U.S. patent application number 16/580801 was filed with the patent office on 2020-03-26 for co-processing hydrothermal liquefaction oil and co-feed to produce biofuels.
The applicant listed for this patent is ExxonMobil Research and Engineering Company. Invention is credited to Jihad M. Dakka, Hyung Rae Kim, William J. Novak, Kirsten E. Schutt, Xiaochun Xu.
Application Number | 20200095510 16/580801 |
Document ID | / |
Family ID | 68281919 |
Filed Date | 2020-03-26 |
United States Patent
Application |
20200095510 |
Kind Code |
A1 |
Novak; William J. ; et
al. |
March 26, 2020 |
CO-PROCESSING HYDROTHERMAL LIQUEFACTION OIL AND CO-FEED TO PRODUCE
BIOFUELS
Abstract
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.degree. C. or
less and an operating pressure of about 200 atm or less. 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 to produce a
cracked product (biofuel). The bio content of the cracked product
provides RIN credits for the cracked product.
Inventors: |
Novak; William J.;
(Bedminster, NJ) ; Schutt; Kirsten E.; (Houston,
TX) ; Dakka; Jihad M.; (Whitehouse Station, NJ)
; Kim; Hyung Rae; (Basking Ridge, NJ) ; Xu;
Xiaochun; (Spring, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Research and Engineering Company |
Annandale |
NJ |
US |
|
|
Family ID: |
68281919 |
Appl. No.: |
16/580801 |
Filed: |
September 24, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62735919 |
Sep 25, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 2200/0469 20130101;
C10L 1/188 20130101; C10G 11/18 20130101; C10G 2300/1081 20130101;
C10G 3/42 20130101; C10G 11/00 20130101; C10G 47/02 20130101; C10L
10/08 20130101; C10G 2300/1059 20130101; C10G 2300/1011 20130101;
C10G 3/57 20130101; C10G 2300/104 20130101; C10G 2300/1074
20130101; C10L 1/04 20130101; C10L 10/18 20130101; C10G 2300/1055
20130101; C10G 7/00 20130101; C10L 1/1855 20130101 |
International
Class: |
C10G 47/02 20060101
C10G047/02; C10L 1/04 20060101 C10L001/04; C10L 10/08 20060101
C10L010/08; C10L 10/18 20060101 C10L010/18; C10L 1/188 20060101
C10L001/188; C10L 1/185 20060101 C10L001/185 |
Claims
1. A method for forming a biofuel composition, comprising:
introducing separately a hydrothermal liquefaction (HTL) oil
derived from cellulosic material, a hydrocarbon co-feed and a
cracking catalyst into a cracking unit to form a mixture; and
processing the mixture at a temperature of about 350.degree. C. or
greater to form a cracked product.
2. The method of claim 1, wherein the cracked product is not
fractionated.
3. The method of claim 1, wherein the cracking unit comprises two
or more injection nozzles coupled with the cracking unit.
4. The method of claim 1, further comprising blending the cracked
product with one or more fuel additive components, wherein the
biofuel composition comprises one or more fuel additive
components.
5. The method of claim 4, wherein the one or more fuel additive
components are 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.
6. The method of claim 1, wherein the biofuel composition has a
water content of about 5% or less.
7. The method of claim 1, further comprising introducing the
hydrocarbon co-feed into the cracking unit using a first nozzle and
introducing the HTL oil into the cracking unit using a second
nozzle.
8. The method of claim 1, wherein the hydrocarbon co-feed comprises
one or more of a straight run (atmospheric) gas oil, a flashed
distillate, a vacuum gas oil, a light cycle oil, a heavy cycle oil,
a hydrowax, a coker gas oil, a gasoline, a naphtha, a diesel, a
kerosene, an atmospheric residue, a vacuum residue, or a
combination thereof.
9. The method of claim 1, wherein the hydrocarbon co-feed is a
vacuum gas oil.
10. The method of claim 8, wherein the ratio of the amount of
cracking catalyst to the total amount of hydrothermal liquefaction
oil and hydrocarbon co-feed is from about 2/1 to about 10/1.
11. The method of claim 1, further comprising introducing a
catalyst additive to the cracking unit.
12. A method for forming a biofuel composition, comprising:
introducing a cellulosic material to a solvent in the presence of a
catalyst at a temperature of about 350.degree. C. or greater and an
operating pressure of about 200 atm or greater to form a first
liquefied product; hydrotreating the first liquefied product with a
source of hydrogen in the presence of a hydrotreatment catalyst to
produce a second liquefied product; introducing the second
liquefied product and a cracking catalyst to a fluidized catalytic
cracking unit at a temperature of about 350.degree. C. or greater
to form a cracked product; hydrotreating the cracked product with a
source of hydrogen in the presence of a hydrotreatment catalyst to
produce a hydrotreated cracked product; and blending the
hydrotreated cracked product with one or more fuel additive
components to form a biofuel composition.
13. The method of claim 12, wherein the cracked product is not
fractionated before blending with the one or more fuel additive
components.
14. The method of claim 12, wherein the one or more fuel additive
components are 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.
15. The method of claim 12, wherein the biofuel composition
comprises the one or more fuel additive components from about 0.1
wt % to about 3 wt %, based on the total weight of the biofuel
composition.
16. The method of claim 12, wherein the biofuel composition has a
water content of about 5% or less.
17. The method of claim 12, further comprising introducing a
hydrocarbon co-feed into the fluidized catalytic cracking unit,
wherein the liquefied product is introduced using a first nozzle to
the fluidized catalytic cracking unit and the hydrocarbon co-feed
is introduced using a second nozzle to the fluidized catalytic
cracking unit.
18. The method of claim 17, wherein the hydrocarbon co-feed
comprises one or more of a straight run (atmospheric) gas oil, a
flashed distillate, a vacuum gas oil, a light cycle oil, a heavy
cycle oil, a hydrowax, a coker gas oil, a gasoline, a naphtha, a
diesel, a kerosene, an atmospheric residue, a vacuum residue, or a
combination thereof.
19. The method of claim 17, wherein the hydrocarbon co-feed is a
vacuum gas oil.
20. The method of claim 12, wherein the solvent is a petroleum
oil.
21. The method of claim 12, wherein hydrotreating the first
liquefied product comprises introducing a hydrogen source and a
hydrogenation catalyst to the liquefaction unit at a temperature of
about 150.degree. C. or greater.
22. The method of claim 12, wherein the first and/or second
liquefied product comprises one or more of gamma-valerolactone,
levulinic acid, tetrahydrofufuryl, tetrahydropyranyl, furfural
hydroxymethylfurfural, mono-alcohol, di-alcohol, mono-ketone,
di-ketone, guaiacol, or syringol.
23. The method of claim 12, wherein the ratio of the amount of
cracking catalyst to the amount of second liquefied product is from
about 2/1 to about 10/1.
24. The method of claim 18, wherein the ratio of the amount of
cracking catalyst to the total amount of second liquefied product
and hydrocarbon co-feed is from about 2/1 to about 10/1.
25. The method of claim 12, further comprising introducing a
catalyst additive to the fluidized catalytic cracking unit.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application No. 62/735,919 filed Sep. 25, 2018, which is herein
incorporated by reference in its entirety.
FIELD
[0002] 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
[0003] 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.
[0004] 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").
[0005] 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 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.
[0006] 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.
[0007] 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.
[0008] Accordingly, there is a need for improved processes and
systems for producing and using bio-oils to produce renewable
fuels.
[0009] References for citing in an Information Disclosure Statement
(37 CFR 1.97(h)): U.S. Pat. No. 9,120,989; U.S. 2013/0118059.
SUMMARY
[0010] 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.degree. 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.degree. C. to about
700.degree. C., such as about 545.degree. C. to about 585.degree.
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 produce a biofuel.
[0011] 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.
[0012] 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.
[0013] 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).
[0014] 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
[0015] 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.degree. 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.degree.
C. to about 700.degree. C., such as about 545.degree. C. to about
585.degree. 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 product
fuel. The bio content of the cracked product provides RIN credits
for the cracked product.
[0016] 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.
[0017] 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).
[0018] 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).
[0019] 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.
[0020] 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.
[0021] As used herein, and unless otherwise specified, the term
"Ce" means hydrocarbon(s) having n carbon atom(s) per molecule,
wherein n is a positive integer.
[0022] 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.
[0023] The term "hydrocarbon co-feed" refers to a co-feed that
contains one or more hydrocarbon compounds.
[0024] 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.
[0025] 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.
[0026] The term "liquefied product" refers to a product that is
liquid at a temperature of about 20.degree. 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.degree. 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.
[0027] 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.
[0028] The term "final liquefied product" refers to a liquefied
product suitable to be directed to the catalytic cracking
process.
[0029] 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.
[0030] 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
[0031] 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.degree. 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.
[0032] 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 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.
[0033] 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).
[0034] 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.
[0035] 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.
[0036] In particular, the process for making cellulosic
RIN-compliant fuel compositions may 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.
[0037] 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.degree. C., such as from about 200.degree. C.
to 425.degree. C., such as from about 250.degree. C. to 350.degree.
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.
[0038] 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.
[0039] 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.
[0040] 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
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.degree. 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.
[0041] 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.
[0042] 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.
[0043] 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
for improved process operability and economics.
[0044] 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 5 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.
[0045] 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.
[0046] 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.
[0047] 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.
[0048] 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.degree. C. or higher, such as about
90.degree. C. or higher, such as about 100.degree. C. or higher,
such as about 120.degree. C. In at least one embodiment, the liquid
solvent includes or is water.
[0049] 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.
[0050] Suitable HTL oil may include a solvent content of from 5 wt
% to 45 wt %, such as from 10 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.
[0051] 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.
[0052] 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.
[0053] 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.
[0054] 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=.DELTA.tmCp
where H is the heat energy absorbed (in Joules), At is the change
in temperature (in .degree. C.), m is the mass (in gram), and Cp is
the specific heat capacity (4.18 J/g.degree. 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.
[0055] 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, Na.sub.2CO.sub.3,
KOH, K.sub.2CO.sub.3, FeSO.sub.4, Ni(OH).sub.2.
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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.
[0060] 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.
[0061] 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.
[0062] 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.degree. C. to 425.degree.
C., such as from about 250.degree. C. to 400.degree. C., such as
from 275.degree. C. to 375.degree. C., such as from about
300.degree. C. to 350.degree. C., alternatively from about
250.degree. C. to 350.degree. 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.
[0063] 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.
[0064] 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.
[0065] Kinematic Viscosity at 40.degree. 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
[0066] 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.degree. C. to about 425.degree. 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.degree. C. to about 700.degree. C.,
such as about 545.degree. C. to about 585.degree. C., thus to
produce one or more cracked product(s). In at least one embodiment,
the final cracked product of 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.
[0067] 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.
[0068] 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.
[0069] In at least one embodiment, an HTL oil is produced from the
HTL conversion of biomass under the conditions of 200.degree. C. to
425.degree. C. (e.g., 350.degree. 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.
[0070] 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-feed and the HTL oil feedstock).
[0071] 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 5 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
[0072] 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.
[0073] 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.degree. C. to
about 700.degree. C., such as about 545.degree. C. to about
585.degree. C., to produce one or more cracked products.
[0074] 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.
[0075] 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.
[0076] 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, 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.
[0077] 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.
[0078] 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.
[0079] 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
%.
[0080] 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.
[0081] 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.
[0082] 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.
[0083] Suitable conventional reactor types are described in for
example U.S. Pat. Nos. 4,076,796; 6,287,522 (dual riser);
Fluidization Engineering, D. Kunii and O. 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.
[0084] 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.
[0085] 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.
[0086] 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).
[0087] 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.
[0088] A number of riser designs use a lift gas as a further means
of providing a uniform 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.
[0089] 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 VGO, 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.
[0090] 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.
[0091] 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).
[0092] 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 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.
[0093] 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.
[0094] 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.
[0095] The hydrocarbon co-feed and the HTL oil may be introduced,
injected, fed, co-fed into 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.
[0096] 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.
[0097] In at least one embodiment, a suitable amount of one or more
HTL oil(s) (such as from 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), VGO (Vacuum Gas Oil), and other petroleum fractions and
blends.
[0098] 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.
[0099] A suitable amount of an HTL oil, such as a cellulosic
RIN-compliant fuel, may be blended with a VGO. VGO 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 VGO
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.
[0100] 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 VGO or as a separate feed.
[0101] 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 %.
[0102] 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%).
[0103] 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 feedstock.
The flash point may be increased, for example, from 50.degree. C.
to 70.degree. 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.
[0104] 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 %.
[0105] 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.
[0106] 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 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.
[0107] 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.
[0108] 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.
[0109] 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.
[0110] 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.
[0111] 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 acid, acetic acid, and levulinic acid.
[0112] 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.
[0113] 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.
[0114] 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, VGO, 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, VGO and/or mixtures thereof.
[0115] 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.
[0116] Optionally, one or more cracked product(s) can be
subsequently hydrotreated with a 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.
[0117] 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.degree. 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.
[0118] 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.
[0119] 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. Pat. No. 9,129,989 which is incorporated herein by
reference.
[0120] 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.
[0121] 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.
[0122] 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.
[0123] 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.degree. C., such as from about 90.degree. C. to about
700.degree. C., such as from about 400.degree. C. to about
700.degree. C., such as from about 545.degree. C. to about
585.degree. C.
[0124] 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.
[0125] 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 (HCl), nitric acid (HNO.sub.3),
sulphuric acid (H.sub.2SO.sub.4), Boric acid (H.sub.3BO.sub.3),
para-toluene sulphonic acid, phosphoric acid (H.sub.3PO.sub.4),
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.
[0126] 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.
[0127] 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, VGO (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 additives may experience enhanced
effectiveness.
[0128] 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.
[0129] 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).
[0130] 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.
[0131] 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/Al.sub.2O.sub.3 catalyst.
[0132] 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,
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.
[0133] 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).
[0134] 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.
[0135] 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).
[0136] 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 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.
[0137] 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).
[0138] 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).
[0139] 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.
[0140] 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.
[0141] 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.
[0142] 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.
[0143] 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.
[0144] 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.
[0145] 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.
[0146] 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).
[0147] 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.
[0148] 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 VGO.
[0149] 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 VGO inlet port of a FCC unit, such as the
processed-HTL oil feedstock may be injected downstream of a VGO
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.
[0150] 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 the HTL oil based feedstock may be
co-processed with a hydrocarbon feedstock in the refinery
system.
Regenerating Catalyst
[0151] 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.degree. C. to about 700.degree. 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.
[0152] 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 Tex., 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.
[0153] 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.
[0154] 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.
[0155] 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.
[0156] 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.
[0157] 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
[0158] 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).
[0159] 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.
[0160] 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 %, such as from
about 10 vol % to about 30 vol % of an HTL oil feedstock.
EXAMPLES
[0161] 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.degree. C. to 500.degree.
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.degree. 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.
(Sep. 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, Colo.).
TABLE-US-00001 TABLE 1 Fast Pyrolysis Hydrothermal Liquefaction
Conditions Feedstock Dry Biomass Wet Biomass Operating Temperature
450.degree. C.-500.degree. C. 350.degree. 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 38% 12%
Basis Water Content 25% 5% Thermal Stability less more
[0162] 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 VGO 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 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-US-00002 TABLE 2 Biogenic Carbon VGO VGO + 5% HTL (%
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 + CO.sub.2 0.8 Total 100 100
Conversion 71 71
[0163] 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/CO.sub.2 results in the actual experiments were
unavailable.
TABLE-US-00003 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.degree. F.
1010.degree. F. 900.degree. F. 900.degree. F. Feed VGO VGO + VGO
VGO + 5% HTL 5% HTL C2 1.06 1.42 0.63 0.7 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
[0164] 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.
[0165] 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.
[0166] 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.
[0167] 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. 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.
[0168] 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.
* * * * *