CATALYSTS & TECHNOLOGIES

TECHNICAL BULLETIN:

Platinum-Rhenium Reforming
Catalyst StartUp & Regeneration
Procedure for Semi-Regenerative Reformers

PLATINUM-RHENIUM REFORMING CATALYST

START UP & REGENERATION PROCEDURE

1. Discontinue feed to the unit. Reduce heater firing and feed rate in steps to avoid
heater damage until feed is discontinued. Recommendation to reduce sulfur on
catalyst, do hot hydrogen sweep. With feed out, increase the reactor inlet
temperatures to 950-975°F (510-524°C) while maintaining maximum recycle gas
circulation. Use purge to remove H2S. Discontinue continuous H2O/Cl injection.
Drain all low points in the system to remove residual liquid hydrocarbons. Continue
recycle gas circulation for at least 2 hours.

2. Stop furnace firing. While maintaining recycle gas circulation, cool the reactor
outlets to 700°F (371°C) or lower. Continue to drain all low points.

3. Shut down compressor. Evacuate the unit to 20" of Hg (51 cm) vacuum and repressure
to 5 psig (0.35 Kg/cm2) with nitrogen added at the compressor discharge. Ideally, the
nitrogen should be from a dedicated source (trailer) used only for reformer regeneration.
RECOMMENDATION: If a plant-wide nitrogen system is used instead, check it for
hydrocarbons and H2S prior to use.

4. Evacuate and repressure again as in Step 3.

5. While maintaining a slight positive pressure with nitrogen, install the isolation blinds.
Ideally, these blinds should be installed in such manner that they can be pulled when
the unit is under hydrogen pressure (end of double block and bleed valves away from
the regeneration loop).

6. Make any necessary connections, such as air and wash water, required for
regeneration.
NOTE: To prevent possible lube oil carry-over from portable air compressor,
use a knock out pot between the compressor and the unit.

7. Evacuate the unit to 20" of Hg (51 cm) vacuum and repressure with nitrogen to
50 psig (3.5 Kg/cm2) or minimum pressure required to start the recycle compressor.
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8. Start the recycle compressor according to its standard start-up procedure. Establish
maximum circulation rate.

9. After circulation established, check all low point drains and drain any accumulated
hydrocarbons. If possible, blow out dead end lines with nitrogen to eliminate as much
hydrocarbon from the system as practical.

10. Fire the heaters to bring the reactor inlet temperatures to 750°F (399°C) at a rate of
100°F/hr (55°C/hr). When the reactor inlet temperatures reach 750°F (399°C), hold that
temperature.

11. During the heat-up, when the reactor inlet temperature reaches 600°F (316°C), start
water injection into the line between the feed/effluent exchanger and condenser. Allow
water level to build in the separator until slightly higher than the normal hydrocarbon
level, then stop water injection.

12. Start the caustic circulation pump and circulate water for 10 minutes. Stop
circulation and drain the separator completely. Hydrocarbon will float on top of the
water, so it is necessary to completely drain the separator.

13. Start water injection, build level in separator, circulate, and drain. Refill and drain
the separator a minimum of 3 times. Continue filling and draining separator until no
evidence of hydrocarbon is observed.

14. After the separator is clean and empty, add a 5 wt% caustic or soda ash in water
solution to the separator. Establish circulation. Keep the liquid level in the separator
lower than the typical hydrocarbon level used during the naphtha processing to
minimise the chance of carrying over the solution into the compressor and on to the
catalyst.

PRIMARY BURN

15. With the reactor inlet temperatures still at 750°F (399°C), start air injection at the
compressor suction. Limit oxygen content at reactor 1 inlet to 0.5 mole%. If a parallel
burn of the last reactor is planned, inject air into last reactor inlet and limit oxygen
content to 0.5 mole%. Limit the temperature increase to 100°F (55°C). Do not exceed
850°F (454°C) at the reactor outlets. If the temperature limits are exceeded, reduce the
air injection rate until the limits are met.
If the reactor outlets are below 850°F (454°C) and the temperature increase is
less than 100°F (55°C), the oxygen content could be increased to approach these
temperature limits. Usually an oxygen content of about 0.8 mole% is sufficient.
However, do not allow the oxygen content to exceed 1.0 mole% during the initial phase
of regeneration.

16. Once the burn is established, begin chloride injection. Chloride should be injected
before the respective reactor's heater. The chloride is to be injected at a molar ratio of
20/1 water/chloride ahead of the first reactor. If a parallel burn is
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 performed, inject chloride at a molar ratio of 30/1 water/chloride ahead of the
reactor used for second air injection point. The water content is determined by
assuming the recycle gas is saturated at its temperature and pressure measured at the
separator. Only the pure chloriding agent is to be injected at this time. Be sure that
there is no naphtha in the chloride injection equipment.

17. Check and record the pH of the circulating caustic wash solution during the burn and
oxidation. Maintain the pH in the 7.5 to 8 range. Drain spent solution and replenish
with fresh solution as required. The solids content of the caustic solution will increase
as the regeneration progresses. This could cause plugging problems. Do not allow the
solids level to exceed 10 wt%. Keep the specific gravity of the solution below 1.07 by
adding fresh water when required.
NOTE: Just before the first burning wave exits the last reactor, the pH of
the circulating solution will drop due to the SO2 and HCI leaving the
reactor. Drain spent solution and replace with fresh solution to hold the
pH at 7.5 to 8.

18. If a parallel burn is being used and the initial burn in the upstream reactors finishes
ahead of the last reactor, carefully watch the oxygen content of the recycle gas entering
the last reactor. When the initial burn finishes in the upstream reactors, the oxygen
being injected ahead of the first reactor will not be consumed and will combine with
oxygen being injected into the last reactor. Likewise, if the initial burn in the last reactor
finishes before the initial burn in the upstream reactors, watch the oxygen content of the
recycle gas entering the first reactor. In either case, hold the oxygen content to 1.0
mole% or less. When the initial burn is completed, the oxygen content in the recycle
gas will increase quickly. Keep air injection at compressor suction and discontinue
secondary injection point. Cut back on air injection to maintain no more than 1.0
mole%. Do not let the oxygen concentration fall below 0.4 mole%. Discontinue
secondary chloride injection.

SECONDARY BURN

19. When the burning wave has passed through all the reactors and the oxygen level has
held steady at 0.5 to 1.0 mole%, for 1 hour, increase the reactor inlet temperatures to
850°F (454°C). If additional burning occurs, hold the reactor inlet temperatures where
they are until the burn subsides. Do not exceed 950°F (510°C) during this step.
Maintain the oxygen concentration at 0.5 to 1.0 mole%.

20. When the reactor inlet temperatures are at 850°F (454°C) and the recycle gas
oxygen concentration is steady at 0.5 to 1.0 mole %, increase the oxygen concentration
to 2.0 mole%. Periodically check and drain water from all the low points. After 2 hours
of holding steady at 850°F (454°C) reactor inlet temperature and 2.0 mole% oxygen
concentration in the recycle gas, the regeneration can be considered complete.
NOTE: If the reactor section requires maintenance or if the catalyst is to
be dumped and screened, this is the time to do it.
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MAINTENANCE

21a. For maintenance, cool the reactors to 700°F (371°C) and block in under a positive
nitrogen pressure. If the catalyst is to be dumped, cool the catalyst to about 100°F
(38°C) before shutting down the recycle compressor.

21b. If maintenance was performed on the unit, it will be necessary to heat the catalyst,
introduce oxygen and chloride into the system and set up the caustic water
wash again. Refer to steps 5, 6, 7, 8, 10, 14, 15, and 16. Once any burning subsides at
750°F (399°C) reactor inlet temperature and 0.5 to 1.0 mole% oxygen, increase inlet
temperatures to 850°F (454°C). When burning again subsides, increase oxygen
concentration to 2.0 mole%. When the system is stable, increase the reactor inlet
temperatures to 950°F (510°C) at 100°F/hr (55°C/hr). Watch for additional burning
since some forms of coke burn only at very elevated temperatures. Go to Step 23.

OXY CHLORINATION

22. If no maintenance or catalyst handling was done, increase the reactor inlet
temperatures to 950°F (510°C) at 100°F/hr (55°C/hr). Watch for additional burning
since some forms of coke burn only at very elevated temperatures.

23. Increase inlet temperatures 10 to 15°F (6 to 8°C) to achieve 950°F (510°C)

catalyst bed temperatures. Do not exceed 975°F (524°C) anywhere in the reactor.

24. When the catalyst beds are lined out at 950°F (510°C), slowly increase the oxygen
concentration. For units with compressors that do not have an inert gas buffer on
the lube system, increase the oxygen concentration to 5 mole%. For those units
that have an inert gas buffer on the compressor lube system, increase the oxygen
concentration to achieve an oxygen partial pressure of 25 psia (1.76 Kg/cm2a).
Minimum acceptable oxygen partial pressure is 10 psia (0.70 Kg/cm2a).
NOTE: Verify the maximum allowable oxygen content for which the
compressor is designed to operate and do not exceed. If the maximum
allowable oxygen content is too low to achieve desired oxygen partial
pressure, attempt to increase system pressure.

25. Maintain these conditions for a minimum of 10 hours but not more than 18 hours.
Continue the chloride injection to maintain the 20/1 water/chloride molar ratio
throughout this period. These conditions can be extended beyond 18 hours, but
little additional benefit is expected.

26. After maintaining the above conditions for the desired time, stop the chloride
injection.

27. Stop the caustic water wash circulation. Drain the solution from the system.
Maintain reactor temperatures in the 950°F (510°C) range.
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28. Flush the caustic water wash system with condensate until the inlet and outlet pH
are the same. Stop water injection and completely drain the water. Maintain
reactor temperatures in the 950°F (510°C) range.

29. Stop air and/or nitrogen injection. Block in the control valve and separator vent.

30. Shut down the heaters. Maintain gas circulation to cool the reactors to 400°F
(204°C). Maintain at least 1.0 mole % oxygen in circulating gas until reactor outlet
temperatures are below 800° F (426° C)

31. When the reactor outlet temperatures reach 400°F (204°C), depressure and
repressure with nitrogen until the oxygen is displaced from the system.
Alternatively, if nitrogen inlet line is small and repressuring takes too much time, use
purge and measure oxygen content. Continue nitrogen purge until acceptable low level
of oxygen reached. Then depressure unit.

REDUCTION

32. Repressure the system with electrolytic grade hydrogen to sufficient pressure to
operate the recycle compressor.

33. Light burners as required to raise reactor inlets by 75°F/hr (42°C/hr) up to 400°F
(204°C) reactor outlet temperature. After each reactor outlet temperature reaches
400°F (204°C), increase rate of heating to 75 – 100 °F/hr (42 - 56°C/hr). Continue
heating until all reactor outlet temperatures reach 940°F (504°C) to a maximum of
950°F (510°C).

CAUTION!
Determine the metallurgical limits on maximum temperature of the heaters in hydrogen
atmosphere and do not exceed.

34. Hold reactor outlet temperatures at 940 to 950°F (504 to 510°C) for at least 1
hour. Extend the hold period 1 hour for every 10° F (6° C) below the reactor outlet
temperature of 950° F (510° C).

35. Cool reactor inlet temperatures to 700°F (371°C) at a rate of 100°F/hr (55°C/hr).

36a. Shut down the compressor and depressure the unit to about 5 psig (0.35 Kg/cm2).
Pull the blinds. Repressure the unit with electrolytic grade hydrogen. Re-heat as
required.

36b. If the position of the blinds do not allow them to be pulled with a hydrogen
atmosphere in the unit, completely depressure the unit and repressure with
nitrogen. Continue to depressure and repressure or to purge with nitrogen
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 until the hydrogen content of the gas in the unit is less than 4 vol % or whatever
guideline the refinery has established. Then pull the blinds. Purge the unit with
nitrogen if there is any possibility that air got into the system when the blinds were
pulled. Repressure with electrolytic grade hydrogen and establish circulation. Re-
heat the reactors to 700°F (371°C).

SULFIDING

37. When the entire reactor train is in the 700 to 725°F (371 to 385°C) range, start the
presulfiding. A sulfiding agent should be injected into the inlet of each rector. The
injection should start with the last reactor and proceed toward the first reactor.
The rate of injection should be adjusted so that it takes 10 to 20 minutes per
reactor. The quantity of sulfiding agent to be added is based upon the amount
required to put 0.07% wt% sulphur on the catalyst. Adding excessive amounts of
sulphur is to be avoided. At the completion of adding the sulfiding agent, check for
H2S at the outlet of the last reactor. Suitable sulfiding agents include H2S, DMS,
and DMDS. The use of a liquid sulfiding agent allows a predetermined amount of
sulfiding agent to be placed in a suitable container and injected into the unit by
pressuring the container with nitrogen. Feed should be introduced to the unit
within 1 hour of completing sulfiding. For each hour delay beyond the 1 hour limit,
add 0.02 wt% sulfur to each reactor. When the delay becomes so long that more
than 0.05% wt% sulfur would have to be added to the unit, wait until it is certain
that feed introduction can occur and add 0.05 wt% sulfur just before feed
introduction.

FEED INTRODUCTION

38. Increase unit pressure to operating level on low pressure units or to at least 200 psig
(14 Kg/cm2) at the separator on high pressure units. While maintaining
reactor outlet temperatures at 700 to 725°F (371 to 385°C), start feed to the unit.
The feed rate should be half the typical rate or preferably higher. If possible, use feed
rate to provide LHSV greater than 0.75 hr-1, even if that rate is greater than half the
typical feed rate.

39. Raise the reactor inlet temperatures to 800°F (427°C) taking 1 hour to reach 800°F
(427°C). Begin chloride injection at a level of 15 ppm wt in the feed. Monitor the HCI in
the recycle gas by checking at the compressor discharge. (See Step # 46). If an
excessive exotherm is observed in the last reactor(s), inject 0.02 wt% sulphur into the
affected reactor(s) by use of the presulfiding apparatus.

40. Hold reactor inlet temperatures at 800°F (427°C) for 4 hours. During these 4 hours,
increase the feed rate to full charge rate. Keep the H2:HC ratio at 6:1 or higher. Line
out the separator pressure and put the separator on level control. Line out the heaters
and put them on control if not already on control. If a separator product sample is
taken, it should appear cloudy which indicates water is being
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 driven out of the system. If high hydrogen purity recycle gas causes compressor
problems, add nitrogen to increase recycle gas mole weight. Keep hydrogen purity
of recycle gas greater than 80 mole %.

41. Raise the reactor inlet temperatures to 850°F (454°C) at a rate of about 4°F/10
minutes (2°C/10 minutes). All temperature adjustments should be made slowly to avoid
wide swings in reactor temperature.

42. After reaching 850°F (454°C), raise the reactor inlet temperatures to 885°F
(474°C) at a rate of about 1°F/10 minutes (1°C/20 minutes). Attention to
temperature adjustments is critical. The unit is still drying out and wide swings in
temperature are to be avoided.

43. Determine the product octane.

DRY OUT

44. If octane level is tolerable, maintain reactor inlet temperatures at 885°F (474°C) for
2 days. If the octane level happens to be higher than needed, lower reactor inlet
temperature until required octane level is reached and hold that temperature for 2 days.
If the octane level at 885°F (474°C) is still too low, slowly increase the reactor inlet
temperature to reach the required octane and hold for 2 days. Do not exceed 900°F
(482°C) during this 2 day period even if the desired octane level is not achieved. For
best unit performance, this dry-out should be done at the lowest acceptable
temperature.

45. Maintain chloride injection at 15 ppm wt. Check the HCI level at the compressor
discharge each shift. The level should be greater than 1 ppm vol but not more than 5
pm vol. When the recycle HCI level climbs over 5 ppm vol and holds there, cut the
chloride addition in half. Continue to monitor the HCI level in the recycle gas and adjust
the addition rate as required. Keep at least 1 ppm vol in the recycle gas at all times
during the dry-out phase. If the HCI level in the recycle gas never reaches 5 ppm vol
after 3 days at an injection rate of 15 ppm wt in the feed, contact your Criterion
representative.

46. After 2 days at the temperature set in step 44, increase the reactor inlet
temperature as needed to achieve the desired product octane level. Increase the
reactor inlet temperature at a rate of 5°F/hr (3°C/hr). Check product octane at each
temperature plateau. If a temperature of greater than 920°F (493°C) is required, hold at
920°F (493°C) for two days before going higher in temperature.

47. After holding at 920°F (493°C) for 2 days if required, increase reactor inlet
temperature to obtain desired product octane level. Raise reactor inlet temperature at a
rate of 5°F/hr (3°C/hr). Check product octane at each temperature plateau.

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48. If available, put the recycle gas moisture analyzer on line as soon as possible.
Monitor the recycle gas moisture level during the drying out period. Once the unit dries
out, it will be necessary to inject water or alcohol to hold the recycle gas moisture level
in the 10 to 20 ppm vol range. The quantity of chlorides being injected should have
been reduced following the guidelines in step 45. When the unit is lined out, the target
recycle gas chloride level is a trace to 1 ppm vol.

ADDITIONAL INFORMATION

All catalyst information supplied by CRITERION is considered accurate but is furnished with
the express understanding that the customer receiving such information shall make its own
assessments to determine suitability of such information for customer's particular purpose. All
purchases of catalyst from CRITERION are subject to CRITERION's standard terms and
conditions of sale (including CRITERION's product warranties) set forth in a sales proposal,
sales contract, order acknowledgement, and/or bill of lading.

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EMAIL - publicaffairs@criterioncatalysts.com

PT-RH/2-02/8-8