Latest Improvement in Middle

Distillates Hydrotreating

Thierry Birchem

1
 Oil Products Demand
World

Market Structure
2009 vs. 2020 • Growth driven
100%
Other* by on-road diesel
AAGR LPG
14.8% 14.7%
09-20 Naphtha
80% 8.1%
6.0%
8.2%
7.1%
Motor • Progressive increase
Gasoline of middle distillate
60% 25.2% 23.9% 0.8% Jet
Kerosene
feed refractoriness
5.7% 6.3% 2.2% On-road
(such as LCO, LCGO)
40%
15.5% 17.7% 2.5% Diesel

20% 13.3% 12.9% 0.9%

Off-road
Diesel
• Tighter quality
specifications for
11.3% 9.2% -0.6% Fuel Oil
0% on-road diesel
2009 2020 all around the world
84.4 96.7 1.2%
Mbdoe Mbdoe AAGR

Other* = Kerosene ( Jet), Refinery Gas, Petroleum Coke, NGL,

Lubricants, Bitumen, Paraffin Wax, Refinery Losses, …
Source: Axens & other sources (2010)
Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 2
 A Fully Integrated Offer of
Proven Technologies

HR Series New Prime-D Revamp

High Perf. Catalysts for ULSD or/& light / heavy
aro. saturation
Products EquiFlow Trays
Full range of Modeling & Quench
Grading Material

Technology

Services Catapac
Dense loading
Studies
APC, POS Tech service
team
Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 3
 Choosing The Right Catalyst

CoMo NiMo

Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 4
 HR 626 Main Features

HR 626

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

Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 6
 HR 626 Superior Stability
Customer’s Stability Pilot Test (2/2)

Sulfur content, wt, ppm Corrected Temp, °C

50 HR 626 Sulfur
420
Other Cat Sulfur

40 HR 626 Temperature 400

Other Cat Temperature

30 380

20 360

10 340

0 320
0 5 10 15 20
Days on line with feed containing 75% SR & 25% LCO
HR 626 superior stability
Axens’ Refining and Petrochemicals Seminar – NPRA
New Delhi, India article on stability
– 28 & 29 April 2011 7
 Industrial Ex-Situ Regeneration
Full Activity Recovery
Industrial Regeneration results
Regeneration Temperature T1 T2 > T1

C (wt %) 0.3 0.2

S (wt %) 0.4 0.3
Surface Area (% of fresh catalyst) 97 96
Bulk Crushing Strength (MPa) 1.51 1.42
RVA vs Fresh HR 626 94 96

Effluent Sulfur Content, ppm

110 Test carried out at iso-WHSV
Regenerated HR 626
90
ULSD service
Fresh HR 626
70 Max 1°C activity loss after
50
RVA < 5% ex-situ regeneration
30

10
343 348 353
Reactor Temperature, °C
Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 8
 Cetane Increase Industrial Feedback
Case 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

Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 9
 Cetane Increase Industrial Feedback
Case Study (2/3)
Delta Cetane Index
14
12
10
8 8 points cetane increase
6
4
2
0
0 200 400 600 800 1000 1200 1400 1600
Days on stream

Delta Density, kg/m3

Days on stream
00 200 400 600 800 1000 1200 1400 1600
-5
-10
-15
-20
-25
-30 30 points density decrease
-35
-40
-45

Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 10
 Cetane Increase Industrial Feedback
Case Study (3/3)
WABT
Temperature, °C
360

355

350

345

340
Test Run WABT
335

330

325

320
0 200 400 600 800 1000 1200 1400 1600

Days on stream

More than 4 years of operation

0.2°C/month catalyst deactivation rate

Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 11
 HR 648 Latest Generation NiMo Catalyst

Brasilian 4.0
Feed Description
Crude
HR 648 >10°C
Sulfur, wt % 0.442 3.5
Nitrogen, ppm 2144

Delta API
Density at 15°C, g/ml 0.8944
3.0
Mono-Aromatics, % w/w 21.0
Di-Aromatics, % w/w 18.0 HR 648 Sample 1
Poly-Aromatics, % w/w 7.8 2.5 HR 648 Sample 2
HR 548 HR 648 Sample 3
HR 548
Distillation Fraction (%w/w) Sim Dist D 7213 2.0
5°C 199
330 335 340 345 350 355 360
30°C 259
Temperature, °C
50°C 300
70°C 339 Delta API
90°C 391
95°C 413

• HR 648 is 10°C more active than HR 548

for density reduction HR 648
• Based on ACE technology
• Available now; Already 5 awards
Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 12
 Conclusion

• Full Set of High Performance ACE™ Catalysts for

Middle Distillates HDT
• 2003: HR 500 Series covering all HDT services
• ~ 260 awards
HR Series
• 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

Axens’ Refining and Petrochemicals Seminar – New Delhi, India – 28 & 29 April 2011 13
Latest Improvement in Middle
Distillates Hydrotreating

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