Professional Documents
Culture Documents
Christian Dupraz
2009 10
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
FCC Feed Pre-treatment (hydrotreating) FCC Naphtha Post-treatment (selective HDS) Combination of both solutions
Drawbacks
Capital cost H2 availability Olefins spec. Coker gasoline sulfur SC gasoline sulfur LSRN sulfur
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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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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
H2 Make-up
Prime-G+ Features
Diolefins hydrogenation Mercaptans conversion to heavier sulfur compounds Isomerization of external to internal olefins Ultra low S LCN with slight octane improvement
Finishing Catalyst
Completes Desulfurization Minimum Olefin Saturation Mercaptans Control
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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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FRCN SHU
Reforming
MoGas Pool
Benefits
Octane retention H2 cons. minimization Olefins reduction
Drawbacks
HDT severity limitation Reforming capacity increase Benzene increase
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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
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003 16
Main Constraints
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FCC 17%
Reformer 81%
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Least expensive solution Impact on existing isomerization unit (C7 limitations) Less flexible
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Reformate splitter followed by conventional hydrogenation on light reformate Integrated splitter + benzene saturation
H2
Product
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BenfreeTM
Off Gas
To Isomerization
BenfreeTM Highlights
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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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
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Main Constraints
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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
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
Sub Saharan Africa Refiners Meeting - Somerset West - October 2003 29
Main Constraints
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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+)
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Drawbacks
Uncertain oxygenates future
Main Constraints
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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)
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Hydrogen
Dryer
MP Steam
Scrubber
R-2
Stab
MP Steam
Isomerate
CW
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Deisohexanizer Recycle
iC5 + nC5 + DMBs
Isomerate DIH
iC5 + DMBs + nC5 + MCP + CH + C7 MCP + CH + C7
Hydrogen
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Ipsorb
iC5 Off Gas C5C6 Feed DIP Isomerization
iC5+nC5+nC6
Hydrogen
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Hexorb
iC5 + DMBs
Off Gas
MPs
Mole Sieves
DIH
iC5 + DMBs + MCP + CH + C7s
Technology Selection
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Hexorb
RON
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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 :
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Hexorb Ipsorb
RON
88 Once through DIH
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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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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
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