NOVEL AND HIGHLY COST EFFECTIVE TECHNOLOGY FOR CAPTURE OF INDUSTRIAL EMISSIONS WITHOUT REAGENT FOR CLEAN ENERGY AND CLEAN ENVIRONMENT APPLICATIONS

Abstract

In this patent we disclose, for the first time, detailed methods of our newly invented state-of-the-art cryogenic technology for the cost effective energy efficient capture of each known component of entire emissions (nearly 100%) such as carbon dioxide (CO2), sulfur oxides (SOx), nitrogen oxides (NOx), carbon monoxide(CO), any other acid vapor, mercury, steam and unreacted nitrogen from industrial plants (coal and natural gas fired power plants, cement plants etc.), in a liquefied or frozen/solidified form, such that each of the components is captured separately and is industrially useful. This new technology includes a novel NH3 power plant to generate auxiliary electrical power from the heat energy of the flue gas to further improve the energy efficiency and cost effectiveness of the capture processes. It is the most cost effective of all existing emission capture technologies. It does not require use of any chemicals/reagents/external cryogens, unlike the current technologies. It uses only a fixed amount of water needed for the cooling process which can be used repeatedly. We present detailed methods of operations, together with scientific and economic analysis of the energy needed and cost involved for the said capture in two specific examples, and advantages of the new technology over the existing ones.

Description

In this patent we disclose, for the first time, detailed methods of our newly invented state-of-the-art cryogenic technology for the cost effective energy efficient capture of each known component of entire emissions (nearly 100%) such as carbon dioxide (CO₂), sulfur oxides (SO_x), nitrogen oxides (NO_x), carbon monoxide(CO), any other acid vapor, mercury, steam and unreacted nitrogen from industrial plants (coal and natural gas fired power plants, cement plants etc.), in a liquefied or frozen/solidified form, such that each of the components is captured separately and is industrially useful. This new technology includes a novel NH₃ power plant to generate auxiliary electrical power from the heat energy of the flue gas to further improve the energy efficiency and cost effectiveness of the capture processes. It is the most cost effective of all existing emission capture technologies. It does not require use of any chemicals/reagents/external cryogens, unlike the current technologies. It uses only a fixed amount of water needed for the cooling process which can be used repeatedly. We present detailed methods of operations, together with scientific and economic analysis of the energy needed and cost involved for the said capture in two specific examples, and advantages of the new technology over the existing ones.

FIELD OF INVENTION

This invention relates to the cost effective and energy efficient capture of components of emissions (toxic acid gases, mercury, CO₂, CO, unreacted nitrogen) contained in the flue gases from power plants and industries in general, without the use of any chemical/reagent (except water) [after removal of fly ashes and mercury oxides]. This new technology is based on (i) the fractional condensation of each component gas at appropriate temperature through compression, cooling with super-cold nitrogen (of the flue gas) obtained at the end of the cycle and isentropic expansion; (ii) generation of auxiliary power from the heat of the flue gas to make the process energy efficient and further cost effective; (iii) scientific analysis of application of this technology to two specific cases of power generation using coal and natural gas. More particularly, this invention relates to the applications for clean energy generations in coal and natural gas power plants and for clean environment for this purpose.

BACKGROUND OF THE INVENTION

Electric power plants and cement factories release flue gas that contains large amount of pollutants (carbon dioxide (CO₂, NO_x (Nitrogen oxides), (x=0.5,1,1.5,2,2.5), SO_x (sulfur oxides), (x=2,3), mercury (Hg) and its oxides, volatile organic compounds(VOCs), soot and particulate matters (PM) along with hot steam and unreacted nitrogen to the atmosphere. The pollutants (except steam and nitrogen) cause environmental pollution and contribute to global warming. Literatures abound on the nature, amount, the effects on health and environment of these emissions, the current state-of-the-art technologies for capturing these emissions, the cost implications to control the emissions in part or full. By studying a number of such literatures [Refs. 1-79, Refs. T1-T5, Refs Z1-Z4, we find that:

• • (i) There is no single technology that can remove/capture, with one installed equipment, mercury and its oxides, sulfur oxides, nitrogen oxides, acid vapors in general, carbon dioxide, carbon monoxide from flue gas of coal power plants and industrial plants in general;
  • (ii) The cost of installation of the different equipment needed for removal/capture of individual component is too high for many countries in the world to afford and even in the USA not all plants can easily be retrofitted with existing clean energy (or full emission capture) equipment, because of high installation and operational costs involved (which can be seen in the cited literature);
  • (iii) The cryogenic techniques [63,64,62p,65,66]] investigated so far have been found to be very energy intensive and have not so far addressed the techniques of separation of various individual toxic component of the flue gas and has mostly focused on separation of CO₂ at costs much higher than the state-of-the art amine technology employed for capture of CO₂. These are found to be not commercially viable for large scale capture of CO₂ and capture of other individual components of flue gas.
  • (iv) The cost of CO₂ capture with current state-of-the-art amine technologies of CO₂ capture is still very high [62,62a-c, 12a, 72-79]. The storage and retrieval of the gaseous CO₂ is quite tedious apart from huge cost involved, as it requires transportation of the captured CO₂ to empty oil or coal fields underground.
  • (v) Environmental pollution from such plants [1-42] is increasing globally and global warming is becoming a threat for humanity, specially, when demands & usage for and uses of fossil fuel power continues to increase globally.
  • (vi) Thus, there is a need to develop a new technology which is very cost effective and energy efficient so that one installed equipment can capture/remove all (nearly 100%) the toxic components like SO_x, NOR, Hg, CO and CO₂ from coal power and other industrial plants such that the removed components can find industrial uses and the cost effective technology/equipment can be employed even in countries which currently do not employ any emission capture technology. Moreover, the new technology would be such that it allows capture of these items in a form or forms that can easily be stored and retrieved when needed for uses. This is where our new emission capture invention excels over all existing state-of-the-art emission capture technologies that can be retrofitted to industrial plants but at very high costs. The new technology is very cost effective with very low operational costs as it does not require any reagent/chemical agent and requires significantly lower energy per ton of pollutant capture than any existing technology. Moreover, our new technology captures the above items in forms that are very easy to store and each component separately.

OBJECTS OF THE INVENTION

Therefore, an object of the invention is to provide a new cryogenic technique that can capture each component of the gaseous emissions (flue gas) from power plants, cement plants and industries in general without the use of any chemical agent or reagent (except fixed amount of water) and with minimum energy usage, high efficiencies and at low cost not heretofore possible. Still another object is to provide a method of separating and capturing each component of the flue gas [mercury, steam, SO₃ (sulfur trioxide), SO₂ (sulfur dioxide), N₂O (nitrous oxide), NO (nitric oxide), NO₂ (nitrogen dioxide), CO₂ (carbon dioxide), CO (carbon monoxide), unreacted nitrogen] from power plants individually in pure form (such that each captured component itself is industrially useful) with one single equipment which is much easier to apply and which produces results, not possible by any technology before. Another object is to capture the heat of the flue gas for production of auxiliary power in an efficient way so as to improve the cost effectiveness and energy efficiency of the whole capture processes further. A final object is to provide an improved apparatus/equipment capable of employing cryogenic technique with auxiliary power generation from the flue gas heat and use of super cooled nitrogen gas produced at the end of the cycle to capture each said component of the flue gas emission from industries in general in most cost effective and energy efficient way, and in forms such that the captured components find industrial applications and can easily be stored.

SUMMARY OF THE INVENTION

This invention is a process by which emission gasses from power plants and industries in general are fractionally condensed using a series of heat exchangers, compressors and expansion valves, to separate, capture and store the constituents (oxides of sulfur and nitrogen, mercury (Hg), carbon monoxide (CO) and most importantly, carbon dioxide (CO₂)) using no chemical/reagent but lowest amount of electrical energy and a fixed amount of water (the fixed amount of water can be repeatedly used). The power required for this is augmented with an ammonia power plant for very high energy efficiency and relatively very low cost.

The objects stated above are attained using methods that include cryogenic technique for capture of individual component of an industrial flue gas comprising the steps of:

• • (a) Capture of the heat of flue gas from the power plants and industrial plants in general for the generation of auxiliary power using anhydrous ammonia turbine.
  • (b) Separation of ashes, soot, mercury oxides etc. from the said flue gas by first using ceramic filters, conventional fabric filter and electrostatic separation similar to conventional technologies.
  • (c) Capture of partial SO₃ and partial mercury through heat exchange in the process of said turbine expansion (step (a)).
  • (d) Capture of SO₃, mercury and steam of the flue gas through compression and cooling in a specially designed coil immersed in a specially designed water tank which is cooled by passing cold nitrogen gas (of the said flue gas) obtained at the end of the cycle through tubes immersed in water and by using radiative heat exchange, if and when necessary (depending on the temperature of the flue gas after the auxiliary power generation) so that a fixed amount of water is maintained at a specified temperature for this capture.
  • (e) Capture of NO₂ and remaining steam of the said flue gas through compression and cooling of the said flue gas in the said similar coiled tubes and tank at specified temperature.
  • (f) Capture of SO₂ of the said flue gas by further compression from step (e) and cooling in a special tank containing heat conducting blackened pebbles or metal chips and helium gas, the tank being cooled at a specified temperature by flowing cold nitrogen gas obtained at the end of the operation.
  • (g) Capture of CO₂ of the flue gas in the form of cold liquid CO₂ (LCO₂) after step (f) by further compression and cooling in another said similar special tank.
  • (h) Conversion to dry ice by throttling said LCO₂ of step (g) in a flash chamber, freezing the dry ice and the dry CO₂ vapor with part of said cold nitrogen gas and cooling the remaining flue gas (after operation g) by flowing (passing) part said super cooled N₂ gas obtained at the end of cycle into the said chamber.
  • (i) Further cooling of the flue gas of step (h) containing mostly N₂ and small percentage of NO, N₂O and CO by the cold N₂ gas exiting the said chamber.
  • (j) By first, second and third stage of isentropic turbine expansion of the compressed flue gas remaining after step (i) to condense, N₂O, NO and finally CO separately into appropriate chambers (tanks) cooled by flow of super cooled N₂ obtained at the end of the cycle following capture of CO.
  • (k) Using the turbine expansion work at step (j) of compressed flue gas to drive some of the shafts of earlier compressors.
  • (l) Using the super-cooled N₂ gas (of the flue gas) obtained at (j) to cool the flue gas at earlier stages of operation as mentioned in (a) to (k).

The methods associated with steps (a) to (l) ensure:

• • Capture of CO₂, SO_x, NO_x, CO and mercury contained in the flue gas from coal and natural gas fired power plants and industries in general, at costs much lower than any existing current technology could allow.
  • The most cost effective and energy efficient means of capturing large volumes of CO₂ of the flue gas from power plants and industrial plants in general and conversion to cold liquefied pure CO₂ and dry ice, which are sources of highly pure CO₂ and which can find large industrial applications currently and in future.
  • The most cost effective and energy efficient means of obtaining pure N₂ gas from the flue gas of power plants.
  • The most cost effective means of mitigating global warming and environmental pollution arising out of the flue gas from power plants and industries in general.

The above methods are supported by scientific analysis of the energy requirement for capture and liquefaction of CO₂ and super cooling of unreacted nitrogen gas of the flue gas, using data in two specific examples of power generation. Detailed methods of scientific analysis of the net energy requirement and the cost involved in two specific examples for the steps g through l (which are described in details in section I) are included in this invention. The estimated cost of capture CO₂ in liquefied and or frozen form includes cost of capture of the toxic components also, the largest part of the flue gas from most fossil-fuel combustion is uncombusted nitrogen [(1) Perry, R. H. and Green, D. W. (Editors) (1997). Perry's Chemical Engineers' Handbook (7th ed.). McGraw Hill. ISBN 0-07-049841-5; (2) Rogers and Mayhew (1992)[80]].

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a block diagram which shows schematically the main equipment in accordance with the invention for capturing each component of flue gas emissions from power and industrial plants separately. It comprises of: (i) NH₃ super heater with ceramic filters; (ii) precipitator/fabric filter; (iii) heat exchangers (some for temperatures above 0° C. and others for temperatures below 0° C. up to slightly above liquid nitrogen); (iv) NH₃ turbine with condenser & pump; (v) partial H₂O and Hg collection chamber; (vi) N-stage compressors with water cooling arrangement using heat exchangers for complete H₂O/SO₃/Hg collection; (vii) sections for productions & collections of liquefied NO₂, SO₂, CO₂, and N₂O including arrangement for appropriate heat exchangers; (viii) sections for production and collection of dry ice from liquefied CO₂; (ix) triple stage N₂ turbine expanders for cooling N₂ gas of the flue gas; (ix) NO & CO collection chambers.

FIG. 2 is the temperature-entropy (T-S) diagram of carbon dioxide during production of liquefied CO₂ and dry ice from the flue gas during steps 12 to 14 in section I.1 of STEPS & PROCESSES INVOLVED TO ACHIEVE THE SAID OBJECTS OF INVENTION.

FIG. 3 is a temperature—entropy (T-S) diagram of a super critical anhydrous NH₃ power plant used to generate auxiliary power by capturing the heat of the flue gas.

FIG. 4 is cross sectional view of the ceramic plates used to capture ashes of the flue gas. The separation of the holes being the same as the diameter (d) of the holes and the distance between the rows of holes is separated by about 3d.

FIG. 5 is an arrangement of the ceramic filters in two chambers to capture ashes and the position of ammonia super heater.

FIG. 6 is a sectional view of the special tubes for condensation of mercury, steam, SO₃ and other components of flue gas with boiling point above 0° C.; These special tubes are to be kept inside the heat exchanger (FIG. 11) after fabric filter or before the N-stage compressor in FIG. 1. The arrangement prevents escape of the flue gas during condensation and collection of components.

FIG. 7 is a sectional view of specialized tubes ABCDE inside a special well insulated chamber to condense each component of flue gases separately. The equipment is used several times in the capture processes described in this invention. Its design depends on the nature of captured items as follows: A. For collection of steam, SO₃, Hg, HCl, NO₂ the tubes are immersed in water inside the chamber and the water is cooled by controlled amount of cold nitrogen gas passing through many turns of heat conducting tubes (not shown in FIG. 7) connecting port X₁X₂ with port Y₁Y₂. B. For collection of liquefied SO₂, CO₂, N₂O, NO, CO, each separately, the chamber does not contain any water and any of the following arrangement is made. (i) The chamber contains the extra tubes of part A and no water. For capture of components with boiling point below 0° C., the chamber is filled with helium gas at pressure 1 to 2 bar in sealed (air tight) condition for capture of components with boiling point below 0° C. (ii) Instead of water, the chamber contains heat conducting pebbles or metal chips arranged on perforated racks horizontally placed (not shown in FIG. 7) such that the rack surround the turns of tubes carrying cold (or super cold, as needed) nitrogen gas. The latter surrounds the turns of tubes carrying flue gas. While the conducting pebbles help retain the low temperature produced by the cold nitrogen, the helium gas speedily conducts away the heat from the surface of the flue gas tubes to the cold conducting pebbles and the tubes carrying the cold nitrogen. The cold nitrogen gas (obtained from the flue gas at the end of the cycle) enters through tube X₁X₂ passes through the said turns of heat conducting tubes connecting X₁X₂ and Y₁Y₂, inside the chamber; it finally exits through Y₁Y₂. In all the arrangements, the cold N₂ gas exits out through Y₁Y₂ to enter another similar cooling chamber. For any of the arrangement, A or B, the chamber is air tight and water leak proof when water is used. Arrangements (i) & (ii) are preferred if very pure nitrogen gas is to be collected at the exit point near a-b₁ in FIG. 1. With arrangement (i) helium gas enables rapid heat exchange between flue gas and the cold nitrogen gas through tubes connecting X₁ X₂ with port Y₁ Y₂. The heat exchange can be further enhanced by using a small fan (not shown in FIG. 7) that will circulate the helium gas throughout the chamber, and thereby increasing the heat exchange rate. For good insulation, the inner walls of the chamber are coated with reflecting materials and the outside walls contains alternate layers of shining aluminum sheets and Styrofoam. This device is the heat exchanger referred to many times for capture of flue gas components with boiling point temperature below 0° C. in FIG. 1 and in the descriptions of methods, claims etc. contained in this disclosure of invention.

FIG. 8 is a sectional view of another type of specialized coiled tubes that also can be used to condense and collect liquefied steam, SO₃, Hg, NO₂, SO₂. The spring at the end of the lower tube prevents escape of the flue gases when enough liquid is not formed.

FIG. 9 is a sectional view of a flash chamber for the formation and collection of dry ice. Very cold N₂ gas, obtained at the end of the cycle, is inserted into the chamber to freeze the remaining dry vapor to solid dry ice through one port and exited out after freezing the dry CO₂ vapor at −78° C. to solid dry ice. The flash chamber contains a throttle valve which is connected to the insulated chamber collecting liquefied CO₂ at step 12 in section I.1

FIG. 10 is a sectional view of flash chamber for collection of N₂O, NO and CO.

FIG. 11 Is a sectional view of heat exchanger used to cool (for capture of components having b.pt above 0 C) compressed flue gas at different steps in this invention. The heat exchanger contains water which is cooled by controlled reverse flow of cold nitrogen gas obtained at the end of the flue gas process cycle. The cold nitrogen gas enters through one port of a several turns of heat conducting tubes and exits out through a second port. These turns of cold nitrogen carrying tubes surrounds the flue-gas flow tubes of FIG. 6 (not shown in FIG. 11) of which the exit pipe for the condensates passes through the bottom of wall of this chamber. The water is stirred as needed (the stirrer not shown in FIG. 11).

The flue-gas flow tubes of FIG. 6-8 are made of special materials that can stand temperature ˜300° C., possess high thermal conductivity and at the same time non-corrosive to the toxic components of the flue gas. Such materials are described in section I.1 [under title “_Protection of equipment from corrosion due to acidic oxides, acid vapors and toxic materials in the flue gas during the entire capture process” before step 1 of the processes of this invention].

The “reverse direction” of cold nitrogen gas flow as mentioned many times in this invention refers to direction from right to left with respect to the equipment schematically shown in FIG. 1.

SPECIFIC (DETAILED) DESCRIPTION

The Present Invention

Our cost effective and energy efficient technique captures toxic components of the flue gas from power plants and industries in general and the carbon dioxide in liquefied or frozen form, as needed, without the use of any chemical/reagent. It generates auxiliary power using anhydrous ammonia to make the processes (of capturing the emissions) further energy efficient and cost effective. The new technique is also going to be especially useful and cost effective to capture the entire carbon dioxide (a global warming agent), if that is left over after controlling the toxic emissions and the particulates using the existing but expensive current state-of-the art technologies, which can be seen in the cited literature Refs. 1-79, Refs T1-T5, Refs.Z1-Z4. The current state-of-the-art technologies for capture of components of emissions of flue gas require extensive uses of both chemicals, water and power and as a result even in advanced countries many power plants cannot afford to apply them. Our very cost effective technology of invention is useful to capture any one or all components of emissions from coal/natural gas/oil fired power plants, generators and emissions from industries, such as cement etc. in general. Thus the technology is useful to prevent environmental pollution and mitigate climate changes resulting from the pollution.

We discuss below in details the various steps/processes involved in our new industrial emission capture technique. Our technique will produce vast amount of pure liquid CO₂ and dry ice (source of very pure CO₂) from the flue gas of the power plants very cost effectively. In this invention, we have used a total of 15 compressors and three turbine expanders and assessed (through rigorous scientific analysis) the energy efficiency & cost efficiency of the new technology in capturing the entire flue gas emissions in two specific cases: coal power generation and natural gas power generation. However, due to space limitation only 5 compressors are shown in FIG. 1. Each compressor block in FIG. 1 may be assumed to be three small compressors. In FIG. 1, the coldest nitrogen gas (1 to 2° C. above its boiling point −196° C.) is obtained at the point i(FIG. 1) after the triple stage expansion. It is divided into two lines at the point r. One goes to the CO₂ flash chamber and the other to the NO condensation chamber. The arrowed line path indicated by the points q-j-k-l-m indicates the flow (in reverse direction) of cold nitrogen obtained at the end of triple stage expansion of compressed flue gas (see the steps below). At the point m, the cold nitrogen gas line is again split in two lines as shown in FIG. 1 and explained below.

The steps involved in separately capturing each component of flue gas (emissions) from coal fired and natural gas fired power plants and industrial plants in general, with this new technology are discussed below in reference to FIG. 1 through 11. In this invention wherever “ammonia” is mentioned, it refers to anhydrous ammonia.

In the steps described below we call our invention the new clean energy technique (NCET).

I.1. Steps/Processes Involved to Achieve the Said Objects of Invention

Protection of Equipment from Corrosion Due to Acidic Oxides, Acid Vapors and Toxic Materials in the Flue as During the Entire Capture Process

In all steps/processes described below, the equipment surfaces, internal and external surfaces of tubes and surfaces of capture-vessels that come in contact with the acidic oxides, acids that may form on reactions of the oxides with condensed steam and other toxic components of the flue gas and or the captured liquefied products of these components, are protected as follows: they are either coated with or made of any one of the following plastics: vespel, torlon, ryton, noryl of craftech industries [http://www.craftechind.com/dont-sweat-4-high-temp-plastics-can-take-heat/#comment-741] or any material that is non-reactive to these components and at the same time the material must have very good thermal conductivity and high range of temperature tolerance.

All of these plastics can tolerate very well temperature around 100° C. Vespel tolerates well temperature up to 300° C. It is used for tubes and vessels at high temperature end of the flue gas processing. These are non-corrosive to all components of flue gas. Alternately, copper tubes with inner and outer coating (about 2 mm thick) with any one of these materials (plastics) are also found to be suitable in this invention for use in the methods described to capture the toxic components of the flue gas. This would ensure better heat transfer required for fast condensation of the components. However, fully plastic tubes are cheaper than the latter ones. It is extremely important for all components of this emission capture plant are coated with non-corrosive, temperature resistant coating/paint with good thermal conductivity. The ammonia super-heater chamber of FIG. 1 and in steps 2 to 5 below is made of such high temperature tolerant and non-corrosive plastic possessing high thermal conductivity. The surface of the chamber is coated with thin layer of a material with high heat absorptivity (for good absorption of heat from flue gas) and low heat emissivity (low heat transfer to the flue gas or surrounding). One of such materials is nickel oxide which has high absorptivity (0.92) and low emissivity (0.08) [http://www.solarmirror.com/fom/fom-serve/cache/43.htm1]. The tubes in FIG. 7 are also made of such materials.

Capture of Fly Ashes, Soot, Mercury Oxides

STEP 1: The new clean energy technology (NCET) is schematically depicted through FIGS. 1-11. The flue gas from the boiler of a power plant [after boiling the water to high pressure steam that drives the turbine] is passed through a series of ceramic filter plates(FIG. 4) arranged in two chambers [FIG. 5] to remove the fly ashes that may include mercury oxides (HgO & Hg₂O) and soot (if coal is used). In the first chamber, each ceramic filter (FIG. 4) is lined with circular holes of a given diameter (for a given filter) that varies from 5 mm to 1 mm. A ceramic plate has holes of a given diameter arranged as shown (FIG. 4). The number of holes in a line and the number of lines can vary depending on volume of flue gas to be filtered out. The separation of holes in a given line is about 2 to 3 times the diameter of one hole. The lines are also similarly separated. Two plates containing holes of same diameter are placed on top of or next to each other in cross position so that x axis (the side cd or ab) of one plate becomes the y axis (the side ad or bc) of the other plate [FIG. 4]. The separation between the plates is six to eight inches. There are five such pairs of ceramic plates in one chamber. The diameter of the holes in a given pair of plates decreases from the previous pair by 1 mm. The last pair has holes of diameter 1 mm. These chambers are well insulated to prevent heat losses from the flue gas. The ceramic plates are arranged so that they can be cleaned easily of the ashes/soot/solid HgO and Hg₂O. The chambers are so designed that the ashes can be removed from time to time easily. The flue gas from coal fired power plants is then passed through fabric filters to remove the remaining ashes/soot. This also can remove some of the mercury oxides. These arrangements (not shown in FIG. 1) are made before the flue gas enters the ammonia super heater in FIG. 1 and FIG. 5. Such arrangement are suitable for flue gas containing high ash, specially, from power plants (e.g., those from India) using coal with high ash content. In this invention we find that such arrangements to remove fly ash, mercury oxides is not necessary if the flue gas is from natural gas fired power plants.

Capture of Flue as Heat for Auxiliary Power Generation Through Steps 2 to 5

Step 2: (After the step/process 1), the flue gas is passed through a chamber [FIG. 1] that contains an ammonia super heater [FIG. 1, FIG. 5] which heats (using the heat of the flue gas) the anhydrous ammonia of the ammonia power plant to high pressure to drive a turbine (FIG. 1) for generation of auxiliary power that augments the output power obtained from the main steam turbine [not included in any drawing here]. The partial ashes collected in the chamber (FIG. 5) including those on the surfaces of ammonia super heater is regularly removed using any conventional method. The arrangement for ash removal can be either on the left or right side of ammonia super heating chamber (FIG. 1), depending on the temperature needed for auxiliary power generation. For an ammonia plant with about 10% efficiency, the first arrangement is quite good. For a plant with around 20% efficiency, the second arrangement is preferred with a special arrangement of ash removal from the surface of the ammonia super heater. In this arrangement, the flue gas is not allowed to escape to air and this arrangement increases the pressure of the gas to enable efficient capture of flue gas heat by the ammonia super heater that in truns help the ammonia turbine function well. After capture of all components, the unreacted nitrogen gas (which is quite pure) is either released to the air or collected. Thus, the pressure does not build up excessively.

In an alternative arrangement the flue gas from the boiler is directly passed through the bottom of a chamber [FIG. 5] and passes vertically upwards through ceramic filters placed horizontally and then through ceramic filters placed vertically in another chamber connected to the first chamber. It then heats the ammonia super heater chamber [FIG. 1] before passing through the chamber containing fabric filters. When the entire chamber is well insulated, the ammonia can be heated to considerably high pressure and temperature leading to good auxiliary power generation. The air preheating coil can be conveniently placed in lower section of this chamber (FIG. 5), if needed. In this arrangement, ash deposition on the surface of the ammonia chamber is minimal. Whatever ash is deposited on ammonia super heater surfaces is removed using any conventional means. However, it is still necessary to have said protective coating (as described earlier) on the ammonia chamber surface to prevent corrosion due to toxic flue gases and high temperature.

Step 3: The flue gas from the said chamber is finally passed through fabric filter to capture any remaining part (from step 1) of the fly ashes. Fabric filter can also capture some of the oxides of mercury [https ://hub.globalccsinstitute.com/publications/coal-quality-impacts-and-gas-quality-control-oxy-fuel-technology-carbon-capture-and-storage-cost-impacts-and-coal-value/62-hg-removal-cost-estimation] which are usually solids at the flue gas temperature. These two steps 1-2 drop the temperature of flue gas. After passing through the fabric filter, the flue gas is passed through an electrostatic precipitator (ESP) [FIG. 1] to remove the soot or any smoke particles which are not previously captured.

Step 4: In steps (1-2) the anhydrous NH₃ gas after collecting the heat from a heat exchanger and from the electrostatic precipitator/fabric filter (FIG. 1) (both of which retains some part of the flue gas heat) is fed back [FIG. 1] to the ammonia super heater. The said ammonia super heater is embedded in FIG. 5 after the ceramic filters. The anhydrous ammonia is superheated at super critical pressure 200 bars at temperature 200° C. by the heat of the flue gas in the chamber(FIG. 5). This leads to the expansion of the ammonia to drive the turbines in an NH₃ power plant so as to generate the auxiliary power. If the flue gas heat is used to pre heat air (APH) used for the combustion of coal, till the flue gas temperature drops to 300° F. (150° C.), then the anhydrous NH₃ gas is heated to 100° C. at pressure around 100 bars. In the latter case, the auxiliary power generated is less than the first case. In this section, it is necessary that the tubes & vessels containing NH₃ inside the superheating chamber has an external coating or wrapping of materials that is non-reactive to the toxic gases and with good thermal conductivity. Graphene film could be such a material (1, 2) [1. A Review on the use of Graphene as a Protective Coating against Corrosion Jianchen Hu, Yanfeng Ji, Yuanyuan Shi , Fei Hui , Huiling Duan and Mario Lanzal , Annals of Materials Science & Engineering, —Volume 1 Issue 3-2014 ISSN: 2471-0245 www.austinpublishinggroup.com, p.1-16; 2. Impermeable barrier films and protective coatings based on reduced graphene oxide, Y. Su, V. G. Kravets, S. L. Wong, J. Waters, A. K. Geim, & R. R. Nair, Nature Communications 5, Article number: 4843 (2014), doi:10.1038/ncomms5843]. Other protective coating that is found suitable is discussed in the beginning of this section.

The superheated ammonia [FIG. 1, FIG. 5] drives the turbine (NH₃ turbine in FIG. 1) and produces auxiliary power [see section 1.2]; it undergoes expansion and cooling. The ammonia is then compressed and passed through a condenser [FIG. 1] which is cooled further by fixed amount of cold water. The water is cooled by a fraction of cold nitrogen gas (see FIG. 1). At point m in FIG. 1, after the collection of liquefied SO₂, the cold N₂ gas stream is divided in two parts; one part goes directly to the ammonia condenser (FIG. 1) to cool the water, which cools the compressed ammonia and the other part enters the chamber of NO₂ condensation (FIG. 1).

Step 5: After the auxiliary power generation, the compressed ammonia gas is passed from the condenser by a pump through a heat exchanger [FIG. 1] and then passed through the electrostatic precipitator/fabric filter [FIG. 1] and back to the ammonia super heater in the closed cycle. The ammonia gas collects heat from the heat exchanger, fabric filter and ash removing chamber before passing through the ammonia super heater in flue gas chamber[FIG. 5] to repeat the steps 1 to 4 [FIG. 1]. The latter arrangement is not shown in FIG. 5. The external surface of the tube(s) in fabric filter and ash removing chamber through which the ammonia gas passes has protective coating. The coating could be similar to that mention in step 1 above.

Successive Condensation of Mercury Vapor (SO₃ (Boiling Point. 44.9° C.), and Steam and Capture Through Steps 6 to 8

Step 6: The first heat exchanger condenses partially (point 3-4 in FIG. 1) the mercury, the steam, and part of sulfur trioxide gas, SO₃, (boiling point 44.9° C.) which are collected. For this the flue gas is passed through a coil of tubes as shown in FIG. 6. The coil is enclosed in this heat exchanger. The heat exchanger is described in FIG. 11. The said coil of tubes has special curved sections (FIG. 6) where condensed liquid from the flue gas accumulates while leaving space on the top for the uncondensed flue gas components to pass without carrying the condensed fluid. It drains the partially condensed components which majorly comprise of steam, mercury. This step partially condenses acid vapors like H₂SO₄, HNO₃ that may be present in the flue gas from power plants [Edwards. Rubin, Toxic Releases from Power Plants, Environ. Sci. Technol. 1999, 33, 3062-3067]. These acid vapors along with some part HCl (hydrochloric acid) and other acid vapors are dissolved also in the partially condensed steam (water). The latter contains small amount of liquid SO₃ which is dissolved in the condensed water of the steam. The draining of these condensates occurs with the automatic opening of the valve when enough liquid pressure is built up (FIG. 6). At this stage small amount of mercury is also drained. Alternatively, the opening of the valve can be arranged electronically (not shown in in FIG. 6 or 1) when condensates reaches a certain level.

Step 7: After fly ash, steam, mercury and SO₃ is collected by steps 1 to 6, the flue gas contains mostly N2, CO₂, and a small percentage of SO₂, oxides of nitrogen and carbon monoxide in very small amount. After steps 1 through 6, the flue gas is cooled further by passing through coils (FIG. 6) in a heat exchanger (between a and b₁ in FIG. 1). The heat exchanger (shown in the section a-b₁ in FIG. 1) contains water at this point and is cooled by passing cold N₂ gas coming from the right through turns of tubes (FIG. 11) immersed in the water. This N₂ gas is in the last leg of its reverse journey before being vented out to atmosphere or being collected as pure nitrogen, if needed. This is the unreacted nitrogen of the flue gas (the production of which is explained in Steps 14 and 15). The flue gas, which is cooled to less than 50° C. through this heat exchanger, is then compressed adiabatically to about 2 to 3 bars [b₁ to b₂ in FIG. 1]. This compressed gas is cooled further by passing the compressed gas at b₂ through tubes immersed in water in a chamber [either FIG. 7 or FIG. 6 combined with FIG. 11] that is maintained around 35° C.±2 through controlled flow of cold nitrogen at low flow rate and using radiator cooling, if necessary, by solar powered fans. The radiator is not shown in FIG. 1. The cold nitrogen gas enters the chamber from right in FIG. 1 in section b₂-b₃. Appropriate temperature controller is used at this stage that controls the flow of the said cold nitrogen gas and the water in the chamber (FIG. 7 or FIG. 11 containing FIG. 6) is stirred to have uniform temperature. It may be necessary to have more than one such chamber if the flow rate of the flue gas is high to ensure condensation of SO₃ and significant part of steam H₂O [section b₂-b₃]. This will increase also the part of acidic gases that dissolves in the condensed water. Here, significant mercury vapor in the flue gas also condenses to metallic elemental liquid mercury and is collected in a container (not shown) that is connected below the water tank. The mercury may be mixed with water (from condensation of steam) and also with HCl or SO₃ which are dissolved in the condensed steam (water). As mercury is much heavier (density 13.6 g/cc) than water (1 g/cc), mercury will be collected at the bottom of the tank and it is drained out separately through taps. This stage of FIG. 7, or FIG. 6 with FIG. 11 is inserted in section b₂-b₃ of FIG. 1 along with a compression pump [not shown in FIG. 1].

The arrangement of the configuration of the flow tubes through which flue gas passes is shown in FIG. 7 and FIG. 6 combined with FIG. 11. In this section, to capture SO₃, H₂O, and mercury(Hg) vapor, the chamber contains fixed amount of water that is cooled by the said cold nitrogen gas passing through turns of tubes one end of which is connected at the port X₁, which would be coiled around the flue gas tubes (not shown) in FIG. 7 with the end being connected to the exit pipe Y₁Y₂ [FIG. 7]. The external surfaces of the both the tubes of (FIG. 6-8) would be made black with paints that have good thermal tolerance (at low temperatures as well as at temperatures of ˜80° C.). This would ensure good thermal radiation from the flue gas tube which in turn would ensure good heat exchange through helium gas and the conducting pebbles (for capture of components with b.pt below 0° C.). The port Y₁Y₂ is connected to other inlets in other sections where such figure (say, FIG. 7) is referred to and where cold nitrogen gas is used to cool the compressed flue gas (for capture of components with b.pt below 0° C.). However, near the point a in FIG. 1 which represents this part (step 7) of the process, the nitrogen gas exiting at Y₁Y₂ reaches the ambient temperature. It is pure when the said N₂ gas is passed through turns of tubes(not shown) surrounding the tubes in FIG. 7 or in FIG. 11, the end of the N₂ gas carrying tubes being connected to the exit port (say, Y₁Y₂ in FIG. 7). The N₂ can be vented out by the emission capture plant or collected at this point for sale/industrial use, since it has no further use in cooling and it must be exited from the emission capture plant. However, chamber of FIG. 7 is used also at other steps. The cold N₂ gas exiting from Y₁Y₂ in other steps is connected to the inlet of another separate cooling chamber of FIG. 7. In many steps where the flue gas is to be cooled below 0° C., the chamber of FIG. 7 does not contain water as mentioned earlier in the description of drawing of FIG. 7.

Proper stirring of water (in the chamber of FIG. 7 or in FIG. 11) in for step 7 is needed to have uniform cooling of water (for capture of flue gas components that have b.pt above 0° C.).

The water temperature is kept at 35° C.±2 in this step 7 [through use of a temperature controller, sensor and flow controller of cold N₂ gas, fans for the heat radiator—these are not shown in FIG. 7] to condense SO₃ & H₂O which is collected at the bottom as shown in FIG. 7 or FIG. 6. Some of the acid vapors in the flue gas gets dissolved in the condensed water. This mixture of dissolved acids, SO₃ & H₂O may also contain partly condensed mercury, which, however, is heavier and will settle at the bottom. If the flue gas is obtained by burning low sulfur content coal, then it is expected that the sulfuric acid formed in the collector [FIG. 6 or FIG. 7] will be fairly dilute. If the flue gas is obtained by burning coal with high sulfur content (similar to Indian coal) then the sulfuric acid formed in the container [FIG. 6 or FIG. 7] may be slightly concentrated. In most of the cases it would be dilute since SO₃ concentration is quite less than that of SO₂ in coal fired power plant. Part of the captured mercury may form compounds with the captured HCl and sulfuric acid [H₂SO₄] in the collection chamber. The compound however will be dissolved and in the form of liquid which can be drained out. The part of the condensed mercury may be collected at the bottom of the container in FIG. 6 or FIG. 7.

It may be mentioned that with the current existing state-of-the-art technologies, in case of a coal fired plant, powdered activated carbon (PAC) is injected into the flue gas for mercury capture [1](Moretti and Jones. 2012). This process costs $45000.00 per pound of Hg removed and $5 million to 6.75 million annually for a 500 MW power plant[1a,b,c,d]. In general, the cost of mercury removal with existing technologies is high [61,61a]. With this new technology, no such injection of materials is needed. This new technology described in this invention is very economical, since only electrical power is used to compress the flue gas and to obtain cold N₂ gas at the end. SO₃ of the flue gas [from coal fired power plants] also liquefies and is collected. Mercury, being heavier, will collect at the bottom. Alternately, both mercury vapor and SO₃ can be collected separately in two chambers maintained at 53° C. (for Hg) and 35° C. (for SO₃) respectively. This process would not be needed if the flue gas comes from natural gas fired power plants. The control of the temperatures is done through a temperature control circuit (not shown in FIG. 1) that regulates the flow of cool nitrogen gas through the water. The internal parts of the compressors have some protective coating so that the compressors are not corroded by toxic components of the flue gas. Such corrosive characteristics is reduced significantly as the flue gas temperature drops successively in this invention.

Step 8: After step 7, the flue gas containing remaining SO₃ under pressure is further cooled by passing through heat exchanger and then compressed to ˜4.5 Bars and passed through tubes immersed in a water tank (c₁ in FIG. 1) similar but different to that of FIG. 6 or FIG. 7 but maintained at around 25° C. by passing controlled amount of said cold nitrogen gas and using temperature controller (not shown in FIG. 1). In this section (stage c₁ in FIG. 1), SO₃, as well as any leftover steam is further liquefied and collected in a chamber connected below the water tank. Mercury (boiling pt. 356.73° C.) is majorly condensed in steps 6 & 7. Some of the remaining mercury is also condensed in this step 8. Any mercury vapor that condenses along with SO₃ or water from steam will settle at the bottom (FIG. 6) and can be separated by gravity. This happens in process at c₁ in FIG. 1. In this chamber, more steam from the flue gas will be collected. Thus, the sulfuric acid formed from the dissolved SO₃ in condensed steam is dilute. The internal linings of the tube in FIGS. 6, 7 & 8 should have protective coating as said earlier.

Capture of Nitrogen Dioxide NO₂ (b.pt 21° C.)

Step 9: To separate NO₂ (boiling point 21° C.), the compressed flue gas is further cooled by passing through tubes (not shown) inside a heat exchanger (after c₁ in FIG. 1). It is then compressed adiabatically (to ˜6-7 bar). This compression is done in two stages. The first compressed gas (3 to 4 bars) is cooled (˜18-19° C.) by passing through tubes inside a heat exchanger, which is cooled by said cold N₂ gas (not shown in FIG. 1). The flue gas is further compressed (6 to 7 bars) and cooled by passing through tubes (FIG. 7) kept immersed in water in a different chamber (FIG. 7), cooled by controlled flow of cold N₂ (from the right) through the chamber (c₂ in FIG. 1), which is maintained at 8° C.±2. This is the third chamber of FIG. 7. This process will condense and separate liquefied NO₂ from the flue gas. In this step the most of the acid vapors HNO₃ (b.pt 83° C.) and H₂SO₄ (b.pt 337) , if present in flue gas, are also condensed. These will also dissolve in the water condensed from the water vapor in the flue gas. This step will also condense and separate most of the remaining mercury vapor in the flue gas. It will further separate the water (in the form of steam) in the flue gas. This step is also performed at stage c₂ of FIG. 1. It is necessary to separate/condense all the steam of the flue gas ahead of subjecting the said flue gas to cryogenic processes below 0° C. in the steps described below, so that compressors are not chocked (due to ice that can form below 0° C. if the flue gas has steam) when compressing flue gas below 0° C. Liquefied NO₂ and water (condensed steam) may be mixed in the collection chambers of either FIG. 6 with FIG. 11, FIG. 7 or FIG. 8. FIG. 8 could be an alternative collection chamber to FIG. 7 for this step. In the case of flue gas from natural gas fired power plants, this step will condense most of the water vapor of the flue gas. This is important so as to prevent the formation of solid ice in the latter cryogenic stages. Formation of ice during the cryogenic processes at latter stages can choke the compressors and expansion valves etc.

Capture of SO₂

Step 10: After step 9 the flue gas contains mostly SO₂, CO₂, N₂O, NO, CO, unreacted nitrogen/oxygen, some traces of noble gases etc. In this invention henceforth we call the unreacted nitrogen/oxygen, some trace noble gases etc. as simply “nitrogen, N₂”, as N₂ is the major component. The flue gas after step 9 is further compressed gas is further compressed to pressure around 8-9 bars (in section c₃-d in FIG. 1). The compressed gas is passed through coils kept in a chamber as shown in FIG. 7, but without water and kept at ˜−14° C.±2. For collection of liquefied SO₂, CO₂, N₂O, NO, CO, each separately, the chamber (FIG. 7, FIG. 8) does not contain any water as mentioned earlier and the arrangement is mentioned in the part B description of drawing of FIG. 7.

For step 10, the said chamber of FIG. 7 (or FIG. 8) is placed between the points d & c₁ in FIG. 1 after the collection of NO₂. The chamber of FIG. 7 in this step does not contain water unlike those in earlier steps (step 9 and above). It contains heat conducting pebbles or metal chips that will facilitate heat conduction from the flue gas tubes to the cold nitrogen gas carrying tubes with the help of helium gas (which has high thermal conductivity) at pressure 1 to 2 bars. Also, the chamber is air-tight with helium gas inside. The helium gas enables good heat conduction for the heat exchange. A small fan inside the chamber operated by a solar power will circulate the helium gas throughout and thus will further enhance the heat exchange rate in chamber of FIG. 7 when used for steps 10-15. Said cold nitrogen gas obtained at the end of the whole cycle of operation, is passed at 2 bar through a tube in this chamber [FIG. 7] such that the chamber is cooled at temperature ˜−14° C. by the controlled flow of cold N₂ gas (obtained at the end of the cycle). This cold N₂ flows from the point k of the CO₂ condensation unit in step 11, to the left of FIG. 1. SO₂ is condensed in the chamber of FIG. 7 kept in the section d-e₁ (FIG. 1) in the form of liquid which is collected in a tank connected to the coils [FIG. 7 or FIG. 8]. Such arrangement also allows rapid collection of the liquefied form of SO₂ captured from the flue gas. This particular step is not necessary for flue gas from clean natural gas fired power plants as it does not contain sulfur dioxide. The cold N₂ coming out of the SO₂ condensation chamber at point 1 (FIG. 1] is divided in two parts at point m [FIG. 1]—one part directly goes to the ammonia condenser unit to cool the water (FIG. 1) that is used to cool the compressed NH₃ gas after the turbine expansion in step 4 above. The other part of the cold N₂ enters the NO₂ condensation chamber. The compression to 8 to 9 bars after step 9 can be done in two stages also and the compressed flue gas from the first stage can be cooled in heat exchanger before being compressed further and entering the chamber of FIG. 7 as discussed in this step.

After this process the flue gas contains mostly unreacted N₂, CO₂, and some small amount of N₂O, NO and much smaller amount of CO (carbon monoxide).

Production of Liquefied CO₂ Captured from the Flue Gas: Process (e₁, e₂, e₃) [FIG. 1]

Step 11: is the multi-stage adiabatic (isentropic) compression (FIG. 1) of the flue gas left over from step 1 to 10 above. This step 11 and the following steps (12 to 16) are performed in stages e₁, e₂, e₃, f, g, h & i in FIG. 1. The flue gas mixture after step 10 (i.e., collection of liquefied SO₂) and coming out at e₁ (in FIG. 1) is compressed adiabatically from initial pressure of about 8 to 9 bars [at temperatures around −10° C.] from steps 9 & 10 above, to a pressure of 26.47 bars using the n-stage compressor. The single compressor shown in FIG. 1 after steps 9 & 10 represents a number of compressors. The total number of compressors used in this technology invention is 15. However, it can be adjusted based on the principle discussed later in section 1.3.2. This adiabatic (isentropic) compression will raise the temperature above −10° C. to around −1 to -3° C. The flue gas after each isentropic compression is passed through heat exchanger (which is cooled by passing said cold N₂ gas) to prevent the temperature rise from −10° C. upward significantly. The finally compressed gas(26.47 bars) is passed through coils in FIG. 7 kept in section e₂ (FIG. 1), entering at port A of FIG. 7l with the chamber kept at −18° C.±2 [maintained by passing cold N₂ gas and a temperature controller]; the chamber is similar to FIG. 7 as said in step 10. In this section, the CO₂ of the compressed flue gas [at 26.47 bars, the saturation pressure of CO₂ at −10° C.] is converted to a super-cooled liquid CO₂ at −10° C., corresponding to stage n in FIG. 1. The liquefied CO₂ thus produced is collected in an insulated container [not shown in FIG. 1 or FIG. 7], to be connected to chamber at n (LCO₂ collector in FIG. 1) and the remaining flue gas is under pressure 26.47 bars. This is the state e in FIG. 2. Since the N₂ content of the flue gas is around 75% or more [by weight] of the whole flue gas [Rogers and Mayhew (1992)[80], also see section 1.3.2] , and the entire N₂ gas is cooled to a few degrees above its boiling point (−196° C.) in this technology, the cold N₂ gas should adequately take care of all the cooling required in earlier steps and this step. Combined cooling of the water tanks by radiators and fans (run by solar power) in the earlier steps would increase the energy efficiency of the capture process. The insulated chamber collecting the liquefied CO₂ in this step is connected via throttle valve (FIG. 1) to the flash chamber (FIG. 9).

Production of Dry Ice from the Captured Liquefied CO₂

Step 12: To produce dry ice, the captured liquefied CO₂ at step 11 above (represented by state e in FIG. 2) is throttled adiabatically (from point n in FIG. 1) into an insulated flash chamber (FIG. 1 & FIG. 9), placed between points o & p in FIG. 1.l This is shown by state fin FIG. 2. Process (e-f) (FIG. 2) is the adiabatic throttling of the liquid carbon dioxide (CO₂) by an expansion valve to atmospheric pressure at state fin an insulated flash chamber (FIG. 1 & FIG. 9), where state f (FIG. 2) is a mixture of solid dry ice and vapor, referred to as dry vapor. This process is an irreversible adiabatic expansion; hence the dashed line (FIG. 2). The design of the flash chamber to collect the dry ice & vapor is shown in FIG. 9. It has a throttling valve for liquid LCO₂ to enter. It has an inlet for very cold N₂ gas (coming after the condensation of CO (carbon monoxide) following the 3′ stage of the triple stage turbine work in FIG. 1) to enter and it has an outlet for this N₂ gas that enters from the point q to the heat exchanger [FIG. 1]. The cool N₂ gas in the chamber of FIG. 9 freezes the dry vapor into dry ice and further freezes the dry ice [FIG. 9]. The flash chamber (FIG. 9) contains an outlet with valve v1 for the dry ice at the bottom to enter a long column at the end of which there is another valve v2 which opens automatically by the weight of the dry ice. This arrangement prevents escape of very cold N₂ gas entering the chamber [FIG. 9], while dry ice is continuously formed and collected. The cold nitrogen gas being regulated to keep the temperature of the flash chamber about −10° C. below −78° C., the sublimation point of dry ice. The super-cooled N₂ gas is obtained by the following steps (steps 14-15). The insulated flash chamber is air tight so that air does not enter from outside. The remaining flue gas after separation of CO₂ (in liquefied and dry ice form) contains mostly unreacted nitrogen (N₂), nitrous oxide, nitric oxide and some traces of carbon monoxide (ignoring traces of noble gases). This remaining part of flue gas moving in the right after point fin FIG. 1 still is at a pressure of 26.49 bars.

Separation of N₂O from the Flue Gas

Step 13: After step 12 and production of liquefied CO₂ and dry ice from the carbon capture of flue gas, the flue gas coming out of e₂ in FIG. 1 is still around −10 ° C. and pressure 26.49 bars. It is subject to further cooling by passing through coils (not shown in FIG. 1 ) in heat exchanger at e₃ (FIG. 1 ) to a temperature of −50° C. to −60° C. by the cold N₂ gas entering the said heat exchanger from the chamber of N₂O at the right in FIG. 1, maintaining the pressure by necessary compression, if needed. The cold N₂ gas from the flash chamber in step 12 enters the N₂O chamber from the right side, through the line marked by the point q in FIG. 1. The cold compressed flue gas then enters the first turbine at point f (FIG. 1). It undergoes the first isentropic expansion there (step 14).

Step 14: It is (i) the first isentropic expansion of the compressed flue gas from step 13 (containing mostly nitrogen gas) (from step 14) (at pressure 26.49 bars) in the first stage of a triple-stage turbine to the boiling point of N₂O (−88.5° C.) at a pressure of about 13.27 bars to 15.6 bars depending on the initial cooling temperature (−50° C. to −60° C.). To collect the liquefied N₂O, this turbine expanded flue gas from first stage turbine is led to a chamber [FIG. 10] kept ˜−96° C.±2 through controlled flow cold nitrogen gas from the right. This causes all the N₂O in the compressed flue gas (at temperature ˜−88.5° C. or slightly higher after the expansion) to condense and liquefy. The liquid N₂O is then collected in an insulating container [FIG. 10]. (ii) In the next stage, the flue gas at pressure around 15 bars coming out of the N₂O condensing chamber of (i) of step 14, is further cooled to temperature around −106 to −110 ° C. by passing through a heat exchanger (at g, FIG. 1 ) which is cooled by cold Nitrogen gas coming from the point q at the right. The heat exchanger can be that shown either in FIG. 7 or FIG. 8. The flue gas is then expanded through the second turbine (FIG. 1 ) to a temperature of −152 ° C. at 4.87 bars. The expanded gas is passed through a chamber kept at −158±2° C., using controlled flow of super cold N₂ that comes right after the third stage of turbine expansion at point I in FIG. 1. A part of this nitrogen (at temperature ˜−194 to −195 ° C.) is fed to this NO capture chamber. Here NO from the expanded flue gas (at pressure 4.87 bars) is condensed to super-cooled liquid (NO) under pressure and collected in a similar insulating chamber (FIG. 10). The liquid NO collection chamber [FIG. 10] is jacketed inside another second chamber that is externally highly well insulated container and the inside of this second chamber (similar to FIG. 10] is cooled by controlled flow of said super cooled N₂ gas (FIG. 1 ) (which has temperature ˜2 degrees above the boiling point of N₂, obtained at the end of the cycle), so that the chamber is maintained at temperatures ˜−156 to −160° C. The conventional insulators such as alternate combination styrofoam and reflecting aluminum foils or any form of good insulation works well for the external jacket. This arrangement is not shown in FIG. 1. The super cooled nitrogen coming from the third stage expansion is split in to two—one goes to the NO condensation chamber and the other to the CO₂ flash chamber (FIG. 1 ). The stage (i) of step 14 may be avoided if the NO concentration overwhelms the N₂O concentration in the flue gas. NB: A triple stage turbine is used rather than a single-stage turbine to avoid the solidification of NO (freezing pt. of −164° C.) from choking and freezing the turbine blades before exiting the turbine. In many boiler or burner, the N₂O concentration is quite significant relative to NO concentration and hence stage (i) is necessary. In this invention we find that it is very important to ensure that the turbine blades do not choke due to freezing of any of the component of the flue gas.

Production of Super-Cooled N₂ and Capture of CO

Step 15: In this step, the flue gas (mostly nitrogen gas at pressure 4.87 bars and temperature around −152° C. to −155° C.) from step 14 further undergoes isentropic expansion by the third turbine (FIG. 1) to atmospheric pressure into an highly insulated and air tight and insulated chamber (not shown). This expansion lowers the temperature of the flue gas (mostly nitrogen) close to its boiling point (−195.8° C.) before exiting at state i (FIG. 1 ) to supply very cold N₂ gas for the various cooling processes in the system (as described above). Here CO (carbon monoxide) with boiling point (−191.5° C.) is condensed at the bottom of the chamber to a super-cooled liquid [FIG. 10] and it is then drained out of the chamber into a well-insulated container [not shown in FIG. 10]. The super-cooled nitrogen gas is then pumped (pump not shown in FIG. 1 or FIG. 10) out of the said chamber in reverse direction to perform the various cooling processes as described in steps 6 to 14 above. The symbol N₂ is used to denote not only the nitrogen but all also the inert noble gases present in air which remain unchanged throughout the combustion reaction, and the negligible unreacted oxygen remaining after the combustion process. The super cooled nitrogen (source of fairly pure nitrogen) obtained at this stage is sent back in reverse direction to perform the cooling in reverse order. After performing all the cooling in reverse order, the nitrogen gas (which is quite pure) reaches ambient temperature at point a, and can be exited in or collected, if needed, as mentioned earlier. It is quite pure (except for the inert noble gas content).

In the steps/processes described above super-cooled nitrogen line is split twice-once at the point r and then at the point m (FIG. 1). The split lines and all lines carrying cold nitrogen gas in reverse flow direction, are wrapped with very good thermal insulation material. Alternate layers of glass wool and reflecting aluminum foil wrapped around such lines with final layers of shining aluminum foil have been found to act as very good insulation in this invention. This gives better control over the various cooling processes described in this invention. If the flue gas from coal fired power plant contains H₂S (b.pt. −60° C.) (T5) then it is captured by following the step 13 but passing the flue gas through a heat exchanger (not shown) placed before the heat exchanger at e₃ (FIG. 1 ) and maintaining it at −68° C., using cold nitrogen gas coming from heat exchanger e₃ on the right, similar to the processes described above.

1.2 Capture of Flue Gas Heat for Production of Auxiliary Power Using Ammonia Turbine for High Energy Efficiency of the Capture Process.

In order to add further energy efficiency to this technology for industrial emission capture, we have incorporated in our technology a method of auxiliary power production using ammonia turbine. It involves the following steps (All steps processes can be found in FIGS. 1, 2 and 3):

Process (6-7) is the adiabatic compression of the saturated liquid at state 6 (FIG. 2) to a compressed liquid at state 7 by the feed pump (FIG. 1: shows the pump).

Process (7-8) is the heating of the compressed liquid NH₃ as it cools the flue gas from processes 1 to 4 (FIG. 1) discussed above, where it is assumed to attain a super critical temperature of 200° C. at a super critical pressure of 200 bars at state 8. This assumption is very reasonable and attainable with the knowledge that typical temperatures of exhaust flue gases from gas turbines ranges between 370° C.-590° C. [https://www. engineeringtoolboxcom/fuels-exhaust-temperatures-d_168.html]. Therefore, by controlling flow rate of NH₃ for a particular plant (depending flue gas flow rate) this temperature for NH₃ can be attained. The flow rate depends on flue gas temperature, concentrations and rate of emission from the power plants.

Process (8-5) is the expansion of the super critical vapor at state 8 to state 5 [FIG. 3] in a turbine [FIG. 1] to produce the engine motive power.

1.2.1. An Example—the Application of the Above Methods

The number subscripts in the following example—refer to FIG. 3. The subscripts f & g refer to saturated liquid & gas respectively.

Thermodynamics Analysis of the Auxiliary Power Generation from the Flue Gas Heat Using Ammonia Turbine

We assess the energy required to liquefy entire CO₂ and to cool the entire unreacted nitrogen gas of the flue gas that would have been emitted, if the entire generated electrical energy of 1.4×10¹⁸ J in UK (2010) was by using (i) coal; (ii) natural gas, using steps g to m in summary of invention and in steps 11 to 15 of section I.1.

From Thermodynamic Property Table for Ammonia (NH₃), PC Model, we find that at

State 8 (Super Critical Vapor FIG. 3):—T₈=200° C., P₈=200 bars, h₈=1497.7 kJ/kg (specific enthalpy), s₈=4.0721 kJ/kg (specific entropy)

In FIG. 2): State 5(FIG. 3) is (Wet Vapor):—T₅=25° C., P₅=10.032 bars, s₅=s₈=4.0721 kJ/kg (Isentropic Expansion), v_f=0.001650 m³/kg (specific volume of saturated liquid at state 5), h_f=298.25 kJ/kg, h_g=1463.5 kJ/kg, s_f=1.1210 kJ/kg, s_g=5.0293 kJ/kg

Therefore, quality (x) of wet vapor is given as

(x)=(s₅−s_f)/(s_g−s_f)=(4.0721−1.1210)/(5.0293−1.1210)=0.7551

Hence specific enthalpy of the wet vapor h₅=h_f+x(h_g−h_f)=298.25+(0.7551)(1463.5−298.25)=1178.13 kJ/kg

The turbine work (step 4 in section I.1) is

W _t2=(_s−h₅)=(1497.7−1178.13)=319.57 kJ/kg

The feed pump work of compression is

W _p =v ₆(P₇−P₆)=0.001650(200−10.032)×100=31.34 kJ/kg

Since v₆=v_f=0.001650 m³/kg

Now h₆=h_f=298.25 kJ/kg, and hence h₇=W_p+h₆=329.59 kJ/kg

The heat supplied is then

Q_in=h₈−h₇=(1497.7−329.59)=1168.11 kJ/kg, and the heat rejected in the condenser is Q_out==h₅−h₆=(1178.13−298.25)=879.88 kJ/kg

The net work W_net=W_t2−W_p=(319.57−31.34)=288.23 kJ/kg, and the net heat is Q_net=Q_in−Q_out=(1168.11−879.88)=288.23, hence net work is equal to net heat as expected. Therefore, the thermal efficiency (η) of the ammonia power cycle will be

η=W_net/Q_in=288.23/1168.1=24.6%

In instances when the temperature of the ammonia gas at state 8 is less than the critical temperature, the NH₃ power cycle in FIG. 2 will take the dashed path described by the Rankine cycle (5′-6-7′-8′-5′) with a lower thermal efficiency than the super critical cycle; since the final temperature of NH₃ at state 8 determines the efficiency.

1.3. Application of the Above Technology of Auxiliary Power Generation to Assess the Overall Energy Requirement for Capture of Emission Components from Power Plants.

As mentioned earlier this new technology requires no use of chemicals/reagents but energy (to drive the compressors and expanders, coolers etc.) to capture the industrial emissions. We take a specific case where correct data are available [Dr Clifford Jones, ©2013] and assess the total energy required from the output power on top of the auxiliary power generated by methods as mentioned.

1.3.1. Estimation of Auxiliary Power Generated by the Ammonia Turbine [FIG. 1] in a Specific Case

From Global Trends and Patterns in Carbon Mitigation by Dr Clifford Jones [©2013 Dr. Clifford Jones & bookboon.com, ISBN 978-87-403-0465-7] the total electric energy generated in the United Kingdom in 2010=1.4×10¹⁸ J. Imagine that this has been generated by steam turbines on a Rankine Cycle with 35% efficiency [this assumption is quite normal in the case of a coal power plant, since the overall coal plant power conversion efficiency ranges from 32% to 42% [Bright Hub Engineering—http://www.brighthubengineering.com/power-plants/72369-compare-the-efficiency-of-different-power-plants/].]. Then the total heat supplied to the steam power plants (QT) will be

Q _T=(1.4/0.35)×10¹⁸J=4.0×10¹⁸J

In general, the combustion efficiencies of power plants are within the range of 70-90% (Rogers and Mayhew 1992) (80). So, in this analysis we have assumed a typical combustion efficiency of 75%. With this efficiency, the enthalpy of combustion (H_e) for the fuels in this study will be

H_c=Q_T/η_c=(4.0/0.75)×10¹⁸J=5.33×10¹⁸ J. if the total mass (m) of the fuel of combustion is known, then the specific enthalpy of combustion (h_c) will be h_c=H_c/m, and this is usually referred to as the calorific value of the fuel.

If 75% of the heat of combustion is supplied to the steam boilers, then 25% of this heat will be retained by the flue gases, which can then be used for the heat requirement source of our Ammonia power plant, and this is equivalent to (0.25)(5.33)×10¹⁸J=1.333×10¹⁸ J.

In FIG. 1; since the NH₃ cycle will be cooling the flue gas to temperatures slightly above ambient, the efficiency of combustion (η_c) of the NH₃ power plant can be as high as 85%. With proper heat insulations in step 1 to 5, this can be achieved. With this efficiency of combustion, the total heat supplied to the NH₃ power plant (Q_T) to heat the working fluid will be

Q _T=(0.85)(1.333)×10¹⁸J=1.133×10¹⁸ J

With a thermal efficiency of 24.67% of the NH₃ power cycle, the net work output of this power plant will be:

W_net=(0.2467)(1.133)×10¹⁸ J=2.795×10¹⁷ J, which will be (0.2795×10¹⁸/(1.4×10¹⁸=19.96% of the total energy generated by the steam turbines.

Therefore, the overall energy generated in a flue gas energy capture by the combined power cycles of the steam and ammonia power plants in a year will be 1.4×10¹⁸J+0.2795×10¹⁸ J=1.68×10¹⁸ J. This is a very novel economic concept, since billions of dollars of excess energy can be produced capturing the waste energy globally, by all our power plants in a day.

(i) 1.3.2. Work of Production of Liquid CO₂ from Carbon Capture

Scientific Analysis of the Energy Requirement in the Processes Involved Since CO₂ and N₂ are the major constituents of the flue gas from coal and natural gas power plants, and since in our technology nitrogen gas is finally cooled to ˜2 degrees above its boiling point, and this very cold nitrogen gas is used to condense most of the component gases of small percentages, it is sufficient to assess the energy required to capture the entire CO₂ in the form of liquid and dry ice and the energy required to cool the nitrogen gas to near its boiling point. From the methods discussed above, it is obvious that the work of production of the liquid CO₂ from carbon capture will involve the difference in the work input to the N-stage compressor and the work output of the nitrogen turbine.

From thermodynamic analysis the minimum specific work done (W_c) on an N-stage isentropic compressor is given as

W _C =c _P T _X N[(P_y/P_x)^{(1/N)(γ−1)/γ}−1]  (1)

Where c_P is the specific heat at constant pressure

T_x is the temperature at inlet to each compressor stage

N is the number of stages

P_y and P_x are the final and initial pressures respectively

γ is the specific gas ratio.

The specific work output (W_t) by a turbine is given as

W _t =c _P(T₁−T₂)  (2)

Where T₁ and T₂ are the inlet and outlet temperatures respectively

Here

T ₁ /T ₂=(P₁/P₂)^(γ−1)/γ  (3)

For isentropic expansion process

By the energy conservation law, the work done on the compression of both the CO₂ and N₂ gases in the N-stage compressor is equivalent to the sum of their individual compressions, and for a reduced compression work as possible, N is taken as 15 (number of compressors) in this study.

The properties of CO₂ are c_P=0.8464 kJ/kgK and γ=1.288; and the states are N=15 stages, P_y=26.47 bars, P_x=1.01325 bars and T_x is taken as 25° C. (298.15 K) after cooling by ambient water. Then from Equation 1, the specific compression work on the CO₂ gas will be

$\begin{array}{c}{W}_C=\left(0.8464\right)\left(298.15\right)\left(15\right)\left[{\left(26.12\right)}^{0.0149}-1\right]\\ =188.51\mathrm{kJ}\text{/}\mathrm{kg}\end{array}$

(T_x is the temperature of CO₂+N₂ mixture at state b₁ (FIG. 1 ), and it is assumed to be about ambient i.e. 25° C.).

Also the properties of N₂ are C_P=1.0404 kJ/kgK and γ=1.400; and the states are N=15 stages, P_y=26.47 bars, P_x=1.01325 bars and T_x is taken as 25° C. (298.15 K) after cooling by ambient water. Then from Equation 1, the specific compression work on the N₂ gas will be

$\begin{array}{c}{W}_C=\left(1.0404\right)\left(298.15\right)\left(15\right)\left[{\left(26.12\right)}^{0.019}-1\right]\\ =297.79\mathrm{kJ}\text{/}\mathrm{kg}\end{array}$

For the temperature (T₂) of the nitrogen gas at stage i (i.e. exhaust temperature) (FIG. 1 ) to be achieved at the boiling point of nitrogen (−195.8° C.) (77.35 k) at atmospheric pressure (1.01325 bars) for the capture of CO (boiling pt. of −191.5° C.), the temperature T₁ at stage g (FIG. 1 ) from equation 3 will be

$\begin{array}{c}{T}_1={T_2\left(P_1/P_2\right)}^{\left(\gamma -1\right)/\gamma }\\ =77.35k{\left(26.471/1.01325\right)}^{0.2857}\\ =77.35\left(2.5406\right)K\\ =196.52K\left(-76.63°C.\right)\end{array}$

The pressure at stage h (FIG. 1 ) at the boiling point of NO (−152° C.) (121.15 k) for the capture of NO under pressure will be

$\begin{array}{c}{P}_h={P_g\left(T_h/T_g\right)}^{\gamma /\left(\gamma -1\right)}\\ =26.49{\left(121.15/196.52\right)}^{3.5}\\ =4.87\mathrm{bars}\end{array}$

Hence from Equation 2, the specific work output (W_t) by the 2-stage turbine will be

$\begin{array}{c}{W}_t=1.0404\left(196.52-121.15\right)+1.0404\left(121.15-77.35\right)\mathrm{kJ}\text{/}\mathrm{kg}\\ =\left(78.41+45.57\right)\mathrm{kJ}\text{/}\mathrm{kg}\\ =123.98\mathrm{kJ}\text{/}\mathrm{kg}\end{array}$

In coal fired power plants the average constituents for 1.00 kg of dry flue gases containing CO₂ and N₂ is estimated at 0.25 kg for CO₂ and 0.75 kg for N₂ (Rogers and Mayhew 1992). While in gaseous fuelled power plants the average constituents for 1.00 kg of dry flue gases containing CO₂ and N₂ is estimated at 0.15 kg for CO₂ and 0.85 kg for N₂ (Rogers and Mayhew 1992).

Therefore, for 1.00 kg of dry flue gases in a coal fired plant, the compression work input for CO₂ will be (0.25) kg×(188.51) kJ/kg=47.13 kJ, and (0.75) kg×(297.79 kJ/kg)=223.34 kJ for N₂, given a specific compression work input of 47.13 kJ+223.34 kJ=270.47 kJ/kg for the mixture of the gases by the energy conservation law.

By the above method, the gaseous fueled (or gas fired) plant will have a specific compression work input of 281.40 kJ/kg for the mixture of the gases.

Since the specific work output of the turbine is 123.98 kJ/kg, the turbine work from the nitrogen in the flue gases in a coal fired plant is estimated at (0.75) kg×(123.98) kJ/kg=92.99 kJ, and that from a gaseous fueled plant is estimated at (0.85) kg×(123.98) kJ/kg=105.38 kJ.

Therefore, the network input into the production of 0.25 kg of liquid CO₂ at state n from a coal fired power plant is estimated at 270.47−92.99=177.48 kJ, which is equivalent to 709.92 kJ per kg of liquid CO₂ at state n [FIG. 1].

Also the network input into the production of 0.15 kg of liquid CO₂ from a gaseous fuel fired power plant is estimated at 281.40−105.38=176.02 kJ, which is equivalent to 1,173.47 kJ per kg of liquid CO₂ at state n.

(ii) 1.3.3. Cryogenic Cooling Process of the Nitrogen Gas Contained in the Flue Gas

We have earlier described in details the methods involved in cooling the nitrogen gas of the flue gas.

The cooling process of the cold N₂ gas at state i starts with cooling the nitrogen gas from −10° C. to −76.63° C. in process (f-g) (FIG. 1 ) and in steps 12 to 14 of section I.1.

The heat reduction in this process for a coal fired plant is given as

0.75×1.0404×(−10+76.63)=0.75×1.0404×dt

dt=66.63° C. (which is the rise in the temperature of the cooling nitrogen in process (i-j)).

Hence the temperature of N₂ at state j will be T_j=−195.8+66.63=−129.17° C.

The heat reduction in cooling of the flue gas from ambient temperature (25° C.) to −10° C. in processes (b₁-b₂ . . . d-e₁-e₂ in FIG. 1 corresponding to steps 6 to 11 in section I.1) is given as

0.25×258.62+0.75×1.0404×35+0.25×0.8464×35=0.75×1.0404×dt

dt=127.35° C. (which is the rise in the temperature of the cooling nitrogen in processes (j-k-l-m), summary of invention), where 258.62 kJ/kg in the latent heat of evaporation of CO₂ at saturated pressure of 26.49 bars.

Hence the temperature of N₂ at state m will be T_j=−129.17+127.35=−1.82° C. ; which can be used to enhance the cooling of water water in the NH₃ power plant and the multi-stage compressor.

Similarly the heat reduction for a gaseous fuel fired plant is given as

0.85×1.0404×(−10+76.63)=0.85×1.0404×dt

dt=66.63° C. (which is the rise in the temperature of the cooling nitrogen in process (i-j) in FIG. 1 ).

Hence the temperature of N₂ at state j will be T_j=−195.8+66.63=−129.17° C.

The heat reduction in cooling of the flue gas from ambient temperature (25° C.) to −10° C. in the said processes (i.e. steps 6 to 11 in section 1.6) is given as

0.15×258.62+0.85×1.0404×35+0.15×0.8464×35=0.85×1.0404×dt

dt=83.90° C. (which is the rise in the temperature of the cooling nitrogen in processes (g to m in Summary of inventions and in steps 11 to 15 of section I.1).

Hence the temperature of N₂ at state m will be T_m=−129.17+83.90=−45.27° C. ; which can also be used to enhance the cooling of water in the NH₃ power plant and the multi-stage compressor.

Therefore, analyses have shown that with a nitrogen temperature of T_i=−195.8° C. (77.35 K) at state i for both the gaseous and coal fired plants, the cryogenic cooling procedure of the system will effectively cool the various gases to the required temperatures needed for carbon capture.

Thus the above analysis shows that using the methods (processes) of invention (as described earlier in details) to capture CO₂ from the flue gas emission in the form of liquid CO₂, the net energy required is (i) 1,173.47 kJ per kg of liquid CO₂ from the flue gas from natural gas power plants; (ii) 709.92 kJ per kg from coal power plants.

I.4. Total Energy Required for Carbon Capture vs Output Power:

a. I.4.1 From Natural Gas Power Plants:

Also, from Global Trends and Patterns in Carbon Mitigation by Dr Clifford Jones, if gaseous fuel (methane) is used in generating the 1.4×10¹⁸ J of electric energy (UK 2010), the estimated CO₂ emitted is 198 million tons, which is equivalent to 198×10⁹ kg. In the above analysis of a gaseous powered plant the energy required to produce 1 kg of liquid CO₂ is estimated at 1,173.47×10³ J/kg, therefore, the total energy required to produce 198×10⁹ kg of liquid or dry ice CO₂ will be equivalent to 198×10⁹ kg×1173.47×10³ J/kg=2.323×10¹⁷ J.

Now as shown earlier the auxiliary power generated by the ammonia power plants is: 2.795×10¹⁷ J. Thus the auxiliary power generated by the ammonia turbine is sufficient enough to capture the entire CO₂ of the flue gas emission from natural gas power plants. No extra power should be necessary from the output power of the plant for the said emission capture from natural gas power plants. As mentioned earlier in the process the N₂ gas is cooled a few degrees above its boiling point and it is sufficient to condense all the nitrous oxides and CO of the flue gas (flue gas from natural gas fired power plants does not contain usually sulfur oxides, mercury, HCl, H₂S etc.). Thus entire capture of emissions from the natural gas power plants can be accomplished using only the auxiliary power generated by the new technology of this invention. The total output power of the plant will remain untouched in this technology for natural gas power plants. As it does not require any chemicals/reagents unlike all existing technologies, it is the most superior and cheapest of all existing other clean energy technologies.

Average cost of electricity in USA is about $0.12 per kWH. With this rate the cost of converting the entire CO₂ to LCO₂/frozen dry ice is $5.76×10⁹, if the entire energy 1.4×10¹⁸ J is generated by natural gas power plant and no auxiliary power is generated using the heat of the flue gas. Now at the current market price, LCO₂ sells at $160 per ton while dry ice sells at $2-$6 per kg. Even after adoption of this technology when LCO₂ will be abundantly available, if LCO₂ sells as low as $0.10 per kg and the frozen dry ice is sold at $0.15 per kg, the entire cost of capture ($5.76×10⁹) of 198 million ton of LCO₂ will will be well-paid off through sale of only a fraction of the total captured LCO₂/or dry ice. It would be quite profitable for natural gas fired power plant to implement the new technology discussed in this paper. Even if the auxiliary power generation (as discussed in this invention) is completely avoided, still cost of capture of entire emissions from natural gas power plants can be realized by selling only 10% of the collected liquefied CO₂ or frozen dry ice at only $0.15 per kg. Both the liquefied CO₂ and frozen dry ice are sources of very pure CO₂ gas, which has many technological uses. If auxiliary power is generated as described in this invention then the entire capture of CO₂ and the associated toxic products contained in the flue gas from natural gas power plants can be accomplished without using any additional energy from the net power output and thus at no additional cost (excluding the maintenance of the plant and labor) to the power plant. The latter will gain hugely through sales of the products (specially, LCO₂ and frozen dry ice) captured using the methods of this invention.

If auxiliary power is not used or generated as described in this invention, then the total cost of CO₂ capture in the form of LCO₂ or frozen dry ice from the flue gas of natural gas power plants amounts to $7.41×2.232/1.305=$13.17 per ton.

I.4.2. From Coal Power Plants

If coal fuel (80% carbon content) is used, the estimated CO₂ emitted is 587 million tons for the energy generation of 1.4×10¹⁸ J of electric energy (UK 2010), which is equivalent to 587×10⁹ kg. In the analysis of a coal fired plant using our methods of invention as described above, the energy required to produce 1 kg of liquid CO₂ is estimated at 709.92×10³ J/kg; therefore, the total energy required to produce 587×10⁹ kg of liquid CO₂ is equivalent to 587×10⁹ kg×709.92×10³ J/kg=4.17×10¹⁷ J. Subtracting the auxiliary energy generated by the ammonia plant, the net energy required from the total output energy=4.17×10¹⁷ J−2.795×10¹⁷ J=1.305×10¹⁷ J. This is just about 9% of the original total output energy before the auxiliary power plant and carbon capture. With $0.12 per kWh, this would cost=$0.12/kWhx1.305×10¹⁷ J/3600000 J/KWh=$4.35 BN. This means the net carbon capture cost of $7.41 per ton of CO₂ capture, the auxiliary power is generated as described in this invention. If the auxiliary power is not generated, then the cost is $23.1 per ton of LCO₂/dry ice captured. This is much lower than the projected and aimed cost of CO₂ at $30 per ton with current state-of-the art amine technology(ies)[Refs T1-T4,Z1-Z5, see also references 62-80]. It is to be noted that the liquefied CO₂ is a source of very pure CO₂, the purity being much higher than that of the gaseous CO₂ captured with the current state-of-the-art amine or any other technology used for carbon capture from flue gas. The purity of the CO₂ in the captured LCO₂ and the frozen dry ice is so high that it can be easily used in food industries, electronics industries, and research laboratories, unlike the CO₂ captured with chemical based technologies.

The current cost of CO₂ capture by amines technique stands at $52-77 per ton. The minimum cost with the existing amine based technique of carbon capture is $65 per ton of CO₂ gas from the flue gas (Luis M. Romeo, Irene Bolea, Jesús M. Escosa, Integration of power plant and amine scrubbing to reduce CO₂ capture costs, Volume 28, Issues 8-9, June 2008, Pages 1039-1046]; [https://hub.globalccsinstitute.com/publications/global-status-ccs-2014/74-carbon-capture-cost]. For second-generation technologies (defined as those technologies that will be ready for demonstration in the 2020-25 time frame with deployment beginning in 2025) the US DOE has targeted a goal of reducing capture cost to around US$40/t CO₂ [Carbon capture Cost-https://hub.globalccsinstitute.com/publications/global-status-ccs-2014/74-carbon-capture-cost]. Moreover, the current technologies including the amine based ones cannot regenerate CO₂, which will be as pure as that available with our methods of invention described above.

With our technology of invention the cost of capture of CO₂ from coal power plants would be $4.2 per ton, if auxiliary power is used and $13.42 per ton, if auxiliary power is not generated (assuming electricity rate $0.12 per kWh). Thus our technology is far more cost effective than any existing technologies and the technologies envisioned by DOE up to 2025 with or without the use of the auxiliary power described in this invention. Moreover, with amine technologies, SO_x, NO_x and mercury must be scrubbed using other existing technologies like FGD, SCR etc [1c-80]. The operating costs are very high. If SO_x and NO_x are captured by amines, amines would be lost and the techniques would be much more costly and prohibitive. With our new methods of invention, the vast amount of unreacted N₂ of the flue gas is cooled a few degrees above the boiling point. This cold nitrogen accomplishes the capture of SO_x, NO_x and Hg without any additional requirement of energy and hence cost.

The cost of pure liquefied CO₂ is $128 to $160 per ton and cost of dry ice is much more than this. Even at half of this price the 587 MT of pure LCO₂ would fetch $37.5 BN. Thus, by selling only a fraction of the captured LCO₂ or frozen dry ice, the capture cost will be paid off with a very good profit left for the power plants with this technology. The new technology allows complete capture (100%) of CO₂ and the toxic gases such as SO₃, SO₂, NO₂, NO, CO etc. each separately. It involves no use of chemicals or reagents unlike the existing state-of-the-art technologies for clean coal and only fixed amount of water, that can be repeatedly used by methods described in this invention. The additional cost of capture of these toxic gases with the new technology is insignificant compared with the huge cost with existing best technologies, as discussed in the beginning.

*An overview of current status of carbon dioxide capture and storage technologies—Edward S. Rubin, John E. Dawson, Howard J. Herzog, International Journal of Green House and Gas Control, vol. 40, P. 378-400. https://doi.org/10.1016/j.ijggc.2015.05.018

II. The Major Advantages of the New Technology Over the Existing Technologies in Capturing Industrial Carbon

• • a. Our technology is far more economical and cost saving compared to existing technologies of carbon capture and including those cryogenic capture technologies that have been attempted in the past [Ref. T1,T2,T3,T4]. Cryogenic capture technology in the past required 660 kWh of energy per ton of CO₂. With our technology, excluding the auxiliary power generation, it requires 197-198 kWh of energy per ton of captured liquefied CO₂, if flue gas is from coal power plant. With the auxiliary power, the technique requires only 62 kWh of energy per ton of liquid CO₂ or dry ice capture. For the flue gas from natural gas power plant, our technology requires 327 kWh of energy per ton of LCO₂ capture, if we exclude auxiliary power generated from the heat of the flue gas. The auxiliary power generated is sufficient enough to capture the entire CO₂ emissions from natural gas power plants, without putting any stress on energy output. Thus our technology is superior to that of the past cryogenic technology. Our technology is much energy efficient compared to the amines techniques of CO₂ separation from flue gases. The energy requirement in the amine technologies range from 3×10⁹ J (833 kWh) to 3.7×10⁹ J (1027 kWh) [Z1-Z4] per ton of CO₂ capture, which is much higher than that of our technology. With or without the auxiliary power generation method of our technology, the net energy stress is the minimal of all existing technologies of CO₂ capture. The overall cost of capture of CO₂ by amine-based technique stands currently at $52-77 per ton. Moreover, unlike existing technologies of CO₂ capture, our technologies capture all components of flue gas emissions including mercury, sulfur oxides, nitrogen oxides and carbon monoxide. With the existing technologies, capture of these components involve huge additional capital and operating costs as they require constant use of chemicals/reagents. Even with the current state of the art amine scrubbing of CO₂ there is continuous loss of amine which must be replenished, adding to the capture cost.
  • b. Our technology captures industrial carbon dioxide in the form of liquefied or frozen (dry ice) which is a very pure form of carbon dioxide unlike the impure carbon dioxide captured with existing technologies. The liquefied or dry ice form of CO₂ has tremendous industrial applications and can be used up faster than gaseous CO₂. These can also be easily stored in well-insulated container much longer than gaseous CO₂ which require high pressure vessel. It can be transported to far distance better than gaseous CO₂. Unlike the current technologies where captured CO₂ in gas form must be transported to empty coal or oil field for storage, the CO₂ captured by our technique can be very easily applied for industrial uses.
  • c. The cost of capture with our technology can be recovered by selling a small fraction of the captured LCO₂ or dry ice. The other captured products can also find good market.

We claim

• • 1. A very cost effective and energy efficient technology of capturing industrial emissions (mercury (Hg) and its oxides, sulfur dioxide (SO₂), sulfur trioxide (SO₃), nitrogen dioxide (NO₂), carbon dioxide (CO₂), nitrous oxide (N₂O), nitric oxide (NO), carbon monoxide (CO)) contained in the flue gas from coal and natural gas fired power plants (all older and newer versions), cement plants and industrial plants in general, each component separately from each other and in the form of industrially useful product that can be conveniently stored, and thus to prevent or reduce/mitigate global warming/climate change/environmental pollution/health effects arising due to such gaseous emissions from the said industries into atmosphere & environment and thus to ensure clean air/environment, using or requiring no chemical reagent and no external cryogen, but only a small fraction of electrical power from the output power of the plants or using the said needed electrical power from any other source and fixed amount of water that can be repeatedly used during the capture process, comprising the steps of:
  • a) Generation of auxiliary electrical power using the heat of the flue gas [in order to reduce the amount of power needed from the output of the power plants to run the engines of the various processes of the cryogenic capture technology] using a turbine that can use anhydrous ammonia contained in an ammonia super-heater, which is heated by the heat of the flue gas, the heat absorption of the said super heater being enhanced by coating on its surface a film of materials with high heat absorptivity and low emissivity and its placement in an insulated chamber containing ceramic filters to filter out the ashes & soot of the flue gas;
  • b) passing the flue gas through ceramic filters, fabric filter, ESP (Electrostatic precipitator), which capture partially the heat, the ashes, soot/floating particulates and partially the mercury and its oxides, with arrangement for removal of the ashes;
  • c) reheating the ammonia after the turbine work by passing through the fabric filter & ESP in reverse direction;
  • d) using successive compressions [after the ammonia power generation (claim 1a)] to specified pressures, successive cooling through use of specialized heat exchangers and successive adiabatic expansions of the said flue gas, throttling of liquefied CO₂ when necessary;
  • e) further cooling of the nitrogen (N₂) gas of the flue gas to a few (about 1 to 2) degrees above its boiling point (−196° C.) for using the said cold N₂ gas (by flowing it in reverse direction) to cool the flue gas at different steps, for individual capture (separation) of the components;
  • f) cooling in process 1d) being accomplished by (i) passing adiabatically compressed flue gas through heat exchangers containing special tubes immersed in fixed amount of water, for capture of components with boiling points above 0° C., the water being cooled by flow of said cold nitrogen gas through turns of tubes that surround the turns of tubes of the flue gas and radiative cooling arrangement, if the latter is needed;
  • g) by passing adiabatically compressed flue gas, for individual capture of its components with boiling points below 0° C., through heat exchangers containing (i) metal chips/or conducting pebbles on racks surrounding the turns of tubes carrying said cold nitrogen gas which in turn surrounds the turns of tubes carrying the said flue gas, all being embedded in the chambers of the said heat exchangers and (ii) helium gas that provides good heat conduction (exchange) between the flue gas tubes and the tubes carrying cold nitrogen gas and the pebbles/metal chips, which are cooled by the said cold nitrogen gas which has temperature just about 2 degree C. above its boiling point (−196° C.) produced through the third stage turbine expansion, following the step of capture of nitric oxide of the flue gas towards the end of a process cycle;
  • h) superior control of cooling the flue gas to desired temperatures as required for capture of individual components of the flue gas, each separately through methods of claim 1f) & 1g), compared to heat exchanger chamber where cold nitrogen gas directly surrounds the said turns of the flue gas tubes as the nitrogen gas directly enters through the inlet port and leaves through the outlet port of the chamber;
  • i) repeating the compression, cooling (as in (ii) of 1e) and expansion successively for 15 to 20 stages, or as necessary, depending on the initial flue gas temperature and concentration of the components;
  • j) fractionally liquefying or freezing each component of emissions at specific temperature and pressure using the processes of claims 1a) to 1i) for cooling the flue gas and using controlled amount of the said super cooled nitrogen gas in successive stages of compression, cooling and expansion;
  • k) using methods to control the temperatures of the chambers to specified temperatures by control of the very cold nitrogen gas obtained by method of claim 1e) and through use of specialized heat exchangers of claim 1f) & 1g), standard temperature controller and standard flow controller device;
  • l) using methods of special coating to prevent corrosion of flow tubes, compressors, etc. due to corrosive components of the flue gas and using flow tubes of special materials to ensure very good thermal conduction of heat between hot flue gas and the cold nitrogen gas carrying flow tubes which are all embedded in the said chambers of heat exchangers;
  • m) utilizing the work generated during turbine expansion (near the end of a cycle) of compressed N₂ for aiding compression of flue gases in successive previous stages employing the n-stage compressors and thus to increase energy efficiency of the whole capture process;
  • 2. A method of capturing and production of liquefied CO₂ and frozen CO₂ (dry ice), liquefied SO₂, liquefied SO₃, liquefied NO₂, liquefied N₂O, liquefied NO, liquefied CO and pure nitrogen gas, each separately, from the flue gas of coal or natural gas power plants/industrial plants in general, without use of any chemical/reagent, except fixed amount of water and a small amount of energy and with a single equipment, at operational cost far lower than that of any technology of industrial emission capture hitherto available and at costs far lower than that of corresponding industrial productions of the said components, each in fairly pure form that is industrially usable;
  • 3. An equipment for very cost effective and energy efficient capture of emission components from industrial flue gas, without using any chemical/reagent and using fixed amount of water that is repeatedly usable and for production of large amount of liquefied CO₂ and frozen dry ice, which are sources of very pure CO₂, comprising
    • a. chambers containing specially designed ceramic filters to remove fly ashes including oxides of mercury;
    • b. fabric filters and electrostatic separators to remove soot, smokes, any floating particles etc.;
    • c. ammonia super heater with ammonia turbine for auxiliary power generation using the heat of the flue gas with the surface of ammonia super heater chamber been coated with films of high heat absorptivity and low emissivity;
    • d. pump & heat exchanger for the ammonia after turbine expansion to capture some of the heat captured by the fabric filter & electro static separator from the flue gas, before the ammonia being fed to the ammonia super heater;
    • e. heat exchangers with collecting chambers for cooling and capturing components of flue gas (Hg, steam, SO₃, NO₂, acid vapors etc.) with boiling point above 0° C., with said heat exchangers containing water, which is cooled by passing cold nitrogen gas, and using flue-gas flow tubes made of special materials that can stand temperature ˜300° C. and with high heat conductivity and non-corrosive to the toxic components of the flue gas;
    • f. heat exchangers for cooling and capturing components (SO₂, CO₂, N₂O, NO, CO) of flue gas with boiling point below 0° C. to specific temperatures at different stages, the cooling being accomplished by passing very cold nitrogen gas (obtained at the end of a cycle of processing the flue gas) in reverse direction, through the turns of tubes that surround the turns of tubes carrying flue gas, all being embedded in the said heat exchanger;
    • g. the said heat exchangers (1f) containing conducting pebbles or metal chips arranged on racks surrounding the flue gas flow tubes and containing helium gas for superior heat conduction (for capture of components with boiling point below 0° C.) between the flue gas in the flue gas flow tubes and the much colder surrounding obtained by passing the said very cold nitrogen gas in reverse direction, through the turns of tubes that surround the turns of tubes carrying flue gas;
    • h. flue gas-flow tubes and cold nitrogen gas flow tubes being made of special materials that can tolerate temperatures up to 300° C. and low temperatures down to −194° C. and that have high thermal conductivity, the flue gas flow tube surfaces being painted black for superior heat radiation for faster cooling of flue gas;
    • i. special chambers for condensation of Hg, SO₃, NO₂ gases and collection of the corresponding liquids;
    • j. compressors to compress flue gas at specific temperatures at different stages to specific pressures and temperatures;
    • k. special chambers for condensation of CO₂ of flue gas and for rapid collections of liquefied CO₂ as needed;
    • l. flash chambers for throttling of liquefied CO₂ and arrangement of dry ice by passing very cold nitrogen gas & rapid collection of dry ice CO₂;
    • m. turbine expanders for expansion of flue gas at specific pressures and temperatures;
    • n. special chambers for rapid condensation & collection of liquefied N₂O, NO and CO;
    • o. split lines to inject cold nitrogen gas at different stages of capture of flue gas components, this being accomplished by reverse flow of cold nitrogen gas obtained after third turbine expansion at the end of the process cycle;
    • p. cold nitrogen feedback lines and means of using very cold nitrogen gas for cooling the incoming flue gas through appropriate heat exchangers;
    • q. methods of good thermal insulation for the split and feedback lines of super cold nitrogen gas;
    • r. standard temperature controller and pressure controller for nitrogen gas flow;
  • 4. Methods of claims 1-2 through the use of equipment of claim 3 further comprising steps to extract the heat of the flue gas and convert it to auxiliary power, using (i) anhydrous ammonia super heater with coating of films of high heat absorptivity and low emissivity material on its external surface, the super heater being situated in the second chamber employed for capture and removal of ash/mercury oxides from flue gas, (ii) raising the pressure of ammonia to around 200 bars and temperature 200° C. (for efficiency around 20%) when the flue gas temperature is around 500° C. or to around 100 bars and temperature 100° C. (for efficiency around 10%) when the flue gas temperature is dropped to around 150° C. due to use of air pre-heating (APH); (iii) using turbine for the auxiliary power generation (iv) heat exchanger processes that also condense partially, the mercury, the steam and the SO₃ (sulfur trioxide) of the flue gas in specialized chamber [the condensate being drained out or collected, as needed] (iv) pump to compress the said turbine-expanded ammonia and to pass the compressed ammonia through a condenser to cool (using part of cold nitrogen gas diverted in reverse direction after capture of SO₂); (v) passing the condensed ammonia through the said heat exchanger chamber and the chamber of fabric filter/electrostatic precipitator to capture part of the flue gas heat trapped there and finally back to the ammonia super heater to complete the cycle, so that the auxiliary power is generated in cycles to reduce the energy cost and to increase the energy efficiency of the capture processes;
  • 5. The methods of claims 1 & 2 through the use of equipment of claim 3 further include steps after reduction of flue gas temperature through method of claim 4, to condense partially mercury vapor, steam, SO₃ (sulfur trioxide) including acid vapors of the flue gas, if any, in specialized chambers embedded in the said heat exchanger following capture of ashes, mercury oxides etc;
  • 6. The methods of claims 1 & 2 further comprising step to capture partial steam (H₂O), sulfur trioxide and mercury of the flue gas by (i) further cooling to temperature less than 50° C. the flue gas remaining after method of claim 5 by passing the said flue gas through turns of tubes immersed in water, which is cooled by passing said cold nitrogen gas through separate turns of tubes immersed in the said water; (ii) adiabatic compression to 2 to 3 bars of the said flue gas from method of claim 6(i) and further cooling of the compressed flue gas by passing through special chamber containing turns of flue gas flow tubes immersed in water, with water being cooled and maintained at 35±2° C. by controlled flow of the said cold nitrogen gas (method of 1e) through separate turns of tubes immersed in the said water, the said flow being in a reverse direction looking from the step of the final capture of steam (H₂O), sulfur trioxide and mercury, as the said components (H₂O, SO₃ and Hg) condenses to respective liquids which are collected;
  • 7. The methods of claims 1 & 2 and the use of equipment of claim 3 further comprise of (i) steps to adiabatically compress the said flue gas after application of method of claim 6 to pressure of 4.5 followed by (ii) cooling of the said compressed flue gas in specialized heat exchanger containing water cooled and maintained to required temperature (25±2° C.) by passing controlled flow of said cold nitrogen gas through turns of tubes immersed in the water of the said heat exchanger, the flow being in reverse direction (after the NO₂ collection chamber seen from the right in ways similar to that of methods of claims 6), for partial capture of steam (H₂O), final capture of sulfur trioxide and final capture of mercury;
  • 8. The methods of claims 1 & 2 and the use of equipment 3 wherein capture of NO₂ in the said flue gas [remaining after applications of methods of claim 7] in the form of liquid is accomplished by (i) adiabatic compression of the said flue gas to 6 to 7 bars pressure and (ii) by cooling to temperature ˜18 to 19° C. [by passing the said flue gas through special chamber, which is cooled by controlled flow of the said cold nitrogen gas using methods of claim 6] and (iii) collection of the liquefied NO₂;
  • 9. The methods of claims 1 and 2 through the use of equipment of claim 3 further comprising steps of (i) adiabatic (isentropic) compression of flue gas remaining after capture of nitrogen dioxide (NO₂) [after step of claim 8], to a desired pressure (6 to 7 bars), (ii) cooling of the compressed said flue gas first to temperature 18±2° C. for condensation of NO₂, acid vapors like HNO₃, H₂SO₄ and part of steam in the flue gas and (iii) then cooling the said flue gas to temperature around 8° C.±2 for complete condensation of any remaining steam, NO₂, the said acid vapors of the flue gas to prevent chocking of the compressors compressing the said flue gas below 0° C. in later stages, (iv) further compression of the flue gas remaining after complete condensation of steam to desired pressure (8 to 9 bars) (iv) passing the said adiabatically (isentropic) compressed gas through special heat exchangers where inside temperature is cooled to ˜−14° C. to −16° C., for complete capture SO₂ of the flue gas in the form of liquid SO₂, the required cooling being accomplished by passing in reverse direction the said cold N₂ gas coming from the point of capture of liquid CO₂ through turns of tubes that surround the turns of tubes carrying the flue gas in separate heat exchanger that does not contain water but conducting pebbles or metal chips on perforated racks that surround the said tubes and helium gas around 2 bars to improve heat exchange between the flue gas and the cold nitrogen gas [noting that the flue gas flows from left to right (forward direction) while very cold N₂ gas flows from right to left (reverse direction)] and (v) rapid collection of liquefied SO₂.
  • 10. The methods of claims 1 & 2 and the use of equipment of claim 3 comprising further steps to liquefy CO₂ (carbon dioxide) contained in the said flue gas by adiabatically (isentropic) compressing the remaining flue gas (after capture of SO₂ in liquefied form in methods of claim 9) to a pressure of 26.47 bars, the said compression being achieved in successive stages accompanied by necessary cooling to prevent the temperature rise due to compressions and further cooling the compressed gas at 26.47 bars to a temperature of −10° C. or slightly below by passing the said compressed flue gas through specialized tubes contained in a special heat exchanger with chambers made for rapid condensation of CO₂, collection of liquefied CO₂, and rapid separation of flue gas from condensed CO₂ and for further processing of the flue gas in later stages, the chambers being cooled and maintained to required temperature (−16 to −20° C.) to condense the compressed CO₂ of the flue gas to liquefied CO₂ (from the said pressurized flue gas at 26.47 bars) by passing the said cold nitrogen gas in reverse directions from the point of capture of nitrous oxide (N₂O) through the said heat exchanger, similar to that in method of claim 9;
  • 11. The methods of claims 1 & 2 and 10 further comprising steps for (i) separation of the flue gas from liquefied CO₂ and speedy collection of the said liquefied CO₂ that is steadily formed out of the said flowing flue gas; (ii) for rapid production of dry ice, using the whole or part of the collected liquefied CO₂ (temp ˜−10° C.), by throttling the latter adiabatically into an enclosed (air tight) and well-insulated chamber (called flash chamber here) inside of which being cooled to about 10 C below −78° C. (the sublimation point of dry ice), by passing said very cold nitrogen gas coming in reverse direction from the stage of collection of liquid carbon monoxide from the flue gas and thus (iii) freezing the dry CO₂ vapor (produced after the said throttling of liquefied CO₂ from method (ii) of claim 11) into dry ice along with freezing further the dry ice formed at the first stage of throttling of said liquefied CO₂ by passing said cold N₂ vapor into the flash chamber and (iv) including methods of continuous separation and collection of the dry ice thus formed in the specially built insulated flash chamber that uses internal heat reflection and good external heat insulation;
  • 12. The methods of claims 1 & 2 through the use of equipment of claim 3 wherein capture of N₂O (nitrous oxide) from the remaining part of the said flue gas (after separation of CO₂) is accomplished by condensing nitrous oxide (N₂O) of the said flue gas into liquid N₂O by: (i) first cooling the compressed flue gas (at 26.4 bars and temperature around −10° C.) coming out after liquefaction of CO₂ contained in the said flue gas in methods of claim 11, to a temperature around −50° C. to −60° C., using said heat exchanger cooled by flow of part of the said very cold nitrogen similar to that of method claim 10 and then (ii) by first stage isentropic expansion of the compressed and cold flue gas to about 13 to 15 bars, depending on the initial temperature after the said cooling, by a first turbine expander into a heat exchanger chamber cooled by the reverse flow of said cold nitrogen gas (coming after capture of nitric oxide by method of claim 13) to a temperature about 6 to 10° C. below the boiling point (−88.5° C.) of nitrous oxide (N₂O), (iii) by collecting the liquefied N₂O into an insulated chamber attached to the heat exchanger, inner walls of which have reflecting coatings and the outer walls well-insulated;
  • 13. The methods of claims 1 to 2 through the use of equipment of claim 3 wherein capture of nitric oxide (NO) from the remaining part of the said flue gas (after capture of CO₂ and N₂O by methods of claims 10-12) is accomplished by further cooling to −106 to −110 ° C., of the said compressed flue gas remaining after separation of CO₂ in methods of claims 11 & 12 and then N₂O in methods of claim 12, followed by second stage isentropic expansion of the compressed flue gas to about 4.87 bars to condense the nitric oxide (NO) gas in the said flue gas to liquefied NO (b.pt. −152° C. at atmospheric pressure) at −152° C. or slightly above (as the pressure is higher than atmospheric pressure) and capture of the liquefied NO into an well-insulated container inside of which contains reflecting walls and cooled to −156 to −160° C. by reverse flow of super cold nitrogen gas produced after the capture of carbon monoxide (CO) at the third stage turbine expansion in method of claim 14;
  • 14. The methods of claims 1 to 2 with the use of equipment of claim 3 where in methods of capturing carbon monoxide (b.pt. −191.5° C. at atmospheric pressure) from the remaining part of the said flue gas (after capturing NO in liquefied form using method of claim 13) by further isentropic expansion (third stage) of the said compressed flue gas (at temperature around −152 ° C.) at pressure about 4.87 bars to atmospheric pressure in order to further lower the temperature of the flue gas to about 1 to 2 degrees above the boiling point of liquid nitrogen (−196° C.) and rapid collection of the said carbon monoxide thus condensed in specialized insulated chamber, so as to accomplish separation of cold nitrogen gas from CO;
  • 15. The methods of claims 1-2, 7-14 comprise of using specialized heat exchanger chambers for capture of components with boiling point above 0° C. and for capture of components with boiling point below 0° C., with means of protection of said heat exchanger tubes with specialized materials for prevention against corrosion due to toxic components of flue gas through use of any of the specialized materials of good thermal conductivity, such as, but not limited to, vespel, torlon, ryton, noryl or any other such suitable material that also ensures tolerance of high initial temperature of the flue gas and further ensures high thermal conduction between the hot said flue gas passing through the turns of said tubes and the surrounding cold temperatures of the said heat exchangers, as required, for rapid cooling of the flue gas in different stages in this invention, high heat radiation from the flue gas tubes to the cold surroundings in the chambers, the said cold temperature being produced by circulation of very cold nitrogen gas obtained at the end of the cycle by methods of claim 14, heat exchanges between the flue gas tubes and the cold nitrogen gas flow tubes being further enhanced for temperatures below 0° C. through use of helium gas and metal chips or conducting pebbles on perforated racks that surround the turns of separate tubes carrying flue gas and the cold nitrogen gas;
  • 16. The methods of claims 1 & 2 and 14 through the use of equipment of claim 3 comprise of cooling the nitrogen gas contained in the flue gas to temperature about 1 to 2 degrees above the boiling point of liquid nitrogen at the third turbine expansion of compressed flue gas and use of this super cooled pure nitrogen gas through pumps in reverse directions and splitting the cold nitrogen flow lines twice, firstly at (i) at the point of feeding cold nitrogen gas to heat exchangers (a) for NO liquefaction (b) for production of dry ice from liquefied CO₂, secondly at (c) at the point of feeding the heat exchanger for NO₂ liquefaction and (d) at the point of feeding the condenser of ammonia power turbine, to perform required cooling at various stages through the use of said heat exchangers for capture of the individual components of pollutants, each component separately from the incoming flue gas stream, without use of any chemical/reagent, the said flue gas being from power plants and industries, in general;
  • 17. The methods of claims 1,2,3,5-11 require use of only fixed amount of water and no chemical/reagent for capture of all or any desired fraction CO₂ from the industrial flue gas and production of large amount of liquefied CO₂ (source of highly pure CO₂) and frozen dry ice (solid CO₂ at −78° C. or below, which is also source of very pure CO₂) from the CO₂ gas contained in the flue gas exiting from coal and natural gas power plants and industries in general, the said fixed amount of water being cooled in specialized chambers by cold nitrogen gas obtained at the end of the cycle.
  • 18. The technologies of claims 1,2, 4 to 15 provide means of producing, after capturing CO₂ of the flue gas, liquefied CO₂ and dry ice (frozen CO₂) in entirety or in amount as needed, together with means of capturing each of the associated components such as, Hg, SO₃, NO₂, SO₂, N₂O, NO, CO, contained in the flue gas emissions from coal and natural gas fired power plants and industries in general, each of the components of SO₂, CO₂, N₂O, NO, CO being captured separately without use of any chemical/reagent except fixed amount of water, at the estimated total energy cost (i) ($7.41 per ton of liquefied/frozen CO₂) from the flue gas from coal fired power plants, when auxiliary power is generated by ammonia turbine and $23.68 per ton of liquefied or frozen CO₂, when auxiliary power is not generated, assuming lkWh of electricity costs $0.12), (ii) at no energy cost to the power plant, to capture entire emitted CO₂ and other associated products if power is generated by using natural gas when auxiliary power is generated as described in methods of claim 4 and used for the said capture; and (iii) at $13.18 per ton of the said cost that includes cost of capture (excluding maintenance and labor) of all the said toxic components when auxiliary power is not generated as described in this invention or is not used for the said capture; (iv) the said capture costs being lower than the lowest cost of any technique hitherto available;
  • 19. The methods of claims 1 & 2, 6 to 15, comprise of utilizing the work generated during turbine expansion (at the final three stages of the cycle) of compressed and cooled flue gas, for partially aiding compression of the flue gas in successive previous stages employing the n-stage compressors and thus to increase energy efficiency of the whole capture process and to reduce the energy cost of all the processes involved.
  • 20. The methods of claim 1, 2, 3-15 wherein most cost effective and energy efficient capture of each component of pollutants contained in the emissions from power plants (using coal and natural gas) and from industrial plants in general is accomplished without use of any chemical/reagent and using only fixed amount of water, depending on flue gas flow rate, its temperature, after auxiliary power production through ammonia turbine, such that the captured components SO₂ (liquid), CO₂(liquid or solid), N₂O (liquid), NO(liquid), CO(liquid), N₂(gas), each being highly pure (in the captured forms) can be stored easily and find large industrial applications in the near and distant future, where the entire capture is made possible at a cost lower than the lowest cost of any technique hither to available.

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Carbon Dioxide Separation from Flue Gases: A Technological Review Emphasizing Reduction in Greenhouse Gas Emissions

Mohammad Songolzadeh, Mansooreh Soleimani, Maryam Takht Ravanchi, and Reza Songolzadeh

The Scientific World Journal, Volume 2014 (2014), Article ID 828131, 34 pages http://dx.doi.org/10.1155/2014/828131

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Claims

1. A very cost effective and energy efficient technology of capturing industrial emissions (mercury (Hg) and its oxides, sulfur dioxide (SO2), sulfur trioxide (SO3), nitrogen dioxide (NO2), carbon dioxide (CO2), nitrous oxide (N2O), nitric oxide (NO), carbon monoxide (CO)) contained in the flue gas from coal and natural gas fired power plants (all older and newer versions), cement plants and industrial plants in general, each component separately from each other and in the form of industrially useful product that can be conveniently stored, and thus to prevent or reduce/mitigate global warming/climate change/environmental pollution/health effects arising due to such gaseous emissions from the said industries into atmosphere & environment and thus to ensure clean air/environment, using or requiring no chemical reagent and no external cryogen, but only a small fraction of electrical power from the output power of the plants or using the said needed electrical power from any other source and fixed amount of water that can be repeatedly used during the capture process, comprising the steps of : a) Generation of auxiliary electrical power using the heat of the flue gas using a turbine that can use anhydrous ammonia contained in an ammonia super-heater, which is heated by the heat of the flue gas, the heat absorption of the said super heater being enhanced by coating on its surface a film of materials with high heat absorptivity and low emissivity and its placement in an insulated chamber containing ceramic filters to filter out the ashes & soot of the flue gas;b) passing the flue gas through ceramic filters, fabric filter, ESP (Electrostatic precipitator), which capture partially the heat, the ashes, soot/floating particulates and partially the mercury and its oxides, with arrangement for removal of the ashes;c) reheating the ammonia after the turbine work by passing through the fabric filter & ESP in reverse direction;d) using successive compressions to specified pressures, successive cooling through use of specialized heat exchangers and successive adiabatic expansions of the said flue gas, throttling of liquefied CO2 when necessary;e) further cooling of the nitrogen (N2) gas of the flue gas to a few (about 1 to 2) degrees above its boiling point (−196° C.) for using the said cold N2 gas (by flowing it in reverse direction) to cool the flue gas at different steps, for individual capture (separation) of the components;f) cooling in process 1d) being accomplished by (i) passing adiabatically compressed flue gas through heat exchangers containing special tubes immersed in fixed amount of water, for capture of components with boiling points above 0° C., the water being cooled by flow of said cold nitrogen gas through turns of tubes that surround the turns of tubes of the flue gas and radiative cooling arrangement, if the latter is needed;g) by passing adiabatically compressed flue gas, for individual capture of its components with boiling points below 0° C., through heat exchangers containing (i) metal chips/or conducting pebbles on racks surrounding the turns of tubes carrying said cold nitrogen gas which in turn surrounds the turns of tubes carrying the said flue gas, all being embedded in the chambers of the said heat exchangers and (ii) helium gas that provides good heat conduction (exchange) between the flue gas tubes and the tubes carrying cold nitrogen gas and the pebbles/metal chips, which are cooled by the said cold nitrogen gas which has temperature just about 2 degree C. above its boiling point (−196° C.) produced through the third stage turbine expansion, following the step of capture of nitric oxide of the flue gas towards the end of a process cycle;h) superior control of cooling the flue gas to desired temperatures as required for capture of individual components of the flue gas, each separately through methods of claim 1f) & 1g), compared to heat exchanger chamber where cold nitrogen gas directly surrounds the said turns of the flue gas tubes as the nitrogen gas directly enters through the inlet port and leaves through the outlet port of the chamber;i) repeating the compression, cooling (as in (ii) of 1e) and expansion successively for 15 to 20 stages, or as necessary, depending on the initial flue gas temperature and concentration of the components;j) fractionally liquefying or freezing each component of emissions at specific temperature and pressure using the processes of claims 1a) to 1i) for cooling the flue gas and using controlled amount of the said super cooled nitrogen gas in successive stages of compression, cooling and expansion;k) using methods to control the temperatures of the chambers to specified temperatures by control of the very cold nitrogen gas obtained by method of claim 1e) and through use of specialized heat exchangers of claim 1f) & 1g), standard temperature controller and standard flow controller device;l) using methods of special coating to prevent corrosion of flow tubes, compressors, etc. due to corrosive components of the flue gas and using flow tubes of special materials to ensure very good thermal conduction of heat between hot flue gas and the cold nitrogen gas carrying flow tubes which are all embedded in the said chambers of heat exchangers;m) utilizing the work generated during turbine expansion (near the end of a cycle) of compressed N2 for aiding compression of flue gases in successive previous stages employing the n-stage compressors and thus to increase energy efficiency of the whole capture process;

2. A method of capturing and production of liquefied CO2 and frozen CO2 (dry ice), liquefied SO2, liquefied SO3, liquefied NO2, liquefied N2O, liquefied NO, liquefied CO and pure nitrogen gas, each separately, from the flue gas of coal or natural gas power plants/industrial plants in general, without use of any chemical/reagent, except fixed amount of water and a small amount of energy and with a single equipment, at operational cost far lower than that of any technology of industrial emission capture hitherto available and at costs far lower than that of corresponding industrial productions of the said components, each in fairly pure form that is industrially usable;

3. An equipment for very cost effective and energy efficient capture of emission components from industrial flue gas, without using any chemical/reagent and using fixed amount of water that is repeatedly usable and for production of large amount of liquefied CO2 and frozen dry ice, which are sources of very pure CO2, comprising a. chambers containing specially designed ceramic filters to remove fly ashes including oxides of mercury;b. fabric filters and electrostatic separators to remove soot, smokes, any floating particles etc.;c. ammonia super heater with ammonia turbine for auxiliary power generation using the heat of the flue gas with the surface of ammonia super heater chamber been coated with films of high heat absorptivity and low emissivity;d. pump & heat exchanger for the ammonia after turbine expansion to capture some of the heat captured by the fabric filter & electro static separator from the flue gas, before the ammonia being fed to the ammonia super heater;e. heat exchangers with collecting chambers for cooling and capturing components of flue gas (Hg, steam, SO3, NO2, acid vapors etc.) with boiling point above 0° C., with said heat exchangers containing water, which is cooled by passing cold nitrogen gas, and using flue-gas flow tubes made of special materials that can stand temperature ˜300° C. and with high heat conductivity and non-corrosive to the toxic components of the flue gas;f. heat exchangers for cooling and capturing components (SO2, CO2, N2O, NO, CO) of flue gas with boiling point below 0° C. to specific temperatures at different stages, the cooling being accomplished by passing very cold nitrogen gas (obtained at the end of a cycle of processing the flue gas) in reverse direction, through the turns of tubes that surround the turns of tubes carrying flue gas, all being embedded in the said heat exchanger;g. the said heat exchangers (1f) containing conducting pebbles or metal chips arranged on racks surrounding the flue gas flow tubes and containing helium gas for superior heat conduction (for capture of components with boiling point below 0° C.) between the flue gas in the flue gas flow tubes and the much colder surrounding obtained by passing the said very cold nitrogen gas in reverse direction, through the turns of tubes that surround the turns of tubes carrying flue gas;h. flue gas-flow tubes and cold nitrogen gas flow tubes being made of special materials that can tolerate temperatures up to 300° C. and low temperatures down to −194° C. and that have high thermal conductivity, the flue gas flow tube surfaces being painted black for superior heat radiation for faster cooling of flue gas;i. special chambers for condensation of Hg, SO3, NO2 gases and collection of the corresponding liquids;j. compressors to compress flue gas at specific temperatures at different stages to specific pressures and temperatures;k. special chambers for condensation of CO2 of flue gas and for rapid collections of liquefied CO2 as needed;l. flash chambers for throttling of liquefied CO2 and arrangement of dry ice by passing very cold nitrogen gas & rapid collection of dry ice CO2;m. turbine expanders for expansion of flue gas at specific pressures and temperatures;n. special chambers for rapid condensation & collection of liquefied N2O, NO and CO;o. split lines to inject cold nitrogen gas at different stages of capture of flue gas components, this being accomplished by reverse flow of cold nitrogen gas obtained after third turbine expansion at the end of the process cycle;p. cold nitrogen feedback lines and means of using very cold nitrogen gas for cooling the incoming flue gas through appropriate heat exchangers;q. methods of good thermal insulation for the split and feedback lines of super cold nitrogen gas;r. standard temperature controller and pressure controller for nitrogen gas flow;

4. Methods of claims 1-2 through the use of equipment of claim 3 further comprising steps to extract the heat of the flue gas and convert it to auxiliary power, using (i) anhydrous ammonia super heater with coating of films of high heat absorptivity and low emissivity material on its external surface, the super heater being situated in the second chamber employed for capture and removal of ash/mercury oxides from flue gas, (ii) raising the pressure of ammonia to around 200 bars and temperature 200° C. (for efficiency around 20%) when the flue gas temperature is around 500° C. or to around 100 bars and temperature 100° C. (for efficiency around 10%) when the flue gas temperature is dropped to around 150° C. due to use of air pre-heating (APH); (iii) using turbine for the auxiliary power generation (iv) heat exchanger processes that also condense partially, the mercury, the steam and the SO3 (sulfur trioxide) of the flue gas in specialized chamber (iv) pump to compress the said turbine-expanded ammonia and to pass the compressed ammonia through a condenser to cool (using part of cold nitrogen gas diverted in reverse direction after capture of SO2); (v) passing the condensed ammonia through the said heat exchanger chamber and the chamber of fabric filter/electrostatic precipitator to capture part of the flue gas heat trapped there and finally back to the ammonia super heater to complete the cycle, so that the auxiliary power is generated in cycles to reduce the energy cost and to increase the energy efficiency of the capture processes;

5. The methods of claims 1 & 2 through the use of equipment of claim 3 further include steps after reduction of flue gas temperature through method of claim 4, to condense partially mercury vapor, steam, SO3 (sulfur trioxide) including acid vapors of the flue gas, if any, in specialized chambers embedded in the said heat exchanger following capture of ashes, mercury oxides etc;

6. The methods of claims 1 & 2 further comprising step to capture partial steam (H2O), sulfur trioxide and mercury of the flue gas by (i) further cooling to temperature less than 50° C. the flue gas remaining after method of claim 5 by passing the said flue gas through turns of tubes immersed in water, which is cooled by passing said cold nitrogen gas through separate turns of tubes immersed in the said water; (ii) adiabatic compression to 2 to 3 bars of the said flue gas from method of claim 6(i) and further cooling of the compressed flue gas by passing through special chamber containing turns of flue gas flow tubes immersed in water, with water being cooled and maintained at 35±2° C. by controlled flow of the said cold nitrogen gas (method of 1e) through separate turns of tubes immersed in the said water, the said flow being in a reverse direction looking from the step of the final capture of steam (H2O), sulfur trioxide and mercury, as the said components (H2O, SO3 and Hg) condenses to respective liquids which are collected;

7. The methods of claims 1 & 2 and the use of equipment of claim 3 further comprise of (i) steps to adiabatically compress the said flue gas after application of method of claim 6 to pressure of 4.5 followed by (ii) cooling of the said compressed flue gas in specialized heat exchanger containing water cooled and maintained to required temperature (25±2° C.) by passing controlled flow of said cold nitrogen gas through turns of tubes immersed in the water of the said heat exchanger, the flow being in reverse direction (after the NO2 collection chamber seen from the right in ways similar to that of methods of claims 6), for partial capture of steam (H2O), final capture of sulfur trioxide and final capture of mercury;

8. The methods of claims 1 & 2 and the use of equipment 3 wherein capture of NO2 in the said flue gas in the form of liquid is accomplished by (i) adiabatic compression of the said flue gas to 6 to 7 bars pressure and (ii) by cooling to temperature ˜18 to 19° C. and (iii) collection of the liquefied NO2;

9. The methods of claims 1 and 2 through the use of equipment of claim 3 further comprising steps of (i) adiabatic(isentropic) compression of flue gas remaining after capture of nitrogen dioxide (NO2), to a desired pressure (6 to 7 bars), (ii) cooling of the compressed said flue gas first to temperature 18±2° C. for condensation of NO2, acid vapors like HNO3, H2SO4 and part of steam in the flue gas and (iii) then cooling the said flue gas to temperature around 8° C.±2 for complete condensation of any remaining steam, NO2, the said acid vapors of the flue gas to prevent chocking of the compressors compressing the said flue gas below 0° C. in later stages, (iv) further compression of the flue gas remaining after complete condensation of steam to desired pressure (8 to 9 bars) (iv) passing the said adiabatically (isentropic) compressed gas through special heat exchangers where inside temperature is cooled to ˜−14° C. to −16° C., for complete capture SO2 of the flue gas in the form of liquid SO2, the required cooling being accomplished by passing in reverse direction the said cold N2 gas coming from the point of capture of liquid CO2 through turns of tubes that surround the turns of tubes carrying the flue gas in separate heat exchanger that does not contain water but conducting pebbles or metal chips on perforated racks that surround the said tubes and helium gas around 2 bars to improve heat exchange between the flue gas and the cold nitrogen gas and (v) rapid collection of liquefied SO2.

10. The methods of claims 1 & 2 and the use of equipment of claim 3 comprising further steps to liquefy CO2 (carbon dioxide) contained in the said flue gas by adiabatically (isentropic) compressing the remaining flue gas (after capture of SO2 in liquefied form in methods of claim 9) to a pressure of 26.47 bars, the said compression being achieved in successive stages accompanied by necessary cooling to prevent the temperature rise due to compressions and further cooling the compressed gas at 26.47 bars to a temperature of −10° C. or slightly below by passing the said compressed flue gas through specialized tubes contained in a special heat exchanger with chambers made for rapid condensation of CO2, collection of liquefied CO2, and rapid separation of flue gas from condensed CO2 and for further processing of the flue gas in later stages, the chambers being cooled and maintained to required temperature (−16 to −20° C.) to condense the compressed CO2 of the flue gas to liquefied CO2 (from the said pressurized flue gas at 26.47 bars) by passing the said cold nitrogen gas in reverse directions from the point of capture of nitrous oxide (N2O) through the said heat exchanger, similar to that in method of claim 9;

11. The methods of claims 1 & 2 and 10 further comprising steps for (i) separation of the flue gas from liquefied CO2 and speedy collection of the said liquefied CO2 that is steadily formed out of the said flowing flue gas; (ii) for rapid production of dry ice, using the whole or part of the collected liquefied CO2 (temp ˜−10° C.), by throttling the latter adiabatically into an enclosed (air tight) and well-insulated chamber (called flash chamber here) inside of which being cooled to about 10 C below −78 ° C. (the sublimation point of dry ice), by passing said very cold nitrogen gas coming in reverse direction from the stage of collection of liquid carbon monoxide from the flue gas and thus (iii) freezing the dry CO2 vapor (produced after the said throttling of liquefied CO2 from method (ii) of claim 11) into dry ice along with freezing further the dry ice formed at the first stage of throttling of said liquefied CO2 by passing said cold N2 vapor into the flash chamber and (iv) including methods of continuous separation and collection of the dry ice thus formed in the specially built insulated flash chamber that uses internal heat reflection and good external heat insulation;

12. The methods of claims 1 & 2 through the use of equipment of claim 3 wherein capture of N2O (nitrous oxide) from the remaining part of the said flue gas (after separation of CO2) is accomplished by condensing nitrous oxide (N2O) of the said flue gas into liquid N2O by: (i) first cooling the compressed flue gas (at 26.4 bars and temperature around −10° C.) coming out after liquefaction of CO2 contained in the said flue gas in methods of claim 11, to a temperature around −50° C. to −60° C., using said heat exchanger cooled by flow of part of the said very cold nitrogen similar to that of method claim 10 and then (ii) by first stage isentropic expansion of the compressed and cold flue gas to about 13 to 15 bars, depending on the initial temperature after the said cooling, by a first turbine expander into a heat exchanger chamber cooled by the reverse flow of said cold nitrogen gas (coming after capture of nitric oxide by method of claim 13) to a temperature about 6 to 10° C. below the boiling point (−88.5° C.) of nitrous oxide (N2O), (iii) by collecting the liquefied N2O into an insulated chamber attached to the heat exchanger, inner walls of which have reflecting coatings and the outer walls well-insulated;

13. The methods of claims 1 to 2 through the use of equipment of claim 3 wherein capture of nitric oxide (NO) from the remaining part of the said flue gas (after capture of CO2 and N2O by methods of claims 10-12) is accomplished by further cooling to −106 to −110 ° C., of the said compressed flue gas remaining after separation of CO2 in methods of claims 11 & 12 and then N2O in methods of claim 12, followed by second stage isentropic expansion of the compressed flue gas to about 4.87 bars to condense the nitric oxide (NO) gas in the said flue gas to liquefied NO (b.pt. −152° C. at atmospheric pressure) at −152° C. or slightly above (as the pressure is higher than atmospheric pressure) and capture of the liquefied NO into an well-insulated container inside of which contains reflecting walls and cooled to −156 to −160° C. by reverse flow of super cold nitrogen gas produced after the capture of carbon monoxide (CO) at the third stage turbine expansion in method of claim 14;

14. The methods of claims 1 to 2 with the use of equipment of claim 3 where in methods of capturing carbon monoxide (b.pt. −191.5° C. at atmospheric pressure) from the remaining part of the said flue gas (after capturing NO in liquefied form using method of claim 13) by further isentropic expansion (third stage) of the said compressed flue gas (at temperature around −152° C.) at pressure about 4.87 bars to atmospheric pressure in order to further lower the temperature of the flue gas to about 1 to 2 degrees above the boiling point of liquid nitrogen (−196° C.) and rapid collection of the said carbon monoxide thus condensed in specialized insulated chamber, so as to accomplish separation of cold nitrogen gas from CO;

15. The methods of claims 1-2, 7-14 comprise of using specialized heat exchanger chambers for capture of components with boiling point above 0° C. and for capture of components with boiling point below 0° C., with means of protection of said heat exchanger tubes with specialized materials for prevention against corrosion due to toxic components of flue gas through use of any of the specialized materials of good thermal conductivity, such as, but not limited to, vespel, torlon, ryton, noryl or any other such suitable material that also ensures tolerance of high initial temperature of the flue gas and further ensures high thermal conduction between the hot said flue gas passing through the turns of said tubes and the surrounding cold temperatures of the said heat exchangers, as required, for rapid cooling of the flue gas in different stages in this invention, high heat radiation from the flue gas tubes to the cold surroundings in the chambers, the said cold temperature being produced by circulation of very cold nitrogen gas obtained at the end of the cycle by methods of claim 14, heat exchanges between the flue gas tubes and the cold nitrogen gas flow tubes being further enhanced for temperatures below 0° C. through use of helium gas and metal chips or conducting pebbles on perforated racks that surround the turns of separate tubes carrying flue gas and the cold nitrogen gas;

16. The methods of claims 1 & 2 and 14 through the use of equipment of claim 3 comprise of cooling the nitrogen gas contained in the flue gas to temperature about 1 to 2 degrees above the boiling point of liquid nitrogen at the third turbine expansion of compressed flue gas and use of this super cooled pure nitrogen gas through pumps in reverse directions and splitting the cold nitrogen flow lines twice, firstly at (i) at the point of feeding cold nitrogen gas to heat exchangers (a) for NO liquefaction (b) for production of dry ice from liquefied CO2, secondly at (c) at the point of feeding the heat exchanger for NO2 liquefaction and (d) at the point of feeding the condenser of ammonia power turbine, to perform required cooling at various stages through the use of said heat exchangers for capture of the individual components of pollutants, each component separately from the incoming flue gas stream, without use of any chemical/reagent, the said flue gas being from power plants and industries, in general;

17. The methods of claims 1,2,3,5-11 require use of only fixed amount of water and no chemical/reagent for capture of all or any desired fraction CO2 from the industrial flue gas and production of large amount of liquefied CO2 (source of highly pure CO2) and frozen dry ice (solid CO2 at −78° C. or below, which is also source of very pure CO2) from the CO2 gas contained in the flue gas exiting from coal and natural gas power plants and industries in general, the said fixed amount of water being cooled in specialized chambers by cold nitrogen gas obtained at the end of the cycle.

18. The technologies of claims 1,2, 4 to 15 provide means of producing, after capturing CO2 of the flue gas, liquefied CO2 and dry ice (frozen CO2) in entirety or in amount as needed, together with means of capturing each of the associated components such as, Hg, SO3, NO2, SO2, N2O, NO, CO, contained in the flue gas emissions from coal and natural gas fired power plants and industries in general, each of the components of SO2, CO2, N2O, NO, CO being captured separately without use of any chemical/reagent except fixed amount of water, at the estimated total energy cost (i) ($7.41 per ton of liquefied/frozen CO2) from the flue gas from coal fired power plants, when auxiliary power is generated by ammonia turbine and $23.68 per ton of liquefied or frozen CO2, when auxiliary power is not generated, assuming lkWh of electricity costs $0.12), (ii) at no energy cost to the power plant, to capture entire emitted CO2 and other associated products if power is generated by using natural gas when auxiliary power is generated as described in methods of claim 4 and used for the said capture; and (iii) at $13.18 per ton of the said cost that includes cost of capture (excluding maintenance and labor) of all the said toxic components when auxiliary power is not generated as described in this invention or is not used for the said capture; (iv) the said capture costs being lower than the lowest cost of any technique hitherto available;

19. The methods of claims 1 & 2, 6 to 15, comprise of utilizing the work generated during turbine expansion (at the final three stages of the cycle) of compressed and cooled flue gas, for partially aiding compression of the flue gas in successive previous stages employing the n-stage compressors and thus to increase energy efficiency of the whole capture process and to reduce the energy cost of all the processes involved.

20. The methods of claim 1,2, 3-15 wherein most cost effective and energy efficient capture of each component of pollutants contained in the emissions from power plants (using coal and natural gas) and from industrial plants in general is accomplished without use of any chemical/reagent and using only fixed amount of water, depending on flue gas flow rate, its temperature, after auxiliary power production through ammonia turbine, such that the captured components SO2 (liquid), CO2 (liquid or solid), N2O (liquid), NO (liquid), CO (liquid), N2 (gas), each being highly pure (in the captured forms) can be stored easily and find large industrial applications in the near and distant future, where the entire capture is made possible at a cost lower than the lowest cost of any technique hither to available.