CATALYST REGENERATION

CATALYST REGENERATION (R-56)

 INTRODUCTION
 The catalyst regeneration follows the following
steps.
 SHUT DOWN
 CARBON BURN
 OXIDATION
 REDUCTION
 UN LOADIND/LOADING OF CATALYST
 PRE-SULFIDING
 START-UP
 INTRODUCTION
 In some situations, the catalyst itself or the
plant hardware is contaminated with excessive
amounts of carbon and sulfur resulting into
formation of sulfate on catalyst.

 This sulfate will promote Platinum crystalline

growth, and interfere with the establishment
of normal catalyst chloride level.
 INTRODUCTION
 If sulfate removal step is taken.

 To remove the excessive sulfur from the

catalyst, a “Sulfate Removal “ step is included.

 Sulfate removal is accomplished by reducing

the sulfur to hydrogen sulfide and also the
chloride addition helps to sulfate removal.
 INTRODUCTION
 Sulfate removal steps are based on;
1. A catalyst sample shows sulfate formation(more
than 0.1 weight percent sulfate).

2. The sulfur history of the plant and catalyst. Use a

sulfate removal steps if;

(a) The unit previously operated on non-hydro

treated feed.
 INTRODUCTION
(b)The naphtha feed averaged, more than 1 wt-PPM
sulfur content during the previous cycle.

(c)In the previous cycle the high presence of sulfur

which damaged the catalyst and also the stability and
selectivity. The presence of high sulfur levels should
have been confirmed by feed or recycle gas analysis.

(d) A history of decreasing cycles.

Steps Should be taken for Sulfate Removal

 Shut down
 Engineering Works
 Carbon burning
 Proof Carbon Burn & Oxidation
 Cool Down
 Nitrogen Purge
 Sulfate removal
Steps Should be taken for Sulfate Removal
 Proof carbon burn( including nitrogen purge)
 Oxidation (second)
 Cool Down
 Nitrogen purge
 Reduction
 Cool down
 Catalyst Un-loading/loading
 Pre-sulfiding, start-up and chloriding
 Performance monitoring
 UNIT SHUTDOWN
a) SOAKING(removing hydrocarbon):
1. Begin reducing the reactors inlet temperature to 454C at approx 30
C per hour.

2. At 482C reactor inlet temperature, begin reducing the feed rate

stepwise to design feed rate but not less than 0.75 LHSV. Strive to
reach at 454C temperature.

3. At 454C temp stop chloride injection, and fresh charge to the unit.
Also maintain max recycle gas circulation.

4. Adjust the heater firing to cool the catalyst bed to 399C at approx 30
C per hour. Drain the product separator and all low point drains.
 UNIT SHUT DOWN
• De-pressurize the UNIT;
1. At 399 C reactor inlet temperatures, shut down the heater
firing. Continue recycle gas circulation for 15 to 20 minutes
to cool the heater tubes.

2. Spade suction and discharge lines of compressor before

evacuation, otherwise the compressor seals will damaged.

3. De-pressurize the unit in to fuel gas system up to pressure of

4.5 kg/cm2, drain completely until gas issues and de-
pressurize the unit completely to flare.
 UNIT SHUT DOWN
 Evacuation by ejector system;
1. Evacuate the unit per normal and create a vacuum of 51-63
cm Hg after isolating all the instrumentation and circuits.

2. Break, purge and raise pressure to 3-5 psig with nitrogen.

Repeat this process twice.

3. Check for H2 in gas. If more than 1% vol. breaking vacuum with

nitrogen and testing hydrogen in gas until it is less than 1%vol.

4. Check calibration of the air flow meter and recycle gas flow
meter.
 CARBON BURNING
 B. Engineering jobs for preparation for regeneration;

 C. Carbon burn;
1. Throughout regeneration, maintain record of all
operating conditions and analytical results and graphing.

2. Pressurize the system with nitrogen up to7 kg/cm2

minimum. Ensure nitrogen used contains less than 0.05%
vol. oxygen. And keep nitrogen line-up for emergency
use.
 CARBON BURNING
3. Establish circulation of nitrogen by start up compressor per
normal procedure. Ensure compressor discharge temperature
does not exceed 121 C. increase system pressure to as maximum.

4. Fire heaters and gradually raise RITS to 385 C at the rate of 20 to

30 deg C per hour. Drain all liquid hydrocarbon from regeneration
gas circuit prior to next step.

5. RIT’s are being raised as per step 4, pump a solution of total

alkalinity 1.5-2% wt caustic equivalent into cooler inlet. When a
desired level is achieved stop the injection and start circulation
from bottom.
 CARBON BURNING
6. After 6 hours of circulation, drain the solution, replace it
with fresh one. Establish circulation as before and it should
not be less than 50% of the naphtha charge rate.

7.Confirm strength of the solution from lab after every ½ hour.

Separator PH should remain between 7.5-8.0 and solids
concentration in circulating water should remain below 6-
7 %.

8.Hold ROT’s at 385 deg C until ROT’s Stabilize. Start recording

inlet and outlet temperatures on half hourly basis
 CARBON BURNING
9.When ROT’s have stabilized . Introduce air at suction of
compressor and gradually build an oxygen level of maximum
0.3%vol. in the circulating gas.

10. When an oxygen level of 0.3%vol in circulating gas is

established, increase air flow rate so as to achieve a max.
0.6%vol oxygen level at the discharge of compressor.

11.If carbon burn of in reactor does not start then slowly raise
the temperature from 385 deg C until carbon burning starts.
 CARBON BURNING
 NOTE;
I. During regeneration continuous check out the furnaces.

II. If sharp temperature rise in charge heater may occurred due

to the burning of sulfide in tubes. Immediately furnace fire
must be reduced to maintain RIT 385C.

III. Under no circumstances, the ROT be allowed to exceed 454

deg C. if it does , reduction of air is to be the quickest step. A
high concentration of oxygen may cause high temperature
which can damage the catalyst and reactor internals.
 CARBON BURNING
12.Position an online O2 analyzer/orsat apparatus at below to
carry out gas analysis for oxygen and carbon dioxide
contents both at inlet and out let of reactors.

13.Simultaneous to the introduction of air start PERC injection

at rate 20:1 mole ratio of water to chloride and maintain this
ratio throughout carbon burn.

14.Monitor HCL and SO2 at reactor out let. The SO2

concentration should be less than 25ppm if it increase then
sulfate removal step would required.
 CARBON BURNING
NOTE;
i. PERC injection rate must be carefully controlled to avoid high
temperatures.

ii. The injection of PERC will tend to increase the delta T of reactor 1 which
must be taken in to account.

iii. Keep the concentration of circulating water solids below 6-7%wt to

avoid foaming problem after every two hour.

iv. Check HCL and SO2 after every two-hour at reactors out let and
separator off gas. If these are detected, it means caustic is not doing it’s
job.
 CARBON BURNING
15.A rise in temperature and decrease in oxygen content at
the reactor out let shows the progress of carbon burning.

16.When carbon is completely removed from reactor it is

indicated by reduction of reactor out let temperature
increase of oxygen content at reactor out let gases.

17.Disappearence of delta T across reactor shows

completion of carbon removal.
 CARBON BURN
18. When primary burning of carbon in both reactors is
complete, maintain RIT’s of both reactors at 385 deg C.

19. When primary burning of carbon is complete continue

circulation of nitrogen containing 0.3-0.8%vol.
oxygen for 4 hour.

20. while maintaining RIT’s at 385 C. air may be supplied

to maintain the above level of oxygen and continue
caustic circulation
 PROOF CARBON BURN AND OXIDATION
 Oxidation of catalyst is required in order to complete the carbon
burning, achieve the desired oxidation state of the active metals
and maintain full dispersion of platinum on catalyst.

 If sulfate removal steps is required then first oxidation will be for

4 hours. Prevent upsets during oxidation, purging and reduction
steps, which can cause damage to catalyst.
 NOTE;
The upsets include hydrocarbon contamination, excessive
catalyst temperature caused by residual carbon at elevated
oxygen concentration and a catalyst deficient in chloride.
 PROOF OF CARBON BURNING
1. Increase RIT’s to 510Cover a period of four hour and
PERC injection at the rate of 20:1 water to chloride.

2. Maintaining 8.0%vol oxygen in recycle gas at

discharge of compressor.

3. Check for residual carbon as will be indicated by

decrease in O2 concentration or increased carbon
dioxide production in circulating gas at out let of each
reactor.
 PROOF OF CARBON BURNING
3. The rate of increase in oxygen content should
be as under:-
O2 mol % Time Min

0.8-1.6 30 Check residual

burning
1.6-2.5 30 same

2.5-3.5 30 same

3.5-5.0 30 same

5.0-8.0 30 same
 PROOF OF CARBON BURNING
4.With RIT’s at 510 C increase oxygen in circulating gas to
as per above schedule.

5.During oxidation measure HCL and SO2 at each reactor

outlet.HCL detected should be more than 50 mol ppm
and SO2 less than %-10ppm.

NOTE;
If it is decided to carry out sulfate removal step than
continue with step of COOL DOWN onwards.
 PROOF OF CARBON BURNING
7.The count for this oxidation should be started after ROT’s have
stabilized.

8.At the conclusion of 11 hour of oxidation, four hour if sulfate

removal is required, discontinue Caustic circulation and drain it out
of the system.
9.Water wash the gas circulation circuit by injecting water and
draining it out. it should take minimum time to fill and drain the
system.

10. Terminate the water flushing when water drained which indicates
no more material is being washed from the sysytem.
 COOLDOWN
 It is important to flush and drain the separator and caustic
circulation loop while gas is being circulated at RIT’s of 510 C.

 other wise the catalyst is being cooled and adsorbing excessive

water.

1. When draining and flushing of the basic water is completed

start reducing RIT’s.
2. Continue max circulation of gas to cool the catalyst at 55 deg C
per hour. maintain the oxygen level in circulating gas 5-mole
percent .
3. When ROT’s are below 204 deg C stop and recycle gas
compressor after cutting of furnaces firing.
 NITROGEN PURGE
 Oxygen must be removed from the unit prior to
introduction of hydrogen for sulfate removal or reduction.

 Once through nitrogen purging is recommended over

repeated evacuations and breaking the vacuum with
nitrogen for the following reasons.

 Evacuation will allow moist ambient air to enter the unit

from leakage. This will result oxygen in unit and water pick
by catalyst.
 NITROGEN PURGING
 Evacuation may allow the contamination of oxidized
hydrocarbons from the colder section and dead-end
lines by the catalyst.

1. Depressurize the unit completely.

2. Purge nitrogen in the unit till the vent purge gas at

discharge of compressor contains less than 0.3 mole
percent oxygen,0.1 mole percent CO2,50ppm sulfur
dioxide.
 NITROGEN PURGING
3.Change the nitrogen purge venting position to compressor
suction. This means purging forward through the reactors
and inter-heater.

4.Continue purging until the vented purge gas contains less

than 0.3 mole percent oxygen and 0.1 mole percent carbon
dioxide.

5.Purge all dead-end lines and at the completion of purging,

remove blinds from compressor suction and discharge in
preparation for sulfate removal step.
 SULPHATE REMOVAL
 Excessive sulfur contamination will interfere with successful
regeneration and this interference will depend up on the
amount of sulfur as sulfate, which form ,on the catalyst
during regeneration.

 Sulfate on catalyst promotes platinum crystalline growth and

severely retards metal activity of the catalyst surface.

 Sulfate and sulfur can be stripped from the catalyst by

circulating relatively high purity HYDROGEN at elevated
temperature of RIT’s 510 deg C.
 SULPHATE REMOVAL
 The addition of chloride during sulfate
removal improves the rate of sulfate removal.

 Caustic circulation is required to neutralize

excess chloride in the condenser and
separator.
 SULFATE REMOVAL
1. Connect supply of hydrogen to the reactor inlet. Inject
hydrogen equivalent to no less than 10 volumes of
hydrogen per volume of catalyst.

2. Venting at suction and discharge of reactor to displace

nitrogen from unit. Purge all dead-end lines and drain
all low point.

3. Pressurize the system with hydrogen to minimum

7kg/cm2 and maximum gas circulation.
 SULFATE REMOVAL
4.Fire heater and raise RIT’s to 510 deg C at about 50 deg
C per hour. Maintain 7kg/cm2 minimum hydrogen
partial pressure throughout the sulfate removal step.

5.At RIT’s of 510 deg C start basic water circulation at the

rate of 350 MTD. Control the separator water pH below
8.5 and max to 9.

6.The total alkalinity of separator water should be

controlled between 0.5-1%wt.
 SULFATE REMOVAL
7. The sulfate removal step should be continued
till H2S concentration at the out let of the last
drop below 5.0 PPM.
8. At the conclusion of the sulfate removal step,
stop PERC injection and basic water circulation.
9.Drain all solution from system low points and
water wash. Cut-off heater fires and cool the
catalyst bed 385 deg C.
 PROOF CARBON BURN
 After sulfate removal step is complete and catalyst bed
has cooled to 385 deg C. shut down, isolate nitrogen
purge compressor.

1. Evacuate and nitrogen purges the system three times.

Each time pull a vacuum up to 25 inches of mercury
and break it with nitrogen up to a pressure of 5 psig.

2. Check H2 in gas if it is more than 1%vol. repeat the

same procedure until it is less than 1% vol.
 PROOF OF CARBON BURN
3. Break the last vacuum with nitrogen and raise
the system pressure to a minimum of 3.5
Kg/cm2. Ensure the nitrogen contains less
than 0.5% vol. oxygen.
4.Again re-installed/lined-up compressor per
normal procedure. Establish maximum
circulation of nitrogen. Discharge
temperature of compressor does not exceed
121 deg C.
 PROOF OF CARBON BURN
5.Fire the heaters and raise the temperature RIT’s to 385 deg at a rate
of 25-30 C per hour. Hold RIT’s at 385 C until ROT’s Stabilize.

6.While the RIT’s raised to 385 C, start PERC Injection at reactor inlet
about 20:1.

7.Introduce air such as to give 0.6-0.8 mole % oxygen at the inlet of

reactor one.

8.Note ROT’s for any carbon burn indication .When all signs of residual
carbon burning disappear proceed to establish oxidation conditions.
OXIDATION,COOL DOWN, NITROGEN PURGE

 Repeat the eleven hours Oxidation as per

procedure described previously. Eleven hours at a
water/chloride at 20:1.

 Subsequent to oxidation Cool Down the system

as per procedure described previously.

 Carry out nitrogen purge of the system as per

procedure described previously.
 REDUCTION
 Reduction is achieved through establishing a
hydrogen atmosphere in the system.

 Raised the ROT’s to 427 c and maintain it until

the metal reduction complete.

 Before proceeding to the reduction step, make

sure that the separator is empty.
 REDUCTION
1. Depressurize the system and purge with hydrogen
equivalent to no less than 10 volume of catalyst and
displace nitrogen from compressor inlet and out let.

2. Pressurize the system with hydrogen up to a minimum

7.0 KG/cm2. its purity should be 75 mole percent
minimum.

3. Establish max recycle gas circulation. Fire the heaters and

raise the ROT’s to 427 C at rate of 55 deg C per hour.
 REDUCTION
4.Whilst are being raised, drain regularly separator and all low
points in the cold section of recycle gas circuit at least every
30minutes.

5.Periodically measure H2S content of each reactor effluent

stream to provide a complete sulfuur history of the
regeneration.

6.Hold the ROT’s at 427 deg C for one hour more.

7.Once the reduction is complete , gradually reduce the RIT’s to
399 C by cut off the fire heaters.
 COOLDOWN
 Prior to reactor unloading the catalyst will be cool down
adopting following steps.
 Stop all heater firing

 Cool the reactor to a temperature to 54 deg C. While the

temperature are being lowered hydrogen can be displaced
with nitrogen to cool the reactor at fast track by establishing
maximum flow rate.

 Check the hydrogen content of recycle gas which should be

less than 1%volume.
 COOL DOWN
 Evacuation and breaking it with nitrogen can be
done to bring the hydrogen level at the desired
level.
NOTE;
Allow natural draft of air to flow up through the
reactors bed after opening the inlet/outlet
nozzles and keep on checking O2 concentration
if less than 19.5%, don’t allow any unloading.
 CATALYST UNLOADING/LOADING
1.UN-LOADING/SEIVING:
Dump and screen the catalyst after cooling to a
temperature at which the catalyst Can be safely
handled and reactors inlet inspected.
2.REACTORS LOADING:
 Inspect the outlet distributor to ensure containment of
the ceramic material.
 While the catalyst loading would be done by densely
loading machine, a proper record of loaded catalyst
must be maintained.
 CATALYST LOADING/UNLOADING
 After the catalyst have been loaded, the layers of ceramic
balls will be carefully loaded and leveled. The experts will
advise the loading of catalyst and ceramic balls.
UNIT BOX UP AND OXYGEN REMOVAL:
 Unit is completely boxed up after loading the catalyst.
 Oxygen must be remove from the unit prior to
introduction of hydrogen for start-up.
 Evacuation and breaking vacuum with nitrogen is
recommended and once the O2 contents are less than
0.3 mole percent take the steps.
 CATALYST LOADING/UNLODING
1. Pressurize the system with Hydrogen up-to a
minimum of 7kg/cm2 pressure.
2. Start compressor and start the gas circulation
after establishing lube oil circulation.
• Light up the furnaces and raise the temperature
to 371 deg C gradually and check for H2S at
reactor’s outlet.
1. If H2S appears at reactor outlet go for feed cut
in, otherwise follow pre-sulfiding procedure .
 PRESULFIDING
1. Prepare a 50% solution of carbon disulfide in
naphtha and half fill one of the PERC vessels.
2. Start PERC pump at least 3-4 hours prior to
carbon disulfide injection to fill the lines.
3. When carbon disulfide solution starts coming
out from valve stops PERC pump and close
valve.
4. Decrease RIT’s temperature to 340 deg C and
hold at this temperature.
 PRESULFIDING
5.Start carbon disulfide solution injection into reactor
and check the H2S concentration at reactor outlet.

6.As soon as H2S is detected at reactor outlet stop

carbon disulfide injection.

7. If gas at Reactor outlet does not test positive for

H2S do not inject more than 0.05%wt.sulfur based
on the catalyst loaded in each reactor.
 START UP AND CHLORIDING
1. Adjust separator to minimum 7.0kg/cm2. hydrogen
partial pressure. Gradually raise RIT’s to 370 deg C.
2. When RIT’s are stable at 370-deg C cut-in naphtha
charge at about 160 MTD.
3. Simultaneous to the introduction of naphtha charge
starts PERC injection to maintain catalyst chloride
level.
4. The PERC injection is made to replace the chloride
being leached from the catalyst by the high moisture
content of recycle gas .
 START UP AND CHLORIDING
5.After naphtha charge has been introduced, the
feed rate should then be further increased step
wise over two-hour period to 240 MTD.
6. At same time begin raising the RIT’s to 470 deg C
about 30 deg C per hour.
7.H2S in recycle gas should be less than 2ppm before
RIT’s raised to 470 deg C.
8.When moisture in recycle gas is reduced to below
200 mole ppm raise RIT’s to 480 C.
 START UP AND CHLORIDING
9.When moisture in recycle gas is less than 30 mole
ppm, naphtha feed rate can be increased to normal
and RIT’s can be raised to achieve the desired
product octane and reduce chloride injection.

10.Whenever moisture in recycle gas decreases to

below 25 mole ppm, water injection in feed should
be established to maintain proper moisture in
recycle gas.
 PERFORMANCE MONITORING
 START catalyst performance monitoring and
keep record of all parameters, condition and
laboratory results.
REQUIREMENT AND SPECIFICATION
1.NITROGEN
 The total volume required is about120 catalyst
volume. twise this quantity is required if
sulfate removal step is included.
 PERFORMANCE MONITORING
 Theoretically volume required 2100 Nm3.
SPECIFICATION

Nitrogen Purity 99.5 mol% min

Oxygen and Noble gases 0.5 mol %max

Carbon monoxide 20 ppm max

Carbon dioxide 20 ppm max chloride

water 5 ppm max

 PERFORMANCE MONITORING
2. HYDROGEN

 The hydrogen volume is required is about 60

times Nm3 of catalyst volume. Twice this
quantity if sulfate removal step is included.

 Theoretically calculated volume required is

100Nm3
PERFORMANCE MONITORING
SPECIFICATION
Source Net Plat-forming
Hydrogen purity 75.0 mole % min
Hydrogen sulfide 5.0 mol % ppm max
Chloride 5.0mol ppm max
Carbon dioxide Nil
Nitrogen Nil
oxygen Nil
 PERFORMANCE MONITORING
4. ORGANIC CHLORIDE
 The total quantity of organic chloride is 3-8
%wt upon total catalyst loaded. Twice this
quantity is required if a sulfate removal step is
included.
 Theoretically calculated total quantity
required: 275 Litres