U.S. patent application number 13/321702 was filed with the patent office on 2012-06-07 for processing biomass with a hydrogen source.
This patent application is currently assigned to KIOR, INC.. Invention is credited to Robert Bartek, Paul O'Connor, Steve Yanik.
Application Number | 20120137572 13/321702 |
Document ID | / |
Family ID | 43126538 |
Filed Date | 2012-06-07 |
United States Patent
Application |
20120137572 |
Kind Code |
A1 |
Bartek; Robert ; et
al. |
June 7, 2012 |
PROCESSING BIOMASS WITH A HYDROGEN SOURCE
Abstract
A method is disclosed including co-processing a biomass
feedstock and a refinery feedstock in a refinery unit. The method
can include producing a liquid product by catalytically cracking or
hyrocracking or hydrotreating a biomass feedstock and a refinery
feedstock in a refinery unit having a fluidized reactor.
Catalytically cracking can include transferring hydrogen from the
refinery feedstock to carbon and oxygen from the biomass feedstock.
Hydrocracking or hydrotreating can include transferring hydrogen
from a hydrogen source to carbon and oxygen from the biomass
feedstock, and to carbon from the refinery feedstock.
Inventors: |
Bartek; Robert; (Centennial,
CO) ; Yanik; Steve; (Colorado Springs, CO) ;
O'Connor; Paul; (Hoevelaken, NL) |
Assignee: |
KIOR, INC.
Pasadena
TX
|
Family ID: |
43126538 |
Appl. No.: |
13/321702 |
Filed: |
May 24, 2010 |
PCT Filed: |
May 24, 2010 |
PCT NO: |
PCT/US2010/035940 |
371 Date: |
February 23, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61180501 |
May 22, 2009 |
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61220794 |
Jun 26, 2009 |
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Current U.S.
Class: |
44/307 ; 422/600;
549/505; 562/513; 568/303; 568/420; 568/799; 568/840; 585/638;
585/733 |
Current CPC
Class: |
C10G 47/34 20130101;
C10G 1/002 20130101; C10G 47/02 20130101; Y02P 30/20 20151101; C10G
47/00 20130101; C10G 2300/1077 20130101; C10G 47/30 20130101; C10G
2300/1014 20130101; C10G 3/50 20130101; C10G 1/08 20130101; C10G
3/56 20130101; C10G 3/57 20130101; C10G 2300/107 20130101; C10G
49/007 20130101; C10G 11/18 20130101; C10G 3/62 20130101; C10G 3/42
20130101; C10G 45/02 20130101; C10G 2300/1011 20130101; C10G
2300/1074 20130101; C10G 1/06 20130101 |
Class at
Publication: |
44/307 ; 585/733;
585/638; 562/513; 568/420; 568/840; 568/799; 568/303; 549/505;
422/600 |
International
Class: |
C10L 1/00 20060101
C10L001/00; C07C 51/00 20060101 C07C051/00; B01J 8/00 20060101
B01J008/00; C07C 29/00 20060101 C07C029/00; C07C 37/50 20060101
C07C037/50; C07D 307/34 20060101 C07D307/34; C07C 1/20 20060101
C07C001/20; C07C 45/00 20060101 C07C045/00 |
Claims
1. A method for co-processing a biomass feedstock and a refinery
feedstock in a refinery unit comprising: producing a liquid product
by catalytically cracking a biomass feedstock and a refinery
feedstock in a refinery unit comprising a fluidized reactor,
wherein catalytically cracking comprises transferring hydrogen from
the refinery feedstock to carbon and oxygen from the biomass
feedstock,
2. A method for co-processing a biomass feedstock and a refinery
feedstock in the presence of hydrogen gas in a refinery unit
comprising: producing a liquid product by hydrocracking or
hydrotreating a biomass feedstock and a refinery feedstock in the
presence of hydrogen gas in a refinery unit comprising a
hydrocracking or hydrotreating reactor, wherein hydro cracking or
hydrotreating comprises transferring hydrogen from the hydrogen gas
to carbon and oxygen from the biomass feedstock and to carbon from
the refinery feedstock.
3. The method of claim 1 or 2, further comprising increasing liquid
product yield by increasing H.sub.2O formation relative to at least
one of CO and CO2 formation.
4. The method of claim 1 or 2, further comprising operating the
refinery unit at a site adjacent to a solid biomass growth
source.
5. The method of claim 1 or 2, wherein the biomass feedstock
comprises a plurality of solid biomass particles.
6. The method of claim 5, wherein the plurality of solid biomass
particles are substantially characterized by an average size
between about 50 and about 1,000 microns and individual sizes
between about 0.1 and about 1,500 microns.
7. The method of claim 5, further comprising a catalyst is in
mechano-chemical interaction with at least as portion of the solid
biomass particles.
8. The method of claim 1 or 2, wherein the biomass feedstock
comprises a heavy liquid fraction of a liquefied biomass
feedstock.
9. The method of claim 1 or 2, wherein the biomass feedstock is
substantially free of mineral contamination capable of inactivating
a catalyst.
10. The method of claim 1 or 2, wherein the refinery unit comprises
a system for at least one of refreshing and regenerating a
catalyst.
11. The method of claim 1 or 2, wherein the refinery feedstock
comprises one or more of an atmospheric gas oil or a vacuum gas oil
from a paraffinic or naphthenic crude source a resid from a
paraffinic or naphthenic crude source, a hydrotreated vacuum gas
oil, a hydro treated resid, and a hydro treated light cycle
oil.
12. A refinery unit for co-processing a biomass feedstock and a
refinery feedstock comprising: a fluidized reactor; a first system
providing a biomass feedstock and a refinery feedstock to the
fluidized reactor; and a second system for at least one of
refreshing and regenerating a catalyst for the fluidized reactor,
wherein the first system and the second system support catalytic
cracking comprising transferring hydrogen from the refinery
feedstock to carbon and oxygen from the biomass feedstock within
the fluidized reactor.
13. A method for providing a refinery unit for co-processing a
biomass feedstock and a refinery feedstock comprising: providing a
fluidized reactor; providing a first system providing a biomass
feedstock and a refinery feedstock to the fluidized reactor; and
providing a second system for at least one of refreshing and
regenerating a catalyst in the fluidized reactor; wherein the first
system and the second system support catalytic cracking comprising
transferring hydrogen from the refinery feedstock to carbon and
oxygen from the biomass feedstock within the fluidized reactor.
14. A refinery unit for co-processing a biomass feedstock and a
refinery feedstock in the presence of hydrogen gas comprising;
hydrocracking or hydrotreating reactor; a first system providing a
biomass feedstock, a refinery feedstock, and hydrogen gas to the
hydrocracking or hydrotreating reactor; and a second system for at
least one of refreshing and regenerating a catalyst in the
hydrocracking or hydrotreating reactor; wherein the first system
and the second system support hydrocracking or hydrotreating
comprising transferring hydrogen from the hydrogen gas to carbon
and oxygen from the biomass feedstock and to carbon from the
refinery feedstock in the hydrocracking or hydrotreating
reactor.
15. A method for providing a refinery unit for co-processing a
biomass feedstock and a refinery feedstock in the presence of
hydrogen gas comprising: providing a hydrocracking or hydrotreating
reactor; providing a first system providing a biomass feedstock, a
refinery feedstock, and hydrogen gas to the hydrocracking or
hydrotreating reactor; and providing a second system for at least
one of refreshing and regenerating a catalyst in the hydrocracking
or hydrotreating reactor; wherein the first system and the second
system support hydrocracking or hydrotreating comprising
transferring hydrogen from the hydrogen gas to carbon and oxygen
from the biomass feedstock and to carbon from the refinery
feedstock in the hydrocracking or hydrotreating reactor.
16. The method of claim 1 or 2, further comprising using a basic
catalyst.
17. The method of claim 1 or 2, further comprising using a zeolite
catalyst.
18. The method of claim 1 or 2, wherein the reactor comprises a bed
reactor.
19. The method of claim 1 or 2, wherein the reactor comprises a
transport reactor.
20. The method of claim 1 or 2, wherein the reactor comprises at
least one of a riser reactor and a downer reactor.
21. The method of claim 1 or 2, further comprising a reaction time
of about 2 seconds or less.
22. The method of claim 1 or 2, further comprising a reaction time
that favors kinetic products relative to equilibrium products.
23. The method of claim 1 or 2, further comprising de-mineralizing
the biomass feedstock.
24. The method of claim 1 or 2, further comprising torrefying the
biomass feedstock at a temperature below about 300.degree. C., to
produce a plurality of solid biomass particles having at least one
of an increased brittleness and an increased susceptibility to
catalytic conversion.
25. The method of claim 1 or 2, further comprising: agitating solid
biomass particles, to reduce a size characterizing at least a
portion of the particles; and separating a biomass-catalyst mixture
comprising the particles and a catalyst into a fine fraction
comprising particles of about a predetermined size and a coarse
fraction comprising particles of greater than about the
predetermined size.
26. The method of claim 24, wherein separating includes using a
high velocity cyclone.
27. The method of claim 5, wherein the plurality of solid biomass
particles are substantially characterized by at least about 80% of
the particles having individual sizes of about 10 microns or
less.
28. The method of claim 1 or 2, wherein the refinery feedstock
comprises a hydrogen donor.
29. The method of claim 1 or 2, wherein the refinery unit comprises
a petrochemical refinery unit.
30. The method of claim 1 or 2, wherein the refinery feedstock
comprises a petrochemical feedstock.
31. The method of claim 1 or 2, further comprising using one or
more of a hydrotreating, hydrocracking, hydrogenation, NiMo, CoMo,
NiCoMo, noble metal, and supported noble metal catalyst.
32. The method of claim 1 or 2, wherein the refinery feedstock
comprises a product or a combination of products derived from crude
oil and destined for further processing.
33. The method of claim 1 or 2, further comprising: providing the
biomass feedstock to the conventional refinery unit using a first
feed system; and providing the refinery feedstock to the
conventional refinery unit using a second feed system.
34. The refinery unit of claim 12 or 14, further comprising: a
first feed system providing the biomass feedstock to the
conventional refinery unit; and a second feed system providing the
refinery feedstock to the conventional refinery unit.
35. The method of claim 5, herein the plurality of solid biomass
particles are substantially characterized by individual sizes by
individual sizes below about 1500 microns.
36. The method of claim 5, wherein the plurality of solid biomass
particles are substantially characterized by at least about 80% of
the particles having individual sizes of about 1500 microns or
less.
37. The method of claim 1 or 2, further comprising using a
water-insoluble catalyst.
38. The method of claim 1 or 2, further comprising using a solid
has catalyst comprising hydrotalcite; hydrotalcite-like material;
clay; layered hydroxy salt; mixed metal oxide; a calcination
product of any of these materials; or a mixture thereof.
39. The method of claim 1 or 2, further comprising using an alumina
catalyst.
40. The method of claim 1 or 2, further comprising using a fluid
catalytic cracking catalyst.
41. The method of claim 1 or 2, further comprising using a
petroleum coke catalyst.
Description
FIELD OF THE INVENTION
[0001] The invention relates to producing a fuel or specialty
chemical product from biomass through a chemical process. The
invention relates more particularly to converting biomass together
with a hydrogen source into a fuel, specialty chemical, and/or
intermediate product.
BACKGROUND OF THE INVENTION
[0002] Biomass, in particular biomass of plant origin, is
recognized as an abundant potential source of fuels and specialty
chemicals. See, for example, "Energy production from biomass," by
P. McKendry--Bioresource Technology 83 (2002) P 37-46 and
"Coordinated development of leading biomass pretreatment
technologies" by Wyman et al., Bioresource Technology 96 (2005)
1959-1966. Refined biomass feedstock, such as vegetable oils,
starches, and sugars, can be substantially converted to liquid
fuels including biodiesel (e.g., methyl or ethyl esters of fatty
acids) and ethanol. However, using refined biomass feedstock for
fuels and specialty chemicals can divert food sources from animal
and human consumption, raising financial and ethical issues.
[0003] Alternatively, inedible biomass can be used to produce
liquid fuels and specialty chemicals. Examples of inedible biomass
include agricultural waste (such as bagasse, straw, corn stover,
corn husks, and the like) and specifically grown energy crops (like
switch grass and saw grass). Other examples include trees, forestry
waste, such as wood chips and saw dust from logging operations, or
waste from paper and/or paper mills. In addition, aquacultural
sources of biomass, such as algae, are also potential feedstocks
for producing fuels and chemicals. Inedible biomass generally
includes three main components lignin, amorphous hemi-cellulose,
and crystalline cellulose. Certain components (e.g., lignin) can
reduce the chemical and physical accessibility of the biomass,
which can reduce the susceptibility to chemical and/or enzymatic
conversion.
[0004] Attempts to produce fuels and specialty chemicals from
biomass can result in low value products (e.g., unsaturated, oxygen
containing, and/or annular hydrocarbons). Although such low value
products can be upgraded into higher value products (e.g.,
conventional gasoline, jet fuel), upgrading can require specialized
and/or costly conversion processes and/or refineries, which are
distinct from and incompatible with conventional petroleum-based
conversion processes and refineries. Thus, the widespread use and
implementation of biomass to produce fuels and specialty chemicals
faces many challenges because large-scale production facilities are
not widely available and can be expensive to build. Furthermore,
existing processes can require extreme conditions (e.g., high
temperature and/or pressure, expensive process gasses such as
hydrogen, which increases capital and operating costs), require
expensive catalysts, suffer low conversion efficiency (e.g.,
incomplete conversion or inability to convert lignocellulosic and
hemi-cellulosic material), and/or suffer poor product
selectivity.
BRIEF SUMMARY OF THE INVENTION
[0005] In various embodiments, the invention includes methods,
apparatuses, kits, and compositions for converting cellulosic
(e.g., including ligno-cellulosic and hemicellulosic) material in
biomass (e.g., including edible and inedible portions) into fuels
and/or specialty chemicals under conditions that can mitigate
equipment cost, energy cost, and/or degradation or undesirable
reaction of conversion product. Examples of fuels include light
gases (e.g., ethane, propane, butane), naphtha, and distillates
(e.g., jet fuel, diesel, heating oil). Examples of chemicals
include light olefins (e.g., ethylene, propylene, butylenes), acids
(e.g., formic and acetic), aldehydes, alcohols (e.g., ethanol,
propanol, butanol, phenols), ketones, furans, and the like. For
example, the invention includes co-processing a biomass feedstock
and a refinery feedstock (or, more generally, a hydrogen donor),
which can improve conversion of the biomass into fuels and/or
specialty chemicals in conventional petroleum refining processes
(e.g., a known refinery unit). The invention also includes adapting
existing refinery processes for co-processing biomass feedstock
(e.g., change operating parameters, catalyst, and feedstock),
retrofitting existing refinery process units for processing biomass
(e.g., adding an extra riser for biomass catalytic cracking or
adding a solid biomass feeder system to introduce biomass), and
constructing new, purpose-built biomass reactors (e.g., employ
commercially available conventional reactor components). Thus, the
methods, apparatuses, kits, and compositions can reduce the cost
and increase the availability of fuel and/or specialty chemicals
derived from biomass.
[0006] In one aspect, the invention features a method for
co-processing a biomass feedstock and a refinery feedstock in a
refinery unit. The method includes producing a liquid product by
catalytically cracking a biomass feedstock and a refinery feedstock
in a refinery unit having a fluidized reactor. Catalytically
cracking includes transferring hydrogen from the refinery feedstock
to carbon and oxygen from the biomass feedstock.
[0007] In another aspect, the invention features a method for
co-processing a biomass feedstock and a refinery feedstock in the
presence of hydrogen gas in a refinery unit. The method includes
producing a liquid product by hydrocracking or hydrotreating a
biomass feedstock and a refinery feedstock in the presence of
hydrogen gas in a refinery unit having a hydrocracking or
hydrotreating reactor. Hydrocracking or hydrotreating comprises
transferring hydrogen from the hydrogen gas to carbon and oxygen
from the biomass feedstock and to carbon from the refinery
feedstock.
[0008] In yet another aspect, the invention features a refinery
unit for co-processing a biomass feedstock and a refinery
feedstock. The refinery unit includes a fluidized reactor; a first
system providing a biomass feedstock and a refinery feedstock to
the fluidized reactor; and a second system for at least one of
refreshing and regenerating a catalyst for the fluidized reactor.
The first system and the second system support catalytic cracking
including transferring hydrogen from the refinery feedstock to
carbon and oxygen from the biomass feedstock within the fluidized
reactor.
[0009] In still another aspect, the invention features a method for
providing a refinery unit for co-processing a biomass feedstock and
a refinery feedstock. The method includes providing a fluidized
reactor; providing a first system providing a biomass feedstock and
a refinery feedstock to the fluidized reactor; and providing a
second system for at least one of refreshing and regenerating a
catalyst in the fluidized reactor. The first system and the second
system support catalytic cracking comprising transferring hydrogen
from the refinery feedstock to carbon and oxygen from the biomass
feedstock within the fluidized reactor.
[0010] In another aspect, the invention features a refinery unit
for co-processing a biomass feedstock and a refinery feedstock in
the presence of hydrogen gas. The refinery unit includes a
hydrocracking or hydrotreating reactor; a first system providing a
biomass feedstock, a refinery feedstock, and hydrogen gas to the
hydrocracking or hydrotreating reactor; and a second system for at
least one of refreshing and regenerating a catalyst in the hydro
cracking or hydrotreating reactor. The first system and the second
system support hydro cracking or hydrotreating comprising
transferring hydrogen from the hydrogen gas to carbon and oxygen
from the biomass feedstock and to carbon from the refinery
feedstock in the hydrocracking or hydrotreating reactor.
[0011] In yet another aspect, the invention features a method for
providing a refinery unit for co-processing a biomass feedstock and
a refinery feedstock in the presence of hydrogen gas. The method
includes providing a hydrocracking or hydrotreating reactor;
providing a first system providing a biomass feedstock, a refinery
feedstock, and hydrogen gas to the hydrocracking or hydrotreating
reactor; and providing a second system for at least one of
refreshing and regenerating a catalyst in the hydrocracking or
hydrotreating reactor. The first system and the second system
support hydrocracking or hydrotreating comprising transferring
hydrogen from the hydrogen gas to carbon and oxygen from the
biomass feedstock and to carbon from the refinery feedstock in the
hydrocracking or hydrotreating reactor.
[0012] In other examples, any of the aspects above, or any method,
apparatus, or composition of matter described herein, can include
one or more of the following features. Method steps can be
performed in the order presented, as well as in any other
combinations or number of iterations.
[0013] In various embodiments, the method can include increasing
liquid product yield by increasing H.sub.2O formation relative to
at least one of CO and CO2 formation.
[0014] In some embodiments, the method can include operating the
refinery unit at a site adjacent to a solid biomass growth
source.
[0015] In certain embodiments, the biomass feedstock includes a
plurality of solid biomass particles. The plurality of solid
biomass particles can be substantially characterized by an average
size between about 50 and about 750 microns and individual sizes
between about 0.1 and about 1000 microns. The plurality of solid
biomass particles can be substantially characterized by an average
size between about 50 and about 1000 microns and individual sizes
between about 0.1 and about 1500 microns. The plurality of solid
biomass particles can be substantially characterized by at least
about 80% of the particles having individual sizes of about 10
microns or less. The biomass feedstock can include a catalyst is in
mechano-chemical interaction with at least a portion of the solid
biomass particles. The biomass feedstock can include a heavy liquid
fraction of a liquefied biomass feedstock. The biomass feedstock
can be substantially free of mineral contamination capable of
inactivating a catalyst.
[0016] In various embodiments, the refinery unit includes a system
for at least one of refreshing and regenerating a catalyst.
[0017] In some embodiments, the refinery feedstock includes one or
more of an atmospheric gas oil or a vacuum gas oil from a
paraffinic or naphthenic crude source, a resid from a paraffinic or
naphthenic crude source, a hydrotreated vacuum gas oil, a hydro
treated resid, and a hydro treated light cycle oil.
[0018] In certain embodiments, the method includes using a basic
catalyst. The method can include using a zeolite catalyst. The
method can include using one or more of a hydrotreating, hydro
cracking, hydrogenation, NiMo, CoMo, NiCoMo, noble metal, and
supported noble metal catalyst. The method can include using a
water-insoluble catalyst. The method can include using a solid base
catalyst comprising hydrotalcite; hydrotalcite-like material; clay;
layered hydroxy salt; mixed metal oxide; a calcinations product of
any of these materials; or a mixture thereof. The method can
include using an alumina catalyst. The method can include using a
fluid catalytic cracking catalyst. The method can include using a
petroleum coke catalyst.
[0019] In various embodiments, reactor includes a bed reactor. The
reactor can include a transport reactor. The reactor can include a
riser reactor. The reactor can include a downer reactor.
[0020] In some embodiments, the method includes a reaction time of
about 2 seconds or less. The method can include a reaction time
that favors kinetic products relative to equilibrium products.
[0021] In certain embodiments, the method includes de-mineralizing
the biomass feedstock. The method can include torrefying the
biomass feedstock at a temperature below about 300.degree. C., to
produce a plurality of solid biomass particles having at least one
of an increased brittleness and an increased susceptibility to
catalytic conversion.
[0022] In various embodiments, the method includes agitating solid
biomass particles, to reduce a size characterizing at least a
portion of the particles. The method can also include separating a
biomass-catalyst mixture comprising the particles and a catalyst
into a fine fraction having particles of about a predetermined size
and a coarse fraction having particles of greater than about the
predetermined size. Separating can include using a high velocity
cyclone.
[0023] In some embodiments, the refinery feedstock includes a
hydrogen donor. The refinery feedstock can include a petrochemical
feedstock. The refinery feedstock can include a product or a
combination of products derived from crude oil and destined for
further processing.
[0024] In certain embodiments, the refinery unit includes a
petrochemical refinery unit.
[0025] In various embodiments, the method includes providing the
biomass feedstock to the conventional refinery unit using a first
feed system and providing the refinery feedstock to the
conventional refinery unit using a second feed system.
[0026] In some embodiments, the refinery includes a first feed
system providing the biomass feedstock to the conventional refinery
unit and a second feed system providing the refinery feedstock to
the conventional refinery unit.
[0027] In certain embodiments, the plurality of solid biomass
particles are substantially characterized by individual sizes by
individual sizes below about 1500 microns. The plurality of solid
biomass particles can substantially characterized by at least about
80% (e.g., by weight) of the particles having individual sizes of
about 1500 microns or less.
[0028] Other aspects and advantages of the invention will become
apparent from the following drawings and description, all of which
illustrate principles of the invention, by way of example only.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The advantages of the invention described above, together
with further advantages, can be better understood by referring to
the following description taken in conjunction with the
accompanying drawings. The drawings are not necessarily to scale,
emphasis instead generally being placed upon illustrating the
principles of the invention.
[0030] FIG. 1 illustrates a sectional view of an exemplary refinery
unit for coprocessing a biomass feedstock and a refinery
feedstock.
[0031] FIG. 2 illustrates a sectional view of an exemplary refinery
unit for coprocessing a biomass feedstock and a refinery feedstock
in the presence of hydrogen gas.
DETAILED DESCRIPTION OF THE INVENTION
[0032] The invention relates to processing biomass with a hydrogen
donor (e.g., refinery feedstock, hydrogen gas), for example, to
convert biomass together with a hydrogen donor into a fuel,
specialty chemical, or intermediate product. The invention includes
refinery units for co-processing a biomass feedstock and a refinery
feedstock (e.g., with or without the presence of hydrogen gas). The
invention also includes methods for co-processing a biomass
feedstock and a refinery feedstock (e.g., with or without the
presence of hydrogen gas). Furthermore, the invention includes
methods for providing (e.g., building, adapting, retrofitting, and
the like) refinery units for coprocessing a biomass feedstock and a
refinery feedstock (e.g., with or without the presence of hydrogen
gas).
[0033] Operation of the refinery units and use of the methods can
include transfer of hydrogen from the hydrogen source (e.g.,
refinery feedstock, hydrogen gas, or a combination thereof) to a
feedstock (e.g., biomass feedstock). Accordingly, the invention
provides a cost-effective alternative to conventional
hydroprocessing (e.g., requiring high pressure and large amounts of
hydrogen gas, and not amenable to continuous processing in a
fluidized type reactor). The invention also provides methods and
apparatus adapted specifically to co-processing a biomass feedstock
and a refinery feedstock. Accordingly, the invention provides
technical advantages (e.g., processing under mild conditions,
product selectivity) and cost advantages (e.g., processing with
lower cost equipment, conditions, reactants, and/or feedstock) over
conventional petrochemical refinery units and methods (e.g.,
hydroprocessing).
[0034] Operation of the refinery units and use of the methods can
also result in higher yield and higher value products being
produced from both the biomass and refinery feedstock. For example,
biomass feedstock including cellulose tends to produce oxygenated
acidic compounds and aromatics. Refinery feedstock including
paraffins tends to produce low octane products having pour point
problems. By co-processing, the biomass feedstock produces
hydrocarbon products that are richer in hydrogen, contain less
undesired oxygenic and acidic groups, and fewer undesired aromatic
compounds. Likewise, by co-processing, the refinery feedstocks
produce higher octane products (e.g. with more olefins) having less
pour point problems. Accordingly, co-processing can have they
synergistic effect of simultaneously or substantially
simultaneously increasing the commercial value and utility of
product streams from both feedstocks.
Solid Biomass Particles
[0035] In various embodiments, biomass includes materials of
photosynthetic (e.g., plant) origin having cellulose,
hemicellulose, and/or lignin Biomass includes materials produced by
photosynthetic conversion of carbon dioxide and water using solar
energy.
[0036] In general, biomass including cellulose, hemicellulose,
and/or lignin originates from land plants. Some aquatic plants
include little or no lignin However, the invention is applicable to
any biomass including any amount of cellulose, hemicellulose,
and/or lignin Biomass sources include, but are not limited to,
cereal grains (e.g., including corn), grasses, sugar cane, trees,
and the like. Biomass sources also include by-products of
agricultural or forestry activities, such as straw, chopped straw,
cotton linters, corn husks, corn stalks, corn cobs, wood chips, saw
dust, bagasse, sugar beet pulp, tree bark, grasses, and the like.
Biomass sources also include aquatic sources such as algae and
seaweed.
[0037] Biomass sources can be used without requiring chemical
pre-processing (e.g., chemically altering the biomass). In various
embodiments, biomass sources include (chemically) unrefined
material of photosynthetic origin. Biomass sources can be subjected
to a drying and/or a particle size reduction step. Such a drying
and/or a particle size reduction step does not significantly change
the relative composition of the biomass in terms of cellulose,
hemicellulose and/or lignin and therefore such a step is not
necessarily considered refining.
[0038] In various embodiments, biomass feedstock can include
particles that are solid and in a finely divided form (e.g., saw
dust and ground straw). Biomass feedstock can include solid
materials as well as materials that might be classified as liquids,
but that have a very high viscosity (e.g., small or large colony
algae). Biomass particles can be prepared from biomass sources and
larger particles by techniques such as milling, grinding,
pulverization, and the like. Conventional paper processing/pulping
methods and equipment can be used to prepare biomass particles. For
example, biomass from sources such as straw and wood can be
converted to particles in a size range of about 5 mm to about 5 cm
using techniques such as milling or grinding.
Pre-Treating Biomass
[0039] In various embodiments, biomass feedstock can be chemically
and/or physically pre-treated. Examples of pretreatment steps in
which recycled aqueous phase can be used include demineralization,
heat treatment, and steam explosion.
[0040] Demineralization can include removing at least a fraction of
a naturally occurring mineral from biomass (e.g., prior to a
pyrolysis or catalytic cracking reaction). Demineralization can
improve control over the reaction of the biomass. Many of the
minerals naturally present in the biomass material can be
catalytically active (e.g., potassium, iron). Although these
materials can catalyze reactions, they can also increase coke
yield, which is generally undesirable. Even when catalytic activity
is desired, it can be preferable to first demineralize the biomass
material so as to control the composition of their catalyst
system.
[0041] One method of demineralization includes contacting biomass
with an aqueous solvent and allowing the biomass material to swell.
After swelling, at least part of the aqueous solvent can then be
removed from the biomass by mechanical action (e.g., kneading,
pressing). Swelling and dewatering steps can be repeated to control
the amount of minerals that are removed from the biomass. In
addition to removing minerals from the biomass, the swelling and
dewatering steps can make the biomass material more susceptible to
a subsequent reaction.
[0042] Although essentially any aqueous solvent can be used for
demineralization, the aqueous phase of a liquid pyrolysis product
can be particularly effective. The effectiveness is believed to be
due to the presence of organic acids (e.g., carboxylic acid, acetic
acid) in the aqueous phase. Without wishing to be bound by any
theory, the acidity of the aqueous phase can facilitate the
mobilization of minerals in the biomass. For example, the chelating
effects of carboxylic acids can contribute to the solubilization
and removal of mineral cations.
[0043] Solvent explosion can include contacted the biomass with a
pressurized solvent at a temperature above its natural boiling
point (e.g., at atmospheric pressure). The pressurized solvent is
in a liquid phase and swells the biomass. Then, the solvent is
de-pressurized, causing rapid evaporation (i.e., boiling) of the
solvent. This rapid evaporation can be referred to as solvent
explosion. The solvent explosion can physically rupture the biomass
material, thereby making it more accessible in a subsequent
reaction.
[0044] Examples of solvents that can be used in solvent explosion
include ammonia, carbon dioxide, water, and the like. If water is
used as the solvent, the process can be referred to as steam
explosion. It will be understood that the term steam explosion can
be considered a misnomer, and that the term water explosion can be
more accurate. Nevertheless, the term steam explosion will be used
herein because it is an accepted term of art. The aqueous phase of
the liquid pyrolysis product can be used in a steam explosion.
[0045] When steam explosion is combined with demineralization, the
steam explosion can be carried out before or after the
demineralization. For example, it can be advantageous to conduct
the demineralization after the steam explosion because the steam
explosion pretreatment can make the minerals more accessible,
thereby making the demineralization more effective.
[0046] Heat treatment can include heating the biomass to a
temperature of about 100-300.degree. C. in an oxygen-poor or
oxygen-free atmosphere. The term oxygen-poor can refer to an
atmosphere containing less oxygen than ambient air. The heat
treatment can carried out in the presence of sufficient solvent
(e.g., water) to swell the biomass material. The heat treatment can
be carried out in a closed vessel to mitigate evaporation of the
solvent. In some examples, the vapor (e.g., steam) formed under
these conditions can displace oxygen present in the vessel and
produce an oxygen-poor atmosphere. In one example, the aqueous
phase of a liquid pyrolysis product can be the solvent in such a
heat treatment.
[0047] Heat treatment can be carried out at a temperature low
enough to mitigate carbon loss due to the formation of gaseous
conversion products (e.g., CO, CO2). A heat treatment can use, for
example, a temperature of about 100-200.degree. C. For example, a
temperature can be about 100-140.degree. C. A heat treatment can
have a duration, for example, of about 2 min to 2 hours. For
example, a duration can be about 20-60 min. In various examples,
pressure can be released at the end of a heat treatment by opening
the heat treatment vessel, which can allows the heat treatment to
be combined with a steam explosion pretreatment step.
[0048] Even where the heat treatment essentially does not produce
any gaseous conversion products, it can still result in a
modification of the biomass. For example, the heat treatment can
make the biomass more brittle and more hydrophobic. Both effects
can be desirable from the perspective of a subsequent reaction. For
example, increased brittleness can facilitate girding the biomass
to a small particle size, to increase reactivity in a pyrolysis
reaction, and increased hydrophobicity can facilitate drying the
biomass.
[0049] A heat pretreatment step can be combined with one or more
additions pretreatment steps (e.g., demineralization, steam
explosion). Because of the increased hydrophobicity of heat treated
biomass, it can be preferable to conduct any demineralization
and/or steam explosion steps prior to the heat treatment; with the
exception that steam explosion can be combined with heat treatment
as described above.
Agitation of Biomass Particles
[0050] In various embodiments, the method includes agitating solid
biomass particles, to reduce a size characterizing at least a
portion of the particles. In some embodiments, agitating is
facilitated by fluid conveyance, including, without limitation, by
gas flow or pneumatic conveyance. Agitating can be conducted in a
vertical vessel, such as a riser or downer. An agitator can include
a conveyor, a riser, or downer. A riser (up flow) or a downer (down
flow) can be, for example, a hollow vertical vessel terminating in
a larger diameter vessel, which houses high velocity (e.g., about
60-80 m/s or 18-24 m/s) cyclones that may or may not be physically
connected to the riser termination point. The height of a riser or
downer can be, for example, between about 15 ft (5 m) and about 60
ft (18 m) and the diameter can be, for example, between about 1 ft
(0.3 m) and about 4 ft (1.2 m). Agitating can be facilitated by a
gas (e.g., gas can convey the particles such that they are abraded
or ground by other particles, catalyst, and/or inorganic
particulate material). The gas can be one or more of air, steam,
flue gas, carbon dioxide, carbon monoxide, hydrogen, and
hydrocarbons, (e.g. methane). The gas can be a gas having a reduced
level of oxygen (compared to air) or can be substantially
oxygen-free. In another embodiment, an agitator can be a mill
(e.g., ball or hammer mill) or kneader or mixer (e.g., for
mechanical, as opposed to pneumatic, agitation).
[0051] In certain embodiments, agitating includes causing the solid
biomass particles to be conveyed at a velocity of greater than
about 1 m/s. For example, the velocity can be measured relative to
a vessel in which the particles are conveyed. Agitating can include
causing the solid biomass particles to move at a velocity of
greater than about 10 m/s. Agitating can include causing at least a
portion of the solid biomass particles to move at a velocity of
greater than about 100 m/s. An agitator can be adapted to cause the
solid biomass particles to move at a velocity of greater than about
1 m/a, greater than about 10 m/s, and/or greater than about 100
m/s. Other velocities include velocities of greater than about 5,
25, 50, 75, 125, 150, 175, 200, 225, and 250 m/s.
[0052] For example, the velocity is selected from the group
consisting of: between about 10 and about 20 m/s; between about 20
and about 30 m/s; between about 30 and about 40 m/s; between about
40 and about 50 m/s; between about 50 and about 60 m/s; between
about 60 and about m/s; between about 70 and about 80 m/s; between
about 80 and about 90 m/s; and between about 90 and about 100 m/s.
The velocity can be about 10 m/s, about 20 m/s, about 30 m/s, about
40 m/s, about 50 m/s, about 60 m/s, about 70 m/s, about 80 m/s,
about 90 m/s, or about 100 m/s. The velocity can be greater than
about 10 m/s, about 20 m/s, about 30 m/s, about 40 m/s, about 50
m/s, about 60 m/s, about 70 m/s, about 80 m/s, about 90 m/s, or
about 100 m/s.
[0053] In various embodiments, agitating solid biomass particles,
to reduce a size characterizing at least a portion of the
particles, is facilitated by agitating solid biomass particles
together with a material that is harder than the biomass. For
example, the material can be a catalyst or another inorganic
particulate material. The amount of size reduction, and thus the
size of the resulting solid biomass particles can be modulated by
the duration of agitation and the velocity of agitation. Other
factors such as the relative hardness of the catalyst or another
inorganic particulate material, the dryness (e.g., brittleness) of
the solid biomass particles, and the method/vessel(s) in which
agitation occurs also modulate the amount of size reduction.
[0054] In embodiments using an abrading or grinding material that
is a catalyst, the catalyst can become embedded in the biomass
particles and/or the biomass particles can become embedded in the
catalyst, which can facilitate catalytic conversion of the biomass.
In such embodiments, agitating can facilitate formation of a
mechano-chemical interaction between at least a portion of the
catalyst and at least a portion of the solid biomass particles,
which can facilitate catalytic conversion of the biomass.
[0055] Agitation can be carried out at an elevated temperature, for
drying the biomass. An elevated temperature can be a temperature
sufficient to dry the biomass, for example, between about 50 and
about 150.degree. C., or below about 200.degree. C. Higher
temperatures can be used, for example, where an agitating gas is
oxygen-poor or substantially oxygen-free. Agitation can also be
carried out at ambient temperature with dried biomass. Drying
increases the hardness of the biomass particles, making the
particles more susceptible to size reduction.
[0056] Agitation can be carried out by various different methods
and in various different vessels. For example, in order of
increasing abrasion, the agitation can be carried out in a fluid
bed, a bubbling or ebullient bed, a spouting bed, or a conveyor. In
one embodiment, agitation is carried out by fluid conveyance,
including without limitation by gas flow or pneumatic conveyance.
In one embodiment, agitation is carried out in a riser or a
downer.
[0057] Agitating solid biomass particles, to reduce a size
characterizing at least a portion of the particles, can result in a
dispersion of particle sizes. For example, proper agitation the
solid biomass particles as described above can result in individual
particles sizes ranging from microns, to tens of microns, to tenths
of centimeters, to centimeters or greater. The biomass can be
subjected to a particle size reduction step, or can be collected in
the form of particles (e.g., algae cells, colonies, flocculated
algae, and the like).
[0058] In various embodiments, the biomass particles are reduced
to, or have, an average particle size of less than about 1000
microns. Alternatively, the biomass particles are reduced to, or
have, an average particle size of greater than about 1000 microns.
The plurality of solid biomass particles can be substantially
characterized by individual sizes below about 2000, 1900, 1800,
1700, 1600, 1500, 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600,
500, 400, 300, 200, or 100 microns. In various embodiments, at
least a fraction of the biomass particles have a size of about
1-2000, 1-1500, 1-1000, or 1000-2000 microns. For example, the
biomass particles can have an average size of less than about 2000,
1750, 1500, 1250, 1000, 750, 500, or 250 microns. In some
embodiments, at least a fraction of the biomass particles are
reduced to a size below about 500, 475, 450, 425, 400, 375, 350,
325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 70, 60,
50, 40, 30, 20, 15, 10, or 5 microns. Individual particles sizes
can range from microns, to tens of microns, to tenths of
centimeters, to centimeters or greater.
[0059] At least a fraction of the biomass particles can be reduced
to a size between about 1 mm and 1 micron. For example, the biomass
particles can have an average size of about 300-500 microns
comprised of mainly individual sizes of about 10-1,000 microns. In
various embodiments, the plurality of solid biomass particles are
substantially characterized by an average size between about 50 and
about 70 microns and individual sizes between about 5 and about 250
microns. In other embodiments, the plurality of solid biomass
particles are substantially characterized by an average size
between about 10 and about 20 microns and individual sizes between
about 5 and about 50 microns. In other embodiments, the plurality
of solid biomass particles are substantially characterized by an
average size between about 100 and about 150 microns and individual
sizes between about 5 and about 500 microns.
[0060] Solid biomass particles do not necessarily assume a
spherical or spheroid shape. For example, solid biomass particles
can be needle shaped and/or assume another cylinder-like or
elongated shape. Accordingly, size does not necessarily correspond
to a single diameter (although it could correspond to an average
diameter or diameter in a singe, for example largest or smallest,
dimension). In various embodiments, size can correspond to the mesh
size or a screen size used in separation and/or sizing the solid
biomass particles.
[0061] International Publication No. WO 2007/128798 A1 by O'Connor,
the disclosure of which is incorporated herein by reference in its
entirety, discloses agitating solid biomass particles and
catalysts. In particular, paragraphs [0027] to [0072] of WO
2007/128798 A1 are incorporated herein by reference.
[0062] International Publication No. WO 2008/009643 A2 by O'Connor,
the disclosure of which is incorporated herein by reference in its
entirety, discloses agitating solid biomass particles and
catalysts. In particular, paragraphs [0009] to [0051] of WO
2008/009643 A2 A1 are incorporated herein by reference.
Separation of Biomass Particles
[0063] In various embodiments, methods include separating a
biomass-catalyst mixture into a fine fraction and a coarse
fraction. The biomass-catalyst mixture includes the biomass
particles and a catalyst. The fine fraction includes particles of
about a predetermined size. The coarse fraction includes particles
of greater than about the predetermined size. Separating the
mixture into a fine fraction and a coarse fraction can have several
effects. For example, a fine fraction can be selected to include
particles of about a predetermined size, below about a
predetermined size, and/or within a predetermined size range. In
some embodiments, the fine fraction can be selected to consist
essentially of particles of about a predetermined size, below about
a predetermined size, and/or within a predetermined size range.
Furthermore, a coarse fraction can be recycled for further size
reduction and/or to produce more of a fine fraction.
[0064] A predetermined size can be selected based upon one or more
requirements of a subsequent reaction. For example, a predetermined
size can be selected to facilitate substantial catalytic conversion
of the fine fraction in a subsequent reaction. A predetermined size
can be selected to facilitate contact, impregnation, and/or
interaction of the catalyst and the biomass. In some embodiments, a
predetermined size can be about 2000, 1900, 1800, 1700, 1600, 1500,
1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600, 500, 450, 400,
350, 300, 250, 200, 150, 100, 50, 45, 40, 35, 30, 25, 20, 15, 10,
or 5 microns, or any individual value there between. In one
embodiment, a predetermined size is about 15 microns. In one
embodiment, a predetermined size is about 10 microns. A
predetermined size can be between about 1 and 2000 microns or
between about 5 and about 1000 microns.
[0065] Separating can be facilitated by a cyclonic action. A
separator can include a single cyclone. Alternatively, a separator
can include a plurality of cyclones arranged, for example, in
parallel, series, as a third stage separator, or as a fourth stage
separator. U.S. Pat. No. 6,971,594 to Polifka, the disclosure of
which is incorporated herein by reference in its entirety,
discloses cyclonic action and cyclone separators that can be
adapted and employed with the invention. In particular, FIG. 2, the
text corresponding to FIG. 2, and the text corresponding to column
4, line 55 to column 11, line 55 of U.S. Pat. No. 6,971,594 are
incorporated herein by reference.
[0066] Separating can be achieved by other known methods. For
example, separating can be achieved by screening, settling,
clarification, and the like.
Catalysts and Inorganic Particulate Materials
[0067] A catalyst can be any material that facilitates the
conversion of organic components of the biomass into fuels,
specialty chemicals, or precursors thereof. In various embodiments,
the catalyst includes a solid particulate catalyst and the
biomass-catalyst mixture includes at least a portion of the
catalyst mechano-chemically interacting with at least a portion of
the solid biomass particles. In some embodiments, the catalyst
includes a catalyst capable of being at least partly dissolved or
suspended in a liquid and the biomass-catalyst mixture includes at
least a portion of the catalyst impregnating at least a portion of
the solid biomass particles. A catalyst can be or include a
water-insoluble catalyst, a fluid catalytic cracking catalyst, and
a petroleum coke catalyst.
[0068] In various embodiments, a catalyst is a particulate
inorganic oxide. The particulate inorganic oxide can be a
refractory oxide, clay, hydrotalcite, hydrotalcite-like material,
clay, layered hydroxy salt, mixed metal oxide, a calcination
product of any of these materials; or a mixture thereof. Suitable
refractory inorganic oxides include alumina, silica,
silica-alumina, titania, zirconia, and the like. In one embodiment,
the refractory inorganic oxides have a high specific surface (e.g.,
a specific surface area as determined by the Brunauer Emmett Teller
("BET") method of at least 50 m2/g). Suitable clay materials
include cationic and anionic clays, for example, smectite,
bentonite, sepiolite, atapulgite, hydrotalcite, and the like.
Suitable metal hydroxides and metal oxides include bauxite,
gibbsite and their transition forms. Other suitable (and
inexpensive) catalysts include lime, brine, and/or bauxite
dissolved in a base (e.g., NaOH), or a natural clay dissolved in an
acid or a base, or fine powder cement (e.g., from a kiln). Suitable
hydrotalcites include hydrotalcite, mixed metal oxides and
hydroxides having a hydrotalcite-like structure, and metal hydroxyl
salts.
[0069] In some embodiments, a catalyst can be a catalytic metal.
The catalytic metal can be used alone or together with another
catalyst, refractory oxide, and/or binder. A catalytic metal can be
used in a metallic, oxide, hydroxide, hydroxyl oxide, or salt form,
or as a metallo-organic compound, or as a material including a rare
earth metal (e.g., bastnesite). In certain embodiments, the
catalytic metal is a transition metal. The catalytic metal can be a
non-noble transition metal. For example, the catalytic metal can be
iron, zinc, copper, nickel, and manganese. In one embodiment, the
catalytic metal is Iron.
[0070] A catalytic metal can be contacted with the biomass by
various methods. In one embodiment, the catalyst is added in its
metallic form, in the form of small particles. Alternatively, the
catalyst can be added in the form of an oxide, hydroxide, or a
salt. In another embodiment, a water-soluble salt of the metal is
mixed with the biomass and the inert particulate inorganic material
to form an aqueous slurry. The biomass and the aqueous solution of
the metal salt can be mixed before adding the inert particulate
inorganic material to facilitate the metal's impregnating the
biomass. The biomass can also be mixed with the inert particulate
inorganic material prior to adding the aqueous solution of the
metal salt. In still another embodiment, an aqueous solution of a
metal salt is mixed with the inert inorganic material, the material
is dried prior to mixing it with the particulate biomass, and the
inert inorganic material is thus converted to a heterogeneous
catalyst.
[0071] The biomass-catalyst mixture can include an inorganic
particulate material. An inorganic particulate material can be
inert or catalytic. An inorganic material can be present in a
crystalline or quasi-crystalline form. Exemplary inert materials
include inorganic salts such as the salts of alkali and alkaline
earth metals. Although these materials do not necessarily
contribute to a subsequent chemical conversion of the polymeric
material, it is believed that the formation of discrete particles
of these materials within the biomass can work as a wedge to
mechanically break up or open the structure of the biomass, which
can increase the biomass surface accessible to microorganisms
and/or catalysts. In one embodiment, the breaking up or opening is
facilitated by crystalline or quasi-crystalline particles.
[0072] Inorganic particulate material can have catalytic
properties. For example, a catalytic inorganic particulate material
can be a metal oxide or hydroxide such as an alumina, silica,
silica aluminas, clay, zeolite, ionic clay, cationic layered
material, layered double hydroxide, smectite, saponite, sepiolite,
metal hydroxyl salt, and the like. Carbonates and hydroxides of
alkali metals, and the oxides, hydroxides and carbonates of
alkaline earth metals can also have catalytic properties. Inorganic
particulate material can include mixtures of inorganic materials.
Inorganic particulate material can include a spent (resid) fluid
catalytic cracking catalyst containing (thermally treated) layered
material. Employing spent catalyst can involve reusing waste
material. The spent catalyst can be ground of pulverized into
smaller particles to increase its dispersibility. Inorganic
particulate material can also include sandblasting grit. Employing
sandblasting grit can involve reusing waste material, which can
include particles of iron, and lesser quantities of other suitable
metals such as nickel, zinc, chromium, manganese, and the like
(e.g., grit from steel sandblasting).
[0073] Contacting the catalyst, and optionally the inorganic
particulate material, with the biomass, can be achieved by various
methods. One method includes heating and fluidizing a mixture of
the particulate biomass material and the inert inorganic material,
and adding the catalyst to the mixture as fine solid particles.
Another method includes dispersing the catalytic material in a
solvent (e.g., water), and adding the solvent to the mixture of
particulate biomass material and the inert inorganic material.
[0074] European Patent Application No. EP 1 852466 A1 by O'Connor,
the disclosure of which is incorporated herein by reference in its
entirety, discloses catalysts and contacting catalysts and biomass.
In particular, paragraphs [0011] to [0043] of EP 1 852466 A1 are
incorporated herein by reference.
[0075] International Publication No. WO 2007/128799 A1 by O'Connor,
the disclosure of which is incorporated herein by reference in its
entirety, discloses catalysts and contacting catalysts and biomass.
In particular, paragraphs [0015] to [0054] of WO20071128799 A1 are
incorporated herein by reference.
Removing Metals and/or Minerals
[0076] In various embodiments, a pretreatment can reduce an ash
content of biomass, or a hazardous disposal characteristic of an
ash that can be subsequently produced. Removal of minerals (e.g.,
ash precursors) from the biomass can reduce the ash content.
Removal of metals (e.g., ash precursors), particularly heavy
metals, can also reduce ash content and prevent metal contamination
of waste products, thereby facilitating disposal of waste by
providing an uncontaminated waste product and reducing the cost of
disposing of the waste product.
[0077] A pretreatment for reducing ash content can include swelling
the biomass with a solvent and then removing solvent from the
swollen biomass material by applying mechanical action to the
biomass material. Ash precursors, such as dissolved minerals and/or
metals, will thus be removed with the solvent. The solvent can be
aqueous. The solvent can include an acid or base (e.g., inorganic
acid or base). The mechanical action can occur in an agitator
and/or a kneader. The mechanical action can be exerted by equipment
such as a high shear mixer, kneader, colloid mill, planetary mixer,
mix-miller, or ball mill. A pretreatment for reducing ash content
can include washing or slurrying with an aqueous phase having pH
above or below neutral, ion exchange (e.g., with ammonium solutions
that would exchange a hydrogen ion with a metal ion), and steam
stripping are possible methods.
[0078] Pretreatment can reduce ash content to less than about 10 wt
%, 9 wt %, 8 wt %, 7 wt %, 6 wt %, 5 wt %, 4 wt %, 3 wt %, 2 wt %,
or 1 wt %, based on dry weight of the biomass material. The
pretreatment can reduce metal (e.g., Fe) content to less than about
3,000, 2,500, 2,000, 1,500, 1,000, or 500 mg/kg, based on dry
weight of the biomass.
Kneaders
[0079] A kneader can be used to knead the solid biomass particles
and the catalyst, to make at least a portion of the solid biomass
particles accessible to at least a portion of the catalyst. The
kneader can be an extruder, miller, mixer, or grinder. The kneader
can operate at greater than ambient temperature, for example, to
facilitate removal or water and/or other solvent. For example, the
kneader can be heated and/or heated gas (e.g., steam) can be
provided to heat the biomass and catalyst.
[0080] In various embodiments, the kneader employs a solvent. The
solvent can be water, an alcohol (e.g., ethanol or glycerol), a
bio-oil or another product from the conversion of the biomass, a
liquid acid, an aqueous solution of an acid or base, liquid CO2,
and the like. In one embodiment, the solvent is water (e.g., added
water and/or water inherently present in the biomass), which can be
selected for its availability, low cost, and/or ease of handling.
In another embodiment, the solvent is a liquid produced during the
subsequent conversion of the biomass, which can be selected for its
availability. A solvent can be selected to improve penetration of a
catalyst into biomass.
[0081] A solvent can also improve penetration of a catalyst into
biomass because a dry biomass can be more difficult to penetrate. A
solvent can also be selected to remove ash precursors. Solvents can
be removed (e.g., by drying) prior to subsequent processing and/or
conversion. A kneader can remove at least a portion of a solvent
absorbed in a biomass (e.g., by mechanical action and draining).
Embodiments employing a kneader and a solvent can reduce the ash
and/or mineral and/or metal content of the biomass.
[0082] In various embodiments, the biomass can be kneaded with one
or more solid catalyst and/or inorganic particulate material. In
some embodiments, the biomass can be kneaded with a dissolved
and/or suspended catalyst. The dissolved and/or suspended catalyst
can be used together with one or more solid catalyst and/or
inorganic particulate material. Kneading can be continued and/or
repeated to produce a biomass-catalyst mixture having the desired
properties (e.g., particle size and/or degree of
sensitization).
[0083] International Publication No. WO 20071128800 A1 by O'Connor,
the disclosure of which is incorporated herein by reference in its
entirety, discloses catalysts and sensitizing biomass, as well as
sensitizing by kneading. In particular, paragraphs [0025] to [0074]
with respect to catalysts and sensitizing biomass, as well
paragraphs
[0084] [0076] to [0086] with respect to sensitizing by kneading, of
WO 20071128800 A1 are incorporated herein by reference.
Disintegrators
[0085] The disintegrator processes plant matter at a location in
close proximity to an agricultural site used to produce such plant
matter, to produce the solid biomass particles. In operation, a
disintegrator can be used to modify the consistency of, e.g.,
biomass feedstock, and/or to reduce its average particle size. The
disintegrator can include at least one of a mill, fragmenter,
fractionator, granulator, pulverizer, chipper, chopper, grinder,
shredder, mincer, and a crusher. Apparatuses including a
disintegrator can process plant matter at a location in close
proximity to an agricultural site used to produce such plant
matter, to produce the solid biomass particles. U.S. Pat. No.
6,485,774 to Bransby, the disclosure of which is incorporated
herein by reference in its entirety, discloses a method of
preparing and handling chopped plant materials. In particular, the
text corresponding to column 1, line 45 to column 4, line 65 of
U.S. Pat. No. 6,485,774 is incorporated herein by reference.
EXAMPLES
[0086] Examples 1 and 2, FIGS. 1 and 2, and the description below
illustrate exemplary methods and apparatuses for co-processing a
biomass feedstock and a refinery feedstock. Catalyst, reaction
vessel(s), pretreatment, treatment, and reaction conditions can
each be selected based upon the type of biomass and the desired
product(s). The methods can be part of a broader method (e.g., a
broader method can include anyone or more steps of harvesting
biomass, pre-processing biomass, further processing, refining,
upgrading, separating, transporting products, intermediates, and
the like).
[0087] In various embodiments, the intermediates include
hydrocarbons from which oxygen can be stripped (e.g., as CO, CO2,
H.sub.2O) to produce traditional fuel or specialty chemical
products such as light gases, naphtha, heating oils, jet fuel, and
the like. In general, processing proceeds by cracking and
deoxygenating (as necessary) polymeric compounds in the biomass
into a fuel or specialty chemical product. In various embodiments,
intermediates can be stripped quickly from the catalysts and
unconverted biomass to limit secondary (e.g., undesired)
reactions.
[0088] The apparatuses can be part of a larger apparatus. For
example, a larger apparatus can include one or more systems for
harvesting, pretreating, further processing, refining, upgrading,
separation, transportation, and the like. The invention can be
carried out at a site adjacent to a biomass growth source. For
example, the site can be near a source of a biomass feedstock,
which can reduce transportation costs for a biomass feedstock and a
liquid product. Operation at a site adjacent to a biomass growth
source can also include other advantages such a recycling water and
ash byproducts to the biomass growth source.
[0089] A system can include a first feed system and a second feed
system, to facilitate co-process a liquid feedstock and a solid
feedstock, or a biomass feedstock and a refinery/petroleum
feedstock. The first feed system can provide the liquid feedstock
to the refinery unit and the second feed system can provide the
solid feedstock to the refinery unit. In embodiments where a
biomass feedstock is co-processed with a refinery/petroleum
feedstock, the first feed system can provide the biomass feedstock
to the refinery unit and the second feed system can provide the
refinery/petroleum feedstock to the refinery unit. The first feed
system can also be adapted to provide a suspension of a solid
biomass feedstock in a liquefied biomass feedstock or a
refinery/petroleum feedstock (e.g., torrefied biomass particles
suspended in a biocrude or crude oil). A system can include a third
feed system that can provide hydrogen gas to the refinery unit.
Example I
[0090] A biomass feedstock and a refinery feedstock can be
coprocessed in a refinery unit. A liquid product can be produced by
catalytically cracking a biomass feedstock and a refinery feedstock
in a refinery unit having a fluidized reactor. Catalytically
cracking includes transferring hydrogen from the refinery feedstock
to carbon and oxygen from the biomass feedstock.
Example 2
[0091] A biomass feedstock and a refinery feedstock can be
coprocessed in the presence of hydrogen gas in a refinery unit. A
liquid product can be produced by hydrocracking or hydrotreating a
biomass feedstock and a refinery feedstock in the presence of
hydrogen gas in a refinery unit having a hydrocracking or
hydrotreating reactor. Hydrocracking or hydrotreating includes
transferring hydrogen from the hydrogen gas to carbon and oxygen
from the biomass feedstock and to carbon from the refinery
feedstock.
[0092] In these and other examples, a biomass feedstock can include
a plurality of solid biomass particles. A plurality of solid
biomass particles can be characterized by an average size between
about 50 and about 750 microns and individual sizes between about
0.1 and about 1000 microns. The plurality of solid biomass
particles can be substantially characterized by at least about 80%
of the particles having individual sizes of about 10 (or 15 or 20)
microns or less. A method can include agitating solid biomass
particles, to reduce a size characterizing at least a portion of
the particles. A method can also include separating (e.g., with a
high velocity cyclone) a biomass-catalyst mixture including the
particles and a catalyst into a fine fraction having particles of
about a predetermined size and a coarse fraction having particles
of greater than about the predetermined size.
[0093] The biomass feedstock can include a catalyst (e.g., a basic
catalyst, a zeolite catalyst). In certain examples, the catalyst
can be one or more of a hydrotreating, hydrocracking, NiMo, CoMo,
NiCoMo, and noble metal catalyst. The catalyst can be in
mechano-chemical interaction with at least a portion of the
plurality of solid biomass particles. For example, the biomass
feedstock can be a plurality of lignocellulosic biomass particles
in mechano-chemical interaction with a basic catalyst. The biomass
feedstock can include an inorganic particulate material. In some
cases, a biomass feedstock can include a deoxygenated liquid
product of pyrolysis or catalytic cracking, a bio-oil, or fraction
of the liquid product or bio-oil. A biomass feedstock can include
plant oil or waste oil (e.g., used fat from a food source such as
used restaurant flying oil). The biomass feedstock can include a
heavy liquid fraction of a liquefied biomass feedstock. The biomass
feedstock can be substantially free of a mineral component (e.g.,
contamination) capable of inactivating a catalyst.
[0094] Solid biomass particles can be pre-processed (e.g.,
chemically and/or physically). For example, the solid biomass
particles can be dried and/or subjected to particle size reduction.
Pre-processing can increase brittleness, susceptibility to
catalytic conversion (e.g., by roasting, toasting, and/or
torrefication, for example, at a temperature below about 300, 375,
350, 325, 300, 275, 250, 225, 200, 175, 150, 125, or 100.degree.
C.) and/or susceptibility to mixing with a petrochemical feedstock
(e.g., by increasing hydrophobicity). Pre-processing can include
de-mineralizing the biomass feedstock (e.g., removing ash
precursors from the solid biomass particles, removing a mineral
component capable of inactivating a catalyst).
[0095] In these and other examples, a refinery feedstock can be a
product or a combination of products derived from oil (e.g., crude
oil, petroleum product, or more generally any fossil fuel or fossil
fuel precursor). Petroleum products are obtained from the
processing of crude oil, natural gas, and other hydrocarbon
compounds. Petroleum products include unfinished oils, liquefied
petroleum gases, pentanes plus, aviation gasoline, motor gasoline,
naphtha-type jet fuel, kerosene-type jet fuel, kerosene, distillate
fuel oil, residual fuel oil, petrochemical feedstocks, special
naphthas, lubricants, waxes, petroleum coke, asphalt, road oil,
still gas, and the like.
[0096] A refinery feedstock can include a hydrogen donor (e.g.,
capable of transferring hydrogen to carbon and oxygen from the
biomass feedstock). A refinery feedstock can be transformed into
one or more components and/or finished products and can be destined
for further processing other than blending. For example the
refinery feedstock can include one or more of an atmospheric gas
oil or a vacuum gas oil from a paraffinic or naphthenic crude
source, a resid from a paraffinic or naphthenic crude source, a
hydrotreated vacuum gas oil, a hydrotreated resid, and a
hydrotreated light cycle oil. Naphthenic feedstocks can be an
effective hydrogen source because they hydrogen atoms are readily
separated from the component napthenes. The refinery feedstock can
include a petrochemical feedstock. A petrochemical feedstock can be
essentially any petroleum or petroleum distillate that can function
as a hydrogen source or hydrogen donor.
[0097] In certain example, hydrogen gas can be present at an
elevated pressure (e.g., using conventional hydroprocessing
parameters) or at a lowered pressure (e.g., at about, or slightly
above, atmospheric pressure). They reaction atmosphere can be
essentially hydrogen gas, hydrogen gas and an inert gas (e.g.,
nitrogen), or hydrogen and a process gas (e.g., steam, CO2).
[0098] In these and other examples, a refinery unit can include a
reactor (e.g., fluidized reactor) that can support catalytic
cracking of the biomass feedstock that includes transferring
hydrogen from the refinery feedstock to carbon and oxygen from the
biomass feedstock. The catalytic cracking can convert the biomass
into hydrocarbon compounds (including carbon from the biomass) and
water (including oxygen from the biomass). Hydrocarbon compounds
can include oxygenated hydrocarbons like aldehydes, alcohols,
ketones, and acids (e.g., for use a specialty chemicals) as well as
straight chain or branched alkynes, alkenes, and alkynes. CO and
CO2 (including both carbon and oxygen from the biomass) can also be
produced. Liquid (e.g., hydrocarbon) product yield can be
increased, controlled, optimized, and/or maximized by increasing
H2O formation relative to at least one of CO and CO2 formation.
[0099] The methods can employ a reaction time that favors kinetic
products relative to equilibrium products. A reaction time can be
about 2 seconds or less (e.g., about 2.1.75, 1.5, 1.25, 1, 0.9,
0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 seconds). A reaction
temperature can be in a range of about 200-1000 Oc. For example,
the reaction temperature can be about 200, 225, 250, 275, 300, 325,
350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650,
675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, or
1000.degree. C. The reaction temperature can be in a range of about
200-1,000, 300-900, 300-850, 400-800, 400-750, 450-700, 450-650,
450-600, 500-600, and 500-550
[0100] A refinery unit can be a conventional petrochemical refinery
unit, for example, a fluid catalytic cracking (FCC) unit. The FCC
unit can be modified or adapted (e.g., retrofitted equipment and/or
altered operating parameters) for co-processing a biomass feedstock
and a petrochemical feedstock. Alternatively, a refinery unit can
be designed and purpose-built (e.g., employing petrochemical
refinery unit hardware and operating parameters).
[0101] The refinery unit can include a fluid bed reactor. A fluid
bed reactor can support high throughput processing (e.g., a
traditional hydro treater reactor can require about 1 hour to
accomplish what a fluid bed reactor can accomplish in about 1
second, due to differences in batch versus continuous operation and
other operating conditions). A refinery unit can include a bed
(e.g., fixed bed and/or ebulating bed) reactor. A refinery unit can
include a transport and/or riser reactor. Catalytic cracking
reactors can include a system for refreshing, replacing,
regenerating, and/or circulating catalyst.
[0102] The refinery unit can include a system for feeding a
feedstock to a reactor. For example, the system can feed a refinery
feedstock to the reactor. The system can feed a biomass feedstock
(e.g., particles, fluidized particles, oil or other liquid) to the
reactor. The system can feed two or more feedstocks to the reactor,
such that the feedstocks mix in the reactor. Alternatively, the
system can feed a pre-mixed feedstock to the reactor. The system
can mix a refinery feedstock and a biomass feedstock, and feed the
mixture to the reactor. In various embodiments, the system can
control one or more operating parameters (e.g., heating of the
individual and mixed feedstocks, flow volume, flow rate, flow
timing, total amounts of feedstocks, and the like).
[0103] A refinery unit can also include anyone or more additional
reaction vessels, knock out drums, strippers, towers, catalyst
regenerators, catalyst coolers, and the like. A refinery unit can
include a system for pre-processing the biomass feedstock. A
refinery unit can include a system for providing biomass feedstock
and petrochemical feedstock to a reaction vessel. A refinery unit
can also include a system for transporting and/or storing a product
(e.g., the liquid product or a fraction thereof).
[0104] A reactor can operate in either a continuous or switching
(e.g., swing reactor) fashion. For example, each train of the
refinery unit (e.g., hydroprocessing, hydrocracking unit) can be
preceded by a pair of switchable guard reactors, so that catalyst
in the reactor not in operation can be replaced to remove
contaminants without allowing a disruptive pressure drop to occur.
A guard reactor can include a system for removing and replacing
spent catalyst with fresh catalyst (e.g., an ebulating bed reactor
with a system to remove spent catalyst and a system to add fresh
catalyst). Where the reactor is operated in a continuous fashion,
the catalyst can be continuously replaced or regenerated. A guard
reactor can help extend catalyst life in the main reactor, by
limiting catalyst deactivation due to contaminants substantially to
the guard reactor.
[0105] In some cases, selecting a biomass feedstock having a
relatively low mineral content (e.g., essentially cellulose) or
de-mineralizing the biomass feedstock (e.g., by preprocessing) can
mitigate the need to replace or regenerate the catalyst. Where the
reactor is operated in a switching fashion, it can be important to
limit the mineral content of the biomass feedstock to ensure
sufficient catalytic activity throughout a reaction cycle. A guard
reaction can also be employed to mitigate inactivation of the hydro
treating catalyst by minerals in the biomass feedstock. Catalyst
(e.g., in a guard reactor) can be selected to have a greater than
average macroporous region pore volume, so that it can tolerate a
greater quantity of contaminants before becoming inactivated. To
some degree, sufficient catalytic activity can be ensured by
selecting more active catalyst or providing more catalyst.
[0106] In these and other examples, a liquid product, or a fraction
thereof, can be used or sold as a final product and/or can be
subject to further processing/upgrading to producing a fuel or
specialty chemical. Examples of fuels include light gases (ethane,
propane, butane), naphtha, and distillates Get fuel, diesel,
heating oil). Examples of chemicals include light olefins
(ethylene, propylene, butylenes), acids (like formic and acetic),
aldehydes, alcohols (ethanol, propanol, butanol, phenols), ketones,
furans, and the like. In general, a liquid product, or a fraction
thereof, is chemically similar or essentially indistinguishable
(e.g., in terms of commercial use and/or commercial value) from a
convention petrochemical product or intermediate.
[0107] FIG. 1 illustrates a sectional view of an exemplary refinery
unit 100 for coprocessing a biomass feedstock and a refinery
feedstock. The refinery unit 100 includes a fluidized reactor 105,
a first system 110, and a second system 115. The first system 110
can provide a biomass feedstock and a refinery feedstock to the
fluidized reactor. The second system 115 can refresh and/or
regenerate a catalyst for the fluidized reactor 105. The first
system 110 and the second system 115 support catalytic cracking
including transferring hydrogen from the refinery feedstock to
carbon and oxygen from the biomass feedstock within the fluidized
reactor 105.
[0108] The invention also includes a method for providing a
refinery unit (e.g., refinery unit 100) for co-processing a biomass
feedstock and a refinery feedstock. The method includes providing a
fluidized reactor (e.g., fluidized reactor 105). The method also
includes providing a first system (e.g., first system 110)
providing a biomass feedstock and a refinery feedstock to the
fluidized reactor. Furthermore, the method includes providing a
second system (e.g., second system 115) for at least one of
refreshing and regenerating a catalyst in the fluidized reactor.
The first system and the second system can support catalytic
cracking that includes transferring hydrogen from the refinery
feedstock to carbon and oxygen from the biomass feedstock within
the fluidized reactor.
[0109] FIG. 2 illustrates a sectional view of an exemplary refinery
unit 200 for coprocessing a biomass feedstock and a refinery
feedstock in the presence of hydrogen. The refinery unit 200
includes a hydrocracking or hydrotreating reactor 205, a first
system 210, and a second system 215. The first system 210 can
provide a biomass feedstock, a refinery feedstock, and hydrogen gas
to the hydrocracking or hydrotreating reactor 205. The second
system 215 for at least one of refreshing and regenerating a
catalyst in the hydrocracking or hydrotreating reactor 205. The
first system 210 and the second system 215 support hydro cracking
or hydrotreating including transferring hydrogen from the hydrogen
gas to carbon and oxygen from the biomass feedstock and to carbon
from the refinery feedstock in the hydro cracking or hydrotreating
reactor 205.
[0110] The invention also includes a method for providing a
refinery unit (e.g., refinery unit 200) for co-processing a biomass
feedstock and a refinery feedstock in the presence of hydrogen gas.
The method includes providing a hydro cracking or hydrotreating
reactor (e.g., hydrocracking or hydrotreating reactor 205). The
method also includes providing a first system (e.g., first system
210) providing a biomass feedstock, a refinery feedstock, and
hydrogen gas to the hydrocracking or hydrotreating reactor.
[0111] Furthermore, the method includes providing a second system
(e.g., second system 215) for at least one of refreshing and
regenerating a catalyst in the hydrocracking or hydrotreating
reactor. The first system and the second system support
hydrocracking or hydrotreating that includes transferring hydrogen
from the hydrogen gas to carbon and oxygen from the biomass
feedstock and to carbon from the refinery feedstock in the
hydrocracking or hydrotreating reactor.
[0112] The refinery units 100, 200 can be used, for example, to
execute methods like the method described in Example 1 and Example
2, respectively. Accordingly, the refinery units 100, 200 can
include anyone or more of the elements, feedstocks, reactions, and
product described in connection with Example 1 and Example 2.
[0113] While the invention has been particularly shown and
described with reference to specific embodiments, it should be
understood by those skilled in the art that various changes in form
and detail can be made without departing from the spirit and scope
of the invention as defined by the appended claims.
* * * * *