Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR UPGRADING BIOMASS DERIVED PRODUCTS
USING LIQUID-LIQUID EXTRACTION
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] The invention relates generally to the alteration of the
ratio of the
specific gravities of the oil and water phases resulting from the conversion
of biomass to
liquid products, which can further include the removal of metals and/or the
modification of
the conductivity, and more particularly to an effective means to reduce the
level of solids
contained in the oil phase. The invention also relates to using liquid-liquid
extraction to
partition desirable carbon containing compounds into the oil phase and
undesirable carbon
containing compounds into the water phase.
2. Description of the Related Art
[0002] In the conversion of biomass to liquid products, the product stream can
contain both an oil phase and a water phase (containing both water present in
the biomass
prior to conversion, and water produced during the conversion process).
Pyrolysis, in
particular flash pyrolysis, has been proposed as one such process for
converting solid
biomass material to liquid products. Pyrolysis in general refers to a process
in which a
feedstock is heated in an oxygen-poor or oxygen-free atmosphere. If solid
biomass is used
as the feedstock of a pyrolysis process, the process produces gaseous, liquid,
and solid
products. It is often the case that the oil phase has a higher specific
gravity than the water
phase, resulting in the oil phase settling to the bottom of a settling vessel,
and emulsions can
also form between the oil and water phases. As a result, any solids present in
the reaction
products also settle into the oil phase, which can cause issues in downstream
processing of
the oil, and can be difficult and expensive to remove.
[0003] Thus, there is a need for an improved system whereby the solids content
of biomass derived oil is reduced.
[0004] In addition, undesirable carbon containing compounds such as aldehydes
and carboxylic acids can be present in the liquid product and such are not
easily upgradable
to transportation fuels. Such undesirable carbon containing compounds can be
present in
the oil phase while desirable carbon containing compounds can be present in
the water
phase, thus lowering the yield of high quality bio-oil for upgrading to fuels.
Thus, there is
also a need for an improved system whereby undesirable carbon containing
compounds are
transferred from the oil phase to the water phase and desirable carbon
containing
compounds are transferred from the water phase to the oil phase.
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BRIEF SUMMARY OF THE INVENTION
[0005] In accordance with an embodiment of the present invention, a process is
provided comprising:
a) providing a first mixture including a first oil phase comprising biomass
derived
carbon containing compounds and a first aqueous phase comprising water;
wherein
the ratio of the specific gravities of the first oil phase to the first
aqueous phase
(SGR1) is greater than 1.0;
b) modifying the specific gravity of at least one of the first oil phase
and the first
aqueous phase, thereby resulting in a second mixture having a second oil phase
and
a second aqueous phase, wherein the ratio of the specific gravities of the
second oil
phase to the second aqueous phase (SGR2) is less than 1.0; and
c) separating the second oil phase from the second aqueous phase.
[0006] In accordance with another embodiment of the present invention, such
process can additionally comprise:
combining at least one specific gravity modifier comprising a diluent with the
first oil phase,
thereby forming the second oil phase, and wherein the specific gravity of the
second oil
phase is lower than the specific gravity of the first oil phase.
[0007] In accordance with another embodiment of the present invention, such
process can additionally comprise:
combining at least one specific gravity modifier comprising a water-soluble
compound with
the first aqueous phase, thereby forming the second aqueous phase, and wherein
the
specific gravity of the second aqueous phase is higher than the specific
gravity of the first
aqueous phase.
[0008] In accordance with another embodiment of the present invention, such
process can additionally comprise:
combining at least one specific gravity modifier comprising a water soluble co-
solvent with
the first aqueous phase, thereby forming the second aqueous phase, and wherein
the
specific gravity of the second aqueous phase is higher than the specific
gravity of the first
aqueous phase.
[0009] In accordance with another embodiment of the present invention, such
process can additionally comprise:
combining at least one specific gravity modifier comprising a diluent, a water-
soluble
compound, a water soluble co-solvent, and combinations thereof, with the first
mixture,
thereby forming the second oil phase and the second aqueous phase.
[0010] In accordance with another embodiment of the present invention, such
process can additionally comprise:
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allowing the second mixture to settle, thereby forming an upper layer
containing the second
oil phase and a lower layer containing the second aqueous phase, wherein the
first oil phase
contains solids, and following the settling, the second oil phase in the upper
layer contains
less solids than the first oil phase.
[0011] In accordance with another embodiment of the present invention, such
process can additionally comprise:
adding a quantity of a conductivity modifier to the first mixture thereby
forming the second
mixture, wherein the conductivity modifier can have a TAN lower than the TAN
of the first
mixture, and wherein the quantity of conductivity modifier is sufficient such
that the electrical
conductivity of the second mixture is lower than the electrical conductivity
of the first mixture.
[0012] In accordance with another embodiment of the present invention, wherein
the first and/or second oil phases further contain metals, a process is
provided comprising:
contacting either the first and/or second mixtures with specific acids for
removal of at least a
portion of the metals from either or both of the first and second oil phases.
[0013] In accordance with another embodiment of the present invention, a
method is provided comprising:
a) contacting an extraction solvent with a first mixture comprising water
and
biomass derived carbon containing compounds including organics A comprising
compounds selected from the group consisting of i) aldehydes, ii) ketones
having
from 3 to 4 carbon atoms per molecule, iii) carboxylic acids having from 2 to
3 carbon
atoms per molecule, and iv) combinations thereof, and organics B comprising
compounds having at least four carbon atoms per molecule, thereby forming a
second mixture comprising an extract and a raffinate, wherein the organics B
are
substantially free of: i) aldehydes, ii) ketones having from 3 to 4 carbon
atoms per
molecule, and iii) carboxylic acids having from 2 to 3 carbon atoms per
molecule ,
wherein the extract and the raffinate are immiscible, the extract comprises
substantially all of the extraction solvent and substantially all of the
organics B, the
raffinate comprises substantially all of the water and substantially all of
the organics
A, and wherein the extraction solvent has a dipole moment greater than about
1.0
debye, a density less than about 1.0, a water solubility at 20 C of less than
about 2.5
g/100 ml of water, and a boiling point in the range of from about 90 to about
300 F;
b) separating the second mixture thereby forming an intermediate product
stream comprising at least a portion of the extract and a waste water stream
comprising substantially all of the raffinate; and
c) removing at least a portion of the extraction solvent from the
intermediate
product stream forming a recovered extraction solvent and a bio-oil product.
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[0014] In accordance with another embodiment of the present invention,
a
method is provided comprising:
a) providing a first mixture comprising water and biomass derived carbon
containing compounds including organics A comprising carbon containing
compounds selected from the group consisting of i) aldehydes, ii) ketones
having
from 3 to 4 carbon atoms per molecule, iii) carboxylic acids having from 2 to
3 carbon
atoms per molecule, and iv) combinations thereof, and organics B comprising
carbon
containing compounds having at least four carbon atoms per molecule, wherein
organics B are substantially free of the organics A, and wherein the first
mixture
includes i) a first oil phase comprising at least a portion of the biomass
derived
carbon containing compounds and at least a portion of the water and ii) a
first
aqueous phase comprising at least a portion of the water and at least a
portion of the
biomass derived carbon containing compounds, wherein the first oil phase and
the
first aqueous phase are immiscible;
b) contacting the first mixture with an extraction solvent thereby forming
a
second mixture comprising a second oil phase and a second aqueous phase;
wherein substantially all of the organics A present in the first oil phase are
partitioned
from the first oil phase to the first aqueous phase and substantially all of
the organics
B present in the first aqueous phase are partitioned from the first aqueous
phase to
the first oil phase, thereby forming the second oil phase comprising
substantially all
of the organics B and substantially all of the extraction solvent and the
second
aqueous phase comprising substantially all of the water and substantially all
of the
organics A, wherein the second oil phase and the second aqueous phase are
immiscible, and wherein the extraction solvent has a dipole moment greater
than
about 1.0 debye, a density less than about 1.0, a water solubility at 20 C of
less than
about 2.5 g/100 ml of water, and a boiling point in the range of from about 90
to
about 300 F; and
c) separating the second mixture thereby forming an intermediate product
stream comprising at least a portion of the second oil phase and a waste water
stream comprising substantially all of the second aqueous phase.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The biomass material useful in the current invention can be any biomass
capable of being converted to liquid and gaseous hydrocarbons.
[0016] Preferred are solid biomass materials comprising a cellulosic material,
in
particular lignocellulosic materials, because of the abundant availability of
such materials,
and their low cost. The solid biomass feed can comprise components selected
from the
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group consisting of lignin, cellulose, hemicelluloses, and combinations
thereof. Examples of
suitable solid biomass materials include forestry wastes, such as wood chips
and saw dust;
agricultural waste, such as straw, corn stover, sugar cane bagasse, municipal
waste, in
particular yard waste, paper, and card board; energy crops such as switch
grass, coppice,
eucalyptus; and aquatic materials such as algae; and the like.
[0017] The biomass can be converted, by any suitable means, to reaction
products comprising, at least in part, a first mixture comprising, consisting
of, or consisting
essentially of water and biomass derived carbon containing compounds which can
include
organics A comprising carbon containing compounds selected from the group
consisting of i)
aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, iii)
carboxylic acids
having from 2 to 3 carbon atoms per molecule, and iv) combinations thereof,
and organics B
comprising carbon containing compounds having at least four carbon atoms per
molecule.
The carbon containing compounds of the organics B can be selected from the
group
consisting of ketones, furans, phenols, catechols, aromatics hydrocarbons
(such as, but not
limited to, alkyl benzenes and naphthalenes), indenols, indanols,
naphthalenos,benzofurans,
and combinations thereof. The first mixture can also comprise i) a first
oil phase (also
referred to as bio-oil) comprising, consisting of, or consisting essentially
of at least a portion
of the biomass derived carbon containing compounds and at least a portion of
the water and
ii) a first aqueous phase (also referred to as process water) comprising,
consisting of, or
consisting essentially of at least a portion of the water and at least a
portion of the biomass
derived carbon containing compounds. The first oil phase (or bio-oil) of the
reaction
products can comprise at least about 8 wt% water. The first oil phase and the
first aqueous
phase can be immiscible. The biomass conversion can be by a method including,
but not
limited to, fast pyrolysis, catalytic pyrolysis, and hydrothermal conversion,
each at elevated
temperatures. The temperatures can range from 300 to 1000 C, or 400 to 700 C.
The first
mixture can have a Total Acid Number (TAN) of at least about 2, or at least
about 3, or at
least about 10, or at least about 20, or at least about 30.
[0018] The biomass feed can be charged to a reaction zone along with a heat
carrier material and/or a catalyst for mixture with the biomass feed and to
transfer heat
thereto. Useful catalysts for this process include those containing catalytic
acidity and
preferably containing zeolite. The biomass feed can be converted to reaction
products
comprising, consisting of, or consisting essentially of: the first mixture
described above, and
optionally light gases and/or char. The reaction products can be removed from
the reaction
zone and the first mixture condensed therefrom. The first mixture can also
comprise, consist
of, or consist essentially of a first oil phase comprising, consisting of, or
consisting
essentially of biomass derived carbon containing compounds, and a first
aqueous phase
comprising, consisting of, or consisting essentially of water, and solids. The
solids can
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include dissolved or suspended solids and can be catalyst fines, char,
unreacted biomass
and ash. The first oil phase can comprise at least a portion of the biomass
derived carbon
containing compounds and at least a portion of the water. The first aqueous
phase can
comprise at least a portion of the water and at least a portion of the biomass
derived carbon
containing compounds and at least a portion of the solids.
[0019] Specific Gravity Modification
[0020] The ratio of the specific gravities of the first oil phase to the first
aqueous
phase (SGR1) can be greater than 1.0, greater than about 1.05, or greater than
about 1.1.
The specific gravity of at least one of the first oil phase and the first
aqueous phase can be
modified, thereby resulting in a second mixture having a second oil phase and
a second
aqueous phase, wherein the ratio of the specific gravities of the second oil
phase to the
second aqueous phase (SGR2) is less than 1.0, preferably less than about 0.99,
and more
preferably less than about 0.97.
[0021] The modification of the specific gravity of at least one of the first
oil phase
and the first aqueous phase can include adding at least one specific gravity
modifier to the
mixture, thereby forming the second mixture.
[0022] A diluent can be combined with the first oil phase, as at least a
portion of
the specific gravity modifier, thereby forming the second oil phase, resulting
in the specific
gravity of the second oil phase being lower than the specific gravity of the
first oil phase.
More particularly, the specific gravity of the second oil phase is less than
1Ø The diluent
preferably has a specific gravity less than about 0.97. The diluent can be
selected from the
group consisting of: light cycle oil, naphtha, toluene, methyl isobutyl
ketone, reformate, a bio-
oil fraction having a specific gravity lower than the specific gravity of the
first oil phase, a
hydrotreated bio-oil fraction having a specific gravity lower than the
specific gravity of the
first oil phase, and combinations thereof.
[0023] The bio-oil fraction can be obtained as a fraction of the first oil
phase
following the specific gravity modification step. The hydrotreated bio-oil
fraction can
optionally be obtained as a fraction of the first oil phase following
hydrotreatment of the first
oil phase.
[0024] The ratio by volume of the diluent to the first oil phase can be in the
range
of from about 0.6:1 to about 2.4:1, and more preferably from about 0.6:1 to
about 1:1. When
light cycle oil is used as the diluent, the ratio by volume of the diluent to
first oil phase can be
in the range of from about 0.05:1 to about 1:1, or from about 0.05:1 to about
0.2:1.
[0025] The modification of the specific gravity of at least one of the first
oil phase
and the first aqueous phase can also include combining a water-soluble
compound, as at
least a portion of the specific gravity modifier (alone or in addition to the
use of a diluent as a
specific gravity modifier), with the first aqueous phase, thereby forming the
second aqueous
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phase, and wherein the specific gravity of the second aqueous phase is higher
than the
specific gravity of the first aqueous phase. Preferably, the specific gravity
of the second
aqueous phase ends up being greater than about 1.05. The water-soluble
compound can
be selected from the group consisting of NaCI, MgC12, KCI, KBr, Na2SO4,
NaHCO3, NaOH,
KOH, NH4OH, alkyl amines, pyridines, quinolines, H2S, ammonia, ammonium
compounds
including: nitrates, sulfides, carbonates (such as ammonium bicarbonate),
hydroxides,
acetates, chlorides, bromides, iodides, and sulfates, and combinations
thereof.
[0026] The water-soluble compound can be added as a solid and dissolved into
the first aqueous phase, and can also, alternatively, be added in the form of
a water-soluble
compound solution. The water-soluble compound is preferably ammonium
bicarbonate,
NaCI, or MgC12. The water-soluble compound is preferably combined with the
first aqueous
phase in a quantity sufficient to result in a specific gravity of the second
aqueous phase
which is greater than about 1.05.
[0027] The modification of the specific gravity of at least one of the first
oil phase
and the first aqueous phase can also include combining a water-soluble co-
solvent, as at
least a portion of the specific gravity modifier (alone or in addition to the
use of one or both of
the diluent or water-soluble compound as specific gravity modifiers), with the
first aqueous
phase, thereby forming the second aqueous phase, and wherein the specific
gravity of the
second aqueous phase is higher than the specific gravity of the first aqueous
phase. The
water soluble co-solvent can be a glycol, and more preferably, is selected
from the group
consisting of ethylene glycol, polyethylene glycol, propylene glycol,
polypropylene glycol,
and combinations thereof. The resulting specific gravity of the second aqueous
phase is
preferably greater than about 1.05.
[0028] More generally, the at least one specific gravity modifier added to the
first
mixture can also be selected from the group consisting of a light cycle oil,
naphtha, toluene,
methyl isobutyl ketone, reformate, a bio-oil fraction having a specific
gravity lower than the
specific gravity of said first oil phase, a hydrotreated bio-oil fraction
having a specific gravity
lower than the specific gravity of said first oil phase, NaCI, MgCl2, KCI,
KBr, Na2SO4,
NaHCO3, NaOH, KOH, NH4OH, alkyl amines, pyridines, quinolines, H2S, ammonia,
ammonium compounds including: nitrates, sulfides, carbonates (such as ammonium
bicarbonate), hydroxides, acetates, chlorides, bromides, iodides, and
sulfates, a glycol, and
combinations thereof.
[0029] The second mixture is preferably allowed to settle in a settling
vessel,
thereby forming an upper layer containing the second oil phase and a lower
layer containing
the second aqueous phase. The first oil phase can contain solids, which can be
present in
an amount of at least about 100, or about 1000, or about 3,000 ppmw. The
solids can
include, but are not limited to, organic and inorganic components, which can
include solid
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catalyst material. Following the settling of the second mixture, the second
oil phase in the
upper layer contains less solids than the first oil phase; and can contain
less than about 25,
or about 10, or about 5 wt% of the solids contained in the first oil phase;
and preferably
contains less than about 80 ppmw solids.
[0030] When a diluent is used as at least one specific gravity modifier, at
least a
portion of the second oil phase in the upper layer can be passed to a
separator for recovery
of at least a portion of the diluent, resulting in a recovered diluent. At
least a portion of the
recovered diluent can be recycled for use as at least a portion of the
diluent.
[0031] Additionally, when a diluent is used as at least one specific gravity
modifier, at least a portion of the second oil phase can be passed to a
separator for
recovery of at least one bio-oil fraction from the second oil phase. At least
one of the bio-oil
fractions can be utilized, as at least a portion of the diluent.
[0032] Further, when a diluent is used as at least one specific gravity
modifier, at
least a portion of the second oil phase can be passed to a hydrotreater for at
least partial
hydrotreating, thereby forming a hydrotreated stream, and at least a portion
of the
hydrotreated stream can be passed to a separator for separation into at least
one
hydrotreated bio-oil fraction. At least one of the hydrotreated bio-oil
fractions can be utilized
as at least a portion of the diluent.
[0033] Conductivity modification
[0034] Alternatively, a quantity of a conductivity modifier can also be added
to
the first mixture thereby forming the second mixture, wherein the quantity of
the conductivity
modifier is sufficient such that the electrical conductivity of the second
mixture is lower than
the electrical conductivity of the first mixture. The first mixture can have
an electrical
conductivity of at least about 900,000, or at least about 950,000 nano Siemens
per meter
(nS/m); and the second mixture preferably has an electrical conductivity less
than about
800,000 or less than about 500,000 nS/m. In one embodiment, the
conductivity modifier
can have a TAN lower than the TAN of the first mixture, and preferably has a
TAN at least
about 2 units lower than the TAN of the first mixture. The electrical
conductivity of the
second mixture is preferably less than about 75%, more preferably less than
about 50%, and
even more preferably less than about 25% of the electrical conductivity of the
first mixture.
[0035] The conductivity modifier can be selected from the group consisting of
an
aqueous solution, a fraction separated from the biomass derived carbon
containing
compounds, a fraction separated from the biomass derived carbon containing
compounds
following hydrotreatment of the biomass derived carbon containing compounds,
and
combinations thereof. The conductivity modifier can comprise an aqueous
solution having a
pH greater than 7 or greater than about 9. The aqueous solution can comprise a
base
selected from the group consisting of NaOH, KOH, NH4OH, alkyl amines,
pyridines,
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quinolines, ammonia, ammonium compounds including: nitrates, sulfides,
carbonates,
hydroxides, acetates, chlorides, bromides, iodides, and sulfates, and
combinations thereof,
and is preferably ammonium bicarbonate or ammonium hydroxide or a combination
thereof.
Combinations of bases can be added separately or simultaneously as a pre-mixed
solution.
If added separately, they can be added at different process conditions
including different
temperature and different pressures. Buffers may also be used to more tightly
control pH.
[0036] In addition, at least a portion of the first mixture and/or the
resulting
second mixture can be in the form of an emulsion comprising a portion of the
biomass
derived carbon containing compounds and a portion of the water. The second
mixture,
including the conductivity modifier described above, can be subjected to
electrostatic
dehydration, resulting in at least a partial breaking of the emulsion, and
freeing from the
emulsion at least 75%, or at least 90%, or at least 95% of the biomass derived
carbon
containing compounds contained in the emulsion or at least 50%, or at least
70%, or at least
95% of the water contained in the emulsion. Also, the second mixture,
following electrostatic
dehydration, preferably has an electrical conductivity less than about 250,000
nS/m. The
electrostatic dehydration is preferably performed in a desalter vessel. Also,
a demulsifier
compound can be added to the first mixture, along with the conductivity
modifier, thereby
forming the second mixture which is then subjected to the electrostatic
dehydration. The
demulsifier can be an alkoxylate derived from a poly amine.
[0037] Acid Treatment
[0038] In addition, the first and second oil phases can each further comprise
metals, which can be selected from the group consisting of Al, Ca, Mg, Si, Fe,
and
combinations thereof. At least a portion of these metals can be removed from
either the first
oil phase or the second oil phase, or both, into either the first or second
aqueous phases by
contact of either or both of the first mixture and the second mixture with
certain acids. If
metals are removed from the first oil phase into the first aqueous phase by
contact with such
acid(s), the conductivity modifier can then optionally be added to form the
second mixture,
having a reduced electrical conductivity, as described above. The removal of
at least a
portion of the metals can also take place from the second oil phase into the
second aqueous
phase following addition of the conductivity modifier, and also optionally,
before or after the
electrostatic dehydration of the second mixture to at least partially break
the emulsion, as
described above.
[0039] The acid can be selected from the group consisting of sulfuric acid,
nitric
acid, hydrochloric acid, phosphoric acid, glycolic acid, aminocarboxylic
acids, hydroxo-
carboxylic acids, dibasic carboxylic acids, monobasic carboxylic acids,
carbonic acid, alpha-
hydroxy carboxylic acids, and their salts, and combinations thereof. The acid
also preferably
has a pH less than about 5.
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[0040] The acid and metal interaction can include, but is not limited to, a
process
selected from the group consisting of: chemically binding at least a portion
of the metals;
removing at least a portion of the metals from the first and or second oil
phases; or
combinations thereof.
[0041] Liquid-Liquid Extraction
[0042] Alternatively, the first mixture can be contacted with an extraction
solvent
thereby forming a second mixture comprising an extract and a raffinate,
wherein the extract
and raffinate are immiscible. The organics B described above can be
substantially free of i)
aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, and iii)
carboxylic
acids having from 2 to 3 carbon atoms per molecule. The term "substantially
free" as used
herein means less than 5, or 3, or 2, or 1, or 0.5, or 0.1 wt%. The extract
can comprise
substantially all of the extraction solvent and substantially all of the
organics B, and the
raffinate can comprise substantially all of the water and substantially all of
the organics A.
The term "substantially all" as used herein means at least 85, or 90, or 95,
or 98, or 100
wt%. The extraction solvent can have a dipole moment greater than about 1.0 or
greater
than about 2.0 or greater than about 4.0 debye; a density less than about 1.0
or less than
about 0.9 or less than about 0.8; a water solubility at 20 C of less than
about 2.5 or less than
about 2.2 or less than about 2.0 g/100 ml of water; and a boiling point in the
range of from
about 90 to about 300 F or from about 200 to about 270 F or from about 200
to about 260
F. The extraction solvent can be substantially unreactive when exposed to
acidic aqueous
media and substantially thermally stable at temperatures up to about 500 F.
Also, the
extraction solvent can comprise a member selected from the group consisting of
methyl
isobutyl ketone, cyclopentyl-methyl-ether, and combinations thereof.
[0043] The second mixture can then be separated thereby forming an
intermediate product stream comprising at least a portion of, or substantially
all of, the
extract and a waste water stream comprising substantially all of the
raffinate. At least a
portion of the extraction solvent can be removed from the intermediate product
stream
forming a recovered extraction solvent and a bio-oil product, and the
recovered extraction
solvent can be recycled as at least a part of the extraction solvent contacted
with the first
mixture, as described above.
[0044] The viscosity of the second mixture is lower than the viscosity of the
first
mixture making it easier to filter. The second mixture can be filtered to
remove at least a
portion of the solids therefrom prior to the separation of the second mixture.
In addition, the
partition coefficients of the organics A for the extract and the raffinate can
each be less than
about 1.0 or less than about 0.7, and the partition coefficients of the
organics B for the
extract and the raffinate can each be greater than about 1.0 or greater than
about 2Ø
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[0045] The bio-oil product can comprise less than about 1.0 or less than about
0.8 or less than about 0.5 wt% of the organics A, and can comprise less than
about 1 or less
than about 0.5 wt% water. Having a lower water content in the bio-oil product
aids in any
subsequent hydrodeoxygenation by both allowing increased volume throughput in
the unit
and increased hydrodeoxygenation activity due to an equilibrium shift (given
that water is a
product of hydrodeoxygenation). The waste water stream separated from the
second
mixture can comprise less than about 0.1 or less than about 0.05 wt% of the
organics B.
[0046] The first aqueous phase (process water) can be separated from the
reaction products described above to form the first mixture, or the reaction
products can be
used as the first mixture. The first mixture can be counter-currently or cross-
currently
contacted with the extraction solvent. Also, the contacting of the first
mixture with the
extraction solvent can be in a manner such that the second mixture is formed
as a static
mixture, with separation of the second mixture by decanting.
[0047] In accordance with another embodiment, the first mixture can be
contacted with the extraction solvent thereby forming an extraction mixture
comprising an
extraction oil phase and an extraction aqueous phase. Substantially all of the
organics A
present in the first oil phase can be partitioned from the first oil phase to
the first aqueous
phase and substantially all of the organics B present in the first aqueous
phase can be
partitioned from the first aqueous phase to the first oil phase, thereby
forming the extraction
oil phase comprising, consisting of, or consisting essentially of
substantially all of the
organics B and substantially all of the extraction solvent and the extraction
aqueous phase
comprising, consisting of, or consisting essentially of substantially all of
the water and
substantially all of the organics A. The extraction oil phase and the
extraction aqueous
phase can be immiscible. The extraction mixture can be separated thereby
forming an
intermediate product stream described above comprising at least a portion of,
or
substantially all of, the extraction oil phase and a waste water stream
comprising
substantially all of the extraction aqueous phase. At least a portion of the
extraction solvent
can be removed from the intermediate product stream forming a recovered
extraction
solvent and a bio-oil product, and the recovered extraction solvent can be
recycled as at
least a part of the extraction solvent contacted with the first mixture, as
described above.
[0048] The viscosity of the extraction mixture is lower than the viscosity of
the
first mixture making it easier to filter. The extraction mixture can further
comprise solids and
can be filtered to remove at least a portion of such solids therefrom prior to
the separation of
the extraction mixture. In addition, the partition coefficients of the
organics A for the
extraction oil phase and the extraction aqueous phase can each be less than
about 1.0 or
less than about 0.7, and the partition coefficients of the organics B for the
extraction oil
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phase and the extraction aqueous phase can each be greater than about 1.0 or
greater than
about 2Ø
[0049] The bio-oil product can comprise less than about 1.0 or less than about
0.8 or less than about 0.5 wt% of the organics A, and can comprise less than
about 1 or less
than about 0.5 wt% water. Having a lower water content in the bio-oil product
aids in any
subsequent hydrodeoxygenation by both allowing increased volume throughput in
the unit
and increased hydrodeoxygenation activity due to an equilibrium shift (given
that water is a
product of hydrodeoxygenation). The waste water stream separated from the
extraction
mixture can comprise less than about 0.1 or less than about 0.05 wt% of the
organics B.
[0050] The first aqueous phase (process water) can be separated from the
reaction products described above to form the first mixture, or the reaction
products can be
used as the first mixture. The first mixture can be counter-currently or cross-
currently
contacted with the extraction solvent. Also, the contacting of the first
mixture with the
extraction solvent can be in a manner such that the second mixture is formed
as a static
mixture, with separation of the second mixture by decanting.
[0051] The following examples are provided to further illustrate this
invention and
are not to be considered as unduly limiting the scope of this invention.
EXAMPLES
Example I
[0052] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil) for the product mixture settled to a position below the water
phase. A 45 ml.
quantity of the raw bio-oil, separated from the product mixture, was mixed
with a 45 ml.
quantity of an un-hydrotreated bio-naphtha fraction of the bio-oil (bio-
naphtha). A 10 ml.
quantity of process water separated from the product mixture was also added to
the raw bio-
oil and bio-naphtha. A total of twenty four (24) 100 ml. samples were prepared
in this way.
The resulting samples were each mixed for around 20 seconds and placed in a
140 F water
bath for around 1 hour. Upon settling, the organic phase (blended bio-oil)
layer for each
sample was flipped and on top, with the water phase on the bottom of the
containers. The
blended bio-oil for each sample was then extracted and all extracted blended
bio-oils
combined in one container. The container was then mixed for around 20 seconds
and an
aliquot was tested for filterable solids through a 0.2 pm PVDF membrane
filter. A sample of
the raw bio-oil separated from the product mixture was also tested for
filterable solids
through a 0.2 pm PVDF membrane filter. The amount of solids in the blended
(flipped) bio-
oil was about 610 ppm (with 1220 ppm attributed to the raw bio-oil portion),
compared to
about 3,558 ppm for the un-flipped raw bio-oil.
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[0053] As can be seen from the data above, the solids content in the bio-oil
drops significantly once the oil and water layers are flipped. This provides
substantial
benefits for downstream processing of the bio-oil, such as hydrotreatment, and
significantly
reduces the cost of any subsequently required solids removal.
Example II
[0054] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil) for the product mixture settled to a position below the water
phase. A 100 ml.
quantity of the raw bio-oil, separated from the product mixture, was mixed
with a 100 ml.
quantity of an un-hydrotreated bio-naphtha fraction of the raw bio-oil.
The 200 ml. bio-
oil/bio-naphtha mixture was split into four samples. Each of the four samples
was combined
with 50 ml. quantities of process water separated from the product mixture.
Three different
demulsifier additives were added to three of the samples. The four samples
were each
mixed for around 20 seconds and placed in a 140 F water bath for around 30
minutes. The
organic phase (blended bio-oil) layer for each sample was flipped and on top,
with the water
phase on the bottom of the containers. The blended bio-oil for each sample was
then
extracted. Each of the four extracted blended bio-oils were mixed for around
20 seconds,
and aliquots of each were tested for filterable solids through a 0.2 pm PVDF
membrane
filter.
The amount of solids contained in the three blended (flipped) bio-oil samples
including desalter additives were about 205, 193, and 400 ppm; and the amount
of solids
contained in the blended (flipped) bio-oil sample not including a desalter
additive was about
492 ppm. The desalter additives used were from Champion Technologies and
designated
as XZ-1677, Code 80 and EC-1-C, respectively.
Example Ill
[0055] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil) for the product mixture settled to a position below the water
phase. A quantity
of the total product mixture was mixed with a quantity of a Light Cycle Oil
(LCO) obtained
from a crude oil refinery. The product mixture/LCO mixture was vigorously
mixed for around
30 seconds. The product mixture/LCO mixture was then centrifuged to separate
out the
blended bio-oil. The blended bio-oil, as well as a sample of the raw bio-oil
from the product
mixture, were then tested for ash content. The ash content of the blended bio-
oil was only
about 0.007 wt%, compared to about 0.146 wt% for the control raw bio-oil.
[0056] As can be seen from the data above, the ash content in the bio-oil
drops
significantly once the oil and water layers are flipped.
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Example IV
[0057] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil, pH of about 4.5) for the product mixture settled to a position
below the product
water phase (pH of about 4-5). Three separate quantities of the total product
mixture were
mixed with quantities of LCO sufficient such that the resulting organic phases
of the mixtures
contained about 5 wt%, about 10 wt%, and about 20 wt% LCO, respectively. The
density of
the product water portions of the three mixtures were also modified by adding
NaCI such that
the resulting product water for each mixture contained about 2M NaCI. For each
of the
mixtures, the organic phase (blended bio-oil) layer was flipped and on top,
with the 2M NaCI
product water phase on the bottom of the container. The density of the bio-oil
vs. percent of
LCO added is shown in Table 1 below.
TABLE 1
% LCO in blended bio-oil
0 5 10 20
Blended bio-oil
1.10 1.08 1.07 1.05
Density (g/m1)
Example V
[0058] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil, pH of about 4.5, density of about 1.095) for the product mixture
settled to a
position below the product water phase. Six separate quantities of the bio-oil
(separated
from the product water) were mixed with quantities of distilled water (pH of
about 7). NaCI
was added to five of the bio-oil/water mixtures such that the distilled water
portions
separately contained about 1M NaCI, about 2M NaCI, about 3M NaCI, about 4M
NaCI, and
about 5M NaCI, respectively. For each of the 3M, 4M, and 5M NaCI mixtures, the
organic
phase (blended bio-oil) layer was clearly flipped and on top, with the water
phase on the
bottom of the container. For the 2M NaCI mixture, the layers were mostly, but
not
completely, flipped, and the layers were not flipped for the 1M NaCI mixture.
Example VI
[0059] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil, pH of about 4.5, density of about 1.095) for the product mixture
settled to a
position below the product water phase. Six separate quantities of the bio-oil
(separated
from the product water) were mixed with quantities of distilled water (pH of
about 7). MgCl2
was added to five of the bio-oil/water mixtures such that the distilled water
portions
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separately contained about 1M MgC12, about 2M MgC12, about 3M MgC12, about 4M
MgC12,
and about 5M MgC12, respectively. For each of the 3M, 4M, and 5M MgC12
mixtures, the
organic phase (blended bio-oil) layer was clearly flipped and on top, with the
water phase on
the bottom of the container. For the 2M MgCl2 mixture, the layers were
partially flipped, and
the layers were not flipped for the 1M MgCl2 mixture.
Example VII
[0060] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil, pH of about 4.5, density of about 1.085) for the product mixture
settled to a
position below the product water phase (pH - 4-5). The product mixture was
separated into
six quantities. NaCl was added to five of the product mixture samples such
that those five
product water portions separately contained about 1M NaCl, about 2M NaCl,
about 3M
NaC1, about 4M NaC1, and about 5M NaC1, respectively. For each of the 3M, 4M,
and 5M
NaCI mixtures, the organic phase layer was clearly flipped and on top, with
the product water
phase on the bottom of the container.
Example VIII
[0061] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle. The
organic phase
(raw bio-oil) for the product mixture settled to a position below the water
phase, and had a
TAN of 6.1. A 20.1 gram quantity of ammonium bicarbonate was combined with an
82 gram
quantity of process water separated from the product mixture to form a
modified water
solution containing about 19.7 wt% ammonium bicarbonate. A 19.9 gram quantity
of the
modified water solution was combined with 91 grams of the raw bio-oil
separated from the
product mixture. The organic phase (raw bio-oil) layer was flipped and on top,
with the
modified water phase on the bottom of the container.
Example IX
[0062] Raw bio-oil was separated from a product mixture produced from the
thermo-catalytic pyrolysis of southern yellow pine wood chips. The raw bio-oil
had a TAN of
6.1; 3.2 vol% water (determined by the Karl Fischer titration method); and
5,000 ppm solids.
A quantity of the raw bio-oil was blended with a quantity of a bio-naphtha
fraction separated
from the raw bio-oil by distillation to form a 50/50 blend (by volume). The
50/50 blend
contained about 4.0 wt% BS&W (basic sediment and water). A quantity of the
50/50 blend
was centrifuged, removing a major portion of the free water and solids,
amounting to about 3
wt%, resulting in a centrifuged blend containing about 1.0 wt% BS&W. A
quantity of the
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centrifuged blend was then neutralized with a 3 wt% NaOH aqueous solution to
reduce the
TAN to about 0 (no TAN measurable). For maximum dehydration, the neutralized
blend was
also treated at 2.5 kV/inch AC electricity following addition of 100 ppm of a
demulsifier
obtained from Croda, commercially available under the trade name Croda D510.
The
resulting neutralized blend contained about 0 wt% (trace) BS&W. Each of the
50/50 blend,
the centrifuged blend, and the neutralized blend were tested for conductivity
at various
temperatures. Results of such tests are shown in Table 2 below.
TABLE 2
"As Is"
Neutralized and Electrostatically
50/50 Blend Centrifuged Blend Treated Blend
BS&W ¨4% ¨1% ¨0%
Temp. (F) Specific Conductivity (nS/m)
80 1,150,000 296,667
90 67,333
120 373,333 88,667
160 502,000 120,667
200 590,000 139,333
240 702,667 140,667
280 826,667 133,333
[0063] As can be seen from the data in Table 2, the addition of a neutralizing
base to the bio-oil/bio-naphtha blend, along with electrostatic treatment,
results in a
significant decrease in conductivity. Thus, rather than leading to an expected
increase in
conductivity, it was unexpectedly found that the addition of a base to the
system actually
reduced the conductivity.
Example X
[0064] Raw bio-oil was separated from a product mixture produced from the
thernno-catalytic pyrolysis of southern yellow pine wood chips. A quantity of
the raw bio-oil
was blended with a quantity of an un-hydrotreated bio-naphtha fraction of the
raw bio-oil to
form a 50/50 blend (by volume), which was then stirred for 1 hour at 300 RPM.
For each of
the acid treatment tests, an 80 ml quantity of the blend was mixed with 20 ml
of an aqueous
acid solution, and blended for 15 seconds. The aqueous acid solutions were
prepared by
mixing the acids into process water produced in the thermo-catalytic pyrolysis
of the wood
chips. As a control, one of the tested samples was prepared using process
water without
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added acid. The samples were placed in a 140 F water bath for 30 minutes. The
samples
were then filtered through a 0.2 pm PVDF membrane filter and tested for metals
using
inductively coupled plasma mass spectrometry (ICP-MS). The metals content
results are
shown in Table 3 below.
TABLE 3
5% 5% 5%
Raw Sulfuric Phosphoric Blank (No 5% Nitric Glycolic
Metal Bio-oil Acid Acid added Acid) Acid Acid
Al 98.5 0 1.147 8.27 0.1339
2.998
Ca 69 0.56 0.797 0.4383 0.4059
1.129
Cl 0.749 0.2386 0.3886 0.563 0.3327
0.2361
Co 0.0427 0.0705 0.1086 0.1128 0
0.0847
Cr 0.3501 0 0.0102 0 0.003
0.0063
Cu 0.1094 0 0.032 0.0556 0.0371
0.032
Fe 12.33 0.0507 0.2298 4.615 0.596
2.287
K 14.07 0.0057 0.0665 0.0096 0.0132
0.0354
Mg 20.71 0 0.0176 0.0092 0
0.012
Mn 8.44 0.2603 0.0999 0.0941 0
0.0043
Mo 0.0143 0 0.0222 0 0 0
Na 1.16 2.999 12.19 3.195 0.2063
3.083
Ni 0.1241 0.0507 0.0516 0.0395
0.0596 0.0654
P 64.3 0.3506 1.731 0.723 1.168
0.512
S 9.66 0 0 0 0 0
Si 9.68 0.0581 0.0597 0.0668 0 0
Ti 2.237 0.562 0.2747 0.809 0
0.562
/ 3.139 0 0.2057 1.468 0.0351
1.444
Zn 1.269 0.0249 0.0634 0.182 0.0126
0.2116
Total Metals 315.885 5.2311 17.4955 20.6509 3.0034
12.7028
[0065] As can be seen from the test results in Table 3, contacting bio-oil,
which
contains metals, with an aqueous acid solution including the above acids
results in a
substantial lowering of the wt% of dissolved metals in the resulting treated
bio-oil.
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Example XI
[0066] Parameters of potential extraction solvents were evaluated for use in
liquid-liquid extraction of bio-oil/water mixtures. Table 4 below sets out
certain properties of
four different solvents. As can be seen in Table 4, methyl isobutyl ketone
(MIBK) and
cyclopentyl methyl ether (CPME) have desirable properties for such liquid-
liquid extraction,
however, the use of cyclopentyl methyl ether is less desirable due to its high
cost.
TABLE 4
Parameter Ethyl Ether Ethyl Acetate MIBK CPME
Density (g/ml) 0.713 0.897 0.800 0.860
Boiling Point ( F) 94 171 241 223
Solubility in Water 6.9 8.3 1.8 1.1
(g/1 00m1)
Dipole Moment 1.15 1.78 4.2 1.27
(Debye)
Stability in Acidic Less stable, Hydrolyzes Stable Less
stable, forms
conditions forms peroxides to acetic acid peroxides
and ethanol
Commercially Yes/Limited Yes, Yes, No, Expensive
available/Cost applicability due $1850/MT $2200/MT specialty
to excess
volatility
Example XII
[0067] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected and allowed to settle into an
oil phase and a
process water phase. The process water phase was separated from the oil phase.
The
process water phase was then extracted with MIBK and produced a raffinate and
an extract.
MIBK was then separated (by distillation) from the extract which formed
recovered MIBK and
a residue which was not solid but an oily liquid material. The results for the
process water
extraction are shown in Table 5 below. The recovered MIBK quantity was 35.9
grams less
than the amount of MIBK added to the process water. It is assumed that most of
the overall
mass loss of 21.30 g was from MIBK. Assuming 21 g of MIBK were lost due to
volatility,
that leaves about 14.9 g of MIBK to account for. With a water solubility of
1.8 g/100m1, the
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amount of MIBK in the raffinate is calculated as follows:
(749.3 g water) x (1 ml/g) x (1.8g MIBK/100m1 water) 13.5 g MIBK. This leaves -
1.4 g MIBK (14.9 g -13.5 g) in the residue.
TABLE 5
Carbon Estimated
Estimated
Mass Mass in organic
pure water
Fraction each compounds
mass
fraction mass
Process Water (g) 1013.6 123.9 229.2 784.4
MIBK (g) 528.4 380.4 528.4 0
Total mass added (g) 1542.0 504.3 757.5 784.4
Raffinate (g) 924.1 74.9 174.8 749.3
Residue (g) 94.6 62.7 94.1 0.5
Recovered MIBK and volatiles 498.9 323.1 492.5 6.4
Water separated from extract (g) 3.1 0.2
3.1
Final Total (g) 1520.7 460.8 761.5 759.2
% Recovery 98.6 91.4 100.5 96.8
Mass lost (g) 21.3
[0068] As can be seen from the results in Table 5, a significant quantity of
carbon
containing compounds can be removed from the process water by extraction with
MIBK and
substantially all of the MIBK is recoverable from the process. Further
quantities of MIBK can
easily be recovered from the raffinate and/or the residue. Also, the wt% yield
of residue from
the organics present in the initial process water is calculated to be: 100 x
(94.1g - 1.4 g
MIBK) / (229.2 g organics in the process water) - 40 wt%.
Example XIII
[0069] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected. The total product mixture was
then
extracted with MIBK and produced a raffinate and an extract. MIBK was then
separated (by
distillation) from the extract which formed recovered MIBK and a residue which
was not solid
but an oily liquid material. The results for the total product mixture
extraction are shown in
Table 6 below. The recovered MIBK quantity was 78.9 grams less than the amount
of MIBK
added to the process water. It is assumed that most of the overall mass loss
of 50.9 g was
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from MIBK. Assuming 50 g of MIBK were lost due to volatility, that leaves
about 28.9 g of
MIBK to account for. With a water solubility of 1.8 g/100m1, the amount of
MIBK in the
raffinate is calculated as follows:
(677.5 g water) x (1 ml/g) x (1.8g MIBK/100m1 water) 12.2 g MIBK. This leaves -
16.7 g MIBK (28.9 g - 12.2 g) in the residue.
TABLE 6
Estimated
Carbon Mass
Mass organic Estimated pure
in each
Fraction compounds water mass
fraction
mass
Process Water (g) 906.7 110.8 205.0 701.7
Process Oil (g) 109.0 74.2 98.9 10.0
Process Water/Oil (g) 1015.6 185.0 303.9 711.7
MIBK (g) 476.8 343.3 476.8 0.0
Total mass added (g) 1492.5 528.3 780.7 711.7
Raffinate (g) 838.4 67.0 160.9 677.5
Residue (g) 177.4 128.1 176.7 0.7
Recovered MIBK and
425.8 299.6 397.9 27.9
volatiles (g)
Final Total (g) 1441.6 494.6 735.5 706.1
% Recovery 96.6 93.6 94.2 99.2
Mass lost (g) 50.9
[0070] As can be seen from the results in Table 6, a significant quantity of
carbon
containing compounds can be removed from the total product mixture by
extraction with
MIBK and substantially all of the MIBK is recoverable from the process.
Further quantities of
MIBK can easily be recovered from the raffinate and/or the residue. Also, the
wt% yield of
organics from the organics present in the initial process water portion of the
total product
mixture is calculated to be: 100 x (176.7g residue - 98.9 g organics in
process oil - 16.7 g
MIBK in residue) /(205 g organics in the process water) - 30 wt%.
Example XIV
[0071] Thermal stability of the bio-oil product is an extremely important
processing parameter, since changes in the chemical and physical composition
by thermal
stress may create chemical changes (polymerization), viscosity changes and
plugging
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issues (solids formation) in the upgrading units (such as hydrotreating
units). A high oxygen
product mixture produced from the thermo-catalytic pyrolysis of southern
yellow pine wood
chips was collected and allowed to settle, and a bio-oil stream was obtained.
Also, a portion
of the total product mixture was then extracted with MIBK and produced a
raffinate and an
extract. MIBK was then separated (by distillation) from the extract which
formed recovered
MIBK and a residue which was not solid but an oily liquid material. The
resulting bio-oil
stream and residue were separately subjected to a thermal stability study by
heating the
extracted oil in autoclave tubes, purged with Argon gas and immersed in a
heated oil bath
for 1 hr and 5 hrs, which is a more than typical residence time in heat
exchangers and
separation tanks. Table 7 shows results from the thermal stability test of the
bio-oil stream
and the residue.
TABLE 7
Bio-Oil Bio-Oil Residue
Residue
Bio-Oil
Stream Stream Residue Heated
1 Heated 5
Stream
Heated 1 hr Heated 5 hrs hr hrs
Density,
, 1.117 1.119 1.128 1.112 1.112 1.115
60 F, Wm'
Carbon, wt% 68.14 68.18 67.58 72.18 71.54 71.50
Hydrogen,
7.35 7.54 7.61 7.69 7.81 7.68
wt%
Nitrogen,
0.22 0.19 0.23 0.19 0.29 0.17
wt%
Water, wt% 9.22 8.16 7.46 0.39 0.95 1.85
Oxygen (dry
17.73 18.33 19.40 19.67 19.70 19.37
basis), wt%
TAN,
80.46 80.83 51.86 102.8 95.86 70.69
mg KOH/g
Viscosity,
110 214 621 1462 1540 2403
25 C, cP
Viscosity
94.4% 465% 5.3% 64.4%
change
[0072] As can be seen from Table 7, the % viscosity change for the MIBK
produced
residue is significantly lower than that for the bio-oil stream. This
demonstrates a significant
increase in stability for the residue over that for the typical bio-oil stream
which has not been
subjected to extraction. The initial viscosity of the residue is higher than
that for the bio-oil
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stream due to the substantial absence of water and light (C1-C4) carbon
containing
compounds which are removed during the MIBK extraction.
Example XV
[0073] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected. The total product mixture was
then
extracted with MIBK and produced a raffinate and an extract. MIBK was then
separated (by
distillation) from the extract which formed recovered MIBK and a residue which
was not solid
but an oily liquid material. The extract was then subjected to spinning/band
distillation for
separation of the residue from the MIBK. The results of such distillation are
shown in Table
8 below. The results in Table 8 demonstrate that substantially all of the MIBK
is removable
from the extract.
TABLE 8
Temp ( F) Fraction Collected % MIBK distribution
153.0 1 0.11
173.0 2 0.66
175.0 3 0.17
190.0 4 0.85
236.5 5 3.55
241.8 6 3.56
241.3 7 3.92
242.5 8 4.01
241.2 9 7.44
241.3 10 7.48
242.6 11 7.36
242.9 12 7.27
242.1 13 7.27
242.9 14 7.46
242.9 15 7.53
238.0 16 21.79
236.0 17 5.36
Residue Pot 1.62
Recovery 97.42
Example XVI
[0074] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected. The total product mixture was
then
extracted with MIBK and produced a raffinate 1 and an extract. MIBK was then
separated
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(by distillation) from the extract which formed recovered MIBK and a residue
which was not
solid but an oily liquid material. The resulting raffinate 1 was then
subjected to an extraction
with MIBK to form a raffinate 2. The resulting raffinate 2 was then subjected
to an extraction
with MIBK to form a raffinate 3. The resulting raffinate 3 was then subjected
to an extraction
with MIBK to form a raffinate 4. The results of the extractions are shown in
Table 9 below
which shows that the low molecular weight oxygenate compounds (C1-C4) such as
formaldehyde, acetaldehyde, butanone, acetic and propanoic acids and
hydroxypropanone,
are very soluble in water so they tend to stay in the water after MIBK
extraction. This is
preferred since hydrotreating such compounds would form C1-C4 alkanes that
would end up
in the gas phase. This would result in hydrogen consumption without the
benefit of
increasing renewable fuel yield.
TABLE 9
Process Water Raffinate
Compound 1 2 3 4 -
Formaldehyde, wt% 4.05 4.50 4.14 4.40
4.15
Acetaldehyde, wt% 1.28 0.88 0.56 0.53
0.38
2-Cyclopenten-1-one, wt% 0.13 0 0 0.04 0
Butanal, wt% 0.03 0.10 0 0 0
2-Butanone, wt% 0.20 0.12 0 0 0
3-Buten-2-one, wt% 0.16 0.14 0.12 0.12
0.11
F u rfu ra I , wt% 0.07 0 0 0 0
Methyl Isobutyl Ketone, wt% 0.00 2.10 1.87 1.86
1.66
Acetic Acid, wt% 5.23 4.99 3.89 3.53
2.66
Propanoic Acid, wt% 0.79 0.49 0.27 0.16 0
1-Hydroxy-2-Propanone, wt% 1.91 2.08 1.87 1.90
1.63
Example XVII
[0075] A product mixture produced from the thermo-catalytic pyrolysis of
southern yellow pine wood chips was collected. The total product mixture was
then
extracted with MIBK and produced a raffinate 1 and an extract. The resulting
raffinate 1 was
then subjected to an extraction with MIBK to form a raffinate 2. The resulting
raffinate 2 was
then subjected to an extraction with MIBK to form a raffinate 3. Each of the
extractions were
at a volume ratio of MIBK to water of 25: 75. Tables 10A-10C show partition
coefficients for
various components between the MIBK extract and the water which were
calculated for
raffinates 1 and 3 in accordance with the following: Kd = [Wt CYO] MIBK
Extract [Wt Vo] Raffinate.
Values indicated as " > 6 " or" > 5 " are due to limits of detection of the
GC/MS Analysis.
The calculated Kd values demonstrate that the lighter components such as
formaldehyde,
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acetaldehyde, acetic acid and 1-hydroxy-2-propanone preferentially stay with
the water
(raffinate).
TABLE 10A
Kd Kd
Organic Compounds
1st Extraction 3rd Extraction
Formaldehyde 0.16 0.01
Acetaldehyde 0.07 0.09
2-MethylFuran >6 >5
2-Cyclopenten-1-one 19.34 1.65
2,5-Dihydrofuran 6.00 >5
Butanal 0.58 >5
2-Butanone 3.14 7.19
Benzene >6 >5
3-Buten-2-one 1.29 0.44
2,5-Dimethyl-Furan >6 >5
Furfural 17.50 >5
2-Pentanone 10.05 8.79
Toluene >6 >5
2,3-Pentanedione 6.21 >5
5-HydroxymethylFurfural >6 >5
Methyl Isobutyl Ketone 37.83 51.33
Acetic Acid 0.68 0.67
Ethylbenzene >6 >5
(p+m)-Xylene >6 >5
Propanoic Acid 2.13 2.63
o-Xylene >6 >5
1-Hydroxy-2-Propanone 0.29 0.16
Styrene >6 >5
lsopropylbenzene >6 >5
n-Propylbenzene >6 >5
2 -Methyl - 2 - cyclope 7.50 >5
3-Ethyltoluene >6 >5
4-Ethyltoluene >6 >5
1,3,5-Trimethylbenzene >6 >5
2-Ethyltoluene >6 >5
1,2,4-Trinnethylbenzene >6 >5
Isobutyl benzene >6 >5
1,3-Benzodioxole >6 >5
Benzofuran >6 >5
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TABLE 10B
Organic Compounds Kd Icl
1 st Extraction 3rd Extraction
1,2,3-Trimethylbenzene >6 >5
Indane >6 >5
Benzaldehyde >6 >5
Indene >6 >5
Phenol 48.66 >5
2,3-Dihydrobenzofuran >6 >5
2-Methylphenol 12.08 >5
2-ethyl-Phenol >6 >5
2-methyl-Benzofuran >6 >5
2-Methylbenzaldehyde >6 >5
(p+m) Cresol 22.44 >5
2-methoxy-Phenol >6 >5
2-Methylindene >6 >5
2,5-dimethyl-Phenol >6 >5
3-ethyl-Phenol >6 >5
2,3-dimethyl-Phenol >6 >5
Naphthalene >6 >5
4-ethyl-Phenol >6 >5
3,4-dimethyl-Phenol >6 2.46
3-Methyl-1,2-benz diol 32.27 >5
2-methyl- Naphthalene >6 >5
1-methyl- Naphthalene >6 >5
1,2-Benzenediol 18.52 >5
2-Ethylnaphthalene >6 >5
4-Methyl-1,2-Benz diol 119.53 >5
,
(+/-)-1-Indanol >6 >5
Eugenol >6 >5
2,6-Dimethylnaphthalene >6 >5
4-Ethylcatechol 30.01 >5
1,3-Benzenediol >6 >5
1-Naphthalenol >6 >5
Acenaphthene >6 >5
Acenaphthylene >6 >5
1,4-Benzenediol 30.85 >5
2-Naphthalenol >6 >5
Fluorene >6 >5
2-Methyl-1-naphthol >6 >5
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TABLE 100
Kd
Organic Compounds
1st Extraction 3rd Extraction
Anthracene >6 >5
Phenanthrene >6 >5
Fluoranthene >6 >5
Pyrene >6 >5
Benz[a]anthracene >6 >5
Chrysene >6 >5
Benzo[b]fluoranthene >6 >5
Benzo[k]fluoranthene >6 >5
Benzo[a]Pyrene >6 >5
Indeno[1,2,3-cd]pyrene >6 >5
Benzo[ghi]perylene >6 >5
Dibenz[a,h]anthracene >6 >5
Levoglucosan >6 >5
Example XVIII
[0076] A low oxygen product mixture produced from the thermo-catalytic
pyrolysis of southern yellow pine wood chips was collected. The total product
mixture was
then extracted with MIBK and produced a raffinate and an extract. MIBK was
then
separated (by distillation) from the extract which formed recovered MIBK and a
residue
which was not solid but an oily liquid material.
Concentrations of volatile organic
components were measured using GC/MS for the product mixture and for the
raffinate.
Also, % C was also determined for such components. The results for the 01-04
volatile
organic components are shown in Table 11 below, and the results for the 05+
volatile
organic components are shown in Tables 12A and 12B below . In addition, the
total carbon
content of the product mixture was analyzed and found to be 3.78 wt% C. By
subtraction,
the total amount of carbon from non-volatile organic components was 0.37 wt%.
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TABLE 11
Product Mixture, Product Mixture, % Raffinate,
Raffinate,
wt% C wt% %C
Formaldehyde 0.39 0.15 0.54 0.22
Acetaldehyde 0.31 0.17 0.14 0.07
2-Cyclopenten-1-one 0.03 0.02 0.00 0.00
2-Butanone 0.02 0.01 0.00 0.00
3-Buten-2-one 0.02 0.01 0.00 0.00
Toluene 0.01 0.00 0.00 0.00
Methyl Isobutyl Ketone 0.00 0.00 2.02 1.46
Acetic Acid 2.08 0.83 2.85 1.14
(p+m)-Xylene 0.01 0.00 0.00 0.00
Propanoic Acid 0.17 0.08 0.09 0.04
1-Hydroxy-2-Propanone 0.05 0.02 0.00 0.00
Total C4- volatiles 3.09 1.29 5.64 2.93
TABLE 12A
Product Mixture, Product Mixture, % Raffinate,
Raffinate,
wt% C wt% %C
2 -Methyl - 2 - cyclope 0.01 0.01 0.00 0.00
4-Ethyltoluene 0.01 0.00 0.00 0.00
1,2,4-Trimethylbenzene 0.01 0.00 0.00 0.00
Benzofuran 0.01 0.00 0.00 0.00
Indane 0.01 0.00 0.00 0.00
Indene 0.01 0.00 0.00 0.00
Phenol 0.53 0.40 0.00 0.00
2-Methylphenol 0.15 0.12 0.00 0.00
2-ethyl-Phenol 0.01 0.01 0.00 0.00
2-methyl-Benzofuran 0.01 0.00 0.00 0.00
(p+m) Cresol 0.33 0.26 0.00 0.00
2-Methylindene 0.01 0.00 0.00 0.00
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TABLE 12B
Product Mixture, Product Mixture, `)/0 Raffinate,
Raffinate,
wt% C wt% %C
2,5-dinnethyl-Phenol 0.07 0.06 0.00 0.00
3-ethyl-Phenol 0.01 0.01 0.00 0.00
2,3-dimethyl-Phenol 0.01 0.00 0.00 0.00
Naphthalene 0.01 0.00 0.00 0.00
4-ethyl-Phenol 0.04 0.03 0.00 0.00
3,4-dimethyl-Phenol 0.02 0.01 0.00 0.00
3-Methyl-1,2-benz diol 0.16 0.10 0.00 0.00
2-methyl- Naphthalene 0.03 0.02 0.00 0.00
1,2-Benzenediol 0.87 0.57 0.00 0.00
2-Ethylnaphthalene 0.01 0.00 0.00 0.00
4-Methyl-1,2-Benz diol 0.25 0.17 0.00 0.00
2,6-Dimethylnaphthalene 0.03 0.02 0.00 0.00
4-Ethylcatechol 0.09 0.06 0.00 0.00
1,3-Benzenediol 0.03 0.02 0.00 0.00
1,4-Benzenediol 0.15 0.10 0.00 0.00
2-Naphthalenol 0.02 0.02 0.00 0.00
2,2-Bifuran 0.04 0.03 0.00 0.00
Methacrolein 0.00 0.00 0.00 0.00
3-Pentanone 0.00 0.00 0.00 0.00
2,5-Dihydrotoluene 0.00 0.00 0.00 0.00
3-Penten-2-one 0.00 0.00 0.00 0.00
Cyclopentanone 0.00 0.00 0.00 0.00
Benzofuran, 7-methyl 0.01 0.00 0.00 0.00
1-Methylindene 0.01 0.01 0.00 0.00
1H-Indenol 0.08 0.07 0.00 0.00
Penten-3-one 0.00 0.00 0.00 0.00
1,3-Dimethylindene 0.01 0.00 0.00 0.00
2-Ethyl-5-methylphenol 0.03 0.02 0.00 0.00
Retene 0.01 0.00 0.00 0.00
Total C5+ volatiles 3.09 2.12 0.00 0.00
Total volatiles 6.18 3.41 5.64 2.93
[0077] As can be seen in Tables 11, 12A and 12B the data show that extraction
of a biomass derived product mixture with MIBK is effective in removing C5+
volatile organic
components from water. Specifically, while the product mixture contained 2.12
wt% C from
C5+ organic volatiles, the raffinate contained at or near 0 wt% C from C5+
organic volatiles
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showing clear partitioning from the water phase to the oil phase. Also, the
wt% C from C1-
C4 volatile organic components is concentrated in the raffinate at 2.93 wt% as
compared to
only 1.29 wt% in the initial product mixture.
[0078] While the technology has been particularly shown and described with
reference to specific embodiments, it should be understood by those skilled in
the art that
various changes in form and detail may be made without departing from the
spirit and scope
of the technology as defined by the appended claims.
