options for gasoline reformulation

8/3/2019 Options for Gasoline Reformulation

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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Options for gasoline reformulation

Christian Dupraz


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European Gasoline Specificatio

RON 95 MON 85 2000 2005 2009

Sulfur, wt. ppm max 150 50 10

Aromatics, vol. % max 42 35

Olefins, vol. % max 18 18Oxygen, wt. % max 2.7 2.7

Benzene, vol. % max 1 1

RVP, kPa max 60 60

E 100C, % min 46 46

E 150C, % min 75 75


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Gasoline Trend

Main Constraints :

-Sulfur reduction

- Benzene reduction

- Aromatics reduction

- Octane retention

- RVP limitation

-Olefins limitation

Other constraint :

-MTBE phase-out in some places


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Main Constrain

SulfurBenzene

AromaticsOlefins

Octane loss compensation


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Sulfur in Gasoline Po

350 ppm S in pool350 ppm S in pool

100

80

Per Centof Pool 6040

20

0Volume Sulfur Contribution

FCC Naphtha Other


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FCC Sulfur Reduction Strategie

Short / Medium Term Solutions

- Low Sulfur Crudes

- FCC Naphtha End-Point Reduction

Longer Term Solutions

- FCC Feed Pre-treatment (hydrotreating)

- FCC Naphtha Post-treatment (selective HDS)- Combination of both solutions


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FCC Feed Pretreatment Technologie

A large variety of processes available

Distillates

Residues

Fixed bed: VGO HDT & Mild HDC

Ebullated bed: T-StarTM

(cracked feedstocks

Fixed bed: HyvahlTM ARDS & VRDS


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FCC Feed Pretreatment Highligh

Benefits

Gasoline sulfur spec

Gasoline yield

LPG yield

LCO sulfur

Delta cokeDiesel co-production

SOx

Drawbacks

Capital cost

H2 availability

Olefins spec.

Coker gasoline sulfur

SC gasoline sulfurLSRN sulfur


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FCC Naphtha Post-Treatme

The Challenge

Selectively remove S with minimum olefins saturation, i.eminimum octane loss

Maximize gasoline yield and minimize hydrogen

consumption with high selectivity and no cracking

Achieve run lengths equivalent to FCC turnaround cycles

Ability to co-process other steams containing S

Meet potential future specs (No regret investment)

Possibility to control olefins content


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Axens Post-Treatment Technolog

Prime-G+The FCC Gasoline Selective Desulfurisation

Technology Benchmark

83 licensed units worldwide since 1999

most of them designed for 10 ppm S

11 units on stream today


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Prime-G+ Proces

Prime-G+

SelectiveHydrogenation

Ultra Low S LCN toPool, TAME or Alky Unit

Splitter

HCN

65C +

Prime-G+

Selective HDSFRCNUltra-Lo

Sulfur

GasolinH2 Make-up


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Prime-G+ Features

1st Step : Selective Hydrogenation- Diolefins hydrogenation

- Mercaptans conversion to heavier sulfur compounds- Isomerization of external to internal olefins

Ultra low S LCN with slight octane improvement

2nd Step : Selective HDS with Dual Catalytic System

Lead Catalyst

Bulk Desulfurization Controlled Olefin Saturation Feed Preparation for 2nd

Catalyst

Finishing Catalyst

Completes Desulfurizatio Minimum Olefin Saturati Mercaptans Control


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Prime-G+ Economics - Staged Investme

Optimum solution site dependent

Potential options- SHU + splitter in a first phase (50 wppm sulfur)

Selective HDS in a second phase (10 wppm sulfur)

- Full scheme with existing splitter in a first phase

Investment in a new splitter in second phase

Most severe cases (high olefins and high sulfur)- Full Prime-G+ scheme in first phase

- Second stage on Selective HDS in a second phase


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FCC Heart-Cut to Reformer (

LCN

HSRN

HDT Reforming

FRCN

MoGasPool

SHUMCN

H2HCN

Prime-G+


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FCC Heart-Cut to Reforming (

Benefits

Octane retention

H2 cons. minimization

Olefins reduction

Drawbacks

HDT severity limitation

Reforming capacity increase

Benzene increase


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Reformer Debottleneckin

TexicapTM + CatapacTM

15 to 30 % additional catalyst

20 % FEED

CAPACITYINCREASE

RG 682 Catalyst

Hydrogen production increaseEnhanced gasoline yieldHigh stability

Welded Plate Type Exchanger

Operating pressure decrease

Improved heat recovery

GASOLINEPRODUCTIO

INCREASE


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Main Constrain

SulfurBenzene

AromaticsOlefins



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Sources of Benzene in Gasolin

FCC17%

Reformer

81%

Other2%


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Benzene Reduction (

Principal source: catalytic reforming units

For a given feedstock and unit, very fewbenzene reduction options exist :

-lower operating severity

- lower operating pressure

- catalyst selection

Each has limited effect on benzene production


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Benzene Reduction (

Two Main Options

Prefractionate (remove benzene precursors)

- Least expensive solution- Impact on existing isomerization unit (C7 limitations- Less flexible

Postfractionate (install reformer splitter)

- Conventional benzene saturation / BenfreeTM- Benzene extraction


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Benzene Saturation Option

Reformate splitter followed by conventional

hydrogenation on light reformate

Integrated splitter + benzene saturation

Benfree from Axens

Both can be associated with an isomerization unitwhere benzene-free light reformate may be co-processed with light naphtha


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Conventional Benzene Saturatio

Off Gas Off Gas

H2

LightReformate Product

Recycle


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BenfreeT

Full RangeReformate

Off Gas

Low BenzeneReformate

C5-C6

H2

To Isomerizat


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BenfreeTMHighligh

Low investment and operating costs

Distillation / Reaction concept ensures:- benzene conversion with no effect on toluene- limits C7s and naphthenes in light reformate

Easy catalyst fill and change-out without stoppingthe splitter

No excess hydrogen required, no hydrogen

recycle compressor Three units on stream


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Benzene Extractio

Simple fractionation of the reformate and sales of abenzene-rich cut for petrochemicals

Extractive distillation or liquid-liquid extraction(Sulfolane)

Depending on benzene market

Bad effect on benzene producer margins

Gasoline yield decrease and octane penalty


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Main Constrain

SulfurBenzene

AromaticsOlefins



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Aromatics - General Commen

Refineries with no other sources of gasoline than

reformate plus light naphtha and/or isomerate will havdifficulties meeting aromatics specification togetherwith octane requirement.

Addition of an octane booster such as MTBE or TAMEwill then be needed.

Presence of an FCC unit solves the problem by dilutionof the aromatics, but with other draw-backs: sulfur andolefins.

R f A ti R d ti


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Reformer Aromatics Reductio

Decrease reformer severity

Significant Octane loss

Reduced Hydrogen production

Change reformer feed cut points (IBP/FBP)

Marginal effect on total aromatics

Oth A ti R d ti St t i


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Other Aromatics Reduction Strategi

Petrochemicals (BTX production)

-Toluene production (by extraction) and xylenesproduction (by fractionation)

- But toluene or xylenes markets are not bigenough to absorb this extra production

Dilution effect :

Etherification

Alkylation

M i C t i


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Main Constrain

SulfurBenzene

AromaticsOlefins


Ol fi R d ti


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Olefins Reductio

Olefins in the gasoline pool comes mostly from light

FCC gasoline.

Treating the FCC C5 cut in a TAME unit will generally

suffice to meet a 14% max. olefin target

HDS of FCC gasoline can also contribute to olefin

reduction with only moderate octane loss (PRIME-G+)

C5 Etherification Rou


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5

for Olefins Reductio

Drawbacks

Uncertain oxygenatesfuture

Benefits

Low RVP

Additional C4 blendingOctane increase

Low Cost MeOHOlefins reduction

Dilution effect

Main Constrain


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Main Constrain

SulfurBenzene

AromaticsOlefins


Octane Loss Compensatio


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Octane Loss Compensatio

Three main options for Octane recovery:

- Light Naphtha Isomerization

- Etherification (MTBE, TAME, ETBE)

- Alkylation

Light Naphtha Isomerizatio


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Light Naphtha Isomerizatio

Benefits

Octane gainDistillation curveSulfur-free

Aromatics-freeOlefins-free

Drawbacks

CapitalH2 availabilityRVP increase

Isomerization is the best light naphtha octaneboosting process for meeting the new gasoline

specifications

Isomerization Technologie


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Isomerization Technologie

Conventional technologies

Once-through process (15 units) Deisohexanizer recycle (6 units)

Advanced recycle technologies

(molecular sieves separation)

Ipsorb (2 units)

Hexorb (no unit up to now)

Once-Through Proces


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(Chlorinated Alumina Catalys

CW

ScrubbeHydrogen

LightNaphtha

Off G

MP

Steam

MPSteam

CW

Isomer

R-1 R-2 Stab

Dryer

Dryer

Deisohexanizer Recyc


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Deisohexanizer Recyc

Off Gas

Isomerization

C5C6 Feed

Hydrogen

iC5 + nC5 + DMBs

DIH

Isomera

iC5 + DMB+ nC5 + M

+ CH + C7

MPs + nC6

MCP + CH + C7

Ipsor


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Ipsor

Isomerization

Off Gas

C5C6 Feed

Hydrogen

Mole

SievesDIP

iC5

Isomera

iC5 + DMBs+ MPs + MC

+ CH + C7s

iC5+nC5+nC6

Hexor


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Hexor

Isomerization

Off Gas

C5C6Feed

Hydrogen

iC5 + DMBs

DIH

MPs + nC5

+ nC6

Isomera

iC5 + DM+ MCP+ CH + C

MCP + CH + C7s

Mole

Sieves

MPs

Technology Selectio


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Technology Selectio

84

Hexorb

Oncethrough

Typical RON

TargetIpsorb

DIH

92

RON

88

Chlorinated

Alumina

Catalyst

ISBL Investment Cost, Million US$10 20

(8,000 BPSD capacity)

New Chlorinated Alumina Cataly


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y

ATIS-2L

Highest activity and lowest cost on the market Common development of Akzo Nobel and Axens

In-house and client testing have shown a clear advantage of

ATIS-2L vs. other catalysts :- higher isomerization activity, i.e. higher RON

- lower catalyst cost

Two batches of ATIS-2L streamed on 2003

Significative performances improvement

Across-the Board ATIS-2L Advantag


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Across the Board ATIS 2L Advantag

Ipsorb

DIH

ISBL Investment Cost, Million US $

Hexorb

Oncethrough

Improvement with ATIS-2L

(8,000 BPSD capacity)

10 20

92

RON

88

84

MTBE Replacement : Pseudo Alkylatio


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MTBE Replacement : Pseudo Alkylatio

Axens Selectopol: Isobutylene Dimerization

Industrially proven Regenerable solid catalyst

No other chemicals involved (e.g. oxygenates) Hydrogenation of the product is needed

Pseudo-alkylate product

(RON+MON)/2 = 93.5 before hydrogenation

95.5 after hydrogenation (90%)

Conclusion


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Optimum solution is refinery-specific

Gasoline pool can be optimized throughcustomized feasibility studies

Axens offers a complete portfolio ofprocesses for attainment of the most

stringent gasoline specifications

options for gasoline reformulation

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