U.S. patent application number 12/625398 was filed with the patent office on 2011-05-26 for hydrogenation of solid carbonaceous materials using mixed catalysts.
This patent application is currently assigned to Chevron U.S.A. Inc.. Invention is credited to Jinyi Han, Alexander E. Kuperman.
Application Number | 20110120915 12/625398 |
Document ID | / |
Family ID | 44061315 |
Filed Date | 2011-05-26 |
United States Patent
Application |
20110120915 |
Kind Code |
A1 |
Kuperman; Alexander E. ; et
al. |
May 26, 2011 |
HYDROGENATION OF SOLID CARBONACEOUS MATERIALS USING MIXED
CATALYSTS
Abstract
This invention encompasses systems and methods for converting
solid carbonaceous material to a liquid product, comprising
maintaining a solid carbonaceous material in the presence of at
least one active source of copper and at least one active source of
a second metal at a reaction temperature of greater than
350.degree. C. and at a pressure in the range of 300 to 5000 psig
for a time sufficient to form a liquid product.
Inventors: |
Kuperman; Alexander E.;
(Orinda, CA) ; Han; Jinyi; (Danville, CA) |
Assignee: |
Chevron U.S.A. Inc.
|
Family ID: |
44061315 |
Appl. No.: |
12/625398 |
Filed: |
November 24, 2009 |
Current U.S.
Class: |
208/403 ;
208/419; 208/421; 208/423 |
Current CPC
Class: |
C10G 1/086 20130101 |
Class at
Publication: |
208/403 ;
208/419; 208/421; 208/423 |
International
Class: |
C10G 1/08 20060101
C10G001/08 |
Claims
1. A process for converting solid carbonaceous material to a liquid
product, comprising maintaining a solid carbonaceous material in
the presence of at least one active source of copper and at least
one active source of a second metal at a reaction temperature of
greater than 350.degree. C. and at a pressure in the range of 300
to 5000 psig for a time sufficient to form a liquid product.
2. The process of claim 1, the process comprising: a) preparing a
combination of the solid carbonaceous material, at least one
hydrocarbonaceous liquid, at least one active source of copper and
at least one active source of the second metal; and b) passing the
combination to a hydroconversion reaction zone and maintaining the
solid carbonaceous material at a reaction temperature of greater
than 350.degree. 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 C.sub.5 to 650.degree. C.
3. The process of claim 2, wherein the step of preparing the
combination comprises: a) preparing a mixture comprising at least
one active source of copper and at least one active source of a
second metal; b) combining the mixture with coal to form
catalyst-containing coal particles; and c) providing a
hydrocarbonaceous liquid to the catalyst-containing coal particles
to prepare the combination.
4. The process of claim 3, further comprising drying the
catalyst-containing coal particles prior to the step of passing the
combination to the hydroconversion reaction zone.
5. The process of claim 3, wherein the mixture further comprises a
surfactant.
6. The process of claim 2, further supplying an active source of
sulfur to the combination.
7. The process of claim 6, wherein the active source of sulfur is
supplied at an atomic ratio of sulfur to metal within the range of
between 0.1 to 1 and 10 to 1.
8. The process of claim 2, further comprising supplying hydrogen or
hydrogen-containing gas to the hydroconversion reaction zone.
9. The process of claim 2, further comprising pretreating the
combination at a pretreatment temperature within the range of
100-350.degree. C. and for a time of between 5 and 600 minutes
prior to passing the combination to the hydroconversion reaction
zone.
10. The process of claim 9, further comprising pretreating the
combination in the presence of an active source of sulfur.
11. The process of claim 9, further comprising pretreating the
combination in the presence of hydrogen or a hydrogen-containing
gas.
12. The process of claim 1, wherein the second metal is selected
from the group consisting of iron, molybdenum, nickel, manganese,
vanadium, tungsten, cobalt, titanium, chromium, zinc and tin.
13. The process of claim 1, wherein the second metal is iron.
14. The process of claim 1, wherein the copper is present in an
amount of 10 ppm to 10 wt %, based on dry, ash free coal.
15. The process of claim 1, wherein the second metal is present in
an amount of 10 ppm to 10 wt %, based on dry, ash free coal.
16. The process of claim 1, wherein copper and the second metal are
present in a molar ratio within the range of between 0.1 to 1 and
10 to 1.
17. The process of claim 1, further comprising maintaining the
solid carbonaceous material in the presence of at least one active
source of sulfur.
18. The process of claim 1, further comprising maintaining the
solid carbonaceous material in the presence of hydrogen or a
hydrogen containing gas.
19. The process of claim 2, further comprising converting at least
25% by weight of the solid carbonaceous material to a liquid
product boiling in the temperature range of C.sub.5 to 650.degree.
C.
20. The process of claim 19, further comprising converting in the
range 30% to 99% by weight of the solid carbonaceous material to
the liquid product.
21. The process of claim 2, further comprising maintaining the
solid carbonaceous material at a reaction temperature in the range
of between 350.degree. C. and 800.degree. C.
22. The process of claim 1, wherein the active source of copper and
the active source of the second metal form a catalyst composition
having a formula:
(R.sup.p).sub.i(M.sup.t).sub.a(L.sup.u).sub.b(S.sup.v).sub.d(C.-
sup.w).sub.e(H.sup.x).sub.f(O.sup.y).sub.g(N.sup.z).sub.h, wherein
R is optional, R is at least a lanthanoid element metal or an
alkaline earth metal; M is copper; L is at least a "d" block
element metal different from the "d" block element metal M;
0<=i<=1; 0<b/a=<5, 0.5(a+b)<=d<=5(a+b),
0<e<=11(a+b), 0<f<=7(a+b), 0<g<=5(a+b),
0<h<=2(a+b), p, t, u, v, w, x, y, z, each representing total
charge for each of: M, L, S, C, H, O and N, respectively, wherein
pi+ta+ub+vd+we+xf+yg+zh=0, S=sulfur, C=carbon, H=hydrogen, O=oxygen
and N=nitrogen.
23. The process of claim 22, wherein L is selected from the group
consisting of iron, molybdenum, manganese, vanadium, tungsten,
cobalt, nickel, titanium, chromium, platinum, palladium, cerium,
zirconium, zinc and tin.
24. The process of claim 23, wherein L is iron.
Description
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. Pat. No. 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.degree. F.
in a preheater, and then reacted under coal liquefaction conditions
in a liquefaction reaction. U.S. Pat. No. 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. Pat. No. 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.degree. C.; and quenching the temperature of the
products to a temperature significantly less than 400.degree.
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 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 copper and at least one active source of
a second metal at a reaction temperature of greater than
350.degree. 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 copper 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.degree. 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 C.sub.5 to 650.degree. C.
[0007] In a further aspect, the step of preparing the combination
comprises preparing a mixture comprising at least one active source
of copper 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.degree. 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.
[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.
[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 copper-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 copper. 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 copper 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.
Catalyst Formula
[0024] In one embodiment, the catalyst composition as expressed in
elemental form is of the general formula
(R.sup.p).sub.i(M.sup.t).sub.a(L.sup.u).sub.b(S.sup.v).sub.d(C.sup.w).sub-
.e(H.sup.x).sub.f/(O.sup.y).sub.g(N.sup.z).sub.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, O
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); O 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 copper (or vice versa).
In some such embodiments, the catalyst is of the formula
(Fe.sub.zCu.sub.1-z).sub.a(S).sub.d(C).sub.e(H).sub.f(O).sub.g(N).sub.h,
wherein the copper to iron ratio is in the range of 9:1-1:9 (as wt.
%). In some such embodiments, the copper 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.
[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.degree. C. (such as about 150-300.degree. C. or even about
180-220.degree. C.). In some such embodiments, the step of
pretreating is conducted at a temperature of about 100-350.degree.
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 5 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, 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, 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.
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 C.sub.10-C.sub.12
tetrahydronaphthalenes, the hexahydrofluorenes, the dihydro-,
tetrahydro-, hexahydro- and octahydrophenanthrenes, the
C.sub.12-C.sub.13 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.degree. C. (650.degree. F.) and a final boiling point of
about 538.degree. C. (1000.degree. 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.degree. C., such as, for example a temperature in the range of
450-900 or 650-850.degree. 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.degree. F.
or higher (FCC-type process oil (500.degree. F.+cut)). In another
embodiment, the hydrocarbonaceous liquid is an FCC-type process oil
boiling at a temperature of about 500.degree. F. or less ("FCC-type
process oil (500.degree. F.-cut)"). In another embodiment, the
hydrocarbonaceous 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.degree.
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 copper
for a time sufficient to form a liquid product from the solid
carbonaceous material. In embodiments, the active source of copper
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 copper; 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: [0041] a) copper
metal; [0042] b) copper containing inorganic compounds, such as the
sulfates, nitrates, carbonates, sulfides, oxysulfides, oxides and
hydrated oxides, ammonium salts and heteropoly acids of copper;
[0043] 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);
[0044] d) copper-containing organometallic compounds including
chelates such as 1,3-diketones, ethylene diamine, ethylene diamine
tetraacetic acid, phthalocyanines, thiocarbamates,
phosphorothioates, and combinations or mixtures thereof
(non-limiting examples include copper alkyl dithiocarbamate, copper
alkyl phosphorodithioate); and/or, [0045] e) copper salts of
organic amines such as aliphatic amines, aromatic amines,
quaternary ammonium compounds, or combinations or mixtures thereof,
and [0046] f) copper-containing minerals, including copper sulfide
minerals.
[0047] 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.
[0048] 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: [0049] a) iron metal;
[0050] b) iron containing inorganic compounds, such as the
sulfates, nitrates, carbonates, sulfides, oxysulfides, oxides and
hydrated oxides, ammonium salts and heteropoly acids of iron;
[0051] 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);
[0052] 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, [0053] e) iron salts of organic
amines such as aliphatic amines, aromatic amines, quaternary
ammonium compounds, or combinations or mixtures thereof, and [0054]
f) iron-containing minerals.
[0055] 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: [0056] 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, [0057] b)
combining the catalyst precursor with a carbonaceous material;
[0058] 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 [0059] d) heating the mixture for a time sufficient
to form a liquid product
[0060] In embodiments, the catalyst precursors are formed by:
[0061] a) mixing a hydrocarbonaceous liquid (such as a liquefaction
solvent) with at least one active source of copper and with at
least one active source of a second metal to form a catalyst
precursor; [0062] b) combining the catalyst precursor with a
carbonaceous material; [0063] 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
[0064] d) heating the mixture for a time sufficient to form a
liquid product
[0065] In embodiments, the catalyst precursors are formed by [0066]
a) mixing a hydrocarbonaceous liquid with an active source of at
least one metal, [0067] 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, [0068] c)
combining the sulfided mixture with a carbonaceous material, [0069]
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 [0070] e) heating the mixture for a
time sufficient to form a liquid product.
[0071] In embodiments, the catalyst precursors are formed by [0072]
a) mixing a hydrocarbonaceous liquid with an active source of at
least one metal; [0073] b) combining the catalyst precursor with a
carbonaceous material; [0074] c) combining the mixture with a
sulfiding agent; [0075] 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 [0076] e)
heating the mixture for a time sufficient to form a liquid
product.
[0077] In another embodiment, one or more catalyst precursors are
formed by [0078] a) mixing one or more metal containing compounds,
a sulfiding agent, and water, to form a colloidal suspension,
[0079] b) combining the colloidal suspension with a
hydrocarbonaceous liquid (such as a liquefaction solvent) to drive
water out of the suspension, [0080] c) combining the suspension
with a carbonaceous material, [0081] 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 [0082] e) heating the
mixture for a time sufficient to form a liquid product.
[0083] In another embodiment, one or more catalyst precursors are
by [0084] 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.degree. C., to form a presulfided product; and [0085] 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.
[0086] In another embodiment, one or more catalyst precursors are
formed by a process comprising: [0087] a) mixing an active source
of copper and an active source of the second metal and water, to
form a colloidal suspension or solution; [0088] b) combining the
colloidal suspension or solution with a solid carbonaceous material
at conditions sufficient to deposit at least a portion of the
copper 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; [0089] 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 [0090] 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 [0091] e)
heating the mixture for a time sufficient to form a liquid
product.
[0092] 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.
[0093] 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 of catalyst
precursor, carbonaceous material, and hydrocarbonaceous liquid
comprises about 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. 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.
[0094] 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.
[0095] 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
[0096] 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.
[0097] 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 in excess of the stoichiometric amount
required to form the catalyst. In one embodiment, the sulfiding
agent is present in a sulfur to copper 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.
[0098] 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.
[0099] 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.
[0100] 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.
[0101] 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.
Catalyst
[0102] 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.
[0103] The catalyst includes any copper-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 III B
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 Sn.
[0104] In embodiments, the sulfided copper-containing catalyst can
be CuS--FeS, CuS--MoS.sub.2, CuS--WS.sub.2, CuS--CoS, CuS--NiS,
ZnS--CuS, CuS--TiS2, CuS--SnS and any of their combinations and
mixtures, for example CuS--MoS.sub.2--TiS.sub.2. In the catalyst
system, Cu can be the rich phase or serve as dopant.
[0105] The amount of copper 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, copper is present in
the catalyst in an amount of 10 ppm to 10 wt %, based on dry, ash
free coal. In some such embodiments, copper is present in the
catalyst in the amount of 0.1 wt % to 5 wt %. An exemplary quantity
of copper, as metal, present in the catalyst is in the amount of
0.5 wt % to 2.5 wt %.
[0106] In embodiments, the second metal in the catalyst is present
in an amount of 10 ppm to 10 wt %, based on dry, ash free coal. In
some such embodiments, the second metal is present in 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 Cu and other metals in
combination can be between 0.1 to 1 and 10 to 1.
[0107] In embodiments, the catalytic materials are added as finely
divided particulate metal solids, their oxides, sulfides, etc.,
e.g., FeS.sub.x; 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
copper and the second metal are added as separate particulate
solids. In other embodiments, the catalyst composition comprises
particles that are richer in copper and leaner in the amount of the
second metal, or particles that are richer in the second metal and
leaner in the amount of copper. In another embodiment, copper and
other metals can form bi-metallic compounds as a catalyst precursor
rather than being added to the feed separately. As an example,
Cu.sub.xFe.sub.(1-x), OOH is prepared by titrating a FeSO.sub.4 and
CuSO.sub.4 mixture solution with NH.sub.3H.sub.2O, followed by
oxidizing in flowing air at elevated temperatures.
Cu.sub.xFe.sub.(1-x), OOH can be pre-sulfided to CuxFe.sub.(1-x)S
before mixing with the feed.
[0108] 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.
[0109] In an embodiment, the catalyst is prepared using a catalyst
precursor comprising a metal that comprises a water-soluble copper
component, such as copper nitrate, copper sulfate, copper acetate,
copper chloride, or a mixture thereof. In another embodiment, the
catalyst is prepared using a catalyst precursor comprising an metal
that comprises a copper compound which is at least partly in the
solid state, e.g., a water-insoluble copper compound such as copper
carbonate, copper hydroxide, copper phosphate, copper phosphite,
copper formate, copper sulfide, copper molybdate, copper tungstate,
copper oxide, copper alloys such as copper-molybdenum or
copper-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 copper 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 copper sulfate aqueous
solution.
[0110] 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.
[0111] 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 copper include copper
nitrate and copper 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
[(NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O], nickel dinitrate
hexahydrate [Ni(NO.sub.3).sub.2.6H.sub.2O], and sodium tungstate
dihydrate [NaWO.sub.4.2H.sub.2O]. 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, naphthenates of molybdenum, chromium, and
vanadium, etc. Suitable oil-soluble compounds can be converted to
dissolution catalysts in situ.
[0112] In embodiments, the particulate catalyst comprises copper
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.
[0113] 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 catalysts, the weight ratio of metal components (i.e.
copper and the second metal components) to support components is in
the range of 10:1 to 1:10.
[0114] 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.
[0115] 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.degree. 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.
[0116] Properly sulfided copper species such as CuS and copper
alkyl dithiocarbamate, copper alkyl phosphorodithioate and sulfided
metallic species such as MoS.sub.2, ammonium tetrathiomolybdate,
NiS, CoS, WS.sub.2, SnS, TiS.sub.2, CuS, FeS, Fe.sub.2S.sub.3, 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 copper-based copper metal,
copper oxide, copper acetate, copper nitrate, copper sulfate and
other copper salts, copper minerals and copper 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, H.sub.2S,
CS.sub.2, and (NH.sub.4).sub.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/(Cu+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
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.
[0117] Any suitable sulfur compound may be used in this regard. In
one embodiment, the sulfiding agent is hydrogen sulfide (H.sub.2S).
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 ((NH.sub.4).sub.2S.sub.x), ammonium
thiosulfate ((NH.sub.4).sub.2S.sub.2O.sub.3), sodium thiosulfate
(Na.sub.2S.sub.2O.sub.3), thiourea (CSN.sub.2H.sub.4), carbon
disulfide (CS.sub.2), 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.
[0118] 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.
Other Additives
[0119] 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.
[0120] 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-methylpyrrolidone; 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 N-containing/P-containing organic additive to be added
generally depends on the desired activity of the final catalyst
composition.
[0121] In another embodiment, the surfactant is an ammonium or
phosphonium of the formula R.sub.1R.sub.2R.sub.3R.sub.4Q+, wherein
Q is nitrogen or phosphorous, wherein at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4 is an aryl or alkyl group having 8-36
carbon atoms (e.g., C.sub.10H.sub.21, C.sub.16H.sub.33,
C.sub.18H.sub.37, or a combination thereof), and wherein the
remainder of R.sub.1, R.sub.2, R.sub.3, R.sub.4 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.
[0122] 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-1-butanol, 4-amino-1-butanol,
2,2-diethoxyethylamine, 4,4-diethoxybutylamine, 6-amino-1-hexanol,
2-amino-1,3-propanediol, 3-amino-1,2-propanediol,
3-amino-1-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).
[0123] 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 embodiment, the
surfactant is pentadecanoic acid, decanoic acid, or other similar
long chain acids. In yet another embodiment, the surfactant is
alginic acid.
[0124] 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.
[0125] 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
[0126] 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 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.
[0127] 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 copper and an
active source of iron in a molar ratio of copper 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.degree. C. and 500.degree. 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.
[0128] 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 copper and an active source of iron in the molar
ratio of copper 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.degree. 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.degree. C. and 500.degree. C. The heated
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.
[0129] 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.
[0130] A catalytic material 205, comprising an active source of
copper and an active source of iron in the molar ratio of copper 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
copper is supplied to the pretreatment zone as an aqueous solution
or slurry of a copper salt such as copper nitrate, copper chloride,
copper sulfate, copper acetate, copper sulfide, copper oxide or
copper 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, copper and iron are added
as organometallic compounds contained in a liquid such as a coal
derived distillate fraction. Exemplary organometallic compounds
include copper 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.degree. 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.degree. C. and 500.degree. 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.
[0131] 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 is passed to pretreatment zone 310. A catalytic material
307, comprising an active source of copper and a catalytic material
comprising an active source of iron 309 in the molar ratio of
copper 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.degree. 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.degree. C. and 500.degree. 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
[0132] 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.
[0133] Suitable hydroconverting temperatures include, but are not
limited to, temperatures greater than about 350.degree. C., such as
greater than about 375.degree. C., about 400.degree. C., about
425.degree. C., about 450.degree. C., about 475.degree. C., about
500.degree. C. In some such embodiments, the step of
hydroconverting the heated material is conducted at a temperature
in the range of between 350.degree. C. and 500.degree. C. In some
such embodiments, the heated material is reacted in the
hydroconversion step for a time of at least 10 minutes.
[0134] 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 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.
[0135] 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 copper
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.degree. 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.degree. C. and
500.degree. C. In some embodiments, the solid carbonaceous material
is heated for a time within the range of 5 minutes to 600
minutes.
[0136] 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). 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.
[0137] 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%.
[0138] 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 C.sub.1-C.sub.3 gases.
Separation of Hydroconversion Products
[0139] 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 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
[0140] 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).
[0141] The recovery system can be operated at any suitable
temperature, such as at a temperature of about 1200-1900.degree.
C., such as about 1300-1800.degree. C., or even 1400-700.degree. 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 Mo0.sub.3, in the case
where the metal is molybdenum, such as described in U.S. Pat. App.
Ser. No. 60/015,096, filed Dec. 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
[0142] 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).
[0143] In one embodiment, for example, a recovered metal of the
catalyst or catalyst precursor (such as MoO.sub.3) 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.
Characterization of the Catalyst 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
(R.sup.p).sub.i(M.sup.t).sub.a(L.sup.u).sub.h(S.sup.v).sub.d(C.sup.w).sub-
.e(H.sup.x).sub.f(O.sup.y).sub.g(N.sup.z).sub.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.
[0144] The catalyst of the formula
(R.sup.P).sub.i(M.sup.t).sub.a(L.sup.u).sub.b(S.sup.v).sub.d(C.sup.w).sub-
.e(H.sup.x).sub.f(O.sup.y).sub.g(N.sup.z).sub.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
(R.sup.p).sub.i(M.sup.t).sub.a(L.sup.u).sub.b(S.sup.v).sub.d(C.sup.w).sub-
.e(H.sup.x).sub.f(O.sup.y).sub.g(N.sup.z).sub.h at least 98 wt. %
of coal feed is converted to lighter products. In a 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.degree. F. (650.degree. C.) boiling point
materials.
[0145] 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 ml/g or from 0.1
to 2.0 ml/g.
[0146] In embodiments, the catalyst has a surface area of at least
5 m.sup.2/g, or at least 10 m.sup.2/g, or at least 50 m.sup.2/g, or
greater than 100 m.sup.2/g, or greater than 200 m.sup.2/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 m.sup.2/g.
[0147] In embodiments, the catalyst has a particle size ranging
from nanometer to micrometer (.mu.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 .mu.m.
[0148] 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.
[0149] 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
[0150] Run 1--A solution of a mixed catalyst precursor iron nitrate
(Fe(NO.sub.3).sub.3.9H.sub.2O) and zinc nitrate
(Zn(NO.sub.3).sub.2.6H.sub.2O) 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 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.degree. C. for up to 24 hours
to remove the methanol. The dried catalyst impregnated coal was
mixed with an FCC-type process oil (500.degree. 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.degree. C., and held at
200.degree. 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.degree. C., and then
held at 430.degree. 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,
CO.sub.2, C.sub.1, C.sub.2 and C.sub.3) 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 (C.sub.4.sup.+) 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.
[0151] 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.
[0152] 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.
TABLE-US-00001 TABLE I Liquid Coal Gas Yield Conversion Yield Run
Reaction Condition (%) (%) (%) 1 430.degree. C., 3 hr, 1% Zn, 1%
Fe, S 73.8 97.8 16.4 2 430.degree. C., 3 hr, 2% Zn, S 50.4 80.6
25.3 3 430.degree. C., 3 hr, 2% Fe, S 68.7 94.8 15.5
Example 2
Fe/Cu
[0153] Run 4--Run 1 was repeated using iron nitrate
(Fe(NO.sub.3).sub.3.9H.sub.2O) and copper nitrate
(Cu(NO.sub.3).sub.2.2.5 H.sub.2O) mixed catalyst precursor at an
iron to coal loading on a dry, ash free basis of 1 wt % iron, and a
copper to coal loading on a dry, ash free basis of 1 wt % copper.
Elemental sulfur was added to sulfide the iron and copper, at a
sulfur to iron molar ratio of 2 to 1 and a sulfur to copper ratio
of 2 to 1. Product yields are tabulated in Table II.
[0154] Run 5--Run 1 was repeated using copper nitrate as the
catalyst precursor at a nickel to coal loading on a dry, ash free
basis of 2 wt % copper. Elemental sulfur was added to sulfide the
copper, at a sulfur to copper ratio of 2 to 1. Product yields are
tabulated in Table II.
TABLE-US-00002 TABLE II Liquid Coal Gas Yield Conversion Yield Run
Reaction Condition (%) (%) (%) 4 430.degree. C., 3 hr, 1% Cu, 1%
Fe, S 71.1 96.6 19.8 5 430.degree. C., 3 hr, 2% Cu, S 71.3 96.3
17.4
Example 3
Zn/Cu
[0155] Run 6--Run 1 was repeated using zinc nitrate
(Zn(NO.sub.3).sub.2.6H.sub.2O) and copper nitrate
(Cu(NO.sub.3).sub.3.2.5 H.sub.2O) mixed catalyst precursor at an
zinc to coal loading on a dry, ash free basis of 1 wt % zinc, and a
copper to coal loading on a dry, ash free basis of 1 wt % copper.
Elemental sulfur was added at a sulfur to zinc molar ratio of 2 to
1 and at a sulfur to copper molar ratio of 2 to 1. Product yields
are tabulated in Table III.
[0156] Run 7--Run 1 was repeated using copper nitrate as the
catalyst precursor at a nickel to coal loading on a dry, ash free
basis of 2 wt % copper. Elemental sulfur was added to sulfide the
copper, at a sulfur to copper molar ratio of 2 to 1. Product yields
are tabulated in Table III.
TABLE-US-00003 TABLE III Liquid Coal Gas Yield Conversion Yield Run
Reaction Condition (%) (%) (%) 6 430.degree. C., 3 hr, 1% Cu, 1%
Zn, S 70.4 97.3 16.8 7 430.degree. C., 3 hr, 2% Cu, S 71.3 96.3
17.4
* * * * *