WO2012099603A1 - Conversion biologique/électrolytique de biomasse en hydrocarbures - Google Patents

Conversion biologique/électrolytique de biomasse en hydrocarbures Download PDF

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WO2012099603A1
WO2012099603A1 PCT/US2011/022029 US2011022029W WO2012099603A1 WO 2012099603 A1 WO2012099603 A1 WO 2012099603A1 US 2011022029 W US2011022029 W US 2011022029W WO 2012099603 A1 WO2012099603 A1 WO 2012099603A1
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electrolysis
fatty acids
volatile fatty
fermentation
biomass
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PCT/US2011/022029
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English (en)
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Anthony B. KUHRY
Paul J. Weimer
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The United States Of America, As Represented By The Secretary Of Agriculture
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Priority to PCT/US2011/022029 priority Critical patent/WO2012099603A1/fr
Publication of WO2012099603A1 publication Critical patent/WO2012099603A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • 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
    • 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
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/52—Propionic acid; Butyric acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • 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

  • the invention is drawn to a novel method to produce hydrocarbon and hydrogen fuels simultaneously from biomass by a combination of fermentation and electrolysis.
  • Cellulosic ethanol is considered to be a more promising long-term source of transportation fuels (Lynd et al., 2002). Cellulosic materials are available in much larger quantities; can be produced on more marginal lands; feature a much larger net energy balance; and do not have a competing human food use.
  • Chemical pretreatment is considered necessary to enhance the accessibility of the feedstock to enzymatic attack, yet such pretreatment adds costs, generates a waste stream, and produces certain chemical products that inhibit sugar fermentation.
  • Contaminating microbes such as lactic acid bacteria can convert considerable amounts of the hydrolyzed sugars to products other than ethanol, necessitating expensive control measures to permit maintenance of the fermentative monoculture; this is already a major problem in the corn ethanol industry, which has become one of the major users of antibiotics in the U.S. (Olmstead, 2009).
  • the most active of the ethanol producers ferment only the hexose fraction of carbohydrate, and even the best strains that utilize the pentose sugar fraction only ferment the carbohydrate fraction but not the other components (proteins, nucleic acids, lipids, organic acids and other phytochemicals) that represent a substantial proportion of plant biomass. This greatly reduces the yield of fuel product.
  • no obvious use has emerged for the unfermented residue - a critical shortcoming given its likely large volume and the likely low profitability of the cellulosic ethanol process.
  • Ethanol has a relatively low energy density (with attendant reductions in vehicle miles-per-gallon), and for most gasoline-powered vehicles can only be blended to a low proportion of the total fuel mixture.
  • photosynthetic algal -based processes either require large areas for cultivation (because of the shallow depth of the photic layer under intense cultivation, while the "dark algal” process or processes based on bacteria that have been genetically engineered for hydrocarbon biosynthesis require sugars as the feedstock (which revisits the high cost of cellulolytic enzymes that has hampered ethanol production via simultaneous saccharification and fermentation).
  • Biorefinery processes that produce various types of biobased fuels from biomass are well known. It is known, for example, that natural mixtures of anaerobic microbial cultures that work together to digest biomass material occur in habitats such as the rumen of ruminant animals, sewage sludge, soil, landfills, aquatic (freshwater, marine, and brackish) sediments, and insect (e.g., termite) guts. These mixed microbial cultures work in concert to provide the necessary enzymes to convert biomass into organic acids.
  • the organic acids are primarily "Volatile Fatty Acids" (VFA) which includes straight and branched chain fatty acids with carbon chain lengths from C2 to C6.
  • VFA Volatile Fatty Acids
  • Ruminal microbes have long been known to convert cellulosic and other feed materials to VFA (Hungate, 1950, 1966), and have also been used for treating organic wastes.
  • RUDAD Rumen-Derived Anaerobic Digestion
  • mixed ruminal microbes including both bacteria and protozoa
  • the process is used exclusively for waste treatment, although as in many other wastewater treatment plants, the methane produced can be used as a fuel to offset the operating energy requirement of the treatment plant.
  • Biorefinery-produced organic acids may be converted into useful fuels by different methods (e.g., those of Holtzapple and of Bradin).
  • Holtzapple et al. (1999) describe processes that produce bio fuels of mixed alcohols (MixAlco) and other products such as mixed ketones, by thermochemical treatment of organic acids that are produced by the action of natural microbial mixtures on biomass material. These processes are described in detail in U.S. patents 5,693,296; 5,865,898; 5,874,263; 5,962,307; 5,986, 133; 5,969, 189; 6,043,392; 6,262,313; 6,395,926, and 6,478,965.
  • MahAlco mixed alcohols
  • Holtzapple are obtained primarily from anaerobic sewage digesters comprising municipal solid waste (MSW) and sewage sludge (SS) that transform chemically pretreated biomass material into volatile fatty acid (VFA) mixtures as described in US patent 6,043,392 under the "Pretreatment and Fermentation” section.
  • the biomass components that are converted into organic acids are: cellulose, hemicellulose, pectin, sugar, protein, and fats.
  • Holtzapple' s process typically uses a "stuck" fermentation, in which microbial methane formation is prevented by keeping the pH low and/or by adding specific (toxic) inhibitors of methanogenesis (e.g., bromoform [CHBr 3 ], or iodoform [CHI 3 ]).
  • specific (toxic) inhibitors of methanogenesis e.g., bromoform [CHBr 3 ], or iodoform [CHI 3 ]
  • Biofuels can also be produced by using specific types of microbes, as opposed to mixed microbial cultures, in order to produce specific types of hydrocarbons exclusively from sugars.
  • Bradin (2007; publication WO 2007/095215 A2) describes a process that produces n-hexane from the fermentation of sugars, using specific natural bacteria or yeast that produce specifically butyric acid as a single product. The butyric acid is then subjected to Kolbe dimerization electrolysis to form n-hexane.
  • the preferred microbes are selected to reduce or eliminate acetic acid as a byproduct because it lowers butyric acid yield.
  • the preferred microbes must be either naturally isolated or genetically engineered pure cultures, and must be cultivated under controlled conditions to prevent culture contamination, thus reducing flexibility and increasing the cost.
  • specific enzymes in order to produce sugars from complex carbohydrates such as cellulose and hemicellulose, specific enzymes must be added to the biomass, thus further adding to the reaction processing time and the cost.
  • the Bradin process also requires the separation of lignin from cellulose and hemicellulose, by other enzymes or oxidizing agents to delignify the biomass prior to fermentation.
  • the single n-hexane product also requires further refinement in order to be used as a transportation fuel.
  • Anaerobic fermentations of plant biomass yield a variety of fermentation end products having high potential energy. Some of these products, like ethanol or butanol, can be recovered by distillation and used directly as motor vehicle fuels. Others, like VFA (e.g., acetic, propionic or butyric acids) can be produced in substantial quantities, but are not directly usable as fuels.
  • VFA e.g., acetic, propionic or butyric acids
  • the literature contains a number of examples of conversions of carboxylic acids to hydrocarbons using electrochemistry.
  • the alkyl groups of fatty acids can be combined tail-to-tail during anodic electrolytic decarboxylation to yield alkanes (e.g., ethane from acetic acid, butane from propionic acid, etc.), the so-called Kolbe reaction.
  • the Kolbe reaction can proceed via dimerization of similar radical species to produce single alkanes, or cross-radical reactions with dissimilar radical species to produce alkane mixtures (see Table 1).
  • fatty acids can be partially cleaved and converted to alkenes (e.g., ethylene from propionic acid) by the so-called Hofer-Moest reaction.
  • the Hofer-Moest reaction can produce alkenes via deprotonation and alcohols via substitution. Under certain reaction conditions, dienes and trienes can also be produced.
  • the hydrocarbon reaction formulas are shown in Formula 1, comparing one-electron (Kolbe) and two-electron (Hofer-Moest) schemes for electrolytic decarboxylation (Adapted from Lund [2001 ] and Seebach et al.
  • the Kolbe and Hofer-Moest reactions are among the oldest reactions described in electrochemistry. Although they can readily convert VFA to alkanes and alkenes (or alcohols and esters), they have generally been used commercially in synthesis of low- volume specialty chemicals.
  • C2 to C6 carbon chain VFA including acetic, propionic, butyric, valeric, and caproic acids. These carboxylic acids were produced by nonsterile anaerobic fermentations.
  • the higher chain VFA butyric, valeric and caproic acids
  • the higher chain VFA were separated and concentrated by liquid-liquid extraction with kerosene. It was theorized that the higher chain VFA could be treated by electrolytic oxidation (Kolbe and Hofer-Moest electrolysis) to produce hydrocarbons, alcohols, and esters.
  • the lower chain VFA acetic, propionic
  • VFA volatile fatty acids
  • H 2 gaseous and liquid hydrocarbons and hydrogen gas
  • CO 2 carbon dioxide
  • the process uses the primary ruminal fermentation, in vitro, for a rapid, high-yield conversion, and can also use an optional secondary fermentation with an augmented microbial inoculum to convert lower chain volatile fatty acids to higher chain volatile fatty acids, if desired.
  • An additional separate fermentation can be used to convert carbon dioxide (CO 2 ) and hydrogen (3 ⁇ 4) produced from the in vitro ruminal fermentation and the electrolysis stages, respectively, into acetic acid, which can then be included as a feedstock in a subsequent electrolysis stage.
  • this carbon dioxide (CO 2 ) and hydrogen (H 2 ) can be converted in a separate bioreactor to methane gas.
  • BEC can convert virtually any type of biomass into a variety of hydrocarbon fuels and hydrogen gas (3 ⁇ 4) without the high temperatures or high energy requirements that are inherent in some other conversion methods, such as pyrolysis.
  • Another object of this invention is to provide a process that uses mixed cultures from ruminal inocula to produce volatile fatty acids from biomass in a single-stage bioreactor, which volatile fatty acids may then be converted into a plurality of hydrocarbon products and hydrogen gas (H 2 ) in a second reactor using a non-biological process employing
  • Another object of this invention is to provide a process for converting mixtures of organic acids produced by microbial anaerobic fermentation of biomass into a variety of gaseous and liquid hydrocarbon fuels, hydrogen and other chemical products, via electrolytic decarboxylation.
  • Another object of this invention is to provide a process for combining organic acids obtained by anaerobic fermentation of biomass with other organic acids already present in plant or animal biomass material, and converting these combined organic acid mixtures into a variety of useful hydrocarbon fuels, hydrogen and other chemical products, via electrolytic decarboxylation.
  • Another object of this invention is to provide a process for combining organic acids obtained by anaerobic fermentation of biomass with other industrial organic chemicals and converting these combined organic mixtures into a variety of useful hydrocarbon fuels, hydrogen and other chemical products, via electrolytic decarboxylation.
  • Another object of this invention is to provide a process that will offer a solution to the ever-growing environmental problem of landfilling cellulosic biomass waste, by economically converting this waste into hydrocarbon fuels, hydrogen and other chemical products, eliminating the need for landfilling of this material.
  • Another object of this invention is to provide a process that will offer an economic solution to biomass waste disposal by utilizing damaged, spoiled, or spent cellulosic commodities to produce hydrocarbon fuels, hydrogen and other chemical products by reprocessing them instead of discarding in landfills.
  • Figure 1 shows a flow diagram describing a preferred embodiment of the invention for producing hydrocarbon fuels, hydrogen, and other biobased products from biomass.
  • Biomass can be any plant or animal material containing carbohydrate (including cellulose, hemicelluloses, starch, pectins, and fructans), protein, nucleic acid, organic acid, or fat.
  • carbohydrate including cellulose, hemicelluloses, starch, pectins, and fructans
  • protein amino acid
  • organic acid organic acid
  • fat a vegetable or derived vegetable
  • biobased fuel or biofuel refers to any transportation fuel produced from biomass.
  • biobased product refers to an industrial product (including chemicals, materials, and polymers) produced from biomass, or a commercial or industrial product (including animal feed and electric power) derived in connection with the conversion of biomass to fuel.
  • Hydrocarbon biobased fuels consist exclusively of carbon and hydrogen, such as alkanes, alkenes, dienes, and trienes.
  • Other chemical biobased products include carbon and hydrogen components combined with other chemical elements such as oxygen, nitrogen, etc.
  • BEC Biological-Electrolytic Conversion
  • the conversion of biomass into organic acids refers to the conversion to volatile fatty acids (VFA), which includes straight and branched chain fatty acids with carbon chain lengths from C2 to C6, including but not limited to acetic, propionic, butyric, isobutyric, 2- methyl butyric, valeric, isovaleric, and caproic acids.
  • VFA volatile fatty acids
  • MCFAs Medium Chain Fatty Acids
  • LCFAs Long Chain Fatty Acids
  • This invention describes a process that converts VFA, by itself, into biobased fuels and biobased products. Additionally, this invention describes a process that converts combinations of both VFA and VFA/MCFA/LCFA into many different biobased fuels and biobased products (see Table 1).
  • MCFA refers to both MCFA and LCFA.
  • the preferred inoculum for use herein in the fermentation to produce the volatile fatty acids from biomass is a mixed culture of microorganisms derived from the rumen contents of a rumen-containing (ruminant) animal.
  • a ruminal inoculum significantly reduces the length of the fermentation and increases yields in comparison to inocula prepared from other sources such as sewage sludge.
  • use of the ruminal inoculum also eliminates the need to suppress methane production during the primary fermentation with chemical inhibitors; the primary fermentation using ruminal inocula to produce volatile fatty acids from biomass as described in this invention is preferably conducted without the addition of methane production inhibitors.
  • the time course for the ruminal fermentation without methanogenic inhibitors is typically 2-3 days, as opposed to 5 to 20 days or longer for anaerobic digestion with sewage sludge inocula and methanogenic inhibitors.
  • the fermentation time course is affected by biomass loading where higher concentrations of biomass solids require longer residence times.
  • fermentation time course for human and animal sewage conversion to methane without inhibitors normally takes about 3 weeks.
  • Another measure of the fermentation time course is the first-order rate constant (k) for conversion of particular biomass components:
  • the use of the ruminal inocula provides other advantages as well.
  • the microorganisms of this mixed culture produce their own enzymes for hydrolyzing and fermenting complex substrates such as cellulose, hemicelluloses, pectins, starches, sugars, proteins, nucleic acids, and dicarboxylic and tricarboxylic acids to the high-energy end product volatile fatty acids.
  • complex substrates such as cellulose, hemicelluloses, pectins, starches, sugars, proteins, nucleic acids, and dicarboxylic and tricarboxylic acids.
  • the biomass substrate does not need to be chemically or enzymatically hydrolyzed to low molecular weight sugars prior to the fermentation, and minimal additional nutrients are used.
  • the ruminal inoculum produces volatile fatty acids rather than ethanol or methane as the primary fermentation products.
  • the microorganisms of the ruminal inoculum also convert not only the carbohydrate (hexoses, pentoses, and their polysaccharides) portion of the biomass, but also the protein, nucleic acid, dicarboxylic and tricarboxylic acid fractions, and some of the lipid fraction to volatile fatty acids. Therefore, yields of volatile fatty acids from these mixed culture fermentations are much higher than in conventional biomass fermentations employing carbohydrate-fermenting microbes.
  • the protein fermentation by the rumen-derived mixed culture is particularly beneficial, in that some of the volatile fatty acids produced (in addition to acetic, propionic, butyric and valeric acids) include 2-methylpropionic (isobutyric), 2-methylbutyric, and 3- methylbutyric (isovaleric) acids. These branched-chain volatile fatty acids, upon subsequent electrolytic conversion, will yield branched-chain hydrocarbons that may have improved fuel performance properties.
  • the ruminal inoculum for use herein may be obtained from any ruminant animal, although caprine (goat), ovine (sheep) and bovine (cattle) species are preferred, and bovine is particularly preferred.
  • the ruminal contents primarily liquid although solids may be included, can be collected from the ruminant animal through an implanted rumen fistula, or through stomach tube, ruminocentesis, or directly from rumen contents at slaughter. Once collected the ruminal contents may be used directly as the inoculum in the fermentation herein.
  • the mixed populations of microorganisms in the contents are first subjected to one or a plurality of successive, small-scale anaerobic fermentations with the desired biomass substrate prior to their use in a larger-scale fermentation.
  • This adaptation of the rumen microorganisms increases their tolerance to the volatile fatty acids, and increases the molar concentration of volatile fatty acids in the fermentation.
  • the rumen contents used herein contain a diverse mixed population of microorganisms, the microbial consortia are relatively stable in culture, and can be maintained by sequential transfer without sterilization of the substrate or reactor vessels.
  • the ruminal inocula from these enrichment cultures are also essentially devoid of the protozoa that reduce the overall efficiency of the fermentation by consuming the fermentative bacteria.
  • RCBP a preferred adapted ruminal inoculum of this invention
  • the ruminal inoculum may be used alone or optionally may be augmented by addition of one or more supplemental pure or mixed cultures of microorganisms.
  • Anaerobic fermentation of biomass with the microorganisms of the ruminal inoculum produce primarily lower chain volatile fatty acids (i.e., propionic and acetic with relatively less butyric and isobutyric) with low amounts of higher chain C5 and C6 volatile fatty acids (valeric and caproic).
  • supplemental inocula can increase the production of the C4, C5, and C6 higher chain volatile fatty acids.
  • these supplemental microorganisms may be used as the inocula for a secondary fermentation of the biomass, following the primary fermentation with the ruminal inoculum.
  • an additional, separate fermentation can be used to convert carbon dioxide (CO 2 ) and hydrogen (3 ⁇ 4) produced from the ruminant inoculum fermentation and the electrolysis stages, respectively, into acetate, which can then be included as a feedstock in a subsequent electrolysis stage.
  • this carbon dioxide (CO 2 ) and hydrogen (H 2 ) can be converted in a separate fermentation to methane gas for use as a fuel.
  • supplemental microorganisms include one or more of the following: Clostridium kluyveri, Clostridium butyricum, Clostridium tyrobutyricum, Butyrvibrio fibrisolvens, mixed culture of microorganisms derived from sewage sludge, landfills, soil or aquatic (freshwater, marine, brackish) environments, or mixed cultures of microorganisms derived from the gut of termites or other insects. Supplementation with the butyric acid producing B. fibrisolvens is preferred, particularly as an augment with the ruminant inoculum in the primary fermentation.
  • B. fibrisolvens is preferred, particularly as an augment with the ruminant inoculum in the primary fermentation.
  • fibrisolvens is capable of utilizing hemicelluloses, and it is envisioned that its use should increase the production of butyric acid. Due to its relatively slow growth rate, C. kluyveri is preferably employed in a secondary fermentation after the ruminant inoculum fermentation. While the organism produces butyric and caproic acids, a suitable electron donor such as ethanol (Kenealy et ah, 1995), or hydrogen gas (H 2 ) (Kenealy and Waselefsky, 1985), can be added to this secondary fermentation to increase the yield of the longer chain VFA (Kenealy et al., 1995). The hydrogen gas (H 2 ) can be supplied as the hydrogen produced by the cathodic reaction in the BEC electrolytic stage.
  • the production of the volatile fatty acids may be effected by fermentation of the biomass with the aforementioned ruminal inoculum in an aqueous medium, using
  • Suitable pH and temperature ranges of the fermentation may typically range between about 4.5 to 7.5 and 30 to 50°C, respectively, with a pH and temperature between about 5.5 to 7.0 and 35 to 45°C, respectively, being preferred.
  • the fermentation may be conducted as a batch, fed-batch or continuous process, in a single- or multi-stage reactor. The fermentation does not require, and is preferably conducted in the absence of, aseptic conditions, without sterilization of the biomass substrate, reactor, or any other components. The fermentation is incubated for a sufficient time to produce volatile fatty acids therein.
  • the precise incubation period for the fermentation may vary somewhat with the biomass substrate and conditions, but the fermentation may be discontinued after about 1 to 4 days, preferably after 2 to 3 days, as the time for completion of the ruminal fermentation is typically 2 to 3 days.
  • volatile fatty acid concentrations in the fermentation broth from about 0.1 M to 0.2 M, up to about 0.3 M, can be obtained by the fermentation process herein.
  • the primary fermentation is preferably conducted without the addition of an effective amount of methane production inhibitors (inhibitors of methanogenesis or methanogenic microorganisms), such as, but not limited to 2-bromoethane sulfonic acid (BES).
  • biomass substrates are suitable for use herein, including plants or parts, residue or waste material thereof.
  • biomass sources include agricultural crops (including fruits and vegetables), trees, forages, grasses, aquatic plants, bagasse, corn stover, corn cobs, hay, flax straw, oat hulls, wood (including timber, forestry slash, and other wood waste), sawdust, paper products, paper processing wastes (including fines from paper recycling), cardboard, and yard or landscape waste, spent sausage casings, mixed stands of vegetation, rotting, spoiled or devalued plant materials, and certain food processing wastes.
  • cellulosic biomass substrates are preferred, animal wastes and waste products, including animal carcasses, may also be used.
  • the biomass fermentations may also include plant material (including plants or parts or materials thereof) that produce organic acids and/or medium chain fatty acids (MCFA) some of which are relatively inert to anaerobic degradation and do not need prior separation processing, which would carry through the fermentation, intact, to serve as precursors for liquid hydrocarbons such as octane and kerosene in the electrolysis stage.
  • plant material including plants or parts or materials thereof
  • MCFA medium chain fatty acids
  • the ruminal microorganisms readily ferment chemically or enzymatically pretreated feedstocks (that is, pretreatments which function to increase the availability of the fermentable substrates in the feedstock to the microorganisms, e.g., pretreatments with acid, base, oxidizing agents, or enzymes, and including but not limited to hydrolysis), no such chemical or enzymatic pretreatments are necessary in the process of the invention, and are preferably omitted.
  • the materials should be reduced in size using conventional techniques such as simple mechanical grinding and/or rolling (e.g., burr milling). This physical pretreatment is preferred in order to decrease feedstock particle size, increase the aggregate surface area, and thus increase the fermentation rate.
  • Any large feedstock particles that remain in the fermentation broth will settle out, and may be separated and re-ground, which mimics the characteristic chewing habits of ruminant animals (chewing the cud).
  • a small amount of nutrients may be added to the fermentation medium to enhance microbial growth, with distillers dried grains (DDGs) or other low-cost nutrients being preferred.
  • DDGs distillers dried grains
  • Other adjuvants which may be added to the fermentation include small amounts of caustic, such as NaOH, KOH or Ca(OH) 2 to produce salts of the volatile fatty acids and adjust pH.
  • Other mineral salts may also be needed in small amounts to provide inorganic components of cell material, or osmotic balance for the microbial cells in the in vitro fermentation process.
  • glycerol a common byproduct of biodiesel production
  • glycerol may also be added to the biomass for fermentation by the ruminant inoculum.
  • glycerol may also be added to the biomass for fermentation by the ruminant inoculum.
  • Other optional adjuvants include alcohols such as methanol, a common contaminant of the glycerol produced by biodiesel manufacture, and which is converted by the rumen microorganisms to a mixture of methane and CO 2 in a ratio of approximately 3 : 1.
  • adjuvants which may be added include organic acids such as those naturally produced and available from natural sources.
  • fruits and fruit processing waste contain hydroxy-, dicarboxylic, and tricarboxylic acids such as malic acid and citric acid.
  • these acids can be included in the process of the invention by addition of the fruit materials or separated acids to the fermentation medium, whereupon the hydroxy-, dicarboxylic, and tricarboxylic acids may be converted by fermentation to volatile fatty acids.
  • the hydroxy-, dicarboxylic, and tricarboxylic acids from the fruit materials may be added after the anaerobic fermentation, directly to the volatile fatty acid salt containing solution, to obtain different electrolytic products.
  • the anaerobic fermentation of many biomass materials with the ruminant inoculum will typically produce C2 to C6 volatile fatty acids.
  • the process may be modified by addition of one or more C8 to C22 MCFA, which will therefore produce even longer chain hydrocarbon products from the subsequent electrolysis, including octane and kerosene.
  • Supplementation with MCFA may be effected by direct addition of MCFA, or by addition of materials incorporating MCFA such as materials from plants that produce MCFA, particularly oilseeds.
  • oilseed oils contain a variety of MCFA, are globally abundant, and may be obtained in large quantities.
  • Common fatty acids available in large supply from various plant sources include, but are not limited to, coconut, palm kernel, cuphea, soybean, rapeseed, peanut, sunflower, andjatropha (see Tables 3, 4 and 5).
  • coconut oil for example, contains a range of fatty acids with a characteristic profile that includes C8 to C18 carbon chain atoms.
  • these MCFA-containing plants or plant materials e.g., seeds per se or the oil recovered from oilseeds may be added to the anaerobic primary
  • the MCFA-containing plant materials may be processed separately from other biomass materials to recover the oilseed oils, which are converted to MCFA salts, and added to the volatile fatty acid-containing fermentation broth solution.
  • the oilseed oils should first be treated with base (caustic pH adjustment) to make carboxylate salts, which can then be subjected to the anodic electrolytic decarboxylation.
  • base caustic pH adjustment
  • carboxylate salts which can then be subjected to the anodic electrolytic decarboxylation.
  • a large variety of hydrocarbon products may then be produced on an industrial scale, limited only to the amount of feedstock.
  • liquid hydrocarbon products may be produced by electrolysis in relatively pure form. This can be readily performed by selecting specific fatty acid profiles from specific sources. For example, seed oil from certain species of Cuphea (e.g., C. painteri, C. hookeriana) may contain
  • C8 caprylic acid
  • CIO capric acid
  • C8 fatty acids react with VFA to produce liquid n-octane and higher carbon chain liquid hydrocarbons like kerosene (see Table 1).
  • Many oilseed plants produce a large percentage of fatty acids in the C12-C18 range, which could be electrolytically converted with VFA into other higher kerosene-type fuels.
  • Some oilseed plants produce even higher chain fatty acids and fats, for example, C20 (peanut oil, fish oil), C22 (rapeseed oil).
  • the resulting hydrocarbons can be readily broken down into more desirable shorter chain alkanes with existing catalytic crackers.
  • volatile fatty acid salt containing solutions these new mixtures of organic acids (volatile fatty acid/MCFA) allow a large variety of hydrocarbon fuels and chemical products to be produced by cross-linking the radical intermediates through the anodic electrolytic decarboxylation process.
  • relatively pure liquid, as well as pure gas products can be produced directly, including high-quality transportation fuels such as n-octane or kerosene. These are all produced relatively pure without large quantities of contaminants such as nitrogen, sulfur, mercury, or particulates.
  • Any traces of contaminating gases can be either recycled to the fermentation broth as nutrients for the microbes, or removed via adsorption to wood chips, or other adsorbent materials, or via reaction with iron or iron salts.
  • the volatile fatty acid mixtures from the fermentation broth typically yield an aqueous solution ratio of approximately 6:2: 1 of acetic, propionic, and butyric acids at a total VFA concentration of about 0.1 M to 0.2 M within a pH range of about 5 to 6.5, although total volatile fatty acid concentrations up to 0.3 M may be produced.
  • the electrolysis of the volatile fatty acids to produce hydrocarbons may be performed directly upon the fermentation broth without further treatment or extraction of the volatile fatty acids therefrom.
  • the microbial cells, lignin-containing residues, and non-carboxylate anions are removed from the broth (containing the carboxylate anions or salts of the VFA) prior to electrolysis.
  • the cells, lignin-containing residues and non-carboxylate anions may be removed by one or more of a variety of techniques, such as filtration, flocculation, settling, centrifugation or precipitation.
  • Soluble proteins may also be removed such as by an additional ultrafiltration step, as some dissolved proteins may decrease current flow to the anode and slow the electrolysis process when carried out in fermented broth.
  • Non-carboxylate anions will also inhibit the electrolysis.
  • the volatile fatty acids are also concentrated or extracted to a higher molar concentration or separated into individual volatile fatty acids, thereby improving yields or allowing the production of specific products.
  • the VFA are separated from the fermentation broth, and concentrated to improve electrolytic efficiency.
  • the volatile fatty acids can be extracted efficiently by liquid-liquid extraction of the fermentation broth with alcohols such as butanol or isopropanol, or with other polar and non-polar organic solvents. Isopropanol can extract volatile fatty acids and is miscible with water, but is insoluble in highly saline solutions.
  • the volatile fatty acids may be concentrated by distillation, capacitive deionization (CDI), evaporation, ultrafiltration, reverse osmosis, forward osmosis, carbon nanotubes, or biomimetics.
  • CDI capacitive deionization
  • the recovered volatile fatty acid solution may also be sequestered stored and processed electrochemically at a later time.
  • Concentrated organic acid substrates maximize the efficiency and effectiveness of the electrolytic process. It is envisioned and anticipated that the preferred electrolysis conditions include a concentrated carboxylate (VFA salts, VFA-MCFA salts) substrate solution relatively free of dissolved proteins and other unwanted anions.
  • VFA salts VFA-MCFA salts
  • the VFA are separated from the fermented broth and concentrated. This can be achieved by several known methods including distillation and liquid-liquid solvent extraction. Although VFA solvent extraction is the preferred concentration method over distillation due to cost considerations, other methods can be used that do not require heat or solvent processing that would otherwise increase the total BEC processing cost.
  • Capacitive Deionization is an economical process that has been used for water purification and can be adapted to concentrate carboxylate (VFA salts, VFA-MCFA salts) anions within aqueous solutions.
  • CDI uses very low voltages and very high surface area electrodes to electrostatically attract and hold anions and cations in aqueous solutions to their respective anode and cathode.
  • High surface area electrodes can be any material but mainly include carbon aerogels, carbon nanofoams, and lower cost carbon electrodes obtained from pyrolysis of papers. The voltages must be below certain oxidation potential and chemical reaction thresholds.
  • Voltages used are generally about 0.5 to 1 volt, since at voltages less than that of about 1.23 volts (see Formula 2), no water oxidation occurs and no oxygen is formed at the anode.
  • CDI can be operated at DC power levels as low as 0.5 Volts and 100 mA. However, at these low voltages, the solvated anions and cations migrate to the high surface area electrodes due to the capacitive ion effect, are adsorbed onto their respective electrode surfaces, and held until a polarity reversal releases them, thus separating anions from cations without distillation, reagents, or electrolysis.
  • VFA salts VFA-MCFA salts
  • VFA-MCFA salts carboxylates
  • Flow-Through Capacitor can be used as a preferred CDI concentration process.
  • Flow-through capacitors use supercapacitors and are specifically designed to separate anions and cations from flowing liquids in an efficient manner at a specific flow rate.
  • An example of a FTC is described in U.S. patent 6,462,935 (the contents of which are incorporated by reference herein) that possesses conically wound supercapacitor electrode surfaces using ferric oxide and carbon powders.
  • the CDI concentration and electrolytic processes can be combined together into a CDI/electrolytic process.
  • the CDI process can be adapted to integrate with the electrolytic stage by using lower voltages first to concentrate the carboxylates, and then by using higher voltages, above the critical potential, to perform the electrolysis. This would involve a simple voltage timing-cycle which would allow sufficient time for the carboxylates to concentrate at the anode before performing the actual electrolytic stage. Then the electrolysis would be performed for a time necessary for hydrocarbon conversion until the carboxylate concentration drops (at the anode) to a lower level, which would start the CDI concentration process again.
  • the potential can be held at 1 volt for a sufficient time to concentrate carboxylates (at the anode) at a desired level, and then the voltage can be increased quickly to over 3 volts for a sufficient time to convert carboxylates to
  • high surface area electrodes are inserted into the fermentation broth with a low applied voltage for a period of time necessary to adsorb and concentrate carboxylate anions at the anode at which point the voltage is increased to commence the electrolysis reaction. This thereby allows the carboxylate concentration process to occur within the VFA fermentation broth and the decarboxylation electrolysis process to be performed in the same vessel.
  • This CDI/electrolysis process may operate at lower current densities (less than 1mA / cm 2 ) due to the high electrode surface area for a given applied voltage (although higher electrolysis voltages can be used to offset this). However, due to the high carboxylate concentration and the high discharge potentials of carboxylates, decarboxylation electrolysis still occurs even at low current densities.
  • the CDI concentration process can include a CDI filter membrane which entirely surrounds the anode within the fermentation broth and separates the anode from the cathode.
  • the CDI filter membrane must be composed of appropriately sized pores which will prevent non-carboxylate anions (larger in size than carboxylate anions of the VFA) from adsorbing onto the anode surface during the CDI concentration process. In this way, many larger sized negatively charged anions within the fermentation broth will be effectively separated from the carboxylate anions during the CDI concentration process.
  • the use of a CDI filter membrane improves carboxylate concentration by removing some non-carboxylate anions that may otherwise inhibit the electrolysis process.
  • the CDI method can be used in a separate process to remove VFA (as carboxylate anions) from the fermentation broth during (concurrent with) the primary rumen fermentation (CDI/Fermentation process).
  • VFA as carboxylate anions
  • the CDI process is used to decrease the VFA concentration of the fermentation broth and can be used at any time during the primary fermentation process. As VFA concentrations increase within the fermentation broth, the fermentation rate typically decreases.
  • use of the CDI/Fermentation process described herein allows the speed of the primary fermentation process to be maximized by removing the VFA during the fermentation.
  • the VFA may be removed continuously or periodically during the fermentation.
  • CDI can be integrated with the fermentation stage in order to continuously or periodically remove VFA from the fermentation broth while separating the fermentation broth from the vessel containing the CDI apparatus.
  • An adaptation of a flow through capacitor (FTC) is preferably used for this purpose.
  • the electrodes of the CDI or FTC are positioned within the fermentation medium and a low voltage is applied as described above.
  • the carboxylates of the VFA are attracted to and sequestered at the surface of the anode, effectively concentrating the VFA at the locality of the anode and thereby decreasing the VFA concentration in the remainder of the fermentation medium (away from the anode).
  • the VFA adsorbed at the anode may then be converted to hydrocarbons by electrolysis in situ by increasing the voltage in the same manner as described for CDI/electrolysis, or alternatively, the VFA may be recovered for subsequent electrolysis by simply separating the electrodes from the fermentation broth.
  • the electrodes may then be placed in the same or different electrolyte solution-containing vessel and electrolysis conducted to produce hydrocarbons as described above.
  • the VFA may be released from the anode into the electrolyte solution-containing vessel by reversing the polarity of the anode, and the electrolysis performed as described above at a later time.
  • the fermentation medium may be continuously passed across or past the electrodes in a single vessel or multiple vessels connected in series. In this way the rumen microorganisms will be allowed to work at peak efficiency and effectiveness and further decrease total fermentation time.
  • the CDI/Fermentation process can include a semi-porous membrane that entirely surrounds the CDI anode similar to that used in the CDI concentration process.
  • the purpose of this membrane is to prevent non-carboxylate anions (larger in size than carboxylate anions of the VFA), and other contaminants such as lignins, cells, and proteins from interfering with or adsorbing onto the anode surface during the
  • the electrolysis stage of the process of the invention converts the complete range of the volatile fatty acid products (including any added MCFA) to hydrocarbon and hydrogen fuels.
  • the volatile fatty acids may be converted into large quantities of gas and liquid hydrocarbons and hydrogen gas (H 2 ) using the Kolbe and/or Hofer-Moest reactions of electrochemical decarboxylation. As described above, the Kolbe Reaction is a
  • decarboxylative coupling dimerization, radical cross coupling
  • alkanes such as ethane and propane
  • Hofer-Moest Reaction an oxidative decarboxylation (deprotonation), which yields alkenes such as ethylene and propylene. Both of these reactions occur simultaneously during electrolysis but can be adjusted to favor one reaction or the other by changing several easily controlled variables as described herein below.
  • the electrolysis converts the volatile fatty acids to mixtures of alkanes, alkenes, H 2 and CO 2 in water, under very mild reaction conditions.
  • predominant hydrocarbon products of the electrolytic conversion typically include methane and ethane from acetic acid, propane, butane and ethylene from propionic acid, and butane, pentane, hexane and propylene from butyric acid.
  • Mixtures having the same proportions of VFA as the major VFA in the typical in vitro ruminal fermentation noted above acetate: propionate: butyrate, 6:2: 1 molar basis
  • All reactions will also yield substantial amounts of H 2 at the cathode.
  • Hydrocarbon products derived from VFA- MCFA mixtures can include alkanes and alkenes with carbon numbers C5 to C22, including n-octane and kerosene.
  • organic chemicals such as glycerol, alcohols, and other readily available organic compounds are added to VFA solutions, the number of electrochemical products increases further.
  • the electrolysis reactions may be conducted in a simple undivided electrochemical cell under mild electrolysis conditions, at or above 3 volts DC (VDC) and at or above 1mA/ cm 2 anode current density, using low-cost carbon or graphite electrodes, at room temperature and ambient pressure, under aqueous conditions.
  • VDC voltage volts DC
  • 1mA/ cm 2 anode current density using low-cost carbon or graphite electrodes, at room temperature and ambient pressure, under aqueous conditions.
  • the anode current density may be much lower due to the high electrode surface area.
  • the pH of the aqueous volatile fatty acid solution may range between 4.5 to 11, preferably between about 5.5 to 8.0.
  • a major component of the volatile fatty acid produced from biomass is acetic acid, it is itself a useful solvent for anodic electrolytic decarboxylation.
  • Non-aqueous solvents are only required for poorly water soluble reactants (e.g., higher chain MCFA). Methanol, ethanol or isopropanol additions can be used as a substrate solvent for these higher-chain fatty acids (MCFA).
  • MCFA higher-chain fatty acids
  • these higher-chain fatty acids can be easily separated and processed separately at very high concentrations and therefore can give very high yields of electrolytic products.
  • the anodic products can be separated from the cathodic products easily during electrolysis by segregating the product receiving vessels from one another. Alternatively, all electrolytic products can be combined easily into a single receiving vessel for further separation or processing. Once collected, the gaseous products (hydrocarbons, H 2 and CO 2 ) may be compressed into high pressure tanks and can be further separated into their component products via gas liquefaction. In this manner, carbon dioxide CO 2 can be removed easily and sequestered from the hydrocarbon and hydrogen fuel products. In the easiest case possible, all electrolysis products (including CO 2 ) can be combined and used as a fuel in a most field-expedient manner without any further processing.
  • semi-permeable membranes are provided within the electrolysis cell between (separating) the anode and cathode electrodes.
  • the use of semi-porous membranes allow the current density to increase by decreasing electrode spacing and therefore cell resistance.
  • the membranes permit electrolytes to carry the current while offering good separation of gas products from anode and cathode.
  • Either semipermeable membranes or salt additions (to provide electrolytes) may be used to decrease cell resistance between the anode and cathode while electronically insulating them from each other, thereby allowing a lower voltage to be used while increasing current density, and improve the product performance.
  • Other semi-porous membranes may be used.
  • Electrodes may be positioned near one another, allowing current to flow without arcing.
  • Power for the electrolytic cell may be provided from any convenient source. However, because any voltage above about 3 VDC is adequate for the electrolysis, alternative sources of electricity such as solar cells, wind generators and even fuel cells may be used as power sources to generate hydrocarbons in rural areas or in field- expedient military situations.
  • organic acids themselves possess good solvation properties
  • electrolysis can be carried out in low-cost aqueous solutions without any solvent additions.
  • the products are hydrocarbon mixtures, hydrogen (H 2 ), and carbon dioxide (CO 2 ) gases, along with several other products including alcohols, but without contaminants (e.g., H 2 S) normally found in natural gas liquids (NGL) exclusively obtained from the petroleum industry.
  • Electrodes constructed from platinum or porous (amorphous) carbon favor the Kolbe or Hofer-Moest reactions, respectively.
  • Carbon and graphite electrodes are preferred for use herein, and specific electrode materials that may be used herein include but are not limited to platinum, diamond, vitreous (glassy) carbon, carbon aerogel, carbon nanofoam, graphite, and others.
  • the preferred electrode material is either platinum or graphite.
  • membranes may be used to separate the anode and cathode, and help to decrease or control the electrochemical cell resistance similar to the membranes used in PEM electrolytic cells that produce hydrogen fuels.
  • reaction variables which can be used to enhance product yields and variability within the electrolytic cell include alternating current (waveforms), magnetic fields, and ultrasonic energy, to name a few.
  • the hydrocarbon products of the electrolysis are spontaneously evolved from solution, and once recovered can be converted to gasoline fractions using well-known and widely practiced industrial chemistry methods (e.g., thermal polymerization), which converts lighter hydrocarbon gases into liquid hydrocarbon fuels.
  • thermal Polymerization for example, is a well-known petroleum refining process that converts lighter hydrocarbon gases into liquid hydrocarbon fuels. This involves cracking feedstocks of saturated hydrocarbons (alkanes) to produce unsaturated hydrocarbons (alkenes). Heat and pressure are applied to the alkane feedstocks at the same time, which produces an end product of "Polymer
  • SHOP Shell Higher Olefin Process
  • Ethylene represents a major alkene product that is derived from the VFA salt containing solutions in the invention process. All alkene products are generated by the Hofer-Moest reaction of oxidative electrolytic decarboxylation. Other well-known refining methods such as the Ziegler-Natta reaction and the Wurtz reaction may be also be used to the same effect as well as other known methods.
  • the various products of this invention may be separated either by well-known methods such as fractionally compressing the gaseous products, distilling the liquid products, or filtering the solid products. This is not necessary in all cases, however, because the gaseous products from VFA-salts electrolysis alone will yield NGL (natural gas liquids) when compressed and liquefied. NGL may not need to be separated in order to be valuable, since they can also be used as mixed products.
  • the fermentation with the ruminal inoculum produces roughly about 10% methane and 20% carbon dioxide as byproducts (based on mass of biomass feedstock) that may be sequestered and reused.
  • the methane may be used to power generators to produce the energy needed in the electrolysis step, or combined with the other hydrocarbon products and refined further.
  • the carbon dioxide produced may be used to deoxygenate the biomass and fermentation medium by displacing air, thereby making it ready for anaerobic fermentation, and may be further sequestered and reused.
  • the H 2 and CO 2 formed at the cathode and anode electrodes, respectively can be combined and converted by methanogenic microbes to produce methane gas, or by acetogenic microbes to produce acetic acid.
  • the leftover inorganic salts after electrolysis may be returned to the bioreactor and combined with the next fermentation batch, which may be a continuous process.
  • the solid fermentation residue, including cells and lignin, can be processed into wood-adhesive products (Weimer, U.S. patent 7,651,582), or used as an animal feed, or used as a fuel to generate electricity for the electrolysis step.
  • the hydrogen (3 ⁇ 4) may be used as a fuel or used as a reactant in refining hydrocarbons or other chemicals.
  • a significant advantage of the process of this invention is evidenced by a comparison of electrical power needed to produce hydrocarbons from VFA-carboxylic acid solutions (see Formula 1) versus producing hydrogen from water (see Formula 2).
  • Potential energy as stated here is bond dissociation energy (BDE).
  • BDE bond dissociation energy
  • ethane and propane produced electrochemically from acetic and propionic acids contain 6 and 9 times, respectively, the potential energy of hydrogen (H 2 ) as a fuel.
  • VFA- MCFA mixtures produce even larger chain hydrocarbon products providing up to 50 times the potential fuel energy of hydrogen- water electrolysis using the same amount of electric power.
  • a MCFA like CI 6 palmitic acid, mixed with VFAs in an electrolytic cell will produce up to CI 8 hydrocarbons (n-octadecane) in carbon chain length through Kolbe cross-radical coupling, which yields a BDE 50-times that of hydrogen using the same amount of electrical power.
  • a mixed microbial consortium obtained from bovine ruminal fluid was fermented in vitro with eastern gamagrass (a harvested native grass) or alfalfa (harvested legume crop). Both are representative of a perennial cellulosic biomass feedstock. Separation of the resulting fermentation broth containing VFAs, from the solid residue (including cells and lignin) was accomplished by filtration and/or centrifugation.
  • the electrolytic apparatus was generally comprised of a simple undivided cell with carbon or graphite plates or rods used for both anode and cathode electrodes. Platinum anodes were also used for comparison purposes. Stainless steel and other metal electrode material were also used for cathodes. Although many anode materials can be used, carbon/graphite electrodes were selected in addition to platinum anodes, for example, due to their low cost and effectiveness on an industrial scale.
  • the electrodes were immersed directly into the fermentation broth which generally had a pH range of about 5.5 - 6.5 at room temperature. pH adjustment was performed in some cases to bring the pH range to about 6.0 - 6.5 to increase the carboxylic salt concentration.
  • Fine mesh porous nylon membranes to minimize electrode spacing
  • salts additions to provide electrolytes
  • Other semi-porous membranes may be used.
  • Membranes permit electrolytes to carry the current while offering good separation of gas products from anode and cathode. Gases were collected above the anode by liquid displacement of the fermented broth samples from Balch tubes (Balch and Wolfe, 1986), which were positioned over the respective anode and cathode. The tubes were then sealed with butyl rubber stoppers while still immersed in the liquid of the electrolysis cell, after which the stoppers were sealed with aluminum crimp seals.
  • Electrolytic cell resistance can be higher without the use of porous or semi -porous membranes or electrolytes because electrodes need to be separated at greater distances to prevent anode/cathode gas products from mixing.
  • Anode current density can be increased to higher levels by decreasing electrode spacing with porous or semi-porous membranes, or by adding MCFA salts or NaCl to the substrate.
  • the electrolytic cell can be adjusted to deliver any current level desired by varying the applied potential, electrode surface area, electrode spacing, substrate concentration, electrolytes and other factors. Current densities at the electrode surfaces are a key factor in electrochemical cell performance. The current density may be balanced equally between anode and cathode or may be designed to be unbalanced.
  • anode current density For example, decreasing the anode surface area or increasing the cathode surface area for the same cell current may increase anode current density.
  • Products and yields can differ and can be controlled using different anode current densities. For example, at lower current densities and higher voltage potentials, alkenes (Hofer-Moest products) are favored over alkanes. At higher anode current densities and lower voltage potentials, alkanes (Kolbe products) are favored over alkenes. There is an inherent flexibility in this invention to tailor products by varying fermentation and electrolytic conditions.
  • Hydrocarbon products derived from VFA mixtures alone include: ethane, propane, butane, pentane, hexane, ethylene, and propylene.
  • pure hydrogen gas (H 2 ) is produced in large quantities, as well as carbon dioxide, which can be sequestered and reused in the deoxygenation/air displacement step.
  • Hydrocarbon products derived from VFA- MCFA mixtures can include alkanes and alkenes with carbon numbers C5 to C20, including n-octane and kerosene (see Table 1).
  • Example Bio-1 Fermentation of eastern gamagrass to VFA.
  • a flask containing 600 mL of Goering-Van Soest medium (Goering and Van Soest, 1970; contents per liter: 8.75 g NaHC0 3 , 1.0 g NH 4 HC0 3 , 1.55 g KH 2 P0 4 , 1.43 g a 2 HP0 4 , 0.15 g MgS0 4 ), 16.4 g of air- dried Eastern gamagrass (ground in a Wiley mill having a 1 mm screen), 1.0 g of Trypticase, and 0.002 g of resazurin, was gassed under a stream of C0 2 , after which 0.6 g of cysteine HC1 and 0.05 g of Na 2 S.9 H 2 0 was added.
  • the flask was inoculated with rumen contents (-80 mL of liquid and 20 g squeezed solids) prepared by mixing similar amounts from two rumen-fistulated cows.
  • the flask was incubated at 39 °C without shaking. After 54 h incubation, samples were removed for fermentation product analysis. Samples were centrifuged at 10,000 x g for 10 min, and 600 uL of the supernatant liquid was combined with 600 uL of CHS (26.45 g Ca(OH) 2 added to 100 mL H 2 0) and 300 uL of CSR (10 g CuS0 4 + 0.4 g crotonic acid per 100 mL aqueous solution).
  • the mixture was frozen, thawed and centrifuged.
  • the supernatant liquid was transferred to tubes containing 28 uL of H 2 S0 4 , and this solution, frozen and thawed twice, then centrifuged.
  • the supernatant liquid was analyzed by high performance liquid chromatography (HPLC), using a 250 mm x 4.6 mm Bio-Rad Aminex HPX-87H analytical column maintained at 45 °C.
  • Samples (50 uL) were eluted with a mobile phase of 0.015 N H 2 SO 4 /0.0034 M ethylenediaminetetracetic acid (EDTA) at a flow rate of 0.7 mL/min, and separated peaks were detected with a refractive index detector.
  • HPLC high performance liquid chromatography
  • Example Bio-2 Production of VFA in stable enrichment cultures.
  • the culture from Example Bio-1 was sequentially transferred for 7 successive transfers of ⁇ 50 g of liquids and solids at 2 to 3 d.
  • the culture medium was the same as described in Example Bio-1, except incubations were conducted at one-half volumetric scale (300 mL medium), and the
  • DDG dried distillers grains
  • Example Bio-3 VFA production from biomass feedstocks by stabilized mixed cultures of ruminal microorganisms. Fermentations were conducted at 39 °C in unshaken Erlenmeyer flasks in 150 mL of a Goering/Van Soest medium supplemented with 4 g dried biomass feedstock (Eastern gamagrass or alfalfa, ground through a 1 mm Wiley mill screen but otherwise not pretreated) and 0.5 g of DDG. Flasks were gassed with CO 2 prior to inoculation but were incubated with vented closures, without additional gas sparging, during the fermentation.
  • Cultures were transferred at intervals of 2 to 4 days by pouring -20% by volume of culture from the previous culture to a flask containing fresh medium. VFA concentrations were determined in culture supematants obtained by centrifugation of 2- to 4- d old cultures at 12,000 x g for 10 min. Results are shown in Table B-l.
  • the number code for the Eastern gamagrass (EGG) and alfalfa (Alf) cultures corresponds to the sequential transfer number of the culture after the original ruminal inoculation. net mM VFA produced
  • Example Bio-4 In vitro VFA production from fermentation of biopolymers by mixed ruminal microorganisms collected from ruminally-flstulated cows. Fermentations were conducted under a CO 2 gas phase in sealed vials containing 100 mg of substrate in 8.5 mL of a Goering/Van Soest medium (except for DNA, 7.2 mg in 1.9 mL medium) supplemented with 1 g of Trypticase per liter plus 1.5 mL of freshly-collected ruminal inoculum (0.3 mL for DNA) squeezed through cheesecloth to remove large feed particles. Results are shown in Tables B-2 and B-3.
  • CS hemicellulose purified from stalks of cicer milkvetch (Astragalus cicer). Fructan from orchardgrass (Dactylis glomerata); Microbial cells from ruminal contents.
  • b IB isobutyric
  • Example Bio-5 Fermentation of other polysaccharides. Polysaccharides (100 mg fresh weight) were fermented for 24 h at 39 °C under a CO 2 atmosphere in sealed, unshaken vials that contained 8.5 mL of Goering/Van Soest buffer and 1.5 mL of squeezed ruminal fluid. Subsamples of culture were centrifuged and the supernatant assayed for VFA by HPLC. Results are shown in Table B-4. Total VFA yield on a weight basis varied from 50.9 to 78.7%, depending on substrate.
  • Example Bio-6 Augmentation of mixed ruminal microflora cultures with ethanol or additional bacteria to shift VFA product ratios. Sealed vials containing 8.5 mL or Modified Dehority medium and microcrystalline cellulose (95 mg dry weight) under a CO 2 atmosphere were amended with additional substrate or an enrichment culture of Clostridium kluyveri-li s bacteria (Ckb). Vials were incubated at 39 °C without shaking for 72 h, after which subsamples of the gas phase were withdrawn for analysis by gas chromatography, and subsamples of liquid phase were withdrawn and centrifuged, and the supernatant phase analyzed for VFA by HPLC. Results are shown in Table B-5 and B-6.
  • Ckb Enrichment culture containing Clostridium kluyveri-like bacteria. Enrichment culture was prepared by inoculation of ruminal contents from lactating dairy cows into a modified Dehority medium (Weimer et al., 1991) supplemented with ethanol, acetic acid and succinic acid; these culture was transferred at 2- to 4-week intervals of incubation at 39 °C.
  • Table B-6 Gas production in cellulose fermentations amended with ethanol and/or cultures of Clostridium kluyveri-like bacteria. Results are corrected for gas produced in vials containing ruminal inocula but lacking added cellulose, ethanol or Ckb mmoles gas per mol anhydro glucose added
  • Ckb Enrichment culture containing Clostridium kluyveri-like bacteria.
  • Example Bio-7 Shift to longer chain VFAs resulting of co-fermentation with glycerol. Sealed vials containing 8.5 mL of Goering and Van Soest medium plus
  • microcrystalline cellulose 95 mg dry weight
  • Vials were incubated at 39 °C without shaking for 24 h, after which subsamples of liquid phase were withdrawn for analysis of VFA by HPLC. Results are shown in Table B-7.
  • Table B-7 VFA production from cellulose fermentations amended with glycerol and/or ethanol. Results are corrected for VFA produced in vials containing ruminal inoculum but lacking added cellulose, glycerol or ethanol.
  • Electrolytic Stage (Electrochemical):
  • Electrode spacing was 1mm using a nylon mesh membrane.
  • Substrate volume was 250 mL, with no pH adjustment.
  • C0 2 was produced at the anode along with the hydrocarbon products noted, and H 2 was produced at the cathode.
  • Example Elec- 1 Electrolysis of centrifuged (unflltered) fermentation broth.
  • Identified gaseous anodic products included n- alkanes (methane, ethane, propane, pentane, hexane), branched alkanes (2-methylpentane, 3- methylpentane) and alkenes (ethylene, propylene, c s-2-pentene).
  • Example Elec-1 Gases were collected and analyzed as described in Example Elec-1. Identified gaseous anodic products included n-alkanes (methane, ethane, propane, hexane), branched alkanes (2- methylpentane) and alkenes (ethylene, propylene, c s-2-pentene).
  • the electrolytic conditions used for example Elec-3 below were a coiled, fine platinum electrode wire (0.033 cm dia. x 120 cm long) for the anode, and a stainless steel plate (2.5 cm x 5 cm) for the cathode. Electrode spacing was 3mm using a nylon mesh membrane. Substrate (butanol extract) volume was 250 mL, with KOH pH adjustment and a cooler starting/ending temperature. In this example, C0 2 was produced at the anode along with the hydrocarbon products noted, and H 2 was produced at the cathode.
  • Example Elec-3 Electrolysis of a butanol extract of filtered fermentation broth. Ultrafiltered fermentation broth (3.00 liters) from Example Elec-1 above was adjusted to pH 3.25 with concentrated HCl, flushed with N 2 gas, then extracted with 788 g of n-butanol. The butanol phase (713 g) was recovered and amended with 200 mL of H 2 0. After adjusting pH to 8.2 with 10 NaOH, 200 mL of additional H 2 0 was added. The butanol and water phases were allowed to separate, and the aqueous phase (containing most of the VFAs) was recovered.
  • the butanol extract was subjected to the following electrolysis conditions:
  • Example Elec-1 Gases were collected and analyzed as described in Example Elec-1. Identified gaseous anodic products included n-alkanes (methane, ethane, propane, butane, pentane, hexane), branched alkanes (2-methylpentane, 3-methylpentane) and alkenes (ethylene, propylene, cis-2- pentene).
  • n-alkanes methane, ethane, propane, butane, pentane, hexane
  • branched alkanes (2-methylpentane, 3-methylpentane
  • alkenes ethylene, propylene, cis-2- pentene
  • BDE Bond Dissociation Energy
  • VFA Volatile Fatty Acids
  • MCFA Medium Chain Fatty Acids
  • Hydrogen 0 436 1 1 Table 3. Fatty acid composition of some plant oils and animal fats of commercial importance.
  • composition varies slightly with varietal source and growth conditions.

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Abstract

Selon l'invention, des hydrocarbures et du combustible à base d'hydrogène, ainsi que d'autres produits, peuvent être obtenus par un procédé utilisant une combinaison d'étapes de fermentation et électrochimiques. Dans le procédé, une biomasse, contenue à l'intérieur d'un milieu de fermentation, est fermentée avec un inoculum comportant une culture mixte de microorganismes issus des contenus du rumen d'un animal présentant un rumen. Ce milieu inoculé est incubé dans des conditions anaérobie et pendant une durée suffisante pour produire des acides gras volatils. Les acides gras volatils résultants sont ensuite soumis à une électrolyse dans des conditions efficaces pour convertir lesdits acides gras volatils en hydrocarbures et en hydrogène, simultanément. Le procédé peut convertir une large gamme de matières de biomasse en une large gamme de longueurs de chaîne d'acides gras volatils et peut convertir ceux-ci en une large gamme de biocarburants et de produits d'origine biologique.
PCT/US2011/022029 2011-01-21 2011-01-21 Conversion biologique/électrolytique de biomasse en hydrocarbures WO2012099603A1 (fr)

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EP2975131A1 (fr) * 2014-07-17 2016-01-20 Evonik Degussa GmbH Synthèse d'alcanes
WO2016012279A1 (fr) * 2014-07-24 2016-01-28 Helmholtz-Zentrum Für Umweltforschung Gmbh - Ufz Procédé de préparation de composés organiques
CN107337313A (zh) * 2017-07-25 2017-11-10 昆明理工大学 一种自动循环的养殖废水处理装置及方法
CN108384816A (zh) * 2018-02-08 2018-08-10 同济大学 短链脂肪酸及利用污泥厌氧发酵生成短链脂肪酸的方法
US10329590B2 (en) 2014-05-13 2019-06-25 Evonik Degussa Gmbh Method of producing nylon
CN112795600A (zh) * 2021-03-05 2021-05-14 山东兆盛天玺环保科技有限公司 一种采用电发酵强化短链挥发性脂肪酸加链产己酸的方法
US11124813B2 (en) 2016-07-27 2021-09-21 Evonik Operations Gmbh N-acetyl homoserine
US11174496B2 (en) 2015-12-17 2021-11-16 Evonik Operations Gmbh Genetically modified acetogenic cell
CN114634953A (zh) * 2022-02-14 2022-06-17 中国科学院广州能源研究所 一种有机垃圾处理方法及其能源化利用系统

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US20100228067A1 (en) * 2007-02-23 2010-09-09 Massachusetts Institute Of Technology Conversion of natural products including cellulose to hydrocarbons, hydrogen and/or other related compounds

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US6927048B2 (en) * 1999-03-11 2005-08-09 Zea Chem, Inc. Process for producing ethanol
US20080311640A1 (en) * 2005-05-03 2008-12-18 Cox Marion E Anaerobic Production of Hydrogen and Other Chemical Products
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Cited By (13)

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Publication number Priority date Publication date Assignee Title
US10329590B2 (en) 2014-05-13 2019-06-25 Evonik Degussa Gmbh Method of producing nylon
CN106795529A (zh) * 2014-07-17 2017-05-31 赢创德固赛有限公司 使用微生物联合kolbe合成制备烷烃的方法
EP2975131A1 (fr) * 2014-07-17 2016-01-20 Evonik Degussa GmbH Synthèse d'alcanes
WO2016008979A1 (fr) * 2014-07-17 2016-01-21 Evonik Degussa Gmbh Procédé pour la production d'alcanes à l'aide de micro-organismes combinés avec une synthèse de kolbe
CN106795529B (zh) * 2014-07-17 2021-01-01 赢创运营有限公司 使用微生物联合kolbe合成制备烷烃的方法
WO2016012279A1 (fr) * 2014-07-24 2016-01-28 Helmholtz-Zentrum Für Umweltforschung Gmbh - Ufz Procédé de préparation de composés organiques
US11174496B2 (en) 2015-12-17 2021-11-16 Evonik Operations Gmbh Genetically modified acetogenic cell
US11124813B2 (en) 2016-07-27 2021-09-21 Evonik Operations Gmbh N-acetyl homoserine
CN107337313A (zh) * 2017-07-25 2017-11-10 昆明理工大学 一种自动循环的养殖废水处理装置及方法
CN108384816A (zh) * 2018-02-08 2018-08-10 同济大学 短链脂肪酸及利用污泥厌氧发酵生成短链脂肪酸的方法
CN112795600A (zh) * 2021-03-05 2021-05-14 山东兆盛天玺环保科技有限公司 一种采用电发酵强化短链挥发性脂肪酸加链产己酸的方法
CN114634953A (zh) * 2022-02-14 2022-06-17 中国科学院广州能源研究所 一种有机垃圾处理方法及其能源化利用系统
CN114634953B (zh) * 2022-02-14 2024-04-16 中国科学院广州能源研究所 一种有机垃圾处理方法及其能源化利用系统

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