WO2013134076A1 - Chain modification of gaseous methane using aqueous electrochemical activation at a three-phase interface - Google Patents

Abstract

In a first aspect, a method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte, a powered electrode including a catalyst, and a gaseous methane feedstock in a reaction area; and activating the methane in an aqueous electrochemical reaction to generate methyl radicals at the powered electrode and yield a long chained hydrocarbon. In a second aspect, method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte with a catalyst in a reaction area; introducing a gaseous methane feedstock directly into the reaction area under pressure; and reacting the aqueous electrolyte, the catalyst, and the gaseous methane feedstock at temperatures in the range of -10 C to 1000 C and at pressures in the range of.1 ATM to 100 ATM.

Description

CHAIN MODIFICATION OF GASEOUS METHA E USING AQUEOUS ELECTROCHEMICAL ACTIVATION A A THREE-PHASE

INTERFACE

1_.0001] The priority of U.S. Application Serial No. 61/608,583, entitled, "An

Electrochemical Process for Direct one step conversion of methane to Ethylene on a Three Phase Gas, Liquid, Solid Interface", and filed March 8, 2012. in the name of the inventor Ed Chen is hereby claimed pursuant to 35 U.S.C. § 1 19(e). This application is commonly assigned herewitii and is also hereby incorporated for all purposes as if set forth verbatim herein.

(0002] The priority of U. S. Application Serial No, 61/71.3,487, entitled, "A Process for Electrochemical Fischer Trospch", filed October 13, 2012, in. the name of the inventor Ed

Chen is hereby claimed pursuant to 35 U.S.C. § 1 19(e), This application is commonly assigned herewith and is aiso hereby incorporated for all purposes as if set .forth verbatim herein,

CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] Not applicable.

STATEMEN REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

|ΘΘ04] Not applicable,

BACKGROUND

(0005) This section of this document introduces information about and/or from the art that may provide context for or be related to the subject matter described herein and/or claimed below. It provides background information to facilitate a better understanding of the various aspects of the claimed subject, matter. This is therefore a discussion of "related" art. That such an is related in no way implies (hat it is also "prior" art. The related art may or

l may not be prior art. The discussion in this section of this document is to be read i» ihis light, arid not as admissions of prior art.

[0006} Prior art commercial processes for converting methane to other hydrocarbons, for example; sometimes include a partial oxidation process that is highly energy intensive and operates under high pressures and temperatures. The actual syngas cleanup step occurs after the syngas has been cooled. Tar, oils, phenols, ammonia and water co-products are condensed from the gas stream and purified and sent on. The gas moves to a cleaning area where further impurities are removed and finally carbon dioxide is removed. The syngas is then passed under high pressures (30 bars) with some more recent "low pressure" processes operating at slightly above 10 bars at approximately 200-400 degrees Celsius to form hydrocarbons, oxygenates, and other carbon and hydrogen based species. The high pressure reactions utilize iron or nickel as their catalysts, while low pressure synthesis often uses cobalt. These processes use solid electrolytes rather than aqueous electrolytes.

|0067 Another problem with methane activation is catalyst deactivation and regeneration, temperature control, and high pressures. Catalysts are often deactivated when the surface is covered by waxes and coke {carbon black). The high temperatures also produce undesirable products such as wax which, tends to deactivate the catalyst. Finally, water is also a byproduct of this reaction.

(ΘΘ08) The art therefore possesses a number of methane activation processes that, e ven if satisfactory in some respects, have several drawbacks. The art furthermore is always receptive to improvements or alternative means, methods and configurations. Therefore the art will well receive the technique described herein.

SUMMARY

[0009] In a. first aspect, a method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte, a powered electrode including a catalyst, and a gaseous methane feedstock in a reaction area: and activating the methane in an aqueous electrochemical reaction to generate methyl radicals at the powered electrode and yield a long chained hydrocarbon. (ΘΘΙ ) to a second aspect method for chain modification of ^'hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte with a catalyst in a reaction area; introducing a gaseous methane feedstock directly into the reaction area trader pressure; and reacting the aqueous electrolyte, the catalyst, and the gaseous methane feedstock at temperatures in the range of -.10 C to 900 C and at pressures in the range of J ATM to 100 ATM.

[Θ011] The above presents a simplified summary of the presently disclosed subject matter in order to provide a basic -understanding of some aspects thereof. The summary is not an exhaustive overview, nor is it intended to identify key or critical elements to delineate the scope of the subject matter claimed below, its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description set forth below,

BRIEF DESCRIPTION OF THE DRAWINGS

(ΘΘ12) The claimed subject matter may be better understood by reference to the following description taken in conjunction with the accompanying drawings, in which like reference numerals identify like elements, and in which; fowl 3] Figure I depicts one particular embodiment of an electrolytic cell in accordance with some aspect s of the presently disclosed technique.

[^' 14J Figure 2 graphically illustrates one particular embodiment of a process in accordance with other aspects of the presently disclosed technique,

I_.0015J Figure 3A-Figure 3B depict a copper mesh reaction electrode as may be used in some embodiments.

|0016] Figure 4A-Figure 4B depict a gas diffusion electrode as may be used in some embodiments.

|0017] Figure 5A-Figure~5B depicts a gas diffusion electrode as may be used in some embodiments. (0018] Figure 6 depicts a portion of an embodiment in which the electrodes are electrically short circuited.

(ΘΘ19) While the invention is susceptible to various modifications and alternative forms, the drawings illustrate specific embodiments herein described in detail by way of example. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particiilar forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives failing within the spirit and scope of the invention as defined by the appended claims.

DETAILED DESCRIPTION

S0020J Illustrative embodiments of the subject matter, claimed below will now be disclosed. In the interest of clarity, not all features of an actual implementation are described in this specification. It will be appreciated that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this d isclosure .

| 21 The presently disclosed technique is a process for converting gaseous hydrocarbons to longer chained liquid hydrocarbons, longer chained gaseous hydrocarbons, branehed-chain liquid hydrocarbons, branched-cham gaseous hydrocarbons, as well as chained and branched-chain organic compounds, in general the method is for chain modification of hydrocarbons and organic compounds, including chain lengthening. This process more particularly uses aqueous electrolytes to act as a reducing atmosphere and hydrogen and oxygen source for hydrocarbon gases. The process in the disclosed technique is Aqueous Electrochemical Activation of Methane (AEAM) on three phase interface of gas- liquid-solid electrode, AEAM directly turns natural gas and other sources of methane (CH₄) into C;;+ hydrocarbons and other organic compounds. One exemplary product is ethylene ((.¾¾} and alcohols such as methanol, ethanol, propanol, andVo butanol. (Θ022] The reaction of hydrocarbon gases may be successfully achieved with an aqueous elecixoc!ieniical solution serving as a liquid ion sQuree along with the supply for hydrogen or singlet oxygen being provided by the aqueous electrolyte through acids and/or bases of the aqueous electrolyte. The gaseous hydrocarbon is balanced with the aqueous electrolyte at a solid phase thin film catalyst which is connected to the reaction electrode of an electrolytic cell The reaction may also be adjusted with different pHs or any kind of additive ia the electrolytic solution , ft⁾t⁾23| The reaction works by utilizing a 3 phase interlace which defines a reaction area. A catalyst, a liquid, and a gas a positioned in the same location and an electric potential is appiied to make electrons availabie to the reaction site. When methane is used as the gas it is possible to create methane radicals which then join with other molecules or parts of molecules or themselves to create longer chained hydrocarbons and/or organic molecules. The reaction site can also cause branched chain production by reacting with a newly created molecule and building on that or continuous chain building. Thus from the simple molecule of methane, CH4, chains of molecules can be built. Existing chained molecules can be lengthened, and existing chained molecules can be branched, A simple example is methane (C¾), can be converted to methanol, C¾(OH). Different voltages create different reaction product distributions or facilitate different reaction, types.

|ΘΘ24] This aqueous electrochemical reaction includes a reaction that proceeds at room temperature and pressure, although higher temperatures and pressures may be used, in general, temperatures ma range from - IOC to 240C, or from -I OC to iOOOC, and pressures may range from , 1 ATM to 10 ATM, or from J ATM to 100 ATM. The process generates reactive methyl radicals through, the reaction on the reaction electrodes. On the reaction electrode, the production of methyl radicals occurs.

{Θ025) in at least some embodiments, the reactants need no pre-treatment. Typically methanol from methane must first go through steam reforming to produce syngas (CO and Hj). The presently disclosed technique can perform the production of methanol without reforming to produce syngas. Similarly, as described further below, the gaseous methane feedstock may be introduced "directly'⁵ into the chamber of an electrochemical ceil. |ΘΘ26} In general, the method introduces a liquid ion source into a first chamber into contact: with a catalyst supporting reaction electrode while counter electrode is disposed in die liquid ion source. The reaction electrode is powered. A gaseous methane feedstock is then introduced directly into a second chamber under enough pressure to overcome the gravitational pressure of the column of electrolyte, which depends on the height of the water, to induce a reaction among the liquid ion source, the catalyst, and the gaseous methane feedstock when the electrodes are powered.

{0027] in the embodiments illustrated herein, the technique employs an electrochemical, cell such as the one illustrated in Figure 1 . The eiectrochemica! cell 100 generally comprises a reactor 105 in one chamber 1 10 of which are positioned two electrodes 1 J 5, I 16, a cathode and an anode, separated by a liquid ion source, i.e. , an. electrolyte 120. Those in the art will appreciate thai the identity of the electrodes 1 15, 1 16 as cathode and. anode is a matter of polarity that can vary by implementation, in the illustrated embodiment, the counter electrode 1 15 is the anode and the reaction, electrode 116 is the cathode. The reaction electrode 1 .16 shall be referred to as the "reaction" electrode and the counter electrode 1 15 the "counter" electrode for reasons discussed further below.

{0028] There is also a second, chamber 125 into which a gaseous methane feedstock 130 is introduced as described below. The two chambers are joined by apertures 1.35 through the wall .1 0 separating the two chambers 1 1 , 125. The reactor 1.05 may be constructed in conventional fashion except a noted herein. For example, materials selection, fabrication techniques, and assembly processes in light of the operational parameters disclosed herein will be readily ascertainable to those skilled in the art.

{0029] Catalysts will be implementation specific depending, at least in part, on the implementation, of the reaction, electrode 1 .16. Depending on the embodiment, suitable catalysts may include, but are not. limited to, nickel, copper, iron, tin, zinc, ruthenium, palladium, rhenium, or any of the other transition or lanthanide metals, or a noble metal such as platinum, palladium, gold, or silver. They may also include products thereof, including for example cuprous chloride or cuprous oxide, other compounds of catalytic metals, as well as organometalic compounds. Exemplary organometallic compounds include, but are not limited to, tetracarbonyl nickel, liihiumdiphenyicuprate, pentamesitylpentacopper, and etharatedimer. (ΘΘ3 ) The electrolyte 120 will also be implementation specific depending, at least in part, on the implementation of the reaction electrode 116. Exemplary liquid ionic substances include, but are not limited to, Alkali or alkaline Earth, salts, such as halides, sulfates, sulfites, carbonates, nitrates, or nitrites. The electrolyte 120 may therefore be, depending upon the embodiment, .magnesium sulfate <MgS), sodium chloride (NaCI), sulfuric acid (H_: SO,j), potassium chloride (KG), hydrogen chloride (HO), hydrogen, bromide (HBr), hydrogen fluoride (HE), potassium chloride (KG), potassium bromide (KBr), and potassium iodide (KI), or any other suitable electrolyte and acid or base known to the art,

|ΘΘ31) The pH of the electrolyte 120 may range from 0 to 3 and concentrations of between 0.1 and 3M may be used. Some embodiments may use water to control pH and concentration, and such water may be industrial grade water, brine, sea water, or even tap water. The liquid ion source, or electrolyte 120, may comprise essentially any liquid ionic substance. In some embodiments, the electrolyte 120 is a halide to benefit catalyst lifetime.

|0032 In addition to the reactor S S, the electrochemical ceil 100 includes a gas source 145 and a power source 150, and an electrolyte source 163, The gas source 145 provides the gaseous methane feedstock 130 while the power source .150 is powering the electrodes 1 15, 1 16 under enough pressure to balance and overcome the gravitational pressure of the column of electrolyte, which depends on the height of the water, sufficien t io maintain t he reaction at the three phase interface 155. The three phase interface 155 defines a reaction area. In some embodiments, this pressure might be, for example, 10000 pascals, or from 0.1 ATM to 10 ATM, or from 0.1 ATM to 100 ATM. The electrolyte source 1 3 provides adequate levels of the electrolyte 120 to ensure proper operations. The three phases at the interface 155 are the liquid electrolyte 120, the solid catalyst of the reaction electrode 116, and the gaseous methane feedstock 130. The product 1 0 is collected in a vessel 165 of some kind in any suitable maimer known to the art. In some embodiments, the products 160 may be forwarded to yet other processes either after collection or without ever being collected at ail. In these embodiments, the products 160 may be streamed directly to downstream processes using techniques well known in the art.

J 0033| The embodiment of Figure 1 includes only a single reactor 105. However, in alternative embodiments, multiple units of these may be arranged for greater efficiencies. In a larger single chamber, pressure would more likely have to be adjusted with electrolyte level rather than changes in gaseous methane feedstock 130 pressure in the chamber 125.

[ΘΘ34) Those in the art will appreciate that some implementation specific details are omitted from Figure 1. For example, various instnirnenta on such as flow regulators, mass regulators, a pH regulator, and sensors for temperatures and pressures are not shown but will typical iy be found in most embodiments. Such instrutrtentation is used in. conventional fashion to achieve, monitor, and maintain various operational parameters of the process. Exemplary operational parameters include, but are not limited to, pressures, temperatures, pH, and the like that will become apparent to those skilled in the art. However, this type of detaii is omitted from the present disclosure because it is routine and conventional so as not to obscure the subject matter claimed below.

[ΘΘ35] The reaction is conceptually illustrated in FIG, 2. In this embodiment, the feedstock 130' is natural gas and the electrolyte 120^* is Sodium Chloride. Reactive hydrogen ions (IT) are fed to the natural gas stream 130' through the electrolyte 120" with an applied cathode potential. The molecules may also in turn react with water on the interface to form alcohols, oxygenates, and ketones. .Exemplar}-' alcohols include but are not limited to methanol, ethanol, propanol bntanoS. in one example of this reaction, the reaction, occurs at room temperature and with an applied cathode potential of 0.0 I V versus SHE to 3.99V versus SHE. The voltage level can. be used to control the resulting product. A voltage of 0. IV may result in a methanol product whereas a 0.5V voltage may result, in butanol.

[ΘΘ36] Still further, very little catalyst deactivation occurs in some embodiments because the catalyst is protected by a layer of chloride, which also acts as an absorbent for the reaciants, and the electrolyte is saturated with. CI^* preventing typical catalyst poisons from bonding with the catalyst and deactivating it, as this would force the release of a CT ion into the liquid, hi addition, this process further prevents the deposition of impurities in water, which could deactivate the catalyst. These aspects will be explored further below.

ΙΘΘ37] Returning now to Figure 1 , additional attention will now be directed to the electrochemical cell. 100. As noted above, the reactor 105 can be fabricated from conventional materials using conventional, fabrication techniques. Notably, the presently disclosed technique operates at room temperatures and pressures whereas conventional processes are performed at temperatures and pressures much higher. Design considerations pertaining to temperature and pressure therefore can be relaxed relative to conventional ^•practice. However, conventional reactor designs may nevertheless be used in some embodiments.

[ΌΘ38] The presently disclosed technique admits variation in the implementation of the electrode at which the reaction occurs, hereafter referred to as the "reaction electrode". The other electrode will be referred to as the "counter electrode". In the embodiment of Figure 1, the reaction electrode 1 16 is the reaction electrode and the counter electrode 115 is the counter electrode. As noted above, those in the art wiii appreciate that the identity of the electrodes 115, 116 as cathode and anode is a matter of polarity thai can vary by implementation,

|ΘΘ39| One such modification is that the copper mesh used in the illustrated embodiment is an 80 mesh rather than a 40 mesh. This mesh may be plated with high current densities to produce fractal foam structures with high surface areas which may be utilized as catalysts in this reaction,

|004 More particularly, the catalyst 305 is supported on a copper mesh 310 embedded in an ion exchange resin 300 as shown in Figure 3A. The catalyst 305 can be a plated catalyst or powdered catalyst, The metal catalyst 305 is a catalyst capable of reducing methane to a lon chained hydrocarbon or organs c compo und and alcohol. Exemplary metals include, but are not limited to. metals such as copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or Santhanide metals, in one embodiment, the metal catalyst is silver, copper, copper chloride or copper oxide. Ion exchange resins are well known in the art and any suitable ion exchange resin known to the art may be used. In one particular embodiment, the ion exchange resin is ATION 1 1 7 by Dupont

(0041) The copper wire mesh 31.0 can be used to structure the catalyst 305 within the resin 300. The assembly 315 containing the catalyst 305 can be deposited onto or otherwise structurally associated with a hydroph.ilie paper 320, as shown in Figure 3B, Electrical leads (not shown) can then, be attached to the copper wire mesh 310 hi conventional fashion. The reaction electrode 320 is but one implementation of the reaction electrode 1 16 i» Figure 1. Alternative implementations will he discitssed below.

[ΘΘ42) The counter electrode 1 1 5, the reaction electrode 1 16 is disposed within a reactor 105 so that, in use. it is submerged in the electrolyte 120 and the catalyst 305 forms one part of the three-phase inter ace 155. When electricity is applied to electrodes 1 15, 1 16, electrochemical reduction discussed above Cakes place to produce fiydrocarboiis and organic chemicals. The reaction electrode 320 receives the electrical power and catalyzes a reaction between the hydrogen in the electrolyte 120 and the gaseous methane feedstock 130.

|0i)43) As mentioned above, the copper mesh 310 in the illustrated embodiment is an mesh in the range of 1 - 400 mesh.

(ΘΘ44) in a second embodiment shown in Figure 4A~Fignre 4B, a gas diffusion electrode 400 comprises a hydrophobic layer 405 Chat is porous to methane but impermeable or nearly impermeable to aqueous electrolytes. In one embodiment of the electrode 400, a imil thick advcarb carbon paper 41 treated with TEFLONf) (i.e., polvtetraflooroetliylene) dispersion (not separately shown) is coated with activated carbon 415 with copper 420 deposited in the pores of the activated carbon 415. The copper 420 may be deposited through a wet impregnation method, electrolytic reduction, or other means of redaction of copper, silver other transition metals into the porous carbon material.

(ΘΘ45) This material is then mixed with a hydrophilic binding agent (not shown), such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), or Nafton. An ink is made from the ^•mixture of impregnated graphite, binding agent, and a!coho! or other organic solvent. The ink i painted onto the hydrophobic layer 405 and then bonded through any means, such as atmospheric drying, heat press, or other means of application of heat,

[0046] The copper 420 impregnated into the ion. electrode 400 is then made into a cuprous haiide through any suitable procedure. One embodiment of the procedure to make the cuprous haiide is to submerge the electrode in a solution of hydrochloric acid and cupric chloride, heat to i 00^oC for 2 hours. Another embodiment submerges the impregnated electrode 400 in 3 M KBr or 3 M l and ran a 4 V pulse of electricit to the electrode 400 in order to form a thin film of cuprous haiide 425, shown in cross-section. Figure 48, in the electrode 400.

[ΘΘ47) In another embodiment, the copper panicles in the electrode are first plated with silver by eiectroless plating or another method, creating a thin film of silver over the copper. Copper may then be plated onto the silver and transformed into a haiide through procedure previously described. In another embodiment, silver particles are deposited into the hydrophilic layer, coated with copper eiectrolytkaily, and then the same procedure for the conversion of the copper layer to a copper haiide layer is conducted.

(0048] in another embodiment, the gas diffusion electrode uses nanoparticles reduced from a solution of Cupric Chloride with an excess of ascorbic acid and 10 grams of carbon graphite. The amalgam was heated to KK C for eight hours. It is then mixed with equal amounts in weight of a hydrophilic binder,

|0049| In another embodiment, a high mesh copper of 200 mesh is allowed to form cuprous chloride in a solution of cupric chloride and hydrochloric acid. This layer of haiide on the surface of the catalyst material allows for catalyst regeneration. This accounts for the abnormally high lifetime of the three phase reaction. The result is then treated in a 1M solution of Cupric Chloride heated to !fK C.

|9050| The electrode 400 therefore includes a covering or coating 425 of cuprous chloride to prevent "poisoning" or fouling of the electrode 400 during operation. The electrodes in this embodiment must be copper so that DO other metals foul the reaction by creating intermediate products which ruin the efficacy of the surface of the copper. Some embodiments also treat the copper with a high surface area powder by electroplating, which will allow for the generation of greater microturbulence, thereby creating more contact and release between the three phase reaction surface. Furthermore, contrary to conventional practice, rather than separate the cathode and anode, the cathode and anode are allowed to remain in the same electrolyte in this embodiment. (The electrolyte is filtered through a pump not shown.) The electrolyte is therefore contacted directly to the gas diffusion electrode 400 rather than through the intercession of a polymer exchange membrane. (0051) Catalysis in this particular embodiment may mcliwfe copper, silver, gold, iron, tin, zinc, ruthenium, platinum., palladium, rheniam, or any of the other transition, or ianthanide metals. In addition, the catalysts may be formed into a metal foam or alternatively it may be deposited through electroiess or electrolytic deposition onto a porous support with a hydrophobic and hydrophiiie layer,

1_.0052] In electrochemical systems, it is often difficult to make a good electrical contact ^'between gas diffmion medium and the current collector. The need for a solid polymer electrolyte to some degree is the first, order solution to the problem, at hand. Carbon paper has a significant resistance across of up to 2Ω that impedes the effective application of gas diffusion electrodes to electrochemical applications. By pressing a wire made from a metal such as nickel, copper, iron, steel, or a noble metal such as platimim, gold, or silver directly into the carbon paper, gas diffusion media may be extended, into applications such as hydrocarbon processing and fuel ceil applications. The production of such papers is relatively straight forward though requires a few enabling aspects for it to work. A small amount of adhesive material is mixed in with activated carbon particles with a high internal porosity, for example a BET of 50m"^:/gram, This serves as the binder which may be applied between existing conductive gas diffusion medium such as a carbon paper, a toray paper, or other conductive gas diffusion, electrodes. Figure 5A. shows one embodiment 500 of the pressed wire mesh 505 in paper 51 . Th wire 505 is first submerged in a slurry of activated carbon and adhesive (not shown), which is mixed in a ratio by weight of 1 : 1 that provides for full conductivity of the thin binding layer. This layer titan presses the wire mesh 505 into the surface of the carbon paper 510, providing uniform conductivity.

(6053] The binder slurry both binds the metal of the wire mesh 505 to the surface of the conductive paper 510, while providing conductivity itself, and holds the wire mesh 505 firm against the conductive paper 5 1 , which overcomes the contact resistance. The surface of the wire mesh 505 is cleaned with a solvent before being applied to the carbon paper 510 to remove any oils from the surface of the contact region, as this may cause unwanted resistance to build up. The wire should be thick enough that the wire mesh 505 forms a slight indentation into the paper 510 as to provide maximum contact area.

(0054] in another embodiment 500', the production of the paper 510 is conducted and deposited directl onto the wire mesh 505, the result of which is shown in Figure 5B. Conductive carbon paper is often made by pyro^'lyxing carbon containing compounds. Thus, by using a conducti ve -materia! with high corrosion resistance in a low oxygen environment, it would be possible to convert carbon containing material directly onto the wire mesh conductor, providing for a single step process to deposit. The process may otherwise be in accordance wit conventional practice for producing and pyrolyzing carbon based materials to form carbon paper such, as polyanalrne based carbon .fiber paper.

S¾055| The technique illustrated in Figure SA-Figure SB can improve the conductivity of the carbon papers 510 and significantly reduce the resistance thereof by up to an ohm or more. In the embodiment 500 of Figure 5 A, more particularly, a carbon paper 510 has a 1- 400 mesh pure copper mesh 505 embedded halfway into the carbon paper 510. In the embodiment 500^* of Figure 5B, the carbon paper 510 has the copper wire mesh 505 embedded in therein such that no metal is showing. Spacing between the wires of the mes 505 can be from 1mm to 1cm. The carbon paper 510 should, generally be as thin as possible while still being sturdy enough to withstand handling in both embodiments.

10056] In one particular embodiment, the electrodes are electrically short circuited within the electrolyte while maintaining a three phase interface. Figure 6 depicts a portion 600 of an embodiment in which the electrodes are electrically short circuited. In this drawing, only a single electrode 605 is shown but the potential is electric potential is drawn across the electrode 605. The companion electrode (not shown) is similarly electrically short circuited.

[ΘΘ57) So, turning now to the process again and referring to Figure 1 , a methane gas or gaseous mixture including methane 130 is introduced into the second chamber 125 of the reactor 105 under pressure. The exemplary embodiments discussed below all include the following design characteristics: (1 ) a three-phase catalytic interface 155 for solid catalyst, gaseous methane feedstock 130, and liquid ion source (e.g.. a liquid electrolyte) 120, (2) a cathode 1 .16 and anode 115 in the same, filtered electrolyte 120, and (3) an electrolyte 120 contacted directly to the reaction electrode, which is the cathode 1 1 .

[0058j The method of operation generally comprises introducing the electrolyte 120 into the .first chamber 110 into direct contact with the powered electrode surfaces 115 and .1 16. The gaseous methane feedstock 130 is then introduced, .into the second, chamber .125 under enough pressure to over come the gravitational pressure of the column of electrolyte, which depends cm the height of the water, to induce the reaction. During the reaction, the electrolyte 20 is filtered, the gaseous methane feedstock 1 30 is maintained at a selected pressure to ensure its presence at the three phase interface 155, and the product 165 is collected. Within this general context, the following examples are implemented..

|^'0059] Above the second chamber 125, but attached to it, is an area for the introduction of a cathode reaction electrode 1 16 where the three-phase interlace 155 will form. Catalysts supported by the reaction electrode .1 16 include copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or lanthani.de metals. In addition, the catalysts may be formed into a metal foam or alternatively it may be deposited through eleetroiess or eiecirytic deposition onto a porous support with a hydrophobic and hydrophilic layer as previously described above. The electrolyte 120 may comprise, for example, potassium chloride (KCI), potassium bromide (KBr), potassium iodide (SO), or any other suitable electrolyte known to the art, j 6 j Tbss particular embodiment implements the reaction electrode 1 16 as the gas diffusion electrode described above with the cuprous halide coating. Alternative embodiments may use another cuprous halide coaling the surface of the metal. Cuprous Oxide, Cupric Oxide, and other varying valence states of copper will also work in. the reaction.

[ΘΘ61] By maintaining a three phase interface between gaseous methane feedstock 130 and the electrolyte 120, the methane will form organic chemicals and form a neatly complete conversion when there is continuous contact, to the gaseous methane feedstock 130 on the three phase interface 155 between the liquid electrolyte 120, the solid catalyst, and the gaseous methane feedstock 130 , Another means of maintaining the three phase in (erf ace is to use a separation membrane which selectively allows hydrogen and water to penetrate. One such membrane is Nafion. Another means is to use a fuel cell type set op but instead of generating a current a current is introduced to generate a chemical.

|ΘΘ62| . Other reaction mechanism also produces organic compounds such as ethers, epoxides, and alcohols, among other compounds. |ΘΘ63| The electrolyte 120 should be relatively concentrated at .1 M-3M and should be a hatide electrolytes discussed above to increase catalyst lifetime. The higher the surface area between the reaction electrode U 6 and the gaseous chambe 125 on one side and the liquid electrolyte 120 on the other side, the higher the conversion rates. Operating pressures could be ranged from only 10000 pascals, or from J atra to 100 ami, or from .1 ami to 100 aim, though Standard Temperature and Pressures (STP) were sufficient for ihe reaction.

[8064| in one embodiment of the gas diffusion electrode (GD.E t an antioxidant layer of ascorbic acid is mixed with the ODE high porosity carbon. The high porosity carbon includes nanotubes, fiil!erines, and other specialized formations of carbon as described above. The high porosity carbon is impregnated through reduction of cupric chloride, or other form of carbon. It is then made into a ha!ide by treatment with a chloride solution under the proper p^'H and temperature of EMF conditions. It also includes a reaction in the solid polymer phase. A paste is made from the impregnated carbon, ascorbic acid, and a hydrophilic binding agent.. This paste is painted onto a hydrophobic layer. Some embodiments include antioxidants in the layer as described above.

[t⁾t | Note that not ail embodiments will manifest all these characteristics and, to the extent they do, they will not necessarily manifest them to the same extent. Thus, some embodiments may omit one or more of these characteristics entirely. Furthermore, some embodiments may exhibit other characteristics in addition to, or in lieu. of. those described herein.

|ΘΘ66] The phrase "^"capable of as used herein is a recognition of the fact that some functions described for the various parts of the disclosed apparatus are performed only when the apparatus is powered and/or in operation. Those in the art having the benefit of this disclosure will appreciate that the embodiments illustrated herein include a number of electronic or electro-mechanical parts that, to operate, require electrical power. Even when provided with power, sorae functions described herein only occur when in operation. Thus, at times, sorae embodiments of the apparatus of the invention are "capable of ^' performing the recited functions even when they are not actually performing them— i.e.. when there is no power or when they are powered but not in operation. |ΘΘ67| The following patent, applications, and publications are hereby incorporated by reference for all purposes as if set forth verbatim herein:

|ΘΘ68] U.S. Application Serial No. 61/608,583, entitled, "An Electrochemical Process for Direct one step conversion of methane to Ethylene on a Three Phase Gas, Liquid, Solid interface," and filed March 8, 2012, in the name of the inventor Ed Chen and commonly assigned herewith.

1_.006 U.S. Application Serial No. 61/713,487, entitled, "A Process for Electrochemical Fischer Trospch," filed October 13, 2012, in the name of the inventor Ed Chen and commonly assigned herewith.

[0070] To the extent that any patent, patent application, or other reference incorporated herein by reference conflicts with the present disclosure set forth herein, the present disclosure controls.

(ΘΘ71] This concludes the detailed description. The particular embodiments disclosed above are illustrative only, as the invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular embodiments disclosed above may be altered or modified and ail such variations are considered within the scope and spirit of the invention. Accordingly, the protection sought herein is as set forth in the claims below.

Claims

WHAT IS CLAIMED:

1 , A method tor chain modification of hydrocarbons and organic compounds comprising: contacting an aqueous electrolyte, a. powered electrode including, a catalyst, and a gaseous methane feedstock in a reaction area; and

activating the methane in an aqueous electrochemical reaction to generate methyl radicals at the powered electrode to yield a product,

2. The method of claim 1 , wherein gaseous methane feedstock is a methane stream or natural gas.

3. The method of claim I , wherein the product includes long chained hydrocarbons.

4. The method of claim 3, wherein the product includes ethylene, butane, or octane.

5. The method of claim 3, wherein the product further includes methanol and higher alcohols.

6. The method of claim .1 , wherein the product includes alcohols.

7. The method of claim 6, wherein the alcohols include methanol, ethano!, propanoL. hutano!.

8. The method of claim 1 , wherein the catalyst comprises a metal, an inorganic salt of a metal, or an organ ora eta Hie compound.

9. The method of claim 6, wherein the aqueous electrolyte includes Alkali or Alkaline Earth Salts.

10. A. method for chain modification of hydrocarbons and organic compounds comprising: contacting a aqueous electrol te with a catalyst in a reaction area;

in roducing a gaseous methane feedstock directly into the reaction area: and

reacting the aqueous electrolyte, the catalyst, and the gaseous methane feedstock at temperatures in the range of -10 C to iOOO C and at pressures in the range of .1

ATM to 100 ATM ,

1 ! , The method of claim 10, wherein gaseous methane feedstock is a methane stream or natural gas.

.12. The method of -claim .10, wherein reacting the aqueous electrolyte, the catalyst, and the gaseous methane feedstock includes powering the reaction electrodes.

13. The method of claim 10, wherein reacting the aqueous electrolyte, the catalyst, and the gaseous methane feedstock includes shorting out the reaction electrodes within the electrolyte while maintaining a three phase interface.

.14. The method of claim 1.0, wherein introducing the aqueous electrolyte into contact with the reaction electrode includes introducing the aqueous electrolyte into direct, contact with a gas diffusion electrode,

15. The method of claim 10. wherein introducing the aqueous electrolyte into contact with the reaction electrode includes introducing liquid reactants into direct contact with a gas diffusion electrode.

16. The method of claim 10.. wherein:

the supported catalyst is a solid; and

the reaction occurs at a three-phase interface between the aqueous electrolyte, the solid catalyst, and the gaseous methane feedstock.

17. The method of claim 10, further comprising leaving the aqueous electrolyte unfsltered during the reaction.

818. The method of claim 8, wherein the catalyst comprises a met l, an inorganic salt of a metal, or an organometaUic compound.

19. The method of claim 18, wherei the cataivsi contains an element selected from the group comprising copper., silver, gold, nickel, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, and a S nthanide metal.

20. The method of claim 18, wherein, the catalyst contains an organometaUic sait of an element selected from the group comprising copper, silver, gold, nickel, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, and a !anthartide metal.

21. The method of claim .18, wherein the catalyst is Cuprous Chloride or Cuprous Oxide.

22. The method of claim 18, wherein the aqueous electrolyte includes Alkali or Alkaline Earth Salts.

23. The method of claim 22, wherein the Alkali or alkaline Earth Salts include Halides, Sulfates, sulfites, Carbonates, Nitrates or Nitrites.

24. The method of claim 22, wherein the aqueous electrolyte is selected from the group comprising magnesium sulfate, sodium chloride, sulfuric acid, potassium chloride, hydrogen chloride), potassiiim chloode, potassium bromide, poiassium iodide, sea salt, and brine.

25. The method of claim 8, wherein the aqueous electrolyte is selected from the group comprising magnesium sulfate, sodium chloride, sulfuric acid, potassium chloride, hydrogen chloride), potassium chloride, potassium bromide, poiassium iodide, sea salt, and brine,

26. The method of claim 8, wherein the aqueous electrolyte has a concentration of between .IM-3M.

27. The method of claim 8, wherein the reaction electrode is a gas diffusion electrode.

28. The method of claim 25, wherein the gas diffusion electrode is coated with a copper containing salt.

29. The method of claim 8, wherein the product includes long chained hydrocarbons.

30. The method of claim 29, wherein the product includes ethylene.

31. The method of claim 29, wherein the product further includes methanol and higher alcohols.

32. The method of claim 8, wherein the product includes alcohols,

33. The method of claim 32, wherein the alcohols include methanol, ethanol, propanol, butanol.