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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
3Axens’ 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
4Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
5Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
Gasoline Pool Constraints
Olefins
Aromatics
Benzene
OctaneRetention
SulfurOctanizing
Benfree
Light NaphthaIsomerization
Prime-G+
Etherification
Polynaphtha
Dimersol-G
6Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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-
7Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
8Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
9Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
10Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
11Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Ligh Cuts Processing
� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
12Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
13Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
14Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing
� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
15Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• 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
16Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
17Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
18Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
Catacol Concept - Reactive Distillation
Isobutene (C4 cut) + Methanol MTBE
ResidualIsobutene
MTBE
19Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
20Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing
� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
21Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• 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
22Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
23Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• 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
24Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
25Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing
� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
26Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
27Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• 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
28Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
Dimersol-G Technology
inhibitor
29Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
30Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing
� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
31Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• 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
32Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
33Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
34Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing
� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
35Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
Optimized reactor design ensures capacity increase without modification
Side-by-Side Arrangement
Easy maintenance
Easy access to
reactors
Low investment
36Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
37Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
38Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• “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
39Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
� 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
40Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
41Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
• Clean Gasoline Challenges• FCC Gasoline and Light Cuts Processing
Options� Prime-G+� Etherification� Polynaphtha� Dimersol-G
• Light Naphtha Isomerization• Octanizing• Benfree
Agenda
42Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
43Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
BenfreeRD
C5+Reformate
Off Gas
Low BenzeneReformate
C5-C6
H2
Isomerization
� High flexibility � Limits C7s and naphthenes in light reformate
Liquid PhaseNi Catalyst
44Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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
45Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011
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