Performance of catalysts in Ammonia plant- IFFCO Kalol experience

Development of new catalysts have totally revolutionized the chemical

processing industries -particularly the ammonia in fertiliser sector.
Catalyst plays an important role in ammonia production. A critical factor
in ammonia production is its very significant energy consumption. The
performance of different catalysts is directly effecting the production of
ammonia plant. Reliability of ammonia plant is dependent on good
performance of various catalyst in use and the conditions under which
they operate. This has become apparent as capacities of existing
ammonia units have been increased, and more demands has been
imposed on the role of catalyst. Attempts have been made to highlights
the experience and various measures taken by IFFCO Kalol for catalyst
handling and operation as a part of energy conservation over the period
of two decades.

INTRODUCTION :

IFFCO Kalol unit operates 1100 tpd capacity ammonia plant. The original 910 tpd M.W. Kellogg
ammonia plant was commissioned in the year 1974 and is based on steam reforming of natural gas. In
Sept.97, 250 tpd naphtha based pre-reformer system is installed as an add-on unit at upstream of primary
reformer. IFFCO Kalol's ammonia and urea plants are being considered as one of the best run plants in
India even though technology adopted is of seventies. Ammonia production may be broadly divided into
four sections:

Feed purification - Desulphurisation (Natural Gas Feed)

Synthesis gas production
Synthesis gas purification
- Hydrogenation and. Sulphur absorption(Naphtha Feed)
- Pre-reformer/Primary Reformer
- Secondary Reformer
- Shift Converters
- CO2 removal
- Methanation

Ammonia synthesis - Ammonia converter

Each of above section contains catalysts and performance of each plays significant role for the next
section. With passage of time, catalyst performance in one section is directly responsible for the
performance of next section. A closely monitoring system is essential to evaluate the performance of
catalyst for each section since from the catalyst loading to end of run condition for each catalyst. Catalyst
should have following characteristic :
Good mechanical strength
High activity
low pressure drop
high tolerance for contaminants
long life time

B.R. Patel BPS Mehta

Sr. Manager (Pro.) Sr.Process Engineer
IFFCO Kalol Unit IFFCO Kalol Unit

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Feed Purification:

Naphtha as Feed to Pre-Reformer:

Feed purification usually involve a hydrogenation step to convert organic sulphur compound to hydrogen
sulphide and subsequent removal of hydrogen sulphide by chemisorption on zinc catalyst in sulphur
absorber. Sulphur compounds like hydrogen sulphide, COS, RSH, CS2, R2S2, R2S and thiophenes are
absorbed on sulphur absorber catalyst -ZnO . H2S reacts by following reaction :-

ZnO + H2S ------- ZnS + H2O

IFFCO Kalol had commissioned the system recently and it is working satisfactorily.

Natural Gas:

In desulphurisation system usually use the activated carbon as catalyst to remove the sulphur compound
from natural gas from 2-3 ppm to less than 0.1 ppm.

Reforming Catalyst:

Steam reforming technology is a persistent challenge to the catalyst manufacturers . The dominant fact
in the trend is energy efficiency. Main demand of catalyst is its operation at lower steam to carbon ratio.

In the pre-reformer, the endothermic reaction is followed by the exothermic methanation and shift
reactions, adjusting the chemical equilibrium between the carbon oxides, methane, hydrogen and water .
The performance of Pre-reformer is directly reflected by the temperature rise/drop across the reactor
depending on the type of feed. For heavier feed stocks, such as naphtha, the overall process is
exothermic, resulting in an overall temperature rise of about 15 to 20 deg C across the pre-reformer. The
specially precipitated, high-nickel catalyst is in the form of cylindrical pellets, has the high activity
required for hydrocarbon steam-reforming reactions at low temperature.

For new catalyst, the outlet concentration of higher hydrocarbon should be negligible and constant.
Deactivation of the pre-reforming catalyst is caused by impurities/ poison in the feed stream i.e. sulphur,
alkali, silica and arsenic etc.

Primary reforming catalyst has under gone significant development since its early application. The
simple tablets shape was superseded by the rashing rings shape, with an increased surface area for higher
activity and higher voidage for reduced pressure drop. Since reforming reaction is strongly film diffusion
controlled and most of reaction occurs at the surface of the catalyst. Activity of catalyst can be improved
by increasing the surface area without effecting the strength .

In secondary reformer, nitrogen is introduced with help of air and oxygen in air is combusted with a
portion of methane from primary reformer. Active catalyst help in lowering the charged volume of
catalyst and increasing the volume of mixing zone. Optimum level of methane slip from primary
reformer is required to maintain the air flow in secondary reformer.

Performance of reforming catalysts is periodically evaluated by considering following parameters and

operating conditions are duly adjusted :
Approach to equilibrium
Methane slip
Pressure drop
Tube skin temperature

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 Reformer Catalysts Performance-IFFCO Kalol
80000

70000
Ammonia Produced per unit

Primary
60000 Reformer
volume of catalyst

50000 Secondary
Reformer
40000

30000

20000

10000

0
1 2 3 4 5 6 7 8 9
Catalyst Charge

Deactivation of reforming catalysts is caused by impurities in feed stream. Number of poisons reduce the
effectiveness of the reforming catalyst. Sulphur, which is the most common of these poisons, may
deactivate some catalyst by a process of chemisorption onto the active surface.

EVALUATION OF REFORMING CATALYSTS:

Pre-Reformer:

Pre-Reformer catalyst is in operation for last seven months and is working satisfactory.

Primary Reformer:

Figure 1 show the performance of Pri-reforming catalysts at IFFCO Kalol. Dotted lines shows the
existing catalyst charge in operation. Charge No 5 and 6 were not utilised properly due to two long
annual plant turn around and due to first Reformer revamp & frequent tube failure before revamp. The
performance of existing charge of primary reformer catalyst is the highest and it is at end of run
condition. It is evident from above graph that ammonia production per unit volume of catalyst had gone
up from 27,145 MT to 80,270 MT in existing catalyst charge.

Secondary Reformer:

For gas based plant, the decision of catalyst charge replacement is generally taken based on pressure
drop across catalyst bed. It is evident from above figure that secondary reformer catalyst performance
was increasing continuously up to charge no 4 from 5377 to 59,013 MT. The last catalyst charge was
having lower performance.

Shift Converter Catalysts

High temperature catalyst (HTS) is used to convert carbon mon-oxides (CO) in reformer effluent gases
to hydrogen and carbon di-oxide (CO2). The catalyst promotes the exothermic reaction as follow :-

CO + H2) ---- CO 2 + H2 h = - 41.1 kJ/mol

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HTS catalyst operates in the temperature range of 370 to 440 deg C and is consists of iron/ chrome.
Active magnetite (Fe3O4) crystals in working catalyst are stabilized by the presence of chromia. Under
severe condition magnetite can be reduced to FeO or even metallic iron. Such change of phases and over
reduction causes crystallite changes in the catalyst that lead to physical degradation, weakening and
fracture of pellets, and increase in pressure drop. Metallic iron promotes side reaction such as Fisher
Tropsh reaction. Such reactions can affect adversely the performance of down stream catalysts.

Low temperature catalyst (LTS) promote the same reaction as the HTS system. The reaction is carried
out at a lower temperature of 190 to 240 deg C to maximize the conversion. Shift reaction kinetics are
slow over an iron based catalyst at above temperature and so a more active copper-zinc catalyst is used
in LTS. Cu-Zn are more susceptible to poison present in the reformed gases. The most common poisons
are sulphur and chloride, few hundreds ppb may cause rapid deactivation of the catalyst. Table-I gives
some of the common LTS catalyst poisons

Shift Catalyst Performance at IFFCO Kalol

30000
Ammonia Produced per unit

25000
Volume of Catalyst

20000
HTS
15000
LTS
10000

5000

0
1 2 3 4 5 6 7 8
Catalyst Charge

EVALUATION OF SHIFT CATALYSTS:

HT Shift Converter:

Figure-2 show the performance of shift catalyst at IFFCO Kalol. Performance of existing HTS catalyst
charge has achieved the highest ammonia production per unit volumes as compare to others catalyst
charges. From trends diagram, there is always improvement in performance of HTS catalysts. Ammonia
produced per unit volume of catalyst had increased from 6696 MT to 28,403 MT.

LT Shift Converter:

Performance of existing LTS catalyst charge is satisfactory. From trends diagram, there is always
improvement in performance of LTS catalysts. Ammonia produced per unit volume of catalyst had
increased from 3445MT to 23133 MT. The performance LTS catalyst is directly effected by poisons
present in feed.

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 Table-I : LTS Shift Catalyst Poisons
Poison Possible Effects on
sources catalyst

Sulphur Hydrocarbon feed stock Covers the active copper surface

Steam
Quench water
Lubricating oil
New HTS catalyst

Air to secondary reformer

Chloride Hydrocarbon feed stock Promote growth of
Steam copper crystals
Quench
Lubricating oil
Air to secondary reformer

Silica Steam Physical blocking of the

Quench catalyst surface and pores
Lubricating oil
Upstream catalyst, brikling,
catalyst bed support materials etc.

Methanator catalyst

The residual amounts of CO, CO2 at exit of CO2 removal section are removed by methanation reaction
over nickel based catalyst. Carbon oxides are poisons to ammonia synthesis catalyst. For majority of
ammonia plant, methanation catalyst lasts more than five years, however it life depends on the efficient
operation of up stream catalyst in shift section and CO2 removal section. Methanator inlet temperature
is maintained at around 290 to 320 deg C. Inlet temperature of Methanator is maintained at around 290
to 320 deg C, which required high level energy to re-heat the process gases from CO2 removal section.

P e rfo rm a n ce o f M e th a n a to r & Am m o n ia S yn th e sis

Ca ta lysts a t IF F CO Ka lo l

160000
Methanator
Ammonia Produced per
unit Volume of Catalyst

140000
120000
100000 A mmonia
80000 Sy nthes is
60000 Cataly s t
40000
20000
0
1 2 3
C at alys t C h ar g e

Ammonia Synthesis Catalyst :

Ammonia synthesis catalyst is based on metallic iron promoted with alkali (potash) and various metal
oxides such as those of aluminum, calcium or magnesium. The main component of the catalyst is
magnetite (Fe3O4). Various promoters in catalyst plays main role in catalyst activity. Such promoters are
classified as structural or electronic depending on their accepted mode of action. Production and
preservation of porous structure during reduction of ammonia synthesis catalyst is main role of
structural promoters such as alumina, magnesia and chromium. Alkali metal such as calcium, potassium
rubidium etc. are essential components of catalyst to attain high activity, are called electronic promoter.

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Ammonia synthesis catalyst has longer life than other catalyst in ammonia plant. Deactivation of catalyst
is slow going process and loss of activity occur by various mechanism, which are common to all the
catalyst. Deactivation may occur by thermal sintering, which lead to loss of iron surface area and hence
activity. Main poisons to synthesis catalyst are oxygenated compounds such as water, CO, CO2.
However, loss of activity resulting from exposure to these compounds is reversible, provided that partial
pressure of the oxygenated compound is low and that the period of exposure is short. Other poisons
such as chloride and sulphur affect the catalyst irreversibly. During the reduction period, the over all
surface area of the catalyst increases steadily. Poisoning of ammonia catalyst is normally considered in
terms of permanent and temporary deactivation. The dotted lines in figure-3 show the performance of
existing catalyst charge.

EVALUATION OF METAHATOR AND AMMONIA SYNTHESIS CATALYSTS

Methanator:

Figure -3 show the performance of methanator and ammonia synthesis catalysts. It can be seen from the
figure that ammonia produced per unit volume of catalyst had increased from 82178 MT in first charge
to 142243 MT in second charge .Performance of existing charge is satisfactory.

Ammonia Synthesis Converter Catalyst:

It can be seen from the figure that ammonia produced per unit volume of catalyst had increased from
17399 MT in first charge to 60706 MT in second charge. Second charge is still in operation and
performance is satisfactory.

Measures to improvement the performance of catalysts at IFFCO Kalol:

From 1967 to this day, IFFCO vision has grown with the need of farmers. IFFCO Kalol was also the first
fertiliser plant in expanding its capacity by adding new equipment in its 22 years plant. This bears
testimony for its maintenance and up-keep of its equipments- quest for existing in quality. ISO-9002
certification in August 96 is only a rededication of its pursuit for quality. With passage of time different
technical audits are conducted to improve the productivity of plant. Some of the operational and
technological measures taken in the area of catalyst performance are as under :

(A)OPERATIONAL MEASURES:

Following measures are taken to improve the performance of catalyst at IFFCO Kalol:-

1. Planned Annual Turnaround.

Annual turnaround of the plant is planned in such a way that maximum utilisation of catalyst is
achieved.

The Start Of Run (SOR) condition parameters like temperature profile of catalyst bed, pressures
drop, steam to carbon ratio, slip of key components etc. for new charge of catalyst are recorded and
maintained to analyse the performance.

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 Performance of all existing catalysts is checked and the catalysts which are likely to be discharged
within next one year are identified and planning is made for expected replacement of the identified
catalyst .

While discarding the catalyst , analysis of end of run (EOR) operating conditions are also recorded
and also ammonia produced by per unit volume of that catalyst charge is analyzed. The discarding
catalyst performance is also measured based on number of plant shut downs experienced by the
catalyst.

Evaluate the SOR condition of new catalyst being put in service and check SOR conditions with
earlier charge and find out the deficiency, if any.

2. Unloading of Catalyst:

Vessel is blinded in all respect from vessel purging to activation of the catalyst .
Vessel is being kept under nitrogen atmosphere till catalyst is oxidised.
Vessel is being inspected for any damage before unloading is being started so that remedial measures
on operation as well as maintenance side can be planned.

3. Loading of catalyst:

Cleaning of the Vessels:

The entire vessel is thoroughly clean for debris with demineralised water.

Removal of dust and broken particles from catalyst is carried out . Personnel exposed to catalyst
dust shall be protected by using dust filtering respiration masks.

The catalyst is charged either by using buckets or by means of loading chute. Crushing of the
catalyst must be avoided by using of walking planks. Each layer of catalyst should be slightly
compacted along the side wall in order to prevent channeling. Prior to the filling, dust and crushed
particles must be removed by screening.

Inspection:

Vessel is thoroughly inspected for cleanliness before loading is started . All internals are verified as per
vessel drawings. In addition , over all inspection is made of all internals for conformance with drawings.
Deficiency in inspection, if any, is noted and paid maximum important to rectify during next catalyst
change over.

Marking Bed Height :

Established the lower tangent line and mark each bed level and support level etc. in accordance with
vessel drawing.

Storing ,Screening and sorting of catalyst:

Prior to loading, catalyst is pass over suitable screen to remove the dust. In case of primary and
secondary reformers, the broken pieces of catalyst are being sorted out.

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 All the areas where catalyst is handled are covered up and drum are kept clear from damp walls.

Catalyst sceening or sorting of broken pieces is planned in such a way that handling of the drum is
minimised.

Stacking of drums is avoided. It is not stored in the vicinity of combustible materials.

Loading of catalyst :

During catalyst loading, care is being taken to ensure that catalyst free fall is not more than specified
by catalyst supplier.

A complete record of quantity of catalyst being loaded and bed height achieved at each stage of
leveling is being noted.

Catalyst loading procedures for each type catalysts are readily available to all operating staff.

Time taken for each step during loading of vessel is noted and this time is compared with earlier best
time and reasons for increased time are analysed.

(4)Activation of catalyst

All operating staffs are well informed about the catalyst activation procedures, catalyst poisons
,effect of change in operating parameters before activation of new catalyst is being started.

During activation, all the process parameters are maintained and observed as per catalyst supplier
recommendation.

Extra care is being taken to meet the unforeseen emergencies to protect the catalyst .

After completion of activation, catalyst is taken in operation and close monitoring of catalyst
performance is made to optimize the plant performance.

(5) Operation of Catalyst:

Lower and upper limit of operating temperatures for each type of catalyst over a period of time with
aging of catalyst are known to the operating staff .

Operating staff is always well informed with catalyst poisons for each type of catalyst.

Extreme care is being taken during any shutdown so that catalyst remains in secured and safe
condition. Following parameters are monitored on regular basis :-
- bed temperatures profiles of each reactors on hourly basis.
- pressures of the each reactors containing catalyst on hourly basis.
- reactors are drains for condensate once in each shift.

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(B)Technological Measures adopted by IFFCO-Kalol:

(1)Primary reformer Catalyst:

Primary reformer catalyst tubes along with harp assembly was replaced with improved material . Better
tubes material allowed to increase the internal diameter of the tubes for loading more catalyst. Catalyst
volume was increased from 13.6 m3 to 14.4 m3 in first Reformer Revamp and it was further increased
to 17.7 m3 in Second Reformer Revamping in Sept. 1993. Following observations are made :

Pressure drop across the reformer has reduced .

Tube skin temperature has reduced .
This helps higher through put and longer catalyst tube life.

(2) Secondary Reformer Catalyst :

With the first charge of the catalyst, it was found that the top and center portion of the catalyst was
found fused and formed lumps. It was observed that removal of this lump was very difficult and if
sufficient care is not taken , this can be detrimental to the refractory of secondary reformer.

Top catalyst layer was fused due to poor mixing of process air and process gas at top of the catalyst
bed. The catalyst volume was reduced by 14 % from 38.74 m3 to 33.29 m3 to provide more area for
mixing zone at top of the catalyst bed.

Performance of catalyst charge, after reduction in volume, was checked in subsequent annual plant
turnaround. Such catalyst fusion was never experienced after above measure.

(3)LT Shift Converter Reduction Procedure:

In original plant, IFFCO Kalol was using natural gas for LTS catalyst heating and for catalyst reduction
. In this procedure , LTS reduction took about five days during start-up .

Nitrogen circulator system was installed with required flow and pressure . Crack gas (mixture of H2 and
N2 ) compressor was installed. With this facility, LTS catalyst can be reduce independent of natural gas.
Ammonia production is being lined up without any loss of natural gas venting. The same facility is now
being utilised for cooling and heating of other catalysts beds as well.

(4)Ammonia Converter Retrofit:

IFFCO Kalol ammonia synthesis converter is having four catalyst beds. In original reactor ,gas flow
across catalyst beds was axial. Ammonia converter retrofit was done by M/S Ammonia Casale in
September 1993. Gas flow through the converter is changed from axial to axial -radial type .

With above changes, catalyst volume had increased from 64.81 m3 to 75.0 m3 and smaller size catalyst
is used in the reactor. Smaller size catalyst have improve the ammonia conversion per pass and hence
reduction in circulator power requirement. The pressure drop across synthesis converter has also
reduced. Energy saving of the tune of 0.27 Gcal /ton of ammonia was achieved with converter retrofit.

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(C) Technological Measures for adaptation of New Catalysts:

Catalysts are procured from different catalyst suppliers. Within the frame work of IFFCO' s purchase
procedure, following technological measures are taken for adaptation of new catalyst and following
measures are taken :-

(1)HT Shift Catalyst:

Changing the catalyst from conventional to low sulfur and copper promoted catalyst. IFFCO had
experienced the following advantage :-
Reduction in Start-up time.
Lower operating Steam to Carbon Ratio.
With this catalyst charge, it is expected that the ammonia production per unit volume of Catalyst will
improved.

(2) LT Shift Catalyst:

Changing the Catalyst from low Copper to High Copper had resulted in significant increased in
Ammonia Production per m3 of Catalyst.

(3) Ammonia Converter:

IFFCO Kalol is using conventional un-reduced catalyst in Ammonia Converter. During catalyst loading,
first bed is loaded with pre-reduced catalyst . By adopting this technological measure, the start-up time
of ammonia converter was reduced considerably from 5 days to 3 days. By using this method,
ammonia water generation due to reduction process was also reduced considerably.

Conclusion:

It may be concluded that catalysts plays an important role in overall productivity of plant. Development
and commercialization of new catalysts with higher activity at lower temperature is main challenge to
catalyst manufacturers. Improvement in performance may be achieved with high activity catalyst with
high stability and high poison resistance. Significant advantages can be gained by proper selection of
catalyst with planning and proper operation. A well planned catalyst loading/unloading method followed
by precise monitored catalyst activation process will not only improve the catalyst life, but the
economics of ammonia production also. This offers an unlimited scope of improving the application of
catalyst by users.

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 Table-IV : Performance of Catalyst at Ammonia Plant-IFFCO KALOL

Sr. Area of Life of Catalyst Catalyst AmmoniaAmmonia

produced
No. Service Ch- From To Months Volume,m3 Produced, t per unit volume
arge
No of catalyst, t/ m3

1 Hydrogenator 1 Sept.97 Till date 7 3.2 138714 43348.13

2 Sulphur 1 Sept.97 Till date 7 19.4 138714 7150.21

absorber

3 Pre-reformer 1 Sept.97 Till date 7 6.6 138714 21017.27

4 Primary 1 Nov.74 Dec.76 24.95 13.6 369179 27145.51

Reformer 2 Jan.77 May.79 27.91 13.6 665628 48943.24
3 June 79 April 81 21.43 13.6 495292 36418.53
4 May-81 Dec.83 30.70 13.6 809852 59547.94
5 Jan.84 March 86 25.80 13.6 572104 42066.47
6 May-86 April-88 23.50 14.4 587378 40790.14
7 May-88 Feb.-91 33.47 14.4 849788 59013.06
8 March-91 Sept.-93 30.07 14.4 726701 50465.00
9 Oct.-93 Till date 53.00 17.4 1396704 78466.00

5 Secondary 1 Nov.74 March 76 16.66 38.74 208339 5377.88

Reformer 2 April 76 May-79 37.79 33.29 827416 24854.79
3 June 79 March-86 80.63 33.29 1867104 56086.03
4 May-86 Nov.-92 78 33.29 1943105 58369.03
5 Nov.92 May-97 54 33.29 1347466 40476.60
6 June-97 Till date 7 33.29 267479 8064

6 HTS 1 Nov.-74 Dec.-76 24.86 55.13 369179 6696.52

2 Jan.-77 April 81 52.67 55.13 1160920 21057.86
3 May-81 March-86 58.3 55.13 1371812 24883.22
4 June 86 June 91 57.67 55.13 1433581 26003.65
5 March-91 May-97 74 55.13 5904475 107100.94
6 June 97 Till date 7 55.13 267479 4851.79

7 LTS 1 Nov.-74 March-76 16.7 58.76 208339 3545.59

2 April 76 Feb.-78 22.33 58.76 483512 8228.59
3 March-78 April 81 36.93 58.76 853680 14528.25
4 May-81 April 85 47.1 58.76 1150279 19575.88
5 May-85 April 88 33.5 58.76 803623 13676.36
6 May-88 Nov.-92 53.9 58.76 1359311 23133.27
7 Nov.-92 May-97 54 58.76 1347466 22931.69
8 June -97 Till date 7 58.76 267479 4552.06

8 Methanator 1 Nov.-74 Dec.-80 73.5 18 1479215 82178.61

2 Feb.-81 Feb.-90 108 18 2560376 142243.11
3 March-92 Till date 70 18 1616990 89832.00

9 Synthesis 1 Nov.-74 Nov.-79 60 64.81 1127684 17399.85

Converter 2 Dec.-79 Sept.-93 165.2 64.81 3934382 60706.40
3 Oct.-93 Till date 50 75 1396704 18622.0

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 Table-I : Existing Charge of different catalysts at Ammonia Plant
Sr Area Nomenclature Catalyst Name of
No of catalyst volume, m3 supplier

1. Desulphurisation C-8-6 28.3 UCIL

2. Hydrogenator TK 550 3.2 H&T
3. Sulphur absorber HTZ-3 19.4 H &T
4. Pre-reformer RKNGR 6.6 H&T
5. Primary reformer ICI-46-8 17.8 ICI
6. Secondary reformer C-14-2/C-15-1 33.29 UCIL
7. Shift reactor-HTS SK-12-LS/
SK-201/
C-12-4 55.13 UCIL
8. Shift reactor-LTS C-18-HC 58.76 UCIL
9. Methantor C-13-4 18.0 UCIL
10. Ammonia converter AS-4/ AS-4F 75.0 H &T

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