JM_1184_1084 cPurification OM art 24/7/06 5:10 pm Page 2

Katalco
Operating manual purification catalysts
and absorbents
JM_1184_1084 cPurification OM art 24/7/06 5:10 pm Page 3

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. Johnson Matthey plc (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. Nothing here in should be considered to provide freedom to operate
under any Patent.
JM_1184_1084 cPurification OM art 24/7/06 5:10 pm Page 4

Contents
Page
Introduction 2
KATALCOJM™ 41-6T, 61-1T, 59-3, 32-4 & 32-5 2
Catalyst storage, handling and charging 4
Health and safety precautions 6
Start-up of KATALCOJM 41-6T/61-1T 7
Operation of KATALCOJM 41-6T/61-1T 10
Shut-down of KATALCOJM 41-6T/61-1T 12
Start-up, operation and shut down of KATALCOJM 59-3 13
Start-up, operation and shut-down of KATALCOJM 32-4/32-5 14
Catalyst discharge 16
Nickel carbonyl hazard 17
JM_1184_1084 cPurification OM art 24/7/06 5:10 pm
Introduction
Sulphur and chlorine compounds are particularly severe
poisons for nickel, iron and copper catalysts used in plants
utilising steam reforming technology for the production of
hydrogen and hydrogen/carbon monoxide mixtures for
downstream use in oil refining, petrochemical, ammonia and
methanol production. The large volumes of hydrocarbon
feedstock to be processed mean that even small traces of
these poisons have a cumulative detrimental effect on the
performance of downstream catalysts. It is therefore
extremely important to purify all the hydrocarbon
feedstocks before they are processed to achieve the long
production runs needed for economic operation.
KATALCOJM 41-6T, 61-1T, 59-3, 32-4 & 32-5
Hydrodesulphurization catalysts
Johnson Matthey Catalysts supplies two catalysts for
hydrodesulphurization (HDS), namely KATALCOJM 41-6T and
KATALCOJM 61-1T which are respectively based on cobalt
oxide/molybdenum oxide and nickel oxide/molybdenum
oxide, in both cases supported on alumina. KATALCOJM 41-6T
is more commonly used for ammonia and hydrogen duties
while KATALCOJM 61-1T is usually used in methanol plants.
The catalysts achieve their highest activity when sulphided
but can also operate under low sulphur conditions when
partially sulphided. In most applications, the catalysts do not
need a special sulphiding stage and an appropriate level of
sulphiding is attained by reaction with the sulphur
compounds in the hydrocarbon feed.
2
Page 5
Organic sulphur compounds must be hydrogenolysed over
KATALCOJM 41-6T or KATALCOJM 61-1T to convert the
sulphur to hydrogen sulphide (H2S). Where present, organic
chloride compounds are also hydrogenolysed over
KATALCOJM 41-6T or KATALCOJM 61-1T to give hydrogen
chloride (HCI), which is then removed by absorption with
KATALCOJM 59-3. Lastly, the H2S is removed by absorption
with KATALCOJM 32-4 or KATALCOJM 32-5.
This manual discusses the principles of start-up, operation
and shut down and the information provided is sufficient for
the preparation of detailed operating instructions, which of
necessity will be plant specific.
KATALCOJM 41-6T and KATALCOJM 61-1T normally operate at
temperatures in the range of 300-400°C (572-752°F) and
at pressures of 25-40 bar (363-580 psi). The preferred
operating temperature is towards the upper end of this range.
In certain circumstances, it is advisable to pre-sulphide the
HDS catalyst. These circumstances are limited to situations
where the carbon oxides concentration is high presenting a
risk of exothermic methanation; the sulphur concentration is
very low such that inadequate sulphiding will occur; the
operating temperature is low such that maximum HDS
activity is necessitated from start of run; the organic sulphur
level is high again necessitating maximum activity
immediately on commissioning; and the nature of the
hydrocarbon feed and partial pressure of hydrogen present a
risk that an exothermic hydrocracking reaction may initiate.
Pre-sulphiding of the catalyst is achieved either by an in situ
sulphide pre-treatment or by supply of pre-sulphided
catalyst. In these situations, Johnson Matthey Catalysts will
advise on the appropriate catalyst selection and procedures.
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Chloride removal absorbents Sulphur removal absorbents

KATALCOJM 59-3 comprises sodium aluminate supported on KATALCOJM 32-4 and KATALCOJM 32-5 comprise granulated
alumina. It will completely remove chlorine present as zinc oxide with a cement binder. These normally operate at
hydrogen chloride (HCI) and should always follow the temperatures in the range of 300-400°C (572-752°F) and at
hydrodesulphurization catalysts in the process sequence to pressures of 25-40 bar (363-580 psi). These products are
avoid detrimental effects of reaction between HCl and the effective and have been used outside of these ranges but are
downstream sulphur removal absorbents. KATALCOJM 59-3 most efficient above 350°C (662°F). Special pre-treatment or
requires no pre-treatment or activation and it normally activation is not required before commissioning.
operates at temperatures in the range of 300-400°C
(572-752°F) and at pressures of 25-40 bar (363-580 psi)
although it can operate over a wider range of conditions,
between 20°C (68°F) and 400°C (752°F) and at pressures
up to 50 bar (725 psi).

Physical properties (typical)

Catalyst KATALCOJM 41-6T KATALCOJM 61-1T KATALCOJM 59-3 KATALCOJM 32-4 KATALCOJM 32-5
Composition Cobalt oxide/ Nickel oxide/ Sodium aluminate/ Zinc oxide/ cement Zinc oxide/
molybdenum oxide/ molybdenum oxide/ alumina cement
alumina alumina
Form trilobe extrusions trilobe extrusions spherical granules spherical granules spherical granules
Diameter (mm) 2.5 2.5 2.0 – 4.75 2.8 – 4.75 2.8 – 4.75
Typical loaded density
(kg/m3) 590 560 870 1140 1350
3
(lb/ft ) 37 35 54 71 84

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Catalyst storage, handling and charging
Before charging, discharging, and handling
hydrodesulphurization catalysts, chloride removal absorbents,
or sulphur removal absorbents, any potential risk to health
during these activities should be assessed and appropriate
precautions taken. In addition the Johnson Matthey Catalysts
manual on “Catalyst Handling” should be consulted.
Drum storage
The hydrocarbon feedstock purification catalysts are
generally supplied in mild steel drums which may be fitted
with polythene liners: if any of these parameters changes
Johnson Matthey Catalysts will notify its customers.
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 there is the risk that the top
drums may fall off the stack, and the lower drums can be
crushed due to the weight of the drums above them. The
metal drums are usually suitable for outside storage for a
few months but should be protected against rain and
standing water. If prolonged storage is expected, 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
catalyst is to be charged. If the lids are removed it is
Physical properties (typical)
Catalyst Net weight (kg)
KATALCOJM 41-6T 132
KATALCOJM 61-1T 132
KATALCOJM 59-3 150
KATALCOJM 32-4 210
KATALCOJM 32-5 230
4
Page 7
important that they should be replaced as soon as possible,
so that contamination of the catalyst is avoided. If the drum
lid cannot be replaced, then the catalyst should be
redrummed without delay. If any contamination occurs it is
difficult to assess the extent of any damage without full
examination of the catalyst. If there is any doubt about the
state of the catalyst it is best not to charge it to the reactor.
Drum handling
Catalyst drums should be handled as carefully as possible.
They must not be rolled. Catalyst drums are often supplied
on pallets, which reduces the likelihood of damage in transit,
but requires suitable fork-lift trucks and a paved area to
handle the pallets. The fork-lift truck to be used for moving
the pallets should be fitted with rim or body clamps to avoid
damage to the drums. The use of containers for either
catalyst 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.
Tare (kg) Drum dimensions (cm)
21 90 x 58 x 58
21 90 x 58 x 58
18 88 x 59 x 59
18 88 x 59 x 59
18 88 x 59 x 59
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Sieving catalyst Charging the converter

Catalysts are screened before they are packed into drums The catalyst may be loaded directly from the drums or from
for despatch, but in some instances attrition can occur in intermediate bulk containers, which are usually brought to
transit if the drums are roughly handled. If the catalyst the charging point. The two general rules for charging
appears dusty, screening should be considered prior to catalysts into vessels are:
loading. A good method of sieving is to pass the catalyst
a)the catalysts should not have a free fall of more than
over a simple inclined screen. This is often the most
50-100 cm (20-40 ins) and
satisfactory method, since vibrating screens can cause
additional unnecessary damage and loss. The screen should b)the catalyst must be distributed evenly as the bed is filled.
contain provision to collect the dust, and at the same time
avoid generating a dusty atmosphere. The mesh size should
be about half the smallest dimension of the catalyst particle.
While the catalyst is being poured over the screen the use
of a vacuum system situated close to the sieve will control
the dust effectively.

Pre-charging checks
Before the catalyst is charged it is important that the
condition of the catalyst support grid in the vessel and any
supporting materials such as inert balls be checked. Some
form of light metal shield or “spider” fitted into the discharge
manhole prevents inadvertent catalyst 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 under filling or overfilling. The desired level can be
marked with chalk before charging is commenced.

It can be valuable to check that thermocouples are correctly

installed before charging is commenced, by warming them
in turn to ensure that the correct indication is given on the
instrument panel.

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Health and safety precautions
Operators should be aware of the hazards associated with the
use of catalyst and draw up the appropriate safety instructions.
Discharged pyrophoric catalysts
Catalysts discharged in the pyrophoric state must be kept
separate from flammable materials. Transport of such catalyst
should only be in metal skips or metal sided trucks. Dumps
of the catalyst should be within reach of water hoses so that
any overheating that occurs can be controlled. High
temperatures can build up in heaps and it is a prudent
precaution to spread the catalyst thinly over the ground until
the oxidation is complete. Under no circumstances should
personnel be allowed to walk over the catalyst until it has
been fully stabilized.
Discharged spent KATALCOJM 32-4 and
KATALCOJM 32-5
The discharged absorbent comprises mainly zinc sulphide
and should not be stored near acids. Accidental contact of
the spent catalyst and acid would result in the evolution of
hydrogen sulphide (H2S).
Note: The European Union and the IARC have decided that it is prudent to classify all insoluble nickel compounds as Category 1 carcinogens.
Appropriate information is contained in the Material Safety Data Sheet sent with all orders.
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Page 9
Dust exposure
Short-term exposure to the metals and metal oxides used in
catalysts 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. Catalysts 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
catalyst 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.
Ergonomics
Physical hazards arise from the handling of drums, materials
and lifting equipment. Personnel should be aware of these
and appropriate precautions taken.
JM_1184_1084 cPurification OM art 24/7/06 5:10 pm
Start-up of KATALCOJM 41-6T and KATALCOJM 61-1T
When using KATALCOJM 41-6T or KATALCOJM 61-1T for the
hydrodesulphurization of light hydrocarbons and gaseous
feedstocks no special activation procedures are usually
necessary. Conversion to the more active sulphided form is
achieved to a sufficient extent by reaction with sulphur
compounds in the feed gas in most situations.
Initial start-up with the use of process gas
1 Purge the vessel free of oxygen using an inert gas or
natural gas. The latter is used of necessity where there is
no available nitrogen system, for example in certain
ammonia plant designs.
2 Heat the catalyst in a flow of inert gas or natural gas at a
rate not exceeding 50°C (90°F) per hour. The alumina
support will usually contain adsorbed moisture, which will
be evolved during the heating stage.
3 The hydrodesulphurization catalyst and downstream
absorbents should be heated to at least 300°C (572°F)
(and ideally to design operating temperature) before the
system is commissioned for hydrodesulphurization with
feed forward to the steam reforming section. If the
temperature is lower, the hydrodesulphurization reaction
and downstream absorbent(s) may not have sufficient
activity with the result that sulphur (and chlorine)
compounds could pass to the reforming section.
4 Raising the pressure will aid heat transfer. Thus, the vessel
pressure may be increased towards normal operating
pressure at any time during the heating stage, however, this
pressure may be constrained by downstream limitations
during start-up. For example, it is usual to maintain a low
pressure in the reformer during heat up and catalyst
reduction. If this is the case, the pressure should be raised
in line with the downstream requirements.
Page 10
5 If the flowsheet demands that the gas used for heating
passes forward to the steam reforming section, then it
must contain a minimal level of organic sulphur (and
organic chlorine) compounds as these will neither be
decomposed reliably below 300°C (572°F) and in the
absence of hydrogen nor be removed by the absorbents
for HCl and H2S removal.
The absorbents will remove low levels of HCl and H2S
even at ambient temperature and levels up to half the
design value in terms of hourly sulphur and chlorine
burden can be tolerated.
Site nitrogen will not normally contain sulphur or chlorine
compounds but, if the catalyst is heated up with natural
gas, care is needed. The level of sulphur (and chlorine)
compounds should be checked. If natural gas must be
used for heating, it should not be routed through the
steam reforming section if the organic sulphur (and
organic chlorine) exceeds 0.1 ppmv and/or the HCl and
H2S exceeds half the design hourly level until the
hydrogen flow has been introduced and the catalyst
temperature exceeds 300°C (572°F). While the conditions
disallow routing of natural gas through the steam
reforming section, the natural gas should be routed to
flare or into a fuel gas stream immediately downstream of
the purification section.
6 The feed gas and hydrogen, or a hydrogen rich gas feed
containing sulphur, may be introduced once the
temperature reaches 300°C (572°F). The HDS catalyst
and downstream absorbents should be sufficiently active
at or above this temperature to break down the organic
sulphur (and chlorine) compounds and absorb HCl and
H2S. In the case of fresh HDS catalyst, the sulphur
compounds in the feed should react and begin the
process of sulphiding this catalyst.
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7 If the feed gas and hydrogen, or a hydrogen rich gas feed
containing sulphur, have to be introduced at a temperature
below 300°C (572°F), it is advisable that this gas does not
feed forward to the sulphur sensitive pre-reformer or
reformer catalysts until this temperature (and ideally
normal operating temperature) is reached. If the flowsheet
demands that the gas passes forward to the steam
reforming section, the normal operating temperature
should be established as quickly as possible subject to any
equipment constraints on heating rate.
Important: If the natural gas or hydrogen rich gas contains
carbon oxides these could methanate over the
unsulphided catalyst in the presence of hydrogen at
temperatures above 300°C (572°F). Once sulphided, the
catalyst’s methanation activity is much lower and so this is
a concern primarily with fresh material or charges which
have been run with less than the minimum recommended
level of sulphur in the feed. The gas temperature will
increase by about 50°C (90°F) for every 1% of carbon
oxides in the total gas flow which methanate. If there is
sufficient carbon oxides and hydrogen present, the
catalyst temperature risks exceeding the maximum design
value for the catalyst (400°C [752°F]) and possibly the
vessel. In this case, it will be necessary to introduce a
blend of gases at an inlet temperature possibly below
300°C (572°F) in order to dilute the carbon oxides to a
level at which the exotherm can be accommodated. If the
conditions are such that this gas may not be completely
desulphurized during this stage, it should not pass to the
primary reformer. As the catalyst becomes sulphided, the
methanation activity should diminish and the exotherm
will reduce. An alternative approach is to use a pre-sulphided
HDS catalyst.
8
Initial start-up with in-situ presulphiding
KATALCOJM 41-6T and KATALCOJM 61-1T can be sulphided if
required by dosing with a sulphur compound to ensure
maximum activity during initial operation. The situations in
which pre-sulphiding should be considered include
situations where the carbon oxides concentration is high
presenting a risk of exothermic methanation; the sulphur
concentration is very low such that an inadequate rate of
sulphiding will occur; the operating temperature is low such
that maximum HDS activity is necessitated from start of run;
the organic sulphur level is high again necessitating
maximum activity immediately on commissioning; and the
nature of the hydrocarbon feed and partial pressure of
hydrogen present a risk that an exothermic hydrocracking
reaction may initiate.
During normal operation the hydrodesulphurization catalyst
will reach an equilibrium sulphur content, which depends on
the level of sulphur in the feedstock. If more sulphur than
this is added during pre-sulphiding the excess sulphur will
be displaced gradually as H2S during normal operation as
the sulphur level equilibrates with that in the feed, however,
this will be absorbed by the zinc oxide bed downstream. An
adequate degree of sulphidation is obtained once the
amount of sulphur added during the procedure is in the
range 1-2 wt% on the catalyst.
1 Purge the reactor free of oxygen using an inert gas or
natural gas. The latter is used of necessity where there is
no available nitrogen system, for example in certain
ammonia plant designs.
2 Heat the catalyst to 200°C (392°F) in a flow of inert gas or
natural gas at a rate not exceeding 50°C (90°F) per hour.
Pressure may be in the range of 10-20 bar (145-290 psi).
Introduce 5-10 mol% hydrogen and add about 1 mol% of
an appropriate sulphiding agent. Examples include carbon
disulphide, dimethyl disulphide, mercaptans or hydrogen
sulphide. The space velocity should be approximately,
400-600 hr-1 and sulphiding should continue until the
catalyst has picked up 1-2% w/w sulphur.
JM_1184_1084 cPurification OM art 24/7/06 5:12 pm
3 The carrier gas exiting the reactors may contain traces of
sulphur compounds and so should not be routed through
the steam reforming section and, ideally, not through the
ZnO beds. The total sulphur exiting the HDS catalyst and
also the ZnO beds should be checked to ensure that the
sulphidation agent is reacting. Sulphur pick up is expected
to be efficient such that little or no sulphur slip should be
observed.
4 Once the target amount of sulphur has been added,
discontinue sulphur addition.
5 Discontinue hydrogen addition. Continue to heat at a rate
not exceeding 50°C (90°F) per hour and commission the
catalyst as described in steps (3) – (7) of the initial start
up procedure. Alternatively, as the catalyst activity has
been augmented by sulphiding, the catalyst bed may be
heated to the normal operating temperature with feed gas
and hydrogen present. In this case, the exit gas should be
analysed to ensure that organo-sulphur compounds are
being converted before gas is fed forward to the steam
reforming section.
During the commissioning period of the purification section
and also of the remainder of the plant, it is very important to
monitor the total sulphur content of gas leaving the
purification section as well as the H2S level to check that
adequate overall purification is being achieved and that there
is adequate conversion of organic sulphur compounds over
the HDS catalyst. This provides assurance that downstream
catalysts are being protected against sulphur poisoning.
Page 12
Commissioning of the HDS catalyst is interlinked with the
start-up of the downstream steam reforming section. The
impact of one procedure on the other must be considered
noting that these are a function of plant design. In some
plants, the desulphurization vessel may be included in the
steam reformer reduction loop in which hydrogen is
recycled. In this case, new unsulphided HDS catalyst may be
in contact with hydrogen at elevated temperature before
sulphur containing gas can be admitted. Prolonged exposure
to hydrogen alone should be avoided as this can lead to
over reduction of the catalyst, but experience indicates that
subsequent problems are very rare. In other plants, natural
gas cracking is used to reduce the reforming catalyst in
which case the gas must be desulphurized usually
necessitating the purification section to be commissioned. It
is also possible to desulphurize adequately at low
throughput rates once the HDS catalyst bed temperature
exceeds 300°C (572°F) although this is less than the design
temperature, which may accelerate the overall plant start up.
Restart of sulphided catalyst
After the KATALCOJM 41-6T and KATALCOJM 61-1T have
been properly sulphided either through the action of the
process gas or through pre-sulphiding, a resulphiding step
should not be required following a plant shut-down.
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Operation of KATALCOJM 41-6T and KATALCOJM 61-1T

KATALCOJM 41-6T and KATALCOJM 61-1T are robust and give 4 Operation above 400°C (752°F) should be avoided to
trouble-free operation for many years. Catalyst performance prevent catalyst deactivation through carbon laydown from
is usually checked periodically by measuring the feedstock accelerated thermal cracking of hydrocarbons and to prevent
sulphur content and the sulphur content of the gas leaving the possible initiation of side reactions such as hydrocracking
the final bed of zinc oxide. Ideally, the extent of or, where carbon oxides are present, methanation.
hydrogenolysis of organic sulphur compounds across the
5 Olefins present will hydrogenate and consume hydrogen.
HDS catalyst should be checked but this requires relatively
Not only will this produce an exotherm but also it may not
sophisticated analytical equipment, which is not always
leave enough hydrogen for the hydrogenolysis of organic
available. Any instantaneous changes in sulphur slip will
sulphur compounds.
often be noticed first from a change in the performance of
the downstream pre-reformer or primary reformer. 6 These catalysts are effective water gas shift catalysts.
Therefore, if CO2 is present in the feed an allowance
KATALCOJM 41-6T and KATALCOJM 61-1T evolve or absorb
should be made for the hydrogen consumed in the
sulphur as the sulphur content of the process gas changes.
reverse water gas shift reaction (1). In most
This corresponds to changes in the sulphide content of the
circumstances, this reaction will attain equilibrium at the
catalysts due to equilibration with the changing process gas
conditions prevailing at the reactor exit. Also, the reaction
sulphur level. Any evolved sulphur will be in the form of H2S,
is endothermic from left to right and may cause a small
which is removed in the downstream absorbent beds.
temperature loss across the HDS vessel.
Although the hydrodesulphurization reactions are
CO2 + H2 CO + H2O (1)
exothermic, the relatively low organic sulphur level means
that there is no detectable temperature rise across the
Hydrogen recycle level
catalyst bed from these reactions.
Hydrogen is required to allow the hydrodesulpurization
When operating with KATALCOJM 41-6T or
reaction to proceed. This may be present in the feed gas
KATALCOJM 61-1T it should be remembered that:
(e.g. certain off gases from other processes) but with
1 Performance is closely related to the quantity of hydrocarbon feeds it is usual to recycle some product
sulphur and the particular sulphur compounds present hydrogen or a hydrogen containing stream from the back
in the feedgas. end of the syngas plant. The hydrogen also inhibits
hydrocarbon thermal cracking reactions from depositing
2 Hydrodesulphurization is not possible in the absence of
carbon in the front end of the plant. Thus, the
hydrogen.
recommended hydrogen level depends on the feed type.
3 Activity is strongly temperature dependent so that
operation below design conditions is not recommended.

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Recommended HDS exit hydrogen levels Feeds containing carbon monoxide

As with all nickel containing catalysts, the exposure of
Recommended
KATALCOJM 61-1T to carbon monoxide leads to a possibility
vol% that nickel carbonyl, a toxic substance, may be formed. Its
Natural gas 2-5 formation under normal operating conditions is extremely
unlikely in a purification reactor containing KATALCOJM 61-1T
Propane, butane 12 unless abnormal operating circumstances arise. Please refer
to the section “Nickel Carbonyl Hazard”.
Naphtha 25
Minimum sulphur level
Naphtha with 20-25 %wt aromatics 30
In order to keep sufficient sulphur on the HDS catalyst to
Naphtha with 25-30 %wt aromatics 35 maintain good activity and to avoid initiation of side
reactions, a minimum feed sulphur level of 2 ppmv is
The recommended hydrogen level is at the HDS vessel exit. recommended. If the level of sulphur is consistently below
Thus, the inlet level must allow for any hydrogen which will this level, periodic or continuous dosing of the catalyst with
be consumed in olefin hydrogenation or reverse water gas sulphur may be advised depending on the particular
shift reactions. circumstances. Johnson Matthey Catalysts will advise on the
need and on the procedure for dosing.
Feeds containing olefins
If the feed contains olefins, these hydrogenate over the HDS
catalyst. This reaction is quite strongly exothermic.
Depending on the level of olefins and the associated
temperature rise due to hydrogenation, it may be necessary
to decrease the inlet temperature to the vessel to maintain
the exit temperature at or below the design maximum of
400°C (752°F). As a minimum inlet temperature of 300°C
(572°F) is required, the exotherm cannot exceed 100°C
(180°F). Where the olefin level will generate a higher
exotherm, alternative catalyst or reactor designs are needed,
on which Johnson Matthey Catalysts can advise.

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JM_1184_1084 cPurification OM art 24/7/06 5:13 pm
Shut-down of KATALCOJM 41-6T and KATALCOJM 61-1T
During a brief plant outage where natural gas or off gas is
the plant feed, hydrodesulphurization catalyst may be left in
an atmosphere of the process gas without any damage to
the catalyst. Where there is a likelihood of some
condensation of the hydrocarbon feedstock with LPG or
naphtha feeds, the reactor should be purged with an inert
gas. Similarly, if carbon oxides are present the reactor should
be purged with an inert gas to avoid the risk that
methanation initiates. For longer outages the reactor should
be purged with an inert gas.
12
Page 15
Hydrodesulphurization catalysts in the sulphided form are
pyrophoric due to both the reactivity of the metal sulphide
phases and finely divided carbon that can build up in the
catalyst over time on line. This and any inadequately purged
hydrogen or feedstock adsorbed on the catalyst can ignite
when the catalyst is discharged from the vessel and is
exposed to air particularly if the catalyst is at elevated
temperature. For this reason if the catalyst is to be
discharged the procedure outlined under “Catalyst Discharge”
must be used. Under no circumstances should air be passed
through the catalyst while it is in the HDS reactor.
JM_1184_1084 cPurification OM art 24/7/06 5:13 pm Page 16

Start-up, operation and shut-down of KATALCOJM 59-3

Start-up Steam
KATALCOJM 59-3 requires no pre-treatment and absorbs HCI Steam does not affect catalyst strength but condensation of
as soon as feedstock is admitted to the catalyst bed. water in the bed must be avoided.

Wetting during loading or any condensation of water on the

Carbon dioxide
absorbent should be avoided as it can cause caking in the
bed and lead to poor gas distribution, high pressure drop and Carbon dioxide has no effect on the chloride capacity of
poor HCl removal. The absorbent may be heated to the KATALCOJM 59-3.
operating temperature with inert gas or process gas. The
reactor must be purged free of air before admitting Organic chlorides
inflammable gas.
Organic chlorides may be removed by thermal cracking at
With KATALCOJM 59-3 HCI absorption occurs even at temperatures above 300°C (572°F), however, these will be
ambient temperature. Thus, if process gas is used for heating, catalytically broken down over the upstream HDS catalysts
HCl will be removed during this stage. Full dechlorination assuming this is present.
capability should not be expected below design operating
temperatures and if the gas is to be fed forward into the Shut-down
process the space velocity should be restricted to no more
KATALCOJM 59-3 is not pyrophoric. However when the
than 50% of design rate.
material is operated in a conventional desulphurization
unit it is possible that finely divided carbon or residual
Operation hydrocarbons may contaminate the catalyst and these
KATALCOJM 59-3 should give trouble-free operation during could ignite during discharge.
its long life. There will be no temperature rise across the bed.
For this reason if the absorbent is to be discharged the
Performance can be assessed, by monitoring the inlet and
procedures outlined under “Catalyst Discharge” must be used.
exit concentration of chloride if the reactor configuration
allows. A record of the total quantity of chloride absorbed will
help to anticipate the time for renewal of the absorbent. The
absorption profile is quite sharp under normal operating
conditions and the exit chloride content will be <<0.1 ppmv
for most of the operating life. When the absorbent
approaches saturation the chloride content of the exit gas
will rise fairly rapidly.

13
JM_1184_1084 cPurification OM art 24/7/06 5:13 pm Page 17

Start-up, operation and shut-down of KATALCOJM 32-4

and KATALCOJM 32-5
Start-up
No special pre-treatment is required before these
absorbents are commissioned. Reaction of H2S with the
high surface area zinc oxide will begin as soon as the
feedstock enters the reactor.
The absorbent may be heated to the operating temperature
with inert gas or process gas. The reactor must be purged
free of air before admitting inflammable gas.
Condensation of water in the absorbent bed should be
avoided as subsequent evaporation can weaken the material
and may cause some disintegration. If any dust in the bed is
wetted then this could cake and lead to maldistribution of
gas at the relatively low operating space velocity.
KATALCOJM 32-series absorbents remove H2S even at
ambient temperature. As temperature is increased the rate
of absorption increases to achieve effective performance at
temperatures above 300°C (572°F) and optimum
performance in the range 350-400°C (662-752°F). Certain
organic sulphur compounds decompose thermally at
normal operating temperatures to liberate H2S, which is then
absorbed. However, this process is of limited efficiency and
should not be relied upon for organic sulphur compound
removal. Unless the organic sulphur is confirmed to be only
mercaptans at levels no higher than 2-3 ppmv with any
other organo-sulphur compounds totalling << 0.1 ppmv,
Johnson Matthey Catalysts always recommends the use of
KATALCOJM 41-6T or KATALCOJM 61-1T for effective organic
sulphur removal.
Operation
KATALCOJM 32-4 and KATALCOJM 32-5 will give trouble-free
service and usually require very little attention during steady
operation until saturated with sulphur. There is no
temperature rise as sulphur is absorbed, and the H2S slip
will be <0.1 ppmv over the design life.
Performance should be followed by recording the inlet and
exit H2S contents at regular intervals during use. The total
sulphur content of the feedstock, which is entirely absorbed
in the bed, can be integrated so that the appropriate time
for replacement may be anticipated.
When operated in a lead/lag configuration it is normal
practice to operate the upstream bed until the sulphur
concentration of the outlet stream is 90% of the inlet
concentration. This maximizes utilization of the absorbent.
Steam and carbon dioxide
KATALCOJM 32-4 and KATALCOJM 32-5 may be used in the
presence of substantial volumes of steam or carbon dioxide.
Care must be taken, however, to prevent condensation of
water because this could cake any dust in the bed and
seriously affect performance. Also, substantial levels of
steam or carbon dioxide are likely to adversely affect
performance in terms of H2S or COS slip.

14
JM_1184_1084 cPurification OM art 24/7/06 5:13 pm Page 18

Temperature Shut-down
When setting the operating temperature, especially during During a brief plant outage where natural gas or off gas is the
plant upsets, the following general rules must be plant feed, KATALCOJM 32-4 and KATALCOJM 32-5 may be left
remembered. in an atmosphere of the process gas without any damage to
the catalyst. Where there is a likelihood of some condensation
1 Although H2S can be absorbed at any temperature,
of the hydrocarbon feedstock with LPG or naphtha feeds, the
sulphur removal is most efficient in the range 350-400°C
reactor should be purged with an inert gas.
(662-752°F). Operation at lower temperatures may lead
to earlier sulphur slip, and a reduced sulphur capacity. The zinc sulphide in spent KATALCOJM 32-4 and
KATALCOJM 32-5 is not pyrophoric but the material may
2 In most plants, changes to the operating temperature of
be contaminated with combustible species such as finely
the hydrodesulphurization catalyst directly affect the
divided carbon or residual adsorbed hydrocarbons. After
operating temperature of the sulphur removal absorbent.
conventional desulphurization duties it is possible that finely
divided carbon, from the pre-heater, may be deposited on
Hydrogen chloride
the absorbent which could ignite during discharge.
KATALCOJM 32-4 and KATALCOJM 32-5 will absorb small
For this reason, the absorbent should be discharged using
amounts of hydrogen chloride (HCI) from the process gas.
the procedure outlined under “Catalyst Discharge”.
This is useful if unexpected traces of HCI contaminate the
plant feedstock but continuous exposure to trace levels or
occasional exposure to large spikes of HCI should be avoided
as these will reduce sulphur absorption efficiency. Additionally,
the zinc chloride (ZnCI2) formed may migrate at normal
operating temperatures with the possible contamination of
downstream equipment and catalysts if there is substantial
formation of ZnCI2. Thus, when chlorides are expected to
contaminate feedstocks on a regular basis an appropriate
chloride removal absorbent such as KATALCOJM 59-3 should
be used in the purification section immediately upstream of
the KATALCOJM 32-series absorbent.

15
JM_1184_1084 cPurification OM art 24/7/06 5:14 pm Page 19
Catalyst discharge and disposal
The catalyst or absorbent is usually discharged from the
reactor with large mobile vacuum units or by gravity flow
from the bottom of the vessel.
The spent materials should be assumed to be potentially
combustible because of adsorbed hydrogen and
hydrocarbons or finely divided carbon that can be present.
In addition, the sulphide phases in the HDS catalysts are
reactive towards air. When discharging from the vessel the
following procedure should be used.
1 Purge the reactor free of hydrocarbon using an inert gas
and reduce the pressure.
2 Cool the reactor to below 50°C (122°F) in a flow of inert gas.
3 Discharge the catalyst or absorbent under a positive
pressure of inert gas. This may be by vacuum extraction or
by gravity flow from the bottom of the converter. In the latter
case, as the material falls from the bottom manhole, water
hoses should be available to wet it in case it overheats.
16
If the material has to be discharged when it is hot it should
be assumed that it is pyrophoric and the following
procedure used.
1 Purge the vessel with an inert gas and reduce the
pressure. Maintain a positive pressure of the inert gas in
the vessel.
2 Discharge the catalyst or absorbent into metal bins or
metal-sided lorries with only the discharge manhole open.
Air must NOT be allowed to enter the vessel otherwise
local overheating could take place.
3 Water hoses should be available in case of overheating.
Water should not be used unless necessary as this could
cause breakdown of the catalyst or absorbent particles.
Through the CATALYST CARE Programme, Johnson
SM
Matthey Catalysts offers the environmentally safe disposal of
its complete product range.
JM_1184_1084 cPurification OM art 24/7/06 5:14 pm Page 20

Nickel carbonyl hazard

Catalysts containing metallic nickel must not be exposed to If carbon monoxide is present in the feed gas or other streams
gases containing carbon monoxide at temperatures below entering the reactor containing KATALCOJM 61-1T, Johnson
200°C (392°F). Observation of this rule avoids the risk of Matthey recommends that, during start-up, nitrogen is used for
the formation of nickel carbonyl, [Ni(CO)4] which is heat up until the rector temperature exceeds ca. 200°C
extremely toxic. It is stable as a colourless liquid at ambient (392°F) and during shut-down a nitrogen purge is initiated
temperature and is reported to have a musty smell, but it while the reactor is above ca. 200°C (392°C). This temperature
has a very low boiling point, 42.5 °C
1 atm (108°F), such should be adjusted as appropriate to the partial pressure of
that there is a significant vapour pressure over the liquid at carbon monoxide in the process gas. In the absence of
normal ambient temperatures. nitrogen another suitable carbon monoxide free gas should be
used. Special care should then be taken to ensure that gases
KATALCOJM 61-1T contains nickel, but not usually in the
containing carbon monoxide do not leak into the vessel as it is
metallic form unless the catalyst has been exposed to
cooled or during any period of shut-down. If it is suspected,
strongly reducing conditions in the absence of sulphur. The
that the catalyst has been exposed accidentally to CO at
majority of feed and recycle streams are free of carbon
conditions which favour nickel carbonyl formation, appropriate
monoxide and during normal operation the temperature is
safety precautions must be taken which are necessarily specific
well above that at which nickel carbonyl is stable. During
to the particular situation. Contact Johnson Matthey Catalysts
start-up and shut-down the catalyst will normally pass
for further advice in such circumstances.
through the dangerous temperature range. In the event that
the usual feed stream or any other gas stream to be passed
through the catalyst contains carbon monoxide, appropriate
precautions should be taken during these operations so that
there is no risk to personnel.

Conditions for the formation of 0.001 ppm Nickel Carbonyl

1 (14.5)
Partial pressure of CO - bara (psia)

30 bara (435 psia)

Favourable 1bara (14.5 psia)
0.1 (1.45)

0.01 (0.145)
Not Favourable

0.001 (0.0145)
0 100 200 300 400
(32) (212) (392) (572) (752)

Temperature °C (°F)

17
JM_1184_1084 cPurification OM art 24/7/06 5:10 pm Page 1

For further information on Johnson Matthey Catalysts, contact your local sales office or visit our website at www.jmcatalysts.com
CATALYST CARE is a service mark of the Johnson Matthey group of companies. KATALCO is a trademark of the
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