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TRICAT’s XpresS Pre-sulfiding Process - Catalyst … · TRICAT’s XpresS Pre-sulfiding Process...

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

The Benefits of True Ex-situ Pre-sulfiding

TRICAT

Conventional In-situ Sulfiding

n Gas or Liquid Phase Using Sulfiding Agent

n Sulfiding Reactions3NiO + 2H2S + H2 Ni3S2 + 3H2O

9CoO + 8H2S + H2 Co9S8 + 9H2O

MoO3 + 2H2S + H2 MoS2 + 3H2O

WO3 + 2H2S + H2 WS2 + 3H2O

TRICAT

• Time Consuming and Often Results in Unexpectedly Poor Performance

• Exothermic Reactions• Yields Large Quantities of Water• Sulfiding Agents Can Be Toxic,

Flammable, Odorous

Conventional In-situ SulfidingProblems

TRICAT

XpresS Pre-sulfidingFeatures

n True Ex-situ Pre-Sulfidingn Sulfiding in Ebullated Bed Reactorn Catalyst Stabilized via Patented Gas

Treatment

TRICAT

“XpresS”Benefits vs. In Situ Sulfiding

n Homogeneously Sulfided, Odor-Free Catalyst

n No External Sulfur Supply or Addition System Required

n Minimal Reactor Exotherms at Start-upn No Water Releasen Greatly Reduced Start-up Time

TRICAT

“XpresS”Benefits vs. Pre-Sulfurizing

n Minimal Reactor Exotherms at Start-up in gas or liquid phase

n No Temperature Holdsn Minimal H2 Consumption during Heat-upn No Product Recycle due to Discolorationn No Water Releasen Reduced Start-up Time

TRICAT

Pre-Sulfiding StepBenefits of XpresS Process

n Sulfiding Medium: H2S/H2- Absence of carbon containing compounds (eg. DMDS) eliminates coking

n Ebullated Bed Operation- Optimizes Solid/Gas mixing- Eliminates concerns about H2 reduction due to breakthrough- Permits high temperature sulfiding to maximize activity

n Minimal H2S evolution during heat-up- Protects sensitive catalysts upstream or downstream of reactor

TRICAT

Passivation StepBenefits of XpresS Process

n Passivation process works by converting surface sites from metal sulfide to stable oxysulfide state

n Use of gaseous passivation step avoids use of smelly, difficult-to-handle hydrocarbon coating

n Ebullated bed also ensures that each particle is treated uniformly and that H2S is effectively removed from pores

TRICAT

Reactivation StepActivity Enhancement with XpresS

n Once loaded, stabilized catalyst completes activation with H2S evolved during feed processing.

n 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

n Catalyst is dry and free-flowing. Loading in air or inert.

n No external sulfur supply required.n No high temperature exotherms.n Liquid or gas phase heat-up.n If gas phase heat-up, introduce feed at normal

operating temperature.

TRICAT

Recent Commercial XpresS Start-UpBelgian Refining Corp.

n TRICAT supplied regenerated/XpresS pre-sulfided catalyst to refinery.

n Catalyst dense loaded into distillate HDT unit w/N2 purge. No exotherms experienced during loading.

n Unit heat up in gas phase with circulating H2 to 230°C with only minor exotherm at H2 introduction.

n Refiner reported:- Turnaround length halved from 12 to 6 days through TRICAT 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 UnitXpresS Start-Up Temperature Profile

June 1999

0

50

100

150

200

250

300

350

-1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Time, Hours

Rea

ctor

Tem

pera

ture

, Deg

C

Reactor Inlet

Reactor Outlet

Begin H Circulation2

Introduce Feed

TRICAT

Belgian Refining Corp. #2 HDS UnitPre-Sulfurized Catalyst Start-Up Temperature Profile

April 1997

0

50

100

150

200

250

300

350

-1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Time, Hours

Rea

cto

r T

emp

erat

ure

, Deg

C

Reactor Inlet

Reactor Outlet

Begin H Circulation2

Introduce Feed

TRICAT

Catalyst Deactivation Rate

300

320

340

360

380

400

420

440

0 5 10 15 20 25

Feed Processed, cu m per kg cat

Norm

alize

d Te

mpe

ratu

re to

Ach

ieve

500

ppm

Sul

fur,

Deg

C

Previous Cycle

Current Cycle

TRICAT

XpresS Usersn Bayern (BP Affiliate)n Agipn Shelln BP – Hamburgn ExxonMobil n OMVn PCKn Veban Wilhelmshavener Raffinerien Belgian Refining Corp.

n DEAn Erdoelchemien TotalFinaElfn Universal Refiningn Idemitsu Kosan (Japan)n Ultramar Diamond Shamrock (US)n INAn Synetixn Haldor Topsoen Procatalysen Miro

TRICAT

XpresS Pre-SulfidingConclusions

n Quality - XpresS Provides Refiner With True Pre-Sulfided Catalyst

n Convenience - Eliminates In-situ Procedures and Activation Steps

n Safety - Eliminates Sulfiding Chemicals and Exotherms During Start-up

n Timeliness - Fastest Start-up Possible

TRICAT


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