ABSTRACT
Abstract
The present invention relates to a high pressure process for Pre-Combustion and Post-Combustion CO2 capture (HP/MP/LP gasification) from a CO2 gas stream (CO2-Stream) by way of CO2 total subcritical condensation (CO2-CC), separation of liquid CO2, higher pressure elevation of obtained liquid CO2 via HP pump, superheating of CO2 up to high temperature for driving of a set of CO2 expander turbines for additional power generation (CO2-PG), EOR or sequestration (First new Thermodynamic Cycle). The obtained liquid CO2 above, will be pressurized at a higher pressure and blended with HP water obtaining high concentrated electrolyte, that is fed into HP low temperature electrochemical reactor (HPLTE-Syngas Generator) wherefrom the cathodic syngas and anodic oxygen will be performed. In particular the generated HP oxygen/syngas will be utilized for sequential combustion (âH2/O2-torchesâ) for super-efficient hydrogen based fossil power generation (Second new Thermodynamic Cycle).
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of application referring to the U.S. Provisional Application with the U.S. Ser. No. 14/392,066 with the priority date of Feb. 21, 2013, then filed for the PCT application of Feb. 19, 2014 with the PCT/EP2014/000443 and WO 2014/127913 A3.
The US national phase was filed Aug. 5, 2015 with U.S. Ser. No. 14/392,066 and the publication date of Dec. 3, 2015 under US 2015/0376801 A1. The most recent amendments were made in correspondence with USPTO Office on Jul. 19, 2018.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable
OTHER PARTIES INVOLVED TO A JOINT RESEARCH AGREEMENT
Not applicable, No other parties involved.
THE OFFICE ELECTRONIC FILING SYSTEM OF USPTO FOR THE PRESENT APPLICATION IN PRIOR
Not applicable
STATEMENT REGARDING PRIOR DISCLOSURES BY THE INVENTOR
PCT note of May 9, 2014
FIELD OF THE INVENTION
Process invention, Art Unit 1794
DESCRIPTION OF THE RELATED PRIOR ART UNDER 37 CFR 1.97 AND 1.98
Not applicable
THE SUMMARY OF THE INVENTION
The field of the present invention relates to a net-zero-carbon-emission process for the capture of carbon dioxide (as the major cause to the global warming) as well as generation of additional electricity by the conversion of the captured carbon dioxide as a new fossil energy resource via the high pressure low temperature electrochemical reaction to oxygen and syngas that can be further processed to high value products i.e. jet fuel, gasoline, methanol, dimethyl ether, ethanol, ammonia, urea, whereas the currently wasted thermal energy is reclaimed in this process for the carbon capture, conversion of carbon dioxide and generation of additional power.
The present process performs a processing for net-zero-carbon-emission super-efficient hydrogen based fossil power plants with high gross efficiency.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The related views to the drawings are presented in the Appendices A, B, C and D as follows:
Appendix A Description of the two new thermodynamic cycles with the associated thermodynamic charts presented in the FIGS. 4A, 4B, 5A, and 5B
Appendix B Description of the major embodiments via FIGS. 1 to 5
Appendix C Further elaboration for the general inventive concept of the present invention with it's three fundamental features (I), (II) and (III) that addresses the solution to the Stationary Sources of CO 2 emission in five principal embodiments according to the FIGS. 6 to 10
Appendix D: List of the abbreviations, acronyms, special expressions, and elements in the embodiments according to the FIGS. 1 to 10
BACKGROUND AND THE DETAILED DESCRIPTION OF THE RELATED ART
As result of increasing world population, the demand for electricity, transportation fuel and the commodity chemicals is increasing rapidly. Simultaneously, the world is encountered with threatening global warming due the emission of carbon dioxide that stems mostly out of the combustion of fossil resources for generation of electricity or conversion of fossil material into chemicals (e.g. transportation fuel, methanol, ethanol, ammonia, etc.). In addition, the higher demand of energy requires more extraction of crude oil and natural gas, while the use of coal is still troublesome or at least limited to some degree, particularly due higher CO 2 emission and other environmental impacts compared with natural gas. The latter fact has led part of coal power plants in United States to a change of fuel towards natural gas resulting to less CO 2 emission. Unfortunately, the intended measures for global reduction of CO 2 are mostly demised or at least lagging far behind. Other political consequences like CO 2 taxes are currently under discussion in some Western countries, that works at the expense of higher costs for generation of electricity an/or chemicals ultimately. The latter impact results inevitable to a misbalance in competitiveness. The increase of expenses due the separation of carbon dioxide via state-of-the-art technologies (both for pre-combustion as well as post-combustion carbon capture) and its further re-compression prior to a national pipeline (if ever ready) and sequestration, provides grave concerns in addition.
As result of these features, the Clean Energy, specifically Clean Coal developments are stalemated in recent years. Other alternatives like sustainable energy by use of biomaterial or waste-to-energy processes are by far unable to address the huge demand of energy, thus they are of marginal significance. Despite broaden outlook of gasification technologies in many perspectives-particularly the coal gasificationâthe extent of carbon emission and the GHG had also put the gasification process in a cul-de-sac, thus recently even some nuclear power plants are set under construction while some other are planned, as though the primary objectives of Clean Coal and the Clean Energy would be not achievable (e.g. in concord to United States Energy Independence and Security Act of 2007).
FIELD OF THE INVENTION
At the other hand the reuse of carbon dioxide as a new fossil energy resource that will reduce the GHG and the demand of primary fossil energy is also restrained due technically and economically unfeasible outcome at the present time. For instance the biological or bacteriological conversion of CO 2 to ethanol doesn't provide substantiated alternative due the low process yield. Respectively the commercial installation of those plants at large scale would not provide a viable way either.
The electrochemical conversion of aqueous solution of CO 2 was more and less subject of scientific investigation at atmospheric pressure and ambient temperature, though under the very low solubility of CO 2 (George Olah et al in reference [1]). A high concentrated aqueous solution requires high pressure CO 2 compression, absorption and cooling, that would lead to a technical-economical unreasonable scale either. The electrochemical conversion of CO 2 and steam under gaseous state was also investigated, without great economical aspect, however. The conversion of gaseous CO 2 /water stream eases slightly the processing, while the required high yield of conversion at technical scale can not be met according to the mass of CO 2 emission (C. R. Graves et al in reference [2]). Both later electrochemical processes require a DC current that was suggested to be supplied by an external power plant; even an adjacent nuclear power plant was suggested.
The current need for a techno-economical feasible CO 2 capture process that resolves the GHG by significant reduction and performs the reuse of CO 2 in a responsive extent under simultaneously preserving the primary fossil energy resources, had initiated the present process invention. Therefore, the present process is now capable to capture and convert the CO 2 in feasible way up to large scale plant (e.g. 1000 MW conventional coal power plant). The capture of all Stationary Sources of CO 2 emission according to the new process is comprised, both, for the post-combustion capture (i.e. flue gas of all kind of fossil power plants, oil & gas, gas treatment, chemical plants, geothermal, aluminum and steel manufacturing as well pulp and paper production) and the pre-combustion capture (i.e. HP/MP and LP gasification plants). At the present time, the Stationary Sources of CO 2 emission reaches out to about 75% of all CO 2 emission globally. Thus the present process invention meets all Clean Energy objectives of United States and many other countries; namely the following prime objectives are attained:
(a) Reduction of energy reliance of the U.S. on foreign resources, e.g. crude oil and natural gas (b) Availing the abundant coal reserve for Clean Energy (c) Viable solution for the global climate warming and control of GHG
In addition, three other goals were accomplished in order to address other current challenges; i.e.:
(d) Ultra Clean Fossil Energy, this term is ascribed to the present process for chemical and power plants due to the providing of Zero Carbon Emission, along with elimination of other emissions that is attained by the deletion of the chimney. For instance, there are no longer pollution of Black Carbon, mercury, antimony, NOx, SOx, and the radioactive constituent from fossil energy resources into the atmosphere (e) Introduction of new surmounting measures for facilitation of super-efficient power plants, whereas the cooling tower and chimney are removed from the scenery of power generation, which are primary culprit for loss of over 40% of the primary thermal input energy (f) Thus the way of nuclear power generation can be abandoned by economical reasons now (g) The attainment for capturing liquid CO 2 within economically inexpensive conditions, resulting in the reuse of carbon dioxide to high-end commodity products like jet fuel, gasoline, methanol, DME, ethanol, fertilizers, etc., that in turn maximizes the efficacious use of fossil energy by preserving the resources. Due this fact the sequestration of carbon dioxide is no longer considerable. The profitability of EOR or IOR application of CO 2 for depleted oil fields via this process shall be analyzed case by case.
The objectives (a) to (g) could be achieved a general inventive concept by the operation of three fundamental features (I), (II) and (Ill) that addresses the techno-economic solution to the Stationary Source of CO 2 emission, wherein:
(I) harnesses the currently wasted energy of power and commodity chemical plants to the atmosphere and integrate the waste heat for post-, and pre-combustion carbon capture through a CO 2 cycle, that is preferably distinguished by sub-critical preheating and superheating for driving of CO 2 turbine and by super-critical condensation of CO 2 that is inherently interlinked with high pressure oxygen and syngas obtained from high pressure low temperature electrochemical generation of syngas (HPLTE-SG) and oxygen from liquid anhydrous CO 2 and water as electrolyte of HPLTE-SG, wherein the economically feasible operation for obtaining liquid carbon dioxide is performed with the CO 2 -cycle with its peculiarities for cooling and condensation CO2-CC, waste heat recovery and process heat utilization by CO2-HR, supply of the required power for driving compressors or turbine-generator of the process CO2-PG (that supplies the CO 2 capture and backs up the electrolysis after AC/DC converter), on demand by a CO 2 closed cooling circuit for waste heat recovery CO2 CCC-HR, which features the CO 2 cycle of this invention (referred to the first new thermodynamic cycle, FIGS. 1, 2, 4A ) to obtain liquid anhydrous carbon dioxide, that (II) is then blended and cooled with purified water for reuse of carbon dioxide as a fossil energy primary resource ( FIG. 3 ,
elements
11 , 12 , 13 , 14 ) at high pressure and low temperature to an electrolyte that is fed to the high pressure low temperature electrochemical reactor HPLTE-SG for generation of anodic oxygen and cathodic syngas (CO/2H 2 ), which is inherently interwined for cooling and condensation media for the above CO 2 -cycle ( FIGS. 5A and 5B ), while driving turbines for AC current, which backs up the process power and the electrolysis after AC/DC converter, wherein the operation of these two section enables the postâas well the pre-combustion carbon capture ( FIGS. 6, 7, 8 and 9 ) at techno-economically feasible extent, more specifically the operation of these two features combined with the feature III, v.i. has led to the, (III) super-efficient hydrogen based fossil power generation with an overall efficiency of 85% to 90% (depending on location of the site and season), which is attained by the operation of the new Second Thermodynamic Cycle, wherein the cathodic pure hydrogen, preferably the hydrogen from a high pressure gasification is combusted with anodic oxygen at various pressures via torches to generate HP/IP/LP Direct Steam for superheated steam or reheating of the steam from the IP and LP sections of the turbine ( FIGS. 4B and 10 ) in a way, that the final steam downstream of the turbine can be regained as pure water while the cathodic chemically pure syngas in stoichiometric composition of CO/2H 2 can be delivered to an adjacent chemical plant for high-end valuable ammonia, methanol, ethanol, fertilizer, gasoline plant that increases the overall efficiency and profitability of the site, lower costs and price of electricity, gasoline, commodity chemicals, ergo shorter period for the return of investment.
The above three fundamental principals of the present invention has evolved to five group of inventive embodiments, which are outlined via the block diagrams in FIGS. 6 to 10 with the list of state-of-the-art as well as the new inventive sections enclosed, which are applicable specifically for (1)post-combustion, (2)pre-combustion and particularly in (3)super-efficient hydrogen based fossile power generation, wherein the reuse of carbon dioxide and Zero-CO 2 emission from the Stationary Sources of CO 2 emission achieved to address the global GHG. These five block diagrams shall serve as over view of the process with their interrelation to the above I, II and III fundamentals of the invention without limiting other inventive sections of each applications, vide Appendix C.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a high pressure process for Pre-Combustion and Post-Combustion CO 2 capture (HP/MP/LP gasification) from a CO 2 gas stream (CO2-Stream) by way of CO 2 total subcritical condensation (CO2-CC), separation of liquid CO 2 , higher pressure elevation of obtained liquid CO 2 via HP pump, superheating of CO 2 up to high temperature for driving of a set of CO 2 expander turbines for additional power generation (CO2-PG), EOR or sequestration (First new Thermodynamic Cycle). The obtained liquid CO 2 above will be pressurized at a higher pressure and blended with HP water obtaining high concentrated electrolyte, which is then fed into HP low temperature electrochemical reactor (HPLTE-Syngas Generator) wherefrom the cathodic syngas and anodic oxygen will be performed. In particular, the generated HP oxygen/syngas will be utilized for sequential combustion (âH 2 /O 2 -torchesâ) for super-efficient hydrogen-based fossil power generation (new Second Thermodynamic Cycle).
BRIEF DESCRIPTION OF THE DRAWINGS
Brief and detailed descriptions for the FIGURES are presented in the Appendix B, and for the Block Diagrams are presented in the Appendix C
DETAILED DESCRIPTION OF THE INVENTION
<div id="p-0023" num="0036" class="description-paragraph"
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of application referring to the U.S. Provisional Application with the U.S. Ser. No. 14/392,066 with the priority date of Feb. 21, 2013, then filed for the PCT application of Feb. 19, 2014 with the PCT/EP2014/000443 and WO 2014/127913 A3.
The US national phase was filed Aug. 5, 2015 with U.S. Ser. No. 14/392,066 and the publication date of Dec. 3, 2015 under US 2015/0376801 A1. The most recent amendments were made in correspondence with USPTO Office on Jul. 19, 2018.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable
OTHER PARTIES INVOLVED TO A JOINT RESEARCH AGREEMENT
Not applicable, No other parties involved.
THE OFFICE ELECTRONIC FILING SYSTEM OF USPTO FOR THE PRESENT APPLICATION IN PRIOR
Not applicable
STATEMENT REGARDING PRIOR DISCLOSURES BY THE INVENTOR
PCT note of May 9, 2014
FIELD OF THE INVENTION
Process invention, Art Unit 1794
DESCRIPTION OF THE RELATED PRIOR ART UNDER 37 CFR 1.97 AND 1.98
Not applicable
THE SUMMARY OF THE INVENTION
The field of the present invention relates to a net-zero-carbon-emission process for the capture of carbon dioxide (as the major cause to the global warming) as well as generation of additional electricity by the conversion of the captured carbon dioxide as a new fossil energy resource via the high pressure low temperature electrochemical reaction to oxygen and syngas that can be further processed to high value products i.e. jet fuel, gasoline, methanol, dimethyl ether, ethanol, ammonia, urea, whereas the currently wasted thermal energy is reclaimed in this process for the carbon capture, conversion of carbon dioxide and generation of additional power.
The present process performs a processing for net-zero-carbon-emission super-efficient hydrogen based fossil power plants with high gross efficiency.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The related views to the drawings are presented in the Appendices A, B, C and D as follows:
Appendix A Description of the two new thermodynamic cycles with the associated thermodynamic charts presented in the FIGS. 4A, 4B, 5A, and 5B
Appendix B Description of the major embodiments via FIGS. 1 to 5
Appendix C Further elaboration for the general inventive concept of the present invention with it's three fundamental features (I), (II) and (III) that addresses the solution to the Stationary Sources of CO 2 emission in five principal embodiments according to the FIGS. 6 to 10
Appendix D: List of the abbreviations, acronyms, special expressions, and elements in the embodiments according to the FIGS. 1 to 10
BACKGROUND AND THE DETAILED DESCRIPTION OF THE RELATED ART
As result of increasing world population, the demand for electricity, transportation fuel and the commodity chemicals is increasing rapidly. Simultaneously, the world is encountered with threatening global warming due the emission of carbon dioxide that stems mostly out of the combustion of fossil resources for generation of electricity or conversion of fossil material into chemicals (e.g. transportation fuel, methanol, ethanol, ammonia, etc.). In addition, the higher demand of energy requires more extraction of crude oil and natural gas, while the use of coal is still troublesome or at least limited to some degree, particularly due higher CO 2 emission and other environmental impacts compared with natural gas. The latter fact has led part of coal power plants in United States to a change of fuel towards natural gas resulting to less CO 2 emission. Unfortunately, the intended measures for global reduction of CO 2 are mostly demised or at least lagging far behind. Other political consequences like CO 2 taxes are currently under discussion in some Western countries, that works at the expense of higher costs for generation of electricity an/or chemicals ultimately. The latter impact results inevitable to a misbalance in competitiveness. The increase of expenses due the separation of carbon dioxide via state-of-the-art technologies (both for pre-combustion as well as post-combustion carbon capture) and its further re-compression prior to a national pipeline (if ever ready) and sequestration, provides grave concerns in addition.
As result of these features, the Clean Energy, specifically Clean Coal developments are stalemated in recent years. Other alternatives like sustainable energy by use of biomaterial or waste-to-energy processes are by far unable to address the huge demand of energy, thus they are of marginal significance. Despite broaden outlook of gasification technologies in many perspectives-particularly the coal gasificationâthe extent of carbon emission and the GHG had also put the gasification process in a cul-de-sac, thus recently even some nuclear power plants are set under construction while some other are planned, as though the primary objectives of Clean Coal and the Clean Energy would be not achievable (e.g. in concord to United States Energy Independence and Security Act of 2007).
FIELD OF THE INVENTION
At the other hand the reuse of carbon dioxide as a new fossil energy resource that will reduce the GHG and the demand of primary fossil energy is also restrained due technically and economically unfeasible outcome at the present time. For instance the biological or bacteriological conversion of CO 2 to ethanol doesn't provide substantiated alternative due the low process yield. Respectively the commercial installation of those plants at large scale would not provide a viable way either.
The electrochemical conversion of aqueous solution of CO 2 was more and less subject of scientific investigation at atmospheric pressure and ambient temperature, though under the very low solubility of CO 2 (George Olah et al in reference [1]). A high concentrated aqueous solution requires high pressure CO 2 compression, absorption and cooling, that would lead to a technical-economical unreasonable scale either. The electrochemical conversion of CO 2 and steam under gaseous state was also investigated, without great economical aspect, however. The conversion of gaseous CO 2 /water stream eases slightly the processing, while the required high yield of conversion at technical scale can not be met according to the mass of CO 2 emission (C. R. Graves et al in reference [2]). Both later electrochemical processes require a DC current that was suggested to be supplied by an external power plant; even an adjacent nuclear power plant was suggested.
The current need for a techno-economical feasible CO 2 capture process that resolves the GHG by significant reduction and performs the reuse of CO 2 in a responsive extent under simultaneously preserving the primary fossil energy resources, had initiated the present process invention. Therefore, the present process is now capable to capture and convert the CO 2 in feasible way up to large scale plant (e.g. 1000 MW conventional coal power plant). The capture of all Stationary Sources of CO 2 emission according to the new process is comprised, both, for the post-combustion capture (i.e. flue gas of all kind of fossil power plants, oil & gas, gas treatment, chemical plants, geothermal, aluminum and steel manufacturing as well pulp and paper production) and the pre-combustion capture (i.e. HP/MP and LP gasification plants). At the present time, the Stationary Sources of CO 2 emission reaches out to about 75% of all CO 2 emission globally. Thus the present process invention meets all Clean Energy objectives of United States and many other countries; namely the following prime objectives are attained:
(a) Reduction of energy reliance of the U.S. on foreign resources, e.g. crude oil and natural gas (b) Availing the abundant coal reserve for Clean Energy (c) Viable solution for the global climate warming and control of GHG
In addition, three other goals were accomplished in order to address other current challenges; i.e.:
(d) Ultra Clean Fossil Energy, this term is ascribed to the present process for chemical and power plants due to the providing of Zero Carbon Emission, along with elimination of other emissions that is attained by the deletion of the chimney. For instance, there are no longer pollution of Black Carbon, mercury, antimony, NOx, SOx, and the radioactive constituent from fossil energy resources into the atmosphere (e) Introduction of new surmounting measures for facilitation of super-efficient power plants, whereas the cooling tower and chimney are removed from the scenery of power generation, which are primary culprit for loss of over 40% of the primary thermal input energy (f) Thus the way of nuclear power generation can be abandoned by economical reasons now (g) The attainment for capturing liquid CO 2 within economically inexpensive conditions, resulting in the reuse of carbon dioxide to high-end commodity products like jet fuel, gasoline, methanol, DME, ethanol, fertilizers, etc., that in turn maximizes the efficacious use of fossil energy by preserving the resources. Due this fact the sequestration of carbon dioxide is no longer considerable. The profitability of EOR or IOR application of CO 2 for depleted oil fields via this process shall be analyzed case by case.
The objectives (a) to (g) could be achieved a general inventive concept by the operation of three fundamental features (I), (II) and (Ill) that addresses the techno-economic solution to the Stationary Source of CO 2 emission, wherein:
(I) harnesses the currently wasted energy of power and commodity chemical plants to the atmosphere and integrate the waste heat for post-, and pre-combustion carbon capture through a CO 2 cycle, that is preferably distinguished by sub-critical preheating and superheating for driving of CO 2 turbine and by super-critical condensation of CO 2 that is inherently interlinked with high pressure oxygen and syngas obtained from high pressure low temperature electrochemical generation of syngas (HPLTE-SG) and oxygen from liquid anhydrous CO 2 and water as electrolyte of HPLTE-SG, wherein the economically feasible operation for obtaining liquid carbon dioxide is performed with the CO 2 -cycle with its peculiarities for cooling and condensation CO2-CC, waste heat recovery and process heat utilization by CO2-HR, supply of the required power for driving compressors or turbine-generator of the process CO2-PG (that supplies the CO 2 capture and backs up the electrolysis after AC/DC converter), on demand by a CO 2 closed cooling circuit for waste heat recovery CO2 CCC-HR, which features the CO 2 cycle of this invention (referred to the first new thermodynamic cycle, FIGS. 1, 2, 4A ) to obtain liquid anhydrous carbon dioxide, that (II) is then blended and cooled with purified water for reuse of carbon dioxide as a fossil energy primary resource ( FIG. 3 ,
elements
11 , 12 , 13 , 14 ) at high pressure and low temperature to an electrolyte that is fed to the high pressure low temperature electrochemical reactor HPLTE-SG for generation of anodic oxygen and cathodic syngas (CO/2H 2 ), which is inherently interwined for cooling and condensation media for the above CO 2 -cycle ( FIGS. 5A and 5B ), while driving turbines for AC current, which backs up the process power and the electrolysis after AC/DC converter, wherein the operation of these two section enables the postâas well the pre-combustion carbon capture ( FIGS. 6, 7, 8 and 9 ) at techno-economically feasible extent, more specifically the operation of these two features combined with the feature III, v.i. has led to the, (III) super-efficient hydrogen based fossil power generation with an overall efficiency of 85% to 90% (depending on location of the site and season), which is attained by the operation of the new Second Thermodynamic Cycle, wherein the cathodic pure hydrogen, preferably the hydrogen from a high pressure gasification is combusted with anodic oxygen at various pressures via torches to generate HP/IP/LP Direct Steam for superheated steam or reheating of the steam from the IP and LP sections of the turbine ( FIGS. 4B and 10 ) in a way, that the final steam downstream of the turbine can be regained as pure water while the cathodic chemically pure syngas in stoichiometric composition of CO/2H 2 can be delivered to an adjacent chemical plant for high-end valuable ammonia, methanol, ethanol, fertilizer, gasoline plant that increases the overall efficiency and profitability of the site, lower costs and price of electricity, gasoline, commodity chemicals, ergo shorter period for the return of investment.
The above three fundamental principals of the present invention has evolved to five group of inventive embodiments, which are outlined via the block diagrams in FIGS. 6 to 10 with the list of state-of-the-art as well as the new inventive sections enclosed, which are applicable specifically for (1)post-combustion, (2)pre-combustion and particularly in (3)super-efficient hydrogen based fossile power generation, wherein the reuse of carbon dioxide and Zero-CO 2 emission from the Stationary Sources of CO 2 emission achieved to address the global GHG. These five block diagrams shall serve as over view of the process with their interrelation to the above I, II and III fundamentals of the invention without limiting other inventive sections of each applications, vide Appendix C.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a high pressure process for Pre-Combustion and Post-Combustion CO 2 capture (HP/MP/LP gasification) from a CO 2 gas stream (CO2-Stream) by way of CO 2 total subcritical condensation (CO2-CC), separation of liquid CO 2 , higher pressure elevation of obtained liquid CO 2 via HP pump, superheating of CO 2 up to high temperature for driving of a set of CO 2 expander turbines for additional power generation (CO2-PG), EOR or sequestration (First new Thermodynamic Cycle). The obtained liquid CO 2 above will be pressurized at a higher pressure and blended with HP water obtaining high concentrated electrolyte, which is then fed into HP low temperature electrochemical reactor (HPLTE-Syngas Generator) wherefrom the cathodic syngas and anodic oxygen will be performed. In particular, the generated HP oxygen/syngas will be utilized for sequential combustion (âH 2 /O 2 -torchesâ) for super-efficient hydrogen-based fossil power generation (new Second Thermodynamic Cycle).
BRIEF DESCRIPTION OF THE DRAWINGS
Brief and detailed descriptions for the FIGURES are presented in the Appendix B, and for the Block Diagrams are presented in the Appendix C
DETAILED DESCRIPTION OF THE INVENTION
High pressure process for both Post-Combustion and Pre-Combustion CO 2 capture from a CO 2 gas stream and/or from any CO 2 containing gaseous process media (referred to CO2-Stream) by way of total and/or partial condensation of CO 2 to liquid carbon dioxide (CO2-CC: Carbon dioxide Capture and Condensation) is invented, whereby the condensation of subcritical CO 2 by trespassing the liquid-vapor two-phase zone and/or more preferably supercritical-subcritical condensation above the critical point is carried out under elevated pressure merely above the critical pressure and below the critical temperature of carbon dioxide:
P*(CO 2 )=1070 psi=73.835 bar
T*(CO 2 )=87.8° F.=31.06° C.
According to the present process invention it is first imperative, to cool down the CO 2 containing gaseous media with the available cooling media e.g. internal process media, cooling water or ambient air (air cooler, hybrid cooler) close over the critical temperature, so the condensation in this first heat exchanger(s) can be suppressed (in the context of present process invention, referred to as Over Critical Gas Cooler). Up to the over critical gas cooling, the water constituent of CO 2 containing gaseous media can be removed by way of condensation of water. Further on, the dehydration of CO 2 containing gaseous process medium takes place i.e. silica gel, organic or inorganic absorbens, so dry dehydrated CO 2 containing process gas (for instance, syngas containing CO 2 /CO/H 2 ) can be processed to the next subcritical heat exchanger(s), wherein a partial CO 2 condensation of upstream gaseous media will take place in countercurrent to the undercooled gases (e.g. H 2 /CO) after the liquid CO 2 separation. The condensation of major part of CO 2 takes place in the Main Condenser and liquid CO 2 collector.
This process considers the condensation of CO 2 from any CO 2 containing sources (referred to CO2-Stream), in particular as of the flue gas of fossil power plants based on coal, biomass, municipal waste, crude oil, petcoke, refined oil intermediates, bulk solid or liquid carbonaceous waste fired power plants as well as natural gas or any offgas (H 2 /CO of steel manufacturing) fired in the combustion chamber of gas turbine in the single cycle or combined cycle power plants.
The present process encompasses also the condensation of CO 2 from any other CO2-Stream i.e. aluminum production, cement industry, steel manufacturing and coke preparation from coal, geothermal source, fermentation off gas, CO 2 constituent in the untreated natural gas off of the well, pulp and paper manufacturing and chemical plants i.e. ammonia, methanol, ethanol, gasoline production plant and air will be considered in this process. In addition, this process comprises also the capturing of CO 2 from CO 2 containing gases obtained either from high pressure syngas (i.e. from high pressure gasifier) directly and/or middle or low pressure syngas (obtained from MP/LP gasifiers) after pressure elevation by a compressor.
The term HP syngas in the sense of this process invention according to FIG. 1 , is ascribed to a syngas which is generated by HP gasifier 1 , so the syngas (after the passing gas clean up 2 , syngas scrubber, syngas cooler, COS hydrolysis, syngas cooling, mercury removal, Acid Gas Removal unit for removal of H 2 S, and injection of steam/ water 5 , to CO-Water Shift Converter 6 , either for partial conversion and stochiometric adjustment of H 2 /CO ratio or total conversion of CO to hydrogen by adding of water/steam into the syngas) shall be obtained in upstream of the CO2-CC unit (process stream 7 ), and upstream of Over Critical Gas Cooler 8 by at least a pressure, slightly above the prevailing critical pressure of carbon dioxide, more preferably it is obtained in a margin of the partial pressure of CO 2 that is close above the critical pressure of the carbon dioxide.
The HP gasifier according to the meaning of present process invention is ascribed to any gasification process wherein the HP gasifier is fed with natural gas, crude oil, coal slurry, biomass, more advantageously fed with carbon rich bulk solid carbonaceous material preferably in powder or dust form, i.e. coal (both in low rank and/or high rank), petcoke, biomass are fed into gasifier via high pressure dry feeding system (e.g. Aerojet Rocketdyne (former PWR) Dry Pump or HP-Dry CCS, High Pressure Dry Continuous Coal Supply in pursuant to PCT/US2010/002482 or EP 09 012 157.5) takes place. The HP/MP/LP gasifier above can be fed either with air or in advanced gasifier with oxygen, preferably that is obtained hereby from the anode of HPLTE-Syngas Generator.
The term MP or LP syngas in the meaning of present process invention, is ascribed to a syngas pressure which is generated by MP or LP gasifier
1 , 2 , so the syngas after passage of gas clean up, syngas scrubber, syngas cooler, COS hydrolysis, syngas cooling, mercury removal, Acid Gas Removal unit for removal of H 2 S, and CO-Water Shift Converter 6 (either partial conversion for adjustment of CO/H 2 ratio or total conversion of CO to hydrogen by adding of water/steam into the syngas, whereas the obtained syngas upstream of the CO2-CC unit will have lower pressure than the critical pressure of carbon dioxide. In this case, an interim compressor ( FIG. 1, 3 , upper comment) shall pressurize the MP/LP syngas to a higher pressure that is preferably slightly above the critical pressure of carbon dioxide required upstream of CO2-CC and Over Critical Gas Cooler. In the latter case, the intercoolers of interim syngas compressor are encompassed within the CO2-HR Unit that comprises Heat Recovery carried out by CO 2 as working process media (akin to HRSG section for water-steam system).
It is from process economics perspective more advantageous, that the present process invention can be applied to for CO 2 removal after a HP Gasification Island, so the operation pressure of the HP row syngas downstream of gasifier and upstream of CO2-CC section prevails above the critical pressure of CO 2 . As described v.i. this kind of gasifier are utmost preeminent gasifiers that can be installed for high efficient syngas generation for chemicals and more specifically for super-efficient hydrogen based power plants.
The condensation of carbon dioxide by an operation pressure-advantageously merely above the critical pressure-requires cooling the gaseous media down below the 31° C. that can be performed with an Auxilliary Cooling Media or process media after CO 2 condensation ( FIG. 1, 16, 17 ) i.e. by cooling water, refrigerant cooling (e.g. by use of Freon), ammonia absorber cooling, ambient air and/or a combination of them, specifically via dry air cooler in the winter season or in cold regions. In the summer season or in warm regions additional cooling circuit is necessary.
According to the present process, low temperature gaseous products of HPLTE-Syngas Generator v.i., that are cathodic H 2 /CO syngas and anodic O 2 with an average temperature of 10° to 25° C. will be involved as a process integrated cooling agent for CO 2 cooling and condensation as well (refer to HPTLE-Syngas Generator in FIG. 3 and the description vide infra). According to the FIG. 5 (exemplary for O 2 and CO, likewise for H 2 constituent of syngas as well), the cooling through each product stream of HPLTE-Syngas Generator can take place repeatedly for cooling of CO 2 either in CO2-CC section and/or for the CO 2 cooling and condensation in the CO 2 power cycle.
More preferably, the additional cooling circuit can be performed by an Auxiliary Cooling Unit (referred to as ACU) via expansion of part of the obtained liquid carbon dioxide to lower pressure level at one side of a heat exchanger, while at the other side the undercooling the carbon dioxide containing gaseous process media to the total condensation of CO 2 will be performed below the critical temperature of carbon dioxide in the Main Condenser. For instance, the expansion of approximately 16 lbs liquid carbon dioxide from 74 barg down to ca. 5.547 barg at â55° C. (triple point of CO 2 at â56.57° C.), enables the condensation of 84 lbs carbon dioxide out of the syngas mixture or any CO 2 containing gas. The residual traces of CO 2 in syngas (e.g. for ammonia process) can be removed by way of a Trim Absorber, so the CO 2 cleansed syngas can be forwarded to methanization reactor, prior to ammonia synthesis section.
The present process considers the release of part of the obtained liquid carbon dioxide in the margin from critical point of CO 2 down to the sublimation line (in the sense of temperature-entropy or pressure-enthalpy chart) that is over the sublimation line of carbon dioxide. The released CO 2 can be recompressed and recycled back to the upcoming CO 2 containing process upstream of CO2-CC. Preferably, the operation pressure of ACU is to be kept above the triple point temperature of CO 2 and the sublimation line of CO 2 at the coolant side in order to avoid the deposits of CO 2 solid sublimates.
The CO2-CC Unit consists specifically of Over Critical Gas Cooler(s) 8 , final dehydration adsorber columns 9 (working intermittently for dehydration/regeneration mode of operation, dehydrated CO 2 stream 10 ), Subcritical Gas Cooler(s) 11 , CO 2 Main Condenser(s) 14 and the ACU the Auxiliary Cooling Unit 19 . The present CO2-CC can be inventively carried out in any region of CO 2 (in the sense of temperature-entropy chart or enthalpy-entropy chart of CO 2 ) i.e. subcritical condensation, condensation on critical point, particularly condensation of CO 2 in supercritical region with cooling systems based on low temperature gaseous products of HPLTE-Syngas Generator, which can be employed repeatedly (refer to FIG. 5 A, B exemplarily), air cooler, cooling tower, coolant system 18 (e.g. ammonia absorber coolant, Freon, refrigerating system), more preferably supported by ACU carried out by release and vaporization of part of liquid CO 2 process media.
In order to conduct the condensation of CO 2 with minimal thermal condensation energy, it is preeminent to cool first the gaseous media by supercritical gas cooler(s) close over the critical point (CO 2 condensate 12 ), then further cooling 13 by trespass the critical point down to subcritical region by subcritical gas cooler(s) and the Main Condenser, 14 with liquid CO 2 streams 20 , and 15 (for semi-open cycle i.e. for EOR, IOR, Urea production). By this measure the minimal cooling performance will be required by the cooling agent or ACU in the summer season.
The CO 2 Main Condenser 14 captures also the gaseous recycle CO 2 stream that is directed from an interim section of the CO 2 back pressure turbine in the CO 2 power generation section (CO2-PG) or is recycled from ACU after re-compression of carbon dioxide stream.
On the grounds of carbon capture features of present process invention an utmost compact and cost efficient way for removal of CO 2 is fulfilled as regards to costs of investment, operation and maintenance costsâcompared with Selexol, Rectisol and Benfield absorption and PSA for removal of CO 2 according to the state-of-the-art processes. This process encompasses the utilization of separated liquid CO 2 for heat recovery and additional power generation via CO 2 expander turbines.
The utilization of CO 2 is carried out by pressure elevation of liquid carbon dioxide by use of HP-Liquid CO 2 pump, typically in margin of 250 to 300 barg or higher pressure under steady operation of pump in CO 2 subcritical temperature, preferably in the margin of 10° to 25° C.
The pressure elevation via pump (either in a single or multiple pumping stages) is considered to be carried out with simultaneous indirect cooling of liquid CO 2 while pumping performed. The cooling of the liquid CO 2 centrifugal pump or reciprocating plunger pump or pump stagesâsuch as like applied in some urea plants or for pressurization of anhydrous ammoniaâcomprises the employment of intercooler(s) and jacket cooling of the pump(s) as well.
The HP liquid CO 2 stream can preferably be processed in part for various other applications like urea manufacturing and/or after heat recovery (not depicted in FIG. 1 ) for HP CO 2 sequestration. It can be also availed for desuperheating of MP CO 2 stream for EOR (Enhanced Oil Recovery) or CO 2 MP-sequestration or delivering to national CO 2 pipe line.
One of peculiarities of present process invention is pertaining to availing of liquid carbon dioxide as feedstock for higher value intermediates, syngas and oxygen, through high pressure low temperature electrochemical conversion of liquid carbon dioxide and water (HPLTE-Syngas Generator). This technically and commercially viable way can be carried out now in large scale commercial plant that produces value added final products which are originally obtained from natural gas and crude oil as well. Hence this, the liquid carbon dioxide can be transported and shipped to another location and sites, where the generation of syngas can take place. This provides a tremendous remedy because the transportation and storage of liquid carbon dioxide is by far less complicated than the transportation of LNG (liquefied natural gas). Therefore, the present process considers the export of liquid carbon dioxide as an auspicious option for safe transportation of energy resources. More specifically, the present process invention comprises in one of the embodiments a HPLTE-Syngas Generator. The side stream for excess CO 2 is processed as HP-liquid CO 2 for sequential blending/cooling with purified water that will be fed into the HPLTE-Syngas Generator.
The heat recovery with HP liquefied CO 2 is first carried out at a pressure, typically in margin of 250 to 300 barg or higher pressure, while the vaporization of liquid CO 2 (also referred to as CO 2 regasification) takes place at the low temperature, as low as the critical temperature of CO 2 of 31° C.
T*(CO 2 )=87.8° F.=31.06° C.
This leads to some preeminent advantageous features that makes the liquid CO 2 predestined to use the entire waste heat and other heat resources that are typically wasted in chemical and fossil power plants (typically through the cooling tower, chimney or to the ambient air). The recovery of those heat sources are also extraordinary important for leveraging of gross thermal efficiency, respectively increase of electric output efficiency of a fossil or nuclear power plant and the chemical plants as well.
According to the present process the heat recovery via liquid carbon dioxide at elevated pressure comprises every kind of heat sources, wherever the potential for the heat source is equal or lower than the critical temperature of liquid carbon dioxide of 10° to 31° C., more advantageously above the critical temperature of CO 2 for heat recovery vs. gaseous carbon dioxide. Specifically, the following prime heat sources are involved in the present process invention:
(a) CO2-HR of residual LP steam downstream of steam backpressure turbine and/or any steam condensation turbine, either for power generation or as driving machine for other working machines i.e. compressors or pumps. The extent of the dissipated energy downstream of steam turbine imposes the utmost greatest loss of thermal energy in any power plants, both fossil and nuclear power plants. This heat is typically lost into the atmosphere by the huge cooling tower, that portrays the scenery of a thermal power plant, usually in extent of 45% and more for most coal fired power plants and even higher in case of nuclear power plants
Depending on seasonal and the vacuum prevailing downstream of the steam condensation turbine, the temperature level at the waste heat side is in the margin of 120° to 130° C., in some plant with vacuum pumps down to 60° to 50° C.
(b) Other waste heat resources i.e. flue gas through the chimney of coal, biomass, oil, natural gas fired plants, stack of combined cycle gas turbine power plants, in particular the single cycle gas turbine power plants. Other wasted heats are i.e. intercoolers of compressor, expansion heat downstream of back pressure steam turbines, or other back pressure expander turbines for offgas. (c) Waste heat recovery includes also the intercoolers of intermediate compressors employed in the site, i.e. syngas compressor of MP/LP gasifier, intercoolers of flue gas compressor ( FIG. 2, 62 with Flue Gas compressions streams 65 and 66 ) of conventional fossil power plants (typically depicted in FIG. 2 , B with both natural circulation of liquid CO2 60 and/or stimulated circulation of liquid CO 2 via pump 63 ), off gas compressor of gaseous effluent of vicinal or adjacent chemical plants (i.e. purge gas of ammonia, methanol plant, DNCG, CNCG of pulp and paper plant) and the natural gas compressor or other hydrocarbon compressors (e.g. propane, butane, ethanol, methanol containing hydro carbonic gaseous off gases). Whereby the HP evaporated CO 2 stream 61 leaves the evaporator 64 to superheater stage (likewise in FIG. 2 A with CO 2 streams 73 , 76 with evaporator
71 , 72 and superheater 75 ). (d) The waste heat recovery in CO2-HR encompasses the heat recovery of intercoolers of ACU's CO 2 recompressor (principally depicted in FIG. 2 , subsection B in a CCC Closed Cooling Circuit arrangement for heat recovery) and/or any other compressor involved in the overall processing namely i.e. Flue Gas, syngas, natural gas and the HP hydrogen compressor. (e) Process waste heats in fossil power plants i.e. steam condensate reflux of power plants and ash cooler. (f) The CO2-HR comprises the superheating upstream of CO 2 turbine i.e. by use of any process heat, specifically indirect process heat that is generated by way of natural gas gasification with the oxygen (preferably obtained at the anode of HPLTE-Syngas Generator), more preferably by way of high pressure gasification and/or re-superheating of regasified CO 2 downstream of each CO 2 expander turbine's section before entering of CO 2 to the next lower pressure section(s) of CO 2 expander turbine ( FIG. 1 , CO2-PG). More preferably, the re-superheating of carbon dioxide will be combined with the steam heat downstream of steam back pressure turbine. (g) Process waste heats in chemical plants, i.e. heat sources downstream of low temperature exothermic reactors i.e. HT- or LT-water gas shift converter, absorption heats of thermal absorber towers (e.g. nitric acid tower), exothermic heat of solution by mixing of process media (v.i. liquid carbon dioxide and water mixture prior to HPLTE-Syngas Generator) as well as intermediate or final product cooler (i.e. ammonia-nitric acid neutralizer of ammonium nitrate fertilizer manufacturing). (h) Waste heat of off gases, purge gases (i.e. from ammonia, methanol and ethanol synthesis) and flue gas of chemical plants (i.e. flue gas of steam reformer). (i) Waste heat sources of auxiliary process media i.e. jacket cooling of reactors, in particular jacket cooling and screen cooling of the gasifier. (j) The CO2-HR includes also the jacket cooling section(s) of the torch(s) implemented for Direct Steam generation and/or resuperheating in super-efficient hydrogen based power plants v.i., by way of CO 2 superheating and/or CO 2 supraheating as inherent part of CO2-HR (referred to as closed-end jacket cooling).
The above CO 2 heat recovery via HP liquid carbon dioxide under (a) to (f) includes the available heat sources for vaporization at 31° C. and superheating of carbon dioxide up to a margin of 150° to 200° C. Thus the captured carbon dioxide for heat recovery is primarily utilized for power generation as a driving agent for turbines. The present process commenced the supraheating (likewise in the meaning for ultra superheated steam) of carbon dioxide that is considered up to 800° C. and higher temperature. The supraheating of carbon dioxide is carried out via,
(k) Integration of all ancillary heat sources and all process sensitive heat sources for supraheating of utilized liquid-gaseous carbon dioxide, specifically Hot Syngas Cooler, both, either integrated in the gasifier or downstream of the gasifier. All process sensible heats in chemical plants, i.e. cracking furnaces, nitric acid plant heat sources downstream of middle or high temperature exothermic reactors i.e. water gas shift converter, ammonia, methanol and ethanol synthesis section. (l) Integration of CO 2 supraheater within the sections of combustion chamber and/or in the HRSG units of conventional fossil power plants, pulp and paper industry (i.e. black liquor recovery boiler, bark boiler) and chemical plants i.e. combustion chamber of primary steam reformer of methanol and ammonia plants. (m) In particular, the CO2-HR of present process invention comprises the waste heat of nuclear power plants for regasification of CO 2 in CO2-CC, which is conventionally wasted by the cooling tower. (n) This process includes also the use of indirect fired furnaces (similar to start-up furnace of ammonia and methanol plant) for supraheating of re-gasified carbon dioxide as well, (o) More specifically, the supraheating upstream of CO 2 turbine i.e. by use of any process heat, specifically indirect process heat that is generated by way of natural gas gasification with the oxygen (preferably obtained at the anode of HPLTE-Syngas Generator), more preferably by way of high pressure natural gas gasification over the critical pressure of CO 2 whereas a slag-free HP syngas is obtained from this heater that is then routed to the main syngas stream (downstream of gas clean-up section of Gasification Island). (p) Specifically, the present process encompasses the supraheating of HP CO 2 re-gasified stream via combustion of H 2 /O 2 stream within the context of super-efficient hydrogen based fossil power plants.
Within the compass of CO2-HR sections, both in superheating and supraheating sections, includes the injection of liquid carbon dioxide as a measure for temperature controlled optimization remedy for optimal heat recovery from various sources of heat in order to cover more heat resources under CO2-HR system.
The CO2-HR section includes the removal of dissolved carbon monoxide in the liquid carbon dioxide process media by way of thermal stripping of liquid carbon dioxide, adsorption of CO with molecular sieves, more preferably by a solid reactants i.e. magnetite according to the reaction (1) that is internally oxidized with a controlled flux of oxygen via reaction (2) with the activated iron (typically used as ammonia synthesis catalyst) or any other reducing agent that oxidizes the traces of carbon monoxide to carbon dioxide ( FIG. 1, 26 ).
Fe 3 O 4 +4COâ3Fe+4CO 2 ââ(1)
3Fe+2O 2 âFe 3 O 4 ââ(2)
In the present process, the removal of impurities, specifically dissolved carbon monoxide will take place, preferably downstream of CO 2 superheater(s) and upstream of CO 2 supraheater.
Similar like ACU, one and/or few number of centralized closed cooling circuit unit(s) is performed according to this process in order to accommodate the heat recovery from various internal resources into the captured carbon dioxide for vaporization of liquid CO 2 for the first stage and the second stage CO 2 superheaters ( FIG. 2 , section A). This measure is important from the following aspects:
(i) The CO2-HR can be easier centralized in the plant arrangement. Because the various waste heat sources can be dispersed in various places in the plant, the decentralized CO2-HR units would lead to a maze of piping and interdict process control system at high expense. (ii) The working pressure of closed cooling circuit can be set for instance at 10 barg with water as heat carrier. Respectively, the operating pressure of one side of the HP heat exchangers can be set at lower working pressure that leads to less expensive equipment from design pressure point of view. (iii) The mass flow rate of circulating closed cycle can be easier accommodated with the rate of the heats to be recovered from, (iv) the CO2-HR units can be set in a staggered arrangement according to the temperature level of waste heat sources and also in respect to process media with propensity to cause fouling in heat exchangers, which can be passed through the tubes of shell-tube heat exchangers preferably. (v) The separation of various cooling process media (like cathodic H 2 /CO and anodic O 2 from HPLTE-Syngas Generator or steam downstream of condensation turbine) against each other is important from plant safety aspects. By use of closed cooling circuit the sources for heat recovery and/or sources for cooling media can be separated physically by shunting of CCC media that operates either under lower working pressure (for instance cathodic H 2 /CO, anodic O 2 , HP/MP/LP syngas from gasification plant island, MP/HP intercoolers of compressors) or at lower pressure, e.g. flue gas heat recovery, LP intercoolers of compressors. In this case, any upcoming leakage can be readily detected and allocated momentarily.
The present process for CO 2 utilization is further distinguished by regain of additional power generation through the utilized HP supraheated carbon dioxide. In addition, this process is capable to reduce the carbon emission down to Zero Emission Concept (by employing HPLTE-Syngas Generator v.i.).
It should be highlighted that in contrast to all actual state-of-the-art processes, the entire present process with CO2-CC, CO2-HR and use of CO2-PG for additional power generation and eventually sequestration, EOR, IOR will be profitable from economics aspects of view for the first time. The CO2-PG unit comprises typically multistage CO 2 back pressure expander turbines and a final turbine that works either in continuous operation or deigned for Peak operation. The first stageâthe HP turbine section; is typically carried out with inlet temperature of 800° C. or higher, operating from 250 to 300 barg with a carbon dioxide to about 75 barg, merely above the critical pressure of carbon dioxide.
Since the condensation enthalpy of water is greater than the vaporization/superheating heat enthalpy of carbon dioxide the mass flow rate of two major cycles for power generation (water-steam Rankin cycle and the new First Thermodynamic Cycle with liquid & re-gasified CO 2 ) are to be accommodated from thermodynamic balances point of view. Hence that, the major part of recycling carbon dioxide will stem from HP section of CO 2 back pressure turbine. The recycle carbon dioxide after regenerative heat exchange and CO 2 -HR (typically with a temperature of 45° to 40° C.) can be sent in part for MP CO 2 sequestration or EOR or delivered after re-liquification for CO 2 export according up to beverage grade.
The remaining recycle CO 2 , or the entire recycle CO 2 (if no sequestration and EOR/IOR are considered) will pass through the cooling heat exchanger (air cooler, hybrid air cooler or water cooler in winter, with additional ACU for summer period or any combination of them) that provides the required cooling capacity for re-liquification of recycle carbon dioxide. The recycle LP CO 2 downstream of ACU and after the recompression of this side stream, merges the recycle CO 2 stream upstream of the CO2-HR heat exchanger.
The second expander stage is distinguished by a MP CO 2 turbine that receives the CO 2 stream downstream of HP turbine section (either without re-superheating or with reheating of supraheated CO 2 stream) and expands the pressure down to MP export CO 2 for EOR/IOR or MP sequestration or delivering to national CO 2 pipeline. Finally, the LP CO 2 turbine is also considered in this process in case, part of the excess CO 2 shall embark for biological, bacteriological or chemical CO 2 conversion to higher value hydrocarbons, ethylene or other products and/or that part of excess CO 2 shall be released into the atmosphere for peak need of electricity or temporarily purposes.
Because the sequestration of carbon dioxide provides only a transitory solution for Green House Gases without any substantive contribution for reducing the loss of thermal energy, the present process invention comprises the chemical conversion of captured carbon as a new inexhaustible feedstock for production of products that are originally available by consumption of fossil energy resources. Hence this, a preservation of the primary fossil energy resources can be attained now.
Therefore, this process includes an electrochemical reductive conversion of liquid carbon dioxide as a precursor for manufacturing of high value commodity mother chemicals (i.e. ammonia, methanol, ethanol, DME dimethylether, propane, butane, etc.), special chemicals, automotive fuel and super-efficient hydrogen based fossil power generation which sustains the fossil energy resources. To some degree, the HPLTE-Syngas Generator is mimicking within fraction of second, what the natural process takes multiple ages for conversion of carbon dioxide to natural gas and crude oil naturally.
Further, the HPLTE-Syngas Generator is designed to perform high mass flow of syngas and oxygen, both required principally for large scale commercial co-generation plants for chemicals and power and/or power generation plants only.
The obtained HP liquid carbon dioxide from CO2-CC will be preferably pressurized by pumping to higher pressure level, blended with an organic electrolyte; more preferably purified water in a serial sequence of liquid carbon dioxide injection into water/water-CO 2 blend and cooling simultaneously, safely below the subcritical temperature in every sequence. The purified water fed to the present HPLTE-Syngas Generator comprises the conventional water cleaning, softening, reverse osmosis, ion exchange filters, mixed bed filter as well as biological and bacteriological purification. The pure water treatment encompasses also oxygen removal e.g. by catalytic hydrogenation of water, typically over Pd catalysts. The CO 2 /water blend is fed into HPLTE-Syngas Generator obtaining gaseous cathodic H 2 /CO and anodic oxygen products ( FIG. 3 ).
CO 2 +2H 2 Oâ[CO+2H 2 ] cathode +[3/2O 2 ] anode ââ(3)
Each of the gaseous products will be directed to a pressure equalizing vessel individually also termed as gas buffer (not depicted in FIG. 3 ), before it will be passed further to an absorber.
According to present process, each product stream of HPLTE- Syngas Generator
30 and 50 undergoes first the dehydration i.e. via gas cooling and/or adsorption process with an adsorbens (e.g. Pillard Clay, molecular sieve, Silica Gel, etc.).
The cathodic 2H 2 /CO is further accompanied with traces of oxygen and CO 2 . The removal of these traces takes place ( FIG. 3, 31 ) according to present device by way of molecular adsorption, absorption, chemisorption, non-catalytic chemical reaction in particular catalytic trickle reactor i.e. over Pd catalyst that is packed within the absorber column, converting the oxygen traces with the accompanied hydrogen to water. The absorber column absorbs the concomitant CO 2 with water 60 to 61 out of cathodic syngas stream 32 .
O 2 +2H 2 â2H 2 Oââ(4)
The desorption of absorbed CO 2 in the discharged absorber water will be carried out either with flush pressure release or more advantageous via thermal stripping, preferably with electric heater operating as reboiler. The desorber stream (not depicted in FIG. 3 ) from cathodic gas absorber 31 shall combusted with oxygen and/or anodic gas desorber stream, generating heat for CO2-HR or preheating of the cathodic and anodic streams 62 upstream of each attributed back pressure expander turbine separately.
The anodic oxygen gas 50 contains traces of H 2 /CO and CO 2 that are to be separated by way of molecular adsorption, absorption, chemisorption, non-catalytic chemical reaction or catalytic reaction i.e. over Pd catalyst. More preferably by way of chemical reaction over a plasma arc or an electric arc; EA ( FIG. 3 ; 51 ) in a controlled manner that hydrogen will be converted with accompanied oxygen to water and CO to CO 2 before the absorption and immediate quenching of these trace products (obtained as water and carbon dioxide 62 ) can take place in the absorber column. The absorber column absorbs the concomitant CO 2 with water out o
CLAIMS
Claims ( 59 )
The invention claimed is:
1. A high pressure process for at least one of post-combustion and/or pre-combustion CO 2 capture from a CO 2 -containing stream, wherein the general inventive concept of this invention is grounded upon the operation of the three principal features, as follows:
(I) first the present process utilizes the chemically pure CO 2 as working media for a first new thermodynamic cycle defined as liquid-gaseous subcritical-supercritical CO 2 power cycle that converts currently useless wasted energy of power and commodity chemical plants to useful power, wherein the CO 2 containing gas at a desired concentration (between 0.4 Vol % to 35 Vol % from the flue gases of fossil power plants and/or 75 Vol % to 99 Vol % from other plants) is taken, then concentrated and compressed to supercritical pressure and then is cooled below the CO 2 critical temperature 31.06 Deg C; thus the CO 2 is separated from the compressed CO 2 Stream by way of supercritical-subcritical condensation in order to obtain liquid CO 2 from that CO 2 Stream wherein the distinctive processing stages of the new super-critical CO 2 thermodynamic power cycle are defined via following thermodynamic steps:
Step-1: isentropic pressure elevation of liquid CO 2 by use of high-pressure pump;
Step-2 isobaric subcritical preheating of liquid CO 2 carried out below the critical point;
Step-3: isobaric vaporization and superheating of CO 2 from subcritical condition over the critical point to the supercritical region;
Step-4: further isobaric CO 2 -HR (heat recovery) which accomplishes primarily the recovery of the waste heat first; by then re-superheating of that CO 2 by use of any process heat utilization;
Step-5: isentropic expansion of supercritical supra-heated CO 2 by a backpressure expander CO 2 turbine in the CO 2 -PG section which encompasses the power for driving compressor(s) and generator(s) wherein the latter AC power can be converted to DC power for backing up the HPLTE-SG electrolysis;
Step-6: isobaric regenerative heat exchange and the condensation of CO 2 from superheated supercritical CO 2 by using an ACU (Auxiliary Cooling Unit with coolant), refrigerants or partial expansion of liquid carbon dioxide to lower pressure and temperature in order to function liquid carbon dioxide as condensing media;
Step-7: isobaric undercooling of liquid CO 2 after the condensation and return of the undercooled liquid CO 2 back to the Step-1 thus the closing of the cycle is performed and then followed by:
(II) wherein then the obtained liquid CO 2 from that said concentrated CO 2 -Stream is further processed via blending and cooling the liquid CO 2 with the purified water in order to prepare an electrolyte at high pressure and low temperature between the sublimation pressure of 5.5 bar and 1000 bar and 5° C. to 1000° C. and by then feeding to a High Pressure Low Temperature Electrochemical Syngas Generator (HPLT-SG); wherein the electrochemical dissociation of that electrolyte is carried out under the same pressure and temperature to an anodic oxygen stream and a cathodic syngas stream (CO/2H 2 ) whereas either of the two product streams (that is cathodic syngas in 2H 2 /CO ratio and oxygen) are integrated in the subpart (I) as condensing media for the supercritical-subcritical CO 2 of the first new thermodynamic cycle repeatedly typically three to eight times over syngas and oxygen turbine;
(III) super-efficient hydrogen based fossil power generation with an overall efficiency of 90% to 95% is then attained by operation of a new second thermodynamic cycle wherein the cathodic pure hydrogen from a high pressure gasification is combusted with the anodic oxygen at various pressures; between 0.01 bar and 1000 bar operation pressure and up to 1000° C. via torches wherein the thermodynamic steps of the second new thermodynamic cycle are as follows:
Step-1: sequential combustion of high-pressure hydrogen with oxygen or oxygen/steam blends whereas that high pressure hydrogen is performed from a syngas which is obtained first by a gasification carried out at least above 73.84 bar yet typically at 300 bar and/or the syngas stems from an IP/LP Gasification Plant Island that operates below the 73.84 bar; then by the sequential combustion for Direct Steam generation is performed by special hydrogen-oxygen torches for generation of high temperature steam at a point 2 â² prevailing in the flame's tong of the torch along the isobaric trajectory defined by the routing left of the critical point of water and above the critical isobaric of the water;
Step-2: injection of temperature controlled water from point 1 and de-superheating of the flame steam and in situ generation of additional Direct Steam whereas the point 2 is attained close upstream of the HP section of the turbine;
Steps-3-8: sequential release of Direct Steam through the typical arrangement of HP/IP/LP (high pressure/intermediary pressure/low pressure) section of the steam turbine with individual reheating section which is carried out by further hydrogen-oxygen combustion;
Step-9: a final isentropic expansion step down in the last stage as LP (low pressure) Direct Steam upstream of the LP section of a turbine;
Step-10: partial or, optionally, total condensation of Direct Steam condensate and reuse of the water for further purpose whereby the undercooled steam condensate is further preheated prior to injection.
2. A process for CO 2 separation from post-combustion and/or pre-combustion, according to claim 1 , by way of condensation of the CO 2 from that said CO 2 -Stream is carried out first by compression above the critical point of CO then processed by way of supercritical cooling of CO 2 -Stream via gas cooler heat exchanger(s) whereas downstream of that gas cooler a CO 2 -free gaseous media is obtained and then the dehydration of CO 2 -Stream is carried out with consequential CO 2 subcritical cooling of that CO 2 -Stream via second gas cooler heat exchanger(s) with downstream residue gases (also referred as CO 2 purge gas) whereby a partial supercritical-subcritical condensation of CO 2 takes first place before the total condensation of CO 2 from that said CO 2 -stream is executed with the CO 2 main Condenser and the carbon dioxide captured in a liquid CO 2 collector and/or in a pressurized storage tank whereas the processing assembly of those two supercritical and subcritical heat exchangers then dehydration column then the Main Condenser by then liquid CO 2 collector and storage tank are referred to CO 2 âCC (carbon dioxide capture and condensation) section of the process.
3. A process according to claim 2 wherein the sources of said CO 2 -stream comprisesâeither pure CO; form and/or in a CO 2 containing gaseous media and/or CO 2 -enriched high concentrated CO 2 -Stream which is referred to the Stationary CO 2 source of emission wherein at least one of flue gas of fossil power plants and/or flue gas of primary steam reformer and/or ammonia and/or methanol and/or gasoline and/or diesel and/or SNG and/or cement and/or steel manufacturing and/or COs of incineration and/or COs removed from natural gas and/or CO 2 containing off gas of oil and gas refineries and/or CO 2 obtained from treatments from refined oil and/or oil fractions and/or coke preparation from coal for the steel manufacturing and/or aluminum manufacturing and/or pulp and paper process and/or geothermal resources and/or fermentation off gases and the ubiquitous CO 2 from the air.
4. The process according to claim 2 wherein the process comprises specifically the removal of CO 2 from the CO 2 -Stream of MP/LP gasification processes of coal and/or biomass and/or natural gas and/or crude oil and/or waste carbonaceous material by shunting of an interim compression stage up to the margin of 74 bar and 500 bar for HP gasification process whereby the CO 2 -Stream of row syngas downstream of syngas cleaning and CO 2 and H 2 S removal is processed upstream of the CO 2 âCC in the margin of 74 bar to 500 bar.
5. The process according to claim 2 , wherein the condensation of the CO 2 from that CO 2 -Stream is carried out at an operation pressure from 5.5 bar and â56° C. over the sublimation line of CO 2 in the range of subcritical pressure of 5.5 bar to supercritical pressure at 500 bar and â55° C. and 31° C.
6. The process according to the claim 2 , wherein the supercritical heat exchanger cools the CO 2 -Stream in the margin of 0.1° C. to 20° C. close over the critical temperature of CO 2 with CO 2 -free and/or CO 2 -diluted purge gases downstream of the CO 2 âCC section in counter flow whereby the water is removed by way of condensation out of that CO 2 -Stream first.
7. The process according to claim 2 wherein the remaining water traces are dehydrated by way of adsorption such as via at least one of molecular sieves and/or Pillared Clays and/or organic and/or inorganic hygroscopic agents and/or silica gel in adsorber beds operating intermittently at a CO 2 supercritical temperature margin of 31.06° C. to 100° C. whereby the adsorption is either carried out under polytropic condition and/or isothermal condition with indirect cooling of adsorber.
8. The process according to claim 2 wherein the supercritical dehydrated CO 2 -Stream is further cooled down by the subcritical gas cooling heat exchanger(s) wherein a partial condensation of CO 2 out of that CO 2 -Stream takes place by cooling with CO 2 -free and/or CO 2 -diluted purge gas downstream of CO 2 âCC section in counterflow is carried out.
9. The process according to claim 2 wherein the total condensation of CO 2 is accomplished by use of a Cooling Media and/or such as at least one of cooling water and/or air cooler and/or hybrid cooler and/or refrigerant cooling and/or Freon and/or ammonia absorption cooling and/or thermoelectric generator heat exchanger and/or internal liquid and/or gaseous low temperature process media that is/are the gaseous products of HPLTE-Syngas Generator yet more preferably by an Auxiliary Cooling Unit (ACU) or any combination of them in the Main Condenser.
10. The process according to claim 2 wherein the ACU is performed by expansion of part of the obtained HP liquid CO 2 down to lower pressure in the margin from the critical temperature and pressure of 73.8 bar and 31.06° C. and above the sublimation line of CO 2 at 5.6 bar and at â55.6° C. whereby the released ACU's CO 2 will be recompressed and cooled with CO 2 -HR and/or Closed Cooling Cycle for Heat Recovery unit (in the CCC-HR section).
11. A process for liquid CO 2 -supercritical CO 2 power cycle, according to claim 1 , wherein heat recovery power generation with a pure CO 2 as working media of this power cycle is carried out with a or a number of liquid CO 2 pump(s) for pressure elevation of cycle's liquid CO 2 before the vaporization and supercritical superheating of power cycle's CO 2 (CO 2 re-gasifying) takes place by recuperation from any kind of waste heat sources with/without consecutive supraheating of power cycle's CO 2 by heating the superheated CO 2 via any process heat whereby the superheated/supraheated power cycle's CO 2 is directed to a set of expander turbines which will be driving generator(s) and/or other craft machines that is a or number of CO 2 -Stream compressor(s) and/or will be driving CO 2 pump(s) is carried out for that liquid CO 2 obtained from the CO 2 -Stream and/or liquid CO 2 pump of the power cycle.
12. The process according to claim 11 wherein the pressurization of liquid CO 2 for the supercritical CO 2 power cycle is carried out by pumping in single and/or in number of stages under simultaneous cooling below the critical temperature in the margin of 10° C. to 25° C. and at an outlet pressure of 5.6 bar to 1000 bar.
13. The process according to claim 11 wherein the preheating of liquid CO 2 and vaporization of liquid CO 2 as well as the superheating of CO 2 in the supercritical CO 2 power cycle is carried out in the margin of 30° C. to 1000° C. and working pressure of 5.6 bar to 1000 bar comprising the use of waste heat upstream of CO 2 -Stream and all other waste heat resources such as at least one of residual LP off steam heat downstream of backpressure and/or condensation steam turbine(s) in all the fossil as well as nuclear power plants and/or the waste heat downstream of the supercritical CO 2 backpressure expander and/or pressure release expander turbine(s) and/or the waste heat of reflux steam condensate and/or flue gas heat prior to the chimney of fossil power plants with coal and/or petcoke and/or biomass and/or crude oil and/or refined oil fractions and/or flue gas stack of single cycle and/or combined cycle gas turbine power plants and/or CO 2 and waste heat of flue gas of steam reformer(s) and/or cracking furnaces and/or heat recovery of jacket cooling of reactors and/or the jacket and internal device cooling of equipment and/or intercooler(s) of compressors.
14. The process according to claim 11 , wherein the waste heat recovery for CO 2 re-gasifying and superheating in the supercritical CO 2 power cycle is performed via heat exchangers directly coupled with the captured CO 2 stream and/or indirectly via one or a number of centralized Closed Cooling Circuits with a heat carrier wherein preferably on operation with conditioned water as heat carrier wherein the vaporization and superheating of the power cycle's CO 2 is carried out in the margin of 31.06° C. to 1000° C.
15. The process according to claim 11 for the power cycle wherein the sources for supraheating of CO 2 in the margin of 200° C. to 1000° and working pressure of 5.6 bar to 1000 bar takes place with the process heat sources such as at least one of combustion chamber of conventional fired power plants and/or gas turbine power plants and/or recovery boiler and bark boiler of pulp and paper manufacturing and/or process heat recovery of chemical processes that is CO water shift converter and/or ammonia and methanol synthesis section and/or absorption heat of absorber towers and/or solution heat of HP carbon dioxide with water (upstream of HPLTE-Syngas Generator) and/or Hot Syngas Gas cooler of gasifier and/or supraheating of CO 2 that is via indirect natural gas fired furnace (that is in the start-up furnace of ammonia/methanol plants) and/or natural gas gasification and/or H2/O2 sequential combustion (that is associated with super-efficient hydrogen based fossil power generation).
16. The process according to claim 11 wherein the power generation of superheated and/or supraheated carbon dioxide is carried out via a set of backpressure expander turbines consisting of HP/MP/LP stages each with/or without re-superheating of CO 2 takes place and whereby the set of the expander turbines drive(s) the generator and/or the ACU's CO 2 ; recycle compressor and/or for the Flue Gas compressor driven by the new first thermodynamic cycle.
17. The process according to claim 11 characterized that the inlet pressure to HP CO 2 expander turbine operates between 5.6 bar and 1000 bar and a temperature margin of 32° C. to 1000° C.
18. The process for liquid CO 2 -supercritical CO 2 power cycle according to claim 17 , wherein the CO 2 stream downstream of HP supercritical CO 2 expander turbine section of the power cycle will be returned back to the CO 2 âCC for CO2-HR and reliquefication in CO 2 âCC in pursuant to semi-closed liquid-gas CO 2 power cycle while the other part of CO 2 is then directed to MP CO 2 expander turbine sectionâwith and/or without re-superheatingâso the MP CO 2 ; stream is performed for heat recovery and temperature control with CO 2 de-superheating ready for sequestration and/or EOR and/or IOR (Improved Oil Recovery) in an open and/or semi-closed new first thermodynamic cycle for other MP applications.
19. The process according to claim 18 wherein the excess CO 2 is exported in liquid aggregate of state from CO 2 HP-pump for liquid CO: applications that is for the urea manufacturing and/or HPLTE-Syngas Generator.
20. The process according to claim 1 , wherein for at least one of carbon capture from CO 2 -Stream wherein the obtained liquid CO 2 and/or the excess liquid CO 2 from that said CO 2 -Stream is pressurized by pump(s) to higher pressure and blended with high pressurized purified water under simultaneous CO 2 subcritical cooling in multiple mixing/cooling stages and fed to a high pressure low temperature electrochemical reactor (referred to HPLTE-Syngas Generator) that delivers cathodic syngas 2H2/CO and anodic oxygen 3/2 O 2 in a way that either of HPLTE-SG product streams can be used for various other applications.
21. The process according to claim 20 wherein the applications of the cathodic 2H 2 /CO intermediate product will comprise specifically 2H 2 /CO for methanol and/or after ratio conditioning with water-gas shift converter for ethanol and/or SNG and/or gasoline and/or kerosene and other transportation fuels as well as methanol and/or DME dimethyl ether and/or aviation fuel in every grade and any other hydrocarbons.
22. The process according to claim 20 wherein the applications of the cathodic intermediate product 2H 2 /CO encompass the conversion of syngas with steam/water via catalytic CO water shift converter to 3H2/CO 2 stream whereby the pure HP/MP/LP hydrogen is obtained after the CO 2 separation by CO 2 âCC wherein the HP/MP/LP hydrogen is supplied for chemicals that is for the ammonia synthesis and/or hydrogenation of middle and/or heavy hydrocarbons to light fraction hydrocarbons for the purpose of automotive fuels and/or gasoline and/or diesel and/or kerosene.
23. The process according to claim 20 wherein the applications of cathodic intermediate product 2H 2 /CO of HPLTE-Syngas Generator comprises the conversion of syngas with steam/water via catalytic CO water shift converter of to 3H2/CO 2 stream whereby the pure HP/MP/LP hydrogen is obtained after the CO separation by CO 2 âCC wherein the HP/MP/LP hydrogenâeither with or without other hydrogen streams obtained from HP/MP/LP gasification processes and/or steam reforming and/or dry reforming with CH/CO 2 is performed for super-efficient hydrogen based fossil power generation.
24. A process wherein an anodic HP/IP/LP oxygen from said HPLTE-SG is applied for oxygen supply for gasification process and/or oxy-fueling of conventional fossil power plant and/or oxy-fueling of gas turbine power plants and/or recovery boiler of pulp and paper and/or chemical plants that is for nitric acid plants and/or oxidation reactors and/or cracking furnaces and/or more advantageously for super-efficient hydrogen based power generation.
25. The process according to claim 20 wherein the operation pressure of HPLTE-Syngas Generator is carried out between the sublimation pressure of 5.5 bar and 1000 bar and 5° C. to 1000° C. preferably between 5° C. to 50°.
26. The process according to claim 20 wherein the HPLTE-Syngas Generator's gaseous products namely the 2H 2 /CO cathodic syngas and anodic 3/2 O 2 oxygen are either totally and/or partially preheated for and then directed to back pressure expander turbine(s) for generating of ancillary powerâdriving AC current generatorâwhereby the AC current is converted to DC supporting the electricity for the electrochemical conversion in general for the HPLTE-SG reactor.
27. The process according to claim 20 wherein the preheating of the HPLTE-Syngas Generator's gaseous products takes place repeatedly upstream of each stage of turbine section of the syngas and/or the oxygen back pressure turbine distinguished in the way that the preheating of HPLTE-Syngas Generator's gaseous products are interlinked with the new first thermodynamic cycle wherein the preheating of syngas and/or oxygen stream upstream of each turbine section is employed to cool and/or condensate the CO 2 from the CO 2 -Stream.
28. The process according to claim 27 wherein the new first thermodynamic cycle for liquid CO 2 -supercritical CO 2 power cycle employs regenerative heat exchanger(s) downstream of the supercritical-subcritical CO 2 expander turbine as a heating source for the preheating of vaporized and/or superheated CO 2 stream of the CO 2 -PG power cycle and/or any gaseous stream more specifically oxygen and 2H2/CO of HPLTE-Syngas Generator with/or without indirect steam generation with/or without utilization for chemical reactors with/or without reboiler of stripper towers and the Boiler Feed Water economizer.
29. The process according to the claim 28 wherein the preheating of the HPLTE-Syngas Generator's gaseous products takes place repeatedly upstream of each stage of turbine section of the syngas and/or the oxygen back pressure turbine which is carried out to perform the cooling and/or condensation of the supercritical and/or subcritical CO 2 from the CO 2 circulating process stream in the new first thermodynamic cycle and/or from the CO 2 -containing syngas from the gasification and/or steam reforming and/or the Dry Reforming.
30. The process according to claim 27 , wherein for at least one of carbon capture and utilization and power generation and chemical conversion via HPLTE-Syngas Generator whereby the HP/MP/LP generated O 2 streams and the H 2 stream obtained originally from the cathodic productâeither with or without other hydrogen streams obtained from HP/MP/LP gasification processes and/or steam reforming and/or dry reforming with CH 4 /CO 2 will be subject to sequential 2H2/O2 combustion whereby Direct Steam stream(s) more specifically HP ultra-superheated Direct Steam is performed for the new second thermodynamic cycle.
31. The process according to the claim 30 wherein the sequential combustion 2H 2 /O 2 is carried out via sequential injection of hydrogen into the main oxygen stream and/or more preferably oxygen injection(s) takes place into the main hydrogen stream by use of H 2 /O 2 torches.
32. The process according to the claim 30 wherein the generated HP Direct Steam and the heat via sequential HP/MP/LP combustion of H 2 /O 2 is availed for preheating of any process intermediates more specifically for the preheating of the high pressure superheated and circulating CO 2 stream of the first new thermodynamic cycle upstream of the supercritical CO 2 cycle in the CO2-PG section.
33. The process according to the claim 30 wherein at least one part of the oxygen obtained from the HPLTE-Syngas Generator is taken for combustion with hydrogen obtained from a gasification process so the HP ultra-superheated Direct Steam is performed upstream of steam turbine while the other oxygen side streams are performed for at least one of oxygen streams such as LOX and/or GOX for gasification process and/or oxy-fueling and/or oxy-fueling in combustion processes for power generation (that is designated for the conventional fossil and/or gas turbine power plants) while at least one other part is prepared as LOX.
34. The process according to the claim 30 wherein the oxygen stream and the hydrogen stream (either from HPLTE-Syngas Generator or obtained from gasification process) is availed for supplementary firing in existing conventional power plant and/or HRSG section of gas turbine combined cycle plants.
35. A process for Direct Steam generation by way of sequential combustion of H 2 /O 2 via torches wherein the torch is specially distinguished with an:
a) external jacket cooling integrated in the Closed Cooling Circuit;
b) internal indirect skirt cooling coils impinged via Boiling Feed Water of MP HRSG section referred to as closed-end jacket cooling;
c) injection of saturated steam into the skirt cooling section of the torch referred to as open-end jacket cooling;
d) injection of water dispersed into the flame path of torch;
e) and/or injection of water in the surrounding field of the flame for de-superheating of the Direct Steam flame by way of temperature controlled measurement so the Direct Steam HP ultra-superheated Direct Steam is formed.
36. The process according to claim 35 that the generation of Direct Steam by way of sequential H 2 /O 2 torches particularly HP ultra-superheated Direct Steam with re-superheating stage(s) is claimed wherein the generated Direct Steam is reheated by above torches in one or more re-superheating stages which then drives MP/LP sections of a the steam turbine(s) that facilitates the new second thermodynamic cycle that is either executed in a semi-open cycle whereby the steam downstream of that said LP turbine section is released into the atmosphere or it is condensed for reuse in a closed cycle or a combination of the two latter embodiments.
37. The process, according to claim 10 , wherein the entire heat recovery units (CO 2 -HR and CCC-HR) with the set of CO 2 turbines (CO 2 -PG) and with the HP Direct Steam generation in combination with its set of Direct Steam turbines with/without indirect steam generation in combination with the set of indirect steam turbines facilitates the new generation of super-efficient hydrogen based fossil power generation.
38. The process for at least one of carbon capture and liquefaction and utilization and chemical conversion according to the claim 37 , wherein the entire heat and/or process recovery units (CO 2 -HR and CCC-HR) with the set of CO 2 turbines (CO 2 -PG) and regenerative heat exchanger(s) of the first thermodynamic cycle with the HP Direct Steam generation in combination with the set of Direct Steam turbines with/or without under-cooled Direct Steam condensate turbine with MP indirect steam generation in combination with the set of indirect steam back pressure turbines and/or indirect steam condensation turbine of the second thermodynamic cycle facilitates the new generation for super-efficient hydrogen based fossil power generation characterized with the overall gross plant efficiency in the margin of 60% to 99% more specifically in the margin of overall gross efficiency of 90% to 95% with effective carbon capture in margin of 60% to 100%, more specifically in margin of 90% to 100% in either case depending on seasonal and regional ambient conditions according to the claim 1 in CID).
39. The process for at least one of post-combustion carbon capture and liquefaction and utilization and chemical conversion and power generation, according to claim 11 , wherein low and/or middle pressure subcritical CO 2 gaseous and other CO 2 pollution emitting sources are first subjected to scrubbing and/or cleaning with Flue Gas heat recovery and compression of Flue Gas over the supercritical pressure of CO 2 that is carried out in either single or multiple compression stage(s) with the associated intercooler/final gas cooler and heat recovery and dehydration of that said Flue Gas takes place before the compressed Flue Gas is treated in CO 2 âCC for separation of liquid CO 2 out of the that Flue Gas wherein the CO 2 -free Flue Gas (off gas) is eventually preheated and then released back into the atmosphere downstream of the off gas expander turbine(s).
40. The device according to claim 1 , consisting of a high pressure low temperature electrochemical reactor (referred to as HPLTE-Syngas Generator) that comprises of two reaction chambers for cathodic (2 H 2 /CO) syngas and anodic oxygen (3/2 O 2 ) production with gas lock and/or liquid lock and/or liquid-gas separation at the top and a diaphragm compartment that is concentric emplaced within the circulating cathodic liquid phase at one side while the anodic liquid phase is circulating at the other side of diaphragm whereby the very high circulation flow of each liquid phase is facilitated on the principals for Mammoth Pump by the evolved gaseous products in each reaction chamber while the migration of ions through the diaphragm in the liquid phase is intensified whereby the HPLTE-Syngas Generator is distinguished preferably with one or more of the peripheral equipment and sections with/without internal cooling coils to govern isothermal reaction condition according to.
41. The device according to the claim 40 the reactor is fed with a blend of liquid CO 2 and water so that either stream is pressurized by pumping under cooling at high pressure and cooled below the critical temperature of CO while the mixing and cooling of liquid CO 2 -water blend is taking place simultaneously.
42. The device according to the claim 40 wherein the operation pressure of the HPLTE-SG reactor is in the margin of 5.5 bar to 1000 bar and the operation temperature in the margin of â56.57° C. and +31.06° C. more preferably in the range of 200 to 400 bar and temperature of +5° to 25° C.
43. The device according to the claim 40 wherein the pressurization of reactor precursors that is water and the liquid carbon dioxide is carried out in the margin of 5.5 bar (over the sublimation pressure of CO 2 ) and 1000 bar for the operation pressure of HPLTE-Syngas Generator according to the claim 42 .
44. The device according to the claim 40 wherein the cooling of reactor precursors that is water and liquid CO 2 is carried out while their pressurizing and mixing is performed in the margin of â56.57° C. (sublimation temperature of CO 2 ) and +31.06° C. the critical temperature of CO 2 .
45. The device according to the claim 40 wherein the blending under subcritical temperature of CO 2 is carried out by multiple injection stages of liquid CO 2 into the water and/or CO 2 -water blend under simultaneous mixing and cooling in every injection stage so an aqueous solution of CO 2 in water in particular high concentrated electrolyte yet more preferably CO 2 saturated aqueous undercooled solution of CO 2 is obtained at any ratio up to the stochiometric ration of CO 2 /H2O of 1:2.
46. The device according to the claim 40 wherein the feedstocks of HPLTE-Syngas Generator is fed into the reactor either by one blend stream of CO 2 âH 2 O wherein the leveling of mass flow rates of both chambers is carried out by diaphragm and/or two separated streams of CO 2 âH 2 O electrolyte into the anodic and cathodic reaction chamber individually in the bottom section of cathodic and anodic reaction chamber wherein the compensation of liquid level occurs through the diaphragm.
47. The device according to the claim 40 wherein the reactor is further distinguished by purification measures for each gaseous product.
48. The device according to the claim 40 wherein the removal of O 2 traces out of the cathodic syngas 2H 2 /CO is either by molecular sieve on the basis of pressure swing adsorption (PSA) and/or absorption and/or chemisorption and/or non-catalytic chemical conversion and/or preferably by a trickle reactor and catalytic conversion of oxygen traces with accompanied hydrogen to water and/or more preferably by passing the cathodic gases through an electric arc momentarily wherein the reaction of oxygen traces with the concomitant hydrogen is performed immediately upstream of water absorber for CO 2 removal.
49. The device according to the claim 40 wherein the removal of CO 2 traces out of the cathodic 2H2/CO takes place in a separate absorber via water and/or more preferably with water in the same trickle reactor above.
50. The device according to claim 40 wherein the discharge of absorber preferably the above trickle reactor is carried out by way of flush pressure release and/or preferably by way of HP thermal desorption carried out with heater that is an electric heater whereas the desorber's off gas of syngas purification section is led to the off gas combustion along with the off gas downstream of anodic oxygen purification section for heat recovery.
51. The device according to claim 40 wherein the removal of H: traces out of the anodic oxygen stream downstream of the reactor is carried out by either molecular sieve on the basis of pressure swing adsorption (PSA) and/or absorption and/or chemisorption and/or non-catalytic chemical conversion and/or more preferably by passing the anodic gas through an electric arc wherein the conversion of hydrogen traces takes place momentarily that is carried out immediately upstream of CO 2 absorber for removal of CO 2 out of anodic oxygen stream.
52. The device according to claim 40 wherein the desorber off gas of the anodic oxygen purification section is led to off gas combustion along with the off gas downstream of cathodic syngas purification section for heat recovery.
53. The device according to the claim 40 wherein the high pressure anodic purified HP oxygen gas stream is preheated repeatedly via any heat sources from the prevailing operation temperature of HPLTE-Syngas Generator of +5° to in one and/or a multiple stage of heat exchanger(s) before it is fed to HP/IP/LP multi-stage oxygen backpressure expander turbine(s) repeatedly that drives an ancillary generator whereas oxygen upstream of the final stage of the oxygen turbine operates to a higher temperature in the margin of 500° C.
54. The device according to the claim 40 wherein the device invention of HPLTE-Syngas Generator comprises the HP/IP/LP multi-stage cathodic gas preheating repeatedly of +5° to â30° C. to in one and/or a multiple stage of heat exchanger(s) before it is fed to each HP/IP/LP multi-stage syngas and/or hydrogen backpressure expander turbine(s) that drives an ancillary generator whereas the final stage of syngas turbine operates to a higher temperature in the margin of 600° C.
55. The device according to claim 54 wherein the preheating stages of the gaseous products of HPLTE-Syngas Generator in upstream of each stage of back pressure turbine section is interconnected with the first thermodynamic cycle whereas these product gases are employed for the condensation of circulating CO 2 stream in the CO 2 -PG downstream of the supercritical-subcritical CO 2 turbine and/or the regenerative heat exchangers of the CO 2 power cycle.
56. The device according to the claim 55 wherein the syngas heat downstream of back pressure expander is integrated as part of syngas preheating in order to accommodate the temperature level of syngas in the water gas shift reactor and/or by way of water injection into the syngas upstream of HP/MP water shift converter.
57. The device according to claim 55 wherein the device invention HPLTE-Syngas Generator encompasses the AC/DC converter for the conversion of gained ancillary AC current to DC current for backing up the power supply of HPLTE-Syngas Generator.
58. The process for high pressure low temperature electrochemical conversion of the electrolyte liquid carbon dioxide-water blend, according to claim 1 , is backed up by supplementary DC power supply current gained by use of the solar power DC generation.
59. The process for high pressure low temperature electrochemical conversion of the electrolyte liquid carbon dioxide-water blend, according to claim 1 , is backed up by supplementary supply of DC current gained by use of the fuel cells for DC back up line which is generated by the combustion of oxygen downstream of the oxygen turbine and the hydrogen downstream of the CO-water shift converters and CO removal either from the (i)HPLTE-SG cathodic product downstream of low pressure section of syngas and/or hydrogen turbine and/or from the (ii) from gasification.
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High pressure process for CO2 capture, utilization for heat recovery, power cycle, super-efficient hydrogen based fossil power generation and conversion of liquid CO2 with water to syngas and oxygen
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