Helping Make

Products BetterTM

Loading, Start-up and Regeneration

I. Introduction and Operating Principle

BASF Catalyst PuriStar®R 3-17RED represents a newly developed technology for the removal of
trace levels of Carbon Monoxide (CO), which are typically around 500 ppb-vol. or less, from
Liquid Hydrocarbons; and in particular, from polymer grade propylene.

The heart of the technology is a special tablet-form catalyst containing CuO, ZnO and ZrO2 plus
promoters. CO removal is achieved by flowing the liquid hydrocarbon through a fixed bed of the
catalyst at mild temperatures, typically 20-40°C.

The R3-17RED is delivered pre-activated and is ready for use. Once delivered to the customer, the
catalyst can be operated with no further pre-treatment.

As CO comes in contact with the surface of the catalyst, CO removal is effected by reaction of CO
with surface sites of the activated metal oxide matrix; the CO thus removed is in a further oxidized
state and remains on the surface of the catalyst until regeneration. During regeneration the
removed CO is rejected from the catalyst bed in the form of CO2 which is carried out by the
regeneration gas.

Due to capacity factors and on-stream requirements, two vessels are generally required for
continuous operation; one vessel is in operation, the other in standby or being regenerated.

II. Loading of the Catalyst

Although the primary purpose of the partial oxidation (step 2 of the factory activation procedure) is
to achieve optimum activity for CO removal, it also provides some passivation, such that a brief
(less than 1 h) exposure to stagnant air at ambient temperature should not cause significant heating
of the catalyst. Nevertheless, IT IS ESSENTIAL TO AVOID OXIDATION OF THE CATALYST
DURING LOADING, otherwise its performance may be adversely affected. Therefore, minimizing
contact of the catalyst with air, and excluding air from the reactor vessel once catalyst loading has
commenced, is a critical requirement for a successful loading.

Loading of the catalyst into the vessels, should be consistent with the following guidelines:

BASF SE
G-CCP/DP
67056 Ludwigshafen
[email protected]
1. Before the catalyst is charged, the vessel should be cleaned, leak-tested, and inspected. The
inside walls and any internals must be clean. The condition of the vessel (if not new) should be
noted with respect to corrosion and wall thickness.

2. Before charging catalyst to the vessel, it is recommended to mark the inside wall of the vessel
with chalk or soap at the targeted heights for the layers of support material, catalyst and hold-
down balls respectively. This will facilitate leveling of the bed, and will also assist in getting the
correct quantities of materials loaded.

3. A suitable bed support must be installed before catalyst loading begins. See Figures 1 - 3 for a
typical bed support design. Any dumped support must be leveled before adding the catalyst.

4. Either before or after installing the bed support, but before beginning to charge the catalyst
itself, the atmosphere inside the vessel must be made inert, by purging with nitrogen and/or
pressurizing/depressurizing repeatedly with nitrogen, until the oxygen content is below
100 ppm. From this point on, a moderate nitrogen sweep from bottom to top should be
maintained throughout the catalyst loading, and any personnel working inside the vessel or on
the platform above the vessel must use a breathing air mask in order to avoid the hazard of
asphyxiation.

5. The catalyst can be charged directly from drums, or from a loading hopper. If loading hoppers
are used they must be nitrogen-purged before catalyst is placed inside, and kept air-free to
avoid oxidation of the catalyst. Only 1 drum at a time should be opened, and it should be
emptied immediately and with minimal air contact, into the hopper or reactor.

6. The catalyst must not be allowed to free-fall more than 1 meter. The free-fall can be controlled
by loading through a funnel with attached hose (hence "sock-loading"). Pinching down on the
end of the hose to keep the hose full of catalyst is advised.

7. If personnel must be inside the vessel during the filling or at any time after catalyst loading has
commenced, boards should be placed on top of the catalyst for the workers to stand on.
Treading directly on the catalyst should be avoided, as this can lead to attrition and the creation
of catalyst fines in the bed.

8. After all catalyst has been loaded into the reactor vessel, the bed must be leveled.

-2-
9. Finally, the hold-down layer of inert balls (see Figure 2) must be put in and leveled, then the
vessel closed and purged further with nitrogen to remove any oxygen which may be present in
the vessel’s atmosphere.

Figure 1

Inert support balls

PuriStar® R3-17RED

Inert support balls

-3-
Bed support and hold-down illustration (continued)

Figure 2. Bed hold-down detail

150 mm of 25mm balls

TOP OF CATALYST
floating screen

Figure 3. Bed support detail

floating screen
CATALYST

75 mm of 6mm balls

75 mm of 12mm balls

Bottom head filled with

Johnson Vee-wire screen “elephant stool” with solid

-4-
III. Putting a Reactor On-Stream

Whether putting a reactor on-stream for the first time after filling with new catalyst, or after having
been regenerated (and/or in standby following regeneration), the same procedure applies (remark:
a preloading by exchange of Nitrogen with Propylene vapor first before charging liquid propylene
can be applied instead of direct dosing of liquid propylene).

1. Pressurize the vessel with nitrogen to a pressure approx. 1 bar higher than the vapor pressure
of propylene at operating temperature. This is to prevent flashing of propylene liquid into vapor
when introducing liquid into the vessel. Do not pressurize too rapidly, however, or the catalyst
bed can be disturbed; recommended maximum rate of pressurization is 1 bar per minute.

2. Introduce liquid propylene from the bottom of the vessel at a controlled rate such that the linear
velocity (rate of rise of the liquid level inside the bed) is preferably between 1 meter per minute
and 2 meters per minute. It is important not to fill too slowly in order that the heat of adsorption
of propylene on the catalyst surface is dissipated by transfer of the heat into the liquid
propylene. And it is important not to fill too fast in order to avoid flotation of the catalyst bed.

3. The pressure inside the vessel should be monitored. Gas may be bled out as necessary to
allow the vessel to fill, but sufficient pressure maintained in order to prevent the propylene from
vaporizing.

4. Once the vessel has been completely filled with liquid, a minimum flow of at least 30% of the
design rate should be established through the bed, and then rates can be gradually brought up
to operating requirements over a reasonable period of time (at least 1 hour).

IV. Regeneration Procedure

Typically the design cycle length of R3-17RED is in the range of 1 – 12 weeks based on design
feed compositions. Actual feed compositions may differ from design, and may vary over time. In
addition, direct analysis of CO at < 1 ppm in propylene is quite challenging. Therefore it is difficult
to predict precisely the best time to regenerate the bed. Correlating cycle length of the CO-removal
beds with consumption of polymerization catalyst (i.e. “mileage”) is probably the best way to judge
when to switch and regenerate the spent bed. The procedure for the regeneration is as follows.

-5-
1. Isolate the vessel to be regenerated; this may involve insertion of pancake blinds as well as
closing of the isolation block valves.

2. Drain the vessel by pressuring or pumping out until the vessel is empty of liquid propylene.

3. Purge with nitrogen at ambient temperature for at least 8 hours, to remove most of the
remaining liquid propylene from the pores of the catalyst. This purge step should be done with
a gas flow of at least 300 Nm3/hr per cubic meter of bed (GHSV = 300 hr-1) A; this nitrogen flow
should be maintained throughout the subsequent steps as well. Initially the purging should be
done with a high backpressure of at least 1 bar above the bed pressure, to retard the rate of
vaporization of propylene within the pores of the catalyst; still, some sub-cooling of the bed may
occur during this step due to the latent heat of vaporization of the olefin. Gradually decrease
the pressure, with an eye on bed temperatures, and continue purging as long as the
hydrocarbon level in the purge gas is dropping sharply (this can be checked via GC or portable
gas monitor).

4. Begin heating with nitrogen, again with a gas flow of at least 300 Nm3/hr per cubic meter of
bed. A minimal backpressure (1 bar or less) is advised for this step and the subsequent steps.
Start with nitrogen at ambient temperature and gradually ramp up the temperature at a rate of
50 °C / hr. Do not exceed this ramp rate in order to avoid excess thermal stress on the catalyst.

5. Continue increasing the nitrogen temperature until the gas temperature entering the reactor is at
a level to ensure a bed temperature of between 200-220°C; then hold the gas temperature at
this temperature and heat the complete bed to this level. The bed is now ready for the oxidative
step (from fifth regeneration onwards).

6. In the first four regenerations, a treatment equivalent to 6 hours N2 at a GHSV of 300 hr-1,
should be carried out, without any dosage of Oxygen. Then proceed to step 13.

7. In the fifth or any regeneration thereafter, a treatment equivalent to 6 hours with 1300 to
1500 ppm-vol of O2 in N2 at a GHSV of 300 hr-1, should be carried out. (Hint: if the N2 system
can only achieve e.g. a GHSV of 200 hr-1, the treatment should still be with 1300 to 1500 ppm-
vol of O2, but with a longer duration of 9 hours). Do not dose more than 3 NL of Oxygen per liter
of catalyst during the regeneration. Per 1000kg of catalyst R3-17RED about 9500 NL air are for
a full regeneration procedure (equivalent to 1990 NL O2).
A
GHSV = Gas hourly space velocity [Nlit Gas / hour / lit catalyst]

-6-
8. Begin adding air into the nitrogen at a rate that results in an oxygen concentration of 1300 to
1500 ppm-vol entering the reactor.

9. Maintain the flow of gas with 1300 to 1500 ppm-vol of oxygen at GHSV = 300 hr-1 and 200-
220°C bed temperature, for a period of at least 6 hours (for 10 m³ catalyst). During this step,
the CO removed during the previous cycle will be rejected from the bed in the form of CO2.
Additionally, any propylene remaining on the surface of the catalyst after the purge (Step 3
above) will be oxidized to CO2 and water.

10. If possible, monitor the effluent gas for hydrocarbon, O2, CO2 and/or H2O. Such measurements
may help confirm the progress of the regeneration.

11. Now the bed must be purged of oxygen and cooled. Stop the air flow. Maintain nitrogen flow
and 200-220°C bed temperature for 4 hours to achieve removal of most of the oxygen from the
catalyst pores, then gradually decrease the gas temperature (max. ramp rate of 50°C / hr) until
the nitrogen temperature is down to 25°C, then continue cooling with N2 at 25°C until the entire
bed has been cooled to below 50°C.

12. Final check of the O2 content of the purge gas with an O2 analyzer should be made to ensure
that the bed has been effectively purged of oxygen (O2 level of < 1 ppm).

13. The regeneration procedure is now completed and the bed can be placed in standby. A positive
nitrogen pressure must be maintained, to prevent the ingress of air, until the bed is placed back
in service.

V. Shut-down and de-commissioning of a Reactor

Shut-down for temporary de-commissioning

If the reactor, containing the PuriStar® R 3-17RED bed needs to be shut down for only a few
hours, it can be kept under propylene. However, if the shut-down is expected to last twelve
(12) hours or more, it is recommended to release the process liquid from the reactor vessel in
order to not accumulate any impurities which might be formed by slow chemical reactions
between the PuriStar® R 3-17RED catalyst and the stagnant propylene liquid, causing

-7-
oligomerization and polymerization reactions. It is recommended to keep purge the reactor
with an inert gas, such as nitrogen.

It is recommended to drain, pressure or pump out the process liquid and then to purge with
nitrogen at ambient temperature and pressure before blocking in the reactor vessels by
valves. The unit should be kept under a dry blanket of inert gas to avoid moisture pick-up and
the need for re-drying before bringing the purification reactor back on-stream.

Shut-down for permanent de-commissioning

If the PuriStar® R 3-17RED bed has reached the end of its lifetime, the reactor vessel needs to
be shut down and de-commissioned in order to remove the catalyst bed from the reactor
vessel. Again, it is necessary to release the process liquid from the reactor vessel as
described above for a temporary shut-down. The partially reduced catalyst has to be re-
oxidized before the reactor can be opened and the catalyst can be exposed to air. Prior to
opening the reactor vessel it must be ensured that the reactor does not contain any flammable
atmosphere. Residues of vaporized hydrocarbons, which could spontaneously ignite if
contacted with the atmospheric oxygen, must be removed by blow-drying the catalyst bed with
ambient-temperature nitrogen at a recommended GHSV of 300 hr-1. During this procedure the
hydrocarbon content of the nitrogen shall be analyzed at the reactor outlet to ensure the
absence of any hydrocarbon residues to levels below the explosion limit.

As the PuriStar® R 3-17RED bed has been operated in its partially reduced form and may
have retained much of its reduction degree, it possesses reactivity when exposed to air. One
option to remove its reactivity is to oxidize the bed with air diluted in nitrogen after carefully
removing residual hydrocarbons to below the explosion limits. This can be performed by
applying a flow of 1% Oxygen in Nitrogen (air mixed with Nitrogen) at a bed temperature of
160degC to avoid any over-temperatures above 230degC caused by exothermic reaction.

-8-
A suitable technique for passivating the catalyst is to flood the vessel with water until the
catalyst is completely covered. Thereafter, the catalyst shall be released through the catalyst-
unloading nozzle at the bottom of the vessel into flow-bins or empty catalyst drums. In these
drums again the catalyst shall be kept under water. In this case the oxygen dissolves slowly
into the water and re-oxidizes the catalyst without significant temperature increase.

We recommend NOT contacting the catalyst with steam or with combinations of steam and air.
With steam the catalyst can undergo hydrothermal degradation, ending up in the formation of
a concrete composite of the catalyst tablets, which could then only be removed from the
reactor by massive mechanical treatment (e.g. pneumatic hammer or explosives).

VI. Unloading and disposal of spent PuriStar® R 3-17RED

After carefully re-oxidizing and then removing the hydrocarbon hold-up of the reactor vessel
and an eventual passivation, the spent PuriStar® R 3-17RED catalyst can then be safely
removed either by allowing it to drop out of a nozzle at the reactor bottom, or by vacuuming it
out of the reactor top with an appropriate vacuum apparatus.

Flooding with water can make the catalyst removal more difficult, however, because if left
under water for a while the PuriStar® R 3-17RED tablets tend to stick together and may not
freely flow out of the vessel by gravity alone. In this case some "rodding out" may be required
to assist in removing the catalyst, if unloading from the bottom of the vessel. Due to the
requirement of special activation of the catalyst an unloaded catalyst cannot be reused.

Prior to making arrangements for disposal or reclamation of spent PuriStar® R 3-17RED, the
EPA TCLP test should be applied to determine the material's classification, i.e. hazardous or
non-hazardous. Up to now, in all cases where the TCLP has been applied with arsenic levels
up to 1 wt%, the material has been classified non-hazardous (it "passes" the TCLP). For the
reactor service and catalyst disposal we recommend different companies depending on the
region, where the plant site is located. For additional information about disposal or reclamation

-9-
of spent catalysts, or current contacts to firms who can assist in the placement of spent
catalysts, please contact your BASF representative or the regional BASF Catalysts Centre.

The data contained in this publication are based on our current knowledge and experience. In view of the
many factors that may affect processing and application of our product, these data do not relieve processors
from carrying out their own investigations and tests; neither do these data imply any guarantee of certain
properties, nor the suitability of the product for a specific purpose. Any descriptions, drawings, photographs,
data, proportions, weights etc. given herein may change without prior information and do not constitute the
agreed contractual quality of the product. It is the responsibility of the recipient of our products to ensure that
any proprietary rights and existing laws and legislation are observed (23.3.2012).

-10-