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© 2016 UOP LLC. A Honeywell Company All rights reserved.
Quenching Our Thirst for Clean FuelsJim RekoskeVP & Chief Technology Officer
Honeywell UOP
22 April 2016 Petrofed Smart Refineries New Delhi, IndiaUOP 7200-0
India’s Demand for Clean Gasoline1
Drivers Trends- Improved economic outlook –
higher spending on Fuels and Plastics – 7.6% annual GDP growth possible over next 5 years
- Need for air quality Improvement – regulations for Fuel specs upgrade
- Dependence on imported crude
- Refinery utilization at or near 100% (nominal basis) for many units
- Demand has caught up with supply – need for new investment planning
- Nationwide upgrade to BS IV fuel by Q1’17 and EBSVI by 2020
- Maximize value from crude imports through efficiency, upgrading
- Automobile sales growth of ~10%
- Gasoline growth outpaces diesel
A Balancing Act: Bharat VI Specs with Maximum Profit
Many constraints – optimal solution?
2
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
More Oxygenates
More Oxygenates
Remove before or after reformer
Remove before or after reformer
Limit on C4s & C5s in IsomerateLimit on C4s &
C5s in Isomerate
Limit on FCC Gasoline
Limit on FCC Gasoline
Limit on FCC Gasoline or Increase Desulfurization
Severity
Limit on FCC Gasoline or Increase Desulfurization
SeverityLimit on ReformateLimit on
Reformate
Limit on “lights”Limit on “lights”
Benzene1 vol%
RVP60 kPa
Olefins18 vol%
Sulfur10
wt-ppm
Aromatics35 vol%
Oxygenates2.7 vol%
DistillationE70/E100
How can I blend more FCC Gasoline and control olefins and sulfur?
How do I drive octane yield and aromatics to the limit?
Where is the rest of my octane going to come from?
A Balancing Act: Bharat VI Specs with Maximum Profit
Many constraints – optimal solution?
3
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
More Oxygenates
More Oxygenates
Remove before or after reformer
Remove before or after reformer
Limit on C4s & C5s in IsomerateLimit on C4s &
C5s in Isomerate
Limit on FCC Gasoline
Limit on FCC Gasoline
Limit on FCC Gasoline or Increase Desulfurization
Severity
Limit on FCC Gasoline or Increase Desulfurization
SeverityLimit on ReformateLimit on
Reformate
Limit on “lights”Limit on “lights”
Benzene1 vol%
RVP60 kPa
Olefins18 vol%
Sulfur10
wt-ppm
Aromatics35 vol%
Oxygenates2.7 vol%
DistillationE70/E100
How can I blend more FCC Gasoline and control olefins and sulfur?
How do I drive octane yield and aromatics to the limit?
Where is the rest of my octane going to come from?
A Balancing Act: Bharat VI Specs with Maximum Profit
Many constraints – optimal solution?
4
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
More Oxygenates
More Oxygenates
Remove before or after reformer
Remove before or after reformer
Limit on C4s & C5s in IsomerateLimit on C4s &
C5s in Isomerate
Limit on FCC Gasoline
Limit on FCC Gasoline
Limit on FCC Gasoline or Increase Desulfurization
Severity
Limit on FCC Gasoline or Increase Desulfurization
SeverityLimit on ReformateLimit on
Reformate
Limit on “lights”Limit on “lights”
Benzene1 vol%
RVP60 kPa
Olefins18 vol%
Sulfur10
wt-ppm
Aromatics35 vol%
Oxygenates2.7 vol%
DistillationE70/E100
How can I blend more FCC Gasoline and control olefins and sulfur?
How do I drive octane yield and aromatics to the limit?
Where is the rest of my octane going to come from?
Indian Refiner Gasoline Pool Requirements
How do we manage both S and olefins in FCC gasoline?
5
BS III BS IV BS VI
Density @ 15 °C kg/m3 720-775 720-775 720-775
E-70E-100E-150
% vol% vol% vol min
10-4540-70
75
10-4540-70
75
10-4540-70
75
FBP °C 210 210 210
Sulfur ppm max 150 50 10
RON Min 91 91 91
MON Min 81 81 81
RVP @ 38 °C kPa 60 60 60
Benzene vol % max 1 1 1
Aromatics vol % max 42 35 35
Olefin vol % max 21 21 18
Oxygen wt% max 2.7 2.7 2.7
Coker Naphtha
Coker Naphtha
OtherOther
FCC NaphthaFCC Naphtha
Sources of sulfur in typical gasoline pool
• FCC naphtha represents ~40% of the volume of the typical refinery’s gasoline pool
UOP Confidential Information
UOP’s Portfolio of FCC Naphtha Desulfurization Technologies
•MeroxTM process- extraction or sweetening of mercaptan components of
FCC Light Naphtha (LCN) and Mid-cut Naphtha (MCN)- Does not remove thiophenes
•SelectFiningTM process- desulfurization and octane retention for FCC FBR,
MCN or HCN
Technology choice is based on octane requirements, feedstock composition, product values and required desulfurization.
UOP Confidential Information
SelectFining Technology Overview
Optimum Flowscheme and Catalysts for particular needs
7
• Achieve low S target in Gasoline Pool• Can achieve <10 wt-ppm S in FCC Gasoline
• Maximum Octane Retention to Meet Specifications• Lowest Hydrogen Consumption
• Flowschemes for Various Feedstocks Optimized for Maximum Economical Value
• One Stage for low sulfur feedstock (or 90% HDS)• Two Stage for high sulfur feedstock and 90% HDS• Depends on feed characteristics and product requirements
• High Stability Specialized Catalysts• Specialized Co/Mo catalyst with optimized metals levels and distribution• Suitable for all FCC naphtha hydrotreating applications where selectivity to
favor desulfurization over olefin saturation is required
UOP Confidential Information
Issues Relating to Hydrotreating FCC Naphtha
Sulfur RemovalSulfur Removal
+ 6H2+ 6H2 H2S +H2S + + Heat+ HeatSS
DesirableDesirableSulfurSulfur
Olefin SaturationOlefin Saturation
+ H2+ H2
CH3CH3
CH3 – CH = C – CH3CH3 – CH = C – CH3
––
CH3CH3
CH3 – CH2 – CH – CH3CH3 – CH2 – CH – CH3
––
UndesirableUndesirableOctaneOctane
Octane loss is dependant on feed/product sulfur contents, and quantity/types of naphtha’s sulfur and olefin species!
UOP Confidential Information
Relative Reactivity of S and Olefins in FCC Gasoline
Incr
easi
ng R
eact
ivity
Increasing Molecular Weight
R-SH
Olefins
C5
C6
C7
C8
SulfurR-S-S-R
C9
S
S
S
S
UOP Confidential Information
UOP One-Stage SelectFining Process
Typical for low sulfur feeds and/or 90% HDS Flowscheme and operating
conditions are similar to NHTs
Steam
ChargeHeater
SelectFiningReactor
MakeupHydrogen
LeanAmine
Debutanizer
LightEnds
Low SulfurNaphtha
Feed
Recycle GasScrubber
RichAmine
ProductSeparator
RecycleCompressor
DieneSaturation
ReactorHYT-2117
N-200 HYT-2018 (S-200)HYT-2118
10
UOP Confidential Information
Impact of % Desulfurization on Olefin SaturationSingle-Stage SelectFining Performance
% O
lefin
Sat
urat
ion
10095 96 98 99
100
20
60
80
97% Desulfurization
FBR FCC NaphthaSulfur = 1800 wppm
Single-Stage SelectFining Unit
40
18 ppm36 ppm54 ppm72 ppm90 ppmTypical Product S
UOP Confidential Information
H2S Impacts Olefin Retention
18.5
19.5
20.5
21.5
0.0% 0.4% 0.8% 1.2%
Tota
l Pro
duct
Ole
fins,
wt%
Volume Percent H2S
Understanding recombination is critical as it directly impacts olefin retention
Feedstock23.8 wt-% Olefins2206 wt ppm Sulfur
UOP Confidential Information
12
• Mitigate with two HDS stages – strip out H2S between stages, as dictated by feed sulfur and product sulfur and octane targets
• Mitigate with polishing reactor downstream of SHDS
H2S
+ H2S
H3CCH3
H3C
H3CCH3
H3CH3C
CH3H3C
SH
+ H2+ H2
Octane
Mercaptan Recombination
UOP Confidential Information
13
UOP Two-Stage SelectFining Process14
Steam
ChargeHeater
First StageReactor
RecycleCompressor
LeanAmine
Debutanizer
LightEnds
Low SulfurNaphtha
Feed
Recycle GasScrubber
RichAmine
ProductSeparator
Second StageReactor
InterstageSeparator
MakeupHydrogen
DieneSaturation
Reactor
Typical for high sulfur feeds with 90% HDS Interstage H2S Stripping Mitigates Recombination
HYT-2117HYT-2018HYT-2118
HYT-2119
UOP Confidential Information
Impact of % Desulfurization on Olefin SaturationSingle-Stage vs Two-Stage SelectFining Performance
% O
lefin
Sat
urat
ion
10095 96 98 99
100
20
60
80
97
Two-Stage SelectFining Unit
% Desulfurization
FBR FCC NaphthaSulfur = 1800 wppm
Single-Stage SelectFining Unit
~ 2 RONC
~ 1 RONC40
18 ppm36 ppm54 ppm72 ppm90 ppmTypical Product S
UOP Confidential Information
SelectFining – Gasoline Desulfurization Optimized, Simply
• Flexible configurations to meet the most demanding challenges of octane retention and sulfur removal
• State-of-the-art, commercially proven catalysts with best-in-class performance
• Configurations in combinations with UOP Merox™ sweetening technology- Enables “molecule management” – directing the sulfur species to the most
efficient conversion process- Unique offerings which can lower both capital and operating costs
A Balancing Act: Bharat VI Specs with Maximum Profit
Many constraints – optimal solution?
17
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
More Oxygenates
More Oxygenates
Remove before or after reformer
Remove before or after reformer
Limit on C4s & C5s in IsomerateLimit on C4s &
C5s in Isomerate
Limit on FCC Gasoline
Limit on FCC Gasoline
Limit on FCC Gasoline or Increase Desulfurization
Severity
Limit on FCC Gasoline or Increase Desulfurization
SeverityLimit on ReformateLimit on
Reformate
Limit on “lights”Limit on “lights”
Benzene1 vol%
RVP60 kPa
Olefins18 vol%
Sulfur10
wt-ppm
Aromatics35 vol%
Oxygenates2.7 vol%
DistillationE70/E100
How can I blend more FCC Gasoline and control olefins and sulfur?
How do I drive octane yield and aromatics to the limit?
Where is the rest of my octane going to come from?
UOP’s Recent Platforming Innovations18
UOP 7299-18 Project IRR improved by 2 - 6 %
Naphtha Feed
CFE
Convective Charge Heater
Modified CatMax™ Internals
Recycle Gas
Reactor Effluent
Cyclemax™ III CCR
Convective Charge Heater19
UOP 7299-19 Estimated savings is $5MM for 50,000 BPSD UnitUOP Confidential Information
Conventional Conventional Convective Charge Heater
Convection
Product Condenser
Recycle Gas
To Separator
Naphtha CFE
To Stack
Stabilizer Preheat
Steam Convection Bank
Charge Heater
IH #1 IH #2 IH #3 To RX4
To RX1
• Features – Charge heater moved to convection section
displacing portion of steam generation – Temperature control achieved by stack gas recycle– Radiant section fouling reduced with stainless
steel tubes– 1 less heater box
• Benefits: – Lower capital cost – Reduced plot space – Less fuel fired – Lower emissions*
*Applicability for individual units to be evaluated
Meeting the Expansion Challenge:Example Max Throughput Revamp
20
UOP 7299-20 Convective heater was a key part of this revampUOP Confidential Information
Capacity raised to 190% nameplate– Unit met / exceeded guaranteed
revamp performance
Key features:– R-264 catalyst– Reactor Bypasses with Rx Addition– CCR expanded 1500 to 3250 lb/hr– Radiant–Convection fired heater– Add a 4th Net Gas Compressor – which also
supplies additional recycle gas
UOP’s revamp experience:– Over 50 CCR Platforming Units and over
25 Regenerator revamp designs
Platforming Innovations Summary• UOP continues to improve best-in-class naphtha reforming technology
• Innovations include all critical sections of the process:- Regeneration- Catalyst- Reactor / Internals- Heaters
• Innovations drive substantial incremental customer value
• Innovations enabled because of unique R&D / Engineering / Equipment interaction
A Balancing Act: Bharat VI Specs with Maximum Profit
Many constraints – optimal solution?
22
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
More Oxygenates
More Oxygenates
Remove before or after reformer
Remove before or after reformer
Limit on C4s & C5s in IsomerateLimit on C4s &
C5s in Isomerate
Limit on FCC Gasoline
Limit on FCC Gasoline
Limit on FCC Gasoline or Increase Desulfurization
Severity
Limit on FCC Gasoline or Increase Desulfurization
SeverityLimit on ReformateLimit on
Reformate
Limit on “lights”Limit on “lights”
Benzene1 vol%
RVP60 kPa
Olefins18 vol%
Sulfur10
wt-ppm
Aromatics35 vol%
Oxygenates2.7 vol%
DistillationE70/E100
How can I blend more FCC Gasoline and control olefins and sulfur?
How do I drive octane yield and aromatics to the limit?
Where is the rest of my octane going to come from?
Where should your C7s go?23
UOP 7299-23C7 Management is critical for meeting BS VI specs
C5 - C6
82
92
RONC
Gasoline Blending
Isomerization330 Units
PI-242PI-244 Feed
To Separation
Makeup Gas
Par-Isom Unit
Light Naphtha
Cl
Make-Up Gas
Stabilizer
Dryers
Penex ReactorsDryers
To Scrubber
To Gasoline or DIH
I-122
I-82I-84
Penex Unit
• None• Once Through
OT
•DIHRecycle
•DIP•Super DIHRecycle
Hydrocarbon Recycle Option
C6 – C11
106+
93
Gasoline Blending
BTX and Gasoline Blending
Reforming304 units
R-264R-284
R-234R-254
Platforming Unit with Cyclemax™ III CCR
CCR
Naphtha Feed
RXs
SEP
Heaters CFE
R-334
C7s?
Processing Feed with Low Light to Heavy Naphtha Ratio in Naphtha Complex
24
UOP 7299-24 Naphtha Complex achieves 92 RONC pool without MTBE
Total Gasoline Yield = 90 Wt-%Meeting EURO V specNo MTBE added
100% Feed
Platforming Unit
95 RONC
100%92 RONC
65% Feed
35% Feed
C4s
NHT
Penex Unit 89+ RONCN
ap S
plit
DIP
SDIH
Naphtha Complex with Penex/IsomEx Process Maximizes Gasoline Yield
25
UOP 7299-25 IsomEx™ achieves higher yield and RONC gasoline without MTBE
Gasoline Yield ~ 95 Wt-%Meeting EURO V specNo MTBE added
CCR Unit
Penex Unit
44%92 RONC
55% Feed
C4s
89+ RONCIsomEx Unit
89-91 RONC
92+ RONC
56%95 RONC
80+ RONC
95 - 102 RONC
DIP
SDIH
DIH
p
15% Feed
DIP
Nap
Spl
it
30% Feed
Nap
Spl
it
NHT
Alternative schemes are available
UOP IsomEx: C7 Solutions for Octane Challenges• Simultaneous increase of gasoline yield and quality
- Meets stringent Euro V specifications without MTBE addition
- Increases naphtha block gasoline yield from 90 to 95%
- Upgrades 56% of the product to premium gasoline (95 RONC)
• Built on generations of paraffin isomerizationexperience
- Proven process configuration- Proven catalysts, yields and stability
• Molecule management: direct the molecules to the perfect technology.
26
27.0 27.825.2
14.3 16.2 16.6
05
101520
2530
3540
4550
2007 2008 2009 2010 2011 2012C
7+ in
Rea
ctor
Fee
d, W
t-%
A Balancing Act: Bharat VI Specs with Maximum Profit
UOP has the proven, commercialized solutions
27
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
UOP Solutions EtherMax™ unit InAlk™ Unit AlkyPlus™ Unit Hydrotreating Platforming™ Unit Penex™ Unit IsomEx™ Unit Par-Isom™ Unit Selectfining™ Unit
More Oxygenates
More Oxygenates
Remove before or after reformer
Remove before or after reformer
Limit on C4s & C5s in IsomerateLimit on C4s &
C5s in Isomerate
Limit on FCC Gasoline
Limit on FCC Gasoline
Limit on FCC Gasoline or Increase Desulfurization
Severity
Limit on FCC Gasoline or Increase Desulfurization
SeverityLimit on ReformateLimit on
Reformate
Limit on “lights”Limit on “lights”
Benzene1 vol%
RVP60 kPa
Olefins18 vol%
Sulfur10
wt-ppm
Aromatics35 vol%
Oxygenates2.7 vol%
DistillationE70/E100
UOP technologies can help refiners meet the rigorous specifications of Bharat VI while maintaining or increasing profit
The principle of Molecule Management – directing molecules to the most efficient, advanced technology – provides real benefits
Complex processing / blending solutions require a strong partner with broad experience…
28
UOP 7200-28