Tops~e

Ammonia Plant Catalysts from a

Theoretical and Operational View Point

24 July 2001
at
Hotel Austral,
Bahia Blanca, Argentina
 Desulphurisation of Hydrocarbon Feedstocks
Using Hydrogenation & Zinc Oxide Catalysts

Primary Reforming Catalysts:

Understanding the Operation

Secondary Reforming. What's the problem?

Presentation of HTS & L TS Operation

· Methanation
The Final Purification

Ammonia Synthesis Catalysts

How do they function? And how should they be operated?

Notes
Desulphurisation of Hydrocarbon Feedstocks
Using
Hydrogenation and Zinc Oxide Catalysts
 - 1-

Desulphurisation of Hydrocarbon
Feedstocks
Using
Hydrogenation & Zinc Oxide Catalysts
by
Mads Feddersen
Hsldor Topse AIS

The first catalytic reactors in an ammonia plant is found in the desulphurisation section, in
which the hydrocarbon feedstock is purified for sulphur and sometimes chlorine.

Ensuring a good operation of the hydrodesulphurisation (HDS) section is important as a

poorly performing liDS-section may be responsible for catalyst failures in the downstream
steam reformer and shift section.

In the new generation of ammonia plants most of the catalytic reactors are designed with less
and less margin and this has increased the demand for catalysts with a high and stable
activity. The proper operation of the desulphurisation section is therefore more important than
ever.

This paper discusses some of the key issues in minimising the sulphur leakage from the HDS
section and how to monitor the performance of same.
 -2-

Desulphurisation System Lay-outs

The desulphurisation (liDS) section typically consists of the following reactors operating in
series:
• One hydrogenator using a cobolt molybdenum (CoMo) based catalyst which
converts the organic sulphur from the hydrocarbon feedstock to H 2S
• Two desulphurisers where the H2S is removed by absorption on zinc oxide

The operating parameters of the hydrogenator and the desulphurisers are closely linked, as the
hydrogenator exit gas enters directly into the first desulphuriser and thus no heat-exchange
nor gas addition takes place between the units.
 -3-

Hydrogenation Reactions
Organic Sulphur
RSH + H2 ~ H2S + RH
COS+ H2 ~ H2S +CO
R1SR2+ 2H2 ~ H2S + R1H + R2H
R1SSR2 + 3H 2 ~ 2H2S + R1H + R2H
Thiophenes + 4H 2 ~ H2 S + Hydrocarbons
Other Reactions
CO+ H 20
HCL+RH

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 C02, 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.
 . 4.

Topsse Hydrogenation Catalyst

Physical and Chemical Characteristics

TK-550

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 Tops~e 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 .
 •5•

The TK-550ffK-250 catalysts are nonnally delivered in the oxidised state where the catalyst
activity is low. The catalyst is therefore activated by sulphiding the CoO and Mo03 compounds
whereby the active CoMoS, phase is fonned:

CoO
+ Sulphur <::::> CoMoS,
Mo03
In most plants the sulphiding media will be the same feedstock as used during nonnal
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 ofCoMoS, phase in the catalyst
depends on the amount of sulphur in the feedstock.
 -6-

- I
CoMo Catalyst Activity as a Function of
Sulphur Content in Natural Gas

a-
·:;
~
~
"i8
l! 1UQfJ - I

0 5 10 15 20 25
Sulphur In Feed, ppm

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
CoMoS, 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 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
strip-off sulphur from an already sulphided hydrogenation catalyst.
 -7•

CoMo Catalyst Activity as a Function of

Operating Temperature

250 300 350 400

Operating Temperature, oc

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 fillS section and
potential sulphur poisoning of the primary reformer catalyst.

At relatively high temperatures the hydrogenation catalyst also possess affinity for cracking
reactions:

It is therefore necessary to operate the hydrogenation catalyst within a certain temperature

range to ensure a satisfactory performance and most of the hydtogenators being designed
today operate at temperatures between 350-400"C.
 - 8-

Catalyst Deactivation
Reduction of Unsulphided Catalyst

• Operation with low sulphur feedstock and

high hydrogen during initial start-up

As mentioned previously, a hydrogenation catalyst will loose 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 Mo0 3 being reduced to Mo0 2.

Contrary to Mo0 3 , the Mo02 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 Mo0 2. This means that the catalyst has irreversibly deactivated.
Furthermore, the Mo0 2 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.
 -9-

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 300°C, 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.

During start-up and shut-down were hydrogen recycle may not be available, the operating
temperature should be reduced to 300°C until the recycle gas is available.

In extreme cases of carbon lay-down, a pressure drop increase will occur across the
hydrogenator.
 - 10-

Catalyst Deactivation
Pore Mouth Plugging

New catalyst Plugged catalyst

Catalyst pore

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 sulphur reactants cannot get in contact with the active CoMoS, 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.
 - II -

The Sulphur Absorption Reaction

Other Reactions

The H2S which have been formed in the hydrogenator is removed in the desulphurisers using
zinc oxide as absorption media:
ZnO + H2S <=> ZnS + H20

Theoretically, 1000 kg pure zinc oxide can maximal absorb:

MWsulpltu/MWz,. 0 X 1000 ( 32/81.4) X 1000 = 393 kg Sulphur
Corresponding to:
MWsulphu/MWz,.sX 100 = (32/97.4) X 100 = 32.8 Wto/o Sulphur

A good performance of the desulphurisers implies that the feedstock going to the reforming
section is practically free of sulphur.

In case C02 is present in the hydrocarbon feedstock, this may to some extent influence the
performance of the zinc oxide. The recycle hydrogen will react with C0 2 and form water:
H2 + C02 <=> co + HP

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 ZnCl 2 . At
normal operating temperatures of HDS sections, ZnC1 2 will sublimate and deposit on
downstream catalysts. Chlorine should therefore be removed upstream the zinc oxide by a
special guard catalyst.
 - 12

Equilibrium H2S Outlet ZnO Vessel

5°/o C02 in Natural Gas

80

l 60
t
~ 40

20

0
300 320 340 310 380 400 420 440
Temperature 'C

If the feedstock contains carbon dioxide, the steam content in the gas will increase
considerably, as the C0 2 in the feedstock will react with the recycle hydrogen according to
the reverse-shift reaction:
C02 + H2 <=* CO + H20

The steam formed from the above reaction will have an impact on the equilibrium content of
H2S on the ZnO. Assuming a C02 content in the feedstock of S% and a hydrogen recycle of
3%, the steam content in the gas equals 0.9% at 400°C. 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
• 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 peiformance 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.
 13-

Sulphur Profile in a Zinc Oxide Bed

Zone 2: Main Absorption Front

Zone 3: Chemisorption Front

Zone 1

Top Bed Bottom Bed

--~~·~ Direction of Gas Flow

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 C0 2 or water, a small amount of H2S will escape the main
absorption front due to the following reactions:

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.
 - 14-

Typical Sulphur Uptake for HTZ-3

40
~ 35
30
i
-..
I'll
a.
::)
25
20
:I 15
.c
a. 10
:;
(/) 5 @
0
100 200 300 400
Operating Temperature, oc

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 370-3800C.

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 370-3800C, the pellets normally become fully saturated.
 - 15-

Absorption Front - Zone 2

Pore Diffusion

------ ;/

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.

With an operating temperature above 300"C, 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 H 2S 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.
 - 16-

Absorption Front - Zone 2

Solid Diffusion

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 H 2S 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.

 - 17-

Chemisorption Front - Zone 3

0 .··
-~· ZnS - • H2S
'
"""""!_-~

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 pan 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 Angstrom (A). 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 (em) 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
Zn0+H2S ~ ZnS+HP
there may in some cases be a small amount of H 2S 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.
 - 18 -

Topsoe Zinc Oxide Catalyst

Physical & Chemical Characteristics

Catalyst HTZ-3 HTZ-5

Shape Cylinders Cylinders
Dimensions OD, mm 4 4
Active Component ZnO ZnO
Other Compounds Traces Traces
Bulk Density, kg/1 1.3 1.0

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/1, the possible attainable absorption capacity is as high
as:
1.3 kg/1 x 393 kg Sfm3 = 510 kg S/m3 HTZ-3

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 HfZ-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.
 • 19-

Common Problems Experienced in the

HDS Section

• C02 in feedstock
rfll twt _, ).(7J ...-ta
I
,
1:>.;- Z'h S";; ~ 1 >'t'"t"'t?
A well-functioning liDS 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 perfonnance 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 liDS section may change.

Generally, the parameters influencing the operation of the liDS 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 liDS section differs significantly from the design
basis, due consideration should be given to evaluate the effect this may have on the efficiency
of the liDS section.
 -20-

Low Operating Temperature

in HDS Section

• Risk of organic sulphur breakthrough due to

insufficient catalyst activity
• Decreased lifetime of zinc oxide due to less
sulphur pick-up capacity

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.

Another factor to consider is the sulphur pick-up capacity of the zinc oxide which decreases
when the operating temperature is lowered. This implies that the lifetime of the zinc oxide
will be shorter.
 - 21 -

High Operating Temperature

in HDS Section

• Potential risk of carbon lay-down from

cracking of hydrocarbons resulting In
reduced catalyst activity

At high operating temperatures the hydrocarbon feedstock may begin to thermally crack
whereby carbon lay-down on the catalyst will occur.
C~ => 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 400"C.

As the carbon will block the access of the reactants to the active CoMaS, 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.
 22-

No Hydrogen Recycle to HDS

• Risk of organic sulphur breakthrough as no

hydrogenation takes place
• The affinity for carbon lay-down on the
catalyst is increased

In order to conven the organic sulphur compounds in the hydrogenator to H2S, it is necessary
to operate continuously with a hydrogen recycle. Funhennore, 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 stan-up when the feedstock flow is relatively low. During stan-up the
hydrogenator the temperature should be in the range 280-300"C to avoid carbon lay-down. As
soon as the recycle hydrogen is available, the operating temperature should be increased
towards design.
 . 23.

Fluctuating Sulphur Levels

3
·-o-H2S·In

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
moreCoMoS,.

The plant only discovered what had actually happened in their HDS section when the tubes in
I, their primary reformer were glowing indicating a severe sulphur poisoning of the catalyst.
 -24-

Monitoring the Performance of the HDS

Section
• Measure
- Organic sulphur & H2 S in the feedstock
- Organic sulphur slip from hydrogenator
- H2 S concentration exit both desulphurisers
• Check the pressure drop across the
hydrogenator & desulphurisers and evaluate
the trend

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 canied 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.
 . 25-

Normal Operation of HDS Section

• Maintain an operating temperature of

360~3aooc

• Ensure an hydrogen recycle which is

close to the recommended (design)
value
• Replace ZnO in lead vessel when H2 S
slip increases from this reactor

In order to utilise the zinc oxide most efficiently it is desirable to operate at a temperature
above 360"C. As for the hydrogenation catalyst the risk of carbon lay-down exists and
therefore the maximum recommended operating temperature is normally 380"C for naphtha
feedstock and 400"C 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.
 -26-

Safety Precautions for

TK-550/250 & ~;t3
··~.7
• Catalyst which has been in operation may be
pyrophoric and could heat up when getting
In contact with air
• Catalyst should be cooled down before
opening the reactor manholes

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.

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.
Primary Reforming Catalysts
Understanding the operation
 - 1-

Primary Reforming Catalysts:

Understanding the Operation

by
Frederik Seby
Hsldor Topsee A/S

The primary reformer is one of the most critical units to operate in an ammonia plant and
successful operation of the unit is closely linked to an understanding of the refonning
catalyst(s) installed.

A number of different parameters will adversely affect the performance of the catalyst(s).
Sulphur even in small quantities will reduce the catalyst activity and visibly cause a
deterioration of the performance of the reformer. The fundamentals of sulphur poisoning are
therefore discussed at length.

Slight poisoning of- and carbon formation on- the refonning catalyst(s) can be overcome to
some extent by a proper regeneration and examples of regeneration procedures are therefore
discussed at length.
 -2-

Steam Reforming Reactions

Steam Reforming
CH 4 + H20 ~ C0+3H 2
CnHm + nH 20 ==? nCO + (n+m/2)H 2
CO+ H 20 ~ C02 +H 2

Thermal Cracking
==? nC + (m/2) H2

The steam reforming reactions consist of (ir-)reversible reactions of hydrocarbons with steam
to form CO and H 2 followed by equilibration of the CO with HzO according to the shift
reaction.

Both the steam reforming of methane and of higher hydrocarbons are highly endothermic
reactions, whereas the shift reaction is exothermic.

The equilibrium content of methane (i.e. the methane leakage) depends mainly on the steam
concentration (as expressed through the Steam-to-Dry-Gas ratio SDG), temperature and
pressure exit the reformer. The higher the temperature and SDG-ratio and the lower the
pressure, the lower will be the methane leakage. For practical reasons, there are limits
downwards for the pressure and limits upwards on the temperature exit the reformer.
Likewise, increasing the SDG-ratio is a very costly way of decreasing the methane leakage.

The typical methane leakage from the reformer in an ammonia plant will be in the range of 7
to 13% vol.

The competing reaction is the thermal cracking of higher hydrocarbons, which reaction is
favoured by higher temperatures.
 -3-

Reforming Catalysts
The steam reforming reaction proceeds on
nickel crystals dispersed on a thermo-stable
carrier

Critical catalyst parameters are:

a large nickel surface
void space
crush strength
geometrical shape
heat transfer

The methane reforming reactions proceed very slowly in gas phase at the temperatures in the
range from 600 to 900°C, whereas the thermal cracking will proceed with more ease. Nickel
catalyses the steam reforming reactions at temperatures where the carbon formation reactions
do not proceed at any appreciable rate, and by providing a large number of active sites on the
nickel surface the steam reforming reaction will be the only reaction of practical imponance.

Besides providing space for a large nickel surface area the carrier must comply with a lot of
other requisites. A well-designed geometrical shape will provide for a large external surface
with easy access to the interior of the catalyst pellet and a high void fraction to provide a low
pressure drop. Funher, the pellet shape must provide for sufficient mechanical strength and at
the same time ensure a sufficient heat transfer at the interior tube wall.
 -4-

Size of Ni Crystals
Volume= 1 Volume= 1
Surface= 18 Surface= 6

The steam reforming reactions take place on the surface of the nickel crystals and not in its
interior and further, not all nickel surfaces are equally suitable. It is therefore of paramount
importance that the reforming catalyst offers a vast nickel surface.

A high content of nickel does not automatically qualify a catalyst. The nickel must be highly
dispersed, i.e. it must be distributed into as tiny crystals as possible to provide the highest
possible surface area.
 5-

Sulphur Poisoning

• Sulphur poisons a
reforming catalyst by
blocking of the active sites ..
• ..whereby fewer sites
become available for the
main reaction ..
• .. and a higher operating
temperature Is required for
a given conversion

As mentioned previously the catalyst relies on a high number of active sites on the nickel
surface. Nickel also has a high affinity for sulphur, however, and even small quantities block
the active nickel sites. Sulphur is omni-present and enters with the feedstock in spite of
careful desulphurisation. Thus depending on the efficiency of the desulphurisation section,
the nickel surface becomes more or less affected

Sulphur blocking the active sites on the reforming catalyst leaves fewer sites available for the
main reforming reaction. With fewer sites to handle a given conversion the remaining sites
will have to work faster and this requires higher temperatures in the catalyst. When the
catalyst temperature increases, so does the temperature of the tube metal. Alternatively, the
conversion will have to be decreased. Sulphur poisoning is thus very serious in that it either
jeopardises the tubes life or the production rate.
 -6-

Sulphur Poisoning ...

... is a dynamic process

Gas Flow =======-=-==--

®............_ ,,,,,.,,,,,~oo~!o
1111~"/ '-..
® s

The interaction of sulphur with the nickel crystals may best be described in terms of
chemisorption being an intermediate between adsorption and chemical reaction:

The chemisorption of sulphur on the nickel surface is very strong in the sense that equilibrium
is largely in favour of the nickel sulphur chemisorption complex. Chemisorption is favoured
by low temperatures and low concentrations of hydrogen and is therefore of greater
importance in the top part of the catalyst loading than in the bottom.

It is important to emphasise that the formation of the sulphur-nickel complex is the result of a
reversible reaction and that sulphur is attached and released from the active site again and
again. The higher the temperature the more frequent are these jumps between the surface
complex and the gas phase, and the sulphur thus moves slowly in the top of the reformer
tubes and faster in the bottom of the tubes.
 - 7-

Sulphur Poisoning ...

... more than proportional effect

120
100
{ 80
60
~
~a:
40
20
0
~ ...~ , ~ ~ ~
Sulphur Coverage, %
~ ... ~

There is not a linear relationship between the catalyst activity and the number of active sites
blocked by sulphur. On the above graphic the activity is seen to decrease more than
proportionally with the fraction of active sites covered with sulphur (Sulphur Coverage).

The reason is that not all active sites on the catalyst are equally accessible due to pore
diffusion. As the sites on the external surface are blocked first by sulphur, the refonning
reaction is forced to take place in the pores of the catalyst with a disproportionate effect on
the activity.
 -8-

Sulphur Poisoning ...

. . . depends on temperature
Sulphur Coverage
1
...,_PPbv=10
-o-ppbv=SO
-t:r- V=100
0.8

0.6

500 550 600 650 700 750 800 850 900

Temperature, •c

Not only does the dynamics of the reaction between gaseous sulphur and the active surface
sites increase with temperature, the equilibrium moves away from chemisorbed sulphur at
higher temperature. Actually, the temperature has a much greater effect on the amount of
chemisorbed sulphur than does changes in the sulphur content of the gas.

The implications are that sulphur has a profound poisoning effect at low temperatures: At the
inlet of most primary reformers, sulphur is quantitatively retained. At the bottom of the
primary reformer, sulphur coverage is too low to give a noticeable effect, and sulphur
poisoning does virtually not exist at the high temperatures prevailing in secondary reformers.
 -9-

Sulphur Poisoning ...

... develops slowly

Calculated Sulphur Coverage

(Based on 7 ppb S In the Feed)

:-vear1
:-vear2
0.8 i-vear3
: - E ulllbrlum
0.8
0.4

0.2

20 40 60 80 100
Tube Length, %

Even though small concentrations of sulphur in the gas will lead to relatively high
equilibrium surface coverage, this equilibrium level is approached only slowly and it will take
years before it is reached. Again the speed with which equilibrium is reached depends on the
sulphur concentration and the temperature.
 - 10-

Sulphur Poisoning May Lead to Carbon

Lay-down and High TWT's
Carbon Formation from
higher Hydrocarbons
Steam to higher
Hydrocarbon Rallo Actual
14
(Low activity)
Critical
12

o~--------------------------------
0 5
m lrom Inlet

As mentioned previously the poisoning of a reformer catalyst wiii cause the catalyst
temperatures to increase at a given throughput and thus a fixed heat duty. At the higher
temperature level the risk is that the steam to higher hydrocarbon exceeds the limits for
carbon formation and carbon is formed. Even if this is not the case, the higher temperature
level will have a significant impact on the life of the reformer tubes.
 -11-

Effect of TWT on Tube Life

•~
.·.
••
.•.
':.

•..
ftl:lll . .
..
-...-r....

Tube Skin Temperature

880 920 1160 1000 "C

(1610) (1680) (1760) (1832) ("F)

Reformer tubes are normally designed for a service life of 100,000 hours at a certain
temperature called the design temperature. The strength of the metal depends very much on
the temperature and as a consequence, so does the actual service life: As a rule of thumb the
life doubles or halves with a change in the tube metal temperature of l5°C.

The actual life of these tubes wiii depend on the history of the reformer operation, i.e. actual
temperatures experienced in the past, on the presence of hot spots and hot bands on the tubes
over periods of time. No tube is stronger than its weakest (i.e. hottest) spot, and proper
monitoring of the reformer tube temperatures is therefore a very important task.
 - 12-

Pyrolytic Carbon Formation

on Sui ur Poisoned Catalyst

With a sulphur poisoned catalyst the steam reforming reactions will not proceed fast enough,
and the temperature may at some points in the reformer exceed the limit for carbon formation.
This carbon is generated from the thermal cracking of higher hydrocarbons.

This type of carbon is deposited on the catalyst surface and especially on the inside surface of
the tubes and it grows into the void space. It will not form inside the catalyst and will thus not
damage the catalyst pellets, but it will block the access to the interior surface of the catalyst.

The temperature in the very top of the reformer is normally too low for the cracking to be
initiated, the carbon will begin forming typically 2-3 meters from the top and extend a couple
of meters further down. A hot band is formed!
 - 13-

Sintering

• Slnterlng Is coalescence of
small crystals Into large ~~~~
ones
• Slnterlng reduces the
activity
• Slnterlng Increases at high
temperatures
'
Theory predicts that metal crystals become unstable at high temperatures and tend to coalesce
into larger ones. This is indeed the case for the catalyst installed in the bottom of the
reformer, where the operating temperature is close to or above soo•c.

When the crystals coalesce, the resulting surface is diminished and so is the catalyst activity.
 - 14-

Sintering of Nickel Surface

(Ceramic Reforming Catalyst)

1.0
~~
CliO')
0.8
·-
z·cc 0.6

:;=~·; 0.4
'iii
0:¢::: 0.2
as
0
1

Sintering is a function of both time and temperature. It is noted that the sintering rate at
550°C, corresponding to the temperature in the top of a typical reformer, is not appreciable at
all.

At 700°C the sintering rate is noteworthy. and just a few months of operation at 800°C will
leave a fraction of the initial nickel surface area available for the reforming reaction.
Fortunately, the requirements in terms of activity are much smaller at higher temperatures,
because of the higher reforming reaction rate and the smaller effect of any sulphur in the
feedstock.
 - 15-

Challenges in Reforming

880
860
00
840 Sintering
!! 820
800 "f<i~wJJC,....,Cv..

J ~
780
760 t
740
720
0 2 4 6 8 10
Distance from Inlet, m

The phenomenas discussed in the previous sections define three distinct challenges in design
of a catalyst charge. The top part should have a high nickel surface, as the temperature is
lowest here and the requirements in terms of activity are at the maximum. Furthermore,
sulphur will have the maximum impact in this zone.

The presence of sulphur in the gas may push the reforming reaction towards the hotter parts
of the catalyst and eventually lead to the formation of pyrolytic carbon in the middle part of
the reformer tube. This will in all cases be aggravated in top-fired reformers where the heat
flux is maximum in the middle portion of the tubes.

Finally, sintering is of concern in the bottom part of the tube. Fortunately, the high
temperature causing the problem also helps to solve it, in that the reaction rate is
comparatively high in this part of the tube.

In top-fired reformers problems therefore become evident by high tube wall temperatures
rather than by an increased approach to equilibrium.
 - 16.

Triple Decker

880
860
840 Slntering
I!!
.
3c 820
G> BOO A-67·7H
"'~ 780
1- 760
740
~ t

720
0 2 4 6 8 10
Distance from Inlet, m

Tops!lle have decided to address these challenges by using up to three different catalysts
depending on the operating conditions and the composition of the natural gas feedstock.

In the top part of the loading we utilise pre-reduced catalyst. This catalyst has been reduced in
our manufacturing plant under ideal conditions and thereby achieve a significantly higher
nickel surt'ace area than what can be obtained during an in-situ reduction. This increase in
nickel surt'ace area helps to accommodate any sulphur in the feedstock and increases the
poisoning resistance.

In the middle part of the loading where carbon formation may occur, Tops¢e utilises a
catalyst promoted with a small amount of potash. The presence of potash on the catalyst helps
removing the carbon deposits, and carbon free operation can therefore be ensured.

The carrier used for the Tops!lle line of reforming catalyst is made of magnesium spinel. This
material has a very high fusion point and forms a very stable basis for the nickel crystals to
minimise the rate of sintering in the bottom of the tubes.
 - 17 -

Topsge Steam Reforming Catalysts

Physical and Chemical Characteristics

R-67R·7H RK·211 RK-201 or

Catalyst RK·89·7H R-87·7H
i

Carrier MgAizO• MgAizO• MgAizO• MgAitO•

Active Component Nl Nl NIO NIO
i
Promoter None KtO KoO None
Shape: 7·Hole 18x11
16x11 16x11 16x11
Size, HxD, mm 20x13
State Prereduced Pre reduced Unreduced Unreduced

Tops0e manufactures pre-reduced catalysts for installation in the top part of the catalyst
loading. Mentioned here is the un-promoted reforming catalyst R-67R-7H, but the potash
promoted pre-reduced catalyst RK-211 may be applied as well depending on the operating
conditions.

In the middle section of the tubes potash promoted catalyst RK-69-7H or the more recent
version RK-201 is applied in top-fired reformers and in reformers where the feedstock
contains higher hydrocarbons on a continuous or intermittent basis.

In the bottom part of the tubes, standard R-67-7H is generally the best choice.

Tops0e manufacture the catalysts in several different sizes. Generally, a relatively small-size
catalyst e.g. 16xll mm will be installed in the top where activity is of most importance.
Because the gas expands by the reforming reaction and the higher temperature, the linear
velocity is highest in the bottom of the tubes and pressure drop is a major consideration.
Large size catalyst pellets are therefore often preferred in the bottom half of the tubes.
 -18.

Reformer Operation:
Normal Start-Up
S/C
900 100
800
700
600 10 ....,.T(in)
500 -D-T(out)
400 -t:r- SIC
300 1
200
100
0 -k::f:--1:.~===~.----+ 0,1
Time

Starting up with a reduced catalyst charge is straight forward:

• The refonner is heated in stagnant atmosphere until the refonner inlet temperature is
350°C
• Steam is introduced at low pressure and in a quantity corresponding to 25% of the
nonnal flow and the heating is continued
• When the outlet temperature is 650°C, natural gas is introduced in a quantity
corresponding to a steam-to carbon (SIC)-ratio of 6-8
• Load is gradually increased and the SIC-ratio is decreased towards nonnal operating
values
 • 19-

Reformer Operation:
Normal Shut-Down
T S/C
1000 100
800
10 ..._T(in)
600
-D-T(out)
400 -0:-S/C
200
0 +-----r-l.!r--lb-.f!r-,.0..~---+ 0.1
Time

Shutting down the reformer is in principle the reverse sequence of the start-up:
• Load is reduced
• The SIC-ratio is gradually increased towards 10-15, while the firing is gradually
reduced and the reformer is depressurised
• The supply of natural gas is the cut-off and the reformer is cooled with steam until the
inlet temperature is 350°C
• Steam is then cut-off
 -20-

Emergency Situations
• Loss of feed and/or fuel
• Loss of steam
• Trip of the ID-fan
• Failure of a reforming tube
• Loss of Instrument air
• Power failure

A number of different upsets may occur during the operation of a reformer and the
consequences will depend on the conditions of the actual upset.

If both feed and fuel gas are lost for instance, the continuing steam flow will normally serve
to protect the refonning catalyst while the reformer is cooled down. 1 '- •' "'?~~e ll• ;•,tor£; Zc.P~~r;;
,,..(';;_ 0,•tt ~c1tC.".~"t·4(;~H ;/!:c (I\Ttn•l11lr.;t.2E (JC'<r~ !<. h•(\1~•··';:; r}, C.. A~ 1\C!A I<.··"';;,_;,:"'"
Trip of the ID-fan will normally result in a complete trip of the plant and should immediately
beattendedto."", .• ~.·u::>J btJI.~i-''1\"' ~~t..I.T"'- ,_.,.._ y~h ",.:, )'- d., v.-l, •._,:z;::,_._ .4·:..''"{-') ~
Old tubes in a reformer may with normal ageing develop isolated cracks. These cracks may
be identified visually as flames propagating from the cracks or seen as a local hot area. If a
crack is observed the plant should be shut down immediately and the tube be isolated or
replaced. If operation is continued in these conditions, the flame may touch a neighbouring
tube and start a "snow-ball" effect.
 -21 -

Whisker - Carbon
Occurs at Low Steam I Carbon
( Loss of Steam )

Complete loss of steam is a most serious condition that fortunately does not happen very
often. When the catalyst is exposed to dry hydrocarbons, carbon whiskers will start to grow
on the nickel crystals inside the pore structure of the catalyst. The physical stress exerted by
these carbon whiskers will cause the catalyst to disintegrate.

Partial Joss of steam is more common. Operation at such reduced SIC-ratios will lead to
carbon formation to a varying degree. Generally, if the SIC-ratio is higher than 1.4, the carbon
formed will not cause disintegration of the catalyst and may be removed in a regeneration
with air and steam.

Please note that operation at low SIC-ratios may also have a detrimental effect on the HTS
catalyst.
 22.

Reformer Operation:
Removal of Sulphur

• Sulphur poisoning Is Desorption of Sulphur

reversible 1

}:'
• Sulphur will be removed In a
sulphur-free gas
• Desorption times are very 1 o.4
long
• Desorption is facilitated by
f 0.2
0+---+---~--~~
high temperatures and
10 100 1000 10000
steam/oxygen nme, hr

Sulphur is chemisorbed on the nickel surface reversibly, and if sulphur is removed completely
from the process gas to the reformer, any chemisorbed sulphur will slowly be removed. A
high temperature will facilitate the desorption because of the more rapid interchange between
the gas phase and the surface and due to the more favourable equilibrium.

Within a practical range of temperatures the rate of desorption is quite low, and it may take
months to recover the activity. Stearn and/or oxygen is therefore often required to remove the
sulphur after a sulphur poisoning.
 - 23-

Reformer Operation:
Regeneration for Sulphur

Steam SV : 4000 and T(exit): 800

.
(,)
1000
950
900
0~
_ TWT's

. 400
300
200
,,
I:
(II
0
850 100 ..
800 0
0 2 4 6 8
Time

Sulphur can effectively be removed from the catalyst by steaming at an increased temperature
level. As an example is shown the successful desulphurisation of a reforming catalyst at 4000
Nm3/m3/hr of steam and at an outlet temperature being increased towards 800°C.

Analysing the gas exit the reformer for S0 2 will serve to indicate when all sulphur has been
removed.

As a result of the steaming, the maximum tube metal temperatures were decreased
considerably.
 -24-

Reformer Operation:
Regeneration for Carbon

Steam SV: 4000 and T(exit): BOO

6

8 9 10 11 12
Time

Very often the sulphur poisoning has been going on for some time before it is detected, and
pyrolytic carbon may have formed in the tubes. Carbon can only partly be removed by
steaming alone. Therefore, oxygen in the form of air has to be added to ensure a complete
removal of the carbon.
c .. 0·~ _.., l ·~.,

Analysing the outlet gas for C02 will serve to determine when all carbon has been removed.
Secondary Reforming
What's the Problem?
 - 1-

Secondary Reformer
Air

The operation of the secondary refonner is closely related to the operation of the primary
refonner, as the process gas enters directly from the primary to the secondary refonner
without any intennediate process steps.

The main operational parameter is the air flow, which is adjusted in order to achieve a
hydrogen/nitrogen ratio of close to 3.0 in the make-up gas at the exit of the methanator.

In the past decade the tendency has been to decrease the catalyst volumes in the secondary
refonner and thereby increase the space velocity in this unit. Due to this, the secondary
reforming catalyst has to "work harder" in order to achieve the desired conversion and the use
of high-active catalyst is mandatory.

A well-designed secondary refonner with a high-active catalyst will require very little
maintenance during turn-arounds. However, in a number of especially older plants various
problems are experienced when operating the secondary refonner and this implies that a lot of
maintenance work has to be done during turn-arounds.

In the following some of these problems are presented and means of eliminating or reducing
the effect they may have on the daily operation is discussed.
 . 2.

Secondary Reforming Reactions

Combustion

CH 4 + 0 2 => C02 + 2H2

Steam Reforming
CH 4 + H20 ¢::} CO + 3H2
Water-Shift

In the secondary refonner the unconverted methane from the primary refonner is converted
into hydrogen and carbon monoxide by steam reforming:
C~+H 2 0 ~ C0+3H2

As the steam reforming reaction requires heat and the secondary refonner is an adiabatic
vessel with no heat input from outside, the required heat is generated by the combustion
reactions:

The combustion reactions take place in the free space between the burner and the top of the
catalyst layer. The temperature in this zone is very high, up to 1500"C and this puts great
demand on the materials used inside the vessel, especially the burner and the refractory used
for insulating the vessel.

As soon as the gas enters the catalyst layer, the steam reforming and water shift reactions
proceed and the temperature gradually drops down through tbe catalyst layer towards around
900"C at the outlet of the catalyst.
 -3-

Topsoe Secondary Reforming Catalysts

Shape
Size, HxD,

The secondary refonning catalyst manufactured by Topsllle is based on a ceramic magnesium

aluminate sphinel carrier, which is able to withstand the very high temperatures prevailing in
the secondary reformer. The high thermo-resistance of the RKS-2-7H catalyst implies that it
is not necessary to install any special heat resistant catalyst on top of the RKS-2-7H.

The carrier is impregnated with Ni using a special technique resulting in an optimum

dispersion of the nickel crystals leading to a high and stable catalyst activity.

As with the primary reforming catalyst, the RKS-2-7H catalyst is delivered in the form of a
tablet penetrated by seven holes. Thereby the catalyst pressure drop is greatly reduced and the
active surface area is larger.

The picture shows pellets of RKS-2-7H which are encapsulated in metal originating from a
burner tip. The burner melted due to an upset in the plant and was totally destroyed whereas
the catalyst was able to continue operation after a skimming removing the melted metal
deposits.
 -4-

Uneven flow distribution in the secondary refonner is a well-known phenomena. It is the result
of improper mixing of the process gas and the process air. In extreme cases it can result in a
cold and a hot side in the secondary refonner and this will have great influence on the
conversion across the refonner.

In the following a number of factors which influence the flow distribution is presented.
 -5-

Problems in Secondary Reformers

Uneven Flow Distribution due to
• Burner design
• Refractory break-down
• Disintegration of hold-down material
• Ruby formation

leading to
• Unoptlmal conversion
• Hot spots on pressure shell
• Pressure drop increase

Uneven flow distribution in a secondary reformer can be ascribed to a number of reasons,

including:

Burner Design
Conventional ring burners have a tendency to erode, whereby the flow through the holes
becomes uneven. At high flow rates the problem becomes even more pronounced. The design
of the burner should ensure that the gasses are properly mixed and locally high temperatures
at the refractory is avoided.

Refractory Break-down
The inner refractory used in the secondary reformer must be of very high purity in order to
withstand the high temperatures. High quality castable refractory has an alumina content of
92-96% and a calcium content of a few percent. The amount of impurities such as silica and
alkali metal should be minimised. In case of less pure materials, it is not unusual to
experience refractory disintegration shortly after installation.

Disintegration of Hold-down Material

As for the refractory, the hold-down material installed on top of the catalyst must be of a very
high alumina purity. It is not unusual to find hold-down material where most of the filling
material has evaporated during operation.

Ruby Formation
A peculiar phenomenon which takes place on the secondary reforming catalyst is the
formation of rubies. Especially when the burner is not performing well, the temperatures
locally may be very high resulting in evaporation of hold-down/refractory material. This
leads to ruby formation in the top of the catalyst bed.
 -6-

Traditionally, the mixing/combustion of the process gas from the primary reformer with the
process air from the air compressor has been done using a ring burner as shown above.

The process air is being introduced through the burner and it is "sprayed" through the holes in
the burner ring into the process gas which flows downwards around these rings. When the two
gasses meet., they ignite due to the combustion reactions.

The large heat evolution implies that great demand is put on the burner lay-out and material and
it is not uncommon to find ring burners where part of the holes seems to have grown by the
influence of erosion as seen on the above picture. Computer simulations indicates that the
erosion is caused by back flow of the hot gasses to the edge of the holes as seen on the right
figure.

When erosion of the holes occurs the air flow-pattem through the burner will become un-ideal
and so will the combustion/l!lixing of the two gasses. In most cases this will result in a
somewhat uneven flow distribution down through the catalyst layer and the overall methane
conversion in the secondary reformer will go down.

In severe cases flame impingement from an eroded burner can damage the refractory and the
pressure shell.
 - 7-

In order to solve the problem with erosion of the holes in the traditional ring burner, a new
design has been developed using small nozzles to distribute the process air at the outlet of the
burner.

The computer simulation of the nozzle burner as illustrated on the right figure reveals that there
is no back-Oow of bot gas to the nozzles themselves and thereby the mechanical wear on these
is minimal. Furthermore, the distribution of the gasses ensures that the temperature level at the
refractory is much lower than with the conventional burner. This will reduce the tendency for
ruby formation as described later on.

Feedback from the industry indicates thst these burners are practically maintenance free even
after 8 years of operation.
 - 8-

Hold-down Material

On top of the secondary refonning catalyst a layer of alumina lumps and alumina tiles is
installed in order to protect the catalyst from agitation and direct flame contact.

The picture shows two target bricks (tiles), which have been operating in secondary
refonners. When installed the left one had a relatively high content of filling materials
(calcium, silica, etc.), which has evaporated during operation. Part of the evaporated materials
deposited further down in the catalyst bed and this lead to crust/ruby fonnation and a
subsequent unideal flow distribution.

In severe cases such evaporating materials cause the pressure drop across the secondary
refonner to increase and the plant must be shut-down for skimming of the catalyst bed and
hold-down materials.

The right target brick is made from almost 100% alumina, which has been fused at a very
high temperature. There is no signs of any evaporation and the material is well-suited for
installation on top of the secondary reforming catalyst.
 -9-

It is not uncommon to encounter rubies in the secondary refonning catalyst.

The rubies are basically formed from chromium from the stainless steel piping and aluminates
originating from the refractory in the top of the secondary reformer or from the transfer line
carrying the process gas from the primary reformer.

When the chromium and the aluminates enter the catalyst layer, they cool down due to the
endothermic (heat consuming) steam reforming reaction
CH4 + H 20 <;::> CO+ 3 H2
whereby they co-condense and deposit on the surface of the catalyst particles.

The rubies will gradually glue together the catalyst particles and a crust formation takes place.
This will of course influence the flow distribution and the pressure drop in a negative way.

Secondary reformers experiencing excessive ruby formation can install a toplayer of a special
catalyst developed by Topsee, RKS-2P, which will spread out the reaction zone in the very top
part of the reactor and thereby allow the rubies to deposit in a broader zone, thus resulting in a
slower pressure drop build-up. This catalyst is loaded in the top 30..50 em of the bed and is
operated in the same manner as the RKS-2-7H.

In plants equipped with high quality refractory and with the Topsee Nozzle Burner the risk of
ruby formation is greatly reduced.
 - 10-

Severe ruby formation may also lead to hot spots on the secondary reformer pressure shell.

When the catalyst pressure drop increases, the hot process gas will try to find alternative ways
in the reactor and a small part of the gas will be forced into the refractory layers through cracks.
This implies that the hot process gas gets closer to the reactor wall and there is less insulation
between the gas and the wall, whereby hot spots will be seen on the outside of the reformer.
The hot spots are easily recognised due to the thermo-resistent paint used on the outside of the
secondary reformer.

The outer refractory layer is very sensitive to hot process gas due to its relatively high content
of volatile silica. The purpose of the inner refractory layer of high alumina purity is therefore to
isolate the process gas from the outer refractory layer.

Small by-passes in the secondary reformer refractory may consequently result in evaporation
of silica from the outer layer of silica-containing refractory and this will lead to fouling of the
waste heat boiler down stream.
 - 11 -

Recommended Inspection
During Turn-arounds

• Check erosion of burner holes

• Check refractory and hold-down material

• Check top 20-30 em of catalyst for rubies

During the scheduled turn-arounds it is worthwhile to include an inspection of the secondary

reformer interior to check the condition of the various materials.

Even though the performance of the reactor seemed to be stable and satisfactory prior to the
tum-around, we recommend to do the following inspections as an insurance for the next
operating cycle.

Burner
In case of a nozzle burner, the nozzles should be visually checked for any wear on the burner
tip. For a traditional ring burner the burner holes should be checked for erosion. In case of
excessive erosion the burner needs to be repaired.

Refractory & Hold-down Material

The refractory in the cone and the part above the catalyst bed should be visually inspected to
detect any break-down. New refractory should be applied to areas with cracks/depressions.
The integrity of the hold-down material should be visually checked as well.

Ruby Formation
The top 20-30 em of catalyst should be checked for deposits of rubies by digging downwards
in the catalyst bed. In case rubies are found, it is recommended to carry out a skimming and
screening of the top 50-60 em of catalyst.
 - 12 -

Monitoring the RKS-2-7H Performance

• Check the pressure drop across the

secondary reformer and evaluate the trend

• Measure the methane leakage by laboratory

analysis

• Check shell for hot spots

The methane leakage at the exit of the secondary reformer 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.

The pressure drop across the secondary reformer should be logged and the development
should be evaluated by comparing with previous data.

Finally, the heat sensitive paint on the pressure shell should be inspected regularly to detect
any hot spots, which could imply that the refractory has disintegrated.
 - 13 -

Normal Operation of RKS-2-7H

• Adjust air-flow to maintain a HJN 2- ratio of

close to 3 at the exit of the methanator

The amount of process air introduced in the secondary refonner should be adjusted in order to
have a HfN2 - ratio of close to 3.0 at the exit of the methanator (make-up gas).

The adjustment of the airflow should be made in small steps, as even small changes in the
HfN 2 - ratio in the make-up gas may have a great influence on the ratio in the ammonia loop.
 - 14

Safety Precautions for

RKS-2-7H

• When physically handling nickel catalyst,

It Is recommended that persons wear
protective clothing I dust masks

When handling nickel containing catalysts, it is normally recommended to avoid contact with
the skin/respiratory system by using appropriate protective clothing.

The highly toxic nickel carbonyl, Ni(C0)4 is formed when CO from the process gas gets in
contact with the nickel contained in the catalyst. As long as the process gas does not get in
contact with the secondary reforming catalyst at temperatures below 200"C, the formation of
nickel carbonyl can be practically prevented.

Apart from the above, the handling of the catalyst is straight forward and as long as the
catalyst is being slightly ox.idised during the normal shut-down of the plant, the catalyst is not
pyrophoric when being unloaded.
 Presentation of
HTS & L TS Operation
 • 1•

HTS and LTS Operation

• Theory
• Normal Operation
• Operational Problems
• Tops0e Shift Catalysts

In this paper the theory behind the water gas shift reaction and equilibrium is presented.

Further, the normal operating conditions of the high and low temperature shift catalysts are
discussed, including ways of optimising the shift operation.

Hereafter follows a discussion of the operational problems that may be experienced with HTS
and LTS operation, including pressure drop problems, catalyst poisoning and by-product
formation.

Finally, Tops0e HTS and LTS catalysts are presented and it is described what Haldor Tops0e
AJS has done to overcome the problems that occur in HTS and LTS operation.
 - 2-

The Water Gas Shift Reaction

I
(The Shift Reaction)
CO + H20 <=> C02 + H2 + Q
Equilibrium Curve

...~
• !
I
I I /
"#. ' I I
I v
t. !
I I
v
i) I I /
.;
ii i I I X
"I.
t
i
v I

- - - .. - - ... ... ...

~I
0 •
u I
•
'"" ... Tlft!PIIWiure, "C

The water-gas shift reaction (in short: the shift reaction) is an exothermic reaction between
carbon monoxide (CO) and water (steam):

It appears from the reaction equation that a higher concentration of water (a higher steam/dry
gas ratio) will move the reaction to the right, whereby the equilibrium CO concentration will
be lower.

Since the reaction is exothermic a temperature increase will shift the equilibrium towards a
higher CO concentration as can be seen from the above graph.

It follows from the above that the lowest CO leakage from the shift converters can be
obtained at high steam/dry gas ratios and low temperatures.
 -3-

Shift Section in Ammonia Plant

i
I i I I
•• Cooling SRExl!-

·~
I i ' I v
f I \ I VI

-HHTS\
t. 10 I

I i !

I' I v I
8 ..
I I
Cooling
~
!~/1
v
-
;-LT$

ll..J./ 1
- - ---.-c- - - - ~
0

~ Tlt .....

At the high temperatures prevailing in the reformer section, the shift reaction will normally
have reached equilibrium. In the example depicted above, where the outlet temperature from
the secondary refonner is around 950°C, the equilibrium concentration of CO is 13%.

The process gas is then cooled, in the waste heat boiler and a number of boiler-feed-water
(BFW) heaters, to 360°C before entering the HTS reactor, in which the gas is converted close
to equilibrium at 425°C, corresponding to 2.8% CO. Subsequently the gas is cooled in a BFW
pre-heater prior to entering the LTS reactor at 210°C. In the LTS reactor equilibrium is
reached.

Quite often plant operators have the impression that the CO slip from the HTS is not very
important, since the CO leakage from the HTS can be dealt with in the LTS.

However, as can be seen from the above graph, the CO leakage from the LTS will be higher
if the process gas enters the LTS with the same temperature but a higher CO concentration. If
the LTS inlet temperature can be decreased further, the same CO leakage can be achieved
provided that the LTS catalyst is able to convert the gas to equilibrium.
 -4-

Normal Operation of Shift Reactors

• S/C ratio 2.8 at primary reformer inlet
(3.0 for hydrogen plants )

• T (Inlet) of LTS must be 15·20°C above dew

point of process gas

• Adjust the Inlet temperatures to maximise AT

across the shift reactors

Due to the risk of Fischer-Tropsch by-product formation (will be dealt with in another
section), it is recommended to operate with a steam-caibon (SIC) ratio of at least 2.8 at the
inlet of the primary refonner. For hydrogen plants the limit for safe operation is considered to
be3.0.

As mentioned above it is advantageous to lower the inlet temperature of the LTS reactor and
increase the Steam-Dry Gas (S/DG) ratio if the only objective is to lower the CO slip.
However, due to the possibility of condensation in the catalyst pores the limit of the LTS inlet
temperature is l5-20°C above the dew point of the gas. A higher SIDG ratio will of course
increase the dew-point. An approximate formula for calculating the dew point is : T(dew
=
point)I"C 100 ·~P(H20), where P(H20) is the partial pressure of water in atmospheres
(abs).

The operation of the HTS vessel can be optimised by adjusting the inlet temperature until the
maximum temperature increase across the reactor is reached. When adjusting the LTS inlet
temperature the aim is to reach a maximum IJ. T across the LTS reactor, whereas the
( methanator IJ.T should reach a minimum. Another method is to look at the approach to
1
equilibrium (ATE, see below). \ . o1 H• t ,_
\., ·-.;: ""< \'\<A\~\J.. '-'v t ( ->
,
w., "t I{ n v. , .'-"'·l t?
. ,_
....._,
,
'' 1
1 'l(. J •._, .- ,~-~ , ·,- J" ,<~,.., ...<.. "...:.," i, ..._, 1......, ~-., ...,_ _
~ (._.~~ ~- ,.J"-
1 ~ !,(? ~'"'""--· ." .~ ~r/·-"
"\ " '- - . J • ')
\
p \ (iJ 11'); •1 (0. e )'' ;1, <. d ,!. r· C\
 -5-

Optimization of Shift Reactors

i
i
: I
I. I'
i OPJ1;'m!
--i>! • 5-10'C !<l--
Temperature

The plot shows the equilibrium curve for the shift reaction as a function of CO and
temperature, which should be kept in mind when optimising a shift converter. At stable
conditions in the reforming section, the inlet CO concentration is given and the shift inlet
temperatures can be varied. When the CO in the feed gas shifts, one will move towards a
lower CO and a higher temperature limited by the equilibrium curve.

Further, the plot shows that if the inlet temperature is low {or the catalyst has a low activity),
the temperature approach will be high (1). It is possible to compensate for this by increasing
the inlet temperature (2), resulting in a lower CO leakage. The approach to temperature
equilibrium {ATE) is illustrated on the plot as the distance between the equilibrium curve and
the exit temperature.

If the inlet temperature is increased too much (3), the reaction will come very close to
equilibrium, whereby the catalyst is not used efficiently. Moreover, the equilibrium CO
concentration will be higher because the equilibrium concentration increases with increasing
temperature for an exothermic reaction.

This is why it is not optimal to operate an fiTS shift converter to reach equilibrium at the exit
of the bed. As indicated by (2) on the plot, calculations show that the optimal CO leakage is
obtained when operating with a temperature approach of about 5-lO"C. The same principles
apply to the LTS operation, but when the LTS catalyst is new equilibrium is often reached in
the bottom part of the bed, since the inlet temperature in most plants cannot be lowered to
less than 190-195°C due to the risk of condensation.
 - 6-

Monitoring the Catalyst Performance

• Monitor the ~P across the shift reactors and

follow the trend

• Measure CO leakage by laboratory analysis

• Record bed temperatures and check for any

irregularities

The operation of the liTS and LTS reactors should be monitored regularly in order to
discover any abnormalities.

The parameters that can and should be checked are:

• Pressure drop across the reactors
• CO slip
• Bed temperatures

If the measured pressure drop starts to increase the plant personnel should investigate what
the reason may be (see below).

Regular measurements of the CO slip by means of laboratory analyses may indicate when an
adjustment of the inlet temperature is required.

By observing the LTS bed temperatures the plant operator may get an indication of the
development in the deactivated zone, also called dead zone. In case the dead zone increases
faster than anticipated or the deactivation rate changes, the reason is probably an augmented
poison level, which requires further investigation.
 -7-

HTS Catalysts
Operational Problems
• Increasing llP
- Carry-over of Boiler Solids
- Catalyst Breakage Due to Boiler Leaks
- Low Catalyst Strength (FT formation)
- Milling of Catalyst
• Catalyst Poisoning
• Iron Carbide Formation

In case the CO leakage from the HTS converter increases abnormally fast, the reason may
either be catalyst poisoning or channelling in the catalyst bed. Normally, the latter situation is
preceded with a considerable pressure drop build-up until the gas manages to find a way
around the obstruction, whereby the pressure drop decreases and channelling is a fact.
Channelling can also occur immediately after commissioning if the catalyst is not loaded
correctly. , ~)

A pressure drop increase in a HTS reactor may be due to various reasons, a~ Lt:~~ ~~<A
...

over of boiler solids from a leaking boiler. In severe cases the boiler soliifm~~ :ven form a
crust on the catalyst surface. Liquid water from a leaking boiler may also damage the catalyst
pellets, if droplets of water re~th.e catalyst pores. The flash evaporation of th.e water inside.
the catalyst pores may lead to atalyst disintegration and pressure drop increase. ...1.. {. •
...P(r~1 .;;) ~-t.e...,.r~,...J&.a:..~ <liQ•~~~· ...t ~ h....
7
The catalyst strength can be reduced by formation of iron-carbide, if the HTS catalyst is · ,__....
operated in the Fischer-Tropsch region (this subject is discussed ih more detail below). ; ~~
c
>vt{/ '1-Cj
-tM lt:../;-~l.>j

Last but not least, a pressure drop build-up can be due to milling of the catalyst and/or the
alumina balls. Milling may take place if the gas inlet system is not properly designed or if a
proper hold-down material has not been installed.
 - 8-

HTS Catalysts Poisons

• Silica
• Phosphorous Alkali

Effect: Physical blocking of the catalyst pores

• Chlorine
• Sulphur
Effect: Lowers the catalyst activity at high
concentrations

Silica poisoning may come from upstream catalysts (for instance the primary reforming
catalyst) or from inen materials like low-spec alumina balls or ceramic balls.

Further, due to the high operating temperatures in the secondary reformer silica compounds
may evaporate from the refractory, especially if the burner is not operating properly, causing
flame impingement of the refractory.

Another source of silica is steam or quench water (if used) and poisoning by silica can be
caused by a boiler leakage. In case of the latter, the catalyst may also be poisoned by
phosphor and/or alkali.

The effect of silica, phosphor and alkali is a physical blocking of the catalyst surface and
pores, limiting the access to the active sites of the catalyst.

The origin of chlorine may be the combustion air used in the secondary reformer and is
mainly observed in plants located close to the sea. Chlorine can also be present in the
feedstock, especially in naphtha.

Likewise sulphur originates from the feedstock and may as chlorine lower the HTS catalyst
activity if present in high concentrations.

However, at the normal operating temperature of the HTS catalyst most chlorine and sulphur
compounds will move on to the LTS reactor.
 -9-

Iron Carbide
• Iron-carbide will catalyse Fischer-Tropsch
by-product formation:
nCO+ (n+m/2)H2 <=> CnHm + nH20

• Iron-carbide reduces catalyst strength

• Fischer-Tropsch reactions consume H2

At low steam-carbon (SIC) ratios, iron carbide may be formed according to the following
reaction:

Formation of iron carbide will weaken the catalyst pellets and in severe cases it may result in
catalyst disintegration and pressure drop increase.

In ammonia plants Haldor Tops~ NS normally recommends a minimum SIC ratio of 2.8 and
in hydrogen plants the recommendation is 3.0. These are the recommendations for Tops(lle
HTS catalyst, SK-201-2, other catalyst manufactures may have different limits.

The presence of iron carbide will catalyse Fischer-Tropsch by-product formation as indicated
by the reaction formula:
nCO+ (n+m/2)H2 ~ CnH.n + nHp

For instance, n=2 and m==6:

2CO + 5H2 ~ C2 ~ + 2H20

It follows from the above, that the Fischer-Tropsch reactions consumes hydrogen, whereby
the efficiency of the shift section is reduced.
 -10-

Problems in LTS Service

• Increasing DP
• Catalyst poisoning
-Sulphur
-Chloride
-Silica
- Phosphor and Alkali
• Methanol By-product formation

Above, the three most common problems for LTS catalysts are listed.

Increasing pressure drop across the catalyst bed may be due to the following reasons:
• Quench water or BFW reaching the LTS catalyst
• Steam condensation at operating temperatures close to or below dew point
• Milling of the catalyst
• Flooding of the reactor
• Dust from upstream HTS catalyst

Depending on the magnitude of the pressure drop increase, channelling of the reactor bed
may occur. In that way a part of the catalyst is by-passed and the apparent activity of the
catalyst decreases.
 - ll -

LTS Catalyst Poisons

Poison Source Effect on MTS catalvst
• HC feedstock
Sulphur • Steam Covers the active Cu-surface
• Quench
• HC feedstock
Growth of Cu-crystals and
Chlorine • Steam
covering the active Cu-surface
• Quench
• Steam
• Quench
Physical blocking of the
Silica • Upstream catalysts
catalyst surface and pores
• Refractory material
• Inert material/support
• Steam
Phosphor Physical blocking of the
• Quench
and Alkali catalyst surface and pores
• Boiler leakage's

Above the type, origin and effect of the most common LTS catalyst poisons are mentioned.

Whereas silica acts in the same way on the IITS and LTS catalysts, sulphur and chlorine have
a much more pronounced effect on the LTS catalyst, partly due to the lower operating
temperature.

Sulphur and chlorine decrease the catalyst activity by covering the active copper surface, but
in addition to this, chlorine enhances the growth of the copper crystals, resulting in a
decreased number of active sites.
 - 12-

LTS Catalysts
MeOH By-Product Formation
Potential Problems
• Environmental regulations of methanol emissions
• Methanol formation consumes valuable hydrogen
• Formation of amlnes gives odour problems
• Process condensate quality may be affected
• Methanol in the C02 may affect downstream
processes

The undesired by-product methanol is mostly formed over the LTS catalyst according to the
following reaction scheme:
3H2 + C0 2 ~ CH30H + H 20 + Q

Regulations are being implemented in many countries world-wide, restricting the allowable
methanol emissions to the atmosphere from hydrogen and ammonia plants.

As it appears from the reaction scheme valuable hydrogen is consumed when methanol is
formed. In a 1500 TPD ammonia plant a traditional LTS catalyst may produce as much as 8
TPD of methanol. Although the amount will decrease to 1-2 TPD over the catalyst lifetime,
the hydrogen loss may equate to an ammonia production loss worth US$ 70,000-400,000 per
year. (the number is based on an ammonia price of US$ 200 per ton and depends on plant
design).

Furthermore. the methanol by-product may affect the quality of the C0 2 gas and the process
condensate (for instance odour problems due to formation of amines), which may have to be
disposed off. For C02 supplied to the food or pharmaceutical industries there are normally
strict specifications on the methanol level.
 - 13-

LTS Catalysts
Factors Influencing MeOH Formation

• Operating temperature and pressure

• Steam/dry gas ratio
• CO concentration in feed
• Space velocity
• Age and activity of catalyst
• Catalyst promoters

A number of factors influence the formation of methanol over an LTS catalyst. The methanol
by-product formation can be reduced by:
• Lowering the operating temperature and the pressure
• Increasing the steam/dry gas ratio
• Decreasing the CO concentration in the feed
• Increasing space velocity (decrease catalyst volume)

A highly active catalyst is desired to obtain a low CO slip from the LTS reactor, but a high
active shift catalyst will also increase the methanol formation. However, the methanol
formation decreases as the LTS catalyst gradually becomes poisoned and deactivates with
time.

The operating temperature has a pronounced effect on the rate of methanol formation since
the activation energy is around three times higher than that of the shift reaction. Industrially it
has been verified that a l0°C decrease in temperature will decrease the methanol formation
by 50%.

A lower pressure will also reduce the methanol formation, but the pressure is not considered a
parameter that can be changed in normal plant operation.

Likewise, the S/DG ratio is dictated by other factors such as primary reformer and HTS
operation and the steam content is normally not used for controlling the methanol formation.
 - 14-

Topsoe High Temperature Shift Catalyst

Physical and Chemical Characteristics

!Catalyst SK-201-2 I
Shape Tablets !

i
I
Size, OD x H, mm 6x6

Chemical Components Fe/Cu/Cr

I (No Cr6+)

1
1mpurltles, Sulphur, ppm 1 <150

In the beginning of the 1980'ies when Tops!l!e described the problems related to operation at
low steam/carbon ratio, the search began for new catalytic systems to solve the problems
associated with Fischer-Tropsch by-product formation.

In 1989 Tops~ started marketing the Copper-promoted iron-chromium HTS catalyst SK-201.

In 1994 a further development of SK-201 was introduced; SK-201-2 is practically free from
hexavalent chromium while the salient operating characteristics of SK-201 have been
maintained.

SK-201-2 has continued to win market shares and today more than 140 charges of SK-201-2
and SK-201 are in industrial operation in both hydrogen and ammonia plants at a wide range
of operating conditions.
 - 15.

Topsoe High Temperature Shift Catalyst

Features of SK-201-2

• A very low sulphur content

• Enhanced mechanical stability at low S/C ratio

• No by-product formation down to SIC ratios of 2.8

• Cr6+ free

• High shift activity enables short loading

Due to the low sulphur content of SK-201-2, typically around 100 ppm by weight, the normal
desulphurisation period during the start-up of the catalyst may be omitted completely.

With the introduction of SK-201 and SK-201-2 the Fischer-Tropsch by-product formation is
effectively inhibited down to SIC ratios of 2.8. As no iron carbide is formed even at low SIC
ratios the mechanical stability is improved considerably, which contributes to a longer
catalyst lifetime.

Compared to SK-201 and other competitive types of HTS catalysts available on the market,
the content of hexavalent chromium in SK-201-2 has been reduced to a minimum (<.Q.05%),
which gives a number of advantages:
• A safer, faster and smoother start-up as the strong exothermic reduction of hexavalent
chromium is avoided.
• No formation of condensate containing hexavalent chromium during start-up.
• Reduced health risks related to the handling of the catalyst.
 - 16.

Industrial Performance of
SK-201 & SK-201-2

20 ao 80 100 120
Age, Month1

Based on extensive laboratory experiments a model for predicting the SK-201/SK-201-2

perfonnance was established and as the plot shows the feed-back from the industry has
confinned this model.

The high activity possessed by SK-201-2 implies that a lower CO leakage can be obtained for
a much longer period of time and that a short-loading of the HIS reactor is possible.

The superior activity of SK-201-2 has in many cases been utilised to short load the HIS
reactor to typically 75% of the design volume. Even plants operating much above design
capacity use short loading of SK-201-2 to save capital investment. It should be emphasised,
that even with a short loading of SK-201-2 the perfonnance is improved when compared with
a full loading of classic HIS catalysts.

Further, because of the high catalyst activity it is beneficial to operate at the lowest possible
inlet temperature in order to minimise the CO leakage due to the equilibrium conditions.
 - 17-

HTS Catalysts
High Void Topping Material TK-20

TK-20
55% void

SK-201·2
40%vold

Spheres
33% void
"1€.-.;-" L..tt, ("'vrl('b )

A short loading of the reactor as described above gives a lower initial pressure drop and
provides space for installation of the high void topping material TK-20.

TK-20 is a shape-optimised seven-hole particle in the size 16xll mm or 20xl3 mm that has a
55% void fraction. The most common topping material is Y2-1" alumina balls, which have a
void fraction of 33%. The high void fraction of TK-20 increases the protection against
pressure drop build-up due to solids (e.g. boiler solids) entering with the feed gas by
providing a larger "storage volume", thereby preventing crust formation.

Due to its density TK-20 cannot replace the normal hold-down function of alumina balls. It is
therefore recommended to install a floating hold-down grid or a 100 mm layer of large (>2")
alumina balls on top of the TK-20.

Several charges of SK-201 and SK-201-2 in operation are installed with a 30 em top-layer of
TK-20 as illustrated above.
 • 18.

Topsee Low Temperature Shift Catalysts

Physical and Chemical Characteristics

Catalyst •

LSK LK-821-2

Shape Cylinders Cylinders

Size, OD x H, mm 4.5 x4.5 4.5 x3.4

Chemical Components Cu/Zn/Cr Cu/Zn/AI

With the first generations of LTS catalysts, lifetimes of about 2 years were obtained, but
when LK-801 and LK-821 were introduced on the market in the 1980'ies by Haldor Topslile
AJS, lifetimes in excess of 5 years became possible.

In 1993 Tops!lle once again recognised the needs of the industry and introduced a new LTS
catalyst with improved mechanical properties. The new catalyst was designated LK-821-2
and is a direct descendant of LK-821 having the same chemical composition.

While the excellent activity of LK-821 was maintained, Tops~e succeeded in doubling the
strength of the reduced catalyst. Furthermore, the resistance towards sulphur poisoning was
improved.

The outstanding features of TopS!IIe low temperature shift catalysts have resulted in a fast
growing number of references throughout the world, since LK-821 and LK-821-2 were
successfully introduced on the market. Today around 200 charges of TopS!IIe LTS catalysts
are in operation in ammonia, hydrogen and methanol plants.
 - 19.

Topsee Low Temperature Shift Catalysts

Features of LSK/LK-821-2

Topsee LTS Catalysts

LSK Properties LK·821·2 Properties
• Chlorine retention • Free ZnO provides Inherent
• Resistance towards sulphur guard
condensate • Unsurpassed sulphur
• Silica retenslon chemisorption capacity
• High and stable activity

LSKILK·821·2 Combination Charge

• High and stable catalyst activity
• High resistance towards poisoning
• High mechanical stability

The optimal LTS loading includes a top layer of LSK (normally 5%) for protection against
chlorine, which is a serious poison forCu/ZniAI based LTS catalysts.

The LSK catalyst has an unmatched high chlorine capacity, as the capacity is not only related
to the Cu in the catalyst, but to Cu!Zn!Cr composition and structure of the guard catalyst.

Another important feature of LSK is the resistance towards damage by liquid water. This is a
very advantageous quality if the feed inadvertently carries droplets of water (mist), for
instance during start-up or in case of plant upsets. The water will then evaporate on the LSK
catalyst, and thus not harm the below LTS catalyst.

Operating experience has furthermore shown that the LSK has a high affinity for trapping
silica.
 -20-

Topsoe LTS Poisoning Model

lttiTTtt
LSK Absorption of Cl

LK-821·2
T I
· Bulk Sulphur
AbflorpUon

Based on intense laboratory investigations and subsequent experience from the industry,
Tops0e has developed an LTS poisoning model, which is a valuable tool for evaluating and
forecasting the performance of an LTS catalyst.

This model takes into account the permanent poisoning caused by sulphur and chlorine as
well as the slow deactivation taking place in the active part of the catalyst bed due to thermal
ageing.

In the figure 'Bulk Sulphur Absorption' refers to the chemical bonding/reaction between
sulphur and the zinc oxide contained in the LTS catalyst:
H 2S + ZnO ~ ZnS + Hp.

Due to the presence of steam the equilibrium concentration of H2S over the ZnO is fairly
high. The sulphur thus escaping the main absorption front will then be chemisorbed on the
copper surface of the fresh catalyst in the lower part of the reactor:
H2S + Cu ~ CuS + H2

Thereby the copper surface is no longer active and the catalyst is deactivated.
 -21 -

S & Cl Profile In Spent LSK/LK-821

I
I
0 6 8 10 12 14 18
Distance from Top Tangent Une

The applicability of the poisoning model is illustrated by analysis of spent LSKJLK-821. The
results of the laboratory analysis are depicted above.

It appears from the graph that the chlorine content in the LSK layer is around 3 times higher
than in the LK-821 bed.

As can be seen the sulphur content in the upper half of the LK-821 charge is more than 4
times higher than in the LSK layer. This level corresponds to the zone of maximum
chemisorption (i.e. where the catalyst is saturated with sulphur and therefore totally
deactivated).

From the poim with maximum sulphur content the concentration decreases (the sulphur
chemisorption front) to a lower level.
 -22-

LTS Catalysts
Benefits of Improved Performance
1200 MTPD Ammonia Plant

Catalyst Malperformlng Topsee I

LTS Catalyst LTS Catalyst 1

CO-leakage, mole o/o dry 0.30 0.25 I

·Ammonia Production Gain 6.8 MTPD I
Production Gain, US$/year• 450,000
.US$ 200/MT NH3 I

In the HI'S and LTS converters most of the CO leaving the reforming section is converted
into C02, whereby each kmole of CO generates one kmole of H 2. Subsequently the CO
leakage from the LTS is reacted in the methanator, where each kmole of CO consumes 3
kmoles of H2 and generates 1 kmole ofCH4 and 1 kmole of water. " ,, " :-<,:.t;, (;;.,Yt .;... u:-
1 t,tt1
Consequently, an extra kmole of CO converted in the LTS corresponds t:·: ;~::~¥s -> ' ""L >'ii{;:
of H2• In an ammonia plant the extra hydrogen wiJJ require additional air to the secondary
reformer and the net gain will therefore be around 3.2 kmoles of H 2•

An extra kmole of CO converted will also mean one kmole less of CH4 in the make-up gas,
which will reduce the purge loss by 4 kmoles of H2 . Thus the total gain by converting 1
kmole of CO is 7.2 kmoles of hydrogen.

A 1200 MTPD ammonia plant consumes about 6250 kmoles of make-up gas corresponding to
7050 kmoles of dry gas exit the LTS converter. If installation of a superior LTS catalyst
results in a reduction of the CO leakage of 0.05% the additional conversiOn will be 3.5
kmoleslhr of CO resulting in a net gain of 25 kmoles/hr or 600 kmoles/day of H2 .

600 kmoles Hfday will be converted to 400 kmoles NH/daY or around 6.8 TPD ammonia.
Assuming a price of USD 200 per ton and 330 production days per year the yearly gain
becomes approximately USD 450.000,00.
 - 23-

Low-Methanol LTS Catalyst

Features of LK-823

• Caesium promoted
• Methanol formation reduced by a factor 8
• Shift activity of LK-821-2 maintained
• Same poisoning resistance
• Unchanged physical characteristics
• Same conversion & lifetime

Promotion of LTS catalysts with significant quantities of alkali, like potassium (K) and
sodium (Na), inhibits methanol formation, but alkali also reduces the shift activity and
catalyst stability considerably.

Through intensive R&D work Topsl?le has managed to modify LK-821-2 such that methanol
by-product formation is drastically reduced. Improved selectivity is obtained by promoting
the new LK-823 catalyst with a small amount of caesium (Cs).

As illustrated in the figure below, the methanol formation across LK-823 is only about one
eight that ofLK-821-2.

A very important aspect of LK-823 is that the improvements in methanol formation have
been obtained while maintaining the same high activity and poisoning resistance as for LK-
821-2. In other words, LK-823 will yield the same shift conversion and catalyst lifetime as
that of its precursor.

Furthermore, promotion with caesium is achieved without compromising the superior crush
strength of LK-821-2.
 -24-

Methanol Formation at LTS Conditions

The graph illustrates that the stabilised methanol fonnation across LK-823 is around one
eight of the MeOH fonnation of LK-821-2.

Extensive feed-back from the industry since LK-823 introduction to the market in the fail of
1997 has verified this.
 . 25.

Industrial Performance of
LK-821, LK-821-2 & LK-823

-
10 30 50 10 70 so so 100
Age. Months

As for the HrS catalyst extensive laboratory research has led to the development of a model
for predicting the performance of LTS catalyst.

The above plot shows the feed-back from the industry as well as the predicted performance.

As it can be seen, the feed-back clearly shows that LK-823 has the same activity as LK-821-
2, despite being promoted with Cs.
 Methanation .
TheFina) Purification
 - 1-

Methanation
The Final Purification

by
Mads Feddersen
Hsldor Tops~~e AIS

The methanator is the last catalytic reactor in the gas preparation section of the ammonia
plant. Its main purpose is to remove the sma11 amounts of carbon oxides (CO + C02) which
are present in the process gas leaving the C02 removal section.

Carbon oxides act as poisons for the ammonia synthesis catalyst and even small amounts of
these compounds will result in Jess activity/conversion in the ammonia converter.

Consequently the carbon oxides must be removed down to a level of a few ppm.

It is therefore important to ensure that the methanation catalyst is performing well.

 -2-

Methanation Reactions

Fast
CO +3H 2

Slow

The two methanation reactions are basically reverse steam reforming reactions.
CO + 3 H 2 <=> CH4 + Hp
C0 2 + 4 H 2 <=> CH4 + 2 H 20

Both reactions consume hydrogen and it is therefore important to reduce the amount of
carbon oxides entering the methanator by operating the shift section and the C02 removal
section in an optimal way.

The CO is converted rapidly in the top part of the methanator catalyst, whereas the
conversion of the C0 2 proceeds much more slowly.

The methanation reactions are heat generating and each 1% of CO being converted results in
a temperature rise of 74"C, whereas 1% of C0 2 converted results in a temperature rise of
60"C.

Under normal operating conditions the amount of CO + C0 2 at the inlet of the methanator is
in the range 0.2-0.4% and as the outlet concentrations of CO + C02 is only a few ppm with a
CO-/CO ratio of 5-10, a temperature increase of 15-30"C in the methanator is seen.
 -3-

Topsee Methanation Catalysts

Catalyst PK-7R

mm 6

The methanation catalyst manufactured by Tops0e is a pre-reduced nickel based catalyst. The
carrier material is a special in-house manufactured alumina.

The carrier is impregnated with Ni using a special dispersion technique and afterwards the
catalyst is reduced at our in-house catalyst reduction facilities in order to obtain a high
catalyst activity.

Pre-reducing of the catalyst implies that it is able to operate at rather low temperatures
providing more flexibility in the daily operation, but also an important issue in plants where it
is difficult to achieve the normal methanator inlet temperature of around 290-300"C.

The pressure drop across the PK-7R catalyst is low as it is supplied in the shape of a ring.
Furthermore, this shape has more void to accommodate any ingress of particles/chemical
substances such as carry-over from the C02 removal section.
 -4-

Carry - Over from

C02 Removal Systems

K2C0 3 from the following C02 removal

systems

• Benfield

• Gianmarco Vetrocoke

• Catacarb

Arsenic Compounds

The process gas which leaves the LTS reactor is practically free of any poisons as these have
been absorbed by upstream catalysts. The methanation catalyst is therefore well protected
against most poisons which normally would deactivate a nickel-based catalyst, such as
sulphur.

The potential poisoning which remains is the possibility of carry-over of various solutions
from the C0 2 removal system and especially the potassium carbonate solution used in the
Benfield, Gianmarco Vetrocoke and the Catacarb process is regularly causing problems in
industrial units when it gets in contact with methanation catalyst. Small amounts of K2C03
occurring during daily operation are not a problem, but in case of carry-over of a major
quantity, which could happen due to a plant upset, the pressure drop in the catalyst bed will
increase. In severe cases the catalyst activity will also be affected due to K2C03 deposits/crust
formation.

Some of the C0 2 removal processes also make use of an arsenic oxide and as arsenic is a very
strong poison for nickel catalysts. Ingress of such compounds will affect the performance of
the methanation catalyst.
 - 5-

The above picture shows the state of a methanation catalyst after it has been subjected to
severe exposure to potassium carbonate a number of times.

During operation the methanator had shown an increasing pressure drop trend and upon
inspection of the catalyst a number of large crusts of catalyst was found. When analysing the
crusts K 2C03 was found in the amounts of 30-60 wt%, indicating that the catalyst particles
had been agglomerated by the potassium carbonate.

Even though a large part of the catalyst bed had been inactive due to the crust formation, the
remainder of the PK catalyst was still able to achieve the desired conversion.
 -6-

Monitoring the PK-7R Performance

• Measure the CO + C02 leakage by laboratory

analysis & on-line analyser

• Check the pressure drop across the

methanator and evaluate the trend

The CO+ C0 2 leakage at the exit of the methanator should be analysed regularly (every shift)
in order to follow the penormance of the catalyst closely. In most plants an on-line analyser is
also available and the results gained in the laboratory and on the analyser should be compared
to check the reliability of both types of analysis.

The pressure drop across the methanator should be logged and the development should be
evaluated by comparing with previous data.
 -7-

Normal Operation of PK·7R

• Adjust inlet temperature to have less

than 10 ppm a-equivalents at outlet

=
• 1 ppm CO 1 a-equivalent
• 1 ppm C02 = 2 O.equlvalent

Operated correctly the methanation catalyst will be able to achieve long lifetimes. Most
charges in industrial operation will last 10-15 years and in some cases the catalyst change-out
criteria is the need for a mechanical inspection of the methanator vessel due to local
regulations.

During the life of the catalyst the main operating parameter is the catalyst inlet temperature.
With a conventional ammonia loop configuration with the make-up gas addition before the
ammonia separator. it is recommended to have a maximum of 10 ppm oxygen equivalents in
the methanator exit gas. One ppm of CO represents 1 oxygen equivalent and C02 represents 2
oxygen equivalents.

In a gas having 1 ppm of CO and 4 ppm of C02 we therefore have

lxl + 4x2 = 9 oxygen equivalents

which is close to the maximum recommended.

When the oxygen equivalents exceed the recommended level of 10 ppm, it is necessary to
increase the methanator inlet temperature by a few degrees and this should bring the CO +
C0 2 slip down.
 -8-

Safety Precautions for PK-7R

• Catalyst which has been In operation may be

pyrophoric and it should be. co. oled down. ~··
before opening reactor manholes J
....._......,.......---·-~.-~.;' --~
• Risk of nickel carbonyl formation at
temperatures below 2002c
• When physically handling nickel catalyst it is
~ recommended that persons wear protective
~ clothing/dust masks

In case it is necessary to inspect the methanator without unloading the catalyst, the following
should be noted.

The methanation catalyst which has been in operation is pyrophoric and could heat up when
getting in contact with air.

Consequently, the catalyst 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 order to avoid chimney effects.

When handling nickel containing catalysts it is normally recommended to avoid contact with
the skin/respiratory system by using appropriate protective clothing.

The highly toxic nickel carbonyl, Ni(C0)4 is formed when CO from the process gas gets in
contact with the nickel contained in the catalyst. As long as the process gas does not get in
contact with the methanation catalyst at temperatures below 200"C, the formation of nickel
carbonyl can be practically prevented. It is therefore recommended to stop the process gas to
the methanator before the inlet temperature reaches 200"C and purge the vessel with nitrogen.
Ammonia Synthesis Catalysts

How do they function?

and
How should they be operated?
 - 1-

Ammonia Synthesis Catalysts

How do they function ?
and
How should they be operated?

by
Frederik Seby
Haldor Topsee AIS

The ammonia synthesis loop is at the core of an ammonia plant. Problems in the gas
preparation train may often be bypassed. but even small upsets with the ammonia synthesis
loop will lead to considerable reductions in the plant production rate.

Proper operation of the ammonia synthesis loop and due care for the ammonia synthesis
catalyst will ensure continuous operation for a great number of years. This presentation will
therefore focus on "good operating practise" and in detail explain about the optimisation of
the operation and the precautions to safeguard the longevity of the catalyst.
 - 2-

Formation of Ammonia
• 3 H2 + N2 -> 2 NH 3
Equilibrium % NH3
• The process is
70
exothermic

t~::
• Is facilitated by high
pressures
• Reaction starts around
350°C
0 +-1- - - . - - - . . . - - - . . ,

300 400 500 600

Temperature, •c

The reaction between molecular nitrogen and hydrogen is largely exotherm and the free
energy of formation is also negative; hence, the equilibrium concentration of ammonia
increases with decreasing temperature.

The volume decreases by the reaction, and the pressure therefore has a large positive impact
on the process: The higher the pressure, the higher the resulting equilibrium concentration
will be.

The formation of ammonia will not proceed un-catalysed at any temperature below 700°C,
but promoted iron catalyses the process and allows the reaction to start around 350°C.
 .3.

Reaction Mechanism 1
• Reactants adsorb on the • Adsorbed N and H
catalyst surface and recombine to form NH
dissociate

-
Ammonia synthesis catalysts consist of elemental iron promoted with alkali and alkaline earth
metals. In the active state, the catalyst consists of a large iron sutface with the promoters
spread over it.

Basically, both N 2 and H2 molecules are adsorbed on the iron surface and dissociate into
elemental nitrogen and hydrogen.

Elemental nitrogen then successively combines with elemental hydrogen and as a first step,
NH is formed.
 -4-

Reaction Mechanism 2
• Adsorbed NH and H • Adsorbed NH 2 and H
recombine to form NH 2 recombine to form NH 3
which desorbs

H• NH3

·~
-
INiH iH iH
IH

Subsequently NH combines with H and yet with another H atom to finalise the synthesis of
NH3.

Finally, NH3 is desorbed from the surface and returns to the gas phase.
 - 5-

Ammonia Synthesis
• Rate determining step Is Conversion at SV=24000

230
dissociation of the N2 - and P=319 atm
25
molecule and optimum 24
H/N2 ratio Is therefore <3 22
.. 21
• Optimum range for H/N2 i 20
ratio Is 2.8 to 3 # 19
18
17
16
15~~~~~--~~~
0 1 2 3 4 5 6 7
H tiN 1 -ratlo

The rate detennining step in the entire sequence of ammonia synthesis catalyst is the
dissociation of the nitrogen molecule on the surface. The more molecules of nitrogen are
present, the higher the "surface concentration" of elemental nitrogen will be and a
comparatively higher pressure of N2 is therefore required for maximum overall reaction rate.

The optimum range of H/N2 is therefore below three. Experience shows, though, that the
reaction becomes very sensitive below the optimum, and ammonia plant operators therefore
try to keep the relation higher than the optimum to avoid losing the reaction.
 -6-

Catalyst Deactivation
• Slntering Is Irreversible
changes In the active
sites on the catalyst
• Sinterlng Increases with
temperature
• Sinterlng does not
exceed a few % per year
• Poisoning may be
reversible/temporary
or irreversible/permanent
• Irreversible poisons are
sulphur and metals
• Reversible poisons are
oxygen and even oil to
some extent

Sintering is the process whereby the active catalyst sites decrease in number and thus
decrease the catalyst activity. The sintering of an ammonia synthesis catalyst is related to
structural changes in the iron matrix: They are irreversible and increase with temperature.

Many single bed conveners (like TVA and NEC) of the type used years back operate at
pressures of 300 bar or even higher. At nigh pressure the equilibrium concentration is also
high and the heat of reaction will lead to high temperatures in the catalyst bed; 550 to 600°C
is not uncommon in these cases. At these temperatures the rate of sintering is appreciable and
the lifetime of the catalyst is limited to five to ten years in these cases.

In modem conveners it is possible to achieve high conversions by radial flow in multiple

beds without resorting to high pressure, and temperatures are often kept below 500°C. At
tltese conditions the deactivation rate is just a few percent per year and a the lifetime of a
charge of synthesis catalyst will normally exceed ten years.

Catalysts will also deactivate in the presence of catalyst poisons which may be of the
temporary or permanent type.
 7-

Reversible Catalyst Poisons

600
0.9 500

a- 0.8 400 :s
:! 0.7 300 3:
~ 0.6 2oo .P
0.5 100
0.4 ~----~--~~----r-----+0
0 5 10 15 20
Time of Run, Months

Reversible poisons are oxygen compounds and to some extent oil (e.g. from leaking
recirculator seals). Oxygen compounds will oxidise the iron surface. Hydrogen is present in a
large excess and will re-reduce the oxidised surface. The implications are that if the oxygen
compounds are removed from the reactor feed flow, the surface compounds are removed
completely. With oxygen present, however, a certain fraction of the iron surface will be
deactivated (or oxidised) and this fraction will increase in proportion to the amount of oxygen
and the temperature.

The most common oxygen compounds present in the make-up gas are CO, C02 and H20.
The two latter are not of much importance for most plants (where the addition of make-up gas
takes place before the final separator) as they are dissolved in the liquid ammonia.

Oil will crack on the iron catalyst at the temperatures prevailing in the reactor and form
carbon. In tum, some of the carbon will methanise at the high partial pressure of hydrogen in
the reactor and slowly be removed as methane.
 -8-

Reversible Poisoning with Oxygen

Development In AVGTF for S-200 Converter
Before and After Oxygen Polaonlng

0 0
~ 0 0

I
0
oo 00 0
0
qs>

I 0 _
-~AVOTF
......

20 40 110 110 100 120

Months In Open~tlon I

A 1350 MTPD ammonia plant featuring a TopSiile S-200 radial flow ammonia converter
loaded with Tops!<!e's KMlR pre-reduced ammonia synthesis catalyst had problems with
reduced catalyst activity after two unscheduled shutdowns.

At the plant it was suspected that CO & C02 in excessive amounts in the make-up gas had
entered the ammonia loop and caused a slight oxidation of the KMlR catalyst. In this plant,
the make-up gas addition is after the ammonia separator, which implies that there is no
possibility of removing any C0 2 present in the make-up gas by forming carbamate in the
separator.

A new charge of molecular sieves was installed after the first stage of the make-up gas
compressor and the performance of the converter was watched closely by submitting
operating data to HaldorTops!<!e AJS.

After the temporary oxygen poisoning, the catalyst has fully regained the activity seen prior
to the poisoning.
 -9-

Irreversible Catalyst Poisons

600
0.9 500
0.8 400 l
f 0.7
0.6
0.5
300
200
100
§
i
0.4 0
0 5 10 15 20
Time of Run, Months

It unfortunately happens that the oil used for the recirculator seals is not of a very good
quality and contains impurities in large quantities. One of these impurities is sulphur, which is
finnly bound by the catalyst and cannot be removed during normal operation. Sulphur is an
irreversible poison for the ammonia synthesis catalyst.

Other irreversible poisons originating from poor quality oil are certain heavy metals.

Chlorine is also an irreversible poison. Chlorine will react with the potassium used as a
catalyst promoter and slowly deplete the catalyst of this essential element. Chlorine is
fortunately not seen often in synthesis loops.
 . 10.

Limits on Catalyst Poisons

• 0 iI: Maximum level acceptable Is 20 mg!NM3 at the

converter inlet

• s + p in 0 iI: Maximum level recommended for

continuous operation Is 0.15%

• Cl in Oil: Maximum level recommended for

continuous operation Is 0.01%

Generally, lubricating oils used for turbines and recirculators are of good quality, and with
today's technology, the leakage is often insignificant. We would recommend, however, that
the lubricating oil specification is checked and verified to be in accordance with the above
specification.
 - 11-

S-200 Converter Operation

• Catalyst Reduction
• Principles of Operation
• Normal Operation
• Optimisation

There are many aspects of the S-200 converter operation which are particular for this type of
converter. To a large extent, the principles which will be presented on the following pages
may be applied for other converter types as well.
 • 12 •

Catalyst Reduction

• Catalyst is supplied as a mixture of Fe2 0 3 and

FeO and should be reduced to Fe to become
active
• Fe20 3 + FeO + 4H 2 <=> 3Fe + 4H 20
• The catalyst is reduced with synthesis gas of
normal composition at low pressure and at
temperatures >380°C

Traditionally, ammonia synthesis catalysts have been supplied as unreduced catalyst, and
even today, when pre-reduced catalysts are available, many plants are using pre-reduced
catalyst in the first bed on! y and then use unreduced catalyst in the subsequent bed( s).

Pre-reduced catalyst KMlR has been reduced in our plant under well-controlled conditions
and is then skin passivated. Thus pre-reduced catalyst does not require much attention during
the initial start-up and the amount of water formed is very small (approximately 20 kg per
MTofKMlR).

Unreduced KMl catalyst will consume a lot of hydrogen and generate a lot of water during
the reduction (approximately 280 kg per MT of KMl), and the reduction of this catalyst
needs to be carefully controlled.
 - 13-

Catalyst Reduction
• The pore structure Is
developed during
reduction
• Slow reduction provides
a fine pore structure
• Rate of reduction Is
controlled by rate of
temperature increase

It is important to realise that the pore structure is developed during the reduction and that the
finer the resulting pore structure is, the better the catalyst activity will be.

You may intuitively argue that if the rate of reaction is too fast, the large amount of water
formed by the reduction in the interior of the catalyst particle will make too large pores by
enlarging the existing ones. You rather want a situation where small tiny pores are formed by
depressing the rate of water formation.

To safeguard the catalyst activity during the catalyst reduction, both the water concentration
and the bed temperatures should be monitored carefully to be within certain limits
recommended by Tops(lle.
 - 14-

Catalyst Reduction

S-200 bed temperatures

Combined KMRIKM Charge
600
500
L.o:.
400 --T(1,ln)
~
~
-o- T(1,out)
300 -t:r-T(2,1n)
200 fL -+E-T(2out)

100 I
I
0~-----r----~------r-----~----~
0 20 40 60 80 100
Reduction time, hr

This is an example of the catalyst reduction of a combination charge of KMlR and KMl in
an S-200 converter. The temperatures in the first bed containing the pre-reduced KMIR
catalyst are raised fairly rapidly and reaction in the first bed picks up fast.

In the second bed, the temperatures are controlled carefully and the increase in bed
temperature is limited to 2-3°C per hour.
 - 15-

Operation of S-200 with LH E

• Temperature to the first
bed is controlled by the
cold shot valve
• Temperature to the
second bed Is control·
led by quench valve IN ~~~>{
• All settings are inter-
dependant and must be
repeated/checked

OUT

The S-200 converter consists of two beds with heat exchange between the two beds (IHE). In
this particular case there is also internal heat exchange of the inlet and outlet gas (LHE). The
major part of the inlet gas is heated by the outlet gas from the 2nd bed in Uffi. Part pf the
inlet is used to cool the process gas between 1st and 2nd beds, and finally, cold inlet gas is
by-passed directly to the 1st bed inlet through the cold shot valve.

The 1st bed inlet temperature is controlled by the cold shot valve and the 2nd bed inlet
temperature is controlled by the quench valve to the IHE flow. Any and all adjustments of
any of these valves, however, are interactive. If for instance you want to increase the inlet
temperature to the 2nd bed, you will close the quench valve. Thereby, more flow will pass
through the main valve and reduce the inlet temperature to the first bed.
 - 16-

Operation of S-200 w/o LHE

• Temperature to the first
bed Is controlled by the
cold shot valve
• Temperature to the
second bed is control·
led by bypass valve
• All settings are inter-
dependant and must be
repeated/checked

In other types of S-200 converters, the heat exchange of the inlet and outlet gas takes place
externally in a waste heat boiler (WHB), a boiler feed water pre-heater (BFW) and a hot
gas/gas exchanger (HEX).

The control principles are a little different in this case. The lst bed inlet temperature is still
controlled by the cold shot valve. However, the temperature to the second bed is controlled by
changing the outlet gas temperature in the hot gas/gas exchanger through a bypass around the
boiler feed water pre-heater.

Again, all adjustments are interactive and a certain fine tuning is required. Experienced
operators master these operations and learn with time "which buttons to push" to obtain the
required effect.
 - 17-

S-200 Optimisation

25

~
20

15 2nd Bed
2"'

7-
;!. 10

0
350 400 450 500 550
Temperature, •c

When optimising the operation of the S-200, it is important to realise two things:
The rate of ammonia production (as measured either by the ll(NH3) or the tlT) is
limited by the equilibrium curve.
The equilibrium curve changes with the operating conditions, and every time the
inert level, the NJH2 ratio, the pressure and the flow change etc, the equilibrium
curve moves.

Very few ammonia plants can maintain all operating parameters in a loop constant over long
periods of time, and optimisation of the converter operation is therefore a perpetual and
continuous task.
 - 18 -

S-200 Optimisation

25

20
..,
::c: 15
z
<fl. 10

5
Operating Curve
0
350 400 450 500 550
Temperature, •c

In principle it is possible to calculate the optimum inlet temperature for a given set of
operating conditions. As mentioned earlier, however, the latter change frequently and the
optimisation therefore has to rely on trial and error for practical purposes.

For a given equilibrium curve, changing inlet temperatures to a bed will define an operating
curve for the outlet temperature. This curve will have a maximum and will never touch the
equilibrium curve. To the left of the maximum, i.e. for decreasing inlet temperatures, the
reaction rate will decrease as well as the conversion will. To the right of the maximum, the
reaction will be fast, but the conversion will be limited by the equilibrium curve.

The maximum on the operating curve will thus define the optimum operating point since the
conversion is maximum here. When the converter feed flow and the make-up gas flow are
both fixed, the conversion will not change much, but the optimum will then appear as a
decrease in the loop pressure.
 . 19.

S-200 Optimisation Procedure

• Change the first bed Inlet temperature up or
down until the lowest loop pressure is found
• Change the second bed Inlet temperature up
or down until the lowest loop pressure is
found
• Continue the procedure on a consecutive
basis In the two beds until optimum is found

-~~~~.? ~- ..~

The simplest way to optimise the operation o an S-200 converter is therefore to change the
bed inlet temperatures one by one while thonitoring the lop pressure. If an increase in
temperature results in a lower loop pressure, the change was towards the optimum and would
merit another increase. On the other hand, if a change in temperature results in a higher loop
pressure, the direction of change was obviously wrong. These deliberate changes in
temperatures may be of the order of 5 to 10°C. A lot of care should be exercised upon
lowering of the temperatures, however, as the reaction may be lost.

As mentioned previously, temperature adjustments in an S-200 converter are interactive in

that an adjustment in bed 1 will affect the temperature level in bed 2. Thus the beds should be
optimised in a consecutive manner until the optimum is found.