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WO2013096225A1 - Décarboxylation d'acide lévulinique en solvants de type cétone - Google Patents

Décarboxylation d'acide lévulinique en solvants de type cétone Download PDF

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Publication number
WO2013096225A1
WO2013096225A1 PCT/US2012/070154 US2012070154W WO2013096225A1 WO 2013096225 A1 WO2013096225 A1 WO 2013096225A1 US 2012070154 W US2012070154 W US 2012070154W WO 2013096225 A1 WO2013096225 A1 WO 2013096225A1
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Prior art keywords
mek
anolyte
levulinate
radicals
hydrogen
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PCT/US2012/070154
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English (en)
Inventor
Sai Bhavaraju
Mukund Karanjikar
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Ceramatec Inc
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Ceramatec Inc
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Priority claimed from US13/357,463 external-priority patent/US8821710B2/en
Application filed by Ceramatec Inc filed Critical Ceramatec Inc
Publication of WO2013096225A1 publication Critical patent/WO2013096225A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B3/29—Coupling reactions
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention describes a method for the manufacture of ketone solvents, such as methyl ethyl ketone ("MEK”) or octanedione.
  • MEK methyl ethyl ketone
  • MEK has a chemical formula of
  • MEK is valuable as an organic solvent and is used as a solvent in many commercial manufacturing processes.
  • MEK is also used in some household products such as varnish and lacquer.
  • MEK can be expensive to produce.
  • a new method for manufacturing MEK is desirable. Such a method is disclosed herein.
  • Levulinic acid is an organic acid that is cheaply produced from naturally occurring hexose sugar materials.
  • hexose sugar materials include one or more rings.
  • Hexose sugar materials include six (6) carbon atoms. Examples of these types of sugar materials include glucose, etc.
  • a sugar monomer which has the formula C 6 Hi 2 0 6 may be reacted as follows to form levulinic acid, water and formic acid:
  • C5H 8 O 3 is the empirical formula of levulinlic acid. However, this acid has the following chemical structure:
  • a decarboxylation reaction may be performed using an electrochemical cell.
  • the formate and levulinate anions are part of an anolyte solution (that also includes a solvent such as water or methanol) and are reacted as follows:
  • the radical species e.g., the MEK radical and the H radical
  • the radical species formed within the anolyte may react together:
  • hydrogen radicals may be created by a Pd anode, by photolysis of hydrogen gas, from Pd and pressurized hydrogen gas, or from another species that donates the H radical (such as an alkane or other organic material).
  • Figure 1 is a flow diagram showing the conversion of sugar moieties into levulinic acid and formic acid
  • Figure 1A is a flow diagram showing the conversion of levulinic acid and formic acid to sodium formate and sodium levulinate.
  • Figure 2 is a schematic view of an embodiment of an electrolytic cell for conversion of sodium levulinate to MEK and other products
  • Figure 3 is a schematic view of another embodiment of an electrolytic cell for conversion of sodium levulinate to MEK and other products
  • Figure 4 is a schematic view of yet an embodiment of an electrolytic cell for conversion of sodium levulinate to MEK and other products
  • Figure 5 is a flow diagram showing an exemplary method of the present embodiments.
  • Figure 6 is another flow diagram showing another exemplary method of the present embodiments.
  • This process is a dehydration reaction as water is produced.
  • the dehydration of a sugar 118 which is performed by treatment with acid, ultimately forms levulinic acid 120 and formic acid 130 in an approximately 3: 1 weight ratio. (Water 140 is also formed.)
  • This transformation has been known for decades. Accordingly, those skilled in the art are familiar with the processes needed to create levulinic acid. Further information regarding the production of levulinic acid is found in the following article:
  • levulinic acid may be used in an electrochemical cell.
  • the levulinic acid may be converted to an alkali metal salt using a saponification reaction as shown in Figure 1A.
  • the saponification reaction involves reacting the levulinic acid 120 and/or the formic acid 130 with a base 160.
  • the base 160 is NaOH.
  • other bases may be used (such as sodium methoxide, sodium ethoxide, KOH, potassium methoxide, etc.)
  • This saponification reaction produces water 140, sodium formate 170 and sodium levulinate 180, all of which may remain in the anolyte.
  • another alkali metal may be used as the corresponding cation.
  • Electrochemical cells have been used to conduct various chemical reactions.
  • the electrochemical cell will generally have an anode and a cathode.
  • the anode may be made of smooth platinum, stainless steel, or may be a carbon based electrode.
  • Examples of carbon based electrodes include boron doped diamond, glassy carbon, synthetic carbon, Dimensionally Stable Anodes (DSA), and lead dioxide. Other materials such as Pd may also be used for the electrode.
  • Kolbe reaction This reaction involves an oxidation (decarboxylation) step. Specifically, in the standard Kolbe reaction, anodic decarboxylation/oxidative coupling of carboxylic acids occurs. This reaction is a free radical reaction and is shown below: 2R-COOH R-R + 2CO
  • This Kolbe reaction is typically conducted in non-aqueous methanolic solutions, with partially neutralized acid (in the form of alkali salt) used with a parallel plate type electrochemical cell.
  • the anolyte used in the cell may have a high density.
  • the Kolbe reaction has been known and used. In fact, the following article summarizes and explains the Kolbe reaction:
  • the Kolbe reaction is a free radical reaction in which two "R radicals” (R») are formed and are subsequently combined together to form a carbon-carbon bond.
  • the present embodiments relate to a modified "Kolbe" reaction. Specifically, the present embodiments involve decarboxylation to form an "R radical” (R») (such as the MEK radical). Hydrogen radicals may be added/formed to couple with the MEK radical, thereby forming MEK.
  • R R radical
  • Hydrogen radicals may be added/formed to couple with the MEK radical, thereby forming MEK.
  • sodium levulinate may be decarboxylated at the anode of a cell to produce an MEK radical.
  • This reaction may be represented as follows:
  • This MEK radical may then be reacted with a H radical ( ⁇ ) to form the MEK.
  • This H radical ( ⁇ ) may be formed in a variety of different ways, including the decarboxylation of sodium formate:
  • an electrochemical cell is shown 200 to which a voltage may be applied.
  • the advanced Kolbe reaction discussed above occurs within the electrochemical cell 200.
  • the cell 200 includes a catholyte compartment 204 and an anolyte compartment 208.
  • the catholyte compartment 204 and the anolyte compartment 208 may be separated by a membrane 212.
  • Other embodiments may be designed in which there is only a single compartment that houses both the anode and the cathode.
  • each cell 200 may be a standard parallel plate cell, where flat plate electrodes and/or flat plate membranes are used. In other embodiments, the cell 200 may be a tubular type cell, where tubular electrodes and/or tubular membranes are used.
  • An electrochemically active anode 218 is housed, at least partially or wholly, within the anolyte compartment 208. More than one anode 218 may also be used.
  • the anode 218 may comprise, for example, a smooth platinum electrode, a stainless steel electrode, or a carbon based electrode.
  • Examples of a typical carbon based electrode include boron doped diamond, glassy carbon, synthetic carbon, Dimensionally Stable Anodes (DSA) and relatives, and/or lead dioxide.
  • Other electrodes may comprise metals and/or alloys of metals, including S ⁇ S, Kovar, Inconel/monel.
  • Other electrodes may comprise Ru0 2 -Ti0 2 /Ti, PtO x -Pt0 2 /Ti, IrO x , C0 3 O 4 , Mn0 2 , Ta 2 0 5 and other valve metal oxides.
  • the cathode compartment 204 includes at least one cathode 214.
  • the cathode 214 is partially or wholly housed within the cathode compartment 204.
  • the material used to construct the cathode 214 may be the same as the material used to construct the anode 218.
  • Other embodiments may be designed in which a different material is used to construct the anode 218 and the cathode 214.
  • the anolyte compartment 208 is designed to house a quantity of anolyte 228.
  • the catholyte compartment 204 is designed to house a quantity of catholyte 224.
  • the anolyte 228 and the catholyte 224 are both liquids, although solid particles and/or gaseous particles may also be included in either the anolyte 228, the catholyte 224, and/or both the anolyte 228 and the catholyte 224.
  • the anode compartment 208 and the cathode compartment 204 are separated by an alkali metal ion conductive membrane 212.
  • the membrane utilizes a selective alkali metal transport membrane.
  • the membrane is a sodium ion conductive membrane 212.
  • the sodium ion conductive solid electrolyte membrane 212 selectively transfers sodium ions (Na + ) from the anolyte compartment 208 to the catholyte compartment 204 under the influence of an electrical potential, while preventing the anolyte 228 and the catholyte 224 from mixing.
  • solid electrolyte membranes include those based on NaSICON structure, sodium conducting glasses, beta alumina and solid polymeric sodium ion conductors. Such materials are commercially available.
  • NaSICON typically has a relatively high ionic conductivity at room temperature.
  • the alkali metal is lithium
  • a particularly well suited material that may be used to construct an embodiment of the membrane is LiSICON.
  • the alkali metal is potassium
  • a particularly well suited material that may be used to construct an embodiment of the membrane is KSICON.
  • the saponification reaction shown in Figure 1A are designed to produce a quantity of an alkali metal salt of levulinic acid 180 (e.g., sodium levulinate).
  • This alkali metal salt of a levulinic acid 180 may be separated and/or purified, as needed.
  • the alkali metal salt of levulinic acid 180 comprises a mixture of fatty acid salts, these compounds may be separated.
  • the alkali metal salt of levulinic acid 180 may not be separated and may comprise a mixture of different salts.
  • the anolyte compartment 208 may include one or more inlets 240 through which the anolyte 228 may be added. Alternatively, the components that make up the anolyte 228 may be separately added to the anolyte compartment 208 via the inlets 240 and allowed to mix in the cell.
  • the anolyte includes a quantity of the alkali metal salt of levulinic acid 180. In the specific embodiment shown in Figure 2, sodium is the alkali metal, so that alkali metal salt of levulinic acid 180 is a sodium salt 180a.
  • the anolyte 228 also includes a first solvent 160, which as noted above, may be an alcohol, such as methyl alcohol 160a. Of course, other types of solvents may also be used.
  • the catholyte compartment 204 may include one or more inlets 242 through which the catholyte 224 may be added.
  • the catholyte 224 includes a second solvent 160b.
  • the second solvent 160b may be an alcohol or water (or a mixture of alcohol and water). As shown in Figure 2, the alcohol is methyl alcohol.
  • the solvent 160b in the catholyte 224 may not necessarily be the same as the first solvent 160a in the anolyte 228. In some embodiments, the solvents 160a, 160b may be the same. The reason for this is that the membrane 212 isolates the compartments 208, 204 from each other.
  • the solvents 160a, 160b may be each separately selected for the reactions in each particular compartment (and/or to adjust the solubility of the chemicals in each particular compartment).
  • the designer of the cell 200 may tailor the solvents 160a, 160b for the reaction occurring in the specific compartment, without having to worry about the solvents mixing and/or the reactions occurring in the other compartment.
  • This is a significant advantage in designing the cell 200.
  • a typical Kolbe reaction only allows for one solvent used in both the anolyte and the catholyte. Accordingly, the use of two separate solvents may be advantageous.
  • either the first solvent 160a, the second solvent 160b, and/or the first and second solvents 160a, 160b may comprise a mixture of solvents.
  • the catholyte 224 may also include a base 150.
  • the base 150 may be NaOH or sodium methoxide, or a mixture of these chemicals.
  • the base 150 may be the same base 150 as used in the saponification reaction of Figure 1A. Alternatively, the base may be a different base than that which was used in the saponification reaction.
  • the anolyte 228 may also include a hydrogen supplier 213 that may be added through an inlet 240.
  • the hydrogen suppler 213 may comprise hydrogen gas in some embodiments. Additionally or alternatively, the hydrogen supplier 213 may be sodium formate. Other chemicals may also be used as the hydrogen supplier 213.
  • the hydrogen supplier 213 may be introduced into the anolyte such that it mixes with the solvent 160 and alkali metal salt of levulinic acid 180 within the anolyte compartment 208. Alternatively, the hydrogen suppler 213 may be pre-mixed with the alkali metal salt of levulinic acid 180 and/or the solvent prior to entering the anolyte compartment 208.
  • the hydrogen gas 270 and/or the base 150 may be extracted through outlets 244.
  • the hydrogen gas 270 may be gathered for further processing for use in other reactions, and/or disposed of or sold.
  • the production of the base 150 is a significant advantage because the base 150 that was consumed in the saponification reaction of Figure 1A is generated in this portion of the cell 200.
  • the base formed in the cell may be collected and re-used in future saponification reactions (or other chemical processes). As the base may be re-used, the hassle and/or the fees associated with disposing of the base are avoided.
  • the reactions that occur at the anode 218 may involve decarboxylation. These reactions may involve an advanced Kolbe reaction (which is a free radical reaction) to form a quantity of a product 271 and carbon dioxide 272.
  • the solvent 160/160a may also be recovered and recycled, if desired, back to the inlet 240 for future use.
  • the carbon dioxide 272 may be vented off (via one or more outlets 248). This is a safe, naturally-occurring chemical that may be collected, disposed of, or re-used. Further, if the hydrogen generator 213 is sodium formate, then the following Kolbe reaction will also occur:
  • the advanced Kolbe reaction may comprise a free radical reaction.
  • the reaction produces (as an intermediate) a MEK radical designated as CH 3 -C(0)-CH 2 CH 2
  • a MEK radical designated as CH 3 -C(0)-CH 2 CH 2
  • Formula (2) produces (as an intermediate) a MEK radical designated as CH 3 -C(0)-CH 2 CH 2
  • MEK radicals are highly reactive. Accordingly, when two of these MEK radicals react together, the following product is formed: CH 3 -C(0)-CH 2 CH 2 . + CH 3 -C(0)-CH 2 CH 2 . ⁇ CH 3 -C(0)-CH 2 CH 2 -CH 2 CH 2 -C(0)-
  • MEK radical (MEK radical) (octanedione)
  • this octanedione makes up a portion of the product 271.
  • the hydrogen generator 213 is present (either from sodium formate or hydrogen gas), there may be quantities of H radicals or hydrogen gas), and as such, the MEK radical can react with these species (either in a radical reaction or in a hydrogen extraction reaction):
  • this reaction produces MEK, which is shown in Figure 2 as making up a portion of the product 271.
  • hydrogen gas may be introduced into the anolyte 228 such that it dissolves or forms a physical mixer in the anolyte.
  • a significant concentration of hydrogen may be used at the electrode (anode 218) surface so that the above described reaction(s) may take place.
  • Supplying excess hydrogen concentration in the anolyte 228 can be achieved by obtaining high hydrogen gas pressures, up to 250 PSI in one embodiment.
  • pressures of about 3, 6, or 9 atmospheres may be used.
  • an embodiment utilizing a tubular cell may have a current density of 50 to 100 mA per square centimeter of membrane area.
  • H radicals ( ⁇ ) are present in the system, such as from decarboxylation of formate or a hydrogen extraction process, these radicals can react together to form hydrogen gas:
  • this reaction can also produce hydrogen gas, which is also shown in Figure 2 as making up a portion of the product 271.
  • FIG 3 an additional embodiment of a cell 300 is illustrated.
  • the cell 300 is similar to the cells that have been previously described. Accordingly, for purposes of brevity, much of this discussion will not be repeated.
  • the cell 300 is designed such that one or more photolysis reactions may occur in the anolyte compartment 208.
  • a photolysis device 310 is designed such that it may emit radiation 312 into the anolyte compartment 208. This radiation may produce hydrogen radicals ( ⁇ ).
  • the hydrogen supplier 213 may be supplied to the anolyte compartment 208 as hydrogen gas that may undergo a photolysis reaction:
  • This photolysis process may be combined with the electrolysis process of the cell described above:
  • the hydrogen radicals and the MEK radicals may then combine to form a mixture of products (discussed above):
  • the photolysis device 310 may be used to conduct decarboxylation and to generate hydrocarbon radicals:
  • photolysis and electrolysis may be used to form the hydrocarbon radicals and/or hydrogen radicals in the anolyte compartment 208: (photolysis and electrolysis)
  • FIG. 4 An alternate embodiment to that of Figure 4 will now be described with reference to the embodiment shown in Figure 3. Because much of the embodiment of Figure 4 is similar to that which is shown in Figure 3, a discussion of portions of the similar features will be omitted for purposes of brevity, but is incorporated herein by this reference.
  • the embodiment of Figure 4 includes a cell 400 having an anolyte compartment 208 and a catholyte compartment 204. Because the anolyte compartment 208 is separate from the catholyte compartment 204, it is possible to create a reaction environment in the anolyte compartment 208 that is different from the catholyte compartment 204. Figure 4 illustrates this concept.
  • hydrogen gas may be used as the hydrogen suppler 213 and may be introduced into the anolyte compartment 208.
  • the hydrogen gas may be pressurized within the cell because the NaSICON membrane can withstand high pressures (such as up to 250 PSI or even as high as 900 PSI).
  • the anolyte compartment 208 may be pressurized by hydrogen gas.
  • the anode 218 could include a component 410 made of Pd or other noble metal (such as Rh, Ni, Pt) or another substrate such as Si, a zeolite, etc. (This component may be all or part of the electrode.) This component 410 may be used separately or in addition to the photolysis device 310.
  • the component 410 may alternatively be separate from the electrode.
  • Pd or Carbon with Pd could be suspended within the cell as a secondary anode or a non- electrochemical hydrogen activating catalyst.
  • the effect of having hydrogen gas in the anolyte compartment 208 is that the hydrogen gas may form hydrogen radicals ( ⁇ ) during the reaction process that react in the manner noted above. These radicals would react with the MEK radical so that the resulting products would be MEK and (other products such as octanedione). If sufficient hydrogen radicals ( ⁇ ) are present, the MEK product would be predominant, or would be the exclusive product.
  • This reaction could be summarized as follows (using Pd as an example of a noble metal, noting that any other noble metal could be used):
  • the particular product (MEK) may be selected.
  • hydrogen gas is produced in the catholyte compartment 204 as part of the reduction reaction.
  • This hydrogen gas 270 may be collected and used as the hydrogen gas that is reacted with the noble metal in the anolyte compartment 208.
  • the cell 400 actually may produce its own hydrogen gas 270 supply that will be used in the reaction.
  • the hydrogen gas 270 that is collected may be used for further processing of the hydrocarbon, such as cracking and/or isomerizing waxes and/or diesel fuel. Other processing using hydrogen gas may also be performed.
  • the hydrogen supplier 213 that is used in the above-recited embodiments may include other chemicals/species that are capable of "donating” or “providing” a hydrogen to the MEK radical (CH 3 -C(0)-CH 2 CH 2 .) in order to form MEK.
  • These species may form hydrogen radicals (or other species) that can react with the MEK radical to form MEK.
  • emboidments may be constructed in which certain organic compounts (such as branched or unbranched alkanes) provide the hydrogen/proton to form the MEK radical. This process is illustrated by the following reaction:
  • MEK radical organic species such as alkane
  • MEK alkene
  • R represents a functional organic group.
  • the embodiment of Figure 4 discloses the use of Pd or another metal as a means to form hydrogen radicals.
  • the embodiment of Figure 4 uses hydrogen gas in conjunction with a component 410 made of Pd or another metal as a means of forming H radicals.
  • the component 410 is absent, but that the anode itself is made of Pd (or another noble metal (such as Rh, Ni, Pt) or another substrate such as Si, a zeolite, etc.).
  • the electrode anode 218) provides the metal that generates the H radicals.
  • the Pd or noble metal provides a catalytic surface whereby the hydrogen may react, thereby aiding the reaction of the hydrogen.
  • Another embodiment may use an electrochemical driving force in addition to a Pd metal anode 218 to facilitate hydrogen radical generation for use in a Pd and sodium levulinate reaction as described above.
  • the processes described herein whereby the MEK radical reacts with H to form MEK may be referred to as "hydrogen abstraction.”
  • the MEK radical "abstracts" a hydrogen from the hydrogen supplier 213 to form MEK.
  • the hydrogen abstraction may involve forming hydrogen radicals by completely terminating the H-H bond in hydrogen gas.
  • Other forms of hydrogen abstraction may involve simply "weakening" the bond so that the MEK radical may react with one of the hydrogen species to form MEK.
  • Other embodiments may be designed in which the hydrogen is abstracted from another species (such as an alkane) or H 2 0, CH 3 OH, etc.
  • the sodium levulinate can react with the methanol solvent to form the levulinic acid, and then this acid undergoes the Kolbe reaction:
  • methanol solvent may be oxidized to formic acid in the cell
  • the formic acid may be formed by reaction with 0 2 (which is formed in the cell from water or methanol)
  • this formic acid may undergo the Kolbe reaction to form hydrogen radicals: HCOOH ⁇ + C0 2 + H. + H +
  • FIG. 2-4 It should be noted that the embodiments of Figures 2-4 are designed in which there are two compartments to the cell. However, those skilled in the art will appreciate that embodiments may be constructed in which there is a single chamber (compartment) in the cell. In this embodiment, the hydrogen gas that is generated in the cathode would be used as the source of the hydrogen supplier.
  • the method 500 comprises obtaining 504 an alkali metal levulinate.
  • this alkali metal levulinate may be obtained by converting a six carbon clutch into levulinic acid and then reacting the levulinic acid with a base to obtain an alkali metal levulinate.
  • this alkali metal levulinate may be purchased or otherwise obtained.
  • the alkali metal levulinate may be a sodium salt (e.g., sodium levulinate).
  • An electrolytic cell will also be obtained 508.
  • An anolyte is also prepared 512.
  • the anolyte may be of the type described herein. Specifically, the anolyte comprises a quantity of the alkali metal levulinate.
  • a hydrogen supplier will also be added 516 to the anolyte. As described in greater detail herein, the hydrogen supplier may comprise a quantity of an alkali metal formate (that was obtained from the six carbon sugar).
  • the hydrogen supplier (additionally or alternatively) may comprise hydrogen gas.
  • Other chemicals may also be used as the hydrogen supplier such as an alcohol (like methanol, ethanol, triglyceride, etc.), water, an alkane, etc.
  • the anolyte may be placed 520 in the electrolytic cell.
  • the alkali metal levulinate may then be decarboxylated 524 in the electrolytic cell.
  • This decarboxylation operates to convert the alkali metal levulinate into MEK radicals that may react with the hydrogen supplier to form MEK.
  • this reaction of MEK radicals with the hydrogen supplier may involve abstracting the H from hydrogen gas, the alcohol, water, the alkane, etc.
  • H radicals are formed (via photolysis or via decarboxylation of formate) which may react with the MEK radicals.
  • the method 600 may be used to form MEK.
  • the method involves obtaining 604 a quantity of a six carbon sugar. Once obtained, the six carbon sugar is converted 608 into an alkali metal levulinate. As noted herein, this process may involve dehydrating the sugar to form levulinic acid and formic acid, and then reacting these acids with a base to form an alkali metal levulinate and an alkali metal formate. If the alkali metal is sodium, sodium levulinate and sodium formate are used.
  • An anolyte will then be prepared 612.
  • the anolyte comprises a quantity of the alkali metal levulinate.
  • a hydrogen supplier may also be included 616 in the anolyte. As noted herein, a variety of different materials may be used as the hydrogen supplier including hydrogen gas, formate, alkanes, water, alcohols, etc.
  • the anolyte may be placed 620 in an electrolytic cell, such as those described herein.
  • the alkali metal levulinate is decarboxylated 624.
  • This decarboxylation may involve electrolysis and/or photolysis.
  • Such decarboxylation forms one or more MEK radicals that react to form MEK.
  • the MEK radicals may react with the hydrogen supplier (or H radicals or other species derived from the hydrogen supplier) to form MEK. It is anticipated that octanedione and hydrogen will be formed as co-products of such radical reactions. For example when MEK radicals react together 2,7-octanedione may be formed and when hydrogen radicals reacti together hydrogen gas may be formed as noted in the reaction scheme in paragraph 40 above.

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Abstract

L'invention concerne des cétones, en particulier la méthyléthylcétone (MEK) et l'octanédione, pouvant être formées à partir de sucres à six atomes de carbone. Le procédé consiste à obtenir une quantité de sucre à six atomes de carbone (604), puis à le mettre à réagir afin de former un acide lévulinique et un acide formique, ces derniers étant ensuite convertis en lévulinate de métal alcalin (608) et en formate de métal alcalin (tels que par exemple, un lévulinate de sodium et un formate de sodium.) Le lévulinate de métal alcalin est placé dans un anolyte (612) avec du gaz hydrogène (616) qui est utilisé dans une cellule électrolytique (620). Le lévulinate de métal alcalin placé dans l'anolyte est décarboxylé (624) afin de former des radicaux MEK, ces derniers réagissant avec le gaz hydrogène afin de former MEK ou des radicaux MEK qui réagissent les uns avec les autres pour former une octanédione. Le formate de métal alcalin peut également être décarboxylé dans la cellule, ce qui permet de former des radicaux hydrogène qui réagissent avec les radicaux MEK afin de former MEK.
PCT/US2012/070154 2011-12-19 2012-12-17 Décarboxylation d'acide lévulinique en solvants de type cétone Ceased WO2013096225A1 (fr)

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US13/357,463 US8821710B2 (en) 2011-01-25 2012-01-24 Production of fuel from chemicals derived from biomass

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WO2011011492A2 (fr) * 2009-07-23 2011-01-27 Ceramatec, Inc. Cellule de décarboxylation pour production de produits à radicaux couplés
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010019020A1 (en) * 1999-12-22 2001-09-06 Basf Aktiengesellschaft Process for electrochemical oxidation of organic compounds
US20110111475A1 (en) * 2009-04-17 2011-05-12 Kuhry Anthony B Biological/Electrolytic Conversion of Biomass to Hydrocarbons
WO2011011492A2 (fr) * 2009-07-23 2011-01-27 Ceramatec, Inc. Cellule de décarboxylation pour production de produits à radicaux couplés

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