ultra low sulfur hsd production - centera tm catalysts are key … · 2015-07-23 · cent era tm...
TRANSCRIPT
International Conference on
Ultra low Sulfur HSD production -CENTERATM Catalysts Are KeyTo unlock potential of Hydrotreaters
Dr. Ujjwal Manna
CONFIDENTIAL
International Conference on ‘Refining Challenges- Way forward’April 16-17, 2012Organised by Petrofed, New Delhi, India
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CONFIDENTIAL
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Long History of Innovation
Type II Technology Type I/II Technology
PLUS
Presulfurized Catalysts Oxidic/Easily Regenerated
CONFIDENTIAL
CENTERATM Is Key to Unlocking Unit PotentialAgenda
• Fundamental Understanding of CENTERATM
Advancements
• Broad application in hydroprocessing units
CONFIDENTIAL
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”
CENTERATM Is Key to Unlocking Unit PotentialAgenda
• Fundamental Understanding of CENTERATM
Advancements
• Broad application in hydroprocessing units
CONFIDENTIAL
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”
CENTERATM Catalyst TechnologyFundamental Story
Element of Technology DescriptionStrong Legacy Builds on Innovations from
CENTINEL GOLD and ASCENT technologies
Better Dispersion Utilizes improved support technology for better dispersion of active metals
Maximum Sulfidation Generates highest possible degree
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Maximum Sulfidation Generates highest possible degree of sulfidation to form ideal Type II active phases
Optimal Assembly of Active Sites (Nanotechnology)
Results in optimal decoration/configuration of promoter metals on MoS2 and higher performance with better metals
Enhanced Retention of Activity
Allows sites to be locked in place
Better Dispersion of MoS2 ParticlesContinuous Improvement Using Better Support
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Particle DiameterCENTINEL: 40 – 45 Å
CENTINEL GOLD: 30 – 35 ÅCENTERA: 25 – 35 Å
10 nm10 nm
NO / FTIRonly Ni
accessible
CENTERA
Ni
NO
Optimal Assembly of Active SitesPromoter Edge Decoration
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CENTINEL GOLD Mo
NO
First shell Mo-Scoordination number = 6
1.0
2.0 DN-3630DC-2618Bulk MoS2
1.0
2.0 DN-3630DC-2618Bulk MoS2
DN-3630DC-2618Bulk MoS2
Maximum SulfidationGenerates Fully Accessible Type II Active Phase
CONFIDENTIAL
0
R [Å]
2 4
-2.0
0.0
1.0
FT
-1.0
0
R [Å]
2 4
-2.0
0.0
1.0
FT
-1.0
Degree of sulfidation as in bulk MoS2
Enhanced Retention of ActivityKeeps Activity Following Activation, Upsets
25%RVA
Increase
Difficult (50%) Cracked Stock Blend: ~70 barg Operation
360
355
CONFIDENTIAL
350
345
340
CENTERATM Is Key to Unlocking Unit PotentialAgenda
• Fundamental Understanding of CENTERATM
Advancements
• Broad application in hydroprocessing units
CONFIDENTIAL
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”
Broad Application in Hydroprocessing UnitsImproved Performance in Many Areas
• Applied across wide range of pressures (20-200 barg)
• Improved HDN
� Drives higher HDS in ULSD service
� Enhances aromatic saturation and conversion in higher pressure applications like FCC PT and HCPT
CONFIDENTIAL
• Improved HDS
� Important in FCC PT, HC and ULSD applications to maximize production of low sulfur gasoline and diesel across an entire cycle
• Improved stability
� Enhanced retention of initial activity
� Significantly lower SOR temperatures lead to lower deactivation rates
CENTERATM DC-2650 CoMo for FCC PTImproved HDS Becoming Critical for ULSG/ULSD Production
140
160
180
Rel
ativ
e V
olu
met
ric
Act
ivit
yHDS - FCC PT
HDN - FCC PT
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80
100
120
140
DC-200 DC-2118 Centinel
DC-2551 Ascent
DC-2650 CenteraR
elat
ive
Vo
lum
etri
c A
ctiv
ity
CENTERATM DN-3620 NiMo for HCPTRelieves HDN Constraints and Provides Big HDS Improvement
Outstanding Performance for LCO Hydrocracking
360
366
371
377
382fo
r 20
0 p
pm
S
DN-3310 11 °C or
40%
HCPT Testing of 100% LCO Feed
P = 78 bar; LHSV = 1.4; TGR = 1265 Nm3/m3 Feed: S = 3.05 wt%; N = 726 ppm
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327
333
338
344
349
355
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Catalyst Age, hrs
T R
eq'd
for
200 DN-3310
DN-3620
40%RVA
Increase
PLUSPLUS
CENTERATM DC-2618 CoMo for Low-Medium Pressure ULSDAdvantage Across the Board, Especially at Low Pressure
15
10
C
CONFIDENTIAL
5
0
20 barg 30 barg 40 barg 40 barg
CENTERATM DN-3630 NiMo for Medium-High Pressure ULSDSignificant HDS Advantage Driven By Improved HDN
ULSD Testing of Heavy Arab Med SRGO Feed
P = 60 barg; LHSV = 1.0 hr-1; TGR = 200 Nm3/m3 Feed: S = 1.67 wt%; N = 185 ppm
360
355
CONFIDENTIAL
350
345
340
CENTERATM Is Key to Unlocking Unit PotentialAgenda
• Fundamental Understanding of CENTERATM
Advancements
• Broad application in hydroprocessing units
CONFIDENTIAL
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easy to move “Beyond ULSD”
675
680
FOpportunity: Evaluate Tradeoffs of Activity and H2 Consumption• Both systems provided activity advantage over incumbent DN-3330 system• Sandwich CoMo/NiMo CENTERATM system showed H2 savings• CENTERATM DN-3630 system gave big activity benefit with some increase in H2 ConsumptionConclusion: Benefits of an all NiMo CENTERATM system allowed more cracked stock processing, which outweighed potential H2 savings
ULSD Testing of Heavy SR/LCO/LKGO BlendFeed: S = 1.1 wt%; N = 950 ppm
P = 42 barg; LHSV < 1.0 hr-1; TGR = 400 Nm3/m3
Case Study #1: Evaluate CENTERATM vs CENTINEL GOLD Systems
CENTERATM Catalysts Provide Significant Performance Benefits
360
CONFIDENTIAL
640
645
650
655
660
665
670
0 100 200 300 400 500 600 700 800 900 1,000 1,100 1,200 1,300
Temp
eratur
e Req
uired
for 8
ppm
Sulfu
r, °F
Catalyst Age, hours
CENTINEL GOLD DN-3330
CENTERA Stack/Sandwich
CENTERA DN-3630
16℉℉℉℉
355
350
345
340
9 °C
Case Study #2: Evaluate CENTERATM vs ASCENT Systems
CENTERATM Catalysts Provide Significant Performance BenefitsOpportunity: ULSD Unit extremely activity constrained. Cycle life <<1 year.• Heavy feed and visbroken components add significant nitrogen, which inhibits HDS for high LHSV unit.• High SOR WABT puts unit in thermodynamically constrained region immediately.• Incorporating CENTERA NiMo significantly improves HDN, HDS. Dramatic reduction in SOR WABT.Conclusion: Benefits of adding NiMo CENTERATM opens up operaing window, and has potential to double cycle length.
ULSD Testing of Heavy SR/VB Blend
CONFIDENTIAL
12°C
ULSD Testing of Heavy SR/VB BlendFeed: S = 0.3 wt%; N = 170 ppm
P = 400 barg; LHSV > 1.5 hr-1; TGR ~ 80 Nm3/m3
360
370
365
355
CENTERATM Is Key to Unlocking Unit PotentialAgenda
• Fundamental Understanding of CENTERATM
Advancements
• Broad application in hydroprocessing units
CONFIDENTIAL
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”
Diesel Hydrotreating Units Are Versatile AssetsCENTERATM Is The Key To Moving Beyond ULSD
CONFIDENTIAL
CONFIDENTIAL
Backup Slides
CENTERATM DC-2618 and DN-3630Features and Benefits
ULSD Feature Customer Benefit
Maximum HDS Performance • DC-2618 - Highest Activity CoMo at
Low-Med P (5-20°F, 3-12°C) vs DC-2533. Comparable to CENTINEL GOLD DC-2318 at Med-High P.
• DN-3630 - Highest Activity Conventional NiMo in Market (8-13°F, 5-8°C) more active than DN-3330.
� Longer runs � Process heavier/harder feeds � Enable diesel upgrading for non-sulfur
properties (e.g. cetane, cold flow) � Enables use of more regen catalyst usage.
Enhanced Retention of Activity Higher SOR activity. Less hyperactivity during first month of operations.
Top Performance CoMo and NiMo for Provides ability to manage both activity and H
CONFIDENTIAL
Top Performance CoMo and NiMo for customized application
Provides ability to manage both activity and H2
consumption. Enables stacking and sandwiching combinations.
Handling and Loading Flexibility No special packaging required. Loading of reactor easily handled in air environment
Normal sulfiding procedures No long holds at intermediate temperatures required for some Type II activations
Robust during startup Extended gas phase heatup (12-hr at 150°C) possible before liquid is introduced. Permits leak testing and reactor wall heating to satisfy temper embrittlement requirements.
Regenerable by ENCORE Best multi-cycle economics
MoS2 - Type I• mainly single layers• incomplete sulfidation• Al-O-Mo bonding still present• poor accessibility of active sites• less active than Type II
Particle Morphology Affects ActivityInteraction with Alumina is Key Determinant
CONFIDENTIAL
MoS2 – Type II• stacked particles • fully sulfided• no Al-O-Mo bonding• high accessibility of active sites • high hydrogenation activity• more active than Type I
CENTERATM Catalyst TechnologyImprovement in Both Direct and Indirect HDS
Comparison of DBT HDS Pathways for CENTERA and ASCENT NiMo CatalystsCENTERA Shows Improvement in Both Reaction Routes
50
60
70
80
90
100M
ole
fra
tcio
n %
CENTERA DN-3630 Hydrogenation HDSASCENT DN-3531 Hydrogenation HDSCENTERA DN-3630 Direct HDSASCENT DN-3531 Direct HDS
DBT hDBT
BP CHB BCH
CONFIDENTIAL
0
10
20
30
40
50
220 230 240 250 260
Temperature (C)
Mo
le f
ratc
ion
%
General ULSD Product Placement
Fee
d D
iffi
cult
y / S
ever
ity
CoMo vs NiMo
NiMo
CoNiMo
Or
CoMo - NiMo
Potential Stacking
Opportunities
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P = 600 psig P = 800 psigP = 400 psig P = 1300 psig
Fee
d D
iffi
cult
y / S
ever
ity
Hydrogenation Environment / H2 Consumption
CoMo
CoMo - NiMo
Combinations
Opportunities
North American Example� Drop-in catalyst for short-term solution� Revamp implemented later with full ULSD solution� High activity catalyst plus dewaxing used to increase feed by 12%� Same dewaxing catalyst used for both cycles (even some regen)
5 05 0S u m m e rS u m m e rW in te rW in te r W in te rW in te r
Catalytic DewaxingCommercially Proven Solutions
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-- 1 01 0
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1 01 0
2 02 0
3 03 0
4 04 0
A u gA u g N o vN o v F e bF e b J u nJ u n S e pS e p D e cD e c M a rM a r
°° FF
c lo u d p o in t fe e dc lo u d p o in t fe e d
d e lta c lo u d p o in td e lta c lo u d p o in tc lo u d p o in t fe e dc lo u d p o in t fe e d
d e lta c lo u d p o in td e lta c lo u d p o in t