EP2658953A1

EP2658953A1 - Derivation and conversion of natural oils with chemical compositions for hydroprocessing to transport fuels

Info

Publication number: EP2658953A1
Application number: EP11806049.0A
Authority: EP
Inventors: Jacob Borden; John W. Shabaker
Original assignee: BP Corp North America Inc
Current assignee: BP Corp North America Inc
Priority date: 2010-12-30
Filing date: 2011-12-12
Publication date: 2013-11-06
Also published as: US20140290127A1; CN103298917B; EA201300666A1; JP2014507511A; BR112013015512A2; MX2013007451A; WO2012091905A1; CA2822348A1; CN103298917A; KR20130133819A; AU2011352922A1

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° Celsius or lower.

Description

DERIVATION AND CONVERSION OF NATURAL OILS WITH CHEMICAL COMPOSITIONS FOR HYDROPROCESSING TO TRANSPORT FUELS

Background

Technical Field

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.

Discussion of Related Art

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.

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 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 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°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).

Rapeseed oils could also be hydrotreated, whereby the glycerides are converted to paraffins, such as by:

· Catalytic reduction by hydrogen (namely, C18 fatty acids become nC18 paraffins + water, and glycerol becomes propane + water) • Catalytic or thermal decarboxylation (namely, C18 fatty acids become nC17 hydrocarbons + C0₂, followed by further reaction to make nC17 paraffins, methane, and CO).

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.

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 2: Comparison of Biodiesel and Renewable Diesel Properties

There is thus a need and desire for alternative glyceride compositions that provide an improved hydrotreating feedstock and final diesel fuel product.

Summary

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.

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.

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° C or lower.

According to some embodiments, the resulting biofuel has a density below about 940 kg/m³ at 15° C. According to some embodiments, the resulting biofuel has a cetane value of at least about 50.

According to some embodiments, the resulting biofuel has an isomerization ratio of less than 2.

According to some embodiments, the resulting biofuel includes a fuel made by a hydrotreating process.

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.

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.

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.

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.

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° C or lower.

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. According to some embodiments, the method further includes blending a quantity of the biofuel with a fossil-derived fuel.

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

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:

The FIGURE schematically shows an apparatus within a biorefinery, according to some embodiments.

Detailed Description

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.

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.

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.

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.

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.

For instance, the tables below show example heterotrophic and photosynthetic micro-organisms with lipid profiles appreciably different as compared to rapeseed oil:

Table 3A: Comparison of Tri-acyl Glyceride Chain Lengths

<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 - - 1 1 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 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 1 1 -

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 1 1 18

Tetraselmis Suscia 2 3 33 2 17

Cyclotella Cryptica 4 - 1 - -

Navicula Muralis - 1 1 12 - -

Nitzschia Alba 3-2 - - 24 - 6

Phaeodactylum Triconutum 7 1 2 - 2

Thalassiosira Pseudon. 3H 1 1 - - - - Tables 3A and 3B are reproduced from the Fats and Oils Handbook; Michael Bockisch; 1998; AOCS Press.

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.

According to some embodiments, the feedstock may have a density below about 940 kg/m³ at 15° C. In some embodiments, the feedstock may have a density between about 830 kg/m³ and about 930 kg/m³, or between about 840 kg/m³ and about 920 kg/m³ at 15° C. Since fuel is sold by volume, not density, the relatively low density of the feedstock increases the efficiency of producing the resulting biofuel.

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 4: Comparison of Tri-acyl Glyceride Saturation Levels

TAG Unsaturation Level

Vegetative Oil-Seed

Rapeseed oil 1 14

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 1 12

Choelastrum Microsporum 108

Dunaliella Tertiolecta 1 17

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 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 C0₂).

Table 5: Reaction Yields and Heat Effects on Model Lipids

Lipid Tripalmitate Tristearate Triolein Trilino- Palm Rape- C16:0 C18:0 C18:1 lenate seed

C18:3

MASS BALANCE (wt% on vegetable oil)

tri-acyl glyceride -100.0 -100.0 -100.0 -100.0 -100.0 -100.0

H₂ -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

CH₄ 1 .5 1 .3 1 .4 1 .4 1 .4 1 .4

C3H8 5.5 4.9 5.0 5.0 5.2 5.0

CO₂ 4.1 3.7 3.7 3.8 3.9 3.8

H₂O 10.0 9.1 9.2 9.3 9.5 9.2

SUM (C15-C18) 81 .5 83.3 83.8 85.0 82.9 84.0

GAS YIELDS (Nm tri-acyl glyceride)

H₂ -248 -225 -291 -426 -276 -316

CH₄ 18 16 16 16 17 16

C3H8 24 21 22 22 22 22

CO₂ 18 16 16 16 17 16

H₂0 106 96 97 98 101 98

Heat of Reaction -746 -990 -1 166 -2012 -1015 -131 1 kJ/kg TAG 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 H₂ consumption.

According to some embodiments, the resulting biofuel may have a pour point of about 20° C or lower, or about 15° C or lower, or about 10° 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° C to about 0° C.

The resulting biofuel may include diesel, jet fuel, or blends with other biofuels and/or petroleum.

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.

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. 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.

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 6: Melting Points of Fatty Acids of Various Chain Lengths

The method may further include producing a biofuel having a pour point of about 20° C or lower, or about 15° C or lower, or about 10° C or lower.

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 .

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.

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 7: Paraffin Data

The Pour Index (PI) is calculated from the melting point (mp) (degrees Fahrenheit) as follows:

PI = i o^{(0,0105(mp+100))}

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 < C12 as a reasonable distribution.

The following tables display the Blend Pour Index and the Blend Pour Point for each of the feedstocks listed in Table 7 above. Table 8: Pour Point Data Without Decarboxylation

Carbon # HVO Products Without Decarboxylation

Soybean Palm Coconut E. Coronata E. Obscura

7

8 8 10 10

9

10 6 10 10

1 1

12 47 20 20

13

14 1 18 30 8

15

16 1 1 45 9 8 36

17

18 89 54 1 1 19 1 1

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 (°F)

Blend Pour 27 24 3 8 9

Point (°C)

Table 9: Pour Point Data with Complete Decarboxylation

Carbon # HVO Products with Complete Decarboxylation

Soybean Palm Coconut E. Coronata E. Obscura

7 9 10 10

8

9 6 10 10

10

1 1 47 20 20

12

13 1 18 30 8

14

15 1 1 45 9 8 36

16

17 89 54 1 1 19 1 1

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 (°F)

Blend Pour 22 18 -7 -1 1

Point (°C)

Table 10: Pour Point Data with 50% Decarboxylation

The Blend Pour Index (BPI) is calculated for each feedstock as follows:

BPI = SUMPRODUCT(Plcn,D_Cn)/SUM(Dcn)

wherein SUMPRODUCT(PI_Cn, D_Cn) = Plci ^* D_Ci + ... + Plcn ^* D_Cn and SUM(Dcn) = Dei + ... + D_Cn.

The Blend Pour Point (BPP) (degrees Fahrenheit) is calculated as follows:

BPP = Log₁₀(BPI)/0.0105-100

The BPP (degrees Celsius) is calculated using the standard conversion from Celsius to Fahrenheit:

F = (9/5)C + 32 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.

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.

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.

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.

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.

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.

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.

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° C to about 700° C, about 150° C to about 350° C, and/or the like.

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.

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, fiocculants, emulsifiers, demulsifiers, viscosity increasers, viscosity decreasers, surfactants, salts, other fluid modifying materials, and/or the like.

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.

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.

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.

Double bonds refer two pairs of electrons shared by two atoms in a molecule.

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.

Transesterification can include use of any suitable alcohol, such as methanol, ethanol, propanol, butanol, and/or the like.

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.

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.

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.

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.

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.

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.

Claims

What is claimed

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° C or lower.

2. The feedstock of claim 1 , wherein the feedstock has a density below about 940 kg/m³ at 15° C.

3. The feedstock of claim 1 or claim 2, wherein the biofuel resulting from hydroprocessing the feedstock has a cetane value of at least about 50.

4. The feedstock of any of claims 1 -3, wherein the feedstock has an iodine value of about 100 or less. 5. The feedstock of any of claims 1 -4, 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 any of claims 1 -4, 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 any of claims 1 -6, wherein the glycerides comprise at least about 10% by weight of fatty acid chains of length C14 or lower. 8. The feedstock of any of claims 1 -6, 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 any of the preceding claims, wherein the biofuel comprises diesel.

10. The biofuel resulting from hydroprocessing the feedstock of any of the preceding claims, wherein the biofuel comprises jet fuel. 1 1 . The biofuel resulting from hydroprocessing the feedstock of claim 9 or 10, wherein the resulting biofuel comprises a fuel made by a hydrotreating process.

12. The biofuel resulting from hydroprocessing the feedstock of claim 1 1 , wherein the glycerides do not undergo isomerization or hydroisomerization.

13. The biofuel resulting from hydroprocessing the feedstock of any of the preceding claims, 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° 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 any of claims 14-16, 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 any of claims 14-1 7, wherein the glycerides comprise at least about 10% by weight of fatty acid chains of length C14 or lower.

19. The method of any of claims 14-1 7, wherein the glycerides comprise at least about 10% by weight of fatty acid chains of length C12 or lower.

20. The method of any of claims 14-19, further comprising blending a quantity of the biofuel with a fossil-derived fuel.

21 . The method of any of claims 14-20, wherein the biofuel comprises diesel.

22. The method of any of claims 14-20, wherein the biofuel comprises jet fuel. 23. A biofuel produced according to the method of any of claims 14-

22.

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.