Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • 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
  • C25B13/00—Diaphragms; Spacing elements
  • C25B13/04—Diaphragms; Spacing elements characterised by the material
• • 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

Definitions

• Sodium salts of alkyl sulfates are useful chemicals that are readily produced. These chemicals generally have the following structure:
• any "R” group may be added to the alkyl sulfate.
• a sodium salt of an alkyl sulfonate ([R-S0 3 ] ⁇ Na + ) will be obtained.
• this alkyl sulfonate may be incorporated into an anolyte for use in an electrolytic cell.
• This anolyte may also include a solvent (such as water, methanol, etc.) and optionally a supporting electrolyte (in addition to the ([R-S0 3 ] ⁇ Na + ).
• the alkyl sulfonate ([R-S0 3 ] ⁇ Na + may also be shown herein as R-S0 3 -Na.
• the anolyte is fed into an electrolytic cell that uses a sodium ion conductive ceramic membrane that divides the cell into two compartments: an anolyte compartment and a catholyte compartment.
• a typical membrane is a NaSICON membrane.
• NaSICON typically has a relatively high ionic conductivity for sodium ions 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.
• 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. Moreover, such membranes are tolerant of impurities that may be in the anolyte and will not allow the impurities to mix with the catholyte. Thus, the impurities (which were derived from the biomass) do not necessarily have to be removed prior to placing the anolyte in the cell.
• the electrolytic cell may use standard parallel plate electrodes, where flat plate electrodes and/or flat membranes are used.
• the electrolytic cell may be a tubular type cell, where tubular electrodes and/or tubular membranes are used.
• An electrochemically active first anode may be found in the cell and may be housed in the first anolyte compartment.
• 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 may also be used for the electrode.
• the first anode allows the desired reaction to take place. In this anolyte compartment of the cell, the oxidation (desulfoxylation) reaction and subsequent radical-radical coupling takes place. In one embodiment, the anodic desulfoxylation/oxidative coupling of sulfonic acids occurs via a reaction that is similar to the known "Kolbe reaction.”
• the standard Kolbe reaction is a free radical reaction and is shown below:
• 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 "R" groups of two carboxylic acid molecules are coupled together, thereby resulting in a coupled radical product.
• 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.
• R radicals
• the coupled radical product may be a hydrocarbon or some other chain.
• the coupled radical product may be a dimer, or a mixed product comprising one or more high- or low-carbon containing material.
• the radical in the coupled radical product may include an alkyl-based radical, a hydrogen-based radical, an oxygen-based radical, a nitrogen-based radical, other hydrocarbon radicals, and combinations thereof.
• hydrocarbons are shown in the examples below as the coupled radical product, the hydrocarbon may be freely substituted for some other appropriate coupled radical product.
• the present embodiments may use a sodium salt (or alkali metal salt) of the sulfonic acid in the anolyte rather than the carboxylic acid itself.
• the present embodiments may involve conducting the following reaction at the anode:
• the electrolyte conductivity may be higher for sodium salts of sulfonic acids than sulfonic acids themselves;
• the anolyte and catholyte may be completely different allowing different reactions to take place at either electrode.
• the cell contains a membrane that comprises a sodium ion conductive membrane.
• This membrane selectively transfers sodium ions (Na + ) from the anolyte compartment to the catholyte compartment under the influence of an electrical potential, while at the same time preventing the anolyte and catholyte from mixing.
• the catholyte may be aqueous NaOH or a non aqueous methanol/sodium methoxide solution.
• the anolyte may be aqueous or non-aqueous.
• An electrochemically active cathode is housed in the catholyte compartment, where reduction reactions take place. These reduction reactions may be written as:
• Hydrogen gas is the product of the reduction reaction at the cathode.
• NaOH sodium hydroxide
• NaOCH 3 sodium methoxide
• This NaOH or NaOCH 3 is the base that was used in a reaction to form R-S0 3 -Na.
• this reaction may actually regenerate (in the catholyte compartment) one of the reactants needed in the overall process.
• This NaOH or NaOCH 3 may be recovered and re-used in further reactions.
• the ability to regenerate and re-use the NaOH or NaOCH 3 is advantageous and may significantly reduce the overall costs of the process.
• a sodium salt of sulfonic acid with a small number of carbon atoms may be added to the anolyte in addition to the R-S0 3 - Na.
• sulfonate may be advantageous in some embodiments because:
• the methyl radical may react with a hydrocarbon group of the sulfonic acid to form hydrocarbons with additional CH 3 - functional group:
• this embodiment may couple two hydrocarbon radicals from the sulfonic acid together (R-R) or couple the radical of the sulfonic acid with a methyl radical from CH 3 -S0 3 -Na), thereby producing mixed hydrocarbon products.
• This mixture of products may be separated and used as desired.
• this embodiment is shown using CH 3 -S0 3 -Na as the additional reactant.
• other sodium salts of a sulfonic acid with a small number of carbon atoms may also be used to couple a carbon radical to the radical of the sulfonic acid.
• Figure 1 is a schematic diagram illustrating the overall process that uses desulfoxylation to produce coupled hydrocarbon products
• Figure 2 is a schematic view of an electrolytic cell for conversion of sodium salts of sulfonic acids to coupled radical products by anodic desulfooxylation and subsequent carbon-carbon bond formation in accordance with the present embodiments;
• Figure 3 is a schematic view of another embodiment of an electrolytic cell for conversion of sodium salts of sulfonic acids to coupled radical products
• Figure 4 is a schematic view of another embodiment of an electrolytic cell for conversion of sodium salts of sulfonic acids to coupled radical products;
• a quantity of a sulfonic acid may be obtained 12.
• This sulfonic acid may be an organic acid and may be obtained from biomass or from any other source.
• Those skilled in the art will appreciate the various different sources of sulfonic acids. Any and all sources of the sulfonic acid fall within the present embodiments.
• the above-recited published patent applications describe biomass as a potential starting material and that the biomass may be converted into sulfonic acids via known methods.
• the sulfonic acid may be converted 14 into the alkyl sodium sulfate (R-S0 3 -Na). This conversion reaction may occur by reacting the sulfonic acid with a base, may occur in an electrochemical cell, or may occur in some other way. In other embodiments, instead of obtaining the sulfonic acid and reacting it to form the alkyl sodium sulfate, the quantity of the alkyl sodium sulfate may be directly obtained (through purchase, etc.).
• the alkyl sodium sulfate may then be subjected to a desulfoxylation electrolysis process 16, in the manner outlined herein. As described herein, this process may produce a quantity of a SO x gas 18 (such as, for example, S0 2 , S0 3 , etc.). A quantity of hydrogen gas 20 may also be produced. Those skilled in the art will appreciate that these gases may be collected, re-used, disposed of, etc., as desired. Further, as part of the desulfoxylation process 16, the sodium ions may be recycled such as, for example, in the form of a base such as NaOH (as shown by arrow 22) and used again to form the R-S0 3 -Na.
• a SO x gas 18 such as, for example, S0 2 , S0 3 , etc.
• hydrogen gas 20 may also be produced.
• these gases may be collected, re-used, disposed of, etc., as desired.
• the sodium ions may be recycled such as, for example,
• the desulfoxylation process 16 operates to couple organic radicals together, thereby forming an R-R hydrocarbon product 24.
• these hydrocarbons may be valuable products, such as fuels, gasoline additives etc.
• An electrochemical cell may be used to conduct the desulfoxylation process 16.
• An example of a typical embodiment of a cell is shown in Figure 2.
• This cell 200 which may also include a quantity of a first solvent 160 (which may be, for example, water or an alcohol like methanol, ethanol, and/or glycerol), may be used to conduct an advanced Kolbe reaction.
• the solvent 160 may be obtained from any source.
• This advanced Kolbe reaction produces a hydrocarbon 170 along with a quantity of SO x 172 gases.
• a quantity of a base 150 is also produced.
• the base is NaOH.
• the hydrocarbon 170 is but one example of any of a number of coupled radical products that may be produced by this process, and may be, for example, a mixture of hydrocarbons.
• the SO x gases 172 produced in the process 200 is a naturally-occurring chemical and may be disposed of, collected, sold, etc.
• the hydrocarbon 170 produced in the process 200 may be of significant value. Hydrocarbons have significant value for use in fuels, diesel fuels, gasoline, medical applications, waxes, perfumes, oils, and other applications and products. With the process of the present invention, different types of hydrocarbons may be used. Hydrocarbons are often classified by the number of carbons in their chain. In addition, hydrocarbons may often be classified into the following "fractions":
• various hydrocarbons could be made in some or all of these fractions.
• embodiments may be constructed in which a C 8 hydrocarbon (octane) is formed, which is a principal ingredient in commercial gasoline.
• a C 12 hydrocarbon may be formed, which may be used in making JP8.
• the exact product that is obtained depends upon the particular starting material(s) and/or the reaction conditions used.
• the present embodiments allow biomass to be converted into synthetic lubricants, gasoline, JP8, diesel fuels, or other hydrocarbons.
• FIG. 2 shows the cell 200 (which may be an electrochemical cell to which a voltage may be applied).
• 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.
• 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.
• 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 , Co 3 0 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 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 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 a sulfonic acid 108 (R-S0 3 -Na). In the specific embodiment shown in Figure 2, sodium is the alkali metal, so that alkali metal sulfonic acid salt 108 is a sodium salt.
• the anolyte 228 also includes a first solvent 160, which, may be water 160a.
• the anolyte 228 may optionally include other alkali metal salts of sulfonic acids (such as, for example, CH 3 -S0 3 -Na). Other mixtures of different alkali metal salts of sulfonic acids 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 water (as shown in Figure 2) or may be alcohol or some other type of solvent of mixture of solvents.
• the solvent 160b in the catholyte 224 is not necessarily 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 may be 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 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 may be a significant advantage because the base 150 that was consumed in the conversion reaction 14 of Figure 1 is regenerated in this portion of the cell 200.
• the base formed in the cell may be collected and re-used in future reactions (or other chemical processes). As the base may be re-used, the hassle and/or the fees associated with disposing of the base may be avoided.
• the reactions that occur at the anode 218 may involve desulfoxylation. These reactions may involve an advanced Kolbe reaction (which is a free radical reaction) to form a quantity of a hydrocarbon 170 and carbon dioxide 172.
• an advanced Kolbe reaction which is a free radical reaction
• the oxidation reactions may be written as follows:
• the SO x gas 172 may be vented off (via outlets 248).
• the coupled radical product 170 may also be collected via an outlet 248.
• a quantity of the solvent 160/160a may be extracted via an outlet 248 and recycled, if desired, back to the inlet 240 for future use.
• 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:
• this R-R hydrocarbon product is designated as hydrocarbon 170.
• the R moiety is being desulfoxylated, as the sulfonyl moeity is removed, leaving only the R» radical that is capable of reacting to form a hydrocarbon.
• CH 3 -S0 3 -Na (or some other sodium salt of sulfonic acid with a small number of carbon atoms) may be part of (or added to) the anolyte 228.
• CH 3 -S0 3 -Na may act as a suitable supporting electrolyte as it is highly soluble in some solvents, providing high electrolyte conductivity.
• CH 3 -S0 3 -Na may itself desulfoxylate as part of the advanced Kolbe reaction and produce CH 3 » (methyl) radicals by the following reaction:
• methyl radicals may then be reacted with hydrocarbon group of the sulfonic acid to form hydrocarbons with additional CH 3 - functional group:
• the methyl radical may react with another methyl radical to form ethane:
• Ethane (CH 3 -CH 3 ) is a hydrocarbon that may form a portion of the hydrocarbon product 170.
• the CH 3 -R formed in the reaction may also be part of the hydrocarbon product 170.
• This R- CH 3 product is shown as numeral 170b.
• a mixture of hydrocarbons may be obtained, and are represented by the structure R-R.
• the various hydrocarbons 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 CH 3 -R or R-R in the product may depend upon the particular reaction conditions, quantities of reactants used in the anolyte, etc.
• the user may thus tailor the specific product formed by using a different reactant.
• a different reactant may be created as different alkyl radicals react together or even react with a methyl radical, a hydrogen radical, etc.
• the different alkyl radicals may be added by adding CH 3 -S0 3 -Na, H-S0 3 -Na, etc. into the anolyte through, for example, an additional port in the anolyte compartment.
• Such a different mixture of products may be, in some embodiments, similar to what would occur in a disproportionation reaction.
• H-S0 3 -Na may be used as part of the anolyte.
• the H-S0 3 -Na like the CH 3 -S0 3 -Na, will undergo desulfoxylation to form a hydrogen radical:
• H-S0 3 -Na 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 (3 ⁇ 4)). (The hydrogen gas may be re-used if desired).
• the use of H-S0 3 -Na may prevent the unnecessary formation of ethane and/or may be used to tailor the reaction to from a 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
• two methyl radicals react (2CH 3 «) and "dimerize” into ethane (CH 3 -CH 3 ).
• the R group is a C 18 H 3 hydrocarbon, then a C 36 H 78 product may be formed.
• a C 8 R-R hydrocarbon may be formed, which may be useable as part of a gasoline.
• a C 6 sodium salt is used, a C 12 R-R hydrocarbon may be formed, which may be useable as JP8.
• Synthetic lubricants, waxes, and/or other hydrocarbons may be formed in the same or a similar manner. Those skilled in the art will appreciate how to use these principals to create desired hydrocarbons.
• the anode 208 or anolyte could include a component 310 made of Pd or other noble metal (such as Rh, Ni, Pt, Ir, or Ru) or another substrate such as Si, a zeolite, etc. (This component may be all or part of the electrode and may be used to immobilize the hydrogen gas on the electrode.) Alternatively, Pd or Carbon with Pd could be suspended within the cell.
• 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 R» radicals so that the resulting products would be R-H and R-R.
• the R-H product may be predominant, or may be the (nearly) 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 By using one or more of the noble metals with hydrogen gas in the anolyte compartment, the particular product (R-H) may be selected.
• hydrogen gas 270 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 320 that is reacted with the noble metal in the anolyte compartment 208. Thus, the cell 300 actually may produce its own hydrogen gas 270 supply that will be used in the reaction. Alternatively, 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 used.
• the R-H product (which is designated as 170e) helps to minimize the formation of the R-R group (which, if the R group is sufficiently, large, may be a hydrocarbon such as a wax).
• FIG. 4 an additional embodiment of a cell 400 is illustrated.
• the cell 400 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 400 is designed such that one or more photolysis reactions may occur in the anolyte compartment 208.
• a photolysis device 410 is designed such that it may emit (irradiate) radiation 412 into the anolyte compartment 208. This irradiation may produce hydrogen radicals ( ⁇ ).
• the hydrogen gas 320 may be supplied to the anolyte compartment 208 using any of the mechanisms described above, as illustrated by the following equation:
• This photolysis process may be combined with the electrolysis process of the cell described above:
• the hydrogen radicals and the hydrocarbon radicals may then combine to form a mixture of products:
• the photolysis device may be used to conduct desulfoxylation and to generate hydrocarbon radicals:
• This combination of electrolysis and photolysis may speed up the rate of the desulfoxylation reaction.
• each of these illustrative embodiments involve separation of the anolyte compartment 208 and the catholyte compartment 204 using the membrane 212.
• specific advantages may be obtained by having such a membrane 212 to separate the anolyte compartment 208 from the catholyte compartment 204.
• the anolyte may be non-aqueous, while the catholyte is aqueous (and vice versa);
• anolyte may be at a higher temperature than the catholyte (and vice versa);
• anolyte may be pressurized and catholyte not (and vice versa);
• anolyte may be irradiated and catholyte not (and vice versa);
• anolyte and/or anode may be designed to conduct specific reactions that are not dependent upon the catholyte and/or cathode reactions (and vice versa);
• the different chambers may have different flow conditions, solvents, solubilities, product retrieval/separation mechanisms, polarities, etc.
• the ability to have separate reaction conditions in the anolyte compartment and catholyte compartment may allow the reactions in each compartment to be tailored to achieve optimal results.
• a membrane comprising, for example, NaSICON
• NaSICON has a high temperature tolerance and thus the anolyte may be heated to a higher temperature without substantially affecting the temperature of the catholyte (or vice versa).
• NaSICON can be heated and still function effectively at higher temperatures.
• polar solvents or non-polar solvents
• the catholyte is unaffected by temperature.
• a different solvent system could simultaneously be used in the catholyte.
• other molten salts or acids may be used to dissolve ionic sodium acids and salts in the anolyte.
• Ionic liquids could be used as the anolyte solvent. These materials not only would dissolve large quantities of sulfonic acid sodium salts, but also, may operate to facilitate the desulfoxylation reaction at higher temperatures. Ionic liquids are a class of chemicals with very low vapor pressure and excellent dissolving abilities/dissolving properties. A variety of different ionic liquids may be used.
• one of the advantages of the present cell is that it produces a base 150 in the catholyte compartment 204.
• this base 150 may then be used as part of the reaction 14 that produces the sodium salt of the sulfonic acid.
• the Na + ions for this reaction come from the anolyte 228 through the membrane.
• embodiments may be made in which the sulfonic acids may be reacted to form alkali metal salts directly in the catholyte compartment 208.
• the conversion reaction 14 occurs within the cell itself to produce the sulfonic acid sodium salt, and this sodium salt is then taken from the catholyte compartment 204 to the anolyte compartment 208 (such as via a conduit).
• This process thus allows the sulfonic acid to be converted to the alkali metal salt 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 (conversion reaction and desulfoxylation within the cell).
• SO x gases operate to produce SO x gases as a result of the desulfoxylation reaction.
• these SO x gases may be converted into S0 3 gas.
• this S0 3 gas may be reacted (in a known manner) with water to form sulfuric acid (H 2 S0 4 ), which is a valuable and useful chemical that may be used, sold, etc.
• the above-recited embodiments have the water react first, thereby producing the acid (R-S0 3 -H) and then this acid product undergoes desulfoxylation.
• the acid (R-S0 3 -H) or the sodium salt acid (R-S0 3 -Na), as desired.
• 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 desulfoxylation process recycled as a fraction of the hydrocarbon product.
• G-type of solvents solvate an -S0 3 -Na group of a alkali metal salt of acid by hydrogen bonding with two different oxygen atoms, whereas the hydrocarbon end of the alkali metal salt of sulfonic acid is solvated by an H-type of solvent.
• the solvency increases with increase of hydrocarbons in the H- type solvent.
• the Pt electrodes may be replaced by other electrodes, as outline herein.
• the base NaOH may be replaced by other bases (such as sodium methylate, or other bases), as desired.
• the solvent, water may be replaced by other solvents, as desired.
• the anode reaction is a desulfoxylation reaction to form SO x and R-R.
• the cathode reaction is a reduction to form hydrogen gas (the H being provided by the water).
• CH 3 -S0 3 -Na (or other R groups) may optionally be used.
• the acidic form of the sodium salt may be used, provided that there is also base to convert it to a sodium salt.
• such polymerization may be desired. In other embodiments, polymerization is not desired. Accordingly, techniques may be employed to reduce the likelihood of polymerization (e.g., "cut off the polymerization). This may involve, for example, forming methyl radicals (CH 3 «) via acetate, forming ⁇ radicals to truncate the R group. Likewise, the techniques associated with using a mixed solvent system may also reduce such polymerization. For example, by using a nonpolar solvent in combination with a polar solvent in the anolyte, the formed hydrocarbon will be pulled into the non-polar solvent quickly, thereby preventing it from polymerizing.
• a nonpolar solvent in combination with a polar solvent in the anolyte

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• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

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• 2014
  • 2014-03-05 WO PCT/US2014/020786 patent/WO2014138252A1/en active Application Filing
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  • 2014-03-05 CA CA2902988A patent/CA2902988A1/en not_active Abandoned
  • 2014-03-05 KR KR1020157027062A patent/KR102013014B1/ko active IP Right Grant
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