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WO2012012799A1 - Procédé électrochimique de conversion de biodiesel en carburant pour l'aviation - Google Patents

Procédé électrochimique de conversion de biodiesel en carburant pour l'aviation Download PDF

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Publication number
WO2012012799A1
WO2012012799A1 PCT/US2011/045215 US2011045215W WO2012012799A1 WO 2012012799 A1 WO2012012799 A1 WO 2012012799A1 US 2011045215 W US2011045215 W US 2011045215W WO 2012012799 A1 WO2012012799 A1 WO 2012012799A1
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composition
biodiesel
carbon
electrochemical reactor
yield
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Sanjeev Mukerjee
Qinggang He
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Northeastern University China
Northeastern University Boston
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Northeastern University China
Northeastern University Boston
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Priority to US13/811,843 priority Critical patent/US20130284606A1/en
Publication of WO2012012799A1 publication Critical patent/WO2012012799A1/fr
Anticipated expiration legal-status Critical
Priority to US15/141,182 priority patent/US20160237361A1/en
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    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • 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
    • C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs
    • C10G15/08—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs by electric means or by electromagnetic or mechanical vibrations
    • 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
    • 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
    • C25B3/23—Oxidation
    • 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
    • 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
    • C25B3/29—Coupling reactions
    • C25B3/295—Coupling reactions hydrodimerisation
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/38—Applying an electric field or inclusion of electrodes in the apparatus
    • 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
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

Definitions

  • Fossil fuels are being replaced by renewable and sustainable energy sources such as biodiesel, biokerosine, and ethanol, which can supply the needs of many types of ground transportation by fueling cars, trucks, and rail.
  • biofuels such as biodiesel are not suitable for use in cold climates because they contain long chain hydrocarbons that can solidify at operating temperatures in such environments.
  • Biofuels are also not suitable for use as aviation fuel, both because of their solidification at the low temperatures encountered at high altitutde and because they lack the high energy density required of an aviation fuel.
  • the invention provides a series of electrochemical processes carried out by directed electrochemical reactors for use in improving the quality of a biofuel, converting a biodiesel fuel to a fuel containing short chain alkanes, and converting the fatty acid methyl esters of a biodiesel fuel into a mixture of aliphatic hydrocarbons.
  • the reactors can be used individually or combined into systems to modify a biofuel for new uses, such as in aviation or motor vehicles and as a replacement for liquified petroleum gas in heating and cooking.
  • One aspect of the invention is an electrochemical reactor for cleaning up biodiesel via selective oxidation of alcohols and glycerol, and thereby producing cogenerated power
  • Yet another aspect of the invention is an electrochemical reactor for hydrogenation of ester moieties in a biodiesel fuel for the generation of aliphatic hydrocarbons.
  • Each of the abovementioned reactors utilizes on-line monitoring of fuel components by analytical methods such as high pressure liquid chromatography and mass spectrometry.
  • the reactors also utilize selected electrocatalysts in conjunction with ion conducting membranes.
  • Still another aspect of the invention is a system for the chemical conversion of a biodiesel to an alkane composition.
  • the system includes a first electrochemical reactor that reduces excess MeOH in a biodiesel source material to yield a first composition containing methyl esters of aliphatic carboxylic acids.
  • the system also includes a second electrochemical reactor that fragments the methyl esters of aliphatic carboxylic acids of the first composition by carbon-carbon double bond cleavage to yield a second composition containing short chain methyl esters of aliphatic carboxylic acids.
  • the system further includes a third electrochemical reactor that hydrogenates the methyl esters of the second composition to yield a third composition comprising alkanes.
  • Another aspect of the invention is a system for the chemical conversion of a biodiesel to an alkane composition.
  • the system includes a first electrochemical reactor that fragments aliphatic chains of a biodiesel source material by carbon-carbon double bond cleavage to yield a first composition containing short chain methyl esters of aliphatic carboxylic acids.
  • the system also includes a second electrochemical reactor that performs a Kolbe reaction, whereby the aliphatic carboxylic acids of the first composition are decarboxylated to yield a second composition containing alkanes.
  • Still another aspect of the invention is a system for the chemical conversion of a biodiesel to an alkane composition.
  • the system includes a first electrochemical reactor that fragments aliphatic chains of a biodiesel source material by carbon-carbon double bond cleavage to yield a first composition containing short chain methyl esters of aliphatic carboxylic acids.
  • the system also includes a second electrochemical reactor that hydrogenates the methyl esters of the first composition to yield a second composition comprising alkanes.
  • Yet another aspect of the invention is a method for the chemical conversion of a biodiesel to an alkane composition.
  • the method includes providing a crude biodiesel composition that contains fatty acid esters and methanol; reducing the amount of methanol by electrochemical oxidation of the methanol to carbon dioxide in a first electrochemical reactor; fragmenting fatty acid chains in a second electrochemical reactor that cleaves the fatty acid chains at carbon-carbon double bonds to yield short chain fatty acids and aldehydes; and hydrogenating the short chain fatty acids and aldehydes in a third electrochemical reactor to yield a composition comprising alkanes.
  • Another aspect of the invention is a method for the chemical conversion of a biodiesel to an alkane composition.
  • the method includes providing a crude biodiesel composition containing fatty acid esters and methanol; fragmenting the fatty acid chains in a first electrochemical reactor that cleaves the fatty acid chains at carbon-carbon double bonds to yield short chain fatty acids and aldehydes; oxidizing the short chain aldehydes to short chain fatty acids; and performing a Kolbe reaction in a second electrochemical reactor, whereby the short chain fatty acids are decarboxylated to form alkanes.
  • Still another aspect of the invention is a method for the chemical conversion of a biodiesel to an alkane composition.
  • the method includes providing a crude biodiesel composition containing fatty acid esters and methanol; fragmenting the fatty acid chains in a first electrochemical reactor that cleaves the fatty acid chains at carbon-carbon double bonds to yield short chain fatty acids and aldehydes; and hydrogenating the short chain fatty acids and aldehydes in a second electrochemical reactor to form alkanes.
  • Fig. 1 is a flow chart showing an embodiment of a system for the conversion of biodiesel to an aviation grade bio-fuel using a series of three electrochemical reactors.
  • Fig. 2 shows the results from a chronoamperometry test using a Pt/C (E-TEK, 30%) catalyst, at 0.55 V vs. a reference hydrogen electrode (RHE) in 1 M ethanol with 0 mM, 1 mM, and 3 mM polyvalent transition metal complex (lead acetate) and PtRuTM/C catalyst at 0.55 V in 1 M ethanol, Pt loading was 15 ug/cm 2 .
  • TM refers to a transition metal.
  • Fig. 3 shows the electrochemical reactions that take place in Reactor II of the system shown in Fig. 1 .
  • Fig. 4A shows a schematic representation of Reactor III of the system shown in Fig. 1 , which carries out hydrogenation of a fatty acid methyl ester.
  • Fig. 4B shows the reaction mechanism carried out in the reactor shown in Fig. 4A.
  • Fig. 5 shows a flow chart for an embodiment of a system for the conversion of a biofuel source containing free fatty acids, fatty acid esters, and tryglycerides into an alkane fuel using three electrochemical reactors.
  • Fig. 6 shows schematic representations of Reactors l-lll from the biofuel conversion system shown in Fig. 5. Each reactor schematic depicts the components of the reactor and the electrochemical mechanism carried out by the reactor.
  • Fig. 7 shows an experimental system (H-cell) for carrying out an electrolysis reaction.
  • Fig. 8 shows NMR spectra for styrene and the resulting products formed after 5 hours' electrolysis and 18 hours electrolysis.
  • Fig. 9 shows the results of GC-MS analysis of electroreductive reaction of methyloctanoate showing the formation of octanol and octanoic acid as well as other products.
  • the invention provides a series of directed electrochemical reactors useful for modifying biofuels in several ways.
  • One type of reactor can be used to clean up biodiesel via selective oxidation of alcohols and glycerol, while simultaneously generating power.
  • a third type of reactor hydrogenates ester moieties and generates aliphatic hydrocarbons from fatty acid esters.
  • Each of these reactors is designed to perform specific tasks and can be outfitted with on-line monitoring of fuel components using known analytical tools such as high pressure liquid chromatography and mass spectrometry.
  • the reactors utilize selected electrocatalysts in conjunction with ion conducting membranes, such as the perfluorinated sulfonic acid prototype represented by DuPont's National® series.
  • the electrochemical reactions of the invention can be integrated into existing biodiesel production technology or can be added to it as a post-production refining process, e.g., to convert biodiesel to aviation fuel.
  • a biofuel is a hydrocarbon-based mixture obtained from plant, animal, or microbial sources which can be used as a fuel in internal combustion engines, jet engines, for heating or cooking, or for generating other forms of energy such as electricity.
  • One type of biofuel is biodiesel, which is a mixture of mono-alkyl esters of long chain fatty acids. Biodiesel is typically produced by transesterification of fats using methanol as the alcohol, but other short chain alcohols such as ethanol, (iso)propanol, or butanol also can be used.
  • the methods according to the present invention can convert such mono-alkyl esters into short chain alkanes having, for example, from about 1 to about 16 carbon atoms in length, or from about 2 to about 12 carbon atoms in length, or from about 3 to about 10 carbon atoms in length.
  • the short chain alkane product can include straight chain unbranched alkanes, but also can contain branched chain, cyclic, unsaturated, or aromatic hydrocarbons.
  • the short chain alkane product of the present invention is essentially free of aromatic hydrocarbons, or is essentially free of unsaturated hydrocarbons, or is essentially free of mono-alkyl esters of long chain fatty acids, or is essentially free of alkanes having a chain length of 12 or more, 14 or more, 15 or more, 16 or more, 17 or more, 18 or more, 20 or more, or 22 or more carbon atoms.
  • the short chain alkane product consists essentially of linear alkanes having a chain length of about 8-1 1 carbon atoms.
  • Figure 1 depicts an embodiment of a system (4) for electrochemical conversion of a biofuel.
  • the system employs three electrochemical reactors which operate in a coordinated fashion to convert esters of long chain unsaturated fatty acids to short chain alkanes.
  • Fig. 1 shows the appropriate positions for each reactor in the system.
  • Reactor I (1 ) carries out the selective electrooxidation of MeOH formed during biodiesel production.
  • Reactor III (3) reduces esters to alkanes, completing the conversion of biodiesel to a fuel suitable for aviation use.
  • a polyvalent transition metal ion complex mediates the methanol oxidation process at the immobilized Pt catalyst active sites for anodic oxidation of methanol.
  • ethanol electro-oxidation on a Pt/C catalyst was studied in the presence of millimolar quantity of a polyvalent transition metal ion complex (lead acetate) using chronoamperometry over a one hour period. The results are presented in Figure 2, and show the significant increase in steady state currents achieved in the presence of the polyvalent transition metal ion complex.
  • the polyvalent transition metal mediation system functions for the electrooxidation of MeOH as well.
  • Reactor I performs the electrooxidation of MeOH to C0 2 in order to reduce the amount of excess MeOH present in a crude biodiesel source composition.
  • methyl esters of fatty acids derived from inedible sources such as rapeseed oil, whose primary constituent is erucic acid
  • Reactor II methyl esters of fatty acids derived from inedible sources, such as rapeseed oil, whose primary constituent is erucic acid
  • Cu catalysts homogenous mediated catalysis
  • the Cu 2 7Cu + redox couple has been applied to a C-C double bond cleavage reaction of styrene [1 ].
  • the methyl ester is first oxidized by Cu 2+ to produce a radical cation.
  • This radical cation electro-migrates to the cathode compartment through a cation exchange membrane and reacts with molecular oxygen to form an oxethyl intermediate species.
  • Two fragments with carbon chain length appropriate for aviation fuel are produced after decomposition of the intermediate species.
  • rhodium-catalyzed carbon-carbon double-bond cleavage [6] and cobalt(H )-catalyzed oxidative cleavage of a carbon-carbon double bond [7] also could be used, the Cu2+/Cu+ redox couple is preferred because the previously used catalysts are expensive due to the value of precious metals or their complicated synthesis process.
  • methyl esters are reduced to alkanes. See, e.g., Fig. 4A and Fig. 4B.
  • SPE solid polymer electrolyte
  • the reactor can be assembled with a Ru0 2 powder anode (62) and a carbon paper cathode (72) painted with catalysts (60, 70) that were hot pressed onto the opposing surfaces of a National cation-exchange membrane (40) [2].
  • the number or capacity of Reactors III can be reduced if all or a portion of the methyl esters are converted to alkanes directly by catalysis.
  • the system of Reactors l-lll described above has several advantages compared to traditional chemical reactions used for similar purpose.
  • Conventional hydrogenation of esters is carried out under high hydrogen pressure and elevated temperature in slurry-phase or fixed-bed reactors. Such methods involve high enegry consumption, low selectivy, and low product yield [8,9,10].
  • the simple mediator method used in the Reactor I needs only a low concentration of a transition metal complex (such as 0.5 mM lead acetate). In addition, the transition metal complex is not consumed and remains as a redox couple once the fuel cell runs.
  • the mediator catalyst used in Reactor II is a common and inexpensive salt, CuCI 2 . No reducing agents are required in Reactor II for the activation of molecular oxygen.
  • Reactor III uses moderate temperature and atmospheric pressure conditions for hydrogenation of methyl esters.
  • Proton donors can be generated by a highly efficient water electrolysis process.
  • Specificity for the electroreduction of esters and alcohols to final alkane products is provided through the use of two specific and exclusive catalysts.
  • the invention also contemplates other combinations of electrochemical reactors for the processing of biofuels.
  • the cloud point of a liquid fuel mixture is reduced through a series of electrochemical reactions.
  • a series of directed electrochemical reactors enable higher efficiency and greater selectivity for conversion of bio-sourced oils such as those containing triglycerides, aliphatic free acids and esters into kerosene grade fuels.
  • the inventors are unaware of any viable process for conversion of bio-derived oils to kerosene-type alkanes in terms of energy balance, flexibility towards feedstock and modularity.
  • Some of the steps in the system of the present invention especially the selective cleavage of the unsaturation at C 8 -Ci 0 part of the aliphatic backbone, have no analog in conventional catalytic routes.
  • Conventional routes for bio-oil upgradation typically involves hydro-deoxygenation [1 1 ].
  • the conventional sulfide based hydrotreating catalysts contaminate products by incorporation of sulfur, deactivate rapidly by coke formation, and are potentially poisoned by trace amounts of water [1 2, 1 3].
  • the process (400) involves the following steps:
  • PATH 1 in case of the presence of free acid would first entail (a) conversion of terminal aldehyde groups obtained in step 1 to acid via low temperature catalytic oxidation and (b) a Kolbe process for conversion of the terminal acid groups to alkane.
  • PATH 2 can be used for fractions containing ester terminal groups.
  • the aldehyde terminal groups obtained in step 1 can be converted to esters via a conventional esterification reaction. This is followed by a special electrochemical reactor for conversion of ester moieties to alcohol (electro-reductive process) and then finally to alkanes.
  • Electrode processes generally do not require the addition of consumable chemical components other than the base feedstock.
  • Electrode potential can be chosen based on the composition of the feedstock, hence providing for a flexible system, modifiable based on feedstock.
  • Electrochemical cells can be designed to operate economically through a wide range of reaction scales.
  • model compounds can be used to mimic the real bio-oil feedstock input.
  • erucic acid can be used.
  • the alternative process involving E-reactor 1 and route 2 can use the ester form of erucic acid as the starting material.
  • the methyl ester of erucic acid is first oxidized by Cu 2+ to produce a radical cation.
  • This radical cation then undergoes a mediated charge transfer with oxygen (1 16) to create an oxethyl intermediate species and Cu + .
  • the Cu + on electro-migration to the cathode compartment (1 19) through a cation exchange membrane (130) (such as National® from Dupont) undergoes redox transformation to Cu 2+ which on reverse electromigration to the anode compartment completes the circuit.
  • a cation exchange membrane such as National® from Dupont
  • Two fragments with relevant carbon chain length for aviation needs can be produced after decomposition of the intermediate species.
  • Structure 1 10 is the anode
  • structure 120 is the cathode
  • structure 150 is the power supply
  • structures 135 and 140 are fluid inlets and outlets, respectively.
  • E-reactor 1 can be followed with catalytic oxidation of aldehyde moieties to either acid or ester terminal groups. In the case of conversion to acid terminal ends, this can be conducted using conventional Tollen's reagent (Ag catalyst in conjunction with NH 3 ).
  • Tollen's reagent Ag catalyst in conjunction with NH 3 .
  • the aldehyde end groups obtained in step 1 can first be converted to ester groups using conventional base catalyzed esterification in conjunction with methanol. Both conversion steps have greater than 95% yield and typically use an 85-95 5 C single pot process followed with phase separation between aqueous and oil phases. These steps are conventional.
  • E-reactor 2 (200) carries out Route 1 (Kolbe Process), the direct conversion of acids to alkanes.
  • a decarboxylative dimerisation known as the "Kolbe Reaction” proceeds via a radical reaction mechanism, yielding aliphatic products directly [17,18].
  • the reaction can be represented as:
  • This reaction can be carried out using metered amounts of acetic acid.
  • R 2 can be a fragment, with two terminal acid groups obtained from previous step.
  • alkanes R Ri and R 2 -R 2 are also likely products.
  • Process design can utilize a proton exchange membrane (240) [18]. The important consideration is using metered amounts of H 2 0 (270) in the cathode (220) compartment for H 2 evolution.
  • RhxS y is a stable electrocatalyst in conjunction with proton exchange membranes.
  • catalysis on a nanocluster surface can be used with different oxidative sites (Pt and alloying element), while in the second strategy individual elements can be used as catalytic sites in a well coordinated crystalline environment.
  • E-Reactor 3 (300) carries out Route 2, the conversion of methyl esters to aviation fuels of alkanes.
  • Route 2 shown in Figures 4 and 6 employs a two level electrochemical reactor arrangement which is specifically designed to deoxygenate the ester containing aliphatic components derived from E-reactor 1 to alkane type products.
  • Two solid polymer electrolyte (SPE) reactors in series can be used for conversion of the C 8 -Cn aliphatic ester moieties to corresponding alkane form at moderate temperature and atmospheric pressure.
  • the first reactor aims at converting ester groups to corresponding alcohols.
  • the reactor is assembled with a Ru0 2 powder anode (360) and a carbon black cathode (370) painted with magnesium catalysts (362, 372) that are hot-pressed onto the opposing surfaces of a National cation-exchange membrane (340) [19].
  • Water (310) is pumped (322) into the Ru0 2 anode compartment in the reactor and electrolyzed to 0 2 and H + under constant applied current (350) (such as about 0.10 A/cm 2 and 1 .5 V); see Figures 4 and 6.
  • constant applied current such as about 0.10 A/cm 2 and 1 .5 V
  • Proton migration through the cation exchange membrane (Nation®, Dupont) to the cathode electrode compartment enables the reduction of the ester (320) moieties to form analogous reduced products (330).
  • the electroreductive method can be adopted for selective transformation of esters to corresponding alcohols [22] and aliphatic alcohols to alkanes [23]. Any free acid species or fragment during these electrochemical processes can be converted to alkanes directly by Kolbe electrolysis [17].
  • the product is the corresponding primary alcohol when the reaction is run in the presence of a proton donor (schematic 1 ) [22].
  • the alcohol moieties can then be transformed to an alkane product by an electro- reductive method on a lead cathode (schematic 2) [23].
  • the electrodes are separate from the ion conducting membrane. Though simple to implement, this rendition requires the greater use of free electrolyte, which presents problems later when purification of the fragments is conducted.
  • Second is the use of half membrane electrode assemblies, wherein either the anode or the cathode would be bonded to the membrane. This method allows for the electrode where the primary process is occurring to be in a high throughput flow through mode.
  • Third is the formulation of an anode and cathode bonded membrane electrode assembly (MEA). Here, electrolyte conductivity and that of the charged species is not a problem; however, proper mass transport of the reactants to the appropriate interfacial reaction zone has to be ensured.
  • the membrane electrode assembly can be designed using porous carbon electrodes (uncatalyzed) using various thicknesses of National® (Dupont) membranes. Carbon electrodes with various levels of porosity can be used for correlating with mass transport measurement (electrochemical polarization measurements).
  • Flow through plates can be designed using graphite plates for effective turnover numbers and charge transfer efficiencies. Both parameters can be measured under glavanostatic conditions with aid of an online GS-MS set up.
  • Membrane electrode assemblies can be designed with Pt/C electrodes on anode and cathode sides (e.g., 60% on C, 0.4 mg/cm 2 loading).
  • the metering arrangement for cathodic hydrogen evolution reaction can be designed in keeping with water activity at the anode stream containing the aliphatic acid moieties.
  • the cell flow through system can be designed for maximizing the TOF and yield per pass. In this case a careful optimization can be made using on line GC/MS equipment and cell operating conditions.
  • the first reactor (E-reactor 3.1 ) can be designed for conversion of the ester moieties to alcohol followed with a second tandem reactor (E-reactor 3.2) for its conversion to alkanes.
  • the membrane electrode assembly for reactor 3.1 can comprise a Ru0 2 anode and a Mg cathode.
  • Ru0 2 and Mg inks can be directly deposited into the Nation membrane in conjunction with a solubilized form of the National polymer. Since 0 2 evolution is occurring at the anode electrode no carbon black is required on that electrode layer. This avoids difficulties in preventing carbon corrosion.
  • Mg catalyst can be used in the same loading as prescribed above. Short periods of voltage reversal are can be used to keep the appropriate TOF's.
  • Reactor 3.2 can be fitted with a Pb/C cathode for electroreduction of alcohol with an interpenetrating proton-conducting phase, typically a sulfonated polymer such as National, and a Ru0 2 anode electrode. These components transport electrons, protons and gas or solution phase reactants and products to and from the electrocatalyst site.
  • the oxygen evolution anode can be similar to the one used in reactor 3.1 . As mentioned earlier, this anode can be directly deposited on the membrane surface (Nations®, Dupont) and does not contain any carbon black. Ti based bipolar plates can be used for E-reactor 3.2. This is due to oxygen evolution anode electrode being used as the proton source.
  • Oxygen from E-reactors 3.1 and 3.2 can be recirculated to E-Reactor 1 .
  • the cell flow through system can be designed for maximizing the TOF and yield per pass. In this case a careful optimization can be made using on line GC/MS equipment and cell operating conditions.
  • the concentration of Cu ion catalyst can be optimized based on a balance of high performance and easy separation from the final products. Solvents with boiling point or viscosity different from the reactant (erucic acid) and the obtained fractions can be used to ensure convenient post-reaction separation.
  • E-reactor 2 In E-reactor 2 (Kolbe Process), careful control of the dissociation of acid moieties can be obtained via adjustments to solvent composition. Central to the success of the Kolbe process is promotion of the reaction between acetic acid and the aliphatic fractions obtained from E-reactor 1 . Considering the mechanism of the Kolbe process, the reaction is initiated by the carboxylate ion undergoing an initial discharge to form an adsorbed radical. RCOO ⁇ RCOO (ads) + e " . Steric considerations can be exploited via the use of Pt alloys and chalcogenide electrocatalysts. However this process can be further promoted by careful adjustment of the solvent conditions to promote dissociation of the acid.
  • Figure 8 clearly shows that aldehyde groups were formed after the electrolysis reaction.
  • the peaks for alehyde groups grew as a function of time, indicating accumulation of the oxidized products with C-C double bond breaking on styrene.
  • Conversion of methyl esters to alkanes proceeds by first transforming the methyl ester into an alcohol followed by a second electroconversion into alkane.
  • the reduction of methyl 1 -octanoate to octanol was demonstrated using an electrolysis process with a LiCI0 4 electrolyte and t-BuOH as a proton source, with magnesium and silver electrodes.
  • the products of this electroreduction were shown using a GC-MS technique.
  • GC-MS also provides detailed structural information for an analyte as a result of diagnostic fragmentation patterns resulting from ionization of the molecule.
  • Figure 9 shows the result of GC-MS analysis using an Agilent 6890 GC with 5973 mass selective detector (30m x 0.25mm HP-MS5 capillary column with the masses acquired from 50- 500Da) for the electroreduction of methyloctanoate.
  • the region specifically related to the methyloctanoate is indicated although other products were detected during the analysis.
  • the presence of underivatized octanoic acid can be corrected by adjusting the ratio of silylating reagent to crude reaction mixture to insure complete derivatization of all hydroxyl containing analytes.

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Abstract

Cette invention concerne des procédés de conversion d'un biocarburant, par exemple un biodiesel, sous forme d'une composition alcane, par exemple un carburant pour l'aviation, du kérosène ou un produit de gaz de pétrole liquéfiés, lesdits procédés impliquant une série de réactions électrochimiques. Les réactions consistent à oxyder le méthanol en dioxyde de carbone, à réduire les esters d'acides gras et à cliver les liaisons doubles C=C des chaînes des acides gras. Les procédés sont effectués par des systèmes constitués de deux réacteurs électrochimiques ou plus.
PCT/US2011/045215 2010-07-23 2011-07-25 Procédé électrochimique de conversion de biodiesel en carburant pour l'aviation Ceased WO2012012799A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014042783A1 (fr) * 2012-09-14 2014-03-20 Liquid Light, Inc. Réduction électrochimique multiphase du co2
US10633749B2 (en) 2014-07-23 2020-04-28 Board Of Trustees Of Michigan State University Electrolyzer reactor and related methods

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3052459B1 (fr) * 2016-06-13 2020-01-24 Bio-Think Melange destine a alimenter une chaudiere ou un moteur diesel comprenant des esters et des alcanes particuliers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090124839A1 (en) * 2006-06-06 2009-05-14 Dumesic James A Production of liquid alkanes in the jet fuel range (c8-c15) from biomass-derived carbohydrates
US20090182166A1 (en) * 2007-12-31 2009-07-16 University Of North Dakota Method for production of short chain carboxylic acids and esters from biomass and product of same
US7722755B2 (en) * 2003-11-12 2010-05-25 Ecr Technologies, Inc. Method of electro-catalytic reaction to produce mono alkyl esters for renewable biodiesel

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329209A (en) * 1979-02-23 1982-05-11 Ppg Industries, Inc. Process using an oxidant depolarized solid polymer electrolyte chlor-alkali cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7722755B2 (en) * 2003-11-12 2010-05-25 Ecr Technologies, Inc. Method of electro-catalytic reaction to produce mono alkyl esters for renewable biodiesel
US20090124839A1 (en) * 2006-06-06 2009-05-14 Dumesic James A Production of liquid alkanes in the jet fuel range (c8-c15) from biomass-derived carbohydrates
US20090182166A1 (en) * 2007-12-31 2009-07-16 University Of North Dakota Method for production of short chain carboxylic acids and esters from biomass and product of same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014042783A1 (fr) * 2012-09-14 2014-03-20 Liquid Light, Inc. Réduction électrochimique multiphase du co2
US10633749B2 (en) 2014-07-23 2020-04-28 Board Of Trustees Of Michigan State University Electrolyzer reactor and related methods
US11668014B2 (en) 2014-07-23 2023-06-06 Board Of Trustees Of Michigan State University Electrolyzer reactor and related methods

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