U.S. patent application number 14/904075 was filed with the patent office on 2016-06-16 for upgrading of bio-oil by reaction with olefins in the presence of a catalyst.
The applicant listed for this patent is BATTELLE MEMORIAL INSTITUTE. Invention is credited to Zia Abdullah, Herman P. Benecke, Daniel B. Garbark, Rachid Taha.
Application Number | 20160168475 14/904075 |
Document ID | / |
Family ID | 51263498 |
Filed Date | 2016-06-16 |
United States Patent
Application |
20160168475 |
Kind Code |
A1 |
Abdullah; Zia ; et
al. |
June 16, 2016 |
Upgrading of Bio-Oil by Reaction with Olefins in the Presence of a
Catalyst
Abstract
Systems, methods, and apparatuses are provided for upgrading a
bio-oil by reaction with an olefin in the presence of a catalyst.
For example, upgraded bio-oil may have improved miscibility with
hydrophobic fuels.
Inventors: |
Abdullah; Zia; (Columbus,
OH) ; Benecke; Herman P.; (Columbus, OH) ;
Garbark; Daniel B.; (Blacklick, OH) ; Taha;
Rachid; (Dublin, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BATTELLE MEMORIAL INSTITUTE |
Columbus |
OH |
US |
|
|
Family ID: |
51263498 |
Appl. No.: |
14/904075 |
Filed: |
July 8, 2014 |
PCT Filed: |
July 8, 2014 |
PCT NO: |
PCT/US2014/045662 |
371 Date: |
January 8, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61843449 |
Jul 8, 2013 |
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61861027 |
Aug 1, 2013 |
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Current U.S.
Class: |
44/451 ; 44/300;
585/14; 585/16; 585/240; 585/310; 585/317; 585/319; 585/324;
585/357; 585/469; 585/638; 585/733 |
Current CPC
Class: |
C10G 2300/80 20130101;
C10L 1/1822 20130101; C10G 1/02 20130101; C10G 3/44 20130101; C10G
2300/1092 20130101; C10L 2200/0469 20130101; C10G 1/002 20130101;
C10L 1/02 20130101; C10L 2290/02 20130101; C10G 3/52 20130101; C10L
2290/24 20130101; Y02P 30/20 20151101; C10G 3/42 20130101 |
International
Class: |
C10G 3/00 20060101
C10G003/00; C10L 1/182 20060101 C10L001/182; C10L 1/02 20060101
C10L001/02; C10G 1/02 20060101 C10G001/02; C10G 1/00 20060101
C10G001/00 |
Claims
1. A method for upgrading a bio-oil, the method comprising
contacting the bio-oil with an olefin in the presence of a catalyst
to form an upgraded bio-oil, the upgraded bio-oil comprising,
compared to the bio-oil, one or more of: a reduced hydroxyl value;
a reduced acid value; a reduced polarity; a reduced miscibility in
a polar solvent; a reduced oxygen concentration, a reduced water
concentration; or an increased average molecular weight.
2. The method of claim 1, further comprising pyrolyzing a biomass
to form the bio-oil prior to contacting the bio-oil with the olefin
in the presence of the catalyst.
3. The method of claim 1, the olefin comprising a C.sub.3-C.sub.5
alkene.
4. The method of claim 1, the olefin comprising one or more of:
propylene, isobutylene, or isoprene.
5. The method of claim 1, further comprising contacting the bio-oil
with a hydrogen donor.
6. The method of claim 5, the hydrogen donor comprising a
C.sub.1-C.sub.10 aliphatic compound that comprises at least one
hydroxyl group bonded to an alkyl carbon.
7. The method of claim 1, further comprising contacting the bio-oil
with at least one of: a C.sub.3-C.sub.5 alcohol, a C.sub.3-C.sub.5
diol, or a C.sub.3-C.sub.5 triol.
8. The method of claim 1, the catalyst comprising one or more of: a
solid acid catalyst, a transition metal catalyst, a liquid phase
acid catalyst, or a vapor phase acid catalyst.
9. The method of claim 1, the catalyst comprising a supported
propylsulfonic acid.
10. The method of claim 1, the bio-oil being at least partially in
a vapor phase.
11. A method for upgrading bio-oil in a vapor phase, the method
comprising: providing a vapor phase bio-oil; and contacting the
vapor phase bio-oil with an olefin in the presence of a catalyst to
provide an upgraded bio-oil.
12. The method of claim 11, the upgraded bio-oil comprising,
compared to the bio-oil, one or more of: a reduced hydroxyl value;
a reduced acid value; a reduced polarity; a reduced miscibility in
a polar solvent; a reduced oxygen concentration, a reduced water
concentration; or an increased average molecular weight.
13. The method of claim 11, further comprising: mixing the vapor
phase bio-oil with the olefin in gas or vapor form to provide a
vapor phase mixture of bio-oil and olefin; and contacting the vapor
phase mixture of bio-oil and olefin to the catalyst to provide the
upgraded bio-oil.
14. The method of claim 11, conducted as a continuous process.
15. The method of claim 11, the providing the vapor phase bio-oil
comprising pyrolyzing a biomass to form the vapor phase
bio-oil.
16. The method of claim 11, the olefin comprising a C.sub.3-C.sub.5
alkene.
17. The method of claim 11, the olefin comprising one or more of
propylene, isobutylene, or isoprene.
18. The method of claim 11, the catalyst comprising one or more of:
a solid acid catalyst, a transition metal catalyst, a liquid phase
acid catalyst, or a vapor phase acid catalyst.
19. The method of claim 11, the catalyst comprising a supported
propylsulfonic acid.
20. The method of claim 11, the vapor phase bio-oil comprising
water, further comprising separating an alcohol from the upgraded
bio-oil, the alcohol produced by contacting the vapor phase bio-oil
comprising water with the olefin in the presence of the
catalyst.
21. A process for converting a pyrolysis oil to one or more
hydrocarbon fuel range products, the process comprising: (a)
reacting a pyrolysis oil with a feed comprising an olefin in the
presence of a catalyst to form a product mixture comprising at
least one of an esterification product and an etherification
product; and (b) contacting the at least one of the esterification
product and the etherification product in a reaction zone with a
hydrotreating catalyst in the presence of hydrogen under reaction
conditions sufficient to convert at least a portion of the at least
one of the esterification product and the etherification product
into one or more fuel range hydrocarbon products.
22. The process of claim 21, further comprising pyrolyzing a
biomass to form the pyrolysis oil prior to reacting the pyrolysis
oil with the feed comprising the olefin in the presence of the
catalyst.
23. The process of claim 21, wherein the olefin comprises a
C.sub.3-C.sub.5 alkene.
24. The process of claim 21, the olefin comprising one or more of
propylene, isobutylene, or isoprene.
25. The process of claim 21, further comprising contacting the
pyrolysis oil with a hydrogen donor.
26. The process of claim 25, the hydrogen donor comprising one or
more of: a C.sub.1-C.sub.10 aliphatic compound that comprises at
least one hydroxyl group bonded to an alkyl carbon.
27. The process of claim 21, further comprising contacting the
pyrolysis oil with at least one of: a C.sub.3-C.sub.5 alcohol, a
C.sub.3-C.sub.5 diol, or a C.sub.3-C.sub.5 triol.
28. The process of claim 21, the catalyst comprising one or more
of: a solid acid catalyst, a transition metal catalyst, a liquid
phase acid catalyst, or a vapor phase acid catalyst.
29. The process of claim 21, wherein the catalyst comprises a
supported propylsulfonic acid.
30. The process of claim 21, wherein the pyrolysis oil is at least
partially in a vapor phase.
31. The process of claim 21, wherein the hydrotreating catalyst
comprises one or more catalysts selected from the group consisting
of: cobalt (Co), molybdenum (Mo), nickel (Ni), titanium (Ti),
tungsten (W), zinc (Zn), antimony (Sb), bismuth (Bi), cerium (Ce),
vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), manganese
(Mn), rhenium (Re), iron (Fe), platinum (Pt), iridium (Ir),
palladium (Pd), osmium (Os), rhodium (Rh), ruthenium (Ru), nickel,
copper impregnated zinc oxide (Cu/ZnO), copper impregnated chromium
oxide (Cu/Cr), nickel aluminum oxide (Ni/Al.sub.2O.sub.3),
palladium aluminum oxide (PdAl.sub.2O.sub.3), cobalt molybdenum
(CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten
(NiMoW), sulfided cobalt molybdenum (CoMo), sulfided nickel
molybdenum (NiMo), and a metal carbide; or a composite or
combination thereof.
32. The process of claim 21, wherein the hydrotreating catalyst
comprises: a) a metal oxide support selected from the group
consisting of a titanium oxide (TiO.sub.2) support, a silicon oxide
support, a zirconia oxide (ZrO.sub.2) support, a niobium oxide
(Nb.sub.2O.sub.5) support, and a support comprising one or more
mixtures of non-alumina metal oxides; and b) a noble metal
composition on the metal oxide support, the noble metal composition
comprising one or more noble metals selected from the group
consisting of: rhodium (Rh), palladium (Pd), gold (Au), and
ruthenium (Ru).
33. An upgraded bio-oil, the upgraded bio-oil produced by a process
comprising contacting a crude bio-oil with an olefin in the
presence of a catalyst to form the upgraded bio-oil, the upgraded
bio-oil comprising, compared to the crude bio-oil, one or more of:
a reduced hydroxyl value; a reduced acid value; a reduced polarity;
a reduced miscibility in a polar solvent; a reduced oxygen
concentration, a reduced water concentration; or an increased
average molecular weight.
34. An upgraded bio-oil, the upgraded bio-oil produced by a process
comprising: providing a vapor phase bio-oil; and contacting the
vapor phase bio-oil with an olefin in the presence of a catalyst to
provide the upgraded bio-oil.
35. A composition comprising one or more hydrocarbon fuel range
products, the mixture of one or more hydrocarbon fuel range
products produced from a pyrolysis oil by a process comprising: (a)
reacting the pyrolysis oil with a feed comprising an olefin in the
presence of a catalyst to form a product mixture comprising at
least one of an esterification product and an etherification
product; and (b) contacting the at least one of the esterification
product and the etherification product in a reaction zone with a
hydrotreating catalyst in the presence of hydrogen under reaction
conditions sufficient to convert at least a portion of the at least
one of the esterification product and the etherification product
into the mixture of the one or more fuel range hydrocarbon
products.
36. A method 800 of improving miscibility of a bio-oil in a
hydrophobic fuel, comprising: 802 providing a miscible bio-oil, the
miscible bio-oil being upgraded, catalytic, or upgraded and
catalytic compared to a starting material bio-oil; and 804
contacting the miscible bio-oil to a hydrophobic fuel to form a
miscible mixture, the miscible bio-oil being characterized by
greater miscibility in the hydrophobic fuel compared to the bio-oil
starting material.
37. The method of claim 36, further comprising contacting an
alcohol to the miscible bio-oil and the hydrophobic fuel to form
the miscible mixture.
38. The method of claim 37, the alcohol including a C.sub.3-C.sub.5
alcohol.
39. The method of claim 37, the alcohol including one or more of
n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or
2-propanol.
40. The method of claim 36, further comprising contacting a
surfactant to the miscible bio-oil and the hydrophobic fuel to form
the miscible mixture.
41. The method of claim 40, the surfactant including one or more of
an anionic surfactant, a cationic surfactant, an amphiphilic
surfactant, or a nonionic surfactant.
42. The method of claim 36, further comprising contacting a
surfactant and an alcohol to the miscible bio-oil and the
hydrophobic fuel to form the miscible mixture.
43. The method of claim 36, including upgrading the bio-oil
starting material to provide the miscible bio-oil by one or more
of: contacting the bio-oil starting material with an olefin in the
presence of a solid acid catalyst to provide the miscible bio-oil;
or contacting the bio-oil starting material with the olefin in a
vapor phase in the presence of a catalyst to provide the miscible
bio-oil, the miscible bio-oil being reduced in one or more of a
hydroxyl value, an acid value, or a water concentration compared to
the bio-oil starting material.
44. The method of claim 36, the hydrophobic fuel including one or
more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet
fuel, kerosene, white gas, liquefied coal fuel, or naphtha.
45. The method of claim 36, the bio-oil starting material including
one or more of: water, organic acids, aldehydes, alkyl hydroxyls,
phenols, or sugars.
46. A bio-oil composition, comprising a miscible ternary mixture
according to each triplet of miscible or partly miscible ranges in
any one of FIG. 7A, 7B, 7C, or 7D, or a combination thereof,
including: a bio-oil, an upgraded bio-oil, a catalytic bio-oil, or
an upgraded catalytic bio-oil in a percentage according to each
corresponding range; an alcohol in a percentage according to each
corresponding range of 1-butanol; and a hydrophobic fuel in a
percentage according to each corresponding range of diesel.
47. The bio-oil composition of claim 46, the miscible ternary
mixture being according to each triplet of miscible or partly
miscible ranges in any one of FIG. 7B, 7C, or 7D, or a combination
thereof.
48. The bio-oil composition of claim 46, at least one said
percentage being within the corresponding miscible percentage
range.
49. The bio-oil composition of claim 46, each said corresponding
percentage range being within each corresponding miscible
percentage range.
50. The bio-oil composition of claim 46, consisting substantially
of the miscible ternary mixture.
51. The bio-oil composition of claim 46, consisting essentially of
the miscible ternary mixture.
52. The bio-oil composition of claim 46, the alcohol including a
C.sub.3-C.sub.5 alcohol.
53. The bio-oil composition of claim 46, the alcohol including one
or more of n-butanol, sec-butanol, iso-butanol, tert-butanol,
n-propanol, or 2-propanol.
54. The bio-oil composition of claim 46, the hydrophobic fuel
including one or more of: diesel, fuel oil, heating oil, bunker
fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel,
or naphtha.
55. The bio-oil composition of claim 46, further comprising a
surfactant.
56. The bio-oil composition of claim 46, further comprising one or
more of an anionic surfactant, a cationic surfactant, an
amphiphilic surfactant, or a nonionic surfactant.
57. The bio-oil composition of claim 46, the miscible bio-oil being
prepared from a bio-oil starting material in a process including
one or more of: contacting the bio-oil starting material with an
olefin in the presence of a solid acid catalyst to provide the
miscible bio-oil; or contacting the bio-oil starting material with
the olefin in a vapor phase in the presence of a catalyst to
provide the miscible bio-oil, the miscible bio-oil being reduced in
one or more of a hydroxyl value, an acid value, and a water
concentration compared to the bio-oil starting material.
Description
[0001] This application claims priority from U.S. Provisional
Patent Application Nos. 61/843,449, filed on Jul. 8, 2013, and
61/861,027, filed Aug. 1, 2013, each of which are entirely
incorporated herein by reference.
BACKGROUND
[0002] The extraction of bio-oil from biomass for use as a biofuel
is an area of interest in the search for reliable alternative
energy sources. Biomass such as, for example, lignocellulosic
substances (e.g., wood), may be subjected to pyrolysis to create a
hot pyrolysis vapor. Bio-oil may be extracted from the hot
pyrolysis vapor. Bio-oil from pyrolysis of wood may contain a
mixture of water, organic acids, aldehydes, phenols, and sugar
derivatives. Bio-oil from pyrolysis of wood may be characterized by
undesirably or unacceptably high hydroxyl value, acid value, or
water concentration. For example, mixtures may exhibit varying
degrees of miscibility/immiscibility with other fuels, particularly
in view of the combination of hydrophobic oil characteristics with
hydrophilic species such as water, organic acids, etc.
Consequently, high hydroxyl value, acid value, and water
concentration may be detrimental, for example, to fuel value, fuel
miscibility, and thermal stability.
[0003] The present application appreciates that extraction of
bio-oil from biomass for use as a biofuel may be a challenging
endeavor.
SUMMARY
[0004] In an embodiment, a method for upgrading a bio-oil is
provided. The method may include contacting the bio-oil with an
olefin in the presence of a catalyst. Compared to the bio-oil, the
upgraded bio-oil may include one or more of: a reduced hydroxyl
value; a reduced acid value; a reduced polarity; a reduced
miscibility in a polar solvent; a reduced oxygen concentration, a
reduced water concentration; or an increased average molecular
weight.
[0005] In an embodiment, a method for upgrading a bio-oil in a
vapor phase is provided. The method may include providing a vapor
phase bio-oil. The method may also include contacting the vapor
phase bio-oil with an olefin in the presence of a catalyst to
provide an upgraded bio-oil.
[0006] In an embodiment, a process for converting pyrolysis oil to
a hydrocarbon fuel is provided. The process may include reacting a
pyrolysis oil in a reactor with a feed in the presence of a
catalyst. The feed may include one or more olefin species. A
product mixture may be formed including at least one of an
esterification and an etherification product. The process may also
include contacting the at least one of the esterification and the
etherification product in a reaction zone with a hydrotreating
catalyst in the presence of hydrogen. The process in the reaction
zone may be conducted under reaction conditions sufficient to
convert at least a portion of the at least one of the
esterification and the etherification product into one or more fuel
range hydrocarbon products.
[0007] In an embodiment, an upgraded bio-oil is provided. The
upgraded bio-oil may be produced by a process including contacting
a crude bio-oil with an olefin in the presence of a catalyst to
form the upgraded bio-oil. The upgraded bio-oil may be
characterized compared to the crude bio-oil by one or more of: a
reduced hydroxyl value; a reduced acid value; a reduced polarity; a
reduced miscibility in a polar solvent; a reduced oxygen
concentration, a reduced water concentration; or an increased
average molecular weight.
[0008] In an embodiment, a composition including one or more
hydrocarbon fuel range products is provided. The mixture of one or
more hydrocarbon fuel range products may be produced from a
pyrolysis oil by a process. The process may include reacting the
pyrolysis oil with a feed including an olefin in the presence of a
catalyst. A product mixture may be formed including at least one of
an esterification product and an etherification product. The
process may also include contacting the at least one of the
esterification product and the etherification product in a reaction
zone with a hydrotreating catalyst in the presence of hydrogen. The
process in the reaction zone may be conducted under reaction
conditions sufficient to convert at least a portion of the at least
one of the esterification product and the etherification product
into the mixture of the one or more fuel range hydrocarbon
products.
[0009] In an embodiment, a method of improving miscibility of a
bio-oil in a hydrophobic fuel is provided. The method may include
providing a miscible bio-oil. The miscible bio-oil may be upgraded,
catalytic, or upgraded and catalytic compared to a starting
material bio-oil. The method may also include contacting the
miscible bio-oil to a hydrophobic fuel to form a miscible mixture.
The miscible bio-oil may be characterized by greater miscibility in
the hydrophobic fuel compared to the bio-oil starting material.
[0010] In various embodiments, a bio-oil composition is provided.
The bio-oil composition may include a miscible ternary mixture. The
miscible ternary mixture may be composed according to each triplet
of miscible or partly miscible ranges in any one of FIG. 7A, 7B,
7C, or 7D, or a combination thereof. The miscible ternary mixture
may include a bio-oil, an upgraded (modified) bio-oil, a catalytic
bio-oil, or an upgraded and catalytic bio-oil in a percentage
according to each corresponding range in FIG. 7A, 7B, 7C, or 7D.
The miscible ternary mixture may include an alcohol in a percentage
according to each corresponding range of 1-butanol in FIG. 7A, 7B,
7C, or 7D. The miscible ternary mixture may include a hydrophobic
fuel in a percentage according to each corresponding range of
diesel in FIG. 7A, 7B, 7C, or 7D.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying FIGs., which are incorporated in and
constitute a part of the specification, illustrate example methods,
and are used merely to illustrate an example embodiment.
[0012] FIG. 1 is a chemical scheme showing that acidity may be
reduced by esterification with an alcohol or an olefin;
[0013] FIG. 2 is a chemical scheme showing reduced hydroxyl value
by acetalization of hydroxyls with aldehyde;
[0014] FIG. 3 is a chemical scheme showing reduced hydroxyl value
by etherification of hydroxyls with olefin;
[0015] FIG. 4 is a flow diagram of a method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil;
[0016] FIG. 5 is a flow diagram of a method for upgrading a bio-oil
in a vapor phase;
[0017] FIG. 6 is a flow diagram of a process for converting a
pyrolysis oil to one or more hydrocarbon fuel range products;
[0018] FIG. 7A is an example ternary phase diagram summarizing
miscibility results versus proportions of diesel fuel, 1-butanol,
and bio-oil of Example 5;
[0019] FIG. 7B is an example ternary phase diagram summarizing
miscibility results versus proportions of diesel fuel, 1-butanol,
and modified catalytic bio-oil of Example 6;
[0020] FIG. 7C is an example ternary phase diagram summarizing
miscibility results versus proportions of diesel fuel, 1-butanol,
and modified bio-oil of Example 7;
[0021] FIG. 7D is an example ternary phase diagram summarizing
miscibility results versus proportions of diesel fuel, 1-butanol,
and catalytic bio-oil;
[0022] FIG. 8 is a flow diagram of an example method of improving
miscibility of a bio-oil in a hydrophobic fuel.
DETAILED DESCRIPTION
[0023] Bio-oil may be obtained from the pyrolysis of various woods.
The resulting bio-oil may contain a mixture of organic acids,
aldehydes, phenols, and sugar derivatives that may be detrimental
to fuel value, fuel miscibility, and thermal stability. Producing
bio-oil by pyrolysis may also produce significant amounts of water.
These characteristics may be improved through the reaction of
acids, phenols, and sugar with olefins to form other compounds such
as alcohols, ethers, and esters.
[0024] Briefly described, in an aspect of the invention, a method
of bio-oil upgrading may increase bio-oil solubility in fuels such
as diesel and may reduce undesirable attributes of bio-oil. The
method may include reacting the bio-oil with olefins in the
presence of a catalyst. The method may independently or
collectively remove water, etherify hydroxyls, and/or esterify
carboxylic acids.
[0025] Briefly described, in another aspect of the present
invention, a method for upgrading bio-oil may include passing vapor
phase bio-oil through a catalyst bed after mixing with an injected
amount of olefin and reacting to upgrade the vapor phase bio-oil.
For example, at least a portion of hydroxyls in the vapor phase
bio-oil may become ethers. In another example, at least a portion
of carboxylic acids in the vapor phase bio-oil may become esters.
In a further example, at least a portion of water present in the
vapor phase bio-oil may be converted to an alcohol form of the
olefin. Benefits of the method for upgrading vapor phase bio-oil
may include lower equipment costs and/or faster reactions due to
increased temperatures. Although water may be undesirable at high
amounts, alcohol produced by reacting the water with the olefin at
the catalyst may be purified to provide a higher value
material.
[0026] FIG. 1 is a chemical scheme showing that acidity may be
reduced by esterification with an alcohol or an olefin. A common
problem with bio-oil may be acidity from carboxylic acids such as
acetic acid. Esterification, as shown in FIG. 1, may remove the
acidity and may also maintain bio-oil mass. Esterification of a
carboxylic acid with an alcohol may include the use of heat over
extended time in order to remove water and shift the reaction
equilibrium toward the ester. Furthermore, bio-oil may contain
various sugars, and heating under acidic conditions may cause
caramelization to occur. Esterification by reaction of carboxylic
acids with an olefin according to the described method may be
favorable, for example, because energetically costly water removal
may be omitted and caramelization may be avoided or reduced.
[0027] FIG. 2 is a chemical scheme showing reduced hydroxyl value
by acetalization of hydroxyls with aldehyde. Hydroxyls originating
from the breakdown of cellulose into sugars may be problematic in
bio-oil. The process depicted in FIG. 2 shows the reaction of
1,2-diols or 1,3-diols with an aldehyde to form an acetal plus
water. The reaction of FIG. 2 may be favored by removing water from
the reaction mixture. However, the reaction of FIG. 2 may not
remove any acidity and may also be associated with energetically
costly water removal.
[0028] FIG. 3 depicts reduced hydroxyl value by etherification of
hydroxyls with olefin The reaction of FIG. 3 may be water
independent and may therefore be favorable compared to the reaction
of FIG. 2. One reaction not specified above involves the acid
catalyzed reaction of olefins with water to initially form alcohols
that may react further with water to form dialkyl ethers. This
reaction removes water from the bio-oil reaction mixtures that
advantageously results in reduced hydrolysis of esters back to
carboxylic acids. Another reaction not specified above is the
acid-catalyzed addition of water to olefins to form alcohols, thus
reducing the bio-oil content and reducing ester and acetal
hydrolysis. For example, 2-propanol is produced by the reaction of
propylene with water over a resin acid catalyst. This may make the
olefin reaction more favorable as it may react with various
non-desired attributes of bio-oil, e.g., free hydroxyls, carboxyls,
water, and the like.
[0029] FIG. 4 is a flow diagram of a method 400 for upgrading a
bio-oil. The method 400 may include 402 contacting the bio-oil with
an olefin in the presence of a catalyst to 404 form the upgraded
bio-oil. Compared to the bio-oil, the upgraded bio-oil may include
one or more of: a reduced hydroxyl value; a reduced acid value; a
reduced polarity; a reduced miscibility in a polar solvent; a
reduced oxygen concentration, a reduced water concentration; or an
increased average molecular weight. The catalyst may cause a
reaction between the olefin and one or more components of the
bio-oil, such as a hydroxyl group, a carboxylic acid group, and the
water. The reaction may be a vapor phase catalytic reaction.
[0030] As used herein, the catalyst may be a solid, liquid, or
vapor composition that catalyzes the reaction between the bio-oil
and the olefin. For example, the catalyst may include one or more
of a solid catalyst such as a solid acid catalyst, a transition
metal catalyst including metal oxides and organometallic complexes,
and the like. The catalyst may be in liquid or vapor form, such as
liquid or vapor HCl or H.sub.2SO.sub.4. In some embodiments, the
catalyst may include a solid resin acid catalyst, such as supported
propylsulfonic acid.
[0031] In some embodiments of the method for reducing at least one
of a hydroxyl value, an acid value, and a water concentration in a
bio-oil, the method may include pyrolyzing a biomass to form the
bio-oil. The pyrolyzing the biomass to form the bio-oil may be
conducted prior to contacting the bio-oil with the olefin in the
presence of the catalyst.
[0032] In several embodiments of the method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, the olefin may include a C.sub.3-C.sub.5 alkene. As
used herein, a C.sub.3-C.sub.5 alkene may include a linear,
branched or cyclic alkylene compound that includes at least one
carbon-carbon double bond, e.g., propylene, 2-methylpropene
(isobutylene), 1-butene, 2-butene, 1,3 butadiene, 2-methyl-1,3
butadiene (isoprene), cyclopropene, cyclobutene, cyclopentene,
cyclopentadiene, or the like. For example, the olefin may include
at least one of propylene, isobutylene, and isoprene.
[0033] In various embodiments of the method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, the method may include contacting the bio-oil with a
hydrogen donor, e.g., the hydrogen donor described herein.
[0034] In various embodiments, the olefin may be fed alone to the
reaction. The olefin may also be fed to the reaction in combination
with the hydrogen donor. The olefin and hydrogen donor may be
independently fed to the reaction. The olefin and/or hydrogen donor
may be fed to the reaction in any stage, for example: in
combination with biomass, during pyrolysis of biomass to provide
the bio-oil, directly to the reaction at the catalyst, after
reaction at the catalyst, after bio-oil condensation, and the
like.
[0035] In several embodiments of the method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, the bio-oil may be at least partially in a vapor
phase. In some embodiments, the bio-oil may be substantially or
completely in the vapor phase. The bio-oil may contain water. The
water may be, independently or together with the bio-oil, at least
partially, substantially, or completely in the vapor phase.
[0036] FIG. 5 is a flow diagram of a method 500 for upgrading a
bio-oil in a vapor phase. The method 500 may include 502 providing
a vapor phase bio-oil. The method 500 may also include 504
contacting the vapor phase bio-oil with an olefin in the presence
of a catalyst to provide an upgraded bio-oil. The catalyst may
cause a reaction between the olefin and one or more components of
the bio-oil, such as a hydroxyl group, a carboxylic acid group, and
the water. The reaction may be a vapor phase catalytic
reaction.
[0037] In various embodiments, the method for upgrading a bio-oil
in a vapor phase may include mixing the vapor phase bio-oil with
the olefin in gas or vapor form to provide a vapor phase mixture of
bio-oil and olefin. The method may also include contacting the
vapor phase mixture of bio-oil and olefin to the catalyst to
provide the upgraded bio-oil.
[0038] In some embodiments, the method for upgrading a bio-oil in a
vapor phase may be conducted as a continuous process or a batch
process.
[0039] In several embodiments, the method for upgrading a bio-oil
in a vapor phase, providing the vapor phase bio-oil may include
pyrolyzing a biomass to form the vapor phase bio-oil.
[0040] In various embodiments, the olefin may include a
C.sub.3-C.sub.5 alkene as described herein.
[0041] In various embodiments of the method for upgrading a bio-oil
in a vapor phase, the method may include contacting the bio-oil
with a hydrogen donor. As used herein, the hydrogen donor may
include a C.sub.1-C.sub.10 aliphatic compound that includes at
least one hydroxyl group bonded to an alkyl carbon. For example,
the hydrogen donor may include a C.sub.1-C.sub.10 linear, branched,
or cyclic aliphatic compound that includes a hydroxyl group bonded
to an alkyl carbon, such as an alcohol, a polyol such as a diol,
and the like. For example, the method may include contacting the
bio-oil with a C.sub.3-C.sub.5 alcohol. The C.sub.3-C.sub.5 alcohol
may include, for example, 1-propanol, 2-propanol, 1-butanol,
2-butanol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol,
2-pentanol, cyclopropanol, cyclobutanol, cyclopentanol, or the
like. The hydrogen donor may also include diols such as ethylene
glycol, propylene glycol, and the like. The hydrogen donor may also
include higher polyols such as triols including glycerol, and the
like. In some embodiments, the hydrogen donor may include at least
one of a C.sub.3-C.sub.5 alcohol, a C.sub.3-C.sub.5 diol, or a
C.sub.3-C.sub.5 triol.
[0042] In various embodiments, the olefin may be fed alone to the
reaction. The olefin may also be fed to the reaction in combination
with the hydrogen donor. The olefin and hydrogen donor may be
independently fed to the reaction. The olefin and/or hydrogen donor
may be fed to the reaction in any stage, for example: in
combination with biomass, during pyrolysis of biomass to provide
the bio-oil, directly to the reaction at the catalyst, after
reaction at the catalyst, after upgraded bio-oil condensation, and
the like.
[0043] In some embodiments, the method for upgrading a bio-oil in a
vapor phase using a catalyst may include any catalyst described
herein. For example, the method for upgrading a bio-oil in a vapor
phase may include using a supported propylsulfonic acid.
[0044] In several embodiments, the method for upgrading a bio-oil
in a vapor phase, the vapor phase bio-oil may include water. The
method may also include separating an alcohol from the upgraded
bio-oil. The alcohol may be produced by contacting the vapor phase
bio-oil including water with the olefin in the presence of the
catalyst.
[0045] In various embodiments, an upgraded bio-oil is provided. In
some embodiments, the upgraded bio-oil may be produced by a process
including contacting a crude bio-oil with an olefin in the presence
of a catalyst to form the upgraded bio-oil. The upgraded bio-oil
may be characterized compared to the crude bio-oil by one or more
of: a lower hydroxyl value; a lower acid value; lower polarity;
lower miscibility in a polar solvent, such as water; lower oxygen
concentration, e.g, measured via elemental analysis; different
molecular weight or molecular weight distribution, e.g., higher
molecular weight; or a lower water concentration. In several
embodiments, the upgraded bio-oil may be produced by a process
including providing a vapor phase bio-oil. The process may also
include contacting the vapor phase bio-oil with an olefin in the
presence of a catalyst to provide an upgraded bio-oil. In various
embodiments, the process for producing the upgraded bio-oil may
include any subject matter described for the various methods
herein.
[0046] FIG. 6 is a flow diagram of a process 600 for converting a
pyrolysis oil to one or more hydrocarbon fuel range products. The
process may include 602 reacting a pyrolysis oil with a feed
including an olefin in the presence of a catalyst. The process may
604 form a product mixture including at least one of an
esterification product and an etherification product. The process
may also include 606 contacting the at least one of the
esterification product and the etherification product in a reaction
zone with a hydrotreating catalyst in the presence of hydrogen. The
process may be conducted in the reaction zone under reaction
conditions sufficient to convert at least a portion of the at least
one of the esterification product and the etherification product
into one or more fuel range hydrocarbon products.
[0047] In some embodiments, the process for converting the
pyrolysis oil to one or more hydrocarbon fuel range products may
include pyrolyzing a biomass to form the pyrolysis oil. The
pyrolyzing the biomass to form the pyrolysis oil may be conducted
prior to reacting the pyrolysis oil with the feed including the
olefin in the presence of the catalyst.
[0048] In several embodiments of the process for converting the
pyrolysis oil to one or more hydrocarbon fuel range products, the
olefin may include a C.sub.3-C.sub.5 alkene as described herein.
For example, the olefin may include at least one of propylene,
isobutylene, and isoprene.
[0049] In various embodiments, the process for converting the
pyrolysis oil to one or more hydrocarbon fuel range products may
include contacting the pyrolysis oil with a hydrogen donor, e.g.,
the hydrogen donor described herein.
[0050] In various embodiments, the olefin may be fed alone to
process 600. The olefin may also be fed to process 600 in
combination with the hydrogen donor. The olefin and hydrogen donor
may be independently fed to process 600. The olefin and/or hydrogen
donor may be fed to process 600 in any stage of process 600. For
example, the olefin and/or hydrogen donor may be fed to the
reaction: in combination with biomass to be pyrolyzed, during
pyrolysis of biomass to provide the pyrolysis oil, directly to the
reaction at the catalyst, after reaction at the catalyst, after
pyrolysis oil condensation, and the like.
[0051] In several embodiments of the process for converting the
pyrolysis oil to one or more hydrocarbon fuel range products, the
catalyst may include any catalyst described herein, for example, a
solid acid catalyst such as a supported alkylsulfonic acid. For
example, the supported sulfonic acid may include supported
propylsulfonic acid.
[0052] In several embodiments of the process for converting the
pyrolysis oil to one or more hydrocarbon fuel range products, the
pyrolysis oil may be at least partially in a vapor phase.
[0053] In several embodiments of the process for converting the
pyrolysis oil to one or more hydrocarbon fuel range products, the
hydrotreating catalyst may include one or more catalysts, or a
combination or composite thereof. Suitable hydrotreating catalysts
may include cobalt (Co), molybdenum (Mo), nickel (Ni), titanium
(Ti), tungsten (W), zinc (Zn), antimony (Sb), bismuth (Bi), cerium
(Ce), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr),
manganese (Mn), rhenium (Re), iron (Fe), platinum (Pt), iridium
(Ir), palladium (Pd), osmium (Os), rhodium (Rh), ruthenium (Ru),
nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated
chromium oxide (Cu/Cr), nickel aluminum oxide (Ni/Al.sub.2O.sub.3),
palladium aluminum oxide (PdAl.sub.2O.sub.3), cobalt molybdenum
(CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten
(NiMoW), sulfided cobalt molybdenum (CoMo), sulfided nickel
molybdenum (NiMo), a metal carbide, or a composite or combination
thereof. The hydrotreating catalyst may include a metal oxide
support. Suitable metal oxide supports may include one or more of a
titanium oxide (TiO.sub.2) support, a silicon oxide support, a
zirconia oxide (ZrO.sub.2) support, a niobium oxide
(Nb.sub.2O.sub.5) support, a support including one or more mixtures
of non-alumina metal oxides, or a combination or composite thereof.
The hydrotreating catalyst may also include a noble metal
composition on the metal oxide support. Suitable noble metals for
the noble metal composition may include one or more of rhodium
(Rh), palladium (Pd), gold (Au), ruthenium (Ru), or a combination
or composite thereof.
[0054] In various embodiments, a composition including one or more
hydrocarbon fuel range products is provided. The mixture of one or
more hydrocarbon fuel range products may be produced from a
pyrolysis oil by a process, such as process 600. The process may
include reacting the pyrolysis oil with a feed including an olefin
in the presence of a catalyst. The process may form a product
mixture including at least one of an esterification product and an
etherification product. The process may include contacting the at
least one of the esterification product and the etherification
product in a reaction zone with a hydrotreating catalyst in the
presence of hydrogen. The process in the reaction zone may be
conducted under reaction conditions sufficient to convert at least
a portion of the at least one of the esterification product and the
etherification product into the mixture of the one or more fuel
range hydrocarbon products.
[0055] The process for producing the mixture of one or more
hydrocarbon fuel range products may include any subject matter
described herein for the process for converting the pyrolysis oil
to one or more hydrocarbon fuel range products.
[0056] Bio-oil starting material may be produced from pyrolysis of
biomass. Catalytic bio-oil starting material may be produced from
pyrolysis of biomass using a catalyst. These bio-oil starting
materials contain a mixture of water, organic acids, aldehydes,
phenols, free hydroxyls, and sugar derivatives which may impact
miscibility and fuel quality, particularly with hydrophobic fuels
such as diesel.
[0057] Briefly stated, the present invention includes methods and
compositions relating to improved bio-oil miscibility in
hydrophobic fuel. For example, the method may include providing a
miscible bio-oil. The miscible bio-oil may be upgraded, catalytic,
or upgraded and catalytic compared to a starting material bio-oil.
The method may also include contacting the upgraded bio-oil to a
hydrophobic fuel to form a miscible mixture. The upgraded bio-oil
may be characterized by greater miscibility in the hydrophobic fuel
compared to the bio-oil starting material
[0058] For example, FIG. 7A depicts an example ternary phase
diagram illustrating the miscibility relationships between bio-oil,
diesel, and 1-butanol. FIG. 7B depicts an example ternary phase
diagram illustrating the miscibility relationships between modified
catalytic bio-oil, diesel, and 1-butanol. FIG. 7C depicts an
example ternary phase diagram illustrating the miscibility
relationships between modified bio-oil, diesel, and 1-butanol. FIG.
7D depicts an example ternary phase diagram illustrating the
miscibility relationships between catalytic bio-oil, diesel, and
1-butanol. As can be seen in FIG. 7A, 7B, 7C, or 7D, higher amounts
of alcohol and lower amounts of diesel may be employed with bio-oil
starting material that is neither upgraded nor produced using a
catalytic pyrolysis of biomass. However, catalytic bio-oil may
improve miscibility with diesel compared to bio-oil prepared by
pyrolysis without catalysis. Upgrading (modification) of the
bio-oils (both catalytic and non-catalytic) may miscibility, in
some examples, significantly. The phase diagrams also show that it
may be easier to dissolve low amounts of diesel into high amounts
of bio-oil compared to low amounts of bio-oil into high amounts of
diesel. This may be due to the polar nature of bio-oil versus the
non-polarity of diesel fuel.
[0059] FIG. 8 depicts an example method 800 of improving
miscibility of a bio-oil in a hydrophobic fuel. The method 800 may
include 802 providing a miscible bio-oil. The miscible bio-oil may
be upgraded, catalytic, or upgraded and catalytic compared to a
starting material bio-oil. The method may also include 804
contacting the miscible bio-oil to a hydrophobic fuel to form a
miscible mixture. The miscible bio-oil may be characterized by
greater miscibility in the hydrophobic fuel compared to the bio-oil
starting material.
[0060] In some embodiments, the method may also include contacting
an alcohol to the miscible bio-oil and the hydrophobic fuel to form
the miscible mixture. The alcohol may include a C.sub.3-C.sub.5
alcohol. The alcohol may include one or more of n-butanol,
sec-butanol, iso-butanol, tert-butanol, n-propanol, or
2-propanol.
[0061] In several embodiments, the method may also include
contacting a surfactant to the miscible bio-oil and the hydrophobic
fuel to form the miscible mixture. The surfactant may include one
or more of an anionic surfactant, a cationic surfactant, an
amphiphilic surfactant, or a nonionic surfactant.
[0062] In various embodiments, the method may also include
contacting a surfactant and an alcohol to the miscible bio-oil and
the hydrophobic fuel to form the miscible mixture.
[0063] In some embodiments, the method may also include upgrading
the bio-oil starting material to provide the miscible bio-oil by
contacting the bio-oil starting material with an olefin in the
presence of a solid acid catalyst to provide the miscible bio-oil.
Additionally or alternatively, the method may also include
upgrading the bio-oil starting material to provide the miscible
bio-oil by contacting the bio-oil starting material with the olefin
in a vapor phase in the presence of a catalyst to provide the
miscible bio-oil. The miscible bio-oil may be reduced in one or
more of a hydroxyl value, an acid value, or a water concentration
compared to the bio-oil starting material.
[0064] Various embodiments include a method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, for example, to provide the miscible bio-oil as
upgraded bio-oil. The method may include contacting the bio-oil
starting material with an olefin in the presence of a solid acid
catalyst to reduce at least one of the hydroxyl value, the acid
value, and the water concentration.
[0065] In some embodiments of the method for reducing at least one
of a hydroxyl value, an acid value, and a water concentration in a
bio-oil, the method may include pyrolyzing a biomass to form the
bio-oil. The pyrolyzing the biomass to form the bio-oil may be
conducted prior to contacting the bio-oil with the olefin in the
presence of the solid acid catalyst.
[0066] In several embodiments of the method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, the olefin may include a C.sub.3-C.sub.5 alkene as
described herein.
[0067] In various embodiments of the method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, the method may include contacting the bio-oil with an
alcohol. As used herein, an alcohol may include a C.sub.1-C.sub.10
linear, branched, or cyclic aliphatic compound that includes a
hydroxyl group bonded to an alkyl carbon. For example, the method
may include contacting the bio-oil with a C.sub.3-C.sub.5 alcohol.
The C.sub.3-C.sub.5 alcohol may include, for example, 1-propanol,
2-propanol, 1-butanol, 2-butanol, sec-butyl alcohol, tert-butyl
alcohol, 1-pentanol, 2-pentanol, cyclopropanol, cyclobutanol,
cyclopentanol, or the like.
[0068] In some embodiments of the method for reducing at least one
of a hydroxyl value, an acid value, and a water concentration in a
bio-oil, the solid acid catalyst may include a supported
propylsulfonic acid.
[0069] In several embodiments of the method for reducing at least
one of a hydroxyl value, an acid value, and a water concentration
in a bio-oil, the bio-oil may be at least partially in a vapor
phase. In some embodiments, the bio-oil may be substantially or
completely in the vapor phase. The bio-oil may contain water. The
water may be, independently or together with the bio-oil, at least
partially, substantially, or completely in the vapor phase.
[0070] Various embodiments include a method for upgrading a bio-oil
in a vapor phase. The method may include providing a vapor phase
bio-oil starting material. The method may also include contacting
the vapor phase bio-oil starting material with an olefin in the
presence of a catalyst to provide an upgraded bio-oil.
[0071] In various embodiments, the method for upgrading a bio-oil
in a vapor phase may include mixing the vapor phase bio-oil with
the olefin in gas or vapor form to provide a vapor phase mixture of
bio-oil and olefin. The method may also include contacting the
vapor phase mixture of bio-oil and olefin to the catalyst to
provide the upgraded bio-oil.
[0072] In some embodiments, the method for upgrading a bio-oil in a
vapor phase may be conducted as a continuous process or a batch
process.
[0073] In several embodiments, the method for upgrading a bio-oil
in a vapor phase may the providing the vapor phase bio-oil
including pyrolyzing a biomass to form the vapor phase bio-oil.
[0074] In various embodiments, the method for upgrading a bio-oil
in a vapor phase the olefin including a C.sub.3-C.sub.5 alkene. The
olefin may include one or more of propylene, isobutylene, or
isoprene.
[0075] In some embodiments, the method for upgrading a bio-oil in a
vapor phase solid acid catalyst including a supported
propylsulfonic acid.
[0076] In several embodiments, the method for upgrading a bio-oil
in a vapor phase, the vapor phase bio alcohol may include water.
The method may also include separating an alcohol from the upgraded
bio-oil. The alcohol may be produced by contacting the vapor phase
bio-oil including water with the olefin in the presence of the
catalyst.
[0077] In various embodiments, an upgraded bio-oil is provided. In
some embodiments, the upgraded bio-oil may be produced by a process
including contacting a crude bio-oil with an olefin in the presence
of a solid acid catalyst to form the upgraded bio-oil. The upgraded
bio-oil may be characterized compared to the crude bio-oil by one
or more of a lower hydroxyl value, a lower acid value, or a lower
water concentration. In several embodiments, the upgraded bio-oil
may be produced by a process including providing a vapor phase
bio-oil. The process may also include contacting the vapor phase
bio-oil with an olefin in the presence of a catalyst to provide an
upgraded bio-oil. In various embodiments, the process for producing
the upgraded bio-oil may include any subject matter described for
the various methods herein.
[0078] In several embodiments of the method of improving
miscibility of a bio-oil in a hydrophobic fuel, the hydrophobic
fuel may include one or more of: diesel, fuel oil, heating oil,
bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied
coal fuel, or naphtha. For example, the hydrophobic fuel may be
diesel.
[0079] In various embodiments of the method of improving
miscibility of a bio-oil in a hydrophobic fuel, the bio-oil
starting material including one or more of: water, organic acids,
aldehydes, alkyl hydroxyls, phenols, or sugars.
[0080] In some embodiments, a bio-oil composition is provided. The
bio-oil composition may include a miscible ternary mixture. The
miscible ternary mixture may be composed according to each triplet
of miscible or partly miscible ranges in any one of FIG. 7A, 7B,
7C, or 7D, or a combination thereof. The miscible ternary mixture
may include a bio-oil, an upgraded (modified) bio-oil, a catalytic
bio-oil, or an upgraded (modified) and catalytic bio-oil in a
percentage according to each corresponding range in FIG. 7A, 7B,
7C, or 7D. The miscible ternary mixture may include an alcohol in a
percentage according to each corresponding range of 1-butanol in
FIG. 7A, 7B, 7C, or 7D. The miscible ternary mixture may include a
hydrophobic fuel in a percentage according to each corresponding
range of diesel in FIG. 7A, 7B, 7C, or 7D.
[0081] In several embodiments of the bio-oil composition, the
miscible ternary mixture may be according to each triplet of
miscible or partly miscible ranges in any one of FIG. 7B, 7C, or
7D, or a combination thereof. At least one said percentage may be
within the corresponding miscible percentage range. Each said
corresponding percentage range may be within each corresponding
miscible percentage range.
[0082] In various embodiments of the bio-oil composition, the
bio-oil composition may consist substantially of the miscible
ternary mixture. The bio-oil composition may consist essentially of
the miscible ternary mixture.
[0083] In some embodiments of the bio-oil composition, the alcohol
may include a C.sub.3-C.sub.5 alcohol. For example, the alcohol may
include one or more of n-butanol, sec-butanol, iso-butanol,
tert-butanol, n-propanol, or 2-propanol.
[0084] In several embodiments of the bio-oil composition, the
hydrophobic fuel may include one or more of: diesel, fuel oil,
heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas,
liquefied coal fuel, or naphtha. For example, the hydrophobic fuel
may be diesel fuel.
[0085] In various embodiments of the bio-oil composition, the
bio-oil composition may further include a surfactant. The
surfactant may include one or more of an anionic surfactant, a
cationic surfactant, an amphiphilic surfactant, or a nonionic
surfactant
[0086] In some embodiments of the bio-oil composition, the miscible
bio-oil may be prepared from a bio-oil starting material in a
process including contacting the bio-oil starting material with an
olefin in the presence of a solid acid catalyst to provide the
miscible bio-oil. Additionally or alternatively, the process may
include contacting the bio-oil starting material with the olefin in
a vapor phase in the presence of a catalyst to provide the miscible
bio-oil. The miscible bio-oil may be reduced in at least one of a
hydroxyl value, an acid value, and a water concentration compared
to the bio-oil starting material. The process for preparing the
miscible bio-oil from a bio-oil starting material may include any
subject matter described herein for preparing the miscible
bio-oil.
EXAMPLES
Example 1
[0087] A sample of bio-oil was obtained, and characterized for
initial values of hydroxyl value, acid value, and approximate water
concentration. A total value of moles of hydroxyl groups may be
determined from the initial values of hydroxyl value, acid value,
and approximate water concentration. The bio-oil was added to a
stirring autoclave reactor. A few mole percent of a solid acid
catalyst, propylsulfonic acid (SILIABOND.RTM., SiliCycle Inc.,
Quebec, Canada), was added to the reactor. The mole percent may be
determined versus the total value of moles of hydroxyl groups, for
example, between about 0.1 mol % and about 10 mol %. The reactor
was closed and purged. An amount of an olefin, propylene, was added
as a gas. The amount of the olefin may be determined according to
the total value of moles of hydroxyl groups, e.g., between about
0.1 mole equivalents and about 2 mole equivalents. The reactor was
sealed. Multiple runs were performed with at different
temperatures, at ambient temperature, at 90.degree. C., and at
120.degree. C. In some runs, alcohols such as 1-butanol or
1-propanol were used to homogenize the bio-oil and increase olefin
solubility. Each run was stirred and allowed to react for 17 hours,
and then poured into a jar, using simple filtration to remove the
solid acid catalyst. The resulting upgraded bio-oil was then
analyzed to determine hydroxyl value, acid value, and approximate
water concentration. All three values were reduced significantly
compared to the starting bio-oil.
Example 2
[0088] A sample of bio-oil was obtained, and characterized for
initial values of hydroxyl value, acid value, and approximate water
concentration. A total value of moles of hydroxyl groups may be
determined from the initial values of hydroxyl value, acid value,
and approximate water concentration. The bio-oil was added to a
stirring autoclave reactor. A few mole percent of a solid acid
catalyst, propylsulfonic acid (SILIABOND.RTM., SiliCycle Inc.,
Quebec, Canada), was added to the reactor. The mole percent may be
determined versus the total value of moles of hydroxyl groups, for
example, between about 0.1 mol % and about 10 mol %. The reactor
was closed and purged. An amount of an olefin, isobutylene, was
added as a gas. The amount of the olefin may be determined
according to the total value of moles of hydroxyl groups, e.g.,
between about 0.1 mole equivalents and about 2 mole equivalents.
The reactor was sealed. Multiple runs were performed with at
different temperatures, at ambient temperature, at 90.degree. C.,
and at 120.degree. C. In some runs, alcohols such as 1-butanol or
1-propanol were used to homogenize the bio-oil and increase olefin
solubility. Each run was stirred and allowed to react for 17 hours,
and then poured into a jar, using simple filtration to remove the
solid acid catalyst. The resulting upgraded bio-oil was then
analyzed to determine hydroxyl value, acid value, and approximate
water concentration. All three values were reduced significantly
compared to the starting bio-oil.
Example 3
[0089] A sample of bio-oil was obtained, and characterized for
initial values of hydroxyl value, acid value, and approximate water
concentration. A total value of moles of hydroxyl groups may be
determined from the initial values of hydroxyl value, acid value,
and approximate water concentration. The bio-oil was added to a
stirring autoclave reactor. A few mole percent of a solid acid
catalyst, propylsulfonic acid (SILIABOND.RTM., SiliCycle Inc.,
Quebec, Canada), was added to the reactor. The mole percent may be
determined versus the total value of moles of hydroxyl groups, for
example, between about 0.1 mol % and about 10 mol %. The reactor
was closed and purged. An amount of an olefin, isoprene, was added
as a liquid. The amount of the olefin may be determined according
to the total value of moles of hydroxyl groups, e.g., between about
0.1 mole equivalents and about 2 mole equivalents. The reactor was
sealed, and the autoclave was pressurized with argon to about 90
pounds per square inch. Multiple runs were performed with at
different temperatures, at ambient temperature, at 90.degree. C.,
and at 120.degree. C. In some runs, alcohols such as 1-butanol or
1-propanol were used to homogenize the bio-oil and increase olefin
solubility. Each run was stirred and allowed to react for 17 hours,
and then poured into a jar, using simple filtration to remove the
solid acid catalyst. The resulting upgraded bio-oil was then
analyzed to determine hydroxyl value, acid value, and approximate
water concentration. All three values were reduced significantly
compared to the starting bio-oil.
Example 4
[0090] A reactor was charged with a reaction mixture including
about 58% w/w crude bio-oil, about 11% w/w 1-butanol, about 31% w/w
isoprene, and about 0.15% (w/w compared to the crude bio-oil) of a
solid acid catalyst, propylsulfonic acid (SILIABOND.RTM., SiliCycle
Inc., Quebec, Canada). The reactor was heated to 80.degree. C. and
pressurized to 90 pounds per square inch gauge, and stirred for 17
h to provide an upgraded bio-oil.
Example 5
[0091] Various proportions of crude bio-oil, diesel fuel, and
1-butanol were mixed and miscibility was determined FIG. 7A shows a
phase diagram 700A summarizing the miscibility results versus the
proportions of crude bio-oil, diesel fuel, and 1-butanol. FIG. 7A
shows that more than 30% w/w of 1-butanol is required to emulsify
the sample of crude bio-oil of EXAMPLE 5 in diesel fuel.
Example 6
[0092] A sample of upgraded catalytic bio-oil was obtained,
prepared by catalytic pyrolysis of biomass followed by upgrading in
a process similar to EXAMPLE 4. Various proportions of the upgraded
catalytic bio-oil, diesel fuel, and 1-butanol were mixed and
miscibility was determined FIG. 7B shows a phase diagram 700B
summarizing the miscibility results versus the proportions of the
upgraded catalytic bio-oil, diesel fuel, and 1-butanol. FIG. 7B
shows that the sample of upgraded catalytic bio-oil of EXAMPLE 6
may be emulsified in diesel fuel with only about 20% w/w
1-butanol.
Example 7
[0093] A sample of upgraded bio-oil was obtained, prepared by
pyrolysis of biomass followed by upgrading in a process similar to
EXAMPLE 4. Various proportions of upgraded catalytic bio-oil,
diesel fuel, and 1-butanol were mixed and miscibility was
determined FIG. 7C is a phase diagram summarizing the miscibility
results versus the proportions of upgraded bio-oil, diesel fuel,
and 1-butanol. FIG. 7C shows a phase diagram 700C indicating that
compared to the crude bio-oil of FIG. 7A, the sample of upgraded
bio-oil of EXAMPLE 7 is significantly more miscible in diesel
fuel.
[0094] To the extent that the term "includes" or "including" is
used in the specification or the claims, it is intended to be
inclusive in a manner similar to the term "comprising" as that term
is interpreted when employed as a transitional word in a claim.
Furthermore, to the extent that the term "or" is employed (e.g., A
or B) it is intended to mean "A or B or both." When the applicants
intend to indicate "only A or B but not both" then the term "only A
or B but not both" will be employed. Thus, use of the term "or"
herein is the inclusive, and not the exclusive use. See Bryan A.
Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995).
Also, to the extent that the terms "in" or "into" are used in the
specification or the claims, it is intended to additionally mean
"on" or "onto." To the extent that the term "selectively" is used
in the specification or the claims, it is intended to refer to a
condition of a component wherein a user of the apparatus may
activate or deactivate the feature or function of the component as
is necessary or desired in use of the apparatus. To the extent that
the term "operatively connected" is used in the specification or
the claims, it is intended to mean that the identified components
are connected in a way to perform a designated function. To the
extent that the term "substantially" is used in the specification
or the claims, it is intended to mean that the identified
components have the relation or qualities indicated with degree of
error as would be acceptable in the subject industry.
[0095] As used in the specification and the claims, the singular
forms "a," "an," and "the" include the plural unless the singular
is expressly specified. For example, reference to "a compound" may
include a mixture of two or more compounds, as well as a single
compounds.
[0096] As used herein, the term "about" in conjunction with a
number is intended to include .+-.10% of the number. In other
words, "about 10" may mean from 9 to 11.
[0097] As used herein, the terms "optional" and "optionally" mean
that the subsequently described circumstance may or may not occur,
so that the description includes instances where the circumstance
occurs and instances where it does not.
[0098] In addition, where features or aspects of the disclosure are
described in terms of Markush groups, those skilled in the art will
recognize that the disclosure is also thereby described in terms of
any individual member or subgroup of members of the Markush group.
As will be understood by one skilled in the art, for any and all
purposes, such as in terms of providing a written description, all
ranges disclosed herein also encompass any and all possible
sub-ranges and combinations of sub-ranges thereof. Any listed range
can be easily recognized as sufficiently describing and enabling
the same range being broken down into at least equal halves,
thirds, quarters, fifths, tenths, etc. As a non-limiting example,
each range discussed herein can be readily broken down into a lower
third, middle third and upper third, etc. As will also be
understood by one skilled in the art all language such as "up to,"
"at least," "greater than," "less than," include the number recited
and refer to ranges which can be subsequently broken down into
sub-ranges as discussed above. Finally, as will be understood by
one skilled in the art, a range includes each individual member.
For example, a group having 1-3 cells refers to groups having 1, 2,
or 3 cells. Similarly, a group having 1-5 cells refers to groups
having 1, 2, 3, 4, or 5 cells, and so forth. While various aspects
and embodiments have been disclosed herein, other aspects and
embodiments will be apparent to those skilled in the art.
[0099] As stated above, while the present application has been
illustrated by the description of embodiments thereof, and while
the embodiments have been described in considerable detail, it is
not the intention of the applicants to restrict or in any way limit
the scope of the appended claims to such detail. Additional
advantages and modifications will readily appear to those skilled
in the art, having the benefit of the present application.
Therefore, the application, in its broader aspects, is not limited
to the specific details, illustrative examples shown, or any
apparatus referred to. Departures may be made from such details,
examples, and apparatuses without departing from the spirit or
scope of the general inventive concept.
[0100] As used herein, "substituted" refers to an organic group as
defined below (e.g., an alkyl group) in which one or more bonds to
a hydrogen atom contained therein may be replaced by a bond to
non-hydrogen or non-carbon atoms. Substituted groups also include
groups in which one or more bonds to a carbon(s) or hydrogen(s)
atom may be replaced by one or more bonds, including double or
triple bonds, to a heteroatom. A substituted group may be
substituted with one or more substituents, unless otherwise
specified. In some embodiments, a substituted group may be
substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of
substituent groups include: halogens (i.e., F, Cl, Br, and I);
hydroxyls; alkoxy, alkenoxy, aryloxy, aralkyloxy, heterocyclyloxy,
and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters;
urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines;
thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides;
amines; N-oxides; hydrazines; hydrazides; hydrazones; azides;
amides; ureas; amidines; guanidines; enamines; imides; isocyanates;
isothiocyanates; cyanates; thiocyanates; imines; nitro groups; or
nitriles (i.e., CN). A "per"-substituted compound or group is a
compound or group having all or substantially all substitutable
positions substituted with the indicated substituent. For example,
1,6-diiodo perfluoro hexane indicates a compound of formula
C.sub.6F.sub.12I.sub.2, where all the substitutable hydrogens have
been replaced with fluorine atoms.
[0101] Substituted ring groups such as substituted cycloalkyl,
aryl, heterocyclyl and heteroaryl groups also include rings and
ring systems in which a bond to a hydrogen atom may be replaced
with a bond to a carbon atom. Substituted cycloalkyl, aryl,
heterocyclyl and heteroaryl groups may also be substituted with
substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as
defined below.
[0102] Alkyl groups include straight chain and branched chain alkyl
groups having from 1 to 12 carbon atoms, and typically from 1 to 10
carbons or, in some examples, from 1 to 8, 1 to 6, or 1 to 4 carbon
atoms. Examples of straight chain alkyl groups include groups such
as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,
and n-octyl groups. Examples of branched alkyl groups include, but
are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl,
neopentyl, isopentyl, and 2,2-dimethylpropyl groups. Representative
substituted alkyl groups may be substituted one or more times with
substituents such as those listed above and include, without
limitation, haloalkyl (e.g., trifluoromethyl), hydroxyalkyl,
thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl,
alkoxyalkyl, or carboxyalkyl.
[0103] Cycloalkyl groups include mono-, bi- or tricyclic alkyl
groups having from 3 to 12 carbon atoms in the ring(s), or, in some
embodiments, 3 to 10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms.
Exemplary monocyclic cycloalkyl groups include, but are not limited
to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
and cyclooctyl groups. In some embodiments, the cycloalkyl group
has 3 to 8 ring members, whereas in other embodiments, the number
of ring carbon atoms ranges from 3 to 5, 3 to 6, or 3 to 7. Bi- and
tricyclic ring systems include both bridged cycloalkyl groups and
fused rings, such as, but not limited to, bicyclo[2.1.1]hexane,
adamantyl, or decalinyl. Substituted cycloalkyl groups may be
substituted one or more times with non-hydrogen and non-carbon
groups as defined above. However, substituted cycloalkyl groups
also include rings that may be substituted with straight or
branched chain alkyl groups as defined above. Representative
substituted cycloalkyl groups may be mono-substituted or
substituted more than once, such as, but not limited to, 2,2-,
2,3-, 2,4-2,5- or 2,6-disubstituted cyclohexyl groups, which may be
substituted with substituents such as those listed above.
[0104] Aryl groups may be cyclic aromatic hydrocarbons that do not
contain heteroatoms. Aryl groups herein include monocyclic,
bicyclic and tricyclic ring systems. Aryl groups include, but are
not limited to, phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl,
phenanthrenyl, anthracenyl, indenyl, indanyl, pentalenyl, and
naphthyl groups. In some embodiments, aryl groups contain 6-14
carbons, and in others from 6 to 12 or even 6-10 carbon atoms in
the ring portions of the groups. In some embodiments, the aryl
groups may be phenyl or naphthyl. Although the phrase "aryl groups"
may include groups containing fused rings, such as fused
aromatic-aliphatic ring systems (e.g., indanyl or
tetrahydronaphthyl), "aryl groups" does not include aryl groups
that have other groups, such as alkyl or halo groups, bonded to one
of the ring members. Rather, groups such as tolyl may be referred
to as substituted aryl groups. Representative substituted aryl
groups may be mono-substituted or substituted more than once. For
example, monosubstituted aryl groups include, but are not limited
to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or naphthyl, which may
be substituted with substituents such as those above.
[0105] Aralkyl groups may be alkyl groups as defined above in which
a hydrogen or carbon bond of an alkyl group may be replaced with a
bond to an aryl group as defined above. In some embodiments,
aralkyl groups contain 7 to 16 carbon atoms, 7 to 14 carbon atoms,
or 7 to 10 carbon atoms. Substituted aralkyl groups may be
substituted at the alkyl, the aryl or both the alkyl and aryl
portions of the group. Representative aralkyl groups include but
are not limited to benzyl and phenethyl groups and fused
(cycloalkylaryl)alkyl groups such as 4-indanylethyl. Representative
substituted aralkyl groups may be substituted one or more times
with substituents such as those listed above.
[0106] Groups described herein having two or more points of
attachment (i.e., divalent, trivalent, or polyvalent) within the
compound of the technology may be designated by use of the suffix,
"ene." For example, divalent alkyl groups may be alkylene groups,
divalent aryl groups may be arylene groups, divalent heteroaryl
groups may be heteroarylene groups, and so forth. In particular,
certain polymers may be described by use of the suffix "ene" in
conjunction with a term describing the polymer repeat unit.
[0107] Alkoxy groups may be hydroxyl groups (--OH) in which the
bond to the hydrogen atom may be replaced by a bond to a carbon
atom of a substituted or unsubstituted alkyl group as defined
above. Examples of linear alkoxy groups include, but are not
limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy.
Examples of branched alkoxy groups include, but are not limited to,
isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, or isohexoxy.
Examples of cycloalkoxy groups include, but are not limited to,
cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, or cyclohexyloxy.
Representative substituted alkoxy groups may be substituted one or
more times with substituents such as those listed above.
[0108] The term "amine" (or "amino"), as used herein, refers to
NR.sub.5R.sub.6 groups, wherein R.sub.5 and R.sub.6 may be
independently hydrogen, or a substituted or unsubstituted alkyl,
alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or
heterocyclyl group as defined herein. In some embodiments, the
amine may be alkylamino, dialkylamino, arylamino, or
alkylarylamino. In other embodiments, the amine may be NH.sub.2,
methylamino, dimethylamino, ethylamino, diethylamino, propylamino,
isopropylamino, phenylamino, or benzylamino The term "alkylamino"
may be defined as NR.sub.7R.sub.8, wherein at least one of R.sub.7
and R.sub.8 may be alkyl and the other may be alkyl or hydrogen.
The term "arylamino" may be defined as NR.sub.9R.sub.10, wherein at
least one of R.sub.9 and R.sub.10 may be aryl and the other may be
aryl or hydrogen.
[0109] The term "halogen" or "halo," as used herein, refers to
bromine, chlorine, fluorine, or iodine. In some embodiments, the
halogen may be fluorine. In other embodiments, the halogen may be
chlorine or bromine.
[0110] The various aspects and embodiments disclosed herein are for
purposes of illustration and are not intended to be limiting, with
the true scope and spirit being indicated by the following
claims.
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