This invention relates to plasma treatment of water.
Nitrogen is a key component of fertilizer and is essential to plant growth and health. Currently, most nitrogen in fertilizers is available in solid form, often as a nitrogen-containing chemical group bound to a chemical carrier. For example, the most common nitrogen fertilizer is ammonium nitrate, which is a nitrate chemical group (NO3−) bound to ammonium (NH3—H), or as urea, two amino radicals (NH2), bound to carbon monoxide (CO). Both ammonium nitrate and urea are highly soluble in water. These common nitrogen fertilizers are mostly manufactured using the Haber-Bosch process. However, both the steam methane reforming to produce the H2 required by the Haber-Bosch process and the Haber-Bosch process itself are energy-intensive and contribute to greenhouse gas emissions. For example, about 2% of global energy consumption and about 2% of anthropogenic carbon dioxide (CO2) emissions is directly attributable to fertilizer production. The harmful consequences of these traditional means of “fixating” nitrogen, i.e., producing compounds of nitrogen where the nitrogen atom is chemically attached with a single bond, illustrate the need for alternative processes for producing fertilizers. Accordingly, it would be an advance in the art to provide improved nitrogen fixation.
This work provide apparatus for producing water-dissolved nitrates, i.e., similar to what is obtained when ammonium nitrate is dissolved in water, using just water, ambient air, and electricity. An air plasma is produced using a gas discharge, and the exposure of this plasma to a shallow water channel flow enriches water with dissolved nitrates.
A gas discharge plasma, when generated in a molecular gas such as air, is composed of electrons, positive and negative ions, excited and neutral atoms, and other reactive molecular species and radicals. Plasma fixation of nitrogen in water, sometimes referred to as “plasma-activated water,” can be generated via air plasma treatment either above or directly in water (i.e., the water is exposed to a plasma stream, or a plasma is generated directly in the water). Such an activation results in the formation of numerous dissolved and chemically active species, often generalized as reactive oxygen and nitrogen species (RONS).
There are several scientific studies that describe processes that treat water with a plasma by (i) exposing the plasma to a free water surface; (ii) produce a plasma directly in water; or (iii) produce a plasma in wither water vapor or mixed water phases (e.g., water mists). Some of these studies use pure air and some use small amounts of air diluted in a carrier gas that is not air. The plasma activates the air-containing gas, or the water itself, and these active species react with the water to become solvated (dissolved) species reactive species. These dissolved species can form nitrates. In addition to nitrates, dissolved species can also include nitrites and peroxides, among others.
When plants are irrigated with this activated water, the nitrates are taken up by the plant roots, and serve as a source of nitrogen to promote plant growth. Production of nitrate ions in water for use as an exogenous fertilizer source is provided. The application of plasma-fixated nitrogen in agriculture has recently gained much attention because of its various interesting properties and potential for sustainable production. In the literature, there is evidence that plasma activated water has been shown to enhance seed germination, plant growth, and that it may also have antiseptic properties as a result of microbial reduction. In this work, we also show that this approach produces an activated water that has a high degree of efficacy by comparing its use to more commonly used fertilizers in treating common turf grass, specifically rye grass and bent grass.
We examine the use of plasma-fixated nitrogen in the fertilization of turf grass because turf grass is considered to be one of the largest irrigated crops in the United States, covering a greater surface area than even irrigated corn. Turf grass is commonly used in residential and commercial lawns, golf courses, and recreational and sports fields. As such, turf grass has the potential to sequester a large amount of excess carbon from the atmosphere and reduce greenhouse gas emissions. The use of sustainable energy in the production of plasma-fixated nitrogen for turf grass growth would further reduce its carbon footprint. This approach for producing plasma activated water in concentrated forms, particularly for recreational fields, and its dispensing into irrigation systems may be uniquely suited to the fertilization of turf grass because of the regular rate of irrigating turf grass. Our results of studies on turf grass also support the use of this plasma-produced fertilizer on agricultural food crops. As described herein, it can be packaged as an appliance of varying size to produce the nitrogen needed for a particular application, enabling the decentralized production of nitrogen. Smaller units can also be manufactured in large numbers and assembled together to produce large-scale manufacturing centers.
Several embodiments described below make use of a chamber in which air (or modified air) is admitted. This air is exposed to a plasma formed by the electrification of a plasma applicator. The chamber also provides a means of introducing the water to be treated. In one embodiment, all of the water to be treated occupies the same chamber at all times. In another embodiment, the water may be transitory, i.e., flows into or out of the chamber in one or more passes, with a large amount of this water stored in a vessel for recirculating through the plasma treatment chamber. In yet another embodiment, the air that is treated by the plasma leaves the chamber and is discarded. In yet another embodiment, the air that is treated by the plasma is reintroduced back into the same chamber, or into the chamber of another fertilization unit. In a further embodiment, the treated air can be bubbled through the water that is being treated, or being stored for treatment and retreatment. In some embodiments, the air drawn from an ambient source can also enter a device that enhances its oxygen content to provide oxygen enriched conditions.
The present approach also allows for the water that is being treated to be controlled in temperature, sometimes higher than ambient to encourage the chemical reactions in the water phase, particularly so when activated air is being recirculated and bubbled through the water to further enhance the capturing of reactive nitrogen. This recirculated air increases the probability of the capture of nitrogen oxides by the water, thereby decreasing the amount of nitrogen oxides that are released into the exhaust and subsequently the environment.
The plasma applicator belongs to a family of so-called dielectric barrier discharges (DBDs) but differs from conventional designs in several important respects, as described in greater detail below.
Applications of this work include the fertilization of water, as described below. It can also be used to sterilize/disinfect water, e.g., by acidifying water to lower its pH. Likely consumers would be agricultural facilities, particularly specialty farms, hydroponic facilities, and indoor farms. Other applications include the maintenance of landscaped parks and athletic recreational areas such as football and baseball fields and the grasses and greens of other sporting venues.
Section A describes general principles relating to embodiments of the invention, and section B is a more detailed description of some exemplary embodiments.
An exemplary embodiment of the invention is an apparatus for treating water, where the apparatus includes:
The apparatus is configured to generate a plasma between the first insulating layer and the air-water interface during operation, e.g., as shown on
The apparatus can be configured to provide nitrogen in water as nitrates and/or nitrites. The apparatus can be configured to acidify water.
The plasma preferably has an electron energy range from 1 eV to 10 eV and a gas temperature of 1000° C. or less, where this gas temperature applies to all ionized and neutral molecular and/or atomic species in the plasma). In other words the ‘gas temperature’ is the temperature of everything in the plasma except the electrons. Such a plasma is non-thermal because the electrons are heated to a temperature higher than the gas temperature.
The first electrode can be configured in various patterns, including but not limited to: square meshes, rectangular meshes, triangular meshes, hexagonal meshes and 1D arrays of elements.
The reaction chamber can be configured as a water reservoir, as in the example of
The apparatus can further include a gas circulation system. The gas circulation system can be configured to bubble air containing activated chemical species from the plasma through the water. The gas circulation system can be configured to provide oxygenated air to the plasma. See
The apparatus can further include a heat sink affixed to the plasma applicator. In such a case, the apparatus can further include a second insulating layer (e.g., 26 on
A pump 12, preferably one that is resistant to chemical attack, can draw processed water near the interface between the water and the plasma using a draw line 11, and return it to the tank using a return line 13, recirculating the water to provide for mixing the processed water with the unprocessed water. This can provide mixing to prevent kinetic saturation of the activated interfacial region. It also provides for a redistribution of heated water as the water near the surface increases in temperature during processing. A second pump 14 can serve as a bubbler to introduce additional dissolved air to the water processed in the tank. One or more ports 15 serve to regulate the air that is processed by the plasma at the plasma-water interface, allowing new air to enter or leave as desired. These ports can be made to be variable in size, depending on the amount of water processed in the tank. The circulation of this air through these ports can be assisted by a blower (not shown). A valve 16 connected to a drain tube 17 can provides a way to transfer processed water into storage bins. A second access port 18 can be used to accommodate various types of sensors (for pH, nitrates, temperature), by diverting some of the processed water over to a small secondary tube appendage 19 filled with static processed water.
The system can be equipped with a means of regulating the water temperature. A temperature control element 20, serviced by an heating/cooling source 21, can be used to add and/or remove heat to raise, lower and/or control the temperature of the process water if so desired to enhance product yield. For example, 20 can include heating and/or cooling elements, and 21 can include an electrical power supply and/or a compressor unit.
The size of the tank 1 is variable. It might be 50 liters, or even 500 liters. The power of the plasma applicator can be 100 W or even 1 kW. For larger tanks, an array of applicators can be used to provide a large enough plasma sheet to fill the free surface of the water in the tank. The nitrate concentration in the water can range from very low values, such as 0 ppm, to very high values (10,000 ppm) and higher. The pH can range from values of 8, down to values of 0.8, representing the formation of processed water that is of moderate acidity. We anticipate that these lower levels of acidity will cause the evolution of absorbed carbon dioxide, CO2. As a side benefit, this approach can also be used to therefore capture CO2 from water.
The plasma applicator is designed to be able to be in very close proximity of the water and sufficiently robust and immune to failure as a result of the possibility that water condenses or splashes on the applicator. An important embodiment is the use of a compound dielectric barrier discharge that is free of any direct contact between the metal and the plasma. An expanded view of the plasma applicator illustrated in
The most important feature on
The ambient air that enters the chamber via port 15 on
In yet another embodiment, as illustrated in
Yet another embodiment is shown on
The lower electrode 5 can be a structured metallic pattern that is screen printed, electroplated, or sputtered onto the lower surface of the dielectric. The particular pattern, examples of which may be square (as shown in
An alternate embodiment is shown in
A plasma 64 is produced on top of the water's free surface as it flows within a channel inside this plasma process unit. The plasma is formed by a similar applicator as shown in
Similar modifications to the design of
In another embodiment, as depicted in
In yet another embodiment, as illustrated in
Yet another embodiment is shown on
Another embodiment has these plasma processing units described in
In various experiments, we have fabricated several small and large versions of devices as shown in
In further experiments to illustrate that the produced plasma fixated nitrogen solution has the efficacy to provide nutrients for plant growth, we have carried out three studies The first is a study on how varying concentrations of our plasma affects germination and growth of turf grass. The second is a study of how the addition of phosphorous (P) and potassium (K) added to plasma-fixated nitrogen solution impacts growth of turf grass. And the third is a comparison of how our plasma-fixated nitrogen performs against other sources of plant nitrogen of equal nitrogen content. The studies are performed by germinating and growing plants by watering with various kinds of treated water, and measuring plant growth. Plant growth is measured via plant height and dry mass.
In the plasma-fixated nitrogen dilution study, 50 uniform rye-grass seeds were placed in 250 mL plastic containers on top of approximately 70 cubic centimeters of coco coir and covered with approximately 20 cubic centimeters of coco coir. For this first study, equal volumes nitrated water were added daily to each respective container. A range of dilutions of the plasma-nitrated water were prepared from a stock solution. The amount of nitrate added to each treatment group (varying dilution) over time was recorded, and final measurements were collected after 17 days following initial planting. After 17 days of growth, the turf grass with higher concentrations of plasma-fixated nitrogen (100:1, 20:1, 10:1, 5:1, 2:1 dilution ratio from the 168 ppm NO3—N stock) were visibly taller, thicker, denser, and greener compared to the groups that received only water (control) or dilute amounts of the fertilizer (100:1 dilution).
To test the effect of adding P—K to plasma-fixated nitrogen stock solution, liquid fertilizer containing only P—K (0-10-10 designation) was diluted by a factor of 1000 in industrial water. This solution was added to 168 ppm NO3-N (nitrates as nitrogen) of plasma-fixated nitrogen stock solution to form an N—P—K complete fertilizer solution. The diluted P—K fertilizer was also tested without the added plasma-fixated nitrogen in this study as a control. 25 uniformly spaced ryegrass seeds were placed in 250 mL plastic containers on top of approximately 250 cubic centimeters of coco coir and covered with approximately a quarter inch (or about 40 cubic centimeters) of coco coir. Equal volumes of water and fertilizer solution were added daily to each respective container. The amount of nitrate added to each treatment group over time was recorded. Measurements were recorded after 19 days following initial planting.
Finally, to compare the performance of plasma-fixated nitrogen in water against other sources of plant nitrogen, 5 seeds were placed in approximately 7 grams of coco coir with a quarter inch of coco coir over the seeds, and either 2.5 mL of water (control), 100 ppm NO3—N plasma-fixated nitrogen solution, 100 ppm sodium nitrate as nitrogen (NaNO3), purchased from ASI sensors, and 100 ppm potassium nitrate as nitrogen (KNO3), purchased from LabChem, were added daily to each respective growth container until germination. After germination, equal volumes of the solutions were added daily to each respective treatment group. The amount of nitrate added to each treatment group over time was recorded. For all of the growth studies described here, the seeds were placed in a custom climate-controlled (T=22° C.) plant growth chamber with 24 hour light exposure during the germination period and 14 hour light exposure during post-germination and plant growth. We found that the plasma-fixated nitrogen performed as well as the other two nitrogen sources and all three of these led to improved turf growth over the nitrogen-free water control.
All three of these growth studies serve to confirm that plasma activation as described herein produces nitrogen fertilizer that improves plant growth and performs equally well as commercially-available sources of fixated nitrogen.
Filing Document | Filing Date | Country | Kind |
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PCT/US2022/026757 | 4/28/2022 | WO |
Number | Date | Country | |
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63180981 | Apr 2021 | US |