WO2014144432A1 - Device and method for aryl-alkyl coupling using decarboxylation - Google Patents
Device and method for aryl-alkyl coupling using decarboxylation Download PDFInfo
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- WO2014144432A1 WO2014144432A1 PCT/US2014/028842 US2014028842W WO2014144432A1 WO 2014144432 A1 WO2014144432 A1 WO 2014144432A1 US 2014028842 W US2014028842 W US 2014028842W WO 2014144432 A1 WO2014144432 A1 WO 2014144432A1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/06—Well-defined hydrocarbons aromatic
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
- C10M109/02—Reaction products
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- 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
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B3/00—Electrolytic production of organic compounds
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- C25B3/23—Oxidation
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- 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
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- 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
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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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
- C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
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- 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 disclosure relates to a method of producing hydrocarbon materials such as lubricants and other useful products. More specifically, the present disclosure provides an electrochemical decarboxylation process in which aryl and alkyl groups are coupled together to form useful products.
- Industrial lubricants are important to many processes and applications and are commonly classified into the following five groups.
- Group I lubricants contain less than 90% saturated hydrocarbons and/or have more than 0.03% sulfur present and are manufactured using solvent extraction and hydro-finishing processes.
- Group II lubricants contain more than 90% saturated hydrocarbons and/or have less than 0.03% sulfur present and are manufactured using hydrocracking and solvent or catalytic dewaxing processes.
- Group III lubricants have more than 90% saturated hydrocarbons and less than 0.03% sulfur present and are manufactured using special processes such as isohydromerization.
- Group IV lubricants are lubricants based on polyalphaolefins.
- Group V lubricants are lubricants that do not fall into any of the other groups such as diesters, polyesters, alkylated naphthalenes, and alkylated benzenes. Each classification of lubricants find use in different applications based on cost and application requirements. The different types of lubricants within Group V provide superior performance compared to the other lubricants classes in regards to a specific property, for example corrosion-resistance.
- One class of compounds that make up the Group V lubricants are alkylated aromatic (AR) compounds.
- AR alkylated aromatic
- the second group constitutes compounds in which naphthalene makes up the aromatic component of the compound.
- the non-aromatic components of AR compounds found in Group V lubricants are usually long chain hydrocarbons with different degrees of saturation.
- the properties of AR compounds are determined by the type of aliphatic and aromatic components that are coupled and also by the number of alkyl components attached to the aromatic center.
- the properties of alkyl-aryl compounds can be easily adjusted by changing the length and/or number of the alkyl components attached to the aromatic component. Thus, one could tailor the properties of the lubricant for specific applications by altering the aliphatic component and by varying the degree that the aromatic group is alkylated.
- Carboxylic acids are a popular starting material for synthesizing industrially important compounds because such acids are economically and environmentally friendly.
- One application using carboxylic acids involves using the acids as alternatives to organohalides in the Heck reaction for the formation of carbon-carbon double bonds.
- the Heck reaction is a catalytic reaction between an organohalide with an alkene and a base to form a substituted alkene.
- Replacing the organohalide of the Heck reaction with a carboxylic acid is more environmentally friendly because CO 2 and H 2 are the only by-products formed as opposed to halide by-products.
- Carboxylic acids are also being investigated as substrates for cross-coupling reactions where the carboxylic acid can act as either the nucleophilic or electrophilic coupling partner.
- the present embodiments relate to methods to alkylate aromatic compounds by performing alkyl-aryl coupling via EDP.
- These alkyl-aryl coupling reactions can be used to prepare compounds suitable for many applications, including, for example, compounds classified as Group V lubricants.
- the EDP converts alkali salts of carboxylic acids to radicals which can then go through radical- radical coupling.
- This process is known as a modified Kolbe electrolysis. When performed in the presence of a single carboxylic acid, this process leads to homocoupling of radical species.
- the electrolysis can also be performed in the presence of more than one carboxylic acid which leads to heterocoupling of radical species.
- the heterocoupling can couple radicals from different carboxylic acids, and as disclosed herein, can couple radicals containing alkyl and aromatic functional groups. Such an alkyl-aryl couple provides an inexpensive method to alkylate aromatic compounds.
- the present embodiments may further involve methods to produce alkylated aromatic compounds that have properties that are desired for Group V lubricants.
- the methods may involve the oxidation of carboxylic acids using an electrochemical cell.
- the electrolysis may be performed in the presence of at least one alkyl carboxylate salt and at least one aryl functionalized compound.
- the aryl compound may itself be a carboxylic acid or an alkali metal salt of a carboxylic acid or, in other embodiments, may be an aromatic compound that interacts with the alkyl through double bonds on its aromatic ring.
- the electrolysis creates radicals which may undergo heterocoupling that generates alkylated aromatic compounds.
- the electrolysis products may be involved in electrophilic substitution reactions which may also generate alkylated aromatic compounds.
- the carboxylic acids may be first converted to alkali metal salts via conventional saponification procedures.
- This saponification reaction may involve reacting the carboxylic acids with an alkali metal base (MOH) at an elevated temperature (or at some other temperature).
- alkali metal bases are lithium hydroxide, sodium hydroxide, potassium hydroxide, alkoxides, etc.
- the generic neutralization can be represented as follows:
- this saponification reaction is carried out in a solvent with an alkoxide present, and the reaction forms an alkali carboxylate which precipitates out of solution.
- the alkali carboxylate salt can be easily isolated to prepare the anolyte needed for the decarboxylation process.
- Alkali carboxylates may then be electrochemically decarboxylated leading to the formation of radical coupling products. Due to the presence of multiple carboxylate ions produced by decarboxylation, both homocoupling and heterocoupling products are obtained.
- This radical coupling process may be performed using a two compartment electrochemical cell which is made using a NaSelect® membrane that is commercially available from Ceramatec, Inc., of Salt Lake City, Utah. The electrolysis in the anolyte compartment follows the modified Kolbe electrolysis as shown in the reaction below.
- the Ri refers to an aliphatic carboxylate salt
- R 2 refers to an aromatic carboxylate salt. While all three of the reactions above can occur during the electrolysis, preferably the electrolysis is performed in a manner that favors the formation of heterocoupling product (Ri— R 2 ) over the homocoupling products (Ri— Ri and R2— R 2 ).
- the electrolysis is performed on an aliphatic carboxylate salt in the presence an aromatic compound, for example, benzene.
- an aromatic compound for example, benzene.
- a substitution reaction occurs that couples the aliphatic group to the aromatic ring (benzene): RiCOaM + C 6 H 6 ⁇ C 6 H 5 — Ri + C0 2 + 2e + H + + M +
- the decarboxylation of the aliphatic carboxylate forms an electrophile which then can undergo electrophilic substitution on an aromatic ring.
- the electrophile can be in the form of a radical or carbocation. The latter is generated by a two electron oxidation during the decarboxylation step instead of a one electron oxidation.
- Figure 1 shows a schematic drawing of an electrochemical cell that may be used to decarboxylate alkali metal salts of carboxylic acids
- Figure 2 is a plot of the potential and current density of the electrochemical decarboxylation of sodium oleate and sodium benzoate;
- Figure 3 shows a gas chromatogram of the products obtained from the electrochemical decarboxylation of sodium oleate and sodium benzoate
- Figure 4 is a plot of the potential and current density of the electrochemical decarboxylation of sodium naphthenate
- Figure 5 shows a gas chromatogram of the products obtained from the electrochemical decarboxylation of sodium naphthenate
- Figure 6 is a plot of the potential and current density of the electrochemical decarboxylation of sodium naphthenate and sodium naphthoate
- Figure 7 shows a gas chromatogram of the products obtained from the electrochemical decarboxylation of sodium naphthenate and sodium naphthoate
- Figure 8 is a plot of the potential and current density of the electrochemical decarboxylation of sodium naphthenate and sodium naphthoate in a mixture of polar and non-polar organic solvents.
- Figure 9 shows a Simulated Distillation (SimDist) of the products obtained from the electrochemical decarboxylation of sodium naphthenate and sodium naphthoate in a mixture of polar and non-polar organic solvents.
- SimDist Simulated Distillation
- Alkane and/or “aliphatic” are defined as a saturated hydrocarbon, or mostly saturated hydrocarbon, and will be used interchangeably throughout the disclosure.
- Alkyl is defined as a hydrocarbon alkane that is missing one bond, such as from the removal of a carboxyl group.
- Aryl is defined as a compound that contains at least one aromatic ring as a functional group or substituent.
- “Aromatic” is defined as a cyclic compound with alternating double and single bonds between carbon atoms forming a ring with a conjugated pie system.
- Carboxylic acid is a compound with the general formula RCO 2 H, where the “R” can represent saturated or unsaturated hydrocarbon chains.
- “Naphthenic acid” refers to a mixture of carboxylic acids with cyclopentyl and cyclohexyl groups with a carbon backbone between 9 and 20 carbons, and a molecular weight of between 120 and 700 amu.
- “Decarboxylation” herein refers to the process of removing CO 2 from a compound, specifically from a carboxylic acid or anion.
- the present embodiments teach a method to produce alkylated aromatics (AR) products which may, for example, be used as components in Group V lubricants.
- AR alkylated aromatics
- the properties of the formed AR products depend on the structure of both the alkyl and aryl components as well as the number of alkyl components that are coupled to a single aryl component.
- Common methods of preparing AR compounds are based on the Friedel-Crafts alkylation which uses a catalyst to alkylate aromatic compounds. Such a process can lead to the formation of monoalkylaromatics (MAR), dialkylaromatics (DAR) and polyalkaromatics (PAR).
- MAR monoalkylaromatics
- DAR dialkylaromatics
- PAR polyalkaromatics
- One advantage of the present embodiments is that it provides control over the number of alkyl chains that attach to the aromatic component, and thus provides control over the properties of the synthesized compounds.
- the alkyl component of the alkyl-aryl coupling product there are a large number of inexpensive carboxylic acid substrates that are available to use as the alkyl component of the alkyl-aryl coupling product. These carboxylic acid substrates can be coupled to a large number of possible aromatic compounds. The abundance of inexpensive substrates enhances the ability to control and fine-tune the properties of the synthesized AR compound to match the specific needs of the lubricant application (or any other desired application).
- the length of the alkyl group may affect the physical properties of the material, such as pour point, viscosity index, and flash point. The substitution on the aromatic system may increase the pour point, the viscosity index, and the flash point.
- the aryl component of the alkyl-aryl compound may affect the thermo-oxidative stability of the formed compound (because the electron-rich aromatic portion of the molecule can scavenge radicals and disrupt oxidation processes).
- Feasible and economical industrial processes for coupling alkyl-aryl compounds involve the use of catalysts and/or high temperatures.
- the present embodiments describe processes for coupling alkyl-aryl compounds that may not require catalysts and/or high temperatures.
- the present processes may use an electrolytic cell 100 schematically represented in Figure 1 .
- the cell 100 may have two compartments, namely an anode chamber 1 and a cathode chamber 2.
- the chambers 1 , 2 may be separated by an alkali metal ion conductive membrane 3.
- This membrane 3 may be, for example, a NaSelect® membrane.
- Anolyte 1 16 may be fed into the anode chamber 1 (which may also be referred to as the "anode compartment").
- components of the anolyte 1 16 are oxidized at the surface of an anode 4, causing decarboxylation of the carboxyl functional group to form radicals and CO 2 .
- these radicals can react to form a long chain aliphatic compound, or, according to another embodiment, they can react to form a polycyclic aromatic compound, and in yet still another embodiment, the radicals can react to form an aryl-alkyl compound.
- the radicals could react leading to all embodiments described above, or only according to one of the above-recited embodiments.
- the anode 4 is housed, either fully or partially, within the anode chamber 1.
- a cathode compartment 2 which may also be referred to as the "cathode chamber"
- a cathode 5 is housed, either fully or partially, in the cathode chamber 2.
- a positive ion must transfer from the anode 4 to the cathode 5, and in the case when the anolyte 1 16 and catholyte 1 17 are separated, there needs to be a path for the positive ions to transfer between the compartments 1 , 2.
- the ion conducting membrane 3 selectively transfers alkali ions (M+), including but not limited to the ions of, sodium, lithium, and potassium, from the anolyte 1 16 to the catholyte 1 17 under the influence of an applied electrical field.
- M+ alkali ions
- the ion conductive membrane 3 is between 10 and 5000 microns thick, or more preferably, the membrane is between 100 and 1000 microns thick, or even more preferably, the membrane is between 200 and 700 microns thick.
- the membrane 3 is in the form of disk with diameters between 0.25 and 25 cm, even more preferably, the diameter is between 1 .27 and 12.7 cm, or most preferably, between 2.54 and 7.62 cm.
- the membrane 3 may be assembled in a scaffold 1 12.
- the membrane 3 is in the form of a cylinder with a diameter between 0.25 and 25 cm, even more preferably, between 1 .27 and 12.7 cm, or most preferably, between 2.54 and 7.62 cm.
- the electrochemical cell 100 can be in a parallel plate configuration which uses flat membranes, for example, as shown in Figure 1 .
- the electrochemical cell 100 is in a tubular configuration which uses tubular electrodes and membranes. It should be clear to one skilled in the art that the cell configurations listed above both have advantages and disadvantages which would lead to one being chosen over the other depending on the requirements of the specific carboxylic salt being decarboxylated. The process described herein can be applied in a variety of cell designs (including those described above and other cell configurations).
- the anode 4 can comprise any suitable material that allows oxidation reactions to occur in the anode compartment 1 when an electrical field 1 1 is applied between the anode 4 and cathode 5.
- anode materials include, but are not limited to, platinum, titanium, nickel, cobalt, iron, stainless steel, lead dioxide, metal alloys, combination thereof, and other known or novel anode materials.
- the anode 4 may be comprised of iron- nickel alloys such as KOVAR® or INVAR®.
- the anode 4 may be comprised of carbon based electrodes such as boron doped diamond, glassy carbon, and synthetic carbon.
- the anode 4 may comprise a dimensionally stable anode (DSA), which may include, but is not limited to, rhenium dioxide and tantalum pentoxide on a titanium substrate.
- DSA dimensionally stable anode
- the cathode 5 may also be fabricated of any suitable cathode material that allows the reduction of water or methanol to produce hydroxide or methoxide ions and hydrogen gas.
- the cathode 5 may be comprised of the materials used for the anode 4.
- the cathode 5 may comprise materials different from that used as the anode 4.
- suitable cathode materials include, without limitation, nickel, stainless steel, graphite, and any other suitable cathode material that is known or novel.
- the electrodes 4, 5 have a smooth morphology such as a foil or thin film.
- the anode 4 and cathode 5 have a high surface area morphology, for example, but not limited to, a foam, grit, or other porous structure.
- the anode 4 and cathode 5 have the same morphology, while in other embodiments, the electrodes 4, 5 have different morphologies.
- the anolyte 1 16 is housed in a reservoir 22 and may be fed into the anode compartment 1 .
- the catholyte 1 17 may likewise be housed in a reservoir 21 and fed into the cathode compartment 2.
- the cathode compartment 2 may be separated from the anode compartment 1 by the ion conductive membrane 3.
- the anolyte 1 16 may comprise a solvent 146 and alkali salts of carboxylic acids 130/130a. (The carboxylic acid itself may also be in the anolyte 1 16, as desired.)
- the anolyte 1 16 may comprise a mixture of alkali salts of carboxylic acids, namely R 1 CO 2 M 130 and R 2 CO 2 M 130a.
- At least one of the acids or salts may be an alkyl carboxylic acid, and another of the salts may be an aryl carboxylic acid.
- the anolyte 1 16 may comprise a compound with an aryl group (such as benzene) that is used as the solvent 146.
- the anolyte 1 16 may only contain one alkali salt of a carboxylic acid 130, which may be an alkali salt of carboxylic acids that is aliphatic in nature.
- the catholyte 1 17 may comprise a solvent 145.
- the solvent 145 may or may not be the same as the solvent 146 in the anode compartment 2.
- One of the advantages of using a cell divided by a membrane 3, is that the solvents used on each side do not have to be the same; rather, the solvent used on each side of the membrane 3 may be tailored for the particular reaction occurring in each separate compartment.
- the catholyte 1 17 may be a conductive solution that may include an alkali metal hydroxide 140 and/or an alkali metal methoxide 150.
- the anolyte and catholyte solvents 146, 145 may be separately selected specifically for the reactions that occur in each compartment and/or the solubility of the chemicals required for the specific reactions. This permits a cell designer to construct an inexpensive catholyte 1 17 which may have different properties than the anolyte 1 16, if desired.
- the catholyte 1 17 may be designed such that it has high ionic conductivity.
- the anolyte solution 1 16 may comprise a solvent 146 that is a polar organic solvent.
- suitable polar organic solvents include, without limitation, methanol, ethanol, isopropanol, n-propanol, acetone, acetonitrile, acrylonitrile and glycerol.
- the solvent 146 may comprise an aromatic solvent.
- aromatic solvents are benzene, xylene, nitro benzene, and toluene.
- the solvent 146 may comprise a mixture of a polar organic solvent and a non-polar organic solvent.
- non-polar organic solvents are hexane, cyclohexane, pentadecane, petroleum ethers, and dodecane.
- the carboxylate salts may be soluble in the polar solvent and the AR products may be soluble in the non-polar solvent, and thus these materials may be easily separated from the reactants.
- the solvent 146 used in the anolyte 1 16 may comprise an ionic liquid (IL).
- IL ionic liquid
- An non-limiting example of an IL is a phosphonium based cation with four substituents.
- the four substituents of the phosphonium cation are each independently an alkyl group, a cylcoalkyl group, an alkenyl group and an aryl group.
- some/all of the substituents are of a similar group.
- some/all of the substituents are the same compound.
- the anion of the ionic liquid is a carboxylate ion, more preferably, a carboxylate ion that is similar to the alkyl carboxylate anion being oxidized during the electrolysis; or most preferably, the carboxylate ion that is the same alkyl anion being oxidized during the electrolysis.
- This means molten salts or acids may be used (in some embodiments) as the solvent 146 to dissolve the carboxylate salts 130/130a in the anolyte 1 16.
- the solvent 146 is the molten salt of the carboxylate anion that is being oxidized.
- the anolyte solution 1 16 may optionally contain a supporting electrolyte which is soluble in the solvent and provides high electrolyte conductivity in the anolyte solution 1 16.
- a supporting electrolytes include an alkali metal hydroxide, alkali metal salts, tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetrabutylammonium tetrafluorobotate, tetramethylammonium perchlorate, and tetraethylammonium perchlorate. It should be appreciable to those skilled in the art that other soluble ionic compounds may be used as a supporting electrolyte.
- the catholyte 1 17 may be comprised of water and an unsaturated alkali hydroxide.
- the hydroxide concentration is between 0.1 and 50% by weight, or more preferably, between 5 and 25% by weight, or most preferably, between 7 and 15% by weight.
- Another embodiment may be constructed in which the catholyte 1 17 comprises alkali methylate.
- the temperature of the catholyte 1 17 may or may not be the same temperature of the anolyte 1 16 (as described above).
- the catholyte product stream may comprise a base which may be used to neutralize the carboxylic acid, thereby producing the alkali metal salt of the carboxylic acid. More specifically, the alkali metal salts of the carboxylic acids 130/130a may be formed (prior to having these materials enter the anolyte 1 16) by reacting the carboxylic acids with a base (such as NaOH, NaOR, KOH, LIOH, LiOR, KOR, etc.) These reactions are shown below:
- the cathode compartment 2 may regenerate the base as part of the reaction (e.g., producing MOH or MOR).
- the cell 100 may regenerate the base (MOH or MOR) that was consumed by the acid neutralization step. Accordingly, the regenerated base may be recovered and re-used in future acid neutralization reactions or other chemical processes.
- the heterocoupling can form alkyl-aryl compounds.
- the oxidation produces a radical or carbocation of an alkyl carboxylic acid or anion.
- the radical or carbocation can then participate in electrophilic substitution reactions with any aromatic groups that are present forming alkyl-aryl compounds.
- the products that may be obtained from the anode compartment 2 are carbon dioxide 25 along with Ri— Ri 24a, R 2 — R 2 24b and/or R— R 2 24c.
- the electrolytic cell 100 may be operated in a continuous mode. In continuous mode, the cell 100 is initially filled with anolyte solution 1 16 and catholyte solution 1 17 and then, during operation, additional solution 1 16, 1 17 is fed into the cell 100, and products, by-products, and/or diluted solutions are removed from the cell 100 without ceasing operation of the cell 100.
- the electrolytic cell 100 is operated in batch mode. In batch mode, the anolyte solution 1 16 and catholyte solution 1 17 are fed initially into the cell 100 and then the cell 100 is operated until a desired concentration of the product is produced, then the cell 100 is emptied and the products are collected. The cell 100 is then refilled to start the process again.
- the feeding of solutions 1 16, 1 17 into the cell 100 may be done using a pre-made solutions or using components that form the solutions in situ. It should be noted in both continuous and batch mode, the anolyte 1 16 can be added to maintain the alkali ion concentration at a certain level.
- the anolyte solution 1 16 may comprise a solvent 146, and at least one alkali metal salt of a carboxylic acid 130/130a.
- the choice of the first carboxylic acid 130 is dependent on the desired structure of the alkyl component of the AR compound being synthesized. These will have a general formula of R 1 CO 2 M, where Ri is a hydrocarbon with a carbon number from 2 to 22. Some non- limiting examples are, butyric acid, lactic acid, 3-hydroxypropanoic acid, valeric acid, myristic acid, palmitic acid, stearic acid, lauric acid, oleic acid, levelunic acid, naphthenic acid, etc.
- the carboxylic acid can also have functional groups present although the majority of the alkyl component should contain single carbon-carbon bonds.
- the anolyte 1 16 can contain a mixture of alkyl based carboxylate salts.
- the anolyte 1 16 may contain at least one carboxylate salt of a second type of carboxylic acid 130a.
- This carboxylic acid 130a will have the general formula of R 2 CO 2 H, where R 2 is an aromatic substituent such as a benzene or naphthalene ring.
- R 2 is an aromatic substituent such as a benzene or naphthalene ring.
- Some non-limiting examples are benzoic acid, naphthoic acid, naphthalenedicarboxylic acid, pamoic acid, hydroxynaphthoic acid, phenylpropanoic acid, phenylbutanoic acid, phenylethonic acid, naphthoic acid, phthalic acid, and trimesic acid.
- the aromatic carboxylic acid can also have additional functional groups and/or have multiple aromatic systems.
- the anolyte 1 16 can contain a mixture of aryl based carboxylate salts.
- the anolyte solution 1 16 may comprise an aromatic compound that is used as the solvent 146.
- This aromatic solvent may contain an alkyl carboxylic acid or an alkali metal salt of an alkyl carboxylic acid or a mixture thereof.
- the aromatic solvent contains a supporting electrolyte.
- the anolyte solution 1 16 may comprise a mixture of an aromatic solvent and a polar organic solvent (that in combination form the solvent 146), where this solvent mixture contains at least one alkali metal salt of a carboxylic acid.
- the R1CO2M and R 2 C0 2 M salts 130, 130a may be added to a suitable electrolyte which is used as the anolyte solution 1 16.
- the anolyte 1 16 can contain a mixture of more than two types of carboxylic acids.
- the anolyte solution 1 16 may optionally include a supporting electrolyte if the conductivity of the anolyte 1 16 is not optimized for the decarboxylation.
- the anolyte solution 1 16 may be fed either continuously or in batch mode into the electrochemical cell, such as cell 100 shown in Figure 1 .
- the applied electric potential 1 1 causes a reaction to occur at the anode 4.
- This reaction causes the decarboxylation of the carboxylate ions leading to the formation of carbon dioxide, and radicals of (R «) according to the reactions shown above.
- the radicals formed in the decarboxylation step can undergo the different coupling reactions (e.g., heterocoupling or homocoupling), as shown above.
- the decarboxylation will permit the homocoupling of the alkyl carboxylate radicals, homocoupling of the aryl carboxylate radicals, and heterocoupling between the two types of radicals.
- the conditions and parameters used in the present embodiments can be modified to promote the heterocoupling over the homocoupling, and vice versa.
- the conditions and parameters can also be used to cause multiple alkylations onto a single aryl group.
- the products obtained from the coupling reactions can then be separated as needed to obtain a material that has the properties required for the lubricant or lubricant additive (or another desired product).
- Additional embodiments may be designed in which the applied electrical potential 1 1 causes the oxidation at the anode 4 to decarboxylate an alkali salt of an alkyl carboxylic acid 130 or mixture of alkyl carboxylic acids 130, 130a in the presence of an aromatic solvent 146.
- the aromatic solvent may be a solvent mixture containing an aromatic compound.
- the decarboxylation can lead to the formation of a radical as describe in the previous embodiment, or it can lead to the formation of a carbocation as shown in the following reaction.
- the radical and/or the carbocation can act as an electrophile and subsequently be involved in an electrophilic substitution reaction.
- the electrophile substitutes one of the substituents on an aromatic group, for example, hydrogen, as shown below as a non-limiting example.
- the product of the initial alkyl-aryl coupling reactions will have an aromatic group still present.
- this aromatic group can then go through further electrophilic substitution reactions with additional radicals or carbocations that are generated at the anode 4.
- electrophilic substitution reactions with additional radicals or carbocations that are generated at the anode 4.
- the oxidation reaction causing the decarboxylation which forms the radical is usually conducted at high current density.
- a highly conductive catholyte 1 17 may be used in the cathode compartment 2 of the cell 100.
- catholyte materials 1 17 are aqueous alkali hydroxide and non-aqueous methanol/alkali methoxide solutions.
- the potential across the cell 100 permits oxidation to occur at the anode 4
- the potential also causes the reduction of the catholyte 1 17 to occur at the cathode 5. (This reduction reaction leads to the formation of hydrogen gas 23 and alkali metal hydroxides.)
- RCO2M is more polar than RCO2H and so more probable to decarboxylate at lower voltages; • The electrolyte conductivity may be higher for alkali metal salts than the acid solutions; and
- the anolyte and catholyte solution can be completely different, allowing favorable reactions to take place at either/both electrodes.
- the examples disclosed herein used an experimental setup which is schematically shown in Figure 1 .
- the cell employed for these experiments was a micro flow cell, allowing both the anolyte and catholyte to be pumped through the cell while minimizing the distance between the electrodes and the membrane.
- the membranes used in the examples consisted of 2.54 cm diameter NaSICON disks of about 1 mm thickness which were housed on scaffolds in the center of the cells. As the scaffold and membrane physically separate the anode and cathode compartments, there was a separate reservoir and temperature controlled hotplate for the anolyte and catholyte. This allowed the chemistry and conditions of each electrolyte to be optimized for the respective electrode reactions.
- a multiple-head parasitic pump was used to pump both electrolytes into the electrolysis cell, and, depending on the temperature of the electrolytes, the tubing between the cell, pump, and reservoir was insulated.
- the anolyte which contains the sodium salts of the carboxylic acids, is made by dissolving at least 10% by weight of both salts into a polar organic solvent. This was conducted using two methods. For the first method, the sodium salts were prepared directly in the polar organic solvent by the addition of the carboxylic acids and NaOH. To ensure the complete de-protonation of the acid, the cell was operated at a pH between 8 and 12, indicative of excess NaOH. The second method consisted of preparing the sodium salts in separate solutions following conventional saponification reactions and then dissolving the prepared salt into a polar organic solvent. For this method, a general saponification procedure was used during which the sodium carboxylates form as the carboxylic acid is neutralized.
- the carboxylic acids were converted to the sodium salts separately and then added to the polar solvent.
- the catholyte can be made from any solution containing sodium salts, and for the examples given herein, an aqueous sodium hydroxide solution was used. To obtain low solution resistance, the temperatures of the electrolytes were increased to 50 °C to improve both the solubility and conductivity.
- a power supply (BP Precision 1786B) was connected and a current density between 10 and 100 mA/cm 2 was applied.
- the voltage and current were monitored using a Data Acquisition Unit (Agilent 3490A) controlled by LabVIEW.
- the applied current density caused oxidation to occur at the anode (smooth platinum) and reduction to occur at the cathode (nickel), with each electrode having an area of 1 1 cm 2 .
- the power supply transports electrons from the anode to the cathode, a charge balance must be maintained across the cell by the diffusion of positively charge ions. Given the high selectivity of the NaSICON membrane for Na + ions, it is the only species that can provide this balance, thus a high concentration of the sodium salt was desired.
- Methanol was the solvent used in the examples given.
- solubility of the all the sodium salts used in the examples were found to be 10-15% by weight after the addition of mild heat.
- the solubility of each salt in methanol was found to be 10% by weight. (Thus, the solutions containing two salts had a total salt concentration of 20% by weight.)
- the GC-MS analysis was conducted using a 60 meter column with a non- polar dimethylpolysiloxane phase which can handle a temperature range between - 60 and 325 °C. A temperature program was used that started the temperature at 35 °C and increased the temperature to 310 °C at 10 minute and then held this temperature for 35 minute. The mass spec range used to analyze the data was 29 to 550 m/z.
- the electrochemical decarboxylation process disclosed herein was used to alkylate an aromatic ring with a long chain aliphatic group.
- the prepared alkylated aromatic compound may have properties that are beneficial for components of Group V lubricants.
- the anolyte for this example consisted of 10% by weight sodium oleate and sodium benzoate in methanol.
- the sodium salts of benzoic and oleic acid had to be prepared from the corresponding acids. This was preformed individually by adding the acids at 20% by weight to methanol and heating the solution to 50 °C. To the heated solution, 7% by weight sodium hydroxide was added, upon which white solids crashed out.
- the anolyte was prepared by adding 10% by weight sodium benzoate and 10% by weight sodium oleate to methanol. An aqueous solution containing 10% by weight sodium hydroxide was used as the catholyte.
- the electrolysis was conducted in batch mode, during which the anolyte and catholyte were cycled through the corresponding anode and cathode compartments of the cell. Both electrolytes were maintained at a temperature of 50 °C. A current density of 18 mA/cm 2 was applied to the cell until enough charge passed to theoretically convert 40% of the total sodium salt. The reactions that occurred during the electrolysis in the anode compartment are shown below.
- the CH 3 (CH 2 )i 5 CH 2 « species is an alkyl radical derived from sodium oleate.
- the ⁇ 5 ⁇ is a phenyl radical derived from the sodium benzoate.
- the anolyte was processed so it could be analyzed with GC.
- the processing consisted of adding 30% H 2 S0 4 to the anolyte solution which caused Na 2 S0 4 to crash out. After centrifuging, the methanol solution was decanted off of the solid material. The liquid was then mixed with ethyl acetate. Using a separatory funnel, the layers were separated and the ethyl acetate layer was analyzed with GC.
- Figure 3 shows a GC of the decarboxylation of a solution containing only sodium oleate.
- This GC shows the elution of the oleic acid at 26.5 minutes and the elution of the homocoupling product (from oleate) as 29.2 minutes.
- the second GC shown in Figure 3 shows the analysis of the decarboxylation of sodium oleate and sodium benzoate.
- This GC shows the elution of the oleic acid at 26.5 minutes and the elution of the hetero-coupling alky-aryl compound at 34.9 minutes.
- EXAMPLE 2 The electrochemical decarboxylation process disclosed herein was used to perform homo/hetero coupling on a mixture of carboxylic acids which contain straight chain aliphatic and aromatic groups, known as naphthenic acid.
- the prepared liquid may have properties that are beneficial for components of Group V lubricants.
- the anolyte for this example consists of 10% by weight sodium naphthenate in methanol.
- An aqueous solution containing 10% by weight sodium hydroxide was used as the catholyte.
- the electrolysis was conducted in batch mode, during which the anolyte and catholyte were cycled through the corresponding anode and cathode compartments of the cell. Both electrolytes were maintained at a temperature of 50 °C. The cell was started at a current density of 9 mA/cm 2 and current was applied to the cell until enough charge passed to theoretically convert 40% of the total sodium salt. The reactions that occurred during the electrolysis in the anode compartment are shown below.
- R nap represents a mixture of cyclopentyl and cyclohexyl aliphatic groups with 9 to 20 carbon backbone and molecular weights between 120 and 700 amu.
- the reaction shown below is simultaneously occurring in the cathode compartment.
- FIG. 4 contains a graph showing voltage and current density verses time for this example.
- the experiment was started by applying a current density of 9 mA/cm 2 and then this current density was increased stepwise to 22 mA/cm 2 , at which time the cell potential reached 31 V. This limit was reached within the first hour, so the current density was decreased to 19 mA/cm 2 until the potential reached the 31 V limit, which occurred within 1 hour.
- the current density was then stepped down three more times before the experiment was terminated after 2 hours.
- the conditions used in this example promoted coupling of the mixture of radicals formed at the anode. Accordingly, this reaction formed a mixture of compounds with the general structures shown below, as a non-limiting example.
- the anolyte was processed so it could be analyzed with GC.
- the post reaction processing consisted of adding 30% H2SO4 to the anolyte solution which caused Na 2 S0 4 to crash out.
- a viscous liquid also formed after the addition of H 2 S0 4 , and this liquid was used for GC-MS analysis.
- the GC results of this liquid are shown in Figure 5. This figure shows that a broad peak was obtained, indicative of a mixture of compounds with slight differences in structure and/or mass.
- MS the identity of the species of this mixture was determined to be the combination of the starting carboxylic acids and a mixture of the coupled products produced by the decarboxylation of these acids.
- Another example of the present embodiments incorporates the alkyl-aryl coupling of EXAMPLE 1 with the coupling demonstrated in EXAMPLE 2.
- the electrochemical decarboxylation process leads to the coupling of a mixture of long chain aliphatic radicals containing rings to be coupled with naphthoate radicals.
- the prepared alkylated naphthalene may have properties that are beneficial for components of Group V lubricants.
- the anolyte for this example consists of 10% by weight sodium naphthenate and sodium naphthoate in methanol. To prepare the anolyte, 10% by weight naphthoic acid was added to methanol followed by the addition of 4% by weight sodium hydroxide. To this solution, 10% by weight sodium naphthenate was added. An aqueous solution containing 10% by weight sodium hydroxide was used as the catholyte.
- the electrolysis was conducted in batch mode, during which the anolyte and catholyte were cycled through the corresponding anode and cathode compartments of the cell. Both electrolytes were maintained at a temperature of 50 °C. A current density of 27 mA/cm 2 was applied to the cell until enough charge passed to theoretically convert 40% of the total sodium salt. The reactions that occurred during the electrolysis in the anode compartment are shown below.
- R na p represents the mixture of carboxylic acids that make up what is termed naphthenic acid. The reaction shown below is simultaneously occurring in the cathode compartment.
- CioH 7 « ⁇ CioH 7 — CioH 7
- the anolyte was processed so it could be analyzed with GC.
- the processing consisted of adding 30% H 2 S0 4 to the anolyte solution which caused Na 2 S0 4 to crash out and a viscous liquid to form. After centrifuging, the methanol layer was separated from the solid and viscous liquid, and then the methanol layer was completely distilled leaving a new solid and a liquid. This new solid and new liquid did not boil under vacuum and temperatures up to 180 °C.
- the solid was filtered from the liquid and was dissolved in ethyl acetate for the GC-MS analysis. The results from this solid in the ethyl acetate are shown in Figure 7.
- the structures shown on the GC in Figure 7 were determined using MS. The MS shows that this fraction of the reaction solution contained the starting naphthenic and naphthoic acids and a small peak due to the elution of the heterocoupling product.
- anolyte consisted of a non-homogenous mixture of a polar electrolyte and a non-polar electrolyte.
- the polar electrolyte was methanol and the non-polar electrolyte was pentadecane.
- methane portion of the electrolyte 10% by weight sodium naphthenate and sodium naphthoate, were dissolved. This was prepared following the method described in EXAMPLE 3, and then pentadecane was added to this layer at 20% by volume.
- the electrolysis was conducted in batch mode, during which the anolyte and catholyte were cycled through the corresponding anode and cathode compartments of the cell.
- the anolyte compartment was setup so that the anolyte was pulled into the cell from the methanol layer and returned to the cell in the pentadecane layer. This was chosen to help selectively pull the polar solvent into the cell for electrolysis, and allow the product obtained to be exchanged into the non- polar solvent following the electrolysis. Both electrolytes were maintained at a temperature of 50 °C.
- Figure 8 contains a graph showing voltage and current density verses time for this example.
- R na p represents the mixture of carboxylic acids that make up what is termed naphthenic acid. The reaction shown below is simultaneously occurring in the cathode compartment.
- Styrene is a desirable chemical in that is it used to make many polymeric materials and plastic materials, including ABS (Acrylonitrile butadiene styrene). Styrene has the formula C6H 5 CH 2 CH 2 . It has the chemical structure of:
- alkali metal benzoate from benzoic acid
- an alkali metal lactate from lactic acid (2-hydropropanoic acid) or 3-hydroxypropanoic acid
- a styrene precursor could be readily made.
- hydropropanoates and benzoate are listed above as being moieties that could be used as part of the present alkyl-aryl coupling reactions.
- a lactate (2- hydropropanoic acid) anion (CH 3 CH(OH)C0 2 ⁇ ) has the following formula.
- the 3-propanoic acid anion (CH 2 (OH)CH 2 C0 2 ⁇ ) has the following formula
- alkali metal benzoate from benzoic acid
- the alkali metal benzoate may be decarboyxlated as follows:
- an alkali metal lactate and/or 3-hydroxpropanoate (from lactic acid or 3-hydroxypropranoic acid) may be decarboxylated as follows:
- the alkali metal benzoate and the alkali metal lactate may be formed from benzoic acid and lactic acid, using a saponification reaction as outlined herein.
- the produced product is 1 -phenylethanol.
- 2- phenylethanol is the product.
- the particular conditions of the cell may be selected to foster heterocoupling as opposed to homocoupling.
- some of the homocoupled radical products (CeH 5 — CeH 5 and CH 3 CH(OH)— CH(OH)CH 3 ) may also be obtained and separated out from the phenylethanol.
- the homocoupling product (CeH 5 — CeH 5 ) may be obtained and separated out from the 1 -phenylethanol and the 2,3-butanediol (or 2- phenylethanol and 1 ,4-butanediol). This separation could leave a mixture of 1 - phenylethanol and 2,3-butanediol (or 2-phenylethanol and 1 ,4-butanediol), which then may be subjected to a dehydration reaction to produce both styrene and butadiene, both are components used to make ABS polymeric materials.
- Butadiene has a formular of CH 2 CHCHCH 2 .
- the butadiene and the styrene could then be used to make ABS or other thermoplastics, as desired.
- the decarboxylation of the hydroxypropanoic acid and benzoic acid and/or salts of the acids can be performed in an electrolyte that uses acrylonitrile as the solvent.
- the electrolyte could also be a mixture of solvents that contains acrylonitrile.
- all three components needed to make ABS materials would be present.
- the decarboxylation of sodium lactate or sodium 3-hydroxpropanoate can be performed in an electrolyte that contains benzene or a mixture of benzene and a polar organic solvent.
- the radical or carbocation can then undergo electrophilic substituent reaction with the benzene and form the 1 -phenylethanol, or the 2-phenylethanol.
- phenylethanol e.g., the 1 -phenylethanol or the 2-phenylethanol
- this product may be subjected to a dehydration reaction to produce styrene.
- 2,3-butantediol or 1 ,4-butanediol
- it may be subjected to a dehydration reaction to produce butadiene.
- One or more catalysts may be used to facilitate/speed this dehydration reaction.
- the above-recited method for producing styrene may not require high temperatures and/or high pressures, nor does it require an ethylbenzene precursor. Rather, the precursors are hydroxypropanoic acids and benzoic acids, which are readily available substrates. Likewise, there will likely be little or no sulfur impurities in the styrene, as are found in some styrenes made via other manufacturing methods. Thus, the resulting styrene may be purer than other commercially available styrene monomers. Also, the present method will likely provide a pathway to produce the both styrene and butadiene in one step, and possibly be produced in the presence of acrylonitrile.
Abstract
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CA2902925A CA2902925A1 (en) | 2013-03-15 | 2014-03-14 | Device and method for aryl-alkyl coupling using decarboxylation |
JP2016502920A JP2016517476A (en) | 2013-03-15 | 2014-03-14 | Allyl-alkyl coupling apparatus and method using decarboxylation |
EP14762729.3A EP2971255A4 (en) | 2013-03-15 | 2014-03-14 | Device and method for aryl-alkyl coupling using decarboxylation |
KR1020157028584A KR20150129806A (en) | 2013-03-15 | 2014-03-14 | Device and method for aryl-alkyl coupling using decarboxylation |
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US5841002A (en) * | 1995-09-28 | 1998-11-24 | Davy Process Technology Limited | Process for the commercial production of polyhydroxy alcohols and glycols |
US20110035995A1 (en) * | 2007-09-12 | 2011-02-17 | Rainer Busch | Biofuel composition and manufacturing process |
US20110226633A1 (en) * | 2009-07-23 | 2011-09-22 | Sai Bhavaraju | Electrochemical synthesis of aryl-alkyl surfacant precursor |
US20110240484A1 (en) * | 2010-04-01 | 2011-10-06 | Justin Pendleton | Production of Alkali Bicarbonate and Alkali Hydroxide From Alkali Carbonate in an Electrolyte Cell. |
US20120316093A1 (en) * | 2011-06-10 | 2012-12-13 | Chevron U.S.A. Inc. | Conversion of fatty acids to base oils and transportation fuels |
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US5841002A (en) * | 1995-09-28 | 1998-11-24 | Davy Process Technology Limited | Process for the commercial production of polyhydroxy alcohols and glycols |
US20110035995A1 (en) * | 2007-09-12 | 2011-02-17 | Rainer Busch | Biofuel composition and manufacturing process |
US20110226633A1 (en) * | 2009-07-23 | 2011-09-22 | Sai Bhavaraju | Electrochemical synthesis of aryl-alkyl surfacant precursor |
US20110240484A1 (en) * | 2010-04-01 | 2011-10-06 | Justin Pendleton | Production of Alkali Bicarbonate and Alkali Hydroxide From Alkali Carbonate in an Electrolyte Cell. |
US20120316093A1 (en) * | 2011-06-10 | 2012-12-13 | Chevron U.S.A. Inc. | Conversion of fatty acids to base oils and transportation fuels |
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