Oil and gas production processes generate large volumes of liquid waste. For example, hydraulic fracturing of shale utilizes large volumes of high-pressure water to fracture shale formation. The wastewater generated during the drilling phase is called flowback water, whereas the water generated during the production phase is called produced water. Both the flowback and produced waters contain various organic and inorganic components, and discharging produced water can pollute surface and underground water and soil. Since approximately 250 million barrels per day (i.e., ˜30 million m3 per day) of produced water are generated globally (see F. I.-R. Ahmadun et al., “Review of technologies for oil and gas produced water treatment,” J. Hazard. Mater., vol. 170, pp. 530-551, 2009), an amount that is expected to continue increasing for an extended period of time, there is a growing need for new methods to treat large volumes of produced water robustly and efficiently. With volatility in the prices of oil and gas, there is a pressing parallel need to reduce the costs of production, including produced water treatment costs.
A variety of methods are currently utilized to treat produced water for the purposes of discharge as well as for recycling and reuse in subsequent hydraulic fracturing operations. This diverse set of water treatment techniques include de-oiling (removing dispersed oil and grease), removal of soluble organics, disinfection, suspended solid particle removal, dissolved gas removal (including hydrocarbon gases, carbon dioxide, and hydrogen sulfide), desalination (removing sodium and chloride ions), and water-softening (reducing calcium and magnesium hardness), among others (see F. I.-R. Ahmadun et al.). Similar water treatment targets can be found in a range of applications cases, other than produced and flowback waters, such as industrial wastewater or process water pre-treatment for discharge or beneficial reuse, municipal wastewater for irrigation reuse, and well water treatment for residential or light commercial use, among others.
Plasma arc discharge generates a significantly elevated temperature beyond 2,000 K around the arc (see A. Czernichowski et al., “Spectral and electrical diagnostics of gliding arc,” Acta Physica Polonica-Series A General Physics, vol. 89, pp. 595-604, 1996; and O. Mutaf-Yardimci et al., “Thermal and nonthermal regimes of gliding arc discharge in air flow,” Journal of Applied Physics, vol. 87, pp. 1632-1641, 2000). In addition, plasma discharge generates active plasma species directly in liquid, i.e., OH, O, O3, H2O2, NOx, UV and electric fields. Thus, if one can successfully generate plasma discharge in produced water, the plasma discharge can be applied for the removal of dispersed oil/grease and soluble hydrocarbons (see N. McIntyre et al., “Uses of ultraviolet/ozone for hydrocarbon removal: Applications to surfaces of complex composition or geometry,” J. Vac. Sci. Technol., A: Vacuum, Surfaces, and Films, vol. 9, pp. 1355-1359, 1991), water softening (see Y. Yang et al., “Removal of CaCO3 scales on a filter membrane using plasma discharge in water,” Int. J. Heat Mass Transfer, vol. 52, pp. 4901-4906, 2009; and Y. Yang et al., “Mineral Fouling Control by Underwater Plasma Discharge in a Heat Exchanger,” J. Heat Transfer, vol. 133, p. 054502, 2011), and disinfection (see H.-S. Kim et al., “Concentration of hydrogen peroxide generated by gliding arc discharge and inactivation of E. coli in water,” Int. Commun. Heat Mass Transfer, vol. 42, pp. 5-10, 2013). These active plasma treatment species may be employed for produced and flowback water from oil and gas exploration as well as, more broadly, wastewater streams from municipalities and a number of other industrial processes.
When a voltage gradient (1 kV/cm or more) is applied across two electrodes (i.e., anode and cathode) separated by approximately 1 cm, free-flowing electrons break down the air, and a plasma discharge takes place with the appearance of lightning. The electrons can also break down low-electric-conductivity liquid (i.e. liquid with a conductivity of 0.1 mS/cm or less) in a similar manner, generating plasma within the liquid matrix. See Yang, Y., et al., Application of pulsed spark discharge for calcium carbonate precipitation in hard water. Water Res., 2010. 44: p. 3659-3668; Yang, Y., Y. I. Cho, and A. Fridman, Plasma Discharge in Liquid: Water Treatment and Applications. 2012, New York: CRC Press; and Kim, H. S., et al., Use of plasma gliding arc discharges on the inactivation of E. Coli in water. Separation Purification Technology, 2013. 120: p. 423-428.
However, when the conductivity of the liquid is higher, such as the conductivity in excess of 10 mS/cm of industrial wastewater, seawater, and produced water, the water itself behaves as an electric conductor. To overcome the adverse effect of high conductivity, one needs to have an airgap between anode and cathode, or at least an airgap around the discharge (i.e., high-voltage) electrode. One of the methods to provide such an airgap is to use a vortex flow of liquid in a cylindrical reactor geometry. The vortex flow creates a low-pressure zone at the center of the reactor, where compressed gas is injected through multiple holes on the side wall of the discharge electrode. See U.S. application Ser. No. 16/258,734 filed on Jan. 28, 2019, entitled “System and Method for Plasma Discharge in Liquid,” published on Aug. 8, 2019 as US 2019/0241447 A1.
As the discharge electrode (i.e., anode) is surrounded by gas in a liquid reactor, plasma (either spark or arc plasma) is generated. The compressed gas in a plasma vortex system not only helps the generation of plasma but also stretches the arc vertically upward, enlarging the physical size of the arc. Furthermore, the injected gas also cools the discharge electrode, reducing the risk of electrode erosion caused by focal regions of high-temperature from the plasma arc. In addition, the vortex flow of water forces the arc to glide around the circular edge of the discharge electrode, an extremely useful process that continuously cools the electrode.
In one implementation of the plasma vortex system, the discharge electrode is located at the bottom end of the cylindrical reactor with the ground electrode at the top end such that the heat energy from the plasma moves away from the discharge electrode. From Ohm's law (i.e., V=iR), the current during plasma discharge is determined by the impedance between the two electrodes, which depends not only on the distance between the two electrodes but also on the conductivity of the liquid. Accordingly, the plasma power supply should be designed to be able to handle the changing impedance due to the changing electric conductivity of the liquid.
Once a pulsed plasma arc (at 20-30 kHz) is suspended in the plasma vortex reactor, a steady supply of reactive oxygen/nitrogen species are generated (i.e., 1O2, OH., H., O., HO2., O2−, O3, H2O2, N., NOx, NO. and charged particles). These oxidizing agents react with and break down organic bonds (C—H, C—C, C═C, C—O, C—N) and inorganic contaminants in liquid. As the half-lives of most reactive species other than ozone are very short, it is essential to have plasma discharge inside water. See Yang, Y., Y. I. Cho, and A. Fridman, Plasma Discharge in Liquid: Water Treatment and Applications. 2012, New York: CRC Press. Furthermore, the aforementioned stretched arc provides a longer contact time and a greater contact surface between the water to be treated and the reactive species. In addition, the UV radiation from the plasma acts as a potent disinfectant, killing and preventing reproduction of bacteria and viruses, without any lamp surface to accumulate biofilm or degrade transmission. See Hijnen, W., E. Beerendonk, and G. J. Medema, Inactivation credit of UV radiation for viruses, bacteria and protozoan (oo) cysts in water: a review. Water research, 2006. 40(1): p. 3-22.
Two shortcomings of the vortex-flow based plasma discharge are a large pressure drop and a large volume of gas needed to provide the airgap around the discharge electrode. Furthermore, due to the centrifugal force generated by the vortex flow, liquid tends to be thrown out along the radial direction in the reactor, whereas the gas remains at the center of the reactor. Naturally, liquid and gas do not get mixed, but rather stay separated. Since the gas contains several useful active plasma species, efficient mixing of liquid and gas would be helpful in enhancing the plasma treatment of water or wastewater.
Therefore, there is a need for a plasma generation method in liquid that requires a smaller pressure drop, a smaller volume of gas, a smaller footprint, and improved mixing between liquid and gas, resulting in continuing improvement in water treatment with pulsed spark or arc discharges with a disinfecting capability for water, river water, seawater, well water, industrial or municipal wastewater, industrial process water, and produced or flowback water from fracking operations.
Various embodiments disclosed herein relate to methods and apparatus for water treatment with venturi plasma discharges. In accordance with one or more embodiments, a water treatment system includes a venturi injector including a venturi inlet that intakes water to be treated, a venturi throat including an orifice in fluid communication with a gas source, a discharge electrode integrated into a gas inlet in fluid communication with the orifice for generating a plasma discharge, thereby producing treated water, and a venturi outlet that discharges the treated water. In some embodiments, the discharge electrode can be a cylindrical discharge electrode. In certain embodiments, the venturi throat can be coaxial with the discharge electrode. In some embodiments, the cylindrical discharge electrode can be a hollow cylindrical discharge electrode. In some of these embodiments, the hollow cylindrical discharge electrode can further include an endcap and a plurality of side openings in the cylinder wall. In certain embodiments, the endcap can further include a central opening. In other embodiments, the cylindrical discharge electrode can be a solid rod. In certain embodiments, the venturi inlet can include a taper in fluid communication with the venturi throat. In some embodiments, the water treatment system can further include a cylindrical insulator around the cylindrical discharge electrode. In some of these embodiments, the venturi outlet can be a ground electrode. In some other embodiments, the water treatment system can further include a ground electrode disposed upstream of the venturi throat. In these specific embodiments, the water to be treated can have an electrical conductivity in a range of between 0.1 mS/cm and 10 mS/cm. In certain other embodiments, the water treatment system can further include a ground electrode disposed downstream of the venturi throat. In these specific embodiments, the water to be treated can have an electrical conductivity in a range of between 10 mS/cm and 250 mS/cm. In certain embodiments, the water treatment system can further include a ground electrode disposed within the venturi throat. In some embodiments, the water to be treated can have an electrical conductivity in a range of between 0.1 mS/cm and 250 mS/cm. In certain embodiments, the gas can include gas to be treated. In some embodiments, the discharge electrode can be a cylindrical discharge electrode having side openings in the cylinder wall. In some of these specific embodiments, the discharge electrode can further include a central opening in fluid communication with the gas inlet. In certain of these specific embodiments, the water treatment system can further include a cylindrical insulator around the cylindrical discharge electrode, and an airgap between the cylindrical insulator and the cylindrical discharge electrode. In some of these specific embodiments, the venturi injector can be a ground electrode. In certain embodiments, the venturi outlet can discharge the treated water into a water holding tank in fluid communication with the venturi inlet. In some embodiments, the water treatment system can further include a gas recirculation system in fluid communication with the gas source.
In accordance with one or more embodiments, a method of water treatment includes flowing water to be treated through a venturi inlet to a venturi throat including an orifice in fluid communication with a gas source, the venturi throat including a discharge electrode integrated into a gas inlet in fluid communication with the orifice, flowing gas from the gas source through side openings in the discharge electrode, and generating a plasma discharge, thereby producing treated water. In some embodiments, the method can further include recirculating the gas to the gas source. In certain embodiments, the method can further include recirculating the treated water to the venturi inlet.
The water treatment systems and methods described herein have many advantages, including a smaller pressure drop, a smaller volume of gas, a smaller footprint, and improved mixing as compared to the plasma vortex system.
The foregoing purposes and features, as well as other purposes and features, will become apparent with reference to the description and accompanying figures below, which are included to provide an understanding of the invention and constitute a part of the specification, in which like numerals represent like elements. The figures are not necessarily drawn to scale, emphasis instead being placed upon illustrating embodiments.
It is to be understood that the figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clearer comprehension of the present invention, while eliminating, for the purpose of clarity, many other elements found in systems and methods of plasma discharge in liquid. Those of ordinary skill in the art may recognize that other elements and/or steps are desirable and/or required in implementing the present invention. However, because such elements and steps are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements and steps is not provided herein. The disclosure herein is directed to all such variations and modifications to such elements and methods known to those skilled in the art.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described.
As used herein, each of the following terms has the meaning associated with it in this section.
The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.
“About” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of ±20%, ±10%, ±5%, ±1%, and ±0.1% from the specified value, as such variations are appropriate.
“HV” as used herein means high-voltage, such as a voltage in excess of 1,000 V.
Ranges: throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Where appropriate, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.
The objective of the systems and methods described herein is to disinfect various types of liquids, including water, river/lake water, seawater, well water, industrial or municipal wastewater, industrial process water, and produced or flowback water from fracking operations, and to remove contaminants in wastewater and leachates and oxidize and decompose them without leaving any treatment gap or secondary waste problems. Various embodiments disclosed herein relate to methods and apparatus for water treatment with venturi plasma discharges. In accordance with one or more embodiments, as shown in
The pressure at the throat 130 can be decreased well below the inlet pressure of liquid. Therefore, the venturi throat 130 is an ideal location where air or other gases can be injected through an orifice 135 in fluid communication with a gas source 150. Depending on the level of the throat pressure, it may be possible to inject gas without the use of a compressor.
Air (or gas) is introduced into the venturi system 100 from gas source 150 through the gas inlet 155 that is in fluid communication with the orifice 135 in order to provide an airgap 186 around the discharge electrode 180, a necessary condition for plasma discharge inside water. The introduction of air into the venturi system 100 generally takes place due to the reduced pressure at the throat 130, which can be explained by the Bernoulli principle. The Bernoulli equation relates the pressure and flow velocity along a streamline as follows:
where P1 and P2 are gauge pressures (psig) at the venturi inlet 120 and throat 130, respectively, V1 and V2 are flow velocities (ft/s) at the venturi inlet 120 and throat 130, respectively, and ρ is the density of water. When the venturi injector 110 is positioned horizontally, the height change is negligible, i.e., Z1=Z2. Furthermore, V1 and V2 are determined by the cross-sectional areas at the venturi inlet 120 and throat 130, respectively. For example, if the venturi inlet diameter is D1 and the throat diameter is D2, then one has the following relation between the two flow velocities:
V
1
D
1
2
=V
2
D
2
2 (2)
Hence, by substituting V2 with
into the above Bernoulli equation, the pressure at the throat 130 becomes:
As an example, consider a water treatment system 100 with a 2″ inlet diameter D1 that delivers a flowrate of approximately 100 gallons per minute (gpm) at an inlet pressure of 40 psig. Note that a flowrate of 100 gpm in a 2″ diameter pipe delivers a flow velocity V1 of 10.2 ft/s. When the throat diameter D2 is 0.8″, i.e., D2/D1=0.4, then the pressure decreases to approximately 13 psig as shown in
If the throat diameter D2further decreases to 0.7″, i.e., D2/D1=0.35, then, as shown in
Once air or gas (optionally including droplets, dust, or other aerosolized solids) is injected to liquid through the orifice 135 at the throat 130, the bulk air is broken into a number of small-size air bubbles due to high liquid velocity at the throat 130, providing improved mixing between liquid and air, as compared to the plasma vortex, thereby enhancing the plasma treatment of the liquid.
The pressure drop in liquid flow is significantly less in the venturi plasma system than in the plasma vortex system. This is due to the fact that in the plasma vortex system the liquid pressure at the exit of the plasma reactor falls to zero gauge pressure due to the centrifugal motion of vortex flow. In contrast, the pressure of liquid at the exit of the venturi injector 110 is still significantly greater than zero gauge pressure because the liquid pressure recovers at the venturi outlet 140 according to the Bernoulli principle, as the cross-sectional area of the exit of the venturi injector 110 is increased.
The flow reactor geometry of the venturi plasma system is a tubular configuration compared to the three-dimensional geometry of the plasma vortex system. Hence, the venturi plasma system is simple in construction and has a small footprint with a smaller pressure drop in connecting pipes, as compared to the plasma vortex system.
In order to generate a plasma discharge in liquid, one needs to have the ground electrode in the reactor. In the venturi plasma system, one can consider a ground electrode 125 disposed within the venturi throat 130, as shown in
As shown in
As shown in
In accordance with one or more embodiments, as shown in
In order to generate a plasma discharge in liquid, one needs to have the ground electrode disposed in the reactor, with the ground electrode in contact with the liquid. In the venturi plasma system 300, one can consider having the venturi outlet 340 grounded, as shown in
Turning back to
As an example, turning back to
In accordance with one or more embodiments, as shown in
Alternatively, as shown in
In accordance with one or more embodiments, as shown in
As shown in
In accordance with one or more embodiments, as shown in
Example 1 is a water treatment system includes a venturi injector including a venturi inlet that intakes water to be treated, a venturi throat including an orifice in fluid communication with a gas source, a discharge electrode integrated into a gas inlet in fluid communication with the orifice for generating a plasma discharge, thereby producing treated water, and a venturi outlet that discharges the treated water.
Example 2 includes the subject matter of Example 1, further including a ground electrode disposed upstream of the venturi throat.
Example 3 includes the subject matter of any of Examples 1 or 2, wherein the water to be treated has an electrical conductivity in a range of between 0.1 mS/cm and 10 mS/cm.
Example 4 includes the subject matter of Example 1, further including a ground electrode disposed downstream of the venturi throat.
Example 5 includes the subject matter of Example 4, wherein the water to be treated has an electrical conductivity in a range of between 10 mS/cm and 250 mS/cm.
Example 6 includes the subject matter of Example 1, further including a ground electrode disposed within the venturi throat.
Example 7 includes the subject matter of Example 1, wherein the water to be treated has an electrical conductivity in a range of between 0.1 mS/cm and 250 mS/cm.
Example 8 includes the subject matter of any of Examples 1-7, wherein the gas includes gas to be treated.
Example 9 includes the subject matter of any of Examples 1-8, wherein the discharge electrode is a cylindrical discharge electrode having side openings in the cylinder wall.
Example 10 includes the subject matter of Example 9, wherein the discharge electrode further includes a central opening in fluid communication with the gas inlet.
Example 11 includes the subject matter of any of Examples 9-10, further including a cylindrical insulator around the cylindrical discharge electrode.
Example 12 includes the subject matter of Example 11, further including an airgap between the cylindrical insulator and the cylindrical discharge electrode.
Example 13 includes the subject matter of Example 11, wherein the venturi injector is a ground electrode.
Example 14 includes the subject matter of Example 1, wherein the discharge electrode is a cylindrical discharge electrode.
Example 15 includes the subject matter of Example 14, wherein the venturi throat is coaxial with the discharge electrode.
Example 16 includes the subject matter of Example 14, wherein the cylindrical discharge electrode is a hollow cylindrical discharge electrode.
Example 17 includes the subject matter of Example 16, wherein the hollow cylindrical discharge electrode further includes an endcap and a plurality of side openings in the cylinder wall.
Example 18 includes the subject matter of Example 17, wherein the endcap includes a central opening.
Example 19 includes the subject matter of Example 14, wherein the cylindrical discharge electrode is a solid rod.
Example 20 includes the subject matter of any of Examples 14-19, wherein the venturi inlet includes a taper in fluid communication with the venturi throat.
Example 21 includes the subject matter of any of Examples 14-19, further including a cylindrical insulator around the cylindrical discharge electrode.
Example 22 includes the subject matter of Example 21, wherein the venturi outlet is a ground electrode.
Example 23 includes the subject matter of any of Examples 1-22, wherein the venturi outlet discharges the treated water into a water holding tank in fluid communication with the venturi inlet.
Example 24 includes the subject matter of any of Examples 1-23, wherein the water treatment system further includes a gas recirculation system in fluid communication with the gas source.
Example 25 is a method of water treatment that includes flowing water to be treated through a venturi inlet to a venturi throat including an orifice in fluid communication with a gas source, the venturi throat including a discharge electrode integrated into a gas inlet in fluid communication with the orifice, flowing gas from the gas source through side openings in the discharge electrode, and generating a plasma discharge, thereby producing treated water.
Example 26 includes the subject matter of Example 25, wherein the gas flowing through side openings in the discharge electrode sweeps out an airgap between a cylindrical insulator and the cylindrical discharge electrode.
Example 27 includes the subject matter of any of Examples 25 or 26, further including recirculating the gas to the gas source.
Example 28 includes the subject matter of any of Examples 25-27, further including recirculating the treated water to the venturi inlet.
The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention.
This application claims the benefit of U.S. Provisional Application No. 63/102,788, filed Jun. 30, 2020, which is hereby incorporated by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/US21/39499 | 6/29/2021 | WO |
Number | Date | Country | |
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63102788 | Jun 2020 | US |