The present invention refers to a method for the treatment of liquids in continuous flow, turning a liquid into a biphasic stream, which is temporarily ionized by a high intensity electric field, keeping an ionization regimen and generating non-thermal plasma in order to promote the degradation of organic compounds and the inactivation of microorganisms in said liquid.
Additionally, the invention refers to a reaction chamber for the treatment of liquids in continuous flow, for the temporary conversion of the liquid in a biphasic stream and the ionization of said biphasic stream inside the reaction chamber.
Finally, the invention also refers to a system for the treatment of liquids in continuous flow, which comprises the reaction chamber of the present invention.
The increasing need of having reliable and compact systems for the treatment of liquids, mainly for decontamination of water, has moved the industry to create different mechanisms of treatment considered non-traditional. Among said treatment mechanisms, the use of plasma for the treatments of fluids can be mentioned.
Within this context, the publication EP 3321233 entitled “Methods and device for in-stream aqueous medium treatment” considers a reactor in which plasma is applied to the stream of liquid to be treated, using a supersonic biphasic flow, since the speed of sound decreases inside the reaction chamber. According to said publication, all pathogen microorganisms known would be eliminated in a short time, simply by implementing the treatment mechanisms disclosed therein, among them, plasma.
However, nothing contained in the publication EP 3321233 refers to providing a method, a reaction chamber and a system for the treatment of a liquid able to treat the liquid effectively, generating a steady state of plasma in a biphasic flow that passes through the reaction chamber, thus promoting the generation of a liquid in which the organic and inorganic compounds have been degraded and the microorganisms present, inactivated.
In addition, patents U.S. Pat. No. 9,023,214 and U.S. Pat. No. 0,475,713 disclose processes to apply particles of plasma to a liquid, more specifically to drops of a liquid suspended in a gaseous medium in order to promote a variety of interactions in said biphasic mixture. In this respect, the present invention is a further development of the cited patents, which increases the efficiency and efficacy of the process and devices disclosed in the cited patents. The present invention, in fact, comprises a complete development of the liquids treatment mechanism, the reaction chamber and the system involved in said treatment, offering an optimal solution for the treatment of waters by transforming the fluid in a biphasic liquid-gas flow and the later ionization of the gaseous phase, thus generating non-thermal plasma.
This process promotes chemical reactions at low temperature and under a continuous flow, generating free radicals, hydrolysis, and oxidation-reduction reactions, among other reactions. Some of the technological applications are oriented to degrade the organic compounds and inactivate microorganisms.
The invention refers to a method for the treatment of liquids in continuous flow, where said method comprises the following steps:
According to an embodiment, the step of receiving the flow of fluid in the reaction chamber also comprises pressurizing and speeding up the flow of liquid under turbulent conditions towards the reaction chamber. Additionally, the flow of liquid speeded up under turbulent conditions generates a pressure drop in the inlet section of the reaction chamber, promoting that the biphasic flow has a great contact surface between the phases forming it.
According to an embodiment, the step of converting the flow of liquid in a biphasic flow is promoted by the partial release of gases dissolved in the liquid to be treated and the partial evaporation thereof.
According to an embodiment, the step of leading the biphasic flow to the central section of the reaction chamber comprises directing said biphasic flow in such a way that it contacts the internal walls of the reaction chamber in its central section.
Said central section can comprise at least a pair of electrodes that generate the electric discharge to produce the electric field applied in said central section. In this context, the step of ionizing the gaseous fraction of the biphasic flow comprises the application of an electric field between the electrodes, which intensity exceeds the breakdown voltage of the gaseous phase of said biphasic flow.
According to an embodiment, the step of directing the biphasic flow under the state of plasma to the discharge section of the reaction chamber comprises reconverting the biphasic flow in the flow of fluid treated.
According to an embodiment, the electric field can be generated through a potential difference between the electrodes, where said potential difference is applied by at least one high-frequency power source. In this context, the step of sustaining the ionization regime generating non-thermal plasma comprises the use of a current limiter in order to limit the current circulating through the electrodes. Said current limiter can be integrated to the at least one power source that applies the potential difference.
According to an embodiment, the electric field can be generated through a potential difference between the electrodes, where said potential difference is applied by at least one DC power source, which can operate at continuous or pulsating mode and it also comprises a current limiter to limit the current circulating through the electrodes.
Said current limiter can be passive in the form of a steady self-adjusting system, or active in the form of a feedback controller.
In addition, the invention refers to a reaction chamber for the treatment of liquids comprising:
According to an embodiment, the inlet section of the reaction chamber comprises at least a nozzle arranged in order to accelerate the flow of liquid in turbulent conditions, promoting the biphasic flow to have a great surface of contact between the two phases. The nozzle can comprise a discharge section expanding into the reaction chamber by increasing the cross-section of said discharge section of the nozzle, generating a pressure drop in the inlet section of the reaction chamber. Additionally, said nozzle can direct the biphasic flow under turbulent conditions to the internal walls of the reaction chamber, mainly in its central section.
According to an embodiment, the internal volume of the reaction chamber is filled with turbulent biphasic flow up to the discharge section of the reaction chamber.
According to an embodiment, the central section comprises at least a pair of electrodes that generate an electric discharge in order to produce the electric field applied in said central section. In this context, according to a preferred embodiment, the electric field between the electrodes has an intensity exceeding the breaking voltage of the biphasic flow's gaseous phase.
Finally, the invention also refers to a system for the treatment of liquids in continuous flow comprising at least one reaction chamber according to the present invention. Additionally, said system can comprise at least one current limiter, able to control the electric field applied in the reaction chamber, limiting the current that circulates through the electrodes.
According to an embodiment, the system also comprises a high-pressure pump upstream the reaction chamber in order to pressurize the fluid to be treated before entering the reaction chamber and increasing the fluid pressure in the range of 0.5 to 150 bar(g), more preferably in the range of 2 to 70 bar(g). In addition, the system can comprise a pressure gauge placed between the at least one high pressure pump and the at least one inlet opening of the reaction chamber, for the adjustment of the reaction chamber's feeding pressure.
Applying feeding pressures of 150 bar(g), it is possible to reach nozzle discharge velocities of around 157 m/s, considering an efficiency of the nozzle for transforming mechanic energy of 82% at said operation point.
By using a vacuum pump at the discharge, it is possible to operate the reaction chamber at feeding pressures of 0.5 bar(g), obtaining flow speeds in the range of 7 m/s when operating a nozzle with an efficiency for transforming mechanic energy of 50% at said operation point.
According to an embodiment, the system also comprises at least one vacuum pump downstream the reaction chamber in order to generate a level of vacuum towards the at least one discharge opening of the reaction chamber, which reaches a value close to the biphasic fluid's vapor pressure. Additionally, the system can comprise a vacuum gauge placed between the at least one discharge opening of the reaction chamber and the at least one vacuum pump, for the adjustment of the vacuum level in the discharge section of the reaction chamber.
According to an embodiment, the system also comprises a flow gauge downstream the reaction chamber, for the adjustment of the throughput of treated liquid.
According to a preferred embodiment, the system comprises at least one high-frequency power source, where the electric field is generated through a potential difference between at least one pair of electrodes in the central section of the reaction chamber, where said potential difference is applied by the at least one power source and is controlled by the at least one current limiter. Said current limiter can be integrated to the at least one power source that applied the potential difference.
According to an embodiment, the system comprises at least one DC power source, which can operate at continuous or pulsating mode, also comprising the use of a current limiter in order to limit the current circulating though the electrodes, where the electric field is generated by a potential difference between the electrodes.
Said current limiter can be passive in the form of a steady self-adjusting system, or active in the form of a feedback controller.
According to an embodiment of the system, the at least one discharge opening in the discharge section of the reaction chamber is connected to at least one conduit with a cross-section greater than the discharge opening, thus facilitating the reconversion of the biphasic flow in a liquid flow.
According to an embodiment, the system can comprise two or more reaction chambers connected to each other in series or in parallel.
The following figures are shown as part of the present invention, which are representations of preferred embodiments of the invention, therefore, they should not be considered as limiting the definition of the claimed invention.
By mentioning the figures attached hereto, the invention has been separated in the different aspects that make it up, in order to define the preferred embodiment of the invention.
The liquid to be treated is pressurized through a high-pressure pump, which rises the pressure in a range of, for example, 2 to 70 bar (g) at the inlet of the reaction chamber to the inlet section of said chamber. The pressurization of the fluid provides the necessary pressure to generate the hydrodynamic condition that enables the formation of plasma, when the reaction chamber is energized. The feeding pressure is adjusted through a pressure gauge as it can be noted in
Additionally, a vacuum pump can be added at the reaction chamber's discharge in order to generate levels of vacuum that can reach values close to the steam pressure of the fluid. The implementation of the vacuum pump reduces the pressure requirements at the inlet of the reaction chamber to generate the hydrodynamic condition. The level of vacuum in the discharge section is adjusted through a vacuum gauge at a level above the steam pressure of the fluid, as it can be noted in
Finally, the flow rate of is controlled through a flow gauge at the discharge, as it can be noted in
Additionally
In the reaction chamber, the liquid to be treated is transformed into a turbulent high-speed biphasic flow, specifically in the inlet section. In said section, the pressure inside the reaction chamber decreases to a point close to the vapor pressure of the liquid.
The gaseous portion of the biphasic flow is generated from the partial evaporation of the liquid, the degassing of the liquid and the plasma reaction gases. There is no injection of external gases.
The biphasic flow generated inside the reaction chamber, in the inlet section, has the characteristics of being turbulent in order to maximize the contact surface between the phases, and to improve the effect of ionized gas on the fluid when the plasma is generated.
For the purposes of this method, turbulence is an irregular flow regime characterized by fast space-temporal changes of pressure and velocity.
The turbulence of the biphasic flow is initially generated by a nozzle that can be placed at the inlet section of the reaction chamber, where said nozzle can have different mechanisms using the energy of the flow to promote the formation of turbulence inside the reaction chamber, as well as external active mechanisms, such as ultrasound, that can help increasing said effect.
In order to allow the turbulence generated in the nozzle to increase the contact surface of the phases, the nozzle discharge expands into the reaction chamber by increasing its cross-section. In current designs, the rate of the gaseous volumetric fraction to the liquid volumetric fraction ranges from 5 to 70, for example, thus allowing a great contact surface between phases.
In reactors of 9.8 mm of internal diameter, for example, with a nozzle having a restriction of 0.6 mm, the volumetric fraction of the gaseous phase can be 270 times that of the liquid phase.
In addition, in reactors of 2.61 mm of internal diameter with a nozzle having a restriction of 1.5 mm, the volumetric fraction of the gaseous phase can be only 2 times the liquid phase.
Pressure drop
The low pressure of the biphasic flow facilitates the initiation of plasma, reducing the electrical breakdown voltage of the gaseous phase. The pressure drop is caused by expanding the high-speed flow of discharge from the nozzle inside the reaction chamber in its inlet section, reaching speeds that vary between 15 and 60 m/s for example.
The pressure reduction causes partial adiabatic evaporation and partial degasification of the fluid, thus filling the reaction chamber internal volume with the turbulent biphasic flow, up to the discharge of the reaction chamber as indicated in
At the discharge of the reaction chamber towards the discharge section, the condensation of the biphasic flow takes place, reducing the velocity of the biphasic flow in an inelastic collision, losing kinetic energy, which causes increase of pressure and density. After the condensation zone of the biphasic flow, a liquid phase is generated, where the gaseous volumetric fraction over the liquid volumetric fraction varies from, for example, 50 to 0.25 when there is ionization of the gaseous fraction in the biphasic flow. A schematic representation of the condensation zone is shown in
The condensation zone tends to be stable in the discharge zone of the reaction chamber, where there is an increase of the inner cross-section when connecting the reaction chamber to a pipe of greater inner diameter at the discharge, as shown in
In order to keep the low-pressure condition of the biphasic flow inside the reaction chamber, it is necessary that the reaction force caused by the momentum variation of the flow, when it slows down during its condensation before leaving the reaction chamber, to be greater than the force of the pressure difference between the discharge pressure and the inner pressure.
The following expression describes the condition on the basis of the balance of forces to be met:
Fmomentum variation>FPressure
ΔV m>A(P2−Pv)
Where ΔV is the speed variation of the biphasic flow when collapsing, when the condensation of the biphasic flow takes place, A is the cross-section where the condensation of the biphasic flow takes place, P2 is the discharge pressure, Ps is the steam pressure of the fluid representing pressure inside the reaction chamber, and m is the mass flow.
Outside the reaction chamber, immediately after the discharge section, the increase of the cross-section A increases the requirement of reaction force abruptly in order to sustain the condition of the low-pressure turbulent biphasic flow. It is at this point where the biphasic flow condensation zone becomes stable.
In order to evaluate at design level the minimum feeding pressure required, a model was developed based on the balance of forces caused by the pressure difference between the internal volume and the discharge section of the reaction chamber, and the variation of the momentum when the flow slows down just before the discharge section of the reaction chamber.
The use of this model allows optimizing the design in order to reduce the requirements of pressure and to reduce the pumping work associated to the pressurization of the liquid.
Below, the model predicting the minimum pressure of operation of the reaction chamber is presented.
For the purposes of calculation of PMin, the pressure inside the reaction chamber is considered as the vapor pressure of the fluid Pv. A1 corresponds to the cross-section of the nozzle constraint at the inlet section of the reaction chamber, and A2 at the inner cross-section of the reaction chamber in its central section. ηnozzle and ηmomentum are the efficiency of the nozzle and the efficiency of the axial momentum respectively. These parameters are determined empirically.
When using the average values of ηnozzle and ηmomentum, the results from the predictive model obtained in experimental way can be compared in two cases of the reaction chambers known in order to generate the hydrodynamic condition with water at 20° C. In the table below, the parameters of the reaction chamber are shown in order to feed the model.
In the chart of
The nozzle efficiency ηnozzle is considered as the efficiency of energy conversion of the pressure variation in kinetic energy. ηnozzle can be expressed as a function of the mass flow and the applied pressure difference ΔP. Where A1 is the nozzle constraint area and ρLiq is the liquid density.
In order to calculate ηnozzle empirically, sweeping was done in the pressure difference applied in the nozzle, comprising the operation points of the reaction chamber. In current designs of the plasma reaction chamber, ηnozzle ranges between 0.2 and 0.95 for example.
The efficiency of the axial momentum ηmomentum corresponds to the loss of momentum of the biphasic flow due to loss of axial speed of the flow along the reaction chamber. This parameter depends on constructive factors, such as length, diameter and roughness of the inner walls of the reaction chamber, in addition to the shape of the nozzle stream, the type of diffuser used and the alignment thereof. This factor is obtained experimentally by solving ηmomentum in the equation of the minimum operating pressure.
In some reaction chambers of the present invention, the values of ηmomentum va varies from, for example, 0.10 to 0.99 depending on its geometric features and the shape of the stream. The values obtained allow predicting ηmomentum in the design of the reaction chamber with similar geometric features and nozzle to those already tried. The ηmomentum value can be used as indicator of the variation of speed inside the reaction chambers and of the amount of energy lost when impacting on the walls.
In current designs, the energy consumption associated with the pumping work consumes an important fraction of the required energy, for example, 10-80% of the total consumption of the system.
The pumping work of the assembly formed by the high-pressure pump and the vacuum pump shown in
The reduction of pressure at the discharge zone helps to reduce the requirement of pressure according to the model minimum feeding pressure evaluated in
When evaluating the specific pumping work using the reaction chamber previously identified as R2, with a content of bubbles of, for example, 18% at the outlet of the reaction chamber, and using the model that predicts the minimum operation pressure of the reaction chamber, based on the minimum requirement of pressure to relate the discharge pressure with that of feeding. Is possible to chart the pumping work required to operate the system with different levels of vacuum at discharge is possible.
In the curve of
Despite the hydrodynamic condition can be generated with low energy requirements, when reducing the discharge pressure, it is necessary for the pressure at the inlet section of the nozzle to be sufficiently high so as to have the necessary mechanic energy to increase turbulence and, therefore, to increase the contact surface between the phases of the biphasic flow. The use of vacuum, therefore, is convenient when the reduction of the feeding pressure does not compromise the contact surface between the phases of the biphasic flow.
The vacuum pump should be able to handle flows with a content of bubbles that may reach 85% of its volumetric composition. As a design requirement, it is convenient to use technologies such as water ring compressors or phases separator, to pressurize the liquid phase independently from the gaseous phase.
The preconditioning zone is the necessary distance from the nozzle outlet at the inlet section, so that the liquid phase of the biphasic flow may reach the internal walls of the reaction chamber.
After the preconditioning zone there is the active zone, where the gaseous fraction of the biphasic flow is ionized. In this way the cooling of the electrodes, which are in contact with the biphasic flow, is ensured, and the electric insulation between the nozzle and the first electrode is improved.
The methods and strategies used are shown below, whether by themselves or combined, in order to maximize the contact surface between the phases of the biphasic flow.
The turbulent biphasic flow is ionized through an electric field applied by the electrodes of the reaction chamber, which are subject to a potential differential able to exceed the breaking voltage of the biphasic medium in the active zone. In order to achieve this, there is a great dependence between the geometry of the reaction chamber, the maximum voltage applicable to the electrodes, and the vapor pressure of the fluid. A simplified way to analyze this dependence is through the Paschen's law, where there is a relationship between voltage (and therefore the maximum electric field), the distance of electrodes, and the vapor pressure of gas for similar constructive conditions of electrodes, as shown in the following equation.
By adjusting these parameters accordingly, it is established a correlation between the distance between the electrodes (de), vapor pressure, and the maximum voltage emitted by the power supply, as shown by
In general, the distance between electrodes is not enough to estimate said voltage. The configuration and the dielectric coefficients play a very important role in the generation of the electric field; this is why the designs of the reaction chamber should be subject to electrostatic simulations in order to estimate the maximum electric field and its distribution.
The use of capacitive electrodes allows injecting electric charges to the biphasic flow capacitively, thus facilitating the homogenization of plasma, generating distributed electrical paths from the walls of the reaction chamber to the inside, using the dielectric medium of the reaction chamber wall as a medium to apply the distributed discharge as shown in
The non-thermal plasma generated in the gaseous fraction has an energy density ranging, for example, between 0.144 and 7 W/mm3.
For example, when using a plasma reactor of 2.61 mm of inner diameters, with a nozzle having a constraint of 1.5 mm and an active zone of plasma formation 35 mm long, it is possible to reach an energy density of 7 W/mm3, using 880 W.
Additionally, when using a plasma reactor of 9.8 mm of inner diameter, with a nozzle having a constraint of 0.6 mm and an active zone of plasma formation of 500 mm long, it is possible to reach an energy density of 0.0133 W/mm3, using 500 W.
The heat generated by the plasma is eliminated with the flow. An additional device to eliminate the heat is not necessary.
Once the plasma is initiated as a result of ionization, it operates steadily. To this effect, enough current is required to operate in the operation zone known as glow discharge (E-H) avoiding the transition to arc discharge (H) as shown in
Due to this, the power supply should be able of working at two different points of operation:
Since the reaction chamber behaves as an open circuit when the plasma is not initiated, and, in order to solve the issue of working in two different operation points, a power supply was designed incorporating a resonating module, which is able to accumulate energy when a significant load is not perceived (plasma not initiated) and, therefore, it increases the voltage several times at the outlet. Next to the resonator there is a step-up transformer in cascade designed with the right turns ratio to provide the necessary voltage and current for the operation under the glow discharge mode.
This model, in both operation modes, as described above, has two similar second order response curves, where without the plasma initiated (red curve Ho(S) in
This way, the operation parameters of the reaction chamber can be adjusted modifying the constructive aspects of both the resonator and the step-up transformer.
As shown in
Considering the conjunction of the aspects composing the present invention, according to a preferred embodiment hereof and the design considerations presented, a reaction chamber is obtained that operates under a method and system for the treatment of liquids in continuous flow, which are not only efficient in energy terms, but also effective, for instance, in the treatment of contaminated water.
This application is the National Stage filing under 35 U.S.C. 371 of International Application No. PCT/IB2018/059072, filed on Nov. 16, 2018, the contents of which are all hereby incorporated by reference herein in their entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/IB2018/059072 | 11/16/2018 | WO | 00 |