5. STM Images of Co-Mo-S / Au
Co-Mo-S Nanocrystal MoS2 MoS2 + Co
Courtesy of Haldor Topsoe
6. Sulfur Vacancies
When exposed to H2
atoms, MoS2 forms two
S vacancies
Courtesy of Haldor Topsoe
7. Active Phase
g-alumina supported Co(Ni)MoS
MET image of CoMoS
10 nm
<L> = 3.9 nm
<n> = 1.6 nm
Layer structure of MoS2
edge decoration by Co or Ni
<L>
n
g-alumina
Courtesy of IFP
Molybdenum Co / Ni Sulfur
8. Sulfiding Reactions
MoO3 + 2 H2S + H2 MoS2 + 3 H2O
CoO + H2S CoS + H2O
3 NiO + 2 H2S + H2 Ni3S2 + 3 H2O
WO3 + 2 H2S + H2 WS2 + 3 H2O
Sour Water Produced: Approximately 10 wt% of catalyst
Hydrogen Consumption: Approximately 1 wt% of catalyst
10. In-situ Sulfiding Issues
Catalyst Quality
• Requires careful attention and takes up valuable
operating time – typically 1-7 days
• If the active phase is not properly formed, catalyst
activity will be affected.
• Exposure of the catalyst to H2 at elevated
temperatures (>450°F) can cause permanent
damage.
11. In-situ Sulfiding Issues
Safety and Environmental
• Requires handling of hazardous and malodorous
sulfiding chemicals such as DMDS or DMS
• Outside contractors may be needed for DMDS
injection
• 2-3 personnel required for H2S sampling
• Risk of H2S stack emissions
• Tail Gas Unit startups
• SRU overload
• Lube units
12. In-situ Sulfiding Issues
Processing
• Off-spec product during startup has to be
reprocessed or downgraded.
• Process interruptions during the startup can
result in restarting the sulfiding step
• Additional hydrogen required (reformer may be
down)
• Sour water formation
• Risk of temperature excursions
• Corrosion caused by high H2S concentrations
13. What is Totsucat®?
Totsucat = Totally Sulfided Catalyst
The catalyst is preactivated,
not just “presulfided”.
14. The Totsucat Process
Patented
• Totsucat is a proprietary patented process
Carefully controlled sulfiding
• Homogenous sulfiding – All oxidic metal sites
are sulfided
• Uses high purity H2S and H2
• Samples tested every two hours to ensure that
the catalyst is adequately sulfided
15. Totsucat Benefits
Load-and-Go reactor startups
No exotherms
Minimal sour water formation
No additional H2 needed at startup
Negligible amounts of H2S released
No odors
No handling of sulfiding chemicals
Catalyst performance is maximized
Upset conditions will not damage the catalyst
16. Typical Totsucat Applications
Temperature Sulfur Sensitive Units Processing
Critical Path Units
Limited Units Units Cracked Feeds
• The cost of • Some units • Reformers and • CFP version of
downtime cannot achieve Isom units Totsucat allows
typically the temperature contain precious startups utilizing
outweighs the levels required metal catalysts cracked stocks
cost of Totsucat for sulfiding, that are
preactivation resulting in sensitive to H2S
inadequately contamination
sulfided
catalysts that
will not perform
as designed
17. Startup with In-Situ Sulfiding
Liquid phase with SR Feed
Temperature (°F)
Cracked
feed
750 H2S breakthrough Stop DMDS
575 DMDS Secondary Sulfiding
SR Feed
Initial •SR Feed + DMDS at 175-300°F
390 •Monitor H2S at outlet
Sulfiding
•Sulfide at 600-660°F
•Sulfiding 3 days of SR feed
200 Drying step •completed in 15-24 hrs
6 12 18 hours 3 days
18. Totsucat G Startup
Liquid phase with SR Feed
Temperature (°F)
Cracked
feed
750
Straight
Run
575
feed
SR Feed introduction at low T (175-450°F)
Go to Start of Run Temp in only 6-10 hours
390 SR Feed for 3-4 Days
Progressively switch to cracked feed
200 Advantages: Simple startup procedure.
No risk of event which could damage the catalyst
6 12 18 hours 3 days
20. Totsucat Versions
G D HC N
Light End Distillate Hydrocracker
Hydrocracking
Applications ULSD Pretreat
Naphtha HT
10 Approved by
Tail Gas 6 References
References UOP and CLG
Gasoline 2 Repeats
4 Repeats 3 References
Post-Treat
22. Totsucat HC
Totsucat for Hydrocrackers
• 3 Commercial References thus far in 2011
Applied Commercially to:
UOP TOPSOE CRITERION CLG AXENS
HC-24 TK-907 Testing Approved Approved
HC-26 Soon
HC-140
HC-150
23. Version – Totsucat E
For units with sufficient sulfur in the feed (>0.5%) and
capable of reaching 600F
Majority of active sites are sulfided
Sulfur in the feed completes the sulfiding process
during a four hour finishing step at startup.
Hydrocarbon passivation is available for loading in air
25. Case Study – Totsucat E for VGO Unit
• Large VGO Unit contained 1.6 million pounds
VGO Unit (725 MT) of catalyst
• In-situ sulfiding would require 72-96+ hours and
In-Situ produce 20,000 gallons (75K liters) of sour water
• With Totsucat E Preactivation, the unit was
online in 12 hours with less than 50 gallons (190
Totsucat liters) of water removed from the separator
26. Totsucat E vs. DMDS – HVGO Unit
Time Gain
TOTSUCAT E vs DMDS:
48+ hrs
Liquid Heat Up rate @
17C/hr S content
S >> 0.5 wt%
Gas Phase Heat up
Rate @ 4C/hr
27. Totsucat Properties
Sulfides are sensitive to oxidation by air
• Classified as self-heating solids
• Class 4.2, UN 3190
Two Types Available
• Non-Passivated - Requires inert loading
• Hydrocarbon Passivation - Allows for
loading under air
29. Issue of Cracked Feed
Cracked Feeds contain olefins, di-olefins, and
aromatics that form gums and tars when
exposed to hyper-active sites on freshly
sulfided catalysts.
30. Issue of Cracked Feeds
Gums and tars formed
during startup
Compounds readily
deposit on catalyst surface
The deposits block catalyst
pores and active sites
Leading to a permanent
loss in catalytic activity
31. Issue of Cracked Feed
To avoid this problem, catalyst
manufacturers recommend a break-in period
of at least three days using only less
reactive straight run feed at startup.
Processing the straight run will form a small
amount of soft coke on the catalyst surface.
This coke gradually reduces the hyperactivity
of the catalyst.
Cracked feeds can then be introduced
without excessive tar and gum formation.
32. Issue of Cracked Feed
Delaying the introduction of cracked feeds
can have significant costs:
• Lost profits from processing cracked
and heavy feeds.
• May need to purchase additional
straight run feed for startup.
• Storage costs for a sufficient quantity of
straight run feed required at startup.
• Storage costs for cracked feeds that
must be held for processing later.
33. Solution: Totsucat CFP
CFP = Cracked Feed Protection
• In addition to Totsucat preactivation, Totsucat
CFP has carbon carefully deposited on the
catalyst surface
• Hyper-active sites are moderated
• Catalytic acidity is also reduced
34. Totsucat CFP Benefits
Totsucat CFP allows the direct introduction of
cracked feeds at 175-450°F
Provides normal cycle lengths without waiting
3-4 days before adding cracked feeds
No additional SR required
No need to store cracked feeds during startup
36. Comments at 90 days on Oil with
Totsucat CFP in ULSD Service
The start of run severity for Cycle 25 was worse compared to
the last cycle (24). Cycle 24 did not have any back up LCO
to work off after the shutdown, whereas cycle 25 (current
cycle) needed to process 325 MBBLs of LCO that had been
stored off-site during the ULSD outage. Backup LCO was
blended in at 3-5 MBD on top of normal LCO production
We are currently ~90 days into this cycle and our actual and
normalized average bed temperatures are 10-15 degrees F
below typical for this point in the cycle.
Deactivation appears to be on the order of 3-5 deg/month,
which is significantly better than our previous average of
nearly 20 deg/month.
37. Case Study 2 – NHT with Totsucat CFP
Naphtha Hydrotreater
Feed: 25-50% Coker Naphtha
Feed Rate: 35,000 BPD
Catalyst Type: NiMo
Catalyst Quantity: 53,000 lbs
38. Case Study 2 – NHT with
Totsucat CFP
Data from 2 Runs
Run 1 – In-situ Sulfiding with 3 Day Break In – Catalyst A,
Sock loaded
Run 2 – Totsucat CFP Preactivation – Startup with 20%
cracked feed – Catalyst A, Dense loaded
39. Case Study 2 – NHT with Totsucat CFP
Reactor Temperature
Reactor Temperature
Reactor Temperature
700
600
Temperature (°F)
500
Inlet Temp - In-Situ Sulfided
400
Inlet Temp - Totsucat CFP
300 Bottom to Inlet ΔT - In-Situ
200 Bottom-Inlet ΔT - Totsucat CFP
100
0
0 50 100 150 200 250 300 350
Days
40. Case Study 2 – NHT with Totsucat CFP
Coker Feed Rate
Reactor Temperature
200
180 In-Situ Sulfided
160
140 Totsucat CFP
120
CBPD
100
80
60
40
20
0
0 100 200 300 400
Days
41. Case Study 3 – CFHT with Totsucat CFP
Cat Feed Hydrotreater
Feed: HVGO / HCGO
Feed Rate: 24,000 BPD
Catalyst Type: NiMo
Catalyst Quantity: 107,000 lbs
42. Case Study 3 – CFHT
In-situ Sulfided Run
Coker Naphtha Feed Rate
LargeradialspreadinbottomTI’sincreasedafter
HCGO introduction. Hot spots likely to limit
cycle length and/or throughput.
MinTI’sofbottombedarenot
much different than Rx Inlet T
indicates maldistribution
and/or non-uniform activity.
43. Case Study 3 – CFHT
In-situ Sulfided Run
Coker Naphtha Feed Rate
Mid-bed and Bottom Radial Spreads Increased
as Cracked Stocks were introduced
HCGO Ramped to 85% of Feed at Day 70
Decreasing effectiveness of the top bed is indicated by
a decline in the % of total bed axial delta T by the mid-
bed and increasing radial spreads in the mid-bed.
44. Case Study 3 – CFHT with Totsucat CFP
Totsucat CFP Enables Early Introduction of Heavy Coker Gas Oil:
Ten Hours After Heatup to 600 F Reactor Inlet T
Coker Naphtha Feed Rate 160
700
140
600
120
500 HCGO Ramped to 90% of Feed 10 hours from heat up
100
Temperature, F
400
%
80
300
60
Rx Inlet T, F
Top Bed Delta T Stable
200 After HCGO In 40 Btm of Bed 1
Avg, F
Bed 1 Delta T, F
100 20
% HCGO in Feed
0 0
0 10 20 30 40 50 60
Hours after Feed-in
45. Case Study 3 – CFHT with Totsucat CFP
Totsucat CFP Run – Mid and Bottom
Bed Radial Spreads
Mid-bedTI’sstableasa%oftotalbeddeltaT
Radial spread of Mid-bedandBottomTI’smuch
lower than previous run
46. Case Study 3 – CFHT with Totsucat CFP
Totsucat CFP Run – Bottom
Coker Naphtha Feed RateBed
47. Startup with Totsucat CFP
Liquid Phase with Cracked Feed
Temperature (°F)
SOR
750 Progressive
Introduction of
575
Cracked
Feed Introduce cracked feed at 175-450°F
Heat up at 35°F/h up to 475°F
390 After 475°F Heat up at 20°F/h up to SOR.
Advantages: Safe fast start-up; Additional 3
to 4 days of cracked feed processed; No
200
need for SR or Cracked Feed storage
6 12 18 hours 3 days
50. Totsucat Commercial Experience
Over 800 Totsucat Lots Treated at EUS totaling
40+ million pounds of catalyst
HDS/HDN Selective Pyrolysis
• Wide variety of Hydrogenation Gasoline
hydrotreating • NiMo and CoMo • CoMo catalysts
catalysts Catalysts
Wax Lube
Hydrofinishing Hydrofinishing
• NiW catalysts • CoMo catalysts
53. Other Eurecat Services
Analysis and Regeneration of Spent Hydrotreating
Catalysts
HDS Activity Testing
Resale of Regenerated Catalysts
• High activity regenerated catalysts available for
immediate delivery
Bulk Nickel Sulfur Guards
REACTIVATION of Palladium on Alumina Catalysts
54. Eurecat Contact Information
Randy Alexander Frederic Jardin Tony Loverdi
Regional Sales Manager –
Director of Sales and Marketing Executive Vice President
Gulf Coast
Randy.Alexander@Eurecat.com Frederic.Jardin@Eurecat.com Tony.Loverdi@Eurecat.com
Phone: 832.284.0612 Phone: 832.284.0614 Phone: 832.284.0607
Nilanjan“Babu”
Chris Buffington Bob Stults
Brahma
Regional Sales Manager –
International Sales Manager Technical Support Manager
Western Region
Chris.Buffington@Eurecat.com Nilanjan.Brahma@Eurecat.com Bob.Stults@Eurecat.com
Phone: 832.284.0608 Phone: 832.284.0609 Phone: 832.284.0602
55. Thanks for your attention.
Please let us know how we can help you.
