U.S. patent application number 13/977251 was filed with the patent office on 2014-10-02 for derivation and conversion of natural oilswith chemical compositions for hydroprocessing to transport fuels.
This patent application is currently assigned to BP Corporate North America Inc.. The applicant listed for this patent is Jacob Borden, John W. Shabaker. Invention is credited to Jacob Borden, John W. Shabaker.
Application Number | 20140290127 13/977251 |
Document ID | / |
Family ID | 45464862 |
Filed Date | 2014-10-02 |
United States Patent
Application |
20140290127 |
Kind Code |
A1 |
Borden; Jacob ; et
al. |
October 2, 2014 |
DERIVATION AND CONVERSION OF NATURAL OILSWITH CHEMICAL COMPOSITIONS
FOR HYDROPROCESSING TO TRANSPORT FUELS
Abstract
Methods, apparatus, and/or feedstock suitable for use in
biofuels production, as well as biofuel compositions. A method of
producing a biofuel includes hydroprocessing glycerides derived
from an oleaginous microorganism and composed of at least 10% by
weight of fatty acid chains of length C16 or lower, and producing a
biofuel having a cold-flow pour point of about 20.degree. Celsius
or lower.
Inventors: |
Borden; Jacob; (San Diego,
CA) ; Shabaker; John W.; (Naperville, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Borden; Jacob
Shabaker; John W. |
San Diego
Naperville |
CA
IL |
US
US |
|
|
Assignee: |
BP Corporate North America
Inc.
Naperville
IL
|
Family ID: |
45464862 |
Appl. No.: |
13/977251 |
Filed: |
December 12, 2011 |
PCT Filed: |
December 12, 2011 |
PCT NO: |
PCT/US11/64367 |
371 Date: |
July 11, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61428291 |
Dec 30, 2010 |
|
|
|
Current U.S.
Class: |
44/307 ;
44/639 |
Current CPC
Class: |
Y02E 50/10 20130101;
C10G 2300/304 20130101; C10G 2300/307 20130101; Y02P 30/20
20151101; C10G 3/50 20130101; C10G 2300/308 20130101; C10L 1/026
20130101; C10G 2300/1011 20130101; C10L 1/02 20130101; Y02E 50/13
20130101 |
Class at
Publication: |
44/307 ;
44/639 |
International
Class: |
C10L 1/02 20060101
C10L001/02 |
Claims
1. A feedstock suitable for biofuels production, the feedstock
comprising: glycerides derived from an oleaginous microorganism;
and at least about 10% by weight of fatty acid chains of length C16
or lower; wherein a biofuel resulting from hydroprocessing the
feedstock comprises a cold-flow pour point of about 20.degree. C.
or lower.
2. The feedstock of claim 1, wherein the feedstock has a density
below about 940 kg/m.sup.3 at 15.degree. C.
3. The feedstock of claim 1, wherein the biofuel resulting from
hydroprocessing the feedstock has a cetane value of at least about
50.
4. The feedstock of claim 1, wherein the feedstock has an iodine
value of about 100 or less.
5. The feedstock of claim 1, wherein the oleaginous microorganism
comprises at least one microorganism selected from the group
consisting of algae, fungi, bacteria, cyanobacteria, and
combinations thereof.
6. The feedstock of claim 1, wherein the oleaginous microorganism
comprises at least one microorganism selected from the group
consisting of Saccharomyces unisporus, Saccharomyces dairensis,
Aspergillus nidulans, Sprilulina maxima, Entomorphtoria coronata,
Entomorphtoria obscura, Cyclotella cryptica, Navicula muralis,
Phaeodactylum triconutum, Thalassiosira pseudonana, genetically
modified Saccharomyces cerevisiae, genetically modified Escherichia
coli, and combinations thereof.
7. The feedstock of claim 1, wherein the glycerides comprise at
least about 10% by weight of fatty acid chains of length C14 or
lower.
8. The feedstock of claim 1, wherein the glycerides comprise at
least about 10% by weight of fatty acid chains of length C12 or
lower.
9. The biofuel resulting from hydroprocessing the feedstock of
claim 1, wherein the biofuel comprises diesel.
10. The biofuel resulting from hydroprocessing the feedstock of
claim 1, wherein the biofuel comprises jet fuel.
11. The biofuel resulting from hydroprocessing the feedstock of
claim 9, wherein the resulting biofuel comprises a fuel made by a
hydrotreating process.
12. The biofuel resulting from hydroprocessing the feedstock of
claim 11, wherein the glycerides do not undergo isomerization or
hydroisomerization.
13. The biofuel resulting from hydroprocessing the feedstock of
claim 1, wherein the isomerization ratio is less than 2.
14. A method of producing a biofuel, the method comprising:
hydroprocessing glycerides derived from an oleaginous microorganism
and composed of at least 10% by weight of fatty acid chains of
length C16 or lower resulting in a biofuel having a cold-flow pour
point of about 20.degree. C. or lower.
15. The method of claim 14, wherein the method is carried out
without the glycerides undergoing isomerization, or
hydroisomerization, or catalytic isomerization, or a significant
amount of isomerization.
16. The method of claim 15, wherein the isomerization ratio is less
than 2.
17. The method of claim 14, wherein the oleaginous organism
comprises at least one of the group consisting of Saccharomyces
unisporus, Saccharomyces dairensis, Aspergillus nidulans,
Sprilulina maxima, Entomorphtoria coronata, Entomorphtoria obscura,
Cyclotella cryptica, Navicula muralis, Phaeodactylum triconutum,
Thalassiosira pseudonana, genetically modified Saccharomyces
cerevisiae, genetically modified Escherichia coli, and combinations
thereof.
18. The method of claim 14, wherein the glycerides comprise at
least about 10% by weight of fatty acid chains of length C14 or
lower.
19. The method of claim 14, wherein the glycerides comprise at
least about 10% by weight of fatty acid chains of length C12 or
lower.
20. The method of claim 14, further comprising blending a quantity
of the biofuel with a fossil-derived fuel.
21. The method of claim 14, wherein the biofuel comprises
diesel.
22. The method of claim 14, wherein the biofuel comprises jet
fuel.
23. A biofuel produced according to the method of claim 14.
24. A biorefinery for producing a feedstock suitable for biofuels
production, the biorefinery comprising: a hydroprocessing unit for
hydroprocessing glycerides derived from an oleaginous microorganism
and composed of at least 10% by weight of fatty acid chains of
length C16 or lower; and no units for carrying out isomerization,
or hydroisomerization, or catalytic isomerization, or a significant
amount of isomerization.
Description
BACKGROUND
[0001] 1. Technical Field
[0002] The invention is directed to methods, apparatus, and/or
feedstock suitable for use in biofuels production, as well as
biofuel compositions resulting from the biofuels production.
[0003] 2. Discussion of Related Art
[0004] Natural oils derived from oil-accumulating organisms have
been employed as foodstuffs, in health and nutrition, as
lubricants, and also as fuels. Natural oils have many sources, such
as from oil-producing seed crops (for example, soya, rapeseed,
jatropha), byproducts of animal processing (for example, lard and
tallow), photosynthetic microorganisms (for example, algae,
microalgae, cyanobacteria), and heterotrophic microorganisms (for
example, yeast, fungi, molds). The wide range of sources naturally
imparts a wide variety of product compositions and characteristics
including, for example, fatty acid saturation level, chain length,
and impurities. These multiple sources of natural oils can be
further expanded through the application of genetic engineering for
the refinement of product characteristics.
[0005] In fuel applications, an important derivative of natural
oils is from transesterification of glycerides. As a result of
their prevalence as foodstuffs, natural oil-seeds and their
compositions have become industry standard. For instance, the
compositional profile of rapeseed oil is seen as the accepted
standard for bio-derived FAME (fatty acid methyl ester). The fatty
acid profile of rapeseed oil is one that is enriched in 18-carbon
fatty acids, and especially unsaturated acids. The table below
shows the breakdown of fatty acid as x:y, wherein x is the number
of carbons and y is the number of unsaturated bonds in the carbon
chain.
TABLE-US-00001 TABLE 1 Fatty Acid Ranges for Rapeseed Fatty Acid
16:0 18:0 18:1 18:2 18:3 % of Total 1-10 0.5-2.5 50-70 15-35
6-12
[0006] Unfortunately, bio-diesel fuels made from oils of these
compositions have certain drawbacks as diesel fuels. As shown in
the table below, the pour point of rapeseed bio-diesel is
relatively high (-7 to -4.degree. C.), and the unsaturated bonds
are subject to oxidative degradation, limiting shelf-life. The
density of rapeseed bio-diesel is relatively high and the cetane is
consistent with finished petroleum diesel, limiting the ability to
extend diesel supply by blending of lower quality, heavy materials
(for example, aromatics).
[0007] Rapeseed oils could also be hydrotreated, whereby the
glycerides are converted to paraffins, such as by: [0008] Catalytic
reduction by hydrogen (namely, C18 fatty acids become nC18
paraffins+water, and glycerol becomes propane+water) [0009]
Catalytic or thermal decarboxylation (namely, C18 fatty acids
become nC17 hydrocarbons+CO.sub.2, followed by further reaction to
make nC17 paraffins, methane, and CO).
[0010] During hydrotreatment, typically around half of the fatty
acids in rapeseed oil react via hydrogenation and the other half
react via decarboxylation. In either case, this process produces
linear paraffins with excellent cetane (i.e. >80), but poor cold
flow properties. Furthermore, the long chain lengths (such as C18)
necessitate further processing (such as isomerization and/or
cracking) in order to improve the cold flow properties of the
product.
[0011] When further processing, particularly isomerization, is
carried out on long-chain paraffinic products of hydrotreating to
improve the cold flow properties, the result is a fuel having
improved cold flow properties, such as the renewable diesel in
Table 2, below. However, the resulting yield loss from carrying out
such further processing is considerable.
TABLE-US-00002 TABLE 2 Comparison of Biodiesel and Renewable Diesel
Properties Diesel FAME Renewable Fuel Rapeseed Diesel (summer)
Methyl Ester (after isom) Density at 15.degree. C. (kg/m.sup.3) 835
885 775-785 Viscosity at 40.degree. C. (mm.sup.2/s) 3.5 4.5 2.9-3.5
Cetane Number 53 51 84-99 Cloud Point (.degree. C.) -5 -5 -5 to -30
LHV Lower Heating Value ~43 38 ~44 (MJ/kg) Heating Value (MJ/l) 36
34 34 Polyaromatic Content (wt %) 4 0 0 Oxygen Content (wt %) 0 11
0 Sulfur Content (mg/kg) <10 <10 <10
[0012] There is thus a need and desire for alternative glyceride
compositions that provide an improved hydrotreating feedstock and
final diesel fuel product.
SUMMARY
[0013] The invention is directed to methods, apparatus, and/or
feedstock suitable for use in biofuels production, as well as
biofuel compositions resulting from the biofuels production. The
resulting biofuels have improved cold flow properties.
Additionally, the methods of the invention are efficient, without
requiring further processing such as isomerization.
[0014] According to some embodiments, the invention is directed to
a feedstock suitable for biofuels production. The feedstock
comprises glycerides derived from an oleaginous (oil-accumulating)
microorganism having at least about 10% by weight of fatty acid
chains of length C16 or lower, and an iodine value of about 100
grams of iodine consumed per 100 gram sample of feedstock, or
less.
[0015] According to some embodiments, the biofuel resulting from
the methods, apparatus, and/or feedstock described herein has a
cold-flow pour point of about 20.degree. C. or lower.
[0016] According to some embodiments, the resulting biofuel has a
density below about 940 kg/m.sup.3 at 15.degree. C.
[0017] According to some embodiments, the resulting biofuel has a
cetane value of at least about 50.
[0018] According to some embodiments, the resulting biofuel has an
isomerization ratio of less than 2.
[0019] According to some embodiments, the resulting biofuel
includes a fuel made by a hydrotreating process.
[0020] According to some embodiments, the resulting biofuel
includes diesel, jet fuel, and/or a blend of any combination of
diesel, jet fuel, other biofuels or petroleum. The resulting
biofuel may be either a fuel or a fuel additive.
[0021] According to some embodiments, the oleaginous microorganism
from which the glycerides are derived includes algae, fungi,
bacteria, and/or cyanobacteria. More particularly, in certain
embodiments, the oleaginous microorganism includes Saccharomyces
unisporus, Saccharomyces dairensis, Aspergillus nidulans,
Sprilulina maxima, Entomorphtoria coronata, Entomorphtoria obscura,
Cyclotella cryptica, Navicula muralis, Phaeodactylum triconutum,
Thalassiosira pseudonana, or combinations thereof.
[0022] According to some embodiments, the glycerides include at
least about 10% by weight of fatty acid chains of length C14 or
lower. In certain embodiments, the glycerides include at least
about 10% by weight of fatty acid chains of length C12 or
lower.
[0023] According to some embodiments, the glycerides do not undergo
isomerization, or hydroisomerization, or catalytic isomerization,
or at least a significant amount of the glycerides do not undergo
any type of isomerization.
[0024] According to some embodiments, the invention is directed to
a method of producing a biofuel. The method includes
hydroprocessing glycerides derived from an oleaginous microorganism
and composed of at least 10% by weight of fatty acid chains of
length C16 or lower. The method produces a biofuel having a
cold-flow pour point of about 20.degree. C. or lower.
[0025] According to some embodiments, the method is carried out
without the glycerides undergoing isomerization, or
hydroisomerization, or catalytic isomerization, or at least without
a significant amount of the glycerides undergoing any type of
isomerization.
[0026] According to some embodiments, the method further includes
blending a quantity of the biofuel with a fossil-derived fuel.
[0027] According to some embodiments, the invention is directed to
a biorefinery for producing a feedstock suitable for biofuels
production. The biorefinery includes a hydroprocessing unit for
hydroprocessing glycerides derived from an oleaginous microorganism
and composed of at least 10% by weight of fatty acid chains of
length C16 or lower. The biorefinery does not include any units
designed for carrying out isomerization, or hydroisomerization, or
catalytic isomerization.
BRIEF DESCRIPTION OF THE DRAWING
[0028] The accompanying drawing illustrates an embodiment of the
invention and, together with the description, serves to explain the
features, advantages, and principles of the invention. In the
drawing:
[0029] The FIGURE schematically shows an apparatus within a
biorefinery, according to some embodiments.
DETAILED DESCRIPTION
[0030] The invention is directed to methods, apparatus, and/or
feedstock suitable for use in biofuels production, as well as
biofuel compositions resulting from the biofuels production.
According to some embodiments, natural oil compositions can be
produced that allow for renewable production of diesel molecules
having improved cold flow properties. According to some
embodiments, alternative glyceride compositions are used to provide
an improved hydrotreating feedstock and final biofuel product. More
particularly, through careful selection of the source organism
and/or genetic engineering glyceride chain lengths and saturation
levels as described herein can result in high-yield hydroprocessing
and generation of a quality diesel fuel. Additionally, the methods
of the invention are efficient, without requiring further
processing such as isomerization.
[0031] According to some embodiments, the invention includes a
renewably-derived feedstock suitable for biofuels production. The
feedstock may include glycerides derived from an oleaginous
microorganism. For example, the oleaginous microorganism may
include algae, fungi, bacteria, cyanobacteria, or combinations of
any of these microorganisms. More particularly, the oleaginous
microorganism may include Saccharomyces unisporus, Saccharomyces
dairensis, Aspergillus nidulans, Sprilulina maxima, Entomorphtoria
coronata, Entomorphtoria obscura, Cyclotella cryptica, Navicula
muralis, Phaeodactylum triconutum, Thalassiosira pseudonana, or a
combination of any of these microorganisms.
[0032] According to some embodiments, the oleaginous microorganism
is genetically modified. More particularly, in certain embodiments,
the microorganism may include genetically modified Escherichia coli
or Saccharomyces cerevisiae.
[0033] The glycerides may include at least about 10% by weight of
fatty acid chains of length C16 or lower. In some embodiments, the
glycerides may include at least about 10% by weight of fatty acid
chains of length C14 or lower. In some embodiments, the glycerides
may include at least about 10% by weight of fatty acid chains of
length C12 or lower. In contrast to glycerides having long chain
lengths, such as C18, the shorter chain lengths of the glycerides
herein can be hydrotreated without requiring further processing,
such as isomerization or hydroisomerization, in order to improve
the cold flow properties of a resulting biofuel product.
[0034] According to other embodiments, the amount of fatty acid
chains of a specific length or lower, such as C16 or lower, may be
between about 10 percent and about 95 percent, between about 20
percent and about 80 percent, at least about 20 percent, at least
about 30 percent, at least about 40 percent, and/or the like.
[0035] For instance, the tables below show example heterotrophic
and photosynthetic micro-organisms with lipid profiles appreciably
different as compared to rapeseed oil:
TABLE-US-00003 TABLE 3A Comparison of Tri-acyl Glyceride Chain
Lengths .ltoreq.C12:0 C14:0 C16:0 C16:1 C16:2 Vegetative Oil-Seed
Rapeseed oil -- -- 1-10 -- -- Coconut oil 60 18 9 -- -- Yeasts
Candida Curvata D -- -- 32 -- -- Cryptococcus Terricolus -- -- 28 2
-- Endomyces Vernalis -- 2 25 7 -- Lipomyces Lipfer -- 2 16 4 --
Rhodosporidium Toruloides -- 1 25 1 -- Rodoturola Glutinis -- 2 30
-- -- Trichosporon Cutaneum -- -- 30 -- -- Molds Aspergillus
Nidulans -- 1 20 1 -- Entomorphtoria Coronata 40 30 8 -- --
Entomorphtoria Obscura 40 8 36 -- -- Fusarium Moiloforma -- 1 14 --
-- Moucor Miehei -- 1 20 4 -- Tricholoma Nudum -- -- 39 1 -- Algae
Chalmydomonas Pyrenoidosa 82 -- -- 30 3 17 Choelastrum Microsporum
-- -- 14 1 5 Dunaliella Tertiolecta -- -- 14 2 2 Scenedesmus
Quadricuada -- -- 14 4 -- Tetraedron Sp. -- -- 19 3 3 Tetraselmis
Suscia -- -- 11 2 -- Cyclotella Cryptica -- 7 28 43 3 Navicula
Muralis -- 17 31 26 -- Nitzschia Alba 3-2 -- 30 21 10 --
Phaeodactylum Triconutum -- 3 16 31 3 Thalassiosira Pseudon. 3H --
29 24 20 --
TABLE-US-00004 TABLE 3B Comparison of Tri-acyl Glyceride Chain
Lengths C16:3 C18:0 C18:1 C18:2 C18:3 Vegetative Oil-Seed Rapeseed
oil -- 5-2.5 50-70 15-35 6-12 Coconut oil -- 3 7 2 -- Yeasts
Candida Curvata D -- 14 44 8 -- Cryptococcus Terricolus -- 6 60 12
2 Endomyces Vernalis -- 12 46 6 1 Lipomyces Lipfer -- 3 62 8 1
Rhodosporidium Toruloides -- 13 46 12 2 Rodoturola Glutinis -- 8 40
16 3 Trichosporon Cutaneum -- 13 46 11 -- Molds Aspergillus
Nidulans -- 18 40 17 -- Entomorphtoria Coronata -- 2 14 2 1
Entomorphtoria Obscura -- 7 4 -- -- Fusarium Moiloforma -- 12 30 42
1 Moucor Miehei -- 6 48 16 10 Tricholoma Nudum -- 7 32 30 -- Algae
Chalmydomonas Pyrenoidosa 82 3 1 4 34 8 Choelastrum Microsporum --
-- 38 13 16 Dunaliella Tertiolecta 6 1 3 6 32 Scenedesmus
Quadricuada -- -- 32 7 29 Tetraedron Sp. -- 2 34 11 18 Tetraselmis
Suscia 2 3 33 2 17 Cyclotella Cryptica 4 -- 1 -- -- Navicula
Muralis -- 11 12 -- -- Nitzschia Alba 3-2 -- -- 24 -- 6
Phaeodactylum Triconutum 7 1 2 -- 2 Thalassiosira Pseudon. 3H 11 --
-- -- --
[0036] Tables 3A and 3B are reproduced from the Fats and Oils
Handbook; Michael Bockisch; 1998; AOCS Press.
[0037] In extension to the above tables, the metabolic pathways and
corresponding genes associated with lipid formation are well
characterized. Modulation of the activity of core lipid synthesis
genes (elongases, desaturases, synthases, reductases, dehydratases,
carboxylases, etc.) can lead to further tailoring of the lipid
profile towards a desired optimum.
[0038] According to some embodiments, the feedstock may have a
density below about 940 kg/m.sup.3 at 15.degree. C. In some
embodiments, the feedstock may have a density between about 830
kg/m.sup.3 and about 930 kg/m.sup.3, or between about 840
kg/m.sup.3 and about 920 kg/m.sup.3 at 15.degree. C. Since fuel is
sold by volume, not density, the relatively low density of the
feedstock increases the efficiency of producing the resulting
biofuel.
[0039] Iodine values are indicative of the overall degree of
unsaturation of a fatty acid. Unsaturated bonds are subject to
oxidative degradation, which limits shelf-life of a resulting
product. According to some embodiments, the feedstock has an iodine
value of about 100 or less, or between about 0 and about 50, or
between about 0 and about 25 grams of iodine consumed per 100 gram
sample. The table below provides iodine value estimates for the
same organisms listed in the preceding tables. The iodine value
estimates are based on mono, di, and tri unsaturated contents and
correlations with known compositions' iodine values.
TABLE-US-00005 TABLE 4 Comparison of Tri-acyl Glyceride Saturation
Levels TAG Unsaturation Level Vegetative Oil-Seed Rapeseed oil 114
Coconut oil 10 Yeasts Candida Curvata D 56 Cryptococcus Terricolus
85 Endomyces Vernalis 65 Lipomyces Lipfer 81 Rhodosporidium
Toruloides 70 Rodoturola Glutinis 72 Trichosporon Cutaneum 63 Molds
Aspergillus Nidulans 67 Entomorphtoria Coronata 20 Entomorphtoria
Obscura 4 Fusarium Moiloforma 96 Moucor Miehei 102 Tricholoma Nudum
78 Algae Chalmydomonas Pyrenoidosa 82 112 Choelastrum Microsporum
108 Dunaliella Tertiolecta 117 Scenedesmus Quadricuada 122
Tetraedron Sp. 105 Tetraselmis Suscia 88 Cyclotella Cryptica 59
Navicula Muralis 38 Nitzschia Alba 3-2 50 Phaeodactylum Triconutum
61 Thalassiosira Pseudon. 3H 49
[0040] A higher saturation level, such as in the predominantly
saturated and mono-unsaturated fatty acids shown in the table
above, minimizes the fouling potential as well as the amount of
hydrogen consumed and heat released by catalytic reduction to
paraffins. The table below illustrates the reaction yields and heat
effects for model lipids undergoing typical 50% hydrogenation and
50% decarboxylation reaction pathways (with 100% conversion and 50%
subsequent methanation of CO.sub.2).
TABLE-US-00006 TABLE 5 Reaction Yields and Heat Effects on Model
Lipids Tri- Tri- Trilino- palmitate stearate Triolein lenate Rape-
Lipid C16:0 C18:0 C18:1 C18:3 Palm seed MASS BALANCE (wt % on
vegetable oil) tri-acyl -100.0 -100.0 -100.0 -100.0 -100.0 -100.0
glyceride H.sub.2 -2.6 -2.4 -3.1 -4.5 -2.9 -3.3 C15 39.5 0.0 0.0
0.0 16.9 1.4 C16 42.1 0.0 0.0 0.0 18.0 1.5 C17 0.0 40.4 40.7 41.3
23.3 39.3 C18 0.0 42.8 43.1 43.7 24.7 41.6 CH.sub.4 1.5 1.3 1.4 1.4
1.4 1.4 C.sub.3H.sub.8 5.5 4.9 5.0 5.0 5.2 5.0 CO.sub.2 4.1 3.7 3.7
3.8 3.9 3.8 H.sub.2O 10.0 9.1 9.2 9.3 9.5 9.2 SUM 81.5 83.3 83.8
85.0 82.9 84.0 (C15-C18) GAS YIELDS (Nm.sup.3/m.sup.3 tri-acyl
glyceride) H.sub.2 -248 -225 -291 -426 -276 -316 CH.sub.4 18 16 16
16 17 16 C.sub.3H.sub.8 24 21 22 22 22 22 CO.sub.2 18 16 16 16 17
16 H.sub.2O 106 96 97 98 101 98 Heat of -746 -990 -1166 -2012 -1015
-1311 Reaction kJ/kg TAG
[0041] A relatively higher level of shorter-chain fatty acids
(e.g., C12, C14, C16) increases product quality (e.g., cold flow
properties) and reduces heat evolution at the expense of a small
amount of additional H.sub.2 consumption.
[0042] According to some embodiments, the resulting biofuel may
have a pour point of about 20.degree. C. or lower, or about
15.degree. C. or lower, or about 10.degree. C. or lower. According
to some embodiments, the resulting biofuel may have a cetane value
of at least about 50, or at least about 60, or at least about 70.
According to some embodiments, an isomerization ratio of the
resulting biofuel may be less than about 2, or between about 1 and
about 2, or between about 0 and about 1. Renewable diesel has an
iso/normal ratio of approximately 0 before hydroisomerization. For
reference, an iso/normal ratio near 2 can lower a cloud point from
roughly 20.degree. C. to about 0.degree. C.
[0043] The resulting biofuel may include diesel, jet fuel, or
blends with other biofuels and/or petroleum.
[0044] According to some embodiments, the resulting biofuel is
blended with a quantity of a fossil-derived fuel. In some
embodiments, the resulting blend comprises less than 5% biofuel. In
some embodiments, the resulting blend comprises between 5% and 10%
of biofuel. In some embodiments, the resulting blend comprises
between 10% and 20% of biofuel. According to other embodiments, the
resulting blend comprises greater than 20% biofuel.
[0045] According to some embodiments, the invention includes a
method of producing a biofuel. The method includes hydroprocessing
glycerides derived from an oleaginous microorganism. For example,
the oleaginous microorganism may include Saccharomyces unisporus,
Saccharomyces dairensis, Aspergillus nidulans, Sprilulina maxima,
Entomorphtoria coronata, Entomorphtoria obscura, Cyclotella
cryptica, Navicula muralis, Phaeodactylum triconutum, Thalassiosira
pseudonana, genetically modified Saccharomyces cerevisiae,
genetically modified Escherichia coli, or a combination of any of
these microorganisms. The method can be carried out without the
glycerides undergoing isomerization, or hydroisomerization, or
catalytic isomerization, or at least without a significant amount
of the glycerides undergoing any type of isomerization. As referred
to herein, the term "significant amount" refers to about 5% or more
of the glycerides being isomerized.
[0046] The glycerides include at least 10% by weight of fatty acid
chains of length C16 or lower. In some embodiments, the glycerides
may include at least about 10% by weight of fatty acid chains of
length C14 or lower. In some embodiments, the glycerides may
include at least about 10% by weight of fatty acid chains of length
C12 or lower.
[0047] The following table illustrates that chain lengths of
C12-C14 remove the need for subsequent processing via
isomerization. Isomerization requires an additional high
temperature, hydrogen-supplied unit operation and can incur a yield
loss to gasoline and low value fuel gas>10% due to undesired
cracking reactions. This yield loss is particularly significant
because the economics of vegetable oil hydrotreating are dominated
by feed costs. Finally, because isomerization is not necessary for
cold flow properties, the hydrotreated product contains linear
paraffins with better cetane than if they had been isomerized.
TABLE-US-00007 TABLE 6 Melting Points of Fatty Acids of Various
Chain Lengths decane -10.degree. C. hexadecane 18.degree. C.
2-methylpentadecane -10.degree. C. octadecane 29.degree. C.
[0048] The method may further include producing a biofuel having a
pour point of about 20.degree. C. or lower, or about 15.degree. C.
or lower, or about 10.degree. C. or lower.
[0049] According to some embodiments, an isomerization ratio of the
resulting biofuel may be less than about 2, or between about 1 and
about 2, or between about 0 and about 1.
[0050] The method may further include blending a quantity of the
biofuel with a fossil-derived fuel. For example, the resulting
biofuel may include diesel, jet fuel, or blends with other biofuels
and/or petroleum.
[0051] A blending calculation can be used to determine the pour
point of paraffin mixtures produced by hydrotreating a number of
natural oils. This calculation is based on a non-linear diesel
blending model that uses pure paraffin component data.
TABLE-US-00008 TABLE 7 Paraffin Data Oil Fatty Acid Distribution
(%) Carbon mp mp Pour Soy- Coco- E. E. # (.degree. C.) (.degree.
F.) Index bean Palm nut Coronata Obscura 7 -91 -131.8 0.5 8 -57
-70.6 2.0 9 10 10 9 -53 -63.4 2.4 10 -30 -22 6.6 6 10 10 11 -26
-14.8 7.8 12 -10 14 15.7 47 20 20 13 -6 21.2 18.7 14 6 42.8 31.6 1
18 30 8 15 10 50 37.6 16 18 64.4 53.2 11 45 9 8 36 17 23 73.4 66.2
18 28 82.4 82.3 89 54 11 19 11 19 32 89.6 97.9 20 37 98.6 121.7 21
40 104 138.7 22 44 111.2 165.0
[0052] The Pour Index (PI) is calculated from the melting point
(mp) (degrees Fahrenheit) as follows:
PI=10.sup.(0.0105(mp+100))
[0053] It should be noted that the pour point is assumed equal to
the melting point for pure paraffins. Also, it was assumed that E.
Coronata and E. Obscura have 40% total.ltoreq.C12 as a reasonable
distribution.
[0054] The following tables display the Blend Pour Index and the
Blend Pour Point for each of the feedstocks listed in Table 7
above.
TABLE-US-00009 TABLE 8 Pour Point Data Without Decarboxylation HVO
Products Without Decarboxylation Carbon # Soybean Palm Coconut E.
Coronata E. Obscura 7 8 8 10 10 9 10 6 10 10 11 12 47 20 20 13 14 1
18 30 8 15 16 11 45 9 8 36 17 18 89 54 11 19 11 Blend Pour 79.1
68.7 27.8 34.4 36.6 Index Blend Pour 80.8 74.9 37.5 46.3 48.9 Point
(.degree. F.) Blend Pour 27 24 3 8 9 Point (.degree. C.)
TABLE-US-00010 TABLE 9 Pour Point Data with Complete
Decarboxylation HVO Products with Complete Decarboxylation Carbon #
Soybean Palm Coconut E. Coronata E. Obscura 7 9 10 10 8 9 6 10 10
10 11 47 20 20 12 13 1 18 30 8 14 15 11 45 9 8 36 16 17 89 54 11 19
11 18 Blend Pour 63.0 52.8 17.9 23.8 25.4 Index Blend Pour 71.4
64.1 19.3 31.1 33.9 Point (.degree. F.) Blend Pour 22 18 -7 -1 1
Point (.degree. C.)
TABLE-US-00011 TABLE 10 Pour Point Data with 50% Decarboxylation
HVO Products with 50% Decarboxylation Carbon # Soybean Palm Coconut
E. Coronata E. Obscura 7 4 5 5 8 4 5 5 9 3 5 5 10 3 5 5 11 23.5 10
10 12 23.5 10 10 13 0.5 9 15 4 14 0.5 9 15 4 15 5.5 22.5 4.5 4 18
16 5.5 22.5 4.5 4 18 17 44.5 27 5.5 9.5 5.5 18 44.5 27 5.5 9.5 5.5
Blend Pour 71.0 60.8 22.9 29.1 31.0 Index Blend Pour 76.3 69.9 29.5
39.4 42.0 Point (.degree. F.) Blend Pour 25 21 -1 4 6 Point
(.degree. C.)
[0055] The Blend Pour Index (BPI) is calculated for each feedstock
as follows:
BPI=SUMPRODUCT(PI.sub.Cn,D.sub.Cn)/SUM(D.sub.Cn)
wherein SUMPRODUCT(PI.sub.Cn, D.sub.Cn)=PI.sub.C1*D.sub.C1+ . . .
+PI.sub.Cn*D.sub.Cn and SUM(D.sub.Cn)=D.sub.C1+ . . .
+D.sub.Cn.
[0056] The Blend Pour Point (BPP) (degrees Fahrenheit) is
calculated as follows:
BPP=Log.sub.10(BPI)/0.0105-100
[0057] The BPP (degrees Celsius) is calculated using the standard
conversion from Celsius to Fahrenheit:
F=(9/5)C+32
[0058] Of the three preceding tables, the data in Table 10, with
50% decarboxylation of the feedstocks, is closest to actual
observations during renewable diesel hydrotreating. The pour point
of coconut oil is the lowest due to some very short paraffin chains
and few very long chains. The E. coronate and E. obscura organisms
are almost as good as, and significantly better than, typical
soybean, palm, or rapeseed products.
[0059] The FIGURE schematically illustrates an apparatus 10 within
a biorefinery, according to one embodiment. The apparatus 10
includes a hydroprocessing unit 12 with a renewably-derived
feedstock 14 and a biofuel product 16. The hydroprocessing unit 12
is designed for hydroprocessing glycerides derived from an
oleaginous microorganism. The glycerides may be composed of at
least 10% by weight of fatty acid chains of length C16 or lower.
Due to the relatively short chain lengths in the glycerides, there
is no need for the biorefinery to include any units for carrying
out isomerization, or hydroisomerization, or catalytic
isomerization, or a significant amount of isomerization.
[0060] Lipid refers to oils, fats, waxes, greases, cholesterol,
glycerides, steroids, sterols, isoprenoids, phosphatides,
cerebrosides, fatty acids, fatty acid related compounds, derived
compounds, other oily substances, and/or the like. Lipids can be
made in living cells and can have a relatively high carbon content
and a relatively high hydrogen content with a relatively lower
oxygen content. Lipids typically include a relatively high energy
content, such as on a mass or volume basis.
[0061] Biological oils refer to lipid materials and/or substances
derived at least in part from living organisms, such as animals,
plants, fungi, yeasts, algae, microalgae, bacteria, and/or the
like, including pyrolysis oils. Biological oils comprise lipids,
triglycerides, diglycerides, monoglycerides, fatty acids,
isoprenoids, sterols, and sterol esters. According to some
embodiments biological oils can be suitable for use as and/or
conversion into renewable materials and/or biofuels.
[0062] Renewable materials refer to substances and/or items that
have been at least partially derived from a source and/or process
capable of being replaced by natural ecological cycles and/or
resources. Renewable materials can include chemicals, chemical
intermediates, solvents, monomers, oligomers, polymers, biofuels,
biofuel intermediates, biogasoline, biogasoline blendstocks,
biodiesel, green diesel, renewable diesel, biodiesel blend stocks,
biodistillates, and/or the like. In some embodiments, the renewable
material can be derived from a living organism, such as plants,
algae, bacteria, fungi, and/or the like.
[0063] Biofuel refers to components and/or streams suitable for use
as a fuel and/or a combustion source derived at least in part from
renewable sources. The biofuel can be sustainably produced and/or
have reduced and/or no net carbon emissions to the atmosphere, such
as when compared to fossil fuels. According to some embodiments,
renewable sources can exclude materials mined or drilled, such as
from the underground. In some embodiments, renewable resources can
include single cell organisms, multicell organisms, plants, fungi,
bacteria, algae, cultivated crops, noncultivated crops, timber,
and/or the like. Biofuels can be suitable for use as transportation
fuels, such as for use in land vehicles, marine vehicles, aviation
vehicles, and/or the like. Biofuels can be suitable for use in
power generation, such as raising steam, exchanging energy with a
suitable heat transfer media, generating syngas, generating
hydrogen, making electricity, and or the like.
[0064] Biodiesel refers to components or streams suitable for
direct use and/or blending into a diesel pool and/or a cetane
supply derived from renewable sources. Suitable biodiesel molecules
can include fatty acid esters, monoglycerides, diglycerides,
triglycerides, lipids, fatty alcohols, alkanes, naphthas,
distillate range materials, paraffinic materials, aromatic
materials, aliphatic compounds (straight, branched, and/or cyclic),
and/or the like. Biodiesel can be used in compression ignition
engines, such as automotive diesel internal combustion engines,
truck heavy duty diesel engines, and/or the like. In the
alternative, the biodiesel can also be used in gas turbines,
heaters, boilers, and/or the like. According to some embodiments,
the biodiesel and/or biodiesel blends meet or comply with
industrially accepted fuel standards, such as B1, B2 (Minnesota),
B5, B7 (EU), B10, B20, B40, B60, B80, B99.9, B100, and/or the
like.
[0065] Biodistillate refers to components or streams suitable for
direct use and/or blending into aviation fuels (jet), lubricant
base stocks, kerosene fuels, fuel oils, and/or the like.
Biodistillate can be derived from renewable sources, and have any
suitable boiling point range, such as a boiling point range of
about 100.degree. C. to about 700.degree. C., about 150.degree. C.
to about 350.degree. C., and/or the like.
[0066] Feedstock refers to materials and/or substances used to
supply, feed, provide for, and/or the like, such as to an organism,
a machine, a process, a production plant, and/or the like.
Feedstocks can include raw materials used for conversion,
synthesis, and/or the like. According to some embodiments, the
feedstock can include any material, compound, substance, and/or the
like suitable for consumption by an organism, such as sugars,
hexoses, pentoses, monosaccharides, disaccharides, trisaccharides,
oligosaccharides, polyols (sugar alcohols), organic acids,
starches, carbohydrates, cellulose, hemicelluloses, biomass, and/or
the like. According to some embodiments, the feedstock can include
sucrose, glucose, fructose, xylose, glycerol, mannose, arabinose,
lactose, galactose, maltose, other five carbon sugars, other six
carbon sugars, other twelve carbon sugars, plant extracts
containing sugars, other crude sugars, and/or the like. Feedstock
can refer to one or more of the organic compounds listed above when
present in the feedstock.
[0067] According to some embodiments, the method and/or process can
include addition of other materials and/or substances to aid and/or
assist the organism, such as nutrients, vitamins, minerals, metals,
water, and/or the like. The use of other additives are also within
the scope of this invention, such as antifoam, flocculants,
emulsifiers, demulsifiers, viscosity increasers, viscosity
decreasers, surfactants, salts, other fluid modifying materials,
and/or the like.
[0068] Organic refers to carbon containing compounds, such as
carbohydrates, sugars, ketones, aldehydes, alcohols, lignin,
cellulose, hemicellulose, pectin, other carbon containing
substances, and/or the like.
[0069] According to some embodiments, the feedstock can be fed into
the fermentation using one or more feeds. In some embodiments,
feedstock can be present in media charged to a vessel prior to
inoculation. In some embodiments, feedstock can be added through
one or more feed streams in addition to the media charged to the
vessel.
[0070] Fatty acids refer to saturated and/or unsaturated
monocarboxylic acids, such as in free form or in the form of
glycerides in fats and fatty oils. Glycerides can include
acylglycerides, monoglycerides, diglycerides, triglycerides,
tri-acyl glycerides, lipids, phospholipids, glycolipids,
sulfolipids, and/or the like.
[0071] Double bonds refer two pairs of electrons shared by two
atoms in a molecule.
[0072] The biological oil can be further processed into the biofuel
with any suitable method, such as esterification,
transesterification, hydrogenation, cracking, and/or the like. In
the alternative, the biological oil can be suitable for direct use
as a biofuel. Esterification refers to making and/or forming an
ester, such as by reacting an acid with an alcohol to form an
ester. Transesterification refers to changing one ester into one or
more different esters, such as by reaction of an alcohol with a
triglyceride to form fatty acid esters and glycerol, for example.
Hydrogenation and/or hydrotreating refer to reactions to add
hydrogen to molecules, such as to saturate and/or reduce
materials.
[0073] Transesterification can include use of any suitable alcohol,
such as methanol, ethanol, propanol, butanol, and/or the like.
[0074] The resulting biofuel can meet and/or exceed international
standards EN 14214:2008 (Automotive fuels, Fatty acid methyl esters
(FAME) for diesel engines) and/or ASTM D6751-09 (Standard
Specification for Biodiesel Fuel Blend Stock (B100) for Middle
Distillate Fuels). The entire contents of EN 14214:2008 and ASTM
D6751-09 are hereby both incorporated by reference in their
entirety as a part of this specification.
[0075] According to some embodiments, the method and/or process can
include temperature control, such as by addition of heat, cooling,
and/or the like. Heat can be supplied by steam, saturated stream,
super heated stream, hot water, glycol, heat transfer oil, heat
transfer fluid, other process streams, and/or the like. Cooling can
be supplied by cooling water, refrigerant, brine, glycol, heat
transfer fluid, coolant, other process streams, and/or the like.
Temperature control can use any suitable technique and/or
configuration, such as indirect heat exchange, direct heat
exchange, convection, conduction, radiation, and/or the like.
[0076] Regarding an order, number, sequence, omission, and/or limit
of repetition for steps in a method or process, the drafter intends
no implied order, number, sequence, omission, and/or limit of
repetition for the steps to the scope of the invention, unless
explicitly provided.
[0077] Regarding ranges, ranges are to be construed as including
all points between upper values and lower values, such as to
provide support for all possible ranges contained between the upper
values and the lower values including ranges with no upper bound
and/or lower bound.
[0078] Basis for operations, percentages, and procedures can be on
any suitable basis, such as a mass basis, a volume basis, a mole
basis, and/or the like. If a basis is not specified, a mass basis
or other appropriate basis should be used.
[0079] It will be apparent to those skilled in the art that various
modifications and variations can be made in the disclosed
structures and methods without departing from the scope or spirit
of the invention. Particularly, descriptions of any of the
embodiments can be freely combined with descriptions of other
embodiments to result in combinations and/or variations of two or
more elements and/or limitations. Other embodiments of the
invention will be apparent to those skilled in the art from
consideration of the specification and practice of the invention
disclosed herein. It is intended that the specification and
examples be considered exemplary only, with a true scope and spirit
of the invention being indicated by the following claims.
* * * * *