GB2545716A

GB2545716A - Improvements in or relating to the separation of radon

Info

Publication number: GB2545716A
Application number: GB1522759.8A
Authority: GB
Inventors: Cipollone Rita; Ranalli Marco
Original assignee: Global H&s Ltd
Current assignee: Global H&s Ltd
Priority date: 2015-12-23
Filing date: 2015-12-23
Publication date: 2017-06-28
Anticipated expiration: 2035-12-23
Also published as: GB201522759D0; GB201611118D0; GB2545765A; GB2545765B; GB2545716B

Abstract

A process for the separation of radon from a mixture of gases consisting mainly of carbon dioxide (CO2) includes adsorption of the radon present in the mixture of gases in a substrate such as active carbon (8) and simultaneous removal of carbon dioxide. The process also includes desorption of radon (Rn) from the substrate, followed by the removal of radon through a washing fluid such as an inert gas and recovery of the substrate. The process happens with no depressurization in the substrate in a thermal cycle including an adsorption phase, a heating phase and a cooling phase. Also disclosed is a plant, an isobaric process and system for the separation of radon from a mixture of gases comprising mainly CO2. The plant may have three separation units (1, 2, 3), a high-temperature heat source (4) and a low-temperature heat absorber (5), a counter-current heat exchanger (6) and tubes (7) for their connection.

Description

Improvements in or Relating to the Separation of Radon

This invention regards a process for the separation of Radon from a mixture of gases consisting mainly of carbon dioxide. Furthermore, the invention regards a respective plant for separating Radon. Carbon dioxide (CO2) is an inert gas, odourless and colourless, and naturally present in the atmosphere in limited concentrations. Carbon dioxide is especially important because it is used in several processes and applications. It is one of the most commercialized and used technical gases in the world, used in several sectors, including refrigeration, food, chemical, medical, pharmaceutical, metal and electronic industries. Carbon dioxide is mainly produced chemically, as a combustion by-product, biologically and extracted from the soil.

Carbon dioxide, like all fluids extracted from the soil, can be contaminated with radioactive gases, including Radon; more precisely, those fluids can contain a mixture of isotopes of Radon gas known as 222Rn (Radon), 220Rn (Thoron), 219Rn (Actinon). Such radioactive gases can provide a mixture of radioactive elements known as "daughter products", produced from the natural decay of Radon. As a consequence, during purification and/or industrial treatment processes, an increasingly radioactive contamination of plants can occur owing to the natural decay of Radon. Furthermore, Radon and its decay products can contaminate the final product, causing dangers in transport and use of the product itself. Among the decay products, Polonium is the most dangerous for health, not only because of its radioactivity but also its toxic properties.

It has been calculated that exposure to Radon, its isotopes, and its decay products are the cause of more than 20000 deaths in the European Union, 3000 of them in Italy alone; furthermore, Radon is the second biggest cause of lung cancer after cigarette smoke.

Most of the techniques known to eliminate Radon from a fluid involve the ageing of the mixture for more than 40 days to allow the nearly complete decay of Radon, whose half-life is 3.8 days. This technique is not applicable for most of the products, except for liquid hydrocarbons that can be stored inside natural caves with low levels of radioactivity for long periods with low expense. Other techniques for the separation of Radon from a mixture of gases, such as distillation, have obtained no significant success, especially in the case of Carbon dioxide, owing to the extreme similarity of the boiling points of Radon and CO2·

Another separation technique is one based on the capacity of Radon to be adsorbed by active carbon. Carbon dioxide has a molecular diameter around 330-361 pm. Radon has a molecular diameter around 417-460 pm, so it is normally bigger than the molecules in which is usually mixed, such as Nitrogen and Oxygen, the main components of air, or Carbon dioxide. As Radon is bigger than CO2, it should not be possible to hold it on a porous substrate, according to the molecular sieve principle, when it is mixed with Carbon dioxide, only using the difference in molecular dimensions.

In trying to take advantage of the different polar characteristics of the molecules for their separation, it is evident that CO2 and Radon are two similarly nonpolar molecules, so their separation using active carbon, that tends to create similar bonds with similarly nonpolar molecules, should not be possible.

Carbon dioxide, as a matter of fact, binds to the pores of active carbon competing with Radon. The concentration of Radon in CO2 is however usually very low, in the order of 10"8/ 10"9ppm, so as the molecules of CO2 are usually much more concentrated than Radon and smaller, they should bind the active carbon more easily than Radon, making the separation not possible. Nevertheless, the Radon molecule is highly polarizable, around 5 A , opposed to CO2 that is less polarizable, around 2.5 A . Carbon dioxide is therefore less affected by the London dispersion force and, as a consequence, by residual van der Waals forces created among active carbon and CO2. Radon, on the contrary, binds with more affinity and is therefore more detained inside the micropores of the active carbon, resulting in a slower flow through them. Active carbons are currently the best substrate in terms of cost/effectiveness ratio for separation, although other possible usable substrates are known. Among the types of active carbons the best results are obtained with the coconut ones, having mean granulometry of 3.5 mm, 450-550 kg/m3 density, 1000-1200 m2/g superficial area.

Affinity of Radon for active carbon has been previously exploited for the measurement of Radon concentration in the air, measuring the gamma radioactivity emitted by the active carbon after the accumulation of Radon decay products.

The capacity of Radon to be adsorbed by active carbon has been used for the filtration of Radon gas from air to solve the problem of Radon contamination in the air of a cleanroom for scientific experiments. See for reference "Low Background Techniques and Experimental Challenges for Borexino and its Nylon Vessels. Andrea Pocar. A dissertation presented to the faculty of Princeton University in candidacy for the degree of Doctor of Philosophy. November 2003". In this case the system used is based on the VS A (Vacuum Swing Adsorption) technique, that is an alternation of cycles of high and low pressure, to favour respectively the adsorption on the active carbon and the desorption of Radon from them. Said technique is applicable to air or Nitrogen containing Radon in activity concentrations that are constant and lower than 10 kBq/m3. The system, however, is not applicable to a fluid that contains high concentrations of Radon, because Radon, that avidly binds to active carbon because of its high polarizability, is not fully desorbed in short times and only with reducing pressure, as in the VSA technique.

Furthermore, the concentration of Radon in the mixture of gases extracted from the soil is highly variable and often reaches concentrations higher than 10 kBq/m3, up to several hundreds of kBq/m3. Finally the VSA technique requires a long time for full desorption, generally 2-3 hours for air. Such long times for desorption of Radon with the VSA technique would cause it to partially decay before it is removed, making the substrate radioactive. The full and quick desorption of Radon from the substrate is then an essential part of the present process. Document CN101450306B is about a method and an apparatus that regenerates the active carbon through depressurization and heating of the active carbons to remove Radon. The method requires the depressurization of a tube full of active carbon and the heating of the active carbon to remove the adsorbed Radon from them; the system involves also the regulation of a valve to control the flow and allow a small amount of air to pass through the tube of active carbon, under the condition that a certain level of depression is maintained, so that it is possible to remove the Radon adsorbed on the carbon. The apparatus includes a control unit, a power supply, the tube of active carbon, a thermometer, a depressurization pump and a flow control valve, and the tube of active carbon is made of a cylinder with the ends closed by lids and heated by two electrodes.

Neither prior art reference directly deals with the removal of Radon from Carbon dioxide. Furthermore, both require intervention on the level of pressure of the flow passing through the separation unit with active carbon. The depressurization of the flow causes an increase in the costs of the process and the plant. Further, the heating of the active carbon in the presence of Oxygen, that is contained in the air used for the vacuum desorption, increases also the risk of an explosive combustion of the active carbon, with serious hazards for safety, and limits the maximum temperatures that can be reached, making the desorption less efficient.

The present invention aims to overcome the drawbacks of the known techniques.

In particular, one of the objectives of the invention is to separate Radon from mixtures of gases containing Carbon dioxide extracted from the soil with a process and a plant that involves several cycles for adsorption and desorption of Radon without regulating the pressure. Furthermore, another aim of the invention is to optimise the cycles for adsorption and desorption with respect to energy costs.

Another objective of the plant is to treat high volumes of fluid with a compact plant that occupies relatively small space with a method that, at the same time, allows a reduction of the production of radioactive waste.

These and other objectives and advantages of the invention are obtained, in the first aspect of the invention, by a process for the separation of Radon from a mixture of gases consisting mainly of Carbon dioxide including adsorption of the Radon present in the mixture of gases on a substrate and simultaneous removal of Carbon dioxide and desorption of Radon from the substrate, followed by its removal through a washing fluid and the recovery of the substrate. The process happens with no depressurization of the substrate, in a thermal cycle consisting in a phase of adsorption, a phase of heating, and a phase of cooling. Preferred embodiments of the first aspect are defined in the dependent claims following claim 1.

In the second aspect of the invention, there is provided a plant for the implementation of a process for the separation of Radon comprising an upstream "daughters filter" and then a control unit, a power supply, and a separating device. The plant includes at least one separation unit, a high-temperature heat source and a low-temperature heat absorber, tubes to connect the separation unit, the heat source, and the heat absorber, several motorized valves that open and close during the functioning of the plant for the adsorption and desorption of Radon in the separation units. Preferred embodiments of the second aspect are defined in the dependent claim following claim 11.

In a further aspect, the present invention provides an isobaric process for the separation of Radon from a mixture of gases comprising Carbon dioxide, wherein the process comprises: adsorption of Radon from the mixture of gases on a substrate; heating the substrate to detach Radon from the substrate; washing the substrate with washing fluid to detach Radon from the substrate; and cooling the substrate.

Preferably, the isobaric process comprises any one or more or combination of the group comprising: heating the substrate to detach Radon from the substrate and, subsequently but together, washing the substrate whilst additionally heating the substrate; constant temperature washing of the substrate after heating; cooling the substrate whilst washing the substrate; subsequent cooling without washing; and/or after cooling, pausing the process in readiness for starting again.

In a yet further aspect, the present invention provides an isobaric system for the separation of Radon from a mixture of gases comprising Carbon dioxide, wherein the system comprises a separation unit comprising: a substrate, for adsorption of Radon from the mixture of gases; means for heating and/or cooling the substrate and/or the separation unit; and means for washing the substrate with a washing fluid, wherein the system comprises: heating the substrate to detach Radon from the substrate; washing the substrate with washing fluid to detach Radon from the substrate; and cooling the substrate.

Preferably, the isobaric system comprises any one or more or combination of the group comprising: heating the substrate to detach Radon from the substrate and, subsequently but together, washing the substrate whilst additionally heating the substrate; constant temperature washing of the substrate after heating; cooling the substrate whilst washing the substrate; subsequent cooling without washing; and/or after cooling, pausing the process in readiness for starting again.

Preferably, the isobaric system comprises any one or more or combination of the group comprising: an active carbon substrate; an upstream ‘daughters filter’; and/or at least three separation units, which are linked thermally so as to provide heat exchange.

For the sake of the continuity of production and to optimise the use of energy it is advantageous to use more than one separation unit, where the thermal cycle of each unit is shifted from the cycle of the previous separation unit by a time equal to the adsorption phase. In that case the plant includes at least three separation units and a counter-current heat exchanger.

One of the advantages obtained by the present invention is to prevent the accumulation of radioactive daughters of Radon inside the refining, condensation and solidification of Carbon dioxide plants that would make them dangerously radioactive, thus reducing the production of radioactive waste and contamination of the plant and the associated risks for the personnel in the plant.

Another advantage regards the increase in the safety of the product, especially if it is used for medical use or for food, and the safety of its storage and transport in bulk.

Another advantage comes from the possibility to treat fluids that contain either low or high concentrations of Radon.

Another advantage of the method is the possibility to easily automate the process: the phases are characterized by relatively long periods of time, in the order of minutes, and require very simple sensors, such as temperature sensors and a chronometer, to properly manage the whole process. The computing power required by a programmable logic controller or computer in charge of the management of the plant is therefore low and the complexity of the code (software) is minimal. Furthermore, owing to the fact that the only moving parts are the valves and that those work with long intervals being open or closed, also in the order of minutes, and with low (atmospheric) pressure, reduced maintenance and long life of the components are guaranteed, which favourably affects the costs for making and managing the plant. It must also be considered that, when working at low (atmospheric) pressures and without vacuum, it is not necessary to use pumps that are expensive to buy and maintain and it is possible to use tanks that are not certified for the use in vacuum conditions and, therefore, they are less expensive and not subject to periodic checks.

The present invention, unlike the Chinese document cited, through a proper management of the temperatures that can be safely raised because of the use of a washing fluid, preferably an inert gas, such as CO2 or Nitrogen, increasing the efficiency of the desorption of the radioactive gas, preventing at the same time explosive combustions. This way the adsorbing substrate does not become radioactive and then, at the end of the life of the substrate itself, it can be disposed of without dangers for the operators and additional costs. Other than the proper management of the temperatures, this objective is achieved through the correct sizing of the container for the adsorbing substrate and the proper regulation of adsorption times, chosen according to the concentration of Radon in the fluid that must be purified.

The invention will now be disclosed, by way of example only, with reference to the following drawings, in which:

Figure 1 is a schematic view of the realization form of a plant for the separation of Radon from C02;

Figure 2 illustrates in detail the separation process in four phases and a pause phase, indicating on the y-axis the temperature and on the x-axis the time;

Figure 3 is a succession of Cartesian coordinate diagrams like the one in Figure 2 that show the temporal succession of the four phases in the separation units that are part of the plant in Figure 1; and

Figure 4 is a Cartesian coordinate diagram of the measurement of radioactivity due to Radon made during the setup of the separation process of the present invention, where the y-axis indicates the radioactivity of 222Rn in kBq/m3 and the x-axis indicates the time (t).

The plant, in one embodiment of the present invention, includes a "daughters filter" upstream of the purification plant, through which the mixture of gases pass before the separation of

Radon. The filter, not shown in the figures, keeps inside it the elements produced from the radioactive decay chain of Radon already present in the mixture, allowing it to remove part of the contaminants and, thereby, reduce the radioactivity of the mixture and the radioactive contamination of the separation unit. The "daughters filter" is preferably constituted by a metal cylinder filled with a compact and inert fibrous material, such as stone wool, that is able to bind the cationic daughters, mainly Pb2+ and Bi3+ and/or characterized by pores small enough to retain them.

As far as the rest of the plant is concerned, this is exemplified in Figure 1, which is a schematic view of an embodiment of the plant for the separation of Radon from CO2 according to the present invention. In this Figure are indicated, with references 1, 2, and 3, three units for the separation of Radon from CO2; with 4 and 5, respectively, a container of high-temperature diathermic fluid or heat source, and a container of low-temperature diathermic fluid or heat absorber. Reference 6 indicates a counter-current heat exchanger connected to the three separation units 1, 2, and 3; for the sake of the schematization, the heat exchanger 6 has been reproduced twice in Figure 1, although there is only one. A net of tubes that connect the three separation units 1, 2, and 3, the two high-temperature and low-temperature containers 4 and 5, and the heat exchanger 6 is indicated with 7, while VI through V26 indicate the motorized valves that open and close during the functioning of the plant. In particular, valves V21, V23, and V25 are connected to the raw gas (Gg), while valves V22, V24, V26 are connected to the washing fluid Gi.

It should be evident that the process according to the present invention can be performed also with a single separation unit, or with more than three separation units. However, it is believed that the number of three represents a good compromise between efficiency and cost of the plant.

Each separation unit 1, 2, and 3 is made of a container, preferably in stainless steel, in the form of a cylinder, able to resist corrosion from the contaminants present in the gas mixture made mainly of Carbon dioxide, but also Sulfuric acid, Hydrogen sulphide, Sulphur dioxide, and other corrosive chemicals. Each container has inside an adsorbing substrate indicated with reference 8 and has a bundle of tubes, indicated collectively with reference 9, that pass through it.

The container of the separation units 1, 2, and 3 has flanges at the ends to allow the easy substitution of the substrate 8 at the end of its life and introduction of the bundle of tubes 9 or other equivalent serpentine-type tubes necessary for exchange of heat.

The shape of the container is chosen in order to allow a regular distribution of the adsorbing substrate 8 and to prevent preferred paths of the fluid to purify that reduce its interaction with the substrate. In each separation unit 1, 2, and 3 the entrance is indicated with 10 and the exit with 11.

Each separation unit 1, 2, and 3 is sized in accordance with the recommended flow speed. In each separation unit there is adsorption of Radon onto the substrate 8 and desorption of Radon. The plant includes further devices, not shown, among which are the sensors for the measurement of temperature, pressure, and flow speed, mechanical and electro-mechanical actuators, fluid recirculation pumps, programmable logic controllers (hardware) with relative code (software) that manage the regular succession of the phases, the resynchronization of the phases in case of malfunctioning and emergencies, the management of alarms, the remote control of the process, the safety devices, the interconnection and support structures, the devices for the proper distribution of the flow of gas in the separation unit and for the proper disposition of the adsorbing substrate, the devices for the measurement of the radioactivity of the substrate and of the concentration of radioactivity owing to Radon upstream and downstream of the plant.

The maximum duration of the adsorption (ad) in each cycle will always have to be lower than the total retention time, indicated as rt in Figure 4 (in order to obtain the maximum purity of the gas). The total duration of the cycle must be set according to the following formulas that allow one to regulate the times in each phase of the cycle to reduce to the lowest amount possible the radioactive contamination of the separation unit and to maximize the duration of the substrate, optimizing at the same time the separation efficiency. The functioning of separation units 1, 2, and 3 is based on a series of cycles of adsorption/desorption of Radon through which Radon inside the substrate is separated from Carbon dioxide and removed to be dispersed in the atmosphere, if allowed by local regulations, or stored in a tank to decay safely, or re-injected in the soil or commercially exploited.

After heating, separation unit 1 is then cooled to a temperature preferably between -10°C and 30°C, and in any case preferably lower than 50°C (in the case of the active carbon chosen for the realization of the prototype), to allow the correct adsorption of Radon in the substrate. Such temperature must be chosen so that the thermal energy of the molecules does not overcome the weak interactions among Radon and the substrate; otherwise, Radon cannot be kept in the substrate itself. Excessively low temperatures, although they might favour the interaction between Radon and the substrate, slow down the movement of Radon towards the pores of the substrate itself, hindering the overall process and increasing the management costs of the plant. The optimal temperature varies also according to the chemical composition of the mixture, being influenced by the action of other molecules that compete with Radon for the binding, and the type of the substrate, being influenced by the high or low affinity between Radon and the substrate.

The container must resist several cycles of heating and cooling and must be impermeable to atmospheric gases, in particular Oxygen, that could lead to explosive combustion of the substrate during high-temperature desorption.

As stated before, the functioning of the plant sees the initial use of a "daughters filter". The filtered mixture is then sent to the separation unit. The mixture flows in controlled conditions of flow, pressure and temperature. Inside the separation unit Radon is kept until a threshold radioactivity level established during the setup of the plant is reached and for an established time. The maximum time of adsorption can be calculated or the level of Radon can be constantly monitored with a detector, preferably based on an ionization chamber, to allow one to identify the moment when the threshold level is reached and to intervene with the next phases of the process.

After the separation process, the purified mixture can be sent as is or it can be collected and sent for further processing, which benefits from the reduction of radioactivity level with lower exposure of workers to ionizing radiation, lower contamination of the downstream industrial plant, and a better quality of the product with regards to safety.

When the threshold level or the threshold time in the first separation unit is reached, the flow of the mixture into separation unit 1 is stopped and, if the plant has a number of separation units higher than one, as in the embodiment described here, the mixture of gases is sent to the next unit, unit 2, in order to allow the plant to work continuously.

When the flow of mixture into the separation unit is stopped, the heating of the unit begins until it reaches the temperature T2, necessary for the detachment of Radon from the separation substrate. Temperature T2, if active carbon is used as a substrate, is preferably between 70 and 120°C. The temperature is then increased further to allow the complete detachment of every Radon molecule, until temperature T3 is reached, preferably between 120 and 180°C, but more preferably between 120 and 150°C, while a washing fluid Gi, for example air or, better, an inert gas, is sent into the separation unit carrying Radon outside the unit. The washing flow is kept for all the time whilst the substrate is over temperature T2. After Radon has been detached, after a time established when setting up the plant, the separation unit is cooled to the starting temperature, preferably lower than 50 °C.

The heat of the diathermic fluid used for heating and cooling the separation unit is preferably recovered using the heat exchanger (6), so that the energy cost of running the plant is reduced. Alternatively to the heat exchanger, to heat and cool the separation units it is possible to use other means that allow one to reach the same goals.

The cycle here outlined is described more precisely in Figure 2. The main components of the plant are described in Figure 1 instead, that is a schematic view of an embodiment of the plant for the separation of Radon from CO2 according to the present invention in four phases, adsorption, heating, constant temperature, and cooling, followed by a pause, better described in Figure 2.

In particular, Figure 2, that has temperature on the y-axis and time on the x-axis, shows the variations of temperature and the temporal succession of adsorption, heating, constant temperature, and cooling phases. The adsorption, heating, constant temperature, cooling, and pause phases are hereby described: 1. adsorption ad of Radon contained in the raw gas Gg on substrate 8 at temperature Tl\ 2. heating ri of substrate 8 until temperature T2 is reached, where thermal agitation induces the detachment of Radon from the substrate. When temperature T2 is reached, washing fluid Gi is sent into the unit and heating continues until temperature T3 is reached; 3. once temperature T3 is reached, it is kept during the constant temperature tc phase for the time necessary to all the substrate to evenly reach temperature T3. The duration of this phase depends on the heating system used and on the configuration of the separation unit, that is preferably designed to maintain this temperature only for a few minutes and can be equal to zero; 4. cooling ra of the separation unit in order to bring the unit's temperature back to the chosen initial value Tl. When the temperature of the separation unit reaches values below T2, the flow of fluid Gi is preferably stopped, since Radon has been completely removed; 5. pause pa, useful to compensate for any delay in the previous phases, in order to maintain the perfect synchronization of the separation units. The duration of this phase depends on the number of separation units used and can be zero.

During the adsorption phase the radioactivity that can be measured at the exit is nearly zero, because all the Radon is kept inside the separation unit and the Carbon dioxide coming out is free from radioactivity. During this period Radon, which because of weak interactions moves slower than CO2 in the substrate, is not able to go out of the separation unit: this is total retention rt phase (Figure 4), which includes the adsorption ad phase. When time passes Radon moves nearer and nearer to the exit of the separation unit, also due to the progressive saturation of the substrate, and, if the flow into the separation unit is not stopped in time, with a deviation of the mixture of raw gas Gg to the next unit, Radon would progressively begin to come out, and in that case Radon adsorption would be partial. To restore the ability of the substrate to completely keep Radon inside, the substrate must be regenerated through thermal desorption de, preferably before the partial adsorption ap starts. The substrate is then heated and, once temperature T2 is reached, Radon starts to progressively come out from the separation unit until it is completely released. The rectangular area shown in Figure 2 represents the part of the temperature-time diagram when desorption de takes place.

Desorption de happens over temperature T2 both in heating phase and in cooling phase. During desorption de Radon is separated from the substrate in a short time, in order to allow it to be completely removed before a significant decay in the substrate, which would otherwise provide radioactive contamination of the substrate itself.

The thermal cycle, when adsorption and desorption of Radon happen, is divided into three fundamental phases, adsorption, heating, and cooling, plus two more phases, constant temperature and pause. The constant temperature phase provides homogeneous heating of the substrate, whilst the pause phase, necessary in the case of more than one separating unit working simultaneously, compensates for any delay in the separation units. The durations of adsorption (ad), heating (n), constant temperature (tc), cooling (ra) phases are determined during sizing of the plant in order to reach the maximum adsorption and desorption of Radon from the substrate in the shortest time possible, minimizing the radioactive decay of the Radon in the substrate.

According to the present invention the plant for the separation of Radon requires preferably three separation units 1, 2, and 3 in the plant, and the thermal cycle in each unit has a delay from the one of the previous separation units equal to the length of the adsorption phase.

The thermal cycle is presented in Figure 3 with a succession of four Cartesian coordinate diagrams A, B, C, and D that show the thermal cycle pictured in Figure 2 for the three separation units of the plant in Figure 1. To facilitate reading, the thermal cycle of separation unit 3 is shown twice. More precisely, diagram B shows the thermal cycle of separation unit 1, diagram C shows the cycle of separation unit 2, and diagrams A and D show two thermal cycles of separation unit 3. Thermal cycles A, B, C, and D are shifted in time to guarantee that in each instant at least one separation unit is in adsorption phase. This way it is possible to provide a continuous functioning of the plant. Alternatively with the same process of the invention Radon could be separated from the mixture of gases using only one separation unit, but not continuously.

The following provides a description of the five functional periods in a plant working with three synchronized units. It must be understood that the division into periods is only for description purposes; although the periods are here indicated as having equal duration, it could not happen in reality.

Period 1 (PI)

In Figure 1 it is shown that separation unit 1 is connected through the opening of valve V23 to the pipe of the raw CO2 to be purified. Its temperature is kept low by the flow of a diathermic fluid in the bundle of tubes of separation unit 1 directed by the opening of valves V7 and V14. At the same time separation unit 3 is heating up, whilst separation unit 2 is resting.

Period 2 (P2)

In the following period P2, whilst separation unit 1 is still in its state (adsorption phase 1), separation unit 3 has reached the desorption temperature owing to the flow of hot diathermic fluid (opening of valves V1 and V4 in the second half of period 1) and, through the opening of valve V22, the flow of washing fluid, for example air or better an inert gas such as CO2 or Nitrogen, starts in separation unit 3. The other separation units remain in their state.

Period 3 (P3)

After the desorption phase has completed (closure of valves VI and V4), separation unit 3 gives its heat, through the counter-current heat exchanger, to separation unit 1 (opening of valves V2, V3, V9, and VI1 and closure of valves V7 and V14). At the same time the flow of raw gas into separation unit 1, that is about to start heating up, is stopped and moved to separation unit 2 (closure of valve V23 and opening of valve V25). Temperature in separation unit 2 is again kept low thanks to the flow of cool diathermic fluid in the bundle of tubes of the same separation unit (opening of valves V15 and V20).

Period 4 (P4)

Separation unit 1 has reached the desorption temperature thanks to the flow of hot diathermic fluid (opening of valves V8 and V13 in the second half of period 3 and closure of valves V2, V3, V9, VI1) and, because of opening of valve V24, flow of washing fluid (for example air or better inert gas, such as CO2 or Nitrogen). At the same time separation unit 3 has finished cooling thanks to the heat exchanger (first half of the third period with the opening of valves V2, V3, V9, VI1) and to the flow of cool diathermic fluid (second half of the third period, opening of valves V5 and V6) and has then started resting phase (fourth period). Separation unit 2 remains in adsorption phase 1 (valves VI5, V20, V25 open).

Period 5 (P5)

Separation unit 1 has completed the desorption phase (closure of valves V8 and V13) and cooling (phase 3) starts, activating the heat exchanger with separation unit 2 (opening of valves V10, V12, V17, VI8). In the second half of period 5, separation unit 1 will finish the cooling phase with the flow of cool diathermic fluid (opening of valves V7 and V14 and the simultaneous closure of valves V10, V12, V17, V18, V24). Separation unit 2, which has received heat from separation unit 1, completes its heating phase thanks to the flow of hot diathermic fluid (opening of valves V16 and VI9) and at the same time the flow of washing fluid (Gz) starts following opening of valve V26. Separation unit 3 remains in adsorption phase (valves V5, V6, and V21 open).

During desorption, based on the composition of the mixture of raw gas, other contaminants can be separated too, such as H2O, H2S, COS, CnHn, etc., increasing the overall efficiency of the plant.

The cycles described repeat themselves in the succession described.

Heater 4 integrates the heat lost because of dispersion and the fact that the efficiency of the exchanger is never equal to 100%. Cooler 5, e.g. cooling tower, dissipates excessive heat build up because the efficiency of the exchanger is never equal to 100%.

Having described the functioning of the plant, one should now consider its sizing. After verifying the ideal substrate and the best separation conditions, depending on the exact composition of the mixture of CO2 that is to be purified, each separation unit must be sized according to the mass flow of the mixture to be purified and the concentration of Radon. Experimental results show that flow speed Vm of the mixture inside the separation unit able to optimise the separation process is preferably equal to 10 meters per minute (around 0.16 m/s) if an active carbon substrate with characteristics equal to those previously described is used. Section S of the separation unit must therefore be calculated according to the following Formula 1: S= Φ/Vm [FORMULA 1] where Φ represents the mass flow of the mixture (in m3/s) into the separation unit and Vm is the speed of the mixture (in m/s).

Accordingly, to guarantee that the residence time of Radon inside the separation unit is much shorter than its decay time, it should remain inside the separation substrate for a time preferably shorter than 50 minutes. This time guarantees that less than 1% of Radon decays inside the separation unit during the run.

This considered, length L (expressed in meters) of the separation unit should be calculated according to the following formula 2: L= Tad X Vm X R [FORMULA 2] where Tad represents the adsoprtion period chosen (expressed in seconds), Vm the speed of the fluid and R the slowdown coefficient of Radon inside the separation unit for the mixture considered (experimentally measured for CO2 adsorbed on active carbon with the characteristics described before as 5.305xl0"3).

With the section (formula 1) and length (formula 2) of the separation unit known, it is easy to calculate the mass of the substrate needed knowing its density using the following formula:

Ms= S x L x d [FORMULA 3] where Ms is the mass of substrate needed in g, S is the ideal section calculated with formula 1, L is the length needed for the ideal adsorption time according to formula 2, d is the density of the substrate in g/m3.

The maximum time of exposure to Radon of the substrate must be calculated knowing the concentration of Radon in the mixture to be purified, so that it is guaranteed that the decay of Radon inside the substrate, in the whole life of the substrate itself, does not cause an accumulation of long-living radioactive daughters (such as 210Pb) that would make the product classifiable as radioactive waste according to local regulations.

During the purification cycle, in fact, part of the Radon adsorbed decays generating 210Pb before Radon is desorbed.

The amount of Radon atoms that bind to the substrate can be calculated as:

NoRn=(Ao x ti/2 Rn x Φ x tc)/ 0.693 [FORMULA 4] where NoRn are the atoms of Radon that will bind to the substrate in each cycle that has the duration of tc seconds, Φ is the flow in m3/s, Ao is the activity of Radon in the raw gas to be purified in Bq/m3. Time tc must be considered as all the time when Radon stays inside the separation unit, until it is completely removed from the unit itself.

Some of the NoRn atoms adsorbed by the separation unit in time tc, some of them (Ndrii) will decay generating an equal number of 210Pb atoms that we will call Nopb. The atoms that will not decay (NtRn) will be removed from the separation unit instead.

NdRti= Nopb = NoRn-NtRn [FORMULA 5]

At the end of a cycle with a duration of tc seconds, the non-decayed atoms of Radon will be:

NtRn= NoRn X e (-0-693/tl/2Rn) tc [FORMULA 6] where ti/2Rn is the half-life of Radon in seconds.

Therefore:

Nopb= NoRn- Nor„ X e tc [FORMULA 7]

The specific activity of 210Pb on the substrate of each unit will be:

Aspb=(0.693 x Nopb)/ (ti/2Pb x Ms) [FORMULA 8] where Ms is the mass of substrate necessary calculated according to formula 3 and expressed in grams.

The number of cycles Nc that is possible to perform for each separation unit before the substrate is considered radioactive according to local regulations is:

Nc = Asi / Aspb [FORMULA 9] where Asi is the maximum specific activity accepted by local regulations for 210Pb, over which the substrate must be considered radioactive, and Aspb is the specific activity expected in the substrate after each cycle and calculated according to formula 8.

The calculations described guarantee that, in case the maximum value of specific activity for 210Pb is respected, law limits for the daughter elements of 210Pb (such as 210Po) are respected too if the specific activity limits for the latter are not lower than the limits for 210Pb. Otherwise the calculation can be repeated in the same manner for any other daughter element of 210Pb and the number of cycles Nc would be calculated using the value of the maximum specific activity accepted by local regulations (Asi) for each daughter element considered. The maximum number of cycles Nc accepted before the substitution of the substrate would then be the lowest among those calculated for each radionuclide.

Figure 4 shows a Cartesian coordinate diagram of the measure of Radon radioactivity performed during the setup of the separation process in the present invention, where radioactivity of 222Rn in Bq/m3 is on the y-axis and time (t) is on the x-axis.

Figure 4 identifies the trend of radioactivity from Radon measured in the entering mixture of raw gas (Gg), and in the mixture purified from Radon coming out of one separation unit (rt and ap) and in the washing fluid (Gz) during desorption phase (de).

Accordingly, it is clear that the present invention has the following advantages, which are here briefly listed: - the accumulation of radioactivity in the substrate and its contamination over the limits allowed by law are prevented because of the use of the stated formulas for the proper sizing of the separation units, of the flows and of the duration of each phase of the cycle; - thanks to synchronization of the separation units, it is possible for the plant to function continuously because the separation units have cycles that are shifted in time; - thanks to synchronization of the separation units, heat is recovered and transferred from one separation unit directly to another.

The plant includes other devices that were not referred to in the description, including sensors for the measurement of temperature, pressure, and flow speed, several mechanical and electromechanical actuators, fluid recirculation pumps, programmable logic controllers with relative code (hardware and software) that manage the regular succession of the phases, the resynchronization of the phases in case of malfunctioning and emergencies, the management of alarms, the remote control of the process, safety devices, the interconnection and support structures, the devices for the proper distribution of the flow of gas in the separation unit and for the proper disposition of the adsorbing substrate, the devices for the measurement of the radioactivity of the substrate and of the concentration of radioactivity due to radon upstream and downstream of the plant.

Claims

1. Process for the separation of Radon from a mixture of gases consisting mainly of Carbon dioxide including the adsorption (ad) of Radon present in the mixture in a substrate (8), the simultaneous removal of Carbon dioxide and the desorption (de) of Radon from the substrate (8) and following removal with a washing fluid (Gi) and recovery of the substrate (8), characterized by the fact that the process takes place with no depressurization of the substrate (8), in a thermal cycle including an adsorption (ad) phase, a heating (ri) phase, and a cooling (ra) phase.

2. Process according to Claim 1, in which the substrate (8) preferably comprises active carbon.

3. Process according to Claim 1 or Claim 2 in which a constant temperature (tc) phase can be added after the heating (ri) phase.

4. Process according to any one of Claims 1 to 3 in which a pause (pa) phase can be added after the cooling (ra) phase.

5. Process according to any one of Claims 2 to 4 wherein the adsorption (ad) phase of the Radon contained in the raw gas (Gg) on the substrate (8) made of active carbon happens at a temperature T1 lower than 80°C, or at a temperature no greater than around 70°C, 60°C, 50°C, or 40°C.

6. Process according to Claim 5 where temperature T1 is preferably between about -10°C and about 30°C.

7. Process according to any one of Claims 2 to 6 in which the desorption from substrate (8) made of active carbon consists in a heating (ri) phase that goes on until a certain temperature T3 over 80°C is reached.

8. Process according to any preceding Claim, characterized by the fact that it is performed simultaneously in more than one unit so that the thermal cycle in each separation unit is shifted from the cycle in the previous separation unit by a time approximately equal to the duration of the adsorption (ad) phase.

9. Process according to Claim 8 in which said thermal cycle is performed in at least three separation units (1, 2, 3) and the thermal cycle of each separation unit is shifted from the cycle of the previous separation unit by a time approximately equal to the duration of the adsorption phase and the cooling (ra) phase of each separation unit is simultaneous to the heating (ri) phase of the following separation unit.

10. Process according to Claim 8 or Claim 9 in which the number of thermal cycles (Nc) that can be performed in each separation unit before the substrate can be considered radioactive according to local regulations is: Nc = Asi / Aspb where Asi is the maximum specific activity accepted by local regulations for 210Pb, over which the substrate must be considered radioactive, and Aspb is the specific activity expected in the substrate after each cycle and calculated according to Aspb=(0.693 x Nopb)/ (ti/2Pb x Ms) where

with NoRn=(Ao x tl/2RnX Φ X tc)/ 0,693 where NoRn are the atoms of Radon bound to the substrate in each cycle that has a duration of tc seconds, Φ is the flow in m3/s, Ao is the activity of Radon in the raw gas to be purified in Bq/m3, ti/2Rn is the half life of Radon in seconds, ti/2Pb is the half life of 210Pb in seconds, Ms is the mass of substrate calculated as Ms= S x L x d and expressed in g, where S= Φ/Vm and L= Tad xVmXR where Tad is the duration of the adsorption in seconds, Vm the speed of the fluid in m/s, R is the slowdown coefficient of Radon, d is the density of the substrate in kg/m3 and tc is the amount of time Radon stays inside the separation unit, until it is completely removed from the unit itself.

11. Plant for implementation of a process for the separation of Radon from a mixture of gases consisting mainly of Carbon dioxide, including adsorption (ad) of the Radon present in the mixture of gases on a substrate (8) and simultaneous removal of Carbon dioxide and desorption (de) of Radon from the substrate (8) followed by removal of Radon through a washing fluid (Gi) and recovery of the substrate (8), a process that happens with no depressurization of the substrate (8) in a thermal cycle including an adsorption (ad) phase, a heating (ri) phase, and a cooling (ra) phase, in a plant that includes an upstream "daughters filter" and then a control unit, a power supply, at least one separation unit (1) containing the adsorbing substrate, a high-temperature heat source (4) and a low-temperature heat absorber (5), tubes (7) to connect the separation unit (1), the heat source (4), and the heat absorber (5), several motorized valves (V1-V26) that open and close during the functioning of the plant for the adsorption and desorption of Radon in the separation unit (1).

12. Plant according to Claim 11, wherein said plant includes at least three separation units (1,2, 3), a high-temperature heat source (4) and a low-temperature heat absorber (5), a counter-current heat exchanger (6), tubes (7) to connect the separation units (1,2, 3), the heat source (4), the heat exchanger (6), and the heat absorber (5), several motorized valves (V1-V26) that open and close during the functioning of the plant for the adsorption and desorption of Radon in the separation units (1,2, 3).

13. Process for the separation of Radon from a mixture of gases consisting mainly of Carbon dioxide, substantially as herein disclosed, with reference to the accompanying description and/or any example herein described.

14. Plant for implementation of a process for the separation of Radon from a mixture of gases consisting mainly of Carbon dioxide, substantially as herein disclosed, with reference to Figure 1 of the accompanying drawings and/or any example herein described.

15. An isobaric process for the separation of Radon from a mixture of gases comprising Carbon dioxide, wherein the process comprises: adsorption of Radon from the mixture of gases on a substrate; heating the substrate to detach Radon from the substrate; washing the substrate with washing fluid to detach Radon from the substrate; and cooling the substrate.

16. An isobaric process as claimed in claim 15 comprising any one or more or combination of the group comprising: heating the substrate to detach Radon from the substrate and, subsequently but together, washing the substrate whilst additionally heating the substrate; constant temperature washing of the substrate after heating; cooling the substrate whilst washing the substrate; subsequent cooling without washing; and/or after cooling, pausing the process in readiness for starting again.

17. An isobaric system for the separation of Radon from a mixture of gases comprising Carbon dioxide, wherein the system comprises a separation unit comprising: a substrate, for adsorption of Radon from the mixture of gases; means for heating and/or cooling the substrate and/or the separation unit; and means for washing the substrate with a washing fluid, wherein the system comprises: heating the substrate to detach Radon from the substrate; washing the substrate with washing fluid to detach Radon from the substrate; and cooling the substrate.

18. An isobaric system as claimed in claim 17 comprising any one or more or combination of the group comprising: heating the substrate to detach Radon from the substrate and, subsequently but together, washing the substrate whilst additionally heating the substrate; constant temperature washing of the substrate after heating; cooling the substrate whilst washing the substrate; subsequent cooling without washing; and/or after cooling, pausing the process in readiness for starting again.

19. An isobaric system as claimed in claim 17 or claim 18 comprising any one or more or combination of the group comprising: an active carbon substrate; an upstream ‘daughters filter’; and/or at least three separation units as claimed in claim 17, which are linked thermally so as to provide heat exchange.

20. An isobaric process for the separation of Radon from a mixture of gases comprising Carbon dioxide, substantially as herein disclosed, with reference to or as shown in the accompanying description and/or any example herein described..

21. An isobaric system for the separation of Radon from a mixture of gases comprising Carbon dioxide, substantially as herein disclosed, with reference to or as shown in Figure 1 of the accompanying drawings and/or any example herein described.