Patent Publication Number: US-2013228470-A1

Title: Method and apparatus for an electrolytic cell including a three-phase interface to react carbon-based gases in an aqueous electrolyte

Description:
The priority of U.S. Application Ser. 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 Mar. 8, 2012, in the name of the inventor Ed Chen is hereby claimed pursuant to 35 U.S.C. §119(e). This application is commonly assigned herewith and is also hereby incorporated for all purposes as if set forth verbatim herein. 
     The priority of U.S. Application Ser. No. 61/639,544, entitled, “Electrochemical Reactor for the use of Aqueous Electrolyte for High Efficiency Reaction of Non Polar Organic Gases”, filed Apr. 27, 2012, in the name of the inventor Ed Chen is hereby claimed pursuant to 35 U.S.C. §119(e). This application is commonly assigned herewith and is also hereby incorporated for all purposes as if set forth verbatim herein. 
     The priority of U.S. Application Ser. No. 61/606,398, entitled, “A Process, Apparatus, and Components for the Production of High Value Chemicals from carbon dioxide Using Modular, Electrochemical Reduction of CO 2  on Three Phase Interphase Gas Diffusion Electrode”, filed Mar. 3, 2012, in the name of the inventor Ed Chen is hereby claimed pursuant to 35 U.S.C. §119(e). This application is commonly assigned herewith and is also hereby incorporated for all purposes as if set forth verbatim herein. 
     The priority of U.S. Application Ser. No. 61/713,487, entitled, “A Process for Electrochemical Fischer Tropsch”, filed Oct. 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 assigned herewith and is also hereby incorporated for all purposes as if set forth verbatim herein. 
     CROSS-REFERENCE TO RELATED APPLICATIONS 
     The technique described herein and illustrated in the appended drawings is related by overlapping disclosure to the following applications, each of which is commonly assigned herewith: 
     U.S. application Ser. No. 13/782,936, entitled “Chained Modification of Gaseous Methane Using Aqueous Electrochemical Activation at a Three Phase Interface”, in the name of Ed Chen on an even date herewith (Attorney Docket No. 2039.000300), 
    
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
     Not applicable. 
     BACKGROUND 
     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 is 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. 
     Some common industrial processes involve the conversion of a gas or components of a gaseous mixture into another gas. These types of processes are performed at high pressures and temperatures. Operational considerations such as temperature and pressure requirements frequently make these types of processes energy inefficient and costly. The industries in which these processes are used therefore spend a great deal of effort in improving the processes with respect to these kinds of considerations. 
     Several configurations of electrolytic cells are available to the art many or all of all of may be competent for their intended purposes. The art, however, is always receptive to improvements or alternative means, methods and configurations. Therefore the art will well receive the launching tool described herein. 
     SUMMARY 
     In a first aspect, an electrolytic cell, comprises: at least one reaction chamber into which, during operation, a aqueous electrolyte and a gaseous feedstock including are introduced, wherein the gaseous feedstock comprises a carbon-based gas; and a pair of reaction electrodes disposed within the reaction chamber, at least one of the reaction electrodes including a solid catalyst and defining, in conjunction with the aqueous electrolyte and the gaseous feedstock, a three-phase interface. 
     In a second aspect, a method for chain modification of hydrocarbons and organic compounds comprises: contacting a gaseous feedstock including a carbon-based gas, an aqueous electrolyte, and a catalyst in a reaction area; and activating the carbon-based gas in an aqueous electrochemical reaction at the reaction electrode and yield a product. 
     In a third aspect, a method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte with a a catalyst and a gaseous feedstock including a carbon-based gas within a reaction area; and reacting the aqueous electrolyte, the catalyst, and the gaseous feedstock at temperatures in the range of −10 C to 1000 C and at pressures in the range of 0.1 ATM to 100 ATM to yield a long chained hydrocarbon. 
     In a third aspect, a gas diffusion electrode, comprises: a hydrophobic layer porous to carbon dioxide and impermeable to aqueous electrolytes; a hydrophilic layer bonded to the hydrophobic layer; and a cuprous halide coating disposed about the bonded hydrophobic and hydrophilic layers. 
     In a fourth aspect, a method for fabricating a gas diffusion electrode, comprising: bonding a hydrophobic layer porous to carbon dioxide and impermeable to aqueous electrolytes to a hydrophilic layer supporting, a copper catalyst; and treating the copper catalyst to create a cuprous 
     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 
       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: 
         FIG. 1  depicts one particular embodiment of an electrolytic cell in accordance with some aspects of the presently disclosed technique. 
         FIG. 2  graphically illustrates the electrochemical Fischer-Tropsch process in accordance with other aspects of the presently disclosed technique. 
         FIG. 3A-FIG .  3 B depict a copper mesh reaction electrode as may be used in some embodiments. 
         FIG. 4A-FIG .  4 B depict a gas diffusion electrode as may be used in some embodiments. 
         FIG. 5A-FIG .  5 B depict a gas diffusion electrode as may be used in some embodiments. 
         FIG. 6  depicts a portion of an embodiment in which the electrodes are electrically short circuited. 
         FIG. 7  graphically illustrates the process of carbon dioxide to ethylene in accordance with one particular embodiment of the presently disclosed technique. 
         FIG. 8  depicts another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique. 
         FIG. 9  depicts another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique. 
         FIG. 10A-FIG .  10 B depict another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique. 
         FIG. 11  depicts another embodiment of an electrolytic cell in accordance with another aspect of the presently disclosed technique. 
     
    
    
     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 modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. 
     DETAILED DESCRIPTION 
     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&#39; 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 disclosure. 
     The presently disclosed technique is a process for converting carbon-based gases such as non-polar organic gases and carbon oxides to longer chained organic gases such as liquid hydrocarbons, longer chained gaseous hydrocarbons, branched-chain liquid hydrocarbons, branched-chain 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, and eventual conversion into liquids including, but not limited to, hydrocarbons, alcohols, and other organic compounds. 
     This process more particularly uses aqueous electrolytes to act as a reducing or oxidizing atmosphere and hydrogen and oxygen source for hydrocarbon gases. The process in the disclosed technique is a chain modification of hydrocarbons and organic compounds using aqueous electrochemical activation of carbon based gases at three-phase interface of a gas-liquid-solid electrode surface. This process turns hydrocarbon gases including, but not limited to, gaseous methane, natural gas, other hydrocarbons, carbon monoxide, carbon dioxide, and/or other organic gases into C 2 + hydrocarbons, alcohols, and other organic compounds. One exemplary product is ethylene (C 2 H 4 ) and alcohols. The process may also turn carbon dioxide (CO 2 ) into one or more of isopropyl alcohol, hydroxyl-3-methyl-2-butanone, tetrahydrofuran, toluene, 2-heptanone, 2-butoxy ethanol, 1-butoxy-2-propanol, benzaldehyde, 2-ethyl-hexanol, methyl-undecanol, methyl-octanol, 2-heptene, nonanol, diethyl-dodecanol, dimethyl-cyclooctane, dimethyl octanol, dodecanol, ethyl-1,4-dimethyl-cyclohexane, dimethyl-octanol, hexadecene, ethyl-1-propenyl ether, dimethyl-silanediol, toluene, hexanal, methyl-2-hexanone, xylene isomer, methyl-hexanone, heptanal, methyl-heptanone, benzaldehyde, octanal, 2-ethyl-hexanol, nonanal, hexene-2,5-diol, dodecanal, 3,7-dimethyl-octanol, methyl-2,2-dimethyl-1-(2-hydroxy-1-methylethyl)propyl ester propanoic acid, methyl-3-hydroxy-2,4,4-triinethylpentyl ester propanoic acid, phthalic anhydride. 
     The reaction of carbon based 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 source through acids and bases. By creating a three phase gas, solid, liquid interface between the carbon-based gases with an electrolyte at a solid phase 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. 
     The reaction utilizes a three phase interface which defines a reaction area. A catalyst, a liquid, and a gas are contacted in the reaction area and an electric potential is applied to make electrons available to the reaction site. When hydrocarbons are used as the reactant gas it is possible to create hydrocarbon 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 propane (C 3 H 8 ) chains of molecules can be built by activating the propane molecule. Existing chained molecules can be lengthened, and existing chained molecules can be branched. A simple example is methane (CH 4 ), can be converted to propanol (C 3 H 7 (OH)). Different voltages create different reaction product distributions or facilitate different reaction types. 
     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 −10 C to 240 C, or from −10 C to 1000 C, and pressures may range from 0.1 ATM to 10 ATM, or from 0.1 ATM to 100 ATM. The process generates reactive activated carbon-based gases through the reaction on the reaction electrodes. On the reaction electrode, the production of activated carbon-based gases occurs. 
     In general, the method introduces a liquid ion source and a gaseous feedstock into a chamber in contact with a catalyst supporting reaction electrode submerged in an electrolyte. The reaction electrode is powered. 
     In the embodiments illustrated herein, the technique employs an electrochemical cell such as the one illustrated in  FIG. 1 . The electrochemical cell  100  generally comprises a reactor  105  in one chamber  110  of which are positioned two electrodes  115 ,  116 , a cathode and an anode, separated by a liquid ion 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 implementation. In the illustrated embodiment, the electrode  115  is the anode and the electrode  116  is the cathode. Because of the interchangeability between electrode  115  and  116  and because in some embodiments of the design the electrodes are electrically short circuited, the reaction electrode is considered to be either or both of the electrode  115  and electrode  116 . 
     There is also a second chamber  125  into which a gaseous feedstock  130  is introduced as described below. The gaseous feedstock  130  may be a carbon-based gas, for example, non-polar organic gases, carbon-based oxides, or some mixture of the two. 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. 
     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, ruthenium, palladium, rhenium, or any of the other transition or lanthanide and actinide 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 inorganic compounds of catalytic metals, as well as organometallic compounds. Exemplary organometallic compounds include, but are not limited to, tetracarbonyl nickel, lithiumdiphenylcuprate, pentamesitylpentacopper, and etharatedimer. 
     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, Polar Organic Compounds, such as Glacial Acetic Acid, 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 (NaCl), sulfuric acid (H 2 SO 4 ), potassium chloride (KCl), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen fluoride (HF), potassium chloride (KCl), potassium bromide (KBr), and potassium iodide (KI), or any other suitable electrolyte and acid or base known to the art. 
     The pH of the electrolyte  120  may range from −4 to 14 and concentrations of between 0.1M and 3M inclusive 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. 
     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 feedstock  130  while the power source  150  is powering the electrodes  115 ,  116  at a selected voltage sufficient to maintain the reaction at the three phase interface  155 . The three phase interface  155  defines a reaction area. In one example, the reaction pressure might be, for example, 10000 pascals or 0.1 ATM to 10 ATM, or from 0.1 ATM to 100 ATM, and the selected pressure may be, for example, between 0.01 V and 10 V. 
     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 feedstock  130  as illustrated in  FIG. 6 . The reaction products  160  are generated in both the electrolyte  120  and in the chamber  125  and may be 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 alt in these embodiments, the products  160  may be streamed directly to downstream processes using techniques well known in the art. 
     The embodiment of  FIG. 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 the pressure of the gaseous feedstock  130  in the chamber  125 . 
     Those in the art will appreciate that some implementation specific details are omitted from  FIG. 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. 
     The reaction is conceptually illustrated in  FIG. 2 . In this embodiment  200 , the feedstock  130 ′ is natural gas and the electrolyte  120 ′ is Sodium Chloride. Reactive hydrogen ions (H + ) are fed to the natural gas stream  130 ′ through the electrolyte  120 ′ with an applied cathode potential of The molecules may also in turn react with water on the interface to form alcohols, oxygenates, and ketones. 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 0.01V may result in a methanol product whereas a 0.5V voltage may result in butanol as well as higher alcohols such as dodecanol. These specific examples may or may not be reflective of the actual product yield and are meant only to illustrate how a product produced can be altered with a change in voltage. 
       FIG. 7  graphically illustrates the process of carbon dioxide to ethylene in accordance with one particular embodiment of the presently disclosed technique. The gaseous feedstock  730  is carbon dioxide. A voltage is applied across the cathode  716  and the anode  715  or a electrically short circuited reaction electrode illustrated in  FIG. 11 . The electrochemical interface in this reactor prevents the deactivation of carbon dioxide by providing sufficient reactants to the surface of the catalyst to consistently produce the desired products without the buildup of carbon black. In one example of this reaction, the reaction occurs at a temperature of −10 C to 210 C and a pressure of 0.1 ATM to 10 ATM to yield ethylene product  765  found in both the gas and electrolyte 
     Returning now to  FIG. 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. 
     The presently disclosed technique admits variation in the implementation of the electrode at which the reaction occurs, hereafter referred to as the “reaction electrode”. As set forth above, either the electrode  115  or the electrode  116 , or both, may be considered to be the reaction electrode depending upon the embodiment. 
     In one embodiment, an 80 mesh copper mesh is used. 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. More particularly, the catalyst  305  is supported on a copper mesh  310  embedded in an ion exchange resin  300  as shown in  FIG. 3A . The catalyst  305  can be a plated catalyst or powdered catalyst. The metal catalyst  305  is a catalyst capable of reducing carbon-based gases to products of interest. 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 and actinide 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. 
     The copper wire mesh  310  can be used to structure the catalyst  305  within the resin  300  or it may be used without a resin. The assembly  315  containing the catalyst  305  can be deposited onto or otherwise structurally associated with an electrically conducting paper  320 , as shown in  FIG. 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  FIG. 1 . The electrical leads may also be connected to short circuit the electrodes. Alternative implementations will be discussed below. 
     The counter electrode  115  and the reaction electrode  116  are 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  115 ,  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 feedstock  130 . 
     As mentioned above, the copper mesh  310  in the illustrated embodiment is a mesh in the range of 1-400 mesh. 
     In a second embodiment shown in  FIG. 4A-FIG .  4 B, a gas diffusion electrode  400  comprises a hydrophobic layer  405  that is porous to carbon-based gases but impermeable or nearly impermeable to aqueous electrolytes. In one embodiment of the electrode  400 , a 1 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, electrolytic reduction, or other means of reduction of copper, silver other transition metals into the porous carbon material. 
     This material is then mixed with a hydrophilic binding agent (not shown), such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), or Nafion. 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. 
     The copper  420  impregnated into the ion electrode  400  is then made into a cuprous 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 KBr or 3 M Kl and run 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  FIG. 4B , in the electrode  400 . 
     In another embodiment, the copper particles 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 transformed into a halide through procedure previously described. In another embodiment, silver particles are deposited into the hydrophilic layer, coated with copper electrolytically, and then the same procedure for the conversion of the copper layer to a copper halide layer is conducted. 
     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 100° C. for eight hours. It is then mixed with equal amounts in weight of a hydrophilic binder. 
     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 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 0.1 to 3M solution of Cupric Chloride heated to 100° C. This treatment is not necessary for the wire mesh catalyst to function. 
     In one embodiment 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 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. 
     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 and actinide 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. 
     In one particular embodiment, the electrodes are electrically short circuited (“shorted”) within the electrolyte while maintaining a three phase interface between carbon-based gases and electrolyte in a mixed slurry pumped through the reactor. In this embodiment, the catalyst in powder form is mixed with the electrolyte to make a slurry.  FIG. 6  depicts a portion  600  of an embodiment in which the electrodes are shorted. In this drawing, only a single electrode  605  is shown but the electric potential is drawn across the electrode  605 . The companion electrode (not shown) is similarly shorted. 
     So, turning now to the process again and referring to  FIG. 1 , carbon-based gases or electrolyte gaseous mixture including gaseous feedstock  130  is introduced into the reaction chamber  125  of the reactor  105  under enough pressure to overcome the gravitational pressure of the column of electrolyte, which depends on the height of the electrolyte, to induce the reaction. The exemplary embodiments discussed below all include the following design characteristics: (1) a three-phase catalytic interface  155  for solid catalyst, gaseous feedstock  130 , and liquid ion source (e.g., a liquid electrolyte)  120 , (2) a cathode  116  and anode  115  in the same, or a shorted reaction electrode, filtered electrolyte  120 , and (3) an electrolyte  120  contacted directly to the reaction electrode, which is the cathode  116 . 
     The method of operation generally comprises introducing the electrolyte  120  into the reaction chamber  110  into direct contact with the powered electrode surfaces  115  and  116 . The gaseous feedstock  130  is then introduced into the second chamber  125  under enough pressure to overcome the gravitational pressure of the column of electrolyte, which depends on the height of the electrolyte, to induce the reaction to induce the reaction. During the reaction, the electrolyte  120  is filtered, the gaseous 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. 
     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  116  include copper, silver, gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or any of the other transition or lanthanide and actinide 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 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. 
     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. 
     By maintaining a three phase interface between the gaseous feedstock  130  and the electrolyte  120 , the carbon-based gases will form organic chemicals and form a nearly complete conversion when there is continuous contact to the gaseous feedstock  130  on the three phase interfaces  155  between the liquid electrolyte  120 , the solid catalyst, and the gaseous feedstock  130 . 
     For carbon dioxide, this reaction mechanism also produces organic compounds such as ethers, epoxides, and C5+ alcohols, among other compounds such as ethers, epoxies and long C5+ hydrocarbons which have not been reported in the prior art. 
     The electrolyte  120  should be relatively concentrated at 0.1M-3M and should be a halide electrolyte as discussed above to increase catalyst lifetime. The higher the surface area between the reaction electrode  116  and the gaseous chamber  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 0.1 atm to 10 atm, though Standard Temperature and Pressures (STP) were sufficient for the reaction. 
     In one embodiment of the was diffusion electrode (GDE) an antioxidant layer of ascorbic 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 through reduction of cupric chloride, or other form of carbon. It is then made into a halide by treatment with a chloride solution under the proper pH 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. 
     The principles discussed above can readily be scaled up to achieve higher yield. Four such embodiments are shown in  FIG. 8-FIG .  11 . 
     For example, those in the art having the benefit of the disclosure associated with  FIG. 1  will realize that the gaseous feedstock  130  and the electrolyte  120  need not necessarily be introduced into separate chambers. One such example is shown in  FIG. 8 . in this stacked embodiment  800 , reactants  805  (e.g., gaseous feedstock and liquid electrolyte, or gaseous feedstock and a slurry of the catalyst and liquid electrolyte) enter a chamber  810  in which they are mixed, the resulting mixture  835  then entering a reaction chamber  840 . A plurality of alternating anodes  820  and cathodes  815  (only one of each indicated) are positioned in the reaction chamber  840 . Each of the anodes  820 , cathodes  815  is a reaction electrode at which a three-phase reaction area forms as described above. The resultant product  845  is collected in the chamber  825 , a portion of which is then recirculated back to the chamber  810  via the line  830 . 
     In the stacked embodiment  900 , shown in  FIG. 9 , the gaseous feedstock  915  and liquid electrolyte  920  are separately introduced at the bottom of the reaction chamber  925 . A plurality of chambers  930  (only one indicated) are disposed between respective anodes  820  and cathodes  815 . Gaseous feedstock  935  and liquid electrolyte  940  are then reacted in the chambers  930  and the resultant gas product  905  and fouled electrolyte  910  are drawn off the top. 
     A cylindrical embodiment  1000  is shown in  FIG. 10A-FIG .  10 B. A mixture  1005  of gaseous feedstock and liquid electrolyte is introduced into the bottom of the embodiment  1000 . The embodiment includes a plurality of alternating, nested anodes  1016  and cathodes  1015  (only one of each indicated). As the mixture  1005  bubbles up it reacts with the catalyst (not shown) on the anodes  1016  and cathodes  1015  that define a plurality of three-phase interface as discussed above. Eventually, the product and fouled electrolyte  1020  are drawn off the top. 
     Another stacked embodiment  1100  is shown in  FIG. 11 . A mixture  1105  of gaseous feedstock and liquid electrolyte is introduced into a chamber  1110 , from which it is then introduced into a reaction chamber  1130  in which a plurality of alternating anodes  1016  and cathodes  1015  are stacked. When the anodes  1016  and cathodes  1015  are powered, they are shorted together. Those in the art will appreciate that, at this point, they lose their identity as a “cathode” or an “anode” because they all have the same polarity and instead all become reaction electrodes. As the mixture  1105  rises in the reaction chamber  1130 , it forms a three-phase reaction at each reaction electrode. The gas product  1405  and the fouled electrolyte  1410  are drawn from the chamber  1125  at the top of the embodiment  1100 . 
     Note that not all 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. 
     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, some functions described herein only occur when in operation. Thus, at times, some 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. 
     The following patent, applications, and publications are hereby incorporated by reference for all purposes as if set forth verbatim herein: 
     U.S. Application Ser. 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 Mar. 8, 2012, in the name of the inventor Ed Chen and commonly assigned herewith. 
     U.S. Application Ser. No. 61/639,544, entitled, “Electrochemical Reactor for the use of Aqueous Electrolyte for High Efficiency Reaction of Non Polar Organic Gases”, filed Apr. 27, 2012, in the name of the inventor Ed Chen and commonly assigned herewith. 
     U.S. Application Ser. No. 61/606,398, entitled, “A Process, Apparatus, and Components for the Production of High Value Chemicals from carbon dioxide Using Modular, Electrochemical Reduction of CO 2  on Three Phase Interphase Gas Diffusion Electrode”, filed Mar. 3, 2012, in the name of the inventor Ed Chen and commonly assigned herewith. 
     U.S. Application Ser. No. 61/713,487, entitled, “A Process for Electrochemical Fischer Tropsch”, filed Oct. 13, 2012, in the name of the inventor Ed Chen and commonly assigned herewith. 
     International Application Ser. No. PCT/US2011/064589, entitled, “Porous Metal Dendrites for High Efficiency Aqueous Reduction of CO2 to Hydrocarbons”, filed Dec. 13, 2011, in the name of the inventor Ed Chen and assigned to The Trustees of Columbia University in the City of New York. 
     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. 
     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.