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Eurecat Sulfiding and Activation Technologies
| Date post: | 19-Oct-2014 |
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Technology |
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Eurecat Sulfiding and Activation Technologies
Oxide catalyst Polymolybdate structure Mo7O24
6-
Sulfided catalyst Lamellar structure MoS2 slabs
Temperature
H2 + Sulfiding Agent
Sulfiding of Hydrotreating Catalysts
CoMo Catalyst Active Phase Structure
S
Mo Co
(0002)
0,615 nm
«CoMoS»
Alumina
NiMo Catalyst
Active Phase Structure
Morphology of an activated NiMoS Structure
(STM Picture)
STM Images of Co-Mo-S / Au
Co-Mo-S Nanocrystal MoS2 MoS2 + Co
Courtesy of Haldor Topsoe
Sulfur Vacancies
When exposed to H2
atoms, MoS2 forms two
S vacancies
Courtesy of Haldor Topsoe
Active Phase
10 nm
<L>
<L> = 3.9 nm
<n> = 1.6 nm
n
g-alumina
g-alumina supported Co(Ni)MoS
Molybdenum Co / Ni Sulfur
Layer structure of MoS2
edge decoration by Co or Ni
MET image of CoMoS
Courtesy of IFP
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
Sulfiding Techniques
A c
t i v
a t
e d
C a
t a
l y s
t
O x
i d i
c C
a t
a l y
s t
OUR SITE
YOUR SITE
In-situ Sulfiding Issues
• 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.
Catalyst Quality
In-situ Sulfiding Issues
• 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
Safety and Environmental
In-situ Sulfiding Issues
• 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
Processing
What is Totsucat®?
Totsucat = Totally Sulfided Catalyst
The catalyst is preactivated,
not just “presulfided”.
The Totsucat Process
• Totsucat is a proprietary patented process
Patented
• 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
Carefully controlled sulfiding
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
Typical Totsucat Applications
Critical Path Units
• The cost of downtime typically outweighs the cost of Totsucat preactivation
Temperature Limited Units
• Some units cannot achieve the temperature levels required for sulfiding, resulting in inadequately sulfided catalysts that will not perform as designed
Sulfur Sensitive Units
• Reformers and Isom units contain precious metal catalysts that are sensitive to H2S contamination
Units Processing Cracked Feeds
• CFP version of Totsucat allows startups utilizing cracked stocks
Temperature (°F)
750
575
390
200
6 12 18 hours 3 days
DMDS
Cracked feed
Drying step
H2S breakthrough
Secondary Sulfiding
Stop DMDS
•SR Feed + DMDS at 175-300°F
•Monitor H2S at outlet
•Sulfide at 600-660°F
•Sulfiding 3 days of SR feed
•completed in 15-24 hrs
Startup with In-Situ Sulfiding
Liquid phase with SR Feed
Initial Sulfiding
SR Feed
Temperature (°F)
750
575
390
200
6 12 18 hours 3 days
Cracked feed
Straight
Run
feed
Totsucat G Startup
Liquid phase with SR Feed
SR Feed introduction at low T (175-450°F)
Go to Start of Run Temp in only 6-10 hours
SR Feed for 3-4 Days
Progressively switch to cracked feed Advantages: Simple startup procedure.
No risk of event which could damage the catalyst
Totsucat® Family
Totsucat Versions
G
Light End Applications
Naphtha HT
Tail Gas
Gasoline Post-Treat
D
Distillate
ULSD
10 References
4 Repeats
HC
Hydrocracking
Approved by UOP and CLG
3 References
N
Hydrocracker Pretreat
6 References
2 Repeats
Catalysts Treated with Totsucat G/D/N
Criterion
Axens
Albemarle
Topsoe
ART
KF-859 KF-757 KF-848 KF-901
KF-647 KF-767 KF-860 KF-905
HR-806 HR-945 HR-448 TG-107
HR-845 HR-538 ACT-951 TG-136
AT535 AT724G AT536 AT475
AT575 AT405 AT580 CR465
DC-2532 DN-3310 C-234 KL-8231
DN-3531 DN-3551 C-534 DC-130
TK-431 TK-576 TK-607 TK-559
TK-437 TK-575 TK-719 TK-743
Totsucat HC
• 3 Commercial References thus far in 2011
Totsucat for Hydrocrackers
Applied Commercially to:
UOP TOPSOE CRITERION CLG AXENS
HC-24
HC-26
HC-140
HC-150
TK-907 Testing
Soon
Approved Approved
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
Totsucat E Applications
• FCC Feed Hydrotreaters • VGO
• Distillate Units • Resid
Units
Applied Commercially to:
ART CRITERION ALBEMARLE TOPSOE AXENS
AT-575
HOP-492K/H
HOP-606H
HOP-608K
HOP-805
HOP-473K
HOP-603K
DN-3551
DC-2551
RN-412
C-411
DN-200
MaxTrap
InterLayer
KF-841
KF-851
KF-901
KF-647
KFR-70
KFR-20
RF-1000
TK-551
TK-525
TK-559
HR-538
HR-548
HR-438
HR-448
HF-858
Case Study – Totsucat E for VGO Unit
VGO Unit
• Large VGO Unit contained 1.6 million pounds (725 MT) of catalyst
In-Situ
• In-situ sulfiding would require 72-96+ hours and produce 20,000 gallons (75K liters) of sour water
Totsucat
• With Totsucat E Preactivation, the unit was online in 12 hours with less than 50 gallons (190 liters) of water removed from the separator
Totsucat E vs. DMDS – HVGO Unit
Liquid Heat Up rate @
17C/hr S content
S >> 0.5 wt%
Gas Phase Heat up
Rate @ 4C/hr
Time Gain
TOTSUCAT E vs DMDS:
48+ hrs
Totsucat Properties
• Classified as self-heating solids
• Class 4.2, UN 3190
Sulfides are sensitive to oxidation by air
• Non-Passivated - Requires inert loading
• Hydrocarbon Passivation - Allows for loading under air
Two Types Available
Packaging
Drums
• Metalized liners
• Heat sealed
Bins
• Sandblasted Clean
• New Gaskets
• Pressure Tested
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.
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
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.
Issue of Cracked Feed
• 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.
Delaying the introduction of cracked feeds
can have significant costs:
Solution: Totsucat CFP
• 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
CFP = Cracked Feed Protection
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
Case Study 1 - Totsucat CFP in
ULSD Service
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.
Case Study 2 – NHT with Totsucat CFP
Feed: 25-50% Coker Naphtha
Feed Rate: 35,000 BPD
Catalyst Type: NiMo
Catalyst Quantity: 53,000 lbs
Naphtha Hydrotreater
Case Study 2 – NHT with Totsucat CFP
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
Data from 2 Runs
Case Study 2 – NHT with Totsucat CFP
Reactor Temperature Reactor Temperature
0
100
200
300
400
500
600
700
0 50 100 150 200 250 300 350
Te
mp
era
ture
(°F)
Days
Inlet Temp - In-Situ Sulfided
Inlet Temp - Totsucat CFP
Bottom to Inlet ΔT - In-Situ
Bottom-Inlet ΔT - Totsucat CFP
Reactor Temperature
Case Study 2 – NHT with Totsucat CFP
Reactor Temperature
020406080
100120140160180200
0 100 200 300 400
CB
PD
Days
Coker Feed Rate
In-Situ Sulfided
Totsucat CFP
Case Study 3 – CFHT with Totsucat CFP
Feed: HVGO / HCGO
Feed Rate: 24,000 BPD
Catalyst Type: NiMo
Catalyst Quantity: 107,000 lbs
Cat Feed Hydrotreater
Case Study 3 – CFHT
Coker Naphtha Feed Rate In-situ Sulfided Run
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.
Case Study 3 – CFHT
Coker Naphtha Feed Rate
Mid-bed and Bottom Radial Spreads Increased
as Cracked Stocks were introduced
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.
In-situ Sulfided Run
HCGO Ramped to 85% of Feed at Day 70
Case Study 3 – CFHT with Totsucat CFP
Coker Naphtha Feed Rate
0
20
40
60
80
100
120
140
160
0
100
200
300
400
500
600
700
0 10 20 30 40 50 60
%
Tem
pe
ratu
re, F
Hours after Feed-in
Totsucat CFP Enables Early Introduction of Heavy Coker Gas Oil: Ten Hours After Heatup to 600 F Reactor Inlet T
Rx Inlet T, F
Btm of Bed 1Avg, F
Bed 1 Delta T, F
% HCGO in Feed
HCGO Ramped to 90% of Feed 10 hours from heat up
Top Bed Delta T Stable After HCGO In
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
Case Study 3 – CFHT with Totsucat CFP
Coker Naphtha Feed Rate Totsucat CFP Run – Bottom Bed
Temperature (°F)
6 12 18 hours 3 days
Progressive Introduction of Cracked Feed Introduce cracked feed at 175-450°F
Heat up at 35°F/h up to 475°F
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
need for SR or Cracked Feed storage
Startup with Totsucat CFP
Liquid Phase with Cracked Feed
750
575
390
200
SOR
Catalyst Companies Approving Totsucat
Totsucat Commercial Experience
Over 800 Totsucat Lots Treated at EUS totaling
40+ million pounds of catalyst
HDS/HDN
• Wide variety of hydrotreating catalysts
Selective Hydrogenation
• NiMo and CoMo Catalysts
Pyrolysis Gasoline
• CoMo catalysts
Wax Hydrofinishing
• NiW catalysts
Lube Hydrofinishing
• CoMo catalysts
Totsucat Processing Sites
Europe – Bitterfeld, Germany
Europe – Gela, Italy USA – Pasadena, Texas
Pasadena, TX Facility
Other Eurecat Services
Analysis and Regeneration of Spent Hydrotreating Catalysts
HDS Activity Testing
• High activity regenerated catalysts available for immediate delivery
Resale of Regenerated Catalysts
Bulk Nickel Sulfur Guards
REACTIVATION of Palladium on Alumina Catalysts
Randy Alexander
Director of Sales and Marketing
Phone: 832.284.0612
Frederic Jardin
Executive Vice President
Phone: 832.284.0614
Tony Loverdi
Regional Sales Manager –
Gulf Coast
Phone: 832.284.0607
Chris Buffington
International Sales Manager
Phone: 832.284.0608
Nilanjan“Babu”Brahma
Technical Support Manager
Phone: 832.284.0609
Bob Stults
Regional Sales Manager – Western Region
Phone: 832.284.0602
Eurecat Contact Information
Please let us know how we can help you.
Thanks for your attention.
