Options for gasoline reformulation

Christian Dupraz

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

European Gasoline Specifications

RON 95 MON 85 Sulfur, wt. ppm max Aromatics, vol. % max Olefins, vol. % max Oxygen, wt. % max Benzene, vol. % max RVP, kPa max E 100C, % min E 150C, % min 2000 150 42 18 2.7 1 60 46 75 2005 50 35 18 2.7 1 60 46 75
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2009 10

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Gasoline Trends
Main Constraints :

Sulfur reduction Benzene reduction Aromatics reduction Octane retention RVP limitation Olefins limitation MTBE phase-out in some places
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Other constraint :
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Main Constraints

Sulfur Benzene Aromatics Olefins Octane loss compensation

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Sulfur in Gasoline Pool

350 ppm S in pool 100 80 Per Cent of Pool 60 40 20 0 Volume FCC Naphtha
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Sulfur Contribution Other

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FCC Sulfur Reduction Strategies

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

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

FCC Feed Pretreatment Technologies A large variety of processes available

Distillates Fixed bed: VGO HDT & Mild HDC Ebullated bed: T-StarTM (cracked feedstocks) Residues Fixed bed: HyvahlTM ARDS & VRDS

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

FCC Feed Pretreatment Highlights Benefits

Gasoline sulfur spec Gasoline yield LPG yield LCO sulfur Delta coke Diesel co-production SOx
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Drawbacks
Capital cost H2 availability Olefins spec. Coker gasoline sulfur SC gasoline sulfur LSRN sulfur
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FCC Naphtha Post-Treatment

The Challenge

Selectively remove S with minimum olefins saturation, i.e. minimum 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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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Axens Post-Treatment Technologie

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
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003 10

Prime-G+ Process

Prime-G+ Selective Hydrogenation

Ultra Low S LCN to Pool, TAME or Alky Unit Splitter

FRCN HCN 65C +

Prime-G+ Selective HDS Ultra-Low Sulfur Gasoline

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H2 Make-up

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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 Desulfurization Minimum Olefin Saturation Mercaptans Control
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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Prime-G+ Economics - Staged Investment

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 Full Prime-G+ scheme in first phase Second stage on Selective HDS in a second phase
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Most severe cases (high olefins and high sulfur)

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

FCC Heart-Cut to Reformer (1)

LCN HSRN HDT MCN H2 HCN Prime-G+
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FRCN SHU

Reforming

MoGas Pool

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

FCC Heart-Cut to Reforming (2)

Benefits
Octane retention H2 cons. minimization Olefins reduction

Drawbacks
HDT severity limitation Reforming capacity increase Benzene increase

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Reformer Debottlenecking
TexicapTM + CatapacTM
15 to 30 % additional catalyst RG 682 Catalyst Hydrogen production increase Enhanced gasoline yield High stability Welded Plate Type Exchanger Operating pressure decrease Improved heat recovery
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20 % FEED CAPACITY INCREASE

GASOLINE PRODUCTION INCREASE

Main Constraints

Sulfur Benzene Aromatics Olefins Octane loss compensation

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Sources of Benzene in Gasoline

Other 2%

FCC 17%

Reformer 81%

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Benzene Reduction (1)

Principal source: catalytic reforming units For a given feedstock and unit, very few benzene reduction options exist :

lower operating severity lower operating pressure catalyst selection

Each has limited effect on benzene production

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Benzene Reduction (2)

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

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Benzene Saturation Options

Reformate splitter followed by conventional hydrogenation on light reformate Integrated splitter + benzene saturation

Benfree from Axens

Both can be associated with an isomerization unit where benzene-free light reformate may be coprocessed with light naphtha
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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Conventional Benzene Saturation

Off Gas Off Gas

H2

Light Reformate Recycle

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Product

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BenfreeTM
Off Gas

Full Range Reformate C5-C6 H2

To Isomerization

Low Benzene Reformate

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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

BenfreeTM Highlights

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 stopping the splitter No excess hydrogen required, no hydrogen recycle compressor Three units on stream
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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Benzene Extraction

Simple fractionation of the reformate and sales of a benzene-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

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Main Constraints

Sulfur Benzene Aromatics Olefins Octane loss compensation

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Aromatics - General Comments

Refineries with no other sources of gasoline than reformate plus light naphtha and/or isomerate will have difficulties meeting aromatics specification together with octane requirement. Addition of an octane booster such as MTBE or TAME will then be needed. Presence of an FCC unit solves the problem by dilution of the aromatics, but with other draw-backs: sulfur and olefins.
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003 27

Reformer Aromatics Reduction

Decrease reformer severity

Significant Octane loss Reduced Hydrogen production

Change reformer feed cut points (IBP/FBP)

Marginal effect on total aromatics
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Other Aromatics Reduction Strategies

Petrochemicals (BTX production)

Toluene production (by extraction) and xylenes production (by fractionation) But toluene or xylenes markets are not big enough to absorb this extra production

Dilution effect :
Etherification Alkylation
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Main Constraints

Sulfur Benzene Aromatics Olefins Octane loss compensation

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Olefins Reduction

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+)

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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C5 Etherification Route for Olefins Reduction Benefits

Low RVP Additional C4 blending Octane increase Low Cost MeOH Olefins reduction Dilution effect
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Drawbacks
Uncertain oxygenates future

Main Constraints

Sulfur Benzene Aromatics Olefins Octane loss compensation

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Octane Loss Compensation

Three main options for Octane recovery:

- Light Naphtha Isomerization - Etherification (MTBE, TAME, ETBE) - Alkylation

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Light Naphtha Isomerization

Benefits
Octane gain Distillation curve Sulfur-free Aromatics-free Olefins-free

Drawbacks
Capital H2 availability RVP increase

Isomerization is the best light naphtha octane boosting process for meeting the new gasoline specifications
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003 35

Isomerization Technologies

Conventional technologies Once-through process (15 units) Deisohexanizer recycle (6 units) (molecular sieves separation) Ipsorb (2 units) Hexorb (no unit up to now)

Advanced recycle technologies

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Once-Through Process (Chlorinated Alumina Catalyst)

Off Gas
CW

Hydrogen
Dryer
MP Steam

Scrubber

R-1 Light Naphtha

Dryer

R-2

Stab
MP Steam

Isomerate
CW

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Deisohexanizer Recycle
iC5 + nC5 + DMBs

Off Gas C5C6 Feed Isomerization

MPs + nC6

Isomerate DIH
iC5 + DMBs + nC5 + MCP + CH + C7 MCP + CH + C7

Hydrogen

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Ipsorb
iC5 Off Gas C5C6 Feed DIP Isomerization
iC5+nC5+nC6

Isomerate Mole Sieves

iC5 + DMBs + MPs + MCP + CH + C7s

Hydrogen

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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Hexorb
iC5 + DMBs

Off Gas

MPs

Isomerate Isomerization C5C6 Feed Hydrogen

MCP + CH + C7s
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003 40

Mole Sieves

DIH
iC5 + DMBs + MCP + CH + C7s

MPs + nC5 + nC6

Technology Selection

92

Typical RON Target

Ipsorb DIH
Once through

Hexorb

RON
88

84 Chlorinated Alumina Catalyst

10 20 ISBL Investment Cost, Million US$ (8,000 BPSD capacity)

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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

New Chlorinated Alumina Catalyst

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

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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Across-the Board ATIS-2L Advantage

Improvement with ATIS-2L

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Hexorb Ipsorb

RON
88 Once through DIH

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10 20 ISBL Investment Cost, Million US $ (8,000 BPSD capacity)

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MTBE Replacement : Pseudo Alkylation

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%)
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Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

Conclusions

Optimum solution is refinery-specific Gasoline pool can be optimized through customized feasibility studies Axens offers a complete portfolio of processes for attainment of the most stringent gasoline specifications

Sub Saharan Africa Refiners Meeting - Somerset West - October 2003

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