JP7806232B2 - Fluidized bed reactor for the continuous generation of thermochemical heat energy and corresponding method and system - Google Patents

Description

[001] The present invention relates to a fluidized bed reactor for the continuous generation of thermochemical heat energy, according to a preferred embodiment, by utilizing solid particles from the reaction calcium oxide + steam -> calcium hydroxide (Ca(OH) ₂ ).

[002] The present invention advantageously relates to a corresponding method for the continuous generation of thermochemical heat energy from the reaction calcium oxide (CaO) + water (H ₂ O) -> calcium hydroxide (Ca(OH) ₂ ) in the gas phase (steam).

[003] The present invention also relates to corresponding systems for storing and releasing thermal energy based on the above reactions and their reverse reactions.

[004] While fossil fuels are a convenient and widely available energy source, environmental aspects have led to growing interest in alternative fuels and energy generation. Accordingly, fuels using low-carbon energy carriers with high energy density have proven to be an alternative for many essential roles of fossil fuels, including electricity and thermal power generation, powering transportation vehicles, and global energy trade. Reversible exothermic reactions, such as CaO, with water are considered one of the most promising reactions for high-temperature thermal energy storage. As recyclable carriers of clean energy, metal fuels are a promising alternative to fossil fuels in the upcoming low-carbon economy. Metals have high energy density and are therefore the fuel in many batteries, energetic materials, and propellants. Metal fuels can be burned with air or reacted with water to release chemical energy at various power generation scales. The products of metal oxy-combustion are solids that can be captured and recycled using clean energy-powered, zero-carbon electrolytic processes, enabling the use of metals as recyclable, zero-carbon solar or electrofuels. The main technological barrier to increased use of metal fuels is the current lack of clean and efficient combustor/reactor/engine technology to convert the chemical energy of metal fuels into motive or electrical energy.

[005] WO 2021/105467 discloses a system for energy storage that includes a fluidized bed apparatus using an energy storage material. The energy storage material includes at least one metal hydroxide selected from CaO, Ca(OH)2, CaCO3, MgO, Mg(OH)2, MgCO3, BaO, Ba(OH)2, BaCO3, and MgH2. In one embodiment, the fluidized bed apparatus includes at least one perforated separator that generates two or more fluidized compartments within the fluidized bed apparatus. This creates multiple fluidized zones in the fluidized bed apparatus. This arrangement allows for different conditions in different zones. The perforated separator is at least partially foraminous. In one embodiment, the perforated separator is horizontally arranged to create upper and lower fluidized zones. In another embodiment, several perforated separators are arranged to create multiple fluidized zones. The perforated separator has the advantage of creating several fluidization zones in which different conditions can be maintained. For example, the temperatures can be different. For example, if a first preheat is followed by a second heating to a higher temperature, the process can be made more efficient. The device for introducing pressurized fluid is not shown in this publication.

[006] An object of the present invention is to provide an improved fluidized bed reactor for generating thermochemical heat energy, with significantly improved performance compared to prior art solutions. This performance is improved, particularly with respect to reliable operation, viability, yield, and efficiency during use of the reactor. It is also an object of the present invention to achieve an industrial-scale reactor capable of uniformly carrying out reactions. It is an object of the present invention to provide an improved fluidized bed reactor for solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn).

[007] The objects of the invention can be achieved substantially as disclosed in the independent claims and in the further claims which describe in detail different embodiments of the invention.

[008] According to one embodiment,
1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form, and an oxidizer in gaseous or vapor form, such as steam or an oxygen-containing gas or vapor; or
2) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe) and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide;
A fluidized bed reactor is provided for continuously generating thermochemical heat energy by using one of the following reactions:
The reactor is
a reactor chamber; and
an inlet disposed at a first end of the reactor chamber for feeding solid particles into the reactor;
an array of fluidization stages disposed within the reactor chamber;
each of the fluidization stages comprising a plurality of nozzles for fluidizing the solid particles with a reactive fluidizing agent, an oxidizing agent, or a hydration compound to initiate and advance the reaction;
the fluidization stage is equipped with one or more heat exchangers for selectively recovering heat released from the reaction;
An outlet is located at the end of the reactor chamber opposite the first end for discharging reaction materials.

[009] According to one embodiment,
1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form, and an oxidizer in gaseous or vapor form, such as steam or an oxygen-containing gas or vapor; or
2) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe) and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide;
A method is provided for continuously generating thermochemical heat energy by using one of the following reactions:
The method is:
providing a raw material of solid particles into the reactor chamber at a first end of the reactor chamber;
fluidizing the solid particles with a fluidizing jet of the first fluidization stage to initiate the reaction;
The generated heat is transferred to a heat exchanger in the reaction chamber;
Continuing the feed of raw materials from the first end of the reactor chamber moves the raw material/partially reacted material mixture to subsequent fluidization stages, where fluidization jets continue to fluidize the mixture, and the released heat is transferred by a heat exchanger, and as fluidization continues, the composition of the mixture changes to more and more of the final material, and after the last fluidization stage, the mixture contains only a small percentage of the raw materials, and in each of the fluidization stages, the temperature, saturation, and flow rate of the fluidization stream control the yield of the reaction;
The reaction materials are removed from the reaction chamber through an outlet.

For purposes of clarity only, the term reactant refers to the final material, i.e., the reaction product, that is removed from the reaction chamber via the outlet. For example, in the case of the reaction of calcium oxide (CaO) with water ( _H2O ) in the gas phase, i.e., steam, the reactant is calcium hydroxide (Ca(OH) ₂ ).

[0011] According to one embodiment, when one of the disclosed metals is used as the solid particles introduced into the reactor chamber and the fluidizing agent is an oxygen-containing gas, a flammable condition is created within the reactor chamber. Generally, when a metal powder is used in conjunction with a staged fluidized reactor chamber, a flammable situation is created as the metal oxidizes.

[0012] The general reaction, reactor, and method disclosed above are suitable for several solid particulate or powdery materials. The invention will now be described in more detail in connection with one of the preferred embodiments. The reaction is calcium oxide (CaO) + water ( _H2O ) → calcium hydroxide (Ca(OH) ₂ ) in the gas phase, i.e., steam, because this is one of the most economically viable alternatives for this purpose. Another preferred embodiment uses magnesium, i.e., MgO + _H2O → Mg(OH) ₂ . Other disclosed materials, i.e., lithium (Li), boron (B), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn), may also be used. In the following disclosure, even though the process is disclosed as using the CaO/Ca(OH) ₂ reaction, the method and reactor are also directly applicable to the other disclosed materials, i.e., alkaline earth metals or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn).

[0013] According to one embodiment, the solid particle size may be within the range of 1 to 1000 μm, or 1 to 500 μm, or 100 to 300 μm. The solid particle size affects both the reaction itself and the fluidity of the particles; the smaller the particle size, the faster the reactivity and fluidity. The particle size can be selected as needed and depending on the actual operating conditions to obtain the desired controllability.

According to one embodiment of the present invention, in addition to introducing a reactive fluidizing agent, an oxidizing agent, or a hydrated compound, a non-reactive fluidizing agent may be introduced into the reactor. A non-reactive fluidizing agent in this case means that it does not participate in the reaction. Advantageously, the non-reactive fluidizing agent improves particle distribution, so that it does not participate chemically but can promote the reaction. According to one embodiment of the present invention, in the case of calcium oxide (CaO) + water (H ₂ O) → calcium hydroxide (Ca(OH) ₂ ) in the gas phase (steam), steam is the reactive fluidizing agent, and air and/or an oxygen-containing gas as a non-reactive fluidizing agent can be introduced into the reactor chamber. According to one embodiment of the present invention, the non-reactive fluidizing agent can be introduced at the same vertical level as the reactive fluidizing agent. According to one embodiment of the present invention, the reactor is equipped with a nozzle for introducing a mixture of the reactive fluidizing agent and the non-reactive fluidizing agent into the reactor chamber through the same nozzle, or the reactor is equipped with separate nozzles for the reactive fluidizing agent and the non-reactive fluidizing agent. Therefore, the mixture of reactive and non-reactive fluidizing agents can be introduced into the chamber through the same nozzle as the reactive fluidizing agent, or the reactor can be equipped with separate nozzles for the reactive and non-reactive fluidizing agents. Here, "nozzle" refers to a device that generates a substantially unidirectional flow over the nozzle. Therefore, the reactive fluidizing agents are preferably introduced through the nozzles separately at each level, since each fluidizing nozzle is arranged in fluid communication with a source of reactive fluidizing agent. According to one embodiment of the present invention, a non-reactive fluidizing agent, such as an inert gas, can be introduced into the reactor chamber, particularly in the case of solid particles of one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn).

[0015] According to one embodiment, when CaO is introduced and the fluidizing agent is steam, calcium hydroxide is formed and no combustion occurs.

[0016] According to one embodiment of the present invention, a fluidized bed reactor is provided for continuously generating thermochemical heat energy by utilizing solid particles from the reaction of calcium oxide (CaO) + water ( _H2O ) -> calcium hydroxide (Ca(OH) ₂ ) in the gas phase (steam).
The reactor is
a reactor chamber; and
an inlet disposed at a first end of the reactor chamber for supplying solid particles of CaO into the reactor;
an array of fluidization stages disposed within the reactor chamber;
each of the fluidization stages comprising a plurality of steam nozzles for fluidizing the CaO with steam to initiate and advance the reaction;
the fluidization stage is equipped with one or more heat exchangers for selectively recovering heat released from the solid material in the reaction;
An outlet is located at the end opposite the first end of the reactor chamber (10) for discharging the Ca(OH) ₂ .

[0017] According to one embodiment of the present invention, there is provided a method for continuously generating thermochemical heat energy from the reaction calcium oxide (CaO) + water ( _H2O ) -> calcium hydroxide (Ca(OH) ₂ ) in the gas phase (steam). The method comprises:
providing solid particles of CaO into the reactor chamber at a first end of the reactor chamber;
fluidizing the CaO with steam jets in a first fluidization stage to initiate the reaction;
The generated heat is transferred to a heat exchanger in the reaction chamber;
By continuing to feed CaO raw material from the first end of the reactor chamber, the partially reacted CaO/Ca(OH) ₂ mixture is moved to subsequent fluidization stages, where fluidization of the mixture by steam jets continues and the released heat is transferred by heat exchangers, and as fluidization continues, the composition of the CaO/Ca(OH) ₂ mixture changes to more Ca(OH) ₂ , and after the final fluidization stage, the mixture contains Ca(OH)2 along with a small percentage of CaO, and in each of the fluidization stages the temperature, saturation, and flow rate of the stream control the yield of the reaction.
The reaction product Ca(OH) ₂ is removed from the reaction chamber via an outlet.

[0018] This results in efficient release of thermochemical heat energy from the raw materials, and the reaction products remain in dry particulate or powder form, allowing for easy storage and relatively simple regeneration to the initial materials via the reverse reaction, i.e., alkaline earth metals or elemental metals, or alkaline earth metals or oxidized metals, e.g., Ca(OH)2 → CaO. This significantly improves the performance of reactors, methods, and systems for continuously generating thermochemical heat energy. The present invention ensures proper fluidization velocity and dispersion of solid particles from bottom to top within the reactor. The temperature response is a function of the steam partial pressure below the equilibrium curve. For example, at 100 kPa (1 bar), the equilibrium temperature is approximately 520°C, and as the temperature exceeds 520°C, the reaction shifts to dehydration. One advantage of this reactor is that the reaction can occur uniformly within the reactor, improving heat recovery via a heat exchanger.

According to an embodiment, an array of fluidization stages is arranged within the reactor chamber, each of which includes multiple steam nozzles for fluidizing the CaO with steam to initiate and advance the reaction. It is preferable to implement an efficient thermochemical process in several stages for maximum efficiency and yield. However, the properties of calcium oxide and the subsequent calcium oxide/calcium hydroxide mixture change during the process/reaction, resulting in different fluidization characteristics. Therefore, by continuing to feed CaO raw material from the first end of the reactor chamber, the _partially reacted CaO/Ca(OH) mixture is transferred to subsequent fluidization stages, where steam jets continue to fluidize the mixture. The released heat is transferred by a heat exchanger. As fluidization continues, the composition of the CaO/Ca(OH) mixture changes _{to more} Ca(OH) until, after the final fluidization stage, the mixture contains Ca(OH) along with a small percentage of CaO. According to one embodiment, the fluidization stage is configured within one compartment, enabling efficient flow and reaction of CaO/Ca(OH) ₂ within the reactor chamber. Prior art document WO 2021/105467 discloses that the reaction is carried out in several compartments separated by vertically divided perforated separators, i.e., perforated separators. Theoretically, horizontal arrangement of the compartments is also possible. However, prior art documents suggest several laboratory-scale examples, with reactor volumes of approximately 600 ml. Since the present invention is intended for industrial-scale operation and megawatt-scale power capacities, the reactor volumes range from several cubic meters to several hundred cubic meters. The inventors have discovered that separators have potential clogging issues and that it would be better to simplify the reactor so that neither separators nor compartments are required. This has a significant impact on the viability and operation of continuously operated reactors, as clogging requires the reactor to be shut down and cooled for several days until the clogging material is removed.

[0020] According to an embodiment of the present invention, the reaction chamber is free of dividing walls and/or compartments and/or perforated separators between fluidization stages. This is due to the arrangement of an array of fluidization stages within the reactor chamber, each of which includes multiple nozzles for fluidizing solid particles with a reactive fluidizing agent to initiate and advance the reaction. The reactor can be designed without compartments separated by perforated plates and/or dividing walls between fluidization stages. This allows the entire reactor chamber to be advantageously utilized to promote the thermochemical reaction and recover heat. This also prevents potential clogging issues or other accumulations of material. By material, we mean raw materials, partially reacted materials, or final products, in other words, reaction materials.

[0021] According to one embodiment of the present invention, one array of fluidization stages is disposed at the bottom of the reactor chamber to form a first fluidization stage, and another array of fluidization stages is disposed at a higher vertical level than the first fluidization stage. Advantageously, different arrays of fluidization stages can be disposed at different vertical levels. Stages at different levels vertically disposed within the reactor chamber or disposed in an inclined configuration of the reactor chamber can be utilized. Advantageously, different fluidization stages or different fluidization levels can provide the following synergistic effects and/or advantages: improving particle distribution through fluidization while simultaneously utilizing the fluidizing agent as a medium for participating in the reaction and forming the final material from the raw materials and fluidizing agent. The fluidizing agent can be "consumed" and/or "captured" in the reaction to form the final material. Note that the raw materials (e.g., CaO) can have a different density than the final product (e.g., Ca(OH)2) being formed. Furthermore, the fluidizing agent (e.g., steam) can have a different density than the raw materials and/or the final product.

[0022] According to one embodiment, the reactor is circular in cross section and has a length greater than its width or diameter. This length allows for efficient fluidization and subsequent reactions, and allows the reactor to include 2 to 5 fluidization stages within the reactor chamber, preferably 3 to 4 fluidization stages. This also allows for optimal adaptation of process efficiency. Nearly all input material reacts to calcium hydroxide, and there is no bypassed or overflow calcium oxide flowing to the reactor outlet.

[0023] According to one embodiment, the reactor is vertical, with the inlet and outlet arranged perpendicular to each other in the reactor chamber. Preferably, in a vertical reactor configuration, the vertical height of the reactor is greater than the horizontal width of the reactor. This vertical configuration allows for control of material flow and simultaneous reaction, with control parameters being the input feed rate (mass flow rate), fluidizing steam velocity at the nozzles of each stage, steam temperature, and saturation (moisture content). Furthermore, according to an embodiment, the steam temperature can be gradually increased, gradually decreased, or maintained constant from one fluidization stage to the next. According to an embodiment, the steam velocity at the steam nozzles can be gradually decreased or increased from one fluidization stage to the next. The size and/or shape of the nozzles can be varied in one fluidization stage and/or multiple fluidization stages to produce favorable fluidization and reaction. Also, according to one embodiment, the reactor is equipped with a gas discharge channel for discharging excess fluidizing agent.

[0024] According to one embodiment, there is provided a system for storing and releasing thermal energy based on the reactions CaO + _H2O → Ca(OH) ₂ and Ca(OH) ₂ + heat → CaO + _H2O . The system comprises the reactor described above for utilizing the method disclosed above. The system further comprises a reservoir for CaO, a reservoir for Ca(OH)2, and a regeneration reactor for the process of converting Ca(OH) ₂ back to CaO. The system is utilized to release heat when needed and to store heat when available.

[0025] The heat generated in the above-mentioned reaction, e.g., CaO + _H2O -> Ca(OH) ₂ , and recovered by a heat exchanger can be utilized, for example, for district heating and/or power generation. The fluidization stage is equipped with one or more heat exchangers for selectively recovering the heat released from the reaction. The term "selectively recover" here means that the heat exchangers can differ from each other in actual design or operating conditions to achieve the most efficient heat recovery at each location in the reactor chamber. Preferably, a portion of the generated heat is used to support the reaction and heat a fluidizing agent, such as steam. Alternatively, the steam introduced into the reactor chamber can be extracted from the reactor's main steam line. There are several possible ways to arrange the heat exchangers. For example, various heat exchanger sequencing arrangements are possible, including superheater, evaporator, and economizer. The first heat exchanger in the reactor chamber is most likely to be the hottest one. In all of the embodiments, the objective is to transfer all the heat generated in the reaction to the heat exchanger and to keep the temperature of the reaction mass at the outlet as low as possible.

[0026] Advantageously, the fluidization stage can promote reaction at the inlet side of the reactor chamber, along with particle distribution through fluidization. Advantageously, fluidization and/or particle velocity can be maintained at a desired level and/or uniformity, thereby preventing potential erosion problems, for example, when fluidization occurs only in the lower part of the reactor chamber. The size and/or shape of the nozzles can be varied in one fluidization stage and/or multiple fluidization stages to produce favorable fluidization and reaction. Stage-based fluidization advantageously allows the reactor volume to be optimized to achieve high intensity of energy release.

[0027] The exemplary embodiments of the invention proposed in this patent application are not to be construed as imposing limitations on the applicability of the appended claims. The verb "comprise" is used in this patent application as an open limitation that does not exclude the presence of unrecited features. Features recited in the dependent claims may be freely combined with each other unless expressly stated otherwise. The novel features that are regarded as characteristic of the invention are particularly set forth in the appended claims.

[0028] The present invention will now be described with reference to the accompanying exemplary schematic drawings.

1 shows a reactor according to one embodiment of the present invention. 1 illustrates a cross-sectional nozzle configuration according to an embodiment of the present invention. 1 shows a reactor according to another embodiment of the present invention. 1 illustrates a system according to one embodiment of the present invention. 1 shows a reactor according to one embodiment of the present invention.

[0029] Figure 1 shows schematically a fluidized bed reactor 1 for the continuous generation of thermochemical heat energy by using one of the following reactions:
1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form, and an oxidizing agent in the form of a gas or vapor, such as steam, air, or oxygen; or
2) Solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide.
Reactor 1 is
a reactor chamber 10;
an inlet 2 disposed at a first end of the reactor chamber 10 for feeding solid particles into the reactor 1;
Within the reactor chamber 10, an array of fluidization stages 3 is disposed;
each fluidization stage 3 comprises a plurality of nozzles 32 for fluidizing the solid particles with a reactive fluidizing agent, an oxidizing agent, or a hydration compound to initiate and advance the reaction;
The fluidization stage 3 is equipped with one or more heat exchangers 4 for selectively recovering heat released from the reaction;
An outlet 5 is located at the end of the reactor chamber 10 opposite the first end for discharging the reaction materials.

[0030] In other words, to fluidize the solid particles with the reactive fluidizing agent, the reactive fluidizing agent is introduced through the nozzles 32 in each of the fluidization stages 3. Multiple nozzles are illustrated for supplying reactive fluidization to fluidize the solid particles. This therefore allows the reactive fluidizing agent to be introduced at different vertical levels through nozzles at different levels in FIG. 1. In addition to supplying a reactive fluidizing agent, it may be possible to supply a non-reactive fluidizing agent from the same nozzle, or to supply a mixture of reactive and non-reactive fluidizing agents from the same nozzle. This allows advantageous control of the fluidization along with the reaction in each fluidization stage 3.

[0031] According to a preferred embodiment, Figure 1 shows a schematic diagram of a fluidized bed reactor 1 for continuously generating thermochemical heat energy by utilizing solid particles from the reaction of calcium oxide (CaO) + water ( _H2O ) -> calcium hydroxide (Ca(OH) ₂ ) in gas phase (steam).
Reactor 1 is
a reactor chamber 10;
an inlet 2 disposed at a first end of the reactor chamber 10 for feeding solid particles of CaO into the reactor 1;
Within the reactor chamber 10, an array of fluidization stages 3 is disposed;
Each of the fluidization stages 3 comprises a plurality of steam nozzles 32 for fluidizing the CaO with steam to initiate and advance the reaction;
The fluidization stage 3 is equipped with one or more heat exchangers 4 for selectively recovering heat released from the solid material in the reaction;
An outlet 5 is arranged at the end of the reactor chamber 10 opposite the first end for discharging Ca(OH) _2. In addition to the reactor 1 itself, FIG. 1 proposes an embodiment in which the raw material CaO is stored in a reservoir 6 and fed from there into the reactor 1 by suitable means, such as a screw conveyor (not shown; valves and other equipment are also not shown in FIG. 1). After the reactor 1, the reacted or final material is transferred to a reservoir 7. The reactor 1 is vertical and has an inlet 2 and an outlet 5 arranged in a mutually perpendicular position in the reactor chamber 10. According to the embodiment shown in FIG. 1, the inlet 2 for introducing the solid particulate material is arranged at the top of the reactor chamber 10, while the outlet 5 for discharging the reacted material is arranged at the bottom of the reactor chamber 10, at the end opposite the inlet 2. FIG. 1 proposes an array of five fluidization stages 3 with nozzles 32 arranged in a suitable pattern, as shown diagrammatically in FIG. 2a or 2b. This pattern can be formed, for example, by pipes 31 with nozzles attached at specific intervals. The term fluidization stage refers to fluidization levels located within a specific vertical distance from one another. In other words, one fluidization stage comprises a nozzle 32 for introducing a reactive fluidizing agent at substantially one vertical level. In other words, the reactive fluidizing agent is introduced through the nozzle 32 to fluidize the solid particles and allow them to participate in the reaction. The vertical distances between the fluidization stages or levels can be equally distributed, meaning at a constant vertical distance from one another. Thus, proper fluidization velocity and distribution of the solid particles from bottom to top within the reactor chamber are ensured. The size and/or shape of the nozzle 32 can be varied within one fluidization stage and/or multiple fluidization stages to achieve favorable fluidization and reaction.

[0032] The pipes 31 form a manifold for steam or any other suitable reactive fluidizer or fluidizing agent, such as air or oxygen. The cross section of the pipes 31 may have a circular or rectangular cross section, to name a few suitable cross sections. In FIG. 1, the heat exchangers are arranged in a basic configuration, with one heat exchanger 4 layer for each fluidization stage 3. However, variations may be made so that the number of heat exchangers 4 is greater than the number of fluidization stages 3, or less than the number of fluidization stages 3. One heat exchanger 4 includes at least one heat exchanger inlet 41 and at least one heat exchanger 4 outlet 42 for a heat transfer medium (water, steam, some other fluid) that transfers heat from the reactor 1. The heat exchanger inlets 41 and outlets 42 can be grouped in any suitable manner and, in one embodiment, can be connected in series or in parallel. The fluid source for the heat exchanger can be from any suitable source. The target for the heated fluid from the heat exchanger can be any suitable source. The actual configuration of the heat exchanger is a matter of reactor or plant design; the inner wall can be formed by the heat exchanger, or the heat exchanger can be configured to extend radially into the reactor chamber 10 (as shown in FIG. 2a), with heat transfer into the heat exchanger 4 being based, for example, on convection or conduction. The heat exchanger can include tubes and can be configured to extend into the reactor chamber as a tube bundle (not shown). Because reaction and heat recovery can occur uniformly within the reactor, the temperature of the exiting particles is reduced. This means that heat is recovered by the heat exchanger 4.

2a and 2b show a horizontal cross section of the reactor chamber of FIG. 1 and schematically illustrate several possible configurations of nozzles 32 arranged on pipes 31 forming the fluidization stage 3. A reactive fluidizing agent is introduced into the reactor chamber 10 through the nozzles. It is also possible to introduce a non-reactive fluidizing agent into the reactor chamber 10 through the nozzles. Since all figures in this disclosure are schematic, elements are not drawn to scale, and relative dimensions are shown for illustrative purposes only. However, all fluidization stages 3 are arranged in one compartment to allow efficient flow and reaction of CaO/Ca(OH) ₂ within the reactor chamber 10. Therefore, the pipes 31 shown in FIGS. 2a and 2b do not form compartments for each fluidization stage 3, and material can pass through the arrangement of pipes 31. Therefore, particle clogging can be avoided or reduced, improving the availability and efficiency of operation compared to known solutions. This configuration of the fluidization stages, or in other words, the fluidization introduction stages, allows the reaction to occur uniformly within the reactor chamber.

[0034] One embodiment of the reactor 1 is proposed in Figure 3. In this embodiment, the fluidization stages 3 are arranged so that there is a central pipe 31 in the central area of the reactor chamber 10, which serves as a manifold for the nozzles 32, and there are further nozzles arranged in the walls of the reactor chamber 10. The fluidization effect is determined by the velocity of the fluidizing medium (such as steam) as well as the appropriate orientation of the nozzles 32. According to the embodiments of Figures 1, 2a, 2b (shown in cross section), and 3, the reactor 1 has a circular cross section perpendicular to the general flow direction, with a length greater than a width. This characteristic affects the reaction time in the reactor, and the length, diameter, and number of stages are suitably parameters selected for the reactor design. Other possible reactor cross-sectional shapes are rectangular or polygonal, such as hexagonal or octagonal. Heat exchangers, not shown in Figures 2b and 3, can be arranged between the fluidization stages as in Figure 1. Similarly, as in Figure 1, one fluidization stage 3 is defined by the vertical distance between nozzles 32 at different vertical levels.

[0035] In Figure 4, a system 100 is proposed for continuously storing and releasing thermochemical heat energy based on one of the reactions by using one of the following reactions:
1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form, and an oxidizing agent in the form of a gas or vapor, such as steam, air, or oxygen; or
2) Solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide.
The system includes a reactor 1, and system 100 further includes a storage section 6 for raw materials, a storage section 7 for final materials, and a regeneration reactor 8 for processing the final materials back into raw materials. System 100 is utilized to release heat when needed and store heat when available. In the reactors of the present disclosure, this energy storage and release and/or energy charging/discharging can be performed in one location, or energy storage can be performed where energy is available and the energy-stored material can then be transported to a location where the energy is discharged from the material.

[0036] In the operation of system 100, 1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form, or 2) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in oxidized form, are considered raw materials that can be stored in reservoir 6, and the reacted compound, or in other terms the final product, i.e., 1) oxidized or 2) hydrated (hydroxide) particles, are the reaction materials that can be considered final materials that can be stored in reservoir 7.

[0037] In Figure 5 an embodiment of a fluidized bed reactor (1) is proposed for the continuous generation of thermochemical heat energy by using one of the following reactions:
1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form, and an oxidizer in gaseous or vapor form, such as steam or an oxygen-containing gas or vapor; or
2) Solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide.
Reactor 1 is
a reactor chamber 10;
an inlet 2 disposed at a first end of the reactor chamber 10 for feeding solid particles into the reactor 1;
Within the reactor chamber 10, an array of fluidization stages 3 is disposed;
each fluidization stage 3 comprises a plurality of nozzles 32 for fluidizing the solid particles with a reactive fluidizing agent, an oxidizing agent, or a hydration compound to initiate and advance the reaction;
The fluidization stage 3 is equipped with one or more heat exchangers 4 for selectively recovering heat released from the reaction;
An outlet 5 is located at the end of the reactor chamber 10 opposite the first end for discharging the reaction materials. In this embodiment, solid particles are used as the raw material for the process, initially stored in a reservoir 6, fed into the reactor 1 and reactor chamber 10 via an inlet 2, and then fluidized to initiate and proceed the reaction. In this embodiment, two rows of fluidizing nozzles are configured. The reactor can be equipped with a single nozzle 32, 32a for introducing a mixture of reactive and non-reactive fluidizing agents into the reactor chamber through the same nozzle 32. In the embodiment of FIG. 5, the reactor is equipped with two rows of nozzles 32, 32a, i.e., configured with separate nozzles so that a nozzle 32 for the reactive fluidizing agent and a nozzle 32a for the non-reactive fluidizing agent are provided. This embodiment may be particularly suitable for materials that require effort to fluidize, i.e., denser particulate materials, or the like. If both reactive and non-reactive fluidizing agents are fed into the reactor chamber 10, the balance of material (volume) input/output may be such that a separate gas discharge channel 9 is required. Depending on the actual process conditions, the gas discharge channel may be equipped with a particle separator or the like to prevent solid particles from escaping the reactor chamber through this route. Such a gas discharge channel may also be required in a reactor 1 having only a single type of fluidizing agent feed, i.e., only a nozzle 32 for the reactive fluidizing agent, if the process requires that the amount of reactive fluidizing agent exceeds the actual amount participating in the reaction.

[0038] According to one embodiment of the present process, steam is introduced as a reactive fluidizing agent, and the temperature of the steam is gradually increased, gradually decreased, or remains the same from fluidization stage 3 to subsequent fluidization stages 3. This process, reactor, and system can have many modes of operation.

[0039] According to one embodiment of the present method, the steam velocity at the steam nozzle 32 gradually decreases or increases from fluidization stage 3 to subsequent fluidization stages 3.

[0040] While the present invention has been described by way of example herein in connection with what are presently considered to be the most preferred embodiments, it will be understood that the invention is not limited to the disclosed embodiments, but is intended to encompass various combinations or modifications of its features and several other applications which fall within the scope of the invention as defined by the appended claims. Details discussed in connection with any of the above-described embodiments may be used in connection with other embodiments where such combinations are technically feasible.

List of components 1 Reactor 10 Reactor chamber 11 Inner wall 100 System 2 Inlet 3 Fluidization stage 31 Pipes 32, 32a Nozzle 4 Heat exchanger 41 Heat exchanger inlet 42 Heat exchanger outlet 5 Outlet 6 Storage (for raw materials)
7. Reservoir (for final product)
8 Regeneration reactor 9 Gas discharge channel

Claims (14)

1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form , and an oxidizing agent in gaseous or vapor form; or
2) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe) and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide;
A fluidized bed reactor (1) for continuously generating thermochemical heat energy by generating heat of reaction accompanying the production of a reaction product by one of the following reactions:
The fluidized bed reactor (1) comprises:
a reactor chamber (10);
an inlet (2) disposed at a first end of the reactor chamber (10) for feeding the solid particles into the fluidized bed reactor (1);
an outlet (5) located at an end of the reactor chamber (10) opposite the first end for discharging reaction materials ;
an array of fluidization stages (3) disposed within the reactor chamber (10) between the inlet (2) and the outlet (5) ;
each of the fluidization stages (3) comprises a plurality of nozzles (32) for fluidizing the solid particles with a reactive fluidizing agent, the oxidizing agent, or the hydrated compound to initiate and advance the reaction;
The array is equipped with one or more heat exchangers (4) for selectively recovering the heat of reaction ;
The fluidized bed reactor (1) is a vertical type,
the inlet (2) and the outlet (5) are arranged in a perpendicular position relative to each other in the reactor chamber (10) ;
the nozzle (32) is arranged on the pipe (31) forming the fluidization stage (3);
A fluidized bed reactor (1) in which all of said fluidization stages (3) are arranged in one compartment to allow flow of solid particles within said reactor chamber (10). A fluidized bed reactor (1) for continuously generating thermochemical heat energy by utilizing the heat of reaction generated from the reaction of calcium oxide (CaO) solid particles + steam (H 2 O) in the gas _phase - > calcium hydroxide ₍ Ca(OH) 2 ),
The fluidized bed reactor (1) comprises:
a reactor chamber (10);
an inlet (2) located at a first end of the reactor chamber (10) for feeding the solid particles of CaO into the fluidized bed reactor (1);
an outlet (5) located at an end of the reactor chamber (10) opposite the first end for discharging Ca(OH) ₂ ;
an array of fluidization stages (3) disposed within the reactor chamber (10) between the inlet (2) and the outlet (5) ;
each of said fluidization stages (3) comprising a plurality of steam nozzles (32) for fluidizing the CaO with steam to initiate and advance the reaction;
The array is provided with one or more heat exchangers (4) for selectively recovering the heat of reaction ;
The fluidized bed reactor (1) is a vertical type,
the inlet (2) and the outlet (5) are arranged in a perpendicular position relative to each other in the reactor chamber (10) ;
the nozzle (32) is arranged on the pipe (31) forming the fluidization stage (3);
A fluidized bed reactor (1) in which all of said fluidization stages (3) are arranged in one compartment to allow flow of solid particles within said reactor chamber (10). 3. The fluidized bed reactor (1) according to claim 1 or 2, wherein the heat exchangers (4) are arranged in the array to form the inner walls (11) of the reactor chambers. The fluidized bed reactor (1) includes:
Nozzles (32, 32a) are provided for introducing a mixture of reactive and non-reactive fluidizing agents into the reactor chamber through the same nozzle (32), or
4. A fluidized bed reactor (1) according to any one of claims 1 to 3 , wherein separate nozzles (32, 32a) are provided for reactive and non-reactive fluidizing agents. 5. The fluidized bed reactor (1) according to any one of claims 1 to 4, wherein the fluidized bed reactor (1) is circular in cross section and has a length greater than its width . 6. The fluidized bed reactor (1) according to any one of claims 1 to 5 , wherein the fluidized bed reactor (1) comprises two to five fluidization stages (3 ) within the reactor chamber ( 10 ). 7. The fluidized bed reactor (1) according to any one of claims 1 to 6, comprising a first set of nozzles (32) for fluidizing the solid particles with a reactive fluidizing agent to initiate and progress the reaction , and a second set of nozzles (32a ) for fluidizing the solid particles with an inert or less reactive fluidizing agent to increase the fluidization of the solid particles. 8. The fluidized bed reactor (1) according to any one of claims 1 to 7 , wherein the fluidized bed reactor ( 1) is provided with a gas discharge channel (9) for discharging excess fluidizing agent. 1) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe), and zinc (Zn) in elemental form , and an oxidizing agent in gaseous or vapor form; or
2) solid particles of an alkaline earth metal or one of the metals from the group consisting of lithium (Li), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), iron (Fe) and zinc (Zn) in oxidized form and its hydrated compound in gaseous or vapor form to obtain a hydroxide;
1. A method for continuously generating thermochemical heat energy by generating heat of reaction associated with the production of a reaction product by one of the following reactions:
supplying a raw material of solid particles to a reactor chamber (10) of a fluidized bed reactor (1) at a first end of said reactor chamber (10);
fluidizing the solid particles with a fluidizing jet introduced through a nozzle (32) of a first fluidization stage (3) in an array of fluidization stages ( 3) to initiate the reaction;
The reaction heat is transferred to a heat exchanger ( 4 ) in the reaction chamber (10),
Continuing the feed of raw materials from the first end of the reactor chamber (10) moves the mixture of raw materials and partially reacted material to a subsequent fluidization stage (3) in which fluidization jets continue to fluidize the mixture, the heat of reaction is transferred by the heat exchanger (4), and as the fluidization continues, the composition of the mixture changes to more and more final material, so that after the last fluidization stage (3) in the array , the mixture contains only a small proportion of the raw materials, and in each of the fluidization stages, the temperature, saturation, and flow rate of the fluidization stream control the yield of the reaction;
The fluidized bed reactor (1) is vertical and has an inlet (2) and an outlet (5) arranged in a mutually perpendicular position in the reactor chamber (10),
The nozzle (32) is arranged on the pipe (31) forming the fluidization stage (3),
all of said fluidization stages (3) are arranged in one compartment to allow flow of solid particles within said reactor chamber (10);
The method wherein the reaction material is removed from the reaction chamber through the outlet (5). A method for continuously generating thermochemical heat energy by utilizing the heat of reaction generated from the reaction of calcium oxide (CaO) solid particles + steam (H ₂ O) in the gas phase → calcium hydroxide (Ca(OH) ₂ ), the method comprising:
supplying solid particles of CaO into a reactor chamber (10 ) of a fluidized bed reactor (1) at a first end of said reactor chamber (10);
fluidizing the CaO by steam jets introduced through nozzles (32) of a first fluidization stage (3) of an array of fluidization stages (3) to initiate the reaction;
The reaction heat is transferred to a heat exchanger (4) in the reaction chamber (10),
The feed of CaO raw material from the first end of the reactor chamber (10) is continued to move the partially reacted CaO/Ca(OH) ₂ mixture to subsequent fluidization stages (3) in the array , where fluidization of the mixture by steam jets continues and the heat of reaction is transferred by the heat exchanger (4), and as the fluidization continues, the composition of the CaO/Ca(OH) ₂ mixture changes to more Ca(OH) ₂ , so that after the last fluidization stage (3) in the array , the mixture contains Ca(OH) ₂ with a small percentage of CaO, and in each of the fluidization stages (3) the steam temperature, saturation, and flow rate control the yield of the reaction;
The fluidized bed reactor (1) is vertical and has an inlet (2) and an outlet (5) arranged in a mutually perpendicular position in the reactor chamber (10),
The nozzle (32) is arranged on the pipe (31) forming the fluidization stage (3),
all of said fluidization stages (3) are arranged in one compartment to allow flow of solid particles within said reactor chamber (10);
The reaction product Ca(OH) ₂ is removed from the reaction chamber (10) via the outlet (5). Steam is introduced as a reactive fluidizer.
11. The method according to claim 9 or 10, wherein the temperature of the steam is gradually increased, gradually decreased or remains the same from one fluidization stage (3) to the subsequent fluidization stage (3). 12. The method according to claim 9, 10 or 11, wherein the steam velocity in the steam nozzle (32) gradually decreases or increases from the fluidization stage ( 3 ) to the subsequent fluidization stage (3). A mixture of reactive and non-reactive fluidizing agents is introduced into the chamber by a nozzle through the same nozzle as the reactive fluidizing agent, or
10. The method according to claim 9, wherein the fluidized bed reactor ( 1 ) is equipped with separate nozzles for reactive and non-reactive fluidizing agents. 1) solid particles of an alkaline earth metal or metal in elemental form and an oxidizing agent in gas or vapor form, or
2) solid particles of alkaline earth metals or metals in oxidized form and their hydrated compounds in gaseous or vapor form to obtain hydroxides;
1. A system (100) for continuously storing and releasing thermochemical heat energy based on one of the reactions by using one of the reactions:
The system comprises the fluidized bed reactor ( 1 ) according to any one of claims 1 to 8 for applying the method according to any one of claims 9 to 13,
The system (100) further comprises a storage section (6) for raw materials, a storage section (7) for final materials, and a regeneration reactor (8) for the process of returning the final materials to raw materials,
The system (100) is utilized to release heat when needed and to store heat when available.