TGTU Catalyst – In-situ Presulphiding

Fernando Maldonado
Business Manager – Gas Treating Catalysts
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 Forms of TGTU Catalyst

Oxide CoMo
Blue

Oxide
NiMo or CoMo
Black

Presulphurized, Presulphided Sulphated Presulphurized/Presulphided

or Sulphided Or Sulphided
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 Tail Gas Treating Unit – Catalyst Activation
The Co-Mo catalyst that is used in the TGTU reactor is manufactured in a metal oxide form. Before the catalyst is utilized in a
TGTU it must be made “active” by converting the metal oxide sites to metal sulfide sites.

States of Catalyst
Sulfiding
200°C – 315°C (390°F – 600°F)
Delivered CoO In H2 and H2S environment CoS Active
Oxide Form MoO3 MoS2 Form
Oxidization/Regeneration
T>150°C (300°F) in an oxidizing environment with no sulphur
components added to recycle gas

Reduction T>200°C (390°F) in H2 environment

with no H2S
Reduction
Even with low H2 PP, reduction to base
metal is possible at T>200°C (390°F)
Reduced in a H2 environment with no H2S
Bad S/U Co
Not possible due to
Mo metals agglomeration
Inactive Form
 Tail Gas Treating Unit – Catalyst Activation

What is the effect on TGTU catalyst operated in an oxidizing environment with sulphur
compounds entering the reactor?

Delivered CoO CoS Active

Oxide Form MoO3 Form
MoS

T>150°C (300°F) in an oxidizing

environment with sulphur components
entering

Sulphated Catalyst
 Sulphiding Chemistry

 The active form of the catalyst is the intimate mixture of the cobalt sulfide
and molybdenum sulfide.

 Cobalt oxide is sulphided in a one-for-one exchange of the sulfur

CoO + H2S CoS + H2O

 The molybdenum is reduced from the Mo (VI) oxide to the Mo (IV) sulfide;
hydrogen is required.

MoO3 + 2H2S + H2 MoS2 + 3H2O

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 TGTU Catalyst Activation: In-situ versus Ex-situ Sulphiding

 The catalyst is converted from the oxide form to the sulphide form via either an in-situ sulphiding
process or an ex-situ third party sulphiding process.
 In in-situ sulphiding process fresh catalyst is loaded into the TGTU reactor and activated using hydrogen
sulphide from Claus feed or Claus tail gas.
 In ex-situ sulphiding, the oxide catalyst is sent from the manufacturing plant to the facilities of a 3rd
party (Porocel or Eurecat) where the catalyst is converted to the sulphide form.
 The two best known ex-situ sulphiding methods are Porocel’s ActiCat TG process and Eurecat’s
TOTSUCAT TG process.

 Criterion TGTU catalysts have been successfully activated by both of the above named ex-situ processes.

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 TGTU Catalyst Activation: In-situ versus Ex-situ Sulphiding

Is a presulfurized TGU catalyst the same thing as a presulfided TGU catalyst?

No – It is important to be precise with nomenclature

 Porocel’s ActiCat TG process converts ~ 50% of the metal oxides to metal sulphides and provides sulphur
within the catalyst pores to complete the conversion of the remaining metal oxides sites to metal sulphide
sites. A catalyst that has undergone this ex-situ sulphiding process is referred to as
a presulphurized catalyst.

 Eurecat’s TOTSUCAT TG process converts 100% of the metal oxides to metal sulphides. A catalyst that has
undergone this ex-situ sulphiding process is referred to as a presulphided or a fully sulphided catalyst.

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 TGTU Catalyst Activation: In-situ Sulphiding
1. Load catalyst in air.
2a. Purge system with N2, or
2b. Run in-line burner near stoichiometric air/fuel ratio
3. Warm catalyst bed to 200°C (390°F) with burner. Care should be exercised that the provisions for adding H2S to the system are ready to operate,
otherwise the exposure of the catalyst to H2 in the absence of H2S can result in irreversible damage to the catalyst. Also, impaired catalyst activity can
result if the catalyst is exposed to hydrogen sulphide for extended periods without hydrogen being present.
4. Switch to substoichiometric conditions, adjust so gas entering reactor contains 2 – 10% H2 + CO.
5. Bleed in H2S (1 – 2%). Hold conditions for 30 minutes and observe catalyst bed temperatures.
6. Ramp catalyst bed temperature to 250°C (475°F) at 15°C (25°F) per hour. Adjust temperature ramp rate to keep temperature difference between reactor
inlet temperature and maximum bed temperature below 25°C (50°F).
7. Before heating catalyst bed past 250°C (475°F), verify H2S concentration in reactor outlet gas stream is greater than 1000 ppm. Ramp catalyst bed
temperature to 315°C (600°F) at about 15°C (25°F) per hour.
8. Continue sampling the reactor outlet gases at one hour intervals. If H2S concentration in the reactor outlet gas falls below 1000 ppm, hold reactor inlet
temperature until H2S level rises above 1000 ppm, then resume ramping temperature.
9. When the catalyst has been fully sulphided the reactor outlet gas H2S concentration equals the reactor inlet gas H2S concentration. Hold the catalyst bed
temperature at 315°C (600°F) for 4 hours. Do not exceed 350°C (650°F) catalyst bed temperature.
10. Cool reactor to less than 280°C (535°F) and prepare for normal operation.

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 Simplified Diagram – In-situ Sulphiding Procedure via Acid Gas Bypass

Incinerator
PC

Incinerator

FC To Amine
Absorber
Acid Gas

Fuel Gas
RGG TGTU Reactor
Steam
Utility N2
Air
Quench
Tail Gas S/U Gas Tower
from SRU Ejector
Steam

LC
Opened
Closed Reactor Effluent Cooler

Sour Water

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 In-situ Sulphiding Procedure via Acid Gas Bypass
1. Load catalyst in air.
2. Isolate TGTU from SRU (verify SRU tail gas valve is closed).
3. Isolate reactor section from amine section of the TGTU (verify quench tower outlet gas valve to amine absorber is closed). Line up quench tower overhead to front of
TGTU.
4. Establish quench tower water circulation.
5. Start the start-up gas steam ejector and establish recycle rate of 30% of process design flow.
6. Add N2 to begin purging reactor system.
7. Set the quench tower pressure controller at ~0.2 barg.
8. Start the RGG burner slightly above stoichiometric air/fuel ratio.
9. Warm catalyst bed to 200°C (390°F) with RGG burner.
10. a. Adjust RGG to substoichiometric operation; target 2% - 10% H2 + CO (reducing gas) to reactor. Prior to adding H2S rich
acid gas, verify O2 content in recycle gas is <0.5% by volume.
b. Slowly add H2S rich acid gas via the acid gas bypass line.
c. Target 1% H2S by volume at reactor inlet. Upon addition of acid gas, sample reactor inlet and outlet process gases. A hand-held Draeger tube sampling
system that provides immediate H2S concentration in % or ppm values is recommended.
11. Hold conditions for 30 minutes and observe catalyst bed temperatures.
12. Ramp catalyst bed temperature to 250°C (475°F) at 15°C (25°F) per hour. Adjust temperature ramp rate to keep temperature difference between reactor inlet
temperature and maximum bed temperature below 25°C (50°F).
13. Before heating catalyst bed past 250°C (475°F), verify H2S concentration in reactor outlet gas stream is greater than 1000 ppm. Ramp catalyst bed temperature to
315°C (600°F) at about 15°C (25°F) per hour.
14. Continue sampling the reactor outlet gases at one hour intervals. If H2S concentration in the reactor outlet gas falls below 1000 ppm hold reactor inlet temperature
until H2S level rises above 1000 ppm, then resume ramping temperature.
15. When the catalyst has been fully sulphided the reactor outlet gas H2S concentration equals the reactor inlet gas H2S concentration. Hold the catalyst bed temperature
at 315°C (600°F) for 4 hours. Do not exceed 350°C (650°F) catalyst bed temperature.
16. Cool reactor catalyst bed to 280°C (535°F) and prepare for normal operation.

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

Incinerator
PC

BTX in Incinerator
acid gas To Amine
FC
Absorber
Acid Gas

Fuel Gas
RGG TGTU Reactor
Steam
Utility N2
Air
Quench
Tail Gas S/U Gas Tower
from SRU Ejector
Steam

LC
Opened
Closed Reactor Effluent Cooler

Sour Water

What can be done to prevent or minimize catalyst damage?

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

BTX in acid gas:

Use Claus tail gas to activate the catalyst. Operate Claus unit at high ratio (>7:1) H2S:SO2. Verify that
SRU reaction furnace temperature is sufficiently high to insure BTX destruction.

Be prepared to add ammonia or caustic to quench water to maintain pH above 6 until the catalyst
activates.

Bypassed acid gas can be used with temporary carbon bed to remove the BTX compounds.

Utilize ex-situ processed TGTU catalyst.

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

No acid
gas flow

How to activate the catalyst?

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

No acid gas flow:

Use high ratio (>7:1) H2S:SO2 Claus tail gas to activate the catalyst.

Be prepared to add ammonia or caustic to quench water to maintain pH above 6 until

the catalyst activates.

Prior to starting in-situ sulphiding verify line is not plugged and valves are operable.

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

Incinerator
PC

Incinerator

FC To Amine
Absorber
Acid Gas

No recycle
Fuel Gas
RGG TGTU Reactor
gas system
Steam
Utility N2
Air
Quench
Tail Gas S/U Gas Tower
from SRU Ejector
Steam

LC
Opened
Closed Reactor Effluent Cooler

Sour Water

How to activate the catalyst?

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

No recycle gas system:

Use once through nitrogen to heat bed. When catalyst bed temperature reaches 200°C
(390°F) either bypassed acid gas or Claus tail gas can be utilized to activate the catalyst.

Prior to starting in-situ sulphiding verify recycle gas system is operable.

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

Incinerator
PC

Incinerator

FC To Amine
Absorber
Acid Gas

Quench
Fuel Gas
Steam
RGG TGTU Reactor water pH
Utility N2 drops
Air

Tail Gas S/U Gas

Quench below 6
Tower
from SRU Ejector
Steam

LC
Opened
Closed Reactor Effluent Cooler

Sour Water

How to prevent or minimize catalyst damage and operational upsets?

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls
During catalyst activation, the quench water pH remains above 6 only through use of caustic or ammonia
addition:
If bypassed acid gas (H2S with no SO2) is utilized during catalyst activation and low quench water pH is observed this is
caused by formation of SO2 and air ingress into the reaction system is the likely cause. Check the following:
1. Verify proper RGG operation. Is the air to natural gas ratio correct? Typically 80% to 90% substoichiometric operation is
targeted.
2. Verify air supply valves to start-up burners or pilots have not been left open.
3. Verify bleeders closed.
4. Verify air is not being drawn in through recycle blower seals.
5. Verify nitrogen is used in all instrument purges.

What can cause low quench water pH if Claus tail gas is used for catalyst activation?
1. Air ingress
2. Non-activated catalyst
3. Hydrogen starvation
4. Incorrect H2S:SO2
5. Catalyst bypassing

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

Loss of
Supplemental Incinerator
Hydrogen FC PC

Supplemental
Hydrogen Incinerator

FC To Amine
Absorber
Acid Gas

Fuel Gas
RGG TGTU Reactor
Steam
Utility N2
Air
Quench
Tail Gas S/U Gas Tower
from SRU Ejector
Steam

LC
Opened

Closed Reactor Effluent Cooler

Sour Water

How to activate the catalyst?

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 TGTU Catalyst Activation: In-situ Sulphiding Pitfalls

Loss of supplemental hydrogen:

If additional hydrogen is needed, lower substoichiometric operation of RGG to make more reducing
gas.

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TGTU Catalyst Activation: In-situ Sulphiding

Questions?

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