Patent Application
20150129430
The present invention is directed to an improved method of converting methane to methanol. The method utilizes inorganic metal oxide cation intermediates as catalysts to oxidize methane to methanol at temperatures not greater than about 160° C. and suitably at room temperature.
A Faradaic reaction is a heterogeneous charge-transfer reaction occurring at the surface of an electrode. Faradaic reactions are typically a defining feature of electrochemical cells. The production of methanol has conventionally been accomplished using a high temperature Fischer-Tropsch process operating at temperatures of about 150-300° C., typically using a transition metal catalyst. The Fischer-Tropsch process involves a collection of chemical reactions that convert a mixture of carbon monoxide and hydrogen into liquid hydrocarbons, including methane, methanol and various alkanes and alkanes. Thus, the production or methanol using this technique requires not only careful selection of the reactants, process conditions and catalysts to favor methanol conversion, but also the ability to separate methanol from the other reaction products.
Methanol can also be made from methane using a series of three reactions known as steam reforming, water shift, and synthesis performed sequentially as follows:
CH4+H2O→CO+3H2
CO+H2O→CO2+H2
2H2+CO→CH3OH
Because the foregoing process requires three separate reactions to occur in sequence, significant amounts of by-products can again be formed which require separation from the methanol product. Also, the high reaction temperatures require significant amounts of energy input. There is a need or desire for an efficient, relatively low temperature process of manufacturing methanol directly from methane.
The present invention is directed to a high efficiency method of converting methane to methanol at temperatures less than about 160° C., suitably room temperature (25° C.) which avoids the need for a high temperature Fischer-Tropsch process. The method includes the step of providing a reactor including an anode, a cathode, a membrane, separator between the anode and cathode. A metal oxide catalyst is provided at the anode, and water or an aqueous solution is provided at the cathode. Methane is fed to the anode, and is converted to methanol and electrons in the presence of the metal oxide catalyst at the anode. The electrons are conducted to the cathode, where they transform at least some of the water to hydrogen gas and hydroxide ions. The hydroxide ions are transferred through the membrane separator to the anode, where they cause regeneration of the metal oxide catalyst. Methanol is recovered from the reactor at the anode, and hydrogen gas can be recovered at the cathode.
Because the reactor operates at low temperature, the energy input required to produce methanol from methane is less than would be required using a conventional Fischer-Tropsch process. Moreover, the method of the invention produces methanol at a production rate that exceeds the theoretical production rate of a purely Faradaic reaction. This is because the reactor is believed to produce methanol using both a Faradaic and a non-Faradic reaction, with the production rate being the sum of the rates for both reactions. The result is a relatively low-cost, low energy, efficient and easy to use method of converting methane to methanol.
Referring to
The anode electrode 22 can include an inert base material formed of carbon felt or cloth, fluoroethylene polymer (e.g., Teflon), nickel foam, anion exchange resin, or a combination thereof. The base material is coated with a metal oxide, or a combination of one or more metal oxides, that serve as catalysts. Suitable metal oxide catalysts include without limitation oxides and hydroxides of nickel, cobalt, copper, silver, platinum, gold, cerium, lead, iron, manganese, zinc, and combinations thereof. Specific examples include without limitation nickel hydroxide iron hydroxide, zinc hydroxide, manganese hydroxide, cobalt hydroxide, cobalt oxide, silver oxide platinum oxide, cerium oxide, zinc oxide, manganese oxide, iron oxide, and combinations thereof.
The cathode electrode 24 can include a base material formed of graphite or another inert material, or a combination thereof. The base material is coated with as metal that serves as a hydrogen recovery catalyst. Suitable metals include without limitation platinum. Group VIII metals of the Periodic Table of Elements (iron, ruthenium, osmium), and combinations thereof.
The membrane separator 16 can be an electrolyte membrane, and can be a porous polymer material that contains an electrolyte. Other suitable membranes include ion conductive materials that have low water transport. It is desirable to restrict the transport of water from the cathode to the anode, because excessive water in the anode dilutes the methanol product. Particularly suitable electrolyte membranes include anionic exchange membranes formed from alkaline ionomers, available from Tokuyama Corporation under the product name NEOSEPTA®. These membranes have high permselectivity to facilitate permeation of specific anions, low electric resistance, low diffusion of liquids, and high mechanical strength. Other examples of anionic exchange membranes include porous membranes sold by Freudenberg under the product name 700/30K, microporous membranes sold by Celgard under the product name CELGARD® 3400, and microporous membranes sold by Daramic under the product name DARAMIC® DP-34.14. Cationic exchange membranes can also be employed in the membrane separator 16. Cationic exchange membranes include without limitation proton exchange membranes formed of sulfonated tetratluoroethylene-based fluoropolymer copolymer, available from Aldrich Chemical Co. under the product name NAFION®.
The anode 12 and cathode 14 also include outer plates 28 and 30 which, in order to facilitate a stable process and long useful life of the reactor 10, are designed to he substantially free of corrosion and leakage. The plates 28 and 30 can be formed of a graphite which has been electroplated with nickel to seal the pores in the graphite to prevent any leakage or corrosion. The plates 28 and 30 can alternatively include a graphite layer and a second, protective metal alloy layer that has been sealed to the graphite layer.
During use of the reactor 10, methane is fed to the anode 12 via inlet stream 32 and is converted to methanol in the presence of the metal oxide catalyst. The chemical reactions at the anode may vary depending on the specific metal oxide catalyst. and whether the environment is basic or acidic. In each case, the methane is oxidized to methanol and the metal oxide catalyst is converted to a non-catalytic state.
For example, the metal oxide catalyst can be a divalent metal hydroxide having the formula M1(OH2), such as β-nickel hydroxide, Ni(OH)2. In this case, the following chemical reactions would occur together at the anode, in a basic environment, and at room temperature without requiring added heat.
M1OH)2+OH−→M1O++H2O+e−
M1O++OH−+CH4→CH3OH+OH−+M1+
M1++½O2→M1O+
M1O++OH−→M1O+OH−
The net chemical reaction at the anode, which is the sum of the individual reactions, yields a converted (non-catalytic) metal hydroxide, methanol, water, and free electrons.
M1(OH)2+CH4+3OH−→M1O+OH−+CH3OH+2H2O+3e−
The foregoing net chemical reaction is Faradaic because of the generation of electrons. Additionally, a non-Faradaic electrochemical reaction occurs in the anode due to the electric current supplied to the reactor. The oxygen supplied to this reaction is the trace oxygen present in the anode from the inlet stream 32.
The non-Faradaic electrochemical reaction causes the total methanol production rate to exceed the theoretical maximum production rate from the Faradaic reaction using the metal oxide catalyst. For example, the methanol conversion rate may exceed the theoretical Faradic rate by at least about 10% or at least about 25%, or at least about 50% or more. The theoretical Faradaic production rate of methanol using the metal oxide catalyst is about 0.75 ml/A.min. Yet the total methanol production rate from the reactor 10, using a 1.4 volt power supply, has been up to about 1.20 ml/A.min, representing a surprising 60 percent improvement.
The methanol is recovered from the anode 12 of reactor 10 via the outlet stream 34, which also includes some unreacted methane. The methanol and methane are then separated, and the unreacted methane is recycled back to the inlet stream 32 via the recycle stream 38. The methanol product is recovered from the combined stream 34 via product stream 36. Because of the dual (Faradaic and non-Faradaic) reactions occurring in the anode 12, the conversion rate of methane to methanol can be quite high. The outlet stream 34 may contain at least about 10% by weight methanol and not More than about 60% by weight methane balanced by water vapor (30%), suitably at least about 40% by weight methanol and not more than about 20% by weight methane balanced by water vapor (40%). The methane gas works both as a carrier gas and a reactant.
The free electrons generated at the anode 12 are conducted to the cathode 14. Water or an aqueous solution is fed to the cathode 14 via inlet 40, typically as a basic or acidic solution. When an acidic. solution is used at the cathode, a bipolar membrane separator 16 is used. The bipolar membrane separator contains an acidic polymer electrolyte overlapped on a basic polymer electrolyte. The basic polymer electrolyte faces the anode and the acidic polymer electrolyte faces the cathode. In the embodiment shown, a 25% w/w potassium hydroxide solution having a pH of about 14 or greater is fed to the cathode 14 via inlet 40. The free electrons interact with the water in the presence of the hydrogen evolution catalyst to generate hydroxide ions and hydrogen gas, the latter of which exits the cathode through outlet 42 and can be recovered for various uses. The hydroxide ions are then transferred through the membrane separator 16 back to the anode 12, where they react with and regenerate the used metal oxide catalyst.
The following chemical reactions typically occur at the cathode 14, where M2 is the hydrogen recovery catalyst, platinum or a Group VIII metal.
M2+H2O+e−→M2H+OH−
M2H→M2+½H2
As indicated, the hydrogen recovery catalyst M2 is self-regenerating. The net chemical reaction at the cathode 14, which is the sum of the foregoing reactions, converts the water to hydroxide ions and hydrogen.
H2O+e−→OH−+½H2
The overall sum of the Faradaic reactions occurring in the anode 12 and cathode 14 is the hydrolysis of methane.
CH4+H2O→CH3OH+H2
The reactor 10, and the foregoing chemical reactions in the anode 12 and cathode 14, can occur at a temperature less than about 160° C., or less than about 100° C. or less than about 50° C., or at ambient temperature (about 25° C.). As shown above, the overall reaction uses only methane and water to produce methanol and hydrogen gas. The other reactants are used only to form intermediate compounds, and are continuously regenerated.
Using a reactor 10 designed as shown in
In the following Examples 1-27, the following acronyms or abbreviations are used.
In each experiment, the reactor was supplied with a current of 8 mA/cm2 (based on 1.48 volts) for at least six hours. Methane was fed to the anode at a rate of 1 ml/min., and aqueous potassium hydroxide (25% w/v) was fed to the cathode at a rate of 0-10. The product stream exiting the anode was analyzed using gas chromatography. In order to calibrate the instrument, various solutions of methanol ranging in concentration from 1 to 5 moles were prepared, each in an aqueous solution of 25% w/v potassium hydroxide. A plot of GC signal (mV) versus molar concentration of methanol was prepared for use as a calibration curve.
The results are summarized in Table 1. The column entitled “observations” indicates the combinations of anode electrode configuration and catalyst, and separator membrane, that resulted in large methanol peaks as an indicator of good methane to methanol conversions. In general, the catalyst combinations of Ni(OH)2 with CoO and CeO2, as well as Ni(OH)2 with CeO2, resulted in the largest methanol peaks in the product stream using various materials for the membrane separator.
Ni(OH)2/Ag/C/CeO2(83:5:10)/
Ni(OH)2/CoO(9:1)Ag/C/CeO2
Ni(OH)2/CoO(9:1)/Ag/C/CeO2
For Examples 28-33, a small reactor was used having an area of about 30 cm2 for the anode and cathode and the membrane separator. The membrane separator was an anionic electrolyte membrane sold by Tokuyama (Japan) under the product name AEM A201. The metal oxide catalyst present at the anode was nickel hydroxide, Ni(OH)2, coated onto a graphite cloth sold by Zoltek under the product name PANEX® 30. The hydrogen recovery catalyst present at the cathode was platinum metal, coated onto a layer of graphite.
The current to the reactor was varied using a cell voltage of 1.30 volts (Example 28), 1.35 volts (Example 29), 1.40 volts (Example 30), 1.43 volts (Example 31), 1.45 volts (Example 32) and 1.50 volts (Example 33). Methane was fed to the anode at a constant rate of 1 ml/min. Aqueous potassium hydroxide (25% w/v) was fed to the cathode at a constant rate of 10 ml/min. For each change in voltage, the reactor was allowed to reach steady state, requiring a time period of at least 3 min.
The methanol signal at the exit stream from the anode was measured using gas chromatography, as described above. The signals for methane, carbon dioxide and oxygen were also measured and recorded. The results are plotted in
While the embodiments of the invention described herein are presently preferred, various modifications and improvements can be made without departing from the spirit and scope of the invention. The scope of the invention is indicated by the appended claims, and all changes that fall within the meaning and range of equivalents are intended to be embraced therein.
This invention was made with government support under DE-AR0000307 awarded by the United States Department of Energy. The government has certain rights in the invention.
