Note: Descriptions are shown in the official language in which they were submitted.
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HYDROGENATION OF SOLID CARBONACEOUS MATERIALS USING MIXED
CATALYSTS
TECHNICAL FIELD
[0001] This invention relates to systems and processes for pretreating a
carbonaceous
material, for liquefying a carbonaceous material, and for improving efficiency
of carbonaceous
material liquefaction.
BACKGROUND
[0002] Much work has been done over the years on processes for obtaining
liquid and
gaseous products from solid carbonaceous materials such as coal. The known
processes include
both catalytic and non-catalytic reactions. In catalytic processes, the
hydrocarbonaceous material
is typically slurried with a solvent and a catalyst, and is reacted in the
presence of molecular
hydrogen at elevated temperatures and pressures.
[0003] U.S. Patent 5,246,570, for example, describes a coal liquefaction
process in which a
mixture of coal, catalyst, and solvent are rapidly heated to a temperature of
600-750 F in a
preheater, and then reacted under coal liquefaction conditions in a
liquefaction reaction. U.S.
Patent 5,573,556 describes a process for converting a carbonaceous material to
normally liquid
products comprising heating a slurry that comprises a carbonaceous material, a
hydrocarbonaceous solvent, and a catalyst precursor to a temperature
sufficient to convert the
catalyst precursor to the corresponding catalyst, and introducing the slurry
into a liquefaction
zone. U.S. Patent 5,783,065 describes a coal liquefaction process comprising
impregnating coal
particles with a catalyst having hydrogenation or hydrogenolysis activity;
introducing the
impregnated coal particles for very short periods into a turbulent flow of
hydrogen containing
gas at a temperature at least about 400 C; and quenching the temperature of
the products to a
temperature significantly less than 400 C.
[0004] Such conventional processes leave much room for improving the liquid
and/or gas
yields of hydroconverted carbonaceous materials, as well as the quality of the
liquid and/or gas
products that are obtained from such processes. Accordingly, a need remains
for improved
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systems and processes for hydroconversion of carbonaceous materials, as well
as improved feed
materials for such systems and processes.
SUMMARY OF THE INVENTION
[0005] The present invention relates to a process for converting a solid
carbonaceous
material to a liquid product, comprising maintaining a solid carbonaceous
material in the
presence of at least one active source of cobalt and at least one active
source of a second metal at
a reaction temperature of greater than 350 C and at a pressure in the range of
300 to 5000 psig
for a time sufficient to form a liquid product.
[0006] In one aspect, the process comprises preparing a combination of the
solid
carbonaceous material, at least one hydrocarbonaceous liquid, at least one
active source of cobalt
and at least one active source of the second metal; and passing the
combination to a
hydroconversion reaction zone and maintaining the solid carbonaceous material
at a reaction
temperature of greater than 350 C and at a pressure in the range of 300 to
5000 psig for a time
sufficient to convert at least a portion of the solid carbonaceous material to
a liquid product
boiling in the temperature range of C5 to 650 C.
[0007] In a further aspect, the step of preparing the combination comprises
preparing a
mixture comprising at least one active source of cobalt and at least one
active source of a second
metal; combining the mixture with coal to form catalyst-containing coal
particles; providing a
hydrocarbonaceous liquid to the catalyst-containing coal particles to prepare
the combination.
[0008] In another aspect, the process of preparing the combination further
comprises drying
the catalyst-containing coal prior to the step of passing the combination to
the hydroconversion
reaction zone.
[0009] In a further aspect, the process further comprises pretreating the
combination at a
pretreatment temperature within the range of 100-350 C and for a time of
between 5 and 600
minutes prior to passing the combination to the hydroconversion reaction zone.
[0010] In a further aspect, before, during or after the step of pretreatment,
at least one active
source of sulfur is added to the solid carbonaceous material in the
preparation of the
combination, wherein the atomic ratio of sulfur to metal components is within
the range of
between 1/1 and 10/1.
[0011] In an aspect, the second metal is iron.
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[0012] Several embodiments of the invention, including the above aspects of
the invention,
are described in further detail as follows. Generally, each of these aspects
can be used in various
and specific combinations, and with other aspects and embodiments unless
otherwise stated
herein.
BRIEF DESCRIPTION OF THE DRAWING
[0013] Fig. 1, Fig. 2, Fig. 3 and Fig. 4 illustrate embodiments of the process
for converting
solid carbonaceous material.
DETAILED DESCRIPTION
[0014] The following terms will be used throughout the specification and will
have the
following meanings unless otherwise indicated.
[0015] The term "catalyst precursor" is used herein to refer to a compound
that is
transformable into a catalyst via chemical reaction with one or more reagents
(such as sulfiding
and/or reducing agents, e.g., hydrogen, such as within a hydrocarbon medium)
and/or via any
other suitable treatment (such as thermal treatment, multi-step thermal
treatment, pressure
treatment, or any combination thereof) whereby the catalyst precursor at least
partially
decomposes into a catalyst.
[0016] The term "active source" is used herein to refer to an atomic,
molecular, complex or
any other form of an element that is a catalyst or a catalyst precursor or
that can be converted
into a catalyst or catalyst precursor. The active source may be in solution,
in slurry or in particle
form. When the active source is deposited on the solid carbonaceous material,
by, for example,
plating, impregnation, coating or washing, a single active source or a mixture
of active sources
may be deposited on individual particles of the solid carbonaceous material.
[0017] The term "catalytic material" is used to refer to one or more active
catalysts or
catalyst precursors. The component(s) of catalytic material may be in slurry
or particle form. In
particle form, single or multiple catalysts may be present on individual
particles. Likewise,
when the catalytic material is deposited on the solid carbonaceous material,
by, for example,
plating, impregnation, coating or washing, a single catalyst, or a mixture of
catalysts or
precursors making up the catalytic material may be deposited on individual
particles of the solid
carbonaceous material.
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[0018] Unless otherwise specified, coal properties as disclosed herein are on
a dry, ash-free
(daf) basis, wherein ASTM 3173 is used for moisture determination and ASTM3174
for ash
quantification.
[0019] "d" block elements refer to elements of the Period Table wherein the d
sublevel of
the atom is being filled. Examples include iron, molybdenum, nickel,
manganese, vanadium,
tungsten, cobalt, copper, titanium, chromium, platinum, palladium, cerium,
zirconium, zinc and
tin.
[0020] Lanthanoid (or lanthanide, or sometimes referred to as rare earths)
elements refer to
the fifteen elements in the Periodic Table with atomic numbers 57 through 71.
[0021] "Oil dispersible" compound means that the compound scatters or
disperses in oil
forming a dispersion. In one embodiment, the oil dispersible compound is oil
soluble which
dissolves upon being mixed with oil.
[0022] For purposes of this disclosure, unless otherwise specified, the
catalyst composition is
defined as the composition of the active source(s) added to the process,
regardless of the form of
the catalytic elements during hydroconversion.
[0023] The present invention relates to the composition and preparation
procedures of a
sulfided cobalt-containing catalyst used for hydroconversion of carbonaceous
material including
coal, shale oil, vacuum residuum and bio-fuel stock such as lignin. The
invention further relates
to a hydroconversion process for converting solid carbonaceous material to a
liquid product in
the presence of a catalyst composition comprising cobalt. In embodiments, the
invention further
relates to a process for converting a carbonaceous material, comprising
pretreating a solid
carbonaceous material at a pretreatment temperature and in the presence of at
least one active
source of cobalt and at least one active source of a second metal; heating the
pretreated material
in the presence of hydrogen to a conversion temperature which is greater than
the pretreatment
temperature; and reacting the heated material for a time sufficient to form
converted products
from the solid carbonaceous material.
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Catalyst Formula
[0024] In one embodiment, the catalyst composition as expressed in elemental
form is of
the general formula (RP);(Mt)a(L )b(S )d(CW)e(H")J(OY)g(NZ)h. The formula
herein refers to the
catalyst solids, constituting the catalyst slurry in oil. In the equation, M
and L each represents
at least a "d" block element from the Periodic Table such as iron, molybdenum,
nickel,
manganese, vanadium, tungsten, cobalt, copper, titanium, chromium, platinum,
palladium,
cerium, zirconium, zinc and tin. M is different from L. R is optional, which
represents at least
one lanthanoid element from the Periodic Table such as La, Ce, Nd, etc. In
another embodiment,
R is at least an alkali earth metal such as magnesium.
[0025] Also in the equation, p, t, u, v, w, x, y, z representing the total
charge for each of the
components (R, M, L, S, C, H, 0 and N, respectively);
pi+ta+ub+vd+we+xf+yg+zh=0; R with a
subscript i ranging from 0 to 1; M and L with subscripts a and b, with values
of a and b
respectively ranging from 0 to 5, and (0 <= b/a <= 5); S represents sulfur
with the value of the
subscript d ranging from 0.5(a + b) to 5(a + b); C represents carbon with
subscript e having a
value of 0 to 11 (a+b); H is hydrogen with the value off ranging from 0 to
7(a+b); 0 represents
oxygen with the value of g ranging from 0 to 5(a + b); and N represents
nitrogen with h having a
value of 0 to 2(a + b).
[0026] In embodiments, M is iron and L is cobalt (or vice versa). In some such
embodiments, the catalyst is of the formula (FezCoi_z)a(S)d(C)e(H)J(O)g(N)h,
wherein the cobalt to
iron ratio is in the range of 9:1-1:9 (as wt. %). In some such embodiments,
the cobalt to iron
ratio is in the range of 1:5 to 5:1; or in the range of 1:10 to 1:5.
Pretreatment Process
[0027] In embodiments, the present invention is related to a system and
process for
pretreating a carbonaceous material, for dispersing one or more catalysts or
catalyst precursors
into a carbonaceous material, for enhancing the conversion of a carbonaceous
material (such as a
naturally-occurring solid carbonaceous material, such as coal) to a liquid
and/or gaseous product,
for producing a carbonaceous material of enhanced reactivity, for improving
efficiency of
carbonaceous material (such as coal) liquefaction, as measured for example by
conversion and
liquid yield, and/or for lowering hydrogen consumption during liquefaction of
carbonaceous
material.
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[0028] In one embodiment, such pretreating of a carbonaceous material is
performed or
accomplished using reaction conditions (or a combination of conditions, such
as temperature,
pressure, and/or duration of pretreatment) at which substantially no
hydroconversion of the
carbonaceous material occurs (i.e., wherein less than about 20%, less than
about 10% or even
less than about 1% of the carbonaceous material is converted) during the
pretreatment step. Any
suitable process or operating conditions can be utilized to pretreat the
carbonaceous material. In
one embodiment, the pretreatment composition is heated to a temperature
sufficient to cause one
or more catalysts or catalyst precursors to disperse into the carbonaceous
material, and is
maintained, held, and/or kept at this pretreatment temperature for a time or
duration sufficient to
disperse one or more of the catalysts or catalyst precursors into the
carbonaceous material to a
desired degree of dispersion, integration, and/or homogeneity. In one
embodiment, the
pretreatment composition is heated to a temperature of about 100-350 C (such
as about 150-
300 C or even about 180-220 C). In some such embodiments, the step of
pretreating is
conducted at a temperature of about 100-350 C for about 10-360 minutes.
[0029] The pretreatment composition is preferably maintained, kept, and/or
held at the
pretreatment temperature for a time or duration sufficient to cause swelling
of the carbonaceous
material and to allow for dispersion (such as complete dispersion and/or
homogenous dispersion)
of the catalyst or catalyst precursor into the carbonaceous material. In one
embodiment, for
example, the pretreatment composition is maintained, kept, and/or held at
suitable temperature
for a suitable duration to cause the total volume of voids of the carbonaceous
material (or of each
particle of carbonaceous material) to increase by greater than about 5%, or
about 25% as
compared to the carbonaceous material prior to pretreatment. In one
embodiment, in this regard,
the pretreatment composition is maintained at the pretreatment temperature for
a time of between
and 600 minutes, or between 10 and 360 minutes.
[0030] Pretreatment of the carbonaceous material can be performed under any
suitable
atmosphere. In one embodiment, the pretreatment of carbonaceous material
occurs under an inert
atmosphere. In another embodiment, the pretreatment occurs under a reducing
atmosphere, such
as under hydrogen and/or a synthesis gas ("syn-gas") pressure. In some
embodiments, for
example, the pretreatment is performed at a pressure between atmospheric
pressure and about
500 psig, e.g., a pressure of about 100-450 psig, or about 200-350 psig. In
other embodiments,
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the pretreatment occurs under a reducing atmosphere at a pressure defined by
the
hydroconversion process, such as at a pressure of about 300-5000 psig, such as
500-3500 psig,
about 1000-3000 psig, or even about 1500-2600 psig. Any suitable syn-gas can
be used in this
regard, such as, for example, a syn-gas that comprises a 1:1 to 2: 1 mixture
of hydrogen with
carbon monoxide, and optionally also contains carbon dioxide, methane, and/or
other
components.
[0031] In one embodiment, such pretreatment is performed or accomplished under
conditions sufficient to deposit at least a portion of the catalyst or
catalyst precursor onto the
solid carbonaceous material during pretreatment. In some such embodiments, one
or more
catalysts or catalyst precursors and a liquid contact the solid carbonaceous
material.
[0032] The pretreatment composition comprising the carbonaceous material, one
or more
catalyst or catalyst precursors, and a hydrocarbonaceous liquid can be
prepared in any suitable
manner. In one embodiment, the carbonaceous material, catalyst or catalyst
precursor, and
hydrocarbonaceous liquid are simply mixed to form a pretreatment composition,
and the
pretreatment composition is subjected to pretreatment conditions. In another
embodiment, the
carbonaceous material is contacted with the catalyst or catalyst precursor in
the presence of the
hydrocarbonaceous liquid, and the pretreatment composition is subjected to
pretreatment
conditions. In another embodiment, the carbonaceous material is ground in the
presence of the
one or more catalysts or catalyst precursors and the hydrocarbonaceous liquid,
to produce a
pretreatment composition in the form of a slurry; and the pretreatment
composition is subjected
to pretreatment conditions. In another embodiment, the carbonaceous material
is ground in the
presence of the hydrocarbonaceous liquid to produce a slurry; the one or more
catalyst precursors
are added to the slurry to form a pretreatment composition; and the
pretreatment composition is
subjected to pretreatment conditions. In other embodiment, the catalyst or
catalyst precursor is
added at the start of the pretreatment process. In another embodiment, the
catalyst or catalyst
precursor is added at intervals throughout a pretreatment process. In other
embodiments, at least
a portion of the catalyst or catalyst precursor is deposited on the
carbonaceous material during
pretreatment.
[0033] Following pretreatment of the carbonaceous material, the carbonaceous
material and
dispersed catalyst or catalyst precursor, optionally together with the
hydrocarbonaceous liquid,
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form an improved feed for a hydroconversion process. Such an improved feed can
be used for
any suitable hydroconversion process to produce a liquid and/or gaseous
product.
Carbonaceous Material
[0034] The carbonaceous material can be any suitable solid carbon containing
material, such
as any naturally occurring solid, or normally solid, carbon containing
material. Specifically, for
example, the carbonaceous material can be coal, such as anthracite, bituminous
coal, sub-
bituminous coal, lignite, or any combination or mixture thereof. The
carbonaceous material can
also be any heteroatom-containing solid carbonaceous material or feed, as well
as any heavy
hydrocarbonaceous feeds, such as, for example, coal, coke, peat, shale oil
and/or a similar
material, such as any solid carbonaceous material containing a relatively high
ratio of carbon to
hydrogen, or combinations or mixtures thereof. In some embodiments, at least a
portion of the
carbonaceous material is in the form of particles, or finely divided
particles, having any suitable
size. For example, at least about 50 wt% of the carbonaceous material is in
the form of particles
having a mean particle diameter of less than about 0.5 inches. In embodiments,
at least greater
than 70 wt% of carbonaceous material is in the form of particles having a mean
particle diameter
in the range of about 0.1 to 0.4 inches. In one embodiment, greater than about
80 wt.% of the
carbonaceous material is in the form of particles having a mean diameter less
than about 0.25
inches. In another embodiment, greater than 80 wt% of the carbonaceous
material is in the form
of particles having a mean diameter in the range of 50 microns to 500 microns,
such as 100
microns. Such particles can be formed in any suitable manner, such as by
grinding at least a
portion of the carbonaceous material. In one embodiment, at least a portion of
the carbonaceous
material is ground in the presence of one or more catalysts or catalyst
precursors and the
hydrocarbonaceous liquid. In another embodiment, at least a portion of the
carbonaceous
material is ground in the presence of the hydrocarbonaceous liquid to form a
slurry, and (such as
subsequently) mixing the slurry with one or more catalysts or catalyst
precursors. In other
embodiments, the carbonaceous material is ground under an inert or a reducing
atmosphere, such
as, for example, hydrogen, nitrogen, helium, argon, syn-gas, or any
combination or mixture
thereof. Any process or equipment may be used to grind the carbonaceous
material, such as, for
example, a hammer mill, a ball mill (such as a wet ball mill, a conical ball
mill, a rubber roller
mill), a rod mill, or a combination thereof.
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Hydrocarbonaceous Liquid
[0035] The hydrocarbonaceous liquid can be any suitable liquid (such as
solvent or diluent)
known in the art to be useful for the liquefaction of carbonaceous materials
(such as solid
carbonaceous materials, such as coal). In one embodiment, the
hydrocarbonaceous liquid is a
hydrogen donor solvent, such as any compound(s) which functions as a hydrogen
donor in
hydroconversion conditions. The hydrocarbonaceous liquid can have any suitable
hydrogen
donatability, such as, for example, a hydrogen donatability greater than about
1.0 wt%, as
determined, for example, by NMR.
[0036] In one embodiment, the hydrocarbonaceous liquid comprises a coal-
derived solvent,
or a distillate fraction thereof. In another embodiment, the hydrocarbonaceous
liquid comprises
a hydrogenated aromatic, a naphthenic hydrocarbon, a phenolic material, or a
similar compound,
or a combination or mixture thereof. In another embodiment, the
hydrocarbonaceous liquid
comprises one or more aromatics, such as one or more alkyl substituted
aromatics. Solvents
known to donate hydrogen during liquefaction include, for example, the
dihydronaphthalenes,
the CIO - C12 tetrahydronaphthalenes, the hexahydrofluorenes, the dihydro-,
tetrahydro-,
hexahydro- and octahydrophenanthrenes, the C12 -C13 acenaphthenes, the
tetrahydro-,
hexahydro- and decahydropyrenes, the di-, tetra- and octahydroanthracenes, and
other
derivatives of partially saturated aromatic compounds. They can be prepared by
subjecting a
distillate stream from atmospheric distillation to a conventional
hydrogenation reactor.
Particularly effective mixed solvents include heavy gas oil fractions (often
called vacuum gas
oils, or VGO) with an initial boiling point of about 343 C. (650 F.) and a
final boiling point of
about 538 C. (1000 F.). This stream comprises aromatics, hydrogenated
aromatics, naphthenic
hydrocarbons, phenolic materials, and similar compounds. If a solvent is used
which does not
have donatable hydrogen, hydrogen may be added from another source.
[0037] The solvent generally boils at a temperature greater than 300 C., such
as, for example
a temperature in the range of 450-900 or 650-850 F. In one embodiment, the
hydrocarbonaceous
liquid is a fluid catalytic cracking (FCC) type process oil cut that boils at
a temperature of about
500 F or higher (FCC-type process oil (500 F+ cut)). In another embodiment,
the
hydrocarbonaceous liquid is an FCC-type process oil boiling at a temperature
of about 500 F or
less ("FCC-type process oil (500 F- cut)"). In another embodiment, the
hydrocarbonaceous
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liquid is a hydrotreated FCC oil. In another embodiment, the hydrocarbonaceous
liquid is tetralin
(1,2,3,4 tetrahydronaphthalene). In another embodiment, the hydrocarbonaceous
liquid
comprises one or more compounds that have an atmospheric boiling point ranging
from about
350-850 F.
[0038] Any suitable ratio of hydrocarbonaceous liquid to carbonaceous material
(such as
carbonaceous particles, or even coal particles) can be used in the context of
the present
invention, such as, for example, a ratio in a range of about 1: 10 to about
10: 1, such as 1:6 to
about 6: 1, or a range of about 1:2 to about 2: 1, by weight of the mixture.
In one embodiment,
the ratio of hydrocarbonaceous liquid to carbonaceous material used in the
pretreatment process
is about 0.75:1 to about 1:1.
Catalyst Precursor
[0039] The process for converting a solid carbonaceous material comprises
heating the
carbonaceous material in the presence of a catalyst composition. In
embodiments, the process
for converting a solid carbonaceous material comprises heating a solid
carbonaceous material in
the presence of at least one active source of cobalt for a time sufficient to
form a liquid product
from the solid carbonaceous material. In embodiments, the active source of
cobalt is provided to
the carbonaceous material is the form of a catalyst precursor that is
transformable into a catalyst
via chemical reaction with one or more reagents and/or via any other suitable
treatment. The
catalyst precursor may be oil soluble, oil dispersible, water soluble and/or
water dispersible. In
embodiments, the process comprises pretreating the solid carbonaceous material
at a
pretreatment temperature and in the presence of at least one active source of
cobalt; heating the
pretreated material in the presence of hydrogen to a conversion temperature
which is greater than
the pretreatment temperature; and reacting the heated material for a time
sufficient to form a
liquid product from the solid carbonaceous material.
[0040] Suitable catalyst precursors include:
a) cobalt metal;
b) cobalt containing inorganic compounds, such as the sulfates, nitrates,
carbonates,
sulfides, oxysulfides, oxides and hydrated oxides, ammonium salts and
heteropoly
acids of cobalt;
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c) salts of organic acids, such as acyclic and alicyclic aliphatic, carboxylic
acids
containing two or more carbon atoms (non-limiting examples include acetates,
oxylates, citrates);
d) cobalt-containing organometallic compounds including chelates such as 1,3-
diketones, ethylene diamine, ethylene diamine tetraacetic acid,,
phthalocyanines,
thiocarbamates, phosporothioates, and combinations or mixtures thereof (non-
limiting examples include cobalt alkyl dithiocarbamate, cobalt alkyl
phosphorodithioate); and/or,
e) cobalt salts of organic amines such as aliphatic amines, aromatic amines,,
quaternary ammonium compounds, or combinations or mixtures thereof, and
f) cobalt-containing minerals.
[0041] In embodiments, the process for converting a solid carbonaceous
material further
comprises heating the solid carbonaceous material in the presence of at least
one active source of
a second metal. In embodiments, the second metal is selected from the group
consisting of iron,
molybdenum, tungsten, nickel, cobalt, titanium and tin. In some such
embodiments, the active
source of the metal is provided to the carbonaceous material is the form of a
catalyst precursor
that is transformable into a catalyst via chemical reaction with one or more
reagents and/or via
any other suitable treatment. The catalyst precursor may be oil soluble, oil
dispersible, water
soluble and/or water dispersible.
[0042] In embodiments, the catalyst composition comprises for converting the
solid
carbonaceous material further comprises at least one active source of iron.
Suitable catalyst
precursors which provide the active iron source include:
a) iron metal;
b) iron containing inorganic compounds, such as the sulfates, nitrates,
carbonates,
sulfides, oxysulfides, oxides and hydrated oxides, ammonium salts and
heteropoly
acids of iron;
c) salts of organic acids, such as acyclic and alicyclic aliphatic, carboxylic
acids
containing two or more carbon atoms (non-limiting examples include acetates,
oxylates, citrates);
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d) iron-containing organometallic compounds including ferrocene, chelates such
as
1,3-diketones, ethylene diamine, ethylene diamine tetraacetic acid,,
phthalocyanines, thiocarbamates, phosphorothioates, and combinations or
mixtures thereof (non-limiting examples include iron alkyl dithiocarbamate,
iron
alkyl phosphorodithioate); and/or,
e) iron salts of organic amines such as aliphatic amines, aromatic amines,,
quaternary ammonium compounds, or combinations or mixtures thereof, and
f) iron-containing minerals.
[0043] The catalyst precursor can be formed in any suitable manner prior to
the
hydroconversion process. In one embodiment, for example, one or more catalyst
precursors are
formed by:
a) mixing a hydrocarbonaceous liquid (such as a liquefaction solvent) with an
active
source of at least one metal (such as a metal oxide, e.g., iron oxide, or
other
compound containing any suitable metal as discussed herein) to form a catalyst
precursor,
b) combining the catalyst precursor with a carbonaceous material;
c) optionally subjecting the mixture to pretreatment conditions (such as under
hydrogen pressure) in a manner such that one or more catalyst precursors form
in
or on the carbonaceous material; and
d) heating the mixture for a time sufficient to form a liquid product.
[0044] In embodiments, the catalyst precursors are formed by:
a) mixing a hydrocarbonaceous liquid (such as a liquefaction solvent) with at
least
one active source of cobalt and with at least one active source of a second
metal to
form a catalyst precursor;
b) combining the catalyst precursor with a carbonaceous material;
c) optionally subjecting the mixture to pretreatment conditions in a manner
such that
one or more catalyst precursors form in or on the carbonaceous material; and
d) heating the mixture for a time sufficient to form a liquid product
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[0045] In embodiments, the catalyst precursors are formed by
a) mixing a hydrocarbonaceous liquid with an active source of at least one
metal,
b) combining the mixture with a sulfiding agent (such as by passing hydrogen
sulfide through the mixture or adding elemental sulfur to the mixture) in a
manner
such that the sulfided metal-containing compound is dispersible,
c) combining the sulfided mixture with a carbonaceous material,
d) optionally subjecting the mixture to pretreatment conditions in a manner
such that
one or more catalyst precursors form in or on the carbonaceous material; and
e) heating the mixture for a time sufficient to form a liquid product.
[0046] In embodiments, the catalyst precursors are formed by
a) mixing a hydrocarbonaceous liquid with an active source of at least one
metal;
b) combining the catalyst precursor with a carbonaceous material;
c) combining the mixture with a sulfiding agent;
d) optionally subjecting the mixture to pretreatment conditions in a manner
such that
one or more catalyst precursors form in or on the carbonaceous material; and
e) heating the mixture for a time sufficient to form a liquid product.
[0047] In another embodiment, one or more catalyst precursors are formed by
a) mixing one or more metal containing compounds, a sulfiding agent, and
water, to
form a colloidal suspension,
b) combining the colloidal suspension with a hydrocarbonaceous liquid (such as
a
liquefaction solvent) to drive water out of the suspension,
c) combining the suspension with a carbonaceous material,
d) optionally subjecting the suspension to pretreatment conditions (such as
under
hydrogen pressure), in a manner such that one or more catalyst precursors form
in
or on the carbonaceous material; and
e) heating the mixture for a time sufficient to form a liquid product.
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[0048] In another embodiment, one or more catalyst precursors are by
a) sulfiding an ammonium containing Group VIB metal compound in an aqueous
phase with hydrogen sulfide, in a substantial absence of hydrocarbon oil, at a
temperature less than about 177 C, to form a presulfided product; and
b) separating ammonia from said presulfided product to form a sulfided
product, in a
manner such that one or more catalyst precursors form in or on the
carbonaceous
material.
[0049] In another embodiment, one or more catalyst precursors are formed by a
process
comprising:
a) mixing an active source of cobalt and an active source of the second metal
and
water, to form a colloidal suspension or solution;
b) combining the colloidal suspension or solution with a solid carbonaceous
material
at conditions sufficient to deposit at least a portion of the cobalt and a
portion of
the second metal onto [wherein depositing onto includes depositing onto the
surface of any fractures, pores, or other openings into the internal volume of
the
solid carbonaceous material] the solid carbonaceous material;
c) combining the solid carbonaceous material having the active sources of the
metals
deposited thereon with a hydrocarbonaceous liquid (such as a liquefaction
solvent); and
d) optionally subjecting the suspension to pretreatment conditions (such as
under
hydrogen pressure), in a manner such that one or more catalyst precursors form
in
or on the carbonaceous material; and
e) heating the mixture for a time sufficient to form a liquid product.
[0050] In some such embodiments, the process further comprises combining the
colloidal
suspension or solution and an active source of sulfur with the solid
carbonaceous material.
[0051] Any suitable amount of the catalytic materials can be used to
hydroconvert the
carbonaceous material in the context of the present invention. In one
embodiment, the mixture
ofcatalyst precursor, carbonaceous material, and hydrocarbonaceous liquid
comprises about
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25-10000 ppm (such as about 50-9000 ppm, about 100-8000 ppm, about 250-5000,
about 500-
3000 ppm, or even about 1000-2000 ppm) of one or more catalyst or catalyst
precursor by
weight, based on the total weight of the mixture. In embodiments, the metal
content of the
catalyst or catalyst precursor refers to added metal, and does not include
metal which is native to
the carbonaceous material or metal which is eroded from processing equipment.
[0052] The catalytic materials can be used in the context of the present
invention in any
suitable form, such as, but not limited to, particulate form, impregnated
within a carbonaceous
material, dispersed in the hydrogen donor solvent, and/or soluble in the
hydrogen donor solvent.
Additionally, the catalytic materials may be used in processes employing
fixed, moving, and
ebullated beds as well as slurry reactors.
[0053] The catalyst precursor(s) can be transformed into a catalyst by thermal
decomposition, such as prior to or during liquefaction, without the addition
of additional
reactants. In other embodiments, following pretreatment, one or more
additional reactants can be
added to the pretreated carbonaceous material mixture (such as prior to or
during the liquefaction
process), to transform the dispersed catalyst precursor into a catalyst. Any
suitable reactants can
be used in this regard, such as for example any suitable sulfiding or reducing
agents.
Sulfiding Agent Component
[0054] In embodiments, the catalyst composition further comprises at least one
active source
of sulfur. In those embodiments in which catalyst precursors are utilized, one
or more sulfur
compounds can be added subsequent to the pretreating step to activate the
catalyst precursor
to its corresponding sulfided active catalyst. The one or more sulfur
compounds can be
introduced at any point of the system, following pretreatment. In one
embodiment, one or
more sulfur compounds are introduced into the pretreatment zone following the
performance
of the pretreatment process and before the pretreatment composition is
delivered to the
liquefaction zone. In another embodiment, one or more sulfur compounds are
introduced
into the liquefaction zone.
[0055] In one embodiment, the catalyst is prepared using a sulfiding agent in
the form of a
solution which, under prevailing conditions, is decomposable into hydrogen
sulfide. Such a
sulfiding agent can be used in any suitable amount in preparing the catalyst,
such as in an amount
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in excess of the stoichiometric amount required to form the catalyst. In one
embodiment, the
sulfiding agent is present in a sulfur to cobalt mole ratio of at least 3 to
1. Additionally, any
suitable sulfiding agent (such as described above with respect to the catalyst
precursor) can be
used.
[0056] In one embodiment, the sulfiding agent is an aqueous ammonium sulfide.
Such a
sulfiding agent can be prepared in any suitable manner, such as from hydrogen
sulfide and
ammonia. This synthesized ammonium sulfide is readily soluble in water and can
easily be
stored in aqueous solution in tanks prior to use.
[0057] Suitable sulfiding agents include, for example, any sulfur compound
that is in a
readily releasable form, such as, for example, hydrogen sulfide, ammonium
sulfide,
dimethyldisulfide, ammonium sulfate, carbon disulfide, elemental sulfur, and
sulfur-containing
hydrocarbons. Elemental sulfur is preferred in some embodiments, because of
its low toxicity,
low cost, and ease of handling. Additional sulfiding agents include, for
example, ammonium
sulfide, ammonium polysulfide, ammonium thiosulfate, sodium thiosulfate,
thiourea, dimethyl
sulfide, tertiary butyl polysulfide, tertiary nonyl polysulfide, and mixtures
thereof. In another
embodiment, the sulfiding agent is selected from the group consisting of
alkali- and/or alkaline
earth metal sulfides, alkali-and/or alkaline earth metal hydrogen sulfides,
and mixtures thereof.
[0058] The sulfiding agent can be added in any suitable form. In one
embodiment, elemental
sulfur is added to the carbonaceous material mixture in the form of a sublimed
powder or as a
concentrated dispersion (such as a commercial flower of sulfur). Allotropic
forms of elemental
sulfur, such as orthorhomic and monoclinic sulfur, are also suitable for use
herein. In one
embodiment, the one or more sulfur compounds are in the form of a sublimed
powder (flowers
of sulfur), a molten sulfur, a sulfur vapor, or a combination or mixture
thereof.
[0059] The sulfiding agent can be used in any suitable concentration. In one
embodiment, a
concentration of sulfur is introduced such that the atomic ratio of sulfur to
metal in the catalyst
precursor is in the range of from about 1: 1 to about 10: 1, such as from
about 2:1 to about 8:1,
about 2:1 to about 7:1, about 2:1 to about 6:1, about 2:1 to about 9:1, about
2:1 to about 8:1,
about 2:1 to 7:1, about 3:1 to about 9:1, about 3:1 to about 8:1, about 3:1 to
about 7:1 or even
about 3:1 to about 6:1.
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Catalyst
[0060] The catalyst contains an active catalytic component in elemental or
compound form.
Examples include finely divided particles, salts, or compounds of the
transition elements,
particularly Groups IV-B, V-B, VI-B or Group VIII of the Periodic Table of the
Elements, as
shown in Handbook of Chemistry and Physics, 45th Edition, Chemical Rubber
Company, 1964.
In embodiments, alkaline earth elements, such as magnesium, may be included.
In
embodiments, lanthanoid (or lanthanide, or sometimes referred to as rare
earths) elements refer
to the fifteen elements in the Periodic Table with atomic numbers 57 through
71, may be
included.
[0061] The catalyst includes any cobalt-containing material that is suitable
for use in a
hydroconversion process for a carbonaceous material (such as coal) when
subjected to and/or
when experiencing suitable catalyzing reaction conditions. The catalyst
further comprises any
suitable metal, such as, for example, a metal selected from the group
consisting of Group IIB
metals, Group IIIB metals, Group IVA metals, Group IVB metals, Group VB
metals, Group VIB
metals, Group VIIB metals, Group VIII metals, or a combination or mixture
thereof, such as in
combination with one or more of oxygen, sulfur, nitrogen, and phosphorous. In
embodiments, a
second metal is selected from the group consisting of Fe, Mo, W, Co, Ni, Cu,
Ti and Sri.
[0062] In embodiments, the sulfided cobalt-containing catalyst can be CoS-FeS,
CoS-MoS2,
CoS-WS2, CoS-NiS, CoS-CuS, CoS-TiS2, CoS-SnS and any of their combinations and
mixtures, for example CoS-MoSz-TiS2. In the catalyst system, Co can be the
rich phase or serve
as dopant.
[0063] The amount of cobalt that is provided as a catalyst component of the
catalyst is
sufficient to catalyze the conversion of the solid carbonaceous material to
liquid hydrocarbons;
likewise, the amount of the second metal that is provided as a catalyst
component is sufficient to
catalyze the conversion of the solid carbonaceous material. In embodiments,
cobalt is present in
the catalyst in an amount of 10 ppm to 10 wt%, based on dry, ash free coal. In
some such
embodiments, cobalt is present in the catalyst in the amount of 0.1 wt% to 5
wt%. An exemplary
quantity of cobalt, as metal, present in the catalyst is in the amount of 0.5
wt% to 2.5 wt%.
[0064] In embodiments, the second metal in the catalyst is present in an
amount of 10 ppm to
wt%, based on dry, ash free coal. In some such embodiments, the second metal
is present in
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the catalyst in the amount of 0.1 wt% to 5 wt%. An exemplary quantity of the
second metal,
expressed as a metal, is in the amount of 0.5 wt% to 2.5 wt%. In some such
embodiments, the
second metal in the catalyst is iron. As such, iron is present in the catalyst
in an amount of 10
ppm to 10 wt%, based on dry, ash free coal. In some such embodiments, iron is
present in the
catalyst in the amount of 0.1 wt% to 5 wt%. An exemplary quantity of iron, as
metal, present in
the catalyst is in the amount of 0.5 wt% to 2.5 wt%. In embodiments, the
molecular ratio
between Co and other metals in combination can be between 0.1 to 1 and 10 to
1.
[0065] In embodiments, the catalytic materials are added as finely divided
particulate metal
solids, their oxides, sulfides, etc., e.g., FeSX ; waste fines from metal
refining processes, e.g.,
iron, molybdenum, and nickel; crushed spent catalysts, e.g., spent fluid
catalytic cracking fines,
hydroprocessing fines, recovered coal ash, and solid coal liquefaction
residues. In embodiments,
the cobalt and the second metal are added as separate particulate solids. In
other embodiments,
the catalyst composition comprises particles that are richer in cobalt and
leaner in the amount of
the second metal, or particles that are richer in the second metal and leaner
in the amount of
cobalt. In another embodiment, cobalt and other metals can form bi-metallic
compounds as a
catalyst precursor rather than being added to the feed separately. As an
example, Co,,Fe(i_X)OOH
is prepared by titrating a FeSO4 and CoSO4 mixture solution with NH3H2O,
followed by
oxidizing in flowing air at elevated temperatures. Co,,Fe(i_X)OOH can be pre-
sulfided to
CoxFe(i_X)S before mixing with the feed.
[0066] In embodiments, at least a portion of the catalyst particles are
attached to, adsorbed
onto, absorbed by, supported on or intimately associated with at least a
portion of the solid
carbonaceous material during conversion of the carbonaceous material. In
embodiments, at least
a portion of the catalyst, or catalyst precursor, is deposited on the solid
carbonaceous material
before or during pretreatment, using an aqueous or an organic liquid to carry
the catalyst or
catalyst precursor to the carbonaceous material. In embodiments, at least a
portion of the
catalyst, or catalyst precursor, is deposited on the solid carbonaceous
material during the step of
heating the material to conversion temperature, or during the conversion
process.
[0067] In an embodiment, the catalyst is prepared using a catalyst precursor
comprising a
metal that comprises a water-soluble cobalt component, such as cobalt nitrate,
cobalt sulfate,
cobalt acetate, cobalt chloride, or a mixture thereof. In another embodiment,
the catalyst is
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prepared using a catalyst precursor comprising an metal that comprises a
cobalt compound which
is at least partly in the solid state, e.g., a water-insoluble cobalt compound
such as cobalt
carbonate, cobalt hydroxide, cobalt phosphate, cobalt phosphite, cobalt
formate, cobalt sulfide,
cobalt molybdate, cobalt tungstate, cobalt oxide, cobalt alloys such as cobalt-
molybdenum or
cobalt-iron alloys, or a mixture thereof. In another embodiment, the catalyst
is prepared using a
catalyst precursor comprising a metal that comprises a water-soluble cobalt
sulfate solution
which optionally also includes a second promoter metal compound, such as an
iron component in
the solute state selected from iron acetate, chloride, formate, nitrate,
sulfate, or a mixture thereof.
In one embodiment, the catalyst is prepared using a catalyst precursor that
comprises a metal
comprising a cobalt sulfate aqueous solution.
[0068] In embodiments, at least a portion of the catalyst particles is
dispersed as particles
separate from the carbonaceous material during the pretreatment step, during
the step of heating
the carbonaceous material to a conversion temperature, or during the
conversion process.
[0069] In embodiments, the catalyst is dissolved or otherwise suspended in the
liquid phase,
e.g., as fine particles, emulsified droplets, etc. The dispersed catalyst can
be added to the coal
before contact with the hydrocarbonaceous liquid, it can be added to the
hydrocarbonaceous
liquid before contact with the coal, or it can be added to the coal-liquid
slurry. In some such
embodiments, the dispersed catalyst is added in the form of an oil/aqueous
solution emulsion of a
water-soluble compound of the catalyst hydrogenation component. The water
soluble salt of the
catalytic metal can be essentially any water soluble salt of metal catalysts.
The nitrate or acetate
may be the most convenient form of some metals. Non- limiting active sources
of cobalt include
cobalt nitrate and cobalt acetate. Non-limiting sources of iron are iron
nitrate or iron acetate.
In embodiments, organometallic complexes such as ferrocene are also employed
as sources of
iron. For molybdenum, tungsten or vanadium, a complex salt such as an alkali
metal or
ammonium molybdate, tungstate, or vanadate may be preferable. Mixtures of two
or more metal
salts can also be used. Particular salts are ammonium heptamolybdate
tetrahydrate
[(NH4)6Mo7O24=4H20], nickel dinitrate hexahydrate [Ni(NO3)2.6H20], and sodium
tungstate
dihydrate [NaWO4=2H20]. Any convenient process can be used to emulsify the
salt solution in
the hydrocarbon medium. The dispersed dissolution catalyst can also be an oil-
soluble
compound containing a catalytic metal, for example, ferrocene, phosphomolybdic
acid,
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naphthenates of molybdenum, chromium, and vanadium, etc. Suitable oil-soluble
compounds
can be converted to dissolution catalysts in situ.
[0070] In embodiments, the particulate catalyst comprises cobalt and a second
metal as an
unsupported catalyst, meaning that the components of the catalyst are not
associated with or
supported on inorganic carriers such as silica, alumina, magnesia, carbon,
etc. In other
embodiments, at least a portion of the metal components of the catalyst
composition are
associated with or supported on at least one inorganic carrier or binder. The
binder material can
comprise any materials that are conventionally utilized as binders in
hydroprocessing catalysts.
Suitable binder material includes, for example, silica, alumina such as
(pseudo) boehmite, silica-
alumina compounds, gibbsite, titania, zirconia, cationic clays or anionic
clays such as saponite,
bentonite, kaoline, sepiolite or hydrotalcite, or combinations or mixtures
thereof. In one
embodiment, one or more binder materials are selected from silica, colloidal
silica doped with
aluminum, silica-alumina, alumina, titanium, zirconia, or a mixture thereof.
In another
embodiment, the binder material comprises a refractory oxide material having
at least 50 wt.% of
titania, on an oxide basis. Any suitable alumina binder can be used in the
catalyst preparation
process. In one embodiment, the alumina binder has a surface area ranging from
100 to 400
m2/g, with a pore volume ranging from 0.5 to 1.5 m/g measured by nitrogen
adsorption.
Similarly, any suitable titania binder can be used in the catalyst preparation
process. In one
embodiment, the titania of the binder has an average particle size of less
than 50 microns (such
as less than about 5 microns) and/or greater than 0.005 microns. In another
embodiment, the
titania of the binder has a BET surface area of 10 to 700 m2/g.
[0071] In some embodiments, the binder material is a binder that has undergone
peptization.
In another embodiment, precursors of the binder materials are used in the
preparation of the
catalyst, wherein the precursor is converted into an effective or functional
binder during the
catalyst preparation process. Suitable binder material precursors, in this
regard, include alkali
metal aluminates (to obtain an alumina binder), water glass (to obtain a
silica binder), a mixture
of alkali metal aluminates and water glass (to obtain a silica alumina
binder), a mixture of
sources of a di-, tri-, and/or tetravalent metal such as a mixture of water-
soluble salts of
magnesium, aluminum and/or silicon (to prepare a cationic clay and/or anionic
clay),
chlorohydrol, aluminum sulfate, or a combination or mixture thereof. In the
case of supported
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catalysts, the weight ratio of metal components (ie. cobalt and the second
metal components) to
support components is in the range of 10:1 to 1:10.
[0072] In embodiments, at least a portion of the catalyst particles comprises
additional
components, such as catalyst promoters. Such promoters are selected from the
group consisting
of a non-noble Group VIII metal (such as Ni, Co, Fe), a Group VIB metal (such
as Cr), a Group
IVB metal (such as Ti), a Group IIB metal (such as Zn), a Group IB metal (such
as Cu) and
combinations and mixtures thereof.
[0073] During the conversion process, during which time the solid carbonaceous
material
contacted with the active sources of the catalyst composition and optionally
pretreated at a
temperature in the range of 100-350 C and then heated to conversion
temperature for conversion
of the carbonaceous material to liquid materials, the active sources of the
catalyst are converted
to their active forms. The conversion process is facilitated by the addition
of sulfur to the
catalyst.
[0074] Properly sulfided cobalt species such as CoS and cobalt alkyl
dithiocarbamate, cobalt
alkyl phosphorodithioate and sulfided metallic species such as MoS2, ammonium
tetrathiomolybdate, NiS, ZnS, WS2, SnS, TiS2, CuS, FeS, Fe2S3, moly alkyl
dithiocarbamate,
iron alkyl dithiocarbamate, titanium alkyl dithiocarbamate, iron alkyl
phosphorodithioate, can be
used directly as catalyst precursors without pre-sulfiding. For a non-sulfided
metal precursor,
including cobalt-based cobalt metal, cobalt oxide, cobalt acetate, cobalt
nitrate, cobalt sulfate and
other cobalt salts, cobalt minerals and cobalt organo compounds; iron-based
iron metal, iron
oxide, ferrous sulfate, ferric nitrate and other iron salts, red mud and other
iron minerals,
ferrocene and other iron organo compounds, molybdenum-based, tungsten-based,
nickel-based,
cobalt-based, titanium-based, copper-based or tin-based metal, oxide, salts,
minerals and organo
compounds, etc., elemental sulfur or other sulfiding agent such as DMDS, H2S,
CS2, and
(NH4)2S can be used to pre-sulfide the catalyst precursor to form metal
sulfides or the sulfiding
agent is added directly during the hydroconversion run to properly sulfide the
catalyst at the
atomic ration of (S/(Co+other metal))=1/1 to 10/1. Alternatively, one or more
sulfur compounds
can be added during, or subsequent to the pretreating step to activate the
catalyst or catalyst
precursor to its corresponding sulfided active catalyst. The one or more
sulfur compounds can
be introduced at any point of the system. Any suitable amount of the one or
more sulfur
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compounds can be used in the context of the present invention. In one
embodiment, one or more
sulfur compounds are introduced into the pretreatment zone following the
performance of the
pretreatment process and before the pretreatment composition is delivered to
the conversion
zone. In another embodiment, one or more sulfur compounds are introduced into
the conversion
(i.e. liquefaction) zone. In one embodiment, a concentration of sulfur is
introduced such that the
atomic ration of sulfur to metal in the catalyst is from about 2:1 to about
10:1.
[0075] Any suitable sulfur compound may be used in this regard. In one
embodiment, the
sulfiding agent is hydrogen sulfide (H2S). In one embodiment, the sulfiding
agent is in the form
of a solution that under prevailing conditions is decomposable into hydrogen
sulfide, present in
an amount in excess of the stoichiometric amount required to form the
catalyst. In another
embodiment, the sulfiding agent is selected from the group of ammonium
sulfide, ammonium
polysulfide ((NH4)2SX), ammonium thiosulfate ((NH4)2S203), sodium thiosulfate
(Na2S2O3),
thiourea (CSN2H4), carbon disulfide (CS2), dimethyl disulfide (DMDS), dimethyl
sulfide (DMS),
tertiarybutyl polysulfide (PSTB), tertiarynonyl polysulfide (PSTN), and
mixtures thereof. In
another embodiment, the sulfiding agent is selected from elemental sulfur and
sulfur containing
hydrocarbons. In another embodiment, the sulfiding agent is selected from
alkali- and/or
alkaline earth metal sulfides, alkali- and/or alkaline earth metal hydrogen
sulfides, and mixtures
thereof. The use of sulfiding agents containing alkali- and/or alkaline earth
metals may require
an additional separation process step to remove the alkali- and/or alkaline
earth metals from the
spent catalyst.
[0076] Elemental sulfur may be added to the pretreatment composition in the
form of a
sublimed powder or as a concentrated dispersion (such as a commercial flower
of sulfur).
Allotropic forms of elemental sulfur, such as orthorhombic and monoclinic
sulfur, as also
suitable for use herein. In one embodiment, the one or more sulfur compounds
are in the form of
a sublimed power (flowers of sulfur), a molten sulfur, a sulfur vapor, or a
combination or
mixture thereof.
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Other Additives
[00771 Any additional additives can be utilized during or subsequent to the
pretreating
step, such as, to enhance or facilitate the pretreatment process (such as by
enhancing,
facilitating, and/or enhancing dispersion of the catalyst or catalyst
precursor into the
carbonaceous material) and/or to enhance or facilitate hydroconversion of the
pretreated
carbonaceous material.
[00781 Any suitable surfactant can be utilized in the context of the
invention, such as to
improve dispersion, metal surface area, morphology, and/or other
characteristics of the
catalyst or catalyst precursor. Suitable surfactants include, for example, any
anionic
surfactant, zwitterionic surfactant, amphoteric surfactant, nonionic
surfactant, cationic
surfactant, or combination or mixture thereof. Suitable non-ionic surfactants
include, for
example, polyoxyethylenesorbitan monolaurate, polyoxyethylenated alkyphenols,
polyoxyethylenated alkyphenol ethoxylates, and the like. Suitable cationic
surfactants
include, for example, quarternary long-chain organic amine salts, quarternary
polyethoxylated long-chain organic amine salts, and the like, such as water-
soluble cationic
amines (e.g., cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium
chloride,
dodecyl trimethyl ammonium amine, nonyl trimethyl ammonium chloride, dodecyl
phenol
quaternary amine soaps, or combinations or mixtures thereof). Suitable anionic
surfactants
such as sodium succinate compounds, include, for example, dioctyl sodium
sulfosuccinate or
sodium bis(2-ethylhexyl)sulfosuccinate). Suitable surfactants can also
comprise solvent
materials having a high surface tension property, such as ethylene carbonate;
benzophenone;
benzyl cyanide; nitrobenzene; 2-phenylethanol; 1,3-propanediol; 1,4-
butanediol; 1,5-
pentanediol; diethyleneglycol; triethyleneglycol; glycerol; dimethyl
sulfoxide; N-methyl
formamide; N-methyl pyrrolidone; and combinations and mixtures thereof.
Suitable
surfactants also include those surfactants having a high surface tension, such
as N-methyl
pyrrolidone. Other examples of surfactants include acetonitrile, acetone,
ethyl acetate,
hexane, diethyl ether, methanol, ethanol, acetyl acetone, diethylcarbonate,
chloroform,
methylene chloride, diethyl ketone, and combination and mixtures thereof. In
another
embodiment, the surfactant comprises a nitrogen- or phosphorous-containing
organic
additive having a carbosulfide phase with enhanced catalytic activities. The
amount of the
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N-containing / P-containing organic additive to be added generally depends on
the desired
activity of the final catalyst composition.
[00791 In another embodiment, the surfactant is an ammonium or phosphonium of
the
formula R1R2R3R4Q+, wherein Q is nitrogen or phosphorous, wherein at least one
of R1, R2,
R3, R4 is an aryl or alkyl group having 8-36 carbon atoms (e.g., C10H21,
C16H33, C18H37, or a
combination thereof), and wherein the remainder of R1, R2, R3, R4 is selected
from the group
consisting of hydrogen, an alkyl group having 1-5 carbon atoms, or a
combination thereof.
Suitable such examples of surfactants include: cetyltrimethylammonium,
cetyltrimethylphosphonium, octadecyltrimethylphosphonium, cetylpyridinium,
myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium,
dimethyldidbdecylammonium, or a combination or mixture thereof. The compound
from
which the above ammonium or phosphonium ion is derived may be, for example, a
hydroxide, halide, silicate, or combination or mixture thereof.
[00801 In one embodiment, the surfactant comprises a nitrogen-containing
organic
additive, such as aromatic amines, a cyclic aliphatic amines, a polycyclic
aliphatic amines, or
a combination or mixture thereof. In another embodiment, the surfactant
comprises a
nitrogen-containing organic additive is selected from compounds containing at
least one
primary, secondary, and/or tertiary amine group (such as hexamethylenediamine,
monoethanolamine, diethanolamine, triethanolamine, N,N-dimethyl-N'-
ethylethylenediamine, or a combination or mixture thereof); amino alcohols
(such as, for
example, 2 (2-amino ethyl amino)ethanol, 2 (2-aminoethoxy, or a combination or
mixture
thereof) ethanol, 2-amino-l-butanol, 4-amino-l-butanol, 2,2-
diethoxyethylamine, 4,4-
diethoxybutylamine, 6-amino-l-hexanol, 2-amino-1,3-propanediol, 3-amino-1,2-
propanediol, 3-amino-l-propanol, or a combination or mixture thereof); and
amino alkoxy-
silanes (such as, for example, 3-glycidoxypropyl) trimethoxysilane, 3-(2-
aminoethylamino)
propyltrimethoxysilane, 3-aminopropyl)trimethoxy-silane, or a combination or
mixture
thereof).
[00811 In another embodiment, the surfactant is an organic carboxylic acid
surfactant or
stabilizer. In one embodiment, for example, the surfactant is citric acid. In
another
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embodiment, the surfactant is pentadecanoic acid, decanoic acid, or other
similar long chain
acids. In yet another embodiment, the surfactant is alginic acid.
[0082] The optional additives can be utilized at any suitable point prior to
or after the
pretreatment process and/or hydroconversion process. In one embodiment, one or
more
additives are combined with one or more of the carbonaceous material,
hydrocarbonaceous
liquid, and one or more catalysts or catalyst precursors prior to
pretreatment. In another
embodiment, the additive(s) are combined with the carbonaceous material,
hydrocarbonaceous liquid, and catalysts or catalyst precursors during the
pretreatment
process. In another embodiment, the additive(s) are combined with the
pretreated
carbonaceous material following pretreatment and before hydroconversion. In
yet another
embodiment, the additive(s) are combined with the pretreated carbonaceous
material
following during hydroconversion.
[0083] The additive(s) can be utilized in any suitable concentration. In one
embodiment,
for example, the additive(s) are utilized in a concentration of about 0.001 to
5 wt.% of the
total pretreatment mixture. In another embodiment, the additive(s) are
utilized in a
concentration of about 0.005 to 3 wt.% of the total pretreatment mixture. In
another
embodiment, the additive(s) are utilized in a concentration of about 0.01 to 2
wt.% of the
total pretreatment mixture. If the additive(s) are solely added to the
hydroconversion
feedstock, the amount to be added ranges from 0.001 to 0.05 wt. % (such as
about 0.005-0.01
wt.%) of the feed, or in any suitable concentration, such as described, for
example, in Acta
Petrolei Sinica, Vol. 19, Issue 4, pp. 36-44, ISSN 10018719 and in Khimiya I
Tekhnologiya
Topilv I Masel, Issue 3, Year 1997, pp. 20-21, ISSN 00231169, the contents of
which are
incorporated herein by reference in their entirety.
Mixing
[0084] Any suitable process or system can be used to combine and/or mix the
carbonaceous
material with the hydrocarbonaceous liquid and the catalysts or catalyst
precursors. In some
embodiments, any suitable mixer is used to simultaneously, successively,
and/or sequentially
mix the carbonaceous material, hydrocarbonaceous liquid, and the catalyst or
catalyst precursors
in a manner suitable to form a homogenous or heterogeneous mixture (or
slurry), as desired. In
other embodiments, a mixer is utilized in conjunction with any suitable
grinder (such as a
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hammer mill, a ball mill, a rod mill, or a combination thereof, or the like),
such that at least a
portion of the carbonaceous material is ground, optionally in the presence of
the
hydrocarbonaceous liquid and/or the one or more catalysts or catalyst
precursors and mixed to
form a homogenous or heterogeneous slurry, as desired. In some embodiments,
the mixer and/or
grinder comprises a gas delivery system for providing an inert or a reducing
atmosphere (such as,
for example, hydrogen, nitrogen, helium, argon, syn-gas, or any combination or
mixture thereof)
during mixing and/or grinding of the carbonaceous material, the
hydrocarbonaceous liquid,
and/or the catalyst or catalyst precursors. In some embodiments, the mixer
and/or grinder are
situated upstream of the pretreatment system. In other embodiments, the mixer
and/or grinder
form a portion of the pretreatment system. In embodiments, the catalyst
precursor used in this
process can be mixed directly to ground coal or other carbonaceous materials
before feeding into
the reactor, or added into coal during coal solvent grinding. The catalyst can
be dissolved and
sprayed onto coal or impregnated onto coal by incipient wetness using
methanol/ethanol or water
as dissolving/wetting agent. The catalyst can also be dispersed or soluble in
the solvent that is
then mixed with coal.
[0085] An embodiment of the invention is illustrated in Fig. 1. Coal feed 3,
with at least 50
wt% of the coal particles having a mean particle diameter of less than 0.5
inches, is combined
with catalytic material 5, comprising an active source of cobalt and an active
source of iron in a
molar ratio of cobalt to iron within the range of between 0.1/1 to 10/1, and
the combination 1 is
passed to preheat furnace 20 for heating to a reaction temperature in the
range of between 350 C
and 500 C. The heated combination of coal and the catalytic material 23
leaving the preheat
furnace is then passed to reaction zone 30 for conversion of at least a
portion of the coal to liquid
product 33.
[0086] Considering an exemplary process of the invention illustrated in Fig.
2, coal feed 103,
with at least 50 wt% of the coal particles having a mean particle diameter of
less than 0.5 inches,
is combined with catalytic material 105, comprising an active source of cobalt
and an active
source of iron in the molar ratio of cobalt to iron within the range of
between 0.1/1 to 10/1, and
the combination 101 is passed to pretreatment zone 110 for maintaining the
combination at a
pretreatment temperature within the range of 100-350 C and for a time of
between 5 and 600
minutes. Following pretreatment, the combination 113 is passed to preheat
furnace 120 for
heating to a reaction temperature in the range of between 350 C and 500 C. The
heated
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combination of coal and the catalytic material 123 leaving the preheat furnace
is then passed to
reaction zone 130 for conversion of at least a portion of the coal to liquid
product 133.
[0087] Considering an exemplary process of the invention illustrated in Fig.
3, coal feed 203,
with at least 80 wt% of the coal particles having a mean particle diameter in
the range of 50
microns to 500 microns, is passed to pretreatment zone 210. In a particular
exemplary process,
coal is supplied to pretreatment zone as a powder. In another exemplary
process, coal is supplied
as a slurry in a hydrocarbonaceous liquid, such as a coal derived distillate
fraction.
[0088] A catalytic material 205, comprising an active source of cobalt and an
active source
of iron in the molar ratio of cobalt to iron within the range of between 3/1
and 1/3, is combined
with the coal particles in the pretreatment zone. In an embodiment, the cobalt
is supplied to the
pretreatment zone as an aqueous solution or slurry of a cobalt salt such as
cobalt nitrate, cobalt
chloride, cobalt sulfate, cobalt acetate, cobalt sulfide, cobalt oxide or
cobalt carbonate. Iron is
supplied to the pretreatment zone as an aqueous solution or slurry of an iron
salt such as iron
nitrate, iron chloride, iron sulfate, iron acetate, iron sulfide, iron oxide
or iron carbonate. In
another embodiment, cobalt and iron are added as organometallic compounds
contained in a
liquid such as a coal derived distillate fraction. Exemplary organometallic
compounds include
cobalt alkyl dithiocarbamate and ferrocene. An active source of sulfur 207 is
added to the
pretreatment zone to supply a sulfur to catalytic metal atomic ratio within
the range of between
2/1 and 6/1. Hydrogen or a hydrogen containing gas 209 is further supplied to
the pretreatment
zone to maintain a pressure within the pretreatment zone within a range of
between atmospheric
pressure and 500 psig. In another embodiment, hydrogen or a hydrogen
containing gas is
supplied to the pretreatment zone to maintain a pressure within the
pretreatment zone within a
range of between 500 psig and 3500 psig. The materials in the pretreatment
zone are maintained
at a pretreatment temperature within the range of 180-220 C and for a time of
between 5 and 600
minutes. Following pretreatment, the combination 213 is passed to preheat
furnace 220 for
heating to a reaction temperature in the range of between 350 C and 500 C. The
heated
combination of coal and the catalytic material 223 leaving the preheat furnace
is then passed to
reaction zone 230 for conversion of at least a portion of the coal to liquid
product 233.
[0089] Considering an exemplary process of the invention illustrated in Fig.
4, coal feed 303,
with at least 50 wt% of the coal particles having a mean particle diameter of
less than 0.5 inches
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is passed to pretreatment zone 310. A catalytic material 307, comprising an
active source of
cobalt and a catalytic material comprising an active source of iron 309 in the
molar ratio of
cobalt to iron within the range of between 0.1/1 to 10/1, are combined with
the coal particles in
the pretreatment zone, and the combination is maintained at a pretreatment
temperature within
the range of 100-350 C and for a time of between 5 and 600 minutes. Following
pretreatment,
the combination 313 is passed to preheat furnace 320 for heating to a reaction
temperature in the
range of between 350 C and 500 C. The heated combination of coal and the
catalytic material
323 leaving the preheat furnace is then passed to reaction zone 330 for
conversion of at least a
portion of the coal to liquid product 333.
Hydroconversion
[0090] The carbonaceous material is subjected to any suitable hydroconversion
and/or
liquefaction conditions to produce a product-enriched hydrocarbonaceous
material comprising
any desired liquid and/or gaseous products. The carbonaceous material (such as
coal) is
introduced into at least one hydroconversion zone wherein the pretreated
carbonaceous material
encounters suitable temperature, pressure, and additives (such as sulfur-
containing compounds)
to at least partially or substantially activate the catalyst or catalyst
precursor of the pretreated
carbonaceous material, and generate liquid and/or gaseous products. In one
embodiment, for
example, greater than about 50 wt.%, such as about 55 wt.%, about 60 wt.%,
about 65 wt.%,
about 70 wt.%, about 75 wt.%, about 80 wt.%, about 85 wt.%, about 90 wt.%,
about 95 wt.%,
about 96 wt.%, about 97 wt.%, about 98 wt.%, or even about 99 wt.% of the
catalyst or catalyst
precursor of the pretreated carbonaceous material becomes active catalyst,
such that it possesses
and/or exhibits hydroconverting activity.
[0091] Suitable hydroconverting temperatures include, but are not limited to,
temperatures
greater than about 350 C, such as greater than about 375 C, about 400 C, about
425 C, about
450 C, about 475 C, about 500 C. In some such embodiments, the step of
hydroconverting the
heated material is conducted at a temperature in the range of between 350 C
and 500 C. In
some such embodiments, the heated material is reacted in the hydroconversion
step for a time of
at least 10 minutes.
[0092] Suitable hydroconverting pressures include, but are not limited to,
within the range of
300-5000 psig (such as within the range of about 300-4800 psig, about 300-4600
psig, about
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300-4400 psig, about 300-4200 psig, about 400-4000 psig, about 500-3500 psig,
1000-3000 psig,
1200-2800 psig, 1400-2600 psig, or even about 1500-2600 psig) of any suitable
gas such as a
hydrogen containing gas (such as a hydrogen/methane mixture, or a
hydrogen/carbon
dioxide/water mixture) atmosphere and/or a syn-gas atmosphere. In one
embodiment, in this
regard, the pretreated carbonaceous material is suitable for low or lower
pressure
hydroconversion (such as a hydroconversion pressure less than about 2000 psig,
such as less than
about 1800 psig, or even less than about 1600 psig). Specifically, for
example, hydroconversion
of the pretreated carbonaceous material can yield at least about 10% higher
(such as at least
about 20%, about 40%, about 60%, about 80%, about 100%, about 150%, about
200%, about
300%, or even at least about 400% higher liquid product yield at a
hydroconversion pressure less
than about 2000 psig (such as less than about 1800 psig, or even less than
about 1600 psig) than
the same carbonaceous material that has not been pretreated. In another
embodiment,
hydroconversion of the pretreated carbonaceous material consumes about 10%
less (such as
about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%,
about 90%,
or even about 100% less) hydrogen, as compared to the same carbonaceous
material that has not
been pretreated.
[0093] In embodiments, the hydroconversion of the solid carbonaceous material
is
accomplished by heating the solid carbonaceous material for a time sufficient
to form a liquid
product. In some such embodiments, the solid carbonaceous material is heating
in the presence
of at least one active source of cobalt and at least one active source of a
second metal. In some
such embodiments, the solid carbonaceous material is heated at a reaction
temperature of greater
than 350 C and at a pressure in the range of 300 to 5000 psig. In some such
embodiments, the
solid carbonaceous material is heated at a reaction temperature in the range
of between 350 C
and 500 C. In some embodiments, the solid carbonaceous material is heated for
a time within
the range of 5 minutes to 600 minutes.
[0094] In one embodiment, hydroconversion and/or liquefaction of the
carbonaceous
material occurs in a single reactor. In another embodiment, hydroconversion
and/or liquefaction
of the carbonaceous material occurs in two or more (such as a plurality) of
zones or reactors for
hydroconversion which may be arranged in any suitable manner (such as in
parallel, or in series
such that, for example, the temperature in each reactor in series is
progressively higher and/or
there is a commensurate increase in the hydrogen partial pressure in each
downstream reactor).
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Preferably, hydroconversion and/or liquefaction of the pretreated carbonaceous
material occurs
in a reactor or zone that is separate and/or distinct from the pretreatment
reactor or zone.
[0095] In one embodiment, hydroconversion and/or liquefaction of the
carbonaceous
material produces a liquid yield greater than about 50%, about 55%, about 60%,
about 65%,
about 70%, about 75%, about 80%, about 85%, about 87%, about 90%, about 95%,
or even
greater than about 99%. In an embodiment, pretreatment of the carbonaceous
material results in a
liquid yield that is at least about 10% higher (such as at least about 15%,
about 20%, about 25%,
about 30%, about 35%, or even at least about 40% higher) than the liquid
product yield of a
similar carbonaceous material that is not pretreated prior to hydroconversion.
In another
embodiment, hydroconversion and/or liquefaction of the pretreated carbonaceous
material
produces a total conversion (such as of coal) greater than about 80%, about
85%, about 90%,
about 95%, or even 99%.
[0096] In some embodiments, pretreatment of the carbonaceous material results
in a total
conversion (such as of coal) that is at least about 5% higher (such as at
least about 10%, about
12%, about 14%, about 16%, about 18%, or even at least about 20% higher) than
the conversion
of a similar carbonaceous material that is not pretreated prior to
hydroconversion. In other
embodiments, hydroconversion and/or liquefaction of the pretreated
carbonaceous material
produces less than about 10% (such as less than about 8%, about 6%, about 4%,
about 3%, about
2%, or even less than about 1%) of CI-C3 gases.
Separation of Hydroconversion Products
[0097] The effluent from the hydroconversion zone can be fed into any suitable
one or more
separation zones. In one embodiment, the effluent is fed into a first
separation zone wherein
lighter products such as gases, naptha, and distillate are removed via
overhead lines. Such a first
separation zone can be run at a substantially atmospheric pressure. A bottoms,
or high boiling,
fraction of the effluent from the first separation zone can optionally be
recycled to the
hydroconversion reaction zone. All or some of the remaining effluent of the
first separation zone
can be passed to a second separation zone wherein it is fractionated into a
gas oil fraction and a
bottoms fraction. The bottoms fraction of the second separation zone can be
passed to a third
separation zone. A portion of the gas oil can be recycled to the
hydroconversion zone. In this
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regard, any suitable high pressure, medium pressure, and low pressure
separators can be used in
the context of the present invention.
Recovery of Catalyst or Catalyst Precursor
[0098] The one or more separation systems or zones can be followed by one or
more catalyst
and/or metal recovery systems or zones in which at least a portion (such as
one or more metals)
of the catalyst and/or catalyst precursor is recovered from one or more
portions or fractions of
the hydroconverted carbonaceous material. In one embodiment, metal from a
metal-containing
catalyst and/or metal-containing catalyst precursor is recovered in the
recovery system from a
solids fraction (such as a residual solids fraction) of the hydroconverted
carbonaceous material
that was separated and/or collected in the separation system (and which may
include ash).
[0099] The recovery system can be operated at any suitable temperature, such
as at a
temperature of about 1200-1900 C, such as about 1300-1800 C, or even 1400-1700
C. In one
embodiment, the recovery system provides an atmosphere of air that is suitable
to cause spent
catalysts (such as molybdenum sulfides) to be oxidized and sublimated to MoO3,
in the case
where the metal is molybdenum, such as described in U.S. Pat. App. Ser. No.
60/015,096, filed
December 19, 2007, the contents of which are incorporated by reference in
their entirety. The
treated spent catalyst, catalyst precursor, and/or recovered metal can be
collected and passed
from the catalyst recovery zone to a catalyst or catalyst precursor
preparation zone.
Catalyst or Catalyst Precursor Preparation
[0100] The one or more recovery systems can be followed by one or more
catalyst or catalyst
precursor preparation systems, in which at least a portion of the catalyst or
catalyst precursor
(such as metal of the catalyst precursor) recovered in the recovery system is
reacted to form a
catalyst or catalyst precursor (such as the same catalyst or catalyst
precursor that was originally
used to pretreat the carbonaceous material).
[0101] In one embodiment, for example, a recovered metal of the catalyst or
catalyst
precursor (such as MoO3) is reacted with a sulfur compound (such as ammonium
sulfide) to form
ammonium tetrathiomolybdate catalyst precursor. The resulting formed catalyst
or catalyst
precursor can then be delivered, optionally in combination with new or fresh
catalyst precursor,
into the pretreatment system and/or the hydroconversion system.
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Characterization of the Catalyst
[0102] In embodiments, a catalyst which is active for converting at least a
portion of the
solid carbonaceous material to a liquid product, having the formula
(Rp)i(M)Q(L )b(S )d(CW)e(H")j(OY)g(NZ)h and having improved morphology and
dispersion
characteristics, can be characterized using techniques known in the art,
including elemental
analysis, Surface Area analysis (BET), Particle Size analysis (PSA), Powder X-
ray Diffraction
(PXRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis
(EDS), and
other methods. In one method, electron microscopy is used to complement the x-
ray diffraction
study. In another method, the surface area of the catalyst is determined using
the BET method.
In yet another method, scanning tunneling microscopy (STM) and density
functional theory
(DFT) can be used to characterize the catalyst.
[0103] The catalyst of the formula (Rp);(Mt)Q(L )b(S )d(CW)e(H")J(OY)g(Nz)h is
characterized as
giving excellent conversion rates in the upgrades of coal depending on the
configuration of the
upgrade process and the concentration of the catalyst used. In one embodiment,
the slurry
catalyst provides conversion rates of at least 70% in one embodiment, at least
75% in a second
embodiment, at least 80% in a third embodiment, and at least 90% in a fourth
embodiment. In
one embodiment of a coal upgrade system employing the catalyst of the formula
(Rp)i(M)a(L )b(S )d(CW)e(H")J(OY)g(Nz)h, at least 98 wt. % of coal feed is
converted to lighter
products. Ina second embodiment, at least 98.5% of coal feed is converted to
lighter products.
In a third embodiment, the conversion rate is at least 99%. In a fourth
embodiment, the
conversion rate is at least 95%. In a fifth embodiment, the conversion rate is
at least 80%. As
used herein, conversion rate refers to the conversion of coal feedstock to
less than 1200 F
(650 C) boiling point materials.
[0104] In one embodiment, the catalyst has a pore volume in the range of from
0.05 to 5.0
ml/g as determined by nitrogen adsorption. In a second embodiment, the pore
volume is in the
range of from 0.1 to 4.0 ml/g, such as from 0.1 to 3.0 mUg or from 0.1 to 2.0
ml/g.
[0105] In embodiments, the catalyst has a surface area of at least 5 m2/g, or
at least 10m2/g,
or at least 50 m2/g, or greater than 100 m2/g, or greater than 200 m2/g , as
determined via the
B.E.T. method. In embodiments, the catalyst is characterized by aggregates of
crystallites of 10
to 20 angstrom, for an overall surface area greater than 100 m2/g.
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[0106] In embodiments, the catalyst has a particle size ranging from nanometer
to
micrometer ( m) size dimensions. Exemplary suspended catalyst particles have a
median
particle size of 0.0005 to 1000 microns, or a median particle size of 0.001 to
500 microns, or a
median particle size of 0.005 to 100 microns, or a median a particle size of
0.05 to 50 microns.
In embodiments, the catalyst in the form of a suspension that is characterized
by a median
particle size of 30 nm to 6000 nm. In embodiments, the catalyst has an average
particle size in
the range of 0.3 to 20 m.
[0107] In embodiments, the catalyst comprises catalyst particles of molecular
dimensions
and/or extremely small particles that are colloidal in size (i.e., less than 1
micrometer or less than
0.1 micrometer or in the range of 0.1 to 0.001 micrometer). In some
embodiments, the catalyst is
dispersed on the coal surface in 1 to 100 nanometer particles by impregnation
of the catalyst
precursor on the coal. In some embodiments, the catalyst forms a slurry
catalyst, in a
hydrocarbon diluent, having "clusters" of the colloidal particles, with the
clusters having an
average particle size in the range of 1 - 100 micrometers.
[0108] As is further illustrated in the following examples, the systems and
processes
described herein can be used to achieve optimization and efficiency in the
production of any
desired proportions (or yield percentages) of liquid and/or gas products
having a variety of
desired properties. Specifically, a full range of hydroconversion products can
be accomplished
under a variety of hydroconversion conditions (such as at low hydrogen
pressure and/or with
short duration) through selection of any of a variety of combinations of
hydrocarbonaceous
liquid, catalysts and/or catalyst precursors, as well as pretreatment and
hydroconversion
conditions. In this manner, the systems and process offers tremendous
flexibility to a user in
being able to achieve desired hydroconversion products from any solid
carbonaceous material
using any of a variety of different combinations of hydrocarbonaceous liquid,
catalyst, and/or
catalyst precursor, as well as pretreatment and hydroconversion conditions.
EXAMPLES
Example 1 (Fe/Zn)
[0109] Run 1 -- A solution of a mixed catalyst precursor iron nitrate
(Fe(N03)3.9H20) and
zinc nitrate (Zn(N03)2.6H20) dissolved in methanol was prepared. A sample of
moisture-free
coal feed (i.e. less than 1 % by weight water) having a particle size of less
than 100 mesh was
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impregnated to incipient wetness with the solution, at a solution to coal
weight ratio of 1 to 1, to
yield an iron to coal loading on a dry, ash-free (daf) basis of 1% iron and a
zinc to coal loading
on a dry, ash free basis of 1 wt% zinc. The catalyst impregnated coal was then
dried under
nitrogen at 105 C for up to 24 hours to remove the methanol. The dried
catalyst impregnated
coal was mixed with an FCC-type process oil (500 F+ cut) as solvent, at a
solvent to coal ratio of
1.6 to 1. Elemental sulfur was added to sulfide the iron and zinc, at a sulfur
to iron molar ratio of
2 to 1 and a sulfur to zinc ratio of 2 to 1. The mixture was then heated
quickly in a vessel to
200 C, and held at 200 C for 2 hours, while the hydrogen partial pressure
within the vessel
increased from about 100 psia to about 1000 psia. The mixture was then further
heated to
430 C, and then held at 430 C for 3 hours under a hydrogen partial pressure of
2500 psia. After
3 hours the reaction vessel containing the sulfided solvent and coal mixture,
hydrogen and any
reaction products was quenched to room temperature. Product gases (CO, C02,
C1, C2 and C3)
were vented through a wet test meter to determine the gas yield. Solids,
primarily unconverted
coal, ash and catalyst sulfide were separated from liquid products (C4+) by
filtration. Coal
conversion was determined as follows:
Coal conversion = (solids recovered - (ash in coal + recovered catalyst))/coal
feed
By subtracting the solvent added at the beginning of the run, oil yield was
determined based on
dry, ash-free basis coal. Product yields are tabulated in Table I.
[0110] Run 2 -- Run 1 was repeated using zinc nitrate as the catalyst
precursor at a zinc to
coal loading on a dry, ash free basis of 2 wt% zinc. Elemental sulfur was
added to sulfide the
zinc, at a sulfur to zinc ratio of 2 to 1. Product yields are tabulated in
Table I.
[0111] Run 3 - Run 1 was repeated using iron nitrate as the catalyst precursor
at an iron to
coal loading on a dry, ash free basis of 2 wt% iron. Elemental sulfur was
added to sulfide the
iron, at a sulfur to iron ratio of 2 to 1. Product yields tabulated in Table I
show that the catalyst
combination containing iron and zinc produces much higher liquid yields and
coal conversion
than do catalysts containing either iron or zinc alone.
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Table I
Run Reaction Condition Liquid Coal Gas
Yield Conversion Yield
1 430 C, 3 hr, 1% Zn, 1% Fe, S 73.8 97.8 16.4
2 430 C, 3 hr, 2% Zn, S 50.4 80.6 25.3
3 430 C,3hr,2%Fe,S 68.7 94.8 15.5
Example 2 (Fe/Co)
[0112] Run 4 -- Run 1 was repeated using iron nitrate (Fe(NO3)3.9H2O) and
cobalt nitrate
(CoNO3)2 6H2O) mixed catalyst precursor at an iron to coal loading on a dry,
ash free basis of 1
wt% iron, and a cobalt to coal loading on a dry, ash free basis of 1 wt%
cobalt. Elemental sulfur
was added to sulfide the iron and cobalt, at a sulfur to iron molar ratio of 2
to 1 and a sulfur to
cobalt ratio of 2 to 1. Product yields are compared with an iron catalyst
precursor in Table II.
Table II
Run Reaction Condition Liquid Coal Gas
Yield (%) Conversion (%) Yield (%)
4 430 C, 3 hr, 1% Co, 1% Fe, S 72.8 97.6 16.8
3 430 C, 3 hr, 2% Fe, S 68.7 94.8 15.5
