1

Latest Improvement in Middle Distillates Hydrotreating

Thierry Birchem

2Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011Source: Axens & other sources (2010)

Market Structure2009 vs. 2020

Oil Products DemandWorld

11.3%

13.3%

15.5%

5.7%

25.2%

6.0%8.1%

14.8%

9.2%

12.9%

17.7%

6.3%

23.9%

7.1%8.2%

14.7%

0%

20%

40%

60%

80%

100%

2009 202084.4

Mbdoe96.7

Mbdoe

• Growth driven by on-road diesel

• Progressive increase of middle distillate feed refractoriness (such as LCO, LCGO)

• Tighter quality specifications foron-road dieselall around the world

Off-road Diesel

Jet Kerosene

Fuel Oil

On-road Diesel

Motor Gasoline

NaphthaLPG

Other*AAGR09-20

0.8%

2.5%

-0.6%

2.2%

0.9%

1.2% AAGR

Other* = Kerosene (� Jet), Refinery Gas, Petroleum Coke, NGL, Lubricants, Bitumen, Paraffin Wax, Refinery Losses, …

3Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

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 ofProven Technologies

Modeling

4Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

Choosing The Right Catalyst

CoMo NiMo

5Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

HR 626

HR 626 Main Features

6Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

HR 626 Superior Stability Customer’s Stability Pilot Test (1/2)

HR 626 stability was tested by customer• 4-week test

• 1 week of stabilization with SR material• 3 weeks with a LCO+SR Blend (25% LCO)

• Two catalysts tested in parallel• Axens HR 626• A state-of-the-art boosted catalyst

• Temperature adjusted twice a day to meet less than 10 wppm sulfur in the product

• Tracking of the reactor temperature• Evaluation of the initial activity• Evaluation of the catalyst stability

7Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

HR 626 Superior Stability Customer’s Stability Pilot Test (2/2)

0

10

20

30

40

50

0 5 10 15 20Days on line with feed containing 75% SR & 25% LCO

Sulfur content, wt, ppm

320

340

360

380

400

420HR 626 SulfurOther Cat Sulfur

HR 626 TemperatureOther Cat Temperature

Corrected Temp, °C

HR 626 superior stabilityNPRA article on stability

8Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

� RVA < 5%

10

30

50

70

110

343 348 353Reactor Temperature, °C

Regenerated HR 626

Fresh HR 62690

Effluent Sulfur Content, ppm

Test carried out at iso-WHSV

� RVA < 5%

10

30

50

70

110

343 348 353Reactor Temperature, °C

Regenerated HR 626

Fresh HR 62690

Effluent Sulfur Content, ppm

Test carried out at iso-WHSV

Industrial Ex-Situ Regeneration Full Activity Recovery

Industrial Regeneration results

0.20.3C (wt %)

96

1.42

96

0.3

T2 > T1

0.4S (wt %)

94RVA vs Fresh HR 626

1.51Bulk Crushing Strength (MPa)

97Surface Area (% of fresh catalyst)

T1Regeneration Temperature

ULSD service Max 1°C activity loss after

ex-situ regeneration

9Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

Cetane Increase Industrial FeedbackCase Study (1/3)

• Asian refinery

• Prime-D unit (started in 2005)

• Axens NiMo

• H2 partial pressure: 88 bar

• Feed • SRGO + 20% cracked stock (LCO + VBGO)

• Density reduction and cetane increase targeted

10Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

Cetane Increase Industrial FeedbackCase Study (2/3)

8 points cetane increase

30 points density decrease

0246

8101214

0 200 400 600 800 1000 1200 1400 1600Days on stream

Delta Cetane Index

Delta Density, kg/m3

-40-35-30-25-20-15-10-50

-45

0 200 400 600 800 1000 1200 1400 1600Days on stream

11Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

Cetane Increase Industrial FeedbackCase Study (3/3)

More than 4 years of operation0.2°C/month catalyst deactivation rate

Days on stream

WABTTemperature, °C

Test Run WABT

320

325

330

335

340

345

350

355

360

0 200 400 600 800 1000 1200 1400 1600

12Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

HR 648 Latest Generation NiMo Catalyst

• HR 648 is 10°C more active than HR 548 for density reduction

• Based on ACE technology• Available now; Already 5 awards

HR 648

41395°C39190°C33970°C30050°C25930°C1995°C

Sim Dist D 7213Distillation Fraction (%w/w)

7.8Poly-Aromatics, % w/w18.0Di-Aromatics, % w/w21.0Mono-Aromatics, % w/w

0.8944Density at 15°C, g/ml2144Nitrogen, ppm0.442Sulfur, wt %

BrasilianCrudeFeed Description

Delta API

2.0

2.5

3.0

3.5

4.0

330 335 340 345 350 355 360

Temperature, °C

Del

ta A

PI

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

HR 548

HR 648 >10°C

13Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011

HR SeriesHR Series

Conclusion

• Full Set of High Performance ACE™ Catalysts for Middle Distillates HDT• 2003: HR 500 Series covering all HDT services

• ~ 260 awards • 2007: HR 626 latest generation CoMo for ULSD

• 76 awards after 3.5 years on the market• 60% as a replacement of competition catalysts

• S2 2010: HR 648 a breakthrough NiMo for cetane improvement• Available now – already 5 awards

• Extensive Licensing Experience • Over 45 years of experience in new Middle Distillates HDT

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

114 awards for ULSD & cetane improvement services• Doubling of awards over the last 4 years

• Dedicated Tech Service for units optimization

14

Latest Improvement in Middle Distillates Hydrotreating