Apparatus and method for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources

Abstract

The invention relates to an apparatus and a method for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources. The apparatus 100 first of all comprises a vessel 10, a first storage for carbon dioxide 20, a first storage for alkaline substance 30, a heat source 50, an expander 60, a reactor tube 70. A first flow of high pressure carbon dioxide 22 released by the first storage for carbon dioxide 20 is heated by a heat source 50 to obtain a second flow of high temperature and high pressure carbon dioxide 52 which is expanded in an expander 60 to obtain mechanical work 61 and a predetermined flow of low pressure carbon dioxide 62. A reactor tube 70 installed on the vessel 10 is suitable for receiving at the inlet the predetermined flow rate of low pressure carbon dioxide 62 released by the expander 60 and a flow of water 71, a predetermined flow rate of alkaline substance 32 and for releasing at the outlet a buffered ionic mixture 76 which, once released into the sea, represents the permanent storage for CO2 in the form of calcium bicarbonates.

Description

"Apparatus and method for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources"DESCRIPTION

[0001] The object of the present invention is an apparatus and a method for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources.

[0002] The effects of the so-called "greenhouse gases" on the climate and above all the correlation between the concentration of CO2 (carbon dioxide) in the atmosphere and global warming have long been known.

[0003] The efforts of the world's scientific and political community in recent years have been concentrated on trying to counteract the increase in greenhouse gas emissions into the atmosphere, in order to limit or prevent the phenomenon of global warming, i.e. the rise in the average global temperature.

[0004] As is well known, a number of initiatives have been promoted at international level aimed at containing CO2 emissions into the atmosphere: the Kyoto Protocol in 1997 and the Paris Agreement in 2015, among others, are worth mentioning.

[0005] The ways identified by the scientific community to prevent global warming are multiple and basically concern the decrease in the use of fossil fuels such as coal, oil and natural gas by promoting the development of renewable energies such as hydro, wind, solar and biomass energy.

[0006] In addition, many efforts of the international community are focused on improving the efficiency of energy use, such as lighting with low-consumption light bulbs, transport with new generations of high-efficiency engines and, in the field of power generation, replacing old, inefficient coal- or oil-fired power stations with new combined-cycle gas turbine and steam turbine plants with energy efficienciesapproaching 60% .

[0007] Despite the on-going technological efforts in the most advanced nations, the forecasts of well-known international institutions on the demand for energy globally over the next few years indicate a sharp increase in the demand for electric energy, thermal energy for industry and fuels for transport.

[0008] Consequently, these forecasts indicate a steady increase in the use of fossil sources such as oil, coal and natural gas, especially by emerging, newly industrialized and developing countries. This consumption is in fact favoured by the huge availability of these resources and by the discovery of new deposits and techniques for the extraction thereof, which factors altogether make these energy sources economically advantageous.

[0009] Using the data provided by these authoritative studies, not only is a decrease in CO2 emissions to combat global warming not expected globally, but a substantial increase in the emissions themselves is instead expected over the next 50 years, mainly due to the increase in world population and to the new industrialization of entire countries.

[0010] The catastrophic effects of such a situation on the climate are easy to understand and difficult to avoid especially because developing nations believe that the renewable energy option is too sophisticated and costly, and are more oriented towards short-term economic development programmes than towards CO2 emission containment and environmental issues.

[0011] Almost all climate simulation models therefore take into consideration, in order to achieve the objectives set by the Paris Agreement, a massive use of CO2 extraction and storage technologies from the exhaust fumes of industrial plants, including the emissions from ships' endothermic engines or directly from the atmosphere, generating so-called "negative emissions".

[0012] Different technologies have therefore been proposed in order to be able to capture and subsequently sequester CO2 from industrial plants or endothermic engines,among which it is worth mentioning:- the use of amines to capture CO2 and the geological storage of captured CO?, a process commonly known as CCS (Carbon Capture and Storage);- the use of calcium hydroxide for the mineralization of CO2 in the form of calcium carbonate or PCC (Precipitated Calcium Carbonate);- the use of calcium hydroxide for the generation of calcium bicarbonates in seawater;- the use of aqueous ammonia solutions (NH3) with generation of ammonium salts, a process commonly known as Chilled Ammonia Process (CAP).

[0013] Different technologies have also been proposed in order to be able to capture and sequester CO2 directly or indirectly from atmospheric air, in order to generate negative emissions.

[0014] The main technologies to generate negative emissions that have been proposed and are known to date are:- forestation that allows CO2 to be absorbed from the atmosphere and carbon to be stored in the form of biomass;- pyrolysis / gasification of biomass to generate charcoal, called Biochar, which stores carbon in a very stable form;- capture of CO2 directly from atmospheric air, known by the acronym DAC (Direct Air Capture), by means of chemical absorbers and the subsequent permanent storage of CO2, for example in geological storage;- combustion / fermentation of biomass with subsequent capture and permanent storage of CO2, a technology known by the acronym BECCS (Bio Energy Carbon Capture and Storage);- acceleration of the natural phenomena of rock washing, called Enhanced Wheatering, which, by reacting with CO2 present in the air, form stable chemical compounds, permanently storing CO2;- growth of the organic substance in the soils by means of appropriate cultivation techniques, also known as Carbon Sequestration Soil;- use of alkaline substances, such as calcium hydroxide, for the direct capture of CO2 from the air by means of processes of direct mineralization of atmospheric CO2 or for processes for the dispersion in the sea known as Liming or Ocean Alcalinity Enhancement.

[0015] In the scientific literature, there is growing evidence of the key role of the use of decarbonized calcium hydroxide, that is, produced without generating CO2 emissions, in the CO2 capture and storage processes and in the generation of negative emissions.

[0016] One of the most advanced technologies for the generation of decarbonized calcium hydroxide is the one described in patent document WO2022137038A1, filed in the name of Cappello.

[0017] This technology allows the generation of decarbonized calcium hydroxide through a calcination process that uses renewable energy and in which the CO2 generated by the calcination process itself is stored in the form of calcium bicarbonates in seawater according to the well-known chemical reaction:2CO2(aq) + Ca(OH)2(aq) Ca(HCO3)2(aq)

[0018] The technology described in WO2022137038A1 provides for the "buffered ionic mixture" rich in calcium bicarbonates to be released directly into the waters of a sea or an ocean.

[0019] The technology described by Cappello, both in the text of WO2022137038A1 and in several scientific articles, has some application limits due to:- the need to disperse large amounts of buffered ionic mixture in a sea, preventing said discharged mixture from mixing with the seawater that feeds the process itself;- the need to rapidly dilute the buffered ionic mixture with seawater to avoid abioticprecipitation of CaCCh due to the localised increase in sea alkalinity.

[0020] These problems, for plants installed on the coast, are generally solved by providing long submarine pipelines, often of large diameter, to ensure that the buffered ionic mixture is discharged away from the coast to an acceptable depth for effective dilution with the surrounding seawater.

[0021] The installation of long submarine pipelines certainly causes an increase in the costs and complicated bureaucratic procedures to obtain the relevant installation permits.

[0022] In a manner known and intuitive in itself, the release into the deep sea, that is, away from the coast, of large amounts of buffered ionic mixture would favour its rapid dilution and diminish the effects of the localised increase in the alkalinity of the sea.

[0023] In a manner known and intuitive in itself, the release into the deep sea of large amounts of buffered ionic mixture could conveniently take place from a vessel where a reactor for the generation of calcium bicarbonates (contactor plus apparatus for pH correction) were installed as described in patent document WO2022137038A1 or in patent document, also in the name of Cappello, WO2022175885A1.

[0024] Again in a manner known and intuitive in itself, the installation of a reactor for the generation of calcium bicarbonates in a vessel presupposes the presence of a CO2 storage installed on the vessel as well as a storage of alkaline substance.

[0025] In a manner known in itself, CO2 being a low density gas, it is necessary to transport and store CO2 on board the vessel in compressed form or in solid (dry ice) or liquid (cryogenic) form.

[0026] In a form known in itself, the vessel needs energy to move the propellers in order to navigate.

[0027] In a form known in itself, the generation of calcium bicarbonates according to patent document WO2022137038A1 involves pumping large amounts of seawater, in the proportion of about 2500 tons of water per ton of CO2 stored in the form of calciumbicarbonates.

[0028] Intuitively, the pumping of large amounts of water requires large amounts of energy that must therefore be produced on board the vessel if the process for the generation of calcium bicarbonates, according to patent document WO2022137038A1, is carried out on board a vessel.

[0029] In a form known in itself, the energy produced on board the vessel is expensive and above all, except in the case of the use of electric batteries or endothermic engines that use biofuels, the generation of mechanical or electrical energy on board the vessel generates fossil CO2 emissions.

[0030] Aim of the present invention is therefore to overcome at least partially the drawbacks mentioned above with reference to the prior art.

[0031] A task of the present invention is to make available a vessel and a method that can allow the dispersion of large amounts of buffered ionic mixture in the sea overcoming the drawbacks of the cost and CO2 emissions of the energy generation necessary for the navigation of a vessel.

[0032] This aim and these tasks are achieved by a vessel in accordance with claim 1 and a method in accordance with claim 4.

[0033] In order to better understand the invention and appreciate its advantages, some exemplary and non-limiting embodiments thereof will be described below, with reference to the attached Figures, in which:

[0034] Figure 1 is a schematic view of a vessel for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources according to the invention.

[0035] Figure 2 is a schematic view of a possible embodiment of a vessel for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide in a multi-stage expander with intermediate heating and heat sources according to the invention.

[0036] Figure 3 is a schematic view of a possible embodiment of a vessel for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources fed by calcium oxide according to the invention.

[0037] Figure 4 A schematically represents the plant for the generation of calcium bicarbonates, called reactor tube, installed on board the vessel according to the invention.

[0038] Figure 4B schematically represents the plant for the generation of calcium bicarbonates installed on board the vessel according to the invention, highlighting the fact that the reactor tube can have a variable section and complex geometric shapes.

[0039] Figure 5 is a schematic view of a possible embodiment of the method in accordance with the invention.

[0040] Figure 6 is the representation of a possible carbon dioxide expansion process in an Enthalpy Pressure diagram in accordance with the invention.

[0041] In the description reference will be made to water meaning thereby water in liquid phase with the characteristics of salinity and temperatures necessary for use in the process in accordance with the invention.

[0042] In the description reference will also be made to H2O meaning the chemical element water.

[0043] In the description reference will also be made to the sea, meaning thereby not only a sea but also an ocean or a salt lake.

[0044] In the description, reference is made to the deep sea, meaning thereby a sea with depths greater than 10 m, preferably greater than 30 m.

[0045] In the description, reference will be made to the vessel meaning any boat, craft, ship, barge or apparatus that is capable of navigating the sea, transporting storages of carbon dioxide and alkaline substance, the reactor tubes, the heat sources and the expanders. If the reactor tube is installed on a vessel other than the vessel where the alkaline substance and / or carbon dioxide storages, expanders and heat sources areinstalled, the vessel is considered to be the set of vessels transporting the reactor tubes, the carbon dioxide and the alkaline substance storages, the heat sources and the expanders.

[0046] In the description, reference will also be made to the logistic base, meaning thereby at least one place where the vessel can be refilled with carbon dioxide, alkaline substance and high temperature thermal substance such as a port, a barge, an offshore platform or a vessel adapted to act as a logistics hub. In accordance with some embodiments of the invention, the vessel sails to the logistic base for refill while, in accordance with other embodiments of the invention, it is the logistic base that sails to the vessel to refill it. In the latter case, the logistic base is represented by support ships that carry out a service for transporting carbon dioxide and thermal substance, alkaline substance and possibly electricity from a port to the vessel that remains mainly in the area where calcium bicarbonates are dispersed.

[0047] In the description reference will also be made to carbonate masses meaning any calcareous (mainly formed by CaCCh) or dolomitic (formed by both CaCOs and MgCCh or CaMg(COs)2) sedimentary carbonate rock such as calcite, aragonite, dolomite, siderite, magnesite, marble. Furthermore, in the expression carbonate masses it is understood to include also any other carbonate material such as shells or corals.

[0048] In the description, reference will be made to oxide, meaning the material formed by calcination of the carbonate masses according to the known chemical reaction:CaCO3(s) CaO(s) + CO2(g) and is formed mainly by calcium oxide CaO and / or magnesium oxide MgO. In the description and in the formulas, CaO will be used as an example of oxide, meaning that the reasonings made also apply to MgO.

[0049] In the description, reference will be made to the hydroxide, meaning the material produced by the hydration of the oxide generated by the calcination of the carbonate masses according to the known reaction:CaO(s) + H2O Ca(OH)2(s)Since the oxide is formed mainly by calcium oxide CaO and / or magnesium oxide MgO, the hydroxide is formed mainly by calcium hydroxide Ca(OH)2 and / or magnesium hydroxide Mg(OH)2. In the description and in the formulas, Ca(OH)2 will be used as an example of hydroxide, meaning that the reasonings made also apply to Mg(OH)2.

[0050] In the description reference will be made to the alkaline substance meaning indifferently both the oxide and the hydroxide. In the description and in the formulas, hydroxide will be used as an example of alkaline substance, it being understood that the reasonings made also apply to oxide.

[0051] In the description reference will be made to calcium bicarbonates meaning thereby the chemical compounds Ca(HCOs)2 and Mg(HCOs)2 generated by the reaction of the hydroxide with CO2 according to the known reaction:Ca(OH)2(aq)+2CO2(aq) Ca(HCO3)2(aq) or of the oxide with H2O and CO2 according to the known reaction:CaO(s) + H2O + 2CO2(aq) Ca(HCOs)2(aq)In the description and in the formulas, Ca(HCOs)2 will be used as an example of calcium bicarbonates, meaning that the reasonings made also apply to Mg(HCOs)2.

[0052] In the description reference will also be made to CO2 meaning the chemical element carbon dioxide.

[0053] In the description reference will also be made to carbon dioxide meaning thereby a substance where CO2 represents a percentage comprised between 70% and 100%, preferably comprised between 95% and 100%. The other gases present in the carbon dioxide may be, for example, N2, 02, Ar and water vapour.

[0054] In the description, reference will be made to the expander, meaning thereby a device capable of transforming the expansion of high pressure carbon dioxide into mechanical work. This mechanical work can also be conveniently used to produce the energy necessary to allow the vessel to navigate at the design speed, to allow the meansfor feeding water to pump a predetermined continuous flow rate of water into the reactor tube or to produce electricity through an electric generator. Turbo-expanders, both radial, axial and pressure jump, as well as screw or piston expanders, fall into the category of the expanders. The expanders may have single-stage or multi-stage expansion with intermediate heating of the fluid subject to expansion. In the description it is considered that several independent expanders in series are similar to multi-stage expanders.

[0055] In the description reference will be made to high temperature meaning thereby temperatures higher than 10 °C, preferably higher than 50 °C.

[0056] In the description reference will also be made to high pressure meaning thereby a pressure greater than 1.5 MPa, preferably higher than 2 MPa.

[0057] In the description reference will also be made to low pressure meaning thereby a pressure of less than 1.5 MPa, preferably less than 0.3 MPa.

[0058] In the description, reference will also be made to medium pressure, meaning thereby a pressure lower than high pressure and greater than low pressure.

[0059] In the description reference will also be made to the storage of alkaline substance meaning thereby not only a hydroxide storage but also an oxide storage.

[0060] In the description, reference will also be made to the means for feeding water meaning thereby pumps such as centrifugal, axial pumps, propellers or ejectors. The means for feeding water can be mounted internally to the reactor tube or directly on the vessel which, by moving, allow a flow of water inside the reactor tube itself in the opposite direction to the movement of the vessel.

[0061] In the description, reference will also be made to the means for feeding carbon dioxide, meaning thereby pumps, compressors, augers or regulating valves depending on the temperature and pressure characteristics of the carbon dioxide.

[0062] In the description, reference will also be made to the means for feeding the alkaline substance, meaning thereby dosing pumps, augers or regulating valves depending on the humidity and pressure characteristics of the alkaline substance.

[0063] In the description, reference will be made to pH meaning thereby the measurement scale indicating the acidity or basicity of a liquid which is defined by the following formula: pH=-logl0[H3O+]

[0064] In the description reference will be made to the design flow rate meaning thereby the sum of the amounts of water, CO2 and alkaline substance that are released in the unit of time by the reactor tube 70 and which allows the permanent sequestration of a predetermined amount of CO2 in the form of calcium bicarbonates.

[0065] In the description reference will be made to the acid mixture meaning thereby a mixture of water and CO2 and where the present CO2 dissolves in the water forming carbonic acid H2CO3 according to the known reaction:The process of mixing CO2 in water to form the acid mixture requires a reaction time which depends on various factors such as temperature, water pressure, partial pressure of CO2 and may take from Is to 1,000s, preferably from 5s to 300s.

[0066] In the description, reference will be made to the buffered mixture meaning thereby an acid mixture where the alkaline substance has been mixed forming a suspension which, by dissolving in the acid mixture, transforms into a buffered ionic mixture. The process of dissolution of the alkaline substance in the acid mixture to form the buffered ionic mixture requires a reaction time that depends on various factors such as the temperature and pH of the mixture and can take from Is to 3,600s, typically between 10s and 600s.

[0067] In the description, reference will be made to the buffered ionic mixture, meaning thereby an acid mixture where the pH has been corrected, by addition of an alkaline substance, to the desired value by means of the well-known chemical reaction:2H2CO3(aq) + Ca(OH)2(aq) Ca(HCO3)2(aq) + 2H2OThe buffered ionic mixture is an ionic mixture containing any insoluble impurities present in the alkaline substance.

[0068] In the description, reference will be made to the plume, meaning thereby the plume, i.e. the portion of the sea where the mixture released by the reactor mixes and dilutes with the surrounding seawater.

[0069] In the description reference will be made to alkalinity meaning thereby the amount of hydroxides OH-, carbonates CO and bicarbonates HCO,2-present in the water.

[0070] In the description, reference will also be made to the heat source, meaning thereby the thermal energy storage (TES) or thermal batteries, indicating thereby a device capable of containing a substance capable of accumulating heat in the form of latent heat or sensible heat, or of releasing heat as a result of a chemical reaction. Calcium oxide CaO hydration devices, called slakers, in which the known exothermic reaction takes place, fall within the definition of heat source:CaO + H2O Ca(OH)2-64.8 kJ / mol endothermic engines, such as the gas turbines or piston engines fed by fuels such as diesel, petrol, LPG, CH4, methanol, ammonia) that, in addition to mechanical work, produce thermal energy, the SOFC (Solid Oxide Fuel Cell) or MCFCs (Molten Carbonate Fuel Cell) fuel cells, the liquid, gaseous or solid fuel boilers and the gasification plants and the heat exchangers that exchange heat with ambient air and seawater. The temperature of the heat source is comprised between 10 °C and 1000 °C, preferably between 80 °C and 500 °C. The heat source can have different temperatures as in the case of an endothermic engine where the exhaust gas can have a temperature of about 300 °C and the cooling water of the engine jackets of about 90 °C.

[0071] In the description reference will also be made to the thermal substance meaning thereby substances in the liquid, gaseous (vapour) or solid phase which are suitable for accumulating and releasing heat by exploiting their sensible or latent heatand the substances which, by means of an exothermic chemical reaction, can generate heat. The definition of thermal substance includes H2O, the PCMs (Phase Change Materials), the metals in both solid and liquid states, rocks and oils.

[0072] In the description, reference will be made to the OD, meaning thereby the Outside Diameter, or outer diameter of a tube with a circular section or the diameter of a tubular structure with a circular section with the same hydraulic characteristics as the tubular structure considered.

[0073] In the description reference will be made to the unit of measurement of energy MWh meaning thereby 3.6xl09Jules.

[0074] In the description reference will be made to the unit of time h meaning one hour or 3,600 seconds.

[0075] In the description reference will also be made to the unit of measurement of pressure MPa meaning thereby absolute 1,000,000 Pascal (Pa). Atmospheric pressure at the sea level is conventionally considered at 101,325 Pa.

[0076] In the description, the dot will be used as a thousands separator and the comma as a decimal separator.

[0077] In the attached figures, reference 100 indicates as a whole a generic apparatus for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources according to the invention, while reference 300 refers to a logistic base, reference 110 refers to the surface of the sea and reference 120 refers to the sea itself.

[0078] The apparatus 100 for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources according to the invention comprises a vessel 10, a first storage for carbon dioxide 20, a first storage for alkaline substance 30, a heat source 50, an expander 60, a reactor tube 70, wherein the vessel 10:- is suitable for transporting the first storage for carbon dioxide 20;- is suitable for transporting the first storage for alkaline substance 30;- is suitable for transporting the heat source 50;- is suitable for transporting the expander 60;- is suitable for transporting the reactor tube 70; and wherein:- the first storage for carbon dioxide 20 is suitable for containing high pressure carbon dioxide 21 and for releasing at the outlet a first flow of high pressure carbon dioxide 22;- the first storage for alkaline substance 30 is suitable for containing an alkaline substance 31 and for releasing at the outlet a predetermined flow rate of alkaline substance 32;- the heat source 50 is suitable for receiving at the inlet the first flow of high pressure carbon dioxide 22 and for releasing at the outlet a second flow of high temperature and high pressure carbon dioxide 52;- the expander 60 is suitable for receiving at the inlet the second flow of high temperature and high pressure carbon dioxide (52), expanding the second flow of high temperature and high pressure carbon dioxide 52 to generate mechanical work 61, and for releasing at the outlet a predetermined flow rate of low pressure carbon dioxide 62; and wherein the reactor tube 70 comprises:- a conduit 78;- means for feeding water 79;- means for feeding carbon dioxide 72;- means for feeding alkaline substance 74; and wherein:- the means for feeding water 79 are suitable for supplying a predetermined continuous flow rate of water 71 coming from the sea 120 to the reactor tube 70;- the means for feeding carbon dioxide 72 are suitable for supplying the predetermined flow rate of low pressure carbon dioxide 62 coming from the expander 60 to the reactor tube 70;- the means for feeding alkaline substance 74 are suitable for feeding a predetermined flow rate of alkaline substance 32 coming from the first storage of alkaline substance 30 to the reactor tube 70; and wherein the reactor tube 70:- is hydraulically connected to the sea 120 to receive at the input a predetermined continuous flow rate of water 71;- is hydraulically connected to the sea 120 to release at the outlet a design flow rate of buffered ionic mixture 76;- is suitable for transporting the predetermined continuous flow rate of water 71, a continuous flow rate of acid mixture 73, a continuous flow rate of buffered mixture 75 and the design flow rate of buffered ionic mixture 76;- is suitable for mixing the predetermined flow rate of low pressure carbon dioxide 62 released by the means for feeding carbon dioxide 72 with the predetermined continuous flow rate of water 71;- is suitable for mixing the predetermined flow rate of alkaline substance 32 released by the means for feeding alkaline substance 74 with the continuous flow rate of acid mixture 73 to form the design flow rate of buffered ionic mixture 76 with desired pH according to the reaction:Ca(OH)2(aq) + 2CO2(aq) Ca(HCO3)2(aq) and wherein the conduit 78:- has a diameter OD comprised between 0.1 m and 10 m, preferably between 0.1 m and 3 m;- has a length of less than 10,000 m, preferably comprised between 10 m and 500 m;- is installed completely or partially on the vessel 10.

[0079] In accordance with some embodiments of the invention, the apparatus 100 further comprises the heat source 50 which:- is suitable for receiving at the inlet at least a first flow of medium pressure carbon dioxide 65 released by the expander 60 and for releasing at the outlet at least a second flow of high temperature and medium pressure carbon dioxide 56; and wherein the expander 60:- is suitable for releasing at the outlet at least the first flow of medium pressure carbon dioxide 65 and for receiving at the inlet at least the second flow of high temperature and medium pressure carbon dioxide 56 released by the heat source 50.

[0080] In accordance with some embodiments of the invention, the apparatus 100 comprises the heat source 50 which:- is suitable for receiving at the inlet a predetermined flow rate of oxide 33 released by the first storage of alkaline substance 30 and a second predetermined flow rate of water 55, for releasing at the outlet a predetermined flow rate of hydroxide 54 and the second flow of high temperature and high pressure carbon dioxide 52;- is suitable for generating heat by means of the known exothermic reaction:CaO + H2O Ca(OH)2(-63.7 Kj / mol) and wherein the reactor tube 70:- is suitable for receiving at the input the predetermined flow rate of hydroxide 54;- is suitable for mixing the predetermined flow rate of hydroxide 54 released by the means for feeding alkaline substance 74 with the continuous flow rate of acid mixture 73 to form the design flow rate of buffered ionic mixture 76 with desired pH according to the reaction:Ca(OH)2(aq) + 2CO2(aq) "> Ca(HCO3)2(aq)

[0081] Note here that the reactor tube 70 may be fed by both the predetermined flow rate of alkaline substance 32 released directly by the first storage of alkalinesubstance 30 and the predetermined flow rate of hydroxide 54 released by the heat source 50.

[0082] Note here that the means for feeding alkaline substance 74 may feed to the reactor tube 70 both the predetermined flow rate of alkaline substance 32 and the predetermined flow rate of hydroxide 54.

[0083] With reference to the embodiments of Figures 1, 2, 3, 4 A, 4B and 5, it is also possible to identify:- the conduit 78 of the reactor tube 70;- means for feeding water 79;- means for feeding carbon dioxide 72;- means for feeding alkaline substance 74;- the continuous flow rate of acid mixture 73 formed by mixing the predetermined flow rate of low pressure carbon dioxide 62 released by the means for feeding carbon dioxide 72 in the predetermined continuous flow rate of water 71 in the conduit 78;- the continuous flow rate of buffered mixture 75 formed by mixing the predetermined flow rate of alkaline substance 32 released by the means for feeding alkaline substance 74 in the continuous flow rate of acid mixture 73;- the design flow rate of buffered ionic mixture 76 released by conduit 78;- the seabed 90;- the plume 80 formed by the release into the sea of the design flow rate of buffered ionic mixture 76;- the vector of the design speed 12 of the vessel 10;- the bow 13 of the vessel 10;- the stern 14 of the vessel 10;- the first storage of alkaline substance 30 transported by the vessel 10;- the high pressure carbon dioxide 21 contained in the first storage for carbon dioxide 20;- the alkaline substance 31 contained in the first storage for alkaline substance 30;- the thermal substance 51 contained in the heat source 50;- the second storage of carbon dioxide 27 belonging to the logistic base 300;- the second storage of high temperature thermal substance 57 belonging to the logistic base 300;- the second storage of alkaline substance 37 belonging to the logistic base 300.

[0084] In a form known in itself, the process of storing CO2 by means of calcium bicarbonates in seawater requires large amounts of seawater for the dissolution of the CO2 and the alkaline substance.

[0085] In known form per se, the ratio between the amount of seawater and CO2 necessary for the storage of CO2 in the form of calcium bicarbonates is about 3,000:1 by weight inside the reactor tube 70 to avoid abiotic precipitation of carbonate during the production process of calcium bicarbonates.

[0086] A skilled person may well understand that, if the reactor tube 70 were installed on land, it would be necessary for the predetermined continuous flow rate of water 71 feeding the process to be taken into a sea area not chemically affected by the discharge of the design flow rate of buffered ionic mixture 76.

[0087] A skilled person may well understand that in order to avoid interference between the plume 80 formed by the design flow rate of buffered ionic mixture 76 and the predetermined continuous flow rate of water 71 which feeds the calcium bicarbonate generation process installed on the mainland it is necessary to appropriately distance the unloading point of the design flow rate of buffered ionic mixture 76 from the withdrawal point of the predetermined continuous flow rate of water 71.

[0088] In a form known in itself, the distancing between the loading area and the unloading area can be obtained by installing an underwater pipeline of appropriatelength that allows, as is also the case with sewer waters, the discharge of the design flow rate of buffered ionic mixture 76 in a fairly deep area away from the coast. In this configuration, the withdrawal works of the predetermined continuous flow rate of water 71 are carried out near the coast so as to maximize their distance from the discharge of the design flow rate of buffered ionic mixture 76.

[0089] In a form known in itself, these underwater pipelines are generally installed using a non-invasive "micro tunneling" technology that allows to dig a tunnel that connects the hinterland to the deep sea without carrying out works on the coast, in particular on the beaches, and not to damage the seabed near the coast itself. In fact, the laying of the pipeline takes place in the ground below the beach and the seabed. The pipeline ends at a certain distance from the coast and at a depth emerging from the seabed in an area sufficiently deep to obtain the desired dilution of the discharged substance with the surrounding waters.

[0090] In a manner known in itself, this laying technology makes it possible not to damage fauna and flora in shallow waters that are generally very sensitive ecosystems, to avoid expensive works for the protection from potential damages caused by anchors or trawl nets and damages caused by particularly violent storm surges.

[0091] In a manner known in itself, by now almost all access to the sea of submarine pipes in industrialized countries is achieved through the micro -tunneling technique also to avoid interfering with the numerous infrastructures on the seabed such as electrical cables, cables for data transmission, oil pipelines, gas pipelines, sewers.

[0092] In a manner known in itself, such construction works of underwater pipelines by means of micro-tunneling are generally limited in diameters of less than about 2m, a few thousand meters in length and are extremely expensive.

[0093] A skilled person will certainly understand the advantages of being able to avoid the construction of an underwater pipeline to disperse the design flow rate of buffered ionic mixture 76 into the sea, especially in the case of large plants where thewater flow rates to be conveyed through the underwater pipelines would be very high. In fact, considering a ratio water-CCh of 3000:1, to store 100,000 ton / y of CO2 it would be necessary to convey 10 m3 / s of buffered ionic mixture which would mean an underwater pipeline of 2m in diameter with a design flow rate of buffered ionic mixture 76 of 3 m / s.

[0094] Referring to Figures 1, 2, 3 and 5, a skilled person will certainly be able to understand the advantages of using a vessel 10 on which to install the reactor tube 70 and carry out the storage process of CO2 in the form of calcium bicarbonates far from the coast, in the deep sea, during navigation without the expensive problem of having to distance the suction area of the predetermined continuous flow rate of water 71 from the unloading area of the design flow rate of buffered ionic mixture 76 with expensive underwater works.

[0095] A skilled person will surely understand that it is appropriate for the vessel 10, during the dispersion operations of the design flow rate of buffered ionic mixture 76, to move at the design speed 12 to avoid interference between the plume 80 formed by the design flow rate of buffered ionic mixture 76 and the predetermined continuous flow rate of water 71 that feeds the calcium bicarbonate generation process installed on the vessel 10.

[0096] A skilled person will understand that, since the vessel 10 is at the sea level, the energy cost of pumping the predetermined continuous flow rate of water 71 through the means for feeding water 79 is minimized as the entire CO2 storage process takes place at the sea level, which would be difficult to achieve if the reactor tube 70 were installed on land.

[0097] A skilled person can understand that the discharge of the design flow rate of buffered ionic mixture 76 into the sea during navigation from a vessel 10 allows it to be dispersed over a large sea surface, unlike what happens, in a manner known in itself, at the point of release from a fixed underwater pipeline that generally requires special diffusers and favourable environmental conditions such as favourable marine currents.

[0098] Intuitively, a skilled person can understand that, even at the sea level, pumping the predetermined continuous flow rate of water 71 by the means for feeding water 79 requires a considerable amount of energy. In fact, considering an ELOCCh ratio of 3,000:1, to store 1 ton of CO2 it would be necessary to convey 3,000 m3of predetermined continuous flow rate of water 71 with an energy consumption of approximately 0.029 MWh / tonco2, if the total differential prevalence of the means for feeding water 79, i.e. the sum of the static prevalence and the friction pressure losses, is 0.025 MPa.

[0099] Intuitively, a skilled person can understand that even navigating the vessel 10 at the design speed 12 requires energy.

[0100] A skilled person will agree that the generation of energy on board any vessel using fossil fuels, such as MFO (Marine Fuel Oil) and diesel, is very expensive and above all would produce unwanted CO2 emissions while the use of renewable fuels, such as bio-diesel, bio-methanol or ammonia, would prove to be even more expensive. In fact, the average untaxed market price for VLFO (V ery Low Sulphur Fuel Oil) in 2024 was about 600 Euro / ton which, used in an endothermic engine with 45% efficiency, would generate mechanical work at 109 Euro / MWh and 3.5 tons of CO2 emissions which, at average values recorded in 2024 by the EU ETS (European Emission Trading System) would generate a penalty of about €65 / MWh. The cost of biodiesel in the same period was about 1,300 Euro / ton which, used in an endothermic engine, would generate mechanical work at 236 Euro / MWh.

[0101] A skilled person may also agree that the use of electric batteries on board the vessel 10 is an expensive solution due to their high investment and operational cost. In fact, the investment cost for an electric battery in 2024 with a capacity of 1 MWh is about 200,000 Euro to which it is necessary to add the cost of electricity which, in areas such as southern Europe in 2024, largely exceeded 100 Euro / MWh.

[0102] A skilled person will, as mentioned above, understand that using traditional fuels with endothermic engines or electric batteries on the vessel 10 cansignificantly increase the cost for storing CO2 in the form of calcium bicarbonates in seawater.

[0103] In a form known in itself, the technologies proposed for the temporary storage of CO2 captured by industrial processes is the use of thermally insulated high pressure vessels, generally at -20 °C and 2.5 MPa in the case of cryogenic CO2, and high pressure vessels at ambient temperature, generally comprised between 10 MPa and 20 MPa and for liquid or supercritical CO2. Additionally, but less commonly, it is possible to store CO2 in solid form, i.e. dry ice, at ambient pressure and at temperatures of - 78 °C.

[0104] Intuitively, a skilled person will certainly understand that even on board the vessel 10 it is convenient to store high pressure carbon dioxide 21 in the first storage for carbon dioxide 20.

[0105] A skilled person will surely understand that the storage of CO2 in the form of calcium bicarbonates in seawater, as described in patent document WO2022137038A1, requires low pressure CO2 (generally <0.2 MPa) as opposed, for example, to the geological storage of CO2 (CCS - Carbon Capture and Sequestration) where high pressure CO2 is required to be injected into storage wells (typically >7 MPa).

[0106] A skilled person will surely agree that, in the case of storage of the CO2 in the form of calcium bicarbonates as described in patent document WO2022137038A1, one could conveniently use the expansion of the high pressure carbon dioxide 21 stored in the first storage for carbon dioxide 20 on the vessel 10 to obtain a predetermined flow rate of low pressure carbon dioxide 62 and at the same time to generate, totally or partially, the energy necessary for the means for feeding water 79 and allow the vessel to navigate at the design speed 12.

[0107] Referring to Figure 6, a skilled person will certainly be able to identify in the known Pressure-Enthalpy diagram of CO2 a carbon dioxide expansion process fromthe first storage for carbon dioxide 20 up to the release of the predetermined flow rate of low pressure carbon dioxide 62 released by the multi-stage expander 60.

[0108] In particular, again referring to Figure 6, the theoretical expansion (without taking into account the pressure losses in the various components of the plant) of the high pressure carbon dioxide 21 of 15 MPa and 20 °C (ambient temperature) can be analysed, which can be representative of a particular expansion of carbon dioxide in a 2-stage expander 60 on the vessel 10 according to the invention; in the particular case analysed, the heat source has a temperature of 100 °C. The high pressure carbon dioxide 21 at 15 MPa and 20 °C (point A) is iso-enthalpically laminated in a lamination valve (not shown in the Figures) up to 3 MPa and -5.5 °C (point B); the carbon dioxide is then isobarically heated by means of a heat exchanger (not shown in the Figures) capable of exchanging heat with the environment until reaching the condition of 3 MPa and 20 °C (Point C); the carbon dioxide is then isobarically heated by the heat source 50 to 100 °C until reaching the condition of 3 MPa and 100 °C (Point D); the carbon dioxide at 100 °C and 3 MPa is then expanded in the first stage of the expander 60 with an efficiency of 75% up to the pressure of 1 MPa and temperature of 35 °C (Point E); the carbon dioxide is then isobarically heated in the heat source 50 to 100 °C and 1 MPa (Point F); the carbon dioxide is expanded in the second stage of the expander 60 with an efficiency of 75% generating the predetermined flow of low pressure carbon dioxide 62 at 0.55 MPa and 65 °C (Point G).

[0109] A skilled person will be able to calculate, using data available in the literature, the energy potentially generated through the expansion of a certain amount of high temperature and high pressure carbon dioxide 52 in the expander 60.

[0110] Suppose one wants to expand carbon dioxide at 3.1 MPa up to 0.55 MPa in a 3-stage 60 expander using a heat source 50 at 30 °C, such as ambient air or the sea 120, a heat source 50 with a temperature of 100 °C, and a heat source 50 with a temperature of 200 °C. One can think of subdividing the expansion of carbon dioxide into 3 stageswith intermediate heating, i.e. from 3.1 MPa to 2.1 MPa and from 2.1 MPa to 1.1 MPa and from 1.1 MPa to 0.55 MPa.

[0111] By making the relative calculations using an expansion efficiency of 75 % , it can be calculated that at 30 °C it is possible to obtain mechanical work 61 equal to about 62.5 kj / kg, or 0.017 MWh / ton of carbon dioxide, at 100 °C of 105.7 kJ, i.e. 0.029 MWh / ton of carbon dioxide, at 200 °C of 111.45 °C, i.e. 0.031 MWh / ton of carbon dioxide.

[0112] A skilled person can easily understand, in view of the above, that the mechanical work 61 produced at a temperature of 30 °C would not be sufficient to generate the energy necessary to feed the means for feeding water 79.

[0113] A skilled person will agree that the best way to increase the mechanical work 61 that can be produced through the expansion of high temperature and high pressure carbon dioxide 52 is to increase the temperature thereof.

[0114] In fact, as demonstrated above, already by heating the high temperature and high pressure carbon dioxide 52 to 100 °C via the heat source 50, enough mechanical work 61 is obtained from the expander 60 to feed the means for feeding water 79.

[0115] A skilled person can surely agree that there will be a temperature and a pressure of the second flow of high temperature and high pressure carbon dioxide 52 at which the mechanical work 61 generated by the expander 60 can be sufficient to feed, partially or totally, the means for feeding water 79 and possibly to allow the vessel 10 to navigate at the design speed 12.

[0116] A skilled person may therefore agree that it is necessary, on the vessel 10, to have available the heat necessary to heat the first flow of high pressure carbon dioxide 22.

[0117] In known form, the heat may be generated by the cooling of a high temperature thermal substance 51, by the hydration reaction of the oxide 33, by the heat generated by an endothermic engine, by a boiler, by a fuel cell, or by any combination thereof.

[0118] Referring to Figure 1, the first flow of high pressure carbon dioxide 22 passes through a high temperature thermal substance 51 in the heat source 50 which transfers its heat to the first flow of high pressure carbon dioxide 22 generating the second flow of high temperature and high pressure carbon dioxide 52 which will subsequently be expanded in the expander 60 generating the mechanical work 61 and releasing the predetermined flow rate of low pressure carbon dioxide 62.

[0119] Referring to Figure 2, it can be seen that the expander 60, with several stages of expansion with intermediate heating, releases at the outlet at least a first flow of medium pressure carbon dioxide 65 which, passing in the heat source 50, is heated generating at least a second flow of high temperature and medium pressure carbon dioxide 56 which is finally conveyed to the expander 60.

[0120] Referring to Figure 3, it can be noted the predetermined flow rate of oxide 33 that feeds the heat source 50 where it is reacted with a second predetermined flow rate of water 55 according to the known exothermic reaction:CaO + H2O Ca(OH)2(-63.7 Kj / mol) generating at the outlet a predetermined flow rate of hydroxide 54 and the second flow of high temperature and high pressure carbon dioxide 52.

[0121] Referring to Figure 5, a skilled person can understand that the vessel 10 can load the high pressure carbon dioxide 21, the possible high temperature thermal substance 51 and the alkaline substance 31 at the logistic base 300 and reach the chosen unloading area by sailing. After reaching the unloading area, the vessel 10 may discharge the design flow rate of buffered alkaline mixture 76 into the sea. Once the high pressure carbon dioxide 21, the possible high temperature thermal substance 51 or the alkaline substance 31 stored on board the vessel 10 are finished, the vessel 10 can return to the logistic base 300 to be refilled with high pressure carbon dioxide 21, possibly high temperature thermal substance 51 and alkaline substance 31.

[0122] Referring again to Figure 5, the refilling process at the logistic base 300 of the vessel 10 according to the invention may take place by physically transferring the high pressure carbon dioxide 21, the possible high temperature thermal substance 51 and the alkaline substance 31 respectively from the storages 27, 57 and 37 of the logistic base 300 to the first storage for carbon dioxide 20, the heat source 50 and the first storage for alkaline substance 30 installed on the vessel 10.

[0123] A second aspect of the invention relates to a method for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources. The method comprises the steps of:- providing a vessel 10;- providing on the vessel 10 a first storage for carbon dioxide 20;- providing on the vessel 10 a first storage for alkaline substance 30;- providing a heat source 50 on the vessel 10;- providing an expander 60 on the vessel 10;- providing a reactor tube 70;- releasing a first flow of high pressure carbon dioxide 22 from the first storage for carbon dioxide 20;- conveying the first flow of high pressure carbon dioxide 22;- feeding the heat source 50 with the first flow of high pressure carbon dioxide 22 to obtain at the outlet a second flow of high temperature and high pressure carbon dioxide 52;- conveying the second flow of high temperature and high pressure carbon dioxide 52;- feeding the second flow of high temperature and high pressure carbon dioxide 52 to the expander 60 to obtain mechanical work 61 and a predetermined flow rate of low pressure carbon dioxide 62;- conveying the predetermined flow rate of low pressure carbon dioxide 62;- feeding the reactor tube 70 with a predetermined continuous flow rate of water 71 and with the predetermined flow rate of low pressure carbon dioxide 62 to obtain a continuous flow rate of acid mixture 73;- conveying the continuous flow rate of acid mixture 73 into the reactor tube 70;- maintaining the continuous flow rate of acid mixture 73 inside the reactor tube 70 for a minimum time necessary for the hydration of CO2 according to the reaction:calculated at the design flow rate;- defining a desired pH of the design flow rate of buffered ionic mixture 76 to be released into the sea 120;- feeding the reactor tube 70 with the predetermined flow rate of alkaline substance 32;- mixing the continuous flow rate of acid mixture 73 with the predetermined flow rate of alkaline substance 32 to obtain a continuous flow rate of buffered mixture 75;- maintaining the continuous flow rate of buffered mixture 75 inside the reactor tube 70 for a minimum time necessary for the complete dissolution of the predetermined flow rate of alkaline substance 32 according to the reaction:Ca(OH)2(aq) + 2CO2(aq) "> Ca(HCOs)2(aq) and obtaining a design flow rate of buffered ionic mixture 76 with the desired pH;- releasing into the sea 120 the design flow rate of buffered ionic mixture 76 with the desired pH.

[0124] In accordance with one embodiment, the method further comprises the steps of:- providing on the vessel 10 a heat source 50 capable of receiving at the input at least a first flow of medium pressure carbon dioxide 65 and releasing at the outlet at least a second flow of high temperature and medium pressure carbon dioxide 56;- providing on the vessel 10 an expander 60 capable of releasing at the outlet at least the first flow of medium pressure carbon dioxide 65 and receiving at the input at least the second flow of high temperature and medium pressure carbon dioxide 56;- conveying the first flow of medium pressure carbon dioxide 65;- feeding the first flow of medium pressure carbon dioxide 65 to the heat source 50;- releasing the second flow of high temperature and medium pressure carbon dioxide 56 from the heat source 50;- feeding the second flow of high temperature and medium pressure carbon dioxide 56 from the heat source 50 to the expander 60.

[0125] In accordance with one embodiment, the method further comprises the steps of:- providing on the vessel 10 a heat source 50 capable of hydrating an oxide according to the known exothermic reaction:CaO + H2O Ca(OH)2(-63.7 Kj / mol)- feeding to the heat source 50 at least one flow rate of oxide 33 released by the first storage of alkaline substance 30 and a second predetermined flow rate of water 55;- releasing at the outlet from the heat source 50 at least a predetermined flow rate of hydroxide 54;- conveying the predetermined flow rate of hydroxide 54;- feeding the predetermined flow rate of hydroxide 54 to the reactor tube 70;- mixing the continuous flow rate of acid mixture 73 with the predetermined flow rate of hydroxide 54 to obtain a continuous flow rate of buffered mixture 75;maintaining the continuous flow rate of buffered mixture 75 inside the reactor tube 70 for a minimum time necessary for the complete dissolution of the predetermined flow rate of hydroxide 54 according to the reaction:Ca(OH)2(aq) + 2CO2(aq) Ca(HCO3)2(aq) and obtaining a design flow rate of buffered ionic mixture 76 with the desired pH.

[0126] It is clear that the specific characteristics are described in relation to different embodiments of the apparatus 100 for dispersing calcium bicarbonates in the sea with exemplary and non-limiting intent.

[0127] A person skilled in the art, for the purpose of satisfying contingent and specific needs, will be able to make further modifications and variants to the apparatus 100 for dispersing calcium bicarbonates in the sea according to the present invention, all contained in the scope of protection of the invention, as defined by the following claims.

Claims

CLAIMS1. Apparatus (100) for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources according to the invention, comprises a vessel (10), a first storage for carbon dioxide (20), a first storage for alkaline substance (30), a heat source (50), an expander (60), a reactor tube (70), wherein the vessel (10):- is suitable for transporting the first storage for carbon dioxide (20);- is suitable for transporting the first storage for alkaline substance (30);- is suitable for transporting the heat source (50);- is suitable for transporting the expander (60);- is suitable for transporting the reactor tube (70); and wherein:- the first storage for carbon dioxide (20) is suitable for containing high pressure carbon dioxide (21) and for releasing at the outlet a first flow of high pressure carbon dioxide (22);- the first storage for alkaline substance (30) is suitable for containing an alkaline substance (31) and for releasing at the outlet a predetermined flow rate of alkaline substance (32);- the heat source (50) is suitable for receiving at the inlet the first flow of high pressure carbon dioxide (22) and for releasing at the outlet a second flow of high temperature and high pressure carbon dioxide (52);- the expander (60) is suitable for receiving at the inlet the second flow of high temperature and high pressure carbon dioxide (52), for expanding the second flow of high temperature and high pressure carbon dioxide (52) to generate mechanical work (61), and for releasing at the outlet a predetermined flow rate of low pressure carbon dioxide (62); and wherein the reactor tube (70) comprises:- a conduit (78);- means for feeding water (79);- means for feeding carbon dioxide (72);- means for feeding alkaline substance (74);and wherein:- the means for feeding water (79) are suitable for supplying a predetermined continuous flow rate of water (71) coming from the sea (120) to the reactor tube(70);- the means for feeding carbon dioxide (72) are suitable for supplying the predetermined flow rate of low pressure carbon dioxide (62) coming from the expander (60) to the reactor tube (70);- the means for feeding alkaline substance (74) are suitable for supplying the predetermined flow rate of alkaline substance (32) coming from the first storage of alkaline substance (30) to the reactor tube (70); and wherein the reactor tube (70):- is hydraulically connected to the sea (120) to receive at the input a predetermined continuous flow rate of water (71);- is hydraulically connected to the sea (120) to release at the outlet a design flow rate of buffered ionic mixture (76);- is suitable for transporting the predetermined continuous flow rate of water(71), a continuous flow rate of acid mixture (73), a continuous flow rate of buffered mixture (75) and the design flow rate of buffered ionic mixture (76);- is suitable for mixing the predetermined flow rate of low pressure carbon dioxide (62) released by the means for feeding carbon dioxide (72) with the predetermined continuous flow rate of water (71);- is suitable for mixing the predetermined flow rate of alkaline substance (32) released by the means for feeding alkaline substance (74) with the continuous flow rate of acid mixture (73) to form the design flow rate of buffered ionic mixture (76) with desired pH according to the reaction:Ca(OH)2(aq) + 2CO2(aq) Ca(HCO3)2(aq) and wherein the conduit (78):- has a diameter OD comprised between 0.1 m and 10 m, preferably between 0.1 m and 3 m;- has a length of less than 10,000 m, preferably comprised between 10 m and 500 m; is installed completely or partially on the vessel (10).

2. Apparatus (100) according to claim 1 rurther comprising the heat source (50) which:- is suitable for receiving at the inlet at least a first flow of medium pressure carbon dioxide (65) released by the expander (60) and for releasing at the outlet at least a second flow of high temperature and medium pressure carbon dioxide (56); and wherein the expander (60):- is suitable for releasing at the outlet at least the first flow of medium pressure carbon dioxide (65) and for receiving at the inlet at least the second flow of high temperature and medium pressure carbon dioxide (56) released by the heat source (50).

3. Apparatus (100) according to any preceding claim comprising the heat source (50) which:- is suitable for receiving at the inlet a predetermined flow rate of oxide (33) released by the first storage of alkaline substance (30) and a second predetermined flow rate of water (55), for releasing at the outlet a predetermined flow rate of hydroxide (54) and the second flow of high temperature and high pressure carbon dioxide (52);- is suitable for generating heat by means of the known exothermic reaction:CaO + H2O Ca(OH)2(-63.7 Kj / mol) and wherein the reactor tube (70):- is suitable for receiving at the input the predetermined flow rate of hydroxide (54);- is suitable for mixing the predetermined flow rate of hydroxide (54) released by the means for feeding alkaline substance (74) with the continuous flow rate of acid mixture (73) to form the design flow rate of buffered ionic mixture (76) with desired pH according to the reaction:Ca(OH)2(aq) + 2CO2(aq) Ca(HCO3)2(aq)4. Method for generating and dispersing calcium bicarbonates in the sea with energy generation through the expansion of carbon dioxide and heat sources, wherein the method comprises the steps of:- providing a vessel (10);- providing on the vessel (10) a first storage for carbon dioxide (20);- providing on the vessel (10) a first storage for alkaline substance (30);- providing a heat source (50) on the vessel (10);- providing an expander (60) on the vessel (10);- providing a reactor tube (70) on the vessel (10);- releasing a first flow of high pressure carbon dioxide (22) from the first storage for carbon dioxide (20);- conveying the first flow of high pressure carbon dioxide (22);- feeding a heat source (50) with the first flow of high pressure carbon dioxide (22) to obtain a second flow of high temperature and high pressure carbon dioxide (52);- conveying the second flow of high temperature and high pressure carbon dioxide (52);- feeding the second flow of high temperature and high pressure carbon dioxide (52) to an expander (60) to obtain mechanical work (61) and a predetermined flow rate of low pressure carbon dioxide (62);- conveying the predetermined flow rate of low pressure carbon dioxide (62);- feeding the reactor tube (70) with a predetermined continuous flow rate of water (71) and with the predetermined flow rate of low pressure carbon dioxide (62) to obtain a continuous flow rate of acid mixture (73);- conveying the continuous flow rate of acid mixture (73) into the reactor tube (70);- maintaining the continuous flow rate of acid mixture (73) inside the reactor tube (70) for a minimum time necessary for the hydration of CO2 according to the reaction:calculated at the design flow rate;- defining a desired pH of a design flow rate of buffered ionic mixture (76) to be released into the sea (120);- feeding the reactor tube (70) with a predetermined flow rate of alkaline substance (32);- mixing the continuous flow rate of acid mixture (73) with the predetermined flow rate of alkaline substance (32) to obtain a continuous flow rate of buffered mixture (75);- maintaining the continuous flow rate of buffered mixture (75) inside the reactor tube (70) for a minimum time necessary for the complete dissolution of the predetermined flow rate of alkaline substance (32) according to the reaction:Ca(OH)2(aq) + 2CO2(aq) Ca(HCO3)2(aq) and obtaining the design flow rate of buffered ionic mixture (76) with the desired pH;- releasing into the sea (120) the design flow rate of buffered ionic mixture (76) with the desired pH.

5. Method according to claim 4, further comprising the steps of:- providing on the vessel (10) the heat source (50) capable of receiving at the input at least a first flow of medium pressure carbon dioxide (65) and releasing at least a second flow of high temperature and medium pressure carbon dioxide (56);- providing on the vessel (10) the expander (60) capable of releasing at the outlet at least the first flow of medium pressure carbon dioxide (65) and receiving at the input at least the second flow of high temperature and medium pressure carbon dioxide (56);- conveying the first flow of medium pressure carbon dioxide (65);- feeding the first flow of medium pressure carbon dioxide (65) to the heat source (50);- releasing the second flow of high temperature and medium pressure carbon dioxide (56) from the heat source (50);- feeding the second flow of high temperature and medium pressure carbon dioxide (56) from the heat source (50) to the expander (60).

6. Method according to claim 4 or 5 further comprising the steps of:- providing on the vessel (10) the heat source (50) capable of hydrating an oxide according to the known exothermic reaction:CaO + H2O Ca(OH)2(-63.7 Kj / mol)- feeding to the heat source (50) at least one flow rate of oxide (33) released by the first storage of alkaline substance (30) and a second predetermined flow rate of water (55);- releasing at the outlet from the heat source (50) at least a predetermined flow rate of hydroxide (54);- conveying the predetermined flow rate of hydroxide (54);- feeding the predetermined flow rate of hydroxide (54) to the reactor tube (70);- mixing the continuous flow rate of acid mixture (73) with the predetermined flow rate of hydroxide (54) to obtain the continuous flow rate of buffered mixture (75);- maintaining the continuous flow rate of buffered mixture (75) inside the reactor tube (70) for a minimum time necessary for the complete dissolution of the predetermined flow rate of hydroxide (54) according to the reaction:Ca(OH)2(aq) + 2CO2(aq) Ca(HCO3)2(aq) and obtaining the design flow rate of buffered ionic mixture (76) with the desired pH.

Images