a global offer for middle distillates · pdf filea global offer for middle distillates...

1

Prime-D Toolbox

A Global Offer

for Middle Distillates Hydroprocessing

Michel Dordon

2Petrofed Petroleum Refining Technologies Seminar- 16-17th April

New Prime-Dfor ULSD or/& aro. saturation

Revamplight / heavy

StudiesAPC, POS Tech service

team

HR Series High Perf. Catalysts

Full range ofGrading Material

Technology

Products

Services

EquiFlow Trays& Quench

CatapacDense loading

A Fully Integrated Offer of Proven Technologies

Modeling


Agenda

Prime-D & Prime-K Technologies for Grassroot

Projects and Revamps

HR Catalysts for Middle Distillates HDT


Revamping Case Study Initial Design

• 29,400 BPSD (non Axens Design)• Sulfur product content: 200-500 wt ppm • Reactor Loading :

• 2006 : 1st

cycle with HR 426 CoMo• 2008 : 2nd

cycle after HR 426 catalyst regeneration


Revamping Case Study Objectives of the Project

• Increase of capacity :+30%

• Continuous 40 ppm ULSD production

• Minimum cost investment

• Minimum plot plan increase


Revamping Case Study Design Feed Properties

• CoMo

catalyst

best suited

for optimum performance of the Unit• New reactor

added

with

improved

gaz/liquid

distribution

Specific Gravity 0.864 Sulfur, wt% 1.219 Total Nitrogen, wt.ppm 377 Total aromatics, % m/m 22.9 Cetane Index 50.3

IBP 193 5% 252

30% 306 50% 321 90% 357 95% 369 EBP 390

SulfurCompounds

Sulfides and Mercapt., wtppm 6023 (49%)

BT, wtppm 1595 (13%)

DBTCompounds

DBT, wtppm 1039 (9%)

4-DBT, wtppm 1834 (15%)

4,6-DBT, wtppm 1702 (14%)

NitrogenCompounds

Neutral Nitrogen, wtppm 97 (26%)

Basic Nitrogen, wtppm 280 (74%)

AromaticCompounds

Mono-Aromatics, wt% 13.4

Di-Aromatics, wt% 8.1

Tri+Aromatics, wt% 1.4

Detailed

Characterization


Unit Before Revamping

H2 m.u.H2 Recycle

Off-Gas

LGO, HGO,VDO

S:200/500

ppm


Unit After Revamping

H2 m.u.H2 Recycle

Off-Gas

LGO, HGO,VDO

S: 40 ppm

Stripper traymodifications

+ 30% capacity

HR 626 LoadingNew Reactor

Addition MU comp

Addition Feed

Pump

ModificationHX scheme

HR 626 LoadingEquiFlow

internals


Objectives Fulfilled

• Two-phase revamp for minimum shut down time (6 weeks)• New equipment implementation before S/D• Piping & equipment modifications during S/D

• Continuous ULSD production at increased capacity (+30%)• HR 626 perf in line with

expectation with

very

low

deactivation

rate (~0.5°C/month)Normalized WABT

320

330

340

350

360

370

380

0 50 100 150 200 250 300 350 400 450 500 550 600 650 700

Days On Stream

Tem

pera

ture

(°C

)


Agenda

Prime-D & Prime-K Technologies for Grassroot

Projects and Revamps

HR Catalysts for Middle Distillates HDT


Axens Catalyst Porfolio A Wide Offer Covering All HDT Services

HR 626HR 608(Kero)

HR 648

LD 402

HDK 776

VeganHRB 618HDB 616

Dewaxing

HR 648

LD 402


Choosing The Right Catalyst

CoMo NiMo


Kero

Application Criteria

HighPressure

LowPressure

CoMo

NiMo for smoke point

Kero

Heaviness

NiMofor ULSK


Diesel Application Criteria

HighPressure

LowPressure

CoMo for HDS

NiMo for HDA≈

40 bar ppH2 (depends

also

on feed

heaviness)



CoMo NiMo


0102030405060708090

100

Aug-07Nov-07

Feb-08May-08

Aug-08Nov-08

Feb-09May-09

Aug-09Nov-09

Feb-10May-10

Aug-10Nov-10

April 11

July-11Oct-11

Jan-12

HR 626 Development Milestones

• End July 2007: Commercialization

• March 2012: 95 references

61 loads started

• Replaced 60% of the time non Axens’

catalysts• Reconducted

several times

HR 626 is a CoMo

catalyst for ULSD based on further improvement of the well-mastered ACE™

Technology

(i.e. calcined

catalysts without any organic additives)

HR 626 Cumulative References


HR 626

HR 626 Main Features


HR 500 Series Industrial Feedback: First Case Study (1)

HR 626 Activity Gain

0

20

40

60

80

100

120

140

630 640 650 660 670 680 690Temperature, °F

Prod

uct S

ulfu

r Con

tent

, wt p

pm

HR 526 HR 626

ACTIVITY GAIN IN ULSD SERVICE: 10-15°F - 6-8°C


HR 626

HR 626 Stability


340

345

350

355

360

365

370

0 10 20 30 40 50 60 70 80 90 100Days on stream

HR 626Reference Catalyst

Normalized WABT, °C

HR 626 Superior Stability Commercial Experience (2/2)

Significantly higher stability of HR 626

Temporary initial higher activity of Non

Axens catalyst

Non Axens Catalyst


HR 626 Regenerability

HR 626


Δ RVA < 5%

10

30

50

70

110

343 348 353Reactor Temperature, °C

Regenerated HR 626Fresh HR 626

90

Effluent Sulfur Content, ppmTest carried out at iso-WHSV

Δ RVA < 5%

10

30

50

70

110

343 348 353Reactor Temperature, °C

Regenerated HR 626Fresh HR 626

90

Effluent Sulfur Content, ppmTest carried out at iso-WHSV

Industrial Ex-Situ Regeneration Full Activity Recovery

Regeneration ResultsHR 626 1st

Reg 2nd

RegC (% wt ) 0.2 0.1S (% wt ) 0.3 0.5Surface Area (% of fresh catalyst) 96 90Bulk Crushing Strength (MPa) 1.42 1.39RWA vs

Fresh HR 626 (Lab Reg) 98 95RWA vs

Fresh HR 626 (Indus Reg) 96 93 (Estimated)

ULSD service Around 1°C activity loss after

each ex-situ regeneration


HR Catalyst Regeneration

• The ACE technology allows 95% activity recovery

compared to fresh HR 626

• single stage air burning

which can achieved by every catalyst regeneration companies

• no chemical treatment

(no organic additive)• easy handling

and activation

• HR catalysts re-use cost• estimated to be at least 3 times less expensive

than boosted catalystsOver the catalyst life, HR catalysts are 30 to 40% less expensive than boosted catalysts


HR 626

HR 626



HR 626 HR 648


0

50

100

150

200

330 340 350 360

Temperature, °C

Prod

uct S

ulfu

r con

tent

, ppm HR 648 Sample 1

HR 648 Sample 2HR 648 Sample 3HR 548

New NiMo

HR 648 Activity Gain

HR 648 is at 6°C more active

than HR 548 on HDS

Delta API

HR 548HR 648

6°C

HR 648

2.0

2.5

3.0

3.5

4.0

330 335 340 345 350 355 360Temperature, °C

Del

ta A

PI

HR 648 Sample 1HR 648 Sample 2HR 648 Sample 3HR 548

HR 548

HR 648 >10°C

Product Sulfur

Improved Hydrogenation activity for • higher cetane boost• higher volume swell

HR 648 is at 10°C more active

than HR 548 on HDA


HR SeriesHR Series

Conclusion

• Full Set of High Performance Catalysts for Middle Distillates HDT• 2007: HR 626

latest generation CoMo

for ULSD• 95 awards after 4 years on the market• 60% as a replacement of competition catalysts

• S2 2010: HR 648

a breakthrough NiMo

for cetane

improvement• 17 awards since mid 2010

• Extensive Licensing Experience for Grassroot

and Revamps• Over 45 years of experience in new Middle Distillates HDT licensing

and revamping projects• Prime-D & Prime-K:

118 awards for ULSD & cetane

improvement services

• Doubling of awards over the last 5 years

• Grading, Internals and Catalyst loading

for an optimum bed operation

• Dedicated Tech Service

for units optimization

28

Prime-D Toolbox

A Global Offer

for Middle Distillates Hydroprocessing

a global offer for middle distillates · pdf filea global offer for middle distillates...

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