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Low temperature shift catalysts

Katalco

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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 2

Case studies 3

KATALCOJM PERFORMANCE - adding value to your plant 6

Advantages of choosing KATALCOJM PERFORMANCE 7

KATALCOJM catalyst selector 10

Catalyst characteristics 11

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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.

IntroductionWhere pressure drop is also a concern, using the KATALCOJMPERFORMANCE 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 well-

established 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 giveslonger 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.

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).

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

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

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

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.

0

0

20 40

20

60 80

40

60

80

120

100

100

% Down bed

%

Exotherm

SOR 54 months

Figure 1: Catalyst exotherm at start of run and

at 4.5 years on-line

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Case study 3 - KATALCOJM extendscatalyst 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 threeyears. 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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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 lastedfor 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.

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, theKATALCOJM 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.

KATALCOJMPERFORMANCE adding value

to your plant

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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 therelative strength of KATALCOJM 83-3X and other

commercially available low methanol products after a

simulated condensation incident.

Operational benefits

Minimum CO slip

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 attemperatures 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.

Low, stable pressure drop

Catalyst strength in service is equally as important as fresh

pellet strength. The KATALCOJM 83-series is formulated togive 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.

Robustness to operational upsets

The stable activity and high strength of KATALCOJM 83-3and 83-3X ensure that the catalyst operates according to

our expectations; however, the catalyst must also be

resistant to operational upsets.

Advantages of choosingKATALCOJMlow temperature shift catalyst

0Fresh

2

Reduced

4

6

8

10

12

14

Meanhorizontalcrushstrength(kgf)

KATALCOJM

83-3X Competitor A Competitor B

Figure 3: Relative strengths of fresh and reduced catalysts

0.00

2.00

4.00

6.00

8.00

10.00

12.00

HCS(Kgf)

KATALCOJM

83-3X Competitor 1 Competitor 2

After reduct ion Afte r condens ing steam

Figure 4: Horizontal crush strength after reduction

and after condensing steam conditions

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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 ofalkali 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 methanolformation rates. This is used to advise on the optimal

operating conditions to minimize methanol formation.

Long life and economic performance

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 bothsulphur and chloride poisons in which the active shift

catalyst itself provides its own protection.

Many ammonia and some hydrogen plants feature LTS

guard reactors. These relatively small vessels contain a

sacrificial catalyst that retains the poisons to protect themain 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.

0

0

2 4

200

6 8 10

400

600

800

1,200

1,000

1412

Months in Operation

MethanolinCondensate(ppmw)

KATALCOJM

83-3(Expected)

KATALCOJM

83-3X(Expected)

Plant data

Figure 5: Plant performance of KATALCOJM 83-3X

0

0

5 10

20

15 20

40

60

80

100

25

Relative levels of accumulated CI

COconversion(%)

KATALCOJM

83-3X KATALCOJM

83-3

Figure 6: Effect of chloride poisoning on CO conversion

for KATALCOJM catalyst range

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Plant Location % Sulphur (w/w) % Sulphur (w/w)

Top Sample Middle Sample

USA 2.1 0.14

Europe 4.4 0.16Australia 2.9 0.09

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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% nearthe bottom. However, for KATALCOJM 83-3 the sulphur

concentrations have been significantly above this level as

indicated in the following examples:

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 mustbe 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 engineerwill provide analysis equipment, ensuring a quick and safe

start-up.

Table 1: Excellent sulphur retention of KATALCOJM 83-3

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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.

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).

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 inoperation 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.

Additional capability withKATALCOJMPERFORMANCE

Figure 7: Pressure drop across a standard Kelloggshift reactor

Figure 8: Pressure drop across a standard Kellogg shift

reactor with STREAMLINE

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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 ofcatalyst 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.

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

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.

KATALCOJM catalyst selector

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Physical properties (typical)

Composition

KATALCOJM 83-3 & 83-3M:

Copper oxide/zinc oxide/alumina

KATALCOJM 83-3X & 83-3MX:

As above, promoted by alkali metals

Catalyst 83-3 83-3M 83-3X 83-3MX

Form pellets pellets pellets pellets

Diameter (mm) 5.2 3.1 5.2 3.1Length (mm) 3.0 3.2 3.0 3.2

Typical loaded density

(kg/m3) 1360 1360 1360 1360

(lb/ft3) 85 85 85 85

Catalyst characteristicsKATALCOJM 83-series

KATALCOJM 83-3M

KATALCOJM 83-3MX

KATALCOJM 83-3

KATALCOJM 83-3X

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PO Box 1

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Tel +1 630 268 6300

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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.

www.jmcatalysts.com 2005 Johnson Matthey Group

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