[go: up one dir, main page]

WO2011011521A9 - Procédé de production de produits à radicaux couplés - Google Patents

Procédé de production de produits à radicaux couplés Download PDF

Info

Publication number
WO2011011521A9
WO2011011521A9 PCT/US2010/042756 US2010042756W WO2011011521A9 WO 2011011521 A9 WO2011011521 A9 WO 2011011521A9 US 2010042756 W US2010042756 W US 2010042756W WO 2011011521 A9 WO2011011521 A9 WO 2011011521A9
Authority
WO
WIPO (PCT)
Prior art keywords
anolyte
solvent
alkali metal
carboxylic acid
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2010/042756
Other languages
English (en)
Other versions
WO2011011521A3 (fr
WO2011011521A2 (fr
Inventor
Sai Bhavaraju
Mukund Karanjikar
Ashok Joshi
David Hunt
Pallavi Chitta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ceramatec Inc
Original Assignee
Ceramatec Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ceramatec Inc filed Critical Ceramatec Inc
Publication of WO2011011521A2 publication Critical patent/WO2011011521A2/fr
Publication of WO2011011521A3 publication Critical patent/WO2011011521A3/fr
Publication of WO2011011521A9 publication Critical patent/WO2011011521A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • 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 biomass may already be in the form of a lipid, a carbohydrate, or lignin, fatty acids, or other forms and may need to be extracted, converted, isolated, and the like from the biomass.
  • the word "obtaining" as used herein throughout may or may not include the steps of extracting, converting, isolating, and the like.
  • a lipid material include fatty acids, esters of fatty acids, triglycerides of fatty acids, fatty acid derivatives, and/or metal salts of fatty acids.
  • lignin material may include resins
  • Examples of carbohydrate material may include cellulose, glucose, among many other examples.
  • this biomass material is obtained (from any source), this material is converted to at least one alkali metal salt of a carboxylic acid.
  • this alkali metal salt is a sodium salt, however, other alkali metal salts may also be used.
  • conversion of the biomass or biomass material (collectively "biomass") into the alkali metal salt of carboxyiic acid involves an intermediate step of conversion into the carboxyiic acid itself. Then, depending upon the source of biomass, another conversion reaction may be needed to convert the biomass into an alkali metal salt of carboxyiic acid.
  • the terms “alkali salt” and “alkali metal salt” are used interchangeably throughout.
  • the alkali metal salt of the carboxylic acid may be derived from the forgoing in the form of wood chips, forestry residue, energy crops (switch grass, miscanthus, sorghum, energy cane and other genetically modified plants), algae, cyanobacteria, jatropha, soy bean, corn, palm, coconut, canola, rapeseed, Chinese tallow, animal fats and products of genetically modified organisms, whether natural, synthetic, man-made, or even genetically altered.
  • the anolyte is electrolyzed within the cell, wherein the electrolyzing decarboxylates the sodium salt of the carboxylic acid and converts the sodium salt of the carboxylic acid into an alkyl radical that reacts to form a coupled radical product, which in one embodiment, may be a hydrocarbon.
  • the various processes described and shown in Figure 1 are not limiting. In certain embodiments, any type of biomass may be used. Also, other processes may be employed within the disclosed methods.
  • the salt of the fatty acid 108 will be added to an electrochemical cell that includes a sodium conducting membrane (or other alkali conducting membrane).
  • An example of a typical embodiment of a cell is shown in Figure 2.
  • This cell which may also include a quantity of a first solvent 160 (which may be, for example, an alcohol like methanol, ethanol, and/or glycerol), may use an advanced Kolbe reaction 167.
  • the solvent 160 may be obtained from the base 150, or may be obtained from any other source.
  • 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 first 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.
  • 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.
  • solid electrolyte membranes examples include those based on NaSICON structure, sodium conducting glasses, beta alumina and solid polymeric sodium ion conductors.
  • NaSICON typically has a relatively high ionic conductivity at room temperature.
  • the alkali metal is lithium, then a particularly well suited material that may be used to construct an embodiment of the membrane is LiSICON.
  • the alkali metal is potassium, then a particularly well suited material that may be used to construct an embodiment of the membrane is KSICON.
  • 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 may be a significant advantage in designing the cell 200.
  • a typical olbe 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 121 of Figure 1.
  • the base may be a different base than that which was used in the saponification reaction (as shown by reference number 150a).
  • the hydrogen gas 270 and/or the base 150/150a 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 150/150a may be a significant advantage because the base 150 that was consumed in the saponification reaction 121 of Figure 1 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 advanced Kolbe reaction may comprise a free radical reaction. As such, the reaction produces (as an intermediate) a hydrocarbon radical designated as R». Accordingly, when two of these R» radicals are formed, these radicals may react together to form a carbon- carbon bond:
  • methyl radicals may then be reacted with hydrocarbon group of the fatty acid to form hydrocarbons with additional CH 3 - functional group:
  • Ethane (CH 3 - CH 3 ) is a hydrocarbon that may form a portion of the hydrocarbon product 170. This ethane is designated as 170c.
  • the CH3-R formed in the reaction may also be part of the hydrocarbon product 170 and is designated as 170b. Thus, a mixture of hydrocarbons may be obtained.
  • the various hydrocarbons 170a, 170b, 170c may be separated from each other and/or purified, such as via gas chromatography or other known methods.
  • the present embodiments may couple two hydrocarbon radicals or couple methyl radicals with hydrocarbon radicals.
  • the amount of the CH3-R or R-R in the product may depend upon the particular reaction conditions, quantities of reactants used in the anolyte, etc.
  • the use of sodium formate as an optional reactant may result in the R-R product being formed as well as a quantity of an R-H product (and even a quantity of hydrogen gas (H 2 )). (The hydrogen gas may be re-used if desired).
  • the use of formate may prevent the unnecessary formation of ethane and/or may be used to tailor the specific hydrocarbon (R-H) product.
  • the particular R group that is shown in these reactions may be any "R” obtained from biomass, whether the R includes saturated, unsaturated, branched, or unbranched chains.
  • R-R product When the R-R product is formed, this is essentially a "dimer" of the R group.
  • the R group is CH 3 (such as is the case with sodium acetate)
  • two methyl radicals react (2CH 3 «) and "dimerize” into ethane (CH 3 - CH 3 ).
  • the R group is a Ci8H 34 hydrocarbon, then a C 3 6H 7 8 product may be formed.
  • the photolysis device may be used to conduct decarboxylation and to generate hydrocarbon radicals:
  • a combination of photolysis and electrolysis may be used to form the hydrocarbon radicals and/or hydrogen radicals in the anolyte compartment 208:
  • anolyte may be at a higher temperature than the catholyte (and vice versa);
  • FIG. 5 another embodiment of a cell 500 is shown. This cell 500 is similar to that which is described above in conjunction with the other Figures. Accordingly, for purposes of brevity, this description will not be repeated, but is incorporated by reference herein.
  • fatty acids may be saponified directly in the catholyte compartment 208.
  • the saponification reaction 121 occurs within the cell itself to produce the fatty acid sodium salt, and this sodium salt is then taken from the catholyte compartment 204 to the anolyte compartment 208 (such as via conduit 510).
  • Fatty acid is added to the catholyte 224 and may react (saponified) as follows:
  • This R-COONa is the sodium salt of the fatty acid 108, which is then introduced into the anolyte compartment 208 either through a conduit 510 (or perhaps through an inlet 240). This sodium salt would then be reacted (decarboxylated), forming coupled radical products such as hydrocarbons. This process thus allows the fatty acid to be saponified in situ (e.g., within the cell). This process would be a one step process (e.g., simply running the cell) rather than a two step process (saponification and decarboxylation within the cell).
  • Triglycerides may also be saponified as used in the present processes. Such saponification may occur within the cell 500 or exterior of the cell. Such saponification of triglycerides may occur, for example, as follows:
  • This hydrocarbon H-(CH 2 ) 3 - CH 2 ) 3 -CH 2 ) 3 -H is non-polar and will migrate to the non- polar/organic solvent.
  • the non-polar nature of the solvent may also operate to terminate the reaction so that a product with nine carbon atoms forms, rather than allowing a larger polymer to form (by repeated addition of the -(CH 2 ) 3 - monomer unit).
  • the reaction conditions for a di-, tri-, or polycarboxylic acid may be tailored to produce a specific product.
  • This use of organic or inorganic solvents may also be applied to the catholyte in a similar manner.
  • the anolyte comprises G-type solvents, H-Type solvents, and/or mixtures thereof.
  • G-type solvents are di-hydroxyl compounds.
  • the G-type compound comprises two hydroxyl groups in contiguous position.
  • H-type solvents are hydrocarbon compounds or solvent which can dissolve hydrocarbons.
  • H-type solvents include, hydrocarbons, chlorinated hydrocarbons, alcohols, ketones, mono alcohols, and petroleum fractions such as hexane, gasoline, kerosene, dodecane, tetrolene, and the like.
  • the H-type solvent can also be a product of the decarboxylation process recycled as a fraction of the hydrocarbon product. This will obviate the need of procuring additional solvents and hence improve overall economics of the process.
  • Figure 6 shows an embodiment of a method 600 that may be used to form a hydrocarbon or a mixture of hydrocarbons.
  • the method involves obtaining 604 a quantity of biomass.
  • the biomass may, in one embodiment, be obtained from any source, such as from algal, plant, microbes, microorganisms, and animals. Once obtained, the biomass is converted 608 into at least one alkali metal salt of a fatty acid.
  • Figure 1 shows a variety of different methods, procedures, reactions, and steps that may be used to convert the biomass into at least one alkali metal salt of a fatty acid. Any and/or all of these steps may be used.
  • An anolyte will then be prepared 612.
  • the anolyte comprises a quantity of the alkali metal salt of the fatty acid.
  • the methods and ingredients outlined herein describe how this anolyte may be prepared.
  • an alkali metal formate, an alkali metal acetate, and/or hydrogen gas may be added 616 to the anolyte.
  • the anolyte may be placed 620 in an electrolytic cell, such as those described herein.
  • the alkali metal salt of the carboxylic acid is decarboxylated 624.
  • This decarboxylation may involve electrolysis and/or photolysis.
  • Such decarboxylation forms one or more radicals that react to form a coupled radical product such as hydrocarbon or a mixture of hydrocarbons. These hydrocarbons may then be collected, purified (as needed) and or used in industry.
  • An electrolytic cell will also be obtained 708.
  • An anolyte is also prepared 712.
  • the anolyte may be of the type described herein.
  • the anolyte comprises a quantity of the alkali metal salt of the fatty acid.
  • a quantity of an alkali metal acetate, a quantity of hydrogen gas, and/or a quantity of an alkali metal formate may optionally be added 716 to the anolyte.
  • the anolyte may be placed 720 in the electrolytic cell.
  • the anolyte is electrolyzed 724 within the cell. This electrolyzing operates to decarboxylate the alkali metal salt of the fatty acid to form alkyl radicals. These alkyl radicals react to form a hydrocarbon or a mixture of hydrocarbons. These hydrocarbons may then be collected, purified (as needed) and/or used in industry.
  • embodiments may be designed in which only the alkali metal salt of the fatty acid will decarboxylate and not the fatty acid.
  • the alkali metal salt of the fatty acid (R-COONa) is more polar than the fatty acid (R-COOH) and thus, the alkali metal salt of the fatty acid is more likely to decarboxylate at lower voltages.
  • embodiments may be constructed in which only the alkali metal salt of the fatty acid decarboxylates and not the fatty acid.
  • this alkyl radical (R») can extract a hydrogen radical ( ⁇ ) from the fatty acid in the anolyte:
  • Alkyl radical (fatty acid) (hydrocarbon) (fatty acid radical)
  • This formed alkyl radical (R») will itself react, either by reacting with another alkyl radical (R «) to form the (dimer) hydrocarbon R-R, or by extracting a hydrogen radical from the fatty acid to create another fatty acid radical (RCOO «).
  • Alkyl radical (Alkyl radical) (hydrocarbon)
  • Alkyl radical (fatty acid) (hydrocarbon) (fatty acid radical)
  • reaction continues to product fatty acid radicals (RCOO*) as it is being consumated and these R-COO» radicals may continue to react in the manner described herein.
  • This reaction is therefore characterized as a free radical "chain reaction.”
  • This chain reaction will continue to react until the fatty acid supply in the anolyte is exhuasted, at which point the alkyl radical (R») will react with another alkyl radical (R») to create the R-R hydrocarbon.
  • the reaction may be quenched using other techniques.
  • An additional application for the present embodiments may be in the field of bio- diesel synthesis.
  • vegetable oil is reacted with methanol in the presence of a sodium methylate catalyst in order to form the bio- diesel product.
  • This bio-diesel product is a methyl ester.
  • the "upper" phase is the non-polar phase and contains the methyl ester (bio-diesel product).
  • the lower phase may be pre-processed through additional reactions (such as saponification or other reactions to increase the content of the sodium salt of the fatty acid).
  • This lower phase could be decarboxylated in a cell having a NaSICON membrane, thereby producing a hydrocarbon (and more particularly a methyl ester) that is non-polar.
  • This produced hydrocarbon/methyl ester product could be used as a new "upper phase” for further processing and/or may be the desired bio-diesel fuel product itself.
  • a NaSICON cell it may be possible to recover and/or re-use the fatty acid in the bio-diesel process, thereby making the process more cost-efficient and environmentally-friendly. This process may also remove the sodium salts from the lower phase.
  • surrogates mixtures of fatty acids
  • the sodium salts of the fatty acid were directly purchased and mixed to make the surrogates.
  • the fatty acids were purchased and converted into the corresponding sodium salts by a saponification reaction using 12-15% sodium methylate/methanol.
  • solvents were considered based upon their ability to form highly concentrated anolyte solutions with the selected acid starting materials. Both single phase and multi phase solvent mixtures were considered. The following solvents were considered based on one or more of the following factors: (1) high solubility at low temperatures, (2) liquids at room or low temperatures, (3) low viscosity, (4) cost, and (5) ease of product separation. Based on the above criteria, the following solvents were identified for Sodium Oleate & Linoleate: (1) Methanol, and (2) Isopropanol + Ethylene glycol.
  • a two compartment micro-reactor with a small gap between the ion-conducting membrane and the anode was fabricated and used in the decarboxylation process.
  • the small (minimal) gap was chosen to create optimum mass transfer conditions in the anolyte compartment.
  • a smooth platinum anode was used where decarboxylation occurs.
  • a 1 " diameter and 1 mm thick NaSelect ion-conducting membrane (available from Ceramatec, Inc., of Utah) was used between the anode and cathode compartment.
  • a nickel cathode was used in the cathode compartment.
  • a 1 liter glass flask sealed with 3-holed rubber stoppers was used.
  • the reactors were operated at constant current densities > 50 mA cm 2 to 200 mA/cm 2 of membrane area. A continuous process may be preferred for large- scale processing in which the starting salt concentration is always maintained and the hydrocarbon product is continuously removed.
  • the hydrocarbon product from the anolyte was at times recovered using a solvent immiscible with the starting solvent mixture. Hexane and Dodecane were the choices for hydrocarbon product recovery. The hexane or dodecane phase was analyzed by GC (gas chromatography) or GC-MS (gas chromatography-mass spectrometry) analysis for the estimation of product. In some cases for quantification purpose, the starting anolyte and final anolyte were submitted without extraction with hexane or dodecane.
  • T able 1 shows the major peaks, name of the chemical identified, retention time in minutes, height in microvolts, area under the curve in ( ⁇ . ⁇ ) and % area under curve.
  • the peaks at retention time at 18.65 and 27.36 are tentatively identified as sodium oleate (CI 8) and C34 hydrocarbon dimer.
  • the area under the curve for C18 peak before and after the test was compared to determine the conversion efficiency.
  • the product conversion efficiency based on this analysis was nearly 80%.
  • ICP inductively coupled plasma
  • This test used an anolyte with the same composition as in Test #2 (sodium oleate and sodium linoleate dissolved in a methanol containing 10% water). The purpose of this test was to determine the product conversion efficiency in a continuous mode of operation while eliminating the formation of fatty acid esters during decarboxylation process. The test was conducted at a constant current density of 200 mA/cm 2 (4 times higher than test #2 but equal to the current density of test #1) for a short period. The Gas Chromatogram (GC) profile for the reacted anolyte showed only hydrocarbons as the products. Thus it appears that operation at high current density may be employed, for some embodiments, to produce the hydrocarbons.
  • GC Gas Chromatogram
  • the selectivity for forming hydrocarbons may be improved by operating the reactor at high current density

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention porte sur un procédé de production de produits à radicaux couplés. Ce procédé comprend l'utilisation d'un sel de métal alcalin dans un anolyte comme partie d'une cellule électrolytique. La cellule électrolytique peut comprendre une membrane conductrice d'ions alcalins (telle qu'une membrane NaSICON). Lors du fonctionnement de la cellule, le sel de métal alcalin de l'acide carboxylique se décarboxyle et forme des radicaux. Ces radicaux sont ensuite liés à d'autres radicaux, donnant un produit à radicaux couplés tel qu'un hydrocarbure.
PCT/US2010/042756 2009-07-23 2010-07-21 Procédé de production de produits à radicaux couplés Ceased WO2011011521A2 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US22807809P 2009-07-23 2009-07-23
US61/228,078 2009-07-23
US25855709P 2009-11-05 2009-11-05
US61/258,557 2009-11-05
US26096109P 2009-11-13 2009-11-13
US61/260,961 2009-11-13
US12/840,401 2010-07-21
US12/840,401 US20110024288A1 (en) 2009-07-23 2010-07-21 Decarboxylation cell for production of coupled radical products

Publications (3)

Publication Number Publication Date
WO2011011521A2 WO2011011521A2 (fr) 2011-01-27
WO2011011521A3 WO2011011521A3 (fr) 2011-05-05
WO2011011521A9 true WO2011011521A9 (fr) 2011-07-07

Family

ID=43499646

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/042756 Ceased WO2011011521A2 (fr) 2009-07-23 2010-07-21 Procédé de production de produits à radicaux couplés

Country Status (2)

Country Link
US (1) US20110024288A1 (fr)
WO (1) WO2011011521A2 (fr)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102317244A (zh) 2009-01-29 2012-01-11 普林斯顿大学 二氧化碳转化至有机产物
US9051656B2 (en) * 2009-07-23 2015-06-09 Ceramatec, Inc. Electrochemical synthesis of aryl-alkyl surfacant precursor
US9957622B2 (en) 2009-07-23 2018-05-01 Field Upgrading Limited Device and method of obtaining diols and other chemicals using decarboxylation
WO2011011537A2 (fr) * 2009-07-23 2011-01-27 Ceramatec, Inc. Procédé de production de produits radicalaires couplés à partir de biomasse
US9206515B2 (en) 2009-07-23 2015-12-08 Ceramatec, Inc. Method of producing coupled radical products via desulfoxylation
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US9493882B2 (en) * 2010-07-21 2016-11-15 Ceramatec, Inc. Custom ionic liquid electrolytes for electrolytic decarboxylation
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
US9057137B2 (en) 2010-08-05 2015-06-16 Ceramatec, Inc. Method and device for carboxylic acid production
US8980126B2 (en) * 2010-10-08 2015-03-17 Semiconductor Energy Laboratory Co., Ltd. Electrode material and method for manufacturing power storage device
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
WO2012103135A2 (fr) 2011-01-25 2012-08-02 Ceramatec, Inc. Production de carburant à partir de produits chimiques issus de biomasse
US8853463B2 (en) 2011-01-25 2014-10-07 Ceramatec, Inc. Decarboxylation of levulinic acid to ketone solvents
US8845875B2 (en) 2012-07-26 2014-09-30 Liquid Light, Inc. Electrochemical reduction of CO2 with co-oxidation of an alcohol
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US8641885B2 (en) 2012-07-26 2014-02-04 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
US20140206896A1 (en) 2012-07-26 2014-07-24 Liquid Light, Inc. Method and System for Production of Oxalic Acid and Oxalic Acid Reduction Products
US9175407B2 (en) 2012-07-26 2015-11-03 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US8858777B2 (en) 2012-07-26 2014-10-14 Liquid Light, Inc. Process and high surface area electrodes for the electrochemical reduction of carbon dioxide
US9873951B2 (en) 2012-09-14 2018-01-23 Avantium Knowledge Centre B.V. High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide
WO2014046797A2 (fr) * 2012-09-19 2014-03-27 Liquid Light, Inc. Production électrochimique conjointe de produits chimiques au moyen d'un sel d'halogénure
JP6387024B2 (ja) * 2013-03-06 2018-09-05 フィールド アップグレーディング リミテッド 脱スルホン酸化を介したアルキルラジカル結合生成物の製造方法
BR112015022205B1 (pt) 2013-03-12 2021-07-13 Dynamic Food Ingredients Corporation Método de descarboxilação de um ácido de carboidrato em uma célula eletroquímica
WO2014144432A1 (fr) * 2013-03-15 2014-09-18 Ceramatec, Inc. Dispositif et procédé pour un couplage aryl-alkyle à l'aide de décarboxylation
CA2924602C (fr) * 2013-09-24 2020-11-17 Ceramatec, Inc. Electrolytes de carboxylate fondu pour procedes electrochimiques de decarboxylation
KR102163589B1 (ko) * 2014-04-04 2020-10-08 에스케이이노베이션 주식회사 나트륨 이차전지용 전해질 및 이를 채용한 나트륨 이차전지
BR112016029237A8 (pt) * 2014-06-13 2018-08-14 Ceram Inc Conversão de ácidos carboxílicos a alfa-olefinas
MX379387B (es) * 2014-07-15 2025-03-10 Advonex Int Corp Proceso de reacción de kolbe de alta productividad para la transformación de ácidos grasos derivados de aceite vegetal y grasa animal.
DE102018000672A1 (de) 2018-01-29 2019-08-14 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Verfahren zur Übertragung eines Zielstoffs zwischen zwei flüssigen Phasen
CN110824807A (zh) * 2019-12-13 2020-02-21 中国科学技术大学 一种速度可调氢自由基束源的产生方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2760926A (en) * 1955-09-14 1956-08-28 Colgate Palmolive Co Process for the preparation of aliphatic ethers
US2867569A (en) * 1956-07-06 1959-01-06 Colgate Palmolive Co Electrolysis process
US4006065A (en) * 1972-06-26 1977-02-01 Otto Meresz Process for the synthesis of pure isomers of long chain alkenes
US3992471A (en) * 1974-08-12 1976-11-16 Uop Inc. Process for the separation of 1,3-butadiene by selective adsorption on a zeolite adsorbent
JPS52145397A (en) * 1976-03-31 1977-12-03 Asahi Chem Ind Co Ltd Electrolysis
US4464236A (en) * 1982-05-10 1984-08-07 The Dow Chemical Company Selective electrochemical oxidation of organic compounds
US4402804A (en) * 1982-05-17 1983-09-06 Ppg Industries, Inc. Electrolytic synthesis of aryl alcohols, aryl aldehydes, and aryl acids
US5084146A (en) * 1990-04-09 1992-01-28 E. I. Du Pont De Nemours And Company Method for preparing perfluoropolyethers
US5290405A (en) * 1991-05-24 1994-03-01 Ceramatec, Inc. NaOH production from ceramic electrolytic cell
TW348175B (en) * 1993-01-06 1998-12-21 Hoechst Ag Process for the preparation of biphenyl derivatives
GB9519975D0 (en) * 1995-09-28 1995-11-29 Davy Process Techn Ltd Process
US6362380B1 (en) * 1996-03-13 2002-03-26 Basf Aktiengesellschaft Preparation of nitrobiphenyls
EP0838435A1 (fr) * 1996-10-25 1998-04-29 Kvaerner Process Technology Limited Procédé et installation pour le traitement des eaux polluées contenant des carboxylates de métal alcalin
US5892107A (en) * 1996-11-08 1999-04-06 Arkenol, Inc. Method for the production of levulinic acid
US6238543B1 (en) * 1997-10-17 2001-05-29 E. I. Du Pont De Nemours And Company Kolbe electrolysis in a polymer electrolyte membrane reactor
US6392091B2 (en) * 1998-11-24 2002-05-21 Tsong-Dar Vincent Lin Process of purifying and producing high purity aromatic polycarboxylic acids
DE19962102A1 (de) * 1999-12-22 2001-06-28 Basf Ag Verfahren zur elektrochemischen Oxidation von organischen Verbindungen
JP5314246B2 (ja) * 2003-12-11 2013-10-16 アメリカン パシフィック コーポレイション イオン伝導性セラミックの固体膜を用いたアルカリアルコラートを生成するための電気分解による方法
DE102005022362B4 (de) * 2005-05-10 2016-12-15 Studiengesellschaft Kohle Mbh Verfahren zur decarboxylierenden C-C Verknüpfung von Carbonsäuren mit Kohlenstoffelektrophilen
US20090074611A1 (en) * 2005-09-15 2009-03-19 Battelle Memorial Institute Photolytic generation of hydrogen peroxide
WO2008124047A1 (fr) * 2007-04-03 2008-10-16 Ceramatec, Inc. Procédé électrochimique pour recycler des produits chimiques alcalins aqueux à l'aide de membranes solides céramiques conduisant les ions
US8518680B2 (en) * 2009-04-17 2013-08-27 The United States Of America, As Represented By The Secretary Of Agriculture Biological/electrolytic conversion of biomass to hydrocarbons
US8246863B2 (en) * 2009-06-26 2012-08-21 Ceramatec, Inc. Alkali metal super ionic conducting ceramic
US9051656B2 (en) * 2009-07-23 2015-06-09 Ceramatec, Inc. Electrochemical synthesis of aryl-alkyl surfacant precursor
US9957622B2 (en) * 2009-07-23 2018-05-01 Field Upgrading Limited Device and method of obtaining diols and other chemicals using decarboxylation
KR101198866B1 (ko) * 2010-12-02 2012-11-07 한국화학연구원 고순도 알킬락테이트 및 젖산의 회수 방법

Also Published As

Publication number Publication date
WO2011011521A3 (fr) 2011-05-05
WO2011011521A2 (fr) 2011-01-27
US20110024288A1 (en) 2011-02-03

Similar Documents

Publication Publication Date Title
US9752081B2 (en) Method of producing coupled radical products from biomass
WO2011011521A9 (fr) Procédé de production de produits à radicaux couplés
WO2011011492A2 (fr) Cellule de décarboxylation pour production de produits à radicaux couplés
EP2668250B1 (fr) Production de carburant à partir de produits chimiques issus de biomasse
US8183421B2 (en) Biofuel production by high temperature non-faradaic electrochemical modification of catalysis
US9051656B2 (en) Electrochemical synthesis of aryl-alkyl surfacant precursor
JP6587640B2 (ja) カルボン酸のα−オレフィンへの変換
US8853463B2 (en) Decarboxylation of levulinic acid to ketone solvents
WO1991019774A1 (fr) Procede electrocatalytique pour l'hydrogenation d'huiles comestibles et non comestibles et d'acides gras
WO2017112557A1 (fr) Procédés et systèmes pour générer un produit de carburant de substitution renouvelable
US9206515B2 (en) Method of producing coupled radical products via desulfoxylation
WO2017112559A1 (fr) Procédés et systèmes pour générer un produit de combustibles renouvelables directement utilisables
WO2013096225A1 (fr) Décarboxylation d'acide lévulinique en solvants de type cétone
JP6387024B2 (ja) 脱スルホン酸化を介したアルキルラジカル結合生成物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10802856

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10802856

Country of ref document: EP

Kind code of ref document: A2