OPERATING INSTRUCTIONS

Johnson Matthey PURASPECTM ABSORBENTS - FOR

PROPYLENE PURIFICATION DUTY

Introduction

These instructions provide information relating to handling PURASPEC 7040 absorbent,

together with guidelines for start-up, operation and shut-down for the PURASPEC 700
process. The requirement for this process is to remove trace amounts of COS and Arsine
from refinery propylene streams.

Johnson Matthey supplies a range of PURASPEC process technologies utilising a variety

of absorbents. The formulation of each is designed and optimised for particular types of
application and conditions. The product formulations are proprietary but following table
summarises the key data for PURASPEC 7040:

ABSORBENT PURASPEC 7040

COMPOSITION CuO / ZnO
Alumina

FORM Spherical Granules

DIAMETER (mm) 2.8 - 4.75

CHARGED
BULK DENSITY 0.75 (47)
kg/l (lbs/ft3)

PURASPECTM is a trademark of the JM Group of Companies

Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at time of going to
press, and is given in good faith, but it is for the User to satisfy itself of the suitability of the Product for its own particular purpose.
JM gives no warranty as to the fitness of the Product for any particular purpose and any implied warranty or condition (statutory or
otherwise) is excluded except to the extent that exclusion is prevented by law. JM accepts no liability for loss or damage (other than
that arising from death or personal injury caused by JM's negligence or by a defective Product, if proved), resulting from reliance on
this information. Freedom under Patent, Copyright and Designs cannot be assumed.

Absorbent Storage, Handling, Charging and Discharging

Before charging, handling and discharging absorbents any potential risk to health during
these activities should be assessed and appropriate precautions taken. In addition Johnson
Matthey's brochure "Catalyst Handling" should be consulted.
Absorbents can be supplied in steel drums (approx. 0.2 m3 (7 ft3)) or Intermediate Bulk
Containers (IBCs e.g.. "big bags", approx. 1 m3 (35 ft3)).

DRUM STORAGE
PURASPEC 7040 is most commonly supplied in steel drums, with polyethylene liners,
which are usually banded on pallets to allow easier movement.
 Absorbent Net Weight Tare Drum Packing
kg (lbs) kg (lbs) Dimensions
cm (in)
PURASPEC 7040 150 (331) 18 (40) 88 x 59 x 59 (35 x 23 x 23)

Drums must not be stacked on their sides or stacked more than four drums high, even when
held on pallets. Taller stacks tend to be unstable and the lower drums can be crushed. The
metal drums are usually suitable for outside storage but they should be kept under cover and
away from damp walls and floors. The lids should be left on the drums until just before the
absorbent is to be charged. If the lids are removed for some reason it is important that they
should be replaced as soon as possible, so that contamination of the absorbent is avoided. If
the drum lid cannot be replaced, then the absorbent should be redrummed without delay. If
the liner is damaged and any contamination occurs it is difficult to assess the extent of any
damage without full examination of the absorbent. If there is any doubt about the state of
the absorbent it is best not to charge it to the reactor.

DRUM HANDLING
Drums should be handled as carefully as possible. They must not be rolled. They are often
supplied on pallets, which reduces the likelihood of damage in transit but requires suitable
fork-lift trucks and a paved area on which to handle the pallets. The fork-lift truck to be
used for unloading the pallets should be fitted with rim or body clamps to avoid damage to
the drums. The use of containers for either drums or palleted drums eases shipment and
further reduces the likelihood of damage in transit, but again suitable fork-lift trucks must
be provided at the
reception point. It is important not to use standard forks to lift the drums under the rolling
hoops, as damage to the drums and catalyst is almost inevitable.

BIG BAGS (IBC)

PURASPEC 7040 can be supplied in polyethylene-lined woven polypropylene bags, fitted
with four canvas lifting loops. Each bag is usually transported on a standard wooden pallet.
They should not be stacked vertically. Absorbent can be stored for long periods in IBCs
provided that they are suitably protected from rain and standing water. Indoor storage is
preferable. IBCs should be inspected carefully when they arrive on site for damage in transit
and periodically prior to charging.

PRE-CHARGING CHECKS
Before the absorbent is charged it is important that the condition of the absorbent support
grid in the vessel and any supporting materials such as inert balls should be checked. In
most instances a layer of 19 mm (3/4 inch) alumina balls on top of the catalyst is
recommended to minimise the effect of plugging from rust or scale. Some form of light
metal shield or "spider" fitted into the discharge manhole prevents inadvertent absorbent
discharge when the manhole cover is removed. The vessel should be clean, dry and free
from loose scale and debris. It is important to ensure that the charging level is clearly
defined, so as to avoid underfilling or overfilling.
It can be valuable to check that any thermocouples and other instrumentation are correctly
installed before charging is commenced by warming them in turn to ensure that the correct
indication is given on the instrument panel.

ABSORBENT CHARGING
The absorbent may be loaded directly from the drums or from intermediate bulk containers
which are usually brought to the charging point. The five general rules for charging
absorbents into vessels are:
a the absorbents should not have a free fall of more than 1 meter (3 ft).
b the absorbent must be distributed evenly as the bed is filled.
c Where ceramic balls are to be used for hold-down, it is important that the bed is levelled.
d Usually vessel entry during charging can be avoided but, if it is necessary to walk on the
absorbent bed, the load should be spread as much as possible by using charging
boards on top of the absorbent.
e The absorbent is hygroscopic, but is supplied dry, so the absorbent should not be exposed
to excessive moisture during loading. If the downstream catalyst or process is extremely
water sensitive, the loading should be done under dry nitrogen.

ABSORBENT DISCHARGE

The absorbent is usually discharged from the vessel by vacuum or by gravity flow from the
bottom of the vessel.
Self-heating effects may be exhibited by all high surface area oxidizable materials. Spent
absorbents are no different in this respect. Furthermore they should be assumed to
be potentially combustible because of the likely presence of adsorbed hydrocarbons.
Spent PURASPEC 7040 is not pyrophoric. However experience has shown that,
under certain conditions, ferrous sulphide, which is classified as pyrophoric, may be
formed on metal surfaces of upstream pipework and subsequently filtered out on top
of the absorbent bed.
When all liquid has been removed from the vessel, the catalyst is discharged from the vessel
according to the following procedure.

1 Refer to shut-down instructions later on is this leaflet for recommended method of

draining liquid propylene from the reactor and initially depressurizing. Purge the
reactor free of propylene using an inert gas ( e.g. nitrogen, containing < 0.01 %
oxygen ). Care must be taken to monitor nitrogen, which has not been produced
cryogenically, to ensure that purity is maintained. Also, the nitrogen should not
contain any reducing gases (hydrogen or carbon monoxide). The recommended
technique is repeated pressurizations and depressurizations followed by a straight
through purge.
2 If hot nitrogen has been used, cool the reactor to below 50 oC (120 o F) in a flow of inert
gas. The propensity towards self- heating is enhanced at elevated temperatures.
3 Discharge the absorbent, ensuring that there is no access of air to the material in the
vessel. Discharge can be by vacuum extraction or by gravity flow from the bottom
of the vessel. In the latter case, as the absorbent falls from the bottom manhole,
water sprays should be available. The propensity towards self-heating can be
negated by minimising the exposure to air. However, if material warming is
observed a gentle spray of water will aid cooling. If it is necessary to use water
sprays care should be taken not to scatter the spent absorbent and to contain liquid
run-off.
4 Discharge the absorbent into suitable containers with only the absorbent discharge
manhole open. Air must prevented from entering the vessel to avoid localised
heating.

DISPOSAL OF DISCHARGED MATERIAL

Through the "PURACARE"TM or "Catalyst Care"SM Program, Johnson Matthey offers the
environmentally safe recycling of their complete product range. Advice is also available on
the material characterisation, packaging, labelling, documentation for transport and
reprocessing, including preparation of Material Safety Data Sheets for the spent material, in
line with ECMA guidelines.

Health and Safety Precautions

Operators should be aware of the hazards associated with the use of absorbents and draw up
the appropriate safety instructions.

1 Discharged Self -heating Absorbents

Absorbents discharged in a potentially self-heating state must be kept separate from
flammable materials. Transport of such absorbent should only be in suitable
containers. Dumps of the absorbent should be within reach of water hoses so that
any overheating that occurs can be controlled. Large quantities of unconfined
material should be avoided as high temperatures can build up within a heap of
oxidising sulphided absorbent.
PURACARETM is a trademark of the JM Group of Companies
Catalyst CareSM is a service mark of the JM Group of Companies

2 Discharged Spent Sulphur Absorbents

The discharged absorbent contains sulphides and should not be stored near acids.
Accidental contact of the spent absorbent and acid would result in the evolution of
hydrogen sulphide (H2S). If the absorbent has been used in an arsine (AsH3)
removal duty then arsenic containing compounds will also be present.

3 Dust Exposure
Short-term exposure to the metals and metal oxides used in absorbents may give rise to
irritation of the skin, eyes and respiratory system. Over exposure can give rise to
more serious effects. Product safety data sheets should be consulted for information.
Absorbents should be handled as far as possible in well-ventilated areas and in a
way which avoids the excessive formation of dust. Operators who handle absorbent
must wear suitable protective body clothing, gloves and goggles. Inhalation of dust
should be avoided, and the appropriate occupational exposure limits should be
strictly observed. If these limits are likely to be exceeded then respiratory protection
should be used. Everyone involved in the handling operation should clean up
afterwards and, in particular, must wash before eating. Clothing should be changed
at the end of each Shift, and more frequently if contamination is heavy.

4 Ergonomics
Physical hazards arise from the handling of drums, materials and lifting equipment.
Personnel should be aware of these and appropriate precautions taken.

Start-up, Operation and Shut-down of PURASPEC 7040

Absorbent For Propylene Purification Duty

START-UP

WARNING: PURASPEC 7040 CONTAINS COPPER OXIDE THAT IF SUBJECTED

TO A REDUCING ATMOSPHERE (HYDROGEN OR CARBON MONOXIDE)
CAN RESULT IN A LARGE EXOTHERMIC REACTION. An exotherm of 30 oC
(55 oF) per 1% hydrogen in the feed is possible.
1 The normal liquid flow direction for this type of service is downflow. If upflow is used
care must be taken to avoid fluidization.

2 It is assumed that prior to the commissioning, the vessel has been sealed, pressure tested
and left under nitrogen pressure greater than that of the vapour pressure of the
hydrocarbon at local ambient temperatures. If the purging with nitrogen is upflow
then care is needed to ensure that the bed does not fluidize.

3 The absorbent can adsorb a few weight percent moisture on standing in air. If the
downstream process cannot tolerate any water, then it is advisable to dry out the
absorbent, or load the catalyst under an inert environment (see loading procedure).
Experience has shown in most cases a dryout is not necessary. If necessary, Johnson
Matthey can be contacted for a drying procedure consisting of hot nitrogen purging.

4 To avoid cooling to sub-zero temperatures through flashing of liquid propylene to vapour

it is recommended that the vessel is initially pressurized with nitrogen either to the
operating pressure or as a minimum to just above the vapour pressure at local
ambient conditions eg. 10.2 bar abs at 20oC. The rate of pressurization should not
exceed 1 bar (14.5 psi) per minute below 10 bars (145 psig) and 10 bars (145 psi)
per minute above 10 bars (145 psig).

5 Allow liquid to enter from the bottom of the vessel. Fill the vessel at a slow rate to avoid
fluidization. Upflow filling also allows the nitrogen to be displaced to flare. All
nitrogen must be removed to avoid gas blanketing of the bed. As the vessel is
filling, increase the pressure up to operating pressure (keeping the exit valve shut).
Monitor the pressure in the vessel. The rate of pressurization should not exceed 1
bar (14.5 psi) per minute below 10 bars (145 psig) and 10 bars (145 psi) per minute
above 10 bars (145 psig).

6 Once at operating pressure slowly open the exit valve and bring the bed into service.
Monitor bed pressure drop.

OPERATION

1 Ensure that the vessel is free from vapour/gas, and kept full during normal operation.
Ensure that no hydrogen or carbon monoxide is present or a possibility exists for a highly
exothermic reaction.

2 The absorbent will give trouble free service and usually requires very little attention
during steady operation until it is saturated with sulphur. There is no temperature
rise as sulphur is absorbed.

3 Absorbent performance should be followed by recording the inlet and exit sulphur and
arsenic contents at regular intervals during use. If available, speciating the sulphur
compounds (H2S, and mercaptans) will help in evaluating performance. The
sulphur and arsenic content of the feedstock, which is absorbed in the bed, can be
integrated so that the appropriate time for absorbent replacement may be
antJMpated.
By-products

Carbon Dioxide is a poison for many downstream catalysts. PURASPEC 7040 does not
release CO2.
A small amount of reaction water is formed. One mole of water is formed for every mole of
H2S in the propylene feed. The product can also adsorb moisture from the
atmosphere during loading. This water will then be desorbed gradually into the
product. Slightly less than one mole of water is released for every mole of
mercaptan removed. Three moles of water is formed for every mole of AsH3
removed.

Temperature
When setting the operating temperature, especially after plant upsets, the following general
rule must be remembered.
Although sulphur and arsine can be absorbed at any temperature, removal is most effJMent
at or above design temperature. Operation at lower temperatures than the optimum when the
bed is almost saturated may lead to sulphur or arsenic slip.

Other Contaminants
1 Ammonia or any other alkali species will poison the acid sites on the alumina support.

2 Heavy metals such as Lead and Vanadium may be partially removed by the absorbent.
These metals will slightly affect the loading of the sulphur.

3 Particulate materials (e.g. rust and scale) can plug the catalyst leading to high pressure
drop. Since propylene streams are normally clean, this is not normallly an issue

SHUT-DOWN

1 If a shut-down is only temporary (less than 24 hours) the vessel can remain filled.

2 During a plant shut-down (over 24 hours) the vessel should be isolated. With propylene
special care should be taken to ensure that boiling in the bed does not occur during
depressurization which may cause serious physical damage to the absorbent due to
movement of the particles. It is also important to ensure that the temperature on
depressurisation does not fall below the design temperature of the vent pipework
and the vessel. Once drained of propylene the vessel should never be depressurized
rapidly as it has been known for liquid held up within the absorbent particles to
suddenly flash off resulting in serious damage.

The liquid propylene should be drained from the vessel without allowing depressurisation to
below the vapour pressure at local ambient conditions eg. 10.2 bar abs at 20oC in
order to prevent boiling. The rate of depressurization should not exceed 1 bar (14.5
psi) per minute above the vapour pressure at local ambient conditions. Pressure
should then be maintained using inert gas eg. nitrogen (with less than 0.01%
Oxygen) whilst purging residual propylene to flare. This will allow trapped
propylene to escape from the absorbent. Special care should be taken to prevent
reducing gases (hydrogen or carbon monoxide) from entering the vessel.

The final rate of depressurization should not exceed 1 bar (14.5 psi) per minute above the
vapour pressure at local ambient conditions and 0.5 bar (7 psi) per minute below
this pressure.
3 When all the liquid has been removed and the vessel depressurised, purge the vessel with
nitrogen (with less than 0.01% Oxygen). The recommended technique is repeated
pressurization and depressurizations followed by a straight through purge.

5 Check for hydrocarbon in the exit stream to make sure the purging is complete.

6 If the vessel is not to be discharged maintain the vessel under nitrogen. Ensure no traces
of reducing gases such as hydrogen or carbon monoxide are present.
The absorbent may be self-heating after use. This may be due to the presence of adsorbed
hydrocarbons or finely divided carbon on the absorbent.
Certain products may become pyrophoric if they have been subjected to unusual process
conditions (i.e. ferrous sulphide from upstream pipework laying on top of absorbent
bed).
For this reason if the absorbent is to be discharged the procedure outlined under "Absorbent
Discharge" must be used.