NZ615261B2 - Methods and catalysts for deoxygenating biomass-derived pyrolysis oil - Google Patents
Methods and catalysts for deoxygenating biomass-derived pyrolysis oil Download PDFInfo
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- NZ615261B2 NZ615261B2 NZ615261A NZ61526112A NZ615261B2 NZ 615261 B2 NZ615261 B2 NZ 615261B2 NZ 615261 A NZ615261 A NZ 615261A NZ 61526112 A NZ61526112 A NZ 61526112A NZ 615261 B2 NZ615261 B2 NZ 615261B2
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- biomass
- pyrolysis oil
- derived pyrolysis
- oxide
- catalyst
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 118
- 239000002028 Biomass Substances 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 230000003635 deoxygenating Effects 0.000 title claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000001264 neutralization Effects 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052803 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001929 titanium oxide Inorganic materials 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N Niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003921 oil Substances 0.000 description 93
- 150000002430 hydrocarbons Chemical class 0.000 description 22
- 239000007789 gas Substances 0.000 description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- -1 cobalt- molybdenum Chemical compound 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001603 reducing Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 235000020986 nuts and seeds Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004642 transportation engineering Methods 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
Disclosed herein are methods and catalysts for deoxygenating a biomass-derived pyrolysis oil. The method comprises the step of contacting the biomass-derived pyrolysis oil with a deoxygenating catalyst in the presence of hydrogen to form a low-oxygen biomass-derived pyrolysis oil effluent, wherein the catalyst comprises a neutral catalyst support, nickel, cobalt, and molybdenum, and wherein the deoxygenating catalyst comprises nickel in an amount calculated as an oxide of from 0.1 to 1.5 wt. %, cobalt in an amount calculated as an oxide of from 2 to 4 wt. %, molybdenum in an amount calculated as an oxide of from 10 to 20 wt. %, and the neutral catalyst support is selected from the group consisting of a titanium oxide, zirconium oxide, niobium oxide, or a theta alumina support. he catalyst comprises a neutral catalyst support, nickel, cobalt, and molybdenum, and wherein the deoxygenating catalyst comprises nickel in an amount calculated as an oxide of from 0.1 to 1.5 wt. %, cobalt in an amount calculated as an oxide of from 2 to 4 wt. %, molybdenum in an amount calculated as an oxide of from 10 to 20 wt. %, and the neutral catalyst support is selected from the group consisting of a titanium oxide, zirconium oxide, niobium oxide, or a theta alumina support.
Description
METHODS AND CATALYSTS FOR DEOXYGENATING BIOMASS-DERIVED
PYROLYSIS OIL
STATEMENT OF PRIORITY
[0001] This application claims priority to U.S. Application No. 13/150,844 which was
filed on June 1, 2011, the contents of which are hereby incorporated by reference in its
entirety.
FIELD OF THE INVENTION
The present invention relates generally to methods and catalysts for producing
biofuels, and more particularly to methods and catalysts for producing low-oxygen
biomass-derived pyrolysis oil from the catalytic deoxygenation of biomass-derived
pyrolysis oil.
BACKGROUND OF THE INVENTION
Fast paralysis is a process during which organic carbonaceous biomass
feedstock, i.e., “biomass”, such as wood waste, agricultural waste, algae, etc., is rapidly
heated to between 300°C to 900°C in the absence of air using a pyrolysis reactor. Under
these conditions, solid products, liquid products, and gaseous pyrolysis products are
produced. A condensable portion (va pors) of the gaseous pyrolysis products is condensed
into biomass-derived pyrolysis oil. Biomass-derived pyrolysis oil can be burned directly
as fuel for certain boiler and furnace applications, and can also serve as a potential
feedstock in catalytic processes for the production of fuels in petroleum refineries.
Biomass-derived pyrolysis oil has the potential to replace up to 60% of transportation
fuels, thereby reducing the dependency on conventional petroleum and reducing its
environmental impact.
[0004] However, biomass-derived pyrolysis oil is a complex, highly oxygenated organic
liquid having properties that currently limit its utilization as a biofuel. For example,
biomass-derived pyrolysis oil has high acidity and a low energy density attributable in
large part to oxygenated hydrocarbons in the oil, which undergo secondary reactions
during storage. “Oxygenated hydrocarbons” as used herein are organic compounds
containing hydrogen, carbon, and oxygen. Such oxygenated hydrocarbons in the biomass-
derived pyrolysis oil include carboxylic acids, phenols, cresols, alcohols, aldehydes, etc.
Conventional biomass-derived pyrolysis oil comprises 30% by weight oxygen from these
oxygenated hydrocarbons. Conversion of biomass-derived pyrolysis oil into biofuels and
chemicals requires full or partial deoxygenation of the biomass-derived pyrolysis oil.
Such deoxygenation may proceed via two main routes, namely the elimination of either
water or CO . Unfortunately, deoxygenating biomass-derived pyrolysis oil leads to rapid
plugging or fouling of the processing catalyst in a hydroprocessing reactor caused by the
formation of solids from the biomass-derived pyrolysis oil. Components in the pyrolysis
oil form on the processing catalysts causing catalytic bed fouling, reducing activity of the
catalyst and causing build up in the hydroprocessing reactor. It is believed that this
plugging is due to an acid catalyzed polymerization of the various components of the
biomass-derived pyrolysis oil that create either a glassy brown polymer or powdery brown
char, which limit run duration and processibility of the biomass-derived pyrolysis oil.
Accordingly, it is desirable to provide methods and catalysts for producing low-
oxygen biomass-derived pyrolysis oils. In addition, it is also desirable to produce low-
oxygen biomass-derived pyrolysis oils without plugging of the catalyst contained in a
reactor, thereby increasing run duration and improving processibility of the biomass-
derived pyrolysis oil. Furthermore, other desirable features and characteristics of the
present invention will become apparent from the subsequent detailed description of the
invention and the appended claims, taken in conjunction with the accompanying drawings
and this background of the invention.
SUMMARY OF THE INVENTION
Methods and catalysts for deoxygenating a biomass-derived pyrolysis oil are
provided herein. In accordance with an exemplary embodiment, a method for
deoxygenating a biomass-derived pyrolysis oil comprises the step of contacting the
biomass-derived pyrolysis oil with a first deoxygenating catalyst in the presence of
hydrogen at first predetermined hydroprocessing conditions to form a first low-oxygen
biomass-derived pyrolysis oil effluent. The first deoxygenating catalyst comprises a
neutral catalyst support, nickel, cobalt, and molybdenum. The first deoxygenating catalyst
comprises nickel in an amount calculated as an oxide of from 0.1 to 1.5 wt. %.
In accordance with another exemplary embodiment, a method for deoxygenating
a biomass-derived pyrolysis oil is provided. The method comprises the step of introducing
hydrogen and a feed stream comprising the biomass-derived pyrolysis oil to a first
hydroprocessing reactor containing a first deoxygenating catalyst. The first
hydroprocessing reactor is operating at first predetermined hydroprocessing conditions to
form a first low-oxygen biomass-derived pyrolysis oil effluent. The first deoxygenating
catalyst comprises a neutral catalyst support, nickel, cobalt, and molybdenum. The first
deoxygenating catalyst comprises nickel in an amount calculated as an oxide of from 0.1
to 1.5 wt. %, cobalt in an amount calculated as an oxide of from 2 to 4 wt. %,
molybdenum in an amount calculated as an oxide of from 10 to 20 wt. %. The neutral
catalyst support is selected from the group consisting of a titanium oxide (T iO ) suppor t, a
zirconium oxide (Z rO ) suppor t, a niobium oxide (N b O ) suppor t, a theta alumina
2 2 5
support, and combinations thereof.
In accordance with another exemplary embodiment, a catalyst for deoxygenating
a biomass-derived pyrolysis oil is provided. The catalyst comprises a neutral catalyst
support, nickel, cobalt, and molybdenum. Nickel is in an amount calculated as an oxide of
from 0.1 to 1.5 wt. %, cobalt is in an amount calculated as an oxide of from 2 to 4 wt. %,
molybdenum is in an amount calculated as an oxide of from 10 to 20 wt. %. The neutral
catalyst support is selected from the group consisting of a titanium oxide (T iO ) suppor t, a
zirconium oxide (Z rO ) suppor t, a niobium oxide (N b O ) suppor t, a theta alumina
2 2 5
support, and combinations thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will hereinafter be described in
conjunction with the following drawing figures, wherein like numerals denote like
elements, and wherein:
schematically illustrates an apparatus for deoxygenating a biomass-
derived pyrolysis oil in accordance with an exemplary embodiment.
DETAILED DESCRIPTION
The following Detailed Description is merely exemplary in nature and is not
intended to limit the invention or the application and uses of the invention. Furthermore,
there is no intention to be bound by any theory presented in the preceding Background of
the Invention or the following Detailed Description.
[0012] Various embodiments contemplated herein relate to methods and catalysts for
deoxygenating a biomass-derived pyrolysis oil. Unlike the prior art, the exemplary
embodiments taught herein produce a low-oxygen biomass-derived pyrolysis oil by
contacting a biomass-derived pyrolysis oil with a deoxygenating catalyst in the presence
of hydrogen at predetermined hydroprocessing conditions. The deoxygenating catalyst
comprises a neutral catalyst support, cobalt, molybdenum and a small amount of nickel
that are disposed on the neutral catalyst support. The inventors have found that the neutral
catalyst support is stable and resistant dissolving over time in the biomass-derived
pyrolysis oil, which typically has a high water content, and therefore provides a robust and
durable support for the catalytically active metals of cobalt, molybdenum, and nickel.
Moreover, the neutral catalyst support does not promote acid catalyzed polymerization of
the various components of the biomass-derived pyrolysis oil that otherwise cause catalyst
plugging. Furthermore, the inventors have found that the catalyst activity of cobalt-
molybdenum, which is relatively low but resist catalyst plugging, can be selectively
increased with the addition of a small amount of nickel to effectively deoxygenate
biomass-derived pyrolysis oil without increasing the catalyst activity to the extent of
causing the catalyst to plug.
It should be appreciated that while the deoxygenated oil produced according to
exemplary embodiments of the present invention is generally described herein as a “low-
oxygen biomass-derived pyrolysis oil,” this term generally includes any oil produced
having a lower oxygen concentration than conventional biomass-derived pyrolysis oil.
The term “low-oxygen biomass-derived pyrolysis oil” includes oil having no oxygen, i.e.,
a biomass-derived pyrolysis oil in which all the oxygenated hydrocarbons have been
converted into hydrocarbons (i .e., a “hydrocarbon product”). Preferably, the low-oxygen
biomass-derived pyrolysis oil comprises oxygen in an amount of from 0 to 5 weight
percent (w t. %). “Hydrocarbons” as used herein are organic compounds that contain
principally only hydrogen and carbon, i.e., oxygen-free. “Oxygenated hydrocarbons” as
used herein are organic compounds containing hydrogen, carbon, and oxygen. Exemplary
oxygenated hydrocarbons in biomass-derived pyrolysis oil include alcohols such as
phenols and cresols, carboxylic acids, alcohols, aldehydes, etc.
Referring to a schematic depiction of an apparatus 10 for deoxygenating
a biomass-derived pyrolysis oil in accordance with an exemplary embodiment is provided.
A feed stream 12 containing a biomass-derived pyrolysis oil and a hydrogen-containing
gas 13 are introduced to a first hydroprocessing reactor 14. The biomass-derived pyrolysis
oil may be produced, such as, for example, from pyrolysis of biomass in a pyrolysis
reactor. Virtually any form of biomass can be used for pyrolysis to produce a biomass-
derived pyrolysis oil. The biomass-derived pyrolysis oil may be derived from biomass
material, such as, wood, agricultural waste, nuts and seeds, algae, forestry residues, and
the like. The biomass-derived pyrolysis oil may be obtained by different modes of
pyrolysis, such as, for example, fast pyrolysis, vacuum pyrolysis, catalytic pyrolysis, and
slow pyrolysis or carbonization, and the like. The composition of the biomass-derived
pyrolysis oil can vary considerably and depends on the feedstock and processing variables.
Examples of biomass-derived pyrolysis oil “as-produced” can contain up to 1000 to 2000
ppm total metals, 20 to 33 wt. % of water that can have high acidity (e .g. total acid number
(T AN) > 150), a nd a solids content of 0.1 wt. % to 5 wt. %. The biomass-derived
pyrolysis oil may be untreated (e.g. “as produced”). However, if needed the biomass-
derived pyrolysis oil can be selectively treated to reduce any or all of the above to a
desired level.
The first hydroprocessing reactor 14 contains a first deoxygenating catalyst. In
an exemplary embodiment, the first deoxygenating catalyst comprises a neutral catalyst
support. As used herein, a “neutral catalyst support” is defined as one that shows less than
% total conversion of 1-heptene in a catalytic test reactor as follows: 0.25 g of solid
support material (ground and sieved to 40/60 mesh) i s loaded in a tubular reactor and
heated under flowing hydrogen (1 a tmosphere, upflow) t o 550 C for 60 minutes. The
reactor is cooled to 425 C, hydrogen flow rate is set at 1 slm (st andard liter per minute),
and 1-heptene is introduced to the catalyst bed (b y injection into or saturation of the
hydrogen stream) a t a rate of ~0.085 g/min. Conversion of 1-heptene is defined by
100*(1 -X(h eptene)) w here X is the mole fraction of 1-heptene in the hydrocarbon product
as determined by gas chromatographic analysis of the reactor effluent stream. Various
options for gas chromatographic analysis as known in the art may be used, and other
analytical methods known in the art may be substituted for gas chromatographic analysis
as long as a mole fraction of n-heptene in the product may be calculated. Preferably, the
neutral catalyst support comprises a titanium oxide (T iO ) suppor t, a zirconium oxide
(Z rO ) suppor t, a niobium oxide (N b O ) suppor t, a theta alumina support, or
2 2 5
combinations thereof, and more preferably comprises a titanium oxide (T iO ) support or a
zirconium oxide (Z rO ) suppor t. The non-alumina metal oxide supports can be mixed
with one or more additional components to improve the physical stability and/or phase
stability of the metal oxide. Components that improve physical stability include, but are
not limited to, carbon, other metal oxides, and clays as known in the art. Components that
improve phase stability include, but are not limited to, base metals, transition metals, non-
metals, lanthanide metals, and combinations thereof. “Theta alumina” as used herein
refers to alumina having a crystallinity as measured by X-ray diffraction corresponding to
that characterized in the Joint Committee on Powder Diffraction Standards number 23-
1009.
[0016] The first deoxygenating catalyst also comprises metals disposed on the neutral
catalyst support. The metals are nickel, cobalt, and molybdenum. In an exemplary
embodiment, nickel is present in an amount calculated as an oxide of from 0.1 to 1.5 wt.
%, and preferably from 0.5 to 1.0 wt. % of the first deoxygenating catalyst. Cobalt is
present in an amount calculated as an oxide of from 2 to 4 wt. %, and preferably 3 wt. %
of the first deoxygenating catalyst. Molybdenum is present in an amount calculated as an
oxide of from 10 to 20 wt. %, and preferably 15 wt. % of the first deoxygenating catalyst.
The term “calculated as an oxide” means that the metal is calculated as a metal oxide.
When metals are initially incorporated onto the neutral catalyst support, they may be
present as a metal oxide, rather than in the metallic state. Therefore, as used herein, if the
metal is “calculated as an oxide,” that means the catalyst has x% metal oxide. The actual
amount of the metal will be somewhat lower depending on the stoichiometry of a specific
oxide. The oxide is removed during deoxygenation leaving the metallic form of the metal
on the neutral catalyst support.
The first hydroprocessing reactor 14 may be, for example, a batch reactor or a
continuous flow reactor, such as, an upflow or downflow tubular reactor with or without a
fixed catalyst bed, a continuously stirred reactor, and the like. Other reactors known to
those skilled in the art for catalytic hydroprocessing of an oil-based feedstock may also be
used. In an exemplary embodiment, the first hydroprocessing reactor 14 is operating at
first predetermined hydroprocessing conditions including a reaction temperature of from
100°C to 400°C, a pressure of from 3200 kPa to 12400 kPa (450 t o 1800 psig), a liquid
hourly space velocity of from 0.25 volume of liquid feed/volume of catalyst/hour (H r ) t o
1.0 Hr , and a hydrogen-containing gas treat rate of 1000 SCF/B to 12000 SCF/B.
The biomass-derived pyrolysis oil contained in the feed stream 12 contacts the
first deoxygenating catalyst at the first predetermined hydroprocessing conditions in the
presence of hydrogen to form a first low-oxygen biomass-derived pyrolysis oil effluent 16
by converting at least a portion of the oxygenated hydrocarbons in the biomass-derived
pyrolysis oil into hydrocarbons. In particular, hydrogen from the hydrogen-containing gas
13 removes oxygen from the biomass-derived pyrolysis oil as water, thereby producing the
low-oxygen biomass-derived pyrolysis oil effluent 16. The oil contained in the low-
oxygen biomass-derived pyrolysis oil effluent 16 may be partially deoxygenated with
some residual oxygenated hydrocarbons, or may be substantially fully deoxygenated
where substantially all of the oxygenated hydrocarbons are converted into hydrocarbons.
The low-oxygen biomass-derived pyrolysis oil effluent 16 is removed from the
first hydroprocessing reactor 14 and pass along to a separation unit 18 to remove water 20
and form a water-depleted low-oxygen biomass-derived pyrolysis oil effluent 22. The
water-depleted low-oxygen biomass-derived pyrolysis oil effluent 22 may be removed
from the apparatus 10 along line 24 ( e.g. if substantially fully deoxygenated) or
alternatively, at least a portion of the water-depleted low-oxygen biomass-derived
pyrolysis oil effluent 22 may be directed along line 26.
In an exemplary embodiment, at least a portion of the water-depleted low-oxygen
biomass-derived pyrolysis oil effluent 22 is passed along line 26 and introduced to a
second hydroprocessing reactor 28. The water-depleted low-oxygen biomass-derived
pyrolysis oil effluent 22 is exposed to a second deoxygenating catalyst in the presence of
an additional hydrogen-containing gas 30 at second predetermined hydroprocessing
conditions in the second hydroprocessing reactor 28 to convert any residual oxygenated
hydrocarbons in the effluent 22 into hydrocarbons and form a second low-oxygen
biomass-derived pyrolysis oil effluent 32. Preferably, the second low-oxygen biomass-
derived pyrolysis oil effluent 32 is substantially fully deoxygenated, i.e., oxygen-free. The
second deoxygenating catalyst may be a conventional hydroprocessing catalyst such as
nickel and molybdenum on a gamma alumina support or others well known in the art, or
alternatively may have a similar composition to the first deoxygenating catalyst. The
second predetermined hydroprocessing conditions include a reaction temperature of from
300°C to 350°C, a pressure of from 3550 kPa to 12400 kPa (500 psi g to 1800 psig), a
-1 -1
liquid hourly space velocity of from 0.5 Hr to 1.5 Hr , and a hydrogen-containing gas
treat rate of 400 SCF/B to 8000 SCF/B. The second hydroprocessing reactor 28 may be a
reactor such as a fixed bed tubular reactor, a stir tank reactor, and the like.
The minimum total amount of hydrogen-containing gas 13 and/or additional
hydrogen-containing gas 30 needed to convert substantially all of the oxygenated
hydrocarbons of the biomass-derived pyrolysis oil contained in the feed stream 12
comprises 1-2 equivalents of hydrogen-containing gas per one equivalent of non-water
oxygen. The non-water oxygen in the biomass-derived pyrolysis oil is derived from the
functional groups of the oxygenated hydrocarbons therein. For example, one equivalent of
an alcohol functional group and a ketone functional group requires 1 equivalent of
hydrogen-containing gas for deoxygenation whereas one equivalent of an ester functional
group requires 2 equivalents of hydrogen-containing gas, and 1 equivalent of a carboxylic
acid functional group requires 1.5 equivalents of hydrogen-containing gas. Therefore, for
example, the more esters and carboxylic acids present in the biomass-derived pyrolysis oil,
the more hydrogen-containing gas is necessary for conversion of all the oxygenated
hydrocarbons therein into hydrocarbons. The minimum amount of hydrogen-containing
gas to substantially deoxygenate the biomass-derived pyrolysis oil is equal to one to three
molar equivalents of the non-water oxygen therein. The amount of non-water oxygen =
A–B wherein A is the total amount of oxygen in the biomass-derived pyrolysis oil as
determined by a combustion method that is well known in the art, and B is the total
amount of oxygen in the water in the biomass-derived pyrolysis oil. To determine B, the
total water content in the biomass-derived pyrolysis oil is first determined by the Karl
Fischer Reagent Titration Method (A STM D1364) as known to one skilled in the art. An
excess of hydrogen-containing gas 13 and/or 30 may also be used.
The second low-oxygen biomass-derived pyrolysis oil effluent 32 can be
removed from the apparatus 10 along line 34. In at least one exemplary embodiment, at
least a portion of the water-depleted low-oxygen biomass-derived pyrolysis oil effluent 22
and/or at least a portion of the second low-oxygen biomass-derived pyrolysis oil effluent
32 are recycled in the apparatus 10 by being directed to the feed stream 12. In one
example, at least a portion of the water-depleted low-oxygen biomass-derived pyrolysis oil
effluent 22 is passed along line 38 and introduced to the feed stream 12 upstream of the
first hydroprocessing reactor 14. In another example, the second low-oxygen biomass-
derived pyrolysis oil effluent 32 is passed along line 36 and introduced to the feed stream
12 upstream of the first hydroprocessing reactor 14. Recycling at least a portion of the
water-depleted low-oxygen biomass-derived pyrolysis oil effluent 22 and/or the second
low-oxygen biomass-derived pyrolysis oil effluent 32 helps control the temperature of the
highly exothermic deoxygenation reaction in the first hydroprocessing reactor 14. The
benefits of recycling at least a portion of either of these effluents 22 and/or 32 include, but
are not limited, increasing hydrogen solubility, immolation of the exotherm by dilution of
the reactive species, and reducing the reaction rate of bimolecular reactants that lead to
plugging of the catalyst. The preferred ratio of the recycled water-depleted low-oxygen
biomass-derived pyrolysis oil effluent 22 and/or the recycled second low-oxygen biomass-
derived pyrolysis oil effluent 32 comprises a ratio of from 1.5:1 to 5:1.
Accordingly, methods and catalysts for deoxygenating a biomass-derived
pyrolysis oil have been described. Unlike the prior art, the exemplary embodiments taught
herein produce a low-oxygen biomass-derived pyrolysis oil by contacting a biomass-
derived pyrolysis oil with a deoxygenating catalyst in the presence of hydrogen at
predetermined hydroprocessing conditions. The deoxygenating catalyst comprises a
neutral catalyst support, cobalt, molybdenum and a small amount of nickel that are
disposed on the neutral catalyst support. The neutral catalyst support is stable and
resistant dissolving over time in the biomass-derived pyrolysis oil, which typically has a
high water content, and therefore provides a robust and durable support for the
catalytically active metals of cobalt, molybdenum, and nickel. Moreover, the neutral
catalyst support does not promote acid catalyzed polymerization of the various
components of the biomass-derived pyrolysis oil that otherwise cause catalyst plugging.
Furthermore, the catalyst activity of cobalt-molybdenum, which is relatively low but resist
catalyst plugging, can be selectively increased with the addition of a small amount of
nickel to effectively deoxygenate biomass-derived pyrolysis oil without increasing the
catalyst activity to the extent of causing the catalyst to plug.
While at least one exemplary embodiment has been presented in the foregoing
Detailed Description, it should be appreciated that a vast number of variations exist. It
should also be appreciated that the exemplary embodiment or exemplary embodiments are
only examples, and are not intended to limit the scope, applicability, or configuration of
the invention in any way. Rather, the foregoing Detailed Description will provide those
skilled in the art with a convenient road map for implementing an exemplary embodiment
of the invention, it being understood that various changes may be made in the function and
arrangement of elements described in an exemplary embodiment without departing from
the scope of the invention as set forth in the appended Claims and their legal equivalents.
Claims (10)
1. A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the step of: 5 contacting the biomass-derived pyrolysis oil with a first deoxygenating catalyst in the presence of hydrogen to form a first low-oxygen biomass-derived pyrolysis oil effluent, wherein the first deoxygenating catalyst comprises a neutral catalyst support, nickel, cobalt, and molybdenum, and wherein the first deoxygenating catalyst comprises nickel in an amount calculated as an oxide of 10 from 0.1 to 1.5 wt. %.
2. The method according to claim 1, wherein the step of contacting includes contacting the biomass-derived pyrolysis oil with the first deoxygenating catalyst that comprises nickel in an amount calculated as an oxide of from 0.5 to 1 wt.%.
3. The method according to claim 1 or claim 2, wherein the step of contacting includes contacting the biomass-derived pyrolysis oil with the first deoxygenating catalyst that comprises cobalt in an amount calculated as an oxide of from 2 to 4 wt. %.
4. The method according to any previous claim, wherein the step of contacting includes contacting the biomass-derived pyrolysis oil with the first deoxygenating catalyst that comprises molybdenum in an amount calculated as an oxide of from 10 to 20 wt. %.
5. The method according to any previous claim, wherein the step of contacting includes contacting the biomass-derived pyrolysis oil with the first deoxygenating catalyst that comprises the neutral catalyst support selected from the group consisting of a titanium oxide (T iO ) su pport, a zirconium oxide (Z rO ) 30 support, a niobium oxide (N b O ) sup port, a theta alumina support, and combinations thereof.
6. The method according to any previous claim, further comprising the step removing water from the first low-oxygen biomass-derived pyrolysis oil effluent to form a water-depleted low-oxygen biomass-derived pyrolysis oil 5 effluent.
7. The method according to claim 6, wherein the first deoxygenating catalyst is contained in a first hydroprocessing reactor and the step of contacting includes introducing a feed stream containing the biomass-derived pyrolysis oil to the first 10 hydroprocessing reactor , and wherein the method further comprises the step of: combining at least a portion of the water-depleted low-oxygen biomass- derived pyrolysis oil effluent with the feed stream for introduction to the first hydroprocessing reactor. 15
8. The method according to claim 6, further comprising the step of: contacting at least a portion of the water-depleted low-oxygen biomass- derived pyrolysis oil effluent with a second deoxygenating catalyst in the presence of hydrogen to form a second low-oxygen biomass-derived pyrolysis oil effluent. 20
9. The method according to claim 8, wherein the first deoxygenating catalyst is contained in a first hydroprocessing reactor and the step of contacting includes introducing a feed stream containing the biomass-derived pyrolysis oil to the first hydroprocessing reactor, and wherein the method further comprises the step of: combining at least a portion of the second low-oxygen biomass-derived 25 pyrolysis oil effluent with the feed stream for introduction to the first hydroprocessing reactor.
10. A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the step of: 30 introducing hydrogen and a feed stream comprising the biomass-derived pyrolysis oil to a first hydroprocessing reactor containing a first deoxygenating catalyst to form a first low-oxygen biomass-derived pyrolysis oil effluent, wherein H0026175 20 28
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/150,844 | 2011-06-01 | ||
US13/150,844 US20120305836A1 (en) | 2011-06-01 | 2011-06-01 | Methods and catalysts for deoxygenating biomass-derived pyrolysis oil |
PCT/US2012/038747 WO2012166402A2 (en) | 2011-06-01 | 2012-05-21 | Methods and catalysts for deoxygenating biomass-derived pyrolysis oil |
Publications (2)
Publication Number | Publication Date |
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NZ615261A NZ615261A (en) | 2015-04-24 |
NZ615261B2 true NZ615261B2 (en) | 2015-07-28 |
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