Maximize Benefits from your PRIME-G+ the most advanced technology for FCC gasoline desulfurization

Annick Pucci

Agenda

Sulfur regulation
Prime-G+ Commercial Update and Keys for Success Maximizing Prime-G+ benefits

Quick tuning Advanced process control Improving Prime-G+ Performances

Catalytic arrangement Scheme modification
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Gasoline Sulfur Content in the World

US: Tier 3 10ppm by 2016 EU: 10 ppm since 2009 Japan/ S Korea: 10 ppm since 2007

CA: 10 ppm for CARB 3 since 2008 Chile: 15ppm since 2010 Nationwide: 150 ppm 26 big cities at 50 ppm to be expanded to 50 cities by 2015
Source: IFQC, 2013
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Gasoline S Specification Trends

Europe
EU 2005 Spec. EU 2009 Spec. 50 ppm S 10 ppm S 30 ppm S 10 ppm S 10 ppm S 10 ppm S

U.S / Canada
Tier 2 (2004-2006) CARB 3 (California) 2016 + Tier 3

Japan / Korea
2007 Spec.

Worldwide trends towards 10 wppm

4

FCC gasoline postreatment challenges

Decrease S in cracked gasoline while minimizing octane loss and hydrogen consumption
(Minimization of Olefin Hydrogenation & no Aromatics Saturation & Cycle matching the FCC turnaround)

Industrially proven with Axens Prime-G+ down to

less than 10 ppm sulfur Prime-G+ the most widely used FCC gasoline HDS technology
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Agenda

Sulfur regulation
Prime-G+ Commercial Update and Keys for Success Maximizing Prime-G+ benefits

Quick tuning Advanced process control Improving Prime-G+ performances

Catalytic arrangement Scheme modification
6

Prime-G+ typical block flow

LCN

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

SHU section
Selective Hydrogenation

Splitter

HDS section
HCN From FCC Prime-G+ Selective HDS

Ultra-Low Sulfur Gasoline

H2 Make-up Large majority of Prime-G+ references with a splitter

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Some Keys for Prime-G+ Success

Performance
Catalytic performances ( activity / selectivity / stability) Process economics ( low CAPEX & OPEX large revamp experience) Flexible technology Non regret investment Reliability
fixed bed reactors familiar to operators Easy control of product sulfur

Single Source Supplier

R&D, Process Design, Catalyst, Start-up, Service such as..
Training, Advanced Process Control, Users conferences, Catalyst Management

Keys for Prime-G+ Success

Process economics Catalytic performances Process flexibility

Maximizing Benefits

Improving performances
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Catalytic Performances

Tailored, unrivaled Catalysts for octane retention

and long cycle length
SHU Catalyst: Dienes and RSH removal

Lead HDS Catalyst: Bulk HDS / controlled olefin saturation

Polishing HDS Catalyst: Remaining HDS / RSH control / almost no olefin saturation

Reliability

Arsenic trapping mass : for HDS catalyst protection against poisoning

Catalyst Replacement Market

100 % of Guarantees Met Synchronization of Cycle length with FCC turnaround

7 competition units went for Axens catalysts

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Industrial SHU performance

LCN (65C-)
S = 10 ppm RSH < 2 ppm

H2

Mercaptans Removal Doctor Test Negative Slight Octane Boost

SHU Feed RON 94.0 82.0 SHU Product 94.3 82.2

FRCN
S = 2100 ppm RSH = 100 ppm

MON

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Prime-G+ HDS Unit performance

Feed Sulfur, wtppm Product Sulfur, wtppm

700 600 500 400 300 200 100 0

0 250 500 750 1000 1250 1500 days on stream

70 60 50 40 30 20 10 0
1750

5.75 years cycle length at

less than 10

ppm S
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Keys for Prime-G+ Success

Process economics Catalytic performances Process flexibility

Maximizing Benefits

Improving performances
13

Prime-G+ wide Design Range

Licensed Units - Design Range

Unit Capacity: 2,500 - 115,000 BPD Feed Sulfur: 30 - 4,100 ppm Olefins Content: 9 - 45 vol. % Feeds: FCC Naphtha, Coker Naphtha, LSR, Heavy PyGas Product S < 10 ppm Cycle equivalent to FCC T/A demonstrated
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Prime-G+ Processing Schemes

Low / Moderate HDS
1-Stage HDS
FCC FRN
SHU HDT

Moderate / High HDS

PG+ 1st Step / 1-Stage HDS
LN FCC FRN
SHU

LSG

LSG

Very High HDS

PG+ 1st Step / 2-Stage HDS
LN FCC FRN FCC FRN
SHU SHU

HDT

2-Stage HDS
HDT 1&2

LSG

LSG

HDT 1&2

PG+

1st

Step = Prime-G+ Selective Hydrogenation Unit (SHU) + Splitter

<10 ppm S achievement Staged investment

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Keys for Prime-G+ Success

Process economics Catalytic performances Process flexibility

Maximizing Benefits

Improving performances
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Process Economics

Low CAPEX
Simple scheme & fixed bed reactors

Low OPEX Low hydrogen consumption Large revamping experience

Reuse of existing idle equipment (Gasoline splitter, HDT reactors) Retrofit of idle units (NHDT , DHDT, Isomerization units, Semi-reg reformers)
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Keys for Prime-G+ Success

Process economics Catalytic performances Process flexibility

Maximizing Benefits

Improving performances
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Maximize benefit by quick tuning

After start-up

Operating feed is often different from design Feed properties are fluctuating a lot Product S specification often needs to be modified based on market demand or gasoline pool optimization

Prime-G+ can accommodate Major parameters to be optimized For Performances adjustment

For energy minimization

SHU & HDS Catalysts Temperature LCN yield Splitter Reflux Ratio minimization HDS Quench & Heater optimization
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Operational Fine Tuning: Splitter Reflux Ratio Minimization

Splitter reflux is fixed at basic

engineering phase as a result of
LCN/HCN separation quality Design feed sulfur in LCN

Depending on actual processed feed and gasoline pool constraints, reflux and LCN draw may be slightly adjusted

S
From SHU

LCN

Main benefits

On-spec LCN thus resulting in minimum

octane loss in downstream HDS HP Steam / fuel gas savings in reboiler Electricity / cooling water savings in overhead condensers

HCN To HDS section

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Advantages of APC

Fine tuning is neglected too often!

To secure pool in case of high fluctuation of feed
quality or product spec
Over-quality S is systematically targeted More octane loss

APC only capable to control gasoline Pool S

without S over-quality in Prime-G+
As Licensor, Axens is in a unique position to boost your Prime-G+ performance by using proprietary models for APC APC benefits are quickly quantifiable
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Sulfur Distribution with & without APC

Average without APC + 1.2 ppm
Sulfur Average = 10.08632 StDev = 0.44321

Target Value

4.5

5.5

6.5

7.5

8.5

9.5

10 10.5 11 11.5 12 12.5 13 13.5 14 14.5 15 15.5 16

22 Product Sulfur Content

APC Strategy
Controlled Diolefin Hydrogenation

LCN
Cut-point optimization and internal reflux control Sulfur Control

Splitter
Selective Hydrogenation

Blend

HCN
From FCC

Prime-G+ Selective HDS

Maximization of Octane Retention

H2 Make-up
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APC Startup Industrial Plant

APC OFF
HDS Temp

TUNING

APC ON WABT -3C Maximize

Run-length

H2 Make-up

H2 Make-up Minimize -20% OPEX

On Spec +/- 0.5ppm

Product Sulfur
MON Loss

MON Loss: -20%

0 7 14 21

Hours

28 24

Prime-G+ APC : Why Work With Axens ?

Prime-G+ is not a simple HDS process APC is not only Sulfur Control, but also
Octane Loss minimization Run Length maximization Energy Consumption minimization.

To minimize Octane Loss, it is mandatory to use HDS

inference based on Kinetic model Axens is in a unique position to offer you the best APC strategy

R.O.I. typically below 6 months

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Prime G+ Users Conference

Technical Conference
Exclusively reserved for licensees

Forum of Exchange
Best practices and operational issues

Good Feedback from Past Conferences 7 conferences already organized.

the 8th conference is scheduled in 2014
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Keys for Prime-G+ Success

Process economics Catalytic performances Process flexibility

Maximizing Benefits

Improving performances
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 Capacity increase

Client Needs After 1st start-up Market demand is evolving, more frequent needs
Processing of higher end boiling point gasoline

Co-processing of more refractory / alternative

feeds Progressive implementation of tighter sulfur specifications in gasoline pool Requirement for
increased octane retention increased cycle length reduced utility consumption

With minimum investment cost

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Improved Performances After 1st Start-Up

Low Cost Options

Use latest generation catalyst Use new reactor internals Rearrangement of catalytic volume

Medium/High CAPEX options

Scheme modifications
Adding a gasoline splitter Adding additional reactors Adding a second HDS stage Rearrangement of HX train

Energy efficiency : Heat integration

Maximum reuse of existing equipment

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Improved Performances : Low cost solutions

Increased octane retention

Higher selectivity catalyst Increased cycle length Higher activity/stability catalyst Unrivalled tailored Prime-G+ catalysts

PG+ SHU

PG+ Main HDS

PG+ Polishing

HR 845

HR 806

HR 841
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Axens R&D strategy

Catalyst formulation
Lab scale screening

Process development
Operating conditions

Axens is committed to continuously improve its existing products

Industrial process
Reactor internals

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Prime-G+ Catalyst Management

Perform analysis of spent catalyst for

Recovery of maximum value from spent catalyst (regenerability diagnostics vs level of contaminants) Optimization of the catalyst loading for achievement of required performance at minimum refill cost Access to the Pool of Axens Regenerated Catalysts New internals

Optimized Loading Diagram

Regenerated (Axens)

Regenerated (Client) Fresh (Axens)

Optimize customer revenue through catalyst life cycle Simplify & ease catalyst change out activities
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Case Study : Hy Mix Improved Distribution

Conventional Distributor Abnormal DT progression
TC1-1 % 100% 90% 80% 70% TC1-2 % TC1-3 % TC1-4 % TC1-5 % TC00 %

Hy-Mix Tray + Dense Loading Smoother operation

TC2-1 % TC2-2 % TC2-3 % TC2-4 %

DT progression

After Hy-Mix: Ideal profile maximize catalyst activity & stability

50% 40% 30% 20% 10% 0% 0 200 400 600 800 1000

60%

Days
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Prime-G+ Scheme Modifications

Mild HDS
Easy to implement & moderate capital expenditure Single stage HDS section with SHU

STARTING SITUATION

SHU FRCN

HDS

Low Sulfur Gasoline to Mogas

H2 Make-up
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Add a Splitter

Intermediate HDS

Prime-G+ 1st Step

ULS LCN to Pool, TAME or Alky Unit

Add a Polishing HDS reactor

Splitter
SHU FRCN HCN 65C+ H2 Make-up HDS Polishing HDS

Moderate revamp cost for :

Low Sulfur Gasoline to Mogas

Tighter S , Longer cycle , Lower octane loss

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High HDS

Minimum product sulfur Optimize cycle, minimize octane loss & H2 cons.

2-stage Prime G+

ULS LCN to Pool, TAME or Alky Unit

H2S
Splitter

SHU FRCN

1st Stage HDS HDS

2nd Stage HDS ULS Gasoline to Mogas

H2 Make-up

HCN 65C+

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Regain octane with Prime-G+ & TAME

MeOH Prime-G+ SHU

TAME
High Purity Ether Ultra Low S FRCN

Splitter
FRCN H2 Makeup

Prime-G+ HDS 25% Olefin reduction & 0.1 bar RVP reduction
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Process Scheme Modifications: Energy Efficiency

Process scheme selection is not only based on performances but more frequently on environmental and utility criteria

Improvement of the unit by thermal integration by

addition of exchangers AXENS can provide expected CO2 footprint of the installed scheme by estimating emissions associated to each utility Axens can propose key modifications of your Prime-G+ in order in order to reduce CO2 emissions
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Conclusion (1/2)

PRIME-G+ leading technology For selective HDS of

FCC gasoline
214 references /148 running units: 100% guarantees met Benefits of Flexible and reliable technology large revamping experience Long run length at <10 ppm S Reduced octane loss

Unrivalled Products
Benchmark catalysts: HR 845/ HR 806/ HR 841 Proven ACT-979 arsenic guard New products to come
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Conclusion (2/2) Ensure the success / Improve your performance

(Technology Licensor + Catalyst Supplier)

Skills

Best strategy for APC

Revamp scenario ranking

Catalyst management
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