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Katalco

Page 2

Katalco

Low temperature shift catalysts

Katalco
PERFORMANCE

Katalco
PERFORMANCE

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Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at time of going
to press and is given in good faith, but it is for the User to satisfy itself of the suitability of the Product for its own particular
purpose. Johnson Matthey plc (JM) gives no warranty as to the fitness of the Product for any particular purpose, and any implied
warranty or condition (statutory or otherwise) is excluded except to the extent that exclusion is prevented by law. JM accepts no
liability for loss or damage (other than that arising from death or personal injury caused by JMs negligence or by a defective
Product, if proved) resulting from reliance on this information. Freedom under Patent, Copyright and Designs cannot be assumed.

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Contents
Page
Introduction

Case studies

KATALCOJM PERFORMANCE - adding value to your plant

Advantages of choosing KATALCOJM PERFORMANCE

KATALCOJM catalyst selector

10

Catalyst characteristics

11

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Introduction
The low temperature shift reactor is vital to the economic
operation of todays ammonia plants, and features in many
hydrogen plant flowsheets. It generates the last 5%
hydrogen and, through low CO slip, minimizes the hydrogen
consumed in the downstream methanation stage. In
ammonia plants this minimizes the synthesis loop purge,
which is twice as important in plants without purge gas
hydrogen recovery units. Additionally, by-product methanol
consumes hydrogen, so reducing plant output, and
methanol emission can be a serious environmental concern.
Johnson Matthey Catalysts offers a world-leading family of
low temperature shift catalysts, the KATALCOJM 83-series.
KATALCOJM 83-series catalysts offer outstanding catalyst
lives and low methanol by-product formation, which are
delivered through world-leading poisons resistance and
activity, and low methanol by-product options. These
features extend catalyst life or enable short loads to fit
planned turnaround cycles, maximize hydrogen production
and address environmental concerns. The result is that
KATALCOJM 83-series catalysts are the number one catalyst
choice in more than 175 of the worlds ammonia and
hydrogen plants.

Where pressure drop is also a concern, using the KATALCOJM

PERFORMANCE STREAMLINE system in conjunction with
KATALCOJM 83-series catalysts can significantly reduce the
pressure drop through the low temperature shift converter.
Here are examples of how KATALCOJM catalysts have already
helped our customers save money:
Installation of KATALCOJM 83-3X in an ammonia plant in
North America has doubled the life of the low temperature
shift catalyst, saving approximately US$ 500,000 in
replacement catalyst costs.
A hydrogen plant in North America switched from wellestablished LTS and guard catalysts to KATALCOJM 83-3X.
Instead of annual replacement of poisoned catalyst,
KATALCOJM 83-3X delivered more than 3 years continuous
service. KATALCOJM 83-3X paid for itself 3 times over.
An ammonia plant in Asia-Pacific has now achieved an 8-year
life from KATALCOJM 83-3 and expects to reach 9 years of
operation before replacing it during a planned shutdown. The
long life has minimized annualized catalyst replacement cost.
Installation of the Johnson Matthey STREAMLINE system in
an ammonia plant in Europe has reduced the pressure drop
across the shift converters by more than 0.5 bar (7 psi),
thereby saving US$ 130,000 each year.

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Case study 1 - KATALCOJM catalyst gives

longer life
Installation of KATALCOJM 83-3 instead of the previous
competitive catalyst saved the operator at least US$ 300,000
in catalyst and unscheduled replacement costs.

0.25 mol%, and pressure drop has increased by only 10%.

The figure below shows the exotherm across the KATALCOJM
catalyst bed after 54 months (4.5 years) on-line.

In this case, a large North American ammonia plant

operating at 1700 stpd expected the competitive catalyst
charge to last 4 years before change-out during a planned
shut-down. However, after 3 years on-line, the CO slip from
the converter was high, so the charge was skimmed and
partially reloaded with the competitive catalyst. Despite this,
the CO slip was still greater than 0.3 mol% when the full
load was replaced after an additional year on-line (giving a
total of 4 years).

By installing KATALCOJM 83-3, the plant has extended the

LTS catalyst life by an additional year. Considering only
catalyst costs, this has saved the plant approximately
US$ 170,000 over the lifetime of the catalyst. The plant has
also avoided the costs associated with the unscheduled
shut-downs and catalyst replacements that occurred when
the competitive charge was installed. The major saving,
however, is that as a direct result of the extension in LTS
catalyst life, combined with the superior performance of
Johnson Matthey high temperature shift and steam
reforming catalysts, the plant has been able to delay a
planned major turnaround by 12 months.

Due to the poor performance of the previous competitive

charge, the same volume of KATALCOJM 83-3 was then
installed. This has operated very well and will have run for
5 years before a scheduled replacement later this year.
Throughout the catalyst life, the CO slip has remained below

Figure 1: Catalyst exotherm at start of run and

at 4.5 years on-line
120

% Exotherm

100
80
60
40
20
0
0

20

40

60

80

100

% Down bed
SOR

54 months

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Case study 2 - STREAMLINE from

KATALCOJM PERFORMANCE gives
consistent low pressure operation

Figure 2: STREAMLINE installed in year 4

25

20
Pressure drop (psi)

Today, reducing pressure drop is extremely important to

many plants as the emphasis on increasing production and
improving energy efficiency continues. One ammonia plant
in Asia-Pacific is now saving more than US$ 250,000 per
annum in energy costs (based on a gas price of
US$3/MMBTU) by installing in its low temperature shift vessel
a system comprised of KATALCOJM 83-3 and STREAMLINE.

15

10

0
Year 1

Year 2
HTS bed

Johnson Matthey Catalysts completed a detailed study of the

low temperature shift vessel installation. This study included
detailed CFD (Computational Fluid Dynamic) modelling of
the internal arrangement at the converter exit. Modelling of
the existing arrangement confirmed a measured pressure
drop of 18 psi (1.25 bar). The CFD work also showed that
minor modifications to the exit nozzle and the installation of
the STREAMLINE system would reduce the pressure drop by
13 psi (0.9 bar) to only 5 psi (0.35 bar).
This was confirmed by the plant performance after the
turnaround, and the savings will pay for the catalyst in less
than 2 years. Savings were also gained in the HTS vessel.

Year 3
LTS bed

Year 4

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Case study 3 - KATALCOJM extends

catalyst life
Installation of KATALCOJM 83-3X instead of the previous
competitive catalyst saved the operator at least US$ 600,000
in catalyst and unscheduled replacement costs.
A large North American hydrogen plant experienced short
catalyst lives due to chloride poisoning. During a 5 year
period, it replaced a competitve LTS catalyst and its
associated guard material 5 times. Catalyst lives averaged
just one year.
The plant then changed to a full bed of KATALCOJM 83-3X,
which gave excellent performance for more than three
years. This saved the operator both replacement catalyst
and unscheduled shut-down costs, estimated to be worth at
least US$ 600,000.
In addition to the cost savings achieved by the plant
operator, this case study also demonstrates the excellent
inherent poisons resistance of KATALCOJM 83-3X products.
The formulation of these products provide chloride and
sulphur guarding properties in addition to excellent shift
activity, delivering longer lives than competitive offerings.

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KATALCOJM PERFORMANCE adding value

to your plant
Some ammonia plants have achieved exceptionally long lives
from KATALCOJM 83-3, in excess of two 4-year turnaround
cycles. In order to do this, the catalyst must have good poison
resistance. It must also be strong enough to withstand plant
upsets, such as steam condensation or water impingement,
ensuring that pressure drop increase across the catalyst bed is
kept to a minimum. KATALCOJM 83-3 was installed in a large
European ammonia plant. After 6.5 years on-line, the
temperature profile was sharp, approximately halfway down
the bed and reaching equilibrium. The charge is expected to
give a 9-year life with consistent, predictable operation.
An ammonia plant operator saved more than US$ 700,000
in replacement catalyst costs by installing KATALCOJM 83-3K
(the predecessor to KATALCOJM 83-3X). The site operates two
similar Kellogg ammonia plants. KATALCOJM 83-3K was
installed in one plant and a competitor's catalyst in the
other. Both charges were expected to last for 4 years. The
competitive charge lasted for only 29 months before being
replaced due to high CO slip. After 3 years on-line, the
KATALCOJM 83-3K charge is operating very well. The
temperature profile is approximately halfway down the bed
with an equilibrium CO slip of 0.3%. The charge is expected
to give at least 4 years on stream with predictions of an
extended life of up to 5 years. By installing KATALCOJM 83-3K,
the operator saved more than US$ 700,000 in replacement
catalyst costs compared to the competitive charge.

A small Kellogg ammonia plant in North America has

demonstrated the benefit of the superior poison resistance of
KATALCOJM 83-3X, which also allowed the operator to reduce
methanol by-product make. This plant has a known chloride
poisoning problem. Previous charges of competitive catalysts
had average lives of only 2 years, with the longest life achieved
in the last decade being 2.5 years. KATALCOJM 83-3X was
installed and has now been on-line for more than 3 years.
The temperature profile is still in the top 40% of the bed and
the charge is expected to last for at least 5 years, more than
doubling the life of the catalyst compared to previous
competitive charges. This represents a saving of nearly
US$ 500,000 in replacement catalyst costs.
A refinery in North America has a long history of chloride
poisoning issues, which have caused significant problems in
recent years. The plant had a competitive low temperature
shift catalyst and guard material installed and these had to
be changed every year due to poisoning problems. The
plant then changed to KATALCOJM 83-3X. This charge lasted
for more than 3 years and was only changed when a power
outage at the refinery caused damage to the catalyst. The
superior performance of KATALCOJM 83-3X has saved the
customer more than US$ 600,000 in replacement catalyst
costs alone.

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Advantages of choosing KATALCOJM

low temperature shift catalyst
Operational benefits
Minimum CO slip

Low, stable pressure drop

Catalyst strength in service is equally as important as fresh
pellet strength. The KATALCOJM 83-series is formulated to
give high strength following reduction and steaming as
shown in Figure 3. The enhanced robustness allows full
advantage to be taken of the high activity by operating at
the lowest possible temperature. The high strength
minimizes the rate of pressure drop rise over time on-line,
which results from hydraulic effects as the catalyst weakens
from thermal sintering, and helps resist breakage following
condensation incidents.

In the case of low temperature shift converters, the most

common operational upsets are condensation on the
catalyst or wetting from an upstream water quench system.
KATALCOJM 83-series catalysts are extremely robust to
withstand these upset conditions. Figure 4 shows the
relative strength of KATALCOJM 83-3X and other
commercially available low methanol products after a
simulated condensation incident.
Figure 3: Relative strengths of fresh and reduced catalysts
Mean horizontal crush strength (kgf)

The position of the thermodynamic equilibrium for the water

gas shift reaction favours maximum CO conversion at low
temperature. The excellent activity of the KATALCOJM 83-series
catalysts accelerates the rate of reaction such that in many
plants, the water gas shift reaction achieves equilibrium at
temperatures below 200C (392F) and remains at or close
to equilibrium throughout the catalyst life. Charges of
KATALCOJM 83-series catalysts are operating successfully at
inlet temperatures as low as 190C (375F), and catalyst
activity is such that in many situations, the minimum
allowable operating temperature is determined by the dew
point of the gas.

14
12
10
8
6
4
2
0
Fresh
KATALCOJM 83-3X

Reduced
Competitor A

Competitor B

Figure 4: Horizontal crush strength after reduction

and after condensing steam conditions

Robustness to operational upsets

12.00
10.00
HCS (Kgf)

The stable activity and high strength of KATALCOJM 83-3

and 83-3X ensure that the catalyst operates according to
our expectations; however, the catalyst must also be
resistant to operational upsets.

8.00
6.00
4.00
2.00
0.00
KATALCOJM 83-3X
After reduction

Competitor 1

Competitor 2

After condensing steam

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Minimum by-products
Low temperature shift catalysts form methanol as a
by-product. Methanol emissions can be an environmental
issue, in some cases exceeding consent limits under
environmental legislation. Problems occur in the treatment
of process condensate and in wet CO2 removal flowsheets.
Methanol also represents a process inefficiency since every
molecule of methanol consumes 2 H2 and 1 CO molecules.
For example, 1.0 tonne of methanol equates to a loss of
about 180 kg H2 and 1.05 tonnes of ammonia or about
100,000 SCFD and 5 tonnes/day for a large hydrogen and
ammonia plant, respectively, with conventional LTS catalyst.
KATALCOJM 83-3X incorporates carefully optimized levels of
alkali promoters and retains excellent high activity for shift
conversion with much reduced activity for methanol
synthesis. Commercial experience with KATALCOJM 83-3X
has shown it to have reduced methanol formation by more
than 80% while still achieving a high activity for the CO shift
reaction. This is illustrated in Figure 5 opposite, which shows
the actual performance of KATALCOJM 83-3X in a plant
requiring low methanol by-products from its LTS converter.
In support of plant operators, Johnson Matthey Catalysts has
developed a kinetic model that accurately predicts methanol
formation rates. This is used to advise on the optimal
operating conditions to minimize methanol formation.

Many ammonia and some hydrogen plants feature LTS

guard reactors. These relatively small vessels contain a
sacrificial catalyst that retains the poisons to protect the
main catalyst bed downstream. By timely renewal of the
guard reactor catalyst, the life of the main bed can be
extended to 10 or more years. For optimal protection, the
guard catalyst should provide the maximum poisons
capacity and a sharp absorption profile.
Due to the method of incorporating the alkali promoters,
KATALCOJM 83-3X gives better poison retention than
KATALCOJM 83-3. This is illustrated in Figure 6, which shows
the effect of cumulative levels of chloride poisons on shift
conversion activity.

Figure 5: Plant performance of KATALCOJM 83-3X

1,200

Methanol in Condensate (ppmw)

JM_726_669 fLTS Brochure

1,000
800
600
400
200
0
0

10

12

14

Months in Operation
KATALCOJM 83-3
(Expected)

Long life and economic performance

KATALCOJM 83-3X
(Expected)

Plant data

Figure 6: Effect of chloride poisoning on CO conversion

for KATALCOJM catalyst range
100

80
CO conversion (%)

The life of most charges of LTS catalyst is determined by

the capacity of the catalyst to absorb trace poisons that are
inevitably present in the process gas. In most ammonia and
hydrogen plants, the key poisons are sulphur and chloride.
The LTS catalyst must be designed to tolerate these poisons
to prolong the active life of the catalyst. KATALCOJM 83-3
and KATALCOJM 83-3X have good self-guarding for both
sulphur and chloride poisons in which the active shift
catalyst itself provides its own protection.

60

40

20

0
0

10

15

20

Relative levels of accumulated CI

KATALCOJM 83-3X

KATALCOJM 83-3

25

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When LTS catalyst becomes fully deactivated and requires

changing, the sulphur concentration in the catalyst is
approximately 1% near the top of the vessel and 0.1% near
the bottom. However, for KATALCOJM 83-3 the sulphur
concentrations have been significantly above this level as
indicated in the following examples:
Table 1: Excellent sulphur retention of KATALCOJM 83-3
Plant Location

% Sulphur (w/w)
Top Sample

% Sulphur (w/w)
Middle Sample

USA

2.1

0.14

Europe

4.4

0.16

Australia

2.9

0.09

The mini versions KATALCOJM 83-3M and KATALCOJM 83-3MX

have greater poison retention than the standard sizes and have
proven to give the longest plant runs ever in service.
Fast start-up
KATALCOJM 83-series catalysts require reduction before they
can be brought on-line. To avoid overheating, this process
must be carefully controlled to an inlet temperature of
about 180C (356F) and the hydrogen addition rate must
be limited. A lower reduction strike temperature allows
earlier introduction of hydrogen and shortens reduction
time. For KATALCOJM 83-series, reduction commences at
temperatures as low as 150C (302F), and research tests
confirm this to be as much as 25C (45F) lower than
competitive catalysts. Also, experience in commercial plants
confirms the catalyst can be safely and rapidly reduced with
a minimum of inconvenience.
Johnson Matthey Catalysts is able to offer on-site support
for LTS catalyst reductions, and our experienced engineer
will provide analysis equipment, ensuring a quick and safe
start-up.

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Additional capability with KATALCOJM PERFORMANCE

STREAMLINE
Many operators, particularly in ammonia plants, want to
minimize pressure drop. The value of pressure drop saved is
typically US$ 10,000/psi or US$ 150,000/bar per year.
Operators have reported pressure drop across the bottom of
a shift converter as high as 0.6 bar (9 psi). The
STREAMLINE low pressure drop system resulted from a
thorough study of all the pressure drop contributors in a
shift converter. This study indicated that the majority of the
pressure drop is due to the support material, outlet collector
and exit nozzle. STREAMLINE involves a specially designed
support system in place of the standard alumina support
balls, without any mechanical modifications to the vessel.
The pressure drop across the annulus in a typical Kellogg
ammonia plant shift reactor is almost 0.5 bar (7.5 psi)
(Figure 7), whereas the pressure drop across the same
vessel is 0.01 bar (0.15 psi) with STREAMLINE installed
(Figure 8).

Based on a 1,000 mtpd production rate, standard Kellogg

ammonia plant with a hydrogen recovery unit installed, the
improvement in ammonia output is 2.0% with new catalyst,
and drops to 0.4% after 8 years. The value of the additional
ammonia produced over the catalyst life is approximately
US$ 4,000,000, and the percent improvement would
double if no hydrogen recovery unit was installed.

Figure 7: Pressure drop across a standard Kellogg

shift reactor

By installing KATALCOJM catalyst and the STREAMLINE

system, a significantly lower pipe-to-pipe pressure drop can
result across the shift vessels, and has been proven in
operation in more than a dozen plants.

LTS quench system designs

For plants operating at relatively high LTS inlet temperatures,
reducing the inlet temperature closer to the dew point will
reduce the CO slip. Lowering the inlet temperature from
235C (455F) to nearer 190-200C (374-392F) should
thereby reduce the exit CO slip from approximately 0.35%
to about 0.15%.
A method of achieving temperature reduction is to install an
upstream quench. The additional steam will also favourably
influence the position of the water gas shift equilibrium.
Johnson Matthey Catalysts has designed and installed a
number of these systems in ammonia plants with significant
improvement to the low temperature shift performance.

10

Figure 8: Pressure drop across a standard Kellogg shift

reactor with STREAMLINE

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KATALCOJM catalyst selector

Johnson Matthey Catalysts manufactures a range of
catalysts for use in low temperature shift converters,
allowing you the optimal choice for loading low temperature
shift and guard reactors, where present.

KATALCOJM 83-3
This is a proven high activity low temperature shift catalyst,
which has demonstrated its ability to deliver long life,
durability to upset conditions and excellent resistance to
poisons. The self-guarding properties mean that a layer of
guard catalyst is not usually required.

KATALCOJM 83-3M

KATALCOJM 83-3MX
This smaller size catalyst offers the same relative benefits of
KATALCOJM 83-3X compared to the non-promoted catalysts,
as noted above. In particular, KATALCOJM 83-3MX has the
best poison resistance in the KATALCOJM 83-3 range. Where
poison levels are higher than normal, installation of a layer
of KATALCOJM 83-3MX on top of the main bed or in a
separate guard bed will extend catalyst life.
Johnson Matthey Catalysts will make detailed
recommendations on the optimal type and volume of
catalyst based upon your individual operating conditions
and requirements. The excellent performance of the
KATALCOJM 83-3 series often exceeds the original plant
design basis and means a lower catalyst volume is required
to achieve a target number of turnaround cycles.

This is a smaller size variant that offers superior activity and

poisons retention where a small pressure drop penalty can
be tolerated. This penalty can be partially compensated for
since a smaller catalyst inventory is usually needed for a
given expected life.

KATALCOJM 83-3X
This catalyst contains an optimized combination of alkali
metal promoters to suppress methanol formation. Methanol
levels are reduced to less than 15% of those achieved with
KATALCOJM 83-3. The promoters also boost poisons pick-up,
resulting in the highest poison capacity of any commercially
available low temperature shift catalyst.

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Catalyst characteristics
KATALCOJM 83-series

KATALCOJM 83-3
KATALCOJM 83-3X
KATALCOJM 83-3M
KATALCOJM 83-3MX
Composition
KATALCOJM 83-3 & 83-3M:
Copper oxide/zinc oxide/alumina
KATALCOJM 83-3X & 83-3MX:
As above, promoted by alkali metals

Physical properties (typical)

Catalyst

83-3

83-3M

83-3X

83-3MX

Form

pellets

pellets

pellets

pellets

Diameter (mm)
Length (mm)

5.2
3.0

3.1
3.2

5.2
3.0

3.1
3.2

Typical loaded density

(kg/m3)
(lb/ft3)

1360
85

1360
85

1360
85

1360
85

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For further information on Johnson Matthey Catalysts, contact your local sales office or visit our Web site at www.jmcatalysts.com.
KATALCO and STREAMLINE are trademarks of the Johnson Matthey Group of companies.

PO Box 1
Belasis Avenue
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UK
Tel +44 (0)1642 553601
Fax +44 (0)1642 522542

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Oakbrook Terrace, Illinois 60181
USA
Tel +1 630 268 6300
Fax +1 630 268 9797

2005 Johnson Matthey Group

www.jmcatalysts.com

930JM/0705/1/AMOG