U.S. patent application number 15/062059 was filed with the patent office on 2016-09-08 for pre-processing bio-oil before hydrotreatment.
The applicant listed for this patent is Battelle Memorial Institute. Invention is credited to Zia Abdullah, Daniel Garbark, Guo-Shuh J. Lee, Rachid Taha, Huamin Wang.
Application Number | 20160257889 15/062059 |
Document ID | / |
Family ID | 56848195 |
Filed Date | 2016-09-08 |
United States Patent
Application |
20160257889 |
Kind Code |
A1 |
Abdullah; Zia ; et
al. |
September 8, 2016 |
Pre-processing Bio-oil Before Hydrotreatment
Abstract
Described are methods and systems for preparing stabilized
bio-oil suitable for subsequent hydrotreatment and forming a
hydrocarbon product from a stabilized bio-oil. For example,
preparing stabilized bio-oil suitable for subsequent hydrotreatment
may include filtering bio-oil effective to remove at least a
portion of particles having an effective particulate diameter
greater than about 10 micrometers; treating the bio-oil effective
to remove at least a portion of inorganic species from the bio-oil;
and catalytically stabilizing the bio-oil to provide the stabilized
bio-oil suitable for subsequent hydrotreatment. Forming a
hydrocarbon product from a stabilized bio-oil may include
hydrotreating the stabilized bio-oil by, for example, contacting
the stabilized bio-oil to a hydrotreatment catalyst in the presence
of hydrogen, thereby providing the hydrocarbon product. Also
included are stabilized bio-oil and hydrocarbon products derived
therefrom.
Inventors: |
Abdullah; Zia; (Columbus,
OH) ; Taha; Rachid; (Dublin, OH) ; Garbark;
Daniel; (Blacklick, OH) ; Wang; Huamin;
(Richland, WA) ; Lee; Guo-Shuh J.; (Richland,
WA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Battelle Memorial Institute |
Columbus |
OH |
US |
|
|
Family ID: |
56848195 |
Appl. No.: |
15/062059 |
Filed: |
March 5, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62245423 |
Oct 23, 2015 |
|
|
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62129007 |
Mar 5, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 3/46 20130101; C10G
2300/1011 20130101; C10G 3/50 20130101; Y02P 30/20 20151101 |
International
Class: |
C10G 3/00 20060101
C10G003/00 |
Goverment Interests
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY-SPONSORED
RESEARCH AND DEVELOPMENT
[0002] This invention was made with Government support under
Contract Nos. DE-AC0576RLO1830 and DE-EE0004391, awarded by the
U.S. Department of Energy. The Government has certain rights in the
invention.
Claims
1. A method 200 for forming a stabilized bio-oil suitable for
subsequent hydrotreatment, comprising: 202 providing the bio-oil;
204 filtering the bio-oil effective to remove at least a portion of
particles having an effective particulate diameter greater than
about 10 micrometers; 206 treating the bio-oil effective to remove
at least a portion of inorganic species from the bio-oil; and 208
catalytically stabilizing the bio-oil, thereby providing the
stabilized bio-oil suitable for subsequent hydrotreatment.
2. The method of claim 1, providing the bio-oil comprising
pyrolyzing biomass to produce the bio-oil in a downflow
reactor.
3. The method of claim 1: providing the bio-oil comprising
pyrolyzing the biomass in a downflow reactor to produce a bio-oil
vapor; and filtering the bio-oil comprising in-line filtering the
bio-oil vapor produced by the pyrolysis effective to remove at
least a portion of the particles having the effective particulate
diameter greater than about 10 micrometers.
4. The method of claim 1, filtering the bio-oil comprising: a first
filtering process effective to remove at least a portion of the
particles having an effective particulate diameter greater than
about 10 micrometers; and a second filtering process effective to
remove at least a portion of the particles having an effective
particulate diameter in micrometers greater than one or more of
about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3,
0.2, and 0.1.
5. The method of claim 4, the second filtering process conducted
using one or more of: a pressure differential in pounds per square
inch of at least about one or more of: 5, 10, 15, 20, 30, 40, 50,
60, 70, 80, 90, 100, 125, 150, 175, and 200; and a temperature in
.degree. C. of at least about one or more of: 30, 40, 50, 60, 70,
80, 90, and 100.
6. The method of claim 1, treating the bio-oil effective to remove
at least a portion of inorganic species from the bio-oil comprising
contacting the bio-oil to one or more of: an ion exchange resin, a
zeolite, and activated carbon.
7. The method of claim 1, treating the bio-oil effective to remove
at least a portion of inorganic species from the bio-oil comprising
reducing the amount of one or more inorganic species in the bio-oil
to a concentration in parts per million of less than one or more of
about: 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1.
8. The method of claim 1, catalytically stabilizing the bio-oil
comprising contacting the bio-oil to a stabilizing catalyst
comprising a metal dispersed on a solid support.
9. The method of claim 1, further comprising: contacting the
bio-oil to a diluting medium to form a diluted bio-oil, and
catalytically stabilizing the bio-oil comprising contacting the
diluted bio-oil to a stabilizing catalyst.
10. The method of claim 9, the diluting medium comprising one or
more of: an organic solvent, a petroleum fuel, water, and a portion
of the stabilized bio-oil.
11. The method of claim 10, further comprising removing at least a
portion of the solvent comprising one or more of: the organic
solvent, the petroleum fuel, and the water from the diluted bio-oil
after catalytically stabilizing the diluted bio-oil.
12. The method of claim 1, catalytically stabilizing the bio-oil
comprising contacting the bio-oil to a stabilizing catalyst
comprising a zeolite.
13. The method of claim 1, catalytically stabilizing the bio-oil
comprising contacting the bio-oil to a stabilizing catalyst under
conditions comprising one or more of: a temperature in .degree. C.
of about one or more of: 40 to 300, 100 to 280, 120 to 270, 130 to
250, 140 to 225, 150 to 200, 160 to 180, and 170; a pressure in PSI
of about one or more of: 500 to 2500, 750 to 2250, 1000 to 2000,
1250 to 1750, 1400 to 1600, and 1500; and a presence of
hydrogen.
14. The method of claim 1, catalytically stabilizing the bio-oil
comprising one or more of: flowing the bio-oil past a stabilizing
catalyst at a liquid hourly space velocity (LHSV) of between about
0.05 hr.sup.-1 to 1 hr.sup.-1; and contacting the bio-oil to the
stabilizing catalyst for a Time On Stream (TOS) in hours of at
least about one or more of: 200, 300, 400, 500, 600, 700, 800, 900,
1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000,
4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.
15. The method of claim 1, catalytically stabilizing the bio-oil
comprising flowing the bio-oil past a stabilizing catalyst, the
method further comprising regenerating the stabilizing catalyst,
comprising one or more of: rinsing the stabilizing catalyst with an
organic solvent; and contacting the stabilizing catalyst with
hydrogen at a temperature in .degree. C. of about one or more of:
250 to 550, 300 to 500, 325 to 475, 350 to 450, 375 to 425, and
400.
16. The method of claim 1, comprising filtering the bio-oil
effective to remove at least a portion of particles having an
effective particulate diameter greater than about 1 micrometer.
17. A method 350 for forming a hydrocarbon product from a bio-oil,
comprising: 352 providing the bio-oil; 354 filtering the bio-oil
effective to remove at least a portion of particles having an
effective particulate diameter greater than about 10 micrometers;
356 treating the bio-oil effective to remove at least a portion of
inorganic species from the bio-oil; 358 catalytically stabilizing
the bio-oil to provide a stabilized bio-oil; and 360 hydrotreating
the stabilized bio-oil comprising contacting the stabilized bio-oil
to a hydrotreatment catalyst in the presence of hydrogen, thereby
providing the hydrocarbon product.
18. The method of claim 17, the hydrotreatment catalyst comprising
one or more of: an active metal catalyst and a sulfided
catalyst.
19. The method of claim 17, hydrotreating the stabilized bio-oil
comprising contacting the stabilized bio-oil to a hydrotreatment
catalyst in the presence of a substantial excess of hydrogen at a
pressure in pounds per square inch gauge of one or more of: 100 to
2000, 500 to 1800, and 1000 to 1500.
20. The method of claim 17, hydrotreating the stabilized bio-oil
comprising contacting the stabilized bio-oil to the hydrotreatment
catalyst under conditions comprising one or more of: a liquid
hourly space velocity (LHSV) of between about 0.05 hr.sup.-1 to 1
hr.sup.-1; and in the presence of hydrogen for a Time On Stream
(TOS) in hours of at least about one or more of: 200, 300, 400,
500, 600, 700, 800, 900, 1000, 1,100, 1,200, 1,300, and 1,400,
1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000,
12,000, and 16,000.
21. The method of claim 17, comprising filtering the bio-oil
effective to remove at least a portion of particles having an
effective particulate diameter greater than about 1 micrometer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Pat.
App. No. 62/129,007, filed on Mar. 5, 2015, and 62/245,423, filed
Oct. 23, 2015, each of which is entirely incorporated by reference
herein.
BACKGROUND
[0003] Pyrolytic bio-oil derived from biomass may have limited
commercial applications because of poor heating value (.about.17
MJ/kg), high oxygen content (.about.45 wt %), high viscosity
(>200 cP), and corrosiveness. It is highly desirable that such
liquid hydrocarbon products produced from bio-oil be substantially
reduced in water content, viscosity, and corrosiveness in order to
provide miscibility with petroleum-based fuels and compatibility
with petroleum refining unit operations.
[0004] Bio-oil may be hydrotreated using heterogeneous catalysts
and may be used to produce improved liquid hydrocarbon products
such as gasoline, kerosene, and diesel fractions. With existing
technology, hydrotreatment catalysts may unfortunately become
deactivated due to carbon deposition from bio-oil polymerization
and coke formation, leading to a low "Time On Stream" (TOS) of a
few hundred hours before a hydrotreatment apparatus must be shut
down for catalyst maintenance. This substantially increases the
cost of such operations and limits the rate and economic viability
of liquid hydrocarbon products produced from bio-oil.
[0005] The lack of solutions in the art to these significant
barriers have substantially limited the production viability of
improved liquid hydrocarbon products from pyrolytic bio-oil. In
recognition of these issues, the U.S. Department of Energy has
called for solutions, for example, in "Upgrading of Biomass Fast
Pyrolysis Oil (Bio-oil)," Funding Opportunity Announcement Number:
DE-FOA-0000342, the entire contents of which are incorporated
herein by reference.
[0006] The present application appreciates that production of
improved liquid hydrocarbon products from pyrolytic bio-oil may be
a challenging endeavor.
SUMMARY
[0007] In one embodiment, a method for preparing stabilized bio-oil
suitable for subsequent hydrotreatment is provided. The method may
include providing the bio-oil. The method may include filtering the
bio-oil effective to remove at least a portion of particles having
an effective particulate diameter greater than about 10
micrometers. The method may include treating the bio-oil effective
to remove at least a portion of inorganic species from the bio-oil.
The method may include catalytically stabilizing the bio-oil. The
method may thereby provide the stabilized bio-oil suitable for
subsequent hydrotreatment.
[0008] In another embodiment, a method for forming a hydrocarbon
product from a stabilized bio-oil is provided. The method may
include providing the stabilized bio-oil. The method may include
hydrotreating the stabilized bio-oil by thereby providing the
hydrocarbon product.
[0009] In one embodiment, a system for forming a hydrocarbon
product from biomass is provided. The system may include a
pyrolysis reactor configured to pyrolyze a biomass input and
provide a bio-oil output. The system may include an inline filter
operatively coupled to receive the bio-oil output. The inline
filter may be configured to remove at least a portion of particles
having an effective diameter greater than about 10 micrometers from
the bio-oil output to provide a coarse-filtered bio-oil output. The
system may include a fine filtration module configured to receive
the coarse-filtered bio-oil output. The fine filtration module may
be configured to remove at least a portion of particles having an
effective diameter greater than about 5 micrometers to provide a
fine-filtered bio-oil output. The system may include a bed
configured to contain an ion exchange resin effective to receive
the fine-filtered bio-oil. The bed may be configured to remove at
least a portion of inorganic species from the fine filtered bio-oil
to produce a reduced-inorganic bio-oil output. The system may
include a first catalytic unit configured to contain a stabilizing
catalyst effective to receive the reduced-inorganic bio-oil. The
first catalytic unit may be configured to stabilize the
reduced-inorganic bio-oil to produce a stabilized bio-oil output.
The system may include a second catalytic unit configured to
contain a hydrotreatment catalyst effective to receive the
stabilized bio-oil. The second catalytic unit may be configured to
hydrotreat the stabilized bio-oil to provide a hydrocarbon output.
The system may include a hydrogen source operatively coupled to
provide hydrogen to one or more of the first catalytic unit and the
second catalytic unit.
[0010] In another embodiment, a method for forming a hydrocarbon
product from a bio-oil is provided. The method may include
providing the bio-oil. The method may include filtering the bio-oil
effective to remove at least a portion of particles having an
effective particulate diameter greater than about 10 micrometers.
The method may include treating the bio-oil effective to remove at
least a portion of inorganic species from the bio-oil. The method
may include catalytically stabilizing the bio-oil to provide a
stabilized bio-oil. The method may include hydrotreating the
stabilized bio-oil comprising contacting the stabilized bio-oil to
a hydrotreatment catalyst in the presence of hydrogen, thereby
providing the hydrocarbon product.
[0011] In another embodiment, a stabilized bio-oil is provided. The
stabilized bio-oil may be prepared according to any of the methods
described herein or prepared using any of the systems described
herein.
[0012] In one embodiment, a stabilized bio-oil is provided. The
stabilized bio oil may be characterized by one or more of: a total
acid number (TAN) value less than 100 mg KOH/g; a water content of
at least about 17 wt. %; a hydrogen to carbon ratio greater than
1.4:1; and an average percentage of aldehyde and ketone groups of
less than about 5%.
[0013] In another embodiment, a hydrocarbon product derived from
bio-oil is provided. The hydrocarbon product derived from bio-oil
may be prepared according to any of the methods described herein or
prepared using any of the systems described herein.
[0014] In one embodiment, a hydrocarbon product derived from
bio-oil is provided. The hydrocarbon product may be characterized
by one or more of the following. The hydrocarbon product may be
characterized by one or more percentages by weight of: about 24%
paraffin, about 5.6% aromatics, about 8.6% naphthalenes, about 59%
nC.sub.5-C.sub.6 alkanes, and about 2.4% olefins. The hydrocarbon
product may be characterized by one or more of: a density in
grams/mL of 0.78-0.86; a total sulfur weight percent of less than
0.08%; a pour point in .degree. C. of less than about 20; a
viscosity in cPs of less than 2; a hydrogen:carbon atomic ratio of
about 1.5:1 to about 2.2:1; and an energy value in mega Joules per
kilogram of about 40 to 45.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The accompanying figures, which are incorporated in and
constitute a part of the specification, illustrate example methods
and apparatuses, and are used merely to illustrate example
embodiments.
[0016] FIG. 1 is a schematic depicting the preparation of
stabilized bio-oil and hydrocarbon products derived therefrom.
[0017] FIG. 2 is a flow diagram of an example method 200 for
preparing a stabilized bio-oil.
[0018] FIG. 3A is a flow diagram of an example method 300 for
preparing a hydrocarbon product.
[0019] FIG. 3B is a flow diagram of an example method 350 for
preparing a hydrocarbon product.
[0020] FIG. 4 is a block diagram of an example for preparing a
hydrocarbon product from biomass.
[0021] FIG. 5 is a table of ICP analyses of bio-oil and synthetic
bio-oil.
[0022] FIG. 6A is a flow diagram illustrating hydrotreatment of
synthetic bio-oil.
[0023] FIG. 6B is a table of conditions used in the hydrotreatment
of synthetic bio-oil without inorganic additives.
[0024] FIG. 6C is a table of conditions used in the hydrotreatment
of synthetic bio-oil without inorganic additives and results
obtained at various time intervals.
[0025] FIG. 6D is a graph illustrating the percentage volume of
C2-C6 hydrocarbon gases detected after hydrotreatment of synthetic
bio-oil without inorganic additives relative to time on stream.
[0026] FIG. 6E is a graph illustrating the density of the product
organic phase obtained after hydrotreatment of synthetic bio-oils
with and without inorganic additives relative to time on
stream.
[0027] FIG. 6F is a graph illustrating the percentage of water in
the product organic phase obtained after hydrotreatment of
synthetic bio-oils with and without inorganic additives relative to
time on stream.
[0028] FIG. 6G is a graph illustrating the percentage volume of
C2-C6 hydrocarbon gases detected after hydrotreatment of synthetic
bio-oils with and without inorganic additives relative to time on
stream.
[0029] FIG. 7 is a flow diagram illustrating hydrotreatment of
pyrolysis bio-oil.
[0030] FIG. 8 is a table summarizing the results of
thermogravimetric experiments.
[0031] FIG. 9A is a transmission electron microscope (TEM) photo
illustrating a metal particle size and metal dispersion of a fresh
catalyst.
[0032] FIG. 9B is a transmission electron microscope (TEM) photo
illustrating a metal particle size and metal dispersion of a spent
catalyst.
[0033] FIG. 10 is a graph of ICP analyses of fresh and spent (post
500 h TOS) catalysts showing that deposition of inorganic
contaminants such as Ca, Fe and S are associated with deactivated
catalyst.
[0034] FIG. 11 is a table reporting the concentration of various
inorganic species measured for the fine-filtered bio-oil before and
after contact with the polystyrene sulfonic acid ion exchange resin
under various conditions.
[0035] FIG. 12 is a table summarizing the conditions used in cycle
1.
[0036] FIG. 13 is a graph illustrating liquid and dry yield ratios
of stabilized bio-oil product/cleaned bio-oil feed.
[0037] FIG. 14 is a graph illustrating the pH of the stabilized
bio-oil product versus time on stream.
[0038] FIG. 15 is graph illustrating the water content in the
liquid phase as determined by the Karl Fisher method.
[0039] FIG. 16A is a graph illustrating the molar hydrogen/carbon
ratio (H/C) of the stabilized bio-oil as function of time on
stream.
[0040] FIG. 16B is a graph illustrating the Total Acidity Number,
TAN (mg KOH/gram of sample) as a function of time on stream.
[0041] FIG. 17A is a graph illustrating the density of the
hydrocarbon product of Zone II versus time on stream.
[0042] FIG. 17B is a graph illustrating the consumption of hydrogen
versus time on stream.
[0043] FIG. 18A is an image of overlay .sup.1H NMR spectra from
about 6 ppm to 13 ppm of fine-filtered bio-oil and
reduced-inorganic bio-oil.
[0044] FIG. 18B is an image of overlay .sup.1H NMR spectra from 0
ppm to about 6 ppm of fine-filtered bio-oil and reduced-inorganic
bio-oil.
[0045] FIG. 19A is an image of overlay .sup.1H NMR spectra from
about 6 ppm to 13 ppm of reduced inorganic bio-oil at TOS=0 h and
stabilized bio-oil at TOS=55-60 h, 106-112 h, 242-252 h, and
312-324 h.
[0046] FIG. 19B is an image of overlay .sup.1H NMR spectra from 0
ppm to about 6 ppm of reduced inorganic bio-oil at TOS=0 h and
stabilized bio-oil at TOS=55-60 h, 106-112 h, 242-252 h, and
312-324 h.
[0047] FIG. 20A is an image of overlay .sup.1H NMR spectra from
about 6 ppm to 13 ppm of reduced inorganic bio-oil at TOS=0 h and
stabilized bio-oil at TOS=466-478 h, 502-514 h, 676-700 h, 773-797
h, 820-844 h, 916-940 h, and 964-1010 h.
[0048] FIG. 20B is an image of overlay .sup.1H NMR spectra from 0
ppm to about 6 ppm of reduced inorganic bio-oil at TOS=0 h and
stabilized bio-oil at TOS=466-478 h, 502-514 h, 676-700 h, 773-797
h, 820-844 h, 916-940 h, and 964-1010 h.
DETAILED DESCRIPTION
[0049] Pyrolytic bio-oil, as produced, includes contaminants that
may tend to foul conventional methods and catalysts for
hydrogenating and cracking bio-oil to form hydrocarbon products.
Such contaminants may include particulates, e.g., of char and ash,
as well as compounds including inorganic atoms such as Al, Ca, Fe,
K, Mg, Na, Si, and S. Such contaminants may arise from the source
biomass, from pyrolysis, by leaching from components of pyrolysis
systems, and the like. As described in the EXAMPLES, such
contaminants were found to foul and deactivate catalysts. Further,
as described in the EXAMPLES, removal of these contaminants may
tend to reduce fouling and catalyst deactivation, leading to
benefits such as better catalyst performance, easier catalyst
regeneration, longer Time On Stream (TOS) operation, and the like.
In particular, embodiments described herein lead to substantially
improved TOS values compared to the prior art.
[0050] Accordingly, FIG. 1 is an example reaction flow diagram 100
illustrating an overview of various aspects of embodiments detailed
herein. Reaction flow diagram 100 shows that a pyrolytic bio-oil
102 may be directed into a filtering step 104 that may produce a
filtered bio-oil 106. The filtered bio-oil 106 may be cleaned of at
least some inorganic species in an ion exchange process 108,
followed by the output of a cleaned bio-oil 110 with reduced
content of the inorganic species. The cleaned bio-oil 110, which
may still contain sulfur species, may be subjected to a mild
catalytic stabilization in a Zone I process 112 to produce a
stabilized bio-oil 114. The stabilized bio-oil 114, which may still
contain sulfur species, may be further hydrotreated and cracked
using a hydrotreatment catalyst, e.g., a sulfided catalyst in a
Zone II process 116, which may output a hydrocarbon fuel product
118.
[0051] FIG. 2 is a flow diagram illustrating an example method 200
for preparing stabilized bio-oil for subsequent hydrotreatment. In
various embodiments, the method may include 202 providing the
bio-oil. The method may include 204 filtering the bio-oil effective
to remove at least a portion of particles having an effective
particulate diameter greater than about 10 micrometers. The method
may include 206 treating the bio-oil effective to remove at least a
portion of inorganic species from the bio-oil. The method may
include 208 catalytically stabilizing the bio-oil. The method may
thereby provide the stabilized bio-oil suitable for subsequent
hydrotreatment.
[0052] In some embodiments, providing the bio-oil may include
pyrolyzing biomass to produce the bio-oil. Providing the bio-oil
may include pyrolyzing biomass to produce the bio-oil. The biomass
may be substantially free of small or large biomass particulates.
For example, the biomass may be characterized by a particulate
diameter distribution of between about 0.5 millimeters and about 5
millimeters. The method may include preparing the biomass prior to
the pyrolyzing by selecting the biomass in a particulate diameter
distribution of between about 0.5 millimeters and about 5
millimeters. Providing the bio-oil may include pyrolyzing biomass
to produce the bio-oil at a temperature in .degree. C. of between
about one or more of: 400 to 600, 400 to 550, and 450 to 500, for
example, 450-500.degree. C.
[0053] In several embodiments, providing the bio-oil may include
pyrolyzing biomass to produce the bio-oil in a downflow reactor.
For example, providing the bio-oil may include pyrolyzing the
biomass in a downflow reactor to produce a bio-oil vapor. Filtering
the bio-oil may include in-line filtering the bio-oil vapor
produced by the pyrolysis effective to remove at least a portion of
the particles having the effective particulate diameter greater
than about 10 micrometers. Further, for example, providing the
bio-oil may include pyrolyzing the biomass in a downflow reactor to
produce a bio-oil vapor and condensing the bio-oil vapor to provide
the bio-oil in condensed form. Filtering the bio-oil may include
in-line filtering the bio-oil in condensed form effective to remove
at least a portion of the particles having the effective
particulate diameter greater than about 10 micrometers.
[0054] In various embodiments, filtering the bio-oil may include
removing at least a portion of the particles having an effective
particulate diameter in micrometers greater than one or more of
about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3,
0.2, and 0.1, for example, an effective particulate diameter
greater than about 0.8 micrometers or greater than about 0.2
micrometers. Filtering the bio-oil may include a first filtering
process effective to remove at least a portion of the particles
having an effective particulate diameter greater than about 10
micrometers. Filtering the bio-oil may include a second filtering
process effective to remove at least a portion of the particles
having an effective particulate diameter in micrometers greater
than one or more of about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7,
0.6, 0.5, 0.4, 0.3, 0.2, and 0.1, for example, an effective
particulate diameter greater than about 0.8 micrometers or greater
than about 0.2 micrometers. Filtering the bio-oil may include a
second filtering process conducted on the bio-oil offline from a
pyrolysis process used to provide the bio-oil. Filtering the
bio-oil may include a second filtering process conducted using a
pressure differential in pounds per square inch (PSI) of at least
about one or more of: 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90,
100, 125, 150, 175, and 200, for example, a pressure differential
of about 80 PSI. Filtering the bio-oil may include a second
filtering process conducted at a temperature in .degree. C. of at
least about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100,
for example, at least about 40.degree. C. or at least about
80.degree. C.
[0055] In some embodiments, treating the bio-oil effective to
remove at least a portion of inorganic species from the bio-oil may
include contacting the bio-oil to one or more of: an ion exchange
resin, a zeolite, and activated carbon. The ion exchange resin may
include any ion exchange resin described herein. The zeolite may
include any zeolite described herein. For example, treating the
bio-oil effective to remove at least a portion of inorganic species
from the bio-oil may include contacting the bio-oil to an ion
exchange resin in a fixed-bed column reactor or a slurry bed
reactor. For example, the fixed-bed column reactor may be operated
in intermittent or continuous flow mode. For example, the slurry
bed reactor may be operated in batch mode. Treating the bio-oil
effective to remove at least a portion of inorganic species from
the bio-oil may include contacting the bio-oil to an ion exchange
resin at a pressure in pounds per square inch gauge (PSIG) of about
one or more of: 0 to 100, 10 to 100, 10 to 75, 10 to 50, 10 to 25,
and 10 to 20. Treating the bio-oil effective to remove at least a
portion of inorganic species from the bio-oil may include
contacting the bio-oil to an ion exchange resin at a temperature in
.degree. C. of about one or more of: 25 to 100, 25 to 75, 30 to 50,
35 to 45, and 40, for example, 40.degree. C.
[0056] Suitable ion-exchange resins may include strongly acidic
cation-exchange resins. The ion exchange resin may be used in
protonated form, for example, including active SO.sub.3H groups or
CO.sub.2H groups. Neutralized sulfonic acid resins, in which some
or all of the protons have been exchanged by a cation such as
lithium, sodium, potassium, magnesium, and calcium may also be
suitable. Resins having a counterion (i.e., sodium, Na+), may be
converted to protonated form by treatment with aqueous acid, e.g.,
hydrochloric acid, nitric acid, sulfuric acid, substituted sulfonic
acids such as p-toluene sulfonic acid, and the like. This is
commonly known in the art as ion-exchange resin activation. The ion
exchange resin may include sulfonated or carboxylated polymers or
copolymers of styrene. For example, the ion exchange resin may
include one or more of: a poly(styrene sulfonic acid), a
poly(styrene carboxylic acid), and a
poly(2-acrylamido-2-methyl-1-propanesulfonic acid).
[0057] Example ion exchange resins may include macroreticular
resins. As used herein, "macroreticular resins" may include two
continuous phases--a continuous pore phase and a continuous gel
polymeric phase. The continuous gel polymeric phase may be
structurally composed of small spherical microgel particles
agglomerated together to form clusters that may form
interconnecting pores. The surface area may correspond to the
exposed surface of the microgel clusters. Macroreticular ion
exchange resins may be made with different surface areas ranging
from 7 to 1500 m.sup.2/g, and average pore diameters ranging from
about 5 to about 10000 nm.
[0058] Example ion exchange resins may include gel-type resins.
"Gel-type resins" may be translucent. Gel-type resins may lack
permanent pore structures. Gel-type resins may include
molecular-scale micropores. The pore structures may be determined
by the distance between the polymer chains and crosslinks that may
vary with the crosslink level of the polymer, the polarity of the
solvent, and the operating conditions. Macroreticular resins may be
used for continuous column flow processes where minimization of
resin swelling/shrinking may be desirable. Gel-type resins may be
used for slurry bed batch processes. Macroreticular resins and
gel-type resins may be used in either continuous column flow or
slurry bed batch processes.
[0059] Suitable ion-exchange resins may include those provided by
Dow Chemical Co., Midland, Mich. under the tradenames/trademarks
DOWEX.RTM. MARATHON C, DOWEX.RTM. MONOSPHERE C-350, DOWEX.RTM.
HCR-S/S, DOWEX.RTM. MARATHON MSC, DOWEX.RTM. MONOSPHERE 650C,
DOWEX.RTM. HCR-W2, DOWEX.RTM. MSC-1, DOWEX.RTM. HGR NG (H),
DOWE.RTM. DR-G8, DOWEX.RTM. 88, DOWEX.RTM. MONOSPHERE 88,
DOWEX.RTM. MONOSPHERE C-600 B, DOWEX.RTM. MONOSPHERE M-31,
DOWEX.RTM. MONOSPHERE DR-2030, DOWEX.RTM. M-31, DOWEX.RTM. G-26
(H), DOWEX.RTM. 50W-X4, DOWEX.RTM. 50W-X8, DOWEX.RTM. 66,
AMBERLYST.TM. 131, AMBERLYST.TM. 15, AMBERLYST.TM. 16,
AMBERLYST.TM. 31, AMBERLYST.TM. 33, AMBERLYST.TM. 35, AMBERLYST.TM.
36, AMBERLYST.TM. 39, AMBERLYST.TM. 40 AMBERLYST.TM. 70,
AMBERLITE.TM. FPC11, AMBERLITE.TM. FPC22, AMBERLITE.TM. FPC23, and
the like. Suitable ion-exchange resins may include those provided
by Brotech Corp., Bala Cynwyd, Pa. (USA) under the trade
names/trademarks PUROFINE.RTM. PFC150, PUROLITE.RTM. C145,
PUROLITE.RTM. C150, PUROLITE.RTM. C160, PUROFINE.RTM.PFC100,
PUROLITE.RTM. C100, and the like. Suitable ion-exchange resins may
include those provided by Thermax Limited Corp., Novi, Mich. under
the tradename/trademark MONOPLUS.TM.. 5100, TULUSION.RTM. T42, and
the like.
[0060] For example, the poly(styrene sulfonic acid) may be
characterized by one or more of: a surface area of about 28 to 37
square meters per gram, a particle diameter of 0.60 to 0.850
millimeters, a particle diameter uniformity coefficient of less
than about 1.6, a total pore volume of 0.15 to 0.25 milliliters per
gram, an average pore diameter of about 200 to 280 angstroms, and
an exchange capacity of at least about 5 milli-equivalents per
gram.
[0061] In several embodiments, the inorganic species may include
one or more of: Al, Ca, Na, K, Mg, Fe, P, Si, S, and Zn. Treating
the bio-oil effective to remove at least a portion of inorganic
species from the bio-oil may include reducing the amount of one or
more inorganic species in the bio-oil to a concentration in parts
per million (ppm) of less than one or more of about: 25, 20, 15,
10, 9, 8, 7, 6, 5, 4, 3, 2, and 1, for example, less than about 6
ppm or less than about 3 ppm. For example, treating the bio-oil
effective to remove at least a portion of inorganic species from
the bio-oil may include reducing a content or amount of one or more
of, or each of: Al, Ca, Na, K, Mg, and Fe in the bio-oil to a
corresponding concentration in ppm of less than one or more of
about: 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1, for example, less than
about 6 ppm or less than about 3 ppm.
[0062] In various embodiments, catalytically stabilizing the
bio-oil may include contacting the bio-oil to a stabilizing
catalyst. The stabilizing catalyst may include a metal dispersed on
a solid support, e.g., a metal oxide, a zeolite, carbon, and the
like. The metal dispersed on a solid support may be acidic. For
example, the metal may include one or more of: Ru, Rh, Re, Pt, Pd,
Ir, Au, Fe, Ni, Nb, and Os. The metal oxide may include one or more
of: titania, ceria, magnesium oxide, niobium oxide, alumina,
amorphous silica alumina, zirconia, zinc oxide, niobic acid,
tungstic acid, molybdic acid, carbon, and silica.
[0063] The method may include contacting the bio-oil to a diluting
medium to form a diluted bio-oil. The method may include diluting
the bio-oil in an organic solvent to form a diluted bio-oil. The
organic solvent may include a protic organic solvent, e.g., an
alcohol. The organic solvent may include an aprotic organic
solvent. The organic solvent may include a polar solvent. The
organic solvent may include a polar protic solvent. The organic
solvent may include a polar aprotic solvent. The organic solvent
may include a nonpolar solvent. The diluting medium may include an
organic solvent including one or more of: a protic solvent, an
aprotic solvent, a polar solvent, and a nonpolar solvent. The
diluting medium may include an organic solvent including one or
more of: methanol, ethanol, 2-propanol, n-butanol, sec-butanol,
tert-butanol, pentanol, hexanol, methyl cyclohexanol, acetone,
methyl ethyl ketone, butanone, ethyl acetate, tetrahydrofuran,
methyl tert-butyl ether, diethyl ether, acetonitrile, dimethyl
formamide, dimethylsulfoxide, and the like. The method may include
diluting the bio-oil in a petroleum fuel to form a diluted bio-oil.
The petroleum fuel may include one or more of: diesel, gasoline,
kerosene, jet fuel, fuel oil, naptha, fractions thereof,
combinations thereof, and the like. The method may include diluting
the bio-oil in a portion of the stabilized bio-oil to form the
diluted bio-oil. The portion of the stabilized bio-oil may include
a light phase. The light phase may include water. The portion of
the stabilized bio-oil may include a heavy phase. The heavy phase
may include the bio-oil. The portion of the stabilized bio-oil may
include one or more of: the light phase and the heavy phase. The
method may include diluting the bio-oil to form the diluted bio-oil
in one or more of: an organic solvent, a petroleum fuel, water, and
a portion of the stabilized bio-oil.
[0064] The method may include diluting the bio-oil in a diluting
medium to form a diluted bio-oil. Diluting the bio-oil in the
diluting medium may include diluting the bio-oil to a percentage by
weight of the diluting medium of about one or more of: 5 to 50, 10
to 45, 15 to 40, 20 to 35, 25 to 35, and 30.
[0065] The method may include contacting the bio-oil to a diluting
medium to form a diluted bio-oil using a positive pressure
differential in pounds per square inch compared to atmospheric
pressure of at least about one or more of: 5, 10, 15, 20, 30, 40,
50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 500, 1000, 1500, 1800,
and 2000.
[0066] The method may include contacting the bio-oil to a diluting
medium to form a diluted bio-oil and catalytically stabilizing the
bio-oil. Catalytically stabilizing the bio-oil may include
contacting the diluted bio-oil to the stabilizing catalyst.
[0067] The method may include removing at least a portion of the
diluting medium from the diluted bio-oil after catalytically
stabilizing the diluted bio-oil. The diluting medium may include
one or more of: the organic solvent, the petroleum fuel, and the
water. The removed diluting medium may be recycled.
[0068] In some embodiments, catalytically stabilizing the bio-oil
may include contacting the bio-oil to a stabilizing catalyst that
includes a zeolite. Further, the solid support may be a zeolite,
e.g., an acidic zeolite. The zeolite may include one or more of: a
Y zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0069] In various embodiments, the stabilizing catalyst may include
the metal dispersed on an acidic metal oxide, For example, the
stabilizing catalyst may include one or more of: Ru, Rh, Re, Pt,
Pd, Ir, Au, Fe, Ni, Nb, and Os; dispersed on one or more of:
titania, ceria, magnesium oxide, niobium oxide, alumina, amorphous
silica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,
molybdic acid, carbon, and silica. For example, catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst including Ru/TiO.sub.2.
[0070] In some embodiments, the stabilizing catalyst may include
the metal dispersed on an acidic zeolite. For example, the
stabilizing catalyst may include one or more of: Ru, Rh, Re, Pt,
Pd, Ir, Au, Fe, Ni, Nb, and Os; dispersed on one or more of: a Y
zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0071] In several embodiments, catalytically stabilizing the
bio-oil may include contacting the bio-oil to a stabilizing
catalyst at a temperature in .degree. C. of about one or more of:
40 to 300, 100 to 280, 120 to 270, 130 to 250, 140 to 225, 150 to
200, 160 to 180, and 170. Catalytically stabilizing the bio-oil may
include contacting the bio-oil to a stabilizing catalyst at a
pressure in PSI of about one or more of: 500 to 2500, 750 to 2250,
1000 to 2000, 1250 to 1750, 1400 to 1600, and 1500. Catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst in the presence of hydrogen. Catalytically
stabilizing the bio-oil may include providing a substantial excess
of hydrogen at a pressure in pounds per square inch gauge of one or
more of: 100 to 2000, 500 to 1800, and 1000 to 1500. Catalytically
stabilizing the bio-oil may include flowing the bio-oil past a
stabilizing catalyst at a liquid hourly space velocity (LHSV) of
between about 0.05 hr.sup.-1 to 1 hr.sup.-1. Catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst for a Time On Stream (TOS) in hours of at
least about one or more of: 200, 300, 400, 500, 600, 700, 800, 900,
1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000,
4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.
[0072] In several embodiments, the method may include regenerating
the stabilizing catalyst, for example, by rinsing the stabilizing
catalyst with an organic solvent. The organic solvent may include a
protic organic solvent, e.g., an alcohol. The organic solvent may
include one or more of: methanol, ethanol, 2-propanol, n-butanol,
sec-butanol, tert-butanol, pentanol, hexanol, methyl cyclohexanol,
acetone, methyl ethyl ketone, butanone, ethyl acetate,
tetrahydrofuran, methyl tert-butyl ether, acetonitrile, and
dimethyl formamide. The method may include regenerating the
stabilizing catalyst by contacting the stabilizing catalyst with
hydrogen at a temperature in .degree. C. of about one or more of:
250 to 550, 300 to 500, 325 to 475, 350 to 450, 375 to 425, and
400. For example, the hydrogen may chemically reduce carbon
accumulation on the stabilizing catalyst to produce gaseous
methane. Such reducing may be desirable compared to oxidative
methods of removing carbon, because hydrogen reduction of carbon to
methane may be less exothermic than carbon oxidation in the
presence of oxygen, leading to less heating and less thermal damage
to the stabilizing catalyst, e.g., by sintering.
[0073] In various embodiments, the stabilized bio-oil may be
characterized compared to the bio-oil. For example, the stabilized
bio-oil may be characterized compared to the bio-oil by a decreased
content of aldehydes and free carboxylic acids. The stabilized
bio-oil may be characterized compared to the bio-oil by an increase
in pH of at least one or more of about: 0.25, 0.5, 0.75, 1, 1.25,
and 1.5. The stabilized bio-oil may be characterized compared to
the bio-oil by a percent increase in dry hydrogen:carbon ratio of
one or more of about: 5, 10, 15, 20, and 25. The stabilized bio-oil
may be characterized compared to the bio-oil by one or more of the
characteristics recited in this paragraph.
[0074] In some embodiments, the bio-oil may be characterized by one
or more of: a density of about 1 to 1.2 grams per milliliter, a dry
hydrogen:carbon ratio of about 1.4:1, a dry oxygen weight
percentage of about 20% to 35%, and a water weight percentage of
about 30% to 45%. The stabilized bio-oil may be characterized by
one or more of: a density of about 1 to 1.1 grams per milliliter, a
dry hydrogen:carbon ratio of about 1.2:1 to 1.8:1, a dry oxygen
weight percentage of about 20% to 35%, and a water weight
percentage of about 20% to 35%.
[0075] In several embodiments, the method may include cooling the
stabilized bio-oil prior to the subsequent hydrotreatment,
insulating the stabilizing catalyst from heat of the subsequent
hydrotreatment, or cooling the stabilizing catalyst against heat of
the subsequent hydrotreatment.
[0076] The method may include conveying the stabilized bio-oil
directly from the catalytically stabilizing to the subsequent
hydrotreatment, for example, as a continuous process.
[0077] The method may include a stabilized bio-oil including one or
more of: a light phase and a heavy phase. The method may include
feeding at least the heavy phase directly from the catalytically
stabilizing to the subsequent hydrotreatment. The method may
include separating the light phase from the heavy phase and feeding
the heavy phase to the subsequent hydrotreatment. The method may
include feeding the light phase and the heavy phase in parallel to
the subsequent hydrotreatment. The method may include controlling a
ratio between the light phase and the heavy phase and feeding the
ratio of the light phase and the heavy phase in parallel to the
subsequent hydrotreatment. The light phase:heavy phase may include
a ratio between about 1:20 and about 20:1.
[0078] The method may include conducting at least a portion of the
method under an inert atmosphere. The inert atmosphere may include
one or more of: nitrogen, carbon dioxide, and a non-condensable gas
product of biomass pyrolysis.
[0079] FIGS. 3A and 3B are flow diagrams illustrating methods of
forming a hydrocarbon product. For example, FIG. 3A is a flow
diagram illustrating an example method 300 for forming a
hydrocarbon product from a stabilized bio-oil. In various
embodiments, the method may include 302 providing the stabilized
bio-oil. The method may include 304 hydrotreating the stabilized
bio-oil by, for example, contacting the stabilized bio-oil to a
hydrotreatment catalyst in the presence of hydrogen, thereby
providing the hydrocarbon product. Further, for example, FIG. 3B is
a flow diagram illustrating an example method 350 for forming a
hydrocarbon product from a bio-oil. In various embodiments, the
method may include 352 providing the bio-oil. The method may
include 354 filtering the bio-oil effective to remove at least a
portion of particles having an effective particulate diameter
greater than about 10 micrometers. The method may include 356
treating the bio-oil effective to remove at least a portion of
inorganic species from the bio-oil. The method may include 358
catalytically stabilizing the bio-oil to provide a stabilized
bio-oil. The method may include 360 hydrotreating the stabilized
bio-oil comprising contacting the stabilized bio-oil to a
hydrotreatment catalyst in the presence of hydrogen, thereby
providing the hydrocarbon product. Methods 300 and 350 may
incorporate of the following aspects.
[0080] For example, the stabilized bio-oil may be characterized by
one or more of: a total acid number (TAN) value less than 100 mg
KOH/g; a water content of at least about 17 wt. %; a hydrogen to
carbon ratio greater than 1.4:1; and an average percentage of
aldehyde and ketone groups of less than about 5%. The TAN may be,
for example, a value in milligrams of potassium hydroxide per gram
of less than one or more of: 100, 90, 80, 70, 60, 50, 40, and 35.
The water content may be, for example, a percent by weight of one
or more of: 17 to 35, 20 to 35, 20 to 30, and 25 to 30. The
hydrogen:carbon ratio may be, for example, one or more of: 1.4:1 to
1.9:1, 1.5:1 to 1.9:1, 1.6:1 to 1.9:1, 1.7:1 to 1.9:1, 1.4:1 to
1.8:1, 1.6:1 to 1.8:1, and 1.7:1 to 1.8:1. The average percentage
of aldehyde and ketone groups, e.g., as measured by .sup.1H NMR may
be a weight percentage of one or more of: less than about 5%, less
than about 4.5%, less than about 4%, less than about 3.5%, between
about 1.5% and about 3.5%, and between about 2% and about 3%.
[0081] In some embodiments, hydrotreating the stabilized bio-oil
may include contacting the stabilized bio-oil to the hydrotreatment
catalyst in the presence of hydrogen at a temperature in .degree.
C. of about one or more of: 200 to 420, 220 to 400, 240 to 380, 260
to 360, 280 to 340, 300 to 320, and 310. Hydrotreating the
stabilized bio-oil may include contacting the stabilized bio-oil to
the hydrotreatment catalyst at a pressure in PSI of about one or
more of: 500 to 2500, 750 to 2250, 1000 to 2000, 1250 to 1750, 1400
to 1600, and 1500.
[0082] In various embodiments, the hydrotreatment catalyst may be
an active metal catalyst or a sulfided catalyst.
[0083] For example, the active metal catalyst may include a metal
dispersed on a solid support, e.g., a metal oxide, a zeolite,
carbon, and the like, each of which may be acidic. For example, the
metal may include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe,
Ni, Nb, and Os. The metal oxide may include one or more of:
titania, ceria, magnesium oxide, niobium oxide, alumina, amorphous
silica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,
molybdic acid, carbon, and silica. The hydrotreatment catalyst may
include a zeolite. Further, the solid support may be a zeolite,
e.g., an acidic zeolite. The zeolite may include one or more of: a
Y zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0084] In various embodiments, the hydrotreatment catalyst may
include the metal dispersed on an acidic metal oxide, For example,
the hydrotreatment catalyst may include a metal including one or
more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal
may be dispersed on a solid support comprising one or more of:
titania, ceria, magnesium oxide, niobium oxide, alumina, amorphous
silica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,
molybdic acid, carbon, silica, a Y zeolite, a Beta zeolite, a ZSM-5
zeolite, a Mordenite zeolite, a Ferrierite zeolite, a Al-MCM-41
zeolite, a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, a
Chabazite zeolite, and carbon. For example, the active metal
catalyst may include one or more of Ru/TiO.sub.2,
Ru/TiO.sub.2--ZSM5 Pd/C, Pd/SiO.sub.2--Al.sub.2O.sub.3,
Pd/Nb/Al.sub.2O.sub.3, Pd/Nb/TiO.sub.2--SiO.sub.2,
Pt/ZrO.sub.2--Al.sub.2O.sub.3, and Pd/Mg/Al.sub.2O.sub.3.
[0085] Further, for example, the hydrotreatment catalyst may
include a sulfided catalyst, e.g., including one or more of: Ni,
Nb, Mo, Co, and W. For example, the sulfided catalyst may include
one or more of sulfided: Ni, Nb, Mo, Co, W, NiMo, and CoMo.
[0086] In some embodiment, hydrotreating the stabilized bio-oil may
include contacting the stabilized bio-oil to the hydrotreatment
catalyst in the presence of a substantial excess of hydrogen at a
pressure in pounds per square inch gauge of one or more of: 100 to
2000, 500 to 1800, and 1000 to 1500. Hydrotreating the stabilized
bio-oil may include contacting the stabilized bio-oil to the
hydrotreatment catalyst at a liquid hourly space velocity (LHSV) of
between about 0.05 hr.sup.1 to 1 hr.sup.-1. Hydrotreating the
stabilized bio-oil may include contacting the stabilized bio-oil to
the hydrotreatment catalyst in the presence of hydrogen for a TOS
in hours of at least about one or more of: 200, 300, 400, 500, 600,
700, 800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750,
2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and
16,000.
[0087] In several embodiments, the hydrocarbon product may include
a liquid fraction characterized compared to the stabilized bio-oil
at 25.degree. C. and 1 atmosphere. The liquid fraction may be
characterized compared to the stabilized bio-oil by one or more
percentages by weight of: about 24% paraffin, about 5.6% aromatics,
about 8.6% naphthalenes, about 59% nC.sub.5-C.sub.6 alkanes, and
about 2.4% olefins. The liquid fraction may be characterized
compared to the stabilized bio-oil by one or more of: a density in
grams/mL of 0.78-0.86; a total sulfur weight percent of less than
0.08%, or less than about 0.01%; a pour point in .degree. C. of
less than about 20; a viscosity in cPs of less than 2; a
hydrogen:carbon atomic ratio of about 1.5:1 to about 2.2:1, e.g.,
about 2.1:1; and an energy value in mega Joules per kilogram of
about 40 to 45 or about 41 to 44 . . . . The liquid fraction may be
characterized compared to the stabilized bio-oil by one or more of
the characteristics described in this paragraph.
[0088] In various embodiments, the hydrocarbon product may include
a C.sub.1-C.sub.4 gas fraction, e.g., one or more of methane,
ethane, propane, butane, and the like. The hydrocarbon product may
include a liquid fraction characterized by one or more of: a
density of about 0.8 to about 0.86 grams per milliliter, a
hydrogen:carbon ratio of about 1.5:1 to about 2.2:1, a dry oxygen
weight percentage of about 0% to about 5%, e.g., less than about
0.5%, and a water weight percentage of about 0% to about 5%, e.g.,
less than about 0.5%.
[0089] In some embodiments, the method may include conducting at
least a portion of the method under an inert atmosphere. The inert
atmosphere may include one or more of: nitrogen, carbon dioxide,
and a non-condensable gas product of biomass pyrolysis.
[0090] In several embodiments, providing the stabilized bio-oil may
include: providing a bio-oil; filtering the bio-oil effective to
remove at least a portion of particles having an effective
particulate diameter greater than about 10 micrometers; treating
the bio-oil effective to remove at least a portion of inorganic
species from the bio-oil; and catalytically stabilizing the
bio-oil, thereby providing the stabilized bio-oil.
[0091] The method may include one or more of: cooling the
stabilized bio-oil prior to hydrotreating the stabilized bio-oil,
insulating the stabilizing catalyst from heat of hydrotreating the
stabilized bio-oil, and cooling the stabilizing catalyst against
heat of hydrotreating the stabilized bio-oil. The method may
include conveying the stabilized bio-oil directly from the
catalytically stabilizing to the hydrotreating.
[0092] The method may include a stabilized bio-oil including one or
more of: a light phase and a heavy phase. The method may include
feeding at least the heavy phase directly from the catalytically
stabilizing to the hydrotreating. The method may include separating
the light phase from the heavy phase and feeding the heavy phase to
the hydrotreating. The method may include feeding the light phase
and the heavy phase in parallel to the hydrotreating. The method
may include controlling a ratio between the light phase and the
heavy phase and feeding the ratio of the light phase and the heavy
phase in parallel to the hydrotreating. The light phase:heavy phase
may include a ratio between about 1:20 and about 20:1.
[0093] In some embodiments, providing the bio-oil may include
pyrolyzing biomass to produce the bio-oil. Providing the bio-oil
may include pyrolyzing biomass to produce the bio-oil. The biomass
may be substantially free of small or large biomass particulates.
For example, the biomass may be characterized by a particulate
diameter distribution of between about 0.5 millimeters and about 5
millimeters. The method may include preparing the biomass prior to
the pyrolyzing by selecting the biomass in a particulate diameter
distribution of between about 0.5 millimeters and about 5
millimeters. Providing the bio-oil may include pyrolyzing biomass
to produce the bio-oil at a temperature in .degree. C. of between
about one or more of: 400 to 600, 400 to 550, and 450 to 500, for
example, 450-500.degree. C.
[0094] In several embodiments, providing the bio-oil may include
pyrolyzing biomass to produce the bio-oil in a downflow reactor.
For example, providing the bio-oil may include pyrolyzing the
biomass in a downflow reactor to produce a bio-oil vapor. Filtering
the bio-oil may include in-line filtering the bio-oil vapor
produced by the pyrolysis effective to remove at least a portion of
the particles having the effective particulate diameter greater
than about 10 micrometers. Further, for example, providing the
bio-oil may include pyrolyzing the biomass in a downflow reactor to
produce a bio-oil vapor and condensing the bio-oil vapor to provide
the bio-oil in condensed form. Filtering the bio-oil may include
in-line filtering the bio-oil in condensed form effective to remove
at least a portion of the particles having the effective
particulate diameter greater than about 10 micrometers.
[0095] In various embodiments, filtering the bio-oil may include
removing at least a portion of the particles having an effective
particulate diameter in micrometers greater than one or more of
about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3,
0.2, and 0.1, for example, an effective particulate diameter
greater than about 0.8 micrometers or greater than about 0.2
micrometers. Filtering the bio-oil may include a first filtering
process effective to remove at least a portion of the particles
having an effective particulate diameter greater than about 10
micrometers. Filtering the bio-oil may include a second filtering
process effective to remove at least a portion of the particles
having an effective particulate diameter in micrometers greater
than one or more of about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7,
0.6, 0.5, 0.4, 0.3, 0.2, and 0.1, for example, an effective
particulate diameter greater than about 0.8 micrometers or greater
than about 0.2 micrometers. Filtering the bio-oil may include a
second filtering process conducted on the bio-oil offline from a
pyrolysis process used to provide the bio-oil. Filtering the
bio-oil may include a second filtering process conducted using a
pressure differential in pounds per square inch (PSI) of at least
about one or more of: 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90,
100, 125, 150, 175, and 200, for example, a pressure differential
of about 80 PSI. Filtering the bio-oil may include a second
filtering process conducted at a temperature in .degree. C. of at
least about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100,
for example, at least about 40.degree. C. or at least about
80.degree. C.
[0096] In some embodiments, treating the bio-oil effective to
remove at least a portion of inorganic species from the bio-oil may
include contacting the bio-oil to one or more of: an ion exchange
resin, a zeolite, and activated carbon. The ion exchange resin may
include any ion exchange resin described herein. The zeolite may
include any zeolite described herein. For example, treating the
bio-oil effective to remove at least a portion of inorganic species
from the bio-oil may include contacting the bio-oil to an ion
exchange resin in a fixed-bed column reactor or a slurry bed
reactor. For example, the fixed-bed column reactor may be operated
in intermittent or continuous flow mode, and the slurry bed reactor
may be operated in batch mode. Treating the bio-oil effective to
remove at least a portion of inorganic species from the bio-oil may
include contacting the bio-oil to an ion exchange resin at a
pressure in pounds per square inch gauge (PSIG) of about one or
more of: 0 to 100, 10 to 100, 10 to 75, 10 to 50, 10 to 25, and 10
to 20. Treating the bio-oil effective to remove at least a portion
of inorganic species from the bio-oil may include contacting the
bio-oil to an ion exchange resin at a temperature in .degree. C. of
about one or more of: 25 to 100, 25 to 75, 30 to 50, 35 to 45, and
40, for example, 40.degree. C. The ion exchange resin may include
one or more of: a poly(styrene sulfonic acid), a poly(styrene
carboxylic acid), and a
poly(2-acrylamido-2-methyl-1-propanesulfonic acid). For example,
the poly(styrene sulfonic acid) may be characterized by one or more
of: a surface area of about 28 to 37 square meters per gram, a
particle diameter of 0.60 to 0.850 millimeters, a particle diameter
uniformity coefficient of less than about 1.6, a total pore volume
of 0.15 to 0.25 milliliters per gram, an average pore diameter of
about 200 to 280 angstroms, and an exchange capacity of at least
about 5 milliequivalents per gram
[0097] In several embodiments, the inorganic species may include
one or more of: Al, Ca, Na, K, Mg, Fe, P, Si, S, and Zn. Treating
the bio-oil effective to remove at least a portion of inorganic
species from the bio-oil may include reducing one or more inorganic
species in the bio-oil to a concentration in parts per million
(ppm) of less than one or more of about: 25, 20, 15, 10, 9, 8, 7,
6, 5, 4, 3, 2, and 1, for example, less than about 6 ppm or less
than about 3 ppm. For example, treating the bio-oil effective to
remove at least a portion of inorganic species from the bio-oil may
include reducing a content of one or more of, or each of: Al, Ca,
Na, K, Mg, and Fe in the bio-oil to a corresponding concentration
in ppm of less than one or more of about: 10, 9, 8, 7, 6, 5, 4, 3,
2, and 1, for example, less than about 6 ppm or less than about 3
ppm.
[0098] In various embodiments, catalytically stabilizing the
bio-oil may include contacting the bio-oil to a stabilizing
catalyst. The stabilizing catalyst may include a metal dispersed on
a solid support, e.g., a metal oxide, a zeolite, carbon, and the
like, which may be acidic. For example, the metal may include one
or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The
metal oxide may include one or more of: titania, ceria, magnesium
oxide, niobium oxide, alumina, amorphous silica alumina, zirconia,
zinc oxide, niobic acid, tungstic acid, molybdic acid, carbon, and
silica.
[0099] The method may include contacting the bio-oil to a diluting
medium to form a diluted bio-oil. The method may include diluting
the bio-oil in an organic solvent to form a diluted bio-oil. The
organic solvent may include a protic organic solvent, e.g., an
alcohol. The organic solvent may include an aprotic organic
solvent. The organic solvent may include a polar solvent. The
organic solvent may include a polar protic solvent. The organic
solvent may include a polar aprotic solvent. The organic solvent
may include a nonpolar solvent. The diluting medium may include an
organic solvent including one or more of: a protic solvent, an
aprotic solvent, a polar solvent, and a nonpolar solvent. The
diluting medium may include an organic solvent including one or
more of: methanol, ethanol, 2-propanol, n-butanol, sec-butanol,
tert-butanol, pentanol, hexanol, methyl cyclohexanol, acetone,
methyl ethyl ketone, butanone, ethyl acetate, tetrahydrofuran,
methyl tert-butyl ether, diethyl ether, acetonitrile, dimethyl
formamide, dimethylsulfoxide, and the like. The method may include
diluting the bio-oil in a petroleum fuel to form a diluted bio-oil.
The petroleum fuel may include one or more of: diesel, gasoline,
kerosene, jet fuel, fuel oil, naptha, fractions thereof,
combinations thereof, and the like. The method may include diluting
the bio-oil in a portion of the stabilized bio-oil to form the
diluted bio-oil. The portion of the stabilized bio-oil may include
a light phase. The light phase may include water. The portion of
the stabilized bio-oil may include a heavy phase. The heavy phase
may include the bio-oil. The portion of the stabilized bio-oil may
include one or more of: the light phase and the heavy phase. The
method may include diluting the bio-oil to form the diluted bio-oil
in one or more of: an organic solvent, a petroleum fuel, water, and
a portion of the stabilized bio-oil.
[0100] The method may include diluting the bio-oil in a diluting
medium to form a diluted bio-oil. Diluting the bio-oil in the
diluting medium may include diluting the bio-oil to a percentage by
weight of the diluting medium of about one or more of: 5 to 50, 10
to 45, 15 to 40, 20 to 35, 25 to 35, and 30.
[0101] The method may include contacting the bio-oil to a diluting
medium to form a diluted bio-oil using a positive pressure
differential in pounds per square inch compared to atmospheric
pressure of at least about one or more of: 5, 10, 15, 20, 30, 40,
50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 500, 1000, 1500, 1800,
and 2000.
[0102] The method may include contacting the bio-oil to a diluting
medium to form a diluted bio-oil and catalytically stabilizing the
bio-oil. Catalytically stabilizing the bio-oil may include
contacting the diluted bio-oil to the stabilizing catalyst.
[0103] The method may include removing at least a portion of the
diluting medium from the diluted bio-oil after catalytically
stabilizing the diluted bio-oil. The diluting medium may include
one or more of: the organic solvent, the petroleum fuel, and the
water. The removed diluting medium may be recycled.
[0104] In some embodiments, catalytically stabilizing the bio-oil
may include contacting the bio-oil to a stabilizing catalyst that
includes a zeolite. Further, the solid support may be a zeolite,
e.g., an acidic zeolite. The zeolite may include one or more of: a
Y zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0105] In various embodiments, the stabilizing catalyst may include
the metal dispersed on an acidic metal oxide, For example, the
stabilizing catalyst may include one or more of: Ru, Rh, Re, Pt,
Pd, Ir, Au, Fe, Ni, Nb, and Os; dispersed on one or more of:
titania, ceria, magnesium oxide, niobium oxide, alumina, amorphous
silica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,
molybdic acid, carbon, and silica. For example, catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst including Ru/TiO.sub.2.
[0106] In some embodiments, the stabilizing catalyst may include
the metal dispersed on an acidic zeolite. For example, the
stabilizing catalyst may include one or more of: Ru, Rh, Re, Pt,
Pd, Ir, Au, Fe, Ni, Nb, and Os; dispersed on one or more of: a Y
zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0107] In several embodiments, catalytically stabilizing the
bio-oil may include contacting the bio-oil to a stabilizing
catalyst at a temperature in .degree. C. of about one or more of:
40 to 300, 100 to 280, 120 to 270, 130 to 250, 140 to 225, 150 to
200, 160 to 180, and 170. Catalytically stabilizing the bio-oil may
include contacting the bio-oil to a stabilizing catalyst at a
pressure in PSI of about one or more of: 500 to 2500, 750 to 2250,
1000 to 2000, 1250 to 1750, 1400 to 1600, and 1500. Catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst in the presence of hydrogen. Catalytically
stabilizing the bio-oil may include providing a substantial excess
of hydrogen at a pressure in pounds per square inch gauge of one or
more of: 100 to 2000, 500 to 1800, and 1000 to 1500. Catalytically
stabilizing the bio-oil may include flowing the bio-oil past a
stabilizing catalyst at a liquid hourly space velocity (LHSV) of
between about 0.05 hr.sup.-1 to 1 hr.sup.-1. Catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst for a TOS in hours of at least about one or
more of: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100,
1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000,
6,000, 7,000, 8,000, 12,000, and 16,000.
[0108] In several embodiments, the method may include regenerating
the stabilizing catalyst, for example, by rinsing the stabilizing
catalyst with an organic solvent. The organic solvent may include a
protic organic solvent, e.g., an alcohol. The organic solvent may
include one or more of methanol, ethanol, 2-propanol, n-butanol,
sec-butanol, tert-butanol, pentanol, hexanol, methyl cyclohexanol,
acetone, methyl ethyl ketone, butanone, ethyl acetate,
tetrahydrofuran, methyl tert-butyl ether, acetonitrile, dimethyl
formamide. The method may include regenerating the stabilizing
catalyst by contacting the stabilizing catalyst with hydrogen at a
temperature in .degree. C. of about one or more of: 250 to 550, 300
to 500, 325 to 475, 350 to 450, 375 to 425, and 400. For example,
the hydrogen may chemically reduce carbon accumulation on the
stabilizing catalyst to produce gaseous methane. Such reducing may
be desirable compared to oxidative methods of removing carbon,
because hydrogen reduction of carbon to methane may be less
exothermic than carbon oxidation in the presence of oxygen, leading
to less heating and less thermal damage to the stabilizing
catalyst, e.g., by sintering.
[0109] In various embodiments, the stabilized bio-oil may be
characterized compared to the bio-oil. For example, the stabilized
bio-oil may be characterized compared to the bio-oil by a decreased
content of aldehydes and free carboxylic acids. The stabilized
bio-oil may be characterized compared to the bio-oil by an increase
in pH of at least one or more of about: 0.25, 0.5, 0.75, 1, 1.25,
and 1.5. The stabilized bio-oil may be characterized compared to
the bio-oil by a percent increase in dry hydrogen:carbon ratio of
one or more of about: 5, 10, 15, 20, and 25. The stabilized bio-oil
may be characterized compared to the bio-oil by one or more of the
characteristics recited in this paragraph.
[0110] In some embodiments, the bio-oil may be characterized by one
or more of: a density of about 1 to 1.2 grams per milliliter, a dry
hydrogen:carbon ratio of about 1.4:1, a dry oxygen weight
percentage of about 20% to 35%, and a water weight percentage of
about 30% to 45%. The stabilized bio-oil may be characterized by
one or more of: a density of about 1 to 1.1 grams per milliliter, a
dry hydrogen:carbon ratio of about 1.2:1 to 1.8:1, a dry oxygen
weight percentage of about 20% to 35%, and a water weight
percentage of about 20% to 35%.
[0111] FIG. 4 is a block diagram illustrating an example system 400
for forming a hydrocarbon product from biomass. In various
embodiments, system 400 may include a pyrolysis reactor 402
configured to pyrolyze a biomass input and provide a bio-oil
output. System 400 may include an inline filter 404 operatively
coupled to receive the bio-oil output. Inline filter 404 may be
configured to remove at least a portion of particles having an
effective diameter greater than about 10 micrometers from the
bio-oil output to provide a coarse-filtered bio-oil output. System
400 may include a fine filtration module 406 configured to receive
the coarse-filtered bio-oil output. Fine filtration module 406 may
be configured to remove at least a portion of particles having an
effective diameter greater than about 5 micrometers to provide a
fine-filtered bio-oil output. System 400 may include a bed 408
configured to receive the fine-filtered bio-oil. Bed 408 may be
configured to remove at least a portion of inorganic species from
the fine filtered bio-oil to produce a reduced-inorganic bio-oil
output. Bed 408 may be configured to configured to contain one or
more of: an ion exchange resin, a zeolite, and activated carbon.
The ion exchange resin may include any ion exchange resin described
herein. The zeolite may include any zeolite described herein.
System 400 may include a first catalytic unit 410 configured to
contain a stabilizing catalyst effective to receive the
reduced-inorganic bio-oil. First catalytic unit 410 may be
configured to stabilize the reduced-inorganic bio-oil to produce a
stabilized bio-oil output. System 400 may include a second
catalytic unit 412 configured to contain a hydrotreatment catalyst
effective to receive the stabilized bio-oil. Second catalytic unit
412 may be configured to hydrotreat the stabilized bio-oil to
provide a hydrocarbon output. System 400 may include a hydrogen
source 414 operatively coupled to provide hydrogen to one or more
of first catalytic unit 410 and second catalytic unit 412.
[0112] In some embodiments, pyrolysis reactor 402 may include a
downflow pyrolysis reactor. Pyrolysis reactor 402 may be configured
to heat to a temperature in .degree. C. of at least about one or
more of: 400 to 600, 400 to 550, and 450 to 500.
[0113] In several embodiments, system 400 may include a condenser
module 416. Condenser module 416 may include a three-stage
condenser. Condenser module 416 may include an electrostatic
precipitator. Condenser module 416 may be operatively coupled
between pyrolysis reactor 402 and inline filter 404 such that
inline filter 404 is configured to receive the bio-oil output in
condensed form from condenser module 416. Inline filter 404 may be
directly coupled to pyrolysis reactor 402 such that inline filter
404 may be configured to receive the bio-oil output in vapor form
from pyrolysis reactor 402. Inline filter 404 may include one or
more of: a bag filter element, a metal mesh filter element, and a
ceramic filter element. Inline filter 404 may be configured to
remove at least a portion of particles having a diameter in
micrometers greater than one or more of about: 10, 9, 8, 7, 6, 5,
4, and 2.
[0114] In various embodiments, fine filtration module 406 may be a
stand-alone unit (not shown). Fine filtration module 406 may
operatively couple inline filter 404 and bed 408 such that fine
filtration module 406 may be configured for inline operation. Fine
filtration module 406 may be configured to remove at least a
portion of particles having a diameter in micrometers greater than
one or more of about: 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6,
0.5, 0.4, 0.3, 0.2, and 0.1. Fine filtration module 406 may include
one or more of: a bag filter element, a metal mesh filter element,
and a ceramic filter element. Fine filtration module 406 may be
operatively coupled to a pressure source 406A configured to operate
fine filtration module 406 using a pressure differential in pounds
per square inch of at least about one or more of: 5, 10, 15, 20,
30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, and 200. Fine
filtration module 406 may be operatively coupled to a heat source
406B configured to operate fine filtration module 406 at a
temperature in .degree. C. of at least about one or more of: 30,
40, 50, 60, 70, 80, 90, and 100.
[0115] In some embodiments, bed 408 may be configured in the form
of a fixed-bed column reactor or a slurry bed reactor. For example,
the fixed-bed column reactor may be configured for continuous or
intermittent flow operation. The slurry bed reactor may be
configured for batch operation. Bed 408 may include the ion
exchange resin. Bed 408 may be operatively coupled to a pressure
source 408A configured to operate bed 408 at a pressure in pounds
per square inch of at least about one or more of: gauge (PSIG) of
about one or more of: 0 to 100, 10 to 100, 10 to 75, 10 to 50, 10
to 25, and 10 to 20. Bed 408 may be operatively coupled to a heat
source 408B configured to operate bed 408 at a temperature in
.degree. C. of about one or more of: 25 to 100, 25 to 75, 30 to 50,
35 to 45, and 40, for example, 40.degree. C. Bed 408 may include as
the ion exchange resin one or more of: a poly(styrene sulfonic
acid), a poly(styrene carboxylic acid), and a
poly(2-acrylamido-2-methyl-1-propanesulfonic acid). For example,
the ion exchange resin may include a poly(styrene sulfonic acid)
characterized by one or more of: a surface area of about 28 to 37
square meters per gram, a particle diameter of 0.60 to 0.850
millimeters, a particle diameter uniformity coefficient of less
than about 1.6, a total pore volume of 0.15 to 0.25 milliliters per
gram, an average pore diameter of about 200 to 280 angstroms, and
an exchange capacity of at least about 5 milliequivalents per
gram.
[0116] In several embodiments, first catalytic unit 410 may include
the stabilizing catalyst. The stabilizing catalyst may include a
metal dispersed on a solid support, e.g., a metal oxide, a zeolite,
carbon, and the like, which may be acidic. The metal may include
one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The
metal oxide may include one or more of: titania, ceria, magnesium
oxide, niobium oxide, alumina, amorphous silica alumina, zirconia,
zinc oxide, niobic acid, tungstic acid, molybdic acid, carbon, and
silica.
[0117] In some embodiments, the stabilizing catalyst may include a
zeolite, e.g., an acidic zeolite. Further, the solid support may be
a zeolite, e.g., an acidic zeolite. The zeolite may include one or
more of: a Y zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite
zeolite, a Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48
zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, and a Chabazite
zeolite.
[0118] In various embodiments, the stabilizing catalyst may include
the metal dispersed on an acidic metal oxide, For example, the
stabilizing catalyst may include one or more of: Ru, Rh, Re, Pt,
Pd, Ir, Au, Fe, Ni, Nb, and Os; dispersed on one or more of:
titania, ceria, magnesium oxide, niobium oxide, alumina, amorphous
silica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,
molybdic acid, carbon, and silica. For example, catalytically
stabilizing the bio-oil may include contacting the bio-oil to a
stabilizing catalyst including Ru/TiO.sub.2.
[0119] In some embodiments, the stabilizing catalyst may include
the metal dispersed on an acidic zeolite. For example, the
stabilizing catalyst may include one or more of: Ru, Rh, Re, Pt,
Pd, Ir, Au, Fe, Ni, Nb, and Os; dispersed on one or more of: a Y
zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0120] In various embodiments, first catalytic unit 410 may be
operatively coupled to a pressure source 410A configured to operate
first catalytic unit 410 at a pressure in PSI of about one or more
of: 500 to 2500, 750 to 2250, 1000 to 2000, 1250 to 1750, 1400 to
1600, and 1500. First catalytic unit 410 may be operatively coupled
to a heat source 410B configured to operate first catalytic unit
410 at a temperature in .degree. C. of about one or more of: 40 to
300, 100 to 280, 120 to 270, 130 to 250, 140 to 225, 150 to 200,
160 to 180, 170, 250 to 550, 300 to 500, 325 to 475, 350 to 450,
375 to 425, and 400. First catalytic unit 410 may be configured to
operate at a liquid hourly space velocity (LHSV) of between about
0.05 hr.sup.-1 to 1 hr.sup.-1. First catalytic unit 410 may be
configured to operate for a TOS in hours of at least about one or
more of: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100,
1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000,
6,000, 7,000, 8,000, 12,000, and 16,000. First catalytic unit 410
may be operatively coupled to an organic solvent source 410C.
[0121] In some embodiments, system 400 may include a heat exchanger
418 operatively coupled between first catalytic unit 410 and second
catalytic unit 412. Heat exchanger 418 may be configured to
actively or passively limit heating of first catalytic unit 410 by
heat from second catalytic unit 412.
[0122] In several embodiments, second catalytic unit 412 may
include the hydrotreatment catalyst. The hydrotreatment catalyst
may be an active metal catalyst or a sulfided catalyst. For
example, the active metal catalyst may include a metal dispersed on
a solid support, e.g., a metal oxide, a zeolite, carbon, and the
like, each of which may be acidic. For example, the metal may
include one or more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and
Os. The metal oxide may include one or more of: titania, ceria,
magnesium oxide, niobium oxide, alumina, amorphous silica alumina,
zirconia, zinc oxide, niobic acid, tungstic acid, molybdic acid,
carbon, and silica. The hydrotreatment catalyst may include a
zeolite. Further, the solid support may be a zeolite, e.g., an
acidic zeolite. The zeolite may include one or more of: a Y
zeolite, a Beta zeolite, a ZSM-5 zeolite, a Mordenite zeolite, a
Ferrierite zeolite, a Al-MCM-41 zeolite, a MCM-48 zeolite, a MCM-22
zeolite, a SAPO-34 zeolite, and a Chabazite zeolite.
[0123] In various embodiments, the hydrotreatment catalyst may
include the metal dispersed on an acidic metal oxide, For example,
the hydrotreatment catalyst may include a metal including one or
more of: Ru, Rh, Re, Pt, Pd, Ir, Au, Fe, Ni, Nb, and Os. The metal
may be dispersed on a solid support comprising one or more of:
titania, ceria, magnesium oxide, niobium oxide, alumina, amorphous
silica alumina, zirconia, zinc oxide, niobic acid, tungstic acid,
molybdic acid, carbon, silica, a Y zeolite, a Beta zeolite, a ZSM-5
zeolite, a Mordenite zeolite, a Ferrierite zeolite, a Al-MCM-41
zeolite, a MCM-48 zeolite, a MCM-22 zeolite, a SAPO-34 zeolite, a
Chabazite zeolite, and carbon. For example, the active metal
catalyst may include one or more of Ru/TiO.sub.2,
Ru/TiO.sub.2--ZSM5 Pd/C, Pd/SiO.sub.2--Al.sub.2O.sub.3,
Pd/Nb/Al.sub.2O.sub.3, Pd/Nb/TiO.sub.2--SiO.sub.2,
Pt/ZrO.sub.2--Al.sub.2O.sub.3, and Pd/Mg/Al.sub.2O.sub.3.
[0124] Further, for example, the hydrotreatment catalyst may
include a sulfided catalyst, e.g., including one or more of: Ni,
Nb, Mo, Co, and W. For example, the sulfided catalyst may include
one or more of sulfided: Ni, Nb, Mo, Co, W, NiMo, and CoMo.
[0125] In several embodiments, second catalytic unit 412 may
include a pressure source 412A configured to pressurize second
catalytic unit 412 to a pressure in PSI of about one or more of:
500 to 2500, 750 to 2250, 1000 to 2000, 1250 to 1750, 1400 to 1600,
and 1500. Second catalytic unit 412 may include a heat source 412B
configured to heat second catalytic unit 412 to a temperature in
.degree. C. of about one or more of: 200 to 420, 220 to 400, 240 to
380, 260 to 360, 280 to 340, 300 to 320, and 310. Second catalytic
unit 412 may be configured to operate at a liquid hourly space
velocity (LHSV) of between about 0.05 hr.sup.-1 to 1 hr.sup.-1.
Second catalytic unit 412 may be configured to operate for a TOS in
hours of at least about one or more of: 200, 300, 400, 500, 600,
700, 800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750,
2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and
16,000.
[0126] In various embodiments, system 400 may include an inert gas
source 420 operatively coupled to provide an inert atmosphere to at
least a portion of system 400. Inert gas source 410 may be
configured to provide one or more of: nitrogen, carbon dioxide, and
a non-condensable gas product of biomass pyrolysis. Inert gas
source 410 may be coincident with, the same as, or operatively
coupled to one or more of pressure sources 406A, 408A, 410A, and
412A. Hydrogen source 414 may be coincident with, the same as, or
operatively coupled to one or more of pressure sources 406A, 408A,
410A, and 412A. Two or more of pressure sources 406A, 408A, 410A,
and 412A may be coincident, the same as each other, or operatively
coupled to each other. Two or more of heat sources 406B, 408B,
410B, and 412B may be coincident, the same as each other, or
operatively coupled to each other.
[0127] In some embodiments, pyrolysis reactor 402, inline filter
404, fine filtration module 406, bed 408, first catalytic unit 410,
and second catalytic unit 412 may be operatively coupled to provide
a continuous process for converting the biomass input to the
hydrocarbon output.
[0128] In several embodiments, system 400 may be configured to
operate for a TOS in hours of at least about one or more of: 200,
300, 400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200, 1,300,
1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000,
8,000, 12,000, and 16,000.
[0129] In various embodiments, a stabilized bio-oil is provided,
prepared according to any of the methods described herein or
prepared using any of the systems described herein. In various
embodiments, a hydrocarbon product derived from bio-oil is
provided, prepared according to any of the methods described herein
or prepared using any of the systems described herein.
[0130] In some embodiments, a stabilized bio-oil is provided. The
stabilized bio oil may be characterized by one or more of: a total
acid number (TAN) value less than 100 mg KOH/g; a water content of
at least about 17 wt. %; a hydrogen to carbon ratio greater than
1.4:1; and an average percentage of aldehyde and ketone groups of
less than about 5%.
[0131] In several embodiments, a hydrocarbon product derived from
bio-oil is provided. The hydrocarbon product may be characterized
by one or more of the following. The hydrocarbon product may be
characterized by one or more percentages by weight of: about 24%
paraffin, about 5.6% aromatics, about 8.6% naphthalenes, about 59%
nC.sub.5-C.sub.6 alkanes, and about 2.4% olefins. The hydrocarbon
product may be characterized by one or more of: a density in
grams/mL of 0.78-0.86; a total sulfur weight percent of less than
0.08%; a pour point in .degree. C. of less than about 20; a
viscosity in cPs of less than 2; a hydrogen:carbon atomic ratio of
about 1.5:1 to about 2.2:1; and an energy value in mega Joules per
kilogram of about 40 to 45. The hydrocarbon product may be
characterized by one or more of: a density of about 0.8 to about
0.86 grams per milliliter, a hydrogen:carbon ratio of about 1.5:1
to about 2.2:1, a dry oxygen weight percentage of about 0% to about
5%, and a water weight percentage of about 0% to about 5%.
EXAMPLES
Example 1
Preparation of Synthetic Bio-Oils with and without Inorganic
Species
[0132] Four synthetic bio-oil compositions were prepared to
determine the effects inorganic species had in deactivating the
hydrotreatment catalyst. The synthetic bio-oils included a mixture
of chemicals with functional groups similar to those found in
pyrolytic bio-oil. The synthetic bio-oil compositions included
carboxylic acids, aldehydes, phenols, polyols, and water, effective
to give the synthetic bio-oil a similar oxygen concentration (28%
wt) as pyrolytic bio-oil. Inorganic species were provided in
synthetic bio-oil compositions that included metal concentrations
comparable to that of pyrolytic bio-oil. The table in FIG. 5
reports species concentrations determined from inductively coupled
plasma (ICP) atomic analyses of pyrolytic bio-oil and synthetic
bio-oil.
[0133] A first synthetic bio-oil composition without inorganic
species was prepared by mixing acetic acid (6.8% by volume),
hydroquinone (9.1% by volume), D-glucose (7.8% by volume),
4-hydroxybenzoic acid (8.0% by volume), methanol (50.7% by volume)
and water (17.6% by volume). The methanol was added to the mixture
in order to solubilize hydroquinone and 4-hydroxybenzoic acid.
[0134] A second synthetic bio-oil composition with inorganic
species was prepared by mixing acetic acid (6.8% by volume),
hydroquinone (9.1% by volume), D-glucose (7.8% by volume),
4-hydroxybenzoic acid (8.0% by volume), methanol (50.7% by volume),
water (17.6% by volume), calcium (101 ppm) in the form of calcium
hydroxide, zinc (52 ppm) in the form of zinc acetate, sodium (49
ppm) in the form of sodium hydroxide, potassium (49 ppm) in the
form of potassium carbonate, magnesium (99 ppm) in the form of
magnesium carbonate, iron (148 ppm) in the form of iron acetate,
aluminum (287 ppm) in the form of aluminum lactate, phosphorus (50
ppm) in the form of phosphorus pentoxide, and sulfur (50 ppm).
[0135] A third synthetic bio-oil composition with
heteroatom-containing species was prepared by mixing acetic acid
(6.8% by volume), hydroquinone (9.1% by volume), D-glucose (7.8% by
volume), 4-hydroxybenzoic acid (8.0% by volume), methanol (50.7% by
volume), water (17.6% by volume), calcium (101 ppm) in the form of
calcium hydroxide, zinc (52 ppm) in the form of zinc acetate,
sodium (49 ppm) in the form of sodium hydroxide, potassium (49 ppm)
in the form of potassium carbonate, magnesium (99 ppm) in the form
of magnesium carbonate, iron (148 ppm) in the form of iron acetate,
aluminum (287 ppm) in the form of aluminum lactate, and phosphorus
(50 ppm) in the form of phosphorus pentoxide. The third synthetic
bio-oil composition with inorganic species did not include a sulfur
additive. A fourth synthetic bio-oil composition with inorganic
species was prepared by mixing acetic acid (6.8% by volume),
hydroquinone (9.1% by volume), D-glucose (7.8% by volume),
4-hydroxybenzoic acid (8.0% by volume), methanol (50.7% by volume),
water (17.6% by volume), and iron (148 ppm) in the form of iron
acetate.
Example 2
Hydrotreatment of Synthetic Bio-Oil without Inorganic Species
[0136] The first synthetic bio-oil without inorganic species was
subjected to hydrotreatment under various conditions. The
efficiency of the catalyst system was determined by analyzing the
products obtained from the hydrotreatment process:
[0137] 1) The catalyst was considered to be active if a biphasic
product resulted with an organic phase with a density of less than
0.8 g/cm.sup.3 and a water content of less than 5%. An aqueous
phase with a density of approximately 1 g/cm.sup.3 and a water
content greater than 90% was desirable. The hydro-deoxygenation
reaction scheme is illustrated below:
##STR00001##
[0138] Catalyst deactivation was indicated by an increase in the
density of the organic phase corresponding to an increase in water
content in the organic phase. An increase in density and water
content in the organic phase may result from remaining bio-oil
hydroxyls that may effectively hydrogen bond with water, thus
drawing the water into the organic phase. Remaining bio-oil
hydroxyls may be indicative of an inefficient or deactivated
catalyst.
[0139] 2) Measurement of non-condensable gases (R-H at higher
temperatures; C.sub.1-C.sub.6 hydrocarbons) released from the
reaction mixture indicated catalyst activity since the detection of
such gases suggested that hydro-deoxygenation was successful.
Methanol used to solubilize the synthetic bio-oil composition was
converted to methane under hydro-deoxygenation conditions. Thus,
assessment of the catalyst activity was made by detection of the
gaseous C.sub.2-C.sub.6 hydrocarbons by gas chromatography (GC)
analysis.
[0140] The first synthetic bio-oil without inorganic species was
subjected to hydrotreatment under the conditions illustrated in
FIGS. 6A-6C. The synthetic bio-oil was subjected to Zone I at
150.degree. C. and passed over a Ru/TiO.sub.2 catalyst at a liquid
hourly space velocity (LHSV) of 0.2 h.sup.-1 in the presence of
H.sub.2 at a 400 mL/min flow rate. The reaction mixture from Zone I
was subsequently subjected to Zone II at 280.degree. C. and passed
over a Ru/TiO.sub.2--ZSM5 catalyst at a LHSV of 0.2 h.sup.-1 in the
presence of H.sub.2 at a 400 mL/min flow rate (entry 1, FIG. 6C).
Samples were analyzed every 4-8 h for a duration of 0-40 h Time on
Stream (TOS) (see graph in FIG. 6D, and sections A and B in FIG. 6D
for parameters). The majority of the synthetic bio-oil was released
as gaseous hydrocarbons. The condensed liquid phase obtained was
mostly aqueous.
[0141] At 40 h TOS to 48 h TOS, the H.sub.2 flow rate had been
increased from 400 mL/min to 600 mL/min, and the LHSV was increased
from 0.2 h.sup.-1 to 0.4 h.sup.-1. The Zone I temperature was
maintained at 150.degree. C. and the Zone II temperature was
maintained at 280.degree. C. (entry 2, FIG. 6C). Samples were
analyzed every 4-8 h by GC (see graph in FIG. 6D, and sections B,
C, and D in FIG. 6D). Increasing the H.sub.2 flow and the LHSV did
not lead to a biphasic mixture.
[0142] At 48 h TOS to 60 TOS, the temperature of Zone II was
decreased from 280.degree. C. to 150.degree. C. The Zone I
temperature was maintained at 150.degree. C., the H.sub.2 flow rate
was maintained at 600 mL/min, and the LHSV was maintained at 0.4
h.sup.-1 (entry 3, FIG. 6C). Samples were analyzed every 4-8 h (see
graph in FIG. 6D, and sections C, D, E, and F in FIG. 6D).
Decreasing the temperature in Zone II, the hydro-deoxygenation
zone, led to poor catalytic activity. Although a biphasic mixture
was obtained, the organic phase contained approximately 30%
water.
[0143] At 60 h TOS to 170 h TOS, the temperature of Zone I was
increased from 150.degree. C. to 200.degree. C. and the temperature
of Zone II was increased from 150.degree. C. to 200.degree. C. The
H.sub.2 flow rate was maintained at 600 mL/min and the LHSV was
maintained at 0.4 h.sup.-1 (entry 4, FIG. 6C, see sections C, D,
and G in FIG. 6D). A biphasic mixture of hydrocarbons and water was
obtained. The organic phase had less than 1% water content and the
aqueous phase was more than 90% water.
Example 3
Hydrotreatment of Synthetic Bio-Oils with and without Inorganic
Species: Analysis of Organic Phase Density
[0144] Based on the results of EXAMPLE 2, operative conditions of
Zone I and Zone II at 200.degree. C. and a LHSV of 0.2 h.sup.-1
were used for studying the hydrotreatment of synthetic bio-oils
with and without inorganic species. FIG. 6E illustrates the density
of the organic phase obtained relative to time on system (TOS) for
the first, second, third, and fourth synthetic bio-oil compositions
described in EXAMPLE 1. The density of the organic phase did not
increase over time for the first synthetic bio-oil composition
without inorganic species. The addition of iron in the fourth
synthetic bio-oil did not adversely affect the density of the
organic phase product until after 24 h, which indicated that the
catalyst had begun to lose activity. The addition of other
heteroatoms, such as those of the second and third synthetic
bio-oils described in EXAMPLE 1, corresponded to a rapid increase
in the density of the organic phase product. From this experiment,
it was concluded that inorganic species deactivate the
catalyst.
Example 4
Hydrotreatment of Synthetic Bio-Oils with and without Inorganic
Species: Analysis of Organic Phase Water Content
[0145] Based on the results of EXAMPLE 2, operative conditions of
Zone I and Zone II at 200.degree. C. and a LHSV of 0.2 h.sup.-1
where used for studying the hydrotreatment of synthetic bio-oils
with and without inorganic species. FIG. 6F illustrates the water
content of the organic phase obtained relative to the TOS for the
first, second, third, and fourth synthetic bio-oil compositions
described in EXAMPLE 1. The water content of the organic phase
remained low throughout the TOS, which indicated that the catalytic
reduction was sustainable. Had the catalyst become deactivated over
time, it was expected that the unreacted hydroxyl-containing
moieties in the organic phase would effectively increase the
organic phase water content. Complimentary to the results in
EXAMPLE 3, the addition of iron as in the fourth synthetic bio-oil
did not adversely affect the water content of the organic phase
product until after 24 h, which indicated that the catalyst had
begun to lose activity. The addition of other heteroatoms, such as
those provided in the second and third synthetic bio-oils described
in EXAMPLE 1, corresponded to a rapid increase in the water content
of the organic phase product. In conjunction with EXAMPLE 3, this
experiment suggests that inorganic species deactivate the
catalyst.
Example 5
Hydrotreatment of Synthetic Bio-Oils with and without Inorganic
Species: Analysis of Gaseous C.sub.2-C.sub.6 Hydrocarbons
Produced
[0146] Based on the results of EXAMPLE 2, operative conditions of
Zone I and Zone II at 200.degree. C. and a LHSV of 0.2 h.sup.-1
were used for studying the hydrotreatment of synthetic bio-oils
with and without inorganic species. FIG. 6G illustrates the
C.sub.2-C.sub.6 hydrocarbon concentration in the non-condensable
gas relative to the TOS in the hydrotreatment process for the
first, second, third, and fourth synthetic bio-oil compositions
described in EXAMPLE 1. The concentration of C.sub.2-C.sub.6
hydrocarbons remained constant throughout TOS for the first
synthetic bio-oil without inorganic species, which indicated that
the catalytic reduction was sustainable. Complimentary to the
results in EXAMPLES 3 and 4, the addition of iron as in the fourth
synthetic bio-oil did not adversely affect the concentration of
C.sub.2-C.sub.6 hydrocarbons released until after 24 h, which
indicated that the catalyst had begun to lose activity. The
addition of other heteroatoms, such as those provided in the second
and third synthetic bio-oils described in EXAMPLE 1, corresponded
to a rapid decrease in the concentration of C.sub.2-C.sub.6
hydrocarbons released. In conjunction with EXAMPLES 3 and 4, this
experiment suggests that inorganic species deactivate the
catalyst.
Example 6
Hydrotreatment of Pyrolysis Bio-Oil
[0147] The results described in EXAMPLES 2-5 suggested that
inorganic species in the bio-oil deactivated the hydrotreatment
catalysts. It was hypothesized that pyrolytic bio-oil would be a
better feedstock for hydrotreatment in that the fluid-cracking
catalyst (FCC) used in the vapor phase catalytic reactor may have
removed some of the inorganic species during the pyrolysis process.
The organic phase obtained from the pyrolysis process was blended
with methanol (10% wt) to improve the homogeneity of the bio-oil
feedstock. The pyrolysis bio-oil composition was subjected to
hydrotreatment for 50 h TOS with fresh catalyst, as illustrated in
FIG. 7. Samples were analyzed every 8 h. After 50 h, the density of
the organic phase obtained had increased from 0.7 g/cm.sup.-3 to
0.9 g/cm.sup.-3, which indicated degradation of product quality and
suggested deactivation of the catalyst. The catalyst was
regenerated by rinsing with methanol at room temperature, and
reducing with H.sub.2 at 400.degree. C. Hydrotreatment was resumed
and revealed an increase in deactivation rate (the organic phase
densities increased at a faster rate). The catalyst was regenerated
two additional times, and each subsequent hydrotreatment process
produced a decrease in product quality at increasingly faster
rates. The increase in deactivation rates from cycle to cycle
suggested non-reversible catalyst deactivation. The C.sub.2-C.sub.6
hydrocarbon non-condensable gases were also monitored during the
experiments. The data from gaseous C.sub.2-C.sub.6 hydrocarbon
detection correlated with the data obtained in the organic phase
analyses.
[0148] The pyrolysis bio-oil used in EXAMPLE 6 was obtained from a
pyrolysis process using a spent FCC catalyst. Bio-oil obtained from
the use of fresh FCC catalyst may effectively increase the removal
of inorganic species prior to hydrotreatment. However, the focus in
removing inorganic species prior to hydrotreatment turned to other
means as described below.
Example 7
Production of Intermediate Bio-Oil
[0149] Bio-oil was produced using a continuous feed pyrolysis
system having a 1 ton per day capacity. A pine saw dust with a
particle size between 2 to 5 mm was continuously fed into the
pyrolysis system as a feedstock. The pyrolysis temperature was
between 450.degree. C. and 500.degree. C. The yield was
approximately 65-70% bio-oil by weight based on initial biomass
weight with a water content of 35-40%. The bio-oil was condensed
and filtered via a two filter system as follows. A 10 micrometer
filter was coupled to the pyrolysis output just after condensation
to provide a coarse-filtered bio-oil. The coarse-filtered bio-oil
was then directed to an ex-situ filter module that included a 0.8
micron. Using pressure up to 80 psi, the coarse-filtered bio-oil
was driven through the 0.8 micron to provide a fine-filtered
bio-oil. This fine-filtered bio-oil was collected and reserved for
further EXAMPLES as described below.
Example 8
Deactivation of Stabilization Catalyst is Associated with Inorganic
Contaminants
[0150] It is known that stabilization catalysts are readily
deactivated in contact with bio-oil. To determine the root cause of
catalyst deactivation, fresh and spent stabilization catalysts were
characterized after 500 h TOS.
[0151] The fresh (reduced at 400.degree. C.), spent (500 h TOS and
washed with methanol) and regenerated (spent, washed with methanol
and reduced) catalysts were analyzed by thermos-gravimetric
analysis in the presence of air from 120.degree. C. (held for 30
min) to 700.degree. C. (held for 30 min) at a rate of 10.degree.
C./min. The weight loss for the spent catalyst was approximately
24%. Reduction of the catalyst at 400.degree. C., 450.degree. C.,
and 500.degree. C. successively removed 90%, 93% and 95% of
material. This removal was attributed to the oxidation of carbon on
the catalyst to CO.sub.2. The remaining carbon (<10%) was
thought to be bonded strongly to the high active metal sites
located in the micro pores. These active sites are thought to be
difficult access, for example, due to diffusion limitations, which
may tend to prevent such sites from actively contributing to
catalysis at steady state. As a consequence, the regeneration of
the catalyst was judged to be efficient and the coke formation was
not judged to be the main cause of catalyst deactivation. FIG. 8
summarizes the results of the thermogravimetric experiments.
[0152] FIGS. 9A and 9B are transmission electron microscope (TEM)
photos showing that the fresh and spent catalysts, respectively,
had similar metal particle sizes (2 to 8 nanometers) and metal
dispersions. However, hydrogen adsorption data at room temperature
indicated that the fresh reduced catalyst had a metal dispersion of
12% and the regenerated spent catalyst had a metal dispersion of
less than 1%. This data indicates that the catalyst deactivation is
not due to a loss of surface area due to sintering.
[0153] FIG. 10 is a graph of ICP analysis of fresh and spent (post
500 h TOS) catalysts showing that deposition of inorganic
contaminants such as Ca, Fe and S are associated with deactivated
catalyst. The increase in certain inorganic metal contaminants not
present in the bio-oil feed, such as the 1,500 ppm of Fe, may
indicated that such species are leaching out of the steel of the
hydrotreatment reactor.
[0154] By contrast, the small amounts of sulfur in the feed (8.92
ppm) compared to the 1,800 ppm of sulfur on the catalyst after 500
h TOS was judged to occur by accumulation of sulfur from the
bio-oil feed on the catalyst.
[0155] In view of these results, EXAMPLE 9 was devised to remove
inorganic contaminants from the bio-oil prior to Zone I
stabilization in order to reduce catalyst deactivation.
Example 9
Ion Exchange Media Removes Inorganic Species from Bio-Oil
[0156] EXAMPLE 8 corresponds to EXAMPLES 2-5 in describing
inorganic species poisoning as the most probable cause of permanent
deactivation of hydrotreatment catalysts, with the poisoning being
associated with inorganic salts and covalent sulfur containing
compounds. Consequently, a variety of media were tested to remove
the inorganic species and covalent sulfur containing compounds from
the bio-oil.
[0157] Preliminary tests showed that a polystyrene sulfonic acid
ion exchange resin (AMBERLYST.TM. 36, Dow Chemical Company,
Midland, Mich.) effectively removed many inorganic species. Samples
of unfiltered, coarse-filtered, and fine-filtered bio-oil from both
batch and flow reactors were contacted to the polystyrene sulfonic
acid ion exchange resin in a slurry reactor at about 40.degree. C.
for about 1 h. FIG. 11 reports the concentration in parts per
million of various inorganic species measured via inductively
coupled plasma (ICP) atomic analysis for the fine-filtered bio-oil
of EXAMPLE 7 before and after contact with the polystyrene sulfonic
acid ion exchange resin under various conditions.
[0158] A fixed bed flow reactor was prepared by loading the
polystyrene sulfonic acid ion exchange resin into a column. A
slurry bed batch reactor was prepared by loading the polystyrene
sulfonic acid ion exchange resin into a 2 L three-necked flask
equipped with a stirrer and a thermocouple. Both reactors were
supplied with the fine-filtered bio-oil of EXAMPLE 7 under nitrogen
and at 40.degree. C.
[0159] FIG. 11 shows that the content of inorganic elements such as
Al, Ca, Fe, K, Mg, Na, Si and S could be decreased, in many cases
below 3.0 ppm, which suggested a successful removal of these
inorganics from bio-oil. The fixed bed flow reactor worked well to
remove inorganic species from the fine-filtered bio-oil to produce
a reduced-inorganic bio-oil as shown for trial #1 in FIG. 11.
However, with the benchtop equipment available, the fixed bed flow
reactor operated at an undesirably low space velocity. The slurry
bed batch reactor required far less time to remove the inorganic
contaminants. Accordingly, the slurry bed batch reactor was
selected for use in further tests to produce the reduced-inorganic
bio-oil.
[0160] In trial #2, operation of the slurry bed batch reactor on a
fine-filtered bio-oil with a relatively higher initial amounts of
most inorganic species was able to remove most species to a
concentration below about 6 ppm. In trial #3, operation of the
slurry bed batch reactor on a fine-filtered bio-oil with a somewhat
lower overall amounts of inorganic species was able to remove most
species to a concentration below about 3 ppm. The amount of K in
trial #3 was removed to below 6 ppm, which was still judged to be
effective.
[0161] The minimal amount of sulfur-containing species removed in
trial #3 compared to other inorganic atoms was thought to indicate
that most sulfur-containing species contained sulfur covalently
bonded in organic compounds, with a lesser amount of sulfur present
in the form of ionic species. By contrast, the effective removal of
inorganic elements such as Al, Ca, Fe, K, Mg, Na, and Si was
thought to indicate the presence of these elements in ionic species
which were readily adsorbed on the ion exchange resin. Six liters
of cleaned, reduced-inorganic bio-oil produced according to this
EXAMPLE was collected and retained for use in subsequent EXAMPLES
including stabilization and hydrogenation/cracking.
[0162] It was thought that if the sulfur was bound covalently, then
it could potentially remain bound to the carbon under subsequent
mild stabilization conditions, which could avoid sulfur poisoning
of the stabilization catalyst in Zone I (EXAMPLE 10). It was
further thought that such stabilized, but sulfur-containing bio-oil
would still be an suitable substrate if a sulfided catalyst was
used for subsequent hydrogenation and cracking in Zone II (EXAMPLE
11).
[0163] The fine-filtered bio-oil (before ion exchange treatment)
and the reduced-inorganic bio-oil (after ion exchange treatment)
were also examined by .sup.1H NMR. FIGS. 18A and 18B illustrate
.sup.1H NMR (proton nuclear magnetic resonance) spectroscopy data
of the fine-filtered bio-oil and the reduced-inorganic bio-oil.
FIG. 18A shows .sup.1H NMR overlay spectra from about 6 ppm to 13
ppm, wherein the bottom spectrum is the spectrum obtained from the
fine-filtered bio-oil and the top spectrum is the spectrum obtained
from the reduced-inorganic bio-oil. FIG. 18B shows .sup.1H NMR
overlay spectra from 0 ppm to about 6 ppm, wherein the bottom
spectrum is was obtained from the fine-filtered bio-oil and the top
spectrum was obtained from the reduced-inorganic bio-oil. No
changes were observed in the functional groups associated with the
bio-oil in the .sup.1H NMR spectra. Thus, the ion exchange resin
treatment at 40.degree. C. reduced inorganic contaminants as shown
in FIG. 10 without significant chemical modifications to the
bio-oil.
Example 10
Use of Reduced-Inorganic Bio-Oil in Production of Stabilized
Bio-Oil (Zone I) Leads to 1,000 Hour TOS with Improved Catalyst
Life and Reduced Corrosion
[0164] Bio-oil hydrotreatment has been performed in a dual zone
reactor, with stabilization in Zone I at about 150 to 300.degree.
C. and hydrogenation and cracking in Zone II at a higher
temperature, e.g., 300 to 400.degree. C. Previous experiments have
shown that in a small-scale dual zone reactor, significant axial
heat transfer takes place from the higher temperature Zone II to
the lower temperature Zone I. This tends to cause undesirably high
temperatures in Zone I and poor temperature control, which can lead
to accelerated coking and catalyst deactivation. Also, operation of
a continuous dual zone reactor does not readily permit sampling and
analysis of the bio-oil between Zones I and II, which is desirable
in these initial experiments. In addition, at the flow rates used
in small-scale test reactors, sulfur from Zone II may contaminate
the catalyst in Zone I. Accordingly, in these initial experiments,
bio-oil stabilization in Zone I and hydrogenation/cracking in Zone
II were conducted separately. Separation of Zone I and Zone II in
these initial experiments allowed provided desired control of the
operating conditions. Production scale operations may operate Zone
I and Zone II directly in series while reducing thermal and sulfur
backflow by using one or more of higher flow rates, baffles,
separation between zones, heat exchangers or insulated conduits
between zones, and the like. Moreover, at production scale,
sampling and analysis may not be needed between Zone I and Zone
II.
[0165] The objective of the Zone I stabilization/hydrotreatment was
to reduce aldehydes and acids and to partially hydrogenate the
bio-oil. Prior to hydrotreatment, the resin-treated bio-oil (38 wt
% water; 1.1 g/cm.sup.3; pH=2) was diluted with methanol (30 wt %)
to achieve a homogeneous bio-oil composition (24 wt % water; 0.99
g/cm.sup.3; pH=2.46) in order to prevent stratification in the
delivery syringe pump, thus providing a uniform feed to the
reactor. Zone I stabilization/hydrotreatment was conducted at high
pressure in the presence of hydrogen. Hydrotreatment was conducted
in three cycles using the same catalyst, Ru/TiO.sub.2. The catalyst
was regenerated twice during the three test cycles. The total TOS
achieved was 1,000 h at a LHSV of 0.2 h.sup.-1. More than 3.5
liters of bio-oil produced was processed. The Zone I
stabilization/hydrotreatment was conducted in three cycles. After
each cycle, the reactor was carefully disassembled and a sample of
catalyst was collected. The catalyst loading and flow rate for
cycle 1 are presented in FIG. 12.
[0166] In cycle 1, the catalyst was subjected to reducing
conditions in-situ at 300.degree. C. with hydrogen. The run started
at 170.degree. C. with a LHSV of 0.2 h.sup.-1 based on bio-oil.
After 516 h TOS, an increase in differential pressure across the
catalyst bed related to carbon deposition on the catalyst was
noted. The system was shut down and the catalyst was carefully
removed. The spent catalyst was washed carefully with methanol to
remove soft carbon, dried at 60.degree. C., and loaded in the
reactor to perform cycle 2.
[0167] In cycle 2, the catalyst as washed with methanol in cycle 1
was subjected to reducing conditions in-situ at 400.degree. C. with
hydrogen to remove additional remaining carbon. Some of the
catalyst was lost due to washing and repacking the catalyst. The
flow of bio-oil was adjusted to reflect the loss of catalyst. The
reaction was then resumed at 170.degree. C. with a LHSV of 0.2
hr.sup.-1. After 440 h TOS (cycle 2), the reactor started plugging,
at which point the reactor was shut down and the catalyst was
carefully removed. The spent catalyst was washed carefully with
methanol to remove soft carbon, dried at 60.degree. C., and loaded
in the reactor to perform cycle 2.
[0168] In cycle 3, the catalyst as washed with methanol in cycle 2
was subjected to reducing conditions in-situ at 400.degree. C. with
hydrogen to remove additional remaining carbon. Some of the
catalyst was lost due to washing and repacking the catalyst. The
flow of bio-oil was adjusted to reflect the loss of catalyst. The
flow of bio-oil was adjusted to reflect these changes. The reaction
was resumed at 170.degree. C. and a LHSV of 0.2 hr.sup.-1. After
260 h TOS, the reaction was stopped as planned.
[0169] In some runs, the reduced-inorganic bio-oil of EXAMPLE 9 was
diluted with methanol to improve homogeneity of the bio-oil and
improve loading into the stabilization reactor with the available
vertically-oriented benchtop syringe pumps. The run described in
FIG. 12, with a LHSV of 0.2 hr.sup.-1, was conducted in the absence
of methanol.
[0170] In each cycle, the liquid yield (stabilized bio-oil
product/reduced-inorganic bio-oil feed) was approximately 100%. Two
phases were obtained during all cycles, a light phase (95% wt) with
a density of approximately 0.97 g/cm.sup.3 and a heavy phase (5%
wt) with a density of 1.07 (g/cm.sup.3). It was easier to discern
two phases in the stabilized bio-oil during the first 400 h TOS.
After 400 h TOS, the stabilized bio-oil had the appearance of a
single phase. Since the yield of the heavy phase was only about 5%,
no measurement was made on the heavy phase after 400 h TOS. FIG. 13
graphs liquid and dry yield ratios of (stabilized bio-oil
product/cleaned bio-oil feed). Dry yield is the total yield
excluding water.
[0171] FIG. 14 is a graph of the pH of the stabilized bio-oil
product versus TOS. The pH of the liquid product increased from 2.4
(in the reduced-inorganic bio-oil feed) to 3.7 after treatment in
Zone I.
[0172] FIG. 15 is a graph of water content in the liquid phase as
determined by the Karl Fisher method. Water content increased
slightly in the light phase to approximately 35% after cycle 1
relative to the water content of the reduced-inorganic bio-oil feed
(approximately 25%). Without wishing to be bound by theory, it is
believed that this can be explained by esterification reactions and
interactions with aldehydes with other functional groups such as
acids, ketones and olefins as well as etherification reactions
which may occur during Zone I stabilization.
[0173] The reduced-inorganic bio-oil (before Zone I) and the
stabilized bio-oil (after Zone I) were also examined by .sup.1H
NMR. FIGS. 19A and 19B illustrate .sup.1H NMR spectroscopy data of
the reduced-inorganic bio-oil and the stabilized bio-oil from 0-324
h TOS. FIG. 19A shows .sup.1H NMR overlay spectra from about 6 ppm
to 13 ppm. The spectrum at TOS=0 h was obtained from the
reduced-inorganic bio-oil. The overlay spectra at TOS=55-60 h,
106-112 h, 242-252 h, and 312-324 h were obtained from the
stabilized bio-oil at the corresponding TOS. FIG. 19B shows .sup.1H
NMR overlay spectra from 0 ppm to about 6 ppm. The spectrum at
TOS=0 h was obtained from the reduced-inorganic bio-oil. The
overlay spectra at TOS=55-60 h, 106-112 h, 242-252 h, and 312-324 h
were obtained from the stabilized bio-oil at the corresponding
TOS.
[0174] FIGS. 20A and 20B illustrate data of the stabilized bio-oil
from 466-478 h TOS with respect to the reduced inorganic bio-oil at
TOS=0 h. FIG. 20A shows .sup.1H NMR overlay spectra from about 6
ppm to 13 ppm. The spectrum at TOS=0 h was obtained from the
reduced-inorganic bio-oil. The overlay spectra at TOS=466-478 h,
502-514 h, 676-700 h, 773-797 h, 820-844 h, 916-940 h, and 964-1010
h were obtained from the stabilized bio-oil at the corresponding
TOS. FIG. 20B shows .sup.1H NMR overlay spectra from 0 ppm to about
6 ppm. The spectrum at TOS=0 h was obtained from the
reduced-inorganic bio-oil. The overlay spectra at TOS=466-478 h,
502-514 h, 676-700 h, 773-797 h, 820-844 h, 916-940 h, and 964-1010
h were obtained from the stabilized bio-oil at the corresponding
TOS. The .sup.1H NMR spectra indicated that Zone I treatment caused
led to reduction of significant amounts of aldehyde and acid
functional groups, partial hydrogenation of aromatics and olefins,
and the appearance of new aliphatic compounds. These results
indicate that esterification, etherification, and partial
hydrogenation reactions were taking place during the Zone I
stabilization/hydrotreatment. These reactions were more pronounced
in the first 500 h and then decreased as TOS progressed. The
disappearance in carboxylic acid resonances suggested that
esterification reactions had occurred during Zone I treatment,
though later reappearance of carboxylic acid resonances suggested
that saponification of the esters may have occurred.
[0175] FIG. 16A displays the molar hydrogen/carbon ratio (H/C) of
the stabilized bio-oil as function of TOS. The H/C ratio is
corrected for the presence of methanol and water. The H/C ratio was
higher than that of the reduced-inorganic bio-oil feed (1.1) but
decreased with TOS suggesting continued catalyst deactivation. Even
after 1,000 h TOS, the H/C ratio was at 1.4, significantly higher
than that of the feed, indicating that the catalyst was still
active.
[0176] FIG. 16B displays the Total Acidity Number, TAN (mg KOH/gram
of sample). The TAN was less than the feed stock even after 1,000 h
TOS. However, the TAN increased with TOS reflecting deactivation of
catalyst. The TAN of the stabilized bio-oil was still lower than
that of the feed after 1,000 h TOS.
[0177] The results of this EXAMPLE indicate that Zone I processing
effectively reduced aldehydes during over the 1,000 h TOS
hydrotreatment operation. FIG. 16A shows that significant
hydrogenation continued to occur, increasing the H/C ratio from 1.1
to 1.4, even at 1,000 h TOS. Moreover, FIG. 14 shows that the pH of
the stabilized bio-oil was fairly constant at about 3.5, relative
to the pH of 2.4 for the reduced-inorganic bio-oil feed. FIG. 16B
shows that the TAN of the product is still lower than the TAN of
the feed. Although there is some indication of deactivation of the
catalyst, these results show that the catalyst was still effective
at reducing the aldehydes in the reduced-inorganic bio-oil feed, in
hydrogenation, and in reducing organic acids. The stabilized
bio-oil produced in this EXAMPLE was collected and reserved for
further use.
Example 11
Production of Hydrocarbon Products by Hydrotreating Stabilized
Bio-Oil
[0178] The stabilized bio-oil produced in EXAMPLE 10 was then
treated in a second stage, Zone II hydrotreatment/cracking process
hydrotreating using a sulfided CoMo catalyst. This EXAMPLE was
conducted at about 310.degree. C. under about 1,500 PSI of
hydrogen. Further runs are contemplated in a temperature range of
280-340.degree. C. under about 1160-1740 PSI of hydrogen.
[0179] In an initial run, the Zone II process was run for 200 h TOS
was successfully finished in this quarter. FIG. 17A is a graph of
the density of the hydrocarbon product of Zone II versus TOS. FIG.
17A shows that the density of the hydrocarbon product of Zone II
increased during the first 60 h TOS and then was relatively
constant from 60-200 h TOS. FIG. 17B shows that H.sub.2 consumption
was also constant during the run. Further runs using this same
catalyst and another stabilized bio-oil sample effectively
demonstrated about 1,400 h TOS.
[0180] To the extent that the term "includes" or "including" is
used in the specification or the claims, it is intended to be
inclusive in a manner similar to the term "comprising" as that term
is interpreted when employed as a transitional word in a claim.
Furthermore, to the extent that the term "or" is employed (e.g., A
or B) it is intended to mean "A or B or both." When the applicants
intend to indicate "only A or B but not both" then the term "only A
or B but not both" will be employed. Thus, use of the term "or"
herein is the inclusive, and not the exclusive use. See Bryan A.
Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995).
Also, to the extent that the terms "in" or "into" are used in the
specification or the claims, it is intended to additionally mean
"on" or "onto." To the extent that the term "selectively" is used
in the specification or the claims, it is intended to refer to a
condition of a component wherein a user of the apparatus may
activate or deactivate the feature or function of the component as
is necessary or desired in use of the apparatus. To the extent that
the terms "operatively coupled" or "operatively connected" are used
in the specification or the claims, it is intended to mean that the
identified components are connected in a way to perform a
designated function. To the extent that the term "substantially" is
used in the specification or the claims, it is intended to mean
that the identified components have the relation or qualities
indicated with degree of error as would be acceptable in the
subject industry.
[0181] As used in the specification and the claims, the singular
forms "a," "an," and "the" include the plural unless the singular
is expressly specified. For example, reference to "a compound" may
include a mixture of two or more compounds, as well as a single
compound.
[0182] As used herein, the term "about" in conjunction with a
number is intended to include .+-.10% of the number. In other
words, "about 10" may mean from 9 to 11.
[0183] As used herein, the terms "optional" and "optionally" mean
that the subsequently described circumstance may or may not occur,
so that the description includes instances where the circumstance
occurs and instances where it does not.
[0184] As stated above, while the present application has been
illustrated by the description of embodiments thereof, and while
the embodiments have been described in considerable detail, it is
not the intention of the applicants to restrict or in any way limit
the scope of the appended claims to such detail. Additional
advantages and modifications will readily appear to those skilled
in the art, having the benefit of the present application.
Therefore, the application, in its broader aspects, is not limited
to the specific details, illustrative examples shown, or any
apparatus referred to. Departures may be made from such details,
examples, and apparatuses without departing from the spirit or
scope of the general inventive concept.
[0185] The various aspects and embodiments disclosed herein are for
purposes of illustration and are not intended to be limiting, with
the true scope and spirit being indicated by the following
claims.
* * * * *