U.S. patent number 3,844,936 [Application Number 05/347,250] was granted by the patent office on 1974-10-29 for desulfurization process.
This patent grant is currently assigned to Haldor Topsoe A/S. Invention is credited to Esmond John Newson.
United States Patent |
3,844,936 |
Newson |
October 29, 1974 |
DESULFURIZATION PROCESS
Abstract
In a process for hydrodesulphurization and hydrocracking of
hydrocarbon oils, especially residual oils and oil fractions, with
hydrogen in a fixed catalyst bed at elevated pressure and
temperature, pressure drop is decreased and catalyst life improved
by placing the catalyst in an annular catalyst bed and passing the
reactants as a gaseous phase containing the hydrogen and a liquid
phase containing the hydrocarbon oil through the catalyst bed,
wherein a predominant phase of said two phases is introduced into
the catalyst bed through the passage means in its outer cylindrical
wall and the other phase through passage means in one of the end
wall of the catalyst bed, and products are collected via the inner
cylindrical wall of the catalyst bed.
Inventors: |
Newson; Esmond John (Birkerod,
DK) |
Assignee: |
Haldor Topsoe A/S (Soborg,
DK)
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Family
ID: |
27259445 |
Appl.
No.: |
05/347,250 |
Filed: |
April 2, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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166139 |
Jul 26, 1971 |
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Foreign Application Priority Data
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Aug 4, 1970 [GB] |
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37659/70 |
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Current U.S.
Class: |
208/108; 208/146;
208/213; 422/218 |
Current CPC
Class: |
B01J
8/0214 (20130101); C10G 49/002 (20130101) |
Current International
Class: |
B01J
8/02 (20060101); C10G 49/00 (20060101); C10g
013/02 (); C10g 023/02 () |
Field of
Search: |
;208/89,108,112,208,209,216,213,146 ;23/288G,288R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Hellwege; James W.
Attorney, Agent or Firm: Rosen; Lawrence Berry; E. Janet
Parent Case Text
This application is a continuation-in-part of Ser. No. 166,139
filed on July 26, 1971 now abandoned.
Claims
1. A process for the hydrodesulphurization and hydrocracking of
heavy hydrocarbon oils including crude oils and residual petroleum
fractions at elevated temperature and pressure in a fixed catalyst
bed, comprising the steps of
a. continuously passing at elevated temperature and pressure a
gaseous phase containing hydrogen through the fixed catalyst
bed,
b. simultaneously therewith passing at elevated pressure and
temperature a liquid phase containing the heavy hydrocarbon oil
through the fixed catalyst bed, said catalyst bed being placed in
an annular space between upper and lower end walls and
substantially vertically and coaxially disposed, substantially
cylindrical walls, at least said cylindrical walls having passage
means for fluids, the axial height of said annular space being at
least twice its width as measured radially between the two
cylindrical walls, wherein a predominant phase of said two phases
is introduced into the catalyst bed through the passage means in
its outer cylindrical wall and the other phase through passage
means in one of the end walls of the catalyst bed,
c. recovering the product hydrocarbon oil via the passage means in
the inner cylindrical wall of the catalyst bed, and
d. removing gases formed in the process and unreacted feed gases
via passage means in any wall of the catalyst bed other than the
bottom end
2. The process of claim 1, wherein the liquid
hydrocarbon-containing phase is introduced into the catalyst bed
through the passage means in its outer cylindrical wall, and the
gaseous hydrogen-containing phase through passage means situated at
selected positions in its lower end wall and the
3. The process of claim 2, wherein the gas to liquid ratio is in
the range
4. The process of claim 1, wherein the liquid
hydrocarbon-containing phase is introduced into the catalyst bed
through passage means situated at selected positions in its top end
wall and the upper part of its outer cylindrical wall, and the
gaseous hydrogen-containing phase through the
5. The process of claim 4, wherein the gas to liquid ratio is in
the range 10:1 to 150:1.
Description
The present invention relates to a process for reducing the sulphur
content of heavy hydrocarbon oils such as residuum oils and crude
oils by contacting a two-phase mixture of liquid hydrocarbon oils
and gaseous hydrogen with a catalyst arranged in a fixed bed
reactor at elevated temperature and pressure. In addition,
hydrocracking of the oils to produce fractions boiling lower than
the feedstock is achieved.
Depending on their origin, heavy petroleum oils contain sulphur
compounds of different types. Thiols, sulphides, and disulphides
predominate in the lower boiling fractions while thiophenic
compounds predominate in the higher boiling fractions. In cracked
petroleum oils and residual oils the sulphur compounds are in the
condensed cyclic form, for instance benzothiophenes. In general,
the resistance of sulphur compounds to the hydrodesulfurization
process increases in the following order: thiophene, 2-ring
thiophene, and thiophene compounds with 4 or more rings.
Other undesirable compounds found in heavy petroleum oils which are
reduced in the hydrodesulfurization and hydrocracking process are
nitrogen and oxygen compounds, commonly heteroatomic compounds.
In addition, the presence of metallic contaminants in the petroleum
oils is of significant importance in the hydrodesulfurization
process. The most common metals are nickel and vanadium, but also
iron, copper, sodium, calcium and zinc are often present. The
metals may occur as chlorides, oxides or sulphides. However, they
are more often in the form of metallo-organic complexes such as
porphyrins and their derivatives. These complexes are associated
with asphalthenes which are non-distillable and therefore
concentrate in residual oil fractions. During the
hydrodesulfurization process the metal compounds are liberated from
the organic compounds and most often deposited in the catalyst
pores and on the outside of the catalyst particles. At the same
time the high molecular weight asphalthenes coagulate and
polymerize and thereby finally lead to the formation of coke
deposits inside or outside the catalyst particles.
Because the sulphur and nitrogen present in petroleum fuel oils
will eventually appear in the flue gases as oxides, they seriously
contribute to the problems of air pollution. Therefore, processes
for reducing the nitrogen and particularly the sulphur content in
residuum oils and crude oils have become of increasing commercial
importance. Among these processes, the hydrodesulphurization
process is one in which the more resistant sulphur compounds can be
removed and thereby converted to easily reclaimed sulphur
compounds.
In the prior art processes of hydrodesulphurization and
hydrocracking the hydrocarbon oils are reacted with hydrogen in the
presence of a catalyst. In order to avoid rapid catalyst
deactivation by the heavier hydrocarbons, a considerable excess of
hydrogen has to be used. While the consumption of hydrogen is
generally of the order of 35-350 normal liter per liter oil (Nl/l
oil), the feed ratio of hydrogen to hydrocarbon oil has to be of
the order of at least 150-6,000 Nl/l oil, preferably between 500
and 2,000 Nl/l oil. This is achieved by recycling the unreacted
hydrogen from the product stream and adding fresh hydrogen before
reintroducing it into the reactor.
The pressure at which hydrodesulphurization and hydrocracking
processes are operated depends on the nature and origin of the
hydrocarbon oils. While low-boiling fractions such as gas oils can
be satisfactorily hydrotreated at a pressure in the range from 25
to 70 atms. abs., heavier fractions such as whole crude oils and
residuum oils require a pressure up to 600 atms. abs., preferably
50 to 200 atms. abs. Also the temperature depends to some degree on
the hydrocarbon oils, normally it is within the range 260.degree.
to 485.degree.C, preferably 315.degree. to 430.degree.C for whole
crudes and residuum oils.
By proper choice of catalyst and process conditions, the degree of
hydrodesulphurization relative to the degree of hydrocracking can
be varied.
In conventional hydrodesulphurization and hydrocracking processes,
the catalyst is arranged in a fixed bed reactor through which the
reactants flow axially downwards. Usually, the operating conditions
are such that only the lighter hydrocarbons of the oil are
vaporized, while the major part of the hydrocarbon oil is present
as a liquid. Therefore, there is a mixed flow of two phases through
the catalyst bed, a gaseous phase consisting of hydrogen and the
lighter part of the hydrocarbons and a liquid phase containing the
remaining heavier hydrocarbons. The liquid phase is thus dispersed
on the surface of and inside the catalyst particles while it flows
downwards under the influence of gravity. The gaseous phase passes
through the interstitial voids between the wetted catalyst
particles. Such a flow arrangement is known as a trickle flow. One
disadvantage of this system is that the two phases have to pass a
long way through the bed which results in a high pressure drop
across the catalyst bed.
In the catalyst bed, demetallation reactions leading to liberation
of metals from the metallo-organic compounds predominate at the top
of the catalyst bed where the fresh hydrocarbon oil is introduced.
Initially, the desulphurization and denitrification reactions take
place throughout the entire catalyst bed. However, the top of the
catalyst bed gradually becomes catalytically inactive for these
reactions as it is being fouled by deposits. These deposits,
consisting mainly of metal compounds and carbonaceous materials,
accumulate in the interstitial voids, the volume of which is
thereby reduced. Therefore, the free passage of the reactants and
products is gradually hindered and eventually the increased
pressure drop makes further operation of the process impossible.
This is an additional disadvantage of the prior art processes,
since the catalyst bed has to be subjected to a periodic cleaning
or regeneration, and in some cases the catalyst has to be replaced
either completely or partly.
In addition to the interstitial deposition of solids there is also
a deposition, particularly of metals and metal compounds in the
pores, inside the catalyst particles and close to their outer
surface. This deposition which eventually renders the interior part
of the catalyst particles inaccessible to the reactants cannot be
avoided, but attempts at reducing the harmful effect have often
been made by decreasing the catalyst particle size. However, for
economic and technical reasons the particle size used in
conventional fixed bed reactors with axial flow is limited to at
least 1 mm.
An object of the present invention is to provide a process for
catalytic hydrodesulphurization and hydrocracking of hydrocarbon
oils in which both the pressure drop and the rate of increase of
the pressure drop with time on stream are lower than in the
conventional fixed bed processes with axial flow.
Another object of the present invention is to provide a process in
which catalyst stability and life are improved compared with a
conventional process.
According to the present invention there is provided a process for
the hydrodesulfurization and hydrocracking of heavy hydrocarbon
oils including crude oils and heavy residual petroleum fractions at
elevated temperature and pressure in a fixed catalyst bed, in which
two phases, one a gaseous phase containing hydrogen and the other a
liquid phase containing the heavy hydrocarbon oil, are passed
continuously through an annular fixed catalyst bed enclosed between
substantially vertical cylindrical coaxial walls with passage means
for liquid and/or gases and top and bottom walls with or without
passage means for liquids and/or gases, the axial height of said
annular bed being at least twice its width, at least one of said
two phases being introduced through said passage means in the outer
cylindrical wall of the said catalyst bed and substantially all of
the products being withdrawn from the catalyst bed through said
passage means in the inner cylindrical wall of the catalyst
bed.
The width of the catalyst bed is defined as the radial distance
between the inner and the outer cylindrical wall of the catalyst
bed. The catalyst bed is preferably circular-cylindrical, but the
cross-section of the walls may deviate from the
circular-cylindrical form and, for instance, may be elliptical. In
that case the width of the catalyst bed is defined as the distance
between the walls, measured perpendicularly to the tangents of the
cross-section. The catalyst bed will be enclosed in a pressure and
temperature resistant reactor vessel. The outer cylindrical wall of
the catalyst bed and its end walls may be in a spaced relationship
to the cylindrical outer wall and the end walls, respectively, of
the reactor vessel; or the reactor vessel walls may constitute the
outer cylindrical wall and/or the top end wall and/or the bottom
end wall of the catalyst bed. The said walls may be flat but are
preferably arched.
When introduced into the reactor, the hydrocarbon oil will normally
be preheated.
The catalyst bed used in the process of the present invention has
an annular form which ideally is limited by two coaxial circular
cylindrical surfaces and two parallel planes at right angles to the
cylinder axis. Normally, the total height of the catalyst bed will
be several times its outer diameter. Characteristic features of the
invention are: (1) the reactants are a two-phase mixture of a
gaseous hydrogen phase and a liquid hydrocarbon oil phase, (2) at
least one of the two phases is introduced into the catalyst through
the outside cylindrical surface of the annular catalyst bed, and
(3) the products are collected through the central opening
extending through the catalyst bed. In this way, the distance that
the reactants have to pass through the catalyst bed has been
greatly reduced, while still the time of contact between the
reactants and the catalyst is high.
In the ideal case, a phase that is introduced through the outside
cylindrical surface would pass strictly radially through the
catalyst bed, whether it be a gaseous phase or a liquid phase. In
practice, there will be deviations from this ideal situation since
there is in general a tendency for a liquid phase to obtain an
axial gradient of downward movement under the influence of gravity
in addition to the radial gradient of inwards movement. Similarly,
there is for the gaseous phase, which is present together with the
liquid phase, a tendency to obtain an axial gradient of upwards
movement in addition to the radial gradient of inwards movement.
Which of the gradients of movements will predominate in an actual
situation for each of the two phases will among other factors
depend on the actual ratio of volumetric flow rates of gaseous
phase to liquid phase.
An approximate value of the actual ratio of volumetric flow rates
of gaseous phase to liquid phase can be calculated from the feed
rates of hydrogen and hydrocarbon oil. For example, 540 Normal
liters of hydrogen per liter of hydrocarbon oil at 100 atms. and
350.degree.C will correspond to 12 volumes of gaseous hydrogen per
one volume of liquid hydrocarbon oil. However, this is only the
approximate ratio of gaseous phase to liquid phase flow rate, since
part of the hydrogen will dissolve in the liquid phase particularly
at high pressures. On the other hand, lighter hydrocarbons of the
hydrocarbon oil may evaporate and thus add a little to the gaseous
phase volume. It is possible in each particular case to correct the
calculated approximate ratio of gaseous phase to liquid phase
accordingly and thus obtain the actual ratio flowing through the
catalyst bed. The ratios which are mentioned in the following are
assumed to be actual values corrected for dissolved gases, and they
will be referred to as gas to liquid ratio.
In the process of the present invention the gas to liquid ratio may
vary within wide limits. In order to illustrate qualitatively how
the flow pattern in the catalyst bed will depend on this ratio, two
extreme cases will be considered.
In one extreme case, it is assumed that the gas to liquid ratio is
low, for example from about 0.05:1 to about 2:1. In this case,
there will be a continuous liquid phase in the catalyst bed with
relatively few gas bubbles. The liquid phase introduced through the
outside cylindrical surface and evenly distributed over this
surface will flow practically in the radial direction inwards
through the annular catalyst bed. Regardless how the gas phase is
introduced, the relatively few gas bubbles will flow practically
axially upwards through the bed under the influence of gravity.
In another extreme case in which it is assumed that the gas to
liquid ratio is relatively high, for example from about 30:1 to
about 150:1, there will be a continuous gaseous phase in the
catalyst bed. When introduced evenly distributed over and through
the outside cylindrical surface of the annular catalyst bed this
gaseous phase will flow practically in the radial direction inwards
through the catalyst bed. Regardless how the liquid phase is
introduced, the radial movement of the gaseous phase will tend to
"blow" the relatively few liquid droplets in the radial direction.
However, the influence of gravity will be strong enough to cause an
additional axial and downward gradient of movement of the liquid
phase in this case.
Those skilled in the art will understand that the flow pattern
schematically described hereinabove will change gradually from one
extreme to the other, when the gas to liquid ratio is changed from
the lower extreme value to the higher extreme value. It will
similarly be understood that in the extreme cases radial flow will
predominate for one of the phases. In this specification it will be
understood that the liquid phase is the predominant one when the
gas to liquid phase is below about 2:1, while the gaseous phase is
the predominant one when the gas to liquid ratio is higher than
about 30:1. However, this higher limit cannot be very well defined,
since it will change with the precise flow arrangements and it may
be possible to make such arrangements that the gaseous phase is the
predominant one, even if the gas to liquid ratio is as low as
10:1.
The flow restrictions in the catalyst bed will always be more
serious for the predominant phase. However, this phase will always
pass radially through the annular bed and thus have to move through
the shorter distance. Therefore, the main objective of the present
invention, a reduction of the total pressure drop, has been
achieved.
However, the more the actual situation in the catalyst bed
resembles one of the extreme cases referred to above, the less
satisfactory and intimate is the mixing of the two phases in the
case when both phases are introduced evenly distributed over the
outside cylindrical surface of the catalyst bed. This is because of
the tendency to separation of the two phases that is a result of
the additional axial gradient of movement of one of them, namely
the one that is far from being the predominant one. However, it is
within the scope of the present invention to compensate for this
tendency by altering the rates at which the two phases are
introduced into the catalyst bed at various positions.
Thus, when the gas to liquid ratio is low and consequently the gas
bubbles move almost entirely upwards through the catalyst bed,
there will be a relatively higher concentration of gas phase in the
upper part of the catalyst bed unless a greater part of the gas
phase is introduced closer to the bottom of the catalyst bed.
Therefore, in this case the rate of hydrogen introduction through
the outside cylindrical surface should be increased with increasing
distance from the top of the bed, e.g., by having the gas inlets
near the bottom situated closer to each other in the outer
cylindrical wall compared to those at the top of the said wall. It
may even be desirable to introduce all the hydrogen at a position
close to the bottom or through the bottom.
Similarly, when the gas to liquid ratio is high and, consequently,
the liquid phase tends to move axially downwards, there will be a
scarcity of liquid phase in the upper part of the catalyst bed,
particularly at some distance from the outside surface. It is
possible to compensate for this scarcity by introducing all or part
of the liquid phase through the top of the catalyst bed.
In both cases one of the phases, namely the one that is not the
predominant one, will have to move over a longer distance through
the catalyst bed, namely almost entirely in the axial direction.
However, this does not significantly increase the total pressure
drop, since the major contribution to pressure drop relates to the
other phase, namely to the predominant phase. Therefore, both kinds
of variations are within the scope of the present invention.
The preferred operating pressure for the process is in the range
50-200 atms. abs., and the preferred temperature is in the range
315.degree.-430.degree.C.
The catalyst used in the process of the invention may be of any
conventional type used commercially in hydrodesulphurization and
hydrocracking of hydrocarbon oils. Such catalyst generally contain
oxides of nickel, cobalt, molybdenum, and/or tungsten, normally
carried on a support material. The support material is a highly
porous oxidic material such as alumina. Other types of support
materials belong to the group of zeolites. Still other types of
support materials can be used. The catalyst is used in the form of
discrete particles of regular or irregular shape. Several factors
have to be taken into account in the selection of particle size and
shape, such as the allowable pressure drop, the desired degree of
desulphurization and the type of hydrocarbon oil.
The catalyst particle size is in the range 0.1-10 mm, preferably
0.2-1 mm. The particle shape may be a conventional shape such as a
cylinder or a sphere. However, catalyst shapes having a much higher
surface to volume ratio are preferred. Such catalyst shapes are
irregularly shaped particles, for example crushed or flake-shaped
catalysts.
The catalyst is arranged in an annular bed which may be contained
in a basket having inside and outside cylindrical surfaces. At
least one of the two phases, the gaseous hydrogen or the liquid
hydrocarbon oil phase, is introduced into the catalyst bed through
the outside cylindrical surface. This introduction may take place
through a system of nozzles or orifices which are designed to
disperse one or both phases in the desired manner through the
catalyst bed. Alternatively, the outside cylindrical surface of the
catalyst basket may be a perforated plate or a metal screen which
is surrounded by a greater diameter vessel so that there is an
annular space between the reactor vessel and the catalyst basket.
This latter alternative is particularly suitable when the gas to
liquid ratio is low, i.e., when the liquid phase is the predominant
one, since the liquid phase will then fill the annular space around
the perforated basket and successively flow through the catalyst
bed in a radial direction. In this case the gaseous hydrogen phase
may be introduced through pipes connected to or extending into the
catalyst basket.
It may be desirable to vary the gas or liquid inlet rate
continuously from bottom to top of the catalyst bed. Thus, when the
gaseous phase is the predominant one it may be advantageous to
place the nozzles, orifices or inlet apertures according to their
individual capacities (which may vary, since they may have varying
effective passage area) more or less densely in such a manner that
the gas passage capacity per unit area of the outer cylindrical
catalyst bed wall increases gradually or stepwise from the upper to
the lower end of said cylindrical wall; in that case the inlet
orifices, nozzles or apertures for the liquid are preferably all
situated at the top end wall of the bed.
Conversely, when the liquid phase is the predominant one, the
nozzles, orifices or inlet apertures for the liquid may be
positioned more or less densely in accordance with their individual
passage capacity in such a manner that the liquid passage capacity
per unit area of the outer catalyst bed wall decreases gradually or
stepwise from the upper to the lower end of said cylindrical wall;
in that case the inlet orifices, nozzles or apertures for admitting
the gas phase are preferably all positioned either in the bottom
end wall of the bed or quite near thereto.
The main advantage of the process of the present invention compared
to hitherto used processes for hydrodesulphurization and
hydrocracking of hydrocarbon oils is related to the predominantly
radial flow of at least one of the two phases. The total pressure
drop over the catalyst bed is primarily associated with the flow of
the predominant phase which is introduced at the higher volume
rate. Since this phase is flowing predominantly radially, a
considerable reduction of the overall pressure drop has been
achieved by the present invention. In contrast to this flow
pattern, both phases in conventional hydrodesulphurization
processes flow axially through the catalyst bed and thus have a
much longer distance to pass through.
In hydrodesulphurization processes, the rate of feeding the
hydrocarbon oil to the catalyst bed is usually defined by the
liquid hourly space velocity (LHSV), which is the volume of liquid
hydrocarbon oil per volume of reactor per hour. For the process of
the present invention, the LHSV will be similar to the LHSV for a
conventional hydrodesulphurization process. Consequently, the LHSV
will be in the range 0.1 to 10, preferably 0.3 to 3.0. The term
"reactor volume" used in this specification is understood to be the
volume actually occupied by the catalyst bed.
The rate of hydrogen introduction is defined by the hydrogen to
hydrocarbon oil ratio. This ratio is usually expressed as the
normal volume of hydrogen (i.e., gaseous volume at 0.degree.C and
at atmospheric pressure) per liquid volume of hydrocarbon oil. In a
conventional hydrodesulphurization process, the hydrogen to oil
ratio is normally of the order from 150 to 5,000 normal liter
H.sub.2 per liter oil (Nl/l oil). In the process of the present
invention it may be within the same range. The actual consumption
of hydrogen depends particularly on the type of hydrocarbon oil,
but typically it may be from 30 to 300 Nl/l oil. However, a certain
excess of hydrogen is required to eliminate carbon deposition on
the catalyst. Part of the hydrogen will become dissolved in the
hydrocarbon oil. The solubility which is much dependent on
operating pressure and temperature, will typically be of the order
8.0 to 34 Nl/l oil. Under the preferred process conditions, excess
of hydrogen required to suppress carbon deposition is higher than
the amount that can be dissolved in the hydrocarbon oil and there
will always have to be a gaseous phase present in any part of the
catalyst bed.
Thus, of the total amount of hydrogen introduced into the catalyst
bed together with the hydrocarbon oil, a part will become dissolved
in the oil, another part will be consumed by the
hydrodesulphurization and hydrocracking reactions, while a third
part remaining as a free gaseous phase will serve to prevent carbon
deposition. The amount of hydrogen required for each of the three
purposes will vary considerably, particularly with the operating
temperature and pressure and with the type and required degree of
conversion of hydrocarbon oil. However, as exemplified previously
in the present specification, it is possible to make an approximate
evaluation of the actual volume of the gaseous phase present in the
catalyst bed. This will be further illustrated in the examples
given later on in the specification (particularly in Example
2).
One further advantage of the radial flow process of the present
invention is that much smaller catalyst particles can be used
compared with the conventional axial flow process, while still
keeping the pressure drop low. In the conventional process, the
size of catalyst particles is limited to at least 1mm. In the
radial flow process the particle size can be as low as 0.2mm or
even less and still the pressure drop will be low compared with the
conventional process. In the smaller catalyst particles a greater
portion of a particle is accessible to the reactants, whereby a
higher catalytic activity is achieved. Furthermore, when small
particles are used, the deposition of metal sulphides and coke in
the pores close to the outer surface of the catalyst particles will
take place in a much larger portion of the total catalyst volume.
The harmful effect of deactivation is thereby much delayed, and
hence also an improved catalyst life is achieved in the present
invention.
A major problem arises in conventional axial flow reactors during
hydrogen processing of residual and crude oils owing to the
deposition of iron, nickel and vanadium sulphides also in the
interstitial void space between the catalyst particles together
with deposition of coke. The iron, nickel and vanadium are
contained in organometallic constituents of the oil. The
consequence of the interstitial deposition is that the pressure
drop across the axial flow reactor soon rises beyond tolerable
commercial limits. It is a further advantage of the radial flow
process of the present invention, particularly in the embodiment in
which the hydrocarbon oil is introduced through the cylindrical
surface of the catalyst basket, that the deposition of solids in
the interstitial voids becomes less harmful, because they are being
spread over a large area. Therefore, the rate of pressure drop
buildup in the hydrodesulphurization process of the present
invention is low compared to the corresponding rate of pressure
build-up in the conventional hydrodesulphurization process. In
consequence, the useful life time of the catalyst will be
increased.
In order that the invention should be better understood, it will
now be described in further detail in the following Examples 1 and
2 and with reference to the attached drawings.
In the drawings,
FIG. 1 shows an axial section of a first embodiment of a reactor to
be used in the process of the invention, and
FIG. 2 an axial section of a second embodiment of a reactor to be
used in the process of the invention.
The figures will be explained in detail in the respective
examples.
EXAMPLE 1
This example illustrates on the basis of design data that the
useful life of a desulphurization catalyst is the longer, the
smaller the particle size of the catalyst. The example will
furthermore illustrate that the pressure drop for a given particle
size is very much smaller in the radial flow process of the
invention than in the conventional axial flow process.
Consequently, it is possible to reduce the catalyst particle size
in the process of the invention, thus achieving an increased
catalyst life. The design data given in Table I (first columm)
relate to a hydrodesulphurization process with radial flow in
accordance with the invention, while design data for a conventional
axial flow process are given (for comparison) in the same Table
(second column). Under these conditions a Kuwait Long Residue oil
containing 4 wt% sulphur is desulphurized to 2 wt% sulphur, while
the original content of metals in the oil, 0.0065 wt% Fe + Ni + V,
is reduced to about the half.
In the conventional axial flow process, both the liquid phase and
the gaseous phase flow axially downwards through the catalyst bed.
In the radial flow process of the invention conducted under the
conditions described in Table I, both phases are introduced through
the outer cylindrical wall and pass more or less completely
radially through the annular bed from where they are collected
through the inner cylindrical wall.
Two cases are considered for each of the two process of Table I,
both carried out with spherical catalyst particles. In one case,
case A, the catalyst particle size is 1.7 mm, while in the other
case, case B, the catalyst particle size is 0.5 mm. Table II gives
for both cases the initial pressure drop and the metal loadings
which is the amount of metals (Fe + Ni + V) finally deposited on
the catalyst. The pressure drop was calculated by well known
methods and found to be in accordance with experimentally
determined values. Values for the metals loading are known from the
conventional desulphurization process, and it is assumed that the
same values will be obtained in the process of the invention for a
given catalyst particle size. The catalyst utilization, which is
the amount of oil that can be processed per unit volume of
catalyst, can be derived from the figures for metals loading and
for amount of metals removed from the oil.
Table I ______________________________________ Design Data
______________________________________ Radial Axial Flow Flow
Process Process ______________________________________ Oil feed
rate m.sup.3 /day 4,100 4,100 Hydrogen feed rate Nl/l oil 825 825
Pressure atm. abs. 100 100 Temperature .degree.C 370 370 Gas to
liquid ratio m 20:1 20:1 Height of catalyst bed m 20 20 Outer
diameter of m 3.40 3.30 catalyst bed Inner diameter of m 0.85 0.00
catalyst bed Volume of catalyst bed m.sup.3 170 170
______________________________________
Table II ______________________________________ Radial Flow Axial
Flow Process Process ______________________________________ Case A:
Catalyst particle size mm 1.7 1.7 Initial pressure drop atm. 1.1
.times. 10.sup.-.sup.3 0.5 Metals loading, 0.23 0.23 g Fe+Ni+V/ml
cat. Catalyst utilization, 7.7 7.7 m.sup.3 oil/l cat. Case B:
Catalyst particle size mm 0.5 0.5 Initial pressure drop atm. 1.1
.times. 10.sup.-.sup.2 1.7 Metals loading, 0.78 0.78 g Fe+Ni+V/ml
cat. Catalyst utilization, 26.0 26.0 m.sup.3 oil/l cat.
______________________________________
As can be seen from Table II, the pressure drop for a given
catalyst particle size is very much smaller in a radial flow
process than in an axial flow process. It is furthermore seen from
the table that the metals loading increases with decreasing
particle size. This is because the metals deposit inside the
catalyst particles close to the outside surface of each particle.
Consequently, the smaller particles can accept more metal per unit
volume of catalyst bed than can the larger particles. The catalyst
utilization or catalyst life is correspondingly improved from 7.7
m.sup.3 oil per liter catalyst of 1.7 particle size to 26.0 m.sup.3
oil per liter catalyst of 0.5 mm particle size. In other words,
more than three times as much oil can be processed on the smaller
catalyst particles than on the larger ones before they have
obtained the maximum amount of metals. However, the use of the
smaller catalyst particles size is only possible in the radial flow
process, because otherwise the pressure drop will be too high. In
case B (0.5 mm catalyst particle size), the critical pressure drop
was found to be 1.7 atms., which is commercially unacceptable,
because it will soon exceed the maximum allowable value as a result
of interstitial deposition of metals and coke.
FIG. 1 illustrates the design of a reactor for conducting the
radial flow process for which design data are given in Table I. The
gas to liquid feed ratio is about 20:1. Since some hydrogen is
consumed by the reaction, the ratio will be a little lower at the
outlet than at the inlet. However, throughout the bed, the ratio is
between the described two extreme ranges, from 0.05:1 to 2:1 and
from 30:1 to 150:1, for which reason it is proposed in the present
specification that only one of the two phases should pass radially
through the annular catalyst bed. Therefore, both the liquid oil
phase and the gaseous hydrogen phase can be introduced through
atomizing nozzles distributed on the outside cylindrical surface of
the bed.
An annular space 11, is substantially filled with a bed of
cobalt-molybdenum oxide catalyst (not shown) on an alumina support
having a particle size of 0.5 mm (case B, Table II). The space
having a height of 20 meters and an outer diameter of 3.40 meters,
is contained in a circular-cylindrical pressure vessel 12 with a
removable cover 13. A central tube 14 extending axially through
space 11 has a diameter of 0.85 meter. It rests loosely on the
bottom of the pressure vessel 12 and is kept in its central
position by an annular bottom wall 15 and an annular top wall 16.
The bottom wall rests on a ring 17 secured to the inside of the
pressure vessel and on a ring 18 secured to the outer surface of
the central tube 14. A sufficient gas tightness at these places is
ensured by appropriate sealings. The slightly conical top wall 16
is kept between flanges of the vessel 12 and the cover 13.
The liquid hydrocarbon oil and hydrogen are both introduced into
the catalyst bed through atomizing nozzles 19 distributed on and
extending through the cylindrical surface of vessle 12. In order to
simplify the drawing, only a few of these nozzles have been shown.
The central tube 14 is provided with apertures 20 through which the
liquid and gaseous products leave the catalyst bed. Only a few of
these apertures are shown in the drawing. Since part of the gaseous
hydrogen phase may move to the top of the catalyst bed, there is a
clearance 21 between the top wall 16 and the central tube 14 so
that the gas can escape this way. The slightly conical form of the
top wall ensures that there will be no permanent accumulation of
gas in the top of the catalyst bed.
The liquid oil phase and the gaseous hydrogen phase will be
separated in the central tube 14 where the liquid phase will move
toward the bottom and leave pressure vessel 12 through a tube 22.
Similarly, the gaseous phase will move upwards and leave the
pressure vessel through a tube 23 on the cover 13.
In order to compensate for the tendency of the gaseous phase to
move upwards and of the liquid phase to move downwards in the
catalyst bed, the gas to liquid ratio of the feed introduced
through the nozzles is adjusted accordingly, so that the ratio is
somewhat increased near the bottom and decreased somewhat near the
top of the catalyst bed, the average gas to liquid ratio still
being 20:1.
EXAMPLE 2
A Kuwait Long Residue oil containing 4 wt% sulphur is desulphurized
to 1 wt% sulphur at a temperature of 350.degree.C and under a
pressure of 150 atms. abs.. At these conditions, the solubility of
hydrogen in the hydrocarbon oil is 17 Nl/loil, while the
consumption of hydrogen for the hydrodesulphurization and
hydrocracking reactions is abt. 85 Nl/l oil. The total amount of
the hydrogen introduced together with the hydrocarbon oil is 153
Nl/l oil. Consequently, there is available as free gaseous hydrogen
in the feeds 136 Nl/l oil and in the products 51 Nl/l oil. Since 1
Normal liter of gas at 350.degree.C and 150 atms. abs. will be
reduced to 0.015 liters, the gas to liquid ratios as previously
defined will be 2:1 and 0.8:1, respectively.
FIG. 2 illustrates how the desulphurization process can be carried
out under these conditions in accordance with the present
invention. Since the gas to liquid ratio is low (between about 2:1
and 0.8:1), the liquid phase is introduced through the outside
cylindrical surface of the catalyst bed and passes radially through
the bed, while the hydrogen mainly is introduced near the bottom of
the catalyst bed. Some hydrogen may also be introduced in the form
of hydrogen dissolved in the liquid hydrocarbon oil.
An annular space 31 for a catalyst bed (not shown) has a height of
20 meters, an outer diameter od 3.40 meters and an inner diameter
of 0.85 meter, which gives a catalyst bed volume of 170 m.sup.3.
This catalyst bed space is contained in a pressure vessel 32 having
a removable cover 33. The vessel is provided with pipes and
auxiliaries for introducing the reactants and collecting the
products. It is furthermore provided with the necessary means for
controlling the operating conditions such as temperature, pressure
and flow rates. These additional means and auxiliaries are not
shown in the drawing.
The catalyst bed space 31 is kept between outer and inner
cylindrical walls. The outer cylindrical wall 34 is a perforated
plate. Its diameter is smaller than the diameter of the pressure
vessel 32, so that it is surrounded by an annular space 46 having a
width of a few cms. The inner cylindrical wall 35 is a perforated
tube. Furthermore, the catalyst bed is supported by a bottom wall
36 resting on a ring 37 secured to the side of the pressure vessel
32. There is an appropriate sealing material between the bottom
wall 36 and the ring 37. The bottom wall 36 is furthermore secured
gas-tight to and thus carried by the inner cylindrical tube 35
resting loosely on the bottom of the pressure vessel 32. Finally,
the catalyst bed has a removable cover 39.
The gaseous hydrogen phase is introduced through perforated pipes
40 extending into the bottom of the catalyst bed through the vessel
and through the cylindrical wall of the catalyst bed. The liquid
hydrocarbon oil is heated and introduced into the annular space 46
surrounding the catalyst bed through one or more tubes 41. The oil
may in advance have been completely or partly saturated with
dissolved hydrogen. From the annular space 46, the liquid oil
enters the catalyst bed 31 through apertures 42, of which only a
few are shown in the drawing, passes radially through the bed in
space 31, and is collected in central tube 35. This tube or inner
cylindrical wall is provided with apertures 43 distributed so that
an almost equal distribution of the oil flowing through the
catalyst bed is achieved. Only a few of these apertures are shown
in the drawing.
In the central tube 35, the two phases separate. The liquid oil
phase moves downwards and leaves the pressure vessel through tube
45, while the gaseous hydrogen phase leaves the vessel through tube
44.
The arrangement of the pipes 40 for hydrogen introduction may not
always be practical, since they require pressure-resistant packing
47 through the vessel 32 and have to pass through holes 48 into the
catalyst bed 31. In an alternative arrangement, the gaseous
hydrogen phase may be introduced into the empty space 38 under
bottom wall 36, from where it enters the catalyst bed through
apertures (not shown) in the bottom wall 36. In this arrangement,
the central tube 35 rests on a gas-tight packing on the bottom of
the pressure vessel 32.
* * * * *