U.S. patent application number 14/777500 was filed with the patent office on 2016-02-04 for vapor phase catalytic reactor for upgarde of fuels produced by fast pyrolysis of biomass.
The applicant listed for this patent is BATTELLE MEMORIAL INSTITUTE. Invention is credited to Zia Abdullah, Herman P. Benecke, G. Bradley Chadwell, James E. Dvorsky, Stephanie Flamberg, Daniel B. Garbark, James E. Mathis, Michael A. O'Brian, Russell K. Smith, Rachid Taha, Slawomir Winecki.
Application Number | 20160032196 14/777500 |
Document ID | / |
Family ID | 50487203 |
Filed Date | 2016-02-04 |
United States Patent
Application |
20160032196 |
Kind Code |
A1 |
Abdullah; Zia ; et
al. |
February 4, 2016 |
Vapor Phase Catalytic Reactor for Upgarde of Fuels Produced by Fast
Pyrolysis of Biomass
Abstract
Vapor phase catalytic reactors and methods for using the same
for upgrade of fuels produced by fast pyrolysis of biomass are
disclosed.
Inventors: |
Abdullah; Zia; (Columbus,
OH) ; Winecki; Slawomir; (Dublin, OH) ;
Chadwell; G. Bradley; (Reynoldsburg, OH) ; O'Brian;
Michael A.; (Columbus, OH) ; Smith; Russell K.;
(Dublin, OH) ; Flamberg; Stephanie; (Plain City,
OH) ; Dvorsky; James E.; (Plain City, OH) ;
Taha; Rachid; (Dublin, OH) ; Mathis; James E.;
(Columbus, OH) ; Benecke; Herman P.; (Columbus,
OH) ; Garbark; Daniel B.; (Blacklick, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BATTELLE MEMORIAL INSTITUTE |
Columbus |
OH |
US |
|
|
Family ID: |
50487203 |
Appl. No.: |
14/777500 |
Filed: |
March 15, 2014 |
PCT Filed: |
March 15, 2014 |
PCT NO: |
PCT/US2014/029946 |
371 Date: |
September 15, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61800262 |
Mar 15, 2013 |
|
|
|
Current U.S.
Class: |
585/240 ;
422/142; 422/145; 422/162 |
Current CPC
Class: |
Y02P 30/20 20151101;
Y02P 20/584 20151101; B01J 38/30 20130101; C10G 11/00 20130101;
C10G 2300/42 20130101; C10G 3/42 20130101; C10G 45/00 20130101;
C10G 3/50 20130101; C10K 3/04 20130101; Y02E 50/10 20130101; C10B
53/02 20130101; Y02E 50/14 20130101 |
International
Class: |
C10G 11/00 20060101
C10G011/00; C10B 53/02 20060101 C10B053/02; C10G 45/00 20060101
C10G045/00; C10K 3/04 20060101 C10K003/04; C10G 3/00 20060101
C10G003/00 |
Claims
1-103. (canceled)
104. A biofuel production system, comprising: a catalytic vapor
phase reactor (VPR); a pyrolysis reactor operatively connected to
the catalytic VPR; a quench system operatively connected to the
catalytic VPR; a water gas shift reactor operatively connected to
the quench system; and a hydrotreatment system operatively
connected to the quench system.
105. The biofuel production system of claim 1, the pyrolysis
reactor being configured to pyrolyze a biomass to produce a
pyrolysis vapor and char, the system further comprising a char
removal system configured to remove the char from the pyrolysis
reactor.
106. The biofuel production system of claim 1, further comprising a
heater operatively coupled to the pyrolysis reactor, the heater
being configured to at least one of internally and externally heat
pyrolysis reactor to a temperature between about 300.degree. C. and
about 600.degree. C.
107. The biofuel production system of claim 106, the heater
comprising one or more of a resistive heating element, a combustor,
a heat exchanger, or a microwave generator.
108. The biofuel production system of claim 1, the catalytic VPR
comprising a catalyst comprising one or more of: a granulated
catalyst; a powdered catalyst; a fluid catalytic cracking catalyst
(FCC); fresh FCC; spent FCC; catalyst impregnated on top of the
fresh FCC; catalyst impregnated on top of the spent FCC; the
granulated catalyst characterized by a granule size between about
50 .mu.m and about 100 .mu.m; the granulated catalyst characterized
by a size distribution of granules, a substantial fraction of the
size distribution being greater than about 20 .mu.m; and a catalyst
selected to catalyze at least one of: deoxygenation, cracking,
water-gas shift, and hydrocarbon formation.
109. The biofuel production system of claim 1, the pyrolysis
reactor and the catalytic VPR being configured together as a single
unit.
110. The biofuel production system of claim 1, further comprising a
conversion system operatively coupled to one or more of: the
catalytic vapor phase reactor, the pyrolysis reactor, and the
hydrotreatment system; the conversion system being configured to
produce a hydrocarbon product from biomass by upgrading a bio-oil
produced by one or more of: the catalytic vapor phase reactor, the
pyrolysis reactor, and the hydrotreatment system.
111. A method for catalytic pyrolysis of biomass, the method
comprising: drying a biomass; pyrolyzing the biomass to create a
pyrolysis vapor; removing at least one of a char and an ash from
the pyrolysis vapor; upgrading the pyrolysis vapor by vapor phase
catalysis to produce an upgraded pyrolysis vapor; and condensing a
bio-oil from the upgraded pyrolysis vapor.
112. The method of claim 111, pyrolyzing the biomass being
conducted at one or more of: a temperature between about
300.degree. C. and about 600.degree. C.; and at a biomass residence
time of about 2 seconds or less.
113. The method of claim 111, upgrading the pyrolysis vapor by
vapor phase catalysis to produce the upgraded pyrolysis vapor being
conducted after pyrolyzing the biomass to create the pyrolysis
vapor and removing at least one of the char and the ash from the
pyrolysis vapor, and before condensing the bio-oil from the
upgraded pyrolysis vapor.
114. The method of claim 111, the pyrolysis vapor comprising one or
more of: water, an organic acid, an aldehyde, a phenol, and a
sugar; or one or more derivatives thereof.
115. The method of claim 111, upgrading the pyrolysis vapor by
vapor phase catalysis comprising one or more of: deoxygenating the
pyrolysis vapor to produce the upgraded pyrolysis vapor; cracking
one or more higher molecular weight components of the pyrolysis
vapor to produce the upgraded pyrolysis vapor; contacting the
pyrolysis vapor to one or more of: a granulated catalyst, a
powdered catalyst, and a fluid catalytic cracking catalyst (FCC);
contacting the pyrolysis vapor to one or more of: fresh FCC, spent
FCC, catalyst impregnated on top of the fresh FCC, and catalyst
impregnated on top of the spent FCC; contacting the pyrolysis vapor
to the granulated catalyst, the granulated catalyst characterized
by particle size and flow characteristics substantially similar to
the FCC; contacting the pyrolysis vapor to a granulated catalyst
characterized by a granule size between about 50 .mu.m and about
100 .mu.m; and contacting the pyrolysis vapor to a granulated
catalyst characterized by a size distribution of granules, a
substantial fraction of the size distribution being greater than
about 20 .mu.m.
116. The method of claim 111, further comprising one or more of:
producing a non-condensable gas comprising CO during the pyrolyzing
the biomass; reacting the non-condensable gas comprising CO in a
water gas shift reaction to form at least one of hydrogen and
CO.sub.2; and hydrotreating the bio oil with hydrogen from the
water gas shift reaction to produce a hydrocarbon fuel product.
117. The method of claim 111, comprising: drying the biomass in a
biomass dryer; placing the biomass in a pyrolysis reactor and
pyrolyzing the biomass at about 500.degree. C. to create a
pyrolysis vapor; directing the pyrolysis vapor to a char and ash
removal system and removing at least one of a char and an ash from
the pyrolysis vapor; directing the pyrolysis vapor to a catalytic
vapor phase reactor and upgrading the pyrolysis vapor to form an
upgraded pyrolysis vapor; directing the upgraded pyrolysis vapor to
a condenser; and extracting a bio-oil from the condenser.
118. A catalytic vapor phase reactor apparatus, the apparatus
comprising: a gas-solid catalytic reactor; a feeding auger; a
return auger; a hot blower; a first blower; a second blower; a
first cyclone; a second cyclone; a third cyclone; a split
connection; a dip leg pipe operatively coupled to the split
connection; a fluidized bed reactor; a bypass connection; and a
catalyst feeding vessel; the feeding auger and the return auger
being operatively connected to the gas-solid catalytic reactor and
the fluidized bed reactor; the first cyclone and the second cyclone
being operatively connected to the gas-solid catalytic reactor; and
the third cyclone being operatively connected to the fluidized bed
reactor, the first blower, and the second blower.
119. The catalytic vapor phase reactor apparatus of claim 118,
further comprising a heater operatively coupled to the gas-solid
catalytic reactor, the heater comprising one or more of: a
resistive heating element, a combustor, a heat exchanger, and a
microwave generator.
120. The catalytic vapor phase reactor apparatus of claim 118, the
gas-solid catalytic reactor comprising a raining bed reactor
configured to contact the pre-upgrade pyrolysis gas and the
catalyst.
121. The catalytic vapor phase reactor apparatus of claim 118, the
fluidized bed reactor being operatively connected to at least one
of the first blower and the second blower.
122. The catalytic vapor phase reactor apparatus of claim 118,
feeding auger and return auger being operatively connected for
feeding of a catalyst into the gas-solid catalytic reactor and the
fluidized bed reactor, and recirculation of catalyst between
gas-solid catalytic reactor and fluidized bed reactor.
123. The catalytic vapor phase reactor apparatus of claim 118,
comprising a catalyst comprising one or more of: a granulated
catalyst; a powdered catalyst; a fluid catalytic cracking catalyst
(FCC); fresh FCC; spent FCC; catalyst impregnated on top of the
fresh FCC; catalyst impregnated on top of the spent FCC; the
granulated catalyst, characterized by a granule size between about
50 .mu.m and about 100 .mu.m; the granulated catalyst,
characterized by a size distribution of granules, a substantial
fraction of the size distribution being greater than about 20
.mu.m; and a catalyst configured to catalyze at least one of:
deoxygenation, cracking, water-gas shift, and hydrocarbon
formation.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional
Patent Application No. 61/800,262, filed on Mar. 15, 2013, which is
incorporated by reference herein in its entirety.
BACKGROUND
[0002] The extraction of bio-oil from biomass for use as a biofuel
is an area of interest in the search for reliable alternative
energy sources. Bio-oil produced by traditional fast pyrolysis
processes is typically of relatively low quality due to the
bio-oil's large degree of oxygenation, significant acidity, storage
instability, tendency to polymerize, and the difficulty involved in
separating the bio-oil from water and polar compounds. The low
quality of the bio-oil limits its applicability in applications
that require high quality fuels, such as transportation
applications. Biofuels intended for these applications usually
require additional processing.
[0003] Improved systems, methods, and apparatuses are needed for
processing bio-oil and making biofuel.
SUMMARY
[0004] In one embodiment, a biofuel production system is provided,
the system may include: a catalytic vapor phase reactor; a
pyrolysis reactor operatively connected to the catalytic vapor
phase reactor; a quench system operatively connected to the
catalytic vapor phase reactor; a water gas shift reactor
operatively connected to the quench system; and a hydrotreatment
system operatively connected to the quench system.
[0005] In one embodiment, a method for catalytic pyrolysis of
biomass is provided. The method may include drying a biomass. The
method may include pyrolyzing the biomass to create a pyrolysis
vapor. The method may include removing at least one of a char and
an ash from the pyrolysis vapor. The method may include upgrading
the pyrolysis vapor by vapor phase catalysis to produce an upgraded
pyrolysis vapor. The method may include condensing a bio-oil from
the upgraded pyrolysis vapor.
[0006] In one embodiment, a method for catalytic pyrolysis of
biomass is provided, the method may include: drying a biomass in a
biomass dryer; placing the biomass in a pyrolysis reactor and
heating the biomass to about 500.degree. C. to create a pyrolysis
vapor; directing the pyrolysis vapor to a char and ash removal
system and removing at least one of a char and an ash from the
pyrolysis vapor; directing the pyrolysis vapor to a catalytic vapor
phase reactor to upgrade the pyrolysis vapor; directing the
pyrolysis vapor to a condenser; and extracting a bio-oil from the
condenser.
[0007] In one embodiment, a catalytic vapor phase reactor apparatus
is provided, the apparatus may include: a gas-solid catalytic
reactor; a feeding auger; a return auger; a hot blower; a first
blower; a second blower; a first cyclone; a second cyclone; a third
cyclone; a split connection; a dip leg pipe; a fluidized bed
reactor; a bypass connection; and a catalyst feeding vessel;
wherein the feeding auger and the return auger are operatively
connected to the gas-solid catalytic reactor and the fluidized bed
reactor; wherein the first cyclone and the second cyclone are
operatively connected to the gas-solid catalytic reactor; and
wherein the third cyclone is operatively connected to the fluidized
bed reactor.
[0008] In another embodiment, a catalytic vapor phase reactor
apparatus is provided, the apparatus may include: a housing may
include an auger device, a catalyst inlet, a catalyst outlet, a
pyrolysis vapor inlet, and a pyrolysis vapor outlet; wherein the
auger device is configured to transport a solid catalyst through at
least a portion of the housing; and wherein the housing is
configured to permit a pyrolysis vapor to flow through at least a
portion of the housing and come into contact with the solid
catalyst.
[0009] In another embodiment, a catalytic vapor phase reactor
apparatus is provided, the apparatus may include: a housing may
include at least one baffle, a catalyst inlet, a catalyst outlet, a
pyrolysis vapor inlet, and a pyrolysis vapor outlet; wherein the
housing is at least one of substantially vertical and inclined;
wherein the housing is configured to permit a solid catalyst to
flow through at least a portion of the housing and over at least
one baffle; and wherein the housing is configured to permit a
pyrolysis vapor to flow through at least a portion of the housing
and come into contact with the solid catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The accompanying figures, which are incorporated in and
constitute a part of the specification, illustrate various example
apparatuses, systems, and methods, and are used merely to
illustrate various example embodiments.
[0011] FIG. 1 illustrates an example arrangement of a biofuels
production system.
[0012] FIG. 2A illustrates an example arrangement of a process for
catalytic fast pyrolysis of biomass.
[0013] FIG. 2B illustrates an example arrangement of a process for
catalytic fast pyrolysis of biomass.
[0014] FIG. 3 illustrates an example arrangement of a catalytic
vapor phase reactor for upgrading bio-oil vapors.
[0015] FIG. 4 illustrates an example arrangement of a catalytic
vapor phase reactor.
[0016] FIG. 5 illustrates an example arrangement of a catalytic
vapor phase reactor.
DETAILED DESCRIPTION
[0017] FIG. 1 illustrates an example arrangement of a biofuels
production system 100. Biofuels production system 100 may include a
catalytic vapor phase reactor ("VPR") 102 operatively connected to
a pyrolysis reactor 104. Pyrolysis reactor 104 may be configured to
receive a biomass 105. In one embodiment, biomass 105 may include a
wood.
[0018] In one embodiment, biofuels production system 100 may
include a conversion system to produce a hydrocarbon product from
biomass 105. The production of the hydrocarbon fuel product may
include upgrading a bio-oil product. In one embodiment, system 100
may be configured to produce at least one of a hydrocarbon fuel
product, a gas, or a chemical, depending upon the catalyst type and
reaction conditions.
[0019] In one embodiment, biomass 105 enters pyrolysis reactor 104
wherein biomass 105 may be pyrolyzed and converted to a pyrolysis
vapor. In one embodiment, pyrolysis reactor 104 operates at an
elevated temperature. In another embodiment, pyrolysis reactor 104
operates at a temperature between about 300.degree. C. and about
600.degree. C. In another embodiment, pyrolysis reactor 104
operates at a temperature between about 350.degree. C. and about
550.degree. C. In another embodiment, pyrolysis reactor 104
operates at a temperature between about 400.degree. C. and about
500.degree. C. In another embodiment, pyrolysis reactor 104
operates at a temperature capable of converting biomass 105 to a
vapor. In one embodiment, char produced in the pyrolysis of biomass
105 may be removed from pyrolysis reactor 104. In one embodiment,
pyrolysis reactor 104 may be internally heated. In another
embodiment, pyrolysis reactor 104 may be externally heated. In
another embodiment, pyrolysis reactor 104 may be heated via
microwaves.
[0020] The pyrolysis vapor created in pyrolysis reactor 104 may be
directed into VPR 102. In one embodiment, VPR 102 may be configured
to at least one of deoxygenate the pyrolysis vapor and break down
higher molecular weight components of the pyrolysis vapor.
[0021] In one embodiment, VPR 102 may be an integral component of
pyrolysis reactor 104, and catalysis takes place in pyrolysis
reactor 104. In another embodiment, catalysis occurs in pyrolysis
reactor 104 and VPR 102 may be eliminated.
[0022] The pyrolysis vapor may leave VPR 102 and enter a quench
system 106, which may be operatively connected to VPR 102. Quench
system 106 may quench the pyrolysis vapor, producing a bio-oil. In
one embodiment, the bio-oil may be upgraded to produce a
hydrocarbon fuel product. The quenching of the pyrolysis vapor in
quench system 106 may produce at least one of a non-condensable gas
and a low oxygen bio-oil.
[0023] In one embodiment, non-condensable gas may be directed from
quench system 106 into a water gas shift reactor 108, which may be
operatively connected to quench system 106. The non-condensable gas
may be processed resulting in at least one of hydrogen and
CO.sub.2. Hydrogen for the upgrading may be obtained via a water
gas shift of the CO in the non-condensable gas exiting quench
system 106.
[0024] In one embodiment, low oxygen bio-oil may be directed from
quench system 106 into a hydrotreatment system 110, which may be
operatively connected to quench system 106. In one embodiment,
hydrogen from water gas shift reactor 108 may be directed into
hydrotreatment system 110. In one embodiment, hydrogen may react
with the low oxygen bio-oil to produce a hydrocarbon fuel
product.
[0025] In one embodiment, biomass 105 may include a wood. Thus, in
some embodiments, the bio-oil produced via pyrolysis may contain a
mixture of water, organic acids, aldehydes, phenols, and sugar
derivatives that require upgrading in order for the bio-oil to be
more readily soluble and usable. In one embodiment, the upgrading
may be achieved through reaction of the acids, phenols, and sugars
with olefins to form esters and ethers. For example, in one
embodiment, the bio-oil in the vapor phase may be passed through a
catalyst bed after mixing with an injected amount of isoprene,
isobutylene, or propylene. In one embodiment, the water may be
converted to an alcohol form of the olefin. In one embodiment, the
alcohols may be etherified. In one embodiment, the carboxylic acids
may be esterified.
[0026] FIG. 2A illustrates an example arrangement of a process 201
configured, for example, for catalytic fast pyrolysis of biomass.
Process 201 may generate high yields of condensable organics that
may be used as liquid fuels. Process 201 may include 250 drying a
biomass. Process 201 may include 252 pyrolyzing the biomass to
create a pyrolysis vapor. Process 201 may include 254 removing at
least one of a char and an ash from the pyrolysis vapor. Process
201 may include 256 upgrading the pyrolysis vapor by vapor phase
catalysis to produce an upgraded pyrolysis vapor. Process 201 may
include 258 extracting a bio-oil from the upgraded pyrolysis vapor
by condensation.
[0027] FIG. 2B illustrates an example arrangement of a process 200
configured, for example, for catalytic fast pyrolysis of biomass.
Process 200 may be included within the scope of process 201.
Process 200 may generate high yields of condensable organics that
may be used as liquid fuels. In one embodiment, process 200 may
include heating of a biomass to about 500.degree. C. for a short
period of time, typically on the order of a second. Process 200 may
include subsequent condensation of organic vapors into a bio-oil
mixed with water. Process 200 may include the upgrading of bio-oil
vapors in a VPR 202.
[0028] Process 200 may include a system including VPR 202, a
pyrolysis reactor 204, a condenser 206, a biomass dryer 212, and a
char and ash removal system 214. Thus, in one embodiment, process
200 may include: introducing a biomass into biomass dryer 212;
transferring dried biomass into pyrolysis reactor 204; and
directing pyrolysis vapor from pyrolysis reactor 204 into char and
ash removal system 214. Char and ash may be separated from the
pyrolysis vapor in char and ash removal system 214. Char and ash
may be discarded from the system.
[0029] Pyrolysis vapor exiting char and ash removal system 214 may
be directed into VPR 202. In one embodiment, pyrolysis vapor may be
upgraded in VPR 202. In one embodiment, pyrolysis vapor may be
contacted with a catalyst after pyrolysis and char/ash removal but
before vapor condensing. Processing of the pyrolysis vapor between
the char/ash removal but before vapor condensing may minimize
contamination of the catalyst with ash and char generated during
pyrolysis.
[0030] In one embodiment, temperatures in VPR 202 and pyrolysis
reactor 204 may be substantially the same, or different. In another
embodiment, residence time of reactants in VPR 202 and pyrolysis
reactor 204 may be substantially the same. In another embodiment,
residence time of reactants in VPR 202 and pyrolysis reactor 204
may be different.
[0031] In one embodiment, VPR 202 utilizes at least one of: a
granulated catalyst, a powdered catalyst, and a catalyst mixture
capable of bio-oil vapor or liquid/vapor upgrade. In another
embodiment, VPR 202 utilizes a fluid catalytic cracking or a
similar granulated catalyst. In one embodiment, the catalyst may be
a granulated catalyst with a typical granule size between about 50
.mu.m and about 100 .mu.m. The catalyst may have very few granules
smaller than about 20 .mu.m. In one embodiment, the catalyst
characteristics provide a desired combination of rapid external
mass transfer in rapid gas-solid reactions combined with relatively
easy gas-solid separation ability. In one embodiment, the catalyst
may be a fluid catalytic cracking ("FCC") catalyst. In one
embodiment, the catalyst may be at least one of: fresh FCC, spent
FCC, catalyst impregnated on top of fresh FCC, catalyst impregnated
on top of spent FCC, and catalysts granulated by other means but
with the same or similar particle size and flow characteristic as
FCC. In another embodiment, the catalyst catalyzes at least one of
the following reactions: deoxygenation, cracking, water-gas shift,
and hydrocarbon formation.
[0032] Upgraded pyrolysis gas may be directed to condenser 206,
where the upgraded pyrolysis gas may be separated into at least one
of: non-condensable gases, upgraded bio-oil, and waste water.
Upgraded pyrolysis gas may be separated via condensation.
[0033] FIG. 3 illustrates an example arrangement of a VPR 300 for
upgrading bio-oil vapors. VPR 300 may include a gas-solid catalytic
reactor 302, a feeding auger 304, a return auger 306, a hot blower
308, a first cyclone 310, a second cyclone 312, and a split
connection 314. Split connection 314 may be operatively connected
to a dip leg pipe 316, a fluidized bed reactor 318, a bypass
connection 320, and a catalyst feeding vessel 322. Fluidized bed
reactor 318 may include a third cyclone 324 operatively connected
to a first blower 326 and a second blower 328.
[0034] In one embodiment, VPR 300 may be configured for continuous
mode operation. In another embodiment, VPR 300 may be configured
for batch mode operation. In one embodiment, VPR 300 may be
configured to operate utilizing air at atmospheric pressure for
catalyst regeneration and does not require the use of gases with
reduced oxygen content, including, for example, inert gases such as
nitrogen, or another gas such as carbon dioxide.
[0035] In one embodiment, each of the components of VPR 300, with
the exception of hot blower 308, first blower 326, and second
blower 328, are configured to operate at relatively high
temperatures. In one embodiment, the operation temperature may be
between about 300.degree. C. and about 700.degree. C. In another
embodiment, the operation temperature may be between about
350.degree. C. and about 650.degree. C. In another embodiment, the
operation temperature may be between about 400.degree. C. and about
600.degree. C. In another embodiment, the operation temperature may
be a temperature as high as may be required to drive a catalytic
upgrade reaction and a catalyst regeneration (coke oxidation)
reaction. In another embodiment, the operation temperature may be a
temperature as high as may be required to avoid condensation of
pyrolysis gases that can occur on surfaces of components, such as
those below about 400.degree. C. In one embodiment, operating
temperature may be generated and/or maintained by placing VPR 300
in a hot box heated by at least one of a gas burner and an electric
heater.
[0036] In one embodiment, a catalytic upgrade reaction takes place
in gas-solid catalytic reactor 302. A catalyst (for example, a
granulated catalyst) may be introduced at the top of gas-solid
catalytic reactor 302. In one embodiment, pre-upgrade pyrolysis gas
may be introduced at the top of gas-solid catalytic reactor 302. In
another embodiment, pre-upgrade pyrolysis gas may be introduced at
one or more of the top, bottom, or side of gas-solid catalytic
reactor 302.
[0037] In one embodiment, pre-upgrade pyrolysis gas and a catalyst
are allowed to rapidly mix within gas-solid catalytic reactor 302
to facilitate sufficient contact with the catalyst surface.
Gas-solid catalytic reactor 302 may include a volume while the
pre-upgrade pyrolysis gas may include a flow rate, which volume and
flow rate may be adjusted relative to one another to optimize the
contact time between pre-upgrade pyrolysis gas and a catalyst. In
one embodiment, the pre-upgrade pyrolysis gas has a residence time
within gas-solid catalytic reactor 302 of about 1 s. In one
embodiment, mass transfer limitations and catalyst reactivity
dictate preferable catalyst-to-pyrolysis gas ratios. In one
embodiment, ratios may be about 1:1. In another embodiment, higher
amounts of catalyst are required. In one embodiment, VPR 300 may be
configured to modulate the catalyst-to-pyrolysis gas ratio over
more than an order of magnitude.
[0038] Gas-solid catalytic reactor 302 may include a reaction
temperature between about 350.degree. C. and about 650.degree. C.
In another embodiment, gas-solid catalytic reactor 302 may include
a reaction temperature between about 400.degree. C. and about
600.degree. C. In another embodiment, gas-solid catalytic reactor
302 may include a reaction temperature between about 450.degree. C.
and about 550.degree. C.
[0039] In one embodiment, gas-solid catalytic reactor 302 may
include a raining bed reactor ("RBR") having a series of angled
baffles configured to facilitate contact between pre-upgrade
pyrolysis gas and a catalyst. In another embodiment, gas-solid
catalytic reactor 302 may include any of a variety of reactor
designs, including those used in static mixers, empty reactor
tubes, and other reactors with features to facilitate catalyst
distribution.
[0040] Following contact with the catalyst in gas-solid catalytic
reactor 302, upgraded pyrolysis gas exits gas-solid catalytic
reactor 302 on at least one of: the bottom, the top, and the side
of gas-solid catalytic reactor 302. Upgraded pyrolysis gas exiting
gas-solid catalytic reactor 302 may include catalyst particles
picked up in gas-solid catalytic reactor 302. Upgraded pyrolysis
gas may be at least substantially separated from the catalyst
particles.
[0041] In one embodiment, at least one of first cyclone 310 and
second cyclone 312 are configured to receive upgraded pyrolysis
gas. In another embodiment, first cyclone 310 and second cyclone
312 operate in series to receive upgraded pyrolysis gas. In another
embodiment, additional cyclones may be used in the system. In
another embodiment, at least one of first cyclone 310 and second
cyclone 312 may be replaced with any of a variety of alternative
solid-gas separation devices, such as baghouses.
[0042] In one embodiment, upgraded pyrolysis gas may be introduced
into first cyclone 310. First cyclone 310 may process the upgraded
pyrolysis gas to separate catalyst particles from the upgraded
pyrolysis gas, which particles may be at least one of returned to
gas-solid catalytic reactor 302 or removed from VPR 300. In one
embodiment, upgraded pyrolysis gas may be directed from first
cyclone 310 to second cyclone 312 where second cyclone 312
processes the upgraded pyrolysis gas to separate remaining catalyst
particles from the upgraded pyrolysis gas, which particles may be
at least one of returned to gas-solid catalytic reactor or removed
from VPR 300. In one embodiment, catalyst particles separated in
second cyclone 312 may be purged from VPR 300.
[0043] In one embodiment, at least one of first cyclone 310 and
second cyclone 312 causes a pressure drop within VPR 300. Such
pressure drop may be undesirable. In one embodiment, pressure
within VPR 300 may be maintained using hot blower 308. Hot blower
308 may force gas into VPR 300 to cause a pressure increase that
substantially balances the pressure drop experienced at first
cyclone 310 and second cyclone 312.
[0044] The catalytic upgrade reaction may generate a considerable
amount of coke. The coke may deposit on the catalyst, which may
block the active sites and pores of the catalyst, thus rendering it
less effective. As such, in one embodiment the coke should be
removed from the catalyst. In one embodiment, the coke may be
removed by continuous oxidation in air at a temperature between
about 400.degree. C. and about 700.degree. C. In another
embodiment, the coke may be removed by continuation oxidation in
air at a temperature between about 450.degree. C. and about
650.degree. C. In another embodiment, the coke may be removed by
continuous oxidation in air at a temperature between about
500.degree. C. and about 600.degree. C. In one embodiment,
oxidation of the coke occurs inside fluidized bed reactor 318.
[0045] In one embodiment, fluidized bed reactor 318 may be
operatively connected to at least one of a first blower 326 and a
second blower 328. At least one of first blower 326 and second
blower 328 causes an air flow within fluidized bed reactor 318. In
another embodiment, at least one of first blower 326 and second
blower 328 may be configured to direct air from fluidized bed
reactor 318 into a distributor (not shown). Air flow and the volume
of fluidized bed reactor 318 may be selected to optimize several
design requirements, including at least one of: (1) air flow
capable of generating appropriate fluidization conditions for the
catalyst used, (2) air flow sufficient to deliver enough oxygen for
coke oxidation, and (3) air flow, temperature, and fluidized bed
reactor 318 volume must facilitate coke oxidation kinetics.
[0046] In one embodiment, the coke burning reaction may be highly
exothermic and heat generated therein may be dissipated through any
of various means, including heat transfer from fluidized bed
reactor 318 to the gas atmosphere surrounding fluidized bed reactor
318. In another embodiment, heat dissipation may be enhanced by
using room temperature air for fluidization. In another embodiment,
heat dissipation may be enhanced by using another cooling medium
directed into fluidized bed reactor 318.
[0047] Oxidation of coke may produce byproducts including carbon
monoxide, carbon dioxide, and water. Significant quantities of
carbon monoxide generated in oxidation of coke may be exhausted
through at least one of third cyclone 324 and first blower 326.
[0048] Catalyst particles from fluidized bed reactor 318 may be
entrained by the fluidizing air and/or exhaust gases. The catalyst
particles may be removed from the fluidizing air to minimize
catalyst losses. Third cyclone 324 may be used to process the
fluidizing air to at least substantially separate catalyst from the
fluidizing air, which catalyst may be at least one of returned to
fluidized bed reactor 318 or discarded from VPR 300.
[0049] Third cyclone 324 may be contained within fluidized bed
reactor 318. In one embodiment, additional cyclones may be utilized
in series with third cyclone 324. In another embodiment, the
additional cyclones and/or third cyclone 324 may be located inside
or outside fluidized bed reactor 318 or a hot box surrounding VPR
300.
[0050] In one embodiment, at least one of first blower 326 and
second blower 328 are needed to maintain a desired pressure balance
between gas-solid catalytic reactor 302 and fluidized bed reactor
318. In another embodiment, at least one of first blower 326 and
second blower 328 permit independent control of air flow in
fluidized bed reactor 318 and internal pressure of fluidized bed
reactor 318.
[0051] In one embodiment, feeding of the catalyst into gas-solid
catalytic reactor 302 and fluidized bed reactor 318, and
recirculation of catalyst between gas-solid catalytic reactor 302
and fluidized bed reactor 318 may be effected by feeding auger 304
and return auger 306. Feeding auger 304 and return auger 306 may be
powered by at least one power source, for example an electric
motor. The electric motor may be placed outside VPR 300 but coupled
mechanically with feeding auger 304 and return auger 306. Feeding
auger 304 and return auger 306 may include auger screws configured
to rotate and advance catalyst material. Flow rate of the catalyst
can be controlled by adjusting the rotation speed of feeding auger
304 and return auger 306. Such adjustment of the rotation speed of
feeding auger 304 and return auger 306 may be utilized to adjust
the catalyst to biomass ratio and effectively control the catalytic
reaction rate. Feeding auger 304 may direct catalyst from catalyst
feeding vessel 322 to gas-solid catalytic reactor 302. Return auger
306 may direct catalyst from gas-solid catalytic reactor 302 to
split connection 314.
[0052] Split connection 314 may be configured to preferably direct
the catalyst to fluidized bed reactor 318 for regeneration. Split
connection 314 may direct catalyst material to dip leg pipe 316
immersed into the catalyst contained in fluidized bed reactor 318.
As a result of the hydrostatic balance of the catalyst within
fluidized bed reactor 318, and the proper pressure balance between
gas-solid catalytic reactor 302 and fluidized bed reactor 318, dip
leg pipe 316 remains at least partially filled with catalyst. The
partially filled state of dip leg pipe 316 acts as a gas lock to
limit the amount of gas that can pass to and from fluidized bed
reactor 318. This gas lock at least substantially separates the
pyrolysis gas atmosphere existing inside gas-solid catalytic
reactor 302, feeding auger 304, and return auger 306, from the
oxygen-rich atmosphere inside fluidized bed reactor 318.
[0053] Bypass connection 320 allows catalyst to bypass fluidized
bed reactor 318 in the event that catalyst may be not accepted into
fluidized bed reactor 318 via dip leg pipe 316. In one embodiment,
catalyst may be required to bypass fluidized bed reactor 318 due to
insufficient fluidization inside fluidized bed reactor 318, or a
loss of air flow into fluidized bed reactor 318. Bypass connection
318 may allow for uninterrupted catalytic upgrade reaction and will
prevent return auger 306 from becoming backed up with catalyst.
[0054] Catalyst processed in fluidized bed reactor 318 may be
transferred to catalyst feeding vessel 322 via a transfer
connection 330. Upon reaching a sufficient level in fluidized bed
reactor 318, catalyst may flow from fluidized bed reactor 318 to
catalyst feeding vessel 322 via transfer connection 330. Similar to
dip leg pipe 316, transfer connection 330 acts as a gas lock to
limit the amount of gas that can pass to and from fluidized bed
reactor 318.
[0055] Catalyst transferred through bypass connection 320 into
catalyst feeding vessel 322 without passing through fluidized bed
reactor 318 may be not processed to remove coke. However, a
catalyst contaminated with coke may be utilized in gas-solid
catalytic reactor 302 until it may be able to enter fluidized bed
reactor 318 for processing.
[0056] FIG. 4 illustrates an example arrangement of a VPR 400. VPR
400 may include a housing 402 containing an auger device 404
configured to move a catalyst material and a biomass pyrolysis
vapor in counter-current directions. VPR 400 may be configured to
bring the pyrolysis vapor and the catalyst into close contact.
Housing 402 and auger device 404 may include substantially circular
cross-sections. In one embodiment, housing 402 may include an inner
diameter that may be substantially the same as or slightly greater
than the outside diameter of auger device 404.
[0057] In one embodiment, VPR 400 may be placed in a heated
enclosure and coupled to a catalyst regeneration system, such as
that illustrated in FIG. 3. VPR 400 may operate in a heated
enclosure between about 300.degree. C. and about 600.degree. C. In
another embodiment, VPR 400 operates in a heated enclosure between
about 350.degree. C. and about 550.degree. C. In another
embodiment, VPR 400 operates in a heated enclosure between about
400.degree. C. and about 500.degree. C. In another embodiment, VPR
400 operates at an elevated temperature configured to prevent
condensation of the pyrolysis vapor.
[0058] In one embodiment, VPR 400 may include an inclined housing
402 and auger device 404. A catalyst may enter VPR 400 via a
catalyst inlet 406. The catalyst may be transported through VPR 400
within housing 402 via rotation of an auger device 404. Catalyst
may exit VPR 400 via a catalyst outlet 408.
[0059] In one embodiment, pyrolysis vapor enters VPR 400 at a
pyrolysis vapor inlet 410. Pyrolysis vapor may move through housing
402 by virtue of a pressure differential, a blower, or a pump.
Pyrolysis vapor may move through housing 402 in contact with the
catalyst. In one embodiment, pyrolysis vapor moves spirally about
auger device 404. In one embodiment, pyrolysis vapor exits VPR 400
via a pyrolysis vapor outlet 412. In one embodiment, pyrolysis
vapor inlet 410 may be near the upper portion of housing 402 and
pyrolysis vapor outlet 412 may be near the lower portion of housing
402. In another embodiment, pyrolysis vapor inlet 410 may be near
the lower portion of housing 402 and pyrolysis vapor outlet 412 may
be near the upper portion of housing 402. In one embodiment,
pyrolysis vapor moves counter-current to the flow of the catalyst.
In another embodiment, pyrolysis vapor moves concurrent to the flow
of the catalyst.
[0060] In one embodiment, pyrolysis vapor flows downward within
housing 402 in a spiral around auger device 404. Limited clearance
between the outside diameter of auger device 404 and the inside
diameter of housing 402 limits the bypass of gas around the
catalyst, forcing pyrolysis vapor to contact the catalyst.
[0061] The catalyst may enter and exit VPR 400 through a double
block valve system (such as that illustrated in FIG. 3) so as to
substantially prevent pyrolysis vapor from exiting VPR 400 with the
catalyst.
[0062] FIG. 5 illustrates an example arrangement of a VPR 500. VPR
500 may include a substantially vertical or inclined housing 502,
within which at least one baffle 504 may be oriented. A catalyst
may enter VPR 500 via a catalyst inlet 506 and may exit VPR 500 via
a catalyst outlet 508. A pyrolysis vapor may enter VPR 500 via a
pyrolysis vapor inlet 510 and may exit VPR 500 via a pyrolysis
vapor outlet 512.
[0063] In one embodiment, at least one baffle 504 may be angled
downward so as to cause a catalyst to pour off at least one baffle
504 with pyrolysis vapor moving through the stream of catalyst
material. In another embodiment, VPR 500 may include a plurality of
baffles 504 in alternating positions and heights within VPR 500,
such that a catalyst pouring over baffles 504 forms successive
curtains as it falls from a higher baffle 504 to a lower baffle
504. Pyrolysis vapor passes through the curtains of catalysts, and
thus contacts the catalyst, as it travels through housing 502.
[0064] In one embodiment, pyrolysis vapor inlet 510 may be oriented
near the top of VPR 500 and pyrolysis vapor outlet 512 may be
oriented near the bottom of VPR 500. In this embodiment, pyrolysis
vapor flows concurrently with the catalyst. In another embodiment,
pyrolysis vapor inlet 510 may be oriented near the bottom of VPR
500 and pyrolysis vapor outlet 512 may be oriented near the top of
VPR 500. In this embodiment, pyrolysis vapor flows
counter-currently with the catalyst.
[0065] In one embodiment, VPR 500 may be placed in a heated
enclosure and coupled to a catalyst regeneration system, such as
that illustrated in FIG. 3. VPR 500 may operate in a heated
enclosure between about 300.degree. C. and about 600.degree. C. In
another embodiment, VPR 500 operates in a heated enclosure between
about 350.degree. C. and about 550.degree. C. In another
embodiment, VPR 500 operates in a heated enclosure between about
400.degree. C. and about 500.degree. C. In another embodiment, VPR
500 operates at an elevated temperature configured to prevent
condensation of the pyrolysis vapor.
[0066] The catalyst may enter and exit VPR 500 through a double
block valve system (such as that illustrated in FIG. 3) so as to
substantially prevent pyrolysis vapor from exiting VPR 500 with the
catalyst.
[0067] In one embodiment, biomass may be directly added to the top
of VPR 400 or VPR 500 to generate pyrolysis vapor while at the same
time catalytically upgrading the pyrolysis vapor in a one-step
process. In this embodiment, a pyrolysis reactor may not be
necessary.
[0068] In various embodiments, a biofuel production system 100 is
provided. The biofuel production system may include a catalytic
vapor phase reactor (VPR) 102. The biofuel production system may
include a pyrolysis reactor 104 operatively connected to the
catalytic VPR 102. The biofuel production system may include a
quench system 106 operatively connected to the catalytic VPR 102.
The biofuel production system may include a water gas shift reactor
108 operatively connected to the quench system 106. The biofuel
production system may include a hydrotreatment system 110
operatively connected to the quench system 106.
[0069] In some embodiments, the pyrolysis reactor 104 may be
configured to receive a biomass 105. The pyrolysis reactor 104 may
be configured to pyrolyze the biomass 105 to produce a pyrolysis
vapor. The biomass 105 may include a wood.
[0070] The pyrolysis reactor 104 may be configured to operate at a
temperature capable of converting at least a portion of biomass 105
to a pyrolysis vapor. The pyrolysis reactor may be configured to
operate at a temperature in .degree. C. of about 250, 275, 300,
325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or
650, e.g., about 500.degree. C., or between about any two of the
preceding values, for example, between about 300.degree. C. and
about 600.degree. C., between about 350.degree. C. and about
550.degree. C., between about 400.degree. C. and about 500.degree.
C., and the like. For example, the pyrolysis reactor 104 may be
configured to operate at a temperature between about 300.degree. C.
and about 600.degree. C.
[0071] In several embodiments, the pyrolysis reactor 104 may be
configured to pyrolyze a biomass 105 to produce a pyrolysis vapor
and char. The system 100 further may include a char removal system
(not shown) configured to remove the char from the pyrolysis
reactor 104. The pyrolysis reactor 104 may be configured to
pyrolyze a biomass 105 to produce a pyrolysis vapor. The pyrolysis
vapor may include one or more of: water, an organic acid, an
aldehyde, a phenol, and a sugar; or one or more derivatives
thereof. A heater (not shown) may be operatively coupled to the
pyrolysis reactor 104. The heater may be configured to at least one
of internally and externally heat pyrolysis reactor 104. The heater
may include one or more of a resistive heating element, a
combustor, a heat exchanger, or a microwave generator.
[0072] In various embodiments, the catalytic VPR 102 may be
configured to receive a pyrolysis vapor. The catalytic VPR 102 may
be configured to modify the pyrolysis vapor to produce a modified
pyrolysis vapor. The catalytic VPR 102 may be configured to produce
a modified pyrolysis vapor by deoxygenating a pyrolysis vapor
produced by pyrolyzing a biomass. The catalytic VPR 102 may be
configured to produce a modified pyrolysis vapor by cracking or
breaking down one or more higher molecular weight components of a
pyrolysis vapor produced by pyrolyzing a biomass. The catalytic VPR
102 may include a catalyst may include one or more of: a granulated
catalyst, a powdered catalyst, and a fluid catalytic cracking
catalyst (FCC). The catalyst may include one or more of: fresh FCC,
spent FCC, catalyst impregnated on top of the fresh FCC, or
catalyst impregnated on top of the spent FCC. The catalytic VPR 102
may include the granulated catalyst. The granulated catalyst may be
characterized by particle size and flow characteristics
substantially similar to the FCC. The catalytic VPR 102 may include
a granulated catalyst characterized by a granule size between about
50 .mu.m and about 100 .mu.m. The granulated catalyst may be
characterized by a size distribution of granules. A substantial
fraction of the size distribution may be greater than about 20
.mu.m. The catalytic VPR 102 may include a catalyst configured to
catalyze at least one of: deoxygenation, cracking, water-gas shift,
and hydrocarbon formation.
[0073] In some embodiments, the pyrolysis reactor 104 and the
catalytic VPR 102 may be configured together as a single unit. The
quench system 106 may be configured to quench a pyrolysis vapor to
form a liquid bio-oil. The quench system 106 may be configured to
quench a modified pyrolysis vapor to form a modified bio-oil. The
bio-oil may be a low oxygen bio-oil. The quench system 106 may be
configured to direct a non-condensable gas into the water gas shift
reactor 108. The water gas shift reactor 108 may be configured to
process a non-condensable gas including CO to form at least one of
hydrogen and CO.sub.2. The hydrotreatment system 110 may be
configured to accept hydrogen from the water gas shift reactor 108.
The hydrotreatment system 110 may be configured to hydrotreat a
bio-oil, e.g., a low oxygen bio-oil, with hydrogen to produce a
hydrocarbon fuel product.
[0074] The biofuel production system 100 may include a conversion
system (not shown). The conversion system may be operatively
coupled to the catalytic vapor phase reactor 102. The conversion
system may be operatively coupled to pyrolysis reactor 104. The
conversion system may be operatively coupled to the hydrotreatment
system 110. The conversion system may be configured to produce a
hydrocarbon product from biomass 105 by upgrading a bio-oil. The
bio-oil may be produced by one or more of: the catalytic vapor
phase reactor 102, the pyrolysis reactor 104, or the hydrotreatment
system 110. The bio-oil may be a liquid or vapor bio-oil. The
bio-oil may be modified or upgraded, e.g., by hydrotreating. The
conversion system may be configured to produce at least one of: a
hydrocarbon fuel product, a gas, or a chemical.
[0075] In various embodiments, a method 201 for catalytic pyrolysis
of biomass is provided. The method may include 250 drying a
biomass. The method may include 252 pyrolyzing the biomass to
create a pyrolysis vapor. The method may include 254 removing at
least one of a char and an ash from the pyrolysis vapor. The method
may include 256 upgrading the pyrolysis vapor by vapor phase
catalysis to produce an upgraded pyrolysis vapor. The method may
include 258 condensing a bio-oil from the upgraded pyrolysis
vapor.
[0076] In various embodiments, pyrolyzing the biomass may be
conducted at a temperature in .degree. C. of about 250, 275, 300,
325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625,
650, 675, or 700, for example, about 500.degree. C., or between
about any two of the preceding values, for example, between about
300.degree. C. and about 700.degree. C., between about 300.degree.
C. and about 600.degree. C., between about 350.degree. C. and about
550.degree. C., between about 400.degree. C. and about 500.degree.
C., and the like. Upgrading the pyrolysis vapor may be conducted at
any of the temperatures or temperature ranges described herein for
pyrolyzing the biomass. Pyrolyzing the biomass and upgrading the
pyrolysis vapor may be conducted at about the same temperature, for
example, at about substantially the same temperature. Pyrolyzing
the biomass and upgrading the pyrolysis vapor may be conducted at
different temperatures, for example, at substantially different
temperatures.
[0077] In some embodiments, pyrolyzing the biomass may be conducted
at a biomass residence time of about 2 seconds or less. Pyrolyzing
the biomass may be conducted at a biomass residence time of less
than about 1 second, for example, about 0.9, 0.8, 0.7, 0.6, 0.5,
0.4, 0.3, 0.2, or 0.1 seconds, or less. Pyrolyzing the biomass and
upgrading the pyrolysis vapor may be characterized by about the
same residence time, for example, about substantially the same
residence time. Pyrolyzing the biomass and upgrading the pyrolysis
vapor may be characterized by different residence times, for
example, substantially different residence times.
[0078] In various embodiments, upgrading the pyrolysis vapor by
vapor phase catalysis to produce the upgraded pyrolysis vapor may
be conducted after pyrolyzing the biomass to create the pyrolysis
vapor and removing at least one of the char and the ash from the
pyrolysis vapor, and before condensing the bio-oil from the
upgraded pyrolysis vapor. The pyrolysis vapor may include one or
more of: water, an organic acid, an aldehyde, a phenol, and a
sugar; or one or more derivatives thereof.
[0079] In some embodiments, pyrolyzing the biomass to create the
pyrolysis vapor may include at least one of internally or
externally heating a pyrolysis reactor. Pyrolyzing the biomass to
create the pyrolysis vapor may include heating by resistive
heating, combustion heating, heat exchanging, or microwave
irradiation. Upgrading the pyrolysis vapor by vapor phase catalysis
may include deoxygenating the pyrolysis vapor to produce the
upgraded pyrolysis vapor. Upgrading the pyrolysis vapor by vapor
phase catalysis may include cracking one or more higher molecular
weight components of the pyrolysis vapor to produce the upgraded
pyrolysis vapor. Upgrading the pyrolysis vapor by vapor phase
catalysis may include contacting the pyrolysis vapor to one or more
of: a granulated catalyst, a powdered catalyst, and a fluid
catalytic cracking catalyst (FCC). Upgrading the pyrolysis vapor by
vapor phase catalysis may include contacting the pyrolysis vapor to
one or more of: fresh FCC, spent FCC, catalyst impregnated on top
of the fresh FCC, or catalyst impregnated on top of the spent FCC.
Upgrading the pyrolysis vapor by vapor phase catalysis may include
contacting the pyrolysis vapor to the granulated catalyst, the
granulated catalyst characterized by particle size and flow
characteristics substantially similar to the FCC. Upgrading the
pyrolysis vapor by vapor phase catalysis may include contacting the
pyrolysis vapor to a granulated catalyst characterized by a granule
size between about 50 .mu.m and about 100 .mu.m. Upgrading the
pyrolysis vapor by vapor phase catalysis may include contacting the
pyrolysis vapor to a granulated catalyst characterized by a size
distribution of granules. A substantial fraction of the size
distribution may be greater than about 20 .mu.m.
[0080] In several embodiments, pyrolyzing the biomass and upgrading
the pyrolysis vapor may be conducted in a single
pyrolysis-catalytic vapor phase reactor unit. The bio-oil may be a
low oxygen bio-oil. Pyrolyzing the biomass may include producing a
non-condensable including CO. The method may include reacting a
non-condensable including CO in a water gas shift reaction to form
at least one of hydrogen and CO.sub.2. The method may include
hydrotreating the bio oil with hydrogen from the water gas shift
reaction to produce a hydrocarbon fuel product. The method may
include hydrotreating the bio oil with hydrogen to produce a
hydrocarbon fuel product.
[0081] In some embodiments, the method may include drying the
biomass in a biomass dryer 212. The method may include placing the
biomass in a pyrolysis reactor 204 and pyrolyzing the biomass at
about 500.degree. C. to create a pyrolysis vapor. The method may
include directing the pyrolysis vapor to a char and ash removal
system 214 and removing at least one of a char and an ash from the
pyrolysis vapor. The method may include directing the pyrolysis
vapor to a catalytic vapor phase reactor 202 and upgrading the
pyrolysis vapor to form an upgraded pyrolysis vapor. The method may
include directing the upgraded pyrolysis vapor to a condenser 206.
The method may include extracting a bio-oil from the condenser
206.
[0082] In various embodiments, a catalytic vapor phase reactor
apparatus 300 is provided. The apparatus may include: a gas-solid
catalytic reactor 302; a feeding auger 304; a return auger 306; a
hot blower 308; a first blower 326; a second blower 328; a first
cyclone 310; a second cyclone 312; a third cyclone 324; a split
connection 314; a dip leg pipe 316 operatively coupled to the split
connection; a fluidized bed reactor 318; a bypass connection 320;
and a catalyst feeding vessel 322. The feeding auger 304 and the
return auger 306 may be operatively connected to the gas-solid
catalytic reactor 302 and the fluidized bed reactor 318. The first
cyclone 310 and the second cyclone 312 may be operatively connected
to the gas-solid catalytic reactor 302. The third cyclone 324 may
be operatively connected to the fluidized bed reactor 318, the
first blower 326, and the second blower 328.
[0083] In some embodiments, the catalytic vapor phase reactor
apparatus may be configured for continuous mode operation. The
apparatus may be configured for batch mode operation. The apparatus
may be configured to operate using air at atmospheric pressure for
catalyst regeneration. The apparatus may be configured for catalyst
regeneration without using gases with reduced oxygen content
compared to air.
[0084] In various embodiments, catalytic vapor phase reactor
apparatus 300 may be configured to operate, at least in part, at a
temperature in .degree. C. of about 250, 275, 300, 325, 350, 375,
400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, or 700,
for example, about 500.degree. C., or between about any two of the
preceding values, for example, between about 300.degree. C. and
about 700.degree. C., between about 300.degree. C. and about
600.degree. C., between about 350.degree. C. and about 550.degree.
C., between about 400.degree. C. and about 500.degree. C., and the
like. In some embodiments, the components of catalytic vapor phase
reactor apparatus 300 may be configured to operate at any of the
preceding temperatures or temperature ranges, with the exception of
hot blower 308, first blower 326, and second blower 328. The
catalytic vapor phase reactor apparatus may be configured at least
in part to operate at a temperature effective to drive one or more
of: a catalytic upgrade reaction, a catalyst regeneration reaction,
or a coke oxidation reaction. The catalytic vapor phase reactor
apparatus may be configured at least in part to operate at a
temperature effective to mitigate condensation of condensable
pyrolysis gases.
[0085] In some embodiments, the catalytic vapor phase reactor
apparatus may include a heater operatively coupled to gas-solid
catalytic reactor 302. The heater may include one or more of a
resistive heating element, a combustor, a heat exchanger, or a
microwave generator.
[0086] In several embodiments, the gas-solid catalytic reactor 302
may be configured to conduct a catalytic upgrade reaction. The
gas-solid catalytic reactor 302 may be configured to accept
introduction of a granulated catalyst. The gas-solid catalytic
reactor 302 may be configured to accept introduction of a
pre-upgrade pyrolysis gas. The gas-solid catalytic reactor 302 may
be configured to mix the pre-upgrade pyrolysis gas and a catalyst
effective to contact the catalyst surface with the pre-upgrade
pyrolysis gas. The gas-solid catalytic reactor 302 may be
configured to conduct the pre-upgrade pyrolysis gas with a
residence time of about 1 second. The gas-solid catalytic reactor
302 may include a raining bed reactor configured to contact the
pre-upgrade pyrolysis gas and the catalyst. The gas-solid catalytic
reactor 302 may be configured to remove coke from the catalyst by
continuous oxidation in air.
[0087] In various embodiments, at least one of the first cyclone
310 and the second cyclone 312 may be configured to receive
upgraded pyrolysis gas. The first cyclone 310 and the second
cyclone 312 may be configured to operate in series to receive
upgraded pyrolysis gas. The first cyclone 310 may be configured to
separate an upgraded pyrolysis gas from at least a first portion of
a plurality of catalyst particles. The first cyclone 310 may be
configured to direct the first portion of the plurality of catalyst
particles separated from the upgraded pyrolysis gas to one of: the
gas-solid catalytic reactor 302; or an exit of the catalytic vapor
phase reactor apparatus. The first cyclone 310 may be configured to
direct upgraded pyrolysis gas to the second cyclone 312. The second
cyclone 312 may be configured to separate the upgraded pyrolysis
gas from at least a second portion of the plurality of catalyst
particles. The second cyclone 312 may be configured to direct the
second portion of the plurality of catalyst particles separated
from the upgraded pyrolysis gas to one of: the gas-solid catalytic
reactor 302; or an exit of the catalytic vapor phase reactor
apparatus.
[0088] In some embodiments, bed reactor 318 may be operatively
connected to at least one of the first blower 326 and the second
blower 328. Feeding auger 304 and return auger 306 may be
operatively connected for feeding of a catalyst into the gas-solid
catalytic reactor 302 and the fluidized bed reactor 318. Feeding
auger 304 and return auger 306 may be operatively connected for
recirculation of catalyst between gas-solid catalytic reactor 302
and fluidized bed reactor 318.
[0089] In several embodiments, split connection 314 may be
configured to direct a catalyst to the fluidized bed reactor 318
for regeneration. Bypass connection 320 may be configured to cause
catalyst to bypass fluidized bed reactor 318. Transfer connection
330 may be configured to direct a catalyst processed in fluidized
bed reactor 318 to catalyst feeding vessel 322.
[0090] In various embodiments, a catalytic vapor phase reactor
apparatus 400 is provided. The apparatus may include a housing 402.
The housing 402 may include an auger device 404, a catalyst inlet
406, a catalyst outlet 408, a pyrolysis vapor inlet 410, and a
pyrolysis vapor outlet 412. The auger device 404 may be configured
to transport a solid catalyst through at least a portion of the
housing 402. The housing 402 may be configured to permit a
pyrolysis vapor to flow through at least a portion of the housing
402 and come into contact with the solid catalyst.
[0091] In some embodiments, the auger device 404 may be configured
to direct the catalyst material and the biomass pyrolysis vapor in
counter-current directions. The auger device 404 may be configured
to direct the catalyst material and the biomass pyrolysis vapor in
concurrent directions. The apparatus may be configured to bring the
pyrolysis vapor and the catalyst into contact. The apparatus may be
configured within a heated enclosure. The heated enclosure
configured to heat to a temperature between about 300.degree. C.
and about 700.degree. C., for example, about any temperature or
temperature range described herein. The apparatus may be
operatively coupled to a catalyst regeneration system, for example
as depicted in FIG. 3 in apparatus 300.
[0092] In various embodiments, a catalytic vapor phase reactor
apparatus 500 is provided. The apparatus may include a housing 502.
The housing 502 may include at least one baffle 504, a catalyst
inlet 506, a catalyst outlet 508, a pyrolysis vapor inlet 510, and
a pyrolysis vapor outlet 512. The housing 502 may be at least one
of substantially vertical and inclined, for example, with reference
to a local direction of gravity. The housing 502 may be configured
to permit a solid catalyst to flow through at least a portion of
the housing 502 and over at least one baffle 504. The housing 502
may be configured to permit a pyrolysis vapor to flow through at
least a portion of the housing 502 and come into contact with the
solid catalyst. The at least one baffle 504 may be angled effective
to cause a catalyst to pour off the at least one baffle 504 with
the pyrolysis vapor moving through the stream of the solid
catalyst. The apparatus further may include a plurality of baffles
504 configured effective to cause a catalyst pouring over the
plurality of baffles 504 to form successive curtains of the
catalyst while falling between each of the plurality of baffles
504. The pyrolysis vapor inlet 510 and the pyrolysis vapor outlet
512 may be configured to direct a pyrolysis vapor to flow
concurrently with the solid catalyst. The pyrolysis vapor inlet 510
and the pyrolysis vapor outlet 512 may be configured to direct a
pyrolysis vapor to flow counter-currently with the solid catalyst.
The apparatus may be configured within a heated enclosure. The
heated enclosure may be configured to heat to a temperature between
about 300.degree. C. and about 700.degree. C., for example, about
any temperature or temperature range described herein. The
apparatus may be operatively coupled to a catalyst regeneration
system, e.g., as described in FIG. 3 and apparatus 300.
[0093] 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 term "operatively connected" is 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. As used in
the specification and the claims, the singular forms "a," "an," and
"the" include the plural. Finally, where the term "about" is used
in conjunction with a number, it is intended to include .+-.10% of
the number. In other words, "about 10" may mean from 9 to 11.
[0094] 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.
* * * * *