Note: Descriptions are shown in the official language in which they were submitted.
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CO-PROCESSING HYDROTHERMAL LIQUEFACTION OIL AND CO-FEED TO
PRODUCE BIOFUELS
FIELD
[0001] The present disclosure relates to processes for producing biofuel
compositions wherein
a hydrocarbon (petroleum) oil and a hydrothermal liquefaction (HTL) oil(s) are
co-processed in a
cracking unit. In particular, the disclosure is directed to processes for
producing fuel compositions
comprising cracking a mixture of hydrocarbon co-feed and an HTL oil derived
from cellulose.
BACKGROUND
[0002] With the rising costs and environmental aspects associated with
fossil fuels, renewable
energy sources have become increasingly important. The development of
renewable fuel sources
provides a means for reducing the dependence on fossil fuels. Accordingly,
many different areas
of renewable fuel research are currently being explored and developed.
[0003] To encourage such research efforts, Congress created the renewable
fuel standard (also
referred to as "RFS") program to reduce greenhouse gas emissions and expand
the nation's
renewable fuels sector while reducing reliance on imported oil. This program
was authorized under
the Energy Policy Act of 2005 and expanded under the Energy Independence and
Security Act of
2007. Examples of such legislation include, but are not limited to, the United
States Environmental
Protection Agency (also referred to as "EPA"), the Energy Independence and
Security Act (also
referred to as "EISA") and California AB 32 - Global Warming Solutions Act,
which respectively
established an RFS and a Low Carbon Fuel Standard (also referred to as
"LCFS"). For instance,
under EISA, the mandated annual targets of renewable content in fuel are
implemented through an
RFS that uses tradable credits (called Renewable Identification Numbers,
referred to herein as
"RINs") to trail and conduct the production, distribution and use of renewable
fuels for
transportation or other purposes (e.g., pharmaceutical, plastics/resins,
etc.). Targets under the
LCFS can be met by trading of credits generated from the use of fuels with a
lower greenhouse gas
emission value than the gasoline baseline. Among such regulations, there are
some related to the
use of cellulosic containing biomass (cellulosic biomass) that can earn
Cellulosic Renewable
Identification Numbers (also referred to as "C-RINs"). The use of cellulosic
biomass can also
support fuel producers in meeting their Renewable Volume Obligations (also
referred to as
"RVO").
[0004] With its low cost and wide availability, biomass has increasingly
been emphasized as
an ideal feedstock in renewable fuel research. Consequently, many different
conversion processes
have been developed that use biomass as a feedstock to produce useful biofuels
and/or specialty
chemicals. Existing biomass conversion processes include, for example,
combustion, gasification,
slow pyrolysis, fast pyrolysis, liquefaction, and enzymatic conversion. One of
the useful products
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that may be derived from the aforementioned biomass conversion processes is a
liquid product
commonly referred to as "bio-oil." Bio-oil may be processed into
transportation fuels, hydrocarbon
chemicals, and/or specialty chemicals.
[0005] Despite recent advancements in biomass conversion processes, many of
the existing
biomass conversion processes produce low-quality bio-oils that are highly
unstable and often
contain high amounts of oxygen. These bio-oils require extensive secondary
upgrading in order to
be utilized as transportation fuels and/or as fuel additives due their
instability. Furthermore, the
transportation fuels and/or fuel additives derived from bio-oil vary in
quality depending on factors
affecting the stability of the bio-oil, such as the original oxygen content of
the bio-oil.
[0006] Bio-oils can be subjected to various upgrading processes in order to
process the bio-oil
into renewable fuels and/or fuel additives. However, prior upgrading processes
have been
relatively inefficient and produce renewable fuels and/or fuel additives that
have limited use in
today's market. Furthermore, only limited amounts of these bio-oil derived
transportation fuels
and/or fuel additives may be combinable with petroleum-derived gasoline or
diesel.
[0007] Accordingly, there is a need for improved processes and systems for
producing and
using bio-oils to produce renewable fuels.
[0008] References for citing in an Information Disclosure Statement (37 CFR
1.97(h)): U.S.
9,120,989; U.S. 2013/0118059.
SUMMARY
[0009] The present disclosure relates to processes for producing biofuel
compositions by
processing hydrocarbon co-feed and a bio-oil obtained via hydrothermal
liquifaction (HTL) of a
cellulosic biomass to form an HTL oil. The cellulosic mass can be processed at
an operating
temperature of about 425 C or less, an operating pressure of about 200 atm or
less, a residency
time of about 5 minutes to about 60 minutes, in the presence of a catalyst.
The HTL oil is co-
processed with a hydrocarbon co-feed (e.g., petroleum fraction) in a cracking
unit, such as an FCC
unit, a coker unit or a visbreaking unit, in the presence of a catalyst, at an
operating temperature of
about 400 C to about 700 C, such as about 545 C to about 585 C, an operating
pressure of about
psig to about 50 psig, such as about 15 psig (1 bar) to about 30 psig (2 bar),
and/or a residency
time of about 1 second to about 30 seconds, such as about 2 seconds to about
10 seconds to produce
a biofuel.
[0010] In an embodiment, a process for generation of biofuels includes
introducing
("feeding") through separate injection nozzles, an HTL oil and a hydrocarbon
(such as Vaccum
Gas Oil (VGO) and/or Resid/De-Asphalted Oil (DAO) to a cracker, such as a
fluidized catalytic
cracking (FCC) unit.
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100111 In at least one embodiment, the present disclosure provides a method
of processing a
hydrocarbon co-feed (e.g., VGO) with an HTL oil in the presence of a cracking
catalyst resulting
in an improved biofuel product.
[0012] In at least one embodiment, a method of preparing a biofuel
includes: i) processing a
hydrocarbon co-feed with a HTL oil feedstock in the presence of a cracking
catalyst; and ii)
optionally, adjusting feed addition rates of the hydrocarbon co-feed, the HTL
oil feedstock, or both,
to target a desirable biofuel product profile, a riser temperature, or a
reaction zone temperature; or
iii) optionally, adjusting the amount of cracking catalyst to combined
hydrocarbon co-feed/HTL
oil ratio (catalyst : oil(s) ratio).
[0013] Further, the present disclosure provides a cracking system wherein
the oils are injected
separately into the cracker unit so that separation of the final biofuel is
not required. For example,
the system can include at least two or more feed nozzles coupled with a
cracking unit for injection
of the oils into the cracking unit.
DETAILED DESCRIPTION
[0014] The present disclosure relates to methods of generating biofuels by
co-processing an
HTL oil, derived from a cellulosic biomass, with a hydrocarbon oil in a
cracking unit. The HTL
oil can be derived from cellulosic biomass processed at an operating
temperature of about 425 C
or less, an operating pressure of about 200 atm or less, a prolonged residency
time of about 5
minutes to about 60 minutes, in the presence of a catalyst to form an HTL oil.
The HTL oil is co-
processed with a hydrocarbon oil (e.g., petroleum fraction) in the presence of
a cracking catalyst
in cracking unit at an operating temperature of about 400 C to about 700 C,
such as about 545 C
to about 585 C, an operating pressure of about 10 psig to about 50 psig, such
as about 15 psig (1
bar) to about 30 psig (2 bar), and/or a residency time of about 1 second to
about 30 seconds, such
as about 2 seconds to about 10 seconds, to form a biofuel which may be a
cellulosic-renewable
identification number-compliant fuel. Processes of the present disclosure
provide biofuel
compositions without any separation process of the cracked product(s). The
cracking process can
be performed using a system of at least two or more injection nozzles on the
cracking unit, which
promotes better blending of the HTL and hydrocarbon oils (and ultimately
cracked product(s)) by
increasing the dispersion, providing additional time-, energy- and cost-
efficiency. In an
embodiment, a process for generation of biofuel oils is described that
includes introducing
("feeding"), separately or as a mixture, HTL oil and hydrocarbon (such as
Vaccum Gas Oil (VGO)
and/or Resid/De-Asphalted Oil (DAO) to a cracking unit such as a fluidized
catalytic cracking
(FCC) unit, such that a portion of the feed HTL oil passes through the FCC (or
alternate cracking
process like coking or visbreaking) reactor section (with some conversion) and
ends up in the
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product fuel. The bio content of the cracked product provides RIN credits for
the cracked product.
[0015] It has been discovered that when HTL oil is the source of the bio-
oil and is processed
along with a hydrocarbon oil, and the two oils are separately injected into
the cracking unit, a useful
biofuel is produced directly and a separation step is not required to obtain
the biofuel. The present
disclosure is directed to a simple, time-effective, energy-effective, and cost-
effective
environmentally-friendly process that combines HTL technology and cracking
technology for
conversion of oils into biofuels. In at least one embodiment, the present
disclosure advantageously
provides a process for meeting renewable fuel targets or mandates established
by governments,
including legislation and regulations for transportation fuel sold or
introduced into commerce in
the United States.
[0016] In at least one embodiment, the present disclosure provides a method
of processing a
hydrocarbon co-feed (e.g., VGO) with a portion thereof blended with an amount
of HTL oil. The
feeds are processed in the presence of a cracking catalyst resulting in an
improved yield of the
biogenic carbon, such as an increase of at least 0.5 wt%, such as from about
0.5 wt% to 3 wt%,
thus relative to the identical process on an equivalent energy or carbon
content basis of the
feedstream where the hydrocarbon co-feed is not blended with any other fuel
feedstock (such as a
HTL oil).
[0017] In at least one embodiment, a method of preparing a biofuel
includes: i) processing a
hydrocarbon feedstock with an HTL feedstock in the presence of a catalyst; and
ii) optionally,
adjusting feed addition rates of the hydrocarbon co-feed, the HTL feedstock,
or both, to target a
desirable biofuel product profile, a riser temperature, or a reaction zone
temperature; or iii)
optionally, adjusting the cracking catalyst to combined hydrocarbon/HTL
feedstock ratio (catalyst
: oil(s) ratio).
[0018] Further, the present disclosure provides a system for separately
injecting the feedstocks
into the cracking unit, for example, by providing at least two or more feed
nozzles coupled with an
FCC unit for injection into the FCC unit.
[0019] Methods and systems for making compositions of the present
disclosure may include
renewable fuel (also referred to as HTL oil or renewable oil) as a feedstock
in cracking units, such
as FCCs, and other refinery systems or field upgrader operations. Renewable
fuels may include
fuels produced from renewable resources. Suitable HTL oils may include
biofuels such as solid
biofuels (e.g., wood used as fuel, cellulosic biomass), biodiesel, bio-
alcohols (e.g., biomethanol,
bio-ethanol, biobutanol) from biomass, and hydrogen fuel (when produced with
renewable energy
sources), catalytically converted biomass to liquids, and thermochemically
produced liquids. In at
least one embodiment, the HTL oil is a cellulosic material from biomass.
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100201 As used herein, and unless otherwise specified, the term "Cn" means
hydrocarbon(s)
having n carbon atom(s) per molecule, wherein n is a positive integer.
[0021] As used herein, and unless otherwise specified, the term
"hydrocarbon" means a class
of compounds containing hydrogen bound to carbon, and encompasses (i)
saturated hydrocarbon
compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of
hydrocarbon
compounds (saturated and/or unsaturated), including mixtures of hydrocarbon
compounds having
different values of n. Additionally, the hydrocarbon compound may contain, for
example,
heteroatoms such as sulphur, oxygen, nitrogen, or any combination thereof.
Suitable hydrocarbon
compounds may include acetic acid, formic acid, levulinic acid and gamma-
valerolactone and/or
mixtures thereof.
[0022] The term "hydrocarbon co-feed" refers to a co-feed that contains one
or more
hydrocarbon compounds.
[0023] The term "fluid hydrocarbon co-feed" refers to a hydrocarbon feed
that is not in a solid
state. The fluid hydrocarbon co-feed can be a liquid hydrocarbon co-feed, a
gaseous hydrocarbon
co-feed, or a mixture thereof. Also, the fluid hydrocarbon co-feed can be fed
to a catalytic cracking
reactor in a liquid state, and/or in a gaseous state, or in a partially liquid-
partially gaseous state.
When injected into the catalytic cracking reactor in a liquid state, and/or in
a gaseous state, or in a
partially liquid-partially gaseous state, the fluid hydrocarbon co-feed may be
vaporized upon entry,
such as the fluid hydrocarbon co-feed may be contacted in the gaseous state
with the FCC catalyst.
A hydrocarbon co-feed can be a petroleum oil.
[0024] The term "liquefaction", also referred to as "liquefying", refers to
the conversion of a
gas material and/or solid material, such as cellulosic material, into one or
more liquid (liquefied)
products.
[0025] The term "liquefied product" refers to a product that is liquid at a
temperature of about
20 C and a pressure of about 1 bar absolute (0.1 MPa). A "liquefied product"
can also refer to a
product that can be converted into a liquid by melting (e.g., melting upon
heat) or dissolving in a
solvent (e.g., an organic solvent). In at least one embodiment, the liquefied
product is a liquefied
product that is liquid at a temperature of about 80 C and a pressure of about
1 bar absolute (0.1
MPa). Suitable liquefied products may be more or less viscous and with a
viscosity that may
extensively vary.
[0026] The term "liquid solvent" is herein understood to be a solvent that
is liquid at the
temperature and pressure at which the liquefaction process is carried out.
[0027] The term "final liquefied product" refers to a liquefied product
suitable to be directed
to the catalytic cracking process.
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100281 The term "cracked product(s)" refers to product(s) obtained after
processing/cracking/breaking down heavy hydrocarbon molecules (usually
nonvolatile) into
lighter molecules (such as light oils (corresponding to gasoline), middle-
range oils used in diesel
fuel, residual heavy oils, a solid carbonaceous product known as coke, and
such gases as methane,
ethane, ethylene, propane, propylene, and butylene) by means of heat,
pressure, and/or catalysts in
a refinery reactor unit, such as an FCC reactor unit. The terms "cracked
product" and "final
liquefied RINs-product" may be used herein interchangeably.
[0029] The term "visbreaking" refers to the untangling of molecules in
fluid during heat
treatment and/or to the breaking of large molecules into smaller molecules
during heat treatment,
which results in a reduction of the viscosity of the fluid.
Hydrothermal Liquefaction
[0030] Hydrothermal liquefaction (HTL) technology produces HTL oil at a
lower temperature
with much longer residency time as compared to, for example, a fast py-oil
process. The HTL
process, also called "hydrous pyrolysis", is used for the reduction of complex
organic materials
such as biowaste and/or biomass into crude oil and other chemicals. The
pathway of HTL can
include three major phases, i) depolymerisation, followed by ii) decomposition
and iii)
recombination/repolymerisation of the reactive fragments. HTL can involve
direct liquefaction of
biomass, with the presence of water and perhaps some catalysts, to directly
convert biomass into
liquid oil, at a reaction temperature of less than 400 C. HTL can have
different pathways for the
biomass feedstock and, unlike biological treatment (e.g., anaerobic
digestion), HTL converts
feedstock into oil rather than gases or alcohol. There are some unique
features of the HTL process
and its product compared with other biological processes: 1) the end product
is a crude oil (which
has much higher energy content of fuels than syngas or alcohol, the energy
content being an
important property of fuels obtained by the amount of heat produced by the
burning of 1 gram of
a substance, and is measured in joules per gram); 2) if the feedstock contains
a lot of water, HTL
does not require drying. As noted above, known processes require extensive
separation of products
after co-processing in the cracking unit which requires high-energy
consumption by large
separators, which counteracts the lower greenhouse gas emissions that the
obtained biofuels are
aiming to achieve. An HTL process of the present disclosure can be performed
in any suitable
HTL reactor, such as described in U.S. Pat. Pub. No. 2013/0118059,
incorporated by reference.
[0031] Suitable biomass, biomass materials, or biomass components, include
but are not
limited to, wood, wood residues, forest debris, sawdust, slash bark, scrap
lumber, manure,
thinnings, forest cullings, begasse, corn fiber, corn stover, empty fruit
bunches, fronds, palm
fronds, flax, straw, low-ash straw, energy crops, palm oil, non-food-based
biomass materials, crop
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residue, slash, pre-commercial thinnings, urban wood and yard wastes, tree
residue, annual
covercrops, switchgrass, mill residues, miscanthus, animal manure (dry and/or
wet), cellulosic
containing components, cellulosic components of separated yard waste,
cellulosic components of
separated food waste, cellulosic components of separated municipal solid
waste, or combinations
thereof. Suitable cellulosic biomass may include biomass derived from or
containing cellulosic
materials. For purposes of the present disclosure, the HTL oil can be an oil
processed from a
cellulosic-containing biomass.
[0032] The biomass can be characterized as being compliant with U.S.
renewable fuel standard
program (RFS) regulations, or a biomass suitable for preparing a cellulosic-
renewable
identification number-compliant fuel, for example. Suitable biomass can be
characterized as being
compliant with those biomass materials specified in the pathways for a D-code
1, 2, 3, 4, 5, 6, or
7-compliant fuel, in accordance with the U.S. renewable fuel standard program
(RFS) regulations,
such as the biomass can be characterized as being compliant with those biomass
materials suitable
for preparing a D-code 3 or 7-compliant fuel, in accordance with the U.S.
renewable fuel standard
program (RFS) regulations or the biomass can be characterized as being
composed of only
hydrocarbons (or renewable hydrocarbon biofuels, also called "green"
hydrocarbons).
[0033] The term "renewable fuel oil" (also referred to as "HTL oil") refers
to a biomass-derived
fuel oil or a fuel oil produced from the conversion of biomass. The HTL oil
used in the process of
the present disclosure is a cellulosic renewable fuel oil (also referred to as
"cellulosic HTL oil"),
and may be derived or prepared from the conversion of cellulosic-containing
biomass which is
processed via HTL to produce an HTL oil. The HTL-processed HTL oil described
herein could
also be blended with various non-hydrodeoxygenated, non-deoxygenated, non-
hydrotreated, non-
upgraded, non-catalytically processed, thermo-mechanically-processed, HTL-
processed HTL oil
and/or other non-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-
upgraded, non-
catalytically processed, thermo-mechanically-processed, HTL-processed HTL oil
that has been
derived from other biomass to form blends of non-hydrodeoxygenated, non-
deoxygenated, non-
hydrotreated, non-upgraded, non-catalytically processed, thermo-mechanically-
processed, HTL-
process HTL oil.
[0034] In at least one embodiment, the HTL oil is a liquid formed from a
biomass including a
cellulosic material, wherein the only processing of the biomass is a thermo-
mechanical process
(specifically including grinding and slow thermal processing (e.g., HTL
process), and optionally
post-processing or enrichment of the HTL oil liquid prior to introduction into
a hydrocarbon
conversion unit.
[0035] In particular, the process for making cellulosic RIN-compliant fuel
compositions may
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include a liquefaction process where a cellulosic material is contacted with a
liquid solvent to
produce a final HTL oil liquefied product. This process may also be referred
to as liquefaction or
liquefying of the cellulosic material. The liquefaction or liquefying may be
carried out by means
of a liquefaction or liquefying reaction.
[0036] In at least one embodiment, the liquefaction process is a
hydrothermal liquefaction
process, meaning that the pyrolysis of a biomass may occur at a reacting
(e.g., operating)
temperature of less than about 425 C, such as from about 200 C to 425 C, such
as from about
250 C to 350 C, and at a residence time of at least 1 minute, such as from
about 1 minute to about
2 hours, such as from about 5 minutes to about 1.5 hours, such as from about
10 minutes to about
1 hour, such as from about 15 minutes to about 45 minutes, such as from about
20 minutes to about
30 minutes.
[0037] A cellulosic material can refer to a material containing cellulose.
In at least one
embodiment, the cellulosic material is a lignocellulosic material. A
lignocellulosic material
includes lignin, cellulose and optionally hemicellulose. One of the advantages
of the liquefaction
process is that the process enables liquefaction not only of the cellulose but
also the lignin and
hemicelluloses.
[0038] For the purposes of this disclosure, any suitable cellulose-
containing material can be
used as cellulosic material. The cellulosic material for use according to the
present disclosure may
be obtained from a variety of plants and plant materials including forestry
wastes, agricultural
wastes, sugar processing residues and/or mixtures thereof Examples of suitable
cellulose-
containing materials include, but are not limited to, agricultural wastes such
as corn cobs, corn
stover, soybean stover, rice straw, rice hulls, oat hulls, corn fibre, cereal
straws such as wheat,
barley, rye and oat straw; grasses; forestry products such as wood and wood-
related materials such
as sawdust; waste paper; sugar processing residues such as bagasse and beet
pulp; or mixtures
thereof.
[0039] The HTL oil formed by liquefaction can be an unenriched liquid (such
as an unenriched
HTL oil) formed from ground-up biomass by a process, such as a slow thermal
processing, wherein
the resulting liquid may be at least 50 wt%, such as at least 60 wt%, such as
at least 70 wt%, such
as at least 75 wt%, such as at 80 wt%, such as at least 85 wt%, such as at
least 90 wt% of the total
weight of the processed biomass. Namely, the liquid (i.e., the HTL oil) yield
from the processed
biomass can be at least 50 wt%, such as at least 60 wt%, such as at least 70
wt%, such as at least
75 wt%, such as at least 80 wt%, such as at least 85 wt%, such as at least 90
wt% of the total weight
of the ground biomass being processed. The term "unenriched" refers to HTL oil
liquid that does
not undergo any further pre- or post-processing including, more particularly,
no
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hydrodeoxygenation, no hydrotreating, no catalytic exposure or contact. For
example, unenriched
HTL oil can be prepared from the ground biomass and then transported and/or
stored, and can be
even heated or maintained at a given temperature; not exceeding about 65 C, on
its way to being
introduced into the conversion unit at the refinery (i.e., refinery FCC unit).
The mechanical
handling associated with transporting, storing, heating, and/or pre-heating of
the unenriched HTL
oil should not be considered an enriching process. An unenriched HTL oil may
include one or more
unenriched HTL oils mixed from separate unenriched assortments and/or
unenriched assortments
generated from different cellulosic biomass (such as assorted varieties of non-
food biomass).
Additionally, mixed compositions can be blended to purposefully provide or
achieve particular
characteristics in the combined unenriched HTL oil.
[0040] In at least one embodiment, the HTL oil includes thermally converted
biomass or
thermo-mechanically converted biomass. Suitable HTL oils may include an HTL
liquid (i.e., HTL
oil), derived or prepared from the conversion of biomass (e.g., cellulosic
biomass). Any suitable
HTL oil may include a non-HDO HTL oil, a non-deoxygenated HTL oil, a non-
upgraded HTL oil,
a thermally-processed cellulosic HTL oil, a thermally-processed, non-upgraded-
cellulosic HTL oil,
a thermally-processed biomass liquid; a thermally-processed-non-upgraded-
biomass liquid, a
thermally processed non-food-based biomass liquid, a thermally-processed non-
food, cellulosic-
based biomass liquid, a thermally-processed non-food-renewable liquid, a
thermally-processed
cellulosic liquid, a slow thermal-processed cellulosic liquid, a slow thermal-
processed bio-oil, a
slow thermal processed biomass liquid or thermo-pyrolytic liquid having less
than 5 wt% solid
content, such as less than 5 wt%, such as less than 4 wt%, such as less than 3
wt%, such as less
than 2 wt%, such as less than 1 wt%, such as less than 0.5 wt% solid content.
Further examples of
suitable HTL oil may include a conditioned HTL oil, a non-hydrotreated-non-
upgraded HTL oil, a
HTL oil or HTL liquid, a thermo-HTL oil or a thermo-HTL liquid, a bio-oil or a
bio-oil liquid, a
biocrude oil or biocrude liquid, a thermo-catalytic HTL oil or a thermo-
catalytic HTL liquid, a
catalytic HTL oil or a catalytic HTL liquid, or any combinations thereof
[0041] In at least one embodiment, the HTL oil may include one or more of a
non-HDO HTL
oil, a non-deoxygenated HTL oil, a non-upgraded HTL oil, a thermally-processed
cellulosic HTL
oil, a slow thermo-mechanically-processed HTL oil, a non-hydrotreated-non-
upgraded HTL oil,
an HTL oil or HTL liquid; or a thermo-HTL oil or a thermo-HTL liquid.
[0042] Moreover, the liquefaction process may include torrefaction, steam
explosion, particle
size reduction, densification and/or pelletization of the cellulosic material
before the cellulosic
material is contacted with the liquid solvent. Such torrefaction, steam
explosion, particle size
reduction, densification and/or pelletization of the cellulosic material may
advantageously allow
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for improved process operability and economics.
[0043] For example, the cellulosic material can be processed into small
particles before being
used in the process of the present disclosure, thus in order to promote
liquefaction. In at least one
embodiment, the cellulosic material is processed into particles having a
particle size distribution
with an average particle size of about 0.01 millimeter or greater, such as of
about 0.05 millimeter
or greater, such as of about 0.1 millimeter or greater, such as of about 0.5
millimeter or greater,
such as from about 0.01 millimeter to about 30 centimeters, such as from about
1 millimeter to
about 20 centimeters, such as from about 2 millimeter to about 10 centimeters,
such as from about
millimeter to about 5 centimeters. For practical purposes of the present
disclosure, the particle
size of the cellulosic material in the centimeter and millimeter range can be
determined by sieving.
[0044] Particularly, the cellulosic material can be a lignocellulosic
material that may involve a
pre-treatment in order to remove and/or degrade undesirable lignin and/or
hemicellulose. Suitable
pre-treatments of lignocellulosic material may include fractionation, pulping
and torrefaction
processes.
[0045] Suitable HTL oils may have a pH in the range of about 0.5 to about
8, such as of 0.5 to
7, such as of about 0.5 to about 6.5, such as of about 1 to about 6, such as
of about 1.5 to about 5,
such as of about 1.5 to 4, such as of about 2 to about 3.5. In at least one
embodiment, the pH of the
HTL oil is less than 8, such as less than 7, such as less than 6.5, such as
less than 6, such as less
than 5.5, such as less than 5, such as less than 4.5, such as less than 4,
such as less than 3.5, such
as less than 3, less than 2.5, such as about 2. For example, the pH of the HTL
oil may be altered or
modified by the addition of an external, non-biomass derived material or pH
altering agent. For
example, the HTL oil may be acidic. Since the HTL oil is injected in a small
quantity into the FCC
(as compared to the total weight of the processed biofuel composition), it has
been discovered that
the risk of corrosion from the acidity generated during the process is limited
and the conversion
process of hydrocarbons to biofuel in the FCC provides desirable biofuel
compositions at pH values
of about 5 to 7. Also, the HTL oil may have the pH resulting from the
conversion of the biomass
from which it may be derived, such as a biomass-derived pH.
[0046] In at least one embodiment, the HTL oil has a solids content from
about 0.002 wt% to
about 10 wt%, such as from about 0.005 wt% to about 8 wt%, such as from about
0.01 wt% to
about 6 wt%, such as from about 0.05 wt% to about 4 wt%, such as from about
0.1 wt% to about
3 wt%, such as from about 0.2 wt% to about 2 wt%, such as from about 0.5 wt%
to about 1 wt%,
based on the total weight of the HTL oil.
[0047] The term "liquid solvent" refers to a solvent that is liquid at a
pressure of about 1 bar
atmosphere (0.1 MPa) and at a temperature of about 80 C or higher, such as
about 90 C or higher,
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such as about 100 C or higher, such as about 120 C. In at least one
embodiment, the liquid solvent
includes or is water.
[0048] In at least one embodiment, the liquid solvent includes or is an
organic solvent. Suitable
organic solvent can be a solvent including one or more hydrocarbon compounds.
Under standard
environmental conditions, hydrocarbon compounds are nonpolar hydrophobic.
[0049] Suitable HTL oil may include a solvent content of from 5 wt% to 45
wt%, such as from
wt% to 35 wt%, such as from 15 wt% to 30 wt%, such as from 20 wt% to 35 wt%,
such as
alternatively 20 wt% to 30 wt%, such as alternatively 30 wt% to 35 wt%, such
as alternatively 25
wt% to 30 wt% water.
[0050] In at least one embodiment, the HTL oil includes an oxygen content
level higher than
that of a hydrocarbon co-feed. For example, the HTL oil may have an oxygen
content level of
greater than 10 wt%, on a dry basis, such as an oxygen content level in the
range of about 10 wt%
to 50 wt%, such as from about 15 wt% to about 40 wt%, such as from about 20
wt% to about 35
wt%, on a dry basis.
[0051] For example, the HTL oil may include a carbon content of about 30
wt% to 90 wt%,
such as of about 35 wt% to 80 wt%, such as of about 40 wt% to 70 wt%, such as
of about 50 wt%
to 60 wt%, and/or an oxygen content of about 20 wt% to 50 wt% oxygen content,
such as of about
30 wt% to 40 wt% oxygen content, on a dry basis.
[0052] In at least one embodiment, the HTL oil includes a carbon content of
at least 35 wt%
of the carbon content contained in the biomass from which it may be derived.
For instance, the
HTL oil may include a carbon content level of from about 35 wt% to about 100
wt%, such as about
40 wt% to about 90 wt%, such as about 45 wt% to about 80 wt%, such as about 50
wt% to about
70 wt%, such as about 55 wt% to about 60 wt%, of the carbon content contained
in the biomass
from which it may be derived. In at least one embodiment, the HTL oil includes
a carbon content
level lower than that of a hydrocarbon co-feed. For example, the HTL oil may
include a carbon
content of from about 30 wt% to about 90 wt%, such as about 40 wt% to 80 wt%,
such as from 50
wt% to about 60 wt%, on a dry basis.
[0053] The energy content is a property of fuels and is defined as the
fuel's primary energy
obtained by the amount of heat produced by the burning of 1 gram of a
substance, and is measured
in joules per gram. The energy content of a fuel is determined by burning an
amount of the fuel
and capturing the heat released in a known mass of water in a calorimeter. The
energy released can
be calculated at initial and final temperatures using the equation
H = At=m=Cp
where H is the heat energy absorbed (in Joules), At is the change in
temperature (in C), m is the
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mass (in gram), and Cp is the specific heat capacity (4.18 J/g C for water).
Dividing the resulting
energy value by grams of biomass burned gives the energy content (in J/g). The
HTL oil may
include an energy content level of at least 20% of the energy content
contained in the biomass from
which it may be derived, such as an energy content level of about 40% to at
least 100% of the
energy content contained in the biomass from which it may be derived. In at
least one embodiment,
the HTL oil includes an energy content level of about 50% to about 99% of the
energy content
contained in the biomass from which it may be derived, such as from about 55%
to 90%, such as
from about 50% to about 80%, such as from about 60% to about 70%, alternately
from about 70%
to about 80% of the energy content contained in the biomass from which it may
be derived.
[0054] In at least one embodiment, a suitable catalyst for HTL processing
is an alkali reagent.
Examples of suitable alkali catalyst for HTL can be, but are not limited to,
Na2CO3, KOH, K2CO3,
FeSO4, Ni(OH)2.
[0055] In at least one embodiment, the organic solvent is partially derived
from cellulosic
material, such as lignocellulosic material, and/or partially derived from a
hydrocarbon source. The
organic solvent may include a mixture of a fraction of a hydrocarbon oil
and/or one or more
hydrocarbon compounds that may be obtained by acid hydrolysis of a cellulosic
material, such as
a lignocellulosic material.
[0056] In at least one embodiment, the organic solvent includes at least
one or more carboxylic
acids, for example, such as formic acid, acetic acid, levulinic acid and/or
pentanoic acid. Such
carboxylic acid(s) can be present before beginning the liquefaction process,
that is, which
carboxylic acid(s) cannot be in-situ generated and/or derived from the
cellulosic material during
the reaction.
[0057] The organic solvent may be water-miscible at the reaction
temperature of the
liquefaction process. The liquefaction process may include contacting the
cellulosic material with
a solvent mixture including the organic solvent with or without the presence
of water.
[0058] During the liquefaction process, water in the solvent mixture may be
generated in-situ.
In at least one embodiment, the organic solvent is present in an amount of
from about 1 wt% to
about 99 wt%, such as from about 5 wt% to about 95 wt%, such as from about 10
wt% to about 90
wt%, such as from about 15 wt% to about 85 wt%, such as from about 20 wt% to
about 80 wt%,
such as from about 25 wt% to about 70 wt%, such as from about 30 wt% to about
70 wt%, such as
from about 40 wt% to about 60 wt%, based on the total weight of water and
organic solvent.
[0059] A cellulosic material and an organic solvent may be mixed in a
solvent mixture at an
organic solvent-to-cellulosic material ratio of 0.5:1 to 50:1, such as 1:1 to
40:1, such as 2:1 to 30:1,
such as 3:1 to 20:1, such as 4:1 to 15:1, such as 5:1 to 10:1, such as 6:1 to
8:1 by weight.
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[0060] In at least one embodiment, the liquefaction process is carried out
in the presence of a
catalyst. The use of a catalyst advantageously allows one to lower the
reaction temperature and
speed up the reaction process.
[0061] In at least one embodiment, an HTL process is conducted in an
aqueous condensed
phase. The HTL may be conducted at an operating temperature of from about 200
C to 425 C,
such as from about 250 C to 400 C, such as from 275 C to 375 C, such as
from about 300 C
to 350 C, alternatively from about 250 C to 350 C. In at least one
embodiment, the HTL is
conducted at an operating pressure of from about 50 atm to about 400 atm, such
as from about 100
atm to about 300 atm, such as from about 150 atm to about 275 atm, such as at
200 atm.
[0062] An HTL process may be conducted at a residence time of from about 1
minute to about
2 hours, such as from about 5 minutes to about 1 hour, alternatively from
about 5 minutes to about
30 minutes. In at least one embodiment, a processed HTL oil is produced at a
carbon yield to
biofuel of about 10% to about 60%, such as from about 15% to about 50%, such
as from about
20% to about 40%. The present disclosure provides a processed HTL oil having a
low heating
value of about 20 MJ/kg to 60 MJ/kg, such as about 25 MJ/kg to about 50 MJ/kg.
[0063] In at least one embodiment, an HTL oil is produced via HTL with an
oxygenates content
of about 15% or lower, such as about 12% or lower, such as about 10% or lower,
and a water
content of about 8% or lower, such as about 5% or lower, such as about 3% or
lower. Without
being bound by theory, the low contents of water and oxygenates can promote a
greater thermal
stability of the HTL oil formed via HTL.
[0064] Kinematic Viscosity at 40 C (KV40) of the HTL oil after HTL can be
at least 500 cSt
or greater, such as 1,000 cSt or greater, such as 1,500 cSt or greater, such
as 2,000 cSt or greater,
such as 2,500 cSt or greater, such as 3,000 cSt or greater, such as 3,500 cSt
or greater, such as at
least 4,000 cSt or greater.
Fluid Catalytic Cracking
[0065] In at least one embodiment, the present disclosure also provides a
process for
conversion of a cellulosic material including: i) a liquefaction process,
including contacting a
cellulosic material with or without an organic solvent at a temperature of
from about 200 C to
about 425 C, optionally in the presence of a catalyst, where the organic
solvent includes a fraction
of one or more hydrocarbon oil(s), to produce an HTL oil (e.g., a final
liquefied product); ii) a
catalytic cracking process, including contacting a mixture of at least part of
the HTL oil and the
organic solvent (fraction of one or more hydrocarbon oil(s)) with an FCC
catalyst in an FCC reactor
at a temperature of from about 400 C to about 700 C, such as about 545 C to
about 585 C, thus to
produce one or more cracked product(s). In at least one embodiment, the final
cracked product of
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stage ii) may suitably be the biofuel composition or any part thereof. For
example, the final cracked
product of stage ii) can be introduced to (e.g., blended with) one or more
additional components to
form a biofuel composition. The final cracked product, with or without
blending to one or more
additional components to form a biofuel composition, is not fractionated after
an FCC process.
Moreover, after an FCC process, the final cracked product, with or without
blending to one or more
additional components to form a biofuel composition, is not further separated
and/or distilled (e.g.,
for additional purification processes) from all the reaction mixture(s) formed
during the cracking
process, with the exception of optionally removing water. The final cracked
product, with or
without blending to one or more additional components to form a biofuel
composition, may be
stored, manufactured, commercialized and/or employed as is, after an FCC
process. Alternatively,
the final cracked product can be blended with one or more additional
components to form a biofuel
composition.
[0066] In at least one embodiment, a refinery method and system may include
an assembly for
introducing the HTL oil, such as an HTL-processed oil, in an amount of at
least about 1 wt% of
the HTL oil, such as about 1 wt% to about 20 wt% of the HTL oil, into an FCC
unit or field
upgrader operation with the contact time of the cracking catalyst being for a
period of about 0.5
seconds to about 40 minutes, such as from about 1 second to about 30 minutes,
such as from about
30 seconds to about 15 minutes, such as from about 1 minute to about 5
minutes, alternately from
about 5 minutes to about 40 minutes.
[0067] Furthermore, the HTL oil can be conditioned prior to introduction
into the refinery
process (e.g., FCC reactor unit) and can be made from several compositions as
discussed above.
In at least one embodiment, an HTL oil is produced from the HTL conversion of
biomass under
the conditions of 200 C to 425 C (e.g., 350 C), at a processing residence
time of at least 1 minute,
such as from 1 minutes to 2h, such as from 5 minutes to 30 minutes, either
with or without a
catalyst. An example of a catalyst used for the cracking process may be Y-
Zeolite, ZSM-5 or other
FCC catalyst, or mixtures thereof (further details will be provided below). A
catalyst additive can
be added to optimize the performance of the FCC catalyst when processing HTL
oil.
[0068] In at least one embodiment, a hydrocarbon co-feed, for example
derived from
upgrading petroleum, includes a gas oil (GO) feedstock, a vacuum gas oil (VGO)
feedstock, a
heavy gas oil (HGO) feedstock, LPG, a middle distillate feedstock, a heavy-
middle distillate
feedstock, a hydrocarbon-based feedstock, Resid/De-Asphalted Oil (DAO) or
combinations
thereof. The hydrocarbon co-feed may be gasoline or diesel. Where a catalyst
is used, the
catalyst/oil ratio can be in the range of about 2/1 to 10/1, such as about 3/1
to 9/1, 4/1 to 8/1, or 5/1
to 7/1, where oil in this ratio is the total amount of oil feedstock
introduced (e.g., hydrocarbon co-
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feed and the HTL oil feedstock).
[0069] In at least one embodiment, the amount of the HTL oil feedstock that
may be
introduced into a refinery for co-processing with a hydrocarbon co-feed, is in
the range of from
about 1 wt% to about 20 wt%, such as from about 2 wt% to about 15 wt%, such as
from about 3%
to about 10%, such as from about 4% to about 8%, relative to the total amount
of feedstock
introduced into the refinery for processing (e.g., hydrocarbon co-feed and the
HTL oil feedstock).
For example, the amount of HTL oil feedstock introduced into the cracking
conversion unit for co-
processing with a hydrocarbon co-feed, may be 1 wt%, relative to the total
amount of feedstock
introduced into the refinery for processing, such as 2 wt%, such as 3 wt%,
such as 4 wt%, such as
wt%, such as 6 wt%, such as 7 wt%, such as 8 wt%, such as 9 wt%, such as 10
wt%, such as 11
wt%, such as 12 wt%, such as 13 wt%, such as 14 wt%, such as 15 wt%, such as
16 wt%, such as
17 wt%, such as 18 wt%, such as 19 wt%, such as 20 wt%, relative to the total
amount of feedstock
introduced into the refinery for processing.
Injection System coupled to the Cracking unit
[0070] In at least one embodiment, an HTL oil is fed to a cracking reactor
in a liquid state
and/or in a gaseous state, or in a partially liquid-partially gaseous state.
When injected into the
reactor in a liquid state, and/or in a gaseous state, or in a partially liquid-
partially gaseous state, the
HTL oil can be vaporized upon entry, such that the HTL oil can be contacted in
the gaseous state
with the cracking catalyst.
[0071] Furthermore, a catalytic cracking process may include contacting the
HTL oil and a
fluid hydrocarbon co-feed (e.g., petroleum oil) with a cracking catalyst, such
as in an FCC reactor
with an FCC catalyst, at a temperature of about 400 C to about 700 C, such as
about 545 C to
about 585 C, to produce one or more cracked products.
[0072] In at least one embodiment, the fluid hydrocarbon co-feed is any non-
solid hydrocarbon
co-feed suitable as a co-feed for a catalytic cracking unit. For example, the
fluid hydrocarbon co-
feed can be obtained from a conventional crude oil (also sometimes referred to
as a petroleum oil
or mineral oil), an unconventional crude oil (that is, oil produced or
extracted using techniques
other than the traditional oil well method) or a Fisher Tropsch oil, and/or
any hydrocarbon listed
above, and/or a mixture thereof.
[0073] In at least one embodiment, the fluid hydrocarbon co-feed is a fluid
hydrocarbon co-
feed from a renewable source, such as a vegetable oil.
[0074] Furthermore, the fluid hydrocarbon co-feed may include a fraction of
a renewable oil
and/or crude oil, such as straight run (atmospheric) gas oils, flashed
distillate, vacuum gas oils
(VGO), light cycle oil, heavy cycle oil, hydrowax, coker gas oils, diesel,
gasoline, kerosene,
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naphtha, liquefied petroleum gases, atmospheric residue ("long residue") and
vacuum residue
("short residue") and/or mixtures thereof The fluid hydrocarbon co-feed may
include paraffins,
olefins and aromatics, and/or mixtures thereof.
[0075] In a at least one embodiment, the fluid hydrocarbon co-feed includes
at least about 5
wt% elemental hydrogen (i.e., hydrogen atoms) or greater, such as about 10 wt%
elemental
hydrogen or greater, such as from about 5 wt% to about 20 wt% elemental
hydrogen based on the
total fluid hydrocarbon co-feed on a wet biomass basis. A high content of
elemental hydrogen,
such as a content of at least 5 wt%, allows the hydrocarbon feed to act as an
inexpensive hydrogen
donor in the catalytic cracking process.
[0076] In at least one embodiment, a fluid hydrocarbon co-feed is present
at a weight ratio of
fluid hydrocarbon co-feed to the HTL oil of 4:6, such as 4.5:5.5, such as 5:5,
such as 5.5:4.5, such
as 6:4, such as 6.5:3.5:, such as 7:3, such as 7.5:2.5, such as 8:2, such as
8.5:1.5, such as 9:1, such
as 9.5:0.5, such as 9.8:0.2, such as 9.9:0.1. The fluid hydrocarbon co-feed
and the HTL oil can be
fed to an FCC reactor in a weight ratio within the above ranges.
[0077] The amount of the HTL oil, based on the total weight of the HTL oil
and fluid
hydrocarbon co-feed supplied to an FCC reactor, can be from about 65 wt% to
about 0.05 wt%,
such as from about 60 wt% to about 0.1 wt%, such as from about 55 wt% to about
1 wt%, such as
from about 50 wt% to about 2.5 wt%, such as from about 45 wt% to about 5 wt%,
such as from
about 10 wt% to about 40 wt%.
[0078] The catalytic cracking process can be carried out in an FCC reactor.
An FCC reactor is
part of an FCC unit. Suitable FCC reactors can be, for example, a fixed bed
reactor, a circulating
fluidized bed reactor, a fluid bed reactor (such as a fluidized dense bed
reactor), a moving bed
reactor, an FCC riser reactor, a multiple FCC riser reactor, and/or a hybrid
reactor such as one or
more of these cited reactors can be coupled together, and the like. In at
least one embodiment, the
catalytic cracking process is carried out in an FCC riser reactor, such as the
FCC reactor is the FCC
riser reactor. The fluid hydrocarbon co-feed can be supplied to such FCC riser
reactor downstream
of the location where one or more liquefied product(s) can be supplied to the
FCC riser reactor.
[0079] In at least one embodiment, a mixture of one or more liquefied
product(s) with a first
hydrocarbon co-feed is supplied to a cracking reactor, such as an FCC riser
reactor, at a first
location and a second fluid hydrocarbon co-feed is supplied to the cracking
reactor, such as the
FCC riser reactor, at a second location downstream of the first location. The
HTL oil and the
hydrocarbon co-feed are injected into the cracking reactor through separate
injection nozzles.
[0080] In at least one embodiment, a mixture of one or more HTL oil(s) and
a first hydrocarbon
co-feed, such as an organic solvent when the organic solvent is chosen from
the described fluid
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hydrocarbon co-feeds, is supplied to an FCC reactor, such as an FCC riser
reactor, at a first location
and a second fluid hydrocarbon co-feed is supplied to the FCC reactor, such as
the FCC riser
reactor, at a second location downstream of the first location.
[0081] Suitable conventional reactor types are described in for example
U.S. Pat. No.
4,076,796; U.S. Pat. No. 6,287,522 (dual riser); Fluidization Engineering, D.
Kunii and 0.
Levenspiel, Robert E. Krieger Publishing Company, New York, N.Y. 1977; Fluid
Catalytic
Cracking technology and operations, Joseph W. Wilson, PennWell Publishing
Company, 1997,
chapter 3, pages 101 to 112; Riser Reactor, Fluidization and Fluid-Particle
Systems, pages 48 to
59, F. A. Zenz and D. F. Othmo, Reinhold Publishing Corporation, New York,
1960; U.S. Pat. No.
6,166,282 (fast-fluidized bed reactor); U.S. patent application Ser. No.
09/564,613 filed May 4,
2000 (multiple riser reactor), the disclosures of which are incorporated
herein by reference.
[0082] For purposes of the present disclosure, the FCC riser reactor can be
an elongated tube-
shaped reactor suitable for carrying out any catalytic cracking reactions. The
elongated tube-shaped
FCC riser reactor can be oriented in a vertical manner.
[0083] The FCC riser reactor may be an "internal" FCC riser reactor or an
"external" FCC riser
reactor, such as the FCC riser reactor is an internal FCC riser reactor that
is a vertical tube-shaped
reactor, which may have a vertical upstream end located outside a vessel and a
vertical downstream
end located inside the vessel. The vessel can be a reaction vessel suitable
for catalytic cracking
reactions and/or a vessel that may include one or more cyclone separators
and/or swirl tubes to
separate catalyst from cracked product. Usage of an internal riser reactor may
advantageously
prevent from any potential clogging and/or fouling that may occur during the
FCC process.
[0084] The length of the riser reactor may vary widely. For purposes of the
present disclosure,
the FCC riser reactor may have a length in the range of from about 1 meter
(3.28 feet) to about 100
meters (328 feet), such as from about 5 meters (16.4 feet) to about 75 meters
(246 feet), such as
from about 10 meters (32.8 feet) to about 60 meters (196.8 feet), such as from
about 15 meters
(49.2 feet) to about 50 meters (164 feet).
[0085] In at least one embodiment, the HTL oil produced in the HTL process
is supplied to an
FCC riser reactor, at the bottom of the FCC riser reactor. This may
advantageously result in an in-
situ water formation at the bottom of the reactor. The in-situ water formation
may lower the
hydrocarbon partial pressure and reduce second order hydrogen transfer
reactions, thereby
resulting in higher olefin yields. In at least one embodiment, the hydrocarbon
partial pressure is
lowered to a pressure in the range of from about 0.01 to 0.50 MPa, such as
from 0.05 to 0.45 MPa,
such as from 0.1 to 0.40 MPa, such as from 0.15 to 0.35 MPa, such as from 0.10
to 0.30 MPa.
[0086] A number of riser designs use a lift gas as a further means of
providing a uniform
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catalyst flow. Lift gas is used to accelerate the catalyst in a first section
of the riser before
introduction of the feed and thereby reduces the turbulence which can vary the
contact time
between the catalyst and hydrocarbons. Hence, there is better catalyst/oil
contacting when a lift gas
is used, and, without being bond by theory, it is believed that the lift gas
can "condition" the FCC
catalyst, so that its performance increases in the cracking reactor.
Therefore, adding a lift gas at the
bottom of the FCC riser reactor could be beneficial for the process.
[0087] Suitable lift gas may include, but are not limited to, steam,
vaporized oil and/or oil
fractions, and/or mixtures thereof. However, the use of a vaporized oil and/or
oil fraction (such as
vaporized liquefied petroleum gas, gasoline, diesel, kerosene or naphtha) as a
lift gas may have the
advantage that the lift gas can simultaneously act as a hydrogen donor and may
prevent or reduce
coke formation. Further, if a fluid hydrocarbon co-feed is used as an organic
solvent in the FCC
process, also vaporized organic solvent may be used as a lift gas.
Alternatively, a heavy feed such
as a gas oil, a VG0, may be added to the FCC riser reactor via feed injection
nozzles. The catalyst
is pre-accelerated up the FCC riser upstream of the feed by injection of lift
gas to the base of the
riser.
[0088] One or more HTL oil(s) and/or any fluid hydrocarbon feed may flow co-
currently in
the same direction. The FCC catalyst can be contacted in a concurrent-flow,
countercurrent-flow
or cross-flow configuration with such a flow of the HTL oil(s) and optionally
the fluid hydrocarbon
feed. In at least one embodiment, the FCC is contacted in a concurrent-flow
configuration with a
concurrent-flow of the HTL oil(s) and optionally the fluid hydrocarbon feed.
[0089] Potential contaminants present in a hydrocarbons feedstock fed to an
FCC reactor, can
be vanadium, nickel, sodium, and iron. The catalyst used in the FCC unit may
favor the absorption
of these contaminants which may then have unfavorable effects on the
hydrocarbons conversion
into a biofuel in the FCC reactor. The main advantage of co-feeding an HTL oil
with one or more
hydrocarbon(s) to an FCC reactor can be that the renewable oil contains little
or none of these
contaminants, thus beneficially extending the life of the catalyst, and
enabling to maintain greater
catalyst activity while improving the magnitude of the conversion into
biofuel(s).
[0090] In at least one embodiment, a system (also referred to as an
apparatus) used for
processing or co-processing a hydrocarbons feedstock, an HTL oil, or
combinations thereof,
includes a refinery system, such as a conversion unit, such as an FCC unit, a
coker, a coking unit,
a field upgrader unit, a hydrotreater, a hydrotreatment unit, a hydrocracker,
a hydrocracking unit,
and/or a desulfurization unit. For instance, the system used for the
hydrocarbons conversion into a
biofuel may be or include an FCC unit operation; may be or include a coker;
may be or include a
hydrotreater; may be or include a hydrocracker. A conversion system of
hydrocarbons into biofuel
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used for processing or co-processing a hydrocarbon co-feed, an HTL oil, or
combinations thereof,
may include a retrofitted refinery system, such as a refinery system including
a retrofitted port for
the introduction of an HTL oil. For example, the conversion system of
hydrocarbons into biofuel
used for processing or co-processing a hydrocarbon co-feed, an HTL oil, or
combinations thereof,
may include a retrofitted FCC refinery system having at least two or more
retrofitted port(s) for
introducing an HTL oil. For example, a retrofitted port may be a stainless
steel port, a titanium or
some other alloy or a combination thereof of high durability, high corrosive
environment material.
[0091] In at least one embodiment, a refinery system used for processing a
hydrocarbon co-
feed with an HTL oil includes a retrofitted refinery system, a FCC, a
retrofitted FCC, a coker, a
retrofitted coker, a field upgrader unit, a hydrotreater, a retrofitted
hydrotreater, a hydrocracker, or
a retrofitted hydrocracker.
[0092] In at least one embodiment, the process of the present disclosure
for converting
hydrocarbons into biofuel(s) includes introducing, injecting, feeding, co-
feeding, an HTL oil into
a refinery system via a mixing zone, at least two or more nozzles, at least
two or more retrofitted
ports, at least two or more retrofitted nozzles, one or more velocity steam
line, or a live-tap. For
example, the process of the present disclosure for converting hydrocarbons
into biofuel(s) may
include processing a hydrocarbon co-feed with an HTL oil. In at least one
embodiment, the process
may include co-injecting a hydrocarbon co-feed and an HTL oil, such as co-
feeding, independently
or separately introducing, injecting, feeding, or co-feeding, a hydrocarbon co-
feed and an HTL oil
into a refinery system. For example, a hydrocarbon co-feed and an HTL oil may
be provided,
introduced, injected, fed, or co-fed at a close distance from each other into
the FCC reactor, the
reaction zone, the FCC reaction riser of the refinery system. Furthermore, the
HTL oil may be
introduced, injected, fed, co-fed into the FCC reactor, the reaction zone, or
the FCC reaction riser
of the refinery system near, upstream, and/or downstream to the delivery or
injection point of the
hydrocarbon co-feed. The hydrocarbon co-feed and the HTL oil can be contacted
with each other
upon introduction, delivery, injection, feeding, co-feeding into the refinery
system, into the reactor,
into the reaction zone, or into the FCC reaction riser. In at least one
embodiment, the hydrocarbon
co-feed and the HTL oil are contacted with each other subsequent to entering
the refinery system,
the reactor, the reaction zone, or the FCC reaction riser. The hydrocarbon co-
feed and the HTL oil
may be first contacted with each other subsequent to entering into,
introduction into, injection into,
feeding into, or co-feeding into the refinery system, the reactor, the
reaction zone, or the FCC
reaction riser. In at least one embodiment, the hydrocarbon co-feed and the
HTL oil are co-blended
prior to injection into the refinery system.
[0093] The hydrocarbon co-feed and the HTL oil may be introduced, injected,
fed, co-fed into
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the refinery system through different or similar delivery systems. For
example, the hydrocarbon
co-feed and the HTL oil may be introduced into the refinery system through at
least two or more
independent or separate injection nozzles. The hydrocarbon co-feed and the HTL
oil may be
introduced into the refinery system near to each other in a FCC reactor riser
in the refinery system.
The HTL oil may be introduced, injected, fed, co-fed into the refinery system
above, below, near
the introduction point of the hydrocarbon fuel feedstock in the refinery
system. In at least one
embodiment, at least two or more injection nozzles are located in a FCC
reactor riser in the refinery
system suitable for introducing the hydrocarbon fuel feedstock and/or the HTL
oil. The HTL oil
may be introduced into the refinery system through a lift steam line located
at the bottom of the
FCC reactor riser. The hydrocarbon co-feed may be introduced into the refinery
system at a first
injection point and the renewable fuel oil may be introduced into the refinery
system at a second
injection point. The first injection point can be, for example, upstream of
the second injection point,
alternatively, and/or downstream of the second injection point, and/or near to
the second injection
point, and/or the first injection point and the second injection point may be
located in a reactor
riser, such as an FCC reactor riser. In at least one embodiment, an HTL oil
may be introduced
below an FCC reactor riser during the conversion process of the hydrocarbon co-
feed.
Additionally, an HTL oil may be injected via a quench riser system upstream,
downstream, or near,
from the introduction point of the hydrocarbon co-feed. In at least one
embodiment, an HTL oil is
injected via a quench riser system located above, below, or near, a petroleum
fraction feedstock
injection nozzle.
[0094] In at least one embodiment, the processing of the hydrocarbon co-
feed with the HTL
oil has a substantially equivalent or greater performance in preparing the
biofuel product, relative
to processing solely the hydrocarbon co-feed in the absence of the HTL oil. In
at least one
embodiment, processing an amount of up to 30 wt%, such as up to 20 wt%, of HTL
oil with the
remainder hydrocarbon co-feed, for instance 0.05:99.95, such as 1:99, such as
2:98, such as 3:97,
such as 4:96, such as 5:95, such as 10:90, such as 20:80 weight ratio of HTL
oil to the hydrocarbon
co-feed may have a substantially equivalent or greater performance in the
resulting fuel products,
relative to processing solely the hydrocarbon co-feed in the absence of the
HTL oil. In at least one
embodiment, processing in the range of from 20:80 to 0.05:99.95 weight ratio
of an HTL oil with
a hydrocarbon co-feed results in a weight percent increase in gasoline or
diesel of more than 0.05
wt%, such as 0.5 wt% or greater, such as 1 wt% or greater, such as 1.5 wt% or
greater, such as 2
wt% or greater, such as 5 wt% or greater, such as 10 wt% or greater, such as
20 wt% or greater,
relative to processing solely the hydrocarbon co-feed in the absence of the
HTL oil.
[0095] In at least one embodiment, a suitable amount of one or more HTL
oil(s) (such as from
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2 wt% to 20 wt% relative to the total weight of feedstock fed) of one or more
HTL oil(s), is blended
with one or more variety of hydrocarbon oils and/or blends of hydrocarbon oils
including HGO
(Heavy Gas Oil), LGO (Light Gas Oil), VG0 (Vacuum Gas Oil), and other
petroleum fractions
and blends.
[0096] For example, an HGO may be a lighter feedstock that can be combined
with one or
more hydrocarbon oil(s), as in a mixed feed stream or as a separate feed
stream, either before, or
after, alternatively before and after, the introduction of one or more
hydrocarbon oil(s). In at least
one embodiment, an HGO is directed to a refinery FCC unit. In an alternate
embodiment, a
hydrocarbon oil is introduced jointly with an HTL oil, before, or after,
alternatively before and
after the introduction of the HTL oil. Either the HTL oil or the hydrocarbon
oil, or both, may be
alternatively fed in a pulse manner. In at least one embodiment, a hydrocarbon
oil is introduced
jointly with an HTL oil (e.g., a cellulosic RIN-compliant fuel) in the feed of
a refinery FCC unit.
[0097] A suitable amount of an HTL oil, such as a cellulosic RIN-compliant
fuel, may be
blended with a VG0. VG0 can be a feedstock fed to a refinery FCC unit. In at
least one
embodiment, a blend of HTL oil, such as a cellulosic RIN-compliant fuel, and
VG0 targets a final
measured TAN (also referred to as "Total Acid Number") of the cracked
product(s) of less than 4,
such as less than 2, such as less than 1, such as in a range of from 0.05 to
1, such as from 0.05 to
0.5, such as from 0.05 to 0.25.
[0098] In at least one embodiment, a suitable amount of HTL oil is blended
(e.g., by co-
feeding) with an HGO (e.g., a lighter feedstock) that can be directed to a
refinery FCC unit, thus
either in combination with a VG0 or as a separate feed.
[0099] In at least one embodiment, a suitable amount of HTL oil is blended
(e.g., by co-
feeding) with lighter hydrocarbon co-feeds such as a light cycle oil (LCO), or
gasoline, or diesel,
with or without a surfactant, alternatively with or without any additive(s).
The content of LCO,
and/or gasoline, and/or diesel blended with an HTL oil may be of about 0.005
wt% to about 98
wt%, such as from about 0.005 wt% to about 90 wt%, such as from about 0.005
wt% to about 80
wt%, such as from about 0.005 wt% to about 70 wt%, such as from about 0.005
wt% to about 60
wt%, such as from about 0.005 wt% to about 50 wt%, such as from about 0.005
wt% to about 40
wt%.
[0100] Suitable HTL oil may include all of the whole fuel produced from the
thermal or
catalytic conversion of biomass, such as a whole fuel produced from the
thermal or catalytic
conversion of biomass with a low water content (e.g., at least less than 15%).
[0101] In at least one embodiment, the flash point of an HTL oil is
increased in order to reduce
the volatile content of the liquid and subsequently co-processed in an FCC
with a hydrocarbon
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feedstock. The flash point may be increased, for example, from 50 C to 70 C,
or greater and can
be measured by the Pensky-Martens closed cup flash point tester (e.g. ASTM D-
93). However,
various methods and apparatus can be used to effectively reduce the volatile
components, such as
flash column, falling film evaporator, devolatilization vessel or tank. If
present, reduction of some
of the volatile components of the HTL oil may improve the reduction of
undesirable components
such as phenols from passing through the FCC reactor and ending up in the
collected water stream.
[0102] Not only do biofuel feedstocks like corn, switchgrass, and
agricultural residues need
water for growth and conversion to bioethanol, but petroleum feedstocks like
crude oil and oil
sands also require large volumes of water for drilling, extraction and
conversion into petroleum
products. Hence, the initial HTL process of the HTL oil before introduction to
the FCC unit is
advantageous since only less than about 12% of water and less than about 5% of
oxygenates are
present, preventing undesirable components to interfere with the HTL oil, the
hydrocarbon, and
the catalyst during the conversion process to biofuel. For example, the water
content of an HTL oil
feedstock that may be introduced into a refinery FCC unit for co-processing
with a hydrocarbon
co-feed (e.g., VGO), may be less than about 12%, such as in the range of about
0.01 wt% to about
12 wt%, such as from about 1 wt% to about 10 wt%, such as from about 1.5 wt%
to 5 wt%. In at
least one embodiment, the water content of the HTL oil feedstock introduced
into the refinery FCC
unit for co-processing with a hydrocarbon co-feed (e.g., VGO) is less than
about 12%, such as in
the range of about 0.01 wt% to about 12 wt%, such as from about 1 wt% to about
10 wt%, such as
from about 1.5 wt% to 5 wt%.
[0103] For purposes of the present disclosure, a hydrocarbon co-feed can be
or include an
organic solvent which may include a polar and/or a non-polar hydrocarbon
compounds (e.g., LCO).
In at least one embodiment, the organic solvent includes at least one or more
polar hydrocarbon
compounds, such as the organic solvent includes more than one, such as more
than two, such as
more than three different polar hydrocarbon compounds.
[0104] In at least one embodiment, the organic solvent includes one or more
carboxylic acids.
A carboxylic acid refers to a hydrocarbon compound including at least one
carboxyl (-COOH)
group, such as the carboxylic acids can be polar hydrocarbon compounds. The
organic solvent
includes equal to or more than about 1 wt% carboxylic acids, such as equal to
or more than about
3 wt% carboxylic acids, such as equal to or more than about 5 wt% of
carboxylic acids, such as
equal to or more than about 10 wt% of carboxylic acids, such as equal to or
more than about 15
wt% of carboxylic acids, such as equal to or more than about 20 wt% of
carboxylic acids, such as
equal to or more than about 25 wt% of carboxylic acids, such as equal to or
more than about 30
wt% of carboxylic acids, such as equal to or less than about 95 wt% of
carboxylic acids, such as
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equal to or less than about 90 wt% of carboxylic acids, such as equal to or
less than about 85 wt%
of carboxylic acids, such as equal to or less than about 80 wt% of carboxylic
acids, such as equal
to or less than about 70 wt% of carboxylic acids, based on the total weight of
organic solvent.
[0105] Suitable organic solvents, including one or more carboxylic acids,
can be, but are not
limited to, formic acid, acetic acid, propionic acid, butyric acid, 4-
oxopentanoic acid acid (also
called "levulinic acid"), pentanoic acid (also called "valeric acid"), caproic
acid, and/or benzoic
acid. In at least one embodiment, the carboxylic acid solvent included in the
organic solvent is
acetic acid. Acetic acid can be simultaneously used as part of the organic
solvent and/or used as an
acid catalyst.
[0106] In an alternate embodiment, an organic solvent includes paraffinic
compounds,
naphthenic compounds, olefinic compounds and/or aromatic compounds. Such
compounds may
be present in refinery streams such as gas oil, fuel oil and/or residue oil.
These refinery streams
may therefore also be suitable as organic solvent in the cracking process.
[0107] In at least one embodiment, a hydrocarbon co-feed includes at least
a portion of cracked
product(s), such as a portion of the cracked product(s) may be recycled to the
cracking process and
further used as organic solvent. In at least one embodiment, equal to or more
than about 5 wt%,
such as equal to or more than about 10 wt%, such as equal to or more than
about 15 wt%, such as
equal to or more than about 20 wt%, such as equal to or more than about 25
wt%, such as equal to
or more than about 30 wt% of the organic solvent is obtained from an
intermediate and/or a final
cracked product.
[0108] In at least one embodiment, any recycle of cracked product(s)
includes a weight amount
of cracked product(s) of 1 to 150 times the weight of the HTL oil, such as 2
to 100 times the weight
of the HTL oil, such as 5 to 50 times the weight of the HTL oil, such as 10 to
20 times the weight
of the HTL oil.
[0109] In at least one embodiment, at least part of the hydrocarbon co-feed
is derived from a
cellulosic material, such as a lignocellulosic material and/or a
hemicellulosic material, such as a
lignocellulosic material. For example, at least part of the hydrocarbon co-
feed may be generated
in-situ during liquefaction of the cellulosic material, such as a
lignocellulosic material and/or a
hemicellulosic material, such as a lignocellulosic material. In another
example, at least part of the
hydrocarbon co-feed may be obtained by acid hydrolysis of a cellulosic
material, such as a
lignocellulosic material and/or a hemicellulosic material, such as a
lignocellulosic material, such
as a lignocellulosic material. Examples of possible hydrocarbon compounds in
the hydrocarbon
co-feed that may be obtained by acid hydrolysis of a cellulosic material, such
as a lignocellulosic
material and/or a hemicellulosic material, such as a lignocellulosic material,
may include formic
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acid, acetic acid, and levulinic acid.
[0110] Further, suitable hydrocarbon compounds attainable from such acid
hydrolysis products
by hydrogenation may also be used. Examples of such hydrogenated hydrocarbon
compounds may
include, but are not limited to, tetrahydrofufuryl compounds (derived from
furfural via
hydrogenation), tetrahydropyranyl compounds (derived from
hydroxymethylfurfural), gamma-
valerolactone (derived from levulinic acid via hydrogenation), ketones, mono-
and di-alcohols
(derived from sugars) and guaiacol and syringol compounds (derived from
lignin). In at least one
embodiment, the hydrocarbon co-feed includes one or more of such hydrocarbon
compounds. Such
hydrocarbon compounds may also be included in the final cracked product.
Accordingly, in at least
one embodiment, the final cracked product or part thereof includes one or more
of the hydrocarbon
compounds listed, optionally hydrogenated, compounds such as guaiacol and/or
syringol
compounds, which can be derived from lignin.
[0111] One or more hydrocarbon compounds in the hydrocarbon co-feed may
advantageously
be obtainable from the HTL oil cracked in the cracking process. The
hydrocarbon compound(s)
may for example be generated in-situ and/or recycled and/or used as a make-up
hydrocarbon co-
feed, affording significant economic and processing advantages.
[0112] During FCC, in at least one embodiment, the hydrocarbon co-feed
includes one or more
hydrocarbon compounds that may be suitable to act as a fluid hydrocarbon co-
feed in the catalytic
cracking phase. The hydrocarbon co-feed used during cracking may include, one
or more
hydrocarbon compounds obtained from, for example, a crude oil (e.g., a
petroleum oil or mineral
oil), a renewable source (e.g., HTL oil), and/or a mixture thereof, such as
the hydrocarbon co-feed
used during cracking may include a fraction of a petroleum oil or renewable
oil. Suitable
hydrocarbon co-feed may include, but are not limited to, diesel, gasoline,
kerosene, naphtha,
liquefied petroleum gases, VG0, a straight run (atmospheric) gas oils,
atmospheric residue ("long
residue") and vacuum residue ("short residue"), flashed distillate, light
cycle oil, heavy cycle oil,
hydrowax, coker gas oils, and/or mixtures thereof. In at least one embodiment,
hydrocarbon co-
feed include(s) diesel, gasoline, VG0 and/or mixtures thereof
[0113] A co-solvent may be used in addition to the hydrocarbon co-feed
already available in
the FCC in order 1) to enhance the solvent power; and 2) to increase the
solubility of poorly-soluble
components present during the cracking process. Suitable co-solvent can be an
organic solvent that
includes hydrocarbons, such as a petroleum oil or a fraction thereof. Such
hydrocarbon co-feed or
organic co-solvent may be a suitable feed to the catalytic cracking phase.
Furthermore, no
separation of the hydrocarbon co-feed or organic co-solvent may be required.
[0114] Optionally, one or more cracked product(s) can be subsequently
hydrotreated with a
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source of hydrogen, such as in the presence of a hydrotreatment catalyst to
produce a hydrotreated
cracked product. For instance, a hydrotreatment process may include
hydrodeoxygenation,
hydrodenitrogenation and/or hydrodesulphurization. One or more hydrotreated
product(s) derived
therefrom can conveniently be used as a biofuel composition. Such biofuel
composition may
conveniently be blended with one or more other components (e.g., additives) to
produce a biofuel
composition. Examples of such components may include, but are not limited to,
anti-oxidants,
corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers
and/or mineral fuel
components, conventional petroleum derived gasoline, diesel and/or kerosene
fractions.
[0115] In at least one embodiment, the FCC process includes contacting an
HTL oil (e.g., a
cellulosic material) concurrently with the fraction of a hydrocarbon (e.g.,
petroleum oil), with a
source of hydrogen, with a hydrogenation catalyst, and optionally with an acid
catalyst, at a
temperature of equal to or more than about 100 C to produce a cracked product
(e.g., final
(RINs)biofuel product(s)). In the FCC unit, cracking and hydrogenation of the
HTL oil and
hydrocarbons may be carried out simultaneously or hydrogenation may be carried
out subsequent
to the cracking.
[0116] In at least one embodiment, a mixture of one or more liquefied
product(s) with a first
hydrocarbon co-feed is supplied to an FCC reactor, such as an FCC riser
reactor, at a first location
and a second fluid hydrocarbon co-feed is supplied to the FCC reactor, such as
the FCC riser
reactor, at a second location downstream of the first location. In at least
one embodiment, a mixture
of one or more HTL oil(s) and a first hydrocarbon co-feed, such as an organic
solvent when the
organic solvent is chosen from the described fluid hydrocarbon co-feeds, is
supplied to an FCC
reactor, such as an FCC riser reactor, at a first location and a second fluid
hydrocarbon co-feed is
supplied to the FCC reactor, such as the FCC riser reactor, at a second
location downstream of the
first location.
[0117] In at least one embodiment, the FCC unit is designed to have at
least two feedstock
injection points, such as two or more feedstock injection points, such as at
least one injection point
for a petroleum oil co-feed and at least one injection point for an HTL oil
feedstock. For example,
an FCC unit has at least two injection points for co-injection of a mixture of
a petroleum fraction
feedstock and an HTL oil feedstock (both petroleum fraction feedstock and HTL
oil feedstock can
be mixed upstream of the injection point) or the system could be fitted with
multiple points of
injection for either, both or mixtures of the feedstock. In an alternate
embodiment, the FCC unit is
retrofitted to include a way of introducing the HTL oil, for example, by
adding an injection point
close to the FCC riser or at some point in the process where the catalyst may
be upflowing. A
suitable FCC unit fitted with at least two feedstock injection points is
described in U.S. Patent No.
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9,129,989 which is incorporated herein by reference.
[0118] Processes of the present disclosure can provide biofuel compositions
(e.g., biolfuel
compositions having RIN credits) without any separation process of the cracked
product(s) after
FCC providing additional time-, energy- and cost-efficiency. Furthermore, an
FCC unit fitted with
two or more feedstock injection points where the FCC unit is located
downstream from a
hydrothermal liquefaction unit provides biofuel compositions with a total acid
number (TAN) of
about 3 mg or greater KOH/g, such as about 6 mg or greater KOH/g, The FCC
process can be
performed using a system of at least two or more injection nozzles on the FCC
unit, which promotes
better blending of the HTL and hydrocarbon oils (and ultimately cracked
product(s)) by increasing
the gas/oil dispersion, providing additional time-, energy- and cost-
efficiency.
[0119] In at least one embodiment, processed and/or unprocessed HTL oil is
fed upstream
and/or downstream of a hydrocarbon (e.g., gas oil (GO); VGO) feed inlet. The
HTL oil can be
introduced in an upstream and/or a downstream section of the FCC riser onto
the FCC catalyst,
thus enabling the hydrocarbons conversion into a biofuel, such as the HTL oil
can be introduced
downstream of the FCC riser. Introduction of the HTL oil in upstream and/or
downstream section
of the FCC riser may thereby imparting properties of the renewable oil (e.g.,
viscosity of the oil;
acid nature; oxidation stability; etc.) In an alternate embodiment, an HTL oil
is introduced
downstream of the hydrocarbons fresh feed injection nozzles. Optionally, a
retrofitted riser with a
retrofitted renewable oil feedstock injection port(s) can be added to the
present system. The term
"retrofitting" refers to the addition of new technology or features to older
systems, such as to install
new or modified parts or equipment in something previously manufactured or
constructed. The
FCC riser may be adapted to include multiple renewable oil feedstock injection
port(s) both before
and after the introduction of the hydrocarbons. Furthermore, The FCC riser may
be retrofitted to
have only one additional renewable oil feedstock injection port positioned
either before or after the
hydrocarbons injection point, alternatively retrofitted to have one or more
renewable oil feedstock
injection(s) port along the hydrocarbons feedstock feed line.
[0120] The FCC unit may include a riser quench system which may inject
vaporizable quench
oil into the FCC riser above the hydrocarbons feed injection nozzles.
Introduction of a quench oil,
such as vegetable oil, may increase the temperature in the mix zone and lower
section of the FCC
riser. In at least one embodiment, the HTL oil feedstock may be injected into
the quench line of
the FCC riser.
[0121] In at least one embodiment, the FCC process includes contacting an
HTL oil with an
organic solvent, optionally in the presence of an acid catalyst, at a
temperature of at least about
90 C, such as from about 90 C to about 700 C, such as from about 400 C to
about 700 C, such
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as from about 545 C to about 585 C.
[0122] In at least one embodiment, the catalyst is an acid catalyst
suitable for cracking of the
HTL oil and/or hydrocarbon co-feed, sufficiently strong to enable cleavage of
the covalent linkages
and dehydration of the HTL oil and hydrocarbons. Suitable acid catalysts can
be, but are not limited
to, a Bronsted acid or a Lewis acid. The acid catalyst of the process of the
present disclosure may
be a homogeneous catalyst or a heterogeneous catalyst, such as the acid
catalyst can be a
homogeneous or a finely dispersed heterogeneous catalyst, such as the acid
catalyst is a
homogeneous catalyst. Furthermore, the acid catalyst can be maintained as a
stable liquid under
the cracking conditions used during the process.
[0123] The acid catalyst can be a Bronsted acid, such as a mineral or an
organic acid, such as
a mineral or an organic acid having a pKa value of from about 2 to 6, such as
from about 2.2 and
4, such as from 2.5 and 3. Suitable mineral acids may include, but are not
limited to, hydrochloric
acid (HC1), nitric acid (HNO3), sulphuric acid (H2504), Boric acid (H3B03),
para-toluene
sulphonic acid, phosphoric acid (H3PO4), Hydrobromic acid (HBr), and mixtures
thereof In at least
one embodiment, the acid catalyst used in the cracking process is sulphuric
acid or phosphoric
acid. Suitable organic acids for the FCC process may include, but are not
limited to, formic acid,
acetic acid, oxalic acid, lactic acid, levulinic acid, citric acid,
trichloracetic acid and mixtures
thereof.
[0124] The acid catalyst can be present in an amount of from about 0.005
wt% to about 50
wt%, such as from about 0.01 wt% to about 45 wt%, such as from about 0.05 wt%
to about 40
wt%, such as from about 0.1 wt% to about 35 wt%, such as from about 0.5 wt% to
about 30 wt%,
such as from about 0.75 wt% to about 25 wt%, such as from about 1 wt% to about
20 wt%, such
as from about 2 wt% to about 15 wt%, such as from about 5 wt% to about 15 wt%,
based on the
total weight of the organic solvent and/or solvent mixture, and the acid
catalyst.
[0125] Strongly acidic catalyst sites on the catalyst promote cracking.
Hence, the hydrogen
forms of zeolites used in FCC unit systems are powerful solid-based acids,
promoting various acid-
catalyzed based reactions (e.g., cracking, isomerisation, alkylation,
dehydration of alcohols,
hydrogenation of the polyaromatics ). The hydrogen forms of zeolites can
effectively promote
hydrogen transfer, thus with longer reactor residence times. The present FCC
unit system benefits
from the characteristics of renewable oil, namely its TAN or acidic nature,
that can lead to an
improvement in cracking or the conversion of, for example, VG0 (i.e., a
synergistic effect) in FCC
operations. Consequently, such procedure advantageously promotes the
production of desirable
products by reducing unwanted products by way of heavy cycle oil and clarified
slurry oil. Further,
additives, such as sulfur-reducing additives, may be added to the catalyst. It
is anticipated that such
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additives may experience enhanced effectiveness.
[0126] The FCC catalyst can be any suitable catalyst for use in a cracking
process. In at least
on embodiment, the FCC catalyst includes any suitable zeolitic component for
the FCC. Also, the
FCC catalyst may contain an amorphous binder compound and/or a filler.
Examples of the
amorphous binder component may include quartz, zirconia, silica, alumina,
magnesium oxide,
calcium carbonate, and/or titania, and/or a mixture thereof of at least two or
more of these
components. Suitable fillers may include clays (such as hydrated aluminum
silicate, also called
"kaolin") and/or silica. For purpose of the present disclosure, the zeolitic
component can be a large,
a medium, and/or a mixture thereof of large and medium pore zeolite which may
include a porous,
crystalline aluminosilicate structure.
[0127] In at least one embodiment, a porous, crystalline aluminosilicate
structure has a porous
internal cell structure on which the major axis of the pores can be from about
0.4 nanometer to
about 0.65 nanometer, alternatively in the range of from about 0.65 nanometer
to about 0.9
nanometer. Examples of large pore zeolites may include, but are not limited
to, faujasite, zeolite Y
or X, ultra-stable zeolite Y, Rare Earth zeolite Y and Rare Earth ultra-stable
zeolite Y. Examples
of medium pore zeolites may include, but are not limited to, the Modernite
Framework Inverted
(MFI) structural type (e.g., ZSM-5), the MTW type (e.g., ZSM-12), the TON
structural type (e.g.,
theta) and the FER structural type (e.g., ferrierite).
[0128] In at least one embodiment, a hydrogenation catalyst for the FCC
process is a
hydrogenation catalyst that is resistant to the combination of the organic
solvent and/or the solvent
mixture and, if present, the acid catalyst. For example, a hydrogenation
catalyst may include a
heterogeneous and/or homogeneous catalyst, such as the hydrogenation catalyst
is a homogeneous
catalyst, alternatively a heterogeneous catalyst. The hydrogenation catalyst
may include a
hydrogenation metal known to be suitable for hydrogenation reactions, such as
for example nickel,
iron, palladium, ruthenium, rhodium, molybdenum, cobalt, copper, iridium,
platinum and gold, or
mixtures thereof.
[0129] The hydrogenation catalyst including such a hydrogenation metal may
be
sulfided. Further, sulfided hydrogenation catalysts may be used such as, for
example, a catalyst
based on Molybdenum sulfide, potentially including Cobalt and/or Nickel as a
promotor, such as
sulfided NiMo/A1203 catalyst.
[0130] With respect to the hydrogenation catalyst being a heterogeneous
catalyst, the catalyst
may include a hydrogenation metal supported on a carrier. Suitable carriers
include for example
carbon, alumina, titanium dioxide, zirconium dioxide, silicon dioxide and
mixtures thereof.
Examples of suitable heterogeneous hydrogenation catalysts may include, but
are not limited to,
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ruthenium, platinum or palladium supported on a carbon carrier, such as
ruthenium supported on
zirconium dioxide or titanium dioxide. Any suitable form of the heterogeneous
catalyst and/or
carrier used for the present process may be a mesoporous powder, granules,
pellets, tablets or any
extrudates, megaporous structure (e.g., honeycomb, cloth, foam, and/or mesh).
The heterogeneous
catalyst may be present in a FCC reactor included in a fixed bed reactor or
ebullated slurry bed
reactor, such as in a fixed bed reactor.
[0131] With respect to the hydrogenation catalyst being a homogeneous
hydrogenation
catalyst, the catalyst may include an organic or inorganic salt of a
hydrogenation metal. Suitable
examples of organic or inorganic salt of a hydrogenation metal can be, but are
not limited to,
acetate-, acetylacetonate-, nitrate-, sulphate- or chloride-salt of palladium,
platinum, nickel, cobalt,
rhodium or ruthenium, such as, in at least one embodiment, the homogeneous
catalyst is an organic
or inorganic acid salt of a hydrogenation metal, where the acid is an acid
already present in the
process as the acid catalyst (described above).
[0132] In at least one embodiment, a source of hydrogen may be any source
of hydrogen
known to be suitable for hydrogenation purposes, which may include hydrogen
gas and/or
hydrogen-donor (e.g., formic acid), such as the source of hydrogen is a
hydrogen gas. Hence, such
hydrogen gas introduced to the FCC reactor at a partial hydrogen pressure that
can be in the range
of from about 0.01 MPa to 30 MPa, such as from about 0.05 MPa to about 28 MPa,
such as from
about 0.1 MPa to about 26 MPa, such as from about 0.5 MPa to about 24 MPa,
such as from about
1 MPa to about 22 MPa, such as from about 2 MPa to about 20 MPa, such as from
about 3 MPa to
about 18 MPa, such as from about 4 MPa to about 16 MPa. A hydrogen gas can be
supplied to an
FCC reactor co-currently, cross-currently or counter-currently to the HTL oil,
such as the hydrogen
gas is supplied counter-currently to the HTL oil.
[0133] In the FCC unit, the cracking process can be carried out at any
total pressure known to
be suitable for cracking processes, such as the cracking process can be
carried out under a total
pressure value of from about 10 psig to about 50 psig, such as about 15 psig
(1 bar) to about 30
psig (2 bar).
[0134] Additionally, during the cracking process in the FCC unit, the HTL
oil and one or more
hydrocarbon(s) are cracked, namely the HTL oil and one or more hydrocarbon(s)
may be converted
into one or more cracked product(s), to produce cracked product(s), such as a
biofuel product. In
at least one embodiment, the final biofuel product is either hydrogenated or
not. Furthermore, the
final cracked product can be contacted/blended with one or more component(s),
such as any fuel
additives (e.g., metal deactivators, corrosion inhibitors, lead scavengers,
fuel dyes, and antioxidant
stabilizers), to form a biofuel composition. Methods of the present disclosure
(e.g., HTL oil + dual
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nozzle system) can provide improved final cracked products that do not need to
be fractionated
before blending with one or more components, saving energy, time, and cost in
product of biofuels.
The one or more components can be selected from an anti-oxidant, a corrosion
inhibitor, an ashless
detergent, a dehazer, a dye, a lubricity improver, a mineral fuel component, a
petroleum derived
gasoline, a diesel, and a kerosene.
[0135] The reaction effluent produced in the cracking process in the FCC
unit may include
insoluble solid materials such as humins (also referred to as "char") and the
cracked product(s),
including the processed-HTL oil and hydrocarbon(s). Moreover, the reaction
effluent may include,
for example, water (expected to be in much lower amount when compare to the
water formed
during fast pyrolysis), co-solvent, acid catalyst and/or hydrogenation
catalyst, and/or gaseous
products (e.g., hydrogen, nitrogen). In at least one embodiment, the cracking
process of the present
disclosure does not include any separation of the final cracked product from a
reaction effluent
produced in the cracking process. Hence, the reaction effluent is not
forwarded to a separation
section. In at least one embodiment, the final cracked product is the RIN-
biofuel product(s).
[0136] The water produced during the cracking process may be removed by
distillation,
pervaporation and/or reversed osmosis. The final cracked product may include
hydrocarbon
compounds and/or a small amount of oxygenates, such as for example alcohols
(e.g., mono- and/or
di-alcohols) and/or ketones (mono- and/or di-ketones).
[0137] In at least one embodiment, the present disclosure provides a method
of processing a
hydrocarbons fraction (e.g., VGO) with a substituted amount of a processed-HTL
oil in the
presence of a catalyst resulting in a sustaining and/or increasing or
improving the yield of a
transportation fuel, such as an increase of at least 0.2 wt% or at least 0.5
wt%, relative to the
identical process on an equivalent energy or carbon content basis of the
feedstream where the
petroleum fraction is not substituted to any other fuel feedstock. Examples of
transportation fuel
yield may be, but are not limited to, a LPG, a gasoline, a diesel fuel, a jet
fuel, an LCO, a heating
oil, a transportation fuel, and/or a power fuel.
[0138] In at least one embodiment, the present disclosure provides a method
of processing a
hydrocarbon fraction (e.g., VGO) with a substituted amount of a processed-HTL
oil in the presence
of a catalyst resulting in an increased or improved yield of the biogenic
carbon, such as an increase
of at least 0.5 wt%, such as an increased or improved yield of the biogenic
carbon of from about
0.5 wt% to 3 wt%, thus relative to the identical process on an equivalent
energy or carbon content
basis of the feedstream where the petroleum fraction is not substituted to any
other fuel feedstock.
Examples of transportation fuel yield may be, but are not limited to, an LPG,
a gasoline, a diesel
fuel, a jet fuel, an LCO, a heating oil, a transportation fuel, and/or a power
fuel.
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101391 In at least one embodiment, a method of preparing a biofuel includes
processing a
hydrocarbon co-feed with a processed-HTL oil feedstock in the presence of a
catalyst. For example,
a method of preparing a biofuel may include providing a processed-HTL oil
feedstock for
processing with a hydrocarbon co-feed in the presence of a catalyst. In at
least one embodiment, a
method of preparing a biofuel includes: i) processing a hydrocarbon co-feed
with a processed-HTL
oil feedstock in the presence of a catalyst; and ii) optionally,
adjusting/catering feed addition rates
of a hydrocarbon co-feed, a processed-HTL oil feedstock, or both, to target a
desirable biofuel
product profile, a riser temperature, or a reaction zone temperature; or iii)
optionally, adjusting the
FCC catalyst to combined hydrocarbon co-feed and processed-HTL oil feedstock
ratio (catalyst :
oil(s) ratio) to target a particular biofuel product profile, a riser
temperature, or a reaction zone
temperature; where the catalyst : oil(s) ratio can be a weight ratio or a
volume ratio.
[0140] In at least one embodiment, feed nozzles that are modified for the
properties of
conditioned renewable fuel feedstock and any suitable nozzles of the FCC are
converted into
stainless steel, or other suitable metallurgy, and adjusted to inject HTL oil
to provide an upgrade
to the traditional systems.
[0141] In at least one embodiment, the addition rate value of the HTL oil
in a refinery FCC
unit that may be processing a hydrocarbon fraction is sufficient to provide
mixing of the HTL oil
with co-feed. Additionally or alternatively, the contact time of the FCC
catalyst and the HTL oil is
about 1 second to about 30 seconds, such as about 2 seconds to about 10
seconds.
[0142] FCC units may use steam to lift the catalyst. The steam can be used
for dilution of the
reaction media at a residence time control. The lift steam can enter the FCC
reactor riser from the
bottom of the unit and/or through at least one or more nozzles on the side of
the reactor. These
nozzles may be located below, above or co-located with the feedstock (either
the HTL oil feed,
hydrocarbon feed or both HTL oil and hydrocarbon feed) injection point.
[0143] In at least one embodiment, a delivery system of the processed-HTL
oil separated from
the hydrocarbon feedstock feed port (or assembly) for introducing the
processed-HTL oil material
into an FCC unit is used. The separate delivery system may include transfer
from storage, preheat
and deliver the processed-HTL oil to an appropriate injection point on the
FCC. To ensure contact
between the processed-HTL oil and the hydrocarbon feedstock the point of
introduction may be
near to the hydrocarbon feedstock injection nozzles which may be located in
the downward section
of the FCC reactor riser.
[0144] In at least one embodiment, the processed-HTL oil is introduced
through one or more
atomizing nozzle(s) that may be inserted into one or multiple steam lines
and/or may be introduced
into one or more recycle lift vapor line(s).
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[0145] The addition rate of the processed-HTL oil may be controlled by a
separate delivery
system (i.e., separate from the hydrocarbon delivery system) into the downward
section of the FCC
reactor riser. In an alternate embodiment, the addition rate of the processed-
HTL oil is controlled
by a separate delivery system into one or multiple lift steam line(s). The
addition rate of the
processed-HTL oil may be controlled by a separate delivery system into an
available port in the
downward section of the FCC reactor riser. In a further alternate embodiment,
the addition rate of
the processed-HTL oil is controlled by a separate delivery system and
introduced into one of the
hydrocarbon nozzles or injectors either separately or with the hydrocarbon
feedstock, such as
separately of the hydrocarbon feedstock.
[0146] In at least one embodiment, a method of the present disclosure
includes: i) producing a
processed-HTL oil based feedstock; ii) introducing the processed-HTL oil based
feedstock into a
refinery system, where the refinery system conversion unit may be selected
from a group including
an FCC, a coker, a field upgrader system, a lube oil refinery facility, a
hydrocracker, and a
hydrotreating unit; iii) and co-processing the processed-HTL oil based
feedstock with a
hydrocarbon feedstock (e.g., VGO). For example, the method may include (i)
producing the
processed-HTL oil based feedstock, which includes a hydrothermal liquefaction
conversion of
biomass, and (ii) conditioning the processed-HTL oil based feedstock to
provide introduction into
the FCC refinery system. Hence, the conditioning of the processed-HTL oil
based feedstock may
include controlling an ash content to be in a range of between 0.001 wt% and 1
wt%; controlling a
pH to be in a range of from about 5 to about 7, such as from about 5 to 6; and
controlling a water
content to be in a range between 0.05 wt% and 0.2 wt%. In at least one
embodiment, the
hydrocarbon feedstock used is a VG0.
[0147] The conversion method of the present disclosure may include
injecting the processed-
HTL oil feedstock into a catalytic riser of a FCC unit. For example, the
processed-HTL oil
feedstock may be injected upstream of a VG0 inlet port of a FCC unit, such as
the processed-HTL
oil feedstock may be injected downstream of a VG0 inlet port of a FCC unit,
such as the processed-
HTL oil feedstock may be injected into a riser quench line of a FCC unit, such
as the processed-
HTL oil feedstock may be injected into a second riser of a two riser FCC unit,
such as the
processed-HTL oil feedstock may be injected into a third riser of a three
riser FCC unit.
[0148] In at least one embodiment, the system used for the conversion
process includes a
production facility for producing a processed-HTL oil based feedstock and a
refinery system,
where the refinery system may be selected from a conversion unit including a
FCC, a coker, a field
upgrader system, a lube oil refinery facility, a hydrocracker, and a
hydrotreating unit, where the
processed-HTL oil based feedstock may be introduced into the refinery system,
and theHTL oil
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based feedstock may be co-processed with a hydrocarbon feedstock in the
refinery system.
Regenerating Catalyst
[0149] In at least one embodiment, the catalytic cracking process includes:
i) an FCC process
including contacting the HTL oil, the hydrocarbons, and an FCC catalyst at a
temperature of from
about 400 C to about 700 C, to produce one or more cracked products and a
spent ("deactivated")
FCC catalyst; ii) a separation process including separating one or more of the
cracked products
from the spent FCC catalyst; iii) a regeneration process including
regenerating spent FCC catalyst
to produce a regenerated FCC catalyst, heat and carbon dioxide; and a
recycling process including
recycling the regenerated FCC catalyst to the FCC process.
[0150] The separation process including separating one or more of the
cracked products from
the spent FCC catalyst can be carried out using one or more cyclone separators
and/or one or more
swirl tubes. Suitable methods of carrying out the separation process are
described in Fluid Catalytic
Cracking; Design, Operation, and Troubleshooting of FCC Facilities by Reza
Sadeghbeigi,
published by Gulf Publishing Company, Houston Texas, 1995, pages 219 to 223,
and Fluid
Catalytic Cracking technology and operations, by Joseph W. Wilson, published
by PennWell
Publishing Company, 1997, chapter 3, pages 104 to 120, and chapter 6, pages
186 to 194,
incorporated herein by reference.
[0151] Furthermore, the separation process may include a stripping process
such as the spent
FCC catalyst may be stripped to recover the products absorbed on the spent FCC
catalyst before
the regeneration process. The recovered products may be recycled and added to
a stream including
one or more cracked products obtained from the catalytic cracking process.
[0152] In at least one embodiment, the regeneration process includes
contacting the spent FCC
catalyst with an oxygen containing gas in a regenerator, in order to produce a
regenerated FCC
catalyst, heat and carbon dioxide. The catalyst activity can be restored
during the regeneration coke
process where the coke that can be deposited on the catalyst, as a result of
the FCC reaction, is
burned off.
[0153] Additionally, the oxygen containing gas may be any suitable oxygen
containing gas
for use in a regenerator, such as air or oxygen-enriched air (OEA). The term
"oxygen enriched air"
refers to air including about 20 vol% oxygen or greater, such as air including
about 25 vol% oxygen
or greater, such as air including about 30 vol% oxygen or greater, based on
the total volume of air.
[0154] The heat produced in the exothermic regeneration process can be used
to supply energy
for the endothermic catalytic cracking process. Moreover, the heat produced in
the exothermic
regeneration process can be used to heat water and/or generate steam. The
steam can be used
elsewhere in the FCC refinery, such as a lift gas in a riser reactor.
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[0155] The regenerated FCC catalyst can be recycled back to the FCC
process. In at least one
embodiment, a side stream of make-up FCC catalyst is added to the recycle
stream to make-up for
loss of FCC catalyst in the reaction zone and regenerator.
Cracked Products and Compositions
[0156] The process of the present disclosure provides one or more cracked
product(s). At this
point of the process, there is no fractionation of any of the cracked
product(s) produced. Hence,
there is no separation process of the cracked product(s) with the blend
components (RFOs and
hydrocarbons) if present. Such simplified, environmentally-friendly, time- and
cost-efficient FCC
process enables access to the desirable biofuel with RIN credits, yet with
grade quality (e.g., low
concentration of sulfur content of from about 0.1 wt% to 2.5 wt% and heavy
metals) . Hence, the
one or more cracked product(s) derived therefrom can conveniently be used
directly as a biofuel
component. As used herein "grade quality" refers to a low to moderate level of
sulfur (e.g., from
0.5 wt% to 2.5 wt%) and low to moderate level of heavy metals (e.g., vanadium
and nickel).
[0157] In at least one embodiment, a cracked product may conveniently be
blended with one
or more other components to produce a biofuel composition. Examples of such
one or more other
components may include any additives such as anti-oxidants, corrosion
inhibitors, ashless
detergents, dehazers, dyes, lubricity improvers and/or mineral fuel
components, but also
conventional petroleum derived gasoline, diesel and/or kerosene. A biofuel
composition can
include one or more other components at an additive content of from about
0.001 wt% to about 30
wt% of any additives, such as from about 0.01 wt% to about 10 wt%, such as
from about 0.1 wt%
to about 3wt%, based on the weight of the biofuel composition.
[0158] In at least one embodiment, a biofuel formed after an FCC process
includes an FCC
product composition derived from catalytic contact of a feedstock including an
HTL oil, such as a
biofuel derived from a hydrocarbon co-feed and an HTL oil feedstock, such as a
biofuel derived
from about 50 wt% to about 99.99 wt%, such as from about 55 wt% to about 99.5
wt%, such as
from about 60 wt% to about 99 wt%, such as from about 65 wt% to about 90 wt%,
such as from
about 70 wt% to about 90 wt% of a hydrocarbon co-feed, and from about 0.01 wt%
to about 50
wt%, such as from about 0.5 wt% to about 45 wt%, such as from about 1 wt% to
about 40 wt%,
such as from about 10 wt% to about 35 wt%, such as such as from about 10 wt%
to about 30 wt%
of an HTL oil feedstock, or a biofuel derived from 50 vol% to about 99.99
vol%, such as from
about 55 vol% to about 99.5 vol%, such as from about 60 vol% to about 99 vol%,
such as from
about 65 vol% to about 90 vol%, such as from about 70 vol% to about 90 vol% of
a hydrocarbon
co-feed, and from about 0.01 vol% to about 50 vol%, such as from about 0.5
vol% to about 45
vol%, such as from about 1 vol% to about 40 vol%, such as from about 10 vol%
to about 35 vol%,
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such as from about 10 vol% to about 30 vol% of an HTL oil feedstock.
EXAMPLES
[0159] Table 1 illustrates comparative results obtained from conventional
data for fast
pyrolysis versus HTL of cellulosic material. When pyrolysis of biomass was
performed by fast
pyrolysis at an operating temperature of from 450 C to 500 C, an operating
pressure of 1 atm, and
at a very short residence time (of less than a second), without the presence
of catalyst, a thermally
unstable oil was produced with high contents of water (25%) and oxygenates
(38%). Fast pyrolysis
produced an oil containing very reactive species (e.g., oxygenates), which is
an issue for fuel
storage and transportation. However, with HTL that required lower operating
temperature (350
C), longer residence time (5 minutes to 30 minutes), and higher pressure (150
atm to 250 atm,
such as 200 atm), produced an oil that was more thermally stable, with less
water and oxygenates
contents (5% and 12%, respectively). This comparative experiment and the
associated
comparative data in Table 1 were provided in Elliott, D.C., et al. (September
2, 2014), Comparative
Analysis of Fast Pyrolysis and Hydrothermal Liquefaction as Routes for Biomass
Conversion to
Liquid Hydrocarbon Fuels, PowerPoint slides presented at the Symposium on
Thermal and
Catalytic Sciences for Biofuels and Biobased Products, TCS 2014 (Denver,
Colorado).
Table 1.
Conditions Fast Pyrolysis Hydrothermal Liquefaction
Feedstock Dry Biomass Wet Biomass
Operating Temperature 450 C ¨ 500 C 350 C
Operating Pressure 1 atm 200 atm
Residence Time <1 sec 5 to 30 min
Carbon Yield to Bio-oil 70% 35%
Oil Product Quality
Oxygen Content, Dry Basis 38% 12%
Water Content 25% 5%
Thermal Stability less more
[0160] Table 2 illustrates prophetic yields developed for the use of HTL
oil blended with
hydrocarbon feedstock (e.g., gasoline, diesel) in the FCC unit. When a
petroleum fraction of VG0
is mixed with a substituted amount of an HTL oil (5%) in the presence of a
catalyst, the quality of
the gasoline or the diesel fuel is not negatively affected. The yield of
gasoline (and diesel) remains
overall the same. The gasoline (or diesel) yield can also be represented in
terms of the amount of
carbon in the feedstock that may be converted to gasoline (or diesel).
Surprisingly, the yields of
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biogenic carbon of gasoline and diesel increase (2% and 1%, respectively).
These yields suggest
that more carbon in the VGO may be going to gasoline (and diesel) production
than would
otherwise be the case without the addition of the HTL oil in the blend. HTL
oil may be
synergistically affecting either the cracking chemistry or catalyst activity
in favor of the gasoline
(or diesel) product. These prophetic results demonstrate that combining a
hydrocarbon fuel with
an HTL oil via a simple process for the production of cost- and time-efficient
generation of biofuels
having RIN credits, i.e., the cellulosic RIN credits.
Table 2.
VGO VGO +5% HTL Biogenic Carbon
(% estimate)
C2 3 3
C3/C4 12 11.8
Gasoline 50 49.2 2%
Ico Diesel 20 20 1%
Bottoms 9 9
Coke 6 6
Water 0.2
CO + CO2 0.8
Total 100 100
Conversion 71 71
[0161] Subsequent to the above prophetic example, actual experiments were
run on an HTL
sample. Table 3 below summarizes two data sets comparing VGO only and VGO + 5%
HTL. The
two data sets have different operating conditions. Results are similar to
those predicted in the
prophetic example. Note that biogenic carbon was not measured, but the
assumptions of the
biogenic carbon shown in Table 2 would be expected to apply to the
experimental data. Also,
water and CO/CO2 results in the actual experiments were unavailable.
Table 3.
Data Set I Data Set II
Exp. # 273 287 275 289
Cat/Oil 6.12 6.12 6.12 4.7
Crack. Temp. 970 F 1010 F 900 F 900 F
Feed VGO VGO +5% HTL VGO
VGO +5% HTL
C2 1.06 1.42 0.63 0.7
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C3/C4 15.73 17.2 11.97 12.48
Gasoline 42.1 39.96 41.8 39.09
Ico Diesel 21.266 22.2 24.16 25.68
Bottoms 15.1 13.7 16.97 16.49
Coke 3.77 4.31 3.81 4.98
Water data unavailable
CO + CO2 data unavailable
Total 99.026 98.79 99.34 99.42
Conversion 63.64 64.1 58.87 57.83
[0162] Overall, processes of the present disclosure can provide thermally
stable biofuel
compositions providing conversion of a hydrocarbon feedstock using an HTL oil,
thus with less
water and oxygenates content. Processes of the present disclosure can provide
biofuel compositions
without any separation (e.g., fractionation) of the cracked product(s) after
FCC providing
additional time-, energy- and cost-efficiency. The FCC process can be
performed using a system
of at least two or more injection nozzles coupled with the FCC unit, which
promotes better blending
of the HTL and hydrocarbon oils (and ultimately cracked product(s)) by
increasing the gas/oil
dispersion, providing additional time-, energy- and cost-efficiency.
[0163] The phrases, unless otherwise specified, "consists essentially of'
and "consisting
essentially of' do not exclude the presence of other processes, elements, or
materials, whether or
not, specifically mentioned in this specification, so long as such processes,
elements, or materials,
do not affect the basic and novel characteristics of the present disclosure,
additionally, they do not
exclude impurities and variances normally associated with the elements and
materials used.
[0164] For the sake of brevity, only certain ranges are explicitly
disclosed herein. However,
ranges from any lower limit may be combined with any upper limit to recite a
range not explicitly
recited, as well as, ranges from any lower limit may be combined with any
other lower limit to
recite a range not explicitly recited, in the same way, ranges from any upper
limit may be combined
with any other upper limit to recite a range not explicitly recited.
Additionally, within a range
includes every point or individual value between its end points even though
not explicitly recited.
Thus, every point or individual value may serve as its own lower or upper
limit combined with any
other point or individual value or any other lower or upper limit, to recite a
range not explicitly
recited.
[0165] All documents described herein are incorporated by reference herein,
including any
priority documents and/or testing procedures to the extent they are not
inconsistent with this text.
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As is apparent from the foregoing general description and the specific
embodiments, while forms
of the present disclosure have been illustrated and described, various
modifications can be made
without departing from the spirit and scope of the present disclosure.
Accordingly, it is not intended
that the present disclosure be limited thereby. Likewise, the term
"comprising" is considered
synonymous with the term "including". Likewise whenever a composition, an
element or a group
of elements is preceded with the transitional phrase "comprising," it is
understood that we also
contemplate the same composition or group of elements with transitional
phrases "consisting
essentially of" "consisting of," "selected from the group of consisting of" or
"is" preceding the
recitation of the composition, element, or elements and vice versa.
[0166] While the present disclosure has been described with respect to a
number of
embodiments and examples, those skilled in the art, having benefit of this
disclosure, will
appreciate that other embodiments can be devised which do not depart from the
scope and spirit of
the present disclosure.
