Latest Developments in Hydrocracking Catalysts

Bertrand Carruette

Agenda

References in Hydrocracking catalysts

In the world Focus in India

Axens Catalysts Offer

Hydrotreatment Catalyst portfolio Hydrocracking Catalyst portfolio Industrial Case Study

Axens technical services offer

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2 Hydrocrackers Operating in India

Refinery 1 (Axens design)

Started-up in 2010 Capacity 1.7 MMTPA Feed origin 100% SRVGO Catalyst combination : HR 448 HYC 652 Pretreatment catalyst replacement with HRK 558 in 2012

Refinery 2 (Competitor design)

Started-up in 2009 (with Axens catalysts) Capacity 1.35 MMTPA Feed origin 100% SRVGO Catalyst combination : HR 448 HYC 652 Pretreatment catalyst replacement with HRK 658 in mid 2013
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Agenda

References in Hydrocracking catalysts

In the world Focus in India

Axens Catalysts Offer

Hydrotreatment Catalyst portfolio Hydrocracking Catalyst portfolio Industrial Case Study

Axens technical services offer

4

Axens Pretreatment Catalyst Portfolio

Increasing HDA Activity Launched in 2012
HRK 1448

HRK 658 HRK 558

Impulse Technology

HR 448

Increasing HDN Activity

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HRK 1448
The cycle length of hydrocracking units is generally limited by the activity of the pretreating catalyst

The challenge in catalyst engineering is to maximize the HDN activity of the pretreating catalyst while maintaining our benchmark catalyst stability

ImpulseTM Technology

Combination of maximal activity with maintained superior stability

Maximum promotion Maximum active phase dispersion Optimized support characteristics including metal-support interactions
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HRK 1448 Relative HDN Activity Gain

Relative Volume Activity (%)

Impulse HRK

HRK 558

1448

Significant HDN activity improvements observed for Impulse catalysts

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Impulse Technology - Summary

A breakthrough technology for maximum refinery profits

Complete high performance Can process more difficult feedstock

without cycle penalty

Additional Flexibility

Maximum Throughput with higher EBP

Opportunity Feed Longer Cycles

Agenda

References in Hydrocracking catalysts

In the world Focus in India

Axens Catalysts Offer

Hydrotreatment Catalyst portfolio Hydrocracking Catalyst portfolio Industrial Case Study

Axens technical services offer

10

Hydrocracking Catalyst Portfolio

Increasing Middle Distillate Selectivity
HDK 776 HDK 766 HDK 786
More active in conversion More selective towards Middle Distillate Diesel cold flow properties improvement

HYK 752

Launched in 2013

HYK 762 most adapted catalysts Axens offers the HYK 743

required cycle length HYC 652 required middle distillate yield HYK 742
HYC 642
HYK 732

Increasing Conversion Activity

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Outstanding stability (HYC 652)

C
Base 430 + 80 Base 420 + 70 Base 410 + 60 Base 400 + 50 Base 390 + 40 Base 380 + 30 Base 370 + 20 Base 360 + 10 Base 350 0 100 200 300 400 500 600 700 800 900

Deactivation rate measured at Refinery 1

0.3 C/month after 1200 days on stream

Operating WABT R-002

Days on Stream
1000 1100 1200 1300
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Outstanding stability (HYC 652)

Deactivation rate measured at Refinery 2

C
Base +100 440
Base + 90 430 Base + 80 420 Base + 70 410

Observed WABT

Base + 60 400
Base + 50 390 Base + 40 380 Base + 30 370 Base + 20 360 Base + 10 350 Base 340 100

0.2 C/month after 900 days on stream

Days on Stream 200 300 400 500 600 700 800

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900

Outstanding stability (HYK 742)

C
Base400 + 50

Deactivation rate measured at a European Refinery

Base390 + 40

0.5 C/month at high LHSV, 4 h-1

Base380 + 30

Base370 + 20

Base360 + 10

Base 350

Days on Stream
0 40 80 120 160 200 240 280 320 360 400 440 480
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Outstanding stability (HYK 742)

C 395 Base + 20
Deactivation rate measured at an Asian Refinery

0.3 C/month after 1000 days on stream

Base + 15 390

Base + 10 385

Base +5 380

Days on Stream
Base 375

200

400

600

800

15

1000

Agenda

References in Hydrocracking catalysts

In the world Focus in India

Axens Catalysts Offer

Hydrotreatment Catalyst portfolio Hydrocracking Catalyst portfolio Industrial Case Study

Axens technical services offer

16

Zeeland Refinery

Located in Vlissingen (Netherlands) Started-up in 1974 Shareholders

Crude distillation capacity : 150,000 BPSD

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Hydrocracker Unit

Started-up in 1986 Feed: SRVGO from VDU + Imported VGO

Feed rate: 455 m3/h (68,500 BPSD) Density: 0.908 - 0.920 t/m3 S: 1.0 1.7 wt% N: 1000 1300 wt ppm

Production
Light Naphtha, Heavy Naphtha Jet Fuel, Light Diesel, Heavy Diesel Base Lube Oils
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Hydrocracker Catalyst Replacement (I/II)

Objectives

90 to 95%wt conversion Maximize Cycle Length Maximize Middle Distillate production (Euro V) Achieve Base Lube Oil group III quality with UCO

Dedicated full pilot test program launched in Total facilities to select the optimized catalyst system among catalyst manufacturer offers
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Hydrocracker Catalyst Replacement (II/II)

Constraint
Unit limited by the pretreatment

Solution
Use of high nitrogen tolerant hydrocracking catalyst to compensate for the pretreatment section
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Hydrocracker Catalyst Cycle 1 Nitrogen Slip

WABT, C 420 TBase + 30
TBase +415 25 TBase +410 20

WABT HYK 742 Op WABT HYK 742 Normalized Nslip

N slip, ppmw 300 250 200 150 100 50

TBase +405 15
TBase + 10 400 TBase + 395 5

TBase 390

100

200 300 Days on oil

400

0 500

Excellent stability (0.4 0.5 C/month) of HYK 742 even under 250 wppm organic Nitrogen permitting an increase in the catalyst cycle length
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Hydrocracker Catalyst Cycle 2 Nitrogen Slip

TBase + 30 TBase + 25 TBase + 20 TBase + 15 TBase + 10 TBase + 5 TBase

HYK 732 / HYK 742 stability not impacted by the Nslip increase
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Case Study Conclusions

Cycle 1 & 2 demonstrated the excellent

performance of HYK 742 and HYK 732 zeolite catalysts

High Nitrogen tolerant zeolite catalyst

is one of the solutions to improve economics of any hydrocracker constrained by pretreatment activity

Axens selected for Cycle 3 (just started-up)

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Agenda

References in Hydrocracking catalysts

In the world Focus in India

Axens Catalysts Offer

Hydrotreatment Catalyst portfolio Hydrocracking Catalyst portfolio Industrial Case Study

Axens technical services offer

24

Technical Services for Hydrocrackers

Technical assistance based in India, New Dehli
AIPL supported by Axens HQ in France

Start-up of the unit

In charge of catalyst loading, unit inspection, review of operating conditions

Follow-up of the unit

Performance follow-up based on data received from the Refinery Recommendations and advices in order to optimize the unit operation In case of troubleshooting, access to Axens troubleshooting team: Tech
Service and Technology Group, Process Group, Mechanical & Corrosion Group, Analytical Group

Axens can supply feed and products analysis

Access to IFPEN State-of-the-Art Analytical know-how.
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Conclusion

Strong R&D : Continuous catalyst development

Pretreatment catalyst
Impulse Technology: A breakthrough technology for maximum refinery profits

Hydrocracking catalyst
Full set of catalyst HYK series Outstanding stability Nitrogen tolerant

Technical Services Team based in India, AIPL

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