ABSTRACT
Abstract
Systems and methods of capturing and sequestering carbon dioxide, comprising mixing a substantially non-aqueous solvent and an alkali such that the solvent and alkali form a solvent suspension, mixing water and a flue gas containing carbon dioxide with the solvent suspension such that a reaction occurs, the reaction resulting in the formation of a carbonate, water and heat.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This is a reissue application of and claims priority to U.S. Pat. No. 7,947,240, issued May 24, 2011.
FIELD OF THE INVENTION
The present invention relates to carbon capture and sequestration systems and methods.
BACKGROUND
The capture and sequestration of carbon dioxide (CO 2 ) emissions needs to be significantly improved if the climate change consequences of such emissions are to be controlled or curtailed. The CO 2 produced from combustion and industrial processes, specifically power plant flue gas, is perhaps the largest single greenhouse gas emission. Most existing carbon capture and sequestration methods take a two-step approach. First, a method is sought for separating CO 2 from the flue gas or other gaseous emission source. These may include capture of the CO 2 in liquid solvents, solid zeolyte or various membranes. However, the capture media need to be regenerated without releasing the CO 2 into the atmosphere, and this is difficult to achieve in standard physical separation processes.
The second step is sequestering the CO 2 gas or liquid by inserting it into underground geological formations or in deep ocean layers. However, very specific geological configurations are required for disposal of the CO 2 , and these are not commonly available at CO 2 emission sites. Thus, transportation adds substantial cost and difficulty. In addition, it is not known whether CO 2 can be permanently sequestered underground. The two-step approach also is not economical because often CO 2 represents only a small percentage of a large volume of flue gas, and treating a large flow stream to recover a small portion of it as CO 2 is wasteful and expensive.
Another approach to CO 2 capture and sequestration involves mining, crushing and transporting rocks to the emission site, where the crushed rock is used to absorb CO 2 . But this requires a good deal of heat and pressure. The energy input and environmental costs of mining the rock and transporting it to and from the CO 2 source, as well as the energy costs of having the crushed rock accept and absorb the CO 2 , are very high.
Other ways to capture CO 2 include chemical absorption using liquids such as amines or aqueous solutions of bases, physical absorption in an appropriate solution and membrane separation. All of these methods have the problem that the absorption media need to be regenerated without losing CO 2 . Other capture methods such as physical adsorption and cryogenic separation require significant amounts of energy in the form of heat or pressure.
Some CO 2 capture methods react CO 2 (or carbonic acid formed from water and CO 2 ) with an aqueous solution of an alkali to form a carbonate. However, a significant drawback of that approach is that the carbonate exits the process in solution with water, requiring further, energy intensive treatment to separate the solids and the water, or it results in a large volume, heavy, wet, cement-like paste that requires energy intensive drying and mechanical systems to control the size, configuration and weight of the resulting dried product.
Although some are examining techniques for capturing and sequestering CO 2 from ambient air, they are not suitable for CO 2 emissions from power plants because of the substantial difference in CO 2 concentration between ambient air and flue gas. Ambient air generally contains between about 0.03% and 0.04% CO 2 , whereas flue gas contains 3.0% or higher concentrations of CO 2 . Removing very small quantities of CO 2 from the very large quantities of ambient air is not as viable and as productive as the capture and sequestration of large amounts of CO 2 from streams, such as flue gas, where the CO 2 is more concentrated.
Therefore, there exists a need for a commercially viable carbon capture and sequestration process that works at industrial scales and is complete and permanent. Specifically, there is a need for a carbon capture system that does not use capture media that require complex and energy-intensive regeneration, and does not yield a heavy, wet end product that requires energy intensive drying and other post-capture processing. There is a further need for a carbon capture and sequestration process that permanently sequesters CO 2 at the site of CO 2 emission. In summary, a need exists for a carbon capture and sequestration system that is cost effective and not energy intensive and results in permanent sequestration of CO 2 .
SUMMARY OF THE INVENTION
The present invention, in its many embodiments, alleviates to a great extent the disadvantages of known carbon capture and sequestration methods by providing a chemical process by which carbon dioxide in the form of carbonic acid is reacted with an alkali to form water and a dry, easily-removable carbonate that precipitates out of solution. Carbon dioxide sequestration is achieved by the above-ground disposal of the resulting carbonate. This process allows for industrial scale CO 2 capture and sequestration at relatively low costs. Embodiments of the present invention also provide permanent, on-site CO 2 capture and sequestration requiring relatively low energy consumption.
In an embodiment of the present invention, known as Vandor's Carbon Capture and Sequestration Cycle (VCCS), a method of capturing or sequestering carbon dioxide is provided in which a substantially non-aqueous solvent is mixed with an alkali such that the solvent and alkali form a solvent suspension. This mixing step may be performed in any suitable mixing vessel. The substantially non-aqueous solvent preferably is an alcohol, and is methanol in a most preferred embodiment. As such, the alkali reacts with the methanol to form methoxide, which may also include solvated metal hydroxide. Water and a flue gas containing carbon dioxide are mixed with the solvent suspension such that a reaction occurs, the reaction resulting in the formation of a carbonate, water and heat. The terms âsolventâ and ânon-aqueous solventâ will be used interchangeably herein to mean any substantially non-aqueous solvent that will tolerate some significant amount of alkali to be dissolved in it, and will force the precipitation of any salt that is produced in the classic acid+base reaction. The non-aqueous solvent contains less than 50% water, and most preferably less than 10% water.
The gas is preferably flue gas from a power plant, but may be any type of exhaust gas containing CO 2 from any industrial process. The gas will contain nitrogen (N 2 ) as well. The term âflue gasâ will be used herein to mean any exhaust gas stream that contains carbon dioxide and either nitrogen or air, the exhaust gas being from a power generation plant's flue, including coal-fired, natural-gas-fired, oil-fired, and landfill gas (LFG)-fired or anaerobic digester (ADG)-fired power plants or from any industrial process including, but not limited to, cement making in kilns, glass, steel, rubber, paper, or other materials manufacturing, the production of ethanol, and from any combination of flue gas and process gas.
In one embodiment, ash is introduced into the solvent, and the alkali is a constituent of the ash. As used herein, the term âashâ will be used to mean fly ash, bottom ash and all types of alkali-containing ash from any source including from coal burning, wood burning and other bio-mass burning.
The chemical process of carbon capture and sequestration comprises mixing the water and the flue gas containing carbon dioxide with the alkali suspended in the solvent, preferably methoxide, so reactions occur that result substantially in the formation of a solid carbonate, water and heat. Small amounts of carbonic acid also are formed in the reactions, and the carbonic acid quickly reacts with the alkali. These reactions may be performed in any suitable reaction vessel. In a preferred embodiment, the carbonate precipitates out of solution and is removed from the vessel. Removal of the precipitated carbonate is preferably performed mechanically, using an auger or another suitable mechanical device that allows for the removal of solids without any liquids leaving the vessel at the same location. Any methanol that remains with the carbonate evaporates upon the addition of modest amounts of low-grade heat.
The water resulting from the reactions in the reaction vessel forms a solution with the solvent, and the method further comprises removing the solution of water and solvent and separating the water from the solvent. After the water and solvent are separated, the separated solvent is re-mixed with the alkali such that the solvent and alkali again form a solvent suspension that can be used for further carbon capture. The separated water is returned to the solvent suspension in the reaction vessel where it joins the flue gas and the methoxide to continue the reaction. In a preferred embodiment, the water is separated from the solvent by chilling the solution of water and solvent in a cryogenic drying vessel. When the solution is chilled, the water falls substantially to the bottom of the cryogenic drying vessel, and the solvent rises substantially to the top of the cryogenic drying vessel. In some embodiments, some carbonate will travel with the solution of water and solvent and precipitate out of the solution in the cryogenic drying vessel. A filter may be used to trap larger solids in the reaction vessel, keeping those larger solids from traveling on to the cryogenic drying vessel.
The remaining water may be separated from the solvent using a hot distillation vessel by applying heat to the solution of water and solvent to at least partially vaporize the solvent. A partial vacuum may be used to draw off vaporous solvent from the distillation apparatus, and the vaporous solvent is condensed to a liquid by cooling to be made suitable for re-use in the carbon capture and sequestration reactions.
Embodiments of the present invention include methods of using nitrogen from the flue gas to provide cooling for the carbon capture and sequestration process. The method may include liquefying the nitrogen and recovering refrigeration from the liquefied nitrogen. The recovered refrigeration from the nitrogen is then used to cool the solvent and provide cooling for the solvent regeneration steps. This use of nitrogen for cooling increases the energy efficiency of embodiments of the invention.
In a preferred embodiment, the flue gas further contains nitrogen and the nitrogen is used in three ways. A first portion of the nitrogen is used for refrigeration during the solvent regeneration process, a second portion is used to enhance the power output of a power plant, and a third portion is sold to off-site customers. All of the nitrogen is first compressed. For the portion used for refrigeration, a refrigerant source provides refrigerant to a heat exchanger, and the nitrogen is chilled in the heat exchanger such that it is substantially liquefied. Refrigeration may be recovered from the substantially liquefied nitrogen after it is pumped to pressure and sent to the power cycle to enhance the power output of the power plant that is the source of the flue gas. The recovered refrigeration is used to provide cooling for the cryogenic solvent removal process, discussed below, that separates the water from the solvent.
A second portion of the nitrogen may be used to enhance the power output of a power plant. In a preferred embodiment, a first portion of this substantially liquefied nitrogen is compressed and heated. The heated compressed nitrogen is directed to a steam cycle of a power plant to enhance the power output of the power plant. A second portion of this substantially liquefied nitrogen may be stored in a storage apparatus. The second portion of the substantially liquefied nitrogen is pressurized by pumping it to pressure. It is then vaporized and directed through a hot gas expander to enhance the power output of the power plant. A third portion of this liquefied nitrogen is sold to off-site customers for a variety of uses, including as a refrigerant and as a fluid to enhance oil and gas well recovery. In a preferred embodiment the liquefied nitrogen is further refined by removing liquid argon, which is approximately 0.9% of the volume of the recovered nitrogen stream, and which is a high-value product that may also be sold in the marketplace.
Embodiments of the present invention include carbon capture and sequestration systems which comprise a carbon capture assembly and a solvent regeneration assembly. The carbon capture assembly comprises a mixing vessel and at least one reaction vessel, and may further include a solvent condenser fluidly connected to the reaction vessel. In the mixing vessel, an alkali is mixed with a substantially non-aqueous solvent to form a suspension. In one embodiment, ash is introduced into the solvent, and the alkali is a constituent of the ash. The non-aqueous solvent preferably is an alcohol, and is methanol in a most preferred embodiment. As such, the alkali reacts with the methanol in the reaction vessel to form methoxide and possibly some metal hydroxide. Minor quantities of dimethyl-carbonate (DMC) may also form, but will quickly decompose due the alkaline conditions.
The reaction vessel is fluidly connected to the mixing vessel so it receives the suspension of alkali and a substantially non-aqueous solvent from the mixing vessel through a first input. The reaction vessel also receives flue gas containing heat and carbon dioxide through a second input and water through a third input such that carbonic acid, carbonate, water and heat are formed in the reaction vessel. More specifically, the carbon dioxide and water and any small amounts of carbonic acid that result from the reactions in the reaction vessel react with the alkali in the vessel, resulting in the formation of a carbonate, water and heat. The flue gas will contain nitrogen as well. In some embodiments, the carbon capture assembly further comprises a solvent condenser fluidly connected to the reaction vessel, where refrigeration is used to condense the solvent portion of the exiting stream, which consists of mostly nitrogen.
The solvent regeneration assembly is fluidly connected to the reaction vessel and comprises at least one heat exchanger, a cryogenic drying vessel fluidly connected to the heat exchanger, and a hot distillation vessel fluidly connected to the cryogenic drying vessel. The solvent regeneration assembly preferably has a plurality of heat exchangers to perform several intermediate heat recovery steps to warm the mostly water stream that arrives at the hot distillation vessel and to cool the methanol vapor that leaves the hot distillation vessel.
The carbonate formed in the reaction precipitates out of solution and is removed from the reaction vessel. The carbon capture assembly may further comprise an auger or other suitable device to remove the precipitated carbonate from the reaction vessel. The water resulting from the reactions forms a solution with the solvent in the reaction vessel, and this solution of water and solvent is removed from the reaction vessel and directed to the solvent regeneration assembly. The water is separated from the solvent by the solvent regeneration assembly, and the separated solvent is returned to the mixing vessel where it is re-mixed with the alkali to form a solvent suspension. Also, the separated water is returned to the reaction vessel to continue the reactions.
In some embodiments, a small portion of the carbonate (e.g., less than 10% by volume) will stay in the solvent and travel with the solvent suspension through the solvent regeneration assembly. When the selected alkali is CaO, the solution of water and solvent is free of any carbonates. When the selected alkali is KH, some carbonate will form a solution with the water+solvent. That small portion of carbonate will fall out of the solvent suspension with the water that is separated from it. First, the separation process uses the cryogenic drying vessel in which the solution of water and solvent is chilled so the water falls substantially to the bottom of the cryogenic drying vessel, and the solvent rises substantially to the top of the cryogenic drying vessel. Part (or in a more energy-intensive option, all) of this separation process uses the hot distillation vessel, where heat is applied to the solution of water and solvent, a partial vacuum draws off vaporous solvent from the hot distillation vessel, and the vaporous solvent is condensed.
Some embodiments may include a nitrogen liquefaction assembly which substantially liquefies nitrogen contained in the flue gas and recovers refrigeration from the substantially liquefied nitrogen. The recovered refrigeration from the nitrogen may be used to cool the solvent and to provide cooling for the solvent regeneration assembly. That portion of the liquid nitrogen is sent to the reg
CROSS-REFERENCE TO RELATED APPLICATION
This is a reissue application of and claims priority to U.S. Pat. No. 7,947,240, issued May 24, 2011.
FIELD OF THE INVENTION
The present invention relates to carbon capture and sequestration systems and methods.
BACKGROUND
The capture and sequestration of carbon dioxide (CO 2 ) emissions needs to be significantly improved if the climate change consequences of such emissions are to be controlled or curtailed. The CO 2 produced from combustion and industrial processes, specifically power plant flue gas, is perhaps the largest single greenhouse gas emission. Most existing carbon capture and sequestration methods take a two-step approach. First, a method is sought for separating CO 2 from the flue gas or other gaseous emission source. These may include capture of the CO 2 in liquid solvents, solid zeolyte or various membranes. However, the capture media need to be regenerated without releasing the CO 2 into the atmosphere, and this is difficult to achieve in standard physical separation processes.
The second step is sequestering the CO 2 gas or liquid by inserting it into underground geological formations or in deep ocean layers. However, very specific geological configurations are required for disposal of the CO 2 , and these are not commonly available at CO 2 emission sites. Thus, transportation adds substantial cost and difficulty. In addition, it is not known whether CO 2 can be permanently sequestered underground. The two-step approach also is not economical because often CO 2 represents only a small percentage of a large volume of flue gas, and treating a large flow stream to recover a small portion of it as CO 2 is wasteful and expensive.
Another approach to CO 2 capture and sequestration involves mining, crushing and transporting rocks to the emission site, where the crushed rock is used to absorb CO 2 . But this requires a good deal of heat and pressure. The energy input and environmental costs of mining the rock and transporting it to and from the CO 2 source, as well as the energy costs of having the crushed rock accept and absorb the CO 2 , are very high.
Other ways to capture CO 2 include chemical absorption using liquids such as amines or aqueous solutions of bases, physical absorption in an appropriate solution and membrane separation. All of these methods have the problem that the absorption media need to be regenerated without losing CO 2 . Other capture methods such as physical adsorption and cryogenic separation require significant amounts of energy in the form of heat or pressure.
Some CO 2 capture methods react CO 2 (or carbonic acid formed from water and CO 2 ) with an aqueous solution of an alkali to form a carbonate. However, a significant drawback of that approach is that the carbonate exits the process in solution with water, requiring further, energy intensive treatment to separate the solids and the water, or it results in a large volume, heavy, wet, cement-like paste that requires energy intensive drying and mechanical systems to control the size, configuration and weight of the resulting dried product.
Although some are examining techniques for capturing and sequestering CO 2 from ambient air, they are not suitable for CO 2 emissions from power plants because of the substantial difference in CO 2 concentration between ambient air and flue gas. Ambient air generally contains between about 0.03% and 0.04% CO 2 , whereas flue gas contains 3.0% or higher concentrations of CO 2 . Removing very small quantities of CO 2 from the very large quantities of ambient air is not as viable and as productive as the capture and sequestration of large amounts of CO 2 from streams, such as flue gas, where the CO 2 is more concentrated.
Therefore, there exists a need for a commercially viable carbon capture and sequestration process that works at industrial scales and is complete and permanent. Specifically, there is a need for a carbon capture system that does not use capture media that require complex and energy-intensive regeneration, and does not yield a heavy, wet end product that requires energy intensive drying and other post-capture processing. There is a further need for a carbon capture and sequestration process that permanently sequesters CO 2 at the site of CO 2 emission. In summary, a need exists for a carbon capture and sequestration system that is cost effective and not energy intensive and results in permanent sequestration of CO 2 .
SUMMARY OF THE INVENTION
The present invention, in its many embodiments, alleviates to a great extent the disadvantages of known carbon capture and sequestration methods by providing a chemical process by which carbon dioxide in the form of carbonic acid is reacted with an alkali to form water and a dry, easily-removable carbonate that precipitates out of solution. Carbon dioxide sequestration is achieved by the above-ground disposal of the resulting carbonate. This process allows for industrial scale CO 2 capture and sequestration at relatively low costs. Embodiments of the present invention also provide permanent, on-site CO 2 capture and sequestration requiring relatively low energy consumption.
In an embodiment of the present invention, known as Vandor's Carbon Capture and Sequestration Cycle (VCCS), a method of capturing or sequestering carbon dioxide is provided in which a substantially non-aqueous solvent is mixed with an alkali such that the solvent and alkali form a solvent suspension. This mixing step may be performed in any suitable mixing vessel. The substantially non-aqueous solvent preferably is an alcohol, and is methanol in a most preferred embodiment. As such, the alkali reacts with the methanol to form methoxide, which may also include solvated metal hydroxide. Water and a flue gas containing carbon dioxide are mixed with the solvent suspension such that a reaction occurs, the reaction resulting in the formation of a carbonate, water and heat. The terms âsolventâ and ânon-aqueous solventâ will be used interchangeably herein to mean any substantially non-aqueous solvent that will tolerate some significant amount of alkali to be dissolved in it, and will force the precipitation of any salt that is produced in the classic acid+base reaction. The non-aqueous solvent contains less than 50% water, and most preferably less than 10% water.
The gas is preferably flue gas from a power plant, but may be any type of exhaust gas containing CO 2 from any industrial process. The gas will contain nitrogen (N 2 ) as well. The term âflue gasâ will be used herein to mean any exhaust gas stream that contains carbon dioxide and either nitrogen or air, the exhaust gas being from a power generation plant's flue, including coal-fired, natural-gas-fired, oil-fired, and landfill gas (LFG)-fired or anaerobic digester (ADG)-fired power plants or from any industrial process including, but not limited to, cement making in kilns, glass, steel, rubber, paper, or other materials manufacturing, the production of ethanol, and from any combination of flue gas and process gas.
In one embodiment, ash is introduced into the solvent, and the alkali is a constituent of the ash. As used herein, the term âashâ will be used to mean fly ash, bottom ash and all types of alkali-containing ash from any source including from coal burning, wood burning and other bio-mass burning.
The chemical process of carbon capture and sequestration comprises mixing the water and the flue gas containing carbon dioxide with the alkali suspended in the solvent, preferably methoxide, so reactions occur that result substantially in the formation of a solid carbonate, water and heat. Small amounts of carbonic acid also are formed in the reactions, and the carbonic acid quickly reacts with the alkali. These reactions may be performed in any suitable reaction vessel. In a preferred embodiment, the carbonate precipitates out of solution and is removed from the vessel. Removal of the precipitated carbonate is preferably performed mechanically, using an auger or another suitable mechanical device that allows for the removal of solids without any liquids leaving the vessel at the same location. Any methanol that remains with the carbonate evaporates upon the addition of modest amounts of low-grade heat.
The water resulting from the reactions in the reaction vessel forms a solution with the solvent, and the method further comprises removing the solution of water and solvent and separating the water from the solvent. After the water and solvent are separated, the separated solvent is re-mixed with the alkali such that the solvent and alkali again form a solvent suspension that can be used for further carbon capture. The separated water is returned to the solvent suspension in the reaction vessel where it joins the flue gas and the methoxide to continue the reaction. In a preferred embodiment, the water is separated from the solvent by chilling the solution of water and solvent in a cryogenic drying vessel. When the solution is chilled, the water falls substantially to the bottom of the cryogenic drying vessel, and the solvent rises substantially to the top of the cryogenic drying vessel. In some embodiments, some carbonate will travel with the solution of water and solvent and precipitate out of the solution in the cryogenic drying vessel. A filter may be used to trap larger solids in the reaction vessel, keeping those larger solids from traveling on to the cryogenic drying vessel.
The remaining water may be separated from the solvent using a hot distillation vessel by applying heat to the solution of water and solvent to at least partially vaporize the solvent. A partial vacuum may be used to draw off vaporous solvent from the distillation apparatus, and the vaporous solvent is condensed to a liquid by cooling to be made suitable for re-use in the carbon capture and sequestration reactions.
Embodiments of the present invention include methods of using nitrogen from the flue gas to provide cooling for the carbon capture and sequestration process. The method may include liquefying the nitrogen and recovering refrigeration from the liquefied nitrogen. The recovered refrigeration from the nitrogen is then used to cool the solvent and provide cooling for the solvent regeneration steps. This use of nitrogen for cooling increases the energy efficiency of embodiments of the invention.
In a preferred embodiment, the flue gas further contains nitrogen and the nitrogen is used in three ways. A first portion of the nitrogen is used for refrigeration during the solvent regeneration process, a second portion is used to enhance the power output of a power plant, and a third portion is sold to off-site customers. All of the nitrogen is first compressed. For the portion used for refrigeration, a refrigerant source provides refrigerant to a heat exchanger, and the nitrogen is chilled in the heat exchanger such that it is substantially liquefied. Refrigeration may be recovered from the substantially liquefied nitrogen after it is pumped to pressure and sent to the power cycle to enhance the power output of the power plant that is the source of the flue gas. The recovered refrigeration is used to provide cooling for the cryogenic solvent removal process, discussed below, that separates the water from the solvent.
A second portion of the nitrogen may be used to enhance the power output of a power plant. In a preferred embodiment, a first portion of this substantially liquefied nitrogen is compressed and heated. The heated compressed nitrogen is directed to a steam cycle of a power plant to enhance the power output of the power plant. A second portion of this substantially liquefied nitrogen may be stored in a storage apparatus. The second portion of the substantially liquefied nitrogen is pressurized by pumping it to pressure. It is then vaporized and directed through a hot gas expander to enhance the power output of the power plant. A third portion of this liquefied nitrogen is sold to off-site customers for a variety of uses, including as a refrigerant and as a fluid to enhance oil and gas well recovery. In a preferred embodiment the liquefied nitrogen is further refined by removing liquid argon, which is approximately 0.9% of the volume of the recovered nitrogen stream, and which is a high-value product that may also be sold in the marketplace.
Embodiments of the present invention include carbon capture and sequestration systems which comprise a carbon capture assembly and a solvent regeneration assembly. The carbon capture assembly comprises a mixing vessel and at least one reaction vessel, and may further include a solvent condenser fluidly connected to the reaction vessel. In the mixing vessel, an alkali is mixed with a substantially non-aqueous solvent to form a suspension. In one embodiment, ash is introduced into the solvent, and the alkali is a constituent of the ash. The non-aqueous solvent preferably is an alcohol, and is methanol in a most preferred embodiment. As such, the alkali reacts with the methanol in the reaction vessel to form methoxide and possibly some metal hydroxide. Minor quantities of dimethyl-carbonate (DMC) may also form, but will quickly decompose due the alkaline conditions.
The reaction vessel is fluidly connected to the mixing vessel so it receives the suspension of alkali and a substantially non-aqueous solvent from the mixing vessel through a first input. The reaction vessel also receives flue gas containing heat and carbon dioxide through a second input and water through a third input such that carbonic acid, carbonate, water and heat are formed in the reaction vessel. More specifically, the carbon dioxide and water and any small amounts of carbonic acid that result from the reactions in the reaction vessel react with the alkali in the vessel, resulting in the formation of a carbonate, water and heat. The flue gas will contain nitrogen as well. In some embodiments, the carbon capture assembly further comprises a solvent condenser fluidly connected to the reaction vessel, where refrigeration is used to condense the solvent portion of the exiting stream, which consists of mostly nitrogen.
The solvent regeneration assembly is fluidly connected to the reaction vessel and comprises at least one heat exchanger, a cryogenic drying vessel fluidly connected to the heat exchanger, and a hot distillation vessel fluidly connected to the cryogenic drying vessel. The solvent regeneration assembly preferably has a plurality of heat exchangers to perform several intermediate heat recovery steps to warm the mostly water stream that arrives at the hot distillation vessel and to cool the methanol vapor that leaves the hot distillation vessel.
The carbonate formed in the reaction precipitates out of solution and is removed from the reaction vessel. The carbon capture assembly may further comprise an auger or other suitable device to remove the precipitated carbonate from the reaction vessel. The water resulting from the reactions forms a solution with the solvent in the reaction vessel, and this solution of water and solvent is removed from the reaction vessel and directed to the solvent regeneration assembly. The water is separated from the solvent by the solvent regeneration assembly, and the separated solvent is returned to the mixing vessel where it is re-mixed with the alkali to form a solvent suspension. Also, the separated water is returned to the reaction vessel to continue the reactions.
In some embodiments, a small portion of the carbonate (e.g., less than 10% by volume) will stay in the solvent and travel with the solvent suspension through the solvent regeneration assembly. When the selected alkali is CaO, the solution of water and solvent is free of any carbonates. When the selected alkali is KH, some carbonate will form a solution with the water+solvent. That small portion of carbonate will fall out of the solvent suspension with the water that is separated from it. First, the separation process uses the cryogenic drying vessel in which the solution of water and solvent is chilled so the water falls substantially to the bottom of the cryogenic drying vessel, and the solvent rises substantially to the top of the cryogenic drying vessel. Part (or in a more energy-intensive option, all) of this separation process uses the hot distillation vessel, where heat is applied to the solution of water and solvent, a partial vacuum draws off vaporous solvent from the hot distillation vessel, and the vaporous solvent is condensed.
Some embodiments may include a nitrogen liquefaction assembly which substantially liquefies nitrogen contained in the flue gas and recovers refrigeration from the substantially liquefied nitrogen. The recovered refrigeration from the nitrogen may be used to cool the solvent and to provide cooling for the solvent regeneration assembly. That portion of the liquid nitrogen is sent to the regeneration assembly under pressure, having been pumped to pressure by a cryogenic pump. The solvent regeneration assembly heats a first portion of the substantially liquefied nitrogen and directs the heated nitrogen to a steam cycle of a power plant to enhance the power output of the power plant. A storage apparatus stores a second portion of the substantially liquefied nitrogen, releases the second portion of the substantially liquefied nitrogen, and directs it to a hot gas expander to enhance the power output of a power plant.
Embodiments of the present invention include methods for separating chemical constituents of flue gas (containing CO 2 , a relatively large portion of N 2 , and a much smaller portion of argon) comprising mixing a substantially non-aqueous solvent and an alkali such that the solvent and alkali form a solvent suspension. Water and a flue gas containing carbon dioxide and nitrogen are introduced to the solvent suspension. The alkali in the solvent suspension is contacted with the water and the carbon dioxide in the flue gas such that a series of fast-paced chemical reactions occur. The reactions result in the formation of a carbonate, water and heat, with the unreacted mostly-nitrogen portion leaving the reaction vessel as a gas, and carrying with it small quantities of vaporized solvent.
That mostly-nitrogen stream is chilled in a solvent condenser so as to liquefy that small solvent portion, which is returned to the methanol+alkali mixing vessel. The remaining mostly-nitrogen gas stream is liquefied by compressing and chilling the nitrogen. In a preferred embodiment, the refrigeration content of the substantially liquefied nitrogen is recovered and used to provide cooling for separating the water from the solvent. The nitrogen portion used for cooling is first compressed by pumping it to pressure using a cryogenic liquid pump and then heated by recovered heat in the solvent regeneration assembly. That nitrogen is then directed to a steam cycle of a power plant, or to a generator-loaded hot gas expander to enhance the power output of the power plant. A second portion of the substantially liquefied nitrogen is stored and then may be vaporized and directed through a hot gas expander to enhance the power output of a power plant. A third portion of the substantially liquefied nitrogen is sold to off-site customers.
Accordingly, it is seen that a chemical process for securely and cost effectively capturing and sequestering carbon dioxide on site at a large scale is provided in which carbon dioxide in the form of carbonic acid reacts with an alkali in a solution to form a carbonate, water and heat. These and other features of the present invention will be appreciated from review of the following detailed description of the invention, along with the accompanying figures in which like reference numbers refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects of the invention will be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a process diagram of an embodiment of a carbon capture and sequestration system in accordance with the present invention;
FIG. 2 is a process diagram of an embodiment of a solvent regeneration assembly in accordance with the present invention;
FIG. 3 is a process diagram of an embodiment of a carbon capture and sequestration system in accordance with the present invention integrated with a power plant; and
FIG. 4 is a process diagram of an embodiment of a nitrogen liquefaction assembly in accordance with the present invention.
DETAILED DESCRIPTION
In the following paragraphs, embodiments of the present invention will be described in detail by way of example with reference to the accompanying drawings, which are not drawn to scale, and the illustrated components are not necessarily drawn proportionately to one another. Throughout this description, the embodiments and examples shown should be considered as exemplars, rather than as limitations on the present invention. As used herein, the âpresent inventionâ refers to any one of the embodiments of the invention described herein, and any equivalents. Furthermore, reference to various aspects of the invention throughout this document does not mean that all claimed embodiments or methods must include the referenced aspects. Reference to temperature, pressure, density and other parameters should be considered as representative and illustrative of the capabilities of embodiments of the invention, and embodiments can operate with a wide variety of such parameters. It should be noted that the figures do not show every piece of equipment, nor the pressures, temperatures and flow rates of the various streams.
The examples of gas, liquid, and solid products produced by various embodiments of the present invention are not intended to be comprehensive. Some minor products of embodiments of the invention, including those that form temporarily and then dissolve, will not be discussed in great detail below but are understood to be included within the scope of the invention. Not all points of heat generation will be mentioned below, but it is understood that all worthwhile heat produced in embodiments of the invention will have the potential for heat recovery and potential use, thus reducing the total energy input required by the process.
FIG. 1 shows two major subsystems of an embodiment of the present invention, a carbon capture assembly 100 , and a solvent regeneration assembly 200 . Carbon capture assembly 100 includes reaction vessel 101 and mixing vessel 102 and preferably includes solvent condenser 103 . The solvent regeneration assembly 200 will be described in detail herein in connection with FIG. 2 . The system shown can be used with any power plant and with any type of exhaust gas, and is particularly well-suited for capturing and sequestering carbon dioxide from flue gas from a coal-fired power plant. Flue gas from engines, such as at LFG sites, produce exhaust gas at close to 900° F. While most such engine-drive systems do not have heat recovery attachments, the low-grade heat content of the flue gas is a significant energy source for embodiments of the present systems and methods.
The chemical process of carbon capture and sequestration comprises contacting the CO 2 +water and some temporarily formed (small quantities) of carbonic acid 14 with the alkali 2 that is suspended in methoxide 5 so there is a reaction that results in the formation of precipitating carbonate 6 , water- methanol solution 10 and heat. To begin with, CO 2 -laden flue gas 1 and water 4 are introduced into the methoxide 5 , both streams entering reaction vessel 101 separately at the same time. That separation allows full control over the flow rate of both streams and allows the water stream 4 to be adjusted in response to any minor amounts of water vapor contained in the flue gas. Reaction vessel 101 receives the methoxide suspension 5 , which consists of alkali 2 and a substantially non-aqueous solvent 12 , from the mixing vessel 102 through a first input 113 , which is preferably an input valve. Reaction vessel 101 receives flue gas 1 through a second input 111 and water through a third input 112 , both preferably input valves. The reactions between the CO 2 +water (and small amounts of temporary carbonic acid 14 ) and the alkali 2 contained in the methoxide 5 occur rapidly (sometimes in less than a second), fully converting the gaseous CO 2 into solid carbonates and byproducts of water and heat.
In a preferred embodiment, the carbonate 6 precipitates out of solution and is removed from reaction vessel 101 mechanically, using an auger 104 or any other device or system suitable for mechanically removing carbonate precipitates. In some embodiments, up to approximately 10% of the volume of the water- methanol solution 10 remaining in reaction vessel 101 will contain suspended carbonate, which will not fall to the bottom of the reaction vessel but will fall out of solution during the methanol regeneration process. The water resulting from the acid+base reactions forms a solution with the solvent. That water- solvent solution 10 is removed through a filter 114 , which prevents larger solids from leaving the reaction vessel, and which will fall to the bottom of the vessel, where they will be mechanically removed. The method further comprises removing water- solvent solution 10 from reaction vessel 101 and separating the water from the solvent. In those embodiments that carry carbonates in the water- solvent solution 10 , the carbonates will separate out with the water. This solution 10 of water and methanol is withdrawn near the top of reaction vessel 101 at a warm temperature that reflects the optimum temperature of the reactions, which will minimize the time required for the reactions.
As a preliminary step, an alkali 2 is mixed with a solvent 12 in mixing vessel 102 , to form a suspension 5 . Any of a number of alkalis known in the art can be selected for neutralizing the CO 2 in flue gas, producing their respective carbonates. The alkali may be a strong or a weak base, and may include such common bases as sodium hydroxide (NaOH) or potassium hydroxide (KOH) in powdered form, or hydrides such as magnesium-, potassium- or sodium hydride (MgH, KH, NaH), or anhydrous ammonia, or calcium oxide (CaO) found in the fly ash (and bottom ash) that is another byproduct of coal-fired or biomass power plants and boilers, or any other suitable alkali, natural or synthetic that will react with the CO 2 .
One advantage of embodiments of the present invention is that it can be used to perform carbon capture and sequestration at large industrial scales. Employing the systems and methods described herein at facilities of all sizes allows use of multiple alkalis, resulting in their respective carbonates. An illustrative list, followed by the chemical symbol of each alkali and the carbonate produced when reacted with CO 2 and the chemical symbol of each carbonate, is provided here:
Ammonia (anhydrous), NH 3 âAmmonium carbonate, (NH 4 ) 2 CO 3
Lithium Hydride, LiHâLithium carbonate, Li 2 CO 3
Lithium Hydroxide, LiOHâLithium Carbonate, Li 2 CO 3
Magnesium Hydride, MgH 2 âMagnesium Carbonate, MgCO 3
Magnesium Hydroxide, Mg(OH) 2 âMagnesium Carbonate, MgCO 3
Potassium Hydride, KHâPotassium Carbonate, K 2 CO 3
Potassium Hydroxide, KOHâPotassium Carbonate, K 2 CO 3
Sodium Hydride, NaHâSodium Carbonate, Na 2 CO 3
Sodium Hydroxide, NaOHâSodium Carbonate, Na 2 CO 3
One embodiment uses potassium hydride (KH), possibly in combination with other alkalis. MgH 2 and ash could be used in combination with the KH to increase the CO 2 capture rate. The hydrides of potassium, sodium, magnesium, (KH, NaH, and MgH, respectively) are less expensive than their hydroxide counterparts (KOH, NaOH, Mg[OH] 2 ), and yield a larger amount of carbonate per unit of hydride than the hydroxides, making the hydrides more economical. Such combinations of alkalis would require multiple mixing vessels and multiple reaction vessels. Some hydrogen may also form as a by-product of using certain hydrides. For example, about 930 L of hydrogen will result from NaH and about 560 L of hydrogen will result from KH for every two pounds of hydride dissolved in methanol. Such an H 2 stream would not be vented, but would be used as fuel in one of several possible locations in embodiments of the invention. For example, the H 2 stream can be sent directly to the combustion chamber of the power plant, or it can be burned in a supplemental heater that provides additional heat to the N 2 stream that is used for enhanced power output. The selection of alkalis and the resultant carbonates will depend on the markets for those carbonates and the relative costs of the alkalis when compared to the value of the carbonates.
A preferred embodiment uses the alkali present in fly ash, the fine powder recovered from flue gas at coal-fired and biomass power plants or coal-fired and biomass boilers, prior to the release of the flue gas to the atmosphere. Similarly, bottom ash, resulting from the remains of the coal or biomass that does not travel up the flue, is a product for which uses are sought, but which is still a significant waste stream. The following discussion on ash covers both fly ash and bottom ash, which have similar chemical components, and all other alkaline ash from any source.
Much of the ash produced at coal-fired power plants does not have a use. Most of it is transported to landfills for disposal, or for other low-value applications. Ash from lignite, a widely-used type coal, contains 15-45% SiO 2 (sand), 20-25% AlO 3 (aluminum oxide), 4-15% Fe 2 O 3 (iron oxide) and 15-40% CaO (calcium oxide), with up to 5% unburned carbon. Sub-bituminous coal will produce fly ash with lesser proportions of CaO (5-30%), which can also be used as an alkali source, but requiring larger amounts of ash to produce the same results. The removal of the iron oxide by magnetic means, preferably when the ash is suspended in methanol, will serve to concentrate the amount of CaO in the methoxide, yielding another profitable byproduct (iron oxide) and reducing the weight and transport costs of the final carbonate-laden solid product stream by the removal of the relatively heavy iron. The CaO contained in fly ash is the same alkali that one can purchase as lime, but in this context is a byproduct of the burning of coal that contained calcium carbonate. Thus, the CaO is obtained from the ash with no additional CO 2 emissions beyond what the power plant normally emits. By contrast, buying manufactured CaO would increase the carbon footprint of this process because manufacturing CaO results in large CO 2 emissions.
One embodiment of the carbon capture and sequestration method hosts the ash and the CO 2 -containing flue gas 1 in methanol 12 , substantially limiting the amount of water in reaction vessel 101 . This allows the reaction to yield a dryer and more controllable (as to size and configuration) end product. In this preferred embodiment, the end product will be uniformly sized granules, requiring little or no post-dryer crushing, yielding a suitable agricultural lime substitute, while minimizing the amount of input energy required by the process.
The glass-like ash may benefit from a rapid cooling process that cracks the microscopic ash particles, thus facilitating the reaction of the alkali in the ash with the CO 2 and water delivered to the reaction vessel by streams
1 and 4 . That rapid cooling preferably includes first warming the ash and then rapidly cooling it in deeply chilled methanol, thus cracking each glass-like bead of microscopic ash. If the reactions occur in warm methanol (as is likely), then the quenching of the ash stream can occur first in one vessel, followed by the mixing of the methanol plus ash solution with warmed methanol in a separate reaction vessel. The heat needed to warm the ash before the rapid cooling may be delivered from one of the many heat recovery points in the process.
It is preferred that the acid+base reaction occur in a host liquid having the alkali, or base, in solution, and allow for easy contact between that base and the CO 2 +water (plus small amounts of temporary carbonic acid) that is formed when CO 2 and water are introduced to alkaline-laden solvent. Therefore, preferred embodiments use a substantially non-aqueous solvent to host the reaction. This is accomplished by withdrawing from the top of reaction vessel 101 the water- methanol solution 10 , at the same rate as the reaction produces water, and replacing the water- methanol solution 10 with an equivalent volume of rich (i.e., substantially water-free) methoxide 5 . The amount of water inflow to the reaction vessel is dependent on the water content of the flue gas and the quantity of water that might remain in solution in the methanol from prior inflow of flue gas.
In addition, the water that is a product of the acid+base reaction needs to be withdrawn from reaction vessel 101 at a sufficient rate so as to prevent the methoxide 5 from hydrolyzing. The mostly dry flue gas 1 is bubbled through the methoxide 5 , along with an appropriate amount of water (stream 4 ), allowing the CO 2 to react with the alkali and temporarily form small quantities of carbonic acid 14 , which also reacts with alkali 2 that is held in solution 5 by the solvent 12 . It is preferred that the flue gas 1 enter reaction vessel 101 at enough pressure, e.g., approximately 16.5 psia, so that the flue gas 1 can rise through the host methoxide 5 and allow the unreacted portion of the flue gas (mostly N 2 ) to leave reaction vessel 101 , as a mostly N 2 and vaporized methanol stream 8 , which is recovered by condensation in solvent condenser 103 . Accounting for pressure drop along the pre-cooling route of the flue gas, the present invention seeks to receive the flue gas at approximately 17 psia.
In a preferred embodiment, the non-aqueous solvent is an alcohol and most preferably, methanol. However, any other suitable non-aqueous solvent that will tolerate some significant amount of alkali to be dissolved in it, and will force the precipitation of any salt that is produced in the classic acid+base reaction may be used. Ethanol is a somewhat costlier alternative, which may be selected if, for example, the process is used to capture and sequester CO 2 produced at an ethanol plant. In that context, the ethanol will be available at the equivalent of a wholesale price, and make-up ethanol will not require any shipping. The purpose of the solvent is to allow the acid+base reactions to occur within a substantially dry liquid, thus avoiding the formation of salt water or carbonates suspended in water, and avoiding an end product with a high percentage of water that must be driven off.
The alkali 2 mixes with the methanol solvent 12 to form methoxide 5 , a solution of methanol and any appropriate hydride or hydroxide base where the base is in suspension. The following is one example of a generic chemical equation for the mixing of an alkali (KH, or potassium hydride) with methanol: 2KH+MeOH yields 2MeOK+H 2 . The methoxide may be refrigerated to recover and counter-act the heat of reaction that will occur when some alkalis are introduced into methanol. The choice of how cold the methoxide should be will depend on which alkali is selected and which carbonate will be the end product of the reaction, and by the methods selected for controlling the temperature of reaction vessel 101 , and thus limiting the boil off of methanol from the reaction vessel.
Mixing the alkali 2 with ambient temperature methanol 12 in mixing vessel 102 creates heat as the two compounds interact, and will produce an ionic solution of methoxide 5 , which may include solvated metal hydroxide. The heat of reaction in the resultant solution, which typically is in the range of about 225° F. to about 300° F., may be recovered and used to warm other segments of the process. It should be noted that some dimethylcarbonate (DMC) will also form in mixing vessel 102 , but will subsequently decompose. After heat recovery, the methoxide 5 is sent to reaction vessel 101 to host the incoming streams of water 4 and mostly dry flue gas 1 , which is bubbled through the methoxide 5 . The flow rate of the methoxide 5 into reaction vessel 101 , as well as the outflow of water- methanol solution 10 from reaction vessel 101 to cryogenic drying vessel 202 (via first heat exchanger 201 ) and to the hot distillation column 205 , will depend, first, on the flow rate of the flue gas 1 and the CO 2 content of the flue gas. Secondly, the flow rates will be strictly controlled so as to never allow more than approximately 10% water in the reaction vessel because a methoxide medium with a larger moisture content will not as readily precipitate the carbonate salt.
Methoxide 5 enters reaction vessel 101 into which the flue gas stream 1 and water 4 are introduced. Some embodiments may use multiple reaction vessels in series to allow for the constant flow of flue gas. A preferred reaction vessel has a height of approximately 40 feet and may be made of stainless steel or appropriately coated carbon steel, or any other material that can tolerate acids, bases, water and heat without corroding. Reaction vessel 101 is fluidly connected to mixing vessel 102 such that the alkali-solvent suspension, here methoxide, enters the reaction vessel through a first input. As discussed in more detail herein, flue gas stream 1 arrives in reaction vessel 101 through a second input having given up some its heat content in a hot distillation step associated with the regeneration of the methanol. The chemical process in the reaction vessel can be summarized by the following equation:
The first step in (1) above is the physical dissolution of carbon dioxide gas in the substantially non-aqueous solvent. This dissolution is reversible, as indicated by the double-headed arrows. The second step in (1) is the capture of CO 2 by the water or the base to form small amounts of carbonate in the free form (carbonic acid, H 2 CO 3 ) and carbonate ions. Ion formation depends on the alkalinity of the solution. The reactions are fast, virtually instantaneous. The carbonate ions are removed from the vessel as metallic salts (e.g., calcium carbonate or potassium carbonate) that precipitate to the bottom, thus allowing the reaction to continue. The alkalinity of the solution and the solubility of the metallic carbonates in the solvent determine the rate of carbonate formation and precipitation. Therefore the actual operation of the reaction will be optimized by controlling the alkalinity of the solvent and the temperature, pressure and flow rates of the various streams, relative to the solubility of the selected carbonate product.
Preferably, the water produced from the acid-base reaction should not exceed approximately 10% of the volume of the methanol in the reaction vessel. Water control is achieved by constantly drawing off water- solvent solution 10 from the reaction vessel and replacing it with pure, regenerated methanol. This solvent regeneration process is discussed in detail below.
The reaction of alkali 2 and carbonic acid 14 produces a carbonate 6 that precipitates to the bottom of reaction vessel 101 , where it is removed by auger 104 or any other device or system that can mechanically remove precipitated carbonate. If KH is used as the alkali, some portion of the carbonate 6 will likely stay in solution in the methanol, and will leave with the water- methanol solution 10 and fall out later during cryogenic drying. The removed material may undergo drying by recovered heat from elsewhere in the process, yielding a fine powder or pellets. The <figure-callout id=
CLAIMS
Claims ( 21 )
What is claimed is:
1. A method of capturing and sequestering carbon dioxide, comprising:
mixing a substantially non-aqueous solvent and an alkali such that the solvent and alkali form a solvent suspension;
mixing water and a flue gas containing carbon dioxide with the solvent suspension in a reaction vessel such that a reaction occurs, the reaction resulting in the rapid formation of a solid dry carbonate, water and heat, the resulting water forming a solution with the solvent, the resulting carbonate being essentially free of organo-metallic products and substantially non-aqueous a metallic salt and being one or more of the carbonates of the group consisting of: ammonium carbonate, lithium carbonate, magnesium carbonate, potassium carbonate, sodium carbonate, or calcium carbonate;
the resulting carbonate precipitating out of solution, requiring no further chemical processing steps without carrying water, falling toward the bottom of the reaction vessel, and accumulating at the bottom of the reaction vessel together with some substantially non-aqueous solvent;
removing the resulting carbonate from the reaction vessel without any water leaving the reaction vessel at the same location; and
evaporating with low-grade heat any remaining non-aqueous solvent.
2. The method of claim 1 further comprising the steps of:
continuously removing a portion of the solution of water and solvent from the reaction vessel;
separating the water from the solvent;
introducing additional alkali to the separated solvent;
re-mixing the separated solvent with the additional alkali such that the solvent and additional alkali form a solvent suspension;
providing additional flue gas containing carbon dioxide; and
returning a portion of the separated water to the solvent suspension to continue the reaction.
3. The method of claim 2 wherein the precipitated carbonate is mechanically removed from the reaction vessel.
4. The method of claim 1 wherein the solvent is an alcohol.
5. The method of claim 4 wherein the alcohol is methanol.
6. The method of claim 5 wherein the alkali reacts with the methanol to form methoxide.
7. The method of claim 6 further comprising introducing ash into the solvent, wherein one or more constituents of the ash are alkalis and the ash contains one or more metal oxides including iron oxide.
8. The method of claim 2 wherein separating the water from the solvent includes chilling the solution of water and solvent in a cryogenic drying vessel such that the water falls substantially to the bottom of the cryogenic drying vessel and the solvent rises substantially to the top of the cryogenic drying vessel.
9. The method of claim 2 wherein separating the water from the solvent includes the steps of: applying heat to the solution of water and solvent, using a partial vacuum to draw off vaporous solvent from a hot distillation vessel, and condensing the vaporous solvent.
10. The method of claim 2 wherein carbon dioxide and water react to form carbonic acid.
11. The method of claim 10 further comprising introducing ash into the solvent, one or more constituents of the ash being alkalis and the ash containing one or more metal oxides including iron oxide, wherein the carbonic acid reacts with the alkalis to substantially neutralize the alkalis.
12. The method of claim 11 wherein the reaction of carbonic acid and the alkalis results in a non-alkaline stream comprising one or more carbonates, sand and iron oxide.
13. The method of claim 2 wherein the reaction temperature is less than about 150 degrees Fahrenheit.
14. A method of separating chemical constituents of flue gas, comprising:
mixing a substantially non-aqueous solvent and an alkali such that the solvent and alkali form a solvent suspension; introducing water and a flue gas containing carbon dioxide and nitrogen to the solvent suspension; contacting the alkali in the solvent suspension with the water and the carbon dioxide in the flue gas in a reaction vessel such that a reaction occurs, the reaction resulting in the rapid formation of a substantially non-aqueous carbonate, water and heat, the carbonate being essentially free of organo-metallic products, and the resulting water forming a solution with the solvent; removing the solution of water and solvent from the reaction vessel such that the resulting carbonate is substantially non-aqueous; and substantially liquefying a portion of the nitrogen by compressing and chilling the nitrogen.
15. A method of capturing or sequestering carbon dioxide, comprising:
mixing methanol and an alkali such that the methanol and alkali form a solvent suspension;
mixing water and a flue gas containing carbon dioxide with the solvent suspension such that a reaction occurs, the reaction resulting in the rapid formation of a substantially non-aqueous solid, dry carbonate, water and heat, the carbonate being essentially free of organo-metallic products a metallic salt and being one or more of the carbonates of the group consisting of: ammonium carbonate, lithium carbonate, magnesium carbonate, potassium carbonate, sodium carbonate, or calcium carbonate, the resulting carbonate precipitating out of solution without carrying water; and
mechanically removing the resulting carbonate from the reaction vessel without any water leaving the reaction vessel at the same location.
16. The method of claim 15 wherein the alkali reacts with the methanol to form methoxide.
17. The method of claim 16 further comprising introducing ash into the solvent, wherein one or more constituents of the ash are alkalis and the ash contains one or more metal oxides including iron oxide.
18. The method of claim 15 wherein the resulting water forms a solution with the methanol and the resulting carbonate precipitates out of solution, requiring no further chemical processing steps, falls toward the bottom of the reaction vessel, and accumulates at the bottom of the reaction vessel together with some methanol.
19. The method of claim 18 further comprising the steps of:
continuously removing a portion of the solution of water and methanol from the reaction vessel such that the resulting carbonate is substantially non-aqueous;
separating the water from the solvent;
introducing additional alkali to the separated solvent;
re-mixing the separated solvent with the additional alkali such that the methanol and additional alkali form a solvent suspension;
providing additional flue gas containing carbon dioxide; and
returning a portion of the separated water to the solvent suspension to continue the reaction.
20. The method of claim 16 wherein the water content of the methanol does not exceed about 10% by volume.
21. A method of capturing and sequestering carbon dioxide, comprising:
mixing a non-aqueous solvent and an alkali such that the solvent and alkali form a solvent suspension; mixing water and a gas containing carbon dioxide with the solvent suspension in a reaction vessel such that a reaction occurs, the reaction resulting in the formation of a solid, dry carbonate, water and heat, the resulting water forming a solution with the solvent, the resulting carbonate being a metallic salt; the resulting carbonate precipitating out of solution without carrying water, falling toward the bottom of the reaction vessel, accumulating at the bottom of the reaction vessel together with some solvent; and mechanically removing the resulting carbonate from the reaction vessel without any water leaving the reaction vessel at the same location.
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