HK1160890A

HK1160890A - Methods and apparatus of electrochemical production of carbon monoxide, and uses thereof

Info

Publication number: HK1160890A
Application number: HK12101252.7A
Authority: HK
Inventors: 伊戈尔‧卢博米尔斯基; V‧卡普兰
Original assignee: 曳达研究和发展有限公司
Priority date: 2008-11-06
Filing date: 2009-11-05
Publication date: 2012-08-17

Description

Electrochemical production method and equipment of carbon monoxide and application thereof

Technical Field

The present invention relates to an electrolytic process, method and apparatus for the production of carbon monoxide, and in particular to the electrolysis of molten carbonate to produce carbon monoxide which can be used for the chemical storage of electrical energy and further as a chemical feedstock for other organic products.

Background

The main sources of wind and solar energy as renewable energy sources are weather and time dependent. Moreover, the geographic areas most suitable for accessing these resources are also remote. Therefore, chemical energy storage/transmission is considered the most likely way to capture renewable energy.

Alternative chemical energy sources may include CO and H₂Hydrocarbons and oxygenated aliphatics synthesized by, for example, the fischer-tropsch process. More recently, the fischer-tropsch process has been considered as a viable process for producing heavier hydrocarbons, such as diesel fuel, and more preferably waxy molecules that can be converted into clean-available lubricants. The energy and feedstock for this purpose currently derives from the combustion of coal, accompanied by CO as a by-product₂And (4) discharging. However, this process increases atmospheric CO₂And can make global climate more severe. Alternatively, CO₂Can be used as a carbon source for producing petroleum substances. This then provides for conditioning atmospheric CO₂The likelihood of concentration.

Due to CO₂Is one of the most thermodynamically stable carbon compounds and thus requires a high energy reductant or an external energy source to convert it to other carbon compounds. It is well known that Carbonates (CO)₃ ^2-) Can be electrochemically reduced as follows:

cathode (1) CO₃ ^2-+2e^-→CO+2O^2-

Anode (2)2O^--2e^-→O₂

However, some by-products may produce elemental carbon at the cathode, or CO at the anode₂：

Cathode: CO 2₃ ^2-+4e^-→C+3O^2-

Or on the anode: CO 2₃ ^2--2e^-→CO₂+^1/2O₂

Furthermore, the CO generated may decompose:

CO←→CO₂+C

methanol is one of the main chemical feedstocks, which is ranked third by volume immediately after ammonia and ethylene. The demand for methanol as a chemical feedstock is constantly increasing worldwide, particularly in view of its increasingly important role (as well as dimethyl ether) as a source of olefins such as ethylene or propylene and as an alternative energy source such as motor fuel additives or in the conversion of methanol to gasoline.

Methanol is not only a convenient and safe way to store energy, but also an excellent fuel as is the dimethyl ether (DME) from which it is derived. Dimethyl ether is readily obtained from methanol by dehydration and is an effective fuel, particularly for use in diesel engines, due to its high octane number and advantageous properties. Methanol and dimethyl ether can be mixed with gasoline or diesel and used as fuel, for example in internal combustion engines or generators. One of the most effective uses of methanol is in fuel cells, particularly in Direct Methanol Fuel Cells (DMFC), where methanol is directly oxidized to carbon dioxide and water using air while generating electricity.

Accordingly, there is a need for an efficient electrochemical process and an efficient electrochemical cell that can reduce carbonates to carbon monoxide (CO) and thereby generate chemical energy sources, such as methanol. Furthermore, the produced CO can be used for energy transmission.

Disclosure of Invention

In one embodiment, the present invention provides a method of electrochemically producing carbon monoxide, the method comprising: heating an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium or a combination thereof, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide.

In one embodiment, the present invention provides a method for producing methanol or hydrocarbons, the method comprising: (a) heating an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium, or a combination thereof, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide; (b) hydrogenating the carbon monoxide to produce methanol or hydrocarbons.

In one embodiment, the present invention provides an electrochemical cell for the production of CO, the electrochemical cell comprising:

a. a power source;

b. a first reaction chamber comprising an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

d. at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium, or a combination thereof;

e. a heating system;

f. a first conduit for conveying CO from the electrochemical cell to a gas collector;

wherein the heating system heats the metal carbonate to form a molten carbonate; the tuyere optionally injects the gas into the molten carbonate; the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments; and CO is formed by applying a voltage and conveyed to a gas collector through the first conduit.

In one embodiment, the invention provides a process for the production of carbon monoxide comprising electrolysis of molten carbonate using the electrochemical cell of the invention.

In one embodiment, the present invention provides an apparatus for producing methanol or carbohydrates, the apparatus comprising:

(i) an electrochemical cell, comprising:

a. a power source;

b. first reaction comprising alkali metal carbonate or mixture of alkali metal carbonate and alkaline earth metal carbonate

A reaction chamber;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

wherein the heating system heats the metal carbonate to form a molten carbonate; the tuyere optionally injects the gas into the molten carbonate; and the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments;

(ii) a second reaction chamber having a reaction chamber for introducing H₂An inlet into the second reaction chamber;

(iii) a first conduit that conveys CO from the electrochemical cell into the second chamber;

(iv) a second conduit that conveys methanol or hydrocarbons from the second reaction chamber to an outlet;

wherein CO is formed by applying a voltage and conveyed to a second reaction chamber through the first conduit; and said CO and H₂Reacting in the second reaction chamber to produce the methanol or hydrocarbon.

In one embodiment, the present invention provides a process for the production of methanol or hydrocarbons, said process comprising reacting carbon monoxide with hydrogen using the apparatus of the present invention.

In one embodiment, the present invention provides an apparatus for producing methanol or hydrocarbons, the apparatus comprising:

(i) a first electrochemical cell, the first electrochemical cell comprising:

a. a power source;

A reaction chamber;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

wherein the heating system heats the metal carbonate to form a molten carbonate; the tuyere optionally injects the gas into the molten carbonate; and the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments; forming CO by applying a voltage;

(ii) a second electrochemical cell, the second electrochemical cell comprising:

a. a power source;

b. a third reaction chamber;

c. at least two electrodes;

wherein H is formed by applying a voltage₂；

(iii) A second reaction chamber;

(iv) a first conduit that conveys CO from the first electrochemical cell to the second chamber;

(v) a third pipeline for passing H₂Is conveyed to the second reaction chamber by the second electrochemical cell；

(vi) A second conduit that conveys methanol or hydrocarbons from the second reaction chamber to an outlet;

wherein the CO is conveyed to the second reaction chamber through the first conduit; said H₂Is conveyed to the second reaction chamber through the third pipeline; and said CO and H₂Reacting in the second reaction chamber to produce methanol or hydrocarbons.

Drawings

The subject matter regarded as the invention is particularly pointed out and distinctly claimed in the concluding portion of the specification. The invention, however, both as to its organization and method of operation, together with objects, features, and advantages thereof, may best be understood by reference to the following detailed description when read with the accompanying drawings in which:

FIG. 1 depicts (a) melting Li₂CO₃Quasi-static current-potential relationship of the medium Ti cathode. (b) Melting Li₂CO₃The quasi-static current-potential relationship of the medium-pressed graphite anode. The linear potential-current relationship indicates that the current is limited by ohmic resistance.

FIG. 2 depicts (a) a chromatogram of the gas in the cathode compartment during electrolysis at 900 ℃; the small proportion of oxygen and nitrogen is present because there is a small amount of air remaining in the compartment; (b) chromatogram of the gas in the anode compartment 3 minutes after the start of electrolysis at 900 ℃. After a while, the oxygen concentration reached 100%. Note that: no CO detection in either compartment₂。

It will be appreciated that for simplicity and clarity of illustration, elements illustrated in the figures have not necessarily been drawn to scale. For example, the dimensions of some of the elements may be exaggerated relative to other elements for clarity. Further, where considered appropriate, reference numerals may be repeated among the figures to indicate corresponding or analogous elements.

Detailed Description

In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the present invention.

In some embodiments, the present invention provides methods, electrochemical cells, and apparatuses for producing carbon monoxide. In one embodiment, the carbon monoxide produced according to the process of the present invention will be used as an alternative energy source. In one embodiment, the carbon monoxide produced according to the process of the present invention will be used for energy transfer. In one embodiment, the carbon monoxide produced according to the process of the present invention will be used for chemical storage of electrical energy. In another embodiment, carbon monoxide may be used as a chemical feedstock for other organic products (e.g., plastics, polymers, hydrocarbons, hydrocarbon carbonylation, fuels, etc.), and in another embodiment, carbon monoxide will be used as a chemical feedstock for the production of methanol. In another embodiment, carbon monoxide will be used as a chemical feedstock for the production of hydrocarbons or oxygenated hydrocarbons.

In one embodiment, the present invention provides a method of electrochemically producing carbon monoxide, the method comprising: heating an alkali metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide.

In one embodiment, the present invention provides a method of electrochemically producing carbon monoxide, the method comprising: heating a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate salt using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises a titanium electrode coated with carbon; wherein a carbon dioxide containing gas is optionally injected into the molten carbonate, thereby producing carbon monoxide. In one embodiment, the present invention provides an electrochemical cell for the production of CO, the electrochemical cell comprising:

a. a power source;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

a. a power source;

b. a first reaction chamber comprising a mixture of an alkali metal carbonate and an alkaline earth metal carbonate;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

d. at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises titanium coated with carbon;

e. a heating system;

a. a power source;

b. a first reaction chamber comprising an alkali metal carbonate;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

d. at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite;

e. a heating system;

wherein the heating system heats the alkali metal carbonate to form molten carbonate; the tuyere optionally injects the gas into the molten carbonate; the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments; and CO is formed by applying a voltage and conveyed to a gas collector through the first conduit.

In one embodiment, the present invention provides a method of electrochemically producing carbon monoxide, the method comprising electrolysing molten carbonate by an electrochemical cell, wherein the electrochemical cell comprises:

a. a power source;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

In one embodiment, the inventive method and electrochemical cell and apparatus for producing carbon monoxide comprise and/or utilize molten carbonate as an electrolyte. In another embodiment, the molten carbonate is formed by heating the carbonate of the present invention.

The carbonate of the present invention means an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate.

The molten carbonate of the present invention means a molten alkali metal carbonate or a mixture of a molten alkali metal carbonate and an alkaline earth metal carbonate.

In one embodiment, the alkali metal carbonate of the present invention comprises lithium carbonate, sodium carbonate, potassium carbonate, or any combination thereof. In another embodiment, the alkali metal carbonate is lithium carbonate (Li)₂CO₃). In another embodiment, the alkali metal carbonate is sodium carbonate (Na)₂CO₃). In another embodiment, the alkali metal carbonate is potassium carbonate (K)₂CO₃). In another embodiment, the alkali metal carbonate comprises at least 50% lithium carbonate (Li)₂CO₃)。

In one embodiment, the alkaline earth metal carbonate of the present invention comprises barium carbonate, strontium carbonate, calcium carbonate, or any combination thereof. In another embodiment, the alkaline earth metal carbonate is barium carbonate. In another embodiment, the alkaline earth metal carbonate is strontium carbonate. In another embodiment, the alkaline earth metal carbonate is calcium carbonate.

In another embodiment, the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of from 1: 1 to 0.95: 0.05 molar ratio, respectively. In another embodiment, the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of 1: 1 molar ratio. In another embodiment, the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of 0.6: 0.4 molar ratio; in another embodiment, the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of 0.7: 0.3 molar ratio; in another embodiment, the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of 0.8: 0.2 molar ratio; in another embodiment, the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of 0.9: 0.1 molar ratio.

In one embodiment, the methods, electrochemical cells, and apparatus of the present invention comprise and/or utilize molten carbonate to produce carbon monoxide. In another embodiment, the molten carbonate is formed by heating the carbonate of the present invention to its melting point. In another embodiment, Li is melted₂CO₃By mixing Li₂CO₃Heating to a temperature of 723 deg.C or higher.

In one embodiment, the methods, electrochemical cells, and apparatus of the present invention comprise and/or utilize molten carbonate as an electrolyte to produce carbon monoxide. In another embodiment, the electrolyte of the present invention is Li₂CO₃. In another embodiment, the electrolyte of the present invention comprises at least 50% Li₂CO₃. In another embodiment, the lithium ions are stable and are not reduced at high temperatures ranging from 780 ℃ to 900 ℃. In another embodiment, the lithium ions do not stabilize the formation of peroxide and percarbonate ions. In another embodiment, as shown in example 2, it was found that the weight loss was 1.2 wt% after heating at 900 ℃ for 2 hours, and the weight did not increase after heating at 900 ℃ for 24 hours.

During electrolysis of the molten carbonate of the present invention for producing carbon monoxide, the concentration of carbonate ions is reduced. In another embodiment, in the electrolytic process of the molten carbonate of the present invention for producing carbon monoxide, the metal carbonate is oxidized and forms a metal oxide. In another embodiment, the metal oxide forms a metal carbonate in the presence of carbon dioxide. In another embodiment, lithium oxide (Li) is formed during electrolysis of molten lithium carbonate for producing carbon monoxide₂O). In another embodiment, lithium oxide (Li)₂O) in the presence of carbon dioxide to form lithium carbonate (Li)₂CO₃). In one embodiment, a carbon dioxide containing gas is added to the electrochemical cell to maintain a constant carbonate ion concentration. In another embodiment, the metal oxide is reacted with carbon dioxide to produce a metal carbonate.

In an electrolytic process of molten carbonate for generating carbon monoxide, in which the molten carbonate is a mixture of alkali metal carbonate and alkaline earth metal carbonate, a metal oxide layer is formed on the surface of the molten carbonate.

In another embodiment, metal oxide crystals are formed on the surface of the molten carbonate. In another embodiment, the metal oxide crystals or layers are in atmospheric CO₂In the presence of a spontaneously produced metal carbonate, wherein the metal carbonate is reused in the electrolytic process, electrochemical cell or apparatus of the present invention.

In the electrolysis of molten carbonates, which are a mixture of alkali metal carbonates and alkaline earth metal carbonates, a metal oxide layer or crystals are formed on the surface of the molten carbonate. In one embodiment, the metal oxide layer or crystals on the surface of the molten carbonate are removed and reacted with CO₂Recycled together to produce metal carbonate. In another embodiment, the recycled metal carbonate may be reused in the electrolytic process, electrochemical cell and/or apparatus of the present invention.

In one embodiment, the metal oxide produces a metal carbonate in the presence of carbon dioxide. In one embodiment, the CO-containing compound reacted with the metal oxide of the present invention₂The gas of (A) is pure or concentrated CO₂. In another embodiment, the CO is reacted with a metal oxide₂Is atmospheric CO₂. In another embodiment, CO is continuously injected into the electrochemical cell during electrolysis₂. In another embodiment, CO₂Diffused into the cell by air.

In another embodiment, the carbon dioxide containing gas comprises carbon dioxide in an amount of 0.01% to 100% by weight of the gas. In another embodiment, the carbon dioxide containing gas comprises carbon dioxide in an amount of 0.03% to 98% by weight of the gas. In another embodiment, the carbon dioxide containing gas comprises 50% to 100% carbon dioxide by weight of the gas. In another embodiment, the carbon dioxide containing gas comprises 80% to 100% carbon dioxide by weight of the gas. In another embodiment, the carbon dioxide containing gas comprises carbon dioxide in an amount of 0.1% to 5% by weight of the gas. In another embodiment, the carbon dioxide containing gas comprises carbon dioxide in an amount of 0.01% to 5% by weight of the gas.

In one embodiment, the methods, electrochemical cells and apparatus of the present invention for producing carbon monoxide comprise and/or use at least two electrodes. In one embodiment, the first electrode is a cathode. In another embodiment, the cathode or first electrode comprises a valve metal. In another embodiment, the cathode or first electrode comprises titanium. In another embodiment, the cathode or first electrode is a titanium electrode. In another embodiment, the cathode or first electrode is a titanium-containing alloy. In another embodiment, the cathode or first electrode is an alloy comprising titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

The term "valve metal" refers to a metal that, when oxidized, allows the passage of current if it is used as a cathode and prevents the flow of current if it is used as an anode. Non-limiting examples of valve metals include magnesium, thorium, cadmium, tungsten, tin, iron, silver, silicon, tantalum, titanium, aluminum, zirconium, and niobium. In another embodiment, the valve metal is covered with an oxide protective layer and therefore does not promote the Boudouard reaction CO ← → CO₂+ C decomposition of the CO produced. In another embodiment, an oxide layer formed on the valve metal surface generally protects it from rapid melting.

In another embodiment, Li is melted₂CO₃The medium titanium electrode does not corrode because it forms Li above 750 deg.C₂TiO₃A protective layer that is electrically conductive and does not significantly affect cell resistance. In another embodiment, the lithium metal is insoluble in titanium, which precludes alloying during electrolysis.

In one embodiment, the methods, electrochemical cells, and apparatuses for producing carbon monoxide of the present invention comprise and/or utilize titanium electrodes. In another embodiment, the titanium electrode of the present invention is prepared from a 5mm thick Ti plate. In another embodiment, the titanium electrode is stable to prolonged exposure to molten carbonate. In another embodiment, a sustained exposure of the titanium electrode to lithium carbonate for about 100 hours indicates that the concentration of titanium in the electrolyte is less than 0.02 mole% (trace amounts) and does not rise upon further exposure. In another embodiment, the titanium electrode is stable to prolonged exposure to the electrolyte, as exemplified in example 3.

In one embodiment, the methods, electrochemical cells and apparatus of the present invention for producing carbon monoxide comprise and/or use at least two electrodes. In another embodiment, the second electrode is an anode. In another embodiment, the anode or second electrode comprises titanium, graphite, or a combination thereof. In another embodiment, the anode or second electrode comprises carbon. In another embodiment, the anode or second electrode is a graphite electrode. In another embodiment, the anode or second electrode is pressed graphite or glassy graphite. In another embodiment, the compacted chemically pure graphite is in molten Li₂CO₃It is not corroded. Electrolysis at 100 hours (100mA/cm at 900 ℃ C.)²) And no weight loss of the graphite electrode was detected after exposure to the electrolyte (no current). In another embodiment, the stability of the graphite electrode is as described in example 3.

In another embodiment, the anode or second electrode is a titanium electrode. In another embodiment, the anode or second electrode is a titanium alloy. In another embodiment, the anode or second electrode is a titanium alloy comprising titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof. In another embodiment, the anode or second electrode is a titanium electrode coated with carbon/graphite.

The method, electrochemical cell and apparatus of the present invention for producing carbon monoxide comprise and/or use an anode. In one embodiment, the anode is a titanium or titanium alloy electrode coated with carbon/graphite. In one embodiment, a graphite coated titanium electrode is prepared by: the titanium electrode or titanium alloy electrode immersed in molten carbonate is subjected to an aging treatment (aging) at a temperature of 700 to 900 ℃ and a negative potential of more than 3 volts for 10 to 60 minutes, whereby the titanium electrode is coated with carbon. In another embodiment, the electrode is used as an anode when a positive potential is applied. In another embodiment, the process for preparing a titanium electrode coated with carbon is as described in example 4.

In another embodiment, the negative potential used to prepare the carbon/graphite coated titanium or titanium alloy electrode is between 3 volts and 5 volts. In another embodiment, the negative potential is between 3 volts and 6 volts. In another embodiment, the negative potential is between 3 volts and 7 volts.

In another embodiment, the temperature used to prepare the carbon/graphite coated titanium or titanium alloy electrode is between 700 ℃ and 900 ℃ and lasts between 10 minutes and 60 minutes. In another embodiment, the temperature is from 750 ℃ to 850 ℃. In another embodiment, the temperature is from 750 ℃ to 900 ℃. In another embodiment, the aging step lasts 20 minutes. In another embodiment, the aging step lasts from 10 minutes to 50 minutes. In another embodiment, the aging step lasts 15 to 60 minutes. In another embodiment, the aging step lasts 30 to 60 minutes. In another embodiment, the aging step lasts from 10 minutes to 20 minutes.

In one embodiment, the methods, electrochemical cells and apparatus of the present invention for producing carbon monoxide comprise and/or use at least two electrodes, wherein a first electrode is a cathode; the second electrode is an anode and optionally the third electrode is a reference electrode. In another embodiment, the reference electrode is a Pt wire.

The ideal reference electrode has a stable, well-defined electrochemical potential. Common reference electrodes include calomel: mercury/mercuric chloride; silver/silver chloride or copper/copper sulfate meet this criterion when it is working properly and should also have zero impedance.

The purpose of the reference electrode in potentiometry is to provide a stable potential against which to measure the working electrode half-cell (e.g., ion-selective electrode, redox potential electrode, or enzyme electrode).

In one embodiment, the process of the invention is carried out under an inert gas. In another embodiment, the process of the invention is carried out in the presence of atmospheric air. In one embodiment, the process of the invention is carried out at atmospheric pressure. In one embodiment, the process of the invention is carried out under pressurized conditions. In one embodiment, the process of the present invention is carried out under high temperature conditions.

In one embodiment, the method, electrochemical cell and apparatus of the present invention for producing carbon monoxide comprises and/or utilizes a heating system, wherein the electrolysis of the alkali metal carbonate is carried out under heating. In another embodiment, the heating system is a furnace. In another embodiment, the electrolysis is carried out at a temperature of 780 ℃ to 950 ℃. In another embodiment, the electrolysis is carried out at a temperature of 800 ℃ to 900 ℃. In another embodiment, the electrolysis is carried out at a temperature of 850 ℃ to 900 ℃. In another embodiment, the electrolysis is carried out at a temperature of 850 ℃ to 950 ℃.

In one embodiment, the method, electrochemical cell and apparatus of the present invention for producing carbon monoxide comprises heating a base and/or an alkali metal carbonate to form a metal carbonate. In another embodiment, the heating is carried out at a temperature of 780 ℃ to 950 ℃. In another embodiment, the heating is carried out at a temperature of from 800 ℃ to 900 ℃. In another embodiment, the heating is carried out at a temperature of 850 ℃ to 900 ℃. In another embodiment, the heating is carried out at a temperature of 850 ℃ to 950 ℃.

In one embodiment, the method and electrochemical cell of the present invention for the production of carbon monoxide comprises electrolysis of carbonate ions. In another embodiment, a potential of 0.9V to 1.2V is applied. In another embodiment, a potential of 1.1 ± 0.05V is applied. In another embodiment, a potential of 1.1V to 1.2V is applied. In another embodiment, a potential of 1.0V to 1.1V is applied.

In one embodiment, electrolysis of molten carbonates of the present invention has a faradaic efficiency of 100% and a thermodynamic efficiency of 80% to 100%. In another embodiment, the thermodynamic efficiency is between 80% and 90%. In another embodiment, the thermodynamic efficiency is about 85 ± 4%.

The term "faradaic efficiency" refers to the energy efficiency that can be achieved when electrolyzing species at a given charge. High faradaic efficiency indicates that less energy is required to achieve the reaction, making the process more feasible.

The term "thermodynamic efficiency" refers to the highest efficiency of an electrochemical cell. Thermodynamic efficiency refers to the ratio of the amount of work performed by the system to the amount of heat generated to perform that work.

Thermodynamic efficiency:

wherein Δ H is the reaction enthalpy and Δ G is the gibbs energy of combustion of CO:in another embodiment, the gibbs energy for CO combustion at 900 ℃ becomes Δ G181 kJ/mole.

In one embodiment, the present invention provides a thermally stable electrochemical cell. In another embodiment, an electrochemical cell comprises a first reaction chamber. In another embodiment, the frame of the first reaction chamber is made of titanium or a titanium alloy. In another embodiment, the titanium alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof. In another embodiment, the frame of the electrochemical cell and/or the first reaction chamber is made of high purity alumina, GeO, a ceramic comprising yttria, beryllium oxide, a lithium beryllium alloy, or a lithium yttrium alloy.

In one embodiment, the present invention provides a method, electrochemical cell and apparatus for producing carbon monoxide. In another embodiment, carbon monoxide is collected from the cathode compartment into a gas collector. In another embodiment, the gas collector is a container, a can, a bottle, a porous material, or a gas collector.

In one embodiment, the present invention provides a method for producing methanol or hydrocarbons, the method comprising: (a) heating an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium or a combination thereof, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide.

In one embodiment, the present invention provides a method for producing methanol or hydrocarbons, the method comprising: (a) heating an alkali metal carbonate to form a molten carbonate; electrolyzing the molten carbonate salt using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate salt, thereby producing carbon monoxide; (b) hydrogenating the carbon monoxide to produce methanol or hydrocarbons.

In one embodiment, the present invention provides a method for producing methanol or hydrocarbons, the method comprising: (a) heating a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises titanium coated with graphite/carbon, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide; (b) hydrogenating the carbon monoxide to produce methanol or hydrocarbons.

(i) an electrochemical cell, comprising:

a. a power source;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

wherein CO is formed by applying a voltage and conveyed to the second reaction chamber through the first conduit, and the CO and H₂Reacting in the second reaction chamber to produce the methanol or hydrocarbon.

(i) a first electrochemical cell, the first electrochemical cell comprising:

a. a power source;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

wherein the heating system heats the metal carbonate to form a molten carbonate; the tuyere optionally injects the gas into the molten carbonate; and the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments; wherein CO is formed by applying a voltage;

(ii) a second electrochemical cell, the second electrochemical cell comprising:

a. a power source;

b. a third reaction chamber;

c. at least two electrodes;

wherein H is formed by applying a voltage₂；

(iii) A second reaction chamber;

(v) a third pipeline for passing H₂Passing from the second electrochemical cell to the second reaction chamber;

wherein the CO is conveyed to the second reaction chamber through the first conduit; said H₂Is conveyed to the station through the third pipelineThe second reaction chamber; and said CO and H₂Reacting in the second reaction chamber to produce methanol or hydrocarbons.

In one embodiment, the present invention provides a process for the production of methanol or hydrocarbons, the process comprising reacting carbon monoxide with hydrogen using an apparatus comprising:

(i) an electrochemical cell, comprising:

a. a power source;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

wherein the heating system heats the metal carbonate to form a molten carbonate; wherein the tuyere optionally injects the gas into the molten carbonate; and the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments;

wherein CO is formed by applying a voltage and conveyed to a second reaction chamber through the first conduit, and wherein the CO and H₂Reacting in the second reaction chamber to produce the methanol or hydrocarbon.

(i) a first electrochemical cell, the first electrochemical cell comprising:

a. a power source;

c. for injecting fluids containing CO₂A tuyere of the gas of (1);

e. a heating system;

(ii) a second electrochemical cell, the second electrochemical cell comprising:

a. a power source;

b. a third reaction chamber;

c. at least two electrodes;

wherein H is formed by applying a voltage₂；

(iii) A second reaction chamber;

(v) a third pipeline for passing H₂From the second electrochemistryThe pool is conveyed to the second reaction chamber;

wherein the CO is conveyed to the second reaction chamber through the first conduit; said H₂Is conveyed to the second reaction chamber through the third pipeline; and said CO and H₂Reacting in the second reaction chamber to produce methanol and hydrocarbons.

In one embodiment, the present invention provides a process, electrochemical cell and apparatus for producing methanol or hydrocarbons wherein a first reaction chamber comprises an alkali metal carbonate or a mixture of alkali metal carbonate and alkaline earth metal carbonate. In another embodiment, the first reaction chamber comprises an alkali metal carbonate. In another embodiment, the first reaction chamber comprises a mixture of an alkali metal carbonate and an alkaline earth metal carbonate.

In one embodiment, the present invention provides methods, electrochemical cells, and apparatus for producing methanol or hydrocarbons comprising at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium, or a combination thereof. In another embodiment, the second electrode is a graphite electrode. In another embodiment, the second electrode is a titanium electrode. In another embodiment, the second electrode is a titanium electrode coated with graphite/carbon.

In one embodiment, the present invention provides a method, electrochemical cell and apparatus for producing methanol or hydrocarbons in which carbon monoxide is formed in the cathode compartment of a first reaction chamber and passed to a second reaction chamber in which hydrogenation of the carbon monoxide is carried out to produce methanol and/or hydrocarbons.

In another embodiment, the hydrogenation of carbon monoxide is carried out in the presence of a catalyst. In another embodiment, the hydrogenation of carbon monoxide is carried out under pressurized conditions. In another embodiment, the hydrogenation is carried out under high temperature conditions.

In one embodiment, the present invention provides a method, electrochemical cell and apparatus for producing methanol or hydrocarbons in which carbon monoxide and hydrogen are reacted. In another embodiment, hydrogen is pumped into the second reaction chamber. In another embodiment, hydrogen is produced by electrolysis of water. In another embodiment, hydrogen gas is produced by electrolysis of water in a second electrolytic cell and is fed to the second reaction chamber of the apparatus of the invention.

In one embodiment, the hydrocarbons are produced by hydrogenating carbon monoxide according to the fischer-tropsch process. In another embodiment, methanol is produced by hydrogenating carbon monoxide in the presence of a heterogeneous catalyst. In another embodiment, the heterogeneous catalyst is a copper/zinc catalyst.

Both methanol (and dimethyl ether) and fischer-tropsch liquids can be produced by catalytic conversion of gaseous feedstocks comprising hydrogen, carbon monoxide, carbon dioxide. This gas mixture is commonly referred to as synthesis gas or "syngas".

In one embodiment, the energy required for the electrochemical cells and equipment of the present invention, such as electrolysis, heating, cooling, pumping, pressurizing pumps, gas filtration systems, or any combination thereof, is provided by renewable energy sources, such as solar energy, wind energy, thermal waves, geothermal heat, and any combination thereof, or by conventional energy sources, such as coal, oil, gas, power generation devices, or any combination thereof.

In some embodiments, the methods, electrochemical cells, and devices of the present invention may be performed and/or used for weeks, or in some embodiments, months, or in some embodiments, years.

In one embodiment, the electrochemical cell and/or apparatus of the present invention may comprise a plurality of inlets for introducing carbon dioxide, hydrogen and/or air. In some embodiments, the electrochemical cell and/or apparatus will comprise a series of conduits for delivering carbon monoxide, hydrogen and other substances to the reaction chamber or gas collector, respectively. In some embodiments, the channels are configured to facilitate contact between introduced substances, which is a desirable application. In some embodiments, the electrochemical cell and/or device will comprise a microfluidic pump or a nanofluidic pump that can facilitate the transport and/or contact of the species introduced into the reaction chamber.

In another embodiment, the electrochemical cell and/or device of the present invention may comprise an agitator in the reaction chamber (e.g., in the second reaction chamber). In another embodiment, the electrochemical cell and/or device may be fitted to a device that mechanically mixes substances, for example by sonication (in one embodiment, or by applying magnetic fields in multiple directions, which in some embodiments will cause movement and consequent mixing of magnetic particles). It will be appreciated by those skilled in the art that the electrochemical cells and/or devices of the present invention, in some embodiments, are modularly designed to accommodate a variety of hybrid machines or tools, and should be considered as part of the present invention.

In one embodiment, the electrochemical cells and devices of the present invention comprise a tuyere. In another embodiment, a gas containing carbon dioxide is injected into the molten carbonate through a tuyere. In another embodiment, the tuyere for the carbon dioxide-containing gas is arranged perpendicular to the reaction chamber. In another embodiment, the tuyere for the carbon dioxide-containing gas is set at an angle of 0.1 to 45 degrees to the vertical of the reaction chamber. In another embodiment, the tuyere for the carbon dioxide-containing gas is set at an angle of 45 to 90 degrees to the vertical of the reaction chamber. In another embodiment, the tuyere for the carbon dioxide-containing gas is set at an angle of 45 to 90 degrees to the vertical of the reaction chamber.

In another embodiment, the tuyere for carbon dioxide-containing gas has a nozzle with a working diameter of 5mm to 50 mm. In another embodiment, the tuyere for carbon dioxide-containing gas has a nozzle with a working diameter of 5mm to 15 mm. In another embodiment, the tuyere for carbon dioxide-containing gas has a nozzle with a working diameter of 10mm to 35 mm. In another embodiment, the tuyere for carbon dioxide-containing gas has a nozzle with a working diameter of 30mm to 45 mm.

In another embodiment, the tuyere nozzle is disposed at a distance from the bottom of the reaction chamber 15 to 40 times higher than the working diameter of the tuyere. In another embodiment, the tuyere nozzle is disposed at a distance from the bottom of the reaction chamber 10 to 40 times larger than the working diameter of the tuyere. In another embodiment, the tuyere nozzle is disposed at a distance from the bottom of the reaction chamber 10 to 30 times higher than the working diameter of the tuyere.

The term "tuyere" refers to a channel, pipe, conduit or other opening through which gas is blown into a furnace, wherein the gas is injected under pressure by a windbox or blower or other means.

The term "bottom of the reaction chamber" refers to the lowest point or surface of the reaction chamber.

In one embodiment, the tuyere is made of titanium. In another embodiment, the tuyere is made of a titanium-containing alloy. In another embodiment, the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

In one embodiment, the carbon monoxide is passed directly to the second reaction chamber so that it does not react with the CO prior to entering the chamber₂Air or water contact. In one embodiment, the transfer is achieved by providing a plurality of separate chambers or channels in the device, transferring various substances into the chambers. In another embodiment, the chamber/channel is configured to allow mixing of the components at a desired time and environment.

In one embodiment, the electrochemical cell and apparatus of the present invention comprises an outlet from one cell that is used as an inlet to the next cell.

In one embodiment, the electrochemical cells and devices of the present invention may further comprise other units that exert environmental controls (such as temperature and/or pressure). In one embodiment, the electrochemical cell and/or apparatus of the present invention (excluding the electrochemical cell comprising a heating system) may comprise a magnetic field source and a mixer to achieve magnetron fluidization. In another embodiment, the electrochemical cell and/or apparatus may comprise a mechanical stirrer, a heat source, a light source, a microwave source, an ultraviolet light source, and/or an ultrasonic wave source. In one embodiment, the device of the invention may comprise a gas sparge.

In one embodiment, the present invention provides a method and apparatus for producing methanol. The two main processes for methanol production utilize either high or low pressure technology. Each process uses pressurized syngas, a mixture of carbon monoxide, carbon dioxide and hydrogen. In the high pressure process, the reaction of the ingredients occurs at a pressure of about 300 atmospheres. In the low pressure process, the reaction is catalyzed with highly selective copper based compounds at pressures of only 50 atmospheres to 100 atmospheres.

In one embodiment, carbon monoxide produced by electrolysis of molten carbonate in a first electrochemical cell undergoes a water gas shift reaction to form CO₂And H₂Then CO₂Reacting with hydrogen to produce methanol. In another embodiment, CO₂And H₂In the presence of a catalyst to produce methanol. In another embodiment, the catalyst comprises zinc, copper or oxides thereof. In another embodiment, the hydrogen is produced from fossil fuel-based syngas or by electrolysis of water. In another embodiment, the invention provides an apparatus comprising two electrochemical cells, wherein the first electrochemical cell electrolyzes molten carbonate to form carbon monoxide and the second electrochemical cell electrolyzes water to form hydrogen (H)₂)。

Methods of electrolyzing water are well known. One representative electrolytic cell configuration for electrolyzing water comprises an anode (+) and a cathode (-) separated by a physical barrier, such as a porous diaphragm constructed of asbestos, a microporous separator constructed of Polytetrafluoroethylene (PTFE), and the like. The anode and cathode compartments of the cell are filled with an aqueous electrolyte containing a small amount of an ion conducting acid or base. By applying a voltage between the electrodes, hydrogen gas is formed at the cathode and oxygen gas is generated at the anode.

Electrodes for the electrolysis of water are well known in the art. The electrode and the process for producing the same have evolved from technologies developed for fuel cells. The battery is described, for example, in: carl Berger, Handbook of Fuel cell technology, pp 401-.

The fischer-tropsch process involves a number of competing chemical reactions that can produce a range of desired products. The most important reactions are those that result in the formation of alkanes. These reactions can be described by chemical equations of the form:

(2n+1)H₂+nCO→C_nH_(2n+2)+nH₂O

wherein "n" is a positive integer. In its simplest form (n ═ 1) results in the formation of methane, which is generally considered an undesirable by-product (particularly when methane is the primary feedstock for the production of synthesis gas). The process conditions and catalyst composition are generally selected to favor higher order reactions (n > 1) and thus reduce methane formation. Most of the produced alkanes tend to be straight-chain, although some branched alkanes may also be formed. In addition to alkane formation, competing reactions can also cause the formation of alkenes as well as alcohols and other oxygenated hydrocarbons. In another embodiment, catalysts were developed that favor some of these products.

Typically, the Fischer-Tropsch process is carried out at a temperature in the range of 150 ℃ to 300 ℃ (302 ° F to 572 ° F). Higher temperatures result in faster reactions and higher conversions, but also tend to promote methane formation. Thus, the temperature is generally maintained in the low to medium portion of the above range. Increasing the pressure results in higher conversion and promotes the formation of long chain alkanes, both of which are desirable. Typically the pressure is in the range of one atmosphere to tens of atmospheres. Even higher pressures are also advantageous chemically, but the gains may not be sufficient to support the additional cost of high pressure equipment.

Various syngas compositions may be used. Optimum H for cobalt based catalysts₂The ratio of CO to CO is about 1.8-2.1. Iron-based catalysts can promote the water gas shift reaction and therefore can tolerate significantly lower proportions.

It is to be understood that many embodiments of the relevant processes, electrochemical cells and apparatus whereby the production of carbon monoxide and further production of methanol or hydrocarbons can be achieved are described herein and any such embodiments represent a part of the present invention, and further that multiple combinations of any of the embodiments as described herein (including combinations of electrodes, alkali metal carbonates, electrochemical cells) in any conceivable combination and use thereof in any method or embodiment thereof as described herein or as would be understood by one of skill in the art are also contemplated.

In order to more fully illustrate the preferred embodiments of the present invention, the following examples are provided. They should in no way be construed, however, as limiting the broader scope of the invention.

Examples

Example 1:

melting Li₂CO₃By electrolysis of

The method and the material are as follows:

preparation of titanium-containing cathode, pressed carbon anode and molten Li₂CO₃An electrochemical cell of electrolyte. Pt wire was used as a quasi-reference electrode. Electrode polarization relative to open circuit potential was measured. The open circuit potential appears to be highly reproducible for Ti cathodes and carbon anodes.

As a result:

and (4) performing cathode reaction. The generated gas was analyzed by linear sweep voltammetry and found to be at a temperature of 800-900 deg.CIn the range, CO formation is low current density (< 1.5A/cm)²) The only reaction. At 900 ℃ and quasi-static conditions, the generation of CO became sufficient for practical applications (100 mA/cm) at a potential offset of-215 mV with respect to the open circuit potential (-0.9V, with respect to Pt)²) (FIG. 1 a). However, at 850 ℃ 100mA/cm²The current density of (a) requires a potential offset of-320 mV (FIG. 1a) with respect to the open circuit potential (-1.1V, with respect to Pt).

The deposition of elemental carbon on Ti electrodes requires a potential shift of > -3V at 900 deg.C, which decreases to ≈ 2V at 850 deg.C and to < -1.5V at 800 deg.C. Thus, the potential window where CO is the only product of the cathode reaction is large enough for the cell to run continuously, but decreases rapidly with decreasing temperature. As long as the cathode is not contaminated with carbon, no reduction of Li ions is observed.

And (4) carrying out anode reaction. It was found that the only product of the anodic reaction was oxygen, without CO, at any condition in the temperature range of 800-900 deg.c₂Is detected (fig. 2 b). However, the current-potential relationship of the graphite anode shows that the current is limited by ohmic losses (FIG. 1b) and that 100mA/cm can be achieved if the potential is shifted by 50mV from the open circuit voltage²The current density of (1). Since the observed ohmic resistance is not correlated with temperature; which cannot be related to the resistance of the electrolyte.

Thermodynamic efficiency:

combustion of CO (CO + at 900 deg.C^1/2O₂←→CO₂) With gibbs energy of Δ G of 181 kJ/mole, which corresponds to a decomposition potential of 0.94V. 100mA/cm on anode and cathode²The current density of (2) requires the application of a voltage of 1.1. + -. 0.05V. The + -50 mV uncertainty results from the difficulty in subtracting the voltage drop of the nichrome wire (2mm diameter) leading to the electrode. An operating voltage of 1.1 + -0.05V corresponds to a thermodynamic efficiency of 85 + -4%. The higher thermodynamic efficiency combined with the high current density means that practical electrochemical systems can be very compact. In addition, it is expected that if the system is operated at lower current densities and ohmic losses to the electrodes are minimized,the efficiency can be further improved.

Example 2:

Li₂CO₃stability as electrolyte

Li₂CO₃(99.5%) was first heated to 450 ℃ for 2 hours to completely lose water. It was then cooled down to determine the weight. The crucible was heated to 900 ℃ for 2 hours. After cooling the crucible to room temperature, the weight loss was determined again. Then, the crucible was heated to 900 ℃ for 24 hours. It was found that the weight loss after heating at 900 ℃ for 2 hours was 1.2% by weight, and that this value did not increase any more after heating at 900 ℃ for 24 hours. The results show that an equilibrium between the melt and air is reached. Weight loss of 1.2 wt.% corresponds to Li₂The equilibrium concentration of O is approximately equal to 0.02 mol%. Thus reacting in air at 900 deg.C

Li₂CO₃←→Li₂O+CO₂

Strongly towards Li₂CO₃The direction is offset. Li₂CO₃Melts at about 735 ℃ and has sufficient conductivity above 800 ℃.

Example 3:

stability of titanium and graphite electrodes

At 100mA/cm²And 250mA/cm²At a constant potential at 900 ℃ under a current density of Li₂CO₃For 100 hours. No significant change in current density and gas generation was observed. After electrolysis, the electrode was analyzed by XRD, which revealed that Li was formed on the Ti cathode₂TiO₃A protective layer and no change was detected on the C anode. The faraday efficiency was determined to be 100% by direct measurement of the gas generation rate.

We also determined that after a device constructed of Ti was exposed to the electrolyte for a sustained period (100 hours), the concentration of Ti in the electrolyte was below 0.02 mol% (trace) and did not increase upon further exposure. Watch with a watch bodyBright Ti in Li₂CO₃There are solubility limitations in the melt.

We have found that pressed chemically pure graphite melts Li even when acting as an anode₂CO₃It is also not corroded. Electrolysis at 100 hours (100mA/cm at 900 ℃ C.)²) And no weight loss of the graphite electrode was detected after exposure to the electrolyte (no current).

Example 4

Preparation process of carbon coating on titanium electrode

The titanium electrode is immersed in the carbonate melt at 900 deg.C under negative potential (3-5V) for ageing treatment. The duration of the ageing treatment was 20 minutes. During the ageing treatment, the titanium electrode is coated with a carbon coating according to the following reaction:

CO₃ ^2-+4e^-→C+3O^2-。

the deposition of elemental carbon on Ti electrodes requires a negative potential shift of > -3V at 900 ℃.

After aging at negative potential, the titanium electrode begins to operate as an anode at positive potential. The carbon coating helps the electrode to operate more properly and reliably.

While certain features of the invention have been illustrated and described in this specification, many modifications, substitutions, changes, and equivalents will now occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

Claims

1. A method of electrochemically producing carbon monoxide, the method comprising: heating an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium or a combination thereof, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide.

2. The method of claim 1, whereby the metal carbonate is oxidized to produce a metal oxide.

3. The process of claim 2, wherein the metal oxide is removed from the reaction mixture and recycled with carbon dioxide to produce the metal carbonate.

4. The method of claim 1, wherein the alkali metal carbonate is lithium carbonate, potassium carbonate, sodium carbonate, or any combination thereof.

5. The method of claim 4, wherein the alkali metal carbonate comprises at least 50% by weight of lithium carbonate.

6. The method of claim 1, wherein the alkaline earth carbonate is barium carbonate, strontium carbonate, calcium carbonate, or any combination thereof.

7. The process according to claim 1, wherein the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of from 1: 1 to 0.95: 0.05 molar ratio each.

8. The method of claim 1, wherein the first electrode is a cathode.

9. The method of claim 1, wherein the cathode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

10. The method of claim 1, wherein the second electrode is an anode.

11. The method of claim 10, wherein the anode is a graphite, pressed graphite, or glassy graphite electrode.

12. The method of claim 10, wherein the anode is a titanium electrode coated with graphite.

13. The method of claim 12, wherein the graphite coated titanium electrode is prepared by: the titanium electrode is coated with carbon atoms by aging the titanium electrode in a carbonate melt at a temperature of 700 ℃ to 900 ℃ and a negative potential of 3 volts to 5 volts for 10 minutes to 60 minutes.

14. The method of claim 10, wherein the anode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

15. The method of claim 1, wherein the heating is performed at a temperature of 850 ℃ to 950 ℃.

16. The method of claim 1, wherein the heating is performed at a temperature of 850 ℃ to 900 ℃.

17. The method of claim 1, wherein the carbon dioxide is absorbed directly from air.

18. The method of claim 1, further comprising collecting the carbon monoxide into a gas trap.

19. The method of claim 18, wherein the gas collector is a canister, a bottle, a porous material, or any combination thereof.

20. A method of making methanol or hydrocarbons, the method comprising: (a) heating an alkali metal carbonate or a mixture of an alkali metal carbonate and an alkaline earth metal carbonate to form a molten carbonate; electrolyzing the molten carbonate using at least two electrodes, wherein a first electrode comprises titanium and a second electrode comprises graphite, titanium, or a combination thereof, wherein optionally a carbon dioxide containing gas is injected into the molten carbonate, thereby producing carbon monoxide; (b) hydrogenating the carbon monoxide to produce methanol or hydrocarbons.

21. The method of claim 20, wherein the electrolysis of step (a) is performed in a first reaction chamber and the carbon monoxide is passed to a second reaction chamber in which the hydrogenation of step (b) is performed.

22. The process of claim 20, wherein the hydrogenated hydrogen used in step (b) is produced by electrolysis of water.

23. The method of claim 20, whereby the metal carbonate is oxidized to produce a metal oxide.

24. The method of claim 23, wherein the metal oxide is removed from the reaction mixture and recycled with carbon dioxide to produce the metal carbonate.

25. The method of claim 20, wherein the alkali metal carbonate is lithium carbonate, sodium carbonate, potassium carbonate, or any combination thereof.

26. The method of claim 25, wherein the alkali metal carbonate comprises at least 50% lithium carbonate.

27. The method of claim 20, wherein the alkaline earth carbonate is barium carbonate, strontium carbonate, calcium carbonate, or any combination thereof.

28. The process according to claim 20, wherein the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of from 1: 1 to 0.95: 0.05 molar ratio each.

29. The method of claim 20, wherein the first electrode is a cathode.

30. The method of claim 29, wherein the cathode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

31. The method of claim 22, wherein the second electrode is an anode.

32. The method of claim 31, wherein the anode is a graphite, pressed graphite, or glassy graphite electrode.

33. The method of claim 31, wherein the anode is a titanium electrode coated with graphite.

34. The method of claim 33, wherein the graphite coated titanium electrode is prepared by: the titanium electrode is coated with carbon atoms by aging the titanium electrode in a carbonate melt at a temperature of 700 ℃ to 900 ℃ and a negative potential of 3 volts to 5 volts for 10 minutes to 60 minutes.

35. The method of claim 31, wherein the anode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

36. The method of claim 20, wherein the heating is performed at a temperature of 850 ℃ to 950 ℃.

37. The method of claim 20, wherein the heating is performed at a temperature of 850 ℃ to 900 ℃.

38. The method of claim 20, wherein the carbon dioxide is absorbed directly from air into the molten carbonate.

39. The process of claim 20, wherein the hydrocarbon is produced by hydrogenating carbon monoxide according to the fischer-tropsch process.

40. The process of claim 20, wherein the methanol is produced by hydrogenating carbon monoxide in the presence of a heterogeneous catalyst.

41. An electrochemical cell for the production of carbon monoxide, the electrochemical cell comprising:

a. a power source;

c. a tuyere for injecting a gas containing carbon dioxide;

e. a heating system;

f. a first conduit for conveying carbon monoxide from the electrochemical cell to a gas collector;

wherein the heating system heats the metal carbonate to form a molten carbonate; the tuyere optionally injects the gas into the molten carbonate; the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments; and, carbon monoxide is formed by applying a voltage and is conveyed to the gas collector through the first conduit.

42. The electrochemical cell of claim 41, wherein the frame of the first reaction chamber is fabricated from titanium or a titanium alloy, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

43. The electrochemical cell of claim 41, wherein the alkali metal carbonate comprises lithium carbonate, sodium carbonate, potassium carbonate, or any combination thereof.

44. The electrochemical cell of claim 41, wherein the alkali metal carbonate comprises at least 50% by weight lithium carbonate.

45. The electrochemical cell of claim 41, wherein the alkaline earth carbonate is barium carbonate, strontium carbonate, calcium carbonate, or any combination thereof.

46. The electrochemical cell of claim 41, wherein the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of each 1: 1 to 0.95: 0.05 molar ratio.

47. The electrochemical cell of claim 41, wherein the first electrode is a cathode.

48. The electrochemical cell of claim 41, wherein the cathode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

49. The electrochemical cell of claim 41, wherein the second electrode is an anode.

50. The cell defined in claim 49 wherein the anode is a graphite, pressed graphite or glassy graphite electrode.

51. The cell defined in claim 49 wherein the anode is a titanium electrode coated with graphite.

52. The electrochemical cell of claim 49, wherein the anode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

53. The electrochemical cell of claim 41, wherein the gas collector is a can, a bottle, a porous material, or any combination thereof.

54. The electrochemical cell of claim 41, wherein the tuyere for the gas has a nozzle with a working diameter of 5mm to 50 mm.

55. The electrochemical cell of claim 54, wherein the nozzle is positioned at a distance from the bottom of the reaction chamber that is between 15 and 40 times greater than the working diameter of the tuyere.

56. The cell defined in claim 41 wherein the tuyere is fabricated from titanium or a titanium-containing alloy, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium or any combination thereof.

57. A method of making carbon monoxide comprising electrolyzing molten carbonate using the electrochemical cell of claim 41.

58. An apparatus for producing methanol or carbohydrates, the apparatus comprising:

(i) an electrochemical cell, comprising:

a. a power source;

A reaction chamber;

c. a tuyere for injecting a gas containing carbon dioxide;

e. a heating system;

(ii) a second reaction chamber having an inlet for introducing hydrogen into the second reaction chamber;

(iii) a first conduit that conveys carbon monoxide from the electrochemical cell into the second reaction chamber;

wherein carbon monoxide is formed by applying a voltage and conveyed to a second reaction chamber through the first conduit; and the carbon monoxide and hydrogen react in the second reaction chamber to produce the methanol or hydrocarbon.

59. The apparatus of claim 58, wherein the frame of the first reaction chamber is fabricated from titanium or a titanium alloy, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

60. The apparatus of claim 58, wherein the alkali metal carbonate comprises lithium carbonate, sodium carbonate, potassium carbonate, or any combination thereof.

61. The apparatus of claim 58, wherein the alkali metal carbonate comprises at least 50% by weight lithium carbonate.

62. The apparatus of claim 58, wherein the alkaline earth carbonate is barium carbonate, strontium carbonate, calcium carbonate, or any combination thereof.

63. The apparatus of claim 58, wherein the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of from 1: 1 to 0.95: 0.05 molar ratio, respectively.

64. The apparatus of claim 58, wherein the first electrode is a cathode.

65. The apparatus of claim 64, wherein the cathode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

66. The apparatus of claim 58, wherein the second electrode is an anode.

67. The apparatus of claim 66, wherein the anode is a graphite, pressed graphite, or glassy graphite electrode.

68. The apparatus of claim 66, wherein the anode is a titanium electrode coated with graphite.

69. The apparatus of claim 66, wherein the anode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

70. The apparatus of claim 58, wherein the outlet of the second reaction chamber is connected by a conduit to a container that collects the methanol or hydrocarbon.

71. The apparatus of claim 58, wherein the tuyere for supplying the gas has a nozzle with a working diameter of 5mm to 50 mm.

72. The apparatus of claim 71, wherein the nozzle is positioned at a distance from the bottom of the reaction chamber that is 15 to 40 times greater than the working diameter of the tuyere.

73. The apparatus of claim 58, wherein the tuyere is fabricated from titanium or a titanium-containing alloy, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

74. A method of making methanol or hydrocarbons comprising reacting carbon monoxide with hydrogen using the apparatus of claim 58.

75. The process of claim 74, wherein said hydrocarbon is produced by reacting said carbon monoxide with hydrogen according to the Fischer Tropsch process.

76. The process of claim 74, wherein said methanol is produced by hydrogenation of carbon monoxide in the presence of a heterogeneous catalyst.

77. An apparatus for producing methanol or hydrocarbons, the apparatus comprising:

(i) a first electrochemical cell, the first electrochemical cell comprising:

a. a power source;

c. a tuyere for injecting a gas containing carbon dioxide;

e. a heating system;

wherein the heating system heats the metal carbonate to form a molten carbonate; the tuyere optionally injects the gas into the molten carbonate; and the at least two electrodes are in contact with the molten carbonate and optionally located in separate compartments; forming carbon monoxide by applying a voltage;

(ii) a second electrochemical cell, the second electrochemical cell comprising:

a. a power source;

b. a third reaction chamber;

c. at least two electrodes;

wherein hydrogen gas is formed by applying a voltage;

(iii) a second reaction chamber;

(iv) a first conduit that conveys carbon monoxide from the first electrochemical cell to the second reaction chamber;

(v) a third conduit that conveys hydrogen from the second electrochemical cell to the second reaction chamber;

wherein the carbon monoxide is conveyed to the second reaction chamber through the first conduit; the hydrogen is conveyed to the second reaction chamber through the third pipeline; and the carbon monoxide and hydrogen react in the second reaction chamber to produce methanol or hydrocarbons.

78. The apparatus of claim 77, wherein the frame of the first reaction chamber is fabricated from titanium or a titanium alloy, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

79. The apparatus of claim 77, wherein the alkali metal carbonate comprises lithium carbonate, sodium carbonate, potassium carbonate, or any combination thereof.

80. The apparatus of claim 77, wherein the alkaline earth carbonate is barium carbonate, strontium carbonate, calcium carbonate, or any combination thereof.

81. The apparatus of claim 77, wherein the mixture of alkali metal carbonate and alkaline earth metal carbonate has a ratio of from 1: 1 to 0.95: 0.05 molar ratio, respectively.

82. The apparatus of claim 77, wherein the first electrode is a cathode.

83. The apparatus of claim 82, wherein the cathode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

84. The apparatus of claim 77, wherein the second electrode is an anode.

85. The apparatus of claim 84, wherein the anode is a graphite, pressed graphite, or glassy graphite electrode.

86. The apparatus of claim 84, wherein the anode is a titanium electrode coated with graphite.

87. The apparatus of claim 84, wherein the anode is a titanium or titanium alloy electrode, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

88. The apparatus of claim 77, wherein the outlet of the second reaction chamber is connected by a conduit to a container that collects the methanol or hydrocarbon.

89. The apparatus of claim 88, wherein the nozzles of the tuyeres have an operating diameter of 5mm to 50 mm.

90. The apparatus of claim 89, wherein the nozzle is positioned at a distance from the bottom of the reaction chamber that is 15 to 40 times greater than its diameter.

91. The apparatus of claim 77, wherein the tuyere is fabricated from titanium or a titanium-containing alloy, wherein the alloy comprises titanium, aluminum, zirconium, tantalum, niobium, or any combination thereof.

92. A method of making methanol or hydrocarbons comprising reacting carbon monoxide with hydrogen using the apparatus of claim 77.

93. The process of claim 92, hydrocarbons are produced by reacting said carbon monoxide with hydrogen according to the Fischer-Tropsch process.

94. The apparatus of claim 92, wherein said methanol is produced by hydrogenating carbon monoxide in the presence of a heterogeneous catalyst.