WO2011073781A2 - Biofuels from lignocellulosic resources - Google Patents
Biofuels from lignocellulosic resources Download PDFInfo
- Publication number
- WO2011073781A2 WO2011073781A2 PCT/IB2010/003276 IB2010003276W WO2011073781A2 WO 2011073781 A2 WO2011073781 A2 WO 2011073781A2 IB 2010003276 W IB2010003276 W IB 2010003276W WO 2011073781 A2 WO2011073781 A2 WO 2011073781A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulosic
- oil
- bio
- lignocellulosic
- biomass
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- bio-products such as biofuels
- biofuels are 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.
- 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.
- 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.
- 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.
- 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.
- 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 (e.g., ethanol production), food production, (e.g., corn production) and any combination thereof.
- the fermentation is oleaginous fermenting which is performed with oleaginous species.
- the oleaginous species have a dry cell biomass and are capable of accumulating lipids at more than 20 % of the dry cell biomass.
- 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.
- 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.
- 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.
- 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
- 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.
- 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.
- 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 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.
- 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.
- 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.
- 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.
- 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
- 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.
- plant biomass feedstock 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.
- Microbial oil 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 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.
- bio-oil 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.
- biofuel refers to a mixture of
- a biofuel includes any fuel derived from a renewable resource.
- a biofuel can include a bio derived diesel fuel or a component of bio-derived diesel fuel, jet fuel, or a component of jet 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.
- pre-treatment 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.
- 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.
- acid e.g., sulfuric acid, nitric acid, and the like
- hydrolysis 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.
- a monomer sugars form such as glucose, xylose, and the like
- the term '3 ⁇ 4ydrolysis is known to convert cellulose polymer molecules into glucose (six carbon sugar) monomer molecules.
- hydrolysis is further known to convert hemi-cellulose polymer into corresponding 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.
- acid diluted and concentrated sulfuric acid, nitric acid, and the like
- enzyme cellulases such as endoglucanase, exoglucanase, beta-glucosidase and hemi-cellulases such as xylanases, beta - xylosidases, and the like
- ionic liquids such as 1,3- Dimethylimidazolium-dimethylphosphat
- carbon conversion efficiency refers to a ratio of amount of carbon converted into biofuel to amount of carbon present in biomass.
- 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.
- process energy efficiency 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'.
- 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.
- biofuel quality 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.
- energy density energy content per kg or per liter of biofuel
- stability acid number
- oxygen content oxygen content
- oxygen content oxygen content
- 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
- lignocellulosic biomass i.e., plant biomass
- lignocellulosic biomass i.e., plant biomass
- carbohydrate polymers primarily
- 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.
- 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.
- 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 more resistant to hydrolysis by chemical or enzymatic attack than starch or hemicellulose polymers.
- 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 is a 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.
- 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.
- embodiments of the invention are not limited to any one of the individual methods described above.
- 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.
- energy loss is reduced at least about 10 to about 25%.
- process energy efficiency increases by 10 to 25 percentage points.
- 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 make-up of the feedstock composition no longer limits the quality of the final hydrocarbon products.
- 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).
- 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.
- the lignocellulosic biomass is first subject to a conventional pretreatment and hydrolysis.
- 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.
- the hydrodeoxygenation and hydroisomerization steps are performed according to processes known as ECOFININGTM (Honeywell).
- 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.
- 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.
- 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.
- U.S. Patent No. 7,578,927 hereinafter '"927
- the hydrocarbon yield per unit of cellulosic portion
- ECOFINTNGTM is increased.
- the separation step further eliminates the dependence of the final product(s) on the composition of the original lignocellulosic resource.
- 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.
- the process energy efficiency of each portion of the lignocellulosic resource is much higher, such as at least about 55 to 60 %.
- the carbon conversion is greater than 60%. In one embodiment, the carbon conversion is about 55 to about 58%.
- 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).
- pyrolysis e.g., > 300 °C.
- 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
- 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.
- the gaseous and solid products have energy value, some of this energy value is lost during the manufacturing of liquid biofuels or hydrocarbons 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.
- 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.
- 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.
- the non-cellulosic portion of the lignocellulosic resource is converted into pyrolysis oil.
- 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.
- a novel separation and conversion process 100 is performed according to the exemplary embodiment shown in FIG. 1.
- 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.
- 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.
- acid pretreatment e.g., sulfuric acid, nitric acid, and the like
- lime pretreatment e.g., lime pretreatment
- ammonia recycle percolation e.g., ammonia recycle percolation
- ammonia fiber explosion pre-treatment e.g., ammonia fiber explosion pre-treatment
- the hydrolysis ⁇ in 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-eellulases such as xylanases, beta- xylosidases, etc.) hydrolysis, ionic liquid (such as 1,3-Dimethylimidazolium-dimethylphosphate, and the like) hydrolysis or other known hydrolysis methods.
- acid diluted and concentrated sulfuric acid, nitric acid, and the like
- enzyme cellulases, such as endoglucanase, exoglucanase, beta-glucosidase and hemi-eellulases such as xylanases, beta- xylosidases, etc.
- ionic liquid such as 1,3-D
- 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.
- lipid fatty acids
- lipid accumulation phase 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.
- challenging conditions such as nitrogen limitation* phosphorous limitation, dissolved oxygen limitation, and the like, are used to trigger lipid accumulation phase.
- lipids become accumulated, both intracellularly and/or extracellularly, mainly during lipid accumulation phase, to some extent, lipid accumulation is possible during the growth phase.
- fungi, bacteria, and yeast microorganisms can be used for fermentation
- a microorganism such as Rhodosporidium toruloids, Lipomyces lipofer, Rhodotorula glutinies v r glutinies, Rhodotorula glutinies, Cryptococcus Curvatus
- hydrolysis and oleaginous fermentation can be carried out simultaneously.
- 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
- the oil- containing microorganisms contain lipids, mainly triacylglycerol (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.
- TAG triacylglycerol
- 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.
- 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).
- 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.
- a recovery treatment step 130 such as a centrifuge step
- 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 hydrodeoxygenation and hydrocracking step 140 as described herein, to produce non-cellulosic-based hydrocarbons 126.
- 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.
- 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%.
- 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.
- the oleaginous fermentation runs were carried out using various lipid (more than 20 % of dry micro-organism biomass) accumulating microorganisms such as Rhodosporidium toruloids (2750), Lipomyces lipofer (1402), Rhodotorula glutinies var glutinies (190), Rhodotorula glutinies (Till) 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.
- the diluted cellulosic solution was used as the sugar source.
- Yeast extract 0.5 gm/liter was used as the nitrogen source.
- micro-nutrients used include K 2 HP0 4 (1.0 gm/liter), MgS0 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 HC1 or 0.1N NaOH.
- the fermentation medium was inoculated with 5 % inoculum (24 hrs, 10 4 CFU/ml).
- the batch fermentation runs were carried out at 200 rpm and the airflow was maintained at 1 WM.
- 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 microorganism) as the anti-foaming agent.
- Anti-foaming agent was added, as 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.
- 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.
- 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 HC1 and after neutralization with 10% KOH solution the lipids were extracted (refluxed at 30 °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 °C) technique was used to recover lipids from chloroform: methanol solution and the recovered lipid were concentrated by nitrogen fluxing. [0067] 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 OmegawaxTM 320 fused silica capillary column (30mX 0.32mmX
- 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 ECOFININGTM 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.
- 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 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).
- 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.
- 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.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112012014085A BR112012014085A2 (en) | 2009-12-18 | 2010-12-16 | method, liquid processing stream, and system. |
CA2783894A CA2783894C (en) | 2009-12-18 | 2010-12-16 | Biofuels from lignocellulosic resources |
EP10837125.3A EP2513261A4 (en) | 2009-12-18 | 2010-12-16 | Biofuels from lignocellulosic resources |
NZ601190A NZ601190A (en) | 2009-12-18 | 2010-12-16 | Biofuels from lignocellulosic resources |
AU2010332478A AU2010332478B2 (en) | 2009-12-18 | 2010-12-16 | Biofuels from lignocellulosic resources |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IN2655/DEL/2009 | 2009-12-18 | ||
IN2655DE2009 | 2009-12-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2011073781A2 true WO2011073781A2 (en) | 2011-06-23 |
WO2011073781A3 WO2011073781A3 (en) | 2011-11-17 |
Family
ID=44167765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2010/003276 WO2011073781A2 (en) | 2009-12-18 | 2010-12-16 | Biofuels from lignocellulosic resources |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP2513261A4 (en) |
AU (1) | AU2010332478B2 (en) |
BR (1) | BR112012014085A2 (en) |
CA (1) | CA2783894C (en) |
NZ (1) | NZ601190A (en) |
WO (1) | WO2011073781A2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013021328A1 (en) | 2011-08-08 | 2013-02-14 | CO.MA.SE. S.r.l. | Process for the production of bioliquid or biofuel |
WO2013006755A3 (en) * | 2011-07-06 | 2013-05-02 | Washington State University Research Foundation | Simultaneous saccharification and fermentation(ssf) of lignocellulosic biomass for single cell oil production by oleaginous microorganisms |
WO2013093836A2 (en) | 2011-12-20 | 2013-06-27 | CO.MA.SE. S.r.l. | Process for the production of bioliquid or biofuel |
IT201600123786A1 (en) * | 2016-12-06 | 2018-06-06 | Consorzio Interuniversitario Naz Per La Scienza E Tecnologia Dei Materiali | Innovative energy self-sustainable biorefinery plant for the conversion of second-generation biomass |
CN115449409A (en) * | 2022-10-19 | 2022-12-09 | 中润油新能源股份有限公司 | Microbial fermentation methanol gasoline and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090031615A1 (en) * | 2007-08-01 | 2009-02-05 | General Electric Company | Integrated method for producing a fuel component from biomass and system therefor |
US20090054711A1 (en) * | 2005-05-04 | 2009-02-26 | Tom Lawrence | Pyrolysis Systems, Methods of Use Thereof, and Methods of Bio-Oil Transformation |
US20090056201A1 (en) * | 2007-08-27 | 2009-03-05 | Endicott Biofuels Ii, Llc | Production of Ester-based Fuels Such As Biodiesel From Renewable Starting Materials |
US20090069610A1 (en) * | 2006-12-01 | 2009-03-12 | North Carolina State University | Process for conversion of biomass to fuel |
US7578927B2 (en) * | 2006-08-31 | 2009-08-25 | Uop Llc | Gasoline and diesel production from pyrolytic lignin produced from pyrolysis of cellulosic waste |
-
2010
- 2010-12-16 AU AU2010332478A patent/AU2010332478B2/en not_active Ceased
- 2010-12-16 CA CA2783894A patent/CA2783894C/en not_active Expired - Fee Related
- 2010-12-16 BR BR112012014085A patent/BR112012014085A2/en not_active IP Right Cessation
- 2010-12-16 WO PCT/IB2010/003276 patent/WO2011073781A2/en active Application Filing
- 2010-12-16 EP EP10837125.3A patent/EP2513261A4/en not_active Withdrawn
- 2010-12-16 NZ NZ601190A patent/NZ601190A/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090054711A1 (en) * | 2005-05-04 | 2009-02-26 | Tom Lawrence | Pyrolysis Systems, Methods of Use Thereof, and Methods of Bio-Oil Transformation |
US7578927B2 (en) * | 2006-08-31 | 2009-08-25 | Uop Llc | Gasoline and diesel production from pyrolytic lignin produced from pyrolysis of cellulosic waste |
US20090069610A1 (en) * | 2006-12-01 | 2009-03-12 | North Carolina State University | Process for conversion of biomass to fuel |
US20090031615A1 (en) * | 2007-08-01 | 2009-02-05 | General Electric Company | Integrated method for producing a fuel component from biomass and system therefor |
US20090056201A1 (en) * | 2007-08-27 | 2009-03-05 | Endicott Biofuels Ii, Llc | Production of Ester-based Fuels Such As Biodiesel From Renewable Starting Materials |
Non-Patent Citations (1)
Title |
---|
See also references of EP2513261A2 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013006755A3 (en) * | 2011-07-06 | 2013-05-02 | Washington State University Research Foundation | Simultaneous saccharification and fermentation(ssf) of lignocellulosic biomass for single cell oil production by oleaginous microorganisms |
US9322038B2 (en) | 2011-07-06 | 2016-04-26 | Washington State University | Simultaneous saccharification and fermentation(SSF) of lignocellulosic biomass for single cell oil production by oleaginous microorganisms |
WO2013021328A1 (en) | 2011-08-08 | 2013-02-14 | CO.MA.SE. S.r.l. | Process for the production of bioliquid or biofuel |
WO2013093836A2 (en) | 2011-12-20 | 2013-06-27 | CO.MA.SE. S.r.l. | Process for the production of bioliquid or biofuel |
IT201600123786A1 (en) * | 2016-12-06 | 2018-06-06 | Consorzio Interuniversitario Naz Per La Scienza E Tecnologia Dei Materiali | Innovative energy self-sustainable biorefinery plant for the conversion of second-generation biomass |
CN115449409A (en) * | 2022-10-19 | 2022-12-09 | 中润油新能源股份有限公司 | Microbial fermentation methanol gasoline and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP2513261A4 (en) | 2013-10-02 |
WO2011073781A3 (en) | 2011-11-17 |
AU2010332478B2 (en) | 2013-10-17 |
BR112012014085A2 (en) | 2016-07-05 |
CA2783894C (en) | 2015-10-13 |
CA2783894A1 (en) | 2011-06-23 |
AU2010332478A1 (en) | 2012-07-19 |
NZ601190A (en) | 2014-10-31 |
EP2513261A2 (en) | 2012-10-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ambaye et al. | Emerging technologies for biofuel production: A critical review on recent progress, challenges and perspectives | |
Gupta et al. | Bioenergy research: advances and applications | |
Ioelovich | Recent findings and the energetic potential of plant biomass as a renewable source of biofuels–a review | |
Demirbas | Producing and using bioethanol as an automotive fuel | |
Afolalu et al. | Biofuel; A sustainable renewable source of energy-a review | |
Singh et al. | A comprehensive review of feedstocks as sustainable substrates for next-generation biofuels | |
AU2010332478B2 (en) | Biofuels from lignocellulosic resources | |
Ioelovich | Energy potential of natural, synthetic polymers and waste materials-A Review | |
Sharma et al. | Second generation bioethanol production from lignocellulosic waste and its future perspectives: a review | |
Guldhe et al. | Bioenergy: a sustainable approach for cleaner environment | |
Gharabaghi et al. | Biofuels: bioethanol, biodiesel, biogas, biohydrogen from plants and microalgae | |
Guo | The global scenario of biofuel production and development | |
Aggarwal et al. | Bioethanol production: Past and present | |
Casas-Godoy et al. | Biofuels | |
Balat | Fuels from biomass–overview | |
Bharathiraja et al. | BIOFUELS: A Promising Alternate for Next Generation Fuels | |
Deb et al. | Development of Acid‐Base‐Enzyme Pretreatment and Hydrolysis of Palm Oil Mill Effluent for Bioethanol Production | |
Cotana et al. | Biomass-based systems | |
Kirakosyan et al. | Plants as sources of energy | |
Alzate et al. | Bioethanol production: Advances in technologies and raw materials | |
Champagne | Biomass | |
Dubey et al. | Biomass: sustainable energy solution from agriculture | |
Kaur et al. | Bioenergy from Agricultural Wastes | |
Misra et al. | Expansion of Agricultural Residues to Biofuel Processing and Production | |
Nasir et al. | Hydrothermal Liquefaction of Lignocellulosic Biomass to Liquid Biofuels: A Review |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10837125 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2783894 Country of ref document: CA |
|
REEP | Request for entry into the european phase |
Ref document number: 2010837125 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010837125 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010332478 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2010332478 Country of ref document: AU Date of ref document: 20101216 Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012014085 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012014085 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120611 |