TRICATs XpresS Pre-sulfiding Process The Benefits of True Ex-situ - PowerPoint PPT Presentation

TRICAT TRICAT’s XpresS Pre-sulfiding Process The Benefits of True Ex-situ Pre-sulfiding

Conventional In-situ Sulfiding � Gas or Liquid Phase Using Sulfiding Agent � Sulfiding Reactions 3NiO + 2H 2 S + H 2 Ni 3 S 2 + 3H 2 O 9CoO + 8H 2 S + H 2 Co 9 S 8 + 9H 2 O MoO 3 + 2H 2 S + H 2 MoS 2 + 3H 2 O WO 3 + 2H 2 S + H 2 WS 2 + 3H 2 O TRICAT

Conventional In-situ Sulfiding Problems • Time Consuming and Often Results in Unexpectedly Poor Performance • Exothermic Reactions • Yields Large Quantities of Water • Sulfiding Agents Can Be Toxic, Flammable, Odorous TRICAT

XpresS Pre-sulfiding Features � True Ex-situ Pre-Sulfiding � Sulfiding in Ebullated Bed Reactor � Catalyst Stabilized via Patented Gas Treatment TRICAT

“XpresS” Benefits vs. In Situ Sulfiding � Homogeneously Sulfided, Odor-Free Catalyst � No External Sulfur Supply or Addition System Required � Minimal Reactor Exotherms at Start-up � No Water Release � Greatly Reduced Start-up Time TRICAT

“XpresS” Benefits vs. Pre-Sulfurizing � Minimal Reactor Exotherms at Start-up in gas or liquid phase � No Temperature Holds � Minimal H 2 Consumption during Heat-up � No Product Recycle due to Discoloration � No Water Release � Reduced Start-up Time TRICAT

Pre-Sulfiding Step Benefits of XpresS Process � Sulfiding Medium: H 2 S/H 2 - Absence of carbon containing compounds (eg. DMDS) eliminates coking � Ebullated Bed Operation - Optimizes Solid/Gas mixing - Eliminates concerns about H 2 reduction due to breakthrough - Permits high temperature sulfiding to maximize activity � Minimal H 2 S evolution during heat-up - Protects sensitive catalysts upstream or downstream of reactor TRICAT

Passivation Step Benefits of XpresS Process � Passivation process works by converting surface sites from metal sulfide to stable oxysulfide state � Use of gaseous passivation step avoids use of smelly, difficult-to-handle hydrocarbon coating � Ebullated bed also ensures that each particle is treated uniformly and that H 2 S is effectively removed from pores TRICAT

Reactivation Step Activity Enhancement with XpresS � Once loaded, stabilized catalyst completes activation with H 2 S evolved during feed processing. � Literature strongly suggests that sulfiding/gas passivation/re-activation enhances activity of the sulfided catalyst by decreasing metal-support interactions. TRICAT

The XpresS Start-up � Catalyst is dry and free-flowing. Loading in air or inert. � No external sulfur supply required. � No high temperature exotherms. � Liquid or gas phase heat-up. � If gas phase heat-up, introduce feed at normal operating temperature. TRICAT

Recent Commercial XpresS Start-Up Belgian Refining Corp. TRI CAT supplied regenerated/ XpresS pre-sulfided � catalyst to refinery. Catalyst dense loaded into distillate HDT unit w/ N 2 � purge. No exotherms experienced during loading. Unit heat up in gas phase with circulating H 2 to 230 ° C � with only minor exotherm at H 2 introduction. Refiner reported: � - Turnaround length halved from 12 to 6 days through TRI CAT initiatives. - Greatly simplified start-up versus in-situ sulfiding or earlier pre-sulfurized catalysts. - ~ 10 ° C lower SOR temp than previous cycle. TRICAT

Belgian Refining Corp. #2 HDS Unit XpresS Start-Up Temperature Profile June 1999 350 Reactor Inlet 300 Reactor Outlet 250 Reactor Temperature, Deg C 200 150 100 Introduce Feed 50 Begin H Circulation 2 0 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Time, Hours TRICAT

Belgian Refining Corp. #2 HDS Unit Pre-Sulfurized Catalyst Start-Up Temperature Profile April 1997 350 Reactor Inlet 300 Reactor Outlet Reactor Temperature, Deg C 250 200 150 100 Introduce Feed 50 Begin H Circulation 2 0 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Time, Hours TRICAT

Catalyst Deactivation Rate 440 Previous Cycle Current Cycle 420 Normalized Temperature to Achieve 500 ppm Sulfur, 400 380 Deg C 360 340 320 300 0 5 10 15 20 25 Feed Processed, cu m per kg cat TRICAT

XpresS Users DEA Bayern (BP Affiliate) � � Erdoelchemie Agip � � TotalFinaElf � Shell � Universal Refining � BP – Hamburg � Idemitsu Kosan (Japan) � ExxonMobil � Ultramar Diamond Shamrock (US) � OMV � INA � PCK � Synetix � Veba � Haldor Topsoe � Wilhelmshavener Raffinerie � Procatalyse � Belgian Refining Corp. Miro � � TRICAT

XpresS Pre-Sulfiding Conclusions � Quality - XpresS Provides Refiner With True Pre-Sulfided Catalyst � Convenience - Eliminates In-situ Procedures and Activation Steps � Safety - Eliminates Sulfiding Chemicals and Exotherms During Start-up � Timeliness - Fastest Start-up Possible TRICAT