CA2866305A1 - 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 METHANE USING AQUEOUS
ELECTROCHEMICAL ACTIVATION AT A THREE-PHASE
INTERFACE
pool] 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. 019(4 This application is commonly assigned herewith and is also hereby incorporated for all purposes as if set forth verbatim.
herein.
(00021 The priority of U.S. Application Serial No. 61/713,487, entitled, "A
Process for Electrochemical Fischer Trospcb", filed October 13, 2012, in the name of the inventor Ed Chen is hereby claimed pursuant to 35 U.S.C. 119(e). This application is commonly, assiened herewith and is also hereby incorporated for all purposes as if set forth verbaiim herein.
CROSS-REFERENCE TO RELATED APPLICATIONS
190031 Not applicable.
STATEMENT REGARDING 'FEDERALLY SPONSORED
.RESEARCH OR DEVELOPMENT
10041 Not applicable.
BACKGROUND
100051 This section of this document introduces information about andlor from the art that may provide context for or be related to the subject matter described herein and'or claimed below. :It provides back.ground 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 art is related in no way implies that it is also "prior" art. The related art may or may not be prior art. The discussion in this section of this document is to be read in this light, and not as admissions of prior art.
[0006] Prior art conunercial processes for converting methane to other hydrocarbons, tbr example; sometimes include a partial oxidation process that is highly energy intensive and operates under high pressures and temperatures. The actuai 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.
10007] 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.
(00081 The art therefore possesses a nwnber of methane activation processes that, even if satisfactory in sonic respects, have several drawbacks. 'The art .furtherrnore 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 chairs 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 electrochetnical reaction to generate methyl radicals at the powered electrode and yield a long chained hydrocarbon.

NON) tia..second aspect; method for 'chain modification . of laydrocarbons and mum&
conipounds comprises: contacting an aqueous electrolyte with a catalyst 111 a reaction area;
introducing a gaseous methane feed.stock 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 900 C and at pressures in the range of .1 .ATM to .100 AT.
100111 The above presents a sill-whiled sun-unary of thepresently disclosed subject illattef in order to provide a basic tinderstauding.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 inatter claimed below. Its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description set forth Mow, BRIEF DESCRIPTION CIF TIIE DRAWINGS
100121 The claimed subject matter may be better understood by reference to the followitk:,!:
description taken in conjunction with the accompanying drawings, in which like reference nimierals identify like elements, and in which:
100131 Figure 1 depicts one particular embodiment of an electrolytie cell in accordance with. some aspects of the presently disclosed technique, 100141 Figure 2 graphically illustrates one particular embodiment of a process in aecordance.with other aspects of the presently disclosed technique, 100151 Figure 3A-figure 3B depict a copper mesh reaction electrode as may be used in some embo di men is.
10016] Figure 4A-Figure 4E3 depict a gas difftision. electrode as may be used in some embo di men is, 100171 Figure 5A-Figure-53 depicts a gas diffusion electrode 'as may be used in some embodiments_ 1001.8) .Figure ( depicts a portion of an embodiment in. 3xilich the eleetrodes are electrically short circuited, 1001.9l 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 particular forms disclosed, but on the contrary, the intention is to cover all modificatic*, equivalents, and alternatives falling .within the: spirit and scope of the itINvitiort as defined by the appended claims.
DETAILED DESCRIPTION
1.00201 Illustrative embodiments Of the subject matter claimed below kvill 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, winch ili 'vary .from one implementation to another. Moreover, it Nvii1 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 disclosure.
[00211 The presently disclosed technique is a process. for converting gaseous hydrocarbons to longer...chained liquid hydrocarbons, longer chained. gaseous hyl,frocarbons,.
branched-ch.ain liquid hydrocarbons, branched.-chain gaseous hydrocarbons, as well as Chained and. branched-chain organic compounds, in t:!eneral, 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 uses. The process in the disclosed technique is Aqueous Electrochemical Activation of Methane (AEA/VI) on three phase interface of gas-liquid-solid electrode. AEAM directly turns natural gas and other sources of tiled-lane (Cl-into C2+ hydrocarbons and other organic compounds, One exemplary product is ethylene (CAL) and alcohols such as methanol, ethanol, prop.anol, andlor butanol.

100221 The reaction of hydrocarbon gases may be successfully achieved with an aqueous electrochemical solution serving as a liquid ion source 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 in the electrolytic solution, (00231 The reaction works by utilizing a 3 phase interface which defines a reaction area.
A catalyst, a liquid, and a gas a positioned in the sante location and an electric potential is applied to make electrons available 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, C114, chains of molecules can be built. 'Existing chained molecules can be lengthened, and existing chained molecules can be branched: A simple example is methane can be converted to methanol, CEI3(011). Different voltages create different reaction product distribation.s or fadlitate different reaction. types.
(00241 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 may range from -IOC to 240C, or from -IOC to 1000C, and pressures may range from .1 ATM to 10 AT, or from .1 ATM to 100 ATM. The process generates motive methyl .radicals through. the reaction on the reaction electrodes. On the reaction electrode, th.e production of methyl radicals occurs.
100251 In at least some embodiments, the reactants need no pre-treatment. Typically methanol front methane must first go through steam reforming to produce swims CO and H2). The presently disclosed technique can perform the production of methanol without reforming to produce synaas. Similarly, as described further below, the gaseous methane feedstock may be introduced "directly" into the chamber of an electrochemical cell, (0026) In general, the method introduces a liquid ion source into a first chamber into contact with. a catalyst supporting reaction electrode while a. counter electrode is disposed in the 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.
10027) In the embodiments illustrated herein, the technique employs an electrochemical cell such as the one illustrated in Figure I. The electrochemical cell 100 generally comprises a reactor 105 in one chamber 110 of which are positioned two electrodes 1.15, 116, a cathode and an anode, separated by a liquid i0T1 source, i.e., an. electrolyte 120.
Those in the art will appreciate that the identity of the electrodes 115, 116 as cathode and anode is a matter of polarity that can vary by implementatim In the illustrated embodiment, the counter electrode 115 is die anode and the reaction electrode 116 is the cathode. The reaction electrode .116 shall be referred to as the "reaction" electrode and the counter electrode 115 the "counter"
electrode for reasons discussed further below.
100281 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 135 through the wall 140 separating the two chambers 110, 125. The reactor 105 may be constructed in conventional fashion except as 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.
(00291 Catalysts will be implementation specific depending, at least in part, on the implementation of the reaction electrode 116. Depending on the embodiment, suitable catalysts may include, but are not limited to, nickel, copper, iron, tin, zinc, mthenium, palladium, rheniunt, 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 compotmds. Exem.plary organometallic compounds include, but are not limited to, tetracarbonyl nickel, lithiumdiphenylcuprate, pentamesitylpentacopper, and etharatedimer.

[00301 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 (H2S0.4), potassium chkvide (KCl), hydrogen chloride (HCI), hydrogen bromide (HBO, hydrogen fluoride (HE), potassium chloride (MI), potassium bromide (KBr), and potassium iodide (KI), or any other suitable electrolyte and acid or base known to the art, (00311 The pH
of the electrolyte 120 may range from 0 to 3 and concentrations of between 0.1M 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.
100321 In addition to the reactor 105, the electrochemical cell 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 115, 116 under enough pressure to balance and overcome the gravitational press= of the column of electrolyte, which depends on the height of the water, sufficient to maintain the 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 Am or from 0.1 ATM to 100 ATM. The electrolyte source 163 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 160 is collected in a vessel 165 of some kind in any suitable manner 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 all. In these embodiments, the products 160 may be streamed directly to downstream processes using techniques well known in the att.
00331 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 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.
[00341 Those in the art will appreciate that some implementation specific details are omitted from Figure 1. For example, various instrumentation such as flow regulators, mass regulators, a pH regulator, and sensors for temperatures and pressures are not shown but will typically be found in most embodiments. Such instrumentation 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 detail is omitted from the present disclosure because it is routine and conventional so as not to obscure the subject matter claimed below.
100351 The reaction is conceptually illustrated in FIG, 2. in this embodiment, the feedstock 130' is natural gas and the electrolyte 1120' is Sodium Chloride.
Reactive hydrogen ions (In are fed to the natural gas stream 130' through the electrolyte 120' with an applied cathode potential. The molecules may also ill MED react with water on the interface to form alcohols, oxygenates, and ketones. .Exemplary alcohols include but are not limited to methanol, ethanol, propanol, butanol. In one example of this reaction, the reaction occurs at room temperature and with an applied cathode potential of 0,01V versus SHE to 1.99V
versus SHE. The voltage level can be used to control the resulting product. A
voltage of 0.1V may result in a methanol product whereas a 0.5V voltage may result in butanol.
100361 Still further, very little catalyst deactivation MCUM in some ern1)odiments because the catalyst is protected by a layer of chloride, which also acts as an absorbent for the reactants, and the electrolyte is saturated with CI 7 preventing typical catalyst poisons from bonding with the catalyst and deactivating it, as this would force the release of a Cf ion into the liquid. ln addition, this process further prevents the deposition of impurities in water, which could deactivate the catalyst. These aspects will be explored further below.

Returning now to Figure I, 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 neventieless be used in some embodiments.
100381 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!, the reaction electrode 116 is the reaction electrode and the counter electrode 115 is the counter electrode. As noted above, those in the art will appreciate that the identity of the electrodes 115, 116 as cathode and anode is a limner of polarity that can vary by implementation.
(00391 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.
100401 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 long chained hydrocarbon or organic compound 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 lanthanide 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 NAFION 117 by Dupont 10041j The copper wire mesh 310 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 hydrophilic paper 320, as shown in Figure 3B.
Electrical leads not shown) can then be attached to the copper wire mesh 310 in conventional fashion. The reaction electrode 320 is but one implementation of the reaction electrode 116 in Figure 1.
Alternative implementations will be discussed below.
100421 The counter electrode 115, the reaction electrode 116 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 interface 155. When electricity is applied to electrodes 1.15, 116, electrochemical reduction discussed above takes place to produce hydrocarbons 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.
10043j As Mentioned above, the copper mesh 310 in the illustrated embodiment is an mesh in the range of 1- 400 mesh.
100441 In a second embodiment shown in Figure 4A-.Figure 4B, a gas diffusion electrode 400 comprises a hydrophobic layer 405 that is porous to methane but impermeable or nearly impemieable to aqueous electrolytes. In one embodiment of the electrode 400, a !mil thick advcarb carbon paper 410 treated with TEFLON* (i.e., polytetrafluoroethylene) 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, electrolydc reduction, or other means of reduction of copper, silver other transition metals into the porous carbon material.
(0045) This material is then mix.ed 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 alcohol or other organic solvent. The ink is 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.
100461 The copper 420 impregnated into the ion. electrode 400 is then made into a caprous halide through any suitable procedure. One embodiment of the procedure to make the cuprous halide is to submerge the electrode in a solution of hydrochloric acid and cupric chloride, heat to 100 C for 2 hours. Another embodiment submerges the impregnated electrode 400 in 3 M K13r or 3 M K1 and. nm a 4 V pulse of electricity to the electrode 400 in order to form a thin film of cuprous halide 425, shown in cross-section Figure 48, in the electrode 400.
100471 In another emtxxliment, the copper panicles in the electrode are first plated with silver by electroless plating or another method, creating a thin film of silver over the copper.
Copper may then be plated onto the silver and transfonned into a halide through procedure previously described. In another embodiment, silver particles are deposited into the hydrophilic layer, coate41 with copper electrolytically, and then the same procedure for the conversion of the copper layer to a copper halide layer is conducted.
100481 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 1 00C for eight hours. It is then mixed with equal amounts ill weight of a hydrophilk binder.
100491 In another enibodiment, 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 halide 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 10(PC.
1905)1 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 no 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 microturbulenee, 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 al .lowed 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) Catalysts in this particular embodiment may include copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or lanthanide metals. In addition, the catalysts may be formed into a metal foam or alternatively it may be deposited through electroless or electrolytic deposition onto a porous support with a hydrophobic and hydrophilic layer.
1.00521 In electrochemical systems, it is often difficult to make a good electrical contact between gas diffusion 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 2fl 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 platinum, gold, or silver directly into the carbon paper, gas diffusion media may be extended into applications such as 'hydrocarbon processing and fuel cell applications. The production of such papers is relatively straight forward though requires a few enabling aspects .fur 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 50m21gram, 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 M. shows one embodiment 500 of the pressed wire mesh 505 in. paper 510. The 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 than presses the wire mesh 505 into the surface of the carbon paper 510, providing uniform conductivity.
100531 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 510, 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 .maximurn contact area.
po541 In another embodiment 500', the production of the paper 510 is conducted and deposited directly onto the wire mesh 505, the result of which is shown in Figure 5B.

Conductive carbon paper is often made by pyrolyzing carbon containing compounds. Thus, by using a conductive -material 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 with conventional practice .for producing and pyrolyzing carbon based materials to form carbon paper such as polyanaline based carbon .fiber paper.
1.00551 The technique illustrated in Figure 5A-Figure 5B 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 5A, more particularly, a carbon paper 510 has a I-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 einbedded in therein such that no metal is showing. Spacing between the wires of the mesh 505 can be from 1mm to lcm. The carbon paper 510 should. generally be as thin as possible while still being sturdy enougl'i to withstand handling in both embodiments.
MIMI In one particular ernbodinient, 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 com.panion electrode (not shown) is similarly electrically short: circuited.
10057j So, turning now to the process again arid 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 116 and anode 115 in the same, .filtered electrolyte 120, and (3) an electrolyte 120 contacted directly to the reaction electrode, which is the cathode 116.
100581 The inethod of operation generally comprises introducing the electrolyte 120 into the first chamber 110 into direct contact with the powered electrode surfaces 115 and .116.
The gaseous tnethane 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 on the height of the water, to induce the reaction. During the reaction, the electrolyte 120 is filtered, the gaseous methane feedstock 130 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.
100591 Above the second Chamber 125, but attached to it., is an area for the introduction of a cathode reaction electrode 116 where the three-phase interface 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 lanthanide metals.
In addition, the catalysts may be fonned into a metal foam or alternatively it may be deposited through electroless or electrytic 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 (Kl), or any other suitable electrolyte known to the art.
100601 This particular embodiment implements the reaction electrode 116 as the gas diffusion electrode described above with the cuprous halide coating.
Alternative embodiments may use another cuprous halide coating the surface of the .metal..
Cuprous Oxide, Cupric Oxide, and other varying valence states of copper will also work in the reaction.
100611 By maintaining a three phase interface between gaseous methane feedstock 130 and the electrolyte 120, the methane will form organic chemicals and form a nearly 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 interface is to use a separation membrane which selectively allows hydrogen and water to penetrate. One such membnute is Nation. Another means is to use a fuel cell type set up but instead of generating a current, a current is introduced to generate a chemical.
100621 Other reaction mechanism also produces organic compounds such as ethers, epox.ides, and alcohols, a:mong other compounds.

10063l The electrolyte 120 should be relatively concentrated at..-11M-W and should be a halide electrolytes discussed aboVe to increase cataly.st lifetime. The higher the surface.area.
between the reaction electrode 116 and .the gaseous. chamber. 1-25 on one side and the liquid electrolyte 120 on the other side, the higher the conversion rates. Operating -pressures could he .ranged from. only 10000 pascals, or from atm to 100 atm, or from .1 atm to 100 atm.:
though Standard Temperature and Pressures (STP) were sufficient for the reaction.
[00641 in one embodiment of the gas diffusion electrode (GI)E) an antioxidant layer of a.scorbic acid is .mixed with the GDE high porosity carbon. The -high porosity carbon includes nanotubes, fullerines, and other specialized formations of carbon as described above The high porosity carbon is impregnated throtmli reduction of cupric chloride, or other ibrrn of cathon. it is then made into a halide by treatment with a chloride solution under the proper and temperature of EISI.F conditions. it also includes a reaction in the solid -polymer phase. A .pasteis made from the impregnated carbon, astorbie kid, and a hydrophilic binding gent. . This paste is painted onto a hydrophobic layer. Sorne embodiments include antioxidants in the laver as described above.
1-)0651 Note that not a.li embodiments wili manifeSt all these characteristies and, to the extent they do, they will not neceaSarily 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.
100661 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 svhen the apparatus is powered andfor 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 eleetro-inechanical parts that, to operate, require electrical power. 'Even when provided with power, some functions described herein only cwt. when ìn operation. 'Thus, at nines, some embodiments of-the apparatus of the invention are. "capable of' performing the recited ftinctions even when they ate not actually performing thetri-----4.e., when there is no power or when they are powered but not in operation.

(0067) The following patent, applications, and publications are hereby incorporated by reference for all purposes as i.f set forth verbatim herein:
10068j U.S.
Application Serial No. 61/608,583, entitled, "An Electrochemical Process fbr 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 here w ith 1.0069] U.S.
Application Serial "No. 61/713,487, entitled, "A Process for Electrochemical Fischer Trospcb," filed October 13, 2012, in the name of the inventor Ed Chen and commonly assigned herewith..
100701 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.
(00711 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 all 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 (17)

1. A method for 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 1, 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, ethanol, propanol, butanol.

8. The method of claim 1, wherein the catalyst comprises a metal, an inorganic salt of a metal, or an organometallic 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 an aqueous electrolyte with a catalyst in a reaction area;
introducing 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 1000C and at pressures in the range of .1 ATM to 100 ATM.

11. 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 10, 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 unfiltered during the reaction.
818. The method of claim 8, wherein the catalyst comprises a metal, an inorganic salt of a metal, or an organometallic compound.
19. The method of claim 18, wherein the catalyst contains an element selected from the group comprising copper, silver, gold, nickel, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, and a lanthanide metal.
20. The method of claim 18, wherein the catalyst contains an organometallic salt of an element selected from the group comprising copper, silver, gold, nickel, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, and a lanthanide 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), potassium chloride, potassium bromide, potassium 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, potassium iodide, sea salt, and brine.
26. The method of claim 8, wherein the aqueous electrolyte has a concentration of between .1M-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.