaphtha

FCC or

Resid FCC

R2R

Gas Plant

Ether.

Catacol

3

4

Naphtha

Desulfurization

Prime- G+

Etherification

Catacol

Oligo.

Polynaphtha

FCC or

Resid FCC

R2R

Gas PlantSweetening

Sulfrex

Sweetening

Sulfrex

Ether.

Catacol

NaphthaHydrotreatment

Isomerization

Octanizing Benfree

GASOLINE

Dimeriz.

Dimersol-G

Contaminants

Removal

Dimeriz.

Dimersol-


Axens: a global technology licensor

• expertise in gasoline pool optimization• Adapt the refinery configuration to meet

gasoline pool specifications• Integrate the gasoline production units

with Conversion units:• Upgrade of Cracked Naphthas through

Isomerization and Reforming • Integration of FCC unit with FCC effluents

units


One example of gasoline pool updrade

REF.RON 96

StraightRun Naphtha

Coker Naphtha

Light FCCNaphtha

HDT

Heavy FCCNaphtha

PreviousGasoline Pool

RON 88S 450wtppmARO 42%vol


NewGasoline Pool

Euro IV

RON 92S 50 wtppmARO 35%volBZ 1.0%vol

New Optimized Pool Configuration

REF.RON 96

StraightRun Naphtha

Coker Naphtha

Light FCCNaphtha

HDT

Heavy FCCNaphtha

HDT ISOMRON 87

PRIME-G+2nd STEP

PRIME-G+1st STEP

RON 98

Heart Cut

LCN

HCN


NewGasoline Pool

Euro IV

RON 92S 50 wtppmARO 35%volBZ 1.0%vol

New Optimized Pool Configuration

REF.RON 96

StraightRun Naphtha

Coker Naphtha

Light FCCNaphtha

HDT

Heavy FCCNaphtha

HDT ISOMRON 87

PRIME-G+2nd STEP

PRIME-G+1st STEP

RON 98

Heart Cut

LCN

HCN

Axens can deliver optimal Gasoline Pool

solutions with State-of-the-art technologies


• Clean Gasoline Challenges• FCC Gasoline and Ligh Cuts Processing



Agenda


Prime-G+ TechnologyMain Events

• 2000 - 1st commercialization (Germany)• 2003 - Kirkpatrick Chemical Eng. Achievement Honor

Award (US magazine Chemical Engineering)• 2008 - Beijing Olympic games: ULSG for Beijing area by

the 150th Prime-G+ reference


Prime-G+ Typical Scheme 10-50 ppm Sulfur Spec

Splitter(Optional)

HCN 65 °C +

H2

FRCN

Prime-G+ SHUSelective

HydrogenationUltra-Low S

LCN

Ultra-Low SHCN

Prime-G+HDS

LCN C5-65 °C

• MAV reduction• Sulfur BP shift

• Sulfur reduction• Minimal Olefins loss

Production of Ultra Low Sulfur Gasoline

with very limited octane loss


• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing



Agenda


• Etherification ReactionsIsobutene (C4 cut) + Methanol MTBE (ETBE)Isoamylenes (C5 cut) + Methanol TAME (TAEE)

• Octane Boost

• Olefin Reduction• RVP Reduction

FCC Light Olefins Upgrading Etherification

RONc *MONc *RVP bara

MTBE ETBE TAME

1181020.4

11498

0.25

TAEE

106950.2

Ethanol

10894

> 1.5

1181020.55


Alcohol MU

HC One or Two ReactorsExpanded bed (C4’s)Fixed bed (C5+)

Main Reaction

Section

C4’sC5’sC6’sC7’s

Alcohol MU

Axens Flexible Offer on Etherification


Reactive DistillationCatacolHigh Conversion

Conventional Fractionator(optional for C5+)

Raffinate + Alcohol

Raffinate + AlcoholEther

Ether

Axens Flexible Offer on Etherification

Main Reaction

Section

C4’sC5’sC6’sC7’s

Alcohol MU

Alcohol MU

HC


Catacol Concept - Reactive Distillation

Isobutene (C4 cut) + Methanol MTBE

ResidualIsobutene

MTBE


Combined Prime-G+ and Etherification

HCN 65 °C +

H2

FRCN

Prime-G+ SHUSelective

Hydrogenation

Ultra Low S LCN

Ultra-Low SHCN

Prime-G+ HDS

LCN C5-65 °C

High Purity Ether

C4’s

Octane Neutral Scheme

AlcoolEtherification





Agenda


• Oligomerisation ReactionsC4 Olefin + C4 Olefin C8 Olefin (Gasoline)C4 Olefin + C4 Olefin + ... C12+ Olefin (Distillate)C5 Olefin + C5 Olefin C10 Olefin (Distillate)C5 Olefin + C5 Olefin + ... C15+ Olefin (Distillate)

• Product Quality

OligomerisationMain Features

>30 Smoke Point, mm *

< -60 °CFreezing Point, °C *

82 - 85MONc *

95 - 99RONc *

Poly Kerosene

PolyGasoline

* After Hydrogenation


Axens Oligomerisation Technology

Raffinate

Prime-G+HDS

LCNC5-65°C

Prime-G+SHU

FCCMax Gasoline

Max C3=

Oligomerisation

Distillates

FCC C4’S

ULSG

Distillates

Kerosene

Raffinate

C4’s

Gasoline

Debutanizer

SplitterSplitter

C5’s

Reaction Section

• Oligomerisation within FCC Block


• Conversion of Light Olefins to Gasoline and Kerosene

• Main Feedstock: FCC or Steam Cracker C4’s• Optional Feeds: FCC C3’s and C5’s• High to Complete Conversion of Iso-Olefins• Partial to High Conversion of Linear Olefins• Regenerable Acid Catalyst• Commercially Proven• Liquid phase – No hydrogen • Optional Product Hydrogenation

Polynaphtha Technology Highlights


Polynaphtha vs Alkylation

• Lower Gasoline Yield (no iC4/nC4 conversion)

But• Similar Gasoline Quality ((RON+MON)/2)• No Waste Effluents• No Environment and Safety Issues• 5 Times Less Investment • Co-Production of Distillate : kerosene /

Diesel





Agenda


1-ButeneEthyleneAlphabutol™

CyclohexaneBenzeneCyclohexane

Olefins C8, C12ButenesDimersol-X™

Gasoline (C6, C9)PropyleneDimersol-G™

1-Butene, 1-Hexene, 1-Octene, …

EthyleneAlphaselect™

ProductFeedTechnology

Most technology developments by Yves Chauvinfrom IFP, 2005 Nobel Price in Chemistry

Axens Homogeneous Catalysis Technologies


• Propylene Upgrading Technology • High quality gasoline production

• Suitable for Isolated Refineries• No petrochemical outlet for propylene

• Homogeneous Catalysis• Catalyst soluble into reactants and products

• Continuous Catalyst Injection and Removal• Optimum Catalyst / Reactants Contacting• Catalyst Injection Copes with Contaminants

Dimersol-G Technology Highlights


Dimersol-G Technology

inhibitor


Dimersol-G Advantages

• High catalytic activity• Low reaction temperature • Very mild reaction pressure

• High once-through conversion (>95%)• 100% Gasoline Yield• Blending RON: 98-118• No need to install a Propane / Propylene splitter• No propylene recycle required• Low equipment size & utilities consumption





Agenda


• Chlorinated alumina• Excellent RON:

+3-4 numbers vs. Zeolite+1-2 numbers vs. Sulfated Zirconia

• Higher product yield

• Operation at low temperature in liquid phase without hydrogen recycle => low investment and low operating costs

Isomerization Catalyst: ATIS 2L

Due to RON demand, Al2O3-Cl catalyst is today’s catalyst of choice


ATIS-2L:The Latest and the New Benchmark

Highest activity and lowest cost on the market

� In-house and client testing have shown a clear advantage of ATIS-2L vs. other catalysts

� The highest isomerization activity, i.e., RON� Reduced catalyst and Platinum inventory

� First industrial batch of ATIS-2L: January 2003� 29 units running with ATIS-2L (mainly in non Axens

isomerization unit: catalyst replacement business)

� 30 units designed with ATIS-2L


Isomerization: DIH Configuration

Off Gas

C5C6 Feed

Hydrogen

DIH

Isomerate

RON 86.5-89.0MP’s + nC6

Low octane

MCP + CH + C7

Moderate octane

iC5 + nC5 + DMB’s

High octane





Agenda


Optimized reactor design ensures capacity increase without modification

Side-by-Side Arrangement

Easy maintenance

Easy access to

reactors

Low investment


Continuous Catalyst Regeneration Targets

• Coke burning occurs once every three to four days• Fatal high temperature and moisture

• Pt sintering• Specific area decline• Loss of mechanical properties• Chlorine elution during burn-off

• Undesirable consequences• Catalyst ageing results from hydrothermal damage• Increased chlorination requirement• Chlorine loss to the process• Attrition

Technology has to challenge

these issues


PrimaryBurn

FinishingBurn

Calcination

Oxy-chlorination

Spent Catalyst

Regenerated Catalyst

DryCombustion Gas

Air

Air

Oxychlorination Calcination Gas

ChloridingAgent+ water

Optimum catalyst “protection”

Regenerator Section: RegenC-2

DryBurnLoop Optimum Chlorine Management


• “Dry Burn Loop” mitigates hydrothermal ageing root causes

• Low and stable chlorine consumption

Exceptional catalyst life(up to 9 years for high severity)

Less catalyst attrition

Secure environmental protection

RegenC-2 Bonus


� High density, BTX mode, optimal Pt%

� High density, Gasoline mode, low Pt%

� Non Axens refill, Low density, optimal Pt%

New CCR Catalyst Series

AR 700 series

CR 600 series

CR 610 series

Commercial experience with CR-600 CR-610 and AR-700 series in Axens and non-Axens designs

• Commercialized in 2008• Higher yields, lower coke make

• Lower Pt content


Axens CCR technologystate-of-the-art technology for gasoline & aromatics production

• Cost-effective technology implementation• Unique combination of catalyst activity and

regeneration quality• Over 100 industrial references

Octanizing / Aromizing



Options� Prime-G+� Etherification� Polynaphtha� Dimersol-G


Agenda


BenfreeC

Reformate splitter followed by conventional hydrogenation on light reformate:

• Can be associated with an isomerization unit• Light naphtha may be co-treated with light reformate

Light Reformate

Off Gas

Recycle

H2

Product

Off Gas


BenfreeRD

C5+Reformate

Off Gas

Low BenzeneReformate

C5-C6

H2

Isomerization

� High flexibility � Limits C7s and naphthenes in light reformate

Liquid PhaseNi Catalyst


BenfreeRD Highlights

• Low cost

• Distillation/Reaction concept ensures:- benzene conversion with no effect on toluene- limits C7’s and naphthenes in Light

Reformate (ideal isomerization feed)

• Easy catalyst fill and change-out withoutstopping the splitter

• No excess hydrogen required, no hydrogenrecycle compressor


Conclusions

• Complex gasoline pool equation : Axens can provide integrated solutions adapted to any refinery configuration

• FCC gasoline and light cuts : excellent expertise for sulfur and olefins management, including etherification and oligomerization (Polynaphtha& Dimersol-G)

• LN Isomerization : significant market share gained with ATIS 2L based isomerization

• Octanizing : innovative catalysts for improved yields with lower Pt content

• Benfree : low cost adjustment of benzene content

46

Gasoline PoolLatest Developments in Catalysts & Technology

3 gasoline pool cd

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