U.S. patent application number 13/996425 was filed with the patent office on 2013-10-31 for production of aromatics from renewable resources.
The applicant listed for this patent is Brian L. Goodall, Geoffrey L. Price, Daniel J. Sajkowski. Invention is credited to Brian L. Goodall, Geoffrey L. Price, Daniel J. Sajkowski.
Application Number | 20130289324 13/996425 |
Document ID | / |
Family ID | 46314518 |
Filed Date | 2013-10-31 |
United States Patent
Application |
20130289324 |
Kind Code |
A1 |
Price; Geoffrey L. ; et
al. |
October 31, 2013 |
PRODUCTION OF AROMATICS FROM RENEWABLE RESOURCES
Abstract
Renewable oils are converted to aromatics, by contact with a
catalytically-active form of gallium, for use in the petrochemical
industry and/or for fuel blending components or additives. The
renewable oil(s) feature high oxygen content, high H/C mole ratios,
and high fatty acid or fatty acid ester content prior to heating
and contact with the catalyst. The catalyst may be, for example, a
gallium-doped version of one or more zeolite-alumina matrix
catalysts with pore sizes having 10 oxygen atoms in the pore mouth,
such as ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35, and
ZSM-22. Aromatics-production from the renewable oils is enhanced at
higher gallium-cation levels, with the preferred level being about
1.0 Ga/framework-Al. While various renewable oils, or "bio-oils,"
may be used, algae oil has exhibited very high BTEX yields over the
gallium cation catalyst, under conditions at or near 1 atm and
approximately 400 degrees C.
Inventors: |
Price; Geoffrey L.; (Tulsa,
OK) ; Goodall; Brian L.; (Spring, TX) ;
Sajkowski; Daniel J.; (Kewadin, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Price; Geoffrey L.
Goodall; Brian L.
Sajkowski; Daniel J. |
Tulsa
Spring
Kewadin |
OK
TX
MI |
US
US
US |
|
|
Family ID: |
46314518 |
Appl. No.: |
13/996425 |
Filed: |
December 27, 2011 |
PCT Filed: |
December 27, 2011 |
PCT NO: |
PCT/US11/67444 |
371 Date: |
June 20, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61427160 |
Dec 24, 2010 |
|
|
|
Current U.S.
Class: |
585/469 |
Current CPC
Class: |
B01J 29/084 20130101;
C10G 2300/1051 20130101; B01J 29/085 20130101; C10G 3/55 20130101;
C10L 1/06 20130101; C10G 2300/1044 20130101; C10G 3/49 20130101;
C10G 2300/1055 20130101; C10G 3/44 20130101; C10G 2300/1014
20130101; B01J 2029/062 20130101; C10G 3/42 20130101; C10G 2300/104
20130101; C10G 2400/02 20130101; B01J 29/405 20130101; C10G 2400/30
20130101; B01J 29/046 20130101; B01J 37/0201 20130101; C10G 3/54
20130101; C10G 2300/4025 20130101; Y02P 30/20 20151101 |
Class at
Publication: |
585/469 |
International
Class: |
C10G 3/00 20060101
C10G003/00 |
Claims
1-54. (canceled)
55. A process for producing BTEX aromatics from a renewable oil
obtained from biomass living in the past 50 years, the process
comprising contacting a feedstock comprising said renewable oil at
an elevated temperature with a catalyst that retains gallium in a
catalytically-active form.
56. The process of claim 55, wherein said biomass comprises a
non-vascular photosynthetic organism.
57. The process as in claim 55, wherein said catalyst is a
gallium-doped form of one or more zeolite-alumina matrix catalysts
with pore sizes having 10 oxygen atoms in the pore mouth.
58. The process as in claim 55, wherein said catalyst is a
gallium-doped form of a zeolitic catalyst selected from the group
consisting of: ZSM-5, ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58,
SSZ-35, and ZSM-22.
59. The process as in claim 55, wherein said catalyst comprises
gallium cations.
60. The process as in claim 55, wherein said elevated temperature
is in the range of 350-555 degree C.
61. The process as in claim 60, wherein said elevated temperature
is in the range of 375-425 degrees C.
62. The process as in claim 56, wherein said feedstock is 100 wt %
oil obtained from a non-vascular photosynthetic organism.
63. The process as in claim 56, wherein said feedstock is 90-100 wt
% oil obtained from a non-vascular photosynthetic organism.
64. The process as in claim 56, wherein said feedstock is 80-100 wt
% oil obtained from a non-vascular photosynthetic organism.
65. The process as in claim 56, wherein said feedstock is 50-100 wt
% oil obtained from a non-vascular photosynthetic organism.
66. The process as in claim 56, wherein said feedstock is 5-100 wt
% oil obtained from a non-vascular photosynthetic organism.
67. The process as in claim 56, wherein said feedstock is 1-20% oil
obtained from a non-vascular photosynthetic organism.
68. The process as in claim 56, wherein said oil obtained from a
non-vascular photosynthetic organism is extracted from
naturally-occurring algae or cyanobacteria.
69. The process as in claim 56, wherein said oil obtained from a
non-vascular photosynthetic organism is extracted from
genetically-modified algae or cyanobacteria.
70. The process as in claim 66, wherein the remainder of the
feedstock that is not oil obtained from a non-vascular
photosynthetic organism is selected from the group consisting of:
one or more fossil oil fractions, one or more refined fossil oil
products or fractions, naphtha, gasoline, jet fuel, diesel, and any
combination thereof.
71. The process as in claim 67, wherein the remainder of the
feedstock that is not oil obtained from a non-vascular
photosynthetic organism is selected from the group consisting of:
one or more fossil oil fractions, one or more refined fossil oil
products or fractions, naphtha, gasoline, jet fuel, diesel, and any
combination thereof.
72. The process as in claim 55, wherein the catalyst has 90-100% of
cation sites occupied by gallium.
73. A process for producing BTEX aromatics from renewable oil, the
process comprising: providing a reactor vessel or riser containing
catalyst, said catalyst comprising a gallium-cation catalyst; and
contacting a feedstock with said catalyst at elevated temperature;
wherein said feedstock comprises renewable oil derived from biomass
living in the past 50 years.
74. The process as in claim 73, wherein said biomass comprises a
non-vascular photosynthetic organism.
75. The process as in claim 73, wherein said elevated temperature
is between 350-555 degrees C.
76. The process as in claim 73, wherein said gallium-cation
catalyst comprises between 10-100 wt % of the total catalyst.
77. The process as in claim 73, wherein said renewable oil
comprises between 5-100 wt % of the feedstock.
78. The process as in claim 73, wherein said gallium-cation
catalyst has 90-100% of cation sites occupied by gallium.
79. The process as in claim 55, wherein the weight percentage of
catalyst comprising a catalytically-active form of gallium is equal
to the weight percentage of renewable oil in the feedstock.
80. The process as in claim 73, wherein the weight percentage of
gallium-cation catalyst is equal to the weight percentage of
renewable oil in the feedstock.
Description
[0001] This application claims priority of U.S. Provisional
Application 61/427,160, filed Dec. 24, 2010 and entitled
"Production of Aromatics from Renewable Resources", the entire
disclosure of which is incorporated herein by this reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates generally to a method for the
production of aromatics from renewable sources. More specifically,
the preferred embodiments related to converting fat- or other
lipid-containing oils derived from biomass, such as oil from
naturally-occurring non-vascular photosynthetic organisms and/or
from genetically modified non-vascular photosynthetic organisms;
canola oil and other oils derived from vegetables such as corn,
soybean, sunflower, and sorghum; and/or oils from other plant
matter, seeds, fungi, bacteria, and other organisms both living and
recently living.
[0004] 2. Related Art
[0005] Aromatics, particularly benzene, toluene, ethylbenzene, and
the xylenes (ortho, meta, and para isomers), which are commonly
referred to as "BTEX" or more simply "BTX," are extremely useful
chemicals in the petrochemical industry. They represent the
building blocks for materials such as polystyrene,
styrene-butadiene rubber, polyethylene terephthalate, polyester,
phthalic anhydride, solvents, polyurethane, benzoic acid, and
numerous other components. Conventionally, BTEX is obtained for the
petrochemical industry by separation and processing of fossil-fuel
petroleum fractions, for example, in catalytic reforming or
cracking refinery process units, followed by BTX recovery
units.
[0006] The patent literature describes refinery schemes proposed
for processing biomass to produce transportation fuels, such as
gasoline, jet, and diesel. See, for example, North Carolina State
University, WO 2008/103204, published 28 Aug. 2008, and entitled
"Process for Convention of Biomass to Fuel". See also, Aravanis, et
al., Publication US2009/0126260, published 21 May 2009, entitled
"Methods of Refining Hydrocarbon feedstocks", and McCall, et al.,
Publication US2009/0158637, published 25 Jun. 2009, and entitled
"Production of Aviation Fuel from Biorenewable Feedstocks". The
patent literature focuses, however, on transportation fuel
production from renewable feedstocks, rather than aromatics
production for the petrochemical industry. Also, the patent
literature focuses on renewable feedstocks that are comprised
mainly of triglycerides, for example, plant oils such as canola,
soy bean, camelina and jatropha oils, and animal fats such as beef
and lamb tallow and chicken fat, which are approximately 100%
triglycerides.
[0007] There is a need for technology that produces high yields of
aromatics from renewable sources. Particularly, there is a need for
"green aromatics" that may be used, in place of petroleum-derived
BTEX, in the petrochemical industry, for polymers, plastics, drugs,
clothing, synthetic rubber, dyes, solvents, and other consumer and
industrial products. There is a need for such "green aromatics"
from algae oils, which have compositions much more complex than
high-triglyceride plant oils and animal fats.
SUMMARY OF THE INVENTION
[0008] The invention comprises methods, catalyst, and/or equipment
for converting one or more renewable oils to aromatics, for
example, for use in the petrochemical industry and/or for blending
components or additives for fuels. The invented processing methods
comprise contacting one or more renewable oils with a
catalytically-active form of gallium, for example, a catalyst
comprising a catalytically-active form of gallium (also called
"gallium-modified" catalyst herein). Such gallium-modified catalyst
may comprise a zeolite or other solid that retains gallium in a
catalytically-active form, for example, as gallium cations. The
invention may comprise products made by said methods.
[0009] Said one or more renewable oils may be obtained from
biomass, which is defined as a mass, or a material including a
substantial amount of said mass, that is alive or that has been
alive within the last 50 years. Examples of such renewable oils are
canola oil and other lipids-based bio-oils derived from vegetables
such as corn, soybean, sunflower, and sorghum; oil from
naturally-occurring non-vascular photosynthetic organisms and/or
from genetically modified non-vascular photosynthetic organisms,
and/or oil from other plant matter, seeds, fungi, bacteria, and
other organisms. The bio-oils may be extracted from their
respective biomass by conventional techniques. As used herein, the
term non-vascular photosynthetic organism includes, but is not
limited to, macroalgae, microalgae and cyanobacteria (blue-green
algae).
[0010] In certain embodiments, said one or more renewable oils
feature a H/C mole ratio of greater than 1.5 (typically 1.7-2.1),
and oxygen content of about 1 to about 35 wt-% (typically 5-15 wt
%). The renewable oil(s) comprise large amounts of fatty acids or
fatty acid esters, including free fatty acids and/or glycerol
esters of fatty acids such as monoglycerides, diglycerides, and/or
triglycerides. The H/C mole ratio, oxygen content, and relative
amounts of free fatty acids and glycerol esters in said one or more
renewable oils may depend on the source of the renewable oil and/or
on the techniques of extraction from the biomass and/or
pre-processing prior to contact with the gallium-modified catalyst,
for example. The fatty acid moieties may range, for example, from
about 4 to about 30 carbon atoms, but typically 10 to 25 carbon
atoms, and even more typically, 16 to 22 carbon atoms. Most
commonly, the fatty acid moieties are saturated or contain 1, 2 or
3 double bonds. Certain embodiments of the renewable oil(s) contain
at least some triglycerides that are glycerol esters of C16-C22
carboxylic acids and therefore may comprise C50+ compounds,
however, many of the diglycerides and/or triglycerides in the
renewable oil(s) decompose to their C-16-C-22 components upon
heating to elevated temperature. The renewable oil(s) may also
comprise other materials such as carotenoids, hydrocarbons,
phosphatides, simple fatty acids and their esters, terpenes,
sterols, fatty alcohols, tocopherols, polyisoprene, carbohydrates
and/or proteins.
[0011] Because of the high hydrogen to carbon ratio of certain
embodiments of the renewable oil(s), and the dehydrogenation
function of certain gallium-modified catalysts, some embodiments of
the invention are expected to produce large amounts of hydrogen,
and this hydrogen may be fed to hydrogen-consuming units in the
refinery, for example, a hydrotreater or hydrocracker. Thus, some
embodiments of the invention may be used both for "green" BTEX
production and for "green" hydrogen production.
[0012] In certain embodiments, the gallium-retaining solid is a
shape-selective material, and more typically, the solid is a
zeolitic material wherein at least some of the cation-exchange
centers are populated with gallium. In certain embodiments, the
gallium-retaining solid(s) is/are gallium-doped version(s) of one
or more zeolite-alumina matrix catalysts with pore sizes having 10
oxygen atoms in the pore mouth, for example, ZSM-5, ZSM-11, ZSM-23,
MCM-70, SSZ-44, SSZ-58, SSZ-35, and ZSM-22. The inventors have
discovered that aromatics-production from the renewable oils is
enhanced at higher gallium levels, with one level being Ga
occupying at least 90% of the cation sites and the protons or other
cations previously at those cation sites having been replaced by
Ga. An exemplary gallium level is 90-100% of the cation sites being
replaced by Ga, which is called "1.0 Ga/framework-Al" herein.
[0013] Catalysts in certain embodiments of the invention may have
gallium loadings above 1.0 Ga/framework-Al, that is, gallium
present in an amount above that equal to 100% cation replacement.
In such cases, extraframework Ga would exist, that is, Ga over and
above the amount corresponding to 1 Ga/framework-Al and residing in
zeolitic pores or on the exterior of the zeolite crystalline
particles.
[0014] Although silica-alumina forms of zeolites are commonly used,
zeolite frameworks may contain other metals, for example, gallium,
boron, iron, phosphorous, germanium, indium, etc. Zeolite
frameworks containing other metals may be suitable for producing
gallium-modified catalyst, for example, for loading with gallium in
cationic form for use as catalysts in certain embodiments of the
invention.
[0015] The solid may be adapted to retain gallium by processes
known to those of skill in the catalyst arts, for example,
incipient wetness impregnation of zeolite with a
gallium-composition dissolved in water. Methods for producing
gallium-doped catalyst are also described in U.S. Pat. Nos.
4,727,206, 4,746,763, 4,761,511, and 5,149,679, the teachings of
which are incorporated herein by this reference.
[0016] Said one or more renewable oils may comprise "whole crude
oil", that is, the entire oil extract from biomass, and/or one or
more fractions of said whole crude oil. Said one or more renewable
oils may comprise whole crude oil(s)/fraction(s) that have been
pre-processed before being fed to the gallium-catalyst process. For
example, "pre-processing" in this context may include degumming,
RBD (Refining, Bleaching, and Deodorizing, which is known in the
art), thermal processing, hydrotreating, and/or other processes
that deoxygenate or otherwise upgrade the renewable oil to some
extent before being fed to the process comprising use of
gallium-modified catalyst. Also, in certain embodiments, said one
or more renewable oils may be co-processed ("co-fed") with other
oils, such as fossil petroleum oils/fractions, to the
aromatics-production processes of this invention.
[0017] The inventors believe that many embodiments of the invention
may be performed in conventional refining process equipment, that
is, existing units or revamped existing units previously used
entirely for fossil petroleum, or new units based on fossil
petroleum technology but purpose-built to be optimized for
renewable oil. Contacting said one or more renewable oils may be
done in various flowschemes and refinery equipment, including but
not limited to, a single reactor or series-flow reactors with
optional removal of the liquid-phase from between the reactors
prior to gas-phase flow to the downstream reactor(s); fixed or
"packed" catalyst bed(s); fluidized catalyst bed(s); and/or moving
bed(s). For example, said existing, revamped, or new units for
certain embodiments of the invention may include those that are the
same or similar to fluidized catalytic cracking (FCC) units (for
example, see FIG. 23), UOP CCR.TM. Cyclar.TM. units (for example,
see FIG. 24), a UOP CCR Platformer.TM. naphtha reformer fixed-bed
reactor(s), or other fixed-bed reactor units, all of which
originated as fossil petroleum technology. Said FCC units have been
designed for gasoline component production from petroleum,
including those FCC units that minimize benzene production relative
to higher octane components in order to maximize octane. Said UOP
CCR.TM. Cyclar.TM. units are moving-catalyst,
continuous-catalyst-regeneration units designed for aromatics
production from petroleum C3 and C4 feeds using gallium catalysts.
Said UOP CCR.TM. Platformer.TM. units are moving-catalyst,
continuous-catalyst-regeneration units designed for high-octane
gasoline production from petroleum naphtha, and typically use
platinum catalysts to produce aromatics-rich liquid product. Said
fixed-bed reactor units are also well known in the refinery arts,
for example, "semi-regen" reformers that are designed for gasoline
component production from petroleum naphtha, and typically use
platinum or rhenium catalysts to produce aromatics-rich liquid
product.
[0018] Feeding high percentages of renewable oils to process units
based on fossil petroleum technology may require adaptation of
equipment and operation upstream of the reactor(s)/riser(s)
reaction zone, as none of the above-mentioned fossil petroleum
units are designed specifically for said renewable oil feedstocks.
The equipment and operation downstream of the reaction zone in
these units, however, are more likely to effectively handle product
streams from a high-percentage renewable oil(s) operation, due to
the BTEX product from such embodiments being generally similar to
the aromatics-rich products of the above-mentioned units. One
possible exception is that modifications may be required in the
equipment or operations downstream of the reaction zone to handle
H2O, CO, and/or CO resulting from the high oxygen content of
certain renewable oils. Alternatively or in addition,
pre-processing for deoxygenation of renewable oils, prior to being
fed to said reaction zone, may prevent excessive water production
and hydrogen consumption in said reaction zone.
[0019] Feeding low-percentages of renewable oils to process units
based on fossil petroleum technology may be a desirable option,
especially because said one or more renewable oils are expected to
be available only in relatively small quantities in the next few
years. Therefore, co-processing of said one or more renewable oils
with other feedstocks may be required and/or beneficial, resulting
in process units that are "fed-in-part" with said one or more
renewable oils, and "loaded-in-part" with gallium-modified
catalyst. While "fed in full" means herein that about 100 wt % (for
example, 99-100 wt %) of the feedstock for a process unit would be
said one or more renewable oils, the term "fed-in-part" means
herein that a lesser percentage of the feedstock would be said one
or more renewable oils. While "loaded-in-full" means herein that
about 100 wt % (for example, 99-100 wt %) of the catalyst for a
process unit would be gallium-modified catalyst (for example,
gallium-cation catalyst), the term "loaded-in-part" means that a
lesser percentage would be gallium-modified catalyst.
[0020] Optimum operating conditions, including conditions of
feedstock contact with catalyst, for such loaded-in-part and
fed-in-part operations may be different from those suggested by the
loaded-in-full and fed-in-full Examples later in this document. For
example, higher temperatures for higher space velocities or
fluidized bed or moving bed conditions may be needed. In such
cases, optimum feedstock-catalyst-contact temperature may be as
high as 600.degree. C., but more typically may be in the
450-550.degree. C. range, for example. Based on the data disclosed
herein and data available to refiners from fossil petroleum
operations, those of skill in the art may optimize the conditions
of such loaded-in-part and fed-in-part operations without undue
experimentation.
[0021] In certain embodiments, said one or more renewable oil(s)
may be pre-processed prior to being fed or co-fed to a unit
containing at least some gallium-modified catalyst. For example,
pre-processing steps may comprise thermal-treatment and/or
hydrotreatment of the renewable oil(s) or fractions thereof. For
example, a processing scheme comprising hydrotreatment, or
thermal-treatment followed by hydrotreatment, of algae oil, is
expected to produce a desirable feed or co-feed for an FCC unit.
Alternatively, a processing scheme comprising thermal-treatment of
a portion of algae oil, for example, a heavy fraction of algae oil,
followed by hydrotreatment of both the thermally-treated and
non-thermally-treated fractions of the renewable oil, may also
produce a desirable feed or co-feed for an FCC unit.
[0022] Embodiments of the invention are not necessarily limited to
the above-mentioned units or co-processing options. Other
processing units, flowschemes and/or other co-feedstocks may
provide synergistic or beneficial results.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1A is a schematic of the laboratory reactor system,
using a single reactor, used in the experiments of Examples I, III,
and IV,
[0024] FIG. 1B is a schematic of the laboratory reactor system,
used in the experiments of Example II, that includes two reactors
in series and is adapted for liquid product removal between
reactors.
[0025] FIG. 2 is a graph of weight-percent yield of liquid products
(triangles) and vapor products (squares) from Runs SAP275-279 on
HZSM-5 catalyst (no gallium) in Example I, showing that increasing
temperature decreases the yield of liquid products while increasing
the amount of vapor products.
[0026] FIG. 3 is a graph of vapor product yields changing with
increasing amounts of gallium (left to right) added to the catalyst
for experiments SAP281-283 in Example I, showing particularly that
propane and ethane changed with increasing gallium. Molecules shown
in this graph represent .about.98% of all vapor products from each
experiment. Results for 0.0 Ga are the mean of SAP284-287 and the
"error bars" show the 95% confidence interval.
[0027] FIG. 4 is a graph of yields of liquid product (triangles),
vapor product (squares), and coke on catalyst (circles) vs.
increasing gallium-loading of the catalyst in experiments
SAP281-283 of Example I. With increasing gallium content, liquid
yield (triangles) increased, coke (circles) stayed almost constant,
and vapor products (squares) decreased. The mean of SAP284-287 (no
Ga) is used in this graph for zero gallium content.
[0028] FIG. 5 is a graph of boiling point distribution of the
organic phase products, for the various gallium loadings
(increasing left to right) in Example I. The majority of the
products fall in the 60-188.degree. C. range.
[0029] FIG. 6 is a graph of benzene, toluene, ethyl-benzene,
xylene, and total BTEX yields, in Example I, showing that BTEX
yield increases with the gallium content of the ZSM-5 catalyst.
[0030] FIG. 7 is a graph of vapor product yields obtained from
algae oil cracking at 400.degree. C., over GaZSM-5 (bars on left)
and HZSM-5 catalyst (bars on right) in Example III.
[0031] FIG. 8 is a graph of yields of individual BTEX components,
total BTEX, and gasoline obtained from algae oil cracking over
catalysts at 400.degree. C., over GaZSM-5 catalyst (bars on left)
and HZSM-5 catalyst (bars on right) in Example III.
[0032] FIG. 9 is a graph of gas phase products produced during
cracking of gas oil in Example IV.
[0033] FIG. 10 is a graph of the BTEX and gasoline yield results
from cracking of gas oil (Example IV) compared to BTEX and gasoline
yield results from cracking of algae oil (Example III), both at 400
degrees C.
[0034] FIG. 11 is a graph of the simulated distillation curve of
the Conoco Phillips gas oil of Example IV compared to the simulated
distillation curve of algae oil of Example III, with a maximum
gasoline boiling point line included for reference.
[0035] FIG. 12 is a graph of the simulated distillations for the
gas oil product (Example IV), algae oil product (Example III) and
canola oil product (Example I) for the respective cracking
experiments.
[0036] FIG. 13 is a graph of conversion % vs. catalyst/oil ratio
for the algae oil feed and vacuum gas oil samples of Example V.
[0037] FIG. 14 is a graph of coke wt % vs. conversion ratio for the
algae oil feed and vacuum gas oil samples of Example V.
[0038] FIG. 15 is a graph of conversion % vs. catalyst/oil ratio
for algae oil feed, hydrotreated algae oils, and vacuum gas oil, in
Example VI. Note that this graph comprises the hydrotreated algae
oil data added to the algae oil feed and vacuum gas oil data of
FIG. 13.
[0039] FIG. 16 is a graph of coke wt % vs. conversion for algae oil
feed, hydrotreated algae oils, and vacuum gas oil, in Example VI.
Note that this graph comprises the hydrotreated algae oil data
added to the algae oil feed and vacuum gas oil data of FIG. 14.
[0040] FIGS. 17-22 are graphs of the wt % yields of gasoline, LCO,
DCO, TC2, TC3, and TC4, respectively, versus conversion %, for the
algae oil feed, hydrotreated algae oils, and vacuum gas oil of
Example VI.
[0041] FIG. 23 is a schematic illustration of one example of a
conventional fluidized catalyst conversion unit (FCC), which may be
adapted to operate in certain embodiments of the invention.
[0042] FIG. 24 is a schematic illustration of one example of a
conventional UOP CCR.TM. Cyclar.TM. unit, which may be adapted to
operate in certain embodiments of the invention.
DETAILED DESCRIPTION
[0043] Referring to the following detailed description, including
Examples I-IX, and the associated tables and figures, there are
described several, but not the only, embodiments of the invented
methods, equipment, and products.
[0044] The inventors believe that the data from the
laboratory-scale experiments of Examples I-VII are roughly
predictive of what would happen in commercial units. For example,
the data in Examples I-III would be roughly predictive of an
operation having packed bed gallium-cation catalyst loaded-in-full,
renewable oil(s) fed-in-full (including canola oil and algae oil),
the feed-catalyst contact at about 1.0 WHSV (weight hourly space
velocity), and the temperature controlled in the range of 350-450
degrees C., for example, 400 degrees C. The data in Example IV
would be roughly predictive of a fossil petroleum gas oil feed
processed over the selected gallium-modified catalyst and
conditions from Example I and III, and, hence, that Example IV may
be used to predict performance differences between the renewable
oils and the gas oil. The data in Examples V and VI would be
roughly predictive of FCC processing of algae oil and hydrotreated
algae oil, respectively. The data in Example VII would be roughly
predictive of thermal treatment of certain algae oils, as a
pre-processing step prior to subsequent upgrading by hydrotreating
and fluid catalytic cracking with gallium-modified catalyst.
[0045] The experimental data of Examples I-III support certain
embodiments wherein renewable oil are processed effectively over
gallium-modified catalyst while achieving very beneficial results
in aromatics and hydrogen production, wherein optionally gas oil
may also be effectively processed over the same gallium-modified
catalyst (Example IV). The combination of the gallium-cation
catalyst data in Examples I-IV and the FCC data in Examples V and
VI supports certain embodiments of the invention wherein algae oils
are upgraded by a pre-processing step of hydrotreating, followed by
fluid catalytic cracking (optionally with petroleum as a co-feed),
wherein the FCC catalyst comprises supplemental gallium-cation
catalyst to further enhance aromatics production from the algae oil
in said fluid catalytic cracking. The combination of the
gallium-catalyst data in Examples I-IV, the FCC data in Examples V
and VI, and the thermal treatment data of Example VII supports
certain embodiments of the invention wherein algae oils are
upgraded by pre-processing steps of thermal treatment and
hydrotreating, followed by FCC fluid catalytic cracking (optionally
with petroleum as a co-feed), wherein the FCC catalyst comprises
supplemental gallium-cation catalyst to further enhance aromatics
production from the algae oil in said fluid catalytic cracking.
[0046] In certain embodiments, one or more renewable oils will be
co-fed (or "fed-in-part") with other oils wherein the combined feed
contacts a gallium-modified catalyst. The broad scope of the
invention may comprise processing any amount of any renewable oil,
including those obtained from biomass by solvent extraction, by the
HTT techniques above, or other biomass treatment/extraction
techniques and fractions thereof, in a operation with
gallium-modified catalyst, with the renewable oil being any
percentage of the total feedstock. For example, one or more
renewable oils may constitute as little as about 1 wt % of the
feedstock to a unit containing the gallium-cation-retaining
catalyst, but due to the large BTEX benefit exhibited by the
catalyst with renewable oil(s), the inventors anticipate that the
renewable oil(s) will eventually constitute a major portion of the
total feedstock of selected process units; for example, at least 5
wt %, at least 10 wt %, at least 50 wt-%, or at least 80 or 90 wt-%
of the total feedstock to the process unit will be said one or more
renewable oil in certain embodiments. Therefore, in such
embodiments, the renewable oil will be in the range of 5-100 wt %,
10-100 wt %, 50-100 wt-% of the feedstock, 80-100 wt % or 90-100 wt
% of the feedstock to one or more selected units. In some
embodiments, components for blending with said one or more
renewable oils prior to processing over gallium-modified catalyst
may be selected from the group consisting of: fossil fuel,
petroleum, C3-C4, naphtha, gasoline, jet fuel, diesel, gas oil,
heavy gas oil, and any combination thereof. In co-processing in an
FCC unit, it is expected that renewable oil(s) may be co-processed
with gas oil/vacuum gas oil, for example. In co-processing in a
Cyclar.TM. unit, it is expected that renewable oil(s) may be
co-processed with C3-C4, for example.
[0047] Certain of the feed-co-processing embodiments also comprise
the gallium-modified catalyst being loaded/charged with other
catalysts into the unit (a "loaded-in-part" operation), for
example, with non-gallium-containing catalysts. The
gallium-modified catalyst may constitute any percentage of the
catalyst load/stream. For example, the gallium-modified catalyst
may constitute as little as about 1 wt % of the catalyst in the
process unit, but, due to the large BTEX benefit exhibited by the
catalyst with renewable oil(s), the inventors anticipate that the
catalyst will eventually constitute at least 5 wt %, at least 10 wt
%, at least 50 wt %, at least 80 wt %, or at least 90 wt % of the
total catalyst in the unit. Therefore, in such embodiments, the
gallium-modified catalyst will be in the range of 5-100 wt %,
10-100 wt %, 50-100 wt %, 80-100 wt %, or 90-100 wt % of the total
catalyst. It should be noted that the term "gallium-modified
catalyst" herein and in the claims is broadly defined as any solid
comprising a catalytically-active form of gallium, which may
include but is not necessarily limited to gallium-cation catalyst,
gallium-doped zeolites, and the other examples of gallium-modified
catalysts in this document.
[0048] For example, in a fluid catalytic cracking unit, it is
expected that renewable oil(s) could be fed-in-part to the FCC
unit, along with gas oils or other petroleum feedstocks. In such
embodiments, only a portion of the total feedstock fed to the FCC
process unit would be renewable oil(s), for example, less than 99
wt % and more likely 1-20 wt % or 5-10 wt % of the total feedstock.
In such embodiments, it is expected that gallium-cation catalyst
would be an additive/supplement to the catalyst stream of the FCC
units, which normally consists essentially of acidic zeolite FCC
catalyst such as zeolite Y catalyst. In such embodiments, only a
portion of the total catalyst loading/charge (stream) would be
gallium-modified catalyst, for example, less than 99 wt % and more
likely 1-20 wt % or 5-10 wt % of the total catalyst load/stream.
The FCC catalyst and gallium-cation catalyst would be regenerated
together in the regenerator section of the FCC unit. Reaction
temperature may be adjusted in such scenarios, to optimize overall
performance based on the mix of catalyst and feeds in the unit, and
would be expected to be in the range of about 400-555 degrees C,
for example.
[0049] Catalyst supplementation or change-out would not necessarily
be required in order to feed said one or more renewable oils to a
UOP Cyclar.TM. unit, as such units have typically used
gallium-cation catalysts for conversion of C3 and C4 feedstock.
Likewise, catalyst regeneration in a Cyclar.TM. unit would be
expected to be effective, as the Cyclar.TM. CCR.TM. regeneration
section is designed for gallium-cation catalysts that are similar
to those of certain embodiments of the invention. Therefore, due to
existing Cyclar.TM. units being loaded with and adapted for gallium
catalyst, it may be possible to feed renewable oil(s) in-full, or
in-part along with C3 and C4 feeds or other feeds, to Cyclar.TM. or
similar units.
[0050] While UOP CCR Platformers.TM. or fixed-bed naphtha reformer
reactor(s) may be candidate units for certain embodiments of the
invention, it may be noted that gallium-cation catalysts are not
expected to require the relatively complex regeneration process
required for the platinum reforming catalysts typically used in
Platformers.TM. and many other naphtha reformers. Certain
gallium-cation catalysts may be regenerated by a coke burning step,
followed by reduction during processing of oil over the catalyst,
that is, at the temperature and in the environment in which the
renewable oil is being processed over the catalyst. Therefore, an
oxidation-only regeneration section such as in an FCC unit, or a
simple batch oxidization, may be effective for regeneration of
certain catalysts of the invention, rather than oxygenation
followed by a special reduction process and equipment such as is
used in a UOP CCR Platformer.TM.. In certain embodiments provided
in a fixed-bed catalytic reformer, it is expected that one of the
series-flow reactors would be loaded with the gallium-cation
catalyst, for example, with the other reactors being loaded with
conventional reforming catalyst, and with adaptation for separate
regeneration of the reactors and, hence, of the multiple types of
catalyst.
[0051] The protonated form of the zeolite/alumina matrix catalyst
used in Examples I-IV may be described as the simplest form of the
zeolite/alumina matrix catalyst, wherein the cation-exchange
centers in the zeolite are fully populated with protons. Each
cation center is associated with an aluminum atom incorporated in
the framework of the zeolite. Therefore, one may say that the
proton to framework-Al ratio of the protonated form is 1/1, and the
form is called "HZSM-5" (the "H" or more strictly "H.sup.+" being a
proton), wherein ZSM-5 stands for "Zeolite Socony Mobil-5"
(structure type MFI--mordenite framework inverted).
[0052] The gallium-loaded forms of the zeolite/alumina matrix
catalyst used in Examples I-IV were prepared with gallium levels
that are cited as a fraction of the cation sites replaced by
gallium. Catalysts were prepared with Ga levels equivalent to 1.0
Ga/framework-Al, 0.33 Ga/framework-Al, and 0.10 Ga/framework-Al. In
these materials, Ga replaced protons. Therefore, for 1.0
Ga/framework, almost all the cation sites were occupied by Ga and
almost all the protons had been replaced by Ga. Therefore, the "1.0
Ga/framework-Al" catalyst may be described as having 90%-100% of
cation sites occupied by Ga or 95-100% of cation sites occupied by
Ga. For the other Ga loadings, only a portion of the protons had
been replaced with Ga. In some tables, the term "0 Ga/framework-Al"
is used, which means zero protons replaced by Ga and which may be
equivalently be referred to as "HZSM-5" (or the "fully protonated
form" of the catalyst). Exemplary catalysts have gallium as
cations, which compensate for the anionic framework of the zeolite.
It may be noted that, many embodiments of the catalysts of this
invention are not acidic-type zeolites comprising gallium instead
of aluminum in the framework.
[0053] Gallium catalysts have been described for producing
aromatics from short-chain fossil-fuel hydrocarbons, especially C2,
C3, and C4. U.S. Pat. No. 4,727,206 discloses gallium catalyst for
feedstocks having methane as a major component, with ethane and
C3-C6 optionally being included in the feedstock. U.S. Pat. No.
4,746,763 discloses gallium catalyst for processing of C2-C6
aliphatic compounds. U.S. Pat. No. 4,761,511 describes catalysts
for aromatics production and suggests that C2-C12 paraffins may be
used as feedstock, but the patent teaches that C2-C8 paraffins are
the preferred feedstock, and that C2-C4 paraffins are the
especially preferred feedstock. U.S. Pat. No. 4,766,265 discloses
liquid aromatic production from ethane (C2). U.S. Pat. No.
4,855,522 mentions gallium catalyst for processing C2-C12
compounds, but focuses on C5-C7 paraffin feedstocks. U.S. Pat. No.
5,149,679 mentions C2-C12 feedstocks, but prefers C2-C6, and
especially prefers C2-C4 feedstocks. UOP Cyclar.TM. units have
utilized some of the catalysts mentioned in these patents with C3
and C4 feedstocks. Thus, gallium-cation catalysts are known, and
those of skill in the catalytic arts will understand how to make
such catalysts.
[0054] The inventors believe, however, that the prior art teaches
away from applying such gallium catalysts to aromatics production
and/or hydrogen production from renewable oils, especially those
with substantial C12+ compounds, substantial C16-C22 fatty
acid/ester chains, and/or even substantial C50+ compounds. It is
not obvious to apply such gallium catalysts to renewable oils that
comprise biological compounds which contain oxygen, such as fatty
acids, triglycerides, aldehydes, ketones, esters, and/or alcohols,
etc. that occur in significant amounts in naturally-occurring plant
oils. The inventors believe that it is surprising and non-obvious
to apply such gallium catalysts, which have been designed for and
applied to C2-C4 feedstocks, to BTEX production and/or hydrogen
production from renewable oils, and, particularly, from canola oil
or algae oil.
[0055] The renewable crude oils of this disclosure may be extracted
by various means from biomass that has been alive within the last
50 years. As an example, the canola oil used in the experiments of
Examples I and II was commercially-available canola oil, which is a
well-known oil obtained from rapeseed. As another example, the
renewable algae oils used in the experiments of Examples III-V were
examples of the category of renewable oils that may be extracted by
various means from of naturally-occurring non-vascular
photosynthetic organisms and/or from genetically-modified
non-vascular photosynthetic organisms. Genetically modified
non-vascular photosynthetic organisms can be, for example, where
the chloroplast and/or nuclear genome of an algae is transformed
with a gene(s) of interest. As used herein, the term non-vascular
photosynthetic organism includes, but is not limited to, algae,
which may be macroalgae and/or microalgae. The term microalgae
includes, for example, microalgae (such as Nannochloropsis sp.),
cyanobacteria (blue-green algae), diatoms, and dinoflagellates.
Crude algae oil may be obtained from said naturally-occurring or
genetically-modified algae wherein growing conditions (for example,
nutrient levels, light, or the salinity of the media) are
controlled or altered to obtain a desired phenotype, or to obtain a
certain lipid composition or lipid panel.
[0056] In certain embodiments, the biomass is substantially algae,
for example, over 80 wt % algae, or over 90 wt % algae, or 95-100
wt % algae (dry weight). Algae biomass of particular interest
comprises photosynthetic algae grown in light. Other embodiments,
however, may comprise obtaining algae biomass or other "host
organisms" that are grown in the absence of light. For example, in
some instances, the host organisms may be photosynthetic organisms
grown in the dark or organisms that are genetically modified in
such a way that the organisms' photosynthetic capability is
diminished or destroyed. In such growth conditions, where a host
organism is not capable of photosynthesis (e.g., because of the
absence of light and/or genetic modification), typically, the
organism will be provided with the necessary nutrients to support
growth in the absence of photosynthesis. For example, a culture
medium in (or on) which an organism is grown, may be supplemented
with any required nutrient, including an organic carbon source,
nitrogen source, phosphorous source, vitamins, metals, lipids,
nucleic acids, micronutrients, and/or an organism-specific
requirement. Organic carbon sources include any source of carbon
which the host organism is able to metabolize including, but not
limited to, acetate, simple carbohydrates (e.g., glucose, sucrose,
and lactose), complex carbohydrates (e.g., starch and glycogen),
proteins, and lipids. Not all organisms will be able to
sufficiently metabolize a particular nutrient and that nutrient
mixtures may need to be modified from one organism to another in
order to provide the appropriate nutrient mix. One of skill in the
art would know how to determine the appropriate nutrient mix.
[0057] In certain embodiments, algae from which suitable oil may be
extracted are Chlamydomonas sp. for example Chlamydomonas
reinhardtii., Dunaliella sp., Scenedesmus sp., Desmodesmus sp.,
Chlorella sp., and Nannochloropsis sp. Examples of cyanobacteria
from which suitable crude oil may be obtained include Synechococcus
sp., Spirulina sp., Synechocystis sp. Athrospira sp.,
Prochlorococcus sp., Chroococcus sp., Gleoecapsa sp., Aphanocapsa
sp., Aphanothece sp., Merismopedia sp., Microcystis sp.,
Coelosphaerium sp., Prochlorothrix sp., Oscillatoria sp.,
Trichodesmium sp., Microcoleus sp., Chroococcidiopisis sp.,
Anabaena sp., Aphanizomenon sp., Cylindrospermopsis sp.,
Cylindrospermum sp., Tolypothrix sp., Leptolyngbya sp., Lyngbya
sp., or Scytonema sp.
[0058] Algae production and extraction technology are known in the
art, including genetically-modified algae growth and extraction,
and certain embodiments of the invention comprise crude algae oil
feedstocks/fractions from any growth and extraction techniques.
Algae may be harvested and dried and then the oil extracted from
lysed or destroyed cells. The cells may be chemically lysed, or
mechanical force can be used to destroy cell walls. Oil may be
extracted from the lysed/destroyed cells using an organic solvent
such as hexane. The algae oil used in Example III was oil extracted
from algae biomass using hexane, and then treated by a conventional
RBD process, such as that known in the food arts for vegetable
oils. The algae oil if Example III was not hydrotreated, reformed,
or cracked prior to being processed in the zeolitic catalyst
cracking processes.
[0059] Alternative Techniques of Obtaining Crude Algae Oil from
Biomass
[0060] Certain embodiments comprise crude algae oils that are
obtained by techniques comprising steps other than or in addition
to solvent extraction. For example, certain embodiments comprise
hydrothermal treatment of the biomass prior to solvent extraction
of the crude algae oil, for example, by heptanes, hexanes, and/or
MIB, and then processing by embodiments of the invention without
RBD treatment. Certain algae oil feedstocks, therefore, have not
been subjected to any RBD processing (the refining, bleaching, and
deodorizing process conventionally known and used for
high-triglyceride bio-oils), nor subjected to any of the individual
steps of refining, bleaching or deodorizing, after being extracted
and before certain upgrading processes of the invention.
[0061] Certain embodiments of said hydrothermal treatment comprise
an acidification step. Certain embodiments of the hydrothermal
treatment comprise heating (for clarity, here, also called "heating
to a first temperature"), cooling, and acidifying the biomass,
followed by re-heating and solvent addition, separation of an
organic phase and an aqueous phase, and removal of solvent from the
organic phase to obtain an oleaginous composition. A pretreatment
step optionally may be added prior to the step of heating to the
first temperature, wherein the pretreatment step may comprise
heating the biomass (typically the biomass and water composition of
step (a) below) to a pretreatment temperature (or pretreatment
temperature range) that is lower than said first temperature, and
holding at about the pretreatment temperature range for a period of
time. The first temperature will typically be in a range of between
about 250 degrees C. and about 360 degrees, as illustrated by step
(b) listed below, and the pretreatment temperature will typically
be in the range of between about 80 degrees C. and about 220
degrees C. In certain embodiments the holding time at the
pretreatment temperature range may be between about 5 minutes and
about 60 minutes. In certain embodiments, acid may be added during
the pretreatment step, for example, to reach a biomass-water
composition pH in the range of about 3 to about 6. It should be
noted that the hydrothermal-treatment and solvent-extraction
methods may be conducted as a batch, continuous, or combined
process.
[0062] Certain embodiments of the hydrothermal-treatment and
solvent-extraction procedures (HTT) may comprise: [0063] a)
Obtaining an aqueous composition comprising said biomass and water;
[0064] b) Heating the aqueous composition in a closed reaction
vessel to a first temperature between about 250 degrees C. and
about 360 degrees C. and holding at said first temperature for a
time between 0 and 60 minutes; [0065] c) Cooling the aqueous
composition of (b) to a temperature between ambient temperature and
about 150 degrees C.; [0066] d) Acidifying the cooled aqueous
composition of (c) to a pH from about 3.0 to less than 6.0 to
produce an acidified composition; [0067] e) Heating the acidified
composition of (d) to a second temperature of between about 50
degrees C. and about 150 degrees C. and holding the acidified
composition at said second temperature for between about 0 and
about 30 minutes; [0068] f) Adding to the acidified composition of
(e) a volume of a solvent approximately equal in volume to the
water in said acidified composition to produce a solvent extraction
composition, wherein said solvent is sparingly soluble in water,
but oleaginous compounds are at least substantially soluble in said
solvent; [0069] g) Heating the solvent extraction composition in
closed reaction vessel to a third temperature of between about 60
degrees C. and about 150 degrees C. and holding at said third
temperature for a period of between about 15 minutes and about 45
minutes; [0070] h) Separating the solvent extraction composition
into at least an organic phase and an aqueous phase; [0071] i)
Removing the organic phase from said aqueous phase; and [0072] j)
Removing the solvent from the organic phase to obtain an oleaginous
composition.
[0073] The composition of crude algae oils obtained by the above
hydrothermal-treatment and solvent-extraction techniques ("HTT
crude algae oils") may differ from the composition of
solvent-extracted and RBD-treated algae oils such as that in
Example III, and certain embodiments of the invention may comprise
said one or more renewable oils comprising, consisting essentially
of, or consisting of said HTT crude algae oils or fractions
thereof.
[0074] The following Examples illustrate certain embodiments of the
methods described herein, wherein a substantially higher yield of
BTEX is achieved by contact with gallium-modified catalyst compared
to non-gallium-modified catalyst. The Examples illustrate and
enable embodiments of the invention, but the invented methods,
apparatus, and/or catalyst are not necessarily limited to the
details therein, for example, algae oils other than those of the
Examples are included in the broad scope of the invention. Also,
various reactor and product recovery configurations,
gallium-retaining catalyst compositions, catalyst-to-oil ratios,
catalyst-feedstock contact time, feedstock conversions,
temperatures, and pressures, including others than those detailed
in the Examples, are included in the broad scope of the invention.
Those of skill in the art of refining operations, after reading and
viewing this disclosure, will understand how to apply the described
technology to commercial refining operations to achieve substantial
benefits such as are illustrated herein.
EXAMPLES
Example Summary
[0075] Examples I-III detail processing of canola oil or algae oil
in multiple tests using zeolite-alumina matrix catalysts, including
catalyst in protonated form and in gallium-cation-retaining form.
The tests showed excellent yields of BTEX from both canola oil and
algae oil, especially when the gallium-form was used, and may be
indicative of the BTEX yields and/or yields trends that may be
achieved with certain other renewable oils, including those from
other plant, non-vascular photosynthetic organism, vegetable, seed,
fungi, and bacteria sources.
[0076] Example IV details processing of fossil petroleum gas oil
over a selected gallium-cation-retaining catalyst from Examples
I-III, for comparison to the results from the renewable oil
processing.
[0077] Examples V and VI detail processing of algae oil and
hydrotreated algae oil by fluid catalytic cracking, compared to
fossil petroleum vacuum gas oil, and describe certain embodiments
wherein the FCC catalyst is supplemented with gallium-modified
catalyst.
[0078] Example VII describes processing of algae oil by thermal
treatment, followed by hydrotreatment and fluid catalytic cracking,
and describes certain embodiments wherein the FCC catalyst is
supplemented with gallium-modified catalyst.
[0079] Example VIII describes an exemplary FCC process unit
commercial application, including structure details of the
fluidized bed and systems for making-up/supplementing catalyst and
additives to said fluidized bed.
[0080] Example IX describes an exemplary purpose-built process unit
commercial application, which may be similar to a UOP Cyclar.TM.
unit and is designed for a feedstock comprised substantially or
entirely of renewable oil.
Analysis of Example Feeds
[0081] The canola oil of Examples I and II was a
commercially-available oil obtained from rapeseed, containing
approximately 60-70 wt-% C18:1 and approximately 12 wt %
oxygen.
[0082] The algae oil of Example III was of the type analyzed in
Tables 1-3 below. One may note the 48.8 wt-% free fatty acids, with
45.5 wt-% being C18:1 free fatty acids (carbon chain length=18,
monounsaturated). A portion of the free fatty acids in this algae
oil may be those naturally-occurring in the algae and a portion may
be fatty acids "freed" from their glyceride compounds during
extraction from the algae. Note also the algae oil oxygen content
of 10.52 wt %.
TABLE-US-00001 TABLE 1 Crude Algae Oil Analyses (weight-%) % C
78.62 % H 11.47 % N 0.22 % O 10.52 S PPM 323.0 P PPM 17.0
TABLE-US-00002 TABLE 2 General Composition of Crude Algae Oil Crude
Algae Oil Parameters (Bottles 1-4) Elements by ICP P (ppm) 56 Fe
(ppm) 19.7 Ca (ppm) 26.5 Mg (ppm) 4.3 Na (ppm) 12.7 K (ppm) 5.1 N
(ppm) 1132 S (ppm) 493 Chlorophyll (ppm) 11654 FFA (% as C18:1)
45.5 Hexane insoluble impurities (%) 0.40 GC composition (%) Short
chain undefined compounds 0.47 FFA/Fatty Alcohols 53.14
Monoglycerides 1.03 Diglycerides 1.13 Triglycerides 3.25
Tocopherols 1.32 Free Sterols 2.59 Waxy like compounds 9.09
Unknown/Not Detected 25.84 Tocopherols .alpha.-tocopherol 820
.beta.-tocopherol Traces .gamma.-tocopherol Traces
.delta.-tocopherol N.D. Unsaps (%) 29.13
TABLE-US-00003 TABLE 3 General Analyzes of Crude Algae Oil Analysis
Crude Algae Oil Acid Value (mg KOH/g) 97.1 Free Fatty Acids (%)
48.8 Insoluble impurities (%) 0.01 Neutral Oil (%) 53.3 Chlorophyll
in Oil (ppm) 5530 Carotenes Profile Astaxanthin (ppm) 143 Lutein
(ppm) 1510 Zeaxanthin (ppm) 624 alpha-Carotene (ppm) 370 trans-beta
Carotene (ppm) 2540 cis-beta Carotene (ppm) 2790 Lycopene (ppm)
<10 Total Carotenes (ppm) 7970 Phospholipids
N-acylphosphatidylethanolamine (%) <0.01 Phosphatidic Acid (%)
<0.01 Phosphatidylethanolamine (%) <0.01 Phosphatidylcholine
(%) <0.01 Phosphatidylinositol (%) <0.01
Lysophosphatidylcholine (%) <0.01 Residual Solvents GC/MS Hexane
(ppm) 16100 Cyclohexanone (ppm) 530 Methyl Benzene (est) (ppm) ~500
Ethyl Benzene (est) (ppm) ~400 Propyl Benzene (est) (ppm) ~150
Chloroform (est) (ppm) ~2.00 Sterols and Stanols (Free) (mg/g) 11.0
Tocopherols and Sterols Delta Tocopherol (mg/100 g) 5.09 Gamma
Tocopherol (mg/100 g) 3.04 Alpha Tocopherol (mg/100 g) 76.0
Cholesterol (mg/100 g) 405 Campesterol (mg/100 g) 34.2 Stigmasterol
(mg/100 g) 124 B-sitosterol (mg/100 g) 780 Other Sterols (mg/100 g)
733
[0083] The algae oil feed tested or referenced in Examples III-VI
was obtained by the HTT steps a-j above and is described in Tables
4-6 below.
TABLE-US-00004 TABLE 4 % Mass Fraction - Algae Oil Feed FRACTION
MASS % Sample Initial-260.degree. F. 260-400.degree. F.
400-490.degree. F. 490-630.degree. F. 630-1020.degree. F.
1020.degree. F. NS-263-061 Algae Oil Feed 0.0 0.5 1.3 6.6 64.1
27.5
TABLE-US-00005 TABLE 5 Compound Classes - Summary for Algae Oil
Feed Class Algae Oil Feed HC-Saturated 2.0 HC-Unsaturated 9.1
Naphthenes and 1.7 Aromatics N-Aromatics 8.6 Nitriles 0.0 Acid
Amides 10.9 Fatty Acids 25.9 Oxygen 1.3 Compounds Sterols 13.6
Sulfur 0.0 Compounds Unknowns 26.9
TABLE-US-00006 TABLE 6 Elemental Analysis - Algae Oil Feed wt %
Algae Oil Feed C 77.9 H 10.7 N 3.9 O 6.8 S 0.37
Experimental Equipment Summary
[0084] Examples I and III used the 20 g scale reactor system 10
schematically portrayed in FIG. 1A. The reactor system was
controlled by a LabVIEW.TM. program and National Instruments DAQ
hardware. For runs using canola oil, a dual piston chromatography
pump 12 pulled reactant from a flask of feedstock 14, and pumped it
up to a furnace 16 containing the reactor 18. For algae oil runs,
the feed pump was an ISCO piston pump with 500 cc capacity which
was able to handle the highly viscose algae oil. No feedstock
preheat furnace 20 was used because it was determined previously
that it was thermally cracking the canola oil before it could reach
the catalyst. The reactant mixed with a heated nitrogen stream 22
just before entering the top of the reactor 18. The mixed nitrogen
and reactant flowed down the reactor through the catalyst bed 24.
Reactor effluents passed through a cooling coil 26 and a liquid
trap 28, both contained in ice baths 30. The cooled vapor left the
liquid trap and passed through a micro-GC 32 and then on to a vent.
An Agilent 2804 micro-GC measured the composition of the vapor
phase every 4 minutes.
[0085] The reactor 18 in Examples I and III was a 1/2 inch diameter
stainless steel reactor tube, measured 24 inches long, and
contained a 10 g catalyst bed 24 centered within the furnace's 18''
heated zone. Glass beads 40 packed in the bottom of the reactor
supported the catalyst bed and glass beads 42 above the bed helped
to vaporize the feed before it reached the catalyst. In preliminary
work, using a preheat furnace for the feedstock resulted in thermal
cracking of the canola oil before it could reach the catalyst, and
so the feedstock preheat furnace 20 was not used in the experiments
in Examples I-III.
[0086] Two thermocouples inserted axially into the catalyst zone of
the tubular reactor measured the temperature 2 inches below the top
and 2 inches above the bottom of the catalyst bed in Examples I and
III. Thermocouples also were mounted in the heated spaces of the
furnace. A LabVIEW.TM.-based control program adjusted the furnace
temperature so that the average of the top and bottom catalyst
temperatures stayed on setpoint. The same program also controlled
the pump and gas flow controllers, while logging all temperatures
and flowrates. The programmable Chromtech.TM. dual-piston pump
supported flowrates from 0.001 to 12.00 mL min, although the
viscosity of the canola oil limited the pump to flowrates of not
more than around 1 mL/min without providing backpressure. The ISCO
pump used to deliver algae oil was programmable to deliver from
0.001 to 204 cc/min of feed. A pair of Brooks Instruments mass flow
controllers worked in tandem to accurately provide nitrogen flow
rates up to 10 SLM. This one-reactor system and its use are further
described below in Example I.
[0087] The mass of liquid product from each experiment of Examples
I and III was measured, and then the organic phase was separated
from the aqueous phase and the mass of the remaining aqueous phase
was measured. When catalyst charges were removed from the reactor,
a small sample was used in a microbalance system to estimate coke
content, then the remainder of the used catalyst was placed in a
horizontal tube furnace to be regenerated by burning in 80/20
Ar/O.sub.2 at 575.degree. C. for 4 hours. The percent difference
between the mass of the catalyst before and after regeneration was
taken as the actual coke content, and this matched well with
microbalance measurements of coke content. The total vapor product
reported for each experiment represents an estimate based on the
micro-GC measurements of the gaseous product composition over time.
The composition data was integrated over time to yield a total
amount of each gaseous product.
[0088] Example II used a reactor system modified, as shown
schematically in FIG. 1B, to include two reactors in series with
liquid removal between the two reactors. Each of the two reactor
structures, reactor loading, temperature control, product
condensation, and product stream measurement and analysis for
Example II were substantially the same as the equipment and methods
described above for the single-reactor Examples I and III. The
two-reactor system and its use are further described below within
Example II.
[0089] Example IV utilized equipment and procedures that were
substantially similar or the same as those used in Examples I and
III, as will be understood from reading Example IV. Example V
utilized equipment and procedures for FCC MAT testing, and Example
VI utilized equipment and procedures for hydrotreating followed by
FCC MAT testing, as will be understood from reading these examples,
respectively.
Example I
Catalytic Cracking of Canola Oil Over GaZSM-5
[0090] Catalytic cracking of canola oil was conducted over a
gallium-doped HZSM-5 zeolite catalyst, hereafter called "GaZSM-5",
in a 20 g scale reactor system The goal of this experimentation was
to optimize formation of aromatics, specifically benzene, toluene,
ethylbenzene, and xylenes (BTEX), for fuel blending or for use as
feed stocks in the chemical industry. Large yields of both BTEX and
light paraffin were observed when cracking canola oil over the
protonated form of ZSM-5, a.k.a., HZSM-5, in comparison to the
other zeolites the inventors have used to crack canola oil, for
example, in comparison to zeolite-.beta.. After conducting cracking
experiments contacting canola oil with HZSM-5, the inventors
conducted similar cracking experiments contacting canola oil with
GaZSM-5, with a goal of further increases in BTEX yields. Excellent
BTEX yields were obtained in the GaZSM-5 experiments, with said
yields being significantly higher than those obtained with the
protonated zeolite form. The inventors believe that the
gallium-doped catalyst effectively convert light paraffins formed
in the cracking process to aromatics, while also converting
high-carbon-number components of the renewable oil to BTEX. The
inventors believe the gallium-doped catalyst increases olefin
production due to the dehydrogenation capability of the gallium,
and that the catalyst dehydrogenates and cracks the C16-C18 chains
of the renewable oil to smaller olefins, especially C5+ olefins.
Due to the shape selectivity of the catalyst, these C5+ olefins are
then cyclized to C5 and C6 ring compounds which are further
converted to aromatics. Thus, it is believed that the high BTEX
selectivity of the catalyst when processing the renewable oils is
due in some part to light paraffin conversion but also,
importantly, to direct conversion of long chains to BTEX without
first being cracked to C2-C4. In this set of experiments, cracking
canola oil over GaZSM-5 produced 39.3% BTEX, compared to cracking
canola oil over HZSM-5, which produced 32.3% BTEX. Also, the
GaZSM-5 reduced the ethane yield from 3.1% to 0.25% and the propane
yield from 21.8% to 14.6%.
Experimental
[0091] Gallium-doped HZSM-5 was prepared at Ga/framework-Al ratios
of 1/10, 1/3, and 1/1; meaning that roughly 1/10, 1/3, or all of
the cation sites hosted Ga cations. In the case of 1/10 and 1/3
Ga/framework-Al ratios, the remaining cation sites still hosted
protons. The first step in production of catalysts was to form
pellets from powdered HZSM-5, which was Mobil ZSM-5 base catalyst
purchased in powdered form from Zeolyst International. This was
accomplished using Zeolyst CBV5524G powder (50/1
SiO.sub.2/Al.sub.2O.sub.3) which was bound with 20 wt %
Al.sub.2O.sub.3 and extruded into 1/16'' pellets and calcined. The
proton content of this material was measured using the temperature
programmed desorption of n-propanamine and found to have an actual
SiO.sub.2/Al.sub.2O.sub.3 ratio of 61/1 (see V. Kanazirev, K. M.
Dooley, G. Price, J. Catal. 146 (1994) 228-236 for this
methodology) The 1/1 GaZSM-5 was then prepared by incipient wetness
impregnation of a 25 g batch of HZSM-5 pellets with 4.77 g
Ga(NO.sub.3).sub.3.xH.sub.2O, where x is determined by microbalance
drying experiments to be approximately 9-11, dissolved in 22.97 g
water. The wet catalyst was dried overnight in an oven at
120.degree. C. The 1/3 and 1/10 catalysts were prepared in a
similar fashion, using 1.52 and 0.51 g Ga(NO.sub.3).sub.3.H.sub.2O,
respectively. Prior to catalytic cracking, the Ga/HZSM-5 was heated
to 500.degree. C. in flowing N.sub.2 (converting the nitrate to the
oxide), and then activated at 500.degree. C. under a 100 mL/min
stream of 30% hydrogen in nitrogen. The activation process is known
to accelerate the ion-exchange of Ga cations for protons in the
zeolite.
[0092] Canola oil was cracked over a HZSM-5 material (that is, no
gallium) at 350, 400, 450, and 500.degree. C. to determine which
temperature would produce the most BTEX. The cracking results
showed the most BTEX at 400.degree. C., so the GaZSM-5 experiments
were also done at that temperature.
[0093] The cracking experiments proceeded as follows: [0094] a) 10
g of the zeolite catalyst was loaded into the reactor; [0095] b) 10
g borosilicate glass beads were poured on top of the zeolite;
[0096] c) Reactor was loaded into the furnace; [0097] d) N.sub.2
flow was established; [0098] e) For the Ga-containing materials,
the reactor was brought to temperature for activation, and the
catalyst was activated; [0099] f) Reactor was brought to the
cracking temperature; [0100] g) Nitrogen co-feed was used during
cracking, 0.0465 SLM (also used to dry the catalyst prior to
reaction); [0101] h) Canola oil feed was started, 0.182 mL/min
(corresponding to WHSV=1); and [0102] i) Total amount of reactant
fed, 10 g
[0103] The total mass balance for each run was performed based upon
the difference between grams of reactant fed and product collected.
Product collected was separated into three parts: 1) the gaseous
product which is continuously measured by the micro-GC system, 2) a
condensed liquid product which is collected from the reactor's
effluent in a trap thermostatted at 0.degree. C., and 3) the coke
which is left on the catalyst. The mass of condensed liquid product
was measured, then a water phase was separated from an organic
phase, and the organic phase analyzed by simulated distillation and
GC-MS. When spent catalyst charges were removed from the reactor, a
small sample was used in a microbalance system to determine coke
content. The rest of the spent catalyst was then subjected to coke
removal in the calcining furnace using a synthetic air made of
O.sub.2 in Ar. The total vapor product recovered was determined by
integrating the micro-GC measurements of the gaseous product
composition over time and using the known N.sub.2 flowrate as an
internal standard.
[0104] Yields were calculated in weight-percent (wt-%), defined as
Y=100.times.PF/RC, wherein Y equaled yield in weight %, PF equaled
weight of product formed, and RC equaled weight of reactant
converted. As the operating conditions selected for the experiments
in all Examples gave 100 conversion of the oil reactant, RC is in
the above equation is identical to what was fed to the reactor
system.
[0105] On average, the mass balances in Table 7, below, accounted
for 98% of the reactant. As shown in FIG. 2, which portrays results
from the preliminary runs SAP275-279 on HZSM-5 catalyst (no Ga),
the yield of liquid products (triangles) generally decreased with
increasing temperature, while the gas products (vapor products,
squares) demonstrated the opposite trend, that is, generally
increasing with increasing temperature. The yield of solid products
did not vary appreciably with temperature.
TABLE-US-00007 TABLE 7 Reaction Conditions and Mass Balances for
Example I (reactant in each experiment being 10 grams) Ga/
Products- Frame- Vapor Liquid Solid Total Feed Experiment work-
Temp Products Products Products Products Difference Number Al (C.)
(g) (g) (g) (g) (%) SAP276 0 350 3.93 5.32 0.45 9.70 -2.97 SAP278 0
400 3.92 5.54 0.37 9.83 -1.68 SAP279 0 450 3.79 5.26 0.38 9.43
-5.71 SAP275 0 500 4.29 5.05 0.42 9.76 -2.36 SAP281 1.0 400 3.31
5.86 0.48 9.65 -3.51 SAP282 0.33 400 3.83 5.45 0.48 9.76 -2.42
SAP283 0.1 400 4.11 5.36 0.40 9.87 -1.31 SAP284 0 400 4.13 5.21
0.37 9.71 -2.87 SAP286 0 400 4.12 5.26 0.39 9.77 -2.29 SAP287 0 400
4.27 5.22 0.36 9.85 -1.53
[0106] Adding gallium to the HZSM-5 (runs SAP281-283) had a much
more pronounced effect, seen in FIG. 3, about twice as much as the
change in temperature. The gallium increased the liquid yield,
while decreasing the yield of gas, compared to the average of runs
SAP284-287. Vapor product yields changed with increasing amounts of
gallium added to the catalyst for experiments SAP281-283,
particularly for propane and ethane. The molecules shown in FIG. 3
represent .about.98% of all vapor products from each experiment.
Results for 0.0 Ga are the mean of SAP284-287 and the "error bars"
show the 95% confidence interval.
[0107] As shown in FIG. 4, increasing Ga content (SAP281-283)
increased the yield of liquid (triangles), while coke (circles)
stayed almost constant and the amount of vapor products (squares)
decreased compared to the mean of SAP284-287 (no Ga).
Product Analysis
[0108] In the gas phase product (see FIG. 3), the propane yield
decreased from 21.8% to 14.6% as the Ga content went up. Likewise,
the ethane yield went from 3.1% to 0.25%, while the hydrogen yield
increased from 0.3% to 1.2%.
[0109] Though the experiments were not performed in an effort to
make gasoline, but to make aromatics, the inventors still
characterized the liquid product by simulated distillation. This is
shown in FIG. 5, which portrays boiling point distribution of the
organic phase products. The majority of the products fall in the
60-188.degree. C. range, which is typical for ZSM-5 catalysts that
primarily produce BTEX.
[0110] The gasoline range material is the fraction which boils
below 225.degree. C. Gasoline requirements (D4814) specify that 10,
50, 90, and 100% of the fuel should boil by certain temperatures,
respectively called T10, T50, T90, and FBP (final boiling point).
The FBP is fixed at 225.degree. C., but the other temperatures vary
both seasonally and regionally. These temperatures provided the
break points for evaluating the composition of the organic phase
liquid products shown in FIG. 5. HZSM-5 is well known for producing
high yields of BTEX, which all have boiling points in the
60-188.degree. C. range. However, the gallium-doped catalyst
performed significantly better than the HZSM-5 in BTEX production,
as evidenced by the yields shown in FIG. 5. As Ga/framework-Al
increased from 0 to 1.0, the yield of products between
60-188.degree. C. increased from 34.6% to 40.8% based on canola oil
converted.
[0111] As shown in FIG. 6, the liquid products were also analyzed
by GC-MS to quantify the BTEX content, which increased with the
gallium content of the ZSM-5 catalyst. The benzene (B.P.
80.1.degree. C.) yield increased from 7.5% to 8.4% as the
Ga/framework-Al increased from 0 to 1.0 and comprised nearly all
the material in the 60-93.5.degree. C. range. Toluene (B.P.
110.6.degree. C.) behaved similarly and had the greatest change in
yield, going from 15.4% up to 19.3%. It also made up just over half
of the material in the 93.5-188.degree. C. boiling point range. The
C8 aromatic yields (ethylbenzene, B.P. 136.degree. C.; p-xylene,
B.P. 138.degree. C.; m-xylene, B.P. 139.degree. C.; o-xylene, B.P.
144.degree. C.) also increased, from 9.5% to 11.6%, with the
increasing gallium content in the catalyst. [0064] For the 1.0
Ga/framework-Al material, the total BTEX yield increased by 7.0
percentage points, so that BTEX comprised 77.3% of the organic
liquid product. Aromatics heavier than the C8 fraction are present
in the organic liquid phase, but these are more difficult to
quantify and are generally less valuable than the BTEX
fraction.
Example I Conclusions
[0112] HZSM-5 catalysts are well known for their ability to produce
high levels of benzene, toluene, and xylenes. Cracking canola oil
with a standard HZSM-5 catalyst yielded about 32.3% BTEX at
400.degree. C., but, by adding gallium to the catalyst, the
inventors observed an increase in the BTEX yield, of 7 wt-%, to
achieve about 39.3% under the same conditions. These BTEX aromatics
comprised 77% of the organic liquid products, so, in addition to
representing a possible renewable source of aromatics for the
chemical industry, it might be possible to blend it directly into
kerosene or diesel to obtain a jet fuel nearly identical to Jet
A-1. Additional testing will be needed to measure the products from
these experiments for the chief properties of jet fuel, such as
freezing point, vapor pressure, viscosity, flash point, and heat of
combustion.
Example II
Catalytic Conversion of Canola Oil to Aromatics by Two Reactors in
Series
[0113] Catalytic conversion of canola oil to aromatics was
conducted using two reactors in series. The goal of the work in
this Example was to optimize the formation of benzene, toluene,
ethylbenzene, and xylenes (BTEX), which are valuable for gasoline
or use as chemicals. Canola oil cracking on H-ZSM-5 has been shown
to generate substantial amounts of light paraffins, for example, 25
wt % oil fed, as shown in Example I. This Example continues
experimentation directed toward achieving "green BTEX" production,
by increased conversion of light paraffins to BTEX and, the
inventors believe, by direct conversion of long chains to BTEX. In
this Example, a multiple-reactor system is employed wherein vapor
products from a primary reactor cracking canola oil over H-ZSM-5 or
GaZSM-5 were fed to a secondary reactor containing GaZSM-5 and
converted to BTEX. In this reactor system, "primary" means the
first reactor to which the oil feedstock is fed, and "secondary"
means the second reactor to which the gas/vapour effluent from the
primary reactor is fed.
[0114] The secondary reactor containing GaZSM-5 raised the BTEX
yield achieved from cracking canola oil over H-ZSM-5 (in first
reactor) from 39.5 wt % oil fed to 43.8 wt %, that is, an increase
of 4.3 wt-% yield. The secondary reactor containing GaZSM-5 also
raised the BTEX yield achieved from cracking canola oil over
GaZSM-5 (in the first reactor) from 46.3 wt % oil fed to 51.2 wt %,
that is, an increase of 4.9 wt-% yield. Note also that the BTEX
yields achieved when both reactors contained gallium-doped catalyst
(46.3 wt-% and 51.2 wt-%) were both significantly higher than the
BTEX yields achieved when protonated catalyst was followed by the
gallium catalyst (39.5 wt-% and 43.8 wt-%).
Catalysts
[0115] The cracking experiments using the protonated form of ZSM-5
catalyst used Zeolyst H-ZSM-5 with a 25/1 Si/framework-Al ratio.
The experiments using the Ga cracking catalyst also used the same
Zeolyst H-ZSM-5 material, with gallium loaded by incipient wetness
addition of Ga(NO.sub.3).sub.3 at a loading of 1 Ga/framework-Al.
The terminology "GaZSM-5(1-1)" is used to emphasize that the
loading is 1 Ga-1 Al.
Experimental
[0116] The cracking process was performed in a two-reactor
configuration, made up of two reactors in series shown in FIG. 1B.
Both reactors were mounted vertically within the furnace. A
thermocouple was centered in each reactor tube to monitor the
temperature in the catalyst bed. This temperature was taken as
reaction temperature and was maintained at a constant set-point by
a LabVIEW based control program that adjusted the furnace power.
The liquid product from the first reactor (11 mm I.D. and 521 mm
overall length) was condensed in the glass cylinder and the vapor
product entered the second reactor (11 mm I.D. and 419 mm overall
length) for further reaction. The liquid product from the second
reactor was condensed in the glass cylinder and the vapor product
flowed to a Micro GC (Agilent G2804A) that analyzed the gas
composition every four minutes.
[0117] The details of the two-reactor system 10' of FIG. 1B are
called-out as follows: nitrogen cylinder 51, gas regulator 52,
valve 53, mass controller 54, syringe pump 55, first (primary)
reactor 56, catalyst 57 in primary reactor, first (primary) furnace
58, thermocouple in the primary reactor (not shown), glass cylinder
60, ice-cooled condenser 61, liquid products 62, secondary furnace
63, secondary reactor 64, catalyst 65 in secondary reactor, glass
cylinder 66 and ice-cooled condenser 67 for secondary reactor
effluent, liquid products 68 of secondary reactor effluent, and gas
chromatograph 67.
[0118] Two experiments were conducted at atmospheric pressure. The
first experiment was done with H-ZSM-5 loaded in the first reactor,
and GaZSM-5(1-1) in the second reactor. A second experiment was
done with GaZSM-5(1-1) loaded in both reactors in series. Reaction
temperatures were set according to the performance of the loaded
catalysts, wherein the optimum reaction temperatures, determined in
previous experimentation, of H-ZSM-5 and GaZSM-5(1-1) for cracking
canola oil are 400.degree. C. and 350.degree. C., respectively. So,
the first reactor (receiving canola oil as feed) was set at
reaction temperature 400.degree. C. when containing H-ZSM-5, and
350.degree. C. when containing GaZSM-5. The second reactor,
containing GaZSM-5(1-1) for both experiments, was set to
450.degree. C. to convert the vapor products from the first
reactor, based on the inventors' earlier work that showed
450.degree. C. was the optimum temperature for propane conversion
to BTEX over GaZSM-5(1-1). In both cases, the first reactor
contained 10 g catalyst and the second reactor contained 5 g
catalyst. Experiment SAP359 is the experiment number for the run
wherein H-ZSM-5 was followed by GaZSM-5(1-1) (primary and secondary
reactors, respectively), and experiment SAP360 is the experiment
number for the run wherein GaZSM-5 was followed by GaZSM-5 (primary
and secondary reactors, respectively).
[0119] Before catalytic conversion, GaZSM-5(1-1) was heated to
500.degree. C. in flowing nitrogen and then activated at
500.degree. C. under a 100 ml/min stream of 30% hydrogen in
nitrogen for at least 1 hr. The activation process drives Ga
cations into the zeolite pores and it replaces protons in the
zeolite. After the activation step, the reactor was cooled to the
desired reaction temperature. Co-feed nitrogen was set to 46.5
ml/min and the canola oil flow rate was set to 0.182 ml/min. The
experiment lasted about 2 hrs and 20 g reactant was fed over that
time period.
[0120] The total mass balance for each run was performed based upon
the difference in grams of the reactant fed and products collected.
The products mainly comprise three parts, gas, liquid and coke.
Table 8 gives the reaction conditions and product mass obtained
from canola oil cracking in each reactor, as well as the total mass
balances. The mass balance was within 5 wt % for these two runs.
Table 9 contains the composition of the products summarized in
Table 8 calculated as the weight percent of total oil fed.
TABLE-US-00008 TABLE 8 Overall mass balances for conversion of
canola oil in two reactors in series, for Example II Temp OLP
Aqueous Residue Coke Catalyst (.degree. C.) Gas (g) Liquid (g) (g)
(g) (g) (g) SAP359 Reactor 1 HZSM-5 400 -- 9.35 9.35 0 0.47 0.26
Reactor 2 GaZSM-5 450 10.03 0.29 0.29 0 0.05 0.05 SAP360 Reactor 1
GaZSM-5 350 -- 11.48 10.69 0.79 0.49 0.56 Reactor 2 GaZSM-5 450
7.21 0.5 0.5 0 0.11 0 Totals All Oil Fed OLP Residue Coke Products
(g) Gas (g) Liquid (g) (g) (g) (g) (g) Difference SAP359 20.00
10.03 9.64 9.64 0.52 0.31 20.50 2.50% SAP360 20.00 7.21 11.98 11.19
0.60 0.56 20.35 1.75%
TABLE-US-00009 TABLE 9 Yield of product or groups obtained from
conversion of canola oil in two reactors in series, for Example II
SAP359 (1.sup.st reactor SAP360 protonated catalyst, 2.sup.nd (both
reactors gallium reactor gallium catalyst) catalyst) Yield of
components or groups in the gas product Methane 10.13% 6.53% Ethane
9.06% 3.82% Propane 7.08% 6.36% Butanes 0.23% 0.18% Pentanes 0.00%
0.01% Hexanes+ 9.81% 8.13% Hydrogen 1.27% 2.03% Olefins 0.43% 0.31%
CO + CO2 12.12% 8.71% Reactor 1 Reactor 2 Reactor 1 Reactor 2 Yield
of components or groups in the organic liquid product (OLP)
0-60.degree. C. 0.26% 0.00% 0.44% 0.00% 0-93.5.degree. C. 9.96%
0.30% 9.58% 0.58% 0-188.1.degree. C. 36.78% 1.14% 42.98% 2.08%
0-225.degree. C. 39.74% 1.26% 45.65% 2.26% 225.degree. C. above
7.01% 0.19% 7.80% 0.24% Yields of aromatics in the OLP Benzene
10.07% 0.31% 9.76% 0.59% Toluene 16.18% 0.55% 20.65% 1.01% Xylenes
6.70% 0.21% 10.71% 0.37% Total BTEX 43.82% 51.22% Total Gasoline
range 50.81% 56.04%
[0121] The 9.81 wt % hexanes+ yield of the SAP359 gas product was
particularly high, compared to the 2.4 wt % yield of hexanes+ in
SAP284-287 (cracking canola oil over H-ZSM-5 at 400.degree. C., see
Example I). This led the inventors to suspect that the BTEX
products were not completely condensing upon leaving the second
reactor. Therefore, three gas product samples were taken during
SAP360 at 30 minute intervals and analyzed using an Agilent 5975
GC-MS to identify the vapor phase products, especially the hexane+
fraction reported by the micro-GC. The GC-MS was set up to only
identify molecules larger than C3. The flame ionization detector
showed 4 primary peaks, which were identified by the mass
spectrometer as benzene, toluene, and xylenes. Some other molecules
were present, but in such low concentrations that they could not be
identified. So, the hexanes+ in the gas as analyzed by the micro-GC
can be regarded as principally aromatics and were included in the
BTEX and gasoline range yield totals.
[0122] Feeding the vapor products from the primary reactor to a
second reactor loaded with GaZSM-5 increased the overall organic
liquid product (OLP) yield in the canola oil cracking as expected.
See, in Table 8, that the OLP yield from the first reactor in the
SAP359 run was 9.35 g, and that the second reactor of that run
added 0.29 g of OLP. See also, that loading gallium-doped catalyst
in both reactors, in run SAP360 increased OLP further, as may be
seen by comparing 11.19 g OLP in SAP360 to 9.64 g OLP in
SAP360.
Example II Conclusions
[0123] Adding another reactor to convert vapor product obtained
from canola oil cracking can improve OLP yield and BTEX yield. The
hexanes+ fraction in the gas products are un-condensed aromatics.
The best total yields of BTEX in this Example were achieved when
all (both) reactors were loaded with gallium-loaded catalyst.
Specifically, cracking canola oil over GaZSM-5 at 350.degree. C.
produced 46.3% BTEX (assuming hexanes+ were un-condensed
aromatics), and adding the second reactor loaded with GaZSM-5 at
450.degree. C. increased the total BTEX yield to 51.22 wt %. As
noted above in this Example, the BTEX yield of 39.45 wt % from
cracking canola oil over H-ZSM-5 at 400.degree. C. increased to
43.82 wt % with the addition of the second reactor containing
GaZSM-5 catalyst at 450.degree. C. The inventors recognize that
further improvements in aromatics yield may be made with further
experimentation. Possible optimization parameters include gallium
loading levels in both reactor beds, amount of catalyst in each
bed, temperatures of each bed, space velocities relative to
feedstocks flowrate and relative to nitrogen feed, and other
possible parameters.
Example III Comparison of Algae Oil Cracking Over GaZSM-5 and
HZSM-5
[0124] Algae oil (sample NL-72-32-03) was subjected to catalytic
cracking over a gallium-doped ZSM-5 (GaZSM-5, 1.0 Ga/framework-Al
in the zeolite) and the proton form of ZSM-5 (HZSM-5) at
400.degree. C. The goal of this work was to compare the formation
of aromatics from algae oil between these two catalysts,
specifically benzene, toluene, ethylbenzenes, and xylenes (BTEX),
for fuel blending or for use as feedstocks in the chemical
industry. It was observed that GaZSM-5 produced more BTEX and less
paraffins (especially propane) compared to HZSM-5, during algae oil
cracking at the same reaction temperature.
[0125] The experiments were performed with the 20 g scale reactor
system, with a single reactor, as described above for Example I,
loaded with 10 g of catalyst. The results of these experiments
showed that cracking algae oil (NL-72-32-03) over GaZSM-5 gave 46.8
wt % yield of BTEX and 48.3 wt % yield of gasoline, compared to
38.9 wt % yield of BTEX and 42.9 wt % yield of gasoline when
cracking algae oil over HZSM-5 under the same conditions. Also,
GaZSM-5 reduced the C.sub.1-C.sub.3 paraffin yield, producing 16.7
wt % C1-C3 paraffin, compared to 25.9 wt % for HZSM-5. GaZSM-5 also
reduced propane yield, producing 6.4 wt % propane, compared to 14.0
wt % for HZSM-5.
Experimental
[0126] GaZSM-5 was made according to the methods reported in
Example I starting with the same Zeolyst CBV5524G powder (50/1
SiO2/Al2O3) which was converted into pellets as in Example I then
loaded with gallium in an identical way to Example I. However, the
only gallium loading level which was used in this study
corresponded to 1.0 Ga/framework-Al in the zeolite, referred to in
this Example as "GaZSM-5." The base ZSM-5 material was used in its
fully protonated form referred to as "HZSM-5." Since HZSM-5 gave
the highest BTEX yield at 400.degree. C. for a canola oil feedstock
in previous work, the algae oil cracking experiments were also done
at that temperature. The GaZSM-5 catalyst was activated at
500.degree. C. under a 100 ml/min stream of 30% hydrogen in
nitrogen for at least 1 hour. This activation process is known to
accelerate the ion-exchange of Ga cations for protons in the
zeolite. For HZSM-5, as usual, the catalyst was dried at
400.degree. C. with nitrogen flow rate of 46.5 ml/min for 2 hours
prior to utilization as a cracking catalyst. Assuming a density of
0.9 g/ml for the algae oil, 10 g of algae oil corresponds to 11.1
ml and the algae oil flow rate was 0.185 ml/min, which corresponds
to WHSV=1.0. Cracking experiments proceeded as follows:
[0127] 10 g of the zeolite catalyst was loaded into the reactor
[0128] Reactor was loaded into the furnace
[0129] N.sub.2 flow was established
[0130] For GaZSM-5, the reactor was brought to 500.degree. C., and
the catalyst was activated
[0131] Reactor temperature was set to 400.degree. C.
[0132] Nitrogen co-feed was established at 0.0465 SLM
[0133] Algae oil feed was started, 0.185 ml/min (corresponding to
WHSV=1.0)
[0134] Total amount of reactant fed, 11.1 ml or 10 g
[0135] As usual, the total mass balance for each run was performed
based upon the difference between grams of reactant fed and product
collected. Product collected was separated into three parts: 1) the
gaseous product which was continuously measured by the micro-GC
system, 2) a condensed liquid product which was collected from the
reactor's effluent in a trap thermostatted at 0.degree. C., and 3)
the coke which was left on the catalyst.
[0136] Table 10 gives the overall mass balances obtained from algae
oil cracking over GaZSM-5 and HZSM-5. It can be seen clearly
GaZSM-5 produced more liquid and less gas compared to HZSM-5. The
detailed product analysis is discussed below.
Product Analysis
TABLE-US-00010 [0137] TABLE 10 Reaction Conditions and Mass
Balances for Algae Oil in Example III (reactant in each experiment
being 10 grams) Products- Vapor Liquid Solid Total Feed Experiment
Temp Products Products Products Products Difference Number Catalyst
(.degree. C.) (g) (g) (g) (g) (%) SAP383 GaZSM-5 400 3.84 5.59 0.77
10.20 2.0 SAP384 HZSM-5 400 4.62 4.97 0.67 10.26 2.6
[0138] In the gas phase product (see FIG. 7), the C1-C3 paraffin
yield decreased with the addition of gallium to the catalyst. For
example, the propane yield decreased from 14.0 wt % to 6.4 wt %.
GaZSM-5 gave a 2.0 wt % yield of hydrogen, compared to HZSM-5
giving only 0.5 wt % yield of hydrogen.
[0139] The liquid products were also analyzed by GC-MS to quantify
the BTEX content. Gasoline yield was obtained via simulated
distillation. GaZSM-5 produced almost 40.8 wt % yield of BTEX in
the liquid product, compared to HZSM-5 producing 34.1 wt % yield of
BTEX. By the simulated distillation, GaZSM-5 gave 42.4 wt % yield
of gasoline in the liquid and HZSM-5 gave 38.1 wt %. By adding
gallium to the HZSM-5 catalyst, BTEX yield and gasoline yield were
increased by 6.7 wt % and 4.3 wt %, respectively, in the liquid
phase. It also showed that BTEX are the major products in the
gasoline for these two materials. For the GaZSM-5, the composition
of BTEX in the gasoline is as high as 96.4%, compared to 89.6% for
the HZSM-5.
[0140] In previous experiments, the actual components corresponding
to hexanes+ were identified, which are reported by the gas analysis
instrument (the micro-GC), and that species turns out to be almost
pure benzene. This makes sense since the C.sub.6 fraction in the
collected liquid product is almost exclusively benzene (as
determined by GC-MS), and since the off-gas is nearly in
vapor-liquid equilibrium with the collected liquid. Therefore, if
the hexanes+ yield from the vapor phase is determined and added
into the benzene yield in the liquid phase, the overall yields from
the two catalysts may be calculated.
[0141] FIG. 8 shows the overall yields obtained from these two
catalysts. For the GaZSM-5 material, the overall BTEX yield and
gasoline range product yield were 46.8% and 48.3%, respectively,
with 96.9% of gasoline range molecules being BTEX. The composition
of BTEX in the liquid product (including hexanes+) was 83.6%. These
excellent yields may be compared to those for HZSM-5, which were
38.9% overall BTEX yield and 42.9% gasoline yield. For HZSM-5,
90.7% of the gasoline fraction was BTEX, and 78.2% of the total
liquid product (including hexanes+) was BTEX. Therefore, FIG. 8
shows that the total BTEX yield ("overall BTEX yield") was
increased by 7.9% by adding gallium to the HZSM-5, and gasoline
yield was also increased by 5.4%.
Conclusions from Example III, and Comparison of Example I (Canola
Oil) and Example III (Algae Oil)
[0142] Adding gallium to HZSM-5 increases BTEX yield and gasoline
yield for algae oil cracking at 400.degree. C. GaZSM-5 also
produced significantly more hydrogen than HZSM-5, which is
consistent with an increased aromatics production.
[0143] One may compare the results from cracking canola oil vs.
algae oil, on the preferred catalyst (GaZSM-5, 1.0 Ga/framework-Al
in the zeolite), by reviewing Example I (Run SAP281) and Example
III (SAP383). These two runs used a single reactor and
substantially the same conditions operating conditions and
catalyst, but Example I, SAP281, processed only canola oil and
Example III, SAP 383, processed only algae oil. Note that both
SAP281 and SAP383 were both conducted at 400 degrees C. reactor
temperature. Cracking of canola oil with the preferred
gallium-doped catalyst produced a BTEX yield of 39.3 wt-% and a
gasoline range (60-225 degrees C.) yield of approximately 43 wt-%.
On the other hand, cracking of algae oil with the preferred
gallium-doped catalyst produced a BTEX yield of 46.8 wt-% and a
gasoline range (60-225 degreed C) of 48.3 wt-%. Thus, under the
same or substantially the same process, it is remarkable that algae
oil produced 7.5 wt % more BTEX and approximately 5 wt-% more
gasoline, compared to canola oil.
Example IV
Catalytic Conversion of Fossil Petroleum Gas Oil Over Ga/ZSM-5 and
HZSM-5
[0144] This Example describes the catalytic cracking of gas oil
(from Conoco Phillips) over HZSM-5 and Ga-doped ZSM-5 (GaZSM-5) at
400 degrees C., for comparison to canola oil and algae oil results
from Examples I and III. The goal of this work was to compare the
formation of aromatics between these two catalysts, specifically
benzene, toluene, and xylenes (BTEX), for fuel blending, or for use
as feedstocks in the chemical industry. It was observed that
Ga/ZSM-5 produced more BTEX and less paraffins (especially propane)
compared to HZSM-5 gas oil cracking at the same reaction
temperature. However, the boost in BTEX yield when Ga was added to
the catalyst was much greater for the renewable oils (algae and
canola oils) and the overall gasoline yields are also greater for
the renewable oils.
Experimental
[0145] GaZSM-5 was made according to the method reported in Example
I, but the only gallium loading level that was used in this Example
corresponded to 1.0 Ga/framework-Al in the zeolite (Ga/ZSM-5). The
base ZSM-5 material was used in its fully protonated form
(H-ZSM-5). Because H-ZSM-5 gave the highest BTEX yield at 400
degrees C. for algae oil feedstock in Example III, the gas oil
cracking experiments of this Example were also done at this
temperature. The Ga/ZSM-5 catalyst was activated at 500 degrees C.
under a 100 ml/min stream of 30% hydrogen in nitrogen for at least
1 hour. This activation process is known to accelerate the
ion-exchange of Ga cations for protons in the zeolite. For H-ZSM-5,
as usual, the catalyst was dried at 400.degree. C. with nitrogen
flow rate of 46.5 ml/min for 2 hours prior to utilization as a
cracking catalyst. The density of the gas oil was calculated to be
0.88 g/ml, so that 10 g of gas oil corresponded to 11.4 ml and the
gas oil flow rate was 0.189 ml/min to correspond to WHSV=1.0.
[0146] The gas oil cracking experiments may be summarized as
follows:
[0147] a) 10 g of the zeolite catalyst was loaded into the
reactor;
[0148] b) Reactor was loaded into the furnace;
[0149] c) N2 flow was established (46.5 ml/min);
[0150] d) For Ga/ZSM-5, the reactor was brought to 500.degree. C.,
and the catalyst was activated;
[0151] e) 30% Hydrogen flow in nitrogen for 1 hr;
[0152] f) Reactor temperature was then decreased to reaction
conditions;
[0153] g) Reactor temperature was set to 400.degree. C.;
[0154] h) Gas oil feed was started, 0.189 ml/min (corresponding to
WHSV=1.0); and
[0155] i) Total amount of reactant fed, 11.4 ml.
[0156] The total mass balance for each run was performed based upon
the difference between grams of reactant fed and product collected.
Product collected is separated into three parts: 1) the gaseous
product which, is continuously measured by the micro-GC system, 2)
a condensed liquid product which, was collected from the reactor's
effluent in a trap and glass adapter at 0.degree. C., and 3) the
coke which, is left on the catalyst and simply measured by mass
difference between the fresh and used catalyst. Table 11 gives the
overall mass balances obtained from gas oil cracking over Ga/ZSM-5
and H-ZSM-5. It can be seen clearly Ga/ZSM-5 produced more liquid
and less gas compared to H-ZSM-5. The detailed product analysis is
discussed below.
TABLE-US-00011 TABLE 11 Mass Balance and Reaction Conditions for
Gas Oil Cracking Experiments Vapor Liquid Solid Total Temp Reactant
Product Product Product Product Experiment Catalyst (.degree. C.)
(g) (g) (g) (g) (g) Difference SB_SAP001 HZSM-5 400 10.00 2.91 6.71
0.77 10.39 3.9% SB_SAP002 GaZSM- 400 10.00 1.95 7.31 0.77 10.02
0.2% 5 (1:1)
Products Analysis
[0157] FIG. 9 shows the gas phase products produced during cracking
of gas oil. It is clear that the C1-C3 paraffin yield decreased
with doping of the zeolite with gallium, and the amount of propane
decreased by a factor of three. It is also clear that a higher
amount of hydrogen product was present in the run utilizing
Ga/ZSM-5 compared to the run utilizing H-ZSM-5. The increased
hydrogen product with the gallium-doped zeolite correlated well
with the previous work involving algae (Example III) and canola oil
(Example I) cracking over Ga/ZSM-5, showing that an increased
amount of BTEX is formed through the addition of Ga.
[0158] In the previous Examples, the actual components
corresponding to Hexanes+ were identified by micro-GC to be almost
pure benzene. This was considered reasonable, because the C6
fraction in the collected liquid product was almost exclusively
benzene, as determined by GC-MS, and because the off gas is nearly
in vapor-liquid equilibrium with the collected liquid. Therefore,
for this Example, if we take the Hexanes+ yield from the vapor
phase, and add it into the benzene yield in the liquid phase, the
overall yields from the two catalysts can be calculated.
[0159] The liquid products were also analyzed by GC-MS to quantify
the BTEX content, and these results are included in Table 12,
below. For comparison purposes, results from cracking of canola oil
(Example I) and cracking of algae oil (Example III) are also
included in Table 12. For comparison purposes, the results from
cracking of gas oil (this Example) are plotted beside the results
from cracking of algae oil (Example III) in FIG. 10. Regarding the
gas oil feedstock, Ga/ZSM-5 produced 40.64% yield of BTEX in the
liquid product, compared to a 39.24 wt % yield by the H-ZSM-5.
Adding Ga to H-ZSM-5 caused the BTEX yield from gas oil to increase
by only 1.6 wt %, compared to about a 7% improvement in BTEX yield
when Ga was added to the catalyst for the canola and algae oil
feedstocks. The data also showed that BTEX were the major products
in the gasoline for this feed stock.
TABLE-US-00012 TABLE 12 Yields of benzene, toluene, ethylbenzene,
xylenes, total BTEX, and Gasoline in wt % for various feed stocks
and catalysts. All experiments run at 400.degree. C. and WHSV =
1.0. Canola Oil Algae Oil Gas Oil 1.0 Ga- H- 1.0 Ga- H- 1.0 Ga- H-
Catalyst ZSM-5 ZSM-5 ZSM-5 ZSM-5 ZSM-5 ZSM-5 Benzene 8.38 7.45
10.74 7.65 13.96 10.44 Toluene 19.31 15.40 19.03 15.46 18.59 18.35
m-, p-Xylene 8.10 6.32 7.14 6.95 5.24 6.69 o-Xylene 2.28 1.78 2.08
2.04 1.56 1.99 Ethylbenzene 1.20 1.35 1.83 2.02 1.30 1.82 BTEX
39.27 32.29 40.82 34.12 40.64 39.29 Gasoline 43.63 37.67 48.86
42.86 48.65 48.56
[0160] A simulated distillation of the Conoco Phillips gas oil is
compared to the simulated distillation of algae oil in FIG. 11.
Simulated distillation of the canola oil is not shown in FIG. 11
because canola oil breaks down before it vaporizes. These feedstock
simulated distillation curves may be compared to the product
simulated distillations that are given in FIG. 12. Gasoline yields
of each of the products from gas oil, canola oil, and algae oil
over the H-ZSM-5 and GaZSM-5 catalysts were also obtained via
simulated distillation, and these results are included in the last
line of Table 12. It may be noted that, when the feedstock was gas
oil, addition of Ga had virtually no effect on the gasoline yields,
which were about 48% in both cases. However, for the renewable
oils, a significant effect of the addition of Ga was noted.
[0161] FIG. 12 also shows how much different the products from the
various feedstocks were. The renewable oils produced much lighter
liquid products than the gas oil produced. Furthermore, since the
algae oil and canola oil feedstocks were heavier than gas oil, a
much greater disparity in the overall reduction in boiling point
distribution of the feedstock resulted when the renewable oils were
the feedstocks.
Conclusions from Example IV
[0162] It may be concluded that, in the gas oil cracking processes
of this Example, the addition of Ga did increase the overall BTEX
yield slightly but it had little to no effect on the overall
gasoline yield. This was in contrast to the same experiments using
canola (Example I) and algae oil (Example III), where large yield
increases in BTEX and gasoline were seen when Ga was added to the
catalyst. Also, liquid products from the renewable oils were much
lighter than the liquid products from gas oil, leading to a
conclusion that, overall, the renewable oils were easier to crack.
Thus, it may be said that the gallium-modification produced a
surprising result in terms of increased BTEX yields and gasoline
yields from renewable oils, including algae oil, while the
gallium-modification had little or no effect on BTEX and gasoline
yields from gas oil. The little or no effect on gas oil may suggest
that providing a gallium-cation catalyst additive to an FCC unit
may be effective in increasing aromatics production from the algae
oil or other renewable oil while not harming BTEX and gasoline
yields from the gas oil to any significant extent.
Example V
FCC Cracking of Algae Oil
[0163] In a loaded-in-part (gallium-cation catalyst) and
fed-in-part (algae oil) FCC operation, the majority of the FCC
catalyst would be maintained as conventional FCC cracking catalyst
(such as Y zeolite) and the majority of the feedstock would be
maintained as a conventional FCC feed (such as gas oil/vacuum gas
oil). Therefore, the yield structure and coke-on-catalyst obtained
from algae oil, under conventional FCC conditions and with
conventional FCC catalyst, are of great interest. This Example
illustrates certain embodiments of fluid catalytic cracking of
algae oil compared to fluid catalytic cracking of vacuum gas oil.
For additional information regarding the structure and function of
a conventional FCC unit, refer to Example VIII and FIG. 23.
[0164] An algae oil was obtained from Nannochloropsis salina by HTT
hydrothermal-treatment and heptane solvent extraction, according to
method steps a-j listed above in the section entitled "Alternative
Techniques of Obtaining Crude Algae Oil from Biomass". The
hydrothermal treatment step (step b in the method listed above) was
conducted at 260 C for 0.5 hour. See the "Algae Oil Feed" analysis
in Tables 4-6, above.
[0165] The algae oil feed was catalytically cracked in a Micro
Catalytic Cracking (MAT) system. MAT equipment and tests are well
known in petroleum refining R & D, and have been designed and
evolved over the years to be highly correlated with large-scale
fluidized catalytic cracking (FCC) units. The predictive ability of
MAT tests is rather remarkable considering they require only grams
of feed, whereas commercial FCC units can process over 100 mbpd of
feed. The MAT tests, like commercial FCC units, operate at cracking
temperatures of about 1000 degrees F. and with very short
catalyst-feed contact times (1-5 seconds), and use zeolite-based
catalysts at atmospheric pressure.
[0166] In this Example, MAT testing was used to compare FCC
processing of algae oil feed ("crude algae oil") and FCC processing
of a reference petroleum feedstock from a European refinery,
specifically, a petroleum-derived vacuum gas oil (VGO) containing
roughly 10 mass % resid, having an API of 22, and a sulfur level of
0.61 wt %. Table 13, below, shows the yield structure in MAT
testing of the standard VGO (first column of data) and the algae
oil feed (second column of data), with the difference calculated
and shown in the third data column.
TABLE-US-00013 TABLE 13 FCC MAT Testing of Extracted Algae Oil Feed
compared to Standard VGO Feed Yields (wt %) Difference Standard
Extracted Algae Oil Algae Oil - VGO Feed Feed VGO C/O ratio 1.981
2.008 0.026 Conversion 50.514 49.885 -0.629 Gasoline
(C5-421.degree. F.) 40.623 29.286 -11.337 Coke yield 2.296 10.047
7.751 LCO yield 18.236 35.631 17.395 LPG yield 6.001 5.536 -0.465
H2 + C1 + C2 + H2S 1.512 3.225 1.713 H2 + C1 + C2 1.512 3.225 1.713
T.C3 3.228 2.313 -0.916 T.C4 2.772 3.223 0.450 C4=/Tot. C4's 0.705
0.759 0.055 C3=/Tot. C3's 0.867 0.528 -0.340 H2 0.148 0.063 -0.085
H2S 0.000 0.000 0.000 CH4 0.544 1.030 0.486 C2+ 0.412 1.193 0.782
C2= 0.408 0.938 0.530 C3+ 0.428 1.092 0.664 C3= 2.800 1.221 -1.580
iC4+ 0.674 0.269 -0.405 nC4+ 0.145 0.506 0.361 iC4= 0.803 1.111
0.308 nC4= 1.150 1.337 0.187 C4= 1.953 2.447 0.494 C4== 0.082 0.000
-0.082 DCO 31.250 14.484 -16.766 wt % recovery 96.276 98.929
[0167] FIG. 13 compares the conversion (percent of the feed
converted to distillate and to lighter components such as gasoline,
plus coke) at a range of catalyst-to-oil ratios (C/O) for the algae
oil feed and the reference petroleum VGO feed. In this test, the
algae oil has approximately the same reactivity as the reference
VGO; this may be inferred by noting that the algae oil feed has a
comparable conversion of about 50% to the VGO at the same C/O
ratio.
[0168] FIG. 14 shows that the coke yield for the algae oil feed is
significantly higher than for the VGO. This is important because
commercial-scale FCC units operate in such a way that the heat
balance drives the conversion of feeds to lower levels when they
have high coke yields. Consequently, the algae oil feed of this
Example is expected to exhibit much lower conversion than VGO in
commercial units due to its high coke yield.
[0169] The yields of gasoline, LCO (distillate range material),
DCO, TC2, TC3, and TC4 from the algae oil and VGO are shown in
FIGS. 17-22, respectively. Note that the corresponding yields from
hydrotreated algae oils, in Example VII below, are also shown in
FIGS. 17-22, for study of the effect of hydrotreating prior to FCC
processing.
[0170] In an FCC unit, higher coke yields are favored by heavier
compounds (especially 1000 degrees F.+ material) and basic
nitrogen-containing compounds in the feed to the unit. The later
react with and poison the acidic catalytic sites in the zeolite
used as the cracking catalyst, thus making coke and also reducing
conversion. Oxygen-containing compounds may also contribute to
increased coke yields, and, separately, to lower conversions.
[0171] Therefore, in a catalytic cracking process, the algae oil
feed of this Example exhibits coke yields that may be problematic
for many FCC units. This suggests that inclusion of this
unhydrotreated algae oil feed in an existing FCC unit as a
significant percent of the total feed would lower the overall
conversion in the FCC unit (compared to the "base-line" operation
without the algae oil feed) due to the impact of the coke on the
unit heat balance. Therefore, certain unhydrotreated algae oils
(for example, certain unhydrotreated HTT hydrothermally-treated and
solvent-extracted algae oils), may be a concern regarding coke on
conventional FCC catalysts. This may impact certain embodiments of
gallium-cation catalyst loaded-in-part, and algae oil fed-in-part
FCC operations, for example, resulting in lower overall conversion
than the base-line FCC operation.
Example VI
Hydrotreating of Algae Oil, Followed by FCC Cracking of
Hydrotreated Algae Oil
[0172] Hydrotreatment of the algae oil feed of Example V was
performed at various conditions (Runs 4SEBR, 5 SEBR, and 6SEBR) to
obtain oil products. These experimental runs were conducted in a
semi-batch reactor (continuous flow of H2 while the oil and
catalyst remained in a well-stirred reactor at pressure and
temperature). At the end of each 1 hour residence time run, the oil
was removed and analyzed as a product sample called "oil product".
See the analysis of the three hydrotreated oil products, compared
to the algae oil feed (of Tables 4-6), in Tables 14-16, below.
TABLE-US-00014 TABLE 14 % Mass Fraction - Algae Oil Feed and
Hydrotreated Samples (4SEBR - 6SEBR) FRACTION MASS % Sample
Initial-260.degree. F. 260-400.degree. F. 400-490.degree. F.
490-630.degree. F. 630-1020.degree. F. 1020.degree. F. NS-263-061
Algae Oil Feed 0.0 0.5 1.3 6.6 64.1 27.5 4 SEBR-CFS 4:
Hydrotreated, 0.0 3.4 7.5 24.3 39.2 25.6 Ni/Mo 370.degree. C., 1000
psi H2 5 SEBR-CFS; Hydrotreated, 0.0 4.9 9.6 36.5 36.4 12.6 Ni/Mo
370.degree. C., 15000 psi H2 6 SEBR-CFS 6; Hydrotreated, 0.0 3.2
6.9 27.9 38.7 23.3 Ni/Mo 370.degree. C., 1800 psi H2
TABLE-US-00015 TABLE 15 Compound Classes - Summary for Algae Oil
feed and Hydrotreated Samples (4SEBR-6SEBR) Algae 6SEBR Class Oil
Feed 4SEBR CSF-4 5SEBR CSF-5 CSF-6 HC-Saturated 2.0 74.2 75.7 58.1
HC-Unsaturated 9.1 0.9 3.2 5.5 Naphthenes and 1.7 3.5 6.5 12.6
Aromatics N-Aromatics 8.6 0.7 0.2 1.2 Nitriles 0.0 0.0 0.0 0.0 Acid
Amides 10.9 0.0 0.0 0.0 Fatty Acids 25.9 0.0 0.0 0.0 Oxygen 1.3 4.8
2.1 5.6 Compounds Sterols 13.6 6.0 1.5 0.1 Sulfur 0.0 0.0 0.0 1.2
Compounds Unknowns 26.9 9.5 10.4 14.0
TABLE-US-00016 TABLE 16 Elemental Analysis - Algae/Oil Feed and
Hydrotreated Samples (4SEBR-6SEBR) wt % Algae Oil Feed 4-SEBR
5-SEBR 6-SEBR C 77.9 82.9 82.3 85.0 H 10.7 13.1 13.4 14.5 N 3.9 1.5
1.5 0.7 O 6.8 0.5 0.5 0.5 S 0.37 0.70 0.76 0.45
[0173] Three variations of catalytic hydrotreating were conducted
at the same temperature (370 degrees C.) with the same catalyst,
but at three pressures ranging from 1000 psi to 1800 psi.
Specifically, 4SEBR, 5SEBR, and 6SEBR were conducted at 1000 psig,
1500 psig, and 1800 psig pressure, respectively. The hydrotreatment
catalyst was a commercially-available NiMo/Al2O3 that had been
pre-sulfided and handled prior to the semi-batch reaction such that
re-oxidation did not occur. The NiMo/Al2O3 catalyst used for these
hydrotreating experiments was a sample of catalyst used for
processing Canadian oil sands, believed to have a pore structure
with BET surface area in the range of 150-250 m2/g, micropores in
the average diameter range of 50-200 Angstroms, and macropores in
the range of 1000-3000 Angstroms.
[0174] The oil products from Runs 4SEBR, 5SEBR, and 6SEBR were used
as feeds for catalytic cracking in the MAT system described above
in Example V. The procedures were consistent with those used for
the algae oil feed vs. VGO comparison of Example V, allowing
comparison of the data from Example V and this Example. The MAT
testing, as discussed above, is predictive of commercial FCC
performance. Limited oil product sample volume from 5SEBR resulted
in limited MAT data for algae oil hydrotreated at 1500 psig.
[0175] Table 17 shows the yield structure in MAT testing of the
standard VGO (first column of data) and of the
high-severity-hydrotreated oil (6SEBR, second column of data), with
the difference calculated and shown in the third data column.
TABLE-US-00017 TABLE 17 FCC MAT Testing of High-Pressure
Hydrotreated Algae Oil compared to Standard VGO Feed Yields (wt %)
Standard Difference VGO Feed 6SEBR 6SEBR - VGO C/O ratio 3.031
2.475 -0.556 Conversion 70.565 70.268 -0.298
Gasoline(C5-421.degree. F.) 48.613 44.357 -4.256 Coke yield 4.492
4.932 0.440 LCO yield 15.870 27.392 11.523 LPG yield 15.208 20.117
4.909 H2 + C1 + C2 + H2S 2.076 0.862 -1.214 H2 + C1 + C2 2.076
0.862 -1.214 T.C3 5.314 6.821 1.507 T.C4 9.894 13.296 3.402
C4=/Tot. C4's 0.679 0.652 -0.027 C3=/Tot. C3's 0.856 0.874 0.018 H2
0.211 0.097 -0.114 H2S 0.010 0.000 -0.010 CH4 0.718 0.230 -0.488
C2+ 0.587 0.146 -0.441 C2= 0.559 0.388 -0.170 C3+ 0.768 0.861 0.093
C3= 4.546 5.961 1.414 iC4+ 2.526 3.608 1.082 nC4+ 0.655 1.019 0.364
iC4= 2.225 2.752 0.528 nC4= 4.489 5.916 1.427 C4= 6.714 8.669 1.955
C4== 0.177 0.000 -0.177 DCO 13.565 2.340 -11.225 wt % recovery
97.786 104.828
[0176] FIG. 15 shows the reactivity of the three hydrotreated algae
oils, compared to the algae oil feed of Example V and VGO, in the
FCC process. The algae oil that had been hydrotreated at higher
severity (6SEBR, 1800 psig) showed superior reactivity compared to
the algae oils hydrotreated at lower severity (4 and 5SEBR), with
the higher-severity-hydrotreated oil being more reactive than the
VGO. That is, conversion of the high-severity-hydrotreated algae
oil in the MAT test is higher than that for VGO at the same C/O
range of about 2-2.5. The moderately-hydrotreated oil (5SEBR, 1500
psig) was about as reactive as the VGO, whereas the material
produced from hydrotreating at 1000 psi was, very surprisingly,
less reactive than the VGO and the crude algae oil feed.
[0177] As shown in FIG. 16, hydrotreating improved the coke yields
relative to those from the crude algae oil of Example V. The coke
yield from the 1800-psig-hydrotreated algae oil was similar to that
of the VGO at the same conversion of about 70 wt %.
[0178] The yields from the hydrotreated algae oils in the MAT
testing are included in FIGS. 17-22. Product yields are best
compared at similar conversions. Therefore, FIGS. 17-22 show weight
% yield key products (y-axis) plotted against conversion (x-axis)
as obtained by varying C/O. These key yields are discussed in the
following paragraph.
[0179] FIG. 17 shows that gasoline yields were lower from algae oil
feed of Example V and its hydrotreated counterparts (the oil
products from 4-6SEBR), compared to those from VGO at similar
conversions. FIG. 18 shows that distillate yields (LCO or "light
cycle oil") were higher from algae oil feed and its hydrotreated
counterparts, compared to those from VGO at similar conversions.
FIG. 19 shows that DCO yields ("decanted oil", the heaviest and
least-valued product from catalytic cracking) were markedly lower
for from algae oil feed (crude algae oil) and its hydrotreated
counterparts, compared to DCO from the VGO at similar conversions.
FIGS. 20-22 show the yields of specific components lighter than
gasoline, that is, TC2, TC3, and TC4.
[0180] The yield structure obtained by MAT (FCC) testing of the
high-severity-hydrotreated algae oil (6SEBR) suggest the
high-severity-hydrotreated algae oil may have a higher value than
VGO, even when the cost of the high-pressure hydrotreating is taken
into account. The higher distillate yields and reduction in
gasoline yields, along with the significant reduction of low-valued
DCO, all increase the value of the hydrotreated algae oil. It
should be noted that the lower coke-on-FCC-catalyst of the
high-severity-hydrotreated algae oil (6SEBR) helps the heat balance
in the FCC, which in turn improves conversion and yields.
[0181] Therefore, in certain embodiments, algae oil will be
hydrotreated prior to being upgraded in an FCC operation. According
to certain embodiments of aromatics and/or hydrogen production
disclosure herein, such an FCC operation would be characterized by
being loaded-in-part with gallium-cation-catalyst and fed-in-part
with algae-oil. Improved coke yields vs conversion for the
hydrotreated algae oil may affect the optimum catalyst and algae
oil percentages, but the gallium catalyst and algae oil percentages
described above (for example, 1-20 wt %, or 5-10 wt %) are expected
to be reasonable starting places for optimization of the
hydrotreated algae oil FCC embodiments.
[0182] Therefore, certain methods of upgrading algae oil may
comprise: [0183] a) obtaining a crude algae oil from algae biomass,
the crude algae oil being a full boiling range algae oil comprising
material in the boiling range of distillate (about 400-630 degrees
F.) and in the boiling range of gas oil (about 630-1020 degrees F.)
and in the boiling range of vacuum bottoms (about 1020 degrees F+),
wherein the total of the distillate plus gas oil boiling range
material is at least 55 wt %, and wherein certain embodiments of
this crude algae oil may be obtained, for example, from any of the
HTT hydrothermal-treatment and solvent extraction methods described
earlier in this document; [0184] b) hydrotreating the crude algae
oil over one or more hydrotreating catalysts adapted for
hydrotreatment of fossil petroleum resid/bitumen (including
oil/bitumen from oil sands or tar sands), and/or over one more
hydrotreating catalysts having a pore structure including
macro-pores and characterized by BET surface areas in the range of
150-250 m2/g, micropores in the average diameter range of 50-200
Angstroms, and macropores in the range of 1000-3000 Angstroms,
wherein said one or more hydrotreating catalysts may comprise Ni/Mo
and/or Co/Mo on alumina or silica-alumina supports having said pore
structure; [0185] c) wherein the hydrotreating conditions are in
the ranges of: 1000-2000 psig (and more typically 1500-2000 psig,
about 0.8-1.5 l/hr LHSV (more typically about 1 l/hr LHSV), 300-425
degrees C. (more typically 350-400 degrees C.), with typical
gas/oil ratios being at least 2000 scf/b; [0186] d) separating, by
conventional separation vessels/methods, the liquid hydrotreated
oil from the hydrotreater effluent, typically meaning separating
the liquid hydrotreated oil from hydrogen and gasses; and [0187] e)
sending the liquid hydrotreated oil or fractions thereof to a
processing unit that is an
[0188] FCC unit comprising at least some gallium-modified catalyst
selected from any of the gallium-catalyst embodiments described in
this disclosure, for example, at least some gallium-cation
catalyst.
[0189] Certain alternative embodiments may comprise step (b)
instead being: hydrotreating the crude algae oil over one or more
hydrotreating catalysts characterized by BET surface areas in the
range of about 150-250 m2/g, and comprising macropores of at least
1000 Angstroms, wherein said one or more hydrotreating catalysts
may comprise Ni/Mo and/or Co/Mo on alumina or silica-alumina
supports having said pore structure. Certain alternative
embodiments may comprise step (b) instead being: hydrotreating the
crude algae oil over one or more hydrotreating catalysts comprising
macropores in the range of at least about 1000 Angstroms. End
products from the above processes of this Example may include one
or more of BTX plant feedstock, gasoline, kerosene, jet fuel,
diesel fuel, or lube base stock, for example. Certain methods of
this Example may comprise, consist essentially of, or consist of
method steps a-e above. Algae oils/fractions may range from very
little to all of the feedstock for the processing unit(s) in steps
b and e above, for example, from about 0.1 volume percent up to 100
volume percent of the liquid feedstock being fed to said processing
unit(s). In many embodiments of step e above, however, the
hydrotreated oil derived from the crude algae oil will be a minor
portion of the entire FCC feedstock (for example, 1-20 wt % or 5-10
wt %) and the gallium-cation catalyst will be only a portion of the
entire FCC catalyst loading (for example, 1-20 wt % or 5-10 wt
%).
Example VII
Thermal-Treatment of Algae Oil, Followed by Hydrotreating and FCC
Cracking of Hydrotreated Algae Oil
[0190] Certain crude algae oils may be thermally treated prior to
being fed to FCC operations such as described in Example VI.
Because of the complex composition and/or the high molecular weight
materials of said certain algae oils extracted from biomass,
thermal treatment prior to processing in any catalytic unit may be
effective in reducing one or more of the following characteristics:
oxygen content and/or other heteroatom content, metals content,
high molecular weight content, 1000 degree F.+ content, 1020 degree
F.+ content, boiling range/distribution, viscosity, and/or catalyst
poisons and/or coke-on-catalyst precursors. In certain embodiments,
several of these characteristics are expected to be related to
catalyst deactivation due to poisoning of catalyst active sites
(such as acidic sites being poisoned by basic nitrogen compounds)
and/or producing coke-on-catalyst. In certain embodiments, thermal
treatment will reduce most or all of these characteristics.
[0191] Therefore, thermal treatment of whole crude algae oil
obtained from biomass is expected to mitigate catalyst deactivation
and/or coke-on-catalyst production caused by the crude algae oil,
thereby extending catalyst life in such units as a hydrotreater, or
improving heat balances in continuous catalyst regeneration systems
such as FCC units. The thermal treatment methods of this Example
may be used in conjunction with hydrotreating over large-pore
catalysts (see Example VI) to improve catalyst lives and/or heat
balances in downstream units.
[0192] In this Example, therefore, a thermal treatment method may
be applied to certain crude algae oils, the method comprising:
[0193] a) obtaining a crude algae oil from algae biomass (for
example, by any of the HTT processes described above), the crude
algae oil being a full boiling range algae oil comprising material
in the boiling range of distillate (about 400-630 degrees F.) and
in the boiling range of gas oil (about 630-1020 degrees F.) and in
the boiling range of vacuum bottoms (about 1020 degrees F+),
wherein the total of the distillate plus gas oil boiling range
material is at least 55 wt %; [0194] b) thermally treating the
crude algae oil (the whole crude algae oil) by heating the crude
algae oil to a temperature in the range of 300-450 degrees C., with
or without added gas or diluent(s), at a pressure in the range of
0-1000 psig (and more typically 0-300 psig), and holding the algae
oil at that temperature for a period of 0 minutes to 8 hours, and
more typically 0.25-8 hours or 0.5-2 hours; [0195] c) separating,
by conventional separation vessels/methods, liquid
thermally-treated oil from the thermal treatment effluent,
typically meaning separating the liquid thermally-treated oil from
hydrogen and gasses and from coke/solids; and [0196] d)
hydrotreating the thermal treatment effluent over one or more
hydrotreating catalysts adapted for hydrotreatment of fossil
petroleum resid/bitumen (including oil/bitumen from oil sands or
tar sands), and/or over one more hydrotreating catalysts having a
pore structure including macro-pores and characterized by BET
surface areas in the range of 150-250 m2/g, micropores in the
average diameter range of 50-200 Angstroms, and macropores in the
range of 1000-3000 Angstroms, wherein said one or more
hydrotreating catalysts may comprise Ni/Mo and/or Co/Mo on alumina
or silica-alumina supports having said pore structure; [0197] e)
wherein the hydrotreating conditions are in the ranges of:
1000-2000 psig (and more typically 1500-2000 psig, about 0.8-1.5
l/hr LHSV (more typically about 1 l/hr LHSV), 300-425 degrees C.
(more typically 350-400 degrees C.), with typical gas/oil ratios
being at least 2000 scf/b; [0198] f) separating, by conventional
separation vessels/methods, the liquid hydrotreated oil from the
hydrotreater effluent, typically meaning separating the liquid
hydrotreated oil from hydrogen and gasses; and [0199] g) sending
the liquid hydrotreated oil or fractions thereof to a processing
unit that is an FCC unit comprising at least some gallium-modified
catalyst selected from any of the gallium-catalyst embodiments
described in this disclosure, for example, at least some
gallium-cation catalyst.
[0200] End products from the above process may include one or more
of BTX plant feedstock, gasoline, kerosene, jet fuel, diesel fuel,
or lube base stock, for example. Certain methods of this Example
may comprise, consist essentially of, or consist of method steps
a-g above. Algae oils/fractions may range from very little to all
of the feedstock for the processing unit(s) in steps b, d, and g
above, for example, from about 0.1 volume percent up to 100 volume
percent of the liquid feedstock being fed to said processing
unit(s). In many embodiments of step g above, however, the
hydrotreated oil derived from the crude algae oil will be only a
portion of the entire FCC feedstock (for example, 1-20 wt % or 5-10
wt %) and the gallium-modified catalyst will be only a portion of
the entire FCC catalyst loading (for example, 1-20 wt % or 5-10 wt
%).
[0201] In alternative embodiments, the above steps of this Example
may be modified so that only a portion of the crude algae oil, such
as a heavy fraction, is thermally-treated, but both the
thermally-treated portion (minus any solids/coke and gasses formed
in the thermal treating) and the un-thermally-treated portion of
the crude algae oil are combined for hydrotreating and subsequent
fluid catalytic cracking.
Example VIII
Fluidized Bed Process Unit Commercial Application
[0202] Certain embodiments may comprise "spiking" relatively small
amounts of renewable oil(s) into a refinery unit previously
operating on non-renewable feedstocks, and providing at least some
gallium-cation catalyst in the unit. For example, by "relatively
small amounts" may be meant that the renewable oil may be added as
1-20 wt % (more typically 5-10 wt %) of a unit's feedstock, with
gallium-cation catalyst being added as 1-20 wt % (more typically
5-10 wt %) of the unit's catalyst. Such a "spiking" approach may be
particularly effective in an fluidized catalyst process unit, for
example, an FCC unit, as further described below.
[0203] As schematically illustrated in FIG. 23, conventional FCC
feedstock is heated and sprayed into the base of a riser (a
vertical or upward-sloped pipe), where the pre-heated feedstock
contacts fluidized zeolite catalyst typically at about 950 to 1030
degree F. (approximately 510 to 555 degree C.). The hot catalyst
vaporizes the feedstock and catalyzes the cracking reactions that
break down the high molecular weight hydrocarbons into lighter
components including LPG (liquid petroleum gas such as C3-C4
olefins), and acyclic or cyclic hydrocarbons (C5-C12). The
catalyst-hydrocarbon mixture flows upward through the riser for
just a few seconds (for example, 2-4 seconds) and then the mixture
is separated via cyclones. The catalyst-free hydrocarbons are
routed to a fractionation column for separating shorter hydrocarbon
products (for example, C3-C12 hydrocarbons) from the heavier fuels.
The shorter hydrocarbons, many of which are suitable as gasoline
products, are more volatile than the heavier fuels. The heavier
fuels include diesels and jet fuels that fractionally distill
between approximately 200 degree C. and 350 degree C. at
atmospheric pressure.
[0204] During the trip up the riser, the cracking catalyst is
"spent" by reactions that deposit coke on the catalyst and greatly
reduce activity and selectivity. The process of coke formation is
important to the overall process because it increases the H/C
(hydrogen to carbon) ratio of the gaseous products to a range more
suitable for gasoline. The spent catalyst is disengaged from the
cracked hydrocarbon vapors and sent to a stripper where it is
contacted with steam to remove hydrocarbons remaining in the
catalyst pores. The spent catalyst then flows into a fluidized-bed
regenerator where air (or in some cases air plus oxygen) is used to
burn off the coke to restore catalyst activity and also provide the
necessary heat for the next reaction cycle. The regenerated
catalyst then flows to the base of the riser, repeating the
cycle.
[0205] Catalyst and additives are typically added to FCC units
using systems each comprising a bin and a lock hopper. The minimum
catalyst addition rates are determined by the physical attrition
and loss of the FCC catalyst as fines that escape capture in the
cyclone systems in both the regenerator flue gas and the oil that
goes from the riser/reactor to the main fractionators. Thus,
catalyst fines show up in the slurry oil that is also sometimes
called decant oil or DCO. Catalyst/additives are added to the FCC
at rates above this physical loss depending on the activity for
conversion and yields that are desired in the FCC. For example, if
a higher activity of catalyst/additive is required, fresh
catalyst/additive will be added at a higher rate. Because this rate
exceeds the physical loss of catalyst/additive, some catalyst in
the unit (the "inventory" of equilibrium catalyst/additive) will
need to be removed to maintain the inventory of catalysts/additive
constant. The inventory of catalyst in the unit is often called
"equilibrium" catalyst/additive because it comprises
catalyst/additive of various ages and activities due to its being
added over time into the unit. This removal of inventory
(equilibrium catalyst/additive), like the addition, is done with
bins and a lock hopper system with the ability to pneumatically
carry the catalyst/additives from the regenerator to eventual
disposal. Both the FCC catalyst and additive systems are based on
the same principles, but are mechanically separate systems so their
addition rates can be independently varied for optimization of both
and therefore the system as a whole.
[0206] The modifications to such a conventional FCC cracking
process to include aromatics production from the renewable oils
according to this invention are expected to be minimal when the
renewable oil(s) and gallium-cation catalyst are in the 1-20 wt %
or 5-10 wt % ranges as discussed earlier in this document.
Conventional FCC cracking catalyst would be maintained as the
majority component of the catalyst contained in the unit, for
example, as 80-99 wt % or 90-95 wt % of the catalyst (when
gallium-cation catalyst is provided as 1-20 wt % or 5-10 wt %,
respectively). The gallium-cation catalyst would be added or
removed as desired by means of the additive bin and lock hopper
system described above. However, some modifications in contact
time, temperature and/or catalyst to oil ratios, for example, may
be made. While it may be desirable to lower FCC catalyst-contact
temperature, in view of the gallium-cation catalyst in the Examples
exhibiting its optimum performance at approximately 400 degrees C.,
it may not be possible to do this in view of most FCC operations on
gas oil and/or heavy gas oil requiring 510-555 degrees C.
Example IX
Purpose-Built Process Unit Commercial Application
[0207] In certain embodiments, a refinery unit may be purpose-built
for processing solely renewable oil(s) over catalyst that is only,
or substantially, a gallium-cation catalyst, to produce excellent
yields of BTEX and/or gasoline and hydrogen. One such purpose-built
unit may be similar to a UOP Cyclar.TM. unit, which comprises a
moving bed of said gallium-cation catalyst and a coke-burning
regeneration section, as schematically portrayed in FIG. 24. Or,
for example, a purpose-built fixed-bed reactor unit may be
effective. Regeneration in both units may be limited to solely
coke-burning followed by reduction during normal operation in the
reactor.
[0208] Both units would be optimized with respect to temperature,
pressure, flowrates, gallium loading, etc., as would be understood
by those of skill in the art. In certain embodiments of a packed
mode configuration at WHSV=1.0, the reactor would be operated at
350-450 degrees C., and more preferably at about 400 degrees C.
Other contacting configurations and conditions may yield optimum
temperatures of 450-500.degree. C., especially with WHSV>1.0.
These purpose-built units would preferably operate on 80-100 wt %,
and more preferably 90-100 wt % renewable oil(s), for example,
algae oil, with the catalyst being 80-100 wt %, or more preferably,
90-100 wt %, gallium-cation-retaining catalyst. Information
regarding conventional UOP Cyclar.TM. units may be obtained from
UOP, Des Plaines, Ill., U.S.A. Information regarding fixed-bed
reactor units may be obtained from several petroleum refinery unit
design companies.
[0209] It may be noted from the above detailed description,
including Example I-IX, that many embodiments may be described as a
process for producing BTEX or gasoline, the process comprising:
contacting, at elevated temperature, a feedstock comprising at
least one renewable oil with a catalyst comprising a
catalytically-active form of gallium to produce a product stream
comprising BTEX. The renewable oil may be canola oil, algae oil,
algae oil extracted from a green alga or a blue-green alga, or
other renewable oil(s), or fractions thereof, for example. It may
be noted from the data herein that certain embodiments of the
process the renewable oil is canola oil, that BTEX may be in said
product stream in a yield of greater than 35 wt-%. It may be noted
from the data herein that certain embodiments of the process the
renewable oil is algae oil, that BTEX may be in said product stream
in a yield of greater than 42 wt-%. In certain of these
embodiments, said product stream comprises a yield of greater than
15% wt-% Benzene. Said catalyst may a zeolitic catalyst that is
gallium-modified to comprise gallium cations in a ratio of about
1/1 Ga/framework-Al, for example. Said contacting may done in many
reactors/vessels/risers, for example: in a single reactor, a series
of reactors, a series of at least a first reactor and a second
reactor, wherein liquid is removed from the intermediate product
stream between the first and second reactors, and vapor from the
first reactor is fed to said second reactor, a fixed-bed reactor,
in a moving catalyst bed, and/or a riser of a fluidized catalytic
cracking unit, for example. In certain embodiments of contact
taking place in a riser, the contacting may take place at 510 to
555 degree C. temperature or at 400-555 degrees C. temperature, for
example. Said contacting may take place for 2-4 seconds. In certain
embodiments, said renewable oil is algae oil that has not been
processed between being extracted from algae and said contacting.
In certain embodiments, said algae oil has been processed in a RBD
process and/or a degumming process, but in certain embodiments the
algae oil has not been processed in a RBD process and/or a
degumming process. In certain embodiments said algae oil has been
hydrotreated prior to said contacting. In certain embodiments, the
catalyst may be a gallium-doped form of one or more zeolite-alumina
matrix catalysts with pore sizes having 10 oxygen atoms in the pore
mouth, for example, selected from the group consisting of: ZSM-5,
ZSM-11, ZSM-23, MCM-70, SSZ-44, SSZ-58, SSZ-35, and ZSM-22. Certain
embodiments may be described as: a process for producing aromatics
(for BTEX feedstocks or for gasoline, for example) and/or hydrogen
from renewable oil, the process comprising: providing a reactor
vessel or riser containing catalyst, said catalyst comprising a
gallium-cation catalyst; and contacting a feedstock with said
catalyst at elevated temperature; wherein said feedstock comprises
renewable oil selected from the group consisting of: oil derived
from biomass living in the past 50 years; canola oil; oils
extracted from vegetables including corn, soybean, sunflower, and
sorghum; algae oil from naturally-occurring algae; algae oil from
genetically modified algae; oil from seeds; oil from fungi; and oil
from a photosynthetic or non-photosynthetic bacteria. Said
renewable oil may be various percentage of the entire feedstock to
these various processes, for example, in the range of about 1 wt %
(or even less, for example, 0.01 wt %) up to 100 wt % of said
feedstock. For example, said renewable oil may 1-20 wt %, 50-100 wt
%, 80-100 wt % of said feedstock, or 90-100 wt % of the total
feedstock. The catalyst comprising a catalytically-active form of
gallium and/or the gallium-cation catalyst mentioned above may, in
certain embodiments, comprise any percentage of the total catalyst
of the process, for example 1 wt % (or even less, for example, 0.01
wt %) up to 100 wt % of said feedstock. For example, the catalyst
comprising a catalytically-active form of gallium and/or the
gallium-cation catalyst may be 1-20 wt %, 50-100 wt %, 80-100 wt %,
or 90-100 wt % of said feedstock. In some embodiments, the weight
percentage of catalyst comprising a catalytically-active form of
gallium and/or the gallium-cation catalyst in the reactor vessel or
riser will be equal to the weight percentage of renewable oil in
the feedstock to the process. In certain embodiments, the riser is
a fluidized catalytic cracking unit (FCC) riser and the catalyst
further comprises a Y-Zeolite FCC catalyst in said riser, so that
the FCC operates on catalyst/additives comprising catalyst
comprising catalytically-active form of gallium and/or the
gallium-cation catalyst, Y-zeolite, and optionally other
conventional FCC additives. In certain embodiments, the reactor
vessel is a moving-bed vessel adapted so that said catalyst moves
through the reactor vessel by gravity. In certain embodiments, the
temperature of contact with the catalyst is an elevated temperature
is in the ranges of 375-425 degrees C. or 350-555 degrees C., but
in other embodiments, it may be different from these ranges based
on the requirements of catalysts with which the gallium catalyst is
mixed. Of particular interest in certain embodiments are renewable
oil(s) obtained from non-vascular photosynthetic organism(s), for
example, naturally-occurring algae or cyanobacteria, or
genetically-modified algae or cyanobacteria. In certain
embodiments, the renewable oil mixed or otherwise combined with
other components that are selected from the group consisting of:
one or more fossil oil fractions, one or more refined fossil oil
products or fractions, naphtha, gasoline, jet fuel, diesel, and any
combination thereof. Certain embodiments of the invention may
comprise any renewable oil product made by an upgrading process
comprising any of the processes described above, for example, a
BTEX-rich stream for a petrochemical plant or other uses, or
gasoline and/or other fuels.
[0210] In the this Description, ranges of temperature, holding
time/residence time/LHSV, gas to oil ratios, BET surface in m2/g,
pore sizes in Angstroms, pressure in psig, and/or other ranges of
variables, are given for many embodiments of the invention. It
should be understood that the ranges are intended to include all
sub-ranges, and to include each incremental amount of temperature,
holding time/residence time/LHSV, gas to oil ratios, BET surface in
m2/g, pore sizes in Angstroms, pressure in psig, and other
variable, within each broad range given. For example, while a broad
range of pressure of 1000-2000 psig is mentioned, certain
embodiments may include any of the following sub-ranges or any
pressure within any of the following sub-ranges: 1000-1050,
1050-1100, 1100-1150, 1150-1200, 1200-1250, 1250-1300, 1300-1350,
1350-1400, 1400-1450, 1450-1500, 1500-1550, 1550-1600, 1600-1650,
1650-1700, 1700-1750, 1750-1800, 1800-1850, 1850-1900, 1900-1950,
and 1950-2000 psig. For example, while broad ranges of 300-425,
300-450, and 350-555 degrees C. are mentioned, certain embodiments
may include any temperature within any of these ranges, or any 10
degrees C. sub-ranges, for example. Examples of 10 degrees
sub-ranges for the range of 300-450 degrees C. are: 300-310,
310-320, 320-330, 330-340, 340-350, 350-360, 360-370, 370-380,
380-390, 390-400, 400-410, 410-420, 420-430, 430-440, 440-450
degrees C. Examples of 10 degrees sub-ranges for the range of
350-555 degrees C. are: 350-360, 360-370, 370-380, 380-390,
390-400, 400-410, 410-420, 420-430, 430-440, 440-450, 450-460,
460-470, 470-480, 480-490, 490-500, 500-510, 510-520, 520-530,
530-540, 540-550, and 545-555 degrees C.
[0211] Also included this disclosure, wherein values such as
degrees, mass percent or weight percent are written or shown in
Tables or Figures, are those values but with "about" inserted
before each value, as one of average skill in the art will
understand that "about" these values may be appropriate in certain
embodiments of this disclosure.
[0212] While certain embodiments have been shown and described
herein, it will be obvious to those skilled in the art that such
embodiments are provided by way of example only. Numerous
variations, changes, and substitutions will now occur to those
skilled in the art without departing from the disclosure. It should
be understood that various alternatives to the embodiments
specifically described herein may be employed in practicing the
invention, and that the invention extends to all equivalents within
the scope of the following claims.
* * * * *