AU2010332478B2 - Biofuels from lignocellulosic resources - Google Patents

Abstract

A method comprising separating a lignocellulosic resource into a substantially cellulosic portion and a substantially non-cellulosic portion; and fermenting the substantially cellulosic portion to produce microbial oil, pyrolyzing the substantially non-cellulosic portions to produce bio-oil or fermenting the substantially cellulosic portion to produce microbial oil and pyrolyzing the substantially non-cellulosic portion to produce bio-oil.

Description

WO 2011/073781 PCT/IB2010/003276 Biofuels from Lignocellulosic Resources Background [00011 The production of bio-products, such as biofuels, is being promoted worldwide as a long term sustainable alternative to fast depleting fossil fuel reserves and to limit the net addition of green house gases into world environment. However, as per current practices in biofuels, a major portion of produced biofuels is from food resources such as corn and vegetable oils. The biofuels production in 2007 (14 billion gallon) was just 1.5 % of global supply of liquid fuels, much less than the mandated demand of biofuels. However, the biofuel production from food resource, as reported by U. N. Food and Agricultural Organization, has increased the food inflation globally by 8-14% in 2007. Summary [0002] The inventors recognize the need for providing robust and sustainable biofuel technologies from multiple types of sustainable and renewable feedstocks to meet the increasing demand for biofuels. The inventors provide herein, for the first time, a novel separating and conversion process for maximizing carbon conversion efficiency, while minimizing processing energy requirements. [0003] A method comprising separating a lignocellulosic resource into a substantially cellulosic portion and a substantially non-cellulosic portion; and fermenting the substantially cellulosic portion to produce microbial oil, pyrolyzing the substantially non-cellulosic portions to produce bio-oil or fermenting the substantially cellulosic portion to produce microbial oil and pyrolyzing the substantially non-cellulosic portion to produce bio-oil is provided. [0004] The lignocellulosic resource may include, but is not limited to, agricultural residue, animal waste, woody biomass, municipal solid waste, industry solid waste and any combination thereof. The industry solid waste may comprise waste from paper production, oil production (e.g., palm oil), alcohol production 1 WO 2011/073781 PCT/IB2010/003276 (e.g., ethanol production), food production, (e.g., corn production) and any combination thereof. [0005] In one embodiment, the fermentation is oleaginous fermenting which is performed with oleaginous species. In one embodiment, the oleaginous species have a dry cell biomass and are capable of accumulating lipids at more than 20 % of the dry cell biomass. In one embodiment, the fermented product contains more than 95 wt% of fatty acids, wherein the fatty acid is a 12 to 24 carbon (C) mono unsaturated hydrocarbon chain or a 12 to 24 C poly-unsaturated hydrocarbon chain. [00061 In one embodiment, the microbial oil is converted to one or more cellulosic-based hydrocarbon products with hydrodeoxygenation and hydroisomerization. The hydrodeoxygenation and the hydroisomerization may both be carried out in the presence of hydrogen, i.e., in a hydrogen atmosphere. [0007] In one embodiment, the one or more cellulosic-based hydrocarbon products comprise diesel fuel, one or more components of diesel fuel, jet fuel, one or more components of jet fuel, gasoline fuel, one or more component of gasoline fuel, naptha, a gasoline/naphtha mixture or any combination of thereof. [0008] In one embodiment, the bio-oil produced with pyrolysis has improved properties (e.g., is less corrosive, contains less oxygen and more carbon, contains more energy content, or any combination thereof) as compared to bio-oil produced [0009] In one embodiment, the bio-oil is converted to one or more cellulosic-based hydrocarbon products with hydrodeoxygenation and hydrocracking. The hydrodeoxygenation and the hydrocracking may both be carried out in the presence of hydrogen, i.e., in a hydrogen atmosphere. [0010] In one embodiment; the one or more non-cellulosic-based hydrocarbon products comprise diesel fuel, one or more components of diesel fuel, gasoline fuel, one or more component of gasoline fuel, naptha, a gasoline/naphtha mixture or any combination of thereof. [0011] Embodiments of the invention further comprise a liquid processing stream comprising a substantially lignocellulosic stream and a substantially non cellulosic stream, wherein the lignocellulosic stream is converted to microbial oil 2 WO 2011/073781 PCT/IB2010/003276 with oleaginous fermentation, the non-cellulosic stream is converted to bio-oil with pyrolysis, or the lignocellulosic stream is converted to microbial oil with oleaginous fermentation and the non-cellulosic stream is converted to bio-oil with pyrolysis. In one embodiment, the microbial oil is converted to cellulosic-based hydrocarbons with hydrodeoxygenation and hydroisomerization and the bio-oil is converted into non-cellulosic based hydrocarbons with hydrodeoxygenation and hydrocracking. [0012] Embodiments of the invention further include a system comprising a, hydrocarbon production facility, the facility comprising separating equipment for separating lignocellulosic biomass into a cellulosic portion and a non-cellulosic portion; and fermentation equipment for converting the cellulosic portion to a microorganism containing medium or pyrolysis equipment for converting the non cellulosic portion to bio-oil, or a combination thereof. Brief Description of the Drawing [00131 FIG. 1 is a simplified flow chart of a separating and conversion process for converting separated lignocellulosic resources into hydrocarbons according to an example embodiment. Detailed Description [0014] In the following description, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments which may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural, chemical and procedural changes may be made without departing from the scope of the present invention. The following description of example embodiments is, therefore, not to be taken in a limited sense, and the scope of the present invention is defined by the appended claims. [0100] The Detailed Description that follows begins with a definition section followed by brief overviews of conventional biomass to alcohol conversion 3 WO 2011/073781 PCT/IB2010/003276 processes and of the increasing need for alternative feedstock, followed by a description of the embodiments and a brief conclusion. Definitions [0015] The term "biomass" is intended herein to refer to any non-fossilized, i.e., renewable, organic matter collected for use as a source of energy. The various types of biomass include plant biomass (defined below), animal biomass (any animal by-product, animal waste, etc.), municipal waste biomass (residential and light commercial refuse with recyclables such as metal and glass removed), industry waste biomass (solid wastes from paper industry, corn industry, palm oil industry, food industry, and the like), paper, cardboard, wood, and other fibrous plant material or plant biomass [0016] The term "plant biomass" or "ligno-cellulosic biomass" as used herein is intended to refer to virtually any plant-derived organic matter (woody or non-woody) available for energy on a sustainable basis. Plant biomass can include, but is not limited to, agricultural crop wastes and residues such as corn stover, wheat straw, rice straw, sugar cane bagasse, and the like. Plant biomass further includes, but is not limited to, woody energy crops, wood wastes and residues such as trees, softwood forest thinnings, barky wastes, sawdust, paper and pulp industry waste streams, wood fiber, and the like. Additionally grass crops, such as switch grass and the like have potential to be produced large-scale as another plant biomass source. For urban areas, the best potential plant biomass feedstock comprises yard waste (e.g., grass clippings, leaves, tree clippings, brush, etc.) and vegetable processing waste. Plant biomass is known to be the most prevalent form of carbohydrate available in nature and corn stover is the largest source of readily available plant biomass. [0017] The term "microbial oil" as used herein, refers to a mixture of long chain (i.e., number of carbon atoms > 12) fatty acids obtained by a fermentation process. Such oils are also commonly referred to as "lipids." Microbial oil is known to have a composition comparable to any edible vegetable oils such as groundnut oil, rapeseed oil, sunflower oil, canola oil, palm oil, soybean oil, olive oil, coconut 4 WO 2011/073781 PCT/IB2010/003276 oil, mustard oil, castor oil, and the like. Microbial oil is also known to have a composition comparable to any non-edible vegetable oils such as jetropha oil (from the seeds of the Jatropha curcas plant), and the like. Microbial oil is further known to have a composition comparable to algae oil. [00181 The term "bio-oil" as used herein, refers to the product obtained after thermal treatment of the lignocellulosic resource, i.e. burning the biomass under controlled and depleted conditions of oxygen resulting in evolution of fumes which are condensed to form bio oil or pyrolysis oil. [00191 The term "biofuel" as used herein, refers to a mixture of hydrocarbons. A biofuel includes any fuel derived from a renewable resource. -As such, a biofuel can include a bio derived diesel fuel or a component of bio-derived diesel fuel, jet fuel, or a component ofjet fuel, and may further include gasoline fuel, a component of gasoline fuel, naptha or gasoline/naptha mixtures. A biofuel may further refer to liquid fuels used for transportation, energy and other power applications. [00201 The term "pre-treatment" as used herein, refers to preprocessing of the raw lignocellulosic resource to bring it into a form that facilitates the subsequent separation, hydrolysis and processing by fermentation and/or pyrolysis. The term pre-treatment is known to break bonds between non-cellulosic portion and cellulosic portion of lignocellulosic resource. The pre-treatment process is further known to separate and/or break the bonds between various components of cellulosic portion such as cellulose, hemi-cellulose, and the like. The pre-treatment process can be carried out using well known methods such as acid (e.g., sulfuric acid, nitric acid, and the like) pre-treatment, lime pre-treatment, ammonia recycle percolation, ammonia fiber explosion pre-treatment, and the like. [0021] The term "hydrolysis" as used herein, refers to processing of the cellulosic portion from lignocellulosic resource to bring it into a monomer sugars form, such as glucose, xylose, and the like, which facilitates the subsequent separation and/or fermentation. The term hydrolysiss" is known to convert cellulose polymer molecules into glucose (six carbon sugar) monomer molecules. The term "hydrolysis" is further known to convert hemi-cellulose polymer into corresponding 5 WO 2011/073781 PCT/IB2010/003276 monomers such as xylose (five carbon sugar) glucose, arabinose, galactose, fructose, mannose, and the like. The hydrolysis process can be carried out using any well known hydrolysis methods such as acid (diluted and concentrated sulfuric acid, nitric acid, and the like) hydrolysis, enzyme (cellulases such as endoglucanase, exoglucanase, beta-glucosidase and hemi-cellulases such as xylanases, beta xylosidases, and the like) hydrolysis, ionic liquids (such as 1,3 Dimethylimidazolium-dimethylphosphate, and the like) hydrolysis, and the like. [00221 The term "carbon conversion efficiency" as used herein, refers to a ratio of amount of carbon converted into biofuel to amount of carbon present in' biomass. The term carbon conversion efficiency further refers to ratio of number of carbon atoms present in biofuel molecule(s) to number of carbon atoms present in biomass molecule. [0023] The term "process energy efficiency" as used herein, refers to a ratio of 'energy content of the biofuel produced from given quantity of biomass' to a sum of 'the energy content of the given quantity of biomass' and 'energy used to convert the given quantity of biomass to biofuel'. The term process energy efficiency can be defined for a conversion step such as fermentation, pyrolysis, and the like, or for an entire conversion process, including for the novel separating and conversion processes described herein. [00241 The term "biofuel quality" as used herein, refers to various properties such as energy density (energy content per kg or per liter of biofuel), stability, acid number, oxygen content, and the like. Generally, biofuels with a high energy content, high stability, a low acid number, and a low oxygen content are considered "high quality" biofuels. Generally, high quality biofuels are known to perform better over the entire life cycle of their use. For example, high stability would imply better "keeping" properties as such fuels do not degrade easily. A low acid number relates to a lower corrosive nature, thus eliminating the need to store such fuels in special containers/equipment. A low oxygen content implies that such fuels are low oxygenated fuels which have higher energy density 6 WO 2011/073781 PCT/IB2010/003276 Conventional Conversion Processes of Biomass to Biofuels [00251 CUrrent feedstock resources, i.e., food related resources are not sustainable to meet the projected (50 billion gallon annually) biofuels demands because of their inflammatory effect on food prices. [00261 The current installed capacities (14 billion gallons annually) worldwide and current technologies are not sufficient enough to meet the projected demand (More than 50 billion gallons annually) of biofuels (bio-ethanol and renewable diesel) worldwide. This is mainly because of their dependencies on feed stocks, such as corn and vegetable oils, which directly complete with food needs. Hence, the development of sustainable biofuel technologies to meet projected renewable fuel demand from sustainable feedstocks to address issues like energy self-sufficiency, food vs. fuel balance and environmental impact is an attractive mega-trend globally. [0027] Sustainable feedstocks which do not alter the food vs. fuel balance are mainly lignocellulosic resources, such as agricultural residue biomass, woody resources, animal wastes and industry solid residues. More than 30 billion metric ton of lignocellulosic material is produced worldwide annually. [0028] Nearly all forms of lignocellulosic biomass, i.e., plant biomass, comprise a heterogeneous complex of carbohydrate polymers (primarily hemicellulose and cellulose) and lignin. Hemicellulose is a polymer of short, highly branched chains of mostly five-carbon pentose sugars (xylose and arabinose), and to a lesser extent six-carbon hexose sugars (galactose, glucose and mannose). These sugars are highly substituted with acetic acid. Because of its branched structure, hemicellulose is amorphous and relatively easy to hydrolyze (breakdown or cleave) to its individual constituent sugars by enzyme or dilute acid treatment. [0029] Cellulose is a linear polymer of glucose sugars, much like starch, which is the primary substrate of corn grain in dry grain and wet mill ethanol plants. However, unlike starch, the glucose sugars of cellulose are strung together by B glycosidic linkages which allow cellulose to form closely-associated linear chains. Because of the high degree of hydrogen bonding that can occur between cellulose chains, cellulose forms a rigid crystalline structure that is highly stable and much 7 WO 2011/073781 PCT/IB2010/003276 more resistant to hydrolysis by chemical or enzymatic attack than starch or hemicellulose polymers. [0030] Lignin, which is a complex polymer of phenylpropanoid units, provides structural integrity to plants, and remains as residual material after the sugars in plant biomass have been fermented to ethanol. Lignin ira by-product of alcohol production and is considered a premium quality solid fuel because of its zero sulfur content and heating value, which is near that of sub-bituminous coal. [0031] Typical ranges of hemicellulose, cellulose, and lignin concentrations. in plants are presented in Table 1. See www.nrel.gov/biomass, National Renewable Energy Laboratory website. Cellulose makes up 30 to 50% of residues from agricultural, municipal, and forestry sources. While cellulose is more difficult to convert to ethanol than hemicellulose, it is the sugar polymers of hemicellulose which can be more readily hydrolyzed to their individual component sugars for subsequent fermentation to ethanol. Although hemicellulose sugars represent the "low-hanging" fruit for conversion to ethanol, the substantially higher content of cellulose represents the greater potential for maximizing alcohol yields, such as ethanol, on a per ton basis of plant biomass. Table 1. Typical Levels of Cellulose, Hemicellulose and Lignin in Plant Biomass and Corn Stover Plant Biomass Corn Stover Component Percent Dry Weight Percent Dry Weight Cellulose 30-50% 38% Hemicellulose 20-40% 32% Lignin 10-25% 17% [0032] Various technical methods exist by which lignocellulosic resources can be converted into bio-energy, including "gasification to synthesis gas" methods "pyrolysis to bio-oil" methods and "fermentation to ethanol" methods. 8 WO 2011/073781 PCT/IB2010/003276 [0033] "Gasification to synthesis gas" methods, however, are known to have a very low energy conversion efficiency and supply chain issues because of distributed availability of low density lignocellulosic material. [0034] Although "pyrolysis to bio-oil" methods address supply chain issues by distributed generation, these methods suffer from low carbon conversion efficiency generally related to improper tuning of operation conditions, high processing energy requirement and sensitivity to feedstock composition variation, which is generally significant. As a result, the quality of the resulting bio-oil is highly dependent on the feedstock used. [0035] While "fermentation to ethanol" methods enjoy a high carbon conversion efficiency compared with pyrolysis and gasification routes, such conversion rates, and overall ethanol yields are, nonetheless, still limited. The conversion rates and ultimate ethanol yield is dependent on several factors, including the biomass type, pretreatment type (e.g., chemical pretreatments, hydrothermal pretreatments, and the like), and so forth. Additionally, the energy requirement for ethanol separation and purification is very high. Furthermore, the availability of lignocellulosic biomass for ethanol production is much more than the projected demand of bio-ethanol. Description of Embodiments [0036] In contrast, embodiments of the invention are not limited to any one of the individual methods described above. As a result, the novel separation and conversion processes described herein exhibit reduced carbon and/or energy loss as compared to conventional conversion methods, since lignin is separated and further processed to produce a portion of the end product. In one embodiment, energy loss is reduced at least about 10 to about 25%. In other word, process energy efficiency increases by 10 to 25 percentage points. Additionally, not only are the energy requirements reduced as compared to pyrolysis only methods, the pyrolysis products are less corrosive, have less oxygen content with more carbon content and have high energy content than products produced by conventional pyrolysis methods which are performed on an intact, non-separated lignocellulosic resource. As a result, the 9 WO 2011/073781 PCT/IB2010/003276 make-up of the feedstock composition no longer limits the quality of the final hydrocarbon products. [0037] Embodiments of the invention provide for separation of a lignocellulosic resource into two primary components, namely, a substantially cellulosic portion (containing mainly cellulose and hemi-cellulose) and a substantially non-cellulosic portion (containing mainly lignin, proteins and other minor components, such as fats, minerals, salts, and the like). [0038] In one embodiment, the lignocellulosic resource is agricultural residue, animal waste, woody biomass, municipal solid waste, industry solid wastes or any combination of these. Industry solid wastes can include solid wastes from paper industry, corn industry, palm oil industry, food industry, first generation biofuel producing industries etc. [0039] In one embodiment, the lignocellulosic biomass is first subject to a conventional pretreatment and hydrolysis. In one embodiment, the substantially cellulosic portion is converted to hydrocarbons via microbial lipid (e.g., oleaginous) fermentation followed by hydrodeoxygenation and hydroisomerization of the resulting microbial oil to produce cellulosic-based hydrocarbons useful as diesel fuel, jet fuel, gasoline fuel and/or mixture of gasoline and naphtha. In one embodiment, the hydrodeoxygenation and hydroisomerization steps are performed according to processes known as ECOFINING Im (Honeywell). In one embodiment, the hydrodeoxygenation and hydroisomerization are performed according to the methods described in PCT Publication WO 2008/058664 Al (hereinafter "'664"), which is incorporated herein by reference in its entirety. [0040] In one embodiment, the substantially non-cellulosic portion is subjected to pyrolysis to produce bio-oil, followed by hydrodeoxygenation and hydrocracking of the bio-oil to produce non-cellulosic based hydrocarbons useful as gasoline fuel, diesel fuel and/or mixture of gasoline and naphtha. In one embodiment, the hydrodeoxygenation and hydrocracking are performed according to the methods described in U.S. Patent No. 7,578,927 (hereinafter "'927"), which is incorporated herein by reference in its entirety. 10 WO 2011/073781 PCT/IB2010/003276 [0041] Since the cellulosic portion of the lignocellulosic resource is treated independently of the non-cellulosic portion, the hydrocarbon yield (per unit of cellulosic portion) by fermentation and the subsequent processes, such as ECOFININGEm, is increased. The separation step further eliminates the dependence of the final product(s) on the composition of the original lignocellulosic resource. [00421 Furthermore, since the non-cellulosic portion of the lignocellulosic resource is treated independently of the cellulosic portion, the hydrocarbon yield (per unit of non-cellulosic portion) by pyrolysis and the subsequent processes, such as hydrodeoxygenation and hydrocracking, is increased. The separation step further eliminates the dependence of the final product(s) on the composition of the original lignocellulosic resource. [0043] In contrast to conventional methods which do not include an initial separation step, the process energy efficiency of each portion of the lignocellulosic resource is much higher, such as at least about 55 to 60 %. In one embodiment, the carbon conversion is greater than 60%. In one embodiment, the carbon conversion is about 55 to about 58%. [0044] In one embodiment, only the non-cellulosic portion of the lignocellulosic resource is converted using a pyrolysis process. The cellulosic portion is converted via a fermentation route, which uses ambient temperatures, as fermentation does not require the higher temperatures of pyrolysis (e.g., > 300 *C). As only lignin is converted by energy intensive pyrolysis, the mass processed via pyrolysis route is much lower than conventional pyrolysis methods, which are performed on an intact, non-separated lignocellulosic resource. This reduces the energy requirement to produce hydrocarbons from the lignocellulosic resource [0045] Furthermore, as less mass is converted via the pyrolysis.route, loss of energy or carbon in the form of gaseous and solid products is minimized. The gaseous product (containing primarily CO, C0 2 , hydrogen and other fuel gases) is one by-product from conventional pyrolysis methods. The solid product (containing primarily charcoal and ash) is another by-product from conventional pyrolysis methods. Although the gaseous and solid products have energy value, some of this energy value is lost during the manufacturing of liquid biofuels or hydrocarbons 11 WO 2011/073781 PCT/IB2010/003276 from lignocellulosic biomass. There are no significant by-products from the fermentation step. As a result, the process energy efficiency is increased when producing hydrocarbons from lignocellulosic resources. [00461 In one embodiment, only the non-cellulosic portion of the lignocellulosic resource is converted using the pyrolysis process, while the cellulosic portion is converted via another route, such as a fermentation route. Hence, with use of the novel separation step described herein, a major portion (cellulosic portion) of a lignocellulosic resource may now be treated at much lower temperatures (around ambient or room temperature) via a fermentation route, as compared with prior art methods. In one embodiment, the non-cellulosic portion of the lignoceliulosic resource is converted into pyrolysis oil. Since this portion consistently contains mostly lignin (with the non-cellulosic portion already separated out), better tuning of the operating conditions, so as to achieve a desired composition of bio-oil, is now possible, as compared with prior art processes in which no separation step occurs, thus providing starting materials, which may be from a variety of sources, and which contain varying amounts of cellulosics and non-cellulosics. Such operating conditions include, but are not limited to, temperature, pressure, residence time, and the like, as well as overall plant design, such as reactor design, heat supply mechanism design, and the like. [0047] As a result, standardization of the pyrolysis process has not been possible, since the changing composition of the feedstock would be felt on the final quality of the bio-oil. By separating the non-cellulosic portion from lignocellulosic resource and subsequent pyrolysis of only the non-cellulosic portion also increases the stability of the resulting bio-oil, thereby allowing for long-term storage with minimal degradation of properties. Pyrolysis of both portions, as is the conventional practice, gives rise to compounds that negatively impact the stability of the bio-oil and also increases its corrosive nature due to increased acids concentration. [0048] The minimal variation in quality of bio-oil will also help increase the hydrocarbon yield by allowing for proper operating condition selection for downstream processing steps such as hydrodeoxygenation and hydrocracking for converting the pyrolysis/bio-oil. See, for example '927. 12 WO 2011/073781 PCT/IB2010/003276 [00491 In one embodiment, a novel separation and conversion process 100 is performed according to the exemplary embodiment shown in FIG. 1. In this embodiment, lignocellulosic biomass 102 is first pretreated and hydrolyzed using any conventional pretreatment and hydrolysis methods in a pretreatment and hydrolysis step 104 to produce a cellulosic portion (monomer sugars) 106 and a non-cellulosic portion 129. [0050] The pretreatment in the pretreatment and hydrolysis step 104 can proceed using well known methods, such as acid pretreatment (e.g., sulfuric acid, nitric acid, and the like), lime pretreatment, ammonia recycle percolation, ammonia fiber explosion pre-treatment, and the like. The hydrolysisin the pretreatment and hydrolysis step 104 can proceed using any well known hydrolysis methods, such as acid (diluted and concentrated sulfuric acid, nitric acid, and the like) hydrolysis, enzyme (cellulases, such as endoglucanase, exoglucanase, beta-glucosidase 'and hemi-cellulases such as xylanases, beta- xylosidases, etc.) hydrolysis, ionic liquid (such as 1,3-Dimethylimidazolium-dimethylphosphate, and the like) hydrolysis or other known hydrolysis methods. [00511 The cellulosic portion 106 is then subjected to oleaginous fermentation in an oleaginous fermentation step 108 to produce a microorganism containing medium 110 and a waste stream (not shown). The microorganisms, (i.e., oleaginous species) used for oleaginous fermentation preferably has the ability to accumulate lipid (fatty acids) at least 20 % of their dry biomass. During the growth phase of fermentation, in which micro-organisms grow in number rapidly, all required substrates, such sugar sources, nitrogen sources, phosphorous source and other mineral sources such as K, Fe, Mn, and the like, are available in favorable concentrations. After the growth phase, challenging conditions, such as nitrogen limitation, phosphorous limitation, dissolved oxygen limitation, and the like, are used to trigger lipid accumulation phase. Although lipids become accumulated, both intracellularly and/or extracellularly, mainly during lipid accumulation phase, to some extent, lipid accumulation is possible during the growth phase. [00521 Although fungi, bacteria, and yeast microorganisms can be used for fermentation, in one embodiment a microorganism, such as Rhodosporidium 13 WO 2011/073781 PCT/IB2010/003276 toruloids, Lipomyces lipofer, Rhodotorula glutinies var glutinies, Rhodotorula glutinies, Cryptococcus Curvatus, is used to ferment the monomer sugars (obtained after hydrolysis step). In another embodiment hydrolysis and oleaginous fermentation can be carried out simultaneously. [0053] The microorganism-containing medium 110 is then subjected to a cell harvesting step 112 in which the microorganisms in the medium are separated or harvested from the media by any suitable means, such as with centrifuge, with filters, and the like, to produce oil-containing microorganism cells 114 and a waste stream (not shown). The microorganism containing medium contains microorganisms which have multiplied and grown (during the oleaginous. fermentation step 108) into the oil-containing microorganism cells 114. The oil containing microorganisms contain lipids, mainly triacylglyederol (TAG) containing long chain fatty acids, in which the hydrocarbon chain of fatty acid contains from 12 to 24 carbon atoms and is mono- or poly unsaturated. [00541 The oil-containing microorganism cells 114, i.e., cells with accumulated lipids, are then subjected to an oil extraction and purification step 118 known in the art to rupture the cell walls, thus releasing the microbial oil 120 contained therein. [0055] The microbial oil 120 is then subjected to hydrodeoxygenation and hydroisomerization 124 to produce a cellulosic-based hydrocarbons 125 and a minor waste stream (not shown). [0056] Referring again to the beginning of the process 100, the separated non-cellulosic portion 129 is first subject to a recovery treatment step 130, such as a centrifuge step, to produce a substantially lignin portion 132 which further contains components such as protein and other minor components. [0057] The substantially lignin portion 132 is thereafter pyrolyzed in a pyrolysis step 136 to produce bio-oil 138.The bio-oil 138 is thereafter subject to a hydro.deoxygenation and hydrocracking step 140 as described herein, to produce non-cellulosic-based hydrocarbons 126. [0058] In contrast to conventional methods which produce hydrocarbons (fuels such as ethanol, bio-diesel, pyrolysis oil, and the like) from lignocellulosic 14 WO 2011/073781 PCT/IB2010/003276 resources, embodiments of the current invention are directed to, for example, (i) separation of the cellulosic from the non-cellulosics and subsequent treatment of the cellulosic portion to produce cellulosic based hydrocarbons such as jet fuel, diesel fuel and the like using a fermentation step followed by hydro-deoxygenation and hydro-isomerization of the fermentation product, and/or (ii) treatment of the non cellulosics to produce non-cellulosic based hydrocarbons such as diesel fuel, gasoline fuel and the like using pyrolysis in the first step followed by hydro deoxygenation and hydrocracking of the pyrolysis oil. [0059] In most embodiments, the overall yields of hydrocarbons (from the lignocellulosic resources)is expected to improve by at least about 10 to 25 %, with a total expected improved yield of biofuel production of at least about 55-65%. [0060] The invention will be further described by reference to the following example, which is offered to further illustrate various embodiments of the present invention. It should be understood, however, that many variations and modifications may be made while remaining within the scope of the present invention. EXAMPLE [0061] The oleaginous fermentation experiments were conducted using cellulosic solutions resulting from pretreatment and hydrolysis of woody biomass containing cellulose at 57 %, hemicellulose 24 % and lignin 18 %. The cellulosic solution resulted from pretreatment and hydrolysis was adjusted to have 10 % sugar (glucose and xylose) concentration. The diluted Cellulosic solution contained glucose and xylose in the ratio of 7:3. [0062] The oleaginous fermentation runs were carried out using various lipid (more than 20 % of dry micro-organism biomass) accumulating micro organisms such as Rhodosporidium toruloids (2750), Lipomyces lipofer (1402), Rhodotorula glutinies var glutinies (190), Rhodotorula glutinies (7312) in a 10 liter fermentor equipped with temperature, agitation speed, pH and dissolved oxygen controllers. The oleaginous microorganisms were purchased from the Institute of Microbial Technology, Chandigarh, India. 15 WO 2011/073781 PCT/IB2010/003276 [00631 The diluted cellulosic solution was used as the sugar source. Yeast extract (0.5 gm/liter) was used as the nitrogen source. Other micro-nutrients used include K 2

HPO

4 (1.0 gm/liter), MgSO 4 (0.1 gm/liter), NaCl (0.5 gm/liter), calcium chloride (0.33 gm/liter) and ferric chloride (0.05 gm/liter). The pH of the fermentation medium was adjusted to 5.4 using 0.1N HCl or 0.1N NaOH. The fermentation medium was inoculated with 5 % inoculum (24 hrs, 104 CFU/ml). [00641 The batch fermentation runs were carried out at 200 rpm and the airflow was maintained at 1 VVM. The fermentation runs were terminated at either 120 hrs or at 144 hrs from the start of the experiment. The fermentation runs were carried out using any one of ground nut (peanut) oil, silicon oil, olive oil (obtained through a commercial supplier) and microbial lipid (generated using same micro organism) as the anti-foaming agent. Anti-foaming agent was addedas and when foaming was observed. The addition of ground nut oil as an anti-forming agent started after 24 hrs. The total quantity of anti-forming agent added never exceeded 0.4-0.5 ml/liter. [0065] During oleaginous fermentation, micro-organism growth was observed until 72 hrs, up to 96 hrs) from the start of the fermentation run. After rapid growth phase nitrogen plus dissolved oxygen limitation was trigger which resulted in intracellular lipid accumulation. The lipid yield from various batch fermentation runs varied from 15 gm/liter to 18.5 gm/liter. The lipid content varied from 58 % - 67 %. The lipid yield (from cellulosic portion only) per kg of woody biomass was 0.17 to 0.19 kg. [00661 After fermentation the micro-organism biomass was collected by centrifugation (8,000 rpm for 20 min). For lipid extraction a chloroform/ methanol mixture was used. The micro-organism biomass was acidified with 4N HCl and after neutralization with 10% KOH solution the lipids were extracted (refluxed at 30 0 C for 3 hrs) using the chloroform/methanol mixture: acidified micro-organism biomass in the volume ratio of 3:1. The chloroform/methanol mixture was prepared using chloroform and methanol in a 2:1 volume ratio. Distillation (at 40 0 C) technique was used to recover lipids from chloroform: methanol solution and the recovered lipid were concentrated by nitrogen fluxing. 16 WO 2011/073781 PCT/IB2010/003276 [00671 The fatty acid content of recovered lipids varied from 98 % - 98.7 %. The recovered lipid had a density ranging from 0.87 to 0.89 gm/ml. Fatty acid profiling of the lipid was carried out using gas chromatography (Shimadzu GC 2014 with an Omegawax Im 320 fused silica capillary column (30mX 0.32mmX 0.25mm)) with a flow rate of 1.l2ml/min. The sample fatty acid profile (weight percentage (wt/o)) obtained is reported in Table 1 below: Table 1. Fatty Acid Profile of Various Lipids Lipid Fatty Acid Content (wt%) Short Chain Fatty Acids (Below C16) 0.28 Palmitic Acid (C 16:0) 19.7 Palmitoleic Acid (C16:1) 0.14 Heptadecanoic Acid (C 17:0) 0.04 Heptaadecenoic (C17:1) 0.03 Stearic Acid (C 18:0) 1.8 Oleic Acid (C18:1) 43.8 Linoleic Acid (C 18:2) 28.3 Linolenic Acid (C18:3) 0.45 Other Long Chain Acids (>C 18) 3.8 [0068] The reported fatty acid profile obtained has a profile similar to that observed in many vegetable oils. The recovered lipid with said fatty acid profile was further processed using techniques known as ECOFININGm to produce diesel "drop in" fuel. (Also see techniques descried in, '664). The yield of diesel drop in fuel from one liter of lipid varied from 913 ml to 927 ml. The energy content of diesel drop in fuel was 44 MJ/kg, and specific gravity was 0.78. The diesel drop in fuel had a cetane number greater than 70 with sulfur content less than two (2) ppm. The diesel drop in fuel contained no polyaromatics. [0069] The process thermal efficiency of oleaginous fermentation process alone was calculated and found to vary in the range of 0.55-0.58. The lifecycle thermal efficiency of oleaginous fermentation process was found to vary in the 17 WO 2011/073781 PCT/IB2010/003276 range of 0.5-0.54. The process thermal and life cycle thermal efficiencies include the energy value of the non-cellulosic portion (i.e. lignin). [0070] Future experimentation will identify the type and concentration of common toxins found in various lignocellulosic resources known to limit the growth of oleaginous microorganisms and resulting lipid production. These likely include sugar degradation products such as furfurals, ferulate, acetates and the like. Once these toxins are identified, a strategy will be developed to properly handle, reduce or eliminate the toxin with various pre-processing techniques. [00711 Other testing will include, but is not limited to: [0072] 1) standardization of fatty acid distribution in microbial lipids to obtain consistent results (better yield and quality of hydrocarbons) from ECOFININGT'; [0073] 2) selection of oleaginous species that will generate the right combination of fatty acids from fermentation and design of fermentation operating conditions to increase yield and production rate of this combination of fatty acids; [0074] 3) selection and standardization of cell harvest and lipid extraction methods for consistent yield and distribution of fatty acids; [0075] 4) standardization of bio-oil (obtained from pyrolysis of non cellulosic portion) characteristics. This will help design optimal operating conditions for hydro-deoxygenation and hydro cracking to increase yield of hydrocarbons from lignin; [0076] 5) selection of pyrolysis operating conditions to handle variations (moisture content and lignin content and other components) in non-cellulosic portion; [0077] 6) determination of improvement in carbon conversion efficiency over conventional single-step conversion approaches; [0078] 7) determination of reduction in processing energy requirement over conventional single-step conversion approaches (measure with respect to either per kg of lignocellulosic resource processed or per kg of hydrocarbons produced); [0079] 8) determination of robustness of the process design to handle feedstock composition variability; and 18 10080] 9) determination of economic benefits or value addition expected over conventional single-stage conversion approaches. Conclusion [0081] Embodiments of the novel process described herein are expected to result in high carbon conversion efficiency, low processing energy requirements and robust design to handle composition variation of lignocellulosic resource. [0082] The resulting hydrocarbon products are useful in jet fuels (as jet fuel or a component in jet fuel), diesel fuel (as diesel fuel or a component in diesel fuel), gasoline fuel (as gasoline fuel or a component in gasoline fuel), naptha, or gasoline/naptha combinations, useful in other heating and lighting applications such as lanterns, cook stoves, and the like. [0083] Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any procedure that is calculated to achieve the same purpose may be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations of the present subject matter. Therefore, it is manifestly intended that embodiments of this invention be limited only by the claims and the equivalents thereof. [0084] Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia. [0085] Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof. 19

Claims (20)

1. A method comprising: separating a lignocellulosic resource into a substantially cellulosic portion and a substantially non-cellulosic portion; and fermenting the substantially cellulosic portion to produce microbial oil, pyrolyzing the substantially non-cellulosic portions to produce bio-oil or fermenting the substantially cellulosic portion to produce microbial oil and pyrolyzing the substantially non-cellulosic portion to produce bio-oil.

2. The method of claim 1, wherein the lignocellulosic resource comprises agricultural residue, animal waste, woody biomass, municipal solid waste, industry solid waste and any combination thereof.

3 The method of claim 2, wherein the industry solid waste comprises waste from paper production, oil production, alcohol production, food production, and any combination thereof.

4. The method of claim 2, wherein the industry solid waste comprises waste from corn production, palm oil production, or ethanol production.

5. The method of any one of claims 1 to 4, wherein the fermenting is oleaginous fermenting and the oleaginous fermenting is performed with oflaginous species.

6. The method of claim 5, wherein the oleaginous species have a dry cell biomass and are capable of accumulating lipids at more than 20 % of the dry cell biomass. 20

7. The method of any one of claims 1 to 6, wherein the microbial oil contains more than 95 wt% of fatty acids, wherein the fatty acid is a 12 to 24 carbon (C) mono unsaturated hydrocarbon chain or a 12 to 24 C poly-unsaturated hydrocarbon chain.

8. The method of claim 7, wherein the microbial oil is converted to one or more cellulosic-based hydrocarbon products with hydrodeoxygenation and hydroisomerization.

9. The method of claim 8, wherein the hydrodeoxygenation and the hydroisomerization of the microbial oil are both carried out in a hydrogen atmosphere.

10. The method of claim 8 or claim 9, wherein the one or more cellulosic-based hydrocarbon products comprise diesel fuel, one or more components of diesel fuel, jet fuel, one or more components of jet fuel, gasoline fuel, one or more component of gasoline fuel , naptha, a gasoline/naphtha mixture or any combination of thereof.

11. The method of any one of claims 1 to 10, wherein the bio-oil is less corrosive as compared to bio-oil produced using both the cellulosic and non cellulosic portions of the lignocellulosic biomass.

12. The method of any one of claims I to 11, wherein the bio-oil has less oxygen content and more carbon content as compared to bio-oil produced using both the cellulosic and non-cellulosic portions of the lignocellulosic biomass.

13. The method of any one of claims 1 to 12, wherein the bio-oil has more energy content as compared to bio-oil produced using both the cellulosic and non cellulosic portions of the lignocellulosic biomass. 21

14. The method of any one of claims 1 to 13, wherein the bio-oil is converted to one or more non-cellulosic based hydrocarbon products using hydrodeoxygenation and hydrocracking.

15. The method of claim 14, wherein hydrodeoxygenation and hydrocracking of the bio-oil are carried out in a hydrogen atmosphere.

16. The method of claim 14 or claim 15, wherein the one or more non cellulosic-based hydrocarbon products comprise diesel fuel, one or more components of diesel fuel, gasoline fuel, one or more component of gasoline fuel, naptha, a gasoline/naphtha mixture or any combination of thereof.

17. A liquid processing stream comprising: a substantially lignocellulosic stream and a substantially non-cellulosic stream, wherein the lignocellulosic stream is converted to microbial oil with oleaginous fermentation, the non-ccllulosic stream is converted to bio-oil with pyrolysis, or the lignocelllosic stream is converted to microbial oil with oleaginous fermentation and the non-cellulosic stream is converted to bio-oil with pyrolysis.

18. The liquid processing stream of claim 17, wherein the microbial oil is converted to cellulosic-based hydrocarbons with hydrodeoxygenation and hydroisomerization.

19. The liquid processing stream of claim 17 or claim 18, whereiri the bio-oil is converted to non-cellulosic-based hydrocarbons with hydrodeoxygenation and hydrocracking.

20. A system comprising: a hydrocarbon production facility comprising 22 separating equipment for separating lignocellulosic biomass into a cellulosic portion and a non-cellulosic portion; and fermentation equipment for converting the cellulosic portion to a microorganism containing medium or pyrolysis equipment for converting the non cellulosic portion to bio-oil, or a combination thereof. 23