Reactive Catalytic Fast Pyrolysis Process and System
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of 61/876,623 filed September 11, 2013, Von Holle
et al., RTI13003usv which is hereby incorporated by reference in its entirety.
1. FIELD OF THE INVENTION
[0002] This invention relates generally to the discovery of a reactive catalytic fast pyrolysis
(RCFP) process utilizing hydrogen at low pressures.
2. BACKGROUND OF THE INVENTION
2.1. Introduction
[0003] A variety of pyrolysis technologies are being investigated for producing liquid
intermediates from biomass that can be upgraded into hydrocarbon fuels. Traditional biomass
flash pyrolysis processes have demonstrated a roughly 70% liquid product yield; however, this
pyrolysis oil product has limited use without significant stabilization and upgrading.
Unfortunately, the physical and chemical properties of fast biomass pyrolysis oils make them
unsuitable for integrating into existing petroleum refineries. Undesired properties of conventional
pyrolysis oil include 1) thermal instability and high fouling tendency; 2) corrosiveness due to high
organic acid content (pH 2.2 to 2.4, typically); 3) immiscibility with refinery feedstocks due to
high water and oxygenates content; and 4) metals (K, Na, and Ca) and nitrogen content, which
foul or deactivate refinery catalysts.
[0004] KiOR Technology (e.g., PCT Publ. No. WO 2011/096912, O'Conner et al.) focuses on
a biomass pretreatment process that produces a composite material that is a blend of finely ground
biomass reacted with a solid base catalyst, like clay or hydrotalcite, at 200 to 350 °C. They
disclose the following: (i) Pretreatment Options; (ii) A moderate temperature torrefaction step
(roasting or toasting) to dry the material and grind it before it is mixed with the solid base
catalyst; (iii) Soaking the biomass in an alkali carbonate aqueous solution to impart inorganic base
catalyst into the biomass; (iv) Biomass catalytic cracking (BCC) is an acid catalyzed cracking and
deoxygenation process at 350 °C to 400 °C; (v) Fast fluidized or entrained bed reactor; or a
transport reactor, much like fluid catalytic cracking; (vi) Regenerate catalyst at temperatures up
to 800 °C to remove coke and provide process heat; (vii) Resulting biocrude is upgraded to
gasoline and diesel and the char and coke by-products are oxidized for process heat.
[0005] U.S. Pat. Publ. No. 2009/0227823 (Huber et al.) described catalytic pyrolysis using
zeolites that are unpromoted or are promoted with metals. The pyrolysis was carried out at a
temperature of 500 to 600 °C and a pressure of 1 to 4 atm (approximately 101 to 405 KPa) to
produce a highly aromatic product with apparent high coke yields and low liquid yields.
[0006] PCT Publ. No. WO 2009/01853 1 (Agblevor) described the use of catalytic pyrolysis to
selectively convert the cellulose and hemicellulose fractions of biomass to light gases and leave
behind pyrolytic lignin. The methods used H-ZSM-5 and sulfated zirconia catalysts in a fluidized
bed reactor to obtain an overall bio-oil yield of 18-21%.
[0007] GTI's IH2 process (hydropyrolysis followed by hydroconversion then C1-C4 gas
reforming to supply hydrogen)(e.g., U.S. Pat. Publ. No. 2010/0256428, Marker et al.) is directed
to a high pressure system with a pressure range from 100-800 psig (for hydropyrolysis,
hydroconversion and gas reforming).
3. SUMMARY OF THE INVENTION
[0008] In particular non-limiting embodiments, the present invention provides a catalytic
biomass pyrolysis process that combines biomass and hydrogen with a catalyst at low pressure
(around 6 bar but optimally at a pressure just high enough to overcome the pressure drop in the
system somewhere around 4.5 bar or less but as low as 0.5 bar) to produce a hydrocarbon-rich
bio-oil intermediate that can be upgraded into finished fuels or blend stocks using conventional
hydroprocessing technology.
[0009] In one embodiment, the invention is a reactive catalytic biomass pyrolysis process
comprising reacting a biomass starting material under pyrolysis conditions in the presence of a
catalyst and a gas feed to the pyrolysis reactor of about 10 volume % to about 90 volume %
hydrogen gas at a pressure of less than about 6 bar to form a stream comprising a pyrolysis
product.
[0010] In another embodiment, the invention is to a catalytic biomass pyrolysis system
comprising: (a) a reactor adapted for reacting a biomass with a catalyst and a gas stream with
about 10 volume % to about 90 volume % hydrogen gas at a pressure of less than about 6 bar
under pyrolysis conditions to form a pyrolysis reaction stream; (b) a separation unit in connection
with the reactor and adapted to form a first stream comprising a solids fraction from the pyrolysis
reaction stream and a second stream comprising a vapors fraction from the pyrolysis reaction
stream; and (c) a condenser unit in communication with the separation unit and adapted to
condense a mixture of bio-crude, water and/or another liquid from the vapors in the second stream
separate from a gas component of the second stream.
4. BRIEF DESCRIPTION OF THE FIGURES
[0011] Figure 1. Detailed view of reactive gas catalytic biomass fast pyrolysis unit operation.
[0012] Figure 2. Integrated catalytic fast pyrolysis.
[0013] Figure 3. Process flow diagram of bench-top 1"-diameter fluidized bed system.
[0014] Figure 4. Comparison of experimental carbon efficiencies for bio-oil from RCFP with
RTI-A9P to theoretical deoxygenation mechanism for reducing the oxygen content of fast
pyrolysis bio-oil.
[0015] Figure 5. Comparison of the carbon efficiency of the bio-crude along with the varying
bio-crude oxygen content across varying technologies investigated.
[0016] Figure 6. Shows the revaporization efficiency at 350 °C for bio-crudes with varying
oxygen contents.
5. DETAILED DESCRIPTION OF THE INVENTION
[0017] This invention relates to the use of catalysts, including hydrodeoxygenation catalysts,
consisting of platinized, metal phosphide, or transition metal promoted catalyst formulations in a
catalytic biomass pyrolysis process utilizing hydrogen at low total pressure for the production of
bio-crudes from biomass. These catalyst formulations have been demonstrated to produce low
oxygen content (below 10 wt ) in the bio-crude while minimizing over cracking and coke
formation to achieve attractive separable bio-crude yields (>21%) resulting in attractive carbon
efficiencies (between about 30% and about 70%). These yields and carbon efficiencies are
similar to those in catalytic fast pyrolysis with various catalysts but produce an improved quality
bio-crude and reduce carbon loss to the aqueous stream. The invention also includes use of
catalysts described in PCT Application No. PCT/US 14/49007, filed July 31, 2014 and U.S.
Provisional Application No. 61/860,637, filed July 31, 2013, Shen et al.
[0018] The invention pertains to: (i) catalyst formulations including promoters to utilize H2 at
a gas feed inlet of >10 volume percent at low total pressure (pressure will only be needed to
operate the reactor, which should be <75psig (~6 bar)); (ii) catalytic process in which H2 is
consumed to reduce oxygen content in the desired organic liquid product through increased water
production (hydrodeoxygenation); (iii) The use of externally generated hydrogen; (iv) The use of
recycled product gases and supplemental hydrogen to achieve the desired hydrogen concentration;
(v) use in catalytic processes with the addition of H2 such as a catalytic fast pyrolysis similar to
that described in PCT/US 13/29379 (Catalytic Biomass Pyrolysis Process), but also as an
improvement to other processes, such as KiOR's biomass catalytic cracking process (PCT Publ.
No. WO 2011/096912, O'Conner et al.) and Ensyn's RTP technology (U.S. Pat. No. 5,792,340,
Freel et al.); (vi) modified catalytic pyrolysis process similar to that described in
PCT/W013/29379.
[0019] More specifically, the invention provides a reactive catalytic biomass pyrolysis process
comprising reacting a biomass starting material under pyrolysis conditions in the presence of a
catalyst and a gas feed to the pyrolysis reactor of about 10 volume % to about 90 volume %
hydrogen gas at a pressure of less than about 6 bar to form a stream comprising a pyrolysis
product.
[0020] In some embodiments, the gas feed to the pyrolysis reactor contains hydrogen derived
from methane. Alternatively, the pyrolysis product comprises a hydrogen-rich pyrolysis gases and
hydrogen from the hydrogen-rich pyrolysis gases is recycled so as to contribute to the gas feed to
the pyrolysis reactor which may or may not be blended with hydrogen from an additional source.
[0021] In preferred embodiments, the gas feed to the pyrolysis reactor is about 30 volume %
to about 90 volume % hydrogen gas, more preferably about 50 volume % to about 90 volume %
hydrogen gas.
[0022] The gas feed to the pyrolysis reactor also contains carbon monoxide, carbon dioxide,
nitrogen, alkanes, alkenes, helium, argon, or a mixture thereof or additional gases from the
hydrogen-rich pyrolysis gases.
[0023] The biomass starting material may be a lignocellulosic material such as an agricultural
residue, a forest residue, a paper sludge, waste paper, or a municipal solid waste. It may be
particularized with an average particle size of about 25 mm or less, an average particle size of
about 0.1mm to about 8 mm.
[0024] The catalyst may be a metal or metal oxide on an acidic support and the metal or metal
oxide is tungsten, molybdenum, chromium, iron, ruthenium, cobalt, iridium, nickel, palladium,
platinum, copper, silver, gold, tin, an oxide thereof, or a combination thereof.
[0025] The acidic support may be silica, alumina, zirconia, tungstated zirconia, sulfated
zirconia, titania, ceria, or a zeolite.
[0026] The catalyst may be a metal or metal oxide on a mixed metal oxide support where the
metal or metal oxide is tungsten, molybdenum, chromium, iron, ruthenium, cobalt, iridium,
nickel, palladium, platinum, copper, silver, gold, tin, an oxide thereof, or a combination thereof,
such as CoMo, NiMo or NiW on a support. Here, the support may be an acidic support and the
acidic support is chosen from silica, alumina, zirconia, tungstated zirconia, sulfated zirconia,
titania, ceria, or a zeolite.
[0027] The catalyst may also be a metal phosphide on an acidic support such as nickel
phosphide, iron phosphide, molybdenum phosphide, tungsten phosphide, copper phosphide,
cobalt phosphide, or chromium phosphide. The catalyst may be a metal phosphide on a mixed
metal oxide support.
[0028] The catalyst may also contain a binder material such as a macroreticulate polymer, a
kieselguhr, a kaolin, a bentonite, clays, or a combination thereof.
[0029] The process may further comprise: transferring the pyrolysis product stream to a
separator; separating a vapor and gas fraction from a solids fraction comprising pyrolysis product
solids and the catalyst; and regenerating and recycling the catalyst into the pyrolysis process. The
vapor and gas fraction may be transferred to a condenser wherein a liquid product is separated
from a gaseous fraction. The liquid product may be separated into an aqueous phase and a bio-oil.
[0030] The bio-oil may have an oxygen content of about 0.5% to about 25% by mass on a dry
basis based on the overall mass of the bio-oil. The bio-oil may be aliphatic compounds, aromatic
compounds, polyaromatic compounds, phenols, aldehydes, ketones, organic acids, hydrocarbons,
or mixture thereof.
[0031] The process may exhibit a carbon conversion efficiency of about 20% or greater by
weight or about 20% to about 65% by weight.
[0032] In another embodiment, the invention is to a catalytic biomass pyrolysis system
comprising: (a) a reactor adapted for reacting a biomass with a catalyst and a gas stream with
about 10 volume % to about 90 volume % hydrogen gas at a pressure of less than about 6 bar
under pyrolysis conditions to form a pyrolysis reaction stream; (b) a separation unit in connection
with the reactor and adapted to form a first stream comprising a solids fraction from the pyrolysis
reaction stream and a second stream comprising a vapors fraction from the pyrolysis reaction
stream; and (c) a condenser unit in communication with the separation unit and adapted to
condense a mixture of bio-crude, water and/or another liquid from the vapors in the second stream
separate from a gas component of the second stream.
[0033] The catalytic biomass pyrolysis system may further comprise (d) a liquid separator
unit in fluid communication with the condenser unit and adapted to separate water or another
liquid from the bio-crude. It may further comprise (e) a catalyst regeneration unit in fluid
communication with the separation unit and adapted to remove non-catalyst solids from the solid
catalyst present in the first stream. It may also further comprise (f) a catalyst delivery stream
adapted to deliver regenerated catalyst from the catalyst regeneration unit to the reactor or (g) a
hydrogen production unit in communication with the condenser unit and adapted to generate
hydrogen from methane or other hydrocarbons for introduction into the reactor.
[0034] The catalytic biomass pyrolysis system may further comprise a hydroprocessing unit in
which the bio-crude from the liquid separator is further processed to remove oxygen and increase
the hydrogen to carbon ratio of the bio-crude material.
[0035] The catalytic biomass pyrolysis system may further comprise an oxidant stream in
fluid communication with the catalyst regeneration unit and adapted to deliver an oxidant to the
catalyst regeneration unit or the condenser unit is in fluid communication with the reactor via a
gas flow stream adapted to transfer a portion of the gas component of the second stream to the
reactor.
[0036] The catalytic biomass pyrolysis system may further comprise a blower unit interposed
between and in fluid communication with the condenser unit and the reactor.
[0037] The catalytic biomass pyrolysis system may further comprise a biomass preparation
unit in fluid communication with the reactor and adapted to transfer the biomass to the reactor.
[0038] The catalytic biomass pyrolysis system may have a biomass preparation unit adapted
to particularize a solid biomass to a size of about 25 mm or less.
[0039] The reactor may be adapted to combine the catalyst and the biomass in a ratio of about
1:10 to about 1000:1 based on mass. The reactor may be a transport reactor.
[0040] In either the process or the system, may be carried out at a temperature of about 200 °C
to about 700 °C, or about 350 °C to about 550 °C.
[0041] The catalyst and the biomass starting material in the pyrolysis reactor may be provided
in a ratio of about 1:10 to about 1000:1 based on mass or a ratio of about 1:5 to about 100:1 based
on mass.
[0042] The process may be carried out at a pressure of up to about 4.5 bar, up to about 2.5 bar
or at ambient pressure.
5.1. Definitions
[0043] The terms "bio-oil" and "bio-crude" can be used interchangeably and are intended to
mean the fraction of reaction products obtained from a pyrolysis reaction that is liquid at ambient
condition. The liquid-phase products may comprise hydrophilic phase compounds, hydrophobic
phase compounds, or a mixture of hydrophilic and hydrophobic phase compounds. In certain
embodiments, the bio-oil comprises a compound or a mixture of compounds such that the bio-oil
is suitable for co-processing with traditional crude oil in existing oil refineries. As such, the biooil
preferably comprises a compound or a mixture of compounds such that the bio-oil is suitable
for undergoing further reactions, such as distillation and/or catalytic processing, that transform the
bio-oil into a biofuel, such as bio-diesel, bio-gasoline, bio-jet fuel, or the like.
[0044] The biomass starting material particularly may comprise a wide variety of cellulosics
and lignocellulosics. For example, the biomass can be derived from both herbaceous and woody
sources. Non-limiting examples of herbaceous or woody biomass sources useful according to the
invention include wood (hardwood and/or softwood), tobacco, corn, corn residues, corn cobs,
cornhusks, sugarcane bagasse, castor oil plant, rapeseed plant, sorghum, soybean plant, cereal
straw, grain processing by-products, bamboo, bamboo pulp, bamboo sawdust, and energy grasses,
such as switchgrass, miscanthus, and reed canary grass. Still further, useful biomass may
comprise "waste" materials, such as corn stover, rice straw, paper sludge, waste papers, municipal
solid wastes, and refuse-derived materials. The biomass also may comprise various grades of
paper and pulp, including recycled paper, which include various amounts of lignins, recycled
pulp, bleached paper or pulp, semi-bleached paper or pulp, and unbleached paper or pulp.
[0045] In the catalytic biomass pyrolysis process, biomass preparation can comprise size
reduction and drying of the biomass. Thus, the biomass can be characterized as being
particularized, which may be a natural state of the biomass or may result from processing steps
wherein a biomass material is converted to a particularized form. Ideally, the size of the biomass
introduced into the reactor can be such that heat transfer rates are high enough to maximize biooil
production. Cost of size reduction and bio-oil yield preferably are balanced. In certain
embodiments of the present process, biomass particles can have an average size of about 25 mm
or less, about 15 mm or less, about 8 mm or less, about 5 mm or less, about 2 mm or less, about
1.5 mm or less, or about 1 mm or less. In specific embodiments, average particle size can be
about 0.1 mm to about 25 mm, about 0.1 mm to 15 mm, about 0.1 mm to about 8 mm, about 0.1
mm to about 5 mm, about 0.1 mm to about 2 mm, or about 0.1 mm to about 1.5 mm.
[0046] Moisture content of the biomass preferably is as close as possible to 0% by mass. In
some instances, this may be cost prohibitive. Moisture content of the biomass can be adjusted
external to the process or internally by integrating a heat source to maintain the input biomass to a
moisture content of about 15% or less by mass, about 10% or less by mass, about 7% or less by
mass, or about 5% or less by mass.
[0047] Biomass pyrolysis can form a cocktail of compounds in various phases, and the
pyrolysis product can contain in the range of 300 or more compounds. In previous methods for
the pyrolysis of biomass, the starting material typically is heated in the absence of added oxygen
to produce a mixture of solid, liquid, and gaseous products depending upon the pyrolysis
temperature and residence time. When biomass is heated at low temperatures and for long times
(i.e., "slow pyrolysis"), charcoal is the dominant product. Gases are up to 80% by weight of the
product when biomass is heated at temperatures above 700 °C. In known methods of "fast
pyrolysis" or "flash pyrolysis", biomass is rapidly heated to temperatures ranging from 400 °C to
650 °C with low residence times, and such methods commonly achieve products that are up to
75% by mass organic liquids on a dry feed basis. Although known methods of flash pyrolysis can
produce bio-oils from various feedstocks, these oils typically are acidic, chemically unstable, and
require upgrading.
5.2. Methodology Overview
[0048] This advanced biofuels technology improves hydrogen utilization and carbon recovery
in a novel, direct biomass liquefaction process. A block flow diagram of this concept is shown in
Figure 1. The primary aspect of this concept is to use hydrogen during catalytic biomass
pyrolysis at ambient pressure to maximize the biomass carbon and energy recovery in a low
oxygen content, thermally stable bio-crude intermediate that can be efficiently and easily
upgraded into a finished biofuel.
[0049] Improved hydrogen utilization during catalytic biomass pyrolysis has the potential to
improve bio-crude yields by reducing char and coke formation while simultaneously reducing the
bio-crude oxygen content. This is achieved by developing a new catalyst for catalytic fast
pyrolysis (CFP) that has high hydrodeoxygenation (HDO) activity but works at or near
atmospheric pressure in the presence of hydrogen. Using the technology described herein, a biocrude
intermediate with < 10 wt% oxygen with greater than about 30% carbon efficiency can be
produced at near atmospheric pressure, which is comparable to traditional hydropyrolysis at high
pressures (300 psig).
5.3. Background
[0050] Using catalysts to improve the physical and chemical properties of bio-oils is currently
an active area of research, development, and demonstration [1-131 . Catalysts can be used
downstream of the pyrolysis reactor to upgrade the pyrolysis vapors or they can be added in direct
contact with the biomass in the primary pyrolysis reactor in a CFP process as shown in Figure 2.
[0051] The goal of these advanced biofuels processes is to produce hydrocarbon-rich liquid
intermediates that can be upgraded using conventional refining technology to produce costcompetitive
gasoline, diesel, and jet fuel that leverages the capital expenditures in the existing
petroleum refining and distribution infrastructure.
[0052] The role of the catalyst in direct biomass liquefaction processes is to control the
chemistry during biomass pyrolysis to minimize carbon loss to char, light gases, and coke and
control deoxygenation. Oxygen removal during direct biomass liquefaction can occur by
dehydration (loss of H20), decarboxylation (loss of C0 2), and decarbonylation (loss of CO).
Dehydration of the cellulose and hemicellulose fractions during biomass pyrolysis (with or
without a catalyst) produces water, referred to as water of pyrolysis that is the most abundant
component of the liquid phase product. Biomass is inherently oxygen-rich and hydrogendeficient,
and the pyrolysis products become even more hydrogen deficient as dehydration occurs.
This increases the tendency for aromatic formation and ultimately leads to char production.
Deoxygenation by CO and C0 2 removal (decarboxylation and decarbonylation) plus any carbon
losses from coke formation on the catalyst lead to lower hydrocarbon liquid yields and lower
energy recovery in the bio-crude intermediate. Thermal or catalytic cracking tends to produce gas
phase products and carbonaceous solids (char and coke).
[0053] A catalytic biomass pyrolysis process has been demonstrated in a 1"-diameter
fluidized bed reactor with a novel catalyst to prove the concept. Catalyst properties are optimized
to minimize gas and coke production and improve catalytic deoxygenation and bio-crude yields.
In the current state of technology, bio-oil from fast pyrolysis contains > 40 wt oxygen. Recent
results demonstrate that catalytic fast pyrolysis (CFP) bio-crudes contain < 20 wt oxygen, with
the organic fraction containing as low as 12 wt oxygen under optimized process conditions.
These oxygen numbers are > 50% lower compared with traditional fast pyrolysis oils. A
comparison of the fast pyrolysis bio-oil (baseline), hydropyrolysis and CFP bio-crude produced
from white oak is shown in Table 1.
Table 1: Product yields and stream
compositions from white oak fast
[0054] Hydropyrolysis is an catalytic
biomass pyrolysis process where biomass and
catalyst are combined at elevated
temperatures, pressure, and a high hydrogen
partial pressure to hydrodeoxygenate biomass
pyrolysis vapors and produce low oxygen
containing hydrocarbon-rich liquid product.
Several groups have demonstrated the
technical feasibility of producing
hydrocarbon liquids from biomass at
hydropyrolysis conditions [14-181 . This pathway has shown the potential to produce very low
oxygen containing intermediates (below 5 wt%, dry basis) with attractive carbon yields (> 30%).
[0055] HDO is thought to be the dominant oxygen rejection pathway during hydropyrolysis.
In 20% H2 at 300 psig total pressure, the hydrogen consumption measured during hydropyrolysis
with the commercial hydrotreating catalyst ranged from 20-25 g per kg of biomass fed. The total
water yield from both liquid product fractions ranges from 35 to 40 wt%. At higher hydrogen
concentrations, the hydrogen consumption increased to 35-38 g/ kg biomass fed though no
significant increase in water yield was measured. This suggests that at higher hydrogen partial
pressures, additional hydrogenation or hydrogen addition reactions are occurring without
additional deoxygenation resulting in higher hydrogen-carbon ratio in the product stream.
[0056] The lower oxygen content bio-crude intermediate will have lower downstream H2
demand. However, hydropyrolysis does have a distinct disadvantage of being a high pressure
conversion process that necessitates feeding solids across a pressure barrier. This makes the
process potentially more complex with higher cost materials of construction compared to an
atmospheric pressure catalytic biomass pyrolysis conversion process. A commercial process that
requires feeding biomass at high pressure has poorer reliability and availability and higher
maintenance costs than an atmospheric pressure process.
[0057] Involvement in technology development for catalytic biomass pyrolysis and
hydropyrolysis has led to unique insights for developing an innovative, new bio-oil process,
RCFP, with higher yields of low oxygen content bio-crude and improved carbon efficiency. The
key to this novel process is developing a robust catalyst that efficiently uses hydrogen for HDO at
about ambient pressure and increases the H/C ratio in volatile products to limit char and coke
formation.
[0058] Recent work by Oyama and colleagues [23-251 has demonstrated hydroprocessing of
cresol at atmospheric pressure and similar work by Lobo [26-281 demonstrated HDO of guaiacol
at atmospheric pressure. Although understanding hydrogen use in biofuels processing has
increased, little attention has been given to effective utilization of hydrogen at near atmospheric
pressure in direct biomass liquefaction pathways.
[0059] The solid acid and metal oxide CFP catalysts were promoted with precious metal or
metal phosphides and tested in the proof-of-concept studies. Hydrogen utilization in RCFP shows
potential to have a significant impact on the development of biomass conversion technologies.
[0060] Precious metals are known to have HDO activity, but clearly lower cost alternatives
are desired for commercial biofuels production processes. The catalyst development efforts
focused on alternatives to precious metals for atmospheric pressure hydrogenation and HDO, such
as Ni, Fe, and other transition metal oxides. Recent literature also suggested that metal phosphides
may be attractive candidates for this process [23-251 .
[0061] Four catalyst classes have been identified as outlined in Table 3. Catalyst classes have
been identified based on the types of materials (formulations) being considered.
Table 2 : Summary of potential catalyst classes for RCFP
Class Description Variables
Precious metal promoted solid acids Precious metal loading
1st iteration: Pt promoted tungstated zirconia and Acid strength
alumina Surface area
1
Additional iterations: alternative promoters (e.g.,
Pd and Au) on additional supports (Ce0 2, Zr0 2,
Ti0 2)
Precious metal promoted mixed metal oxides Precious metal loading
1st iteration: Pt on Fe20 3/CuO Metal oxide composition (high Fe and
2 Additional iterations: alternate promoters (Pd, high Cu)
Au) with additional metal oxides: NiO, Sn0 2, Surface area
CoO Additional promoters and supports
Metal phosphide promoted solid acids Phosphide loading
1st iteration: Ni2P on tungstated zirconia and Acid strength
3 alumina Surface area
Additional iterations: alternative phosphipdes Additional promoters and supports
(Fe2P and Co2P) and supports (Ce0 2, Zr0 2, Ti0 2)
Metal phosphide promoted mixed metal oxides Phosphide loading
1st iteration: Ni2P on Fe20 3/CuO Metal oxide composition (high Fe and
4 Additional iterations: alternative phosphides high Cu)
including (Fe2P. Co2P) and metal oxides (NiO, Surface area
Sn0 2, CoO) Additional promoters and supports
[0062] The Class 1 materials combine the acid-cracking activity with metals known to
provide hydrogenation activity.
[0063] The Class 2 materials are metal oxides that have the potential to selectively remove
oxygen through two simultaneous steps: direct deoxygenation over a supported metal or reduced
metal oxide catalyst with variable valence states and indirect deoxygenation that uses catalytic
hydrogen production for in-situ hydrotreating. Addition of precious metal provides additional
hydrogenation activity and hydrogen dissociation on the catalyst surface.
[0064] The materials in Class 3 contain metal phosphides for hydrogen utilization that replace
the precious metal in the Class 1 materials. The Class 3 materials have similar functionality
compared with the Class 1 materials; however, studies of metal phosphides have recently shown
the ability to facilitate the use of hydrogen in hydroprocessing.
[0065] Similarly, metal phosphides for hydrogen utilization in the Class 4 materials replace
the precious metal in the Class 2 materials.
[0066] One of ordinary skill will recognize many units are regularly used to characterize
pressure. For clarity, Table 3 shows conversion from psig to bar to atmospheres of pressure.
[0067] Table 3
[0068] Unless defined otherwise, all technical and scientific terms used herein have the same
meaning as commonly understood by one of ordinary skill in the art to which this invention
belongs. The article "a" and "an" are used herein to refer to one or more than one (i.e., to at least
one) of the grammatical object(s) of the article. By way of example, "an element" means one or
more elements.
[0069] Throughout the specification the word "comprising," or variations such as "comprises"
or "comprising," will be understood to imply the inclusion of a stated element, integer or step, or
group of elements, integers or steps, but not the exclusion of any other element, integer or step, or
group of elements, integers or steps. The present invention may suitably "comprise", "consist of,
or "consist essentially of, the steps, elements, and/or reagents described in the claims.
[0070] It is further noted that the claims may be drafted to exclude any optional element. As
such, this statement is intended to serve as antecedent basis for use of such exclusive terminology
as "solely", "only" and the like in connection with the recitation of claim elements, or the use of a
"negative" limitation.
[0071] Where a range of values is provided, it is understood that each intervening value, to the
tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper
and lower limits of that range is also specifically disclosed. Each smaller range between any
stated value or intervening value in a stated range and any other stated or intervening value in that
stated range is encompassed within the invention. The upper and lower limits of these smaller
ranges may independently be included or excluded in the range, and each range where either,
neither or both limits are included in the smaller ranges is also encompassed within the invention,
subject to any specifically excluded limit in the stated range. Where the stated range includes one
or both of the limits, ranges excluding either or both of those included limits are also included in
the invention.
[0072] The following Examples further illustrate the invention and are not intended to limit
the scope of the invention. In particular, it is to be understood that this invention is not limited to
particular embodiments described, as such may, of course, vary. It is also to be understood that
the terminology used herein is for the purpose of describing particular embodiments only, and is
not intended to be limiting, since the scope of the present invention will be limited only by the
appended claims.
[0073]
6. EXAMPLES
[0074] Proof-of-Concept Studies
[0075] Many industrial refining processes like hydrocracking, isomerization, and naphtha
reforming use hydrogen to control coke formation on the catalyst surface. Carbon deposition is
the primary cause of catalyst deactivation, but catalyst activity can be recovered by oxidizing this
carbon. The heat released during catalyst regeneration also maintains the process temperature.
The addition of hydrogen in refinery unit operations can be adjusted to optimize product yields
and manage the process heat balance.
[0076] This concept was extended by investigating the impact of adding hydrogen in an CFP
process. An initial goal was to add hydrogen to an atmospheric pressure CFP process to control
char and coke formation— the primary sources of carbon loss in the current process. Several
catalysts from previous screening studies and new promoted catalysts were tested in a 1"-diameter
fluidized bed CFP reactor system. The reactor temperature was fixed at 500°C, and a constant
biomass feedrate of 1-2 g/min was maintained for all experiments. The two main variables were
hydrogen concentration in the reactor and catalyst composition.
[0077] 1"-Diameter Fluidized Bed Reactor System
[0078] A bench-top fluidized bed reactor system for investigating catalytic biomass pyrolysis
is shown in Figure 3. The RTI-CFP catalyst was tested in this reactor system where white oak
sawdust was fed directly into the fluidized catalyst bed so pyrolysis takes place in the presence of
the catalyst. The fluidized-bed reactor is a 1"-diameter quartz tube reactor externally heated in a
furnace. An inert bed of silicon carbide acts as a support for the catalyst bed through which a ¼"-
diameter tube injects the solid feed into the bottom of the catalyst bed. The exit of the reactor has
a disengagement zone for solids collection and a condensation train for liquids collection. An
online micro GC system is used to measure permanent gas composition.
[0079] In the feed system, the biomass was loaded in a syringe modified with an adapter that
injects a sweep-gas and allows the exit of an entrained-biomass stream. The biomass feed rate was
controlled by adjusting the sweep-gas feed rate and the head space in the syringe. The reactor
operates at temperatures between 350 °C and 600 °C, with 1 to 2 SLPM gas feed rate and a 0.5 to
1.5g/min biomass federate. The reactor holds 25 to 60 g of catalyst that provides a total residence
time in the reactor between 1 to 2 sec. Biomass was fed directly into the catalyst bed where
pyrolysis takes place in the presence of the catalyst. The condensation system consists of an
impinger cooled in an ice bath followed by an electrostatic precipitator and a second impinger
cooled in a dry ice/acetone bath. Mass closures are consistently around 92 to 95% in this system.
The product yields from biomass catalytic pyrolysis with numerous catalysts at a wide range of
process conditions were measured in this system.
[0080] Catalyst Development and Testing
[0081] Catalysts for increased deoxygenation and carbon efficiency were screened for
catalytic fast pyrolysis (fast pyrolysis in the presence of a catalyst as the heat transfer medium) in
the presence of a reactive gas, namely hydrogen. Coke formation is the main source of carbon loss
and catalyst deactivation, so catalysts with a lower propensity for coke production were sought to
enhance carbon efficiency and increase bio-oil yields. Many industrial refining processes like
hydrocracking, isomerization and naptha reforming utilize hydrogen to control coke formation on
the catalyst surface.
[0082] A material for conventional catalytic fast pyrolysis - RTI-A9 was disclosed in coowned
PCT Publ. No. WO/2014/089131 claiming the benefit U.S. Provisional Application No.
61/733,142, filed December 4, 2012, Dayton et al. RTI-A9 has good conversion but has a high
coking tendency due to its strong acidic nature. If RTI-A9 is promoted with 0.5 % platinum (RTIA9P)
the high coking tendency prevails under an inert environment. However, with the addition
of hydrogen in the reactor gas at atmospheric pressure, the coke production decreases and the biocrude
yield increases compared to its unpromoted counterpart. The bio-crude oxygen content is
reduced and the carbon efficiency into the bio-crude fraction increases. This is due to coke
prevention from the addition of both platinum and hydrogen into the system leading to more
hydrodeoxygenation or HDO. The effect of added hydrogen correlates with an increase in carbon
efficiency and a decrease in oxygen content (see graphs). The hydrocarbon concentration in the
aqueous fraction also decreases as more hydrogen is added as deoxygenated hydrocarbons are
more easily separated into the organic fraction. At -93% hydrogen, the water content of the
aqueous fraction is -93% as compared to around -80% in the aqueous phase without added
hydrogen. Better hydrocarbon separation equates to easier downstream processing and potentially
easier aqueous fraction cleanup. Other catalysts tested include a metal oxide redox catalyst (RTIA2)
described in co-owned WO 2013/13438 (PCT/US 13/29379) Catalytic Biomass Pyrolysis and
RTI-A2 promoted with platinum. When this RTI-A2 catalyst is in its reduced form it does a good
job deoxygenating the pyrolysis vapors to around -12% oxygen but in poor yields because of
coke formation and hydrocarbons dissolved in the aqueous fraction. This coke formation is
reduced with this redox catalyst in the presence of ¾ and stays more active because the hydrogen
in the reactor atmosphere keeps the catalyst in a more reduced state. The organic bio-crude yield
increased using the platinized RTI-A2 catalyst with hydrogen. Coke formation is reduced so the
hydrodeoxygenation activity of the catalyst remains high and the lower oxygen content of the biocrude
contains more hydrophobic hydrocarbon products that do not dissolve in the aqueous
fraction.
Table 4: Summary of the effect of hydrogen concentration on catalytic biomass pyrolysis with RTI-A9, RTIA9P,
RTI-A2, and RTI-A2P
Organic 16.2 19.3 20.2 20.2 14.1 17.8 18.8 21.1 12.3 28.6
wt% Oxygen in 18.8 18.5 16.2 16.5 22 16.5 11.1 4.24 11.0 12.7
bio-oil
Bio-oil carbon 23.7 28.3 25.4 28.0 19.8 24.8 31.1 36.9 19.2 35.6
efficiency
[0083] Table 4 shows mass balances and the carbon efficiency versus oxygen content for the
bio-crudes produced by catalytic fast pyrolysis of white oak at 500 °C with the RTI-A9 acid
catalyst with varying ¾ volume percent. As the concentration of hydrogen increases, there is a
very slight decrease in oxygen content and very slight increase in carbon efficiency along with a
slight decrease in solids (char + catalyst coke). Table 4 also shows the oxygen content for the biocrudes
produced by the RTI-A9 catalyst with varying ¾ volume percent.
[0084] For comparison, the mass balance and carbon efficiency in the bio-crude for the
catalytic pyrolysis of white oak at 500 °C over RTI-A9P. It is seen that as the partial
pressure/concentration of hydrogen increases, there is a corresponding increase in the carbon
efficiency into the bio-oil. The carbon efficiency increase as the hydrogen concentration increase
using the platinized catalyst. This is largely due to the decrease in solids, due to reduced coke
formation in the presence of hydrogen as the hydrogen concentration increases. The oxygen in the
bio-oil reduces with increasing hydrogen concentration due to an increase in water formation from
improved hydrodeoxygenation activity.
[0085] Figure 4 indicates the carbon efficiency for deoxygenating fast pyrolysis bio-oil to a
desired oxygen content based on one of three potential deoxygenation mechanisms;
hydrodeoxygenation (HDO), decarboxylation (C02) and decarbonylation (CO). These theoretical
calculations assume there is a fixed amount of char and permanent gases that result from pyrolysis
and that no other carbon by-products are formed in the deoxygenation. It is known that
deoxygenating fast pyrolysis bio-oil is challenging with significant losses to light gasses and
coking. Those losses mean that the actual carbon efficiency for deoxygenating fast pyrolysis biooil
is significantly lower than any of the theoretical values. The theoretical calculations however
demonstrate the effect of each deoxygenation mechnasim on the carbon efficieny. In comparing
these theoretical yields with experimental yields from RCFP with RTI-A9P, it can be seen that
bio-oil yields are trending upward even with increased deoxygenation of the product indicating
shifts toward increased hydrodeoxygenation.
[0086] Figure 4 shows a comparison of experimental carbon efficiencies for bio-oil from
RCFP with RTI-A9P to theoretical deoxygenation mechanism for reducing the oxygen content of
fast pyrolysis bio-oil.
[0087] With selected catalysts, there is an increase in carbon efficiency in the bio-crude as the
concentration of hydrogen in the reactor atmosphere increases and a corresponding decrease in the
oxygen content of the bio-crude. This higher carbon efficiency corresponds to the decrease in
solids as the coke formation on the catalyst decreases in the presence of hydrogen. The lower
oxygen content in the bio-crude also correlates with an increase in water production from HDO.
[0088] The material balances and oxygen content of the organic bio-crude phase for
hydropyrolysis (HYP) and two CFP experiments are compared with CFP with added hydrogen;
which is refer as reactive gas CFP (RCFP), using different catalysts in Table 5. Comparing the
material balances for the three bio-oil pathways represented in Table 5, hydropyrolysis clearly
generates the most aqueous phase product but also produces bio-crude with the lowest oxygen
content. This represents efficient HDO of the biomass hydropyrolysis products. The CFP biocrude
yields with and without added hydrogen at atmospheric pressure are comparable to the
hydropyrolysis bio-crude yields, but the oxygen contents of these products are higher. Note,
however, the lower oxygen content of the RCFP bio-crudes compared with the CFP bio-crudes.
The solids yield of the RCFP processes is lower than the solids produced from the CFP process
due to less coke formation.
Table 5 : Experimental material balances for CFP and hydropyrolysis (HYP) processes compared
with the new proposed Reactive Gas CFP (RCFP) process with selected catalysts.
HYP RCFP RCFP RCFP CFP CFP
Catalyst Catalyst 2 Catalyst Conditions Conditions
1 3 1 2
Yields o n wt% input basis (biomass+hh)
Gas 17.61 18.84 25.53 21.22 21.66 21.01
Solid 8.68 19.00 12.9 6.07 19. 1 21.8
Aqueous Phase 45.95 3 1.44 33.33 33.00 32.62 32.95
Liquid
Bio-crude 21.95 22.16 25.28 28.83 21.88 17.89
Bio-crude Oxygen Content (wt% - dry basis)
1.5 8.9 12.7 11.3 18 14.9
[0089] The bio-crude yields from the three bio-oil pathways are highlighted in Table 6. The
water content of these phase-separated bio-crude samples was measured using Karl-Fischer
titration and is also shown. The RCFP bio-crude samples tend to contain more water, while the
hydropyrolysis and CFP bio-crudes more effectively phase separate. The water content in the biocrudes
is also a function of the oxygen content. The density of the hydropyrolysis bio-crude is
-0.80 g/ml, and the low oxygen content clearly makes it more hydrophobic. The CFP bio-crude
on the other hand has a density of -1.1 g/ml with higher oxygen content. Phase separation of the
denser CFP bio-crude and the aqueous phase is effective. The RCFP bio-crudes have lower
oxygen content than the CFP bio-crudes. The density of the RCFP bio-crude is less than 1 g/ml
but less hydrophobic than the hydropyrolysis bio-crude, so separating the organic and aqueous
phases is not as easy. The separation may be improved by further reducing the oxygen content of
the bio-crude produced by RCFP.
[0090] The hydrocarbon content of the aqueous phase collected from the three bio-oil
pathways is also a function of the deoxygenation efficiency of the process. The carbon content of
the CFP aqueous phase products ranges from 5-7 wt based on the input biomass. The carbon
content of the RCFP aqueous phase products is between 2.5-5 wt of the input biomass, and the
hydropyrolysis aqueous phase contains 0.5 wt of the input carbon. The carbon content of the
RCFP aqueous phase also decreases as the hydrogen concentration in the reactor increases.
[0091]
Table 6: Experimentally determined yields and oxygen contents for CFP and HYP bio-crudes
compared with bio-crudes produced from the RCFP process.
HYP RCFP RCFP RCFP CFP CFP
Catalyst 1 Catalyst 2 Catalyst 3 Conditions 1 Conditions 2
Bio-crude Composition - wt% of biomass fed basis
Bio-crude, dry 22.15 18.17 18.71 23.13 19.86 15.88
Water in Bio- 0.34 4 6.5 5.84 2 2
crude
Liquid Organic 16.85 17.3 17.85 21.87 18.8 14.24
C4-C6 5.3 0.87 0.86 1.26 1.06 1.64
Bio-crude Oxygen Content - wt% dry basis
1.5 8.9 12.7 11.3 18 14.9
[0092]
Table 7 : Summary of the biofuel yield and hydrogen demand for three bio-oil pathways.
CFP RCFP HYP
Fuel Yield (gal/ton) 52 64 76
Conversion H2 Demand scf/bbl 0 1264 5322
Upgrading H2 Demand scf/bbl 4200 3539 1980
[0093] The commercial viability of these three bio-oil pathways can be assessed by
comparing how the relative yields, hydrogen demand, and carbon recovery potential affects the
preliminary techno-economics of each process. The biofuels yield and hydrogen demand is
calculated from the experimental material balances presented in Table 7 and bio-crude oxygen
content presented in Table 6. The calculated fuel yield presented in Table 7 is based on upgrading
the bio-crudes produced from each process in a hydroprocessing step. The calculation assumes no
carbon losses during hydroprocessing. The hydrogen demand determined for each conversion
process shown in Table 7 was experimentally measured while the hydrogen demand for upgrading
is calculated by assuming the remaining oxygen in the bio-crude is removed as water and the
hydrogen-to-carbon ratio in the finished biofuel is two. The volumetric yield of the finished
biofuels is based on a density of 0.8 g/ml, similar to diesel.
[0094] The total hydrogen demand for each process effectively correlates with bio-crude yield
because more hydrogen is required to deoxygenate and upgrade the intermediate bio-crude
produced. The CFP and RCFP processes have about the same hydrogen demand for upgrading,
but the RCFP process uses hydrogen in the conversion step so the total hydrogen demand is
higher. Less hydrogen is required for deoxygenating the hydropyrolysis bio-crude because it has
low oxygen content, but the hydrogen demand during hydropyrolysis is comparatively high
because carbon efficiency is higher and there is near complete HDO in the conversion step.
[0095] The preliminary results for the proposed RCFP process demonstrate the potential for
producing a low oxygen content bio-crude with high carbon efficiency. Table 8 highlights the
strengths and weakness of this novel bio-oil pathway compared to CFP and hydropyrolysis.
Optimizing catalyst performance and process conditions are essential for maximizing biofuel
yields and minimizing overall hydrogen demand of the process while reducing wastewater
treatment and disposal costs.
Table 8: Strengths and weaknesses of CFP, hydropyrolysis, and RCFP bio-oil
Process Strengths Weaknesses
• Ambient pressure technology • Bio-crude oxygen contents > 10
• No hydrogen required for wt
distributed stand-alone systems • Bio-crude still has significant
• Anhydrosugars and carboxylic fraction of carboxylic acids and
acids reduced so bio-crude has PAHs
CFP
lower TAN and improved thermal • Increased carbon loss to aqueous
stability phase
• High CH4 potential from the • Hydrogen demand for upgrading to
aqueous phase finished fuels
• Catalyst coking
• Bio-crude oxygen contents < 5 wt • High bio-crude aromatic content
• Increased aliphatic content and near • Higher capital costs for pressurized
complete reduction of ketones and equipment
acids in the bio-crude • High hydrogen pressure
• High carbon efficiency with low Hydropyrolysis • Unproven commercial reliability for
carbon loss to aqueous phase feeding biomass across pressure
• Bio-crude: low TAN and very good boundary
thermal stability
• Utilizes hydrogen for HDO
• Low catalyst coking
• Ambient pressure technology • Increased hydrogen demand
• Higher carbon efficiency compared • Hydrogen source required for stand
to CFP and nearing that of alone concepts
hydropyrolysis • Higher carbon loss to aqueous phase
• Bio-crude has reduced TAN and than hydropyrolysis
RCFP higher thermal stability compared to • High bio-crude phenolic content
CFP
• Lower PAHs, ketones and
carboxylic acids in bio-crude
compared to CFP
• Utilizes hydrogen to increase HDO
[0097] Abbreviations: PAH (polyaromatic hydrocarbons), TAN (total acid number).
[0098] Catalytic Fast Pyrolysis with platinized or transition metal promoted catalysts
utilizing Hydrogen at low total pressure
[0099] Background
[00100] A catalytic fast pyrolysis process utilizing hydrogen (RCFP) through the use of
platinum promoted, metal phosphide promoted, or transition metal catalysts. The process is
similar to that described in co-owned PCT/WO 13/29379 Catalytic Biomass Pyrolysis and coowned
U.S. Provisional Application No. 61/733,142, filed December 4, 2012, Dayton et al.
except there is hydrogen present at a minimum amount (>10 volume percent of fluidization gas
feed) during the catalytic pyrolysis step in the process to enhance hydrodeoxygenation or HDO.
[00101] The platinized catalyst is a platinum promoted solid acid or metal oxide catalyst
believed to promote decarboxylation, decarbonylation, and dehydration through catalytic
cracking. Acid catalysts are well known for promoting catalytic cracking reactions. Acidic,
high surface area catalysts have been used for hydrocarbon cracking and the recent literature
suggests that such solid acids catalyze both C-C and C-0 bond breaking. Use of relatively small
pore zeolites, such as ZSM-5, may not be appropriate because large organic molecules are
cracked into moderate molecular weight hydrocarbons. Also, zeolites tend to produce large
amounts of coke relatively fast reducing bio-crude yields. As in fluid catalytic cracking (FCC)
processing, strong acid catalysts tend to produce coke precursors that lead to carbon deposition on
the catalyst. Catalyst regeneration is achieved by using oxygen/air to oxidize surface carbon.
[00102] These platinum promoted or transition metal catalysts have been shown to produce
low oxygen content (<10 ) in the bio-crude while minimizing over cracking and significantly
reducing coke formation to achieve attractive bio-crude yields (>21%) and energy recovery in the
liquid product.
[00103] Table 9. Comparison of catalytic fast pyrolysis technologies
[00104] Above in Table 9 is a comparison of catalytic fast pyrolysis technologies investigated.
Key points and assumptions made are:
[00105] (i) Bio-crude Yield includes all C4-6 gas species in addition to collected organic
liquid, does not include carbon lost to aqueous phase; (ii) Theoretical Fuel Yield is based on H/C
of 2 and density of 0.8 g/ml, assumes no carbon loss in hydroprocessing; (iii) Biomass fed at
bench-scale typical had a moisture content of 7-9 wt ; (iv) RCFP is an catalytic fast pyrolysis
process based on process conditions and catalyst.
[00106] Figure 5. Compares the carbon efficiency of the bio-crude along with the varying biocrude
oxygen content across varying technologies investigated.
[00107] Currently hydropyrolysis, or pyrolysis in the presence of hydrogen at high pressure
(300 psig) has led to the best bio-crude yields and subsequently the highest theoretical fuel yields.
This high pressure hydrogen process though involves large capital costs due to the materials of
construction and problems associated with solids feeding across a large pressure barrier. Catalytic
fast pyrolysis in a low pressure hydrogen atmosphere or RCFP, aims to achieve the same biocrude
yields and quality as hydropyrolysis but at low total pressure thus decreasing capital costs
and problems associated with feeding at pressure. RCFP has shown to produce good bio-crude
yields with good deoxygenation that are better than current catalytic fast pyrolysis technology but
not quite as good as the hydropyrolysis technology.
[00108] Competitive Advantages
[00109] Feed prep and handling costs are much lower in the disclosed technology compared
with numerous and various biomass preparation steps/options in KiOR process or with the
challenges of feeding solids across pressure barrier as required in standard hydropyrolysis
processes. While the bio-crude physical and chemical properties are difficult to directly compare,
the thermal stability of bio-crude described here is such that >80 revaporizes at an oxygen
content of 20wt at 350 °C; almost twice as much compared to bio-oil (non-catalytic). See plot
below.
[00110] Figure 6 shows the revaporization efficiency at 350 °C for bio-crudes with varying
oxygen contents.
[00111] One non-limiting application of the invention is utilizing hydrogen and platinized
catalysts in catalytic fast pyrolysis would be similar to that described in PC17W013/29379.
However it is reasonable to expect that this technology could be applied to competing processes.
In KiOR's processes, the platinized catalyst is likely a suitable replacement for the zeolite catalyst
in the biomass catalytic cracking step and hydrogen would need to replace the inert nitrogen
carrier. Similarly the platinized catalysts could replace sand in Ensyn's RTP technology and
hydrogen would need to replace the nitrogen.
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[00112] It is to be understood that, while the invention has been described in conjunction with
the detailed description, thereof, the foregoing description is intended to illustrate and not limit
the scope of the invention. Other aspects, advantages, and modifications of the invention are
within the scope of the claims set forth below. All publications, patents, and patent applications
cited in this specification are herein incorporated by reference as if each individual publication or
patent application was specifically and individually indicated to be incorporated by reference.

CLAIMS
What is claimed is:
1. A reactive catalytic biomass pyrolysis process comprising reacting a biomass starting
material under pyrolysis conditions in the presence of a catalyst and a gas feed to the
pyrolysis reactor of about 10 volume % to about 90 volume % hydrogen gas at a pressure
of less than about 6 bar to form a stream comprising a pyrolysis product.
2. The process of claim 1, wherein the gas feed to the pyrolysis reactor contains hydrogen
derived from methane.
3. The process of claim 1, wherein the pyrolysis product comprises a hydrogen-rich pyrolysis
gases and hydrogen from the hydrogen-rich pyrolysis gases is recycled so as to contribute
to the gas feed to the pyrolysis reactor.
4. The process of claim 3, wherein the gas feed to the pyrolysis reactor is blended with
hydrogen from an additional source.
5. The process of claim 1, wherein the gas feed to the pyrolysis reactor is about 30 volume %
to about 90 volume %hydrogen gas.
6. The process of claim 1, wherein the gas feed to the pyrolysis reactor is about 50 volume %
to about 90 volume %hydrogen gas.
7. The process of claim 1, wherein the gas feed to the pyrolysis reactor also contains carbon
monoxide, carbon dioxide, nitrogen, alkanes, alkenes, helium, argon, or a mixture thereof.
8. The process of claim 3, wherein the gas feed to the pyrolysis reactor contains additional
gases from the hydrogen-rich pyrolysis gases.
9. The process of claim 1, wherein the biomass starting material comprises a lignocellulosic
material.
10. The process of claim 1, wherein the biomass starting material is an agricultural residue, a
forest residues, a paper sludge, waste paper, or a municipal solid waste.
11. The process of claim 1, wherein the biomass starting material is particularized with an
average particle size of about 25 mm or less.
12. The process of claim 11, wherein the biomass starting material has an average particle size
of about 0.1mm to about 8 mm.
13. The process of claim 1, wherein the catalyst comprises a metal or metal oxide on an acidic
support and the metal or metal oxide is tungsten, molybdenum, chromium, iron,
ruthenium, cobalt, iridium, nickel, palladium, platinum, copper, silver, gold, tin, an oxide
thereof, or a combination thereof.
14. The process of claim 13 wherein, the acidic support is silica, alumina, zirconia, tungstated
zirconia, sulfated zirconia, titania, ceria, a zeolite or a combination thereof.
15. The process of claim 1, wherein the catalyst comprises a metal or metal oxide on a mixed
metal oxide support where the metal or metal oxide is tungsten, molybdenum, chromium,
iron, ruthenium, cobalt, iridium, nickel, palladium, platinum, copper, silver, gold, tin, an
oxide thereof, or a combination thereof.
16. The process of claim 1, wherein the catalyst comprises a CoMo, NiMo or NiW on a
support.
17. The process of claim 16 wherein, the support is an acidic support and the acidic support is
silica, alumina, zirconia, tungstated zirconia, sulfated zirconia, titania, ceria, a zeolite or a
combination thereof.
18. The process of claim 1, wherein the catalyst comprises a metal phosphide on an acidic
support.
19. The process of claim 18, wherein the metal phosphide is nickel phosphide, iron phosphide,
molybdenum phosphide, tungsten phosphide, copper phosphide, cobalt phosphide, or
chromium phosphide.
20. The process of claim 18, wherein the acidic support is silica, alumina, zirconia, tungstated
zirconia, sulfated zirconia, titania, ceria, a zeolite or a combination thereof.
21. The process of claim 1, wherein the catalyst comprises a metal phosphide on a mixed
metal oxide support.
22. The process of claim 21, wherein the metal phosphide is nickel phosphide, iron phosphide,
molybdenum phosphide, tungsten phosphide, copper phosphide, cobalt phosphide, or
chromium phosphide.
23. The process of claim 1, wherein the catalyst contains a binder material.
24. The catalyst of claim 23, wherein the binder is a macroreticulate polymer, a kieselguhr, a
kaolin, a bentonite, clays, or a combination thereof.
25. The process of claim 1, wherein said reacting is carried out at a temperature of about 200
°C to about 700 °C.
26. The process of claim 1, wherein said reacting is carried out at a temperature of about 350
°C to about 550 °C.
27. The process of claim 1, wherein the catalyst and the biomass starting material in the
pyrolysis reactor are provided in a ratio of about 1:10 to about 1000:1 based on mass.
28. The process of claim 1, wherein the catalyst and the biomass starting material in the
pyrolysis reactor are provided in a ratio of about 1:5 to about 100:1 based on mass.
29. The process of claim 1, wherein said reacting is carried out at a pressure of up to about 4.5
bar.
30. The process of claim 29, wherein said reacting is carried out at a pressure of up to about
2.5 bar.
31. The process of claim 1, wherein said reacting is carried out at ambient pressure.
32. The process of claim 1, further comprising: transferring the pyrolysis product stream to a
separator; separating a vapor and gas fraction from a solids fraction comprising pyrolysis
product solids and the catalyst; and regenerating and recycling the catalyst into the
pyrolysis process.
33. The process of claim 32, wherein the vapor and gas fraction is transferred to a condenser
wherein a liquid product is separated from a gaseous fraction.
34. The process of claim 33, wherein the liquid product is separated into an aqueous phase and
a bio-oil.
35. The process of claim 34, wherein the bio-oil has an oxygen content of about 0.5% to
about 25% by mass on a dry basis based on the overall mass of the bio-oil.
36. The process of claim 34, wherein the bio-oil is an aliphatic compound, an aromatic
compounds, a polyaromatic compound, a phenol, an aldehyde, a ketone, an organic acid, a
hydrocarbons or mixture thereof.
37. The process of claim 35, wherein the process exhibits a carbon conversion efficiency of
about 20% or greater by weight.
38. The process of claim 37, wherein the process exhibits a carbon conversion efficiency of
about 20% to about 65% by weight.
39. The process of claim 1, further comprising isolating a bio-oil fraction from the pyrolysis
product.
40. A catalytic biomass pyrolysis system comprising:
(a) a reactor adapted for reacting a biomass with a catalyst and a gas stream with about
10 volume % to about 90 volume % hydrogen gas at a pressure of less than about 6
bar under pyrolysis conditions to form a pyrolysis reaction stream;
(b) a separation unit in connection with the reactor and adapted to form a first stream
comprising a solids fraction from the pyrolysis reaction stream and a second
stream comprising a vapors fraction from the pyrolysis reaction stream; and
(c) a condenser unit in communication with the separation unit and adapted to
condense a mixture of bio-crude, water and/or another liquid from the vapors in the
second stream separate from a gas component of the second stream.
41. The catalytic biomass pyrolysis system of claim 40, further comprising (d) a liquid
separator unit in fluid communication with the condenser unit and adapted to separate
water or another liquid from the bio-crude.
42. The catalytic biomass pyrolysis system of claim 41, further comprising (e) a catalyst
regeneration unit in fluid communication with the separation unit and adapted to remove
non-catalyst solids from the solid catalyst present in the first stream.
43. The catalytic biomass pyrolysis system of claim 42, further comprising (f) a catalyst
delivery stream adapted to deliver regenerated catalyst from the catalyst regeneration unit
to the reactor.
44. The catalytic biomass pyrolysis system of claim 43, further comprising (g) a hydrogen
production unit in communication with the condenser unit and adapted to generate
hydrogen from methane or other hydrocarbons for introduction into the reactor.
45. The catalytic biomass pyrolysis system of claim 41, further comprising a hydroprocessing
unit in which the bio-crude from the liquid separator is further processed to remove
oxygen and increase the hydrogen to carbon ratio of the bio-crude material.
46. The process of claim 40, wherein said reacting is carried out at a pressure of up to about
4.5 bar.
47. The process of claim 40, wherein said reacting is carried out at a pressure of up to about
2.5 bar.
48. The process of claim 40, wherein said reacting is carried out at about ambient pressure.
49. The catalytic biomass pyrolysis system of claim 40, further comprising an oxidant stream
in fluid communication with the catalyst regeneration unit and adapted to deliver an
oxidant to the catalyst regeneration unit.
50. The catalytic biomass pyrolysis system of claim 40, wherein the condenser unit is in fluid
communication with the reactor via a gas flow stream adapted to transfer a portion of the
gas component of the second stream to the reactor.
51. The catalytic biomass pyrolysis system of claim 50, further comprising a blower unit
interposed between and in fluid communication with the condenser unit and the reactor.
52. The catalytic biomass pyrolysis system of claim 40, further comprising a biomass
preparation unit in fluid communication with the reactor and adapted to transfer the
biomass to the reactor.
53. The catalytic biomass pyrolysis system of claim 52, wherein the biomass preparation unit
is adapted to particularize a solid biomass to a size of about 25 mm or less.
54. The catalytic biomass pyrolysis system of claim 53, wherein the reactor is adapted to
combine the catalyst and the biomass in a ratio of about 1:10 to about 1000:1 based on
mass.
55. The catalytic biomass pyrolysis system of claim 40, wherein the reactor is a transport
reactor.
The catalytic biomass pyrolysis system of claim 40, wherein the reactor is adapted to a
function at a temperature of about 200 °C to about 700 °C.
The catalytic biomass pyrolysis system of claim 40, wherein the reactor is adapted to
function at a temperature of about 350 °C to about 550 °C.