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%metal
oxide
Surface
area (m2/g)
Wt. Metal
oxide per
unit surface
area
Cat. Reforming
1.0
200
0.00005
Hydrodesulphurization 16
300
0.0005
Catalytic Rich Gas
60
150
0.004
Steam Reforming
15
10
0.015
Effective contamination of 500 ppmw
ppm
impurities
per unit
surface area
2.5
1.7
3.3
50
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The feed flow to a reactor generally ensures that poisons are deposited on the
inlet catalyst and will be retained at the inlet (e.g., silica) or migrate further down
through the bed (e.g. chloride, sulfurs.) Those poisons that are volatile will be
easily removed as the temperature increases and hence we do not see
significant contamination levels on the catalyst surface near the outlet of the bed
where a reasonable temperature gradient exists from inlet to outlet. An example
of this would be in a steam reformer duty.
The distribution of the poison within the reactor and across the catalyst particles
is determined by the kinetics of the poisoning reaction and the mobility of the
poison. As poison concentrations are usually low and poisoning reactions fast,
most poisoning reactions are strongly diffusion limited with consequent poison
deposition near the outside of the catalyst pellet. Methanol synthesis catalysts
employ copper as an active component. Copper catalysts are very susceptible to
chloride attack and readily form copper chlorides, which because of their low
melting points are sufficiently mobile to migrate from the exterior to the interior of
the pellet. Chlorides can also react with some metals form volatile metal chloride
species and increase the rate of sintering of the catalyst.
The inlet section of the catalyst bed may have the highest reaction duty. Small
changes to the activity of the inlet catalyst are therefore more important than are
changes in activity to catalyst at higher temperatures and will have a major effect
on the overall process.
Poisoning, and the effects of poisoning, can be a complicated process to
understand or model due to the various reaction pathways and mechanisms
involved. The actual severity of a poisoning episode in commercial plants is
dependent upon several inter-related factors. For example, feedstock
composition, plant throughput, contaminant concentrations, duration of episode
etc..
The effects of permanent poisons cannot be mitigated against, as the poisons
cannot be adequately removed. Loss of activity may be reflected in a number of
different ways but often is indicated by increased hydrocarbon slippage,
reduction in cycle length, increased pressure drop across the catalyst, Blockages
of the porosity, removal of active metal sites and agglomeration of the active
metal by poisons often lead to an increase in the relative rate of carbon
deposition. This can lead to severe process problems and the need for
premature catalyst change-out.
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Sulfur may be the primary initiating poison; carbon and steam the secondary
major poisons.
The effects of poisons are therefore a complex interplay of many factors involving
both physical and chemical changes to a catalyst surface. The secondary effects
of poisoning often have as significant effect as the primary causes. Removal of
catalyst poisons from the feedstock to be utilized is essential and can only be
achieved by close attention to desulfurization or other processes from which
poisons emanate. In addition to increased control of the source of poisons the
adoption of high performance poison traps is an alternative avenue to explore.
The extent of poisoning, as determined by most analytical techniques, is reported
as a bulk value. The true level of poisoning, as seen by the catalyst phase is
probably several orders of magnitude higher as the poison is deposited on the
surface where the active metal concentration is lower. Analysis of a deactivated
catalyst needs to be supplemented by additional information, such as surface
analysis and element distribution across the pellet.
Permanent Poisons
-
The actual chemistry involved can be complex as the metal sulfides are not
always stoichiometric and can be polymorphic in nature. It has been reported that
that the specific interaction depends upon the oxidation state of the sulfur
impurity, i.e, how many electron pairs are available for bonding of s & p- valence
electrons with d-orbitals of the metals and whether they are shielded by other
ligands. The reported order of decreasing toxicity for sulfur poisons is:
H2S< SO2 < S03
Changes in catalyst surface chemistry are reflected in changes to the activityselectivity of the process. Sulfur is considered a temporary poison for many
catalysts, such as nickel based steam reforming catalysts. This implies that the
loss in activity-selectivity of the catalyst may be substantially recovered by
removal of the source of contamination and the adsorbed sulfur poisoning the
catalyst surface. The specific surface area and the porosity of the catalyst are
important in determining how long the catalyst will continue to perform in the
presence of sulfur. It is possible to recover most, if not all the activity-selectivity
following a minor (or short duration) sulfur-poisoning excursion. In severe cases
of sulfur poisoning the reaction mechanisms are substantially modified permitting
non-selective secondary reactions to predominate.
Severe sulfur poisoning invariably leads to carbon laydown on the catalyst
surface. To maintain the activity-selectivity balance and cycle length of the
catalytic process, and to retard unselective side reactions, it is essential that the
catalyst surface is maintained in a sulfur free clean state.
The temporary effect of sulfur poisoning is used to advantage in the start up of
high activity precious metal catalysts in Catalytic Reformers. The fresh catalyst
has a very high initial activity and start-up conditions at feed-in may lead to
thermal runaways, excessive hydrocracking and dehydrogenation reactions
resulting in carbon deposition and loss of cycle life.
Low levels of sulfur may be introduced to the catalyst during start-up to moderate
the initial high activity by adsorbing on super active sites that promote
hydrogenolysis and coking. This pre-treatment with a poison then allows the
feed-in to be controlled without excessive carbon laydown. Under normal run
conditions, with sulfur free feedstock, sulfur adsorbed on the catalyst surface
bleeds off and a stable activity is obtained.
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Chlorides
The effect of chloride poisoning is very similar to, but more rapid in action, than
the thermal ageing of the catalysts. The chloride ion is very mobile and can
migrate through the whole process gas system. It can then react with active
metal sites (such as Ni or Cu) to prevent free access to these sites and so alter
the structure of the reduced metal crystallites and so enhance the thermal
sintering process. This type of ageing is very destructive and because the
structure has been destroyed, the catalyst cannot be properly regenerated even
if the poison source is removed. The chloride ion is extremely reactive and so the
symptoms of poisoning appear very quickly. Also, chlorides attack many metal
alloy surfaces and induce stress corrosion cracking even at concentrations in the
low ppm chloride range.
The initial chloride contaminant can be present as organic or inorganic forms in
the process feedstock or by inefficient removal in the boiler feed water system
supplied from the demineralization units.
It should also be stressed that many chlorides, particularly organic chlorides,
have relatively high vapor pressures and so organic chlorides, such as solvents
for maintenance work cleaning turbines etc, must also be banned from the sites
to avoid possibilities of chloride ion ingress.
Boiler Feed water impurities
The main impurities associated with a boiler feed water system are silica,
sodium, calcium and other metal ions. Correct control of the demineralization
plant and the steam system is crucial to minimize solids carryover into the
process stream.
The primary cause of industrial catalyst deactivation is due to a physical pore
blocking or pore narrowing effect. The deposited contaminants hinder the
transport of reactants into the active interior pore structure of the catalyst.
Transport of the reactants becomes more difficult through increased diffusion
resistance caused by the plugging in the mouth of the pores.
Silica is often transported in the steam in the form of microencapsulated hydrated
silica droplets, rather than actually dissolved in the steam, and a properly
designed impingement plate or demister pad should reduce any solids carryover
to acceptable limits.
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Sodium can also be carried over and is destructive for catalyst surfaces, as it will
react with deposited silica and other catalytically active components. Deactivation
by silica is therefore a purely physical (and not a chemical) effect of particulates
on the surface blocking access to the active sites. Deactivation in this manner,
accompanied by subsequent carbon deposition, is a consequence of pore
blocking mechanisms.
Heavy Metals
The usual heavy metals that are encountered hydrocarbon streams, though
much more infrequently now are: Arsenic, lead, vanadium, mercury, nickel and
cadmium. These metals may be present in a number of forms, ranging from
metallic, inorganic or organo metallic species and all are permanent poisons for
precious metal and base metal catalysts.
Heavy metals are considered a very severe permanent poison for all catalytic
systems. The heavy metals also tend to be absorbed onto the walls of the
containment vessels from where they may be slowly re-released to further poison
future catalyst charges.
Arsenic and mercury are particularly problematic as they readily alloy with many
active metal species to form an inactive surface alloy. This effectively reduces
the available surface area for subsequent reaction. If arsenic poisoning has
occurred it is essential to thoroughly clean the reactor vessel by a combination of
chemical and mechanical methods. Washing and wire brushing the vessel before
re-charge of a fresh catalyst batch should provide a greater degree of safety
against future contamination.
Most of these heavy metals will be removed in the hydrodesulfurization reactors,
as they tend to build up on the Comox or Nimox Surface.
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Industrial experience has shown that specially tailored pore size distributions
within the HDS catalysts lead to increased metals removal and longer HDS cycle
life before the need for a catalyst change-out. As concentrations should be
limited to < 5ppb to protect catalysts.
Vanadium and nickel are known poisons encountered in FCC units. Vanadium is
initially present as organometallic species in the feedstock but this converts to a
vanadium oxide species in the regenerator. The vanadium is then able to migrate
to zeolite crystals and form a low melting eutectic with the silica alumina of the
zeolite. This leads to a permanent destruction of the zeolite crystal structure and
a significant loss in activity.
Nickel is a poison when deposited on a catalyst surface as it can act as a strong
dehydrogenation catalyst, which contributes, to carbon deposition. The effect of
nickel is well documented in FCC units where nickel also increases the unwanted
light ends gas production. Nickel does not appear to affect the intrinsic activity
but does adversely affect the selectivity of the reaction.
Water can act as a poison for some catalysts, particularly those operating under
reducing conditions. A number of mechanisms are possible for catalyst
deactivation. Hydrothermal ageing is much more rapid than thermal sintering
alone and leads to a permanent loss of activity through crystallite growth and
agglomeration. Water may dissolve some soluble components within the catalyst
system. For example, excess water has a negative impact upon catalytic
reformer catalysts by dissolving chlorides from the catalyst and reducing the acid
site density on the catalyst surface. This affects the ability of the catalyst to
perform skeletal isomerization reactions.
Organo nitrogen components can also be poisons for a variety of catalysts: such
as hydrocracking and catalytic reforming catalysts. These compounds react to
form ammonia which then neutralizes acid functions on the catalyst surface.
Generally, this effect is reversible if the source of organo nitrogen is removed and
the acidity restored. In catalytic reforming, the basic nitrogen compounds adsorb
on the acid sites and reduce isomerization and cracking activity but do not
appear to have little effect on dehydrogenation activity.
Iron oxide is a known poison for many hydrocarbon processing catalysts.
Unfortunately, iron is a known catalyst for many reactions itself and therefore can
promote dehydrogenation reaction pathways, leading to carbon deposition on the
catalyst surface.
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Also, finely divided iron oxide is quite reactive with other contaminant
components, such as Na or Si and accumulate on the catalyst surface and
eventually form new low temperature phases. These can grow and cause
masking of active sites and pore obstruction and plugging which reduce catalyst
activity.
Carbon monoxide (and other electron pair donors such as NH3, PH3, H2S, and
H2O) is a severe poison for many catalysts due to the reactivity associated
with an unshared pair of electrons. The CO molecule is readily able to coordinate
with metals to form a chemisorbed species that inhibits the surface mobility of
adsorbed species. CO may also form volatile metal carbonyls with some metals
at low temperatures. CO is sometimes used to achieve improved selectivity in
hydrogenation reactions by utilizing a partial poisoning effect with palladium
catalysts.
Poison
HCl
H2S
NH3, Organic bases
V,Ni
metals
Hg
Catalysts
Cu
Ni
Pt/ chlorided Al2O3
Zeolites
CoMo NiMo
Pd
Process
Methanol Synthesis
Steam Reforming
Cat. Reforming
FCC
HDS
Hydrogenation
Foulants
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The following notes are a broad description of the nature of carbon coke
deposits on high severity process catalysts such as Steam Reforming and
HDS catalysts. The influence of catalyst and feedstock on the formation of
carbon is described together with an overview of the wave front technique for
the removal of carbon using steam-oxygen (air) procedures.
THE NATURE OF CARBON DEPOSITS FORMED ON CATALYSTS
Carbon deposits formed on hydro processing or steam-reforming catalysts
may be grouped into three broad types:
A Fine, loose, sooty type carbons.
B Hard, pitch-like polymeric carbons.
C Hard, graphitic type carbons.
Whilst the name carbon is loosely applied to these deposits the term is
strictly incorrect as all types of carbon found on catalysts contain low levels of
chemically bonded hydrogen to the skeletal carbon structures.
The carbon deposits are often, in reality, ultra high molecular weight
hydrocarbons, which are formed via thermal-catalytic dehydrogenation (loss
of hydrogen) of the feedstock components. Dehydrogenation reactions
produce highly unsaturated double bonded hydrocarbon monomers that
readily polymerize and further dehydrogenate to produce carbon rich
deposits. Often a part of the carbon deposit can be solubilized in solvents,
indicating a hydrocarbon nature.
The above types of carbon are often formed as amorphous or filamentous
deposits on the catalyst surface. The filamentous type carbon deposits
usually indicating operations at very low steam to carbon ratios with feeds
containing high molecular weight hydrocarbons or from CO disproportionate
through the Boudouard reaction, via the reaction mechanism
2CO
C + CO2.
CARBON FORMATION
Carbon deposits form by thermal and catalytic dehydrogenation of
hydrocarbons on the catalyst surface or in the gas phase. The carbon
forming mechanism is highly complex and encompasses both thermal
cracking breakage of C-C bonds and loss of hydrogen from one fragment;
and catalytic dehydrogenation loss of hydrogen without C-C bond scission
reaction routes.
The mechanisms are favored by high temperature (550-650oC), low hydrogen
partial pressures, acidic catalysts and high molecular weight or unsaturated
feed components.
FEEDSTOCK COMPOSITION EFFECTS
The composition of the feedstock used has a significant effect on the nature
of the carbon deposit and therefore on the ease of carbon removal.
TYPE A CARBONS
Loose, sooty type A carbon deposits (whisker carbon) are generally found
when processing low molecular weight feedstocks such as a good quality
Natural Gas.
Except under exceptional circumstances pure methane will not form
dehydrogenated species, which give rise to unsaturated monomers. Methane
will not form a double bond on the single carbon atom, and hence
dehydrogenation of methane leads to the deposition of single atom pure
carbon species, which are readily removed in the steam reforming reaction
under normal process conditions.
If not removed by steam, the carbon forms loose agglomerates and is easily
removed by oxidation in air. Carbon from methane does not normally lead to
resinous-polymeric deposits. The methane decomposition reaction can be
depicted by:
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Whisker carbon
CH4
C + 2H2
TYPE B CARBONS
This type of carbon deposit, which can be broadly described as a heavy
resinous-polymeric like deposit, is the more common form of carbon found on
the majority of catalytic processes such as high severity Catalytic Reforming,
steam reforming, HDS and Cat Cracking. The deposits are formed from the
dehydrogenation of alkanes, naphthenes and aromatic feed components from
ethane upwards.
Dehydrogenation reactions on the catalyst surface give rise to unsaturated
double bond compounds, which may further polymerize to higher molecular
weight compounds.
These in turn dehydrogenate and polymerize further to the ultimate carbon
deposit, a resinous, carbon rich and hydrogen deficient coke. Cracking of
the C-C bonds of the skeleton without cracking off the Hydrogen leads to the
formation of highly reactive methane fragment species. These species are
formed rapidly without the deposition of polymeric coke.
The level of potential polymer precursors in the feed and the process
conditions dictate the rate of carbon builds up.
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dehydrogenation
H
H H
C = CCCH +
H
H H
H--CCCC--H
H H
H2
Polymerization Coke
H H
Undesired
pathway
Butane
Desired
pathway
C+C+C+C
CnH2n +n H2
CnHn + H2
Aromatics + H2
Coke
TYPE C CARBONS
The hard, graphitic, unreactive type of carbon deposit generally derives from
processing feedstocks, which contain significant levels of single and
condensed aromatic ring hydrocarbons Benzene and above.
The aromatic type molecule is hydrogen deficient, by nature of the aromatic
double bond structure, and is capable of further dehydrogenation and linking
of aromatic rings to form multi-ring, graphitic form, hydrogen deficient carbon
polymers.
The graphitic forms of condensed ring aromatics are normally associated with
high heat duty, hydrogen deficient processes. The deposits build up slowly
with time on stream and are exceedingly difficult to remove even with full air
oxidation techniques.
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Dependent on the nature of the process, the feedstock and the catalyst, the
deposited carbon will range from the sooty, easily burnt, to the graphitic,
unreactive carbon. Those processes operating with light feeds at low severity
i.e. naphtha HDS will have a significant amount of light, easily burnt off
carbon, at the end of the cycle life.
A steam reformer processing naphtha or natural gas with heavy end
components, which has suffered a low steam to carbon operation over a
prolonged period, or a unit with aromatic or heavy aliphatic feed
contaminants; will produce a significant amount of graphitic and resinous
carbon.
The naphtha hydrotreater will be able to be regenerated easily at low
temperature with low oxygen levels whereas the steam reformer will require
higher temperatures and oxygen levels to remove the carbon.
The requirements of temperature and oxygen cannot be prejudged prior to
regeneration (as normally samples of the carbon are not available) and
therefore each regeneration carried out is unique and liable to upset unless
adequately monitored and controlled.
Reactor size and catalyst volume are important considerations it is easier to
control the burning of carbon coated catalyst in a 100mm diameter steam
reformer tube than in a 2 m diameter x 4 m carbon coated HDS catalyst
loaded reactor.
CARBON BURNING IN AIR
Examination of the ignition temperatures of varying molecular weights of
carbon polymers carbons in pure air shows an almost linear graph of
temperature with carbon number. That is the light carbons burn first and
graphite last. Broadly a light carbon deposit will start to burn in air from 300oC
and the graphitic type carbon from 580oC to as high as 680oC in air.
The oxidative burning of carbon is highly exothermic, with potential
temperatures in excess of 1000oC produced at the point of carbon burn.
When a mixture of light carbon soot and graphite is heated in air to a
temperature at which the soot begins to burn, but below that temperature at
which the graphite normally burns, it is found that both soot and graphite
burn. The exotherm from soot burning is sufficient to raise the temperature to
above that required to pyrolyze the graphite and both forms of carbon are
removed by the runaway exotherm.
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Removing the potential for graphite burning is only achieved by removing the
source of oxygen. Reduction of the temperature, whilst retaining the oxygen
level will not be sufficient to stop gross carbon burning. This summarizes the
basis of the regeneration procedure commonly used in a wide variety of
catalytic hydrocarbon processing reactors employing the wave front
technique.
Regeneration of carbonized catalysts by heating the catalyst in an inert
atmosphere, up to or above the temperature at which the light carbon burns,
and then introducing an initial pulse of low level of oxygen is an established
commercial procedure. The procedure allows an oxygen and carbon burn
wave front to move, in a controlled manner, through the catalyst bed. If the
oxygen level is low enough on the first burn, the exotherm which is a
function of the rate of carbon burn will not be sufficient to substantially
increase the surface temperature and therefore uncontrolled burning does not
take place. The technique allows the carbon to be removed by burning off
layers of carbon in steadily increasing levels of oxygen.
CARBON REMOVAL BY STEAMING
Steaming is a recognized procedure for decoking catalysts. The method is
simple and does not have the potential risks associated with oxygen decoking
i.e. over burn and runaway exotherms.
Steaming however is only suitable for the light/medium type of carbon
deposits, which are readily gasified on the catalyst surface by low
temperature steam in conjunction with the catalyst nickel component. With
the heavier and graphitic types of carbon the rate of removal by steam is too
slow to make this method attractive.
The catalyst surface composition plays a more significant part in catalyzing
carbon removal by steam than it does when using the oxygen removal
procedure. Additions of alkali, such as potash, to the catalyst composition
enhance the rate of carbon removal, as does a high intrinsic metal dispersion.
In those cases where the carbon deposition is judged to be light i.e. of recent
origin and from a clean feed, steaming is an adequate and effective method
to remove carbon. In those cases where the deposits are hard old and
from a feedstock containing high molecular weight or aromatic components,
steaming will not be an adequate means of removing the carbon case.
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
Web Site: www.GBHEnterprises.com
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
Web Site: www.GBHEnterprises.com
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
Web Site: www.GBHEnterprises.com
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
Web Site: www.GBHEnterprises.com