U.S. patent application number 14/284605 was filed with the patent office on 2014-09-11 for aromatic hydrocarbons from depolymerization and deoxygenation of lignin.
This patent application is currently assigned to UOP LLC. The applicant listed for this patent is UOP LLC. Invention is credited to John Qianjun Chen, Mark Blaise Koch.
Application Number | 20140250773 14/284605 |
Document ID | / |
Family ID | 47596046 |
Filed Date | 2014-09-11 |
United States Patent
Application |
20140250773 |
Kind Code |
A1 |
Chen; John Qianjun ; et
al. |
September 11, 2014 |
AROMATIC HYDROCARBONS FROM DEPOLYMERIZATION AND DEOXYGENATION OF
LIGNIN
Abstract
Processes are disclosed that achieve a high conversion of lignin
to aromatic hydrocarbons, and that may be carried out without the
addition of a base. Depolymerization and deoxygenation, the desired
lignin convention steps to yield aromatic hydrocarbons, are carried
by contacting a mixture of lignin and a solvent (e.g., a lignin
slurry) with hydrogen in the presence of a catalyst. A preferred
solvent is a hydrogen transfer solvent such as a single-ring or
fused-ring aromatic compound that beneficially facilitates
depolymerization and hinders coke formation. These advantages
result in favorable overall process economics for obtaining fuel
components and/or chemicals from renewable sources.
Inventors: |
Chen; John Qianjun;
(Glenview, IL) ; Koch; Mark Blaise; (Mount
Prospect, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UOP LLC |
Des Plaines |
IL |
US |
|
|
Assignee: |
UOP LLC
Des Plaines
IL
|
Family ID: |
47596046 |
Appl. No.: |
14/284605 |
Filed: |
May 22, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13190751 |
Jul 26, 2011 |
8772557 |
|
|
14284605 |
|
|
|
|
Current U.S.
Class: |
44/451 |
Current CPC
Class: |
B01J 23/883 20130101;
C10L 1/1616 20130101; C10G 1/065 20130101; C10L 1/14 20130101; C10L
2200/0469 20130101; C10L 1/02 20130101; C10L 2200/0423 20130101;
C10G 2300/305 20130101; C10L 1/1824 20130101; C10L 1/023 20130101;
B01J 21/12 20130101 |
Class at
Publication: |
44/451 |
International
Class: |
C10L 1/02 20060101
C10L001/02 |
Claims
1. A fuel composition comprising a lignin conversion product, the
lignin conversion product prepared by the process comprising: (a)
contacting hydrogen, in the presence of a catalyst, with a mixture
of lignin and an aromatic-containing solvent under reaction
conditions effective to convert at least a portion of the lignin
and provide a lignin conversion effluent having an increased
quantity of aromatic hydrocarbons relative to the mixture, wherein
the aromatic-containing solvent contains at least about 50% by
volume aromatic hydrocarbons and the reaction conditions comprise a
hydrogen partial pressure from 700 kPa (100 psig) to about 21 MPa
(3000 psig); and (b) separating the lignin conversion product from
the lignin conversion effluent.
2. The fuel composition comprising a lignin conversion product of
claim 1 wherein the aromatic-containing solvent comprises a single
ring or fused ring aromatic compound.
3. The fuel composition comprising a lignin conversion product of
claim 1 wherein the aromatic-containing solvent comprises a
byproduct of a hydrocarbon conversion process.
4. The fuel composition comprising a lignin conversion product of
claim 3 wherein, wherein the byproduct is a C.sub.9 hydrocarbon
fraction.
5. The fuel composition comprising a lignin conversion product of
claim 1 wherein the catalyst has both a hydrogenation function and
an acid function.
6. The fuel composition comprising a lignin conversion product of
claim 5 wherein the hydrogenation function is a catalytic metal
selected from the group consisting of ruthenium, platinum,
palladium, iron, cobalt, nickel, molybdenum, tungsten, and mixtures
thereof.
7. The fuel composition comprising a lignin conversion product of
claim 5 wherein the acid function is an acidic support material
selected from the group consisting of a clay, a zeolite, a
non-zeolitic molecular sieve, a mixed metal oxide, sulfated
zirconia, and mixtures thereof.
8. The fuel composition comprising a lignin conversion product of
claim 1 wherein the reaction conditions include a temperature from
about 200.degree. C. (392.degree. F.) to about 600.degree. C.
(1112.degree. F.), and a weight hourly space velocity (WHSV) from
about 0.1 hr.sup.-1 to about 20 hr.sup.-1.
9. The fuel composition comprising a lignin conversion product of
claim 1 wherein the lignin is obtained from the pyrolysis of
biomass.
10. The fuel composition comprising a lignin conversion product of
claim 1 wherein the biomass is selected from the group consisting
of hardwood, softwood, hardwood bark, softwood bark, corn fiber,
corn stover, sugar cane bagasse, switchgrass, miscanthus, algae,
waste paper, construction waste, demolition waste, municipal waste,
and mixtures thereof.
11. The fuel composition comprising a lignin conversion product of
claim 1 wherein at least a portion of the lignin is obtained as a
byproduct of wood pulping.
12. The fuel composition comprising a lignin conversion product of
claim 1 wherein at least a portion of the lignin is obtained as a
co-product of ethanol production from biomass.
13. The fuel composition comprising a lignin conversion product of
claim 1 wherein the lignin conversion product comprises less than
about 0.1% organic oxygen by weight.
14. The fuel composition comprising a lignin conversion product of
claim 1 wherein the lignin conversion product comprises at least
about 97% hydrocarbons by weight.
15. The fuel composition comprising a lignin conversion product of
claim 1 wherein the lignin conversion product comprises from about
55% to about 85% aromatic hydrocarbons by weight.
16. The fuel composition comprising a lignin conversion product of
claim 1 wherein the lignin conversion product has a research octane
number (RON) from about 95 to about 105.
17. The fuel composition comprising a lignin conversion product of
claim 1 comprising: (a) from about 50% to 98% petroleum derived
gasoline by weight; (b) from 1% to about 20% ethanol by volume; and
(c) from 1% to about 30% of the lignin conversion product by
weight.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional application of co-pending
application U.S. application Ser. No. 13/190,751 filed Jul. 26,
2011, the contents of which are hereby incorporated by reference in
its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to methods of making aromatic
hydrocarbons from the conversion (depolymerization and
deoxygenation) of lignin, in addition to fuel compositions
comprising a lignin conversion product.
DESCRIPTION OF RELATED ART
[0003] Environmental concerns over fossil fuel greenhouse gas (GHG)
emissions have led to an increasing emphasis on renewable energy
sources. Wood and other forms of biomass including agricultural and
forestry residues are examples of some of the main types of
renewable feedstocks being considered for the production of liquid
fuels. Energy from biomass based on energy crops such as short
rotation forestry, for example, can contribute significantly
towards the objectives of the Kyoto Agreement in reducing GHG
emissions.
[0004] Lignocellulosic biomass represents a vast amount of
renewable resources available in virtually every part of the world.
Lignin is generally present in such biomass in an amount of 15-30%
by weight. Lignin-containing residues are generated industrially in
large quantities, for example from both ethanol production from
biomass and the Kraft process for converting wood pulp to cellulose
fibers. It is expected that the lignin supply will continue to
increase as ethanol plants using biomass feedstocks such as wood,
forestry waste, sawdust, straw, corn stover, sugar cane bagasse,
switchgrass etc. are implemented. Since the lignin byproduct is
normally burned for its fuel value, alternative end uses have the
potential to improve the overall economics of biomass-to-ethanol
conversion, paper manufacturing, and other industries that produce
lignin residues. Given the molecular structure of lignin, a
cross-linked phenolic polymer having an abundance of aromatic
rings, the art has recognized the possibility of converting lignin
to high value end products, and particularly aromatic
hydrocarbon-containing fuel components.
[0005] Presently, however, attempts to use of lignin as a feedstock
for the production of chemicals or transportation fuel blending
components continue to prove commercially impractical due to the
high costs of reagents and equipment, as well as the limited
conversion to these desired end products. For example,
base-catalyzed depolymerization of lignin followed by hydrotreating
and hydrocracking is a leading concept for making hydrocarbon
fuels, with a representative publication in this field being
Johnson et al., Fuel Chemistry Preprints, 47(1): 380-1 (2002). The
economics of this process are unfavorable for a number of reasons,
and particularly the high cost of the base (e.g., hydroxide
solution) that is consumed in the reaction, the limited conversion,
and the upgraded metallurgy required to handle the corrosivity of
the base under elevated temperatures and pressures. Consequently,
improvements in methods for converting lignin to hydrocarbon fuel
components, or otherwise renewable analogs of petrochemicals (e.g.,
aromatic hydrocarbons) used in the manufacture of plastics and
other end products, are continually being sought.
SUMMARY OF THE INVENTION
[0006] The present invention is associated with the discovery of
processes that achieve a high conversion of lignin to aromatic
hydrocarbons, and that may be carried out without the addition of a
base. Conventionally used strong bases, such as sodium hydroxide or
potassium hydroxide, (i) must be replaced in the reaction medium
continuously or discontinuously, (ii) require expensive corrosion
resistant metallurgy, and (iii) pose chemical handling risks.
Advantageously, depolymerization and deoxygenation, the desired
lignin conversion steps to yield aromatic hydrocarbons, may be
carried out in one stage whereby a mixture of lignin and an
aromatic-containing solvent (i.e., a solvent comprising at least
one aromatic hydrocarbon) is contacted with hydrogen in the
presence of a catalyst. Such lignin conversion methods are
associated with favorable overall economics, relative to
conventional routes for obtaining fuel components and/or chemicals
from renewable sources.
[0007] Embodiments of the present invention are directed to methods
of making aromatic hydrocarbons. Representative methods comprise
contacting hydrogen, in the presence of a catalyst, with a mixture
(e.g., a slurry) of lignin and an aromatic-containing solvent under
reaction conditions. The conditions are effective to convert (i.e.,
depolymerize and deoxygenate) at least a portion of the lignin and
provide a lignin conversion effluent having an increased quantity
of aromatic hydrocarbons relative to the starting feed mixture. The
methods further comprise separating a lignin conversion product
(e.g., enriched in aromatic hydrocarbons) from the lignin
conversion effluent.
[0008] Particular embodiments of the present invention are directed
to methods for making aromatic hydrocarbons as described above or
otherwise a fuel composition or component of a fuel composition.
Representative methods comprise mixing, with a solvent comprising a
single ring or fused ring aromatic compound, a feedstock comprising
lignin to provide a lignin slurry. The methods further comprise
contacting the lignin slurry with hydrogen under catalytic
depolymerization/deoxygenation conditions to provide a lignin
conversion effluent and separating a lignin conversion product from
the lignin conversion effluent.
[0009] Processes according to any of the above embodiments may
additionally comprise blending the lignin conversion product with
from 1% to 99% by weight of a petroleum derived fuel such as
gasoline. Further embodiments of the invention are therefore
directed to methods of preparing fuel compositions described
herein. The methods comprise blending a lignin conversion product,
and particularly a component produced according to methods
described herein, with a petroleum derived component.
Representative amounts of the lignin conversion product and
petroleum derived components are also described herein. Yet further
embodiments of the invention are directed to fuel compositions, and
especially motor fuel compositions, comprising a blend of
components including the lignin conversion product, which contains
aromatic hydrocarbons obtained from the
depolymerization/deoxygenation of lignin, according to the methods
described herein.
[0010] These and other embodiments and aspects pertaining to the
present invention are apparent from the following Detailed
Description.
DETAILED DESCRIPTION
[0011] The lignin used as a feedstock in processes described herein
may be obtained from a variety of biomass sources, and particularly
residues from wood and crops, including forestry wastes, sawdust,
straw, corn stover, and bagasse. Lignin is understood in the art to
refer to the cross-linked, polymeric macromolecule that bonds to
cellulose and hemicellulose, thereby conferring strength to plant
(e.g., wood) cell walls. The utility of lignin as a precursor for
making aromatic oxygenates through depolymerization and ultimately
aromatic hydrocarbons through deoxygenation resides in the high
content of aromatic rings in the biomolecule. These rings originate
from three aromatic monomers, namely p-coumaryl alcohol, coniferyl
alcohol, and sinapyl alcohol, which are methoxylated to various
extents.
[0012] According to representative embodiments, the lignin may be
obtained as a byproduct of wood pulping, and particularly the
"black liquor" that results from the conversion of wood into wood
pulp consisting almost pure cellulose fibers. This conversion, as
part of the Kraft process, breaks the bonds linking lignin to the
cellulose, thereby separating lignin into the black liquor, which
may have a solids content ranging from about 10%-80%, depending on
the evaporator stage at which the black liquor is removed from the
Kraft process. Alternatively, the lignin may be obtained as a
co-product of the manufacture of ethanol from biomass (i.e.,
cellulosic ethanol). A further source of lignin (pyrolytic lignin)
may be obtained from the pyrolysis, or thermal decomposition, of
biomass, in the substantial absence of oxygen (or in the presence
of significantly less oxygen than required for complete
combustion). "Fast pyrolysis" of biomass has recently gained
significant commercial interest and refers generally to
technologies involving rapid heat transfer to the biomass
feedstock, which is maintained at a relatively high temperature for
a very short time. The temperature of the primary pyrolysis
products is then rapidly reduced before chemical equilibrium is
achieved. The fast cooling therefore prevents the valuable reaction
intermediates, formed by fragmentation of the biomass building
blocks, from degrading to non-reactive, low-value final products. A
number of fast pyrolysis processes are described in U.S. Pat. No.
5,961,786; Canadian Patent Application 536,549; and by Bridgwater,
A. V., "Biomass Fast Pyrolysis," Review paper BIBLID: 0354-9836, 8
(2004), 2, 21-49. Fast pyrolysis processes include Rapid Thermal
Processing (RTP), in which an inert or catalytic solid particulate
is used to carry and transfer heat to the feedstock. RTP has been
commercialized and operated with very favorable yields (55-80% by
weight, depending on the biomass feedstock) of raw pyrolysis oil.
The separation of pyrolytic lignin from raw pyrolysis oil is
described, for example, in U.S. Pat. No. 7,578,927.
[0013] Suitable biomass sources for cellulosic ethanol production
and biomass pyrolysis can be any lignocellulosic material, and
especially a plant material, including a hardwood (e.g.,
whitewood), a softwood, or a hardwood or softwood bark. Energy
crops, or otherwise agricultural residues (e.g., logging residues)
or other types of plant wastes or plant-derived wastes, may also be
used as plant materials. Specific exemplary plant materials include
corn fiber, corn stover, and sugar cane bagasse, in addition to
"on-purpose" energy crops such as switchgrass, miscanthus, and
algae. Short rotation forestry products, as energy crops, include
alder, ash, southern beech, birch, eucalyptus, poplar, willow,
paper mulberry, Australian blackwood, sycamore, and varieties of
paulownia elongate. Other examples of suitable biomass include
organic waste materials, such as sawdust, waste paper and
construction, demolition, and municipal wastes.
[0014] According to representative methods for converting lignin to
aromatic hydrocarbons as fuel components or chemical intermediates,
the lignin is mixed with a suitable solvent, preferably having the
capability to facilitate hydrogen transfer in the reaction medium.
Representative solvents are aromatic-containing solvents comprising
one or more aromatic hydrocarbons (e.g., single ring aromatic
compounds such as benzene, toluene, and xylenes and/or fused ring
aromatic compounds such as tetralin and its alkylated derivatives).
The solvent may or may not have the capability to dissolve all of
the lignin (as required to form a lignin solution) in the
lignin/solvent mixture. Often, at least some of the lignin is not
dissolved, such that the lignin mixture is a lignin slurry. Without
being bound by theory, it is believed that aromatic hydrocarbons
and/or other compounds beneficially introduce a hydrogen transfer
functionality to the solvent, thereby limiting detrimental coke
formation and/or re-polymerization reactions that limit conversion
and reduce product yields, as well as shorten catalyst life.
[0015] Aromatic hydrocarbon-containing byproducts of hydrocarbon
conversion processes are therefore suitable for use in all or part
of representative aromatic-containing solvents. Such byproducts
generally comprise a significant fraction (e.g., generally at least
about 10% by volume, typically least about 50% by volume, and often
at least about 75% by volume) of aromatic hydrocarbons, including
benzene and naphthalene and their alkylated derivatives. Other
representative aromatic-containing solvents, as byproducts of
hydrocarbon conversion processes, include C9 and higher carbon
number (C9+) hydrocarbon fractions that may be obtained, for
example, from catalytic reforming (e.g., used to produce aromatic
hydrocarbons from naphtha feedstocks), and more particularly from
the separation (e.g., fractionation) of catalytic reforming
effluents into such fractions.
[0016] The mixture of lignin and solvent, for example an
aromatic-containing solvent, is contacted with hydrogen in the
presence of catalyst under conditions which promote the
depolymerization of lignin to aromatic oxygenate substituents
(e.g., phenol, and its alkoxylated derivatives) and also the
deoxygenation (or hydrodeoxygenation) of these substituents or
intermediates to aromatic hydrocarbons. The catalyst may be present
in the form of solid particles comprising a catalytically active
metal disposed on a support, with suitable metals and supports
being described below. The catalyst, either supported or otherwise
unsupported (e.g., in the form of fine particles of a compound
containing the catalytically active metal), may be used in a fixed
bed or moving bed, such as in the case of a slurry reactor.
Homogeneous systems operating with catalysts that are soluble in
the reactants and products may also be used. Catalytic
depolymerization/deoxygenation conditions will vary depending on
the quality of the lignin conversion effluent desired, with higher
severity operations directionally resulting in greater conversion
of organic oxygenate intermediates and other oxygenated species
(e.g., carboxylic acids) by hydrogenation.
[0017] Typical reaction conditions include a temperature from about
40.degree. C. (104.degree. F.) to about 700.degree. C.
(1292.degree. F.), often from about 200.degree. C. (302.degree. F.)
to about 600.degree. C. (1112.degree. F.), and a hydrogen partial
pressure from about 700 kPa (100 psig) to about 21 MPa (3000 psig),
often from about 5.5 MPa (800 psig) to about 13.8 MPa (2000 psig).
In addition to pressure and temperature, the residence time of the
lignin mixture (e.g., lignin slurry) and hydrogen in the
depolymerization/deoxygenation reaction zone can also be adjusted
to increase or decrease the reaction severity and consequently the
quality of the resulting lignin conversion effluent. With all other
variables unchanged, lower residence times are associated with
lower reaction severity. The inverse of the residence time is
related to a variable known as the Weight
[0018] Hourly Space Velocity (WHSV, expressed in units of hr-1),
which is the weight flow rate of the feed (e.g., the lignin
mixture) divided by the catalyst weight and represents the
equivalent number of catalyst beds (on a weight basis) of feed
processed per hour. Therefore, increasing the WHSV, or flow rate of
feed processed over a given quantity of catalyst, directionally
decreases residence time and consequently the extent of the
depolymerization and deoxygenation conversion reactions. A typical
range of WHSV according to the present invention is from about 0.1
hr-1 to about 20 hr-1, often from about 0.5 hr-1 to about 10 hr-1.
The quantity of hydrogen used may be based on the stoichiometric
amount needed to completely convert the oxygen present in the
lignin to H2O. In representative embodiments, the reaction may be
carried out in the presence of hydrogen in an amount ranging from
about 90% to about 600% of the stoichiometric amount.
[0019] Suitable catalysts have a hydrogenation function that
promotes the deoxygenation of lignin and its depolymerized
substituents to produce water and aromatic hydrocarbons. The
hydrogenation function is generally a catalytic metal, which may be
noble or non-noble. Representative catalysts include those
comprising at least one Group VIII metal as a hydrogenation
function, such as iron, cobalt, and nickel (e.g., cobalt and/or
nickel) and/or at least one Group VI metal, such as molybdenum and
tungsten. Noble metals, such as ruthenium, palladium, and platinum,
may also be used for the hydrogenation function. A representative
hydrogenation function is therefore selected from the group
consisting of ruthenium, platinum, palladium, iron, cobalt, nickel,
molybdenum, tungsten, and mixtures thereof (e.g., a mixture of
cobalt and molybdenum).
[0020] A Group VIII metal, when used, is typically present in the
catalyst in an amount ranging from about 2 to about 25 weight
percent, and normally from about 4 to about 20 weight percent,
based on the volatile-free catalyst weight. A Group VI metal is
typically present in an amount ranging from about 1 to about 25
weight percent, and normally from about 2 to about 25 weight
percent, also based on the volatile-free catalyst weight. A
volatile-free catalyst sample may be obtained by subjecting the
catalyst to drying at 200-350.degree. C. (392-662.degree. F.) under
an inert gas purge or vacuum for a period of time (e.g., 2 hours),
so that water and other volatile components are driven from the
catalyst. In general, the hydrogenation function is disposed on a
high surface area support material such as a refractory inorganic
oxide (e.g., silica, alumina, titania, and/or zirconia). A carbon
support may also be used. A representative catalyst therefore
comprises a metal selected from the group consisting of nickel,
cobalt, tungsten, molybdenum, and mixtures thereof (e.g., a mixture
of cobalt and molybdenum), deposited on any of these support
materials, or combinations of support materials.
[0021] Preferably, the catalyst has both a hydrogenation function,
as described above, and an acid function, which is generally a
support material that imparts acidity to the catalyst. Acidity may
be determined, for example in units of millimoles of acid sites per
gram of catalyst, by temperature programmed desorption (TPD) of a
quantity of ammonia, from an ammonia-saturated sample of the
catalyst, over a temperature from 275.degree. C. (527.degree. F.)
to 500.degree. C. (932.degree. F.), which is beyond the temperature
at which the ammonia is physisorbed. The quantity of acid sites
therefore corresponds to the number of moles of ammonia that is
desorbed in this temperature range. Representative acid functions
include acidic support materials for the hydrogenation function,
and such support materials may be used as the entire, solid
catalyst support or otherwise may be incorporated (e.g., by
blending) into a relatively non-acidic support (e.g., silica or
high Si/Al ratio zeolite) to impart acidity. Some acid functions
may otherwise be used as binders (e.g., of zeolite crystallites)
and/or fillers in an overall catalyst composition. Representative
acidic support materials that can serve as the acid function
include clays (e.g., minugel, kaolin, kaolinites, halloysite,
etc.), zeolites, non-zeolitic molecular sieves, mixed metal oxides,
sulfated zirconia, and other materials that contain acid sites and
that can be used in varying amounts to regulate the overall acidity
of the catalyst.
[0022] It is within the scope of the invention to use more than one
type of catalyst for carrying out the
depolymerization/deoxygenation of lignin, and different catalysts
may be used in the same or a different reaction vessel. Two or more
different catalysts and one or more quench points may also be
utilized in a reaction vessel or vessels to provide the lignin
conversion effluent.
[0023] After reaction of lignin, in the lignin mixture, in the
presence of hydrogen, a catalyst, and conditions as described
above, the effluent obtained directly from the lignin
depolymerization/deoxygenation reaction (i.e., the lignin
conversion effluent) prior to any downstream separation and
purification steps, has an organic oxygen content that is generally
reduced to less than about 20%, and often to less than about 10% of
the oxygen content of the liquid feedstock, namely the lignin
mixture (e.g., lignin slurry). Organic oxygen originally present in
the lignin molecular structure is therefore generally converted, to
a large extent, to water that is easily separated from the desired
hydrocarbons recovered in the lignin conversion product.
Accompanying its decrease in organic oxygen is an increase in the
heating value, on a mass basis, of the lignin conversion effluent.
This heating value increases typically by a factor ranging from
about 1.5 to about 3, compared to that of the lignin.
[0024] Fractionation or other separation methods may then be used
to separate the desired aromatic hydrocarbons, as a lignin
conversion product, from hydrogen, light hydrocarbons, water, and
other lower value byproducts present in the effluent. At least a
portion of the separated hydrogen, optionally together with light
hydrocarbons, may be recycled to the reactor (or
depolymerization/deoxygenation reaction zone), such that the
combined gas stream of make-up hydrogen (which may be of varying
purity) and recycle hydrogen is sufficient to achieve a hydrogen
partial pressure within the ranges described above. The lignin
conversion product, obtained after this separation of byproducts,
comprises predominantly hydrocarbons, typically at least about 90%
hydrocarbons (e.g., from about 90% to about 99.9% hydrocarbons) by
weight, and often at least about 97% hydrocarbons (e.g., from about
97% to about 99.5% hydrocarbons) by weight.
[0025] The organic oxygenate content of the lignin conversion
product is generally less than about 1% by weight and typically
less than about 0.1% by weight, with lower amounts of organic
oxygen being generally associated with more severe
hydrodeoxygenation conditions (e.g., higher temperatures and
hydrogen partial pressures, and lower LHSV). While a reduction in
organic oxygenates (e.g., phenol derivatives such as alkylated
phenols) directionally increases heating value, this improvement in
the quality of the lignin conversion product is achieved at the
expense of increased energy required for the
depolymerization/deoxygenation reactions. Optimization of the
organic oxygen content is therefore possible, depending on the
intended end use. If desired, for example, further processing may
be used to reduce the organic oxygenate content to less than 10
ppm, and even less than 1 ppm by weight, rendering the lignin
conversion product suitable as a blending component for a number of
transportation fuels, including aviation fuel. Advantageously, the
aromatic hydrocarbon content of the lignin conversion product is
relatively high, generally from about 40% to about 90%, and
typically from about 55% to about 85%. Associated with this level
of aromatic hydrocarbons is a high research octane number (RON),
generally from about 93 to about 107, and typically from about 95
to about 105, such that the lignin conversion product has favorable
characteristics for blending into fuel compositions, and
particularly gasoline compositions comprising petroleum derived
gasoline and conventional gasoline blending components such as
ethanol, as discussed in greater detail below.
[0026] The lignin conversion product is separated from the total
lignin conversion effluent using any of a number possible
separation/purification steps including single-stage and/or
multiple stage vapor-liquid equilibrium contacting (e.g., flash
separation and/or distillation). According to representative
embodiments, the lignin conversion product may be separated from
light byproducts of the depolymerization/deoxygenation reaction,
and particularly light byproducts comprising C4 and lower carbon
number (C4-) hydrocarbons and/or methanol that are present in the
lignin conversion effluent (e.g., as cracked hydrocarbon
byproducts). According to particular embodiments, at least some of
the hydrogen used in the reaction may advantageously be produced
from these light byproducts, for example by catalytic steam
reforming. Representative processes may therefore further comprise
generating, from at least a portion of the light byproducts, at
least a portion of the hydrogen for contacting with the mixture of
lignin and the aromatic-containing solvent in the
depolymerization/deoxygenation reaction.
[0027] The generation of hydrogen from byproducts (e.g., light
hydrocarbons) of the depolymerization and deoxygenation reactions,
can involve, in the overall production of aromatic hydrocarbons
from lignin, integration with a hydrogen generation unit. In an
exemplary embodiment, a catalytic steam reformer, in which at least
a portion of the C4-hydrocarbons and/or at least a portion of the
methanol are catalytically reformed in the presence of steam, is
integrated with catalytic lignin conversion unit or reaction zone.
Representative steam reforming catalysts include alumina supported
nickel oxide. Importantly, the generation of hydrogen in this
manner (i.e., from byproducts obtained from the processing of
feedstocks comprising renewable carbon) reduces, or can even
eliminate, the amount of hydrogen that must be obtained from
external fossil sources (imported), thereby beneficially lowering
the lifecycle greenhouse gas (GHG) emission value of the aromatic
hydrocarbon product. Therefore, the carbon footprint of end
products, including fuel compositions having the aromatic
hydrocarbons as blending component, or plastics (e.g., purified
terephthalic acid) made from the aromatic hydrocarbons, is
reduced.
[0028] The lignin conversion product, following separation from the
lignin conversion effluent, may therefore be blended with
comparable petroleum derived components and possibly other suitable
additives. In a fuel composition, the lignin conversion product may
be present in the composition in an amount of typically up to about
50% by weight or more. While such compositions may comprise or
consist of entirely one or more components derived from renewable
sources, such as the lignin conversion product and optionally a
pyrolysis derived component and/or corn-, sugar-, or
biomass-derived ethanol, the compositions generally comprise blends
of the lignin conversion product component and at least one
petroleum derived component. Relatively high proportions of the
lignin conversion product and optionally other component(s) derived
from renewable sources (i.e., greater than 50% by weight) will be
primarily a function of the commercial scale production volumes of
these components that may ultimately be achieved using lignin
conversion, pyrolysis, and other biofuel production methods
compared to petroleum refining. In any event, by blending the
lignin conversion product with conventional petroleum derived
gasoline according to fuel compositions described herein, the
carbon footprint of the blend can be reduced.
[0029] Representative fuel compositions according to embodiments of
the invention comprise from about 1% to about 50% of the lignin
conversion product, having a high content of aromatic hydrocarbons
as described above. A particular fuel composition, for example, may
comprise from 1% to about 30% of the lignin conversion product by
weight, in addition to from about 50% to 98% or more (e.g., from
about 50% to about 99%) petroleum derived gasoline by weight and
optionally ethanol. When ethanol is incorporated into the
composition, it is typically present in an amount from 1% to about
20% by volume. As a result of being subjected to deoxygenation
conditions in the presence of hydrogen, this component may have a
higher heating value than ethanol, among other properties (e.g.,
density and boiling range according to ASTM D86) meeting the
standards established for petroleum derived components used in
gasoline blending. Of more general interest with respect to the
compositions described herein are automotive spark-ignition engine
fuels.
[0030] While the lignin conversion product can meet the gasoline
standards required of petroleum derived gasoline, its carbon
footprint is greatly reduced according to U.S. government GHG
emission accounting practices, in which emissions associated with
the combustion of biomass derived fuels are not reported in the
lifecycle GHG emission value, as biomass is renewed over a very
short time frame compared to petroleum derived components.
Lifecycle assessment values of emissions in terms of CO2
equivalents, from raw material cultivation (in the case of plant
materials) or raw material extraction (in the case of fossil fuels)
through fuel combustion, can be calculated using SimaPro 7.1
software and IPCC GWP 100a methodologies.
[0031] In representative fuel compositions associated with the
present invention, the lignin conversion product may be blended
with petroleum derived gasoline. Representative methods according
to the invention, for example, comprise blending the lignin
conversion product, separated from the lignin conversion effluent,
with from 1% to 99% by weight of petroleum derived gasoline. Often,
the petroleum derived gasoline is present in the resulting fuel
composition in an amount from about 30% to about 98% by weight.
According to particular fuel compositions, (i) generally from 1 to
about 50%, and typically from 1 to about 30%, of the lignin
conversion product by weight is blended with (ii) generally from
about 30% to about 99%, and typically from about 50% to about 98%
of petroleum derived gasoline by weight, optionally in addition to
(iii) generally from 1% to about 30%, and typically from 1% to
about 20%, ethanol by volume.
[0032] Overall, aspects of the invention are directed to methods
for converting lignin to valuable end products with favorable
economics, at least partly as the result of reduced chemical (e.g.,
caustic) requirements. Other aspects are directed to products
obtained from these methods. Those having skill in the art, with
the knowledge gained from the present disclosure, will recognize
that various changes could be made in these methods and products
without departing from the scope of the present invention.
Mechanisms used to explain theoretical or observed phenomena or
results, shall be interpreted as illustrative only and not limiting
in any way the scope of the appended claims.
[0033] The following examples are set forth as representative of
the present invention. These examples are not to be construed as
limiting the scope of the invention as other equivalent embodiments
will be apparent in view of the present disclosure and appended
claims.
Comparative Example 1
[0034] Lignin Conversion in the Presence of a Non-Aromatic
(hexadecane) Solvent
[0035] A 25 gram portion of lignin Indulin AT (industrial Kraft
lignin) and 161 grams of hexadecane were charged into a 500 ml
autoclave reactor. A 5 gram portion of ground Ni--Mo/SiO2-Al2O3
catalyst was then added to the reactor. The reactor was then sealed
and purged with nitrogen. Hydrogen gas was thereafter used to
pressure the reactor to reach 3.6 MPa gauge pressure (524 psig) at
room temperature, and the reaction mixture of lignin and hexadecane
solvent was stirred at 1500 rpm. The reactor temperature was then
raised from room temperature to 392.degree. C. (738.degree. F.),
held at this temperature for 7 hours, and cooled down. The reaction
product (containing the lignin conversion effluent) was filtered.
The amount of dry solids recovered was 16.6 grams, corresponding to
11.6 grams of unconverted lignin (16.6 g solid minus 5.0 g
catalyst=11.6 g). The calculated lignin conversion was therefore
54%.
Example 1
[0036] Lignin Conversion in the Presence of an Aromatic (toluene)
Solvent
[0037] A 25 gram portion of lignin Indulin AT (industrial Kraft
lignin) and 161 grams of toluene were charged into a 500 ml
autoclave reactor. A 5 gram portion of ground Ni--Mo/SiO2-Al2O3
catalyst was then added to the reactor. The reactor was then sealed
and purged with nitrogen. Hydrogen gas was thereafter used to
pressure the reactor to reach 3.5 MPa gauge pressure (511 psig) at
room temperature, and the reaction mixture of lignin and toluene
solvent was stirred at 1000 rpm. The reactor temperature was then
raised from room temperature to 392.degree. C. (738.degree. F.),
held at this temperature for 7 hours, and cooled down. The reaction
product (containing lignin conversion effluent) was filtered. The
amount of dry solids recovered was 5 grams, corresponding to the
entire weight of the catalyst charged to the reactor. Since no
unconverted liquid was present in the recovered solids, based on
this weight, the calculated lignin conversion was 100%.
[0038] These experiments demonstrate the significant improvement in
lignin conversion obtained when an aromatic-containing solvent is
used.
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