KR102013014B1 - Method of producing coupled radical products via desulfoxylation - Google Patents

Abstract

Provided are methods for preparing coupled radical products. The method includes obtaining a sodium salt of sulfonic acid (R-SO ₃ -Na). Alkali metal salts are then used in the anolyte as part of the electrolytic cell. The electrolytic cell may comprise an alkali ion conductive membrane (such as a NaSICON membrane). When the cell is running, the alkali metal salt of sulfonic acid is desulfonylated and radicals are formed. These radicals then bind to other radicals to produce coupled radical products, such as hydrocarbons. The resulting hydrocarbons can be, for example, saturated, unsaturated, branched, or unbranched, depending on the starting material.

Description

METHOD OF PRODUCING COUPLED RADICAL PRODUCTS VIA DESULFOXYLATION

<Cross-reference of Prior Application>

This application claims priority to US patent provisional application 61 / 773,610, filed March 6, 2013. This application is also a partial continuing application of US patent application 12 / 840,508 (the '508 application), filed July 21, 2010. The '508 application was filed on July 23, 2009, US Provisional Application No. 61 / 228,078, filed on November 5, 2009, and US Patent Application 61 / 258,557, filed on November 13, 2009; Insist on / 260,961. This application is also a partial continuing application of US patent application 12 / 840,401, filed July 21, 2010. This application is also a partial continuing application of US patent application 12 / 840,913. This application is also a partial continuing application of US patent application 13 / 612,192.

Such patent provisional applications and patent formal applications are expressly incorporated herein by reference.

Sodium salts of alkyl sulfates are useful chemicals that are readily prepared. Such chemicals typically have the following structure:

^{_{[R-SO 3] - Na}} +

One particular example of this type of chemical is sodium dodecylbenzenesulfonate commonly used in detergents:

Of course, any "R" group can be added to the alkyl sulfate.

Sodium salts of alkyl sulfates are generally found in detergents, cosmetics, surfactants, shampoos, chromatography and other useful products / processes. Accordingly, such chemicals are considered readily available, safe and biodegradable.

At the same time, there is a need for new methods that can react the sodium salts of alkyl sulfates to form various organic chemicals. Such a method is disclosed herein.

Sodium salts of alkyl sulfonates ^{_{([R-SO 3] -}} Na +) will be obtained. Once obtained, such alkyl sulfonates can be incorporated into the anolyte for use in electrolytic cells. Such anolyte may also include a solvent (such as water, methanol, etc.) and optionally a supporting electrolyte (in addition to ([[R—SO ₃ ] ⁻ Na ⁺ )). For convenience, the alkyl sulfonate ^{_{([R-SO 3] -}} Na +) may be represented also as R-SO ₃ -Na herein.

The anolyte is fed to an electrolytic cell using a sodium ion conductive ceramic membrane that divides the cell into two compartments, the anolyte compartment and the catholyte compartment. Typical membranes are NaSICON membranes. NaSICON typically has a relatively high ionic conductivity for sodium ions at room temperature. Alternatively, if the alkali metal is lithium, then a particularly very suitable material that can be used to construct the embodiment of the membrane is LiSICON. Alternatively, if the alkali metal is potassium, then a particularly very suitable material that can be used to constitute the embodiments of the membrane is KSICON. Other examples of such solid electrolyte membranes include those based on NaSICON structures, sodium conductive glass, beta alumina and solid polymeric sodium ion conductors. Such materials are commercially available. In addition, such membranes are resistant to impurities that may be present in the anolyte and will not allow impurities to mix with the catholyte. Thus, impurities (derived from biomass) do not necessarily have to be removed before placing the anolyte in the cell.

Electrolytic cells can use standard parallel plate electrodes, where flat plate electrodes and / or flat membranes are used. In other embodiments, the electrolytic cell may be a tubular type cell, where tubular electrodes and / or tubular membranes are used.

An electrochemically active first anode can be found in the cell and 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, dimensional stability anode (DSA), and lead dioxide. Other materials can also be used for the electrodes. The first anode carries out the desired reaction. In this anolyte compartment of the cell, an oxidation (desulfoxylation) reaction and subsequent radical-radical coupling are performed. In one embodiment, the anode desulfurization / oxidation coupling of sulfonic acid occurs via a reaction similar to the known “Kolbe reaction”. The standard Kolbe reaction is a free radical reaction, which is shown below:

_{2R-COOH → RR + 2CO 2} + 2e - + 2H +

(Carboxylic acid) (coupled radical product)

This Kolbe reaction is typically performed in methanolic non-aqueous solutions, in which partially neutralized acids (in the form of alkali salts) are used with parallel plate type electrochemical cells. The anolyte used in the cell may have a high density.

)이 형성되고 후속적으로 함께 배합되어 탄소-탄소 결합을 형성하는 자유 라디칼 반응이다. 사용되는 출발 물질에 따라, 커플링된 라디칼 생성물이 탄화수소 또는 일부 다른 사슬일 수 있음이 통상의 기술자에 의해 인지될 것이다. 커플링된 라디칼 생성물은 이량체, 또는 하나 이상의 고탄소 또는 저탄소 함유 물질을 포함하는 혼합 생성물일 수 있다. 커플링된 라디칼 생성물에서 라디칼은 알킬-기초 라디칼, 수소-기초 라디칼, 산소-기초 라디칼, 질소-기초 라디칼, 다른 탄화수소 라디칼, 및 그의 조합을 포함할 수 있다. 따라서, 탄화수소가 커플링된 라디칼 생성물로서 하기 실시예에 나타나 있으나, 탄화수소는 일부 다른 적절한 커플링된 라디칼 생성물로 자유롭게 대체될 수 있다.As can be seen from the Kolbe reaction, the "R" groups of the two carboxylic acid molecules are coupled together resulting in a coupled radical product. In one embodiment, the Kolbe reaction consists of two “R radicals” (R

) Is a free radical reaction that is formed and subsequently combined together to form a carbon-carbon bond. Depending on the starting materials used, it will be appreciated by those skilled in the art that 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 carbon or low carbon containing materials. Radicals in the coupled radical product may include alkyl-based radicals, hydrogen-based radicals, oxygen-based radicals, nitrogen-based radicals, other hydrocarbon radicals, and combinations thereof. Thus, while hydrocarbons are shown in the examples below as coupled radical products, hydrocarbons may be freely replaced by some other suitable coupled radical product.

However, as mentioned above, embodiments of the present invention may use sodium salts of sulfonic acids (or alkali metal salts) rather than carboxylic acids themselves at the anode. Thus, rather than using a standard Kolbe reaction (using carboxylic acid in the form of fatty acids), embodiments of the invention may include performing the following reactions at the anode:

_{2 ([R-SO 3]} - Na +) → RR + 2SO x + 2e - + 2Na +

(Sodium salt of alkyl sulfonate) (coupled radical product)

Again, this embodiment couples two “R” groups together to form a coupled radical product, such as a hydrocarbon. There is a distinct advantage to using the sodium salt of sulfonic acid instead of sulfonic acid itself:

And ^{_{([R-SO 3] -}} Na +) is more polar than the R-SO ₃ -H Therefore, it will be more talsul sulfonation (a reaction) at a lower voltage;

Electrolyte conductivity may be higher for the sodium salt of sulfonic acid than for sulfonic acid itself;

The anolyte and catholyte can be completely different so that different reactions can be carried out at each electrode.

As mentioned above, the cell contains a membrane comprising a sodium ion conductive membrane. This membrane selectively transfers sodium ions (Na ⁺ ) from the anolyte compartment to the catholyte compartment under the influence of electrical potential, while simultaneously preventing the anolyte and catholyte from mixing.

The catholyte may be an aqueous NaOH solution or a methanol / sodium methoxide nonaqueous solution (the anolyte may be aqueous or nonaqueous). The electrochemically active cathode is received in the catholyte compartment, where the reduction reaction is carried out. This reduction reaction can be recorded as follows:

_{^{2Na + + 2H 2 O + 2e}} - → 2NaOH + H 2

_{^{2Na + + 2CH 3 OH + 2e}} - → 2NaOCH 3 + H 2

Hydrogen gas is the product of a reduction reaction at the cathode. NaOH (sodium hydroxide) or NaOCH ₃ (sodium methoxide) is also prepared. Such NaOH or NaOCH ₃ is the base used in the reaction to form R-SO ₃ -Na. Thus, this reaction can actually regenerate (in the catholyte compartment) one of the reactants required for the whole process. This NaOH or NaOCH ₃ can be recovered and reused in further reactions. The ability to regenerate and reuse NaOH or NaOCH ₃ is advantageous and can significantly reduce the overall cost of the process.

In an alternative embodiment, the sodium salt of sulfonic acid (eg CH ₃ SO ₃ -Na) having a small number of carbon atoms other than R-SO ₃ -Na can be added to the anolyte. The addition of such sulfonates may be advantageous in some embodiments, which:

Because it is highly soluble in the solvent, it can serve as a suitable supporting electrolyte to provide high electrolyte conductivity in the anolyte solution;

(메틸 라디칼)를 생성할 것이고:It is desulfonated on its own (in the electrolytic process) and CH ₃ by

Will produce (methyl radicals):

+ 2SO_x + 2e^- + 2Na⁺ 2CH ₃ -SO ₃ -Na → CH ₃

^{_{+ 2SO x + 2e - + 2Na}} +

                      (Methyl radical)

This is because the methyl radicals can then react with the hydrocarbon groups of sulfonic acids to form hydrocarbons with additional CH ₃ -functional groups:

+ R

→ CH₃-RCH ₃

+ R

→ CH ₃ -R

(Methyl radical) (radical of sulfonic acid)

Thus, in one embodiment, by using CH ₃ -SO ₃ -Na as part of the anolyte solution, this embodiment couples two hydrocarbon radicals from sulfonic acid together (RR) or the radicals of sulfonic acid and CH ₃ − Coupling a methyl radical from SO ₃ -Na can produce a mixed hydrocarbon product. This mixture of products can be separated and used as desired. Of course, this embodiment has been shown to use CH ₃ -SO ₃ -Na as a further reactant. Alternatively, sodium salts of other sulfonic acids having a small number of carbon atoms can also be used to couple the carbon radicals to the radicals of sulfonic acid.

It will be appreciated that various different hydrocarbons or coupled radical products may be formed using embodiments of the present invention. For example, the particular "R" group selected may be selected and / or tailored to produce hydrocarbons that may be used for diesel, gasoline, wax, JP8 ("jet propellant 8"), and the like. The particular application of the hydrocarbon may depend on the starting material chosen.

It should be noted that the embodiments described above using the "desuloxylation reaction" are similar to the "decarboxylation" reaction described in the following published patent applications:

United States Patent Application Publication 2011/0024288

United States Patent Application Publication 2011/0027848

United States Patent Application Publication 2011/0168569

US Patent Application Publication 2013/0001095.

All published patent applications described above are expressly incorporated herein by reference. However, one of ordinary skill in the art will recognize that the reactions, reaction conditions, reactants and the like disclosed in the "decarboxylation" process in the documents described above may equally be applied to the "desulfoxylation" reactions of the present invention. In addition, the examples used herein focus on Na as the alkali metal. Those skilled in the art will appreciate that other alkali metals, or alloys of alkali metals, may be used with or in place of Na.

BRIEF DESCRIPTION OF DRAWINGS To facilitate the understanding of the above-described and other features and advantages of the present invention, the more specific disclosure of the invention briefly described above will be referenced with reference to specific embodiments thereof illustrated in the accompanying drawings. It is to be understood that such drawings illustrate only exemplary embodiments of the invention and are therefore not to be considered limiting of its scope, the invention is further described and described in further detail and detail using the following accompanying drawings. Will be:
1 is a system diagram illustrating the overall process of using desulfonoxylation to produce a coupled hydrocarbon product;
2 is a schematic of an electrolytic cell for converting the sodium salt of sulfonic acid into a coupled radical product by anode desulfurization and subsequent carbon-carbon bond formation in accordance with an embodiment of the present invention;
3 is a schematic of another embodiment of an electrolytic cell for converting the sodium salt of sulfonic acid to a coupled radical product;
4 is a schematic of another embodiment of an electrolytic cell for converting the sodium salt of sulfonic acid to a coupled radical product.

Referring now to FIG. 1, an overall process 10 for producing a coupled radical product is disclosed. As shown in FIG. 1, a predetermined amount of sulfonic acid (R-SO ₃ H) can be obtained (12). Such sulfonic acids may be organic acids and may be obtained from biomass or from any other source. Those skilled in the art will recognize various different sources of sulfonic acid. Any and all sources of sulfonic acid are within embodiments of the invention. The published patent application described above describes biomass as a potential starting material and describes that biomass can be converted to sulfonic acid by known methods.

Once sulfonic acid is obtained, sulfonic acid can be converted to alkyl sodium sulfate (R-SO ₃ -Na) (14). This conversion reaction may occur by reacting sulfonic acid with a base, in an electrochemical cell, or in some other way. In other embodiments, instead of obtaining sulfonic acid and reacting it to form alkyl sodium sulfate, an amount of alkyl sodium sulfate can be obtained directly (via purchase or the like).

Desuloxylated electrolysis process 16 may then be performed on the alkyl sodium sulphate in the manner outlined herein. As described herein, this process can produce an amount of SO _x gas 18 (eg, such as SO ₂ , SO _3, etc.). An amount of hydrogen gas 20 may also be produced. Those skilled in the art will appreciate that such gases may be collected, reused, disposed, etc. as desired. In addition, as part of the desulfurization process 16, sodium ions, such as, for example, in the form of bases such as NaOH, can be recycled (represented by arrow 22) and used again to form R-SO ₃ -Na. Can be.

At the same time, the desuloxylation process 16 is run to couple the organic radicals together to form the R-R hydrocarbon product 24. As mentioned above, such hydrocarbons may be valuable products such as fuels, gasoline additives and the like.

The electrochemical cell can be used to perform the desulfurization process 16. An example of a typical embodiment of the cell is shown in FIG. 2. Advanced Kolbe using such a cell 200 which may also include an amount of a first solvent 160 (which may be, for example, water or an alcohol such as methanol, ethanol, and / or glycerol). The reaction can be carried out. Solvent 160 may be obtained from any source. This advanced Kolbe reaction produces hydrocarbon 170 with a predetermined amount of SO _x 172 gas. An amount of base 150 is also generated (in the embodiment of FIG. 2, the base is NaOH). However, hydrocarbon 170 is one example of any of a variety of coupled radical products that may be produced by this process, which may be, for example, a mixture of hydrocarbons. Similarly, the SO _x gas 172 produced in process 200 is a naturally occurring chemical, which may be disposed of, collected, sold, or the like.

The hydrocarbon 170 produced in the process 200 (and more specifically the advanced Kolbe reaction) can 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. In the process of the present invention, various types of hydrocarbons can be used. Hydrocarbons are often classified by the number of carbons in their chain. In addition, hydrocarbons can often be classified into the following "fractions":

C ₁ methane fraction

C ₂ -C ₅ natural gas fraction

C ₆ -C ₁₀ gasoline fraction

C ₁₀ -C ₁₃ JP8 Fraction

C ₁₄ -C ₂₀ Diesel Fraction

C ₂₀ -C ₂₅ fuel oil fraction

C ₂₀ -C ₃₀ Wax

Note that this classification is not accurate and may vary depending on the particular embodiment. For example, the "gasoline fraction" can have some C ₁₁ , the JP8 fraction can have some C ₁₄ , and the like.

By forming coupled radical products according to embodiments of the present invention, various hydrocarbons may be prepared in some or all of these fractions. For example, embodiments may be configured such that C ₈ hydrocarbons (octane), which is a major constituent in commercial gasoline, is formed. Likewise, C ₁₂ hydrocarbons can be formed that can be used in the preparation of JP8. Of course, the exact product obtained depends on the particular starting material (s) and / or reaction conditions used. Accordingly, embodiments of the present invention allow the biomass to be converted to synthetic lubricants, gasoline, JP8, diesel fuel, or other hydrocarbons.

2 shows a 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. Catholyte compartment 204 and anolyte compartment 208 may be separated by membrane 212.

The specifics of each cell 200 will depend on the particular embodiment. For example, cell 200 may be a standard parallel plate cell in which flat plate electrodes and / or flat plate membranes are used. In other embodiments, cell 200 may be a tubular type cell in which tubular electrodes and / or tubular membranes are used. An electrochemically active first anode 218 is at least partially or wholly contained within the anolyte compartment 208. More than one anode 218 may also be used. The anode 218 may include, for example, a smooth platinum electrode, a stainless steel electrode, or a carbon based electrode. Examples of typical carbon based electrodes include boron doped diamond, glassy carbon, synthetic carbon, dimensional stability anodes (DSA) and the like, and / or lead dioxide. Other electrodes may include metals and / or alloys of metals, including S. S, Kovar, Inconel / monel. Other electrodes can include RuO ₂ -TiO ₂ / Ti, PtO _x -PtO ₂ / Ti, IrO _x , Co ₃ O ₄ , MnO ₂ , Ta ₂ O _5, and other valve metal oxides. In addition, other materials such as SnO ₂ , Bi ₂ Ru ₂ O ₇ (BRO), BiSn ₂ O ₇ , precious metals such as platinum, titanium, palladium, and platinum clad titanium, carbon materials such as glassy carbon, BDD, or hard carbon can be used. Further embodiments may have RuO ₂ -TiO ₂ , hard vitrems carbons, and / or PbO ₂ . Again, this only serves as an example of the type of electrode that can be used. Cathode compartment 204 includes one or more cathodes 214. The cathode 214 is partially or wholly contained within the cathode compartment 204. The material used to make up the cathode 214 may be the same material used to make up the anode 218. Other embodiments may be designed such that different materials are used to construct the anode 218 and cathode 214.

Anolyte compartment 208 is designed to receive a predetermined amount of anolyte 228. Catholyte compartment 204 is designed to receive a predetermined amount of catholyte 224. In the embodiment of FIG. 2, the anolyte 228 and the catholyte 224 are both liquid, but solid particles and / or gaseous particles may be anolyte 228, catholyte 224, and / or anolyte 228. And catholyte 224 may also be included.

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. For example, in the case of sodium, the membrane is sodium ion conductive membrane 212. The sodium ion conductive solid electrolyte membrane 212 is capable of selectively transferring sodium ions (Na ⁺ ) from the anolyte compartment 208 to the catholyte compartment 204 under the influence of an electrical potential, while the anolyte 228 and the catholyte 224 ) To prevent mixing. Examples of such solid electrolyte membranes include those based on NaSICON structures, sodium conductive glass, beta alumina and solid polymeric sodium ion conductors. NaSICON typically has a relatively high ionic conductivity at room temperature. Alternatively, if the alkali metal is lithium, then a particularly very suitable material that can be used to construct the embodiment of the membrane is LiSICON. Alternatively, if the alkali metal is potassium, then a particularly very suitable material that can be used to constitute the embodiments 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 making up the anolyte 228 can be added separately to the anolyte compartment 208 via the inlet 240 and mixed in the cell. The anolyte contains a predetermined amount of alkali metal salt 108 (R-SO ₃ -Na) of sulfonic acid. In the particular embodiment shown in FIG. 2, the sodium is an alkali metal so that the alkali metal sulfonic acid salt 108 is a sodium salt. The anolyte 228 also includes a first solvent 160, which may be water 160a. Of course, other types of solvents may also be used. The anolyte 228 may optionally include other alkali metal salts of sulfonic acid (eg, such as CH ₃ —SO ₃ —Na). Other mixtures of various alkali metal salts of sulfonic acid can also be used.

Catholyte compartment 204 may include one or more inlets 242 through which catholyte 224 may be added. The catholyte 224 includes a second solvent 160b. The second solvent 160b may be water (as shown in FIG. 2) or some other type of solvent of an alcohol or mixture of solvents. Significantly, solvent 160b in catholyte 224 is not necessarily the same as first solvent 160a in anolyte 228. In some embodiments, solvents 160a, 160b may be identical. The reason for this is that the membrane 212 isolates the compartments 208, 204 from each other. Thus, solvents 160a and 160b may each be individually selected for reaction in each particular compartment (and / or to adjust solubility of chemicals in each particular compartment). Thus, the designer of cell 200 can tailor solvents 160a and 160b to allow reactions to occur in certain compartments without having to worry about the solvents mixing and / or reactions occurring in other compartments. . This may be a significant advantage in designing the cell 200. Typical Kolbe reactions only account for the one solvent used in both the anolyte and catholyte. Thus, it may be advantageous to use two separate solvents. In other embodiments, the first solvent 160a, the second solvent 160b, and / or the first and second solvents 160a, 160b may comprise a mixture of solvents.

Catholyte 224 may also include base 150. In the embodiment of FIG. 2, base 150 may be NaOH or sodium methoxide, or a mixture of these chemicals.

Now, the reactions occurring at anode 218 and cathode 214 will be described. As with all electrochemical cells, this reaction can occur when voltage source 290 applies a voltage to cell 200.

At the cathode 214, a reduction reaction is performed. This reaction uses sodium ions and a solvent to form an additional amount of base 150 as well as hydrogen gas 270. As an example the reduction reaction using the chemical of FIG. 2 can be recorded as follows:

_{^{2Na + + 2H 2 O + 2e}} - → 2NaOH + H 2

_{^{2Na + + 2CH 3 OH + 2e}} - → 2NaOCH 3 + H 2

Hydrogen gas 270 and / or base 150 may be extracted through outlet 244. Hydrogen gas 270 may be collected and / or disposed of or sold for further processing for use in other reactions. The production of base 150 may be a significant advantage since base 150 consumed in the conversion reaction 14 of FIG. 1 is regenerated in this portion of cell 200. Thus, the base formed in the cell can be collected and reused in subsequent reactions (or other chemical processes). Since the base can be reused, bothersome situations and / or costs associated with the disposal of the base can be avoided.

The reaction occurring at anode 218 may include desulfurization. This reaction may include an advanced Kolbe reaction (which is a free radical reaction) to form a predetermined amount of hydrocarbon 170 and carbon dioxide 172. As an example, the oxidation reaction using the chemical of FIG. 2 can be recorded as follows:

_{2R-SO 3 -Na → RR +} SO x + 2e - + 2Na +

(Sodium salt of sulfonic acid) (coupled radical product)

SO _x gas 172 may be exhausted (via outlet 248). The coupled radical product 170 may also be collected through the outlet 248. For example, an amount of solvent 160 / 160a may be extracted through outlet 248 and recycled back to inlet 240 for subsequent use if desired.

로서 명시된 탄화수소 라디칼을 (중간체로서) 생성한다. 이에 따라, 이러한 R

라디칼 2개가 형성되는 경우, 이러한 라디칼은 함께 반응하여 탄소-탄소 결합을 형성할 수 있다:Advanced Kolbe reactions may include free radical reactions. As such, the reaction is R

To produce hydrocarbon radicals (as intermediates). Accordingly, such R

When two radicals are formed, these radicals can react together to form a carbon-carbon bond:

+ R

→ R-R R

+ R

→ RR

(Hydrocarbon radicals) (hydrocarbon radicals) (new hydrocarbons)

라디칼만을 남긴다.As shown in FIG. 2, this RR hydrocarbon product is designated hydrocarbon 170. In essence, the R moiety is desuloxylated when the sulfonyl moiety is removed and only reacts to form a hydrocarbon.

Leaves only radicals.

(메틸) 라디칼을 생성할 수 있다:As mentioned above, further salts of sulfonic acids can be used in FIG. 2. For example, CH ₃ -SO ₃ -Na (or the sodium salt of some other sulfonic acid having a small number of carbon atoms) can be part of (or added to) the anolyte 228. CH ₃ -SO ₃ -Na can act as a suitable supporting electrolyte because it is highly soluble in some solvents and thus provides high electrolyte conductivity. At the same time, CH ₃ -SO ₃ -Na is desuloxylated itself and CH ₃ as part of the advanced Kolbe reaction by

It can generate (methyl) radicals:

+ SO_x + 2e^- + 2Na⁺ 2CH ₃ -SO ₃ -Na → 2CH ₃

^{_{+ SO x + 2e - + 2Na}} +

                        (Methyl radical)

The methyl radical can then react with the hydrocarbon group of sulfonic acid to form a hydrocarbon with additional CH ₃ -functional groups:

+ R

→ CH₃-RCH ₃

+ R

→ CH ₃ -R

Alternatively or additionally, the methyl radical may react with another methyl radical to form ethane:

+ CH₃

→ CH₃-CH₃ CH ₃

+ CH ₃

→ CH ₃ -CH ₃

Ethane (CH ₃ —CH ₃ ) is a hydrocarbon that may form part of the hydrocarbon product 170. CH ₃ -R formed in the reaction may also be part of the hydrocarbon product 170. (This R-CH ₃ product is indicated as symbol 170b.) Thus, a mixture of hydrocarbons can be obtained, which is represented by structure RR. If desired, various hydrocarbons may be separated and / or purified from one another, such as by gas chromatography or other known methods. Embodiments of the invention may couple two hydrocarbon radicals or couple a methyl radical and a hydrocarbon radical. The amount of CH ₃ -R or RR in the product may depend on the amount of reactants used in the particular reaction conditions, anolyte, and the like.

The above example involves the use of CH ₃ -SO ₃ -Na in addition to acid salts to produce a reactive methyl radical to produce CH ₃ -R in addition to the RR product. However, CH ₃ in addition to or instead of -SO ₃ -Na, may use a different salt having a carbon number of less than CH ₃ -SO ₃ -Na. Such salts with a small number of carbons can produce, for example, ethyl radicals, propyl radicals, isopropyl radicals, and butyl radicals during desulfurization. Materials that produce H radicals may also be used. Thus, by varying any component, additional hydrocarbons can be formed in the cell 200. Thus, the user can tailor the particular product formed by using different reactants. Thus, it is possible to react different alkyl radicals together or even react with methyl radicals, hydrogen radicals and the like to produce a mixture of products. Different alkyl radicals can be added, for example, by adding CH ₃ -SO ₃ -Na, H-SO ₃ -Na and the like to the anolyte via an additional port in the anolyte compartment. Several mixtures of these products may be similar to those that will occur in disproportionation reactions in some embodiments.

In a similar manner, instead of and / or using CH ₃ -SO ₃ -Na, H-SO ₃ -Na can be used as part of the anolyte. During the electrochemical reaction, H-SO ₃ -Na, like CH ₃ -SO ₃ -Na, will undergo desulfurization to form hydrogen radicals:

+ 2SO_x + 2e^- + 2Na⁺ 2H-SO ₃ -Na → 2H

^{_{+ 2SO x + 2e - + 2Na}} +

                        (Hydrogen radical)

These hydrogen radicals will then react to form:

+ R

→ H-RH

+ R

→ HR

And / or

+ H

→ H₂ H

+ H

→ H ₂

Using H-SO ₃ -Na as an optional reactant can form not only the RR product but also an amount of RH product (and even an amount of hydrogen gas (H ₂ )). (Hydrogen gas can be reused if desired). Using H-SO ₃ -Na can be used to prevent the formation of unnecessary ethane and / or to tailor the reaction to form a specific hydrocarbon (RH) product.

₎이 반응하고 에탄 (CH₃-CH₃)으로 "이량체화된다". R기가 C₁₈H₃₄ 탄화수소인 경우, 이어서 C₃₆H₇₈ 생성물이 형성될 수 있다. 이러한 간단한 원리를 사용할 뿐만 아니라 H-SO₃-Na 또는 작은 사슬 염을 사용함으로써, 임의의 목적하는 탄화수소가 수득될 수 있다. 예를 들어, C₄ 나트륨 염을 사용함으로써, 가솔린의 일부로서 사용가능할 수 있는 C₈ R-R 탄화수소가 형성될 수 있다. 마찬가지로, C₆ 나트륨 염이 사용되는 경우, JP8로서 사용가능할 수 있는 C₁₂ R-R 탄화수소가 형성될 수 있다. 합성 윤활제, 왁스, 및/또는 다른 탄화수소가 동일한 또는 유사한 방식으로 형성될 수 있다. 통상의 기술자는 목적하는 탄화수소를 생성하기 위해 이러한 원리를 사용하는 방법을 인지할 것이다. The particular R group shown in this reaction may be any "R" obtained from biomass, whether or not R comprises saturated, unsaturated, branched, or unbranched chains. When the RR product is formed, it is essentially the "dimer" of the R group. For example, if the R group is CH ₃ , two methyl radicals (2CH ₃

₎ Reacts and "dimerizes" with ethane (CH ₃ -CH ₃ ). If the R group is a C ₁₈ H ₃₄ hydrocarbon, then the C ₃₆ H ₇₈ product can be formed. By using this simple principle as well as using H-SO ₃ -Na or small chain salts, any desired hydrocarbons can be obtained. For example, by using C ₄ sodium salt, C ₈ RR hydrocarbons may be formed that may be usable as part of gasoline. Likewise, when a C ₆ sodium salt is used, C ₁₂ RR hydrocarbons may be formed which may be usable as JP8. Synthetic lubricants, waxes, and / or other hydrocarbons may be formed in the same or similar manner. Those skilled in the art will recognize how to use these principles to produce the desired hydrocarbons.

)을 형성할 수 있다는 점이다. 이러한 라디칼은 R

라디칼과 반응하여 생성된 생성물이 R-H 및 R-R이 되게 할 것이다. 충분한 수소 라디칼 (H

)이 존재하는 경우, R-H 생성물이 우세하거나, 또는 (거의) 전적인 생성물일 수 있다. 이러한 반응은 다음과 같이 요약될 수 있다 (귀금속의 예로서 Pd를 사용하며, 임의의 다른 귀금속이 사용될 수 있음을 유념하기 바람):The alternative embodiment of FIG. 2 will now be described with reference to the embodiment shown in FIG. 3. Since many embodiments of FIG. 3 are similar to those shown in FIG. 2, discussion of portions of similar features will be omitted for brevity, which is incorporated herein by reference. Since the anolyte compartment 208 is separated from the catholyte compartment 204, it is possible to create a reaction environment in the anolyte compartment 208 that is different from the catholyte compartment 204. 3 illustrates this conception. For example, hydrogen gas (H ₂ ) 320 may be introduced into the anolyte compartment 208. In some embodiments, anolyte compartment 208 may be pressurized by hydrogen gas 320. In some embodiments, anode 208 or anolyte may comprise component 310 consisting of Pd or other precious metal (such as Rh, Ni, Pt, Ir, or Ru) or another substrate such as Si, zeolite, or the like. have. (These parts can be all or part of the electrode and can be used to immobilize hydrogen gas on the electrode.) Alternatively, carbon can be suspended in the cell together with Pd or Pd. The effect of having hydrogen gas in the anolyte compartment 208 is such that the hydrogen gas is reacted with hydrogen radicals (H) during the reaction process in the manner mentioned above.

) Can be formed. These radicals are R

The product produced by reaction with the radicals will be RH and RR. Sufficient hydrogen radicals (H

) Is present, the RH product may be dominant or (almost) total product. This reaction can be summarized as follows (using Pd as an example of a noble metal, keeping in mind that any other precious metal can be used):

R-SO ₃ -Na + H ₂ and _{Pd → Pd-H x → Pd} + HR + SO x + e - + Na +

By using one or more precious metals and hydrogen gas in the anolyte compartment, the particular product (R-H) can be selected. In the embodiment of FIG. 3, hydrogen gas 270 is produced in the catholyte compartment 204 as part of the reduction reaction. This hydrogen gas 270 may be used as hydrogen gas 320 that is collected and reacts with the noble metal in the anolyte compartment 208. Thus, cell 300 can actually produce a hydrogen gas 270 feed itself that will be used in the reaction. Alternatively, the collected hydrogen gas 270 can be used for further processing of hydrocarbons, such as cracking and / or isomerization of wax and / or diesel fuel. Other processing using hydrogen gas may also be used. The R-H product (specified by (170e)) helps to minimize the formation of R-R groups (which can be hydrocarbons, such as waxes, if the R groups are large enough).

)을 생성할 수 있다. 수소 가스(320)는 다음의 식에 의해 예시되는 바와 같이 상기 기재된 임의의 메커니즘을 사용하여 애노드액 구획(208)에 공급될 수 있다:Referring now to FIG. 4, a further embodiment of cell 400 is illustrated. Cell 400 is similar to the cell previously described. Accordingly, for the sake of brevity, many of these discussions will not be repeated. In the embodiment of FIG. 4, cell 400 is designed such that one or more photolysis reactions can occur in anolyte compartment 208. Specifically, the photolysis device 410 is designed such that it can emit (irradiate) radiation 412 to the anolyte compartment 208. These investigations are based on hydrogen radicals (H

) Can be created. Hydrogen gas 320 may be supplied to anolyte compartment 208 using any mechanism described above as illustrated by the following equation:

+ H

H ₂ → H

+ H

       (photolysis)

This photolysis process can be combined with the electrolysis process of the cell described above:

             (Electrolysis)

+ 2SO_x + 2e^- + 2Na⁺ 2R-SO ₃ -Na → 2R

^{_{+ 2SO x + 2e - + 2Na}} +

(Sodium salt of sulfonic acid) (hydrocarbon radicals)

The hydrogen radicals and hydrocarbon radicals may then be combined to form a mixture of products:

+ 2R

→ H-R + R-R + H₂ 2H

+ 2R

→ HR + RR + H ₂

Alternatively, the desulfurization can be carried out using a photolysis device and generate hydrocarbon radicals:

             (photolysis)

+ 2 SO_x + 2e^- + 2Na⁺ 2R-SO ₃ -Na → 2R

^{_{+ 2 SO x + 2e - +}} 2Na +

(Sodium salt of sulfonic acid) (hydrocarbon radicals)

Thus, a combination of photolysis and electrolysis can be used to form hydrocarbon radicals and / or hydrogen radicals in the anolyte compartment 208:

                     (Photolysis and electrolysis)

2R-SO ₃ -Na + H ₂ → RR + RH + H ₂

This combination of electrolysis and photolysis can speed up the desulfurization reaction.

Additional embodiments can be designed using this photolysis technique. For example, the following reactions can occur:

               (Electrolysis)

+ 2 SO_x + 2e^- + 2Na⁺ 2R-SO ₃ -Na → 2R

^{_{+ 2 SO x + 2e - +}} 2Na +

(Sodium salt of sulfonic acid) (hydrocarbon radicals)

        (Photolysis and / or electrolysis)

→ 2R⁺ + 2e^- 2R

→ 2R ^{+ +} 2e ^-

                    (photolysis)

H ₂ + 2e ^- → 2H ^-

^{2H - + 2R + → 2R-} H

Combinations of these reactions (use of photolysis and electrolysis) form carboions and H ⁻ anions, which can be combined to form hydrocarbons. Thus, photolysis can be used as an additional mechanism for forming hydrocarbons. As discussed above, hydrocarbons are used in this example, but the coupled radical product need not be a hydrocarbon. In certain embodiments, the methods and apparatus of the present invention can be used to produce non-hydrocarbon radicals, which can be coupled together to form useful coupled radical products.

Referring now generally to FIGS. 2-4, note that each of these exemplary embodiments includes separation of the anolyte compartment 208 and the catholyte compartment 204 using the membrane 212. As described herein, certain advantages can be obtained by having such a membrane 212 to separate the anolyte compartment 208 from the catholyte compartment 204. These benefits include:

Two separate environments for different reaction conditions—for example, the anolyte may be non-aqueous while the catholyte may be aqueous (and vice versa);

The anolyte can be at a higher temperature than the catholyte (and vice versa);

The anolyte may be pressurized and the catholyte may not be pressurized (and vice versa);

The anolyte may be irradiated and the catholyte may not be irradiated (and vice versa);

The anolyte and / or anode can be designed to carry out a specific reaction which is not dependent on the catholyte and / or cathode reaction (and vice versa);

Different chambers may have different flow conditions, solvents, solubility, product recovery / separation mechanism, polarity, and the like.

The ability to have separate reaction conditions in the anolyte compartment and catholyte compartment can allow the reaction in each compartment to be tailored to achieve optimal results.

Likewise, membranes comprising, for example, NaSICON have high temperature resistance and therefore the anolyte can 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). This means that polar solvents (or nonpolar solvents) which dissolve the sulfonic acid and sodium salts at high temperatures can be used in the anolyte. At the same time, the catholyte is not affected by temperature. Indeed, different solvent systems can be used simultaneously in the catholyte. Alternatively, other molten salts or acids may be used to dissolve the ionic sodium acid and salt in the anolyte. Long chain hydrocarbons, ethers, triglycerides, esters, alcohols, or other solvents may dissolve the acid and sodium salts. Such compounds can be used as anolyte solvents without affecting the catholyte. Ionic liquids can be used as the anolyte solvent. Such materials can be run to dissolve large amounts of sodium sulfonate salts as well as to promote the desulfurization reaction at higher temperatures. Ionic liquids are a class of chemicals that have very low vapor pressures and good solubility / dissolution properties. Various different ionic liquids can be used.

As described above, one of the advantages of the cell of the present invention is that it produces base 150 in catholyte compartment 204. As mentioned above, this base 150 can then be used as part of the reaction 14 to produce the sodium salt of sulfonic acid. Na ⁺ ions for this reaction come from the anolyte 228 through the membrane. Alternatively, embodiments can be made such that the sulfonic acid can react in the catholyte compartment 208 to immediately form an alkali metal salt. In other words, the conversion reaction 14 takes place in the cell itself to produce sodium sulfonate salt, which is then taken from the catholyte compartment 204 into the anolyte compartment 208 (eg, via a conduit). Thus, this process causes the sulfonic acid to be converted into an alkali metal salt in situ (eg in a cell). This process will be a one step process (eg, the cell is simply operated) rather than a two step process (conversion reaction and desulfurization in the cell).

It should be noted that the embodiments described above operate to produce SO _x gas as a result of the desulfurization reaction. By methods known in the art, such SO _x gas can be converted to SO ₃ gas. This SO ₃ gas can then react with water (in a known manner) to form sulfuric acid (H ₂ SO ₄ ), a valuable and useful chemical that can be used, sold, and the like.

SO ₃ + H ₂ O → H ₂ SO ₄

Additional embodiments may be designed such that R-SO ₃ -Na reacts in water in the following manner:

^{_{H 2 O → 2H + + ½O}} 2 + 2e -

R-SO ₃ -Na + H ⁺ → R-SO ₃ -H + Na ⁺

+ 2SO_x + 2e^- +2R-SO ₃ -H → 2R

+ 2SO _x + 2e ^- +

In other words, the embodiments described above produce an acid (R-SO ₃ -H) by first having a reaction of water, and then this acid product undergoes desulfurization. One skilled in the art will recognize how to adjust various conditions to desuloxylate acid (R-SO ₃ -H) or sodium hydrochloric acid (R-SO ₃ -Na) as desired.

In one embodiment, the anolyte comprises a G-type solvent, an H-type solvent, and / or a mixture thereof. G-type solvents are dihydroxyl compounds. In one embodiment the G-type compound comprises two hydroxyl groups at adjacent positions. H-type solvents are hydrocarbon compounds or solvents capable of dissolving hydrocarbons. For example, H-type solvents include hydrocarbons, chlorinated hydrocarbons, alcohols, ketones, monoalcohols, and petroleum fractions such as hexane, gasoline, kerosene, dodecane, tetrolene and the like. The H-type solvent can also be the product of the desulfonoxylation process recycled as a fraction of the hydrocarbon product. This will eliminate the need to obtain additional solvents and thus improve the overall economics of the process.

As a further disclosure, the G-type solvent solvates the -SO ₃ -Na group of the alkali metal salt of the acid by hydrogen bonding having two different oxygen atoms, but the hydrocarbon end of the alkali metal salt of sulfonic acid is a H-type solvent. Solvated by For a given G-type solvent, solvent performance is increased by increasing the hydrocarbon in the H-type solvent.

The following table shows some non-limiting examples of G-type and H-type solvents:

Although there are certain advantages of using separate cells, it should be noted that embodiments may be configured such that the cells are not separated. Such cells can be summarized as follows:

Pt || R-SO ₃ -Na + NaOH + H ₂ O || Pt

The Pt electrode may be replaced with another electrode as outlined herein. In addition, the base NaOH can be replaced with other bases (such as sodium methylate, or other bases) as desired. Likewise, the solvent, water, may be replaced with another solvent as desired. In this embodiment, the anode reaction is a desulphoxylation reaction forming SO _x and RR. The cathode reaction is a reduction that forms hydrogen gas (H is provided by water). In other embodiments, CH ₃ -SO ₃ -Na (or other R groups) can optionally be used. Similarly, acid forms of sodium salts can be used, provided there is also a base to convert it to sodium salts.

Many examples provided herein include using monosulfonic acid, but disulfonic or polysulfonic acid may also be used. However, when using disulfonic or polysulfonic acid, steps may be taken to avoid or reduce polymerization (in some embodiments). This polymerization reaction is summarized by the following disulfonic acid, but similar reactions are possible for polysulfonic acid:

                        (Desulfurization)

R-R

Na-SO ₃ -RR-SO ₃ -Na →

RR

(Sodium salt of disulfonic acid)

R-R

라디칼은 이어서 중합되도록 줄세워질 수 있다:Since these hydrocarbon radicals have reactive sites at each end, these

RR

The radicals can then be decreased to polymerize:

R-R

+

R-R

R-R

+

R-R

........

RR

+

RR

RR

+

RR

....

)을 형성하는 것, H

라디칼을 형성하여 R기의 길이를 줄이는 것을 포함할 수 있다. 마찬가지로, 혼합 용매 시스템을 사용하는 것과 연관된 기법이 또한 이러한 중합을 감소시킬 수 있다. 예를 들어, 애노드액에서 극성 용매와 배합된 비극성 용매를 사용함으로써, 형성된 탄화수소가 비극성 용매로 빠르게 당겨져 이것이 중합되는 것이 방지될 것이다.In some embodiments, such polymerization may be desired. In other embodiments, no polymerization is desired. Thus, techniques can be used to reduce the likelihood of polymerization (eg, “block” polymerization). This is, for example, via methyl acetate (CH ₃

Forming), H

Forming radicals to reduce the length of the R groups. Likewise, techniques associated with using mixed solvent systems can also reduce this polymerization. For example, by using a nonpolar solvent combined with a polar solvent in the anolyte, the hydrocarbon formed will be quickly pulled into the nonpolar solvent to prevent it from polymerizing.

Various examples of the techniques described herein can be readily used and performed. Some of these examples include:

                            (Hydrocarbon (hexane))

_{2C 3 H 7 SO 3 -Na →} C 6 H 14 + 2SO x + 2e - + 2Na +

                            (Wax-like hydrocarbon)

_{2C 18 H 34 SO 3 -Na →} RR + 2SO x + 2e - + 2Na +

                            (Hydrocarbons in organic layer)

_{Na-SO 3 - (CH 3} ) 3 -SO 3 -Na → RR + 2SO x + 2e - + 2Na +

C ₁₇ H ₃₃ SO ₃ -Na + C ₁₇ H ₃₁ SO ₃ -Na + CH ₃ SO ₃ -Na

¡Æ a mixture of products comprising C ₁₇ and C ₁₈ hydrocarbons

The present invention can be embodied in other specific forms without departing from its structure, method, or other essential features as broadly described herein and claimed below. The described embodiments are to be considered in all respects only as illustrative and not restrictive. Accordingly, the scope of the invention is indicated by the appended claims rather than by the foregoing disclosure. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (9)

Obtaining a sodium salt of alkyl sulfonic acid;
Preparing an anolyte for use in an electrolytic cell comprising an anolyte compartment, a catholyte compartment, and a NaSICON membrane separating the anolyte compartment from the catholyte compartment, wherein the anolyte is contained within the anolyte compartment and the catholyte is Contained within the catholyte compartment, wherein the anolyte comprises a first solvent or solvent mixture and a predetermined amount of sodium salt of alkyl sulfonic acid; And
Electrolyzing the anolyte in the cell to desulfonate the sodium salt of alkyl sulfonic acid, convert the sodium salt of alkyl sulfonic acid to one or more alkyl radicals, and the alkyl radicals react to form a coupled radical product
A method for producing a coupled radical product comprising a. The method of claim 1 wherein the sodium salt of alkyl sulfonic acid is derived from biomass. The method of claim 2, wherein the coupled radical product comprises a hydrocarbon. The process of claim 1 wherein the sodium salt of alkyl sulfonic acid comprises CH ₃ -SO ₃ -Na. 5. The method of claim 4, by electrolysis of the anolyte in the cell by a sulfonated sodium salt of an alkyl sulfonic acid de-solidifying step talsul the CH ₃ -SO ₃ -Na least one of CH ₃ -SO ₃ -Na alkyl radical Wherein the alkyl radicals react to form coupled radical products. The method of claim 5, wherein the alkyl radical comprises a methyl radical. The method of claim 1, wherein the anolyte further comprises H-SO ₃ -Na. Claim 7, the electrolysis stage the anolyte is sikimyeo switching the H-SO ₃ -Na by talsul sulfonated H-SO ₃ -Na by the one or more hydrogen radicals which, the radicals coupled to the hydrogen radical reaction product in It further comprises forming a. The method of claim 1, further comprising feeding hydrogen gas to the anolyte compartment and photolysing the hydrogen gas to form one or more hydrogen radicals.

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