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Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
CONTENTS
1 INTRODUCTION
2 THERMAL SINTERING
3 CATALYST POISONING
5 SUMMARY
TABLES
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
FIGURES
REFERENCES
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
It should be noted that the effects of both thermal sintering and reactant induced
poisoning reduce the catalyst activity and therefore in order to maintain
production rates, the converter operating temperatures have to be increased
which in turn increases the rate of by-product formation.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
It is widely accepted that the methanol synthesis activity under typical industrial
conditions is directly related to the copper metal area. Catalyst manufacture
requires, therefore, the preparation of phases that will give high and stable
copper surface area. This is exceptionally difficult to achieve since the very small
(50 Å to 100 Å diameter) copper crystallites which are present in freshly reduced
catalyst have a high surface to volume ratio. This means that the energetics of
the copper crystals are dominated by the high-energy atoms which are located at
the surface of the crystallites rather than those which from the bulk of crystallites.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
It is clear from Figure 1 that neither zinc oxide nor alumina has a Hϋttig or
Tammann temperature which is close to the operating temperature of a synthesis
convertor. However, the range of temperatures which are covered by the Huttig
and Tammann temperatures of copper metal are almost identical to those
experienced by an operating methanol synthesis catalyst which is typically
between 200 and 300°C dependent upon catalyst age and converter type.
Two mechanisms which have been suggested for the sintering of metal catalysts
are atomic migration and particle migration. Both of these mechanisms are
shown schematically in Figure 2. Since methanol synthesis catalysts operate at
temperatures below the Tammann temperature of copper it can be expected that
most of the sintering that occurs can be attributed to particle growth by the
atomic migration mechanism. However, at more elevated temperatures for
example in a poorly controlled reduction process, the particle migration model
would become operable.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Particle Growth
It has been shown that it is possible to describe the rate of sintering processes
which proceed by the atomic migration model by a form of rate equation which is
called the Generalized Power Rate Law equation (GPLE). The general from of
the GPLE is given below.
dS
Sintering Rate = − = k (S - S ∞ )n
dt
At any given point the sintering rate is dependent on the surface area of the
catalyst (S) to a specified power (n) and therefore the rate of sintering of the
catalyst can be expected to be faster at the start of the catalyst life when the
surface area is highest.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Data has been produced for the sintering of methanol synthesis catalysts using a
methanol sidestream unit. This unit was designed to allow exposure of reduced
catalyst samples to the plant supply, giving exposure to synthesis gas,
pressures, temperatures and space velocities identical to the plant synthesis
converter. Figure 3 shows copper surface area data at the inlet and outlet of the
sidestream unit for VULCAN VSG-M101 fitted to second order GPLE models.
From the second order GPLE model the sintering rate constants, k, can be
derived (Table 3). As expected (k) is higher at the outlet point of the sidestream
unit, which has a mean operating temperature of 280 oC. This clearly exemplifies
the influence of the Arrhenius component of the rate constant (k) within the GPLE
on the rate of loss of copper surface area.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
From the model an estimate of (S∞) the limiting value of the active surface area of
VULCAN VSG-M101 can be made of 12.7 m2/g. This is a reasonable fit to plant
data for VULCAN VSG-M101 catalyst discharged after a number of years on line
(Table 4).
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
1
240°C 250°C 260°C 270°C
0.5
0.3
0.2
100 200 300 400
Time (Days)
In summary, all highly dispersed copper containing catalysts are likely to undergo
a process of thermal sintering at the reaction temperatures which exist in
methanol synthesis converters. It is likely that the sintering process occurs by an
atomic migration mechanism.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
For example, silica (which would lower the synthesis activity and promote by-
product formation) and chloride (which causes very high rates of copper
crystallite sintering) are both potent poisons for copper catalysts but are rarely
transported onto the synthesis catalyst in any significant quantities in well
operated methanol plants. However iron, nickel and sulfur are often found in
significant quantities on discharged synthesis catalysts and the characteristic
behavior of these poisons will therefore be discussed in some detail.
Sulfur is a powerful poison for copper catalysts. Electron rich sulfur containing
compounds have a strong affinity for the surface of copper crystallites. The zinc
oxide component of the methanol synthesis catalysts plays a critical role in
resisting sulfur poisoning because the thermodynamics that are associated with
the formation of zinc sulfide are more favorable than those of copper sulfide
formation. A schematic representation of the mechanism of sulfur adsorption on
a copper/zinc/alumina is shown below.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
The final formation of bulk zinc sulfide is the rate determining part of the process
and the transfer of sulfur from the copper to the zinc will continue until all of the
zinc oxide is covered with sulfur. At this point the rate of sulfur pick up on the
catalyst will decrease and ‘slip’ of sulfur will continue through the catalyst bed.
An effective catalyst requires an intimate mixture of Cu and ZnO and a high free
ZnO surface area. Figure 6 shows the correlation between the sulfur capacity of
a catalyst and total surface area. A high surface area is achieved through careful
control of the manufacturing process.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
1.4
% methanol at 334 hrs
1.2
0.8
0.6
0.4
0 5000 10000 15000
ppm Ni + Fe
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
5000
4000
3000
2000
1000
As can be seen in Figure 9 the sulfur and iron contaminants are located with high
specificity on the edge of the particles. The nickel contamination, however,
penetrates to a much higher degree throughout the particles. This suggests that
nickel may indeed be a more potent poison for methanol synthesis catalysts than
iron, as suggested by other workers1.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
CO2 Interactions:
CO2 Hydrogenation:
Oxygen Removal:
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
It is also possible that the combination of reactions [1] and [2], which add oxygen
to the catalyst surface, and reactions [4] and [5], which facilitate the removal of
oxygen, could enhance the rate of sintering of the catalyst. This may occur
because the interaction of oxygen with copper has been found to cause
‘reconstruction’ of the copper crystallite surface. This is a change to the physical
structure of the copper surface, which can create mobility among the copper
atoms and, in consequence, may promote catalyst sintering.
The effect of CO2 on the rate of copper catalyst deactivation has been found to
vary between different types of synthesis catalyst. This probably reflects the
disparate preparation routes of the catalysts and the different amounts of
oxidation, and surface reconstruction, which the copper surfaces within each
catalyst, will experience.
For example, the data in Figure 10 reveal the effect of CO2 partial pressure on
the relative activity of two synthesis catalysts after these catalysts (VULCAN
VSG-M101 and a competitive material) had been treated at a total pressure of 80
bar and a reaction temperature of 285 oC for a time of 147 hours in a laboratory
reactor. After subjecting the catalysts to this deactivation treatment with a
reaction gas which contained CO2 at a total pressure of 3 bar, the relative activity
of the deactivated catalysts was fond to be identical to that of the freshly reduced
materials. However, when the catalysts were subjected to a reaction gas
containing CO2 at a pressure of 12 bar the competitive catalyst deactivated at a
considerably faster rate than VULCAN VSG-M101. These data indicate that
catalyst formulation and catalyst manufacturing procedures can play a significant
role in generating synthesis catalysts which are resistant to the permanent
deactivation which can be induced by CO2.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
5 SUMMARY
There appear to be three main processes which can be expected to influence the
rate of deactivation of methanol synthesis catalysts
The first of these processes, sintering of the copper component of the catalyst is
common to all catalysts in all converters. The rate of the sintering process is
principally controlled by reaction temperature. Low reaction temperatures have
been shown to reduce the rate at which a catalyst will move towards a low, and
limiting, copper surface area. Catalysts with high surface areas will show large
activity benefits towards the start of life but a prolonged; though slightly reduced
activity benefit will also be observed throughout the life of the catalyst.
Catalyst poisoning can also occur in some synthesis converters. The most
common catalyst poisons are sulfur, iron and nickel. The impact of sulfur on the
activity can be reduced if the catalyst is formulated in such as way that the zinc
oxide component is allowed to act as a ‘sink’ for the sulfur poison.
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
References
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries