CA2241068A1 - Electrochemical conversion of hydrocarbons - Google Patents

Abstract

A process and apparatus are described for producing higher hydrocarbons from lower hydrocarbons, e.g. by gas phase electrocatalytic polymerization of methane. This is done using an electrolysis cell having an anode chamber on one side of a solid electrolyte and a cathode chamber on the other side of the solid electrolyte. According to this process, methane-containing gas is passed through the anode chamber to contact a catalytic anode which is connected to one side of the solid electrolyte, this solid electrolyte comprising a solid proton conducting membrane. An inert gas or oxygen is passed through the cathode chamber to contact a catalytic cathode which is connected to the other side of the proton conducting membrane.
The membrane is designed so that H+ is capable of passing through the membrane from the anode chamber to the cathode chamber. As a consequence, C-2 and higher hydrocarbons are formed in the anode chamber and hydrogen or water is formed in the cathode chamber.

Description

Electrochemical Conversion of Hydrocarbons Backqround of the Invention This invention relates to a process for producing C-2 and higher hydrocarbons from lower hydrocarbons, and particularly, direct gas phase electrocatalytic polymerization of lower hydrocarbons, such as methane, to produce higher hydrocarbons, e.g. ethane and gasoline range hydrocarbons.
There remains an interest in the energy industry to produce gasoline range hydrocarbons from natural gas or methane. A series of patents for this purpose where granted to George Olah, i.e. U.S. Patents 4,433,192, 4,513,164, 4,465,893 and 4,467,130. Krist et al U.S. Patent 5,064,733 describes the electrochemical conversion of CO2 and CH4 to C-2 hydrocarbons using a single electrochemical cell. This was accomplished by means of a cell divided by way of a solid electrolyte with methane containing gas being introduced into one side of the cell and carbon dioxide into the other side of the cell. The process of that patent is primarily concerned with proton conductors used to dimerize methane. The process is operated at quite high temperatures in the order of 600 to 1000~C and no H2 can be produced.
It is the object of the present invention to polymerize and dimerize lower hydrocarbons in order to produce higher hydrocarbons, including unsaturated hydrocarbons.

Summary of the Invention One embodiment of this invention comprises a process for gas phase electrocatalytic polymerization of methane, ethane or ethanol to produce higher hydrocarbons and hydrogen. This is done using an electrolysis cell having an anode chamber on one side of a solid electrolyte and a cathode chamber on the other of the solid electrolyte. According to this process, methane-, ethane- or methanol-containing gas is passed through the anode chamber to contact a catalytic anode which is connected to one side of the solid electrolyte, this solid electrolyte comprising a solid proton conducting membrane. An inert gas or oxygen is passed through the cathode chamber to contact a catalytic cathode which is connected to the other side of the proton conducting membrane. The membrane is designed so that H+ is capable of passing through the membrane from the anode chamber to the cathode chamber. As a consequence, when methane is used as feedstock C-2 and higher hydrocarbons are formed in the anode chamber and hydrogen or water is formed in the cathode chamber.
A further embodiment of this invention is an electrochemical cell for gas phase electrocatalytic polymerization of methane, ethane or ethanol to produce higher hydrocarbons and hydrogen. This cell comprises an anode chamber on one side of the solid electrolyte and a cathode chamber on the other side of the electrolyte. The solid electrolyte comprises a solid proton conducting membrane separating the anode chamber from the cathode chamber. A
catalytic anode is connected to one side of the proton conducting membrane and a cathode is connected to the other side of the membrane. Means are provided for passing methane, ethane or methanol in contact with the catalytic anode and means are also provided for passing an inert gas or oxygen in contact with the cathode. Finally, means are included for withdrawing higher hydrocarbons from the anode chamber and for withdrawing hydrogen or water from the cathode chamber.
The membrane capable of transferring the H+ from the anode chamber to the cathode chamber may be selected from a variety of materials, e.g. perfluorosulphonic acid, polybenzimidazole or an inorganic material, e.g. a zeolite such as HZSM-5. The anode and cathode may also be formed from a variety of different materials, such as compressed carbon powder loaded with metal catalyst, carbon cloths supporting metal catalyst, nickel mesh impregnated with metal catalyst, etc. Among particularly useful catalysts, there may be mentioned noble metals, such as Pt, Pd, Ru, etc. The body of the electrolysis cell may also be formed from a variety of materials such as Teflon, a carbon black, metal, etc.
While perfluorosulphonic acid (Nafion ) polymer provides a good proton conducting membrane, it is thermally stable only -at temperatures below about 120~C at atmospheric pressure.
Therefore, the use of the Nafion membrane requires a methane activation catalyst which is active under 120~C for the methane coupling reaction. It is found that the working temperature of the Nafion membrane can be increased by treating the Nafion membrane with phosphoric acid. Also, the polybenzimidazole membrane treated with H3PO4 is effective at higher temperatures.

Brief Description of the Drawinqs The above and further advantages of this invention will be seen in reading of the description of the preferred embodiments together with reference to the drawings wherein:
Fig. 1 is a schematic representation of a Teflon electrolysis cell according to the invention;
Fig. 2 is a schematic representation of a carbon block electrolysis cell;
Fig. 3 is a schematic representation of a high pressure, high temperature stainless steel electrolysis cell;
Fig. 4 is a plot of potential v. time;
Fig. 5 is a typical GC analysis;
Fig. 6 is a plot of potential v. time for a phosphonic acid treated Nafion membrane;
Fig. 7 is a plot of ~ CH4 conversion v. reaction temperature;
Fig. 8 is a plot of potential v. load on a PBI membrane based cell;
Fig. 9 is a plot of potential v. load for different arrangements of gas-catalytic electrode contact;
Fig. 10 is a plot of potential v. load showing the effect of catalysts on a PBI membrane based cell;
Fig. 11 is a plot of potential v. load showing the effect of temperature on a PBI membrane based cell; and Fig. 12 is a plot of current density at different resistance loads.

CA 0224l068 l998-06-l9 Description of the Preferred Embodiments Figure 1 shows a teflon electrolysis cell having teflon body portions 10 and 11, each with a flow inlet connector 12 and a flow outlet connector 13. Each body portion also has a body cavity 14 connected to the flow connectors 12 and 13.
Electrodes 15 and 16 fit within recesses in the body cavities with membrane 17 held between the electrodes 15 and 16.
A carbon block electrolysis cell is shown in Figure 2.
In this embodiment, a pair of carbon blocks 20 and 21 are used to form the body of the electrolysis cell. Slots 22 are provided in the carbon blocks to provide flow to the electrodes 23 and 24 which are held between the blocks 20 and 21. A membrane 25 iS held between the electrodes 23 and 24 to complete the cell.
A high temperature, high pressure stainless steel cell is shown in Figure 3. This consists of an outer tubular steel body 30 having ceramic end inserts 32 to provide flow connectors 33 and 34 which are insulated from the steel tube 30. The ceramic inserts 32 are held in place by end compression nuts, not shown.
Mounted within steel tube 30 iS a porous nickel tube 35 of smaller diameter than steel tube 30 SO as to provide an annular space 36 between porous nickel tube 35 and steel tube 30. A layer comprising a PBI membrane 37 iS formed on the outside surface of the nickel tube 35, sealing the pores of the tube. A nickel mesh 37 iS wrapped around the tube 35, this mesh supporting a metal catalyst. The mesh is tightly wrapped onto the tube using a nickel wire 38 which also acts as the electrical contact.
In the test work carried out to evaluate the present invention, the following instrumentation and gas analyses were used.
Instrumentation The electrochemical data were recorded using a Solartron 1286 electrochemical interface managed by Coware software.
Cyclic voltammetry and linear sweep voltammetry were used to monitor any changes while constant potential and constant current modes were used to perform gas phase electrolysis.
Gas Analysi~
The gas phase reaction feed and product from the cell were analyzed using a gas chromatography (Varian Vista 6000 CX, CDS 401 Computer Data System). The gas chromatography was equipped with a 50/80 Poropak N.2 column (Sulpeco) through which all components in the gas phase were eluted. The lighter components (such as H2, N2, ~2 and CH4) were then passed through a molecular sieve 13X (Sulpeco) for separation and detection by a thermal conductivity detector (TCD). The heavier components (such as CO, CO2, C2H4, C2H6, and C2H2) passed through a methanizer to convert them to methane, and were subsequently detected by a flame ionization detector (FID).
Argon served as a carrier gas for this GC system. The standard sample injection volume was approximately 1 ~L. The column temperature was programmed from 65~C, constant for 10 min., to 130~C at a rate of 5~C/min. Then the temperature was kept constant at 130~C until the completion of the analysis.
The instrument was calibrated using a UHP external calibration standard gas tank (Matheson Gas Products). Component peak detection was automatically performed by the CDS. The gas effluent from the cell was on-line analyzed every one hour and three samples were taken for each operation condition.
Cataly~t Preparation a) Carbon supported metal catalyst A weighted amount of H2PtCl6, palladium chloride (PdCl2) or ruthenium chloride (RuCl3)(Aldrich) was dissolved in 200 mL
deionized water. The water solution was heated at lukewarm temperature to dissolve the chemical in water completely.
Then a weighted amount of carbon powder was added into the solution. The amount of carbon added was calculated for a 10 wt~ of metal loading. The resulting solution was violent~y stirred and heated in air at 80~C until it dried out. The dried carbon powder loaded with metal catalyst was then baked in an oven under a small stream of hydrogen flow. The oven temperature was programmed for heating at a rate of 2~C/min.

from room temperature to 300~C. The temperature was kept constant at 300~C for 4h.
For hydrophobic treatment of the catalyst, a weighted amount of FEP emulsion (ElectroChem, Inc.) with a drop of Triton-X-100 (Fisher Scientific) was added into the carbon water solution before the drying process.
b) Nickel mesh supported catalyst The metal chemical-water solution was first prepared in the same way as above. Then a desired size of the nickel mesh (matching the cell size) was dipped into the solution. An overnight impregnation was allowed. The nickel mesh impregnated with metal catalyst (Pt, Pd or Ru) was taken out of the solution and dried at 80~C for 30 min. Then it was baked in an oven at 300~C for 4h in a hydrogen atmosphere.
The baking procedure was same as for the carbon based catalyst.
Preparation of Catalytic Electrode The method of the preparation of the catalytic electrode varied according to membrane and cell being used.
a) Electrode using Nafion membrane An accurately weighed sample at approximately 1 gram of powder carbon-metal catalyst was pressed into a pellet under a pressure of 5001b in a die. The pellet size and shape was made to fit to the size of the cell. The pellet was then coated with Nafion solution to ensure adhesion to the Nafion membrane (purchased from Du Pont). The Nafion membrane was sandwiched between two pellets as shown in Fig. 1. The prepared Nafion membrane-carbon catalyst pellet was baked in an oven for 20 minutes at 120~C before use.
b) Electrode using phosphoric acid treated Nafion membrane A piece of 2x2 inch Nafion membrane, which conforms to the size of a carbon block cell, was completely dipped into a 85~ phosphoric acid solution and boiled for at least 4 hours.
Then the membrane was taken out of the solution and left to dry to an incipient wetness. Carbon metal catalyst, prepared as described above, was loaded onto a carbon cloth (purchased from Du Pont). The metal catalyst precursor was dissolved in an ethanol solution in a glass bottle. Then the carbon cloth was dipped into the solution. The glass bottle was mounted onto a horizontal motor turning at a slow speed of around 5rpm. While turning, an infra-lamp was used to heat the glass bottle until all the ethanol solvent in the bottle vaporized away. By this method, the carbon supported metal catalyst was deposited onto the carbon cloth. Two pieces of catalyst loaded carbon cloth, together with the phosphoric acid treated membrane, were sandwiched in a carbon block cell as shown in Fig. 2.
c) Electrode Using PBI membrane Poly[2,2'-(m-phenylene)-5,5'bibenzimidazole] ~PBI) was obtained in powder form from Hoechst-Celanese. The polymer was dissolved in a dimethylacetamide solution (Aldrich) and 1 wt% LiCl was added as a stabilizing agent. The solution was heated at 130~C with reflux under atmospheric pressure for at least 2 hours. After cooled down to the ambient temperature, the solution was used to coat the external surface of a porous nickel tube. A layer of PBI membrane was formed on the outside surface of the nickel tube, sealing the pores of the tube. The tube was pressure tested for seal. The PBI
membrane-nickel tube was dipped into a phosphoric acid solution (85% concentration) overnight. Then it was ready to load catalyst. .
For loading a carbon supported metal catalyst, the catalyst was dissolved in a water-cellulose solution, forming a black paste. The paste was applied to the nickel tube with PBI membrane on the surface using a paint brush. The tube, after being coated with the carbon catalyst paste, was left to dry at ambient temperature. For the nickel mesh supported metal catalyst, the metal mesh was tightly wrapped onto the tube using a nickel wire, as shown in Fig. 3.
Testing Method a) Electrolysis Mode The channels were purged by nitrogen or argon gas. Then methane gas was introduced into the cathode side to replace the nitrogen/argon gas. After the electrical cell reached a constant operation temperature, a potential was applied to the cell. The current along the cell, with constant potential applied, was monitored and recorded by computer software from Coware. The composition of the effluent was analyzed by an on-line GC.
b) Fuel Cell Mode Both the anode and cathode channels of the cell were first purged by nitrogen or argon gas. Under an inert gas atmosphere, the cell was heated to a desired operation temperature at a controlled rate of 1~2~C/min. At the same time, the potential output of the cell was monitored by a Solartron 1286 instrument. After steady state was established at the operation condition, oxygen gas was introduced to replace the nitrogen gas in the cathode side and a reducing gas, such as H2, CH30H, C2H6 or CH4 was introduced to the anode side. The potential output as a function of time was recorded using Coware software.

Exam~le 1 In order to test the effect of the gas mode, both the anode and cathode channels of an electrolytic cell according to the invention were filled with flowing oxygen gas.
After a steady-state potential base line was established, the anode side of the oxygen gas was replaced by a pure methane gas. The change of the potential was monitored.
Figure 4 presents the testing as conducted with a Teflon cell as shown in Fig. 1 loaded with a Nafion membrane/Carbon-Pt electrode. The testing was conducted at 80~C and atmosphere pressure. When the gas phase was shifted from ~2/~2 to CH4/O2 mode, a temporary high potential peak (~600 mV) appeared.
With time, the potential value dropped to around 150 mV at 100 min. and continued to drop with time. The temporary high potential peak was checked by running a different gas shifting mode. The methane (anode)/argon (cathode) mode was operated first. Then the argon gas was replaced by oxygen gas. With this mode, the temporary high peak disappeared. This experimental fact indicated that when gas shifted from ~2/~2 to -CH4/02 as cited above, the ~2 and CH4 gases may meet and react in the anode side of the cell in the transition stage.
The methane may also react with preadsorbed oxygen on the catalytic electrode surface and thereby produced a high potential peak. With the second operation mode, the possibility of direct reaction between methane and oxygen was avoided. Hence the temporary high potential peak was eliminated. It is believed that the catalytic electrode might be active for a methane oxidation reaction but not favorable for methane activation in the absence of oxygen. In the GC
analysis of the effluent gas from the methane side, occasionally ppm level of ethylene or ethane was detected.
Unwanted ppm level CO2 product also appeared with the process.

Example 2 To search for a possible condition under which the methane can be activated, selected metal catalysts (e.g., Pt, Ru and Ta) were tested in a range of temperatures within thermally stable limits of the Nafion membrane. Table 1 shows the tested catalytic electrodes and temperature ranges.

2 0 Table 1 Catalytic Electrochemical Cells Using Nafion Membrane Type of Cell Anode Cathode TemlJe~lule ~C
Teflon Pt-Vulcan Carbon on Pt-Vulcan Carbon on 90 - 120 Stainless Steel Mesh Stainless Steel Mesh Teflon Ru-Vulcan Carbon on Pt-Vulcan Carbon on 90 - 120 Stainless Steel Mesh Stainless Steel Mesh 2 5 Carbon Block Pt-Activated Carbon on Pt-Activated Carbon on 70 - 90 Carbon Cloth Carbon Cloth Carbon Block Pt-Vulcan Carbon on Carbon Pt-Vulcan Carbon on 70 - 90 Cloth Carbon Cloth Carbon Block Ta-Activated Carbon on Pt-Activated Carbon on 90 Carbon Cloth Carbon Cloth Carbon Block Ru-Vulcan Carbon on Pt-Activated Carbon on 90 Carbon Cloth Carbon Cloth In the test, a CH4/N2 operational mode was used. At each test temperature, potential from 0.5 to 4 volts was applied.
Some activity was usually present at 0.8 volt and easily measurable activity was always present at 1 volt. The effluent gas composition on the methane side was on-line analyzed by gas chromatography. Only ppm level of C-2 products (ethane and/or ethylene) was detected. A typical GC
analysis is presented in Figure 5.
For the methane fuel cell, a general reaction step can be suggested as follows:
Catalyst surface on anode side: CH4 ca~uly~r > CH3 ~~~ H ca~uly~ ) CH3 +H (slow) H---e poten~ial ) H+ (fast) CH3 ~+CH3 . caratyst ~ C2H6 (fast) Membrane H+ (anode) poren~ial ) H+ (cathode) (slow) Catalyst surface on cathode side: H+ ~ e catalyt~ ) H ~ (fast) H + H cataly~ ) H (fast) The reaction rate depends on the catalyst activity able to split the methane and the proton conducting efficiency through the membrane. A possible explanation for the low concentration of C-2 hydrocarbons could be attributed to either an ineffective protonic membrane or an inactive catalyst surface.
When C2H6 is used as feedstock, the above reactions change as follows:
C2H6~C2Hj H~C2Hs +H
C2H5- + C2H5 ~ ~ ca~a~ys~ C4HIo Example 3 The thermal stability of the Nafion membrane may be increased up to 210~C after being treated with phosphoric acid. This increase provides the flexibility of operating the cell at a higher temperature. The CH4/O2 fuel cell mode was conducted at 180~C to test this membrane. Table 2 shows the test conditions and the electrode compositions.

Table 2 Catalytic Electrochemical Cells Using Phosphoric Acid Treated Nation Membrane Type of Cell Anode Cathode Temperature ~C
Carbon Block Pt-Activated Pt-Activated 180 Carbon/Carbon Cloth Carbon/Carbon Cloth Carbon Block Ru-Activated Pt-Activated 180 Carbon/Carbon Cloth Carbon/Carbon Cloth Figure 6 shows the change of potential with passage of time. As the figure shows, a drastic jump occurred when the gas mode shifted from CH4/N2 to CH4/02. However GC analysis of the gas effluent from the anode side did not show the amount of c-2 and higher hydrocarbons corresponding to the measured potential. Trace amounts of ethane or ethylene appeared. It was also noted that the CO2 peak appeared in the effluent throughout the test. The reason for the appearance of CO2 in the effluent may be due to the leakage of air into the system.
15 C~2 which leaked into the system with the air was directly detected by GC in the effluent. The oxygen in the air may also react with methane on the catalytic electrode, resulting in the production of CO2. A possible explanation for the high potential could be due to the full decomposition of the 20 activated methane. As soon as one hydrogen atom dissociates from the adsorbed methane on the catalyst surface according to the following reaction:
CH4 catalyst ) CH3 H carU~ ) CH3 +H
the dissociation reaction may continue as follows:
CH catal~st ~ CH2 H cataly~l ) CH2 +H
CH2 . cafalyst ) CH, H catnlysl , CH +H

CH, . calulyst ) C ~ ~ ~ H cat~ st ) C +H
According to this mechanism, carbon should accumulate on 25 the catalytic electrode surface of the anode side instead of forming c-2 and higher hydrocarbons, which would explain why only ppm level of C- 2 products were detected in the effluent in some experiments.

CA 02241068 1998-06-l9 Example 4 To check the activity of the catalyst used to prepare the catalytic electrode, a tube reactor was set up to conduct the catalytic reaction of methane oxidation. Pt/Vulcan carbon XC-72 was selected for the test. Figure 7 presents the experimental results. At 180~C, the conversion of methane oxidation reached about 25~ which indicated that the catalyst did activate the methane. However, considering the preparation procedure of the electrode, the catalyst electrode had to be pressed to contact the membrane. The acidic liquid on the membrane would cover or contaminate the solid catalyst surface directly. Since the catalyst electrode and the membrane must be pressed tightly together to keep a good contact, the phosphoric acid liquid in the membrane was squeezed out and absorbed by the solid catalyst. The active site of the solid catalyst would be covered by the liquid phosphoric acid which deactivates the catalyst.

Exam~le 5 a) Proton conductivity It is well known that methane is one of the most stable hydrocarbons. High temperature is required to activate the methane. However, limited by the thermal stability of the Nafion membrane, the reaction temperature was restricted to below 120~C in this study. The catalyst, as tested, showed a notable activity only after 180~C. Therefore, a protonic membrane operable around and above 200~C is highly desirable.
A PBI membrane has been reported in the literature to be a potential candidate as a protonic membrane for high temperature purposes. This is because of its exceptional high thermal stability (<500~C). To verify if this membrane has a proton conducting function, testing of a H2/O2 fuel cell mode was conducted first. Then CH3OH/O2 and CH4/O2 modes were tested. Figure 8 presents the test result at 130~C.
As the result shows, the obtained potential value follows the following order:
CH4/02 < C2H6/02 ' CH3oH/o2 ' H2/~2 This order exactly follows the order of the catalyst oxidation activity towards these chemicals. It suggests that the PBI membrane might function for proton conducting while its rate was limited by the catalyst activity towards different chemical compounds.
b) Effect of gas electrode contact arrangement The potential obtained from the above test was relatively small as compared to the test result from the phosphoric acid treated Nafion membrane. Tests by loading different catalysts onto the PBI membrane was conducted in a range of temperature up to 225~C. ~igure 9 compares the result by exposing ~2 and H2 gases on different gas electrode contact arrangements.
When ~2 was on the Pt-carbon side and H2 was on the nickel metal side, the cell produced a potential of 700 mV and higher as compared to 120 mV obtained from the gas-electrode contact in a reverse arrangement, i.e., with ~2 on the nickel side, and H2 on the Pt-carbon side. In the first arrangement, H2 was put in contact with the nickel metal. Nickel metal is a well known hydrogenation and dehydrogenation catalyst. Therefore in this case, H2 was activated by nickel metal and ~2 was activated by the Pt-carbon catalyst, which arrangement resulted in the production of the high potential. In the second arrangement, ~2 was on the nickel metal side. It is well known in the petrochemical industry that nickel metal is not a good oxidation catalyst. It appears that the ~2 was not activated in the second arrangement, which resulted in a low potential.
c) Effect of different catalytic electrodes The use of a carbon based catalyst produced a few problems. The carbon based catalyst had to be mixed with cellulose for adhesion purposes. However, the prepared cell could not be baked at a high temperature to remove the cellulose in the catalyst because of the presence of phosphoric acid in the cell. The dried carbon on the surface tended to shrink, thereby breaking the PBI membrane which was in a jelly state. The liquid phosphoric acid on the surface may also poison the Pt-carbon catalyst.

CA 0224l068 l998-06-l9 .~

An alternative method was to use nickel mesh loaded with Pt or Pd catalyst. The use of nickel mesh supported metal catalyst greatly facilitated the preparation of the catalytic electrode. The prepared nickel mesh supported catalytic electrode was baked at 300~C in an oven under a small hydrogen gas stream. The weak point using this method was that the contact between the membrane and the electrode relied on physical contact by a nickel wire. Figure 10 compares the two types of electrodes from tests using a H2/02 fuel cell mode.
The carbon based electrode showed a better activity but the difference was not large. The available data indicates that the Pt-carbon catalyst is more active than the Pt-nickel catalyst for ~2 activation.
d) Effect of Temperature Figure 11 shows HPHT cell testing results at different temperatures for a nickel mesh supported catalytic PBI
membrane electrode. As the figure shows, the potential increased with temperature increases. At 225~C, potentials as high as 640 mV were obtained at a resistance load of 10 mega ohm.
For a H2/02 fuel cell mode, the thermodynamic equilibrium calculation predicted a maximum theoretical potential of 1230 mV. Considering all types of inevitable potential losses in the electrode interfaces, the potential of 640 mV obtained from the experiment was reasonably high. However the current density converted from a potential-load test shows an amount only in the order of 10-3 mA/cm2 (Figure 12).

Claims (9)

1. A process for gas phase electrocatalytic polymerization of a hydrocarbon selected from the group consisting of methane, ethane and methanol to produce higher hydrocarbons and hydrogen using an electrolysis cell having an anode chamber on one side of a solid electrolyte and a cathode chamber on the other side of the solid electrolyte, said process comprising:
passing hydrocarbon-containing gas through said anode chamber to contact a catalytic anode which is connected to one side of the solid electrolyte, said solid electrolyte comprising a solid proton conducting membrane, passing an inert gas or oxygen through said cathode chamber to contact a catalytic cathode which is connected to the other side of the proton conducting membrane, passing H+ through the membrane from the anode chamber to the cathode chamber, and thereby forming higher hydrocarbons in the anode chamber and forming hydrogen or water in the cathode chamber.

2. A process according to Claim 1 wherein the hydrocarbon-containing gas is a methane-containing gas.

3. A process according to Claim 1 wherein the membrane is formed from perfluorosulphonic acid, polybenzimidazole or an inorganic material, e.g. a zeolite.

4. A process according to Claim 3 wherein the perfluorosulphonic acid polymer membrane is treated with phosphoric acid.

5. A process according to Claim 1 wherein the catalytic anode and cathode are formed of compressed carbon powder loaded with metal catalyst.

6. A process according to Claim 1 wherein the anode and cathode are formed of carbon cloth supporting metal catalyst.

7. A process according to Claim 1 wherein the anode and cathode are formed of nickel mesh impregnated with metal catalyst.

8. An electrochemical cell for gas phase electrocatalytic polymerization of hydrocarbon-containing gas to produce higher hydrocarbons and hydrogen, said electrochemical cell comprising:
an anode chamber on one side of a solid electrolyte and a cathode chamber on the other side of the solid electrolyte, said solid electrolyte comprising a solid proton conducting membrane separating the anode chamber from the cathode chamber, a catalytic anode is connected to one side of said proton conducting membrane and a cathode connected to the other side of the membrane, means for passing hydrocarbon-containing gas in contact with the catalytic anode, means for passing an inert gas or oxygen in contact with the cathode, means for withdrawing higher hydrocarbons from the anode chamber and means for withdrawing hydrogen or water from the cathode chamber.

9. A cell according to Claim 8 wherein the cell is formed of Teflon, a carbon block, or metal.