Impact of a low

methanol low
temperature shift
catalyst at Petrokemija

Authors:

NENAD ZECEVIC, R. KAMENSKI, Petrokemija Plc, Kutina, Croatia

JOHN ROBERT BRIGHTLING, H. AGARWAL, Johnson Matthey Plc,

Billingham, UK

This article was first published at Nitrogen and Syngas Conference, 5-8
March 2013, Berlin, Germany

This paper will look at how the operators of an ammonia plant selected
their LTS catalysts and the criteria that they used when comparing
catalysts, including legislation and operational constraints. This case study
will present the design conditions and will compare its actual performance
with previous charges in respect of both methanol formation and the
water gas shift reaction.

INTRODUCTION

One of the most expensive catalysts in ammonia production is the low

temperature shift catalyst (LTS catalyst). If proper care is not taken, the
:
 life time of this catalyst can be significantly shorter in comparison with
the other catalysts which will cause, in turn, very high operational
costs. The performance of the LTS catalyst can trigger di!erent
operational problems and lead to poor economics and even shutdown
of the plant. Besides achieving good LTS catalyst activity, a very
important factor in performance of the same is good selectivity. Plant
operators have to look at reactions other than the water gas shift that
can occur across the LTS catalyst. From an operational, economic,
legislation as well as environmental stand point of view the most
important reaction which must be avoided is the methanol synthesis
reaction. Due to this, the operators must choose the best LTS catalyst
on the market to be on the safe side regarding the operational,
economic, legislation and environmental requirements associated with
this methanol make. In the case of proper LTS catalyst choice, the
operator mitigates many plant and environmental problems by
reducing the amount of methanol produced in the LTS converter.

PETROKEMIJA LTS CATALYST SELECTION CRITERIA

In the shift conversion step, carbon monoxide reacts with steam to

form equivalent amounts of hydrogen and carbon dioxide. Since the
shift conversion reaction is reversible one in which reaction rate is
favoured by high temperatures and the equilibrium by low
temperatures, two stages are provided each utilizing a di!erent type of
catalyst, as illustrated in Figure 1. Initially, the process gas from the
secondary reformer which contains from 12.0% to 15.0% of CO (dry
gas basis) is passed through a bed of iron oxide/chromium oxide
catalyst at 350°C to 380°C and then over a copper oxide/zinc oxide
catalyst at approximately 200°C to 220°C both of them at alumina
carrier. The final residual CO content of the gas is 0.2% to 0.4%. If the
reaction is near equilibrium, a decrease in temperature will likely
improve conversion, however if it is not near equilibrium a
:
 temperature decrease will reduce the shifting reaction. Conversely, if
the reaction is near equilibrium, an increase in temperature will result
in a loss of conversion. The temperature conditions selected for the
shift converter are based on a higher temperature for the high
temperature section to take advantage of the higher reaction rate for
the high CO content of the inlet gas and comparatively lower
temperature for the low temperature section to take advantage of a
favourable equilibrium conditions for the lower CO concentrations in
this section of the converter. To achieve the best performance in
activity and life time of the both shift catalyst di!erent manufacturers
vary the concentrations of the iron, chromium, copper, zinc and
alumina. To enhance catalyst properties, producers include di!erent
additives, usually alkali metals to suppress methanol synthesis
reaction.

Fig. 1: Two stage process for water gas shift conversion

Copper is the active component in the LTS catalyst for the water gas
shift and methanol synthesis reaction, since the both reactions can
take place simultaneously across the LTS catalyst, according to the
:
 following reactions:

In ammonia production plants excessive formation of methanol can

lead to:
1. loss of ammonia production due to H₂ and CO consumption,
2. contamination of CO₂ that can cause problems for downstream
users,
3. contamination of process condensate with ammonia, amine and
methanol.

From the above mentioned reactions it is easy to calculate that for

each tonne of methanol made across the LTS converter due to poor
selectivity; approximately 1.1 tonnes of ammonia is lost. For safety
reasons the produced CO2 must be free of the methanol and if the
proper LTS catalyst is not chosen there is a danger of CO2
contamination, which must be solved with alternative methanol
removal systems. Depending of the operating and capital costs, this
can be some kind of scrubber or catalytic oxidation reactor.

During the catalyst reactions in the reforming catalyst sections and

HTS catalyst section it is also produced trace levels of ammonia. This
ammonia can react with the methanol across the LTS catalyst to
produce amines, mainly methylamine. A higher methanol
concentration therefore results in a higher amine concentration in the
LTS catalyst e"uent. Very high concentration of ammonia, amine and
methanol at the inlet of the process condensate stripping unit may
cause very high contamination of the stripped process condensate
and, when using stripping system with low pressure steam, eventually
:
 can be vented to the atmosphere. In the case of very high
contamination of the process condensate, the contaminants can have
a negative influence in further process streams during the subsequent
treatment of the process condensate with ion exchange resins and
also have a negative influence on environmental pollution of air. In
many parts of the world there are also new environmental rules which
regulate the amount of VOC content emitted from ammonia plants. In
the case of Petrokemija the national legislation requirements from the
Regulation of Limit Emission Levels of the Pollutants in the Air from the
Stationary Sources do not recognized methanol as a specific pollutant.
Instead it is classified in a general manner according to the article 22,
similar to overall carbon content in organic matter, which has a limit of
50mgm-3 or a mass flow of 500g per hour. The limit for methanol in
the process condensate is 50mgl-1as a result of its impact on the
functional groups of the ion exchange resins that are used for the
treatment of the process condensate from the stripper column.

Due to the above mentioned operational, economic, legislation and

environmental constraints Petrokemija must consider to choose the
best LTS catalyst on the market, which will ensure as high as possible
activity and in the same time as much as possible low selectivity
against methanol synthesis reaction.

DISADVANTAGES OF THE CURRENT PROCESS CONDENSATE

STRIPPING SYSTEM AND POSSIBILITIES FOR IMPROVEMENTS IN
METHANOL REDUCTION

Figure 2 shows the current system for the LTS converter and the
related equipment for the LTS catalyst reduction, with the process
condensatestream to the process condensate stripping system and
subsequent CO2 stream to downstream users. The main process
stream treated in the process condensate stripping system is the CO
:
 shift converter e"uent condensate. Treatment of condensate is
carried out by steam stripping in a packed tower which operates at
close to atmospheric pressure. The combined process condensate
stream at 116°C enters the top of the stripper and flows down through
two packed sections where, on contact with steam, the bulk of the
ammonia, carbon dioxide, methanol and dissolved gases are stripped
out. According to the design basis, condensate feed is expected to
have up to 1000 ppm of NH3, 3000 ppm of CO2 and from 200 to 2000
ppm of CH3OH depending of activity and selectivity of the LTS catalyst
in the ammonia unit. The high activity of the LTS catalyst results in the
production of relatively large amounts of CH3OH in the process
condensate and at times levels of up to 2000 ppm can be expected.
The residual CH3OH content of the treated process condensate is
expected to vary depending upon the amount in the stripper feed. On
average this is expected to be in the order of 100ppm. The overhead
vapours from the stripper column, containing mainly steam, NH3, CO2
and CH3OH are vented to atmosphere. Stripped process condensate is
pumped from the bottom of the column to the process condensate
treatment facility that uses ion exchange resins.
:
 FROMTHEHTS
CONVERTER
HYDROGEN
STEAM

SYNGAS BFW CONDENBATE

CO:TO
DOWNSTREAM
USERS
CONDENSATE

BENFIELDSYSTEM CW CW
FORCO.REMOVAL

NITROGEN

10€
CONDENSATE

STRIPPEDPROCESSCONDENSATETO
WATERTREATMENTUNIT
(IONEXCHANGERESIN)

Fig. 2: LTS process loop with related equipment for LTS catalyst
reduction and process condensate stripping system

In attempt to determine how to handle methanol made across LTS

catalysts, ammonia plant operators recognize that methanol formation
not only leads to environmental pollution, but can also a!ect the
operability and profitability of the plant. Because of these factors
ammonia plant operators can consider a number of solutions to
prevention of methanol contamination of the environment and
process systems. These solutions concentrate on either the
destruction of the methanol formed or the control of by-product
formation:

1. high pressure process condensate stripper – destruction of

methanol in the primary reformer,
2. condensation of the stripper overheads followed by a pump to inject
it into primary reformer,
3. lowering the LTS converter inlet temperature,
:
 4. increasing the steam to gas ratio to the LTS converter,
5. lower the plant operating pressure,
6. adjusting the temperature in the condensate separator,
7. reducing the catalyst volume which decreases contact time,
8. simply waiting for the catalyst to lose methanol activity,
9. install the best LTS catalyst on the market which can achive best
activity and selectivity against formation of the methanol with the
longest possible life time.

The first two proposed methods are e!ective at removing methanol

from the process condensate, but they nothing to solve the problem of
amine production and CO2 contamination which directly a!ects end
consumers. They also have relatively high investment costs.

Formation of methanol across the LTS convertor is controlled by

kinetics rather than equilibrium. Reduction in the operating
temperature will therefore lead to a decrease in methanol production.
The operator must therefore keep the inlet temperature to the LTS
converter as low as possible, taking into account minimum
temperature limitations due to the dew point of the process gas
stream. The minimum operating inlet temperature should be at least
20°C above the process gas stream, which in practice is usually
between 193°C and 202°C. The temperature margin between the
operating temperature and dew point should be carefully controlled to
prevent condensation on the catalyst which can be detrimental to its
performance. Lower operating temperatures also impact on the
activity if the catalyst. Increasing the steam to gas ratio at the inlet of
the LTS converter can reduce the methanol make depending on the
life and operating temperature of the LTS catalyst. Increasing the mass
flow rate of steam to the primary reformer reduces methanol make by
reducing the CO partial pressure and average operating temperature
of the LTS converter. However, increased steam to gas ratio can lead
:
 to higher plant fuel requirements and increased front end pressure
drop. A higher operating pressure will also increase the amount of
methanol make across an LTS catalyst. However, the operating
pressure is usually fixed and cannot be changed to a!ect methanol
make.

Decreasing the contact time between the process gas and the LTS
catalyst (increasing the space velocity) will also decrease the amount of
methanol make. In plants with only one LTS converter a reduction in
catalyst volume will also lead to reduction in catalyst life.

Changes to the operating temperature and pressure of the process

condensate separator can a!ect the amount of methanol in the
process condensate and CO2 exit from the stripper column as
illustrated in Figure 3. If the temperature in the condensate separator
is above 120°C, 50 to 75% of the methanol can go overhead with the
vapour going to the CO2 absorber column, while in the case of the
lower temperature the main content of the methanol will stay in the
condensate. However, the overall content of the methanol will stay the
same.

Methanol formation is always highest at the start of run and decays

quickly with time.
:
 Fig. 3: Dependence of the methanol vapour/liquid concentrations
with the temperature

Ammonia plants that include a low process condensate stripping

system as part of the initial designdo not have many options for
adjusting process conditions, because most plants have been designed
to operate at a fixed pressure and steam to gas ratio to minimize
energy consumption and maximize production. Changes such as those
outlined above can adversely a!ect both energy consumption and
plant rate. The best solution in such cases is using the best low
methanol variant LTS catalyst on the market which will reduce the
methanol make and in the same time to achieve the minimum CO
slippage with longest life time.

THERMODYNAMICS AND EQUILIBRIUM

Thermodynamically, low operating temperatures are favoured for any

exothermic reaction. The reaction rate, however, decreases as the
:
 operating temperature decreases. Beyond a threshold temperature,
the water gas shift and methanol synthesis reactions will cease to
occur. Figure 4 shows the relative activity of LTS catalyst at di!erent
temperatures. Therefore, a judicial choice between the kinetic viability
and thermodynamic limitations are necessary to balance the catalyst
performance with reactor operating conditions.

Fig. 4: Relative activity versus temperature dependence for the

water gas shift reaction

The temperature dependence of the equilibrium constant Kp for the

water gas shift reaction can be defined with the two following
equations:

Where Z = (1000/T)-1 with T being the absolute temperature (in Kelvin).

The variation of the heat of reaction may be calculated with the

following formula:
:
 To keep the temperature low the heat of reaction must be removed in
an appropriate way, and to achieve a su#cient reaction rate e!ective
catalyst have to be applied.The introduction of the copper-zinc based
low temperature shift catalyst in 1963made it possible to take
advantage of the lower equilibrium CO concentrations at temperature
around 200°C, shown for various steam to gas ratios in figure 5. Low
CO concentrations even at very low steam to gas ratios are attainable
with a su#ciently active LTS catalyst.

Fig. 5: Equilibrium CO concentrations in LTS catalyst in the case of

average process gas stream at the inlet of LTS converter during
the production of ammonia

One significant di!erence between the methanol synthesis and water

gas shift reactions is the impact of the partial pressure of water, which
:
 acts as an oxidant agent. The oxidation potential in a shift reactor is
higher than in methanol reactor. The nature of a catalyst surface
reflects its exposed feed composition. According to literature,
depending upon the reaction conditions, the morphology of Cu
particles may change their shape reversibly. This indicates that catalyst
surfaces change dynamically according to the reaction atmosphere.
Taking into account all dynamic features, it is possible to design a
Cu/Zn/Al catalyst suitable for the water gas shift reaction with
minimum activity toward the methanol synthesis reaction. Alkali
metals have been shown to impact the relative rates of water gas shift,
methanol synthesis and higher alcohol synthesis reactions; their
impact is in general ion specific in the following order:

Cs > Rb > K > Na ≈ Li

In LTS catalyst manufacture, if the Cu/ZnO catalyst is correctly doped

with Cs it has a strong e!ect on the relative water gas shift and
methanol synthesis reaction rates. The optimum concentration of Cs
to minimise the relative methanol synthesis reaction rate is a function
of where it is deposited on the Cu crystal face.

Experimental and industrial data show that shift selectivity increases

with time on-stream. This is due to crystalline changes in the structure
of the catalystunlike the water gas shift reaction, where catalyst activity
depends on the structure of the copper crystals present on the
catalyst surface, methanol formation depends only on the total copper
surface area of the catalyst. The copper surface area in LTS catalysts
sinters rapidly at the start of life as a consequence of the operating
temperature and the presence of steam. Since methanol formation in
an LTS reactor is kinetically limited, such changes in copper area have
a direct impact on the levels of methanol formed over the catalyst. As
a result, methanol by-product formation, which is highest at the start
:
 of catalyst life, falls rapidly within the first 6 months of operation as the
copper surface area of the catalyst falls by sintering. Therefore, if the
methanol formation rate can be controlled at start-of-run conditions, it
will remain in control throughout the life of the catalyst. As stated
earlier, this can be done by changing operating process conditions for
the catalyst or changing the whole catalyst.

CASE STUDY – OPERATION WITH LTS CATALYSTS KATALCOJM 83-3X

IN PETROKEMIJA AMMONIA PLANT AND ACHIEVED SAVINGS

Due to the constraints previously mentioned in this paper, Petrokemija

decide not to invest in very costly equipment or changes in plant
operating conditions. Instead the plant chose a lower cost alternative
by installing a more selective LTS catalyst.

From the operation, legislation, environmental and economic stand

point of view Petrokemija wanted to achieve following benefits from
the LTS catalyst:

1. minimum CO slip,
2. low and stable pressure drop,
3. robustness to operational upsets,
4. minimum by-products ( methanol and amine),
5. long life and economic performance,
6. good self guarding for sulphur and chloride poisons,
7. fast procedure of reduction and start-up.

In satisfying all these requirements Petrokemija recognized that the

KATALCOJM 83-3X series of LTS catalysts from Johnson Matthey was
best solution. From 1998 until 2004, the LTS ran with a combined
loading of KATALCOJM 83-3 (70%) and CCE C18-HCS (30%). In February
2005 this was replaced by a full charge KATALCOJM 83-3X which
:
 operated with very satisfactory results until it was changed out during
a planned shutdown in December 2011 (nearly 7 years later). Due to
the performance of the previous charge, KATALCOJM 83-3X was
installed again during the last overhaul and successfully reduced in
February 2012. Again, its performance to date has met expectations.

KATALCOJM 83-3 catalyst is a high activity low temperature shift

catalyst with long life, durability to upset conditions and has excellent
resistance to the poisons as it is aself-guardcatalyst (no specialty guard
layer required). KATALCOJM 83-3 catalyst is a mixture of CuO and ZnO
on alumina carrier in the shape of pellet 5.2 x 3.0 mm and with a bulk
density of 1380 kgm-3. KATALCOJM 83-3X catalyst contains an
additional optimized combination of alkali metal promoters to
suppress the methanol formation. Methanol levels are reduced to less
than 15% of those achieved with KATALCOJM 83-3 catalyst. The
promoters also boost poisons pick-up, resulting in the highest poison
capacity of any commercially available low temperature shift catalyst.
The catalyst is made in the form of pellets with dimension of each
pellet as 5.2 x 3.0 mm and with a bulk density of 1360 kgm-3.

In the Petrokemija ammonia plant, the shift conversion step consists

of two vertical single bed reactors and the necessary exchangers to
remove heat from the process gas as it passes from the high
temperature converter to the low temperature converter. Flow of the
process gas is downward through the catalyst bed. After the high
temperatures shift converter, partially shifted gas must be cooled
before entering the second stage. A portion of the heat is used to
produce high pressure steam in the heat exchanger, with the
remainder utilized to heat the methanator feed. A trim cooler enables
the low temperature shift inlet temperature to be further controlled.
The shift converter e"uent is cooled prior to entering the CO2
removal system. The cooling scheme consists of quenching the shift
:
 e"uent to the dew point by injection of recycled process condensate
and utilization of the available heat to regenerate the Benfield solution
used for CO2 removal and to preheat the boiler feed water. The water
condensed from the process gas at this point provides the quench
water for the shift e"uent with the net condensate going to the
condensate stripper. This is illustrated in Figure 2.

The low temperature shift converter contains one bed of catalyst with
a volume of 108.8 m3. As the catalyst is self-guarding, the whole of the
bed provides shift activity throughout the life of the charge, with the
top portion of the bed retaining trace amounts of sulphur and chloride
poisons that pass through the high temperature shift converter.

During operation KATALCOJM 83-3/CCE C18-HCS and KATALCOJM 83-

3X catalyst were monitored via three main factors:

1. CO slip
2. pressure drop through the bed of catalyst
3. concentration of the methanol in the condensate at the inlet to the
column of  the stripper condensate

The process conditions for all three charges of LTS catalyst wereas
follows:

1. process gas flow at the inlet of LTS converter = 195000 Nm-3h-1 to

200000 Nm3h-1
2. steam to gas ratio at the inlet of primary reformer = 3.5
3. pressure at the inlet of LTS converter = 28.0barₐbs to 29.0barₐbs
4. inlet temperature to the LTS converter = 200°C to 202°C

Figure 6 shows the CO concentration in the outlet process stream of

the LTS converter. In all three cases, the start of run CO slip is very low
:
 and meets equilibrium. The CO slip remained below 0.2% throughout
the life of both of the first two charges, as predicted by Johnson
Matthey. The same performance is expected for the most recent
charge.

Fig. 6: CO concentrations exit the LTS converter for three charges

of LTS catalysts, 1998 to 2012

Figure 7 shows pressure drop during the life time of the catalyst. In the
case of ordinary catalyst KATALCOJM 83-3/ CCE C18-HCSthere was an
increase inpressure drop which had a negative influence on the energy
demand at the front end of the plant.

However, with a full charge of KATALCOJM 83-3X,the pressure drop

:
 stayed approximately the same during the whole life time. This
guaranteed very high potentially in energy savings, particularly in the
operation of the air and natural gas compressors.

Fig. 7: Pressure drop through the catalyst bed for three charges of
the LTS catalysts, 1998 to 2012

Figure 8 shows the methanol concentration profile through the life

time of all three charges. In all three cases the expected higher
methanol content at the beginning of the run is seen clearly. The
decrease in activity for methanol formation during the early part of the
catalyst life is clearly seen in the decrease in methanol formed over
time. It is also very obvious that the concentration of the methanol
from KATALCOJM 83-3X which uses an alkali promoter to suppress the
methanol synthesis reaction is less than 15% of the methanol made
with ordinary LTS catalyst. This data proves the main advantage of the
KATALCOJM 83-3X catalyst.
:
 Fig. 8: Methanol concentrations in process condensate at the inlet
of stripper process column for three charges of LTS catalysts, 1998
to 2012

The last installed charge of LTS catalyst KATALCOJM 83-3X has been in
operation since February 2012. The performance of the charge has
been continuously monitored via the concentration of the methanol in
the raw CO2 from the top of the stripper column in the Benfield
system by one of the end users of the CO2 (Figure 9). The medium for
the washing the synthesis gas in the absorption column is a hot
solution of potassium carbonate with the mass concentration of 29.0
to 30.0% and activator LRS 10 with a mass concentration around 3.0%.
The purity of CO2 is always higher than 99.0%. The temperature of the
process gas at the outlet of the vessel for the process condensate
separation is below 120°C. The concentration of methanol in the raw
CO2 is between 40 ppm and 80 ppm, which is 20 to 25% of the overall
methanol concentration from the outlet of the LTS converter. The
:
 archived result is consistent with literature data, which says that when
operating in a temperature regime below 120°C, 50 to 70% of the
overall methanol content remains in the process condensate.

Fig. 9: Methanol concentrations in the raw CO2 at the outlet of

stripper CO2 column in the Benfield system for KATALCOJM 83-3X,
February 2012 to December 2012

FINANCIAL SAVINGS ACHIEVED

From the methanol synthesis reactions (2& 3) it is clear that every

molecule of methanol consumes 2 molecules of H2 and 1 molecule of
CO. This means that each 1.0 tonne of methanol equates a loss of
about 187 kg of H2 and 1.1 tonnes of ammonia.

The value of pressure drop is also very significant and from the
industrial experience it can be concluded that lowering the pressure
:
 drop for 1 bar saves around €120.000 per year. In the case of
Petrokemija with yearly production of 450.000 tonnes of liquid
anhydrous ammonia and steam to gas ratio of 3.5 at the inlet of
primary reformer, the savings resulting from the installation of the
charge of KATALCOJM 83-3X equate to approximately €450.000. This
estimate is based on savings due to less methanol production
improving ammonia production, and does not include the impact of
the lower pressure drop in the front end of the plant or the lower
methanol content in the synthesis loop that acts as an inert gas.

CONCLUSIONS

One of the main problems during the water gas shift reaction step in
ammonia production is the simultaneously reaction to make
methanol. The impact of the methanol synthesis reaction during the
ammonia production is variable and the main constraints are the
impact on operability, profitability, legislation and environmental
pollution in water and air. Due to this, ammonia operators must take
certain measures to satisfy all relevant requirements. One of the best
measures is to install the right LTS catalyst which will insure the
maximum operability and reliability of the plant, energy savings,
meeting the legislation requirements and prevention of the all
environmental issues.

In solving of all imposed constraints, Petrokemija recognized the

benefit of using the improved LTS catalyst, KATALCOJM 83-3X from
Johnson Matthey. In the KATALCOJM 83-3X catalyst, Petrokemija
recognized the outstanding catalyst life time and low methanol by-
product formation, in conjunction with very good poisons resistance
and activity. These features enable the maximum period of using the
catalyst which fits the plants turnaround cycles, maximizes hydrogen
production and address environmental concerns.
:
 Parallel to using the improved LTS catalyst Petrokemija are developing
a new project to installa medium pressure stripper column for process
condensate to achieve even better energy savings and minimum
environmental pollution according to the legislation demands.

ABBREVIATIONS

HTS – High Temperature Shift

LTS – Low Temperature Shift

N – Normal conditions at 101325 Pa and 273.15 K

VOC – Volatile Organic Carbon

References

EFMA (2000). “Production of Ammonia”, Best Available Techniques for

Pollution Prevention and Control in the European Fertilizer Industry

Yara, Brunsbüttel Comments on D2 (2004). “TWG’s comments on the

second draft BREF”, personal communication.

European Commission (1997). “Pilot Document for Ammonia

Production”.

Regulation of Limit Emission Levels of Pollutants in the Air from the

Stationary Sources, NN 124/2012.

Jim Richardson, Jayanta Bandyopadhyay and Yeping Cai, LTS catalyst

Design: Maximizing Shift Converter Performance, Ammonia Technical
Manual, AIChE 2002.
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 J.D. Grunwaldt, A.M. Molenbroek, N.Y.Topsoe, H.Topsoe and
B.S.Clausen, J.Catalyst, 194, 452 (2000).

J.G. Nunan, C.E. Bogdan, K. Klier, K.J. Smith, C.W.Young and

R.G.Herman, J.Catalyst, 113, 410 (1988).

Nakamura, M.Campbell and C.T.Campbell, J.Chem., Soc.Faraday Trans.,

86, 2725 (1990)

M.V. Twigg, Catalyst Handbook, Wolfe Publishing Ltd. (1989).

Max Appl, Ammonia – Principles and industrial Practice, Wiley-VCH,

(1999).

Anderson, P.V. Broadhurst, D. Cairns, F.E. Lynch and C.Park, The

science of catalysis Part 3: Water gas shift and methanation, Nitrogen
and Syngas, 312, July – August 2011.

Pach, Causes and consequences of by-product formation in ammonia

plants, Ammonia Technical Manual, AIChE 2009.

P.V. Broadhurst, I. Johnston, C. Park, Development of a Kinetic Model

for Methanol Formation over Low Temperature Shift Catalysts,
Nitrogen Conference, 2006.

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