1. Field
The present invention relates to a plasma generation reactor. In particular it relates to a reactor that is configured with a plurality of surfaces between two electrically excited electrodes. This structure allows glow discharge operation at high frequencies and high voltage potentials resulting in high overall ionization of target gasses or fluids to be treated.
2. Prior Art
It is known that glow discharge is generated by placing a dielectric material between two electrodes and applying a high-voltage alternating current or a periodic pulse voltage, and in the plasma field resulting there from, active species, radicals, and ions are generated so as to facilitate decomposition and further reaction of a gas or liquid (refer to U.S. Pat. No. 5,414,324). Plasmas formed in this manner are commonly referred to as dielectric barrier discharges. Further it is known that gasses decomposed by the application of dielectric barrier discharge can be reformed into more desirable forms. For example process and automobile exhaust gasses have been treated with such reactors (refer to U.S. Pat. No. 7,507,934).
The plasma and resulting ion formation in dielectric barrier discharges is dependent on the periodic change in the direction of current flow through the reactor. This periodic change in the direction of flow is controlled by the applied AC or pulsed DC voltage and the rate of change of current flow is controlled by the rate of change of the applied voltage, commonly referred to as dV/dt, at the reactor electrodes. Ion formation in the plasma is greatest during the most rapid field change (U.S. Pat. No. 7,399,944). In maximizing ion formation it is generally desirable to operate dielectric barrier discharges at higher frequencies and higher dV/dt.
Ions in dielectric barrier discharges are concentrated at the surfaces inside the plasma field (U.S. Pat. No. 7,298,092). Therefore, increasing surface area in the plasma field is a generally accepted method of increasing reactor plasma generation capacity.
Finally, it is also generally desirable to increase the size of dielectric barrier discharge reactors to accommodate higher volume processing.
In present dielectric barrier discharge reactor designs increasing the reactor size while maintaining a high surface area to gas/fluid volume ratio directly increases the capacitance of the reactor. This higher capacitance is in conflict with the desire to operate at higher frequencies and provide higher dV/dt at the reactor. As a result, present dielectric barrier discharge reactor designs incur practical limitations in achieving increased ion formation rates due to limitations in operating frequency and dV/dt as the surface areas are increased.
One approach to solving the capacitance problem is to increase the space between the plasma generation electrodes. However, wide spaces for plasma generation result in relatively high percentages of gas remaining un-ionized in areas away from surfaces. Further, when re-combination of ions into more desirable species is required, a surface to hold the ionized particle until recombination occurs will accelerate the recombination. It has also been shown (U.S. Pat. No. 7,298,092) that these larger distances between electrodes lead to instabilities in plasma current across the dielectric surfaces. These instabilities can cause parts of the reactor to have weak or non-existent plasma current flow. The prior art does not address the current understanding that streamer formation is not only a function of the distance between electrodes, but also a function of the distance between the dielectric surfaces. Finally, streamer formation is exacerbated at the pulse cycle end, or in low frequency driven systems and is the subject of extensive research (U.S. Pat. No. 7,399,944). One method to solve this problem is to simply increase the drive frequency of the reactor. However this is difficult on slower, higher capacitance reactors.
This leads to a desire for a reactor with low capacitance and high surface area to gas/fluid volume ratio indicating that smaller distances between surfaces is desirable. The present invention presents a novel solution to these problems.
Multiple electrode designs as described in U.S. Pat. No. 7,507,934 attempt to solve one of these limitations and describe a method of increasing the reactor surface area to gas ratio. However, these designs involving multiple electrically connected electrodes result in much higher reactor capacitance.
In addition, it is known that multiple electrically interconnected electrode designs such as intermediate electrodes and multiple electrode designs (U.S. Pat. No. 7,507,934) are used in some plasma reactors such as depicted in
As a general class of reactor design, multiple electrode designs suffer from high capacitance and plasma current non-uniformity particularly as the surface area is increased. This characteristic of the prior art has lead to a diversity of electrode designs to mitigate this non-uniform plasma current problem.
Various electrode configurations and designs result in more uniform plasma current conduction than others and further result in more desirable plasma discharges. These include slotted or perforated electrodes such as in U.S. Pat. Nos. 6,005,349 and 6,818,193. In addition perforated dielectrics have been used to enhance the desirable characteristics of plasma as in U.S. Pat. No. 5,872,426. However, using variations of electrodes does not resolve the capacitance issue. In addition these perforated electrodes cause areas of weakened plasma field in areas around the perforations.
As stated above, it has been shown that higher operating frequencies result in higher plasma energy into a reactor. U.S. Pat. No. 7,507,934 discusses frequencies of greater than 100 Hz, but fails to address operation of that design at higher frequencies. Multi-electrode designs such as these increase the capacitance dramatically over two electrode versions making higher frequency operation more problematic and therefore further limiting the efficiency of the reactor.
The present invention has for its object to provide a method and an arrangement of a plasma reactor and reactor systems for use in gas and/or fluid chemical reactions. For purposes of clarity, the term gas will be used for both gas and other fluid materials to be reacted. In addition, the term electrode may be used to identify plasma generation electrodes (numbers 26 and 28) and the term element or elements may be used generally for identifying all elements (numbers, 27, 36, 37a, 37b, 41, 42, 43, 44, 46, 47, 48, 56, 57, 61, 62, 65, 66, 71, 74 and 81) between the plasma generation electrodes and not directly connected to the plasma generation electrodes. Spaces between the various elements and electrodes may be maintained by spacers 23.
For illustration purposes the following design is reviewed. This summary reviews one embodiment of a plasma reactor that can be used for many chemical synthesis and separation applications. For clarity purposes in this example, a hydrogen and nitrogen disassociation and recombination reaction to form ammonia is considered. Also, in many applications, gasses not used in the desired end product can be used with the reactant gas to enhance the effects and rate of the reaction, but again for simplification these will not be considered in this example. Those familiar with the art will also realize that catalysts, promoters, porous and non-porous particles and surfaces used alone or in various combinations, microstructures, surface textures, particles including nano-particles can be used either in a fluid form or as part of the electrodes and are included as part of this invention.
A multi-element reactor designed to disassociate nitrogen and hydrogen and recombine the disassociated ions into ammonia is presented according to this invention. In this form, the reactor consists of two electrically excited, isolated electrodes and a number of non-electrically excited dielectric elements in combination with conductive elements in the middle with spaces between the electrodes. A mixture of nitrogen and hydrogen gas is passed through the spaces created by the electrodes, dielectric elements, and electrically isolated conductive elements. The plasma generation electrodes are electrically excited with sufficient energy (AC or pulsed DC voltages can be used in this application) to create a plasma capable of molecular disassociation in some or all the spaces between the electrodes of some or all the molecules in the spaces. A percentage of the nitrogen and hydrogen molecules disassociate or partially disassociate according to known art and become ions. These ions move toward one of the plasma generation electrodes or dielectric elements according to the electric charge and become available for a reaction with other ions. As the majority of most recombination reactions occur at a surface, it is desirable for a large amount of surface area to be available for recombination reaction. Thus by minimizing the distance from surface to surface and increasing the number of spaces using non-electrically excited electrodes, the surface area available for recombination sites is increased. Further, by minimizing the thickness of the total thickness of the dielectrics, the excitation energy is not generally increased compared to that required for a conventional single space reactor.
In one embodiment, a five dielectric element design (six spaces) reactor was used with plasma generation electrodes on each end. This reactor comprised 228 square cm of surface area in the reactor and using approximately 100 micron spaces between elements resulted in an initial capacitance of 25.7 pF. This compares favorably to a traditional two electrode tube reactor with approximately 1580 um spacing from electrode to electrode and a surface area of 205 square cm resulting in a reactor capacitance of 141 pF. This reduction in the reactor capacitance by more than five-hundred percent greatly simplifies the drive electronics.
This novel approach to reactor design allows an increase in surface area, and a reduction in capacitance, without a dramatic increase in the excitation voltage required to create a plasma. In addition, the current required for creating the excitation voltage to generate the plasma is reduced as a function of total surface area in the reactor due to the low reactor capacitance. Finally, by creating multiple surfaces close to each other, the formation of filaments was greatly reduced, resulting in a more uniform glow plasma.
The first embodiment results in a plasma generation device comprising: a plurality of dielectric elements which are disposed between two or more unit plasma generation electrodes creating a plurality of spaces between said unit plasma generation electrodes. Said unit plasma generation electrodes may or may not be dielectrically isolated from said spaces The plasma generation electrodes being capable of generating plasma in the spaces by application of an AC or pulsed DC voltage, or some combination thereof between the unit plasma generation electrodes, wherein the plasma is generated in the spaces formed by the plurality of dielectric elements.
These and other objects are achieved by the present invention having a plurality of plasma formation plasma discharge spaces allowing a continuous, semi-continuous or batch mode gas or gas mixture flow. Said plasma discharge spaces comprising at least two spaced electrically excited electrodes (Plasma Generation Electrodes 26), and at least one center electrically isolated electrode (dielectric elements, or other elements described herein) wherein at least one plasma pulse is generated by applying an energizing voltage to the electrodes causing a plasma current and a displacement current. The plasma dielectric elements may or may not be electrically conductive depending on the particular requirements of the design, but when electrically conductive at least one non-conductive surface is placed between or adhered to the face of the two electrodes forming a space which is dielectrically isolated from the plasma generation electrodes 26. The present invention therefore provides a plurality of spaces and electrically isolated dielectric elements or other elements being excited by plasma generation electrodes 26.
A second embodiment of this invention allows the ability to modify the intensity of the plasma at various points within the reactor by variation of dielectric constant in materials used in various parts of the reactor. This can be accomplished using several approaches, each having utility in various applications. For example, the dielectric constant of the dielectric elements, the dielectric coating on the isolated conductive elements, when present, or complete elements with varying dielectric constant, is effective in altering the plasma intensity in the adjacent space.
Another method of changing the plasma intensity at various points, while controlling the gas flow through the reactor, is to vary the space between elements. This can be done generally by changing the space from element to element. This results in a plasma dielectric element according to the description above, wherein the distance between the adjacent dielectric elements to each other varies over the entire length and width and is different than the distance between the dielectric elements adjacent to each other in the remaining portion. In addition, spacing can be changed over just a portion of an element by changing the general shape and thickness of the element. This has additional utility as a flow control system to direct gasses to desirable areas, to maintain a gas in the plasma for a longer or shorter duration, or to mix gasses. This results in a dielectric element wherein with respect to the plasma dielectric elements in the remaining portion, the distance between the plasma dielectric elements adjacent to each other is further varied over a portion, or the entire plasma dielectric element.
All of the electrode and element surfaces can be additionally coated, impregnated, or manufactured from materials that enhance the desired reaction. These materials can be promoters, catalysts or porous materials including nano-particles, or combinations of the same which increase the surface area and/or enhance the desired reaction.
In several embodiments of this invention, conductive elements used in concert with dielectrically isolated elements are used to increase the reactor element usefulness. Plasma energy will be transferred to any conductor within the plasma field via capacitive coupling. By using a single conductive surface dielectrically isolated on both side, the plasma energy supplied from the electrodes can be re-distributed over the surface of such an element. In addition, by using a partial conductor, dielectrically isolated in one area of an element, plasma energy can be focused on a desired location within a space. Finally, by changing the space from area to area by modifying the thickness, and placement of the conductor with an element, both gas flow through any space and plasma strength at any point with the reactor can be modified.
Through experiments conducted by the inventors, it has been shown that increasingly small spacing in a multi-dielectric reactor shown in
a)(b)(c) schematically show an example of a plasma generation device of the prior art (U.S. Pat. No. 7,507,934).
a), (b), (c) are schematic views of one embodiment of the present invention showing a two unit plasma generation electrode version of a distributed dielectric reactor.
d) is a schematic view of one embodiment of the present invention showing a two unit plasma generation electrode version with non-dielectrically isolated plasma generation electrodes and one embodiment of the electrical connection to the unit plasma generation electrodes.
a) is a cross sectional schematic view of one embodiment of the present invention showing variation in the thickness of the plasma dielectric elements across the reactor.
b) is a cross sectional schematic view of one embodiment of the present invention showing variation in the thickness, composition and structure of the dielectric elements across the reactor.
a) is a cross sectional schematic view of one embodiment of the present invention showing dielectric elements and a conductive element which is not isolated by a dielectric from the adjacent space where plasma forms.
b) is a cross sectional schematic view of one embodiment of the present invention showing dielectric elements and a conductive element which performs complex functions and is not isolated by a dielectric from the adjacent space where plasma forms.
c) is a cross sectional schematic view of one embodiment of the present invention showing dielectric elements and a conductive element which is isolated on one side by a dielectric from the adjacent space where plasma forms.
d) is a cross sectional schematic view of one embodiment of the present invention taken parallel to the indicated gas flow showing interconnected spaces for extension of the fluid flow path through the plasma generation device.
e) is a cross sectional schematic view of one embodiment of the present invention taken parallel to the indicated gas flow showing a porous material affixed to one end of the plasma generation device through which process fluid must pass.
a) and
Embodiments of the present invention will be described below in detail with reference to the drawings. The present invention is not limited to the following embodiments and changes in design and modifications could be made appropriately based on a common knowledge of a person skilled in the art without departing from the spirit and scope of the present invention. By integrating the various design features and elements described herein in various combinations, and with fewer or greater number of elements, reactors can be designed using the methods and elements in this invention to produce similar of different desired reaction outcomes.
a),
a), 2(b) and
Using common methods known to those skilled in the art, multi-layer reactors are assembled by stacking tabular dielectric elements and spacers, and where desired, micro spheres or other shapes for dimensional stability are added to the region 24. In one embodiment, low alkaline glass one hundred microns (100 um) thick is used for both spacers 23 and dielectric elements 27, with one hundred micron diameter micro spheres dispersed between the dielectric elements in the region 24 for dimensional stability. This stack is then heated to a temperature which caused the dielectric elements 27, spacers 23 and micro spheres to adhere to each other and become one unit. Electrodes consisting of a slice of a semiconductor silicon wafer cut to the desired dimensions and coated with a glass of like expansion coefficients are then sealed to the unit using a glass frit to form the electrodes. The unit reactor was then inserted into an appropriate housing and sealed to create channels for gas or fluid to flow into and out of the unit reactor. A person skilled in the art will be able to assemble this type of reactor unit in a variety of ways with good results. The various embodiments below are assembled using similar simple techniques and will be obvious to anyone skilled in the art.
b) is a cross sectional schematic view of reactor 30 cut along line B-B′ as shown in
c) is a is a cross sectional schematic view of reactor 30 cut along line B-B′ as shown in
d) shows a cross sectional schematic of a second embodiment of the reactor and conductors 21 in which there is no dielectric isolation between the conductor and the adjacent region 24. As only one side of any region must be dielectrically isolated for plasma to form, these non-isolated unit plasma generation electrodes can be used where there is dielectric isolation on the opposing side. Non-dielectrically isolated electrodes 28 are advantageous in unit reactors with a high number of dielectric elements 27 as this eliminates one layer of dielectric that can be added back into the design and used to form an additional region 24. In addition, non-dielectrically isolated electrodes 28 allow simplified construction and can be formed using conventional means to create entry and exit points for fluid or gas used in the plasma reaction. Where non-dielectrically isolated electrodes 28 are used with non-dielectrically isolated conductive elements 56, the plasma will transition to arc mode in region 24 adjacent to the electrodes 28. Although not effective for ionization, this is useful in reactors for other purposes. In all of the embodiments, both electrodes 26 and conductors 28 can be used as required for construction and performance.
a) is a cross sectional schematic view of an embodiment of the present invention with a plurality of dielectric elements 47, 48, and 49 placed between the unit plasma generation electrodes 26 creating a plurality of plasma spaces 24a. In this embodiment, said dielectric elements 46, 47, and 48 are made of materials of different thicknesses both in the direction perpendicular to the gas flow and in line with the gas flow and at various directions toward and away from the gas flow. This allows channeling of various gasses and fluids and the creation of different strength plasmas in various areas to affect the outcome of the reaction.
a) is a cross sectional schematic view of an embodiment of the present invention with one or a plurality of dielectric elements 27 and one or a plurality of conductive elements 65 placed between the unit plasma generation electrodes 26 creating a plurality of plasma spaces 24. Conductive elements 65 can be arbitrarily thin or very thick without negatively impacting the performance of the reactor unit. Plasma will form in the regions 24 adjacent to the conductive surface as only one side in each region 24 needs to have dielectric isolation in order to form plasma, this embodiment simplifies the design of some of the elements in the reactor and allows for a higher degree of complexity without sacrificing the plasma function.
Conductive elements 65 and 66 such as those in
c) is a cross sectional schematic view of an embodiment of the present invention with a plurality of conductive elements 61 dielectrically isolated on one side 62 placed between the unit plasma generation electrodes 26 creating a plurality of regions 24. The conductive portion of these elements can be continuous or discontinuous over the surface enabling the plasma to be concentrated, diluted, distributed, or re-distributed throughout the space in a manner that affects the reaction outcome.
d) is a cross sectional schematic view of an embodiment of the present invention with a plurality of dielectric elements configured in such a manner as to increase the distance the gas must travel before exiting the reactor. The dielectric elements 82 have been shortened and dielectric elements 81 have been placed blocking some of the entrances and exits from the reactor causing the gas flow to be extended through the unit reactor. Using this embodiment on part or all of a unit reactor, gas flows can be modified to optimize the process desired. In addition constructions using holes between layers can be used for other purposes such as mixing gasses between reactor layers.
e) is a cross sectional schematic view of an embodiment of the present invention with a plurality of dielectric elements 83 configured in such a manner as to direct the gas through the reactor and through the blocking element of porous material 84 before exiting the reactor. Said porous material is used to enhance the surface area as the gas exits the plasma. In addition, catalysts and other reaction promoters can be coated onto the surface, embedded in or otherwise contained in said porous material. Using this embodiment on part or all of a unit reactor, gas flows can be modified to optimize the process desired.
a) is an isometric schematic view of an embodiment of the present invention with a plurality of conductive elements 71 having dielectric isolation 74 Dielectric spacers 73 are placed between elements 74 creating a plurality of regions 24. The conductive portion of both the plasma generation electrodes 21 and the elements 71 and 74 can be continuous or discontinuous over the surface enabling the plasma to be concentrated, diluted, distributed, or re-distributed throughout the space in a manner that affects the reaction outcome. Further the conductive portion of the isolated elements 71 extend beyond the plasma generation electrodes 21 enabling the plasma field to be extended beyond the electrode.
In all embodiments, elements 27, 36, 37a, 37b, 41, 42, 43, 44, 46, 47, 48, 56, 57, 61, 62, 65, 66, 71, 74, 82, and 83 can be used in a unit reactor with plasma generation electrodes both dielectrically isolated 26 and non-dielectrically isolated 28.
Accordingly, the apparatus and method of the present invention provide:
From the foregoing, it may be seen that the invention of the distributed dielectric barrier discharge reactor apparatus and method of using the same is particularly well suited for the proposed usages thereof. Furthermore, since certain changes may be made in the above invention without departing from the scope thereof, it is intended that all matter contained in the above description or shown in the accompanying drawings be interpreted as illustrative and not in a limiting sense. It is also to be understood that the following claims are to cover certain generic and specific features described herein.