U.S. patent application number 13/526132 was filed with the patent office on 2013-12-19 for liquefaction of carbonaceous material and biomass to produce a synthetic fuel.
The applicant listed for this patent is Ramesh K. Sharma. Invention is credited to Ramesh K. Sharma.
Application Number | 20130338411 13/526132 |
Document ID | / |
Family ID | 49474675 |
Filed Date | 2013-12-19 |
United States Patent
Application |
20130338411 |
Kind Code |
A1 |
Sharma; Ramesh K. |
December 19, 2013 |
LIQUEFACTION OF CARBONACEOUS MATERIAL AND BIOMASS TO PRODUCE A
SYNTHETIC FUEL
Abstract
The present invention relates to production of fuels from
carbonaceous material and biomass. In some examples, the
carbonaceous material is nonpetroleum fossil fuel or petroleum
residuals. Various embodiments of the present invention provide a
method of liquefaction of carbonaceous material and biomass. The
method includes providing or obtaining a feed mixture, the mixture
including carbonaceous material and biomass. The method also
includes subjecting the feed mixture to liquefaction, to provide a
product slurry. Various embodiments of the present invention
provide a method of fuel production from carbonaceous material and
biomass. The method includes separating the product slurry from the
liquefaction, to give a conversion component. The method also
includes processing the conversion component, to give a fuel.
Inventors: |
Sharma; Ramesh K.; (Grand
Forks, ND) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sharma; Ramesh K. |
Grand Forks |
ND |
US |
|
|
Family ID: |
49474675 |
Appl. No.: |
13/526132 |
Filed: |
June 18, 2012 |
Current U.S.
Class: |
585/240 ;
44/281 |
Current CPC
Class: |
C10G 1/083 20130101;
C10G 3/47 20130101; C10G 1/002 20130101; C10G 3/50 20130101; C10G
3/46 20130101; C10G 1/065 20130101; Y02P 30/20 20151101 |
Class at
Publication: |
585/240 ;
44/281 |
International
Class: |
C10G 1/06 20060101
C10G001/06; C10L 1/32 20060101 C10L001/32 |
Goverment Interests
STATEMENT OF GOVERNMENT SUPPORT
[0001] This invention was made with government support under U.S.
Department of Energy (DOE) Cooperative Agreement No.
DE-FC26-0SNT43291 entitled "EERC-DOE Joint Program on Research and
Development for Fossil Energy-Related Resources," Subtask 3.5
entitled "Catalytic Coal Liquefaction to Produce Transportation
Fuels," Energy & Environmental Research Center (EERC) Fund
15159, and U.S. Department of Energy Cooperative Agreement No.
DE-FC26-0SNT43291 entitled "EERC-DOE Joint Program on Research and
Development for Fossil Energy-Related Resources," Subtask 3.8
entitled "Analysis of Multiple Pathways for Converting Coal to
Liquid Transportation Fuels," EERC Fund 16344. The government has
certain rights in this invention.
Claims
1. A method of liquefaction of carbonaceous material and biomass,
comprising: providing or obtaining a feed mixture, the mixture
comprising carbonaceous material and biomass; and subjecting the
feed mixture to liquefaction, to provide a product slurry; wherein
the carbonaceous material comprises a nonpetroleum fossil fuel or a
petroleum refinery residue.
2. The method of claim 1, wherein the carbonaceous material
comprises coal, coal tar, wax from a FT process, petroleum refinery
residue, vacuum bottoms, tar sand, bitumen, or a combination
thereof.
3. The method of claim 2, wherein the coal comprises coal powder,
pulverized coal, or a combination thereof.
4. The method of claim 2, wherein the coal comprises lignite, brown
coal, jet coal, subbituminous coal, bituminous coal, steel coal,
anthracite, graphite, or a combination thereof.
5. The method of claim 1, wherein the biomass comprises
plant-derived oil, algae-derived oil, biomass pyrolysis oil, waste
oil, yellow grease, brown grease, tar, or animal fat.
6. The method of claim 1, wherein the mass ratio of carbonaceous
material to biomass is about 0.01-10 to 1.
7. The method of claim 1, wherein the mixture further comprises
solvent.
8. The method of claim 7, wherein the solvent comprises a
carbonaceous material-derived heavy liquid.
9. The method of claim 1, wherein the liquefaction comprises direct
liquefaction.
10. The method of claim 1, wherein subjecting the feed mixture to
liquefaction comprises contacting the feed mixture with a
liquefaction catalyst and hydrogen gas at a temperature of about
200.degree. to about 600.degree. C., at a pressure of about 50 to
about 300 atm.
11. The method of claim 10, wherein the liquefaction catalyst
comprises a cobalt-molybdenum catalyst.
12. The method of claim 10, wherein the hydrogen gas is provided
from a supply integrated in the method.
13. The method of claim 10, wherein the pressure during the
liquefaction is about 150 to about 250 atm.
14. The method of claim 10, wherein the temperature during
liquefaction is about 400.degree. to about 500.degree. C.
15. A method of fuel production from carbonaceous material and
biomass, comprising: performing the method of claim 1; separating
the product slurry, to give a conversion component; and processing
the conversion component, to give a fuel.
16. The method of claim 15, wherein the method is substantially or
fully integrated with respect to the fuel production.
17. The method of claim 15, wherein separating the product slurry
comprises distilling, wherein the conversion comprises at least
part of the distillate from the distilling.
18. The method of claim 15, wherein processing the distillate
comprises: hydrotreating the conversion component, to give a
hydrotreated material; hydrogenating the hydrotreated material, to
give a hydrogenated material; optionally isomerizing at least some
of the hydrotreated material, to give an isomerized material;
optionally aromatizing at least some of the hydrotreated material,
to give an aromatized material; and blending the isomerized
material and the aromatized material, to give the fuel; wherein at
least one of isomerizing and aromatizing is performed, or both
isomerizing and aromatizing are performed.
19. The method of claim 18, wherein isomerizing is performed.
20. The method of claim 18, wherein aromatizing is performed.
21. The method of claim 18, wherein both isomerizing and
aromatizing are performed.
22. The method of claim 15, wherein the fuel comprises a liquid
transportation fuel.
23. A method of liquefaction of coal and biomass, comprising:
providing or obtaining a feed mixture, the mixture comprising coal
and biomass, the biomass comprising plant-derived oil,
algae-derived oil, biomass pyrolysis oil, waste oil, yellow grease,
brown grease, tar, or animal fat; and subjecting the feed mixture
to liquefaction, to provide a product slurry, the liquefaction
comprising contacting the feed mixture with a liquefaction catalyst
and hydrogen gas at a temperature of about 350.degree. to about
500.degree. C., at a pressure of about 150 to about 250 atm.
24. A method of fuel production from coal and biomass, comprising:
providing or obtaining a feed mixture, the mixture comprising coal
and biomass, the biomass comprising plant-derived oil,
algae-derived oil, biomass pyrolysis oil, waste oil, yellow grease,
brown grease, tar, or animal fat; subjecting the feed mixture to
liquefaction, to provide a product slurry; distilling the product
slurry, to give a distillate; and hydrotreating the distillate, to
give a hydrotreated material; hydrogenating the hydrotreated
material, to give a hydrogenated material; isomerizing at least
some of the hydrotreated material, to give an isomerized material;
aromatizing at least some of the hydrotreated material, to give an
aromatized material; and blending at least some of the isomerized
material and at least some of the aromatized material, to give a
fuel.
Description
BACKGROUND OF THE INVENTION
[0002] Refining of petroleum crude is the most common pathway for
the production of fuels. However, petroleum is a limited and
nonrenewable resource, and the extraction, transportation, and
refining of petroleum can be problematic from an environmental,
political, and energy efficiency standpoint. Several competitive
technologies allowing production of synthetic fuels from other
sources such as coal or natural gas are currently being developed
or are at advanced stages of development. In addition, most
competitive technologies do not produce all of the key constituents
needed to produce synthetic fuels, such as aviation fuels. At best,
they produce blendstocks that need to be mixed with
petroleum-derived fuels or blendstocks to meet the key requirements
of particular fuels, such as aviation fuels.
[0003] Recently, the U.S. Department of Defense expressed interest
in a universal fuel for military use, preferably from a synthetic
process to improve energy security. Termed Battlefield Use Fuel of
the Future (BUFF), the fuel is very similar to jet fuel in
specifications, but has more stringent flash point specifications
(60.degree. C.).
SUMMARY OF THE INVENTION
[0004] Various embodiments of the present invention provide a
method of liquefaction of carbonaceous material and biomass. The
method includes providing or obtaining a feed mixture. The feed
mixture includes carbonaceous material and biomass. The method also
includes subjecting the feed mixture to liquefaction. The
liquefaction provides a product slurry. The carbonaceous material
includes a nonpetroleum fossil fuel or a petroleum refinery
residue.
[0005] Various embodiments of the present invention provide a
method of fuel production from carbonaceous material and biomass.
The method includes providing or obtaining a feed mixture. The feed
mixture includes carbonaceous material and biomass. The method also
includes subjecting the feed mixture to liquefaction. The
liquefaction provides a product slurry. The carbonaceous material
includes a nonpetroleum fossil fuel or a petroleum refinery
residue. The method also includes separating the product slurry.
Separating the product slurry provides a conversion component. The
method also includes processing the conversion component.
Processing provides a fuel.
[0006] Various embodiments of the present invention provide certain
advantages of other methods of liquefaction and fuel production. In
some embodiments, the ratio of carbonaceous material and biomass
can be adjusted to generate a desired mixture of products. Some
embodiments of the present invention can provide a synthetic fuel
facility that can produce a fully or substantially fully synthetic
fuel that meets JP-5/JP-8 specs or JP-5/BUFF specs. Some
embodiments of the present method have a smaller carbon footprint
than other methods of liquefaction and other methods of fuel
production, such as petroleum fuel production or other methods of
synthetic fuel production. Some embodiments of the present
invention can provide a fully or substantially synthetic
kerosene-dominant refinery in which the naphtha and distillate that
are coproduced are easily refinable to meet final fuel specs,
rather than having to be sold as naphtha or distillate blendstocks.
Some embodiments are integrated or substantially integrated with
respect to fuel production, such that all or most components of a
desired fuel, such as jet fuel, are generated in a single refinery
without the need for the addition of other blendstocks, such as
petroleum-derived blendstocks. In some embodiments, the ability to
generate materials that are fully or substantially fully refinable
into a synthetic fuel can be advantageous for refinery locations
far from markets for intermediate blendstock products or for
refineries used as a strategic asset for the production of fuel for
military use, including, for example, for production of synthetic
aviation fuels. Some embodiments can refine fuel precursors into a
desired fuel more efficiently than other refining techniques, for
example with less consumption of energy or valuable materials than
other methods. In some embodiments, in the refining process, the
proportion of hydrogenated material subjected to a
hydroisomerization process or aromatization process can be varied
to achieve a desired fuel blend. Various embodiments of the method
are flexible, allow tailoring of the secondary products, and can
accommodate different refining technology preferences. In some
examples, the method can be less complex than other refining
techniques and can allow the production of fuels such as aviation
fuels, while, in some embodiments, coproducing chemicals or other
transportation fuels. In some examples, the present invention can
allow elimination of substantial gas cleanup equipment, reducing
the overall size of the plant.
[0007] In various embodiments, the present invention provides a
method of liquefaction of coal and biomass. The method includes
providing or obtaining a feed mixture. The feed mixture includes
coal and biomass. The biomass includes plant-derived oil,
algae-derived oil, biomass pyrolysis oil, waste oil, yellow grease,
brown grease, tar, or animal fat. The method also includes
subjecting the feed mixture to liquefaction. The liquefaction
provides a product slurry. The liquefaction includes contacting the
feed mixture with a liquefaction catalyst and hydrogen gas at a
temperature of about 200.degree. to 450.degree. C., at a pressure
of about 50 to 450 atm.
[0008] In various embodiments, the present invention provides a
method of fuel production from coal and biomass. The method
includes providing or obtaining a feed mixture. The mixture
includes coal and biomass. The biomass includes plant-derived oil,
algae-derived oil, biomass pyrolysis oil, waste oil, yellow grease,
brown grease, tar, or animal fat. The method also includes
subjecting the feed mixture to liquefaction. The liquefaction
provides a product slurry. The method also includes distilling the
product slurry. Distilling provides a distillate. The method also
includes hydrotreating the distillate. Hydrotreating provides a
hydrotreated material. The method also includes hydrogenating the
hydrotreated material. Hydrogenating provides a hydrogenated
material. The method also includes isomerizing at least some of the
hydrotreated material. Isomerizing at least some of the
hydrotreated material provides an isomerized material. The method
also includes aromatizing at least some of the hydrotreated
material. The aromatizing provides an aromatized material. The
method also includes blending at least some of the isomerized
material and at least some of the aromatized material. The blending
provides a fuel.
BRIEF DESCRIPTION OF THE FIGURES
[0009] In the drawings, which are not necessarily drawn to scale,
like numerals describe substantially similar components throughout
the several views. Like numerals having different letter suffixes
represent different instances of substantially similar components.
The drawings illustrate generally, by way of example, but not by
way of limitation, various embodiments discussed in the present
document.
[0010] FIG. 1 illustrates a flow sheet of process fuel production
from carbonaceous material and biomass, in accordance with various
embodiments.
[0011] FIG. 2 illustrates the distillation profile of a coal-canola
oil-derived liquid, in accordance with various embodiments.
[0012] FIG. 3 illustrates the distillation profile of a coal-algae
oil-derived liquid, in accordance with various embodiments.
[0013] FIG. 4 illustrates the distillation profile of a
coal-wax-derived liquid, in accordance with various
embodiments.
[0014] FIG. 5 illustrates distillation profiles for coal-canola
oil-derived fuels, in accordance with various embodiments.
[0015] FIG. 6 illustrates the wt % of n-paraffins in a fuel sample
produced by an embodiment of the method of the present invention,
as compared to a JP-8 fuel sample.
[0016] FIG. 7 illustrates a gas chromatography (GC) chromatogram of
a fuel sample produced by an embodiment of the method of the
present invention, as compared to a JP-8 fuel sample.
[0017] FIG. 8 illustrates quartz crystal microbalance
(QCM)-determined mass accumulation and headspace oxygen of a fuel
sample produced by an embodiment of the method of the present
invention, as compared to a JP-8 fuel sample.
[0018] FIG. 9 illustrates distillation profiles for coal-algae
oil-derived fuels, in accordance with various embodiments.
[0019] FIG. 10 illustrates distillation profiles for
coal-wax-derived fuels, in accordance with various embodiments.
DETAILED DESCRIPTION OF THE INVENTION
[0020] Reference will now be made in detail to certain claims of
the disclosed subject matter, examples of which are illustrated in
the accompanying drawings. While the disclosed subject matter will
be described in conjunction with the enumerated claims, it will be
understood that they are not intended to limit the disclosed
subject matter to those claims. On the contrary, the disclosed
subject matter is intended to cover all alternatives,
modifications, and equivalents, which can be included within the
scope of the presently disclosed subject matter as defined by the
claims.
[0021] References in the specification to "one embodiment," "an
embodiment," "an example embodiment," and the like, indicate that
the embodiment described can include a particular feature,
structure, or characteristic, but every embodiment may not
necessarily include the particular feature, structure, or
characteristic. Moreover, such phrases are not necessarily
referring to the same embodiment. Further, when a particular
feature, structure, or characteristic is described in connection
with an embodiment, it is submitted that it is within the knowledge
of one of ordinary skill in the art to effect such feature,
structure, or characteristic in connection with other embodiments
whether or not explicitly described.
[0022] Values expressed in a range format should be interpreted in
a flexible manner to include not only the numerical values
explicitly recited as the limits of the range, but also to include
all the individual numerical values or subranges encompassed within
that range as if each numerical value and subrange is explicitly
recited. For example, a range of "about 0.1% to about 5%" or "about
0.1% to 5%" should be interpreted to include not only about 0.1% to
about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%)
and the subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%)
within the indicated range.
[0023] In this document, the terms "a," "an," or "the" are used to
include one or more than one, unless the context clearly dictates
otherwise. The term "or" is used to refer to a nonexclusive "or"
unless otherwise indicated. In addition, it is to be understood
that the phraseology or terminology employed herein, and not
otherwise defined, is for the purpose of description only and not
of limitation. Any use of section headings is intended to aid
reading of the document and is not to be interpreted as limiting;
information that is relevant to a section heading may occur within
or outside of that particular section. Furthermore, all
publications, patents, and patent documents referred to in this
document are incorporated by reference herein in their entirety as
though individually incorporated by reference. In the event of
inconsistent usages between this document and those documents so
incorporated by reference, the usage in the incorporated reference
should be considered supplementary to that of this document; for
irreconcilable inconsistencies, the usage in this document
controls.
[0024] In the methods of manufacturing described herein, the steps
can be carried out in any order without departing from the
principles of the invention, except when a temporal or operational
sequence is explicitly recited.
[0025] Furthermore, specified steps can be carried out concurrently
unless explicit claim language recites that they be carried out
separately. For example, a claimed step of doing X and a claimed
step of doing Y can be conducted simultaneously within a single
operation, and the resulting process will fall within the literal
scope of the claimed process.
DEFINITIONS
[0026] The term "about" as used herein can allow for a degree of
variability in a value or range, for example, within 10%, within
5%, or within 1% of a stated value or of a stated limit of a range.
When a range or a list of sequential values is given, unless
otherwise specified any value within the range or any value between
the given sequential values is also disclosed.
[0027] The term "substantially" as used herein refers to a majority
of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%,
96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999%
or more.
[0028] The term "organic group" as used herein refers to but is not
limited to any carbon-containing functional group. For example, an
organic group may be an oxygen-containing group such as alkoxy
groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups,
carboxyl groups including carboxylic acids, carboxylates, and
carboxylate esters; a sulfur-containing group such as alkyl and
aryl sulfide groups; and other heteroatom-containing groups.
[0029] The term "substituted" as used herein refers to an organic
group as defined herein or a molecule in which one or more hydrogen
atoms contained therein are replaced by one or more non-hydrogen
atoms. The term "functional group" or "substituent" as used herein
refers to a group that can be or is substituted onto a molecule or
onto an organic group.
[0030] The term "alkyl" as used herein refers to straight chain and
branched alkyl groups and cycloalkyl groups having from 1 to 40
carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in
some embodiments, from 1 to 8 carbon atoms. Examples of
straight-chain alkyl groups include those with from 1 to 8 carbon
atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
n-heptyl, and n-octyl groups. Examples of branched alkyl groups
include, but are not limited to, isopropyl, isobutyl, sec-butyl,
t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As
used herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and
anteisoalkyl groups as well as other branched chain forms of alkyl.
Representative substituted alkyl groups can be substituted one or
more times with any of the groups listed herein, for example,
amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen
groups.
[0031] The term "alkenyl" as used herein refers to straight- and
branched-chain and cyclic alkyl groups as defined herein, except
that at least one double bond exists between two carbon atoms. Thus
alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20
carbon atoms, or 2 to 12 carbons or, in some embodiments, from 2 to
8 carbon atoms. Examples include, but are not limited to, vinyl,
--CH.dbd.CH(CH.sub.3), --CH.dbd.C(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH.sub.2, --C(CH.sub.3).dbd.CH(CH.sub.3),
--C(CH.sub.2CH.sub.3)--CH.sub.2, cyclohexenyl, cyclopentenyl,
cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among
others.
[0032] The term "alkynyl" as used herein refers to straight- and
branched-chain alkyl groups, except that at least one triple bond
exists between two carbon atoms. Thus, alkynyl groups have from 2
to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12
carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples
include, but are not limited to --C.ident.CH,
--C.ident.C(CH.sub.3), --C.ident.C(CH.sub.2CH.sub.3),
--CH.sub.2C.ident.CH, --CH.sub.2C.ident.C(CH.sub.3), and
--CH.sub.2C.ident.C(CH.sub.2CH.sub.3) among others.
[0033] The term "acyl" as used herein refers to a group containing
a carbonyl moiety wherein the group is bonded via the carbonyl
carbon atom.
[0034] The term "cycloalkyl" as used herein refers to cyclic alkyl
groups such as, but not limited to, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In
some embodiments, the cycloalkyl group can have 3 to about 8-12
ring members, whereas in other embodiments, the number of ring
carbon atoms ranges from 3 to 4, 5, 6, or 7.
[0035] The term "aryl" as used herein refers to cyclic aromatic
hydrocarbons that do not contain heteroatoms in the ring. Thus aryl
groups include, but are not limited to, phenyl, azulenyl,
heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl,
triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl,
anthracenyl, and naphthyl groups. In some embodiments, aryl groups
contain about 6 to about 14 carbons in the ring portions of the
groups. Aryl groups can be unsubstituted or substituted, as defined
herein. Representative substituted aryl groups can be
mono-substituted or substituted more than once, such as, but not
limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8
substituted naphthyl groups, which can be substituted with carbon
or noncarbon groups such as those listed herein.
[0036] The term "heterocyclyl" as used herein refers to aromatic
and nonaromatic ring compounds containing 3 or more ring members,
of which one or more is a heteroatom such as, but not limited to,
N, O, and S. Thus a heterocyclyl can be a cycloheteroalkyl, or a
heteroaryl, or if polycyclic, any combination thereof. In some
embodiments, heterocyclyl groups include 3 to about 20 ring
members, whereas other such groups have 3 to about 15 ring
members.
[0037] The term "heteroaryl" as used herein refers to aromatic ring
compounds containing 5 or more ring members, of which one or more
is a heteroatom such as, but not limited to, N, O, and S; for
instance, heteroaryl rings can have 5 to about 8-12 ring members. A
heteroaryl group is a variety of a heterocyclyl group that
possesses an aromatic electronic structure.
[0038] The terms "halo" or "halogen" or "halide," as used herein,
by themselves or as part of another substituent mean, unless
otherwise stated, a fluorine, chlorine, bromine, or iodine
atom.
[0039] The term "haloalkyl" group, as used herein, includes
mono-halo alkyl groups, poly-halo alkyl groups wherein all halo
atoms can be the same or different, and per-halo alkyl groups,
wherein all hydrogen atoms are replaced by halogen atoms, such as
fluoro. Examples of haloalkyls include trifluoromethyl,
1,1-dichloroethyl, 1,2-dichloroethyl,
1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.
[0040] The term "monovalent" as used herein refers to a substituent
connecting via a single bond to a substituted molecule. When a
substituent is monovalent, such as, for example, F or Cl, it is
bonded to the atom it is substituting by a single bond.
[0041] The term "solvent" as used herein refers to a liquid that
can dissolve a solid, liquid, or gas. Nonlimiting examples of
solvents are silicones, organic compounds, water, alcohols, ionic
liquids, and supercritical fluids.
[0042] The term "independently selected from" as used herein refers
to referenced groups being the same, different, or a mixture
thereof, unless the context clearly indicates otherwise. Thus,
under this definition, the phrase "X.sup.1, X.sup.2, and X.sup.3
are independently selected from noble gases" would include the
scenario where, for example, X.sup.1, X.sup.2, and X.sup.3 are all
the same, where X.sup.1, X.sup.2, and X.sup.3 are all different,
where X.sup.1 and X.sup.2 are the same but X.sup.3 is different,
and other analogous permutations.
[0043] The term "air" as used herein refers to a mixture of gases
with a composition approximately identical to the native
composition of gases taken from the atmosphere, generally at ground
level. In some examples, air is taken from the ambient
surroundings. Air has a composition that includes approximately 78%
nitrogen, 21% oxygen, 1% argon, and 0.04% carbon dioxide, as well
as small amounts of other gases.
[0044] The term "room temperature" as used herein refers to ambient
temperature, which can be, for example, between about 15.degree.
and about 28.degree. C.
[0045] The term "brown grease" as used herein includes waste
vegetable oil, animal fat, grease, and the like, such as trap
grease (e.g., grease recovered from wastewater), sewage grease
(e.g., from a sewage plant), and black grease. Brown grease from
traps and sewage plants is typically unsuitable for use as animal
feed. The term brown grease also encompasses other grease having a
free fatty acid (FFA) content greater than 20% and being unsuitable
for animal feed.
[0046] The term "yellow grease" as used herein includes for example
used frying oils such as, for example, those from deep fryers. It
also encompasses lower-quality grades of tallow from rendering
plants.
[0047] The term "renewable" as used herein refers to
nonpetroleum-derived. A feedstock can be considered renewable if it
contains a proportion of materials derived from nonpetroleum
sources, for example, about 1, 5, 10, 20, 30, 40, 50, 60, 70, 80,
90, 95, or about 99 wt % of the feedstock can include materials
derived from nonpetroleum sources. Likewise, a fuel can be
considered renewable if it contains a proportion of hydrocarbons
derived from nonpetroleum sources, for example about 1, 5, 10, 20,
30, 40, 50, 60, 70, 80, 90, 95, or about 99 wt % of the fuel can
include hydrocarbons derived from nonpetroleum sources.
Nonpetroleum sources can include, for example, any biological
source, such as plants, animals, or organisms such as algae.
[0048] The term "blendstock" as used herein refers to a composition
that can be blended with any other suitable composition to form a
fuel. A blendstock can form any suitable proportion of the final
fuel product, for example about 1, 5, 10, 20, 30, 40, 50, 60, 70,
80, 90, 95, or about 99 wt % of the final product. In some
examples, distillation can be used to form distinct blendstocks
(e.g., having a particular range of hydrocarbon chain lengths or
particular proportions of certain types of hydrocarbon compounds)
from a product mixture, and any number of different distinct
blendstock forms from one or different products can be blended in
suitable proportions to form a fuel.
[0049] Generally, psi pressures given herein are gauge pressures
unless otherwise indicated.
[0050] The term "fuel" as used herein can refer to a hydrocarbon
mixture, such as, for example, a distillate fuel, jet fuel, diesel
fuel, compression ignition fuel, gasoline, spark ignition fuel,
rocket fuel, marine fuel, or other fuel, qualifying as such by
virtue of having a set of chemical and physical properties that
comply with requirements delineated in a specification developed
and published by ASTM International (ASTM), European Standards
Organization (CEN), and/or the U.S. military. In some examples, a
fuel can be a liquid transportation fuel, for example, for surface
or air transport. Surface transport includes both terra firma and
oceanic transport. Fuels of this type are included, but not limited
to, ASTM specifications D975 (Diesel Fuel Oil), D1655 (Aviation
Turbine Fuels), D4814 (Automotive Spark Ignition Fuel); military
specifications MIL-DTL-83133G (Turbine Fuel, Aviation, Kerosene
Type), MIL-DTL-25576D (Propellant, Rocket-Grade Kerosene),
MIL-DTL-38219D (Turbine Fuel, Low Volatility), MIL-DTL-5624U
(Turbine Fuel, Aviation), MIL-DTL-16884L (Fuel, Naval Distillate),
and other such specifications for similar fuels.
[0051] As used herein, "kerosene" indicates a mixture including
hydrocarbons having a carbon number range from about C9 to C16 and
having a boiling point range of from about 149.degree. to
288.degree. C.
[0052] As used herein, "integrated" in terms of an integrated
process or an integrated method with respect to a feature such as
fuel production can indicate that the method or process can produce
a fuel without the addition of any blendstocks from outside the
process. For example, an integrated process for fuel production
that is integrated with respect to the fuel can produce a synthetic
fuel without the need for any petroleum-derived blendstocks. In
another example, an integrated process that is integrated with
respect to a solvent used as a starting material can use solvent
that is generated as a product of the process and recycled back to
the beginning. In another example, an integrated process that
integrated with respect to hydrogen gas that is used as a starting
material can use hydrogen gas that is generated as a by-product of
the process and recycled back or hydrogen gas that is purposefully
generated as a side product and recycled back. A process integrated
with respect to a particular feature can require the feature during
a start-up period before an integrated steady state is
achieved.
[0053] As used herein, "vacuum bottoms" refers to the residual
material left behind after vacuum distillation of hydrocarbon
mixtures and can include, for example, hydrocarbon waxes, heavy
oils, and petroleum residuals. Vacuum bottoms can be obtained from,
for example, a petroleum refinery. Vacuum bottoms can be, for
example, a viscous tarry sludge.
Description
[0054] Embodiments of the present invention are not limited to any
particular mechanism of action. Petroleum-derived aviation fuels
include paraffinic/isoparallinic, aromatic, and naphthenic
hydrocarbons. The hydrocarbons derived from plants are primarily
paraffinic and from coal are mainly aromatics and naphthenes; thus
generally hydrocarbons from these sources can only be used as
blendstocks to generate other fuels. However, by deriving
hydrocarbons from a suitable combination of coal and plant- or
animal-derived material, various embodiments of the present
invention advantageously allow the integrated or substantially
integrated generation of a synthetic aviation fuel.
[0055] Various embodiments of the present invention provide a
method of producing a synthetic fuel, for example, an aviation
fuel, from a combination of carbonaceous material, such as coal,
and renewable material. The method can include liquefaction coupled
with an upgrading process to give the fuel. In some examples, the
overall process can include a) liquefaction; b) catalytic
hydrotreating of carbonaceous material liquids, such as coal
liquids, to remove heteroatoms; c) saturation to hydrogenate the
aromatics to naphthenes; d) aromatization of at least part of the
saturated product stream; and e) catalytic isomerization of at
least part of the saturated product stream to produce isoparaffins.
In one example, blending the products from Steps d and e together
in the appropriate ratios can allow control over the composition of
the product fuel. In another example, adjusting the ratios of the
carbonaceous material and the biomass can allow control over the
composition of the product fuel. By controlling the composition of
the product fuel, various fuels can be produced, such as, for
example, gasoline, naptha, kerosene, jet fuel, or diesel fuel.
[0056] In various examples, the fuels produced by the present
method can not only meet but even exceed the military aviation
fuel-screening criteria, advantageously providing a pathway to
energy security to the U.S. military and the entire nation. In some
examples, fuels produced by the method of the present invention can
meet or exceed the specification parameters for JP-8, a
petroleum-based jet fuel widely used by the U.S. military,
including parameters such as freeze point, density, and flash
point. In some examples, the fuel can meet or exceed the thermal
stability specification of JP-8 fuel as determined by a QCM test.
In various examples, the present method can produce fuels that can
look and act identically or superiorly to petroleum-derived fuels
and that can thus be used interchangeably without any special
requirements, providing renewable options across the spectrum of
fuel needs. In some examples, superior qualities of the fuels of
the method as compared to petroleum-derived equivalent fuels can
include cleaner burning with less particulate emissions and having
a lower concentration of sulfur-containing compounds and
aromatics.
[0057] Herein the invention has been described with what feedstocks
are presently considered the preferred embodiments; however, it is
to be understood that the invention is not limited to the disclosed
embodiments, but rather is intended to cover various other readily
available feedstocks within the scope of the appended claims. For
example, adding tank bottoms or petroleum residuals, which are
generally considered as waste streams (for example in the petroleum
refining industry), as a feedstock for liquefaction can provide a
pathway for producing the key components of the transportation
fuels, for example, aviation fuels. In various embodiments, the
present method can be used to recover salable hydrocarbons from
tank bottoms or petroleum residuals, thus reducing the volume of
waste. Various examples of the liquefaction method provided by the
present invention can provide major economic and environmental
benefits to oil producers, while reducing their economic and
environmental liabilities.
Liquefaction of Carbonaceous Material and Biomass
[0058] Various embodiments of the present invention provide a
method of liquefaction of carbonaceous material and biomass. The
method includes providing or obtaining a feed mixture. The feed
mixture includes carbonaceous material and biomass. The method also
includes subjecting the feed mixture to liquefaction. The
liquefaction provides a product slurry. The carbonaceous material
includes a nonpetroleum fossil fuel or a petroleum refinery
residue.
[0059] The feed mixture includes a carbonaceous material. The
carbonaceous material can be any suitable carbonaceous material
that is either not provided from petroleum products or that is a
waste product from petroleum refining. For example, the
carbonaceous material can be a nonpetroleum fossil fuel or a
petroleum refinery residue, including petroleum waste greases and
other by-products of petroleum refining and other industrial
processes. Examples of nonpetroleum fossil fuels can include coal,
coal tar, wax from a Fischer-Tropsch (FT) process, petroleum
refinery residue, tar sand, or bitumen. Examples of coal can
include lignite, brown coal, jet coal, subbituminous coal,
bituminous coal, steel coal, anthracite, and graphite. In some
examples, the coal can be Illinois No. 6 coal. The coal can be in
any suitable form, such as pulverized coal, coat powder, or coal
dust. A single carbonaceous material can be used, or a combination
of carbonaceous materials can be used.
[0060] The feed mixture includes biomass. The biomass can be any
suitable biomass from which fuel components can be derived. The
biomass can be renewable. For example, the biomass can be an oil
derived from a biomaterial, such as an oil derived from plants such
as crops or an oil derived from algae. The crops represent a major
renewable resource that can be converted into hydrocarbons. If
crops or oils derived therefrom are added to coal as a feed for
direct liquefaction, in some examples, substantial reduction in
greenhouse gases can be achieved. The biomass or bio-oil can be
derived from any suitable biomaterial, such as, for example, straw,
stalks, cobs, beets, beet pulp, seed hulls, bagasse, algae, corn
starch, potato waste, sugar cane, or fruit waste. The biomass can
be biomass pyrolysis oil. The biomass can be waste oils or waste
grease that is produced as a waste stream from food industry and
industrial processes. The biomass can be animal fat. The biomass
can be grease, such as brown grease or yellow grease. The biomass
can be a tar. In some examples, mixing biomass or biomass-derived
fuel with carbonaceous materials such as coal potentially enhances
the liquid fuel yield and improves fuel quality to meet
specifications of transportation fuel.
[0061] Algae or algae oil can be advantageously selected as the
biomass in embodiments of the present invention. Algae is one of
the fastest-growing renewable resources. Algae is increasingly
studied as feed for fuel production. Microalgae can be used as a
CO.sub.2 avoidance approach that can be applied to coal-fired
utility plants. The carbon dioxide generated from coal and biomass
combustion as well as other industrial processes, including
liquefaction processes, can be used as a nutrient for microalgae
growth. As a result, for example, carbon-neutrality can be
increased, and the coal industry can reduce its carbon footprint.
Therefore, the use of algae as an additive to coal for fuel
production is also attractive as it can reduce the carbon
footprints of the liquefaction process or even make it
carbon-neutral.
[0062] The feed mixture is a mixture of at least the carbonaceous
material and the biomass. The mixture can be mixed to any suitable
extent, and by any suitable method, provided that the mixture is
suitable for liquefaction as described herein. The mixture can be
any suitable proportion of carbonaceous material and biomass. For
example, the mass ratio of carbonaceous material to biomass can
equal to or less than about 0.001:1, 0.002:1, 0.004:1, 0.008:1,
0.01:1, 0.02:1, 0.04:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1,
0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1,
1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 5:1, 10:1, 25:1, 50:1, 75:1,
100:1, 250:1, 500:1, 750:1, or less than or equal to about 1000:1.
In some embodiments, the mass ratio of carbonaceous material to
biomass can be about 0.00001-99,999 to 1, about 0.01-10 to 1, or
about 0.05-0.7 to 1.
[0063] The feed mixture can further include a solvent. The solvent
can be any suitable solvent, provided the feed mixture can be
subjected to the liquefaction process described herein. For
example, the solvent can be any suitable organic solvent. In some
examples, the solvent can be a carbonaceous material-derived heavy
liquid, such as a coal-derived heavy liquid, such as a mixture of
hydrocarbons derived from coal having a boiling point of about
343.degree. to 538.degree. C. In some embodiments, the solvent is
derived from nonpetroleum fossil fuel or from a petroleum refinery
residue. In some examples, the solvent can be derived at least in
part or wholly from the product of the liquefaction method or from
the product of the fuel-production method, as described herein. By
deriving the solvent from the products of the process, the process
can be integrated with respect to solvent requirements. In other
examples, the solvent can be in whole or in part derived from
materials not produced by embodiments of the present method. The
amount of solvent can be any suitable amount. For example, the mass
ratio of solvent to carbonaceous material and biomass can be less
than or equal to about 0:1, 0.001:1, 0.002:1, 0.004:1, 0.008:1,
0.01:1, 0.02:1, 0.04:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1,
0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1,
1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 5:1, 10:1, 25:1, or less than or
equal to about 50:1. In some examples, the mass ratio of solvent to
carbonaceous material and biomass can be about 0-2 to 1, or about
0.1-1.6 to 1.
[0064] The method includes subjecting the feed mixture to
liquefaction. The liquefaction can be any suitable liquefaction,
such that a product mixture is formed from which fuel can be
derived. The liquefaction can be a direct liquefaction, wherein the
feed mixture is converted directly into a liquid fuel that can be
upgraded to meet specific fuel specifications. In some examples,
the liquefaction can be a carbonization liquefaction, such as
including coking coal between about 360.degree. and 750.degree. C.
In some examples, the liquefaction can be a hydrogenation
liquefaction, such as a Bergius process, solvent refined coal-I or
-II processes, consul synthetic fuels process, H-coal process,
Exxon donor solvent process, integrated two-stage liquefaction,
multistage slurry phase liquefaction, or NUS Corporation
hydrogenation process. In some embodiments, subjecting the feed
mixture to liquefaction can include contacting the feed mixture
with a liquefaction catalyst and hydrogen gas. In some embodiments,
the temperature during the contacting of the feed mixture and the
liquefaction catalyst during the liquefaction can be about
200.degree. to 700.degree. C., about 200.degree. to 600.degree. C.,
about 300.degree. to 600.degree. C., about 350.degree. to
500.degree. C., about 400.degree. to 500.degree. C., about
450.degree. C., or about 400.degree. C. In some embodiments, the
pressure during the contacting of the feed mixture and the
liquefaction catalyst during the liquefaction can be about 50 to
450 atm, about 100 to 350 atm, about 150 to 250 atm, or about 200
atm.
[0065] The liquefaction catalyst can be any suitable liquefaction
catalyst. For example, the liquefaction catalyst can be iron-based
catalysts such as a nickel catalyst, cobalt catalyst, a molybdenum
catalyst, or any combination thereof. In some examples, the
liquefaction catalyst is a nickel-molybdenum catalyst or a
cobalt-molybdenum catalyst, and can be sulfided or unsulfided. In
some examples, the concentration of the catalyst can be about
250-350 ppm, about 100-500 ppm, or about 10-1000 ppm.
[0066] The hydrogen gas can be provided from any suitable source of
hydrogen gas. For example, the hydrogen gas can be partially or
fully commercially obtained. In other examples, the hydrogen gas
can be generated on-site. The hydrogen gas can be partially or
fully generated from the liquefaction process or from the fuel
upgrading method; for example, the hydrogen can be generated from a
by-product of the liquefaction or fuel-upgrading process, such that
the method of fuel production or liquefaction is integrated with
respect to hydrogen gas.
[0067] The product of the liquefaction is a product slurry. The
product slurry contains the unupgraded fuel derived from the
carbonaceous material and the biomass, along with any solids
remaining from the carbonaceous material and the biomass. The fuel
in the product slurry generally contains significant amounts of
contaminants such as sulfur, oxygen, and nitrogen, which can be
removed via an upgrading process, such as the fuel production
process described herein.
Method of Fuel Production from Carbonaceous Material and
Biomass
[0068] Various embodiments of the present invention provide a
method of fuel production from carbonaceous material and biomass.
The method includes providing or obtaining a product slurry or a
material having similar qualities thereto, which can be a product
of embodiments of the liquefaction process herein, or which can be
obtained or provided in any suitable fashion. The method also
includes separating the product slurry. Separating the product
slurry provides a conversion component. The method also includes
processing the conversion component. Processing provides a fuel. In
some embodiments, the method of making a fuel from carbonaceous
material and biomass is substantially or fully integrated.
[0069] In some embodiments, the present invention provides a method
of fuel production from carbonaceous material and biomass. In other
embodiments, the present invention provides a method of fuel
production from a product slurry or similar mixture derived from
carbonacoues material and biomass.
[0070] The method of fuel production can include separation of the
product slurry. The separation can be any suitable separation, such
that a fraction or part of the product slurry is provided that is
suitable for upgrading to a fuel that meets a fuel specification.
In some examples, the separating can include filtering, such as
using gravity or pressure to drive the product slurry through a
filter medium, for example a frit or filter aid, to separate the
solids from the liquid. In some examples, the separating can
include a distillation with any suitable number of stages and at
any suitable temperature and pressure. The distillation can produce
a distillate, and any suitable fraction of the distillate can be
brought forward in the method. In some examples, a distillation can
be performed to provide a fraction having a boiling point of about
110.degree. to 390.degree. C., or about 149.degree. to 343.degree.
C. The separated fraction that proceeds to later steps of the fuel
production method can be referred to as the conversion
component.
[0071] The conversion component resulting from the separation of
the product slurry can be processed to give a fuel. The fuel that
results from the method can be any suitable fuel. The processing
can clean the fuel of contaminants such as sulfur, oxygen, and
nitrogen and can cause the fuel to have the proper mixture of
hydrocarbons such that the properties of the fuel are in accordance
with any of various fuel specifications.
[0072] The fuel that results from the processing can be any
suitable fuel. The fuel can be a liquid transportation fuel. For
example, the fuel can be gasoline, naphtha, kerosene, jet fuel, or
diesel fuel. The fuel can comply with any suitable fuel standard.
In some embodiments, a fuel produced by the process has a
composition that complies with JP-5, JP-8, or BUFF
requirements.
[0073] In some embodiments, the method of fuel generation can be
fully integrated with respect to the fuel produced, such that the
fuel produced from the process without any additives or added
blendstocks is sufficient to meet a particular fuel specification.
In some examples, the method can be substantially or partially
integrated, such that the method of fuel generation produces a fuel
that only requires a small amount of additives or blendstocks to
meet a particular fuel specification, such that the final fuel that
meets the specification includes equal to or less than about 99.999
wt % of the product of the method of fuel generation, 99.99, 99.9,
99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 85, 80, 75, 50, or about 25
wt % of the product of the method of fuel generation.
Processing
[0074] The processing can be any suitable processing that provides
a fuel that meets a particular fuel specification from the
conversion component. The processing can be any suitable processing
that provides at least part of a fuel that meets a particular fuel
specification (e.g., in some examples, the process can provide a
blendstock) from the conversion component. In some examples, the
processing can be any suitable method of fuel upgrading and
preparation that is known to one of ordinary skill in the art. For
example, the processing can include any one or any combination of
hydrotreating, hydrogenating, isomerizing, aromatizing, and
blending in any suitable order.
[0075] In some embodiments, the processing can include first
hydrotreating, next hydrogenating, next either isomerizing or
aromatizing or a combination thereof, and next blending. In some
examples, one portion of the hydrogenated product can be
isomerized, one portion of the hydrogenated product can be
aromatized, and the products or product of isomerization,
aromatization, or both can be suitably blended to produce a fuel
meeting a particular specification. In some embodiments, a portion
or all of the hydrogenated product can be isomerized, but no
portion of the hydrogenated product be subjected to aromatization.
In some embodiments, a portion or all of the hydrogenated product
can be aromatized, but no portion of the hydrogenated product
subjected to isomerization. For example, the mass ratio of
hydrogenated product that is isomerized to hydrogenated product
that is aromatized can be equal to or less than about 0.001:1,
0.002:1, 0.004:1, 0.008:1, 0.01:1, 0.02:1, 0.04:1, 0.08:1, 0.1:1,
0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1,
1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 5:1,
10:1, 25:1, 50:1, 75:1, 100:1, 250:1, 500:1, 750:1, or less than or
equal to about 1000:1. In some examples, the mass ratio of
hydrogenated product that is isomerized to hydrogenated product
that is aromatized can be about 0 to about 99, 999:1.
[0076] Between any of hydrotreating, hydrogenating, isomerizing,
aromatizing, and blending, a separation can occur to selectively
only bring particular products forward to the next step. For
example, a distillation can be performed to only bring a particular
fraction of the distillate forward.
[0077] In any of hydrotreating, hydrogenating, isomerizing, and
aromatizing, the liquid hourly space velocities (LHSV) can be about
0.01 reactor volumes/hr (e.g., hr.sup.-1) to 20 hr.sup.-1, about
0.1 to 8 hr.sup.-1, about 0.5 to 4 hr.sup.-1, or about 0.8 to 1.2
hr.sup.-1. Any suitable time of reaction and hydrogen flow rate can
be used depending on the space velocity conditions, pressure,
temperature, and other conditions, suitable to bring about the
desired chemical transformation.
Hydrotreating the Conversion Component
[0078] In some embodiments, the processing can include
hydrotreating. For example, the conversion component can be
hydrotreated. Hydrotreating gives a hydrotreated material. The
hydrotreating can be any suitable hydrotreating that provides a
material suitable for moving forward in the processing to produce
all or at least part of a fuel that meets a particular fuel
specification. In some examples, the hydrotreating can be any
suitable method of hydrotreating that is known to one of ordinary
skill in the art.
[0079] The term "hydrotreatment" as used herein is used to refer to
a catalytic process performed in the presence of hydrogen that
includes reductive chemical reactions, such as, for example,
reduction of unsaturated bonds and reduction of carbon to lesser
oxidation states via removal of bonds to oxygen or other
heteroatoms, including, for example, carboxylate reduction,
carboxylate decarboxylation, carboxylate decarbonylation, alkene
reduction, reduction of conjugated or aromatic unsaturated bonds,
reduction of any carbon-oxygen bond including, for example,
conversion of glycerine to propane, or other reactions including
carbon-carbon bond cracking and cycloparaffin formation via
cyclization, or cycloparaffin formation via cyclization followed by
hydrogenation/saturation of conjugated or nonconjugated C--C bonds,
or aromatization. For example, hydrotreatment can include a
catalytic process whereby oxygen is removed from organic compounds,
for example as water (hydrodeoxygenation); sulfur from organic
sulfur compounds, for example as dihydrogen sulfide
(hydrodesulfurization); nitrogen from organic nitrogen compounds,
for example as ammonia (hydrodenitrogenation); and halogens from
organic compounds, for example, as chlorine from organic chloride
compounds as hydrochloric acid (hydrodechlorination).
[0080] In some embodiments, hydrotreating can include contacting
the conversion component with a hydrotreatment catalyst and
hydrogen gas. The contacting can be any suitable contacting. For
example, the hydrotreatment catalyst and hydrogen gas can be
contacted with the conversion component in a reactor. The
hydrotreating can occur at any suitable temperature, pressure, and
for any suitable time such that the hydrotreating generates
suitable hydrotreated material for moving forward in the
processing. The temperature can be about 150.degree. to 800.degree.
C., about 250.degree. to 600.degree. C., about 200.degree. to
500.degree. C., about 250.degree. to 450.degree. C., about
300.degree. to 550.degree. C., about 300.degree. to 400.degree. C.,
or about 340.degree. to 530.degree. C. Reactor pressures can be
about 1 to 750 atm, about 10 to 500 atm, about 10 to 300 atm, or
about 100 to 150 atm. In some embodiments, reactor pressures can be
about 25 to 250 atm, while in some embodiments, reactor pressures
can be about 60 to 200 atm.
[0081] The hydrotreating catalyst can be any suitable hydrotreating
catalyst. The hydrotreating catalyst can include one or more metals
from IUPAC groups 6, 8, 9, and 10 of the periodic table of the
elements. In some examples, the one or more metals can be selected
from palladium (Pd), platinum (Pt), nickel (Ni), and combinations
thereof. In embodiments, the catalyst is a nickel-molybdenum (NiMo)
catalyst including nickel and molybdenum. In some embodiments, the
catalyst is a cobalt-molybdenum (CoMo) catalyst. The hydrotreating
catalyst can include supported or unsupported metals. In various
embodiments, the catalyst includes a support. In applications, the
support includes alumina, silica, or a combination thereof. The
catalyst can be a supported NiMo or CoMo catalyst. In embodiments,
NiMo/Al.sub.2O.sub.3--SiO.sub.2 or CoMo--Al.sub.2O.sub.3 catalyst
is utilized. In some embodiments, a Ni catalyst is utilized. In
some embodiments, a molybdenum catalyst is utilized. In some
embodiments, a catalyst with any suitable proportion of Ni and Mo
is utilized.
[0082] Catalysts having any suitable type or combination of active
sites or structures can be used as the hydrotreating catalyst. In
various examples, catalysts with Type I active sites or structures
can be utilized; in other examples, catalysts without Type II
active sites or structures can be utilized. In various examples,
catalysts with Type II active sites or structures can be utilized;
in other examples, catalysts without Type II active sites or
structures can be utilized.
Hydrogenating the Hydrotreated Material
[0083] In some embodiments, the processing can include
hydrogenating. For example, the hydrotreated material can be
hydrogenated. Hydrogenation gives a hydrogenated material. The
hydrogenating can be any suitable hydrogenating that provides a
material suitable for moving forward in the processing to produce
all or at least part of a fuel that meets a particular fuel
specification. In some examples, the hydrogenating can be any
suitable method of hydrogenating that is known to one of ordinary
skill in the art. Hydrogenation can include the reaction of
hydrogen with unsaturated bonds, including aromatic or conjugated
bonds, such as carbon-carbon unsaturated bonds, carbon-heteroatom
unsaturated bonds, or heteroatom-heteroatom unsaturated bonds, to
form a saturated bond.
[0084] Any suitable proportion of the hydrotreated material can be
hydrogenated in the hydrogenation step. For example, about 1, 5,
10, 20, 30, 40, 50, 60, 70, 80, 90 or about 95 wt % of the
hydrotreated material can be hydrogenated. In some examples,
multiple contactings, or passes, can be performed to elicit a
desired proportion of hydrogenation. In some example, each
contacting or pass provides about 1, 5, 10, 20, 30, 40, 50, or
about 60 wt % hydrogenation of the hydrocarbon. Any suitable number
of contacting or passes can be conducted, for example, 1, 2, 3, 4,
5, 6, or 7 contactings or passes can be conducted.
[0085] In some embodiments, hydrogenating can include contacting
hydrotreated material with a hydrogenation catalyst and hydrogen
gas. The contacting can be any suitable contacting. For example,
the hydrogenation catalyst and hydrogen gas can be contacted with
the hydrotreated material in a reactor. The hydrogenating can occur
at any suitable temperature, pressure, and for any suitable time
such that the hydrogenation generates suitable hydrogenated
material for moving forward in the processing. In some examples,
during the hydrogenating the temperature can be about 50.degree. to
400.degree. C., about 50.degree. to 300.degree. C., about
100.degree. to 250.degree. C., about 100.degree. to 150.degree. C.,
about 150.degree. to 200.degree. C., about 200.degree. to
250.degree. C., or about 250.degree. to 300.degree. C. In some
examples, during the hydrogenating, the pressure can be about 10 to
250 atm, about 25 to 175 atm, or about 68 to 136 atm.
[0086] The hydrogenation catalyst can be any suitable hydrogenation
catalyst. The catalyst can include one or more metals from IUPAC
groups 6, 8, 9, and 10 of the periodic table of the elements. The
hydrogenation catalyst can be any hydrogenation catalyst known to
one of ordinary skill in the art. For example, the catalyst can be
a palladium catalyst, a platinum catalyst, a nickel catalyst, or a
catalyst including any combination of at least two of palladium,
platinum, and nickel. The hydrogenation catalyst can be
unsupported. In some embodiments, the hydrogenation catalyst can be
supported on any suitable support, for example, on alumina or
silica-alumina. In some examples, the hydrogenation catalyst is a
platinum-zeolite catalyst.
Isomerizing the Hydrotreated Material
[0087] In some embodiments, the processing can include isomerizing.
Isomerizing gives an isomerized material. For example, at least
some of the hydrogenated material can be isomerized. The
isomerizing can be any suitable isomerizing that provides a
material suitable for moving forward in the processing to produce
all or at least part of a fuel that meets a particular fuel
specification. In some examples, the isomerizing can be any
suitable method of isomerizing that is known to one of ordinary
skill in the art. Isomerizing can be an optional step. In some
embodiments, isomerizing is performed. In other embodiments,
isomerizing is not performed. In some examples, at least one of
aromatizing and isomerizing is performed. In some embodiments, both
aromatizing and isomerizing are performed. In some embodiments,
aromatizing and isomerizing are performed simultaneously,
sequentially, or any combination thereof.
[0088] Isomerizing can include breaking and reforming carbon-carbon
bonds to create branched hydrocarbons from straight-chain
hydrocarbons or to increase the branching of already-branched
hydrocarbons. In some embodiments, depending on the process
conditions, such as the type of catalyst, temperature, and pressure
used, some aromatization can occur in the isomerizing step,
although the isomerization step substantially causes isomerization
as compared to aromatization. In other embodiments, the isomerizing
step causes predominantly or only isomerization as compared to
aromatization.
[0089] In some examples, the isomerization step can include a
dewatering step. The dewatering step can include removal of water
from the starting material for the isomerization step. The
dewatering step can include any suitable procedure that removes a
suitable amount of water from the hydrocarbon starting material. In
some examples, the dewatering step can include cooling the
hydrocarbon mixture to any suitable temperature; for example the
hydrocarbon mixture can be cooled to ambient temperature (e.g.,
20.degree.-30.degree. C.). The dewatering step can include allowing
the less polar hydrocarbon-containing phase to separate from a more
polar water-containing phase. The water-containing phase can then
be physically separated from the hydrocarbon-containing phase. In
some examples, the hydrocarbon can be placed in contact with
molecular sieves, for instance 4-.ANG. molecular sieves, which can
further remove water. Generally, for larger amounts of water, a
phase separation can be performed first, then a second step
contacting with molecular sieves.
[0090] In some examples, the isomerization step can include a
deacidification step. The deacidification step can include removal
of acid from the starting material for the isomerization step. Any
suitable method of acid removal can be used for the deacidification
step. In one example, removal of the water-containing phase during
a dewatering step can substantially remove the acid, because of
preference of the acid to reside in the more polar water-containing
phase, advantageously combining dewatering with deacidification. In
some examples, treatment of the undewatered or dewatered
hydrocarbons with a basic material can allow for deacidification.
In some embodiments, contacting the hydrocarbons with molecular
sieves can further deacidify the hydrocarbons, because of basic
properties of certain molecular sieves, advantageously combining
dewatering with deacidification.
[0091] In some embodiments, isomerizing can include contacting
hydrogenated material with a isomerization catalyst and hydrogen
gas. The contacting can be any suitable contacting. For example,
the isomerization catalyst and hydrogen gas can be contacted with
the hydrogenated material in a reactor. The isomerization can occur
at any suitable temperature, pressure, and for any suitable time
such that the isomerization generates suitable isomerized material
for moving forward in the processing. Any suitable proportion of
the hydrogenated material can be isomerized in the isomerization
step. For example, about 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90
or about 95 wt % of the hydrogenated material can be isomerized. In
some examples, multiple contactings, or passes, can be performed to
elicit a desired proportion of isomerization of the hydrogenated
material. In some example, each contacting or pass provides about
1, 5, 10, 20, 30, 40, 50, or about 60 wt % isomerization of the
hydrogenated material. Any suitable number of contacting or passes
can be conducted, for example, 1, 2, 3, 4, 5, 6, or 7 contactings
or passes can be conducted.
[0092] Any suitable isomerization catalyst can be used to effect
the isomerization. For example, catalysts which possess a suitable
balance of catalytic metal dehydrogenation/hydrogenation activity
and support acidity can be used. Support acidity can be a
controlling feature, along with operational temperature, which can
determine the amount of carbon chain cracking that will occur.
Strongly acidic supports can result in greater amounts of chain
cracking at a given temperature than a weakly acidic support at the
same temperature. Support acidity can be controlled by the
silica-alumina ratio in the support. Additionally, the
silica-alumina ratio in the support can control the pore size of
the support. Pore size can also control cracking to a certain
degree, again based upon operational temperature. Isomerization
catalysts with strong dehydrogenation/hydrogenation activity and
weak support acidity may find greater utility in the production of
diesel fuel fractions. Isomerization catalysts with moderate
acidity and strong dehydrogenation/hydrogenation activity may find
greater utility in the production of jet fuel fractions.
Isomerization catalysts with strong acidity may find greater
utility in production of naphtha fractions. Suitable isomerization
catalysts include any suitable isomerization catalyst known to one
of ordinary skill in the art, such as those having two or more
catalytic metals and a silica-alumina support, wherein the metals
and support can be present in any suitable proportion. The catalyst
can include one or more metals from IUPAC Groups 6, 8, 9, and 10 of
the periodic table of the elements. The isomerization catalyst can
be any isomerization catalyst known to one of ordinary skill in the
art. For example, the catalyst can be a palladium catalyst, a
platinum catalyst, a nickel catalyst, a molybdenum catalyst, or a
catalyst including any combination of at least two of palladium,
platinum, nickel, and molybdenum. The isomerization catalyst can be
unsupported. In some embodiments, the isomerization catalyst can be
supported on any suitable support, for example, on alumina or
silica-alumina. In various embodiments, the isomerization catalyst
can include a nickel-molybdenum catalyst.
[0093] Any suitable temperature can be used during the
isomerization. For example, operation of an isomerization catalyst
at a moderately low temperature, such as about 280.degree. to
380.degree. C. or about 320.degree. to 340.degree. C., may find
utility in the production of diesel fuel, especially
low-cloud-point diesel fuel. Operation of an isomerization catalyst
at moderate temperature may find utility in the production or jet
fuel. Operation of an isomerization catalyst at high temperature,
such as about 320.degree. to 420.degree. C. or about 360.degree. to
380.degree. C., may find utility in the production of naphtha and
gasoline-blendstock fuels. Suitable temperature ranges can include,
for example, about 100.degree. to 500.degree. C., about 200.degree.
to 450.degree. C., about 250.degree. to 400.degree. C., about
300.degree. to 360.degree. C., or about 330.degree. to 400.degree.
C.
[0094] Any suitable pressure can be used during the isomerization.
For example, operation of an isomerization catalyst at high
hydrogen pressure, such as about 600 to 900 psig or about 700 to
800 psig, may suppress the dehydrogenation activity of the
catalyst, resulting in only slight isomerization, but potentially
significant cracking. Operation of an isomerization catalyst at
moderate hydrogen pressure, such as about 250 to 700 psig, may
provide high isomerization with only slight cracking. Operation of
an isomerization catalyst at low hydrogen pressure, such as about
150 to 250 psig, may suppress the hydrogenation activity of the
catalyst, resulting in significant cracking as well as alkene
production. Suitable hydrogen pressures can include about 100 to
900 psig. Suitable isomerization pressures can include about 1 to
200 atm, about 5 to 150 atm, about 10 to 100 atm, or about 30 to 70
atm.
[0095] Any suitable liquid flow rate can be used during the
isomerization. For example, a liquid flow rate of about 0.1 to 20
reactor volumes per hour or about 0.5 to 10 reactor volumes per
hour can be a suitable flow rate.
[0096] Any suitable amount of the hydrogenated material can be
subjected to isomerization, such that sufficient isomerized
material is generated to form a desired fuel blend. For example,
equal to or less than about 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%,
70%, 80%, 90%, or about 100% of the hydrogenated material can be
subjected to the isomerization. For example about 50%-95%, about
75%-95%, about 80%-90%, or about 85% of the hydrogenated material
can be subjected to the isomerization.
Aromatizing the Hydrotreated Material
[0097] In some embodiments, the processing can include aromatizing.
Aromatizing gives an aromatized material. For example, at least
some of the hydrogenated material can be aromatized. The
aromatizing can be any suitable aromatizing that provides a
material suitable for moving forward in the processing to produce
all or at least part of a fuel that meets a particular fuel
specification. In some examples, the aromatizing can be any
suitable method of aromatizing that is known to one of ordinary
skill in the art. Aromatizing can be an optional step. In some
embodiments, aromatizing is performed. In other embodiments,
aromatizing is not performed. In some examples, at least one of
aromatizing and isomerizing is performed. In some embodiments, both
aromatizing and isomerizing are performed. In some embodiments,
aromatizing and isomerizing are performed simultaneously,
sequentially, or any combination thereof.
[0098] Aromatization includes the removal of hydrogen atoms to
produce aromatic unsaturated in carbon-carbon bonds. Depending on
the process conditions, such as the type of catalyst, temperature,
and pressure used, some isomerization can occur in the
aromatization step, although the aromatization step substantially
causes aromatization as compared to isomerization. In some
embodiments, the aromatizing step causes predominantly or only
aromatization as compared to isomerization.
[0099] In some examples, the aromatization step can include a
dewatering step. The dewatering step can include removal of water
from the starting material for the aromatization step. The
dewatering step can include any suitable procedure that removes a
suitable amount of water from the hydrocarbon starting material. In
some examples, the dewatering step can include cooling the
hydrocarbon mixture to any suitable temperature, for example the
hydrocarbon mixture can be cooled to ambient temperature (e.g.,
20.degree.-30.degree. C.). The dewatering step can include allowing
the less polar hydrocarbon-containing phase to separate from a more
polar water-containing phase. The water-containing phase can then
be physically separated from the hydrocarbon-containing phase. In
some examples, the hydrocarbon can be placed in contact with
molecular sieves, for instance 4-.ANG. molecular sieves, which can
further remove water. Generally, for larger amounts of water, a
phase separation can be performed first, then a second step
contacting with molecular sieves.
[0100] In some examples, the aromatization step can include a
deacidification step. The deacidification step can include removal
of acid from the starting material for the aromatization step. Any
suitable method of acid removal can be used for the deacidification
step. In one example, removal of the water-containing phase during
a dewatering step can substantially remove the acid, because of the
preference of the acid to reside in the more polar water-containing
phase, advantageously combining dewatering with deacidification. In
some examples, treatment of the undewatered or dewatered
hydrocarbons with a basic material can allow for deacidification.
In some embodiments, contacting the hydrocarbons with molecular
sieves can further deacidify the hydrocarbons, because of basic
properties of certain molecular sieves, advantageously combining
dewatering with deacidification.
[0101] Any suitable proportion of the hydrocarbon can be aromatized
in the aromatization step. For example, about 1, 5, 10, 20, 30, 40,
50, 60, 70, 80, 90 or about 95 wt % of the hydrocarbon can be
aromatized. In some examples, multiple contactings, or passes, can
be performed to elicit a desired proportion of aromatization of the
hydrocarbon. In some examples, each contacting or pass provides
about 1, 5, 10, 20, 30, 40, 50, or about 60 wt % aromatization of
the hydrocarbon. Any suitable number of contacting or passes can be
conducted, for example, 1, 2, 3, 4, 5, 6, or 7 contactings or
passes can be conducted.
[0102] In some embodiments, aromatizing can include contacting
hydrogenated material with an aromatization catalyst and hydrogen
gas. The contacting can be any suitable contacting. For example,
the aromatization catalyst and hydrogen gas can be contacted with
the hydrogenated material in a reactor. The aromatization can occur
at any suitable temperature, pressure, and for any suitable time
such that the aromatization generates suitable aromatized material
for moving forward in the processing. In some examples, during the
aromatization, the temperature can be about 100.degree. to
1000.degree. C., about 350.degree. to 750.degree. C., or about
500.degree. to 550.degree. C. In some examples, during the
aromatization, the pressure can be about 50 to 750 psig, about 100
to 500 psig, about 250 to 350 psig, about 1 to 200 atm, about 5 to
150 atm, about 10 to 100 atm, or about 20 to 40 atm.
[0103] The aromatization catalyst can be any suitable aromatization
catalyst. The catalyst can include one or more metals from IUPAC
Groups 6, 8, 9, and 10 of the periodic table of the elements. The
aromatization catalyst can be any aromatization catalyst known to
one of ordinary skill in the art. For example, the catalyst can be
a palladium catalyst, a platinum catalyst, a nickel catalyst, or a
catalyst including any combination of at least two of palladium,
platinum, and nickel. The aromatization catalyst can be
unsupported. In some embodiments, the aromatization catalyst can be
supported on any suitable support, for example, on alumina or
silica-alumina. In some examples, the aromatization catalyst is
platinum on zeolite.
[0104] Any suitable amount of the hydrogenated material can be
subjected to aromatization, such that sufficient aromatized
material is generated to form a desired fuel blend. For example,
equal to or less than about 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%,
70%, 80%, 90%, or about 100% of the hydrotreated material can be
subjected to the aromatization. For example about 50%-95%, about
75%-95%, about 80%-90%, or about 85% of the hydrogenated material
can be subjected to the isomerization.
Blending the Isomerized Material and the Aromatized Material
[0105] In some embodiments, the processing can include blending.
Blending gives a fuel. For example, at least some of the isomerized
material and at least some of the aromatized material can be
blended. The blending can be any suitable blending that provides
all or at least part of a fuel that meets a particular fuel
specification. In some examples, the blending can be any suitable
method of blending that is known to one of ordinary skill in the
art.
[0106] Any suitable proportion of isomerized material and
aromatized material can be blended to generate a fuel having a
particular specification. In order to achieve a desired mass ratio
of isomerized material and aromatized material, any suitable amount
of the isomerized material or aromatized material can be use to
form the blend. For example, in the blend, the mass ratio of the
isomerized material blended to the aromatized material blended can
be equal to or less than about 0.001:1, 0.002:1, 0.004:1, 0.008:1,
0.01:1, 0.02:1, 0.04:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1,
0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1,
1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 5:1, 10:1, 15:1, 20:1, 25:1, 50:1,
75:1, 100:1, 250:1, 500:1, 750:1, or less than or equal to about
1000:1, depending on the type of fuel desired. In some examples,
the blend includes the mass ratio of the isomerized material in a
mass percent of about 50%-95%, with the remainder aromatized
material, for example, 80-90 wt % isomerized material, about 83-88
wt % isomerized material, or about 85% isomerized material. In some
examples, the blended material is sufficient to fulfill a
particular fuel specification. In other embodiments, the blended
fuel is combined with a suitable blendstock to generate a fuel that
fulfills a particular fuel specification.
[0107] A flowchart corresponding to one embodiment of the present
invention is illustrated in FIG. 1. The present invention provides
a method of fuel production from coal and biomass. The method (100)
includes providing or obtaining a feed mixture (102, 104, and 106).
The mixture can include coal (102) and bio-oil (104). The mixture
can also include a coal-derived solvent (106). The method also
includes subjecting the feed mixture to liquefaction (110). The
liquefaction can include contacting the feed mixture with hydrogen
gas and a catalyst (108). The liquefaction provides a product
slurry (112). The method also includes distilling the product
slurry. Distilling provides distillate fractions, such as naphtha
(114), distillate fraction (116, conversion component), solvent
(118), and residue (120). The method also includes hydrotreating
the distillate (124). The hydrotreating (124) can include
contacting the distillate with hydrogen gas and a hydrotreating
catalyst (122). Hydrotreating provides a hydrotreated material. The
method also includes hydrogenating the hydrotreated material (128).
Hydrogenating can include contacting the hydrotreated material with
hydrogen gas and a hydrogenation catalyst (126). Hydrogenating
(128) provides a hydrogenated material. The method also includes
isomerizing at least some of the hydrotreated material (132).
Isomerizing can include contacting the hydrotreated material with
hydrogen gas and an isomerization catalyst (130). Isomerizing at
least some of the hydrotreated material (132) provides an
isomerized material. The method also includes aromatizing at least
some of the hydrotreated material (134). Aromatizing can include
contacting the hydrogenated material with hydrogen gas and an
aromatization catalyst (136). The aromatizing provides an
aromatized material. The method also includes blending at least
some of the isomerized material and at least some of the aromatized
material. The blending provides a composite fuel (138). The
composite fuel can include naphtha (140) which can be reformed or
used as motor gasoline (146). The composite fuel can include jet
fuel (142) which can be tested (148) to demonstrate if it meets jet
fuel specifications. The composite fuel can include heavy oil (144)
which can be recycled or used as a diesel additive. Alternatively,
the isomerized and aromatized products can be distilled and
appropriately blended to give a composite fuel that only or
predominatly includes jet fuel or another desired fuel
fraction.
EXAMPLES
[0108] The present invention can be better understood by reference
to the following examples which are offered by way of illustration.
The present invention is not limited to the examples given
herein.
[0109] General Methods.
[0110] The liquefaction of coal-biomass mixtures was performed,
producing a volume of middle distillate for further
hydroprocessing/product quality testing to produce liquid fuels.
The tests for producing middle distillate were carried out in a
2-gallon autoclave rated at 347 atm at 340.degree. C. with an
ability to provide for hydrogen flow. The coal used was Illinois
No. 6 coal.
Example 1
Production of Solvent
[0111] Initial tests were performed to produce test coal-derived
solvent for the liquefaction runs. A slurry including coal
tar-derived solvent (b.p., 343.degree.-538.degree. C.) was formed
with predried pulverized coal. The slurry was contacted with a
commercial presulfided CoMo catalyst under a hydrogen pressure in
the autoclave. The experiment was run at 450.degree. C., a pressure
of 78 atmo, and under a constant flow of 13 scfh hydrogen for 60
minutes. The product slurry was distilled to produce test
coal-derived solvent (b.p., 343.degree.-538.degree. C.). The
liquefaction procedure was repeated using the solvent generated to
produce solvent using a recycled solvent.
Example 2
Runs 1-3: Liquefaction of Canola Oil and Coal
[0112] After a desired quantity of the test coal-derived solvent
was generated using the recycled solvent, a slurry including coal,
canola oil, vacuum bottoms (e.g., hydrocarbon waxes similar to
petroleum residue left after refining of crude oil) and
coal-derived solvent (having a mass ratio of 0.8:0.2:1.0:1.0), and
0.03 wt % of commercial presulfided CoMo catalyst was placed in the
autoclave. The sulfur in the coal was enough to keep the catalyst
sulfided during the run. The reactor was charged with 70 atm
hydrogen pressure and placed in the heating jacket. The reactor was
heated to 350.degree. C. to convert triglycerides into paraffins
via hydrolysis and decarbonylation and then heated and pressurized
to the temperature and pressure shown in Table 1, which also shows
other operating conditions. A constant hydrogen flow was maintained
throughout the run. The runs were carried out in hydrogen
flow-through mode (13.18 scfh). At the end of the run, the reactor
was cooled to room temperature and degassed. The gas was metered
into a gas bag, and total volume of the gas was recorded. The
reactor was opened, and the contents of the reactor were distilled
to obtain the following fractions: naphtha (b.p., <149.degree.
C.), distillate (b.p., 149.degree.-343.degree. C.), heavy oil
(b.p., 343.degree.-538.degree. C.), and residue (b.p.,
>538.degree. C.).
TABLE-US-00001 TABLE 1 Operating Conditions for Liquefaction Tests.
AC Run Coal Bio- Vac. Run Size, Pressure, Temp., Time, Agitation,
Catalyst, Charge, oil, Solvent, Bottoms, No. cm.sup.3 atm .degree.
C. min rpm ppm g g g g 1-3 7570 225 450 60 900 300 600 200 800 800
4-5 7570 218 450 60 900 300 600 200 800 800 6-7 7570 176 450 60 900
300 600 200 800 800
[0113] Upon standing, the naphtha fraction separated into two
layers: the upper oily layer and the aqueous bottom layer. The oily
layer was saved for further analysis, and the aqueous layer was
rejected. A complete mass balance was obtained, and the yields are
shown in Table 2. The conversion is based on the wt % of dry
ash-free coal and bio-oil or wax used for liquefaction. All of
these fractions were analyzed by gas chromatography-mass
spectroscopy (GC-MS), as discussed in Example 5.
TABLE-US-00002 TABLE 2 Composition of the Distillate. Run Water,
Naphtha Middle Distillate No. Conversion wt % (<149.degree. C.),
wt % (149.degree.-343.degree. C.), wt % 1-3 73.3 14.7 12.0 46.6 4-5
71.5 15.4 14.1 42.0 6-7 75.5 11.3 13.2 51.0
Example 3
Runs 4-5: Liquefaction of Algae Oil and Coal
[0114] Coal, algae oil, and catalyst were slurried in a
coal-derived solvent. A similar procedure to that used in Example 2
was used. Operating conditions and yield data are given in Tables 1
and 2.
Example 4
Runs 6-7: Liquefaction of Waxes and Coal
[0115] Waxes from FT synthesis of syngas, coal, and catalyst were
slurried in a coal-derived solvent. A similar procedure to that
used in Example 2 was used. The operating conditions and yield data
are given in Tables 1 and 2.
Example 5
Analysis of Examples 2-4, Runs 1-7
[0116] The raw coal liquids produced from the fractional
distillation of liquefaction slurry were analyzed by elemental
analysis, density, gas chromatographic distillation (GCD) and GC-MS
to determine product quality of the distillates. These data are
needed to design an appropriate upgrading scheme to produce
specification-compliant fuels. The yield data and hydrocarbon types
are presented in Tables 3-5. The distillation profiles of
coal-canola oil-derived, coal-algae oil-derived, and
coal-wax-derived middle distillates are shown in FIGS. 2, 3, and 4,
respectively.
TABLE-US-00003 TABLE 3 Distillation Data for Coal-Biomass-Derived
Fuels Coal- Coal- Coal- Coal- Coal-FT Coal-FT Sample Canola,
Canola, Algae, Algae, Resid, Resid, Identification <149.degree.
C. 149.degree.-343.degree. C. <149.degree. C.
149.degree.-343.degree. C. <149.degree. C.
149.degree.-343.degree. C. Yield 9.0% 58.2% 9.2 56.5 10.8 59.8 GC
Distillation wt % Off at .degree. C. 38 3.67 0.8 65 9.24 7.75 18.46
82 41.23 0 26.17 0 29.14 93 45.13 0 32.61 0 31.71 121 72.60 0.16
75.56 0.60 82.95 0 149 96.64 0.86 96.69 2.85 100 1.22 177 100 7.41
100 13.00 9.53 204 0 14.28 23.31 18.12 232 0 32.47 48.51 37.61 260
0 42.44 58.44 48.24 288 0 56.38 76.17 66.48 315 0 94.67 96.94 87.03
343 0 100.00 100 95.74 343 + 0 0.00 0 100 wt % Off 149.degree. C.-
96.64 0.86 96.69 2.85 100 0 177.degree. C.- 100 7.41 100 13.00 --
9.53 232.degree. C.- -- 32.47 -- 48.51 -- 37.61 343.degree. C.+ --
0 -- 0.0 -- 4.26
TABLE-US-00004 TABLE 4 Hydrocarbon-Type Analysis of Raw Distillate
from Coal Biomass Liquefaction Coal-Canola Coal-Algae Coal-FT Resid
149.degree.- 149.degree.- 149.degree.- <149.degree. C.
343.degree. C. <149.degree. C. 343.degree. C. <149.degree. C.
343.degree. C. Paraffins 64.1 47.86 51.4 31.73 45.8 56.59
Naphthenes 19.09 2.02 35.82 7.96 33.09 3.44 Aromatics 16.81 50.12
12.78 60.31 21.11 39.96
TABLE-US-00005 TABLE 5 Hydrocarbon Type Analysis of Raw Coal-Canola
Oil- Derived Distillate Composition, wt % by MS Middle Distillate
Paraffins 5.43 1-R Naphthenes 2.40 2-R Naphthenes 0.00 3-R
Naphthenes 0.00 4+-R Naphthenes 0.00 Total Naphthenes 7.83 1-R AR
41.84 2-R AR 45.76 3-R AR 4.57 4+-R AR 0.00 Total AR 92.17 Total
100
Example 6
Upgrading of the Products of Liquefaction
[0117] The coal liquids (distillate fraction having b.p.
149.degree.-343.degree. C.) obtained from the liquefaction of coal
and bio-oil or wax mixtures were upgraded to produce JP-8-compliant
fuel. Upgrading can remove heteroatoms such as nitrogen, sulfur,
and oxygen along with hydrocracking and hydrogenation to produce
distillate fuels including paraffins/isoparaffns, aromatics, and
naphthenes, which are key constituents of jet fuel. The upgrading
scheme is described below.
[0118] Stage 1--Hydrotreating.
[0119] The catalytic hydrotreatment of the coal liquids was carried
out using a commercial hydrotreating catalyst to produce
JP-8-compliant jet fuel. Initial tests were conducted using coal
liquid produced from the distillation of coal tar to validate the
catalyst and reactor system and optimize the conditions. The
hydrotreatment was carried out in a tubular reactor packed with a
nickel-molybdenum hydrotreating catalyst on a silica-alumina
support diluted with an equal volume of glass beads in a small
continuous reactor (SCR), with a temperature of about
365.degree.-370.degree. C. and a pressure of about 136 atm, with a
space velocity of about 0.3/h (e.g. 0.3 reactor volumes per hour).
The catalyst was presulfided using n-dodecane spiked with 1.5 wt %
dimethyl disulfide (DMDS). The presulfidation was carried out by
passing the sulfiding solution through the catalyst bed until
H.sub.2S breakthrough was observed in the product gas as indicated
by an online laser analyzer.
[0120] After the desired amount of coal liquid was hydrotreated,
the hydrotreated product was washed twice with water to remove
chlorine that may have been present, and nitrogen was passed
through the washed oil to expel any dissolved ammonia and hydrogen
sulfide that may have been present. The resulting product was
passed through a tubular reactor packed with acidic clay to remove
residual nitrogen compounds. The hydrotreated liquid was
fractionally distilled to remove the naphtha fraction (b.p. room
temperature--121.degree. C.). Each fraction was analyzed using ASTM
International standards to evaluate the efficacy of the
process.
[0121] Stage 2--Hydrogenation.
[0122] The hydrotreated product (b.p. >121.degree. C.) was
hydrogenated using a commercial platinum-zeolite catalyst to
saturate the aromatic rings to produce naphthenic fuel. The
hydrogenation was carried out in a tubular packed-bed reactor using
SCR as described earlier, with a temperature of about 150.degree.
C. and a pressure of about 100 atm, and a space velocity of about
1.1/h. The catalyst was preactivated prior to hydrogenation of the
fuels. The hydrogenation was carried out until complete saturation
of the aromatics was achieved as indicated by GC-MS.
[0123] Stage 3--Aromatization.
[0124] Aromatization can generate lubricity, which is desired for a
synthetic jet fuel. A portion of the hydrogenated product from
Stage 2 was aromatized (about 20 wt %) using commercial catalyst to
convert the naphthenes into aromatic hydrocarbons. The catalyst and
process conditions were selected in order to maximize the yield of
aromatic hydrocarbons and minimize the coke and gas, using a
temperature of about 520.degree. C., a pressure of about 34 atm, a
space velocity of about 0.3/h, and a platinum-zeolite catalyst. The
aromatized product was fractionally distilled to produce the
following fractions: naphtha (b.p. <135.degree. C.), jet
fraction (b.p., 135.degree.-212.degree. C.), heavy oil (b.p.
>212.degree. C.).
[0125] Stage 4--Hydroisomerization.
[0126] GC-MS analysis of the fuel generated by liquefaction of the
coal-bio-oil mixture and upgraded by Stages 1 and 2 hydroprocessing
indicated only straight-chain paraffins and naphthenes. In order to
improve the resulting fuel properties further, a portion of the
hydrogenated product was isomerized (about 80 wt %) using a
commercial nickel-molybdenum catalyst to produce branched paraffins
using a temperature of about 350.degree. C. and a pressure of about
50 atm, with a space velocity of about 3/h. The GC-MS data were
used to determine the n-paraffin/isoparaffin ratio. The resulting
product was fractionally distilled to generate the following
fractions: naphtha (b.p. <121.degree. C.), jet fraction (b.p.,
121-246.degree. C.), diesel (b.p. >246.degree. C.).
Example 7
Preparation of Jet Fuel Sample
[0127] The jet fractions from Stage 3 (135.degree.-212.degree. C.)
and Stage 4 (121.degree.-246.degree. C.) were analyzed by GC-MS to
determine the hydrocarbon types. Based on the GC-MS data, the
desired volumes of these jet fractions were blended together to
produce composite fuels that contains at least 8 vol % aromatic
compounds. The final fuel mixture was approximately 85 wt %
isomerized product and approximately 15% aromatized product.
Example 8
Testing of Jet Fuel Sample
[0128] The jet fuel produced above was analyzed using a set of ASTM
International standard tests to evaluate the fuel properties. The
fuel properties were compared with the specification for JP-8 fuels
to determine specification compliance.
Example 9
Fuel from Coal and Canola Oil
[0129] Fuels were produced from the liquefied product of the coal
and canola oil combination of Runs 1-3 using the procedure of
Example 7. The fuels were tested using ASTM International
standards, and the results are given in Tables 6-8. The data
indicate that the jet fuel meets the key components and exceeds
military specifications for JP-8 fuel. The distillation profiles
for the coal-canola oil-derived fuels are given in FIG. 5.
TABLE-US-00006 TABLE 6 Distillation Data for Coal-Canola
Oil-Derived Fuels Distillation Profile (GCD) <121.degree. C.
121.degree.-246.degree. C. +246.degree. wt % Off at .degree. F. 100
9.24 150 41.23 180 45.13 0 200 72.60 0 250 96.64 1.21 300 100 8.43
350 0 29.83 400 0 64.59 450 0 86.78 2.56 500 0 94.57 8.40 550 0
99.80 31.91 600 0 100 73.36 650 0 97.79 650+ 0 0.21 wt % Off at
.degree. F. <300.degree. F. 100 8.43 0 350.degree. F. -- 29.83 0
450.degree. F. -- 86.78 2.56 +650.degree. F. -- 100 0.21
TABLE-US-00007 TABLE 7 Hydrocarbon Type Analysis of Coal-Canola
Oil-Derived Fuels Sample Identification 121.degree.-246.degree. C.
wt % Total Paraffins 38.74 n-Paraffins 18.33 isoParaffins 20.41
Naphthenes 50.22 1R-Naphthenes 18.33 2R-Naphthenes 28.56
3R-Naphthenes 3.33 Aromatics 11.04 1R-Naphthenes 8.01 2R-Naphthenes
3.03 3R-Naphthenes 0
TABLE-US-00008 TABLE 8 Fuel Properties of Coal-Canola Oil-Derived
Jet Fuel Grade: JP-8 EERC CB Jet2011 Specifications MIL-DTL-83133F
121-246.degree. C. Color, Saybolt No limit Clear, colorless
Aromatics, vol % 25.0 max. 7.2 Sulfur, wppm 3000 max. -- Nitrogen,
wppm -- -- Thermal Stability Tube <3 visual 1.4 Rating, Color
Density, g/cm.sup.3 at 15.degree. C. or 0.775-0.840 0.804 at
15.degree. C. API Gravity 51.0-37.0 43.6 at 60.degree. F. Flash
Point, .degree. C. 38 min 46 Freeze Point, .degree. C. -47 max. -62
Naphthalene, vol % 3.0 max. <0.3 Heat of Combustion, MJ/kg 42.8
43.2 Hydrogen Content, wt % 13.4 min. --
[0130] A 500-mL sample of coal-canola oil-derived jet-fuel (EERC CB
Jet2011) was tested at the Fuels Branch, U.S. Air Force Research
Laboratory (AFRL). The fuel underwent evaluations for use as a
propulsion fuel for military aviation systems according to Tier I
as outlined in the "Alternative and Experimental Jet Fuel and Jet
Fuel Blend Stock Evaluation" protocol developed by AFRL. The fuel
sample was evaluated in comparison to a representative
petroleum-derived propulsion fuel. Results from testing with EERC
CB Jet2011 and the representative JP-8 fuel are shown in Table
9-11, along with JP-8 specification limits. The results indicate
that this fuel meets the JP-8 specifications. It has lower
aromatics (7 vol %) by JP-8 specification method D1319, as compared
to the JP-8 specification limit (maximum 25 vol %) and the
representative JP-8 value (19 vol %). FIG. 6 shows the wt % of
n-paraffins (C7-C19) in the sample, as compared to the
representative sample of JP-8. FIG. 7 shows GC results of the
sample, as compared to the representative sample of JP-8.
TABLE-US-00009 TABLE 9 Results of Testing MIL-DTL-83133G 7492
Specification Test Spec. Requirement BJet2011 4751 JP-8 Aromatics,
vol % .ltoreq.25 6.6 18.8 Olefins, vol % 0.6 0.8 Heat of Combustion
.gtoreq.42.8 43.2 43.3 (measured), MJ/kg Distillation: IBP,
.degree. C. 153 159 10% recovered, .degree. C. .ltoreq.205 171 182
20% recovered, .degree. C. 178 189 50% recovered, .degree. C. 196
208 90% recovered, .degree. C. 235 244 EP, .degree. C. .ltoreq.300
260 265 Residue, % vol .ltoreq.1.5 1.3 1.3 Loss, % vol .ltoreq.1.5
0.4 0.8 Flash Point, .degree. C. .gtoreq.38 46 51 Freeze Point,
.degree. C. .ltoreq.-47 -62 -50 API Gravity at 60.degree. F.
37.0-51.0 43.3 44.4 Density at 15.degree. C., kg/L 0.775-0.840
0.809 0.804
TABLE-US-00010 TABLE 10 Hydrocarbon Type Analysis by D2425 for
Coal-Canola Oil-Derived Jet Fuel and JP-8 Fuel D2425 (mass %) EERC
CB Jet2011 JP-8 Paraffins (normal + iso) 39 49 Cycloparaffins 54 30
Alkylbenzenes 5.4 13 Indans and Tetralins 1.5 5.8 Indenes and
C.sub.nH.sub.2n-10 <0.3 0.6 Naphthalene <0.3 <0.3
Naphthalenes <0.3 1.0 Acenaphthenes <0.3 <0.3
Acenaphthylenes <0.3 <0.3 Tricyclic Aromatic <0.3 <0.3
Total 100 100
TABLE-US-00011 TABLE 11 Weight Percent of Paraffins for Coal-Canola
Oil-Derived Jet Fuel and JP-8 Fuel 7492 CB n-Paraffins, wt %
Jet2011 4751 JP-8 n-Heptane 0.036 0.10 n-Octane 0.44 0.34 n-Nonane
1.79 1.21 n-Decane 2.53 3.48 n-Undecane 2.47 4.24 n-Dodecane 1.73
3.71 n-Tridecane 1.05 2.84 n-Tetradecane 0.46 1.79 n-Pentadecane
0.30 0.87 n-Hexadecane 0.068 0.27 n-Heptadecane 0.074 0.089
n-Octadecane 0.023 0.024 n-Nonadecane <0.001 0.008 Total
n-Paraffins 11.0 19.0
[0131] Thermal stability characteristics of this fuel were assessed
using QCM under typical experimental conditions (i.e., 140.degree.
C., air-saturated fuel, 15 hours). QCM results for the fuels (see
Table 12 and FIG. 8) show that the biofuel produces a level of
deposits (1.4 .mu.g/cm.sup.2) that is below that of the
representative JP-8 fuel (3.0 .mu.g/cm.sup.2) and below the average
range of JP-8 fuels of 2 to 6 g/cm.sup.2. In FIG. 8, solid curves
and closed markers illustrate mass accumulation, and dashed curves
and open markers illustrate headspace oxygen profiles. With regard
to oxygen consumption in the biofuel, the oxygen is consumed at a
fairly rapid rate (within 5 hours), indicating that it contains no
antioxidant.
TABLE-US-00012 TABLE 12 Data from QCM Thermal Stability Analysis
15-hr Mass Accumulation, Fuel Description .mu.g/cm.sup.2 EERC CB
Jet2011 1.4 JP-8 3.0
Example 10
Fuel from Coal and Algae Oil
[0132] Fuels were produced from the liquefied product of the coal
and algae oil combination of Runs 4-5 using the procedure of
Example 7. The fuels were tested using ASTM International
standards, and the results are given in Tables 13-15. The data
indicate that the jet fuel meets the key components and
specifications of JP-8 fuel. The distillation profiles for the
coal-algae oil-derived fuels are given in FIG. 9.
TABLE-US-00013 TABLE 13 Distillation Data for Upgraded Coal-Algae
Oil-Derived Fuel Distillation Profile (GCD) <121.degree. C.
121.degree.-246.degree. C. +246.degree. C. wt % Off at .degree. F.
100 0 150 8.7 180 37.5 0 200 68.9 0.17 250 94.6 3.26 300 100 12.31
350 0 31.00 400 0 62.60 450 0 86.50 0.50 500 0 94.70 19.10 550 0
100 39.9 600 0 98.2 650 0 100 650+ 0 0 wt % Off at .degree. F.
<300.degree. F. .sup. 100 12.31 0 350.degree. F.- -- 31.00 0
450.degree. F.- -- 62.60 0.5 550.degree. F.- 100 39.90 600.degree.
F.- -- -- 98.2
TABLE-US-00014 TABLE 14 Hydrocarbon Type Analysis of Coal-Algae
Oil-Derived Fuel Sample Identification 121.degree.-246.degree. C.
wt % Total Paraffins 25.35 n-Paraffins 19.55 isoParaffins 5.80
Naphthenes 60.87 1R-Naphthenes 21.15 2R-Naphthenes 35.64
3R-Naphthenes 4.08 Aromatics 13.78 1R-Aromatics 9.17 2R-Aromatics
4.60 3R-Aromatics 0
TABLE-US-00015 TABLE 15 Fuel Properties of Coal-Algae Oil-Derived
Fuel JP-8 EERC CAO Jet2011 Grade Specification MIL-DTL-83133F
121.degree.-246.degree. C. Color, Saybolt No limit Clear, colorless
Aromatics, vol % 25.0 max. 10.2 Sulfur, wppm 3000 max. -- Nitrogen,
wppm -- -- Thermal Stability Tube <3 visual -- Rating, color
Density, g/cm.sup.3 at 15.degree. C. 0.775-0.840 0.819 at
15.degree. C. or gravity API at 60.degree. F. 51.0-37.0 45.3 Flash
Point, .degree. C. 38 min 39 Freeze Point, .degree. C. -47 max.
-58.6 Naphthalene, vol % 3.0 max. 0 Hydrogen Content, wt % 13.4
min. --
Example 11
Fuel from Coal and Coal-Wax-Derived Fuels
[0133] Fuels were produced from the liquefied product of the coal
and wax combination of Runs 6-7 using the procedure of Example 7.
The fuels were tested using ASTM International standards, and the
results are given in Tables 16-18. The data indicate that the jet
fuel meets the key components and properties of JP-8. The
distillation profiles for the coal-wax-derived fuels are given in
FIG. 10.
TABLE-US-00016 TABLE 16 Distillation Data for Coal-Wax-Derived Fuel
Distillation Profile (GCD) <121.degree. C. 121.degree.
C.-246.degree. C. >246.degree. C. wt& Off at .degree. F. 100
0 150 8.4 180 46.3 0 200 69.1 0.10 250 98.3 2.79 300 100 12.68 350
0 36.13 400 0 69.21 450 0 91.56 3.00 500 0 97.04 18.02 550 0 100
76.64 600 0 99.34 650 0 100 650+ 0 0 wt % Off at .degree. F.
<300.degree. F. .sup. 100 12.68 0 350.degree. F.- -- 36.13 0
450.degree. F.- -- 91.56 3.00 550.degree. F.- 100 76.64 600.degree.
F. (315.degree. C.)- -- -- 99.34
TABLE-US-00017 TABLE 17 Hydrocarbon Type Analysis of
Coal-Wax-Derived Fuel 121.degree.-246.degree. C. Sample
Identification wt % Total Paraffins 40.69 n-Paraffins 22.58
isoParaffins 18.11 Naphthenic 48.69 1R-Naphthenes 22.70
2R-Naphthenes 24.61 3R-Naphthenes 1.38 Aromatics 10.61 1R-Aromatics
8.16 2R-Aromatics 2.45 3R-Aromatics 0
TABLE-US-00018 TABLE 18 Fuel Properties of Coal-Wax-Derived Fuel
JP-8 EERC CAO Jet2011 Grade Specifications MIL-DTL-83133F
121.degree. C.-246.degree. C. Color, Saybolt No limit Clear,
colorless Aromatics, vol % 25.0 max. 7.90 Sulfur, wppm 3000 max. --
Nitrogen, wppm -- -- Thermal Stability Tube <3 visual -- Rating,
Color Density, g/cm.sup.3 at 15.degree. C. 0.775-0.840 0.803 at
15.degree. C. or gravity API at 15.degree. C. (60.degree. F.)
51.0-37.0 43.63 Flash Point, .degree. C. 38 min 40 Freeze Point,
.degree. C. -47 max. -61.6 Naphthalene, vol % 3.0 max. 0 Hydrogen
Content, wt % 13.4 min. 14.0
[0134] The terms and expressions which have been employed are used
as terms of description and not of limitation, and there is no
intention in the use of such terms and expressions of excluding any
equivalents of the features shown and described or portions
thereof, but it is recognized that various modifications are
possible within the scope of the invention claimed. Thus it should
be understood that although the present invention has been
specifically disclosed by preferred embodiments and optional
features, modification and variation of the concepts herein
disclosed may be resorted to by those of ordinary skill in the art
and that such modifications and variations are considered to be
within the scope of this invention as defined by the appended
claims.
Additional Embodiments
[0135] The present invention provides for the following exemplary
embodiments, the numbering of which is not to be construed as
designating levels of importance.
[0136] Embodiment 1 provides a method of liquefaction of
carbonaceous material and biomass, including providing or obtaining
a feed mixture, the mixture including carbonaceous material and
biomass, and subjecting the feed mixture to liquefaction, to
provide a product slurry; wherein the carbonaceous material
includes a nonpetroleum fossil fuel or a petroleum refinery
residue.
[0137] Embodiment 2 provides the method of Embodiment 1, wherein
the carbonaceous material includes coal, coal tar, wax from a FT
process, petroleum refinery residue, vacuum bottoms, tar sand,
bitumen, or a combination thereof.
[0138] Embodiment 3 provides the method of Embodiment 2, wherein
the coal includes coal powder, pulverized coal, or a combination
thereof.
[0139] Embodiment 4 provides the method of any one of Embodiments
2-3, wherein the coal includes lignite, brown coal, jet coal,
subbituminous coal, bituminous coal, steel coal, anthracite,
graphite, or a combination thereof.
[0140] Embodiment 5 provides the method of any one of Embodiments
1-4, wherein the biomass includes plant-derived oil, algae-derived
oil, biomass pyrolysis oil, waste oil, yellow grease, brown grease,
tar, or animal fat.
[0141] Embodiment 6 provides the method of any one of Embodiments
1-5, wherein the mass ratio of carbonaceous material to biomass is
about 0.01-10 to 1.
[0142] Embodiment 7 provides the method of any one of Embodiments
1-6, wherein the mixture further includes solvent.
[0143] Embodiment 8 provides the method of Embodiment 7, wherein
the solvent includes a carbonaceous material-derived heavy
liquid.
[0144] Embodiment 9 provides the method of any one of Embodiments
1-8, wherein the liquefaction includes direct liquefaction.
[0145] Embodiment 10 provides the method of any one of Embodiments
1-9, wherein subjecting the feed mixture to liquefaction includes
contacting the feed mixture with a liquefaction catalyst and
hydrogen gas at a temperature of about 200.degree. to about
600.degree. C., at a pressure of about 50 to about 300 atm.
[0146] Embodiment 11 provides the method of Embodiment 10, wherein
the liquefaction catalyst includes a cobalt-molybdenum
catalyst.
[0147] Embodiment 12 provides the method of any one of Embodiments
10-11, wherein the hydrogen gas is provided from a supply
integrated in the method.
[0148] Embodiment 13 provides the method of any one of Embodiments
10-12, wherein the pressure during the liquefaction is about 150 to
about 250 atm.
[0149] Embodiment 14 provides the method of any one of Embodiments
10-13, wherein the temperature during liquefaction is about
400.degree. to about 500.degree. C.
[0150] Embodiment 15 provides a method of fuel production from
carbonaceous material and biomass, including performing the method
of any one of Embodiments 1-14; separating the product slurry, to
give a conversion component; and processing the conversion
component, to give a fuel.
[0151] Embodiment 16 provides the method of Embodiment 15, wherein
the method is substantially or fully integrated with respect to the
fuel production.
[0152] Embodiment 17 provides the method of any one of Embodiments
15-16, wherein separating the product slurry includes distilling,
wherein the conversion includes at least part of the distillate
from the distilling.
[0153] Embodiment 18 provides the method of any one of Embodiments
15-17, wherein processing the distillate includes hydrotreating the
conversion component, to give a hydrotreated material;
hydrogenating the hydrotreated material, to give a hydrogenated
material; optionally isomerizing at least some of the hydrotreated
material, to give an isomerized material; optionally aromatizing at
least some of the hydrotreated material, to give an aromatized
material; and blending the isomerized material and the aromatized
material, to give the fuel; wherein at least one of isomerizing and
aromatizing is performed or both isomerizing and aromatizing are
performed.
[0154] Embodiment 19 provides the method of Embodiment 18, wherein
isomerizing is performed.
[0155] Embodiment 20 provides the method of any one of Embodiments
18-19, wherein aromatizing is performed.
[0156] Embodiment 21 provides the method of any one of Embodiments
18-20, wherein both isomerizing and aromatizing are performed.
[0157] Embodiment 22 provides the method of any one of Embodiments
18-21, wherein the hydrotreating includes contacting the conversion
component with a hydrotreatment catalyst and hydrogen gas at a
temperature of about 200.degree. to about 500.degree. C., at a
pressure of about 10 to about 300 atm, sufficient to give the
hydrotreated material.
[0158] Embodiment 23 provides the method of Embodiment 22, wherein
the hydrotreatment catalyst includes palladium (Pd), platinum (Pt),
nickel (Ni), nickel-molybdenum (NiMo), cobalt-molybdenum (CoMo), or
any combination thereof.
[0159] Embodiment 24 provides the method of any one of Embodiments
18-23, wherein the hydrogenating includes contacting the
hydrotreated material with a hydrogenation catalyst and hydrogen
gas at a temperature of about 50.degree. to about 300.degree. C.,
at a pressure of about 10 to about 250 atm, sufficient to give the
hydrogenated material.
[0160] Embodiment 25 provides the method of Embodiment 24, wherein
the hydrogenation catalyst includes a platinum-zeolite
catalyst.
[0161] Embodiment 26 provides the method of any one of Embodiments
18-25, wherein the isomerizing includes contacting the hydrotreated
material with an isomerization catalyst and hydrogen gas at a
temperature of about 200.degree. to about 450.degree. C., at a
pressure of about 5 to about 150 atm, sufficient to give the
isomerized material.
[0162] Embodiment 27 provides the method of Embodiment 26, wherein
the isomerization catalyst includes a nickel-molybdenum
catalyst.
[0163] Embodiment 28 provides the method of any one of Embodiments
18-27, wherein the aromatizing includes contacting the hydrotreated
material with an aromatization catalyst and hydrogen gas at a
temperature of about 350.degree. to about 750.degree. C., at a
pressure of about 10 to about 150 atm, sufficient to give the
aromatized material.
[0164] Embodiment 29 provides the method of Embodiment 28, wherein
the aromatization catalyst includes a platinum-zeolite
catalyst.
[0165] Embodiment 30 provides the method of any one of Embodiments
18-29, wherein the mass ratio of hydrotreated material subjected to
isomerizing to hydrotreated material subjected to aromatizing is
about 1-20 to 1.
[0166] Embodiment 31 provides the method of any one of Embodiments
18-30, wherein the mass ratio of isomerized material blended to
aromatized material blended is about 1-20 to 1.
[0167] Embodiment 32 provides the method of any one of Embodiments
15-31, wherein the fuel includes a liquid transportation fuel.
[0168] Embodiment 33 provides the method of any one of Embodiments
15-32, wherein the fuel is gasoline, naphtha, kerosene, jet fuel,
or diesel fuel.
[0169] Embodiment 34 provides the method of any one of Embodiments
15-33, wherein the fuel has a composition that complies with JP-5,
JP-8, or BUFF requirements.
[0170] Embodiment 35 provides a method of liquefaction of coal and
biomass, including providing or obtaining a feed mixture, the
mixture including coal and biomass, the biomass including
plant-derived oil, algae-derived oil, biomass pyrolysis oil, waste
oil, yellow grease, brown grease, tar, or animal fat and subjecting
the feed mixture to liquefaction, to provide a product slurry, the
liquefaction including contacting the feed mixture with a
liquefaction catalyst and hydrogen gas at a temperature of about
350.degree. to about 500.degree. C., at a pressure of about 150 to
about 250 atm.
[0171] Embodiment 36 provides a method of fuel production from coal
and biomass, including providing or obtaining a feed mixture, the
mixture including coal and biomass, the biomass including
plant-derived oil, algae-derived oil, biomass pyrolysis oil, waste
oil, yellow grease, brown grease, tar, or animal fat; subjecting
the feed mixture to liquefaction, to provide a product slurry;
distilling the product slurry, to give a distillate; and
hydrotreating the distillate, to give a hydrotreated material;
hydrogenating the hydrotreated material, to give a hydrogenated
material; isomerizing at least some of the hydrotreated material,
to give an isomerized material; aromatizing at least some of the
hydrotreated material, to give an aromatized material; and blending
at least some of the isomerized material and at least some of the
aromatized material, to give a fuel.
[0172] Embodiment 37 provides the apparatus or method of any one or
any combination of Embodiments 1-36 optionally configured such that
all elements or options recited are available to use or select
from.
* * * * *