Hydrogenation Reactions

In the hydrogenator the organic sulphur present in the hydrocarbon feedstock is converted into
H2S. The reactions require the presence of a small amount of hydrogen which is normally supplied
as a recycle stream from downstream units.
The organic sulphur may be present as a great number of different compounds and some of the
reactions are shown above.
If chloride compounds are present in the natural gas, these will also be hydrogenated into hydrogen
chloride.
In some cases where natural gas contains CO2, a reverse shift reaction with the recycle hydrogen
will take place and form CO and water.
This last reaction may influence the performance of the zinc oxide reactors which will be described
later on.
Topsoe hydrogenation reactions
The TK-550 catalyst and the recently improved version TK-250 are cobolt molybdenum (CoMo)
based catalyst. The active metals are contained on a specially Topse manufactured alumina
carrier. This catalyst formulation has proven to be the most suitable for converting organic sulphur
in feedstocks ranging from natural gas to naphtha.
The catalyst is supplied in the shape of a ring in order to reduce the reactor pressure drop.
Furthermore, the ring shaped catalyst will have a much higher tolerance against pressure drop
increases caused by solid particles in the feedstock .
The TK-550/TK-250 catalysts are normally delivered in the oxidised state where the catalyst activity
is low. The catalyst is therefore activated by sulphiding the CoO and MoO 3 compounds whereby the
active CoMoSx phase is formed:
CoO
+ Sulphur CoMoSx
MoO3
In most plants the sulphiding media will be the same feedstock as used during normal operation,
but in some special cases the sulphiding of the catalyst takes place ex-situ by a specially designated
company.
It follows from the above sulphiding reaction that the amount of CoMoS x phase in the catalyst
depends on the amount of sulphur in the feedstock.
The degree of sulphiding and thereby the catalyst activity depends to some extent on the amount
of sulphur present in the feedstock used as sulphiding media and during normal operation. With
more than 5 ppm of total sulphur in the feedstock, the activity is at a high and constant level. With
a lower sulphur content in the natural gas, the amount of the active CoMoSx phase in the catalyst
will be lowered and the catalyst activity is likewise lower.
This is not a problem as long as the low sulphur content in the feedstock is constant, but if the
organic sulphur content suddenly increases, the catalyst may not convert these compounds
sufficiently for a short period (days) due to insufficient activity. The primary reformer catalyst will
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then be poisoned. After a few days the catalyst has again been sufficiently sulphided and the slip of
organic sulphur goes down.
It is therefore important to note that operation with a practically sulphur free feedstock will stripoff sulphur from an already sulphided hydrogenation catalyst.
The operating temperature is another parameter which plays an important role with regard to the
activity of the hydrogenation catalyst.
At low temperatures the hydrogenation reactions progress very slowly and the conversion is not
optimal. This may lead to organic sulphur breakthrough from the HDS section and potential sulphur
poisoning of the primary reformer catalyst.
At relatively high temperatures the hydrogenation catalyst also possess affinity for cracking
reactions:
CH4

C + 2 H2

It is therefore necessary to operate the hydrogenation catalyst within a certain temperature range
to ensure a satisfactory performance and most of the hydrogenators being designed today operate
at temperatures between 350-400oC.
As mentioned previously, a hydrogenation catalyst will lose activity when operated on a feedstock
with low sulphur content. This deactivation is reversible as the catalyst picks up more sulphur and
gains activity when exposed to feedstocks with higher sulphur levels.
However, at certain conditions the catalyst may deactivate irreversibly.
If the catalyst is not presulphided during the initial start-up and is operated on hydrocarbon feed
with no or very low sulphur content in the gas, it will remain in the oxidic state for a long time. If
the operating temperature is high and the hydrogen recycle is high, there is a possibility of the
MoO3 being reduced to MoO2.
Contrary to MoO3, the MoO2 is very difficult to sulphide. The reaction is extremely slow, and for all
practical purposes it is not possible to sulphide the catalyst if the molybdenum has been
transformed into MoO2. This means that the catalyst has irreversibly deactivated. Furthermore, the
MoO2 has a high activity for hydrocracking which especially is a problem if the feedstock is naphtha.
If the catalyst is presulphided during initial start-up, the risk for reduction of the molybdenum is
minimised.
The most common cause for deactivation of a hydrogenation catalyst is carbon lay-down on the
catalyst.
If the catalyst is operated without hydrogen recycle at temperatures above 300C, the hydrocarbon
will start to form carbon in the pores of the catalyst. The rate of carbon formation increases with
temperature and the mole weight of the hydrocarbon feedstock. The carbon is only formed as a
thin layer covering the active CoMoS phase whereby this phase is isolated from the reactants.
Even short periods (hours) without hydrogen recycle at normal operating temperatures will cause
carbon lay-down and it is therefore recommended that when operating the plant, hydrogen recycle
must always be present.
Being the first catalyst in the plant, the hydrogenation catalyst is exposed to all the impurities
present in the feedstock. Some of these impurities will deactivate the catalyst by means of pore
mouth blocking whereby the catalyst pores gradually get plugged. When this happens, the organic
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sulphur reactants cannot get in contact with the active CoMoSx sites and the hydrogenation
reactions are therefore transferred downwards in the reactor where the catalyst pores have not yet
been plugged.
Normally, pore mouth plugging is experienced in the very top of the catalyst bed and the influence
on the performance of the hydrogenator is insignificant. Of course it depends on the amount of
poisons in the feedstock and high amounts of these will shorten the catalyst lifetime.
The most common pore mouth blocking substances are: iron, nickel and lead.
The Sulphur Absorption Reaction
The H2S which have been formed in the hydrogenator is removed in the desulphurisers using zinc
oxide as absorption media:
ZnO + H2S

ZnS + H2O

Theoretically, 1000 kg pure zinc oxide can maximal absorb:

MWsulphur/MWZnO x 1000 =

( 32 / 81.4 ) x 1000 = 393 kg Sulphur

Corresponding to:
MWsulphur/MWZnS x 100 = (32 / 97.4 ) x 100 = 32.8 Wt% Sulphur
A good performance of the desulphurisers implies that the feedstock going to the reforming
section is practically free of sulphur.
In case CO2 is present in the hydrocarbon feedstock, this may to some extent influence the
performance of the zinc oxide. The recycle hydrogen will react with CO2 and form water:
H2 + CO2 CO + H2O
According to the sulphur absorption reaction this implies that the presence of water will push the
equilibrium with H2S and ZnS and this can result in an increased slip of H2S from the desulphurisers.
In case chlorine is present in the feedstock, this will react with zinc oxide and form ZnCl2. At normal
operating temperatures of HDS sections, ZnCl2 will sublimate and deposit on downstream catalysts.
Chlorine should therefore be removed upstream the zinc oxide by a special guard catalyst.
If the feedstock contains carbon dioxide, the steam content in the gas will increase considerably, as
the CO2 in the feedstock will react with the recycle hydrogen according to the reverse-shift
reaction:
CO2 + H2

CO + H2O

The steam formed from the above reaction will have an impact on the equilibrium content of H 2S
on the ZnO. Assuming a CO2 content in the feedstock of 5% and a hydrogen recycle of 3%, the
steam content in the gas equals 0.9% at 400C. The corresponding equilibrium content of H2S on
ZnO becomes 34 ppb.
From the curve and from the shift equation it is obvious that there are two ways to reduce the level
of hydrogen sulphide:

Reduce the temperature in the HDS section

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Reduce the H2 recycle

It is noted that the temperature has a greater impact on the equilibrium sulphur content on ZnO
than the amount of hydrogen recycle.
However, as previously discussed both the hydrogen recycle and the temperature play a vital role
with regard to the performance of the HDS section. If the hydrogen recycle is reduced, the
hydrogenation reaction rate on the CoMo catalyst is decreased and there is a risk that organic
sulphur starts to leak. If the temperature is decreased, the reaction rate on the CoMo catalyst is
again reduced and the sulphur absorption efficiency of the ZnO becomes lower. The optimum
solution differs from case to case and it may be necessary to analyse samples of the feedstock in
order to provide the best recommendations.
Sulphur Profile in a Zinc Oxide Bed
The sulphur uptake in a zinc oxide reactor consists of various zones as illustrated in above figure.
Zone 1:
The zinc oxide in this zone is fully saturated with sulphur and the sulphur uptake as ZnS depends on
the operating temperature of the zinc oxide.
Zone 2:
This is the main absorption front where the zinc oxide still has capacity for absorbing the sulphur.
The sulphur is transported through the catalyst pellets by means of solid diffusion and pore
diffusion mechanisms until full saturation is achieved.
Zone 3:
If the feedstock contains CO2 or water, a small amount of H2S will escape the main absorption front
due to the following reactions:
CO2 + H2

CO + H2O

H2O + ZnS

H2S + ZnO

The H2S which may escape the main absorption front will then be chemisorped by the still fresh
catalyst in the lower part of the reactor.
The most important parameter for obtaining a high sulphur absorption capacity in Zone 1 is the
operating temperature and generally a maximum sulphur uptake is achieved at operating
temperatures above 370-380oC.
When operating at low temperatures, the diffusion of sulphur is slow and only the outer shell of the
catalyst gets saturated with sulphur and the centre of the pellet is still pure zinc oxide.
At higher operating temperatures, the sulphur penetrates deeper into the interior of the pellet and
the saturated shell gets thicker and thicker implying that the saturation degree increases and the
utilisation of the zinc oxide improves significantly.
When operating above 370-380oC, the pellets normally become fully saturated.
The H2S entering the desulphurisation reactor is transported to the first available zinc oxide
molecule via pore diffusion and this takes place in the absorption front (Zone 2).
Pore diffusion is very dependent on the operating temperature and to some extent on the amount
of H2S in the gas.
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With an operating temperature above 300C, the H2S molecules are able to penetrate the entire
porous system of the zinc oxide pellets. At lower operating temperature, the degree of penetration
goes down, but this can be compensated for by using a more porous zinc oxide (see below).
In case the H2S content in the hydrogenated feedstock is below a few ppm, the driving force for the
diffusion of the H2S in the pores is low and most of the H2S molecules will be unable to get deep
into the pores, implying that they can only be absorbed on the external surface whereby the
efficiency of the zinc oxide will go down.
Therefore, when operating on feedstocks containing low amounts of sulphur, a zinc oxide with
larger pores (lower density) is recommended.
When the H2S has been absorbed on the zinc oxide in the catalyst pores and thus have become ZnS,
it is being transported further into the solid catalyst mass by solid diffusion.
Basically, solid diffusion means that the sulphur in the ZnS phase has a tendency to spread towards
the ZnO phase. The driving force in this phenomena is the H2S continuously entering the catalyst
pores and thereby pushing forward the sulphur already absorbed. A high sulphur content thus
favours the solid diffusion.
As previously shown, the solid diffusion is also favoured by high temperatures.
In case any sulphur is left after the main absorption front (Zone 2), this will be chemisorped on the
fresh zinc oxide in the lower part of the reactor.
The chemisorption takes place on the surface of the zinc oxide and it is limited to cover only one
atomic layer, meaning that the thickness of this layer is only around 4 ngstrom (). Put in another
way, if these layers were stacked on top of each other, it would require 25,000,000 layers to reach
one centimeter (cm) of height.
The chemisorption process is a result of the formation of a strong chemical bond between the
sulphur from the gas phase and the zinc present in the catalyst surface. It is difficult to break this
bond and as such the sulphur is fixed on the catalyst surface.
As the chemisorped sulphur only covers one atomic layer, the amount of sulphur being trapped by
chemisorption is rather low. However, as the absorption of sulphur in Zone 1 and 2 is limited by the
reaction
ZnO + H2S

ZnS + H2O

there may in some cases be a small amount of H2S which cannot be absorbed by the zinc oxide due
to the chemical equilibrium. As mentioned previously, this will be the case when the feedstock
contains water and/or carbon dioxide.
The small amount of sulphur which is not absorbed by the zinc oxide in Zone 2, will then be
chemisorbed by the zinc oxide in Zone 3 and the result will be a practically sulphur-free feedstock.
Topsoe Zinc Oxide Catalyst
The HTZ-3 & HTZ-5 zinc oxide is delivered in the form of extruded cylindrical pellets consisting of
almost 100% pure zinc oxide. The catalyst does not require any activation and can be put into
normal service right after loading.
HTZ-3 is the work-horse within sulphur absorption. Being almost 100% pure zinc oxide and with a
bulk density as high as 1.3 kg/l, the possible attainable absorption capacity is as high as:
1.3 kg/l x 393 kg S/m3 = 510 kg S/m3 HTZ-3
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Being a high density product, HTZ-3 is suitable for feedstocks having a sulphur content of more
than 5 ppm.
For feedstocks with less sulphur content, the porous HTZ-5 zinc oxide is normally preferred. The
larger pore volume of this catalyst facilitates the pore diffusion of the sulphur from the sulphur lean
feedstocks.
A well-functioning HDS section is essential for the protection of downstream catalysts and it is
therefore important to consider what impact changed operating parameters or feedstock
properties will have on the performance of the hydrogenation and zinc oxide catalysts.
A specific plant is designed on a well-defined basis. However, after the plant has been
commissioned, the actual operating conditions may differ from the design basis. Also in case of
capacity upgrading, the operating conditions in the HDS section may change.
Generally, the parameters influencing the operation of the HDS section may be divided into two
groups:

Plant operating parameters controlled during the daily operation. These include
operating temperatures & pressures, recycle rate, etc.

Change in feedstock delivered at battery limits. This includes feedstock composition,

pressure, etc.

In the event that the daily operation of the HDS section differs significantly from the design basis,
due consideration should be given to evaluate the effect this may have on the efficiency of the HDS
section.
In case the operating temperature drops below the recommended level, there is a risk of
insufficient conversion of the organic sulphur compounds in the hydrogenator. As these organic
sulphur compounds will travel unconverted through the zinc oxide, one will experience sulphur
breakthrough from the HDS section and a potential sulphur poisoning of the primary reformer
catalyst.
One should note that it is quite difficult to get reliable analysis of low organic sulphur contents and
by using conventional laboratory methods, the detection limit is around 50-100 ppb. of organic
sulphur which is sufficient to poison the primary reforming catalyst.
Therefore one should always operate the hydrogenator at a temperature which is close to the
design temperature.
At high operating temperatures the hydrocarbon feedstock may begin to thermally crack whereby
carbon lay-down on the catalyst will occur.
CH4

C + 2H2

The rate of carbon formation increases with the operating temperature and the mole weight of the
hydrocarbon feedstock. For plants operating on natural gas and with 2-5% of recycle hydrogen,
thermal cracking will not occur at temperatures below 400C.
As the carbon will block the access of the reactants to the active CoMoSx phase, small amounts of
carbon lay-down will influence the catalyst activity, which may reduce the conversion of the organic
sulphur and sulphur breakthrough from the HDS section may occur.
In severe cases of carbon lay-down, a pressure drop increase will be noticed across the
hydrogenator.
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In order to convert the organic sulphur compounds in the hydrogenator to H2S, it is necessary to
operate continuously with a hydrogen recycle. Furthermore, carbon lay-down will occur when the
hydrogen recycle is interrupted. Both scenarios will imply that sulphur breakthrough will occur, as
discussed previously.
Operating the hydrogenator without hydrogen recycle should only take place in natural gas based
plants during start-up when the feedstock flow is relatively low. During start-up the hydrogenator
the temperature should be in the range 280-300C to avoid carbon lay-down. As soon as the recycle
hydrogen is available, the operating temperature should be increased towards design.
The above figure shows actually measured sulphur levels from an industrial unit at a time when the
sulphur content of the feedstock changed.
The unit had been operating on a practically sulphur-free feedstock for a long period of time
(years). However, suddenly both the organic and inorganic (H2S) sulphur content in the feedstock
increased within a very short time. Immediately thereafter the organic sulphur leakage from the
hydrogenator increased and it peaked after a couple of hours and then gradually decreased as the
hydrogenation catalyst gained activity due to the formation of more CoMoSx.
The plant only discovered what had actually happened in their HDS section when the tubes in their
primary reformer were glowing indicating a severe sulphur poisoning of the catalyst.
The organic sulphur content at the exit of the hydrogenator and the H2S content at the exit of the
two desulphurisers should be analysed regularly (every shift) in order to follow the performance of
the catalyst closely. Furthermore, the equipment/reagents used for making these analysis should
be calibrated and checked to obtain reliable results.
Sulphur analysis of the feedstock should also be carried out regularly, especially if the source of the
feedstock changes (different gas wells for instance).
The pressure drop across the hydrogenator & desulphurisers should be logged and the
development should be evaluated by comparing with previous data.
In order to utilise the zinc oxide most efficiently it is desirable to operate at a temperature above
360oC. As for the hydrogenation catalyst the risk of carbon lay-down exists and therefore the
maximum recommended operating temperature is normally 380C for naphtha feedstock and
400C for natural gas feedstock.
Hydrogen recycle should be present at all time and it should be as close as possible to the
recommended value (design value).
Normally the zinc oxide is loaded in two separate vessels placed in series. It is considered good
practice to replace the zinc oxide in the lead vessel when the outlet sulphur analysis from this
vessel starts increasing. In this way the second vessel is desulphurising the natural gas when the
lead vessel is by-passed and the catalyst is being replaced. In the remainder of the time the second
vessel acts as an guard/insurance.
In case it is necessary to inspect the reactors in the HDS section without unloading the catalyst, the
following should be noted.
The hydrogenation catalyst which has been in operation is pyrophoric and could heat up when
getting in contact with air.
Hydrogen chemisorped on the zinc oxide surface may heat up when getting in contact with air.

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Consequently, both types of catalysts should be cooled down before opening the reactor manholes.
It is considered good practice to inject nitrogen into the reactors when the manhole is open and to
only open one manhole in each reactor in order to avoid chimney effects.

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