Refining-Petrochemicals-Chemicals-Engineering

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REFORMING CATALYST REGENERATION

I - SHUTTING DOWN THE UNIT FOR REGENERATION ...............................................................1

II - PREPARING THE CIRCUITS, INSTALLING ANALYZERS, CHECKING STOCKS

OF CHEMICALS .............................................................................................................................2

III - COKE COMBUSTION ....................................................................................................................3

IV - OXYCHLORINATION - CALCINATION.........................................................................................8

V - CATALYST REDUCTION.............................................................................................................11

VI - SULFURIZATION..........................................................................................................................12

VII - OIL-IN ............................................................................................................................................14

Figure: CATALYTIC REFORMING - Semi-regeneration unit - Regeneration loop

RA REF - 00090_A_A - Rev. 2 23/02/2009

© 2009 - IFP Training
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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

I - SHUTTING DOWN THE UNIT FOR REGENERATION

Normal shutdown procedure for the unit: reaction temperature and feed
• Reactor inlet temperature is lowered to 460°C flow rate are lowered simultaneously. Then the feed is cut off
• Feed flow rate is reduced to 60% of the normal value

• FEED IS CUT OFF

• Recycle gas is circulated at maximum flow rate and reactor inlet

temperature is raised to 510°C
• A maximum amount of hydrocarbons are eliminated from the unit (hot
• Temperature remains at 510°C for at least 2 hours. Hydrocarbons are hydrogen desorption) before beginning the coke combustion phase in order
purged in separators and low points to limit the amount of heat released and avoid any localized overheating of
catalytic beds
• "Hydrogen stripping" of the hydrocarbons remaining in the reaction
• 510°C temperature stage is extended if hydrocarbons are still being purged
section is completed

• Reactor inlet temperature is lowered to 200°C

Unit is cooled down to allow purging and inerting
• Furnaces are shut down
• Recycle compressor is shut off

• Reaction section is DECOMPRESSED Gaseous phase consisting of hydrogen and hydrocarbons is eliminated. It is
replaced by nitrogen gas (inert gas) so that the combustion phase can be
• NITROGEN scavenging to PURGE; compressions; decompressions carried out by introducing a controlled amount of air in the nitrogen

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

II – PREPARING THE CIRCUITS, INSTALLING ANALYZERS, CHECKING

STOCKS OF CHEMICALS

• Reaction section is isolated by blind flanges from any circuits that may • Safety aspect
contain hydrocarbons

• Combustion air injection line is prepared at the recycle compressor intake • Circuits required for the different regeneration phases are prepared

• Sampling devices are prepared • Sampling devices and analyzers (used to check that operations take
place properly) are installed
• Oxygen analyzer is installed
• Stocks of chemicals and materials (used during regeneration) are
checked
• Pump and chlorinated compound (DCP) injection lines are checked
(see figure in Appendix)
• Anticorrosion loop (ACL) is prepared

• Stocks are checked: nitrogen, DCP, caustic, electrolytic hydrogen,

sulfurization agent (DMDS), etc.

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• Coke deposited on catalyst surface during previous cycle is eliminated by

III - COKE COMBUSTION burning
COKE COMBUSTION REACTIONS
Coke is made up of carbon (C) and hydrogen (H) and the combustion
reactions are as follows:

C + O2 CO2 + 7800 kcal/kg

x x
x + ( + 1)
4
+ 2 12 kg 32 kg 44 kg of burned carbon

D CH 1084 A
x x • Because of the platinum present on the catalyst, no carbon monoxide (CO)
CHx + (
4
+ 1) O2 CO2 + 2
H 2O
is formed when the carbon in the coke is burned (platinum catalyzes the
formation of CO2 even in the presence of very little oxygen)

1 1
H + 4 O2 2 H 2O + 28600 kcal/kg
1 kg 8 kg 9 kg of burned hydrogen

• Water is necessarily formed during coke combustion. It flushes the chlorine

out of the catalyst, forming HCl (hydrogen chloride gas)

• COMBUSTION OF A TON OF COKE RELEASES 9000 THERMIES ON

THE AVERAGE

The heat released by coke combustion is considerable. This heat flow must
be eliminated while combustion is taking place in order to limit catalyst bed
temperature increase.

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

INITIAL COMBUSTION PROCESS

• Unit is under nitrogen pressure that is approximately 1 bar lower than the • Combustion air can be inlet at the lowest pressure point in the unit: the
pressure of the air circuit used for combustion recycle compressor intake
• The higher this pressure, the easier it is to eliminate the heat released by
combustion as:
– the density of the circulating gas is higher
– the mass flow rate delivered by the recycle compressor is higher (lower
compression ratio)
• Recycle compressor is started up
maximum flow rate • Maximum combustion heat flow is eliminated by recirculating inert gas
(make corrections in the recycle gas flowmeter indications: molar mass and
pressure are different from normal operating conditions)
• Recycle gas coolers are at maximum duty • Compressor discharge temperature is limited
• Water content in the recycle gas is limited: the gas is saturated in water
at the separator temperature
Application in the Appendix: Determining the water content in the gas at
the separator outlet according to the drum temperature and pressure
• Combustion can be initiated only after a certain temperature level has been
• Furnaces are lit, temperatures are raised by 50°C/hour reached (approximately 400°C)
• The appendix 2 shows the principle of coke burning in a moving bed: the
catalyst moves down into the regenerator while the burning gas goes
through the catalyst bed from the left (into) to the right (center pipe).
Thus the front flame is the result of the both moving, diagonally.

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• ANTICORROSION LOOP (ACL) is activated at about 300°C. Caustic is • Corrosion is limited in the cold part of the unit (air coolers, flash drum):
circulated upstream from the air coolers toward the flash drum:
Chlorine is necessarily elutriated from the catalyst by the water formed
– monitor its flow rate when the hydrogen in the coke burns. Elution releases hydrogen chloride
gas (HCl) in the recycle gas. As a result, a hydrochloric acid solution is
– adjust caustic makeup depending on the pH indication in the flash formed which is particularly corrosive for metallic materials as soon as the
drum water condenses.

This corrosion is limited by the caustic in the ACL neutralizing the acid
solution. The reaction is as follows:

HCL + NaOH NaCl + H2O

hydrochoric caustic salt water
acid

If the pH drops, then the caustic makeup in the anticorrosion loop must be
increased to offset caustic consumption. The drum level is maintained by
purging. Active caustic concentration is checked by monitoring the pH in
B101 (should be slightly greater than 7).

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• Pure DCP injection is started at approximately 350°C to keep a molar ratio: • The recycle gas is saturated in water. Chlorine elution from the catalyst is
offset by DCP injection so as to keep an optimum chlorine rate in the
H 2O catalyst. Additionally, chlorine injection during combustion helps keep the
HCI = 20 platinum from being sintered during combustion as shown in Figure 1.
Platinum dispersion in air decreases very quickly with time when no chlorine
in the reaction section during combustion is injected. However, it remains constant and even increases slightly if
chlorine is injected in adequate amounts to keep the chlorine content in the
catalyst at around 1% mass.
• Air injection is started at 400°C • Combustion usually starts as soon as the O2 concentration reaches 0.1%
volume in the gases at the inlet to the first reactor
• Oxygen concentration is monitored at reaction section inlet and outlet. CO2
concentration is monitored at the outlet • Combustion process can be monitored

• Maximum of 0.5 to 0.6% volume of O2 at the reaction section inlet • Heat release is limited

Air flow rate is adjusted so that: • OVERHEATING should be prevented, even locally

t of the bed does not exceed 50°C When the alumina in the catalyst is raised to a high temperature in the
presence of steam, it changes its structure and then loses its catalytic
or properties. In particular, its surface area decreases quite considerably if the
temperature rises as shown in Figure 4.
maximum reactor outlet t does not exceed 450°C
with 0.1% O2

T of 10°C OVERHEATING DURING COMBUSTION

MEANS IRREMEDIABLE LOSS OF
• Combustion is monitored reactor by reactor ALUMINA SURFACE AREA

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

H 2O • Chlorine rate is held on the catalyst during combustion to keep the platinum
• DCP injection is adjusted to keep the HCl ratio at a value of 20 from being sintered

• When the
t of the last reactor becomes zero and the oxygen percentages
• End of the initial combustion phase of the reaction section inlet and outlet remain identical, the primary
combustion phase can be considered completed

SECONDARY COMBUSTION PROCESS • If necessary, coke elimination is completed

• Reactor inlet temperature is raised to 510°C , with 0.5% volume O2 • Combustion may be resumed. If t rises, air is cut off to prevent any
overheating
• Monitoring: reactor outlet t 520°C max

H 2O
• HCl ratio is held = 20

• End of secondary combustion • The coke elimination phase is theoretically completed if the temperature
remains stable at 510°C with 0.6 to 0.8% volume of oxygen

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• The aim of this regeneration phase is to REDISPERSE the metals on the

IV - OXYCHLORINATION - CALCINATION surface of the alumina in order to restore the initial hydrodehydrogenating
activity of the catalyst
• Temperature is raised to 510°C • If combustion is resumed, air injection is lowered (prevent localized
overheating)
• O2% is increased gradually to 5% volume of oxygen

• Oxychlorination: platinum crystallites are chemically attacked at high

• EIGHT-HOUR STAGE: temperature by oxygen and chlorine. Slightly volatile metallic species
(oxychlorides) are formed, which migrate on the alumina surface and
at 510°C
become fixed once again on the free surface sites, thereby redispersing
with 5% O2 the metals

So that REDISPERSION can take place, the alumina needs a maximum

and HCl at reactor outlet > 50 ppm
number of free surface sites and this implies that:
(DCP injection is adjusted). – The coke has been totally eliminated during the combustion phase
– The alumina is not sulfated, i.e. that combustion occurred without
any SULFUR present. This is because any sulfur oxides that are
formed (SO2 and especially SO3) attack the reactive sites on the
alumina surface and form alumina sulfate, which is chemically inert
(If the catalyst contains a lot of sulfur before regeneration, or if any
SO2 is detected in the combustion gases, then a SPECIAL
REGENERATION PROCEDURE must be used, which includes sulfur
removal stages)

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

H 2O • Calcination phase, maximum elimination of the water trapped by the

• The % of O2 is raised to 8% at 510°C; HCl = 20 alumina during the previous regeneration phases
This is because there must be the least possible water present on the
for 4 hours
catalyst for the reduction phase to run properly

• Water is eliminated to keep the alumina from reabsorbing it during the

• DCP injection is stopped
cooling stage which follows
• The anticorrosion loop is shut down and water is used for quick rinsing
• All low points are purged to eliminate the water

COOLING • The unit is cooled down so that it can be inerted with nitrogen

• The temperature is lowered to 400°C with O2 = 8%

• Furnaces are switched off at 400°C

• Cooling takes place to 200 - 250°C

• A maximum amount of water is eliminated to keep the catalyst alumina
• Low points are purged and all water is carefully eliminated from reabsorbing it at low temperature
• Compressor is shut off and isolated

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• NITROGEN scavenging PURGE, compressions, decompressions until there • The inert atmosphere is implemented in order to be able to introduce the
is 0.3% O2 in the nitrogen hydrogen required for the reduction phase

• Pressure should not be lowered too much (1.7 bar minimum) • Hydrocarbons that may be trapped in the insulating refractory of the reactors
should not be desorbed. The presence of these hydrocarbons is highly
Pressure surges should be avoided detrimental to the catalyst during the reduction phase which follows

AT THE END OF THIS PHASE THE CATALYST IS IN A HIGHLY

UNSTABLE STATE.

EVERY EFFORT MUST BE MADE NOT TO PUT IT IN CONTACT WITH:

– WATER
– HYDROCARBONS

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• The aim of the reduction phase is to transform the platinum oxychlorides

V – CATALYST REDUCTION (light yellow catalyst) -- redispersed on the alumina surface during the
oxychlorination phase -- into metallic platinum (gray catalyst)

This chemical reaction consumes hydrogen (a necessary reactant for the

reduction) and produces water. The reaction can be written:
Cl Cl Cl Cl
Pt Pt
O O O O Pt Cl Pt Platinum oxychloride + H2
Metallic platinum + H2O
+ H2 + H 2O

D CH 2057 A
• Pure hydrogen must be used for this reduction, since some of the reduced
platinum is extremely reactive during the reaction and will transform any
hydrocarbon into coke. As a result, reforming hydrogen must therefore not
• Pure, perfectly dry, electrolytic hydrogen is introduced be used for start-up and hydrocarbons must not be released from the
refractory of the reactors by pressure surges

• The indications of the recycle flow meter are corrected. The recycle
• The compressor is started up compressor is checked to be sure it is operating outside its surging zone

• The furnaces are lit, the temperature is raised to 485°C • Figure 3 shows there is an optimum reduction temperature that yields
maximum dispersion of metallic platinum. If the temperature is too low, only
part of the platinum is reduced. On the other hand, too high a temperature
promotes sintering of the metal, thereby reducing dispersion
• The temperature is held at 485°C for 4 hours
• Figure 3 also shows the detrimental effect of water during the reduction
– pressure is maintained by pure H2 make up phase. The degree of platinum dispersion achieved after reduction on a
dried catalyst is much lower than with a dried, calcined catalyst
– the water is purged from low points and separators

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• Water present during the reduction phase in fact promotes platinum

agglomeration. The water makes the platinum oxychlorides mobile and they
migrate on the catalyst surface. These oxychlorides are instantaneously
reduced when they encounter platinum atoms that have already been
reduced. Then very large platinum crystallites are formed that cause poor
metallic dispersion.

• The aim of sulfurization is to temporarily curb the overly high activity of the
VI – SULFURIZATION metals that were formed during the reduction phase. These metals in fact
promote the hydrocarbon HYDROGENOLYSIS reaction (bond breakage in
the presence of hydrogen). The reaction is also called METHANIZATION
since it produces mainly methane and coke which is then deposited on the
catalyst surface.
• Reactor t is lowered to 430°C, sulfurization is begun and continues at
400°C
• DMDS (dimethyl disulfide) breaks down when hydrogen is present to form
the sulfurization agent H2S according to the reaction below:
• DMDS is injected reactor by reactor (3, 1, 2), corresponding to

0.2% mass of sulfur in relation to the catalyst CH3 — S — S —CH3 + 3H2
2H2S + 2CH4

for a period of three hours. DMDS Methane

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

The metallic function is temporarily poisoned due to the H2S that was
generated. It sulfurizes the platinum according to the following reversible
reaction for example:

R — Pt + H2S R— Pt — S + H2
Platinum
sulfide

Platinum sulfide does not cause the parasite hydrogenolysis reaction

• Proper implementation of sulfurization can be monitored. DMDS is injected

reactor by reactor, since the aim is to sulfurize the metals present on the
• Check for the presence of H2S in the gases at the outlet of each of the catalyst rather than the metal walls of the furnaces, exchangers and lines in
reactors the reaction section

00090_A_A © 2009 - IFP Training

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• Oil in with a dry desulfurized (or low sulfur) feed

VII - OIL-IN Unit is dried and the sulfur is gradually eliminated from the catalyst

• Temperature 400°C ; pressure greater than 10 bar by pure H2

• Overseverity should be avoided by a low flow rate, catalytic beds should be
makeup
well "drained"
• Feed flow at 60% of the nominal rate
• In the event of exothermicity greater than 5°C in the reactors, the
• Temperature is gradually raised to 460°C temperature must no longer be raised

• Pressure increase is monitored until operating pressure is reached • The gas produced by the reactions allows pressure to be increased in the
unit
• Flow is increased to nominal rate
• The unit is dried while the chlorine rate is held on the catalyst. Meanwhile,
as the most hydrogenolyzing metallic sites "calm down", sulfur in the H2S
• Drying and sulfur removal phase, chlorinated compound is injected form is eliminated to restore the metallic function to normal activity

• First STAGE at 460°C • The temperature is raised in stages depending on the water and H2S
content of the recycle gas with appropriate injection of the chlorinated
compound

as long as: there is water in the recycle gas > 200 ppm volume
and H2S > 10 ppm volume.

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REFORMING CATALYST REGENERATION

OPERATIONS COMMENTS

• Second STAGE at 470°C • Ditto

as long as H2O > 100 ppm and

H2S > 10 ppm

2 ppm mass of chlorine in relation to the feed is injected

• Third STAGE at 480°C • Ditto

as long as the H2O content remains greater than 50 ppm

1 ppm mass of chlorine is injected

• SEVERITY IS ADJUSTED TO GET THE REQUIRED PERFORMANCE • Normal operation of the unit is begun

00090_A_A © 2009 - IFP Training

 Chloriding To other reactors Sulfurizing
agent
for agent
regenr. (DMDS)

Oxygen analyser if
second injection.

Steam

SC
TRC TRC TRC
T
FG FG FG
TR
TR TR F
TR Oxygen
TR analyzer
TR TR FRC
TR
Atm. Caustic soda
TR TR PR Air
TR 50%
FRC

Second air TR FR Nitrogen Caustic

injection (if any) Demineralized
soda
water
solution
Water PC
FRC

F LRC
TR
CATALYTIC REFORMING FRC pH
Semi regenerative Unit F
— Regeneration loop —

D PCD 155 W
© 2009 - IFP Training