WO2009108327A1

WO2009108327A1 - Production of hydrocarbons from carbon dioxide and water

Info

Publication number: WO2009108327A1
Application number: PCT/US2009/001207
Authority: WO
Inventors: Patrick G. Grimes
Original assignee: Grimes, Maureen A.
Priority date: 2008-02-26
Filing date: 2009-02-25
Publication date: 2009-09-03

Abstract

A process for producing liquid and gaseous hydrocarbons from carbon dioxide and water comprising of a carbonizing step and a de-carbonizing step. The carbonizing step comprises of at least one absorbing reactor to first convert carbon dioxide into aqueous carbonate by reacting with a recycle alkaline solution of aqueous hydroxide and recovers the exothermic reaction heat. The de-carbonizing step comprises of at lest one electrochemical cell to synthesis the end product of hydrocarbons and oxygen from the reduction oxidation reaction of carbonate and water along with the production of aqueous hydroxide for recycling. The electrochemical reaction in the de-carbonizing step is driven by electrical energy input as well as thermal energy addition including the recovered heat from the carbonizing step.

Description

PRODUCTION OF HYDROCARBONS FROM CARBON DIOXIDE AND WATER

[0001] This application claims the benefit of the filing date of United States Provisional Patent Application No. 61/067,286 filed February 26, 2008, the disclosure of which is hereby incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] Modern society is heavily dependent on fossil hydrocarbons as its primary source of energy. Petroleum dominates the transportation market while coal and natural gas dominate the power generation market. This dependence is becoming progressively less sustainable from the economic, political and environmental points of view. Anthropogenic carbon dioxide emissions are increasing along with energy demand and escalating costs. As one of the greenhouse gases (GHGs), carbon dioxide concentration is steadily growing in the atmosphere. To keep GHGs at a manageable level, large deceases in carbon dioxide (CO₂) emissions will be required. Major efforts are underway to try to find methods: to re-use emitted carbon dioxide in industrial processes; to convert carbon dioxide into valuable fuel, chemicals or materials; to capture and sequester carbon dioxide; and to develop zero- and low- carbon-emission technologies to increase energy conversion efficiency. These efforts have yet to produce significant or economical methods of re-using carbon dioxide in order to meet the global goals of GHG of stabilization and reduction .

[0003] Various carbon capture and sequestration (CCS) technologies are being developed and selected geological sites for storage are under testing for long-term effects. More research and development will be required so that emitted or atmospheric carbon dioxide can be captured inexpensively, transported and then safely and economically sequestered. Even with success in proving CCS methods, there will be an expense penalty for capital equipment, operations and energy for our energy providers that will be passed on to consumers.

[0004] There are direct uses of captured carbon dioxide that are beneficial in certain but limited industrial processes. Carbon dioxide can be used like a solvent to drive out marketable methane from coal seams, as well as to enhance oil recovery. For enhanced oil recovery, carbon dioxide is injected under pressure into the oil reservoir where it can expand and push additional oil to a production wellbore, plus help to lower the viscosity of the trapped heavy crude oil. These types of carbon dioxide re-uses are limited by geography and geology and will have a small effect on the goal of GHG stabilization and reduction. There are few direct methods to convert carbon dioxide into useful products. Compounds with commercial value that can be synthesized from carbon dioxide include methanol, acetic acid, formic acid, formaldehyde, synthesis gas, and others. More research and development will be required to recycle carbon dioxide into larger amounts of usable fuels, chemical or materials.

[0005] Carbon dioxide is not the lowest energy state of carbon. Carbonate is the lowest energy state of carbon. The formation of carbonates from carbon dioxide is exothermic and thermodynamically favorable. As part of nature's carbon cycle, which is essential for all living processes, atmospheric carbon dioxide has slowly been converted into million of gigatonnes (Gt) of carbonate minerals. Methods need to be developed to release and use that energy and transform that carbon dioxide into a useful product in a commercially viable in an industrial process. The challenge is to find new processes to convert carbon dioxide into commercial useful products and to use the recovered heat energy released during the formation of carbonates to improve the economics of carbon dioxide conversion methods. [0006] An early patent in this field, Canadian Patent No. 787831 (June 18, 1968), P. Grimes et al., teaches a liquid phase process for making hydrogen by reforming various oxidizable reactants. Liquid phase reforming can be conducted in various aqueous electrolytes but the reforming kinetics are more favorable in alkaline electrolytes, especially hydroxides, the preferred electrolytes. Conductive catalysts are used to promote reforming reactions by activating electrochemical pathways. The following reaction describes the overall liquid phase reforming of methanol to produce hydrogen:

CH₃OH (liquid) + H₂O (liquid) -♦ CO₂ + 3H₂

[0007] The patent discloses a batch process using a mixture of water, an ionic conductive electrolyte, and an organic compound (fuel) which reacts in the presence of an electronically conductive catalyst, oxidizing the various hydrocarbons and producing hydrogen. The reactions are said to occur in the liquid phase and are believed to proceed via electrochemical pathways. Thus, for convenience herein, this type of liquid phase reforming in alkaline electrolytes is also referred to as electrochemical reforming (ECR) . Alcohol and a wide range of organic fuels, including biomass, are disclosed as well as the production of high-pressure hydrogen. High-pressure hydrogen production is disclosed and hydroxides are described as preferred electrolytes.

[0008] A recent patent application in this field, PCT Patent Application Number PCT/2006/024644 published on January 4, 2007 to P. Grimes for Efficient Production of Fuel, teaches an electrochemical processes conducted in liquid phase for producing fuel from a variety of different reactants. The patent application discloses methods to produce hydrogen, methane, methanol or ammonia fuels in a reactor which comprises the step of combining at least one oxidizable reactant and one reducible reactant and at least one electrolyte to form a mixture and conducting a fuel-producing reaction in the presence of an electron transfer material, wherein the mixture permits the movement or transport of ions and electrons to facilitate the efficient production of the fuel.

[0009] Carbon dioxide is the reducible reactant for two processes in which methanol is the fuel produced. In one of the examples methanol is converted from methane and carbon dioxide extracted from the air or another convenient source in a three-step process. The methanol produced will have a higher fuel value due to the additional input of CO₂ from the air or another source. The three-step procedure uses converter, electrochemical cell and separator devices to perform this conversion. In the s converter process methane is compressed and mixed with sulfuric acid containing Fe⁺²/Fe⁺³ sulfates redox salts (redox couple) , resulting in a homogenous catalyst. The redox system oxidizes the methane to CO₂ + 4H₂O, converting the ferrous ions to ferric ions, (Fe⁺² to Fe⁺³) . In the electrochemical cell, the ferrous salt solution at the anode electrode converts the ferric ions to ferrous ions with the release of eight electrons to the cell anode electrode. The catalyst system is homogenous /heterogeneous (corresponding to the redox couple/electron transfer material, with or without catalyst (s) ) and the ferrous ion salts and oxidized ions are returned to the reactor, thus completing the anode salt system. In the meantime, the eight protons formed in the oxidation reactions are transferred through the cell membrane to the cathode system. Since the CO₂ released by the anode requires only 6e and 6H⁺ in order to convert CO₂ to CH₃OH, the remaining 2e and 2H⁺ can react on the electrode to produce additional methanol. To do so, a 1/3 of a mole of CO₂ extracted from the air or from other sources can be added to the anode CO₂ stream that is moving to the cathode, creating an additional 1/3 mole of methanol, which is made at the cathode system. In the separator step, the cathode electrolyte is taken to a reservoir and a slipstream is used to remove the methanol and water produced in the reaction.

[0010] The produced methanol can be transported to any market, region or distribution center by conventional liquid tankers, trucking, rail, barges, etc. or other means and stored in conventional tanks until needed. At a distribution center, the methanol can be provided directly to end-users or converted back to methane in order to supply natural gas pipelines.

[0011] U.S. Patent No. 3,959,094 issued on May 25, 1976 to M. Steinberg for Electrolytic Synthesis of Methanol from CO₂ discloses that methanol and oxygen can be produced from carbon dioxide and water by a three-step process using an absorber, electrolytic cell and a stripper with KOH and K2CO₃ circulating between the three devices. The first step is to have carbon dioxide from air be absorbed by a solution of KOH to form K2CO₃ and water. An aqueous solution of KOH and K₂CO₃ moves to a vat, which is an electrolytic cell with an anode and a cathode. The second step disclosed provides electrical energy to the vat for the electrolysis of the alkaline potassium carbonate in the cell where the carbonate is reduced at the cathode and hydroxide and oxygen are formed at the anode. Oxygen is released out of the vat and the mixture of methanol, K₂CO₃ and KOH in solution is moved to the stripper. The third step disclosed stated that distillation is used to separate methanol as an end product from the K₂CO₃ and KOH solution, which is recycled back to Step 1 along with the addition of makeup water. However, this process only produces methanol, an oxygenated hydrocarbon, and not high value commodities such as gaseous and liquid hydrocarbons. Also, this approach is economically unfavorable because the methanol produced in Step 2 does not come out of the electrolytic cell separate from the alkaline solution and is an additional step to perform the separation. The capital cost of the stripper and the additional energy required to perform the distillation could be avoided if the desired product exits the electrolytic cell separate from the alkaline solution and oxygen. In addition, the electrolytic cell disclosed does not allow for the input of thermal energy, which could be in the form of low grade waste heat of 200°C or less, that can reduce the amount of electrical energy required to produce at a lower cost the same amount of end product. Furthermore, the vat as an electrolytic cell, allows for the oxygen generated at the anode to oxygenate the cathode produced gases or liquids as they are formed or circulate inside the vat. [0012] U.S. Patent No. 4,256,079 issued on June 20, 1981 to R. Goodrich et al., Electrolytic Reduction of SuIfidic Spent Alkali Metal Waste discloses a method for removing sulfur compounds, such as sulfides and mercaptans from a hydrocarbon fluid and to regenerate alkali metal hydroxide as a two-step process. The first step exposes the hydrocarbon fluid to be treated, to a alkali metal hydroxide solution and subsequently to carbon dioxide, which results in the formation an aqueous alkali metal carbonate salt solution and volatile sulfur compounds that exit the system. In second step, the aqueous alkali metal carbonate salt solution pass into an electrolytic cell wherein the alkali metal salt is converted to alkali metal hydroxide as an electrical energy is applied to the cell. The regenerated alkali metal hydroxide is passed to the first step in the process to complete this cyclic method. Experimental results disclosed an aqueous sodium carbonate salt solution with a pH of 9.0 entering the electrolytic cell and leaving as sodium hydroxide solution with a pH 14.0.

[0013] U.S. Patent No. 5,928,806 issued on July 27, 1999 to G. Olah et al . , Recycling of Carbon Dioxide into Methyl Alcohol and Related Oxygenates for Hydrocarbons, discloses a method of using a regenerative electrochemical cell system based on a fuel cell, to oxidize methyl alcohol or other oxygenated hydrocarbons coupled with a regenerative cell to reduce carbon dioxide to form oxygenated hydrocarbons. A mode of the regenerative electrochemical cell system intakes carbon dioxide produced as a by-product of industrial processes along with water and electrical energy into the second electrochemical cell to produce methyl alcohol and related compounds. However, this process only produces methanol, an oxygenated hydrocarbon, and not high value hydrocarbons. Also, this approach is economically unfavorable due to the large amount of electrical energy required for direct electroreduction of carbon dioxide and the formation of protons to allow for the synthesis of methyl alcohol and related compounds within the cell. In addition, the electrochemical cell disclosed does not allow for the input of thermal energy, which could be in the form of low-grade waste heat of 200°C or less that can reduce the amount of electrical energy required.

[0014] Presently there remains a need for simple, economical, efficient methods for converting carbon dioxide into hydrocarbons, especially using carbon dioxide emitted from fossil fuel combustion and other industrial processes venting CO₂ into the atmosphere. Furthermore, there is a need for a process that uses carbon dioxide to produce a high value commodity of gaseous and liquid hydrocarbons compared to the cost penalty of carbon capture sequestration (CCS) technologies.

SUMMARY OF THE INVENTION

[0015] The present invention provides a two-step carbon capture and re-use process for synthesizing liquid and gaseous hydrocarbons from carbon dioxide and water. The process first step for converting carbon dioxide into hydrocarbon fuel comprises at least one absorbing reactor; an intake of carbon dioxide as an reactant; an intake of recycled aqueous solution of hydroxide ions as an reactant; output of the produced aqueous solution of carbonate ions; and the means to extract the heat generated from the absorbing exothermic chemical reaction producing carbonate and transfer the recovered heat to the second step in the process. The second step for converting carbon dioxide into hydrocarbon fuel comprises of at least one electrochemical cell with at least one each of an anode, a cathode and a separator; a thermal energy input; an electrical energy input; providing an input of aqueous solution of carbonate ions from the first-step and the addition of water; recycle the regenerated aqueous solution of hydroxide ions to the first step; and the output of end product of hydrocarbons and oxygen.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Fig. 1 depicts a flowchart for a carbon capture and re-use process to generate hydrocarbons from carbon dioxide by recycling an alkaline solution between an absorber and an electrochemical device and providing inputs of thermal and electrical energy.

[0017] Fig. 2 depicts a flowchart for a carbon capture and re-use process to generate hydrocarbons from carbon dioxide by recycling an sodium hydroxide and sodium carbonate solutions between an absorber and an electrochemical device and providing inputs of thermal and electrical energy.

DETAILED DESCRIPTION OF THE INVENTION

[0018] This invention discloses a process to synthesize liquid and gaseous hydrocarbons from captured carbon dioxide and the addition of water. This process, referred to as carbon capture and re-use (CCR) , converts carbon dioxide and water into hydrocarbon fuels by using a two- step process. The first step uses an intake of carbon dioxide to convert a solution of hydroxide ions in the carbonizer device into a solution of carbonate ions. The second step occurs in a de-carbonizer device which elect rochemically converts the aqueous solution of carbonate ions and water, along with an input of energy, into hydrocarbons, oxygen and hydroxide ions. The solution of hydroxide ions is recycled back to the carbonizer. The energy added can be in the form of electricity, heat or some combination thereof.

[0019] Fig. 1 shows the process flow of the first embodiment of the invention using the carbon captures and re-use (CCR) process for hydrocarbon fuel generation out of the system input reactants of carbon dioxide and water. The other system inputs are heat and electrical energy. The main components of the process are an absorber device called the carbonizer and an electrochemical device called the de-carbonizer. The other system output is oxygen. [0020] The solution of hydroxide ions recycled from the decarbonizer enters the carbonizer to chemically react with carbon dioxide according to the following exothermic ionic reaction:

2OH^' _(aq) + CO₂ → CO₃ ⁼ ₍aq) + H₂O (1)

[0021] The carbonizer reactor may represent an absorption reactor, an absorption tower, an absorption column, an open pond facilities or their combinations. The sources of carbon dioxide that will react with solutions of hydroxide ions can be from, but not limited to, air, atmospheric carbon dioxide, direct capture of combustion or industrial emissions, carbon capture and storage (CCS) processes or any combination of these or other carbon dioxide sources . [0022] The carbonizer reaction (1) produces carbonate ions and water and then the aqueous solution is sent to an electrolytic decarbonizer reactor. Another molecule of water is needed as input for each molecule of carbonate ion reduced in the decarbonizer. The electrolytic decarbonizer is an electrochemical device having at least one cell. Each cell is equipped with at least one each of an anode, a cathode and a separator. The oxidation reaction occurs at the anode and the reduction reaction occurs at the cathode. Anodes and cathodes can be made of precious and non- precious metals, mostly Group VIII of the Periodic Table. The reduction of the carbonate solution in the electrolytic decarbonizer is driven by the input combination of electrical energy and thermal energy according to the following net ionic reaction:

CO₃-_(aq) + 2H₂O → CH₂) + 2OH^" ₍aq) + 1.5O₂ (2)

[0023] Half-cell redox reactions of the overall reaction (2) take place on the electrodes of the electrolytic decarbonizer. Six electrons are consumed on the cathode for each molecule of generated hydrocarbon.

Cathodic reduction:

C0₃ ⁼ + 5H₂O + 6e^~ → CH₂) + 8OH^" (3)

[0024] Six anions of hydroxide are used to produce one and half molecule of oxygen on the anode and give up six electrons . Anodic oxidation: 6OH^' → 3H₂O + 1 . 5O₂ +6e^" ( 4 )

[0025] Low or medium grade heat sources can be used as an additional driving force for the electrochemical reaction (2) and reduces the amount of electrical energy needed to achieve the same output of hydrocarbons. The heat recovered from exothermic absorbing reaction taking place in the carbonizer reactor may also be utilized as a heat source for the de-carbonizer .

[0026] The evolved hydrocarbons can be low-carbon number hydrocarbon, hydrocarbon with medium carbon number, high- carbon number hydrocarbon or their mixtures, saturated or non-saturated. The number of carbon atoms in the hydrocarbon can be controlled by a residence time in the electrolytic decarbonizer and the operating parameters of the decarbonizer such as temperature, pressure, electric potential and choice material of the electrodes. [0027] After the completion of the overall reaction (2) the cathodic reduction products are hydrocarbons and excess hydroxide ions. Gaseous oxygen is evolved at the anode as a result of anodic oxidation of hydroxide ions . For the overall system, the cycling of two types of ionic solutions between the reactors eliminates the need to replenish the ionic solution feedstock, since it is not consumed in producing the two system end products: hydrocarbon fuels and oxygen.

[0028] The carbonate solution and water (2) produces hydrocarbons, hydroxide ions and oxygen. Once the ionically conductive electrolyte solution has been regenerated back to hydroxide and transferred to the carbonizer reactor, the other half of the carbonizing/de-carbonizing cycle is complete and cyclical process can start over. The cycling system between carbonizer and de-carbonizer continues to capture and consume carbon dioxide and produce hydrocarbons as long as the other inputs are continuously provided. Since the carbonization process is exothermic, the recovered heat is combined with the other heat inputs as the thermal energy input to drive the de-carbonization process .

[0029] In a second embodiment of the present invention uses alkali metals and alkaline earth metals to form the alkaline hydroxide solutions and carbonate solutions that are cycled between the carbonizer and decarbonizer to evolve products of hydrocarbon fuels and oxygen from the reactants of carbon dioxide and water. Figure 2 shows the process flow of the carbon capture and re-use (CCR) process for hydrocarbon fuel generation out of the system input reactants of carbon dioxide and water with the sodium hydroxide entering the carbonizer and the sodium carbonate being sent to the de-carbonizer. The other system inputs are heat and electrical energy.

[0030] The solution of sodium hydroxide recycled from the decarbonizer enters the carbonizer to chemically react with the carbon dioxide according to the following exothermic ionic reaction:

2NaOH _(aq) + CO₂ → Na₂CO₃ <_aq) + H₂O (5)

[0031] The carbonizer reactor may represent an absorption reactor, an absorption tower, an absorption column, an open pond facilities or their combinations. The sources of carbon dioxide that will react with a solution of hydroxide ions can be from, but not limited to, air, atmospheric carbon dioxide, direct capture of combustion or industrial emissions, carbon capture and storage (CCS) processes or any combination of these or other carbon dioxide sources.

[0032] The carbonizer reaction (5) produces aqueous sodium carbonate and water and then is sent to an electrolytic decarbonizer reactor. Another molecule of water is needed as input for each molecule of sodium carbonate reduced in the decarbonizer. The electrolytic decarbonizer is an electrochemical device having at least one cell. Each cell is equipped with at least one each of an anode, a cathode and a separator. The oxidation reaction occurs at the anode and the reduction reaction occurs at the cathode. Anodes and cathodes can be made of precious and non-precious metals, mostly Group VIII of the Periodic Table. The reduction of the sodium carbonate in the electrolytic decarbonizer driven by the input combination of electrical energy and thermal energy according to the following net ionic reaction:

Na₂CO_3(aq) + 2H₂O → CH₂) + 2NaOH_(aq) + 1.5O₂ (6)

[0033] Half-cell redox reactions of the overall reaction (6) take place on the electrodes of the electrolytic decarbonizer. Six electrons are consumed on the cathode for each molecule of generated hydrocarbon.

Cathodic reduction:

Na₂CO₃ + 5H₂O + 6e^' → CH₂) + 8NaOH (7)

[0034] Six moles of sodium hydroxide are used to produce one and half molecule of oxygen on the anode and give up six electrons. Anodic oxidation:

6NaOH → 3H₂O + 1.5O₂ +6e^' (8)

[0035] Low or medium grade heat sources can be used as an additional driving force for the electrochemical reaction (6) and reduces the amount of electrical energy needed to achieve the same output of hydrocarbons. The heat recovered from exothermic absorbing reaction taken place in the carbonizer reactor may also be utilized as a heat source for the de-carbonizer .

[0036] The evolved hydrocarbons can be low-carbon number hydrocarbon, hydrocarbon with medium carbon number, high- carbon number hydrocarbon or their mixtures, saturated or non-saturated. The number of carbon atoms in the hydrocarbon can be controlled by a residence time in the electrolytic decarbonizer and the operating parameters of the decarbonizer such as temperature, pressure, electric potential and choice material of the electrodes. [0037] After completion of the overall reaction (6) the cathodic reduction products are hydrocarbons and excess aqueous sodium hydroxide. Gaseous oxygen is evolved at the anode as a result of anodic oxidation of sodium hydroxide. For the overall system, the cycling of two types of ionic solutions between the reactors - eliminates the need to replenish the ionic solution feedstock, since it is not consumed in producing the two system end products : hydrocarbon fuels and oxygen.

[0038] Once the ionically conductive electrolyte solution has been regenerated back to sodium hydroxide and transferred to the carbonizer reactor, the other half of the carbonizing/de-carbonizing cycle is complete and cyclical process can start over. The cycling system between carbonizer and de-carbonizer continues to capture and consume carbon dioxide and produces hydrocarbons as long as the other inputs are continuously provided. Since the carbonization process is exothermic, the recovered heat is combined with the other heat inputs as the thermal energy input to drive the de-carbonization process.

Claims

CLAIMSWhat is claimed is:

1. A cyclic process for converting carbon dioxide and water into hydrocarbon fuel and oxygen, comprising the steps of:

(a) providing an input of carbon dioxide;

(b) providing an input of hydroxide ions in an aqueous solution;

(c) providing a carbonizing device for carbon dioxide and hydroxide ions to chemically react to form carbonate ions;

(d) providing the produced carbonate ions in an aqueous solution as an input to a de-carbonizing device;

(e) providing an input of water and energy to the decarbonizing electrochemical device;

(f) electrochemically reacting the carbonate ions and water in an oxidation-reduction reaction to produce liquid and gaseous hydrocarbons, oxygen and hydroxide ions;

(g) recycling said hydroxide ions to step (b) of this cyclic process;

(h) providing the produced hydrocarbon fuel and oxygen as a output of the cyclic process;

(i) reproducing said steps (a) to (h) sequentially and continuously to produce hydrocarbon and to consume carbon dioxide.

2. The process of claim 1, wherein said source of carbon dioxide can be from but not limited to, air, atmospheric carbon capture, direct capture of combustion or industrial carbon dioxide emissions, carbon capture and storage (CCS) processes or any combination of these or other carbon dioxide sources.

3. The process of claim 1, wherein said carbonizer device can be an absorption reactor, an absorption tower, an absorption column, an open pond facilities or combinations thereof.

4. The process of claim 1, wherein said de-carbonizer device can be an electrochemical reactor having at least one cell. Each cell is equipped with at least one each of an anode, a cathode and a separator.

5. The electrochemical cell of claim 4, wherein said anodes and cathodes can be made of precious and non- precious metals, mostly from Group VIII of the Periodic Table.

6. The process of claim 1, wherein said energy can be electrical energy, thermal energy or combinations thereof.

7. The thermal energy of claim 6 can be from a low or medium grade heat source, recovered heat from the exothermic reactions of the carbonizing device, or combinations thereof.

8. The evolved hydrocarbons of claim 1 wherein said hydrocarbons can be low-carbon number hydrocarbon, hydrocarbon with medium carbon number, high-carbon number hydrocarbon or their mixtures, saturated or non-saturated.

9. A cyclic process for converting carbon dioxide and water into hydrocarbon fuel and oxygen, comprising the steps of:

(a) providing an input of carbon dioxide;

(b) providing an input of metal hydroxide in an aqueous solution; (c) providing a carbonizing device for carbon dioxide and hydroxide ions to chemically react to form carbonate ions;

(d) providing the produced metal carbonate in an aqueous solution as an input to a de-carbonizing device;

(f) electrochemically reacting the aqueous metal carbonate and water in and oxidation-reduction reaction to produce liquid and gaseous hydrocarbons, oxygen and aqueous metal hydroxide;

(g) recycling said aqueous metal hydroxide to step (b) of cyclic process;

(h) providing the produced hydrocarbon fuel and oxygen as an output of the cyclic process;

10. The process of claim 9, wherein said source of carbon dioxide can be from but not limited to, air, atmospheric carbon capture, direct capture of combustion or industrial carbon dioxide emissions, carbon capture and storage (CCS) processes or any combination of these or other carbon dioxide sources.

11. The process of claim 9, wherein said aqueous metal hydroxide and metal carbonate can be formed from metals selected from the group consisting of alkali metal compounds, alkali earth metal compounds, and mixtures thereof and alloys thereof.

12. The process of claim 9, wherein said carbonizer device can be an absorption reactor, an absorption tower, an absorption column, an open pond facilities or combinations thereof.

13. The process of claim 9, wherein said de-carbonizer device can be an electrochemical reactor having at least one cell. Each cell is equipped with at least one each of an anode, a cathode and a separator.

14. The electrochemical cell of claim 13, wherein said anodes and cathodes can be made of precious and non- precious metals, mostly Group VIII of the Periodic Table.

15. The process of claim 9 wherein said energy can be electrical energy, thermal energy or combinations thereof.

16. The thermal energy of claim 15 can be from a low or medium grade heat source, recovered heat from the exothermic reactions of the carbonizing device, or combinations thereof.

17. The evolved hydrocarbons of claim 9 wherein said hydrocarbons can be low-carbon number hydrocarbon, hydrocarbon with medium carbon number, high-carbon number hydrocarbon or their mixtures, saturated or non-saturated.