Catalyst Performance Evaluation

Ammonia Team

Catalyst Evaluation Report

Fertial Arzew,
Ammonia I
Algeria

Plant Dataset Date:

Feb-2010

Prepared By: Reza Ebadi

Johnson Matthey Catalysts

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

INTRODUCTION

The starting point for analysis of a plant data-set is a calculation of a theoretical heat and
mass balance from the plant data provided. Using the calculated theoretical heat and mass
balance, the difference between measured and theoretical process parameters is
determined. These differences are used to calculate standard errors based on the expected
error in any particular measurement. The plant data, if necessary, are then varied to
minimise the root mean square (RMS) error to obtain an overall best fit to the theoretical
heat and mass balance. It is the calculated ‘best fit’ data which are used to comment upon
the actual plant data (flows and analysis) and the calculated approach to equilibrium (ATE)
for each catalyst.

The CATPER catalyst evaluation program, which is Johnson Matthey proprietary simulates
the main process units of ammonia plants and has been developed over the years to meet
the needs of plant operators to assess plant operation and characterise catalyst
performance.

During the fitting calculation, CATPER sums the adjustments to each measurement into a
root mean square (RMS) value. The RMS value is a measure of the total amount of
adjustment necessary to give consistency with the model, and is a measure of the quality of
the plant data. In general, the lower the RMS value, the better the fit between the measured
and calculated values. An RMS value of less than 0.5 is regarded as a good fit, i.e. most
measurements lie within their 95% confidence limits. An RMS less than 1.0 is regarded as a
reasonable fit and an RMS of greater than 1.0 indicates a poor fit.

The calculated Root Mean Square Error (RMS Error) for 10th Feb 2010 dataset is 0.881
indicating a reasonable fit to the measured data.

We have used Johnson Matthey proprietary programs ‘SHIFT’ and ‘AMMCON’ to evaluate
the performance of HT and LT shift converters and also ammonia converter based on the
calculated results of ‘CATPER’.

Plant rate is reported to be 730 TPD against design 1000 TPD. Reason of such low
throughput is not known to us.

The full summary of the CATPER output is given in Appendix I.

PRIMARY REFORMER 13m3 S-C G90-LDP and 13m3 S-C G91, Installed May 2009

Date Time on line S/C* Exit Temp* Exit CH4* ATE Delta P
Years (Ratio) (°C) (%) (°C) (bar)
10 Feb. 10 0.75 4.02/4.28 760/765 8.35 / 9.19 0 2.7
* Measured/Calculated

In general good agreement between measured and calculated parameter have been
achieved however and as can be seen from above table calculated inlet steam carbon ratio
is marginally higher than measured value while exit CH4 slip is higher than reported one.

Catalyst tubes pressure difference is 2.7 bar however normalized pressure drop should be
considered as an indication of catalyst performance in conjunction with CH4 slip.
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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Normalized pressure drop is calculated as following:

DPNormalized = DPReported x (FlowDesign / FlowActual) ^ 2

As can be seen Pressure drop is proportional to second power of flow, in other words if 730
TPD can be considered as if reformer exit flow is 73% of design reformer exit flow then
reported pressure drop is equivalent to 5.07 bar. Fertial is asked to investigate this matter.

Having high inlet S/C ratio, high CH4 slip and pressure drop can potentially be an indication
of catalyst poor performance and insufficient activity which is likely to cause carbon
formation in the hottest parts of tubes.

It is recommended to keep a close eye on the performance of the primary reforming catalyst
and in particular reformer tubes wall temperature and appearances.

Hot banding, giraffe necking, tiger tailing and hot tubes are totally unwanted phenomenon
and will cause tubes short service life and failure. It should be noted that visible hot bands
tubes are typically operating at least 20 to 40ºC above design temperature.

Carbon Formation and Prevention

Reformer tube appearance - Carbon laydown

Hot Band Giraffe Hot Tube

Necking

To prevent hot bands and hot spotting in the tubes, methods of preventing carbon formation
are:
• Use more active catalyst
• Use better heat transfer catalyst
• Reduce levels of higher hydrocarbons
• Increase the steam ratio
• Use promoted catalyst (e.g. KATALCOJM 25-4Q) that reduces probability of carbon
formation
• Use UNIDENSE loading technique for an even distribution of catalysts across the
tubes.

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Effect of Tube Wall Temperature

on Tube Life
20

Tube Life (Years)

Design
10
+ 20°C Carbon to be avoided
5
2
as 20ºC increase in
TWT will reduce the
1 tube life by 50%
0.5
0.2

850 900 950 1000

(1560) (1650) (1740)
(1830) Temperature °C (°F)

With good catalyst activity and high degree of carbon resistance the catalyst life can be
around 6-8 years while with poor catalyst activity and high degree of carbon resistance the
catalyst life can be around 3-4 years, making the catalyst cost double per year.

Typical Tube Failure – Top fired

30-40% down Tube where

Carbon Formation will
result in hotter tubes

However a more significant cost is from unplanned tube failures plant downtime, most plants
such as Fertial Arzew have no means of isolating a leak e.g. by pigtail nipping so furnace
cool down, repair and restart for a single tube failure may typically take 3-5 days so lost
product sales may be €2 to 3 M, also a unplanned tube failure normally causes damage to
adjacent tubes

As explained in introduction the CATPER evaluation looks at the performance of the

reformer overall from a heat and mass balance and is not a way of assessing whether the
catalyst is performing correctly in terms of keeping the tubes cool and preventing carbon
formation.

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

SECONDARY REFORMER 26.4 m3 of C14-2-01, installed Feb 2008

Date Time on line Exit CH4 ATE Exit Temp. Delta P

Year (%) (°C) (°C) (bar)
10 Feb 10 1 0.34 13.7 931.2 0.3

Calculated approach to equilibrium is in the range of 14 oC with good methane slip

however as plant capacity is low all these parameter should be under view once
throughput increased.

HIGH TEMPERATURE SHIFT 78m3 Sud-Chemie G3C, Installed August 2006

Date Time on Temp. rise* Exit CO* ATE Delta P

line (°C) (%) (°C) (bar)
Year
10 Feb 10 3.5 62 / 49.9 2.16 / 2.10 47.2 Not Reported
* Measured/Calculated

Performance of any water gas shift catalyst can be assessed by CO slip and pressure drop
out of the bed in conjunction with inlet condition and in particular steam/dry gas ratio. As per
CATPER results exit CO is very good however pressure drop has not been reported.
To have a more sensible understanding for the performance of this HTS catalyst we have
used Johnson Matthey proprietary software ‘SHIFT’ result of which for temperature rise and
CO gradient are plotted in following figures.

Fertial Arzew Plant1 HTS Temperature Profile

420

400
Temperature

380

360

340
0 20 40 60 80 100
%of bed depth

Calculated Tem. Profile Plant Data

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Fertial Arzew Plant1 HTS CO slip Profile

12.00
10.00
CO dry mol%

8.00

6.00
4.00
2.00
0.00
0 20 40 60 80 100
%of bed depth

Calculated CO slip Profile Plant Data

Following table shows exit condition of HTS based on ‘SHIFT’ output and ‘CATPER’ output.

Components H2 N2 CO CO2 CH4 Ar

SHIFT(mol% dry) 60.65 20.06 1.48 17.26 0.32 0.23
Fitted Plant data 60.41 20.19 2.1 16.75 0.32 0.23
Fertial Arzew Plant1 HTS Exit Condition

As can be seen from CO and CO2 compositions this catalyst charge is not performing as
expected. Reason of having such a low CO is having a very high steam/carbon ratio at
primary reformer inlet.

LOW TEMPERATURE SHIFT 71.4m3 of C-18 AMT, Installed August 2006

Date Time on Temp. rise* Exit CO* ATE Delta P

line (°C) (%) (°C) (bar)
Year
10 Feb 10 3.5 12 / 12.4 0.18 / 0.17 28.6 Not Reported
* Measured/calculated

There’s a good agreement between measured and calculated results however catalyst
performance should be evaluated by kinetic basis software such as ‘SHIFT’ therefore same
HTS we have used Johnson Matthey proprietary software ‘SHIFT’ for this purpose.

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Fertial Arzew Plant1 LTS Temperature Profile

210.0
208.0
206.0
Temperature

204.0
202.0
200.0
198.0
196.0
194.0
0 20 40 60 80 100
%of bed depth

Calculated Temp Profile Plant Data

Fertial Arzew Plant1 LTS CO slip Profile

2.50

2.00
CO dry mol%

1.50

1.00

0.50

0.00
0 20 40 60 80 100 120
%of bed depth

Calculated CO Slip Plant Data

Expected exit conditions at the exit of LTS catalyst bed and also fitted plant data are shown
below:

Components H2 N2 CO CO2 CH4 Ar

SHIFT(mol% dry) 61.18 19.8 0.1 18.38 0.31 0.23
Fitted Plant data 61.16 19.81 0.17 18.32 0.31 0.23

Unfortunately pressure drop is not reported as this could be an indication of catalyst

performance however in terms of CO and CO2 this catalyst is expected to be performing
better.

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

METHANATOR 19m3 of C14-4-04, Installed August 2006

Good agreement between measured gas analyses inlet and exit the methanator and
calculated data is observed. Observed temperature rise is also in good agreement with the
calculated value.

Date Time on Temp. rise* Delta P

line (oC) (bar)
Years
10 Feb 10 3.5 15 / 16.9 --
* Measured/calculated

This catalyst is performing well and reaction completes in one third of the bed however
pressure drop not been mentioned

AMMONIA SYNTHESIS 76.5 m3 of KM1(R), Installed August 2006

As described above performance of Ammonia synthesis catalyst was evaluated by JM

proprietary AMMCON software. The following figure illustrates ammonia mol% versus
temperature along Ammonia converter catalyst bed.

Fertial Arzew Plant1 Ammonia Converter Operating

Curve

16.00

14.00

12.00
NH3 Concentration

10.00

8.00

6.00

4.00

2.00

0.00
320.0 370.0 420.0 470.0 520.0 570.0 620.0 670.0
Temperature (C)

Operating Line Maximum Rate Curve Equilibrium Curve

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

As can be seen from above figure ammonia synthesis converter is not performing well.
Operating line is expected to be around max rate curve and close to equilibrium curve at the
exit of each bed.
Approach to equilibrium at the exit of each bed is shown in the following table:

Bed 1 2 3
ATE (oC) 109 47.2 59

The contribution of each bed in total ammonia production is calculated to be as follows:

Bed 1 2 3
Contribution% 29.88 37.36 32.76

As can be observed first bed has very less contribution as expected.

To show the performance of KATALCOJM 35-8 and KATALCOJM 35-4 in a modern ammonia
converter with double age of Fertial (7.6 vs 3.5 year) following operating line and contribution
which were achieved.

Operating Line of NH3 Converter with KATALCO 35-8 and 35-

4 Catalysts

18.00
16.00
14.00
12.00
NH3 mole%

10.00
8.00
6.00
4.00
2.00
0.00
350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0
Temperature (C)

Operating Line Max Rate Curve Equilibrium Curve

Date ATE(beds 1/2/3) %bed contribution

(beds 1 / 2 / 3)
8 Apr. 09 10.2 / 13.1 / 16.2 59.5 /21 /19.5

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

I hope you find this report useful but should you have any comments it would be very
welcome.
Please do not hesitate to contact us in case you have any technical query.

Best Regards

Reza Ebadi

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

APPENDIX I: CATPER Output

DATAFIT RESULTS

Title Fertial Arzew

Date 10-Feb-2010
RMS error 0.881

FEED AND H2 RECYCLE

NG Recycle

H2 % 0.00 74.34
N2 % 5.44 24.60
CH4 % 83.48 0.76
Ar % 0.00 0.30
CO % 0.00 0.00
CO2 % 0.21 0.00
C2H6 % 7.85 0.00
C3H8 % 2.10 0.00
C4H10 % 0.92 0.00
C5H12 % 0.00 0.00

Measured Calculated
value value

Recycle flow Nm3/hr 250.0

NG Nm3/hr 19176.0 19361.3

PRIMARY REFORMER

Present YES
Catalyst #1 type G90 EW
Catalyst #1 volume m3 13.0
Catalyst #2 type G90 LDP
Catalyst #2 volume m3 13.0
Installation date 01-May-2009
Time online days 285.

Measured Calculated
value value

Pressure drop bar 2.70

Exit pressure barg 29.30

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Steam flow te/hr 67.70 72.75

Exit temperature (TI) degC 760.0 765.1
Exit H2 % 70.23 69.06
Exit N2 % 1.35 1.55
Exit CH4 % 8.35 9.19
Exit Ar % 0.00
Exit CO % 8.17 7.80
Exit CO2 % 11.90 12.40

Inlet steam : carbon ratio 4.024 4.283

Exit dry gas flow Nm3/hr 72046.8
Exit steam : dry gas ratio 0.931
Exit wet gas flow Nm3/hr 139157.7
Equilibrium temperature degC 765.1
M/S approach degC 0.0

SECONDARY REFORMER

Present YES
Catalyst #1 type C 14-2
Catalyst #1 volume m3 26.4
Catalyst #2 type
Catalyst #2 volume m3 0.0
Catalyst #3 type
Catalyst #3 volume m3 0.0
Installation date 01-Feb-2008
Time online days 740.
Reference exit wet gas flow Nm3/hr 181503.3

Measured Calculated
value value

Pressure drop bar 0.30

Normalised pressure drop bar 0.30
Temperature drop degC 0.0
Exit pressure barg 29.30

Air flow Nm3/hr 31746.2 27143.2

Air temperature degC 519.0 516.0
Steam flow te/hr 6.70 6.72
Exit temperature degC 910.0 931.2
Exit H2 % 57.34 57.14
Exit N2 % 21.82 21.85
Exit CH4 % 0.34 0.34
Exit Ar % 0.27 0.25
Exit CO % 11.23 10.53
Exit CO2 % 9.00 9.88

Inlet steam : carbon ratio 4.422 4.678

Exit dry gas flow Nm3/hr 102059.0

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Exit steam : dry gas ratio 0.778

Exit wet gas flow Nm3/hr 181503.3
Equilibrium temperature degC 917.5
M/S approach degC 13.7

HTSHIFT

Present YES
Catalyst #1 type G 3C
Catalyst #1 volume m3 78.0
Installation date 01-Aug-2006
Time online days 1289.
Reference exit wet gas flow Nm3/hr 181503.3

End of reaction zone m

Temperature profile Depth Temp

m degC
#1 0.040 343.0
#2 0.480 380.0
#3 0.960 406.0

Measured Calculated
value value

Additional H2 Nm3/hr 0.0

Quench temperature degC
Pressure drop bar 0.30
Normalised pressure drop bar 0.30
Exit pressure barg 26.70

Temperature before quench degC

Quench flow te/hr
Inlet temperature degC 344.0 350.1
Exit temperature degC 406.0 400.0
Exit H2 % 61.08 60.41
Exit N2 % 20.20 20.19
Exit CH4 % 0.31 0.32
Exit Ar % 0.25 0.23
Exit CO % 2.16 2.10
Exit CO2 % 16.00 16.75

Inlet dry flow Nm3/hr 102059.0

Inlet steam : dry gas ratio 0.778
Inlet wet flow Nm3/hr 181503.3
Dew point at inlet degC 188.9
Temperature rise degC 62.0 49.9
Exit dry gas flow Nm3/hr 110486.1
Exit steam : dry gas ratio 0.643
Exit wet gas flow Nm3/hr 181503.3

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Equilibrium temperature degC 447.2

WGS approach degC 47.2
CO conversion % 80.1

LTSHIFT

Present YES
Catalyst #1 type C 18 AMT
Catalyst #1 volume m3 71.4
Installation date 01-Aug-2006
Time online days 1289.
Reference exit wet gas flow Nm3/hr 181503.3

End of reaction zone m

Temperature profile Depth Temp

m degC
#1 0.260 205.0
#2 0.390 207.0
#3 0.530 208.0

Measured Calculated
value value

Pressure drop bar

Normalised pressure drop bar
Exit pressure barg 24.20

Temperature before quench degC

Quench flow te/hr
Inlet temperature degC 196.0 195.8
Exit temperature degC 208.0 208.2
Exit H2 % 61.57 61.16
Exit N2 % 19.70 19.81
Exit CH4 % 0.31 0.31
Exit Ar % 0.24 0.23
Exit CO % 0.18 0.17
Exit CO2 % 18.00 18.32

Inlet dry flow Nm3/hr 110486.1

Inlet steam : dry gas ratio 0.643
Inlet wet flow Nm3/hr 181503.3
Dew point at inlet degC 180.5
Temperature rise degC 12.0 12.4
Exit dry gas flow Nm3/hr 112605.4
Exit steam : dry gas ratio 0.612
Exit wet gas flow Nm3/hr 181503.3
Equilibrium temperature degC 236.8

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

WGS approach degC 28.6

CO conversion % 91.7

CO2 REMOVAL

Present YES

Measured Calculated
value value

Exit H2 % 75.0 74.9

Exit N2 % 24.10 24.24
Exit CH4 % 0.38 0.38
Exit Ar % 0.30 0.28
Exit CO % 0.22 0.21
Exit CO2 % 0.02 0.02

Exit dry gas flow Nm3/hr 91993.3

Exit steam : dry gas ratio 0.000

METHANATOR

Present YES
Catalyst #1 type C14-4-04
Catalyst #1 volume m3 19.0
Installation date 01-Aug-2008
Time online days 558.
Reference exit wet gas flow Nm3/hr 91566.8

End of reaction zone m

Temperature profile Depth Temp

m degC
#1 0.000 270.0
#2 0.080 266.0
#3 0.460 285.0
#4 0.840 285.0

Measured Calculated
value value

Pressure drop bar

Normalised pressure drop bar

Temperature rise degC 15.0 16.9

Exit H2 % 74.34 74.68
Exit N2 % 24.60 24.42
Exit CH4 % 0.76 0.62
Exit Ar % 0.30 0.28
Exit CO % 0.00

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Fertial Arzew Plant1, Arzew, Algeria
Catalyst Performance Evaluation
Ammonia Team

Exit CO2 % 0.00

Exit dry gas flow Nm3/hr 91336.1

Exit steam : dry gas ratio 0.003

SYNGAS AND RECYCLE

Measured Calculated
value value

Additional H2 Nm3/hr 0.0

Recycle flow Nm3/hr 250.0

H2:N2 ratio 3.058

Product flow (after recycle) Nm3/hr 91086.1

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Fertial Arzew Plant1, Arzew, Algeria