U.S. patent number RE39,073 [Application Number 10/953,621] was granted by the patent office on 2006-04-18 for slurry bubble column (c-2391).
This patent grant is currently assigned to ExxonMobil Research and Engineering Company. Invention is credited to Eric Herbolzheimer, Enrique Iglesia.
United States Patent |
RE39,073 |
Herbolzheimer , et
al. |
April 18, 2006 |
Slurry bubble column (C-2391)
Abstract
The present invention is a method for optimally operating a
three phase slurry bubble column. The constituents of the three
phases, gas, liquid, and solids, are determined by the chemical
reaction in the column. The method includes injecting the gas phase
into the column with an appropriate velocity so that the solid
phase is fluidized while still maintaining "plug flow" over the
column length.
Inventors: |
Herbolzheimer; Eric
(Bedminster, NJ), Iglesia; Enrique (Moraga, CA) |
Assignee: |
ExxonMobil Research and Engineering
Company (Annandale, NJ)
|
Family
ID: |
24007560 |
Appl.
No.: |
10/953,621 |
Filed: |
September 29, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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07929084 |
Aug 12, 1992 |
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07732244 |
Jul 18, 1991 |
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07504746 |
Apr 4, 1990 |
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Reissue of: |
08063969 |
May 20, 1993 |
05348982 |
Sep 20, 1994 |
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Current U.S.
Class: |
518/700;
518/705 |
Current CPC
Class: |
C10G
2/342 (20130101); B01J 8/22 (20130101); Y02P
20/582 (20151101); B01J 2208/00725 (20130101) |
Current International
Class: |
C07C
27/00 (20060101) |
Field of
Search: |
;518/700,705,715 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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914374 |
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Jul 1954 |
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DE |
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977498 |
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Nov 1966 |
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DE |
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0313375 |
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Apr 1989 |
|
EP |
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0450861 |
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Oct 1991 |
|
EP |
|
450859 |
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Jul 1995 |
|
EP |
|
0450861 |
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Jul 1995 |
|
EP |
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709645 |
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Jun 1954 |
|
GB |
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2104405 |
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Mar 1983 |
|
GB |
|
WO 99/03574 |
|
Jan 1999 |
|
WO |
|
85/5317 |
|
Jul 1985 |
|
ZA |
|
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|
Primary Examiner: Parsa; J.
Attorney, Agent or Firm: Bakun; Estelle C.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. Ser. No. 929,084, filed
Aug. 12, 1992, now abandoned, which is a continuation of U.S. Ser.
No. 732,244, filed Jul. 18, 1991, now abandoned, which is a
continuation of U.S. Ser. No. 504,746, filed Apr. 4, 1990, now
abandoned.
Claims
What is claimed is:
1. A method for optimally operating a large diameter three phase
(gas, liquid, solid) slurry bubble column having a diameter greater
than 15 cm for Fischer-Tropsch synthesis over a supported cobalt
catalyst in which solid particles are fluidized in the liquid phase
by bubbles of the gas phase, comprising: (a) injecting the gas
phase into said column at an average gas velocity along said
column, U.sub.g>2 cm/sec, such that the flow regime is in the
substantial absence of slug flow; (b) fluidizing the solid
supported cobalt catalyst particles of average diameter,
d.sub.p>5 .mu.m, to the height, H>3m, of the expanded liquid
in the column by operating with a catalyst settling velocity,
U.sub.s, and dispersion coefficient, D, such that
.times..ltoreq..times. .times.>.times. .times. ##EQU00015##
.times..times..rho..rho..mu..times..function..times.
.times.>.times. .times..times. .times. ##EQU00015.2## and (c)
maintaining plug flow in said column by operating with a gas phase
velocity, U.sub.g, expanded liquid height, H, and dispersion
coefficient, D, such that U.sub.g.gtoreq.0.2D/H, where H>3 m,
U.sub.g>2 cm/sec wherein .rho..sub.s=effective density of the
particles .rho..sub.l=density of the liquid .mu.=viscosity of the
liquid f(C.sub.p)=hindered settling function
.Iadd.C.sub.p.Iaddend.=volume fraction of solids in the slurry
(liquid plus solids) U.sub.L=liquid velocity along the column
H=height of the expanded liquid in said reactor g=gravitational
constant d.sub.p=diameter of particles m=meters.
2. The process of claim 1 wherein said supported catalysts
comprises additional promoters selected from the group consisting
of Group I, Group II, Group V, and Group VII metals.
3. The method of claim 1 wherein the stochiometric consumption
ratio (H.sub.2/CO) is between (1.8-2.2)H.sub.2:CO.
4. The method of claim 3 wherein said support contains TiO.sub.2,
SiO.sub.2, Al.sub.2O.sub.3, HiO.sub.2 or mixtures thereof.
5. The method of claim 4 wherein said catalyst further contains
promotors selected from Group I, II, V and VII and combinations
thereof of the periodic table.
6. The method of claim 5 wherein said catalyst comprises Co, and a
TiO.sub.2 support.
7. The method of claim 1 wherein said liquid phase is the
indigenous product generated in the CO hydrogenation reaction.
8. The method of claim 1 wherein said liquid is hydrocarbon
synthesis wax, said solid is a supported cobalt suitable for the
synthesis of such wax at typical Fischer-Tropsch conditions, and
U.sub.s=1.1.times.10.sup.-4 d.
9. The method of claim 1 wherein said gas velocity,
U.sub.g.gtoreq.1 D/H.
10. The method of claim 9 wherein said gas velocity,
U.sub.g.gtoreq.10 D/H.
11. The method of claim 1 wherein said catalyst particles have a
diameter greater than 30 microns.
12. The method of claim 1 wherein H is greater than 10 meters.
13. The method of claim 1 wherein U.sub.L.ltoreq.1/2 U.sub.p.
14. The method of claim 1 wherein U.sub.L.gtoreq.0.5 cm/second.
15. The method of claim 7 wherein U.sub.L is determined in the
absence of liquid recycle.
16. The method of claim 1 wherein said bubble column diameter is
greater than 20 cm.
.Iadd.17. The method of claim 1 further including recycling the
liquid in the column..Iaddend.
.Iadd.18. A method for optimally operating a large diameter three
phase (gas, liquid, solid) slurry bubble column having a diameter
greater than 15 cm for Fischer-Tropsch synthesis over a supported
cobalt catalyst in which solid particles are fluidized in the
liquid phase by bubbles of gas phase comprising: (a) injecting the
gas phase into said column at an average gas velocity along said
column U.sub.g>8 cm/sec, such that the flow regime is in the
substantial absence of slug flow; (b) fluidizing the solid
supported cobalt catalyst particles of average diameter
d.sub.p>5 .mu.m, to the height, H>3 m, of the expanded liquid
in the column such that the value of the profile of the
concentration of the catalyst particles at the height of the
expanded liquid is no less than about 13.5% of the value of the
profile of the catalyst concentration at the bottom of the expanded
liquid; and (c) maintaining plug flow in said column by operating
with a gas phase velocity, U.sub.g, expanded liquid height, H, and
gas phase dispersion coefficient, D, such that U.sub.g.gtoreq.0.2
D/H..Iaddend.
.Iadd.19. A method for optimally operating a large diameter three
phase (gas, liquid, solid) slurry bubble column having a diameter
greater than 15 cm for Fischer-Tropsch synthesis over a supported
cobalt catalyst in which solid particles are fluidized in the
liquid phase by bubbles of gas phase comprising: (a) injecting the
gas phase into said column at an average gas velocity along said
column such that the flow regime is churn turbulent in the
substantial absence of slug flow; (b) fluidizing the solid
supported cobalt catalyst particles of average diameter
d.sub.p>5 .mu.m, to the height, H>3 m, of the expanded liquid
in the column such that the value of the concentration profile of
the catalyst particles at the height of the expanded liquid is no
less than about 13.5% of the value of the catalyst concentration
profile at the bottom of the expanded liquid; and (c) maintaining
plug flow in said column by operating with a gas phase velocity,
U.sub.g, expanded liquid height, H, and gas phase dispersion
coefficient, D, such that U.sub.g.gtoreq.0.2 D/H..Iaddend.
.Iadd.20. A method for optimally operating a large diameter three
phase (gas, liquid, solid) slurry bubble column having a diameter
greater than 15 cm for Fischer-Tropsch synthesis over a supported
cobalt catalyst in which solid particles are fluidized in the
liquid phase by bubbles of gas phase comprising: (a) injecting the
gas phase into said column at an average gas velocity along the
column U.sub.g>8 cm/sec such that the flow regime is churn
turbulent in the substantial absence of slug flow; (b) fluidizing
the solid supported cobalt catalyst particles of average diameter
d.sub.g>5 .mu.m, to the height, H>3 m, of the expanded liquid
in the column such that the value of the concentration profile of
the catalyst particles at the height of the expanded liquid is no
less than about 13.5% of the value of the catalyst concentration
profile at the bottom of the expanded liquid; and (c) maintaining
plug flow in said column by operating with a gas phase velocity,
U.sub.g, expanded liquid height, H and gas phase dispersion
coefficient, D, such that U.sub.g.gtoreq.0.2 D/H..Iaddend.
.Iadd.21. The method of claim 18 further including recycling the
liquid in the column..Iaddend.
.Iadd.22. The process of claim 18 wherein hydrogen synthesis wax is
a product of the process and the catalyst particles are separated
from said hydrocarbon synthesis wax by filtration or decantation or
other methods..Iaddend.
.Iadd.23. The method of claim 19 further including recycling the
liquid in the column..Iaddend.
.Iadd.24. The process of claim 19 wherein hydrocarbon synthesis wax
is a product of the process and the catalyst particles are
separated from said hydrocarbon synthesis wax by filtration or
decantation or other methods..Iaddend.
.Iadd.25. The method of claim 20 further including recycling the
liquid in the column..Iaddend.
.Iadd.26. The process of claim 20 wherein hydrocarbon synthesis wax
is a product of the process and the catalyst particles are
separated from said hydrocarbon synthesis wax by filtration or
decantation or other methods..Iaddend.
Description
BACKGROUND OF THE INVENTION
The present invention relates to the optimal operation of a slurry
bubble column reactor. Such columns have three phases in which
solid catalyst particles are held in suspension in a liquid phase
by bubbling gas phase reactants.
Slurry bubble column reactors operate by suspending catalytic
particles in a liquid and feeding gas phase reactants into the
bottom of the reactor through a gas distributor which produces
small gas bubbles. As the gas bubbles rise through the reactor, the
reactants are absorbed into the liquid and diffuse to the catalyst
where, depending on the catalytic system, they can be converted to
both liquid and gaseous products. If gaseous products are formed,
they enter the gas bubbles and are collected at the top of the
reactor. Liquid producests are recovered by passing the slurry
through a filter which separates the liquid from the catalytic
solids. A principal advantage of slurry reactors over fixed bed
reactors is that the presence of a circulating/agitated slurry
phase greatly increases the transfer rate of heat to cooling
surfaces built into the reactor. Because reactions of interest are
often highly exothermic, this results in reduced reactor cost (less
heat transfer equipment is needed) and improved stability during
reactor operations. A distinct advantage of bubble columns over
mechanically stirred reactors is that the required mixing is
effected by the action of rising bubbles, a process significantly
more energy-efficient than mechanical stirring.
In any reaction, the rate of conversion of reactants to products
and the product selectivity depend on the partial pressure of the
reactants in contact with the catalyst. Thus, the mixing
characteristics of the reactor become critical in determining
catalyst performance because they will determine the gas phase
composition (and therefore, the partial pressure of the reactants)
at any particular axial position in the reactor.
In fully backmixed reactors (CSTR), the composition of reactants
(gaseous) and products (liquids and gases) and condition of the
catalyst is identical at every point within the reactor. The
reactant concentration (or gas partial pressure) controls catalyst
performance by providing the driving force for the reaction and
determines the conversion occurring in the reactor. Thus, even
though pure reactant feed is entering the reactor, catalyst
performance is driven by the uniform reactant gas phase
concentration present throughout the reactor and equal to the
reactant gas phase concentration exiting the reactor. This fully
backmixed system has a low relative productivity per volume of
reactor for any reactions having positive pressure order rate
kinetics.
The other extreme in reactor mixing occurs in plug flow reactors
where the catalyst is stationary relative to the flow of reactants
and products (liquids and gases). The feed undergoes reaction as it
enters the reactor and the reaction continues as the unreacted feed
proceeds through the reactor. Thus, the concentration and partial
pressure of reactants decrease along the path of the reactor;
therefore, the driving force of the reaction also decreases as the
concentration of liquid and gaseous products increase. Thus, the
catalyst at the exit portion of the plug flow reactor never sees
fresh feed. The plug flow system provides maximum productivity for
a given reactor volume for any reactions showing positive pressure
order kinetics.
The important difference between the CSTR and plugflow reactor
systems is that the gas phase reactant concentration that provide
the kinetic driving force for the reaction differ significantly in
the fully backmixed system, the reactant concentration is the same
at every point in the reactor; in the plug flow system, the
reactant concentration steadily decreases along the path of the
catalyst bed from inlet to outlet and the reaction rate is obtained
by integrating the rate function from inlet to outlet. Because the
reactant concentration at any point in a CSTR system always
corresponds to outlet conditions, the productivity in a fully
backmixed system will always be lower than the productivity in a
plug-flow system for reactions with positive pressure order
kinetics.
Reactor systems exhibiting plug-flow and well stirred
characteristics represent extremes in reactor performance. In
practice, plug-flow reactors may exhibit some backmixed traits and
backmixed reactors may exhibit some plug-flow traits. Deviations
from the ideal systems are due to the dispersion of the reactant
gases in the reactor. Extent of backmixing is a function of the
mechanical energy imparted to the system. The reactor geometry also
affects backmixing and small L/d (i.e., reactor length to reactor
diameter) ratios, less than 3, favor complete backmixing. However,
higher energy input reactors with greater L/d can also achieve
complete backmixing. Conversely, plug-flow behavior is favored by
high L/d ratios. The degree of backmixing that can occur in a
plug-flow reactor can be represented by the Peclet number, Pe. (See
Carberry, J. J., "Chemical and Catalytic Reaction Engineering",
McGraw-Hill, 1976, or Levenspiel, O., "Chemical Reaction
Engineering", Wiley, 1972).
High Peclet numbers, e.g., greater than 10, lead to plug-flow
behavior while low Peclet numbers, e.g., less than 1, correspond to
well-mixed systems and are typical of CSTR's. By definition, the
dispersion coefficient for an ideal CSTR is infinity and the Peeler
number approaches zero.
These considerations show that the scale-up of slurry reactors from
laboratory to commercial units is not straightforward. For example,
as the reactor vessel is made taller, the height to which the
catalyst is fluidized is likely not to increase proportionally or
at all, and the added reactor volume remains unused. Also, as the
reactor diameter increases, the mixing intensity increases and may
result in an increase in the fluidization height but could also
increase the Peclet number and move the reactor performance from
plug-flow to well-mixed with a corresponding decrease in conversion
of products to reactants.
This difficulty is obvious in previous attempts to apply slurry
reactors to the important process of Fischer-Tropsch synthesis of
hydrocarbons (predominantly C.sub.10+) form synthesis gas (carbon
monoxide and hydrogen) using iron catalysts. The sole previous
scale-up efforts reported in the literature for commercial size
units (5 ft. diameter) were the Rheinpreussen tests in the 1950's
(see H. Storch, N. Columbis, R. B. Anderson, "Fischer-Tropsch and
Related Synthesis", Wiley (1951) New York and J. Fable, "Advances
in Fischer-Tropsch Catalysis", Verlag (1977) Berlin). Moving from
laboratory to commercial units, they sequentially built systems in
which the dispersion was too low to adequately fluidize the
particles to systems with dispersions high enough to cause
backmixed reactor behavior in the commercial size reactor. To date,
the optimal implementation of large scale systems has not been
achieved or described. A methodology for such a scale-up process is
described in this invention.
Optimum performance of slurry bubble column reactors require
adequate fluidization of the catalyst particles while maintaining
backmixing of the reactants in the gas phase. If the conditions in
the reactor are such that the particles settle, difficulties arise
because the reaction zone is short. Then in order to achieve high
conversions, the reaction rate per volume must be very high and the
catalyst can easily become starved of reactants because of
limitations in the rate at which reactants can be transferred from
the gas bubbles to the particles suspended in the liquid. This
condition results in poor catalyst utilization, poor reaction
selectivity, and eventually to catalyst deactivation. Also, for
exothermic reactions, the heat release takes place in the short
reaction zone, imposing severe requirements on the heat transfer
equipment.
The tendency of the particles to settle can be overcome, however,
by maximizing the dispersion effects resulting from the rising gas
bubbles and from the mixing patterns that they induce. These
dispersion effects can be enhanced by increasing either the
effective reactor diameter or the flow rate of gas through the
reactor. If the dispersion is increased too much, however, the gas
phase will also become well mixed and the reactor performance will
change from that of a plug flow reactor to that of a backmixed
reactor.
Eri et al in U.S. Pat. No. 4,857,559 have discussed the relative
merits of operating a Fischer-Tropsch reactor with a feed gas
containing various levels of diluents such as methane, carbon
dioxide, and nitrogen. In fixed bed reactors, they have indicated
that the presence of a diluent such as nitrogen in the feed is
disadvantageous since it will increase the pressure drop across the
reactor bed. In a slurry or fluidized bed reactor they indicate
that diluent has beneficial effects, in that it provides additional
mixing energy to the system to keep the catalyst suspended.
Moreover they note that added diluent will not have a great effect
on pressure drop in the slurry or fluidized bed reactors.
Eri et al also indicated that diluents will have a disadvantageous
effect on the fixed bed reactor since it will, at constant overall
pressure, lead to a net reduction in the partial pressure of
reactant gases present with a concomitant net reduction in the
overall volumetric productivity of the system. They failed to
indicate, however, that a similar reduction in productivity would
result in slurry or fluidized bed reactors as the diluent reduces
the reactant gas partial pressure. Consequently, the improved
catalyst fluidization achieved with added diluent is offset by the
reduced productivity and subsequent diluent processing steps
associated with product recovery.
The preferred embodiment of the present invention is the
Fischer-Tropsch synthesis of hydrocarbons using CO catalysts. The
Fischer-Tropsch reaction involves the catalytic hydrogenation of
carbon monoxide to produce a variety of products ranging from
methane to higher alliphatic alcohols. The methanation reaction was
first described by Sabatier and Senderens in 1902. The later work
by Fischer and Tropsch dealing with higher hydrocarbon synthesis
(HCS) was described in Brenastoff-Chem, 7, 97 (1926).
The reaction is highly exothermic and care must be taken to design
reactors for adequate heat exchange capacity as well as for their
the ability to continuously produce and remove the desired range of
hydrocarbon products. The process has been considered for the
conversion of carbonaceous feedstocks, e.g., coal or natural gas,
to higher value liquid fuel or petrochemicals. The first major
commercial use of the Fischer-Tropsch process was in Germany during
the 1930's. More than 10,000 B/D (barrells per day) of products
were manufactured with a cobalt based catalyst in a fixed-bed
reactor. This work has been described by Fischer and Pichler in
Ger. Pat. No. 731,295 issued Aug. 2, 1936.
Commercial practice of the Fischer-Tropsch process has continued in
South Africa in the SASOL plants. These plants use iron based
catalysts and produce gasoline in fluid-bed reactor and wax in
fixed-bed reactors.
Research aimed at the development of more efficient CO
hydrogenation catalysts and reactor systems is continuing. In
particular, a number of studies describe the behavior of iron,
cobalt or ruthenium based catalysts in slurry reactors together
with the development of catalyst compositions and improved
pretreatment methods specifically tailored for that mode of
operation.
Farley et al in The Institute of Petroleum, vol. 50, No. 482, pp.
27-46, February (1984), describe the design and operation of a
pilot-scale slurry reactor for hydrocarbon synthesis. Their
catalysts consisted of precipitated iron oxide incorporating small
amounts of potassium and copper oxides as promoters. These
catalysts underwent both chemical and physical changes during
activation with synthesis gas in the slurry reactor.
Slegeir et al in Prepr. ACS Div. Fuel Chem, vol. 27, p. 157-163
(1982), describe the use of supported cobalt catalysts for the
production of hydrocarbons from synthesis gas at pressures above
500 psi in a CSTR slurry reactor.
Rice et al in U.S. Pat. No. 4,659,681 issued on Apr. 21, 1987,
describes the laser synthesis of iron based catalyst particles in
the 1-100 micron particle size range for use in a slurry
Fischer-Tropsch reactor.
Dyer et al in U.S. Pat. No. 4,619,910 issued on Oct. 28, 1986, and
U.S. Pat. No. 4,670,472 issued on Jun. 2, 1987, and U.S. Pat. No.
4,681,867 issued on Jul. 21, 1987, describe a series of catalysts
for use in a slurry Fischer-Tropsch process in which synthesis gas
is selectively converted to higher hydrocarbons of relatively
narrow carbon number range. Reactions of the catalyst with air and
water and calcination are specifically avoided in the catalyst
preparation procedure. Their catalysts are activated in a fixed-bed
reactor by reaction with CO+H.sub.2 prior to slurrying in the oil
phase in the absence of air.
Fujimoto et al in Bull. Chem. Soc. Japan, vol. 60, pp. 2237-2243
(1987), discuss the behavior of supported ruthenium catalysts in
slurry Fischer-Tropsch synthesis. They indicate that the catalyst
precursors were ground to fine powders (<150 mesh), calcined if
needed, and then activated in flowing hydrogen before addition to a
degassed solvent and subsequent introduction to the slurry
reactor.
SUMMARY OF THE INVENTION
The present invention is a method for optimally designing and
operating a three-phase slurry bubble column reactor. The
constituents of three phases, gas, liquid, and solids, are defined
by the desired chemical reaction. The method includes injecting the
gas phase into a column of a given diameter in such a way as to
provide substantial absence of slug flow and with an appropriate
velocity so that the solid phase is fluidized while still
maintaining "plug flow" reactor behavior over the column
length.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a comparison of the volume needed for plug-flow and
well-mixed reactors in order to achieve a given conversion.
FIG. 2 shows a comparison of the reactor volume required to achieve
different degrees of conversion of reactant to product as a
function of degree of backmixing.
FIG. 3A shows a schematic diagram of a tracer test configuration
designed to determine the extent of backmixing in a bubble column
reactor.
FIG. 3B shows the acceptable range for the tracer response in the
effluent to guarantee Pe greater than 1 (i.e., plug flow
behavior).
FIG. 4 shows the decay length of the solids concentration as a
function of gas velocity for a 15 cm diameter by 5 meter tall
non-reactive bubble contains operating with hydrocarbon synthesis
(HCS) wax and titania particles.
FIG. 5 shows the decay length of the solids concentration as a
function of a solids concentration for a 15 cm diameter
non-reactive bubble column.
FIG. 6 shows the acceptable operating range in a slurry bubble
column in D/U.sub.gL vs. (U.sub.s-U.sub.L)/U.sub.g parameter
space.
FIG. 7 shows the acceptable operating range for the Fischer-Tropsch
catalyst/wax system in a slurry bubble column in D/H vs. catalyst
diameter parameter space.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The optimal operation of a slurry bubble column reactor requires
that the solid phase be fluidized in the liquid phase over the
entire height of the column. The solid phase is fluidized by upward
forces caused by rising gas bubbles and acting against the tendency
of the particles to settle under the downward gravitational
force.
Generally, the catalyst powders employed in this invention comprise
a Group VIII metal such as iron, cobalt or ruthenium or mixtures
thereof on an inorganic oxide support. These catalysts may contain
additional promoters comprising Group I, Group II, Group V, or
Group VII metals alone or in combination. The preferred catalyst
powders of this invention comprise cobalt or cobalt and thoria on
an inorganic oxide support containing a major amount of titania,
silica or alumina. The catalyst may also contain a promoter metal,
preferably rhenium, in an amount sufficient to provide a catalyst
having a rhenium:cobalt weight ratio greater than about 0.01 to 1,
preferably 0.025:1 to about 0.1 to 1. The catalyst contains about 2
to 50 wt % cobalt, preferably 5 to 20 wt % cobalt.
The catalyst metals are supported on an inorganic refractory oxide
comprising titania, silica or alumina. Preferably, the support
material is comprised of major amounts of titania and more
preferably the titania has a rutile:anatase ratio of at least about
2:3 as determined by x-ray diffraction (ASTM D2730-78), preferably
about 2:3 to about 100:1 or higher, more preferably about 4:1 to
100:1 or higher, e.g., 100% rutile. The surface area of the
preferred support is, generally, less than about 50 m.sup.2/gm
(BET).
Cobalt-rhenium/titania catalysts exhibit high selectivity in the
synthesis of hydrocarbon liquids from carbon monoxide and hydrogen.
The catalysts employed in the practice of this invention may be
prepared by techniques known in the art for the preparation of
other catalysts. The catalyst powder can, e.g., be prepared by
gellation, or cogellation techniques. Suitably, however, the metals
can be deposited on a previously pilled, pelleted, beaded,
extruded, or sieved support material by the impregnation method. In
preparing catalysts, the metals are deposited from solution on the
support in preselected amounts to provide the desired absolute
amounts, and weight ratio of the respective metals, cobalt and
rhenium. Suitably, the cobalt and rhenium are composited with the
support by contacting the support with a solution of a cobalt
containing compound, or salt, or a rhenium-containing compound, or
salt, e.g., a nitrate, carbonate or the like. Optionally, the
cobalt and rhenium can be coimpregnated on the support. The cobalt
and rhenium compounds used in the impregnation can be any
organometallic or inorganic compounds which decompose upon heating
in nitrogen, argon, helium or other inert gas, calcination in an
oxygen containing gas, or treatment with hydrogen at elevated
temperatures to give the corresponding metal, metal oxide, or
mixtures of the metal and metal oxide phases, of cobalt and
rhenium. Cobalt and rhenium compounds such as the nitrate, acetate,
acetylacetonate, naphthenate, carbonyl, or the like can be used.
The amount of impregnation solution should be sufficient to
completely wet the carrier, usually within the range from about 1
to 20 times of the carrier by volume, depending on the metal, or
metals, concentration in the impregnation solution. The
impregnation treatment can be carried out under a wide range of
conditions including ambient or elevated temperatures.
The catalyst after impregnation, is dried by heating at a
temperature above 30.degree. C., preferably between 30.degree. C.
and 125.degree. C., in the presence of nitrogen, or oxygen, or
both, or air, in a gas stream or under partial vacuum.
The catalyst particles, if necessary, are converted to the desired
particle size range of nominally 1-200 microns average diameter by
crushing, ultrasonic treatment, or other methods known to those
skilled in the art. The material can then be sieved, if necessary,
to produce a powder that is predominantly within the desired
particle size range.
The slurry liquid used in the process is a liquid at the reaction
temperature, must be relatively or largely or significantly
chemically inert under the reaction conditions and must be a
relatively good solvent for CO/hydrogen and possess good slurrying
and dispersing properties for the finely divided catalyst.
Representative classes of organic liquids which can be utilized are
high boiling paraffins, olefins, aromatic hydrocarbons, alcohols,
ethers, amines, or mixtures thereof. The high boiling paraffins
include C.sub.10-C.sub.50 linear or branched parafinic
hydrocarbons; the olefins include poly x-olefin liquids; the
aromatic hydrocarbons include C.sub.2-C.sub.20 single ring and
multi and fused ring aromatic hydrocarbons; the ethers include
aromatic ethers and substituted aromatic ethers where the ether
oxygen is sterically hindered from being hydrogenated; the amines
include long chain amines which can be primary, secondary, and
tertiary amines, wherein primary amines preferably contain at least
a C.sub.12 alkyl group in length, secondary amines preferably
contain at least two alkyl groups being C.sub.7 or greater in
length, and tertiary amines preferably contain at least three alkyl
groups being C.sub.6 or higher in length. The slurry liquid can
contain N and O in the molecular structure but noted S, P, As or
Sb, since these are poisons in the slurry process. Representative
examples of specific liquid slurry solvents useful are dodecane,
tetradecane, hexadecane, octadecane, cosane, tetracosane,
octacosane, dotriacontane, hexatriacontane, tetracontane,
tetratetracontane, toluene, o-, m-, and p-xylene, mesitylene,
C.sub.1-C.sub.12 mono- and multi-alkyl substituted benzenes,
dodecylbenzene, naphthalene, anthracene, biphenyl, diphenylether,
dodecylamine, dinonylamine, trioctylamine, and the like. Preferred
liquid hydrocarbon slurry solvent is octacosane or hexadecane.
(Most preferred really is HCS wax, i.e., the product of the FT
reaction.)
In addition to CO hydrogenation, the improved process of the
present invention can be applied to hydrogenation, aromatization,
hydrodesulfurization, hydrodenitrogenation, resid hydroprocessing,
hydroforminglation and related reactions. These are described in
more detail in "Applied Heterogeneous Catalysis", J. F. LePage et
al, Editions Tecnip Paris (1987).
The height to which the catalyst can be fluidized is given by
D/(U.sub.s-U.sub.L) where D is the dispension coefficient for the
particles, U.sub.s is the particle settling velocity (see Example
2) and U.sub.L, is the liquid velocity along the column. This
liquid flow along the column may be produced by removing liquid
from the top of the reactor at a rate equal to the liquid product
production rate plus any extra liquid which is injected back into
the bottom of the reactor as liquid recycle. While such liquid
recycle can enhance the fluidization height it is usually an
undesirable operating mode because the pumps and added filters
greatly add to the construction and operating costs and to the
complexity of operating procedures of the reactor. If this
fluidization height exceeds the actual physical height of the
reactor, the catalyst concentration becomes more uniform than is
necessary for efficient operation. Hence, excellent reactor
performance can be achieved when the reactor is designed and the
operating conditions are picked such that H=D/(U.sub.s-U.sub.L) or
D=H(U.sub.s-U.sub.L), where H is the expanded height of the liquid
in the column.
This ability to fluidize the particles arises from mixing induced
by the gas bubbles and, therefore, at the expense of some
backmixing of the reactants. Plug-flow behavior can still be
achieved, however, because for gas mixing the importance of the
dispersion must be compared to U.sub.g, the gas velocity, rather
than to the particle setting velocity U.sub.g. Specifically, the
degree of backmixing of the gas is measured by the Peclet number,
defined by Pe=U.sub.gH/D. If the dispersion is maintained at that
just required to fluidize the particles (i.e., if the reactor
conditions are such that D=0.5 H(U.sub.s-U.sub.L), then
Pe=U.sub.g/(U.sub.s-U.sub.L)>>1 and plug flow behavior will
prevail. In practical terms, this requires a design with
intermediate values of the reactor diameter and gas velocity. Low
particle settling velocities increase the window of acceptable
operating parameters but is not by itself a necessary conditions
for good performance (see Example 7).
It is the object of the present invention to avoid the need for
substantial quantities of diluent in the reactant feed gas stream,
while simultaneously operating with a well suspended catalyst bed
in a plug flow mode. This will not only lead to substantially
higher productivity per unit volume of reactor space, but also
eliminate the need to first produce and then separate diluent from
products and various reactant gas recycle streams. All of these
factors lead to energy and investment savings, thereby improving
the overall economic attractiveness of the process.
While these are the primary constraints for efficient reactor
performance, there are auxiliary conditions important in scale-up.
For example, the total reactor volume must be controlled to yield
the desired conversion rate of reactants to products for the
intrinsic catalyst activity. This normally sets a minimum height
for the reaction zone (i.e., minimum liquid and fluidization
height) for economic reactor operation. Also, while making the
catalyst particles smaller improves the fluidization it also
greatly increases the difficulty in separating them from the liquid
product stream. Hence, catalyst particle diameters of less than 5
microns should be avoided. A more preferred diameter is greater
than 30 microns. Finally, if the effective reactor diameter is too
small, the flow regime has large gas slugs (i.e., slug flow) rising
through the column rather than a dispersion of small gas bubbles
typical of bubbly or churn tubulent flow which give better mass
transfer performance. Hence, bubble column diameters of less than
10 cm should not be used for either obtaining data for scaleup or
for commercial units (see Gas-Liquid-Solid Fluidization Engineering
Liang-Shih Fan, Butterworths, Boston (1989)). Reactors with small
effective diameters also can lead to unreasonable complexity and
construction cost when designed for systems large enough to convert
commercial feed rates of reactants.
EXAMPLES 1
Comparison of Reactor Volume Needed for a Given Conversion in Plug
Flow and Well Mixed Reactors
For isothermal reactors with constant catalyst density being
supplied with reactant at a volumetric rate F, the reactor volume
(V) required for given exit concentration or conversion is: .times.
.times..times..times..times. .intg..times..times.
.times..times..intg..times..times. .times..times..times..times.
.times. ##EQU00001## where J=C.sub.o-C/C.sub.o is the conversion,
J.sub.g is the exit conversion, r is the reaction rate C is the
concentration C.sub.o is the inlet concentration.
Assuming first order kinetics (the HCS reaction order in total
pressure is about 0.7), we find: .times.
.times..function..times..times. .times..times. .times. ##EQU00002##
where k is the reaction rate constant. Therefore, the ratio of
volume requirements for a given conversion is: .times..times.
.times. ##EQU00003##
As shown in FIG. 1, the required reactor volume is much less for
the plug flow system at moderate or high conversions. A detailed
model is available for calculating the effects of non-uniform
catalyst distribution at intermediate mixing conditions for
arbitrary kinetic expressions in specific applications.
EXAMPLE 2
Transition from Plug Flow to Backmixed Behavior
A given reactor generally exhibits behavior intermediate between
plug-flow and well-mixed. For reaction rates that are first order
in the concentration of reactants, the reactant concentration, C,
at any vertical distance from bottom of the reactor, x, can be
determined by solving the convection-diffusion equation:
.times..differential..differential..times..differential..times..different-
ial. ##EQU00004## where U.sub.g is the average velocity of the gas
along the reactor, D is the gas phase dispersion coefficient, and k
is the reaction rate constant. Defining Z=x/H where H is the height
of expanded liquid zone, this equation can be rewritten as:
.differential..differential..times..differential..times..differential..ti-
mes. ##EQU00005## where Pe=HU.sub.g/D is the Peclet number. As Pe
approaches zero the dispersion dominates and the reactor is
well-mixed, while as Pe approaches infinity, the dispersion becomes
negligible and plug-flow behavior is achieved.
This model can be solved to determine the reactor volume necessary
for a given conversion as a function of Peclet number. The results
are plotted in FIG. 2. If the Peclet number is above 10, we see
that effectively plug flow behavior is achieved and that the
reactor volume requirements become independent of Peclet
number.
EXAMPLE 3
Experimental Procedure to Determine the Dispersion in a Given
Reactor
Example 2 demonstrates the importance of the Peclet number in
determining the reactor performance. While calculating or measuring
the reaction zone height and the gas velocity is relatively
straightforward, it is difficult to know a priori the dispersion
coefficient. The dispersion coefficient depends on the gas
throughput velocity as well as on the reactor geometry. As the
reactor diameter is increased, the dispersion increases rapidly.
The problem is complicated by the need to provide internal reactor
structures within the reactor in order to improve heat removal. A
general correlation for the dispersion coefficient as a function of
geometric configuration is not possible because different internal
configurations will produce different and poorly understood mixing
patterns. In fact, the geometry of the internal design is the key
factor the designer can use to control the mixing behavior of a
slurry bubble column reactor for a given outside diameter and
height that are determined by volume requirements (i.e., by
requirements to achieve a desired conversion).
The Peclet number of a given reactor can be determined from a
tracer test for the reactor or a geometrically equivalent
non-reactive mockup unit at milder but well defined conditions.
Inert gas is fed to the bottom of the reactor and after allowing
the system to equilibrate a small concentration of a tracer gas is
added to the feed stream as a step function (cf. FIG. 3A). Then by
measuring the shape of the concentration profile of the tracer in
the gas outlet stream, the Peclet number can be determined for the
reactor by matching experimental results to model calculations.
The model describing this test using a tracer that is insoluble in
the liquid is:
.differential..differential..differential..differential..times..different-
ial..times..differential. ##EQU00006## where t is the time measured
from the tracer injection multiplied by U.sub.gH/E with E being the
gas holdup in the column. The Peclet number is the only parameter
in this equation. For infinitely large Peclet numbers (i.e.,
plug-flow), the output is a delayed step function; and as the Pe
number is decreased (backmixing increases), the output response is
more spread out in time. If the response pulse falls outside of the
shaded area in FIG. 3B, the Peclet number is less than 1, and the
reactor begins to give decreased conversion because of
backmixing.
The same tests can be performed using a soluble tracer, but the
required model and its interpretation of results are more
complicated. The required procedure is obvious to those
knowledgeable of the art and can yield additional information not
germane to this invention.
EXAMPLE 4
Catalyst Distribution as a Function of Gas Velocity
The catalyst distribution is determined by a balance of
gravitational settling of the particles and dispersion created by
the upward flow of the gas bubbles. This balance results in a
profile of the catalyst concentration, .times.
.times..function..times. ##EQU00007## where U.sub.g is the particle
settling velocity, U.sub.L is the liquid velocity along the reactor
, D is the dispersion coefficient of the liquid, x is the vertical
distance from the bottom of the reactor, and A is a constant that
depends on the total volumetric solids concentration in the
reactor. The solids concentration decreases by a factor of 2.7 each
time the height in the slurry increases by an amount equal to
D/(U.sub.g-U.sub.L). While U.sub.g is given primarily by the
composition of the liquid and by the size and density of the
catalyst particles, D is governed by the effective reactor diameter
and by the gas velocity. FIG. 4 shows the decay length of the
catalyst concentrations as a function of gas velocity as measured
in a 6 inch diameter by 5 meter tall non-reactive bubble column
using Fischer-Tropsch wax and titania particles. These data
demonstrate a ten-fold change in bed height (i.e., dispersion
coefficient) over the velocity range of interest in commercial
reactors (i.e., from 2-25 cm/sec). As discussed in Example 3, the
qualitative form of this curve will remain the same but the decay
lengths will be different for reactors with different diameters and
internal structures because of their marked effect on the
dispersion coefficient.
EXAMPLE 5
Experimentally Determined Solids Decay Length
The solids distributions of glass beads and of titania particles in
HCS wax were determined in a 6'' diameter non-reactive bubble
column by taking samples from the vessel at 1 meter intervals. The
temperature was 400.degree. F. and the pressure was 280 psig for
gas velocity below 8 cm/sec and 150 psig for gas velocities about 8
cm/sec. The decay length was obtained by taking the slope of a line
segment joining the data points when plotted as the logarithm of
solids concentration versus height. In FIG. 5, the decay length in
each zone is plotted versus the average concentration in the zone
for superficial gas velocities of 2-16 cm/sec.
The data can be correlated reasonably by:
D/U.sub.g(feet)=0.2(1+20C.sub.p.sup.2+3000C.sub.p.sup.4I/U.sub.o(cm/sec)
for U.sub.g<4 cm/sec
D/U.sub.g(feet)=1.2(1+3C.sub.p.sup.2+550C.sub.p.sup.4)/U.sub.o(cm/sec)
for U.sub.g>8 cm/sec where C.sub.p is the volume fraction of
solids in the slurry and U.sub.o is the Storkes settling velocity
defined by .times..times..mu..times. ##EQU00008## where d.sub.p is
the diameter of the particle, .rho..sub.s is the density of the
particle, pl is the density of the suspending liquid, .mu. is the
viscosity of the liquid, and g is the gravitational constant. For
velocities between 4 and 8 cm/sec a linear interpolation works
well.
This demonstrates a marked increase in the fluidization height when
the solids loading is increased above 20%. Most of this increase is
due to a reduction in the particle settling velocity as the solids
concentration increases (see R. H. Davis and A. Acrivos, Annual
Review of Fluid Mechanics 17, 19, 1985).
EXAMPLE 6
Method for Predicting Solids Distribution in a Slurry Bubble Column
Reactor
The data of Example 5 allow one to predict the catalyst
distribution in a slurry bubble column reactor via the following
algorithm. Suppose the reactor is charged with n species of
particles each of which has a Stokes setting velocity U.sub.i and
average concentration C.sub.io. A given species may or may not be
catalytic. The concentration of each species must satisfy the
differential equation. dd.times..function..times. ##EQU00009##
where x is the vertical distance from the bottom of the reactor,
F(U.sub.g, C.sub.p) is the function D/U.sub.s given in Example 5,
U.sub.g is the gas velocity at height x, and C.sub.p is the local
value of the total solids concentration (i.e.,
C.sub.p=.SIGMA.C.sub.l.
The algorithm begins by guessing the values of all the C.sub.i's a
the bottom of the reactor and then the equation for the C.sub.i's
are integrated numerically until the top of the slurry is reached.
The gas velocity is computed by requiring a given overall
conversion, J, and assuming the extent of reaction at any height is
proportional to the fraction of the total catalyst inventory below
that height.
When the integration reaches the top of the slurry, the total
predicted inventory for each solid species is compared to the known
charge; i.e., we check that
.times..intg..times..times.d.intg..times..times..times.d
##EQU00010## where E is the volume fraction of gas (i.e., the gas
holdup) at vertical distance x and H is the height of the
slurry.
If these equalities are not satisfied, the assumed concentrations
at the bottom of the reactor were not correct and they are adjusted
using a Newton-Raphson interation technique. The equations are then
integrated starting from the new values and the interations are
continued until convergence is obtained.
This procedure can be easily extended to include the use of liquid
flow along the reactor. The right hand side of the above equations
are modified by subtracting the liquid velocity from the setting
velocity of species i.
EXAMPLE 7
Determination of Operating Conditions for Slurry Reactors
As pointed out above, the dispersion coefficient should be large
enough to fluidize the particles adequately over the height of the
reactor, e.g.: .times. .times..ltoreq..times. .times..times.
.times..gtoreq..times. .times. ##EQU00011## but small enough that
the gas flow remains plug flow, e.g.: .ltoreq..times..times.
.times..times. .times..ltoreq..times. .times. ##EQU00012##
Together, these require an intermediate dispersion coefficient that
satisfies the conditions: .times. .times..gtoreq..gtoreq..times.
.times..times. .times..times. .times..gtoreq..gtoreq..times.
.times. ##EQU00013##
Hence for optimum performance, the reactor geometry and operating
conditions must be chosen such that they lie within the shaded
triangle shown in FIG. 6.
EXAMPLE 8
Application to Fischer-Tropsch Synthesis with Co/Re Catalyst on
Titania
For the catalyst/wax system being considered, the Reynolds number
for the settling particles is small and U.sub.s is given by Stokes
law times a monotonically decreasing function [f(C.sub.p)] which
varies between 1 and 0 as the volume fraction of catalyst in the
slurry is increased from 0 to the concentration at maximum packing.
The "hindered settling function", is described in R. H. Davis and
A. Acrivos, Annual Review of Fluid Mechanics 17 (1985). Hence, for
the catalytic system of greatest interest.
.times..times..mu..times..function..times..times..times..functi-
on. ##EQU00014## where d.sub.p is the particle diameter,
.rho..sub.s is the effective density of the particles
(approximately 2.7 gf/cm.sup.3), .rho..sub.l is the density of the
wax (0.7 gr/cm.sup.3), .mu. is the viscosity of the wax (0.01
gr-cm/sec), g is the gravitational constant, c is the volume
fraction of solids in the slurry, and f(c) is 1 for a dilute slurry
and a monotonic decreasing function of solids volume fraction at
higher solids loading. Hence, for our system. U.sub.s
(cm/sec)=1.1.times.10.sup.-4 [d.sub.p (.mu.m)].sup.2 Assuming the
gas phase Peclet number must be at least 2 to maintain plug flow
behavior, the acceptable operating range is shown in FIG. 7 for the
case where U.sub.g=5 cm/sec and no liquid recycle is used.
It is clear that while the D/H design range is quite broad for
small particles because of our ability to fluidize such particles
without extensive backmixing, this range narrows significantly for
large particles. Particles with greater than 100 .mu.m diameters
cannot be effectively fluidized without a backmixing debit on the
kinetic driving force. Practical restrictions on the size of
catalyst particles that can be effectively separated from the
liquid medium by filtering decantation, or other methods
considerably narrow the allowable range of particle sizes and
therefore design D/H parameters.
* * * * *