ELECTROCHEMICAL AND THERMAL DIGESTION OF ORGANIC MOLECULES
Various examples are provided for electrochemical digestion of organic molecules. In one example, among others, a method includes providing a fluid mixture including organic molecules to a reaction vessel including at least one current distribution part suspended within the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders. Current flow can be controlled through the fluid mixture to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture. In another example, a device includes a pipe section surrounding a fluid mixture including organic molecules, a current distribution part positioned within the pipe section and suspended in the fluid mixture, and an electrical coupling assembly configured to provide an electrical potential to the current distribution part for heating and electrolysis of the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders.
This application is a continuation of U.S. patent application Ser. No. 14/908,744, filed Jan. 29, 2016, which is the 35 U.S.C. § 371 national stage application of PCT Application No. PCT/US2014/048625, filed Jul. 29, 2014, which claims priority to and the benefit of, U.S. Provisional Patent Application entitled “ELECTROCHEMICAL AND THERMAL DIGESTION OF ORGANIC MOLECULES” having Ser. No. 61/859,450, filed Jul. 29, 2013, all of which are hereby incorporated by reference in their entireties.
This application is related to U.S. patent application entitled “Electrochemical Digestion of Organic Molecules” having Ser. No. 13/630,776, filed Sep. 28, 2012 and U.S. patent application entitled “Electrochemical Processing of Fluids” having Ser. No. 12/890,659, filed Sep. 25, 2010, both of which are hereby incorporated by reference in their entirety.
BACKGROUNDPresently, organic molecules are broken down, or digested, using expensive enzymes and/or microbes or by driving a high pressure water slurry of the organic molecules above 375° C. to spontaneously break down the molecules. This process is called “supercritical fluid” method where the temperature and pressure are at a point where a distinct liquid and gas phases do not exist. Both methods work well, but are expensive to achieve. The first has a high cost of enzymes or microbes and the second has a high-energy cost to heat the water slurry.
Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
Disclosed herein are various examples related to electrochemical digestion of organic molecules. Reference will now be made in detail to the description of the embodiments as illustrated in the drawings, wherein like reference numbers indicate like parts throughout the several views.
The breakdown of long-chain organic molecules may be accomplished electrochemically by passing an electrolyte including the organic molecules between energized electrodes that include a reactive surface. A varying voltage may be applied to the electrodes to produce singlet oxygen to decompose the organic molecules. When water is electrolyzed, diatomic hydrogen is generated from the moment it is split from water by: 2H2O+2e−→H2+2OH−. However, the oxygen is liberated as singlet oxygen (also called a “nascent oxygen” or “atomic oxygen”) by the equation:
2OH−=½O2+H2O+2e−.
The singlet oxygen may remain for several milliseconds or more before combining with another singlet oxygen to form the stable diatomic oxygen molecule O2. In some cases, the singlet oxygen may remain for as long as a tenth of a second or more. If the atom reaches another reactive atom such as, e.g., carbon, hydrogen or oxygen within an organic molecule, it can react with that molecule, fracturing the long chain. Organic molecules such as, e.g., cellulose or proteins may be decomposed by reacting with the singlet oxygen. In the case of cellulose, which is composed of thousands of glucose rings, it will break this long chain into smaller fragments. When the singlet oxygen remains in the electrolyte for an extended period of time, the singlet oxygen can continue to react with the organic molecules as the electrolyte flows out of between the electrodes.
Organic molecules may include, e.g., cellulose, hemicellulose, lignin, starch (e.g., amylose and amylopectin) algae (e.g., for lipid extraction), viruses and bacterium for decontamination, etc.
The organic molecules may be decomposed very efficiently when the proper waveform (or wave shape) is applied to the electrodes of a reaction vessel. The process may also be used to kill pathogens in microbiology laboratories or to render the lipids from the cell vesicles in algae. Shortening of the chain, removing excess oxygen atoms, breaking cell walls, and/or destroying organisms may be carried out on organic molecules such as, but not limited to, cellulose, hemicellulose, lignin, starch (e.g., amylose and amylopectin) algae (e.g., for lipid extraction), viruses and bacterium for decontamination, etc. Any organic compound may be attacked using this method. Applications may include but are not limited to:
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- Increasing the energy density of organic materials such as, e.g., cellulosic and lignin materials, among others, by reducing the oxygen content in component chains;
- Breaking the thousands of carbon cellulose chain into C5 or C6 sugars for cellulosic ethanol production;
- Breaking open (or lyse) the vesicle wall of algae containing lipids for bio-fuels;
- Destroying biological agents such as viruses and bacterium through oxidation of their protein membranes, etc.; and/or
- Digesting organic molecules such as, e.g., cellulose, polysaccharides, lignin, hemicellulose, proteins, algae, viruses, bacterium and/or solids suspended in wastewater.
The reaction vessel may include one or more cells defined by electrodes where electrolyte including organic molecules can be disposed between the electrodes for electrochemical digestion. The reactive surface of an electrode may include, e.g., a metallic current collector coated with a plurality of nano powders to catalyze the reaction to increase the surface area. In other implementations, the electrodes may include, but are not limited to: metallic electrodes with some amount of platinum metal plated or added such as nano powders on the surface; titanium electrodes with a flash plating of platinum; or electrodes catalyzed with noble metals such as, e.g., platinum, ruthenium or palladium and/or mixtures or alloys thereof. In some cases, the noble metal catalysts may be mixed or alloyed with other transition metals.
In various embodiments, a high-surface area electrode may include three components. The first component may be a substrate such as a plate or other structure having a regular or complex geometry and having a smooth or rough surface and including of transition metals including among others, nickel, iron, stainless steel, or silver. The first component may be defined by a reticular structure, a plate, a random textile, channeled, dendritic, foam, or other self-similar patterned or unpatterned structure with internal channels and/or external grooves and/or pits, spines, fins, or any kind of structure that permits fluids or fluid components to reach a surface or surfaces thereof, including a surface of a material layered on the substrate, either by convection, advection or diffusion. The second component may include one or more transition metals such as, e.g., nickel, gold, silver and/or other metals attached to (or disposed on) the first component, for example by electroplating. The third component may include metal particles such as, e.g., nano-sized metal particles and/or mixed nano-micron sized particles of transition metals including, but not limited to, iron, tin, nickel, silver, manganese, cobalt and alloys and oxides of these metals.
The third component may be partially embedded in the second component and may principally include nano and/or micron sized particles partially embedded in the second component but exposed such that when the completed electrode is immersed in the electrolyte, the third component is in intimate contact with the electrolyte. The third component may be partially covered by the second component but, due to the second component's overlying the third component closely, so conforming to the third component size and shape that the third component imparts a roughness to the surface of the second component that is responsive to the size and shape of the third component. This electrode may be used in electrochemical devices, including, but not limited to, hydrogen-generating electrodes in a water electrolyzer system, organic digestion systems and/or fuel cells. The very high surface area, with a high percentage of surface atoms, may render the surface highly catalytic to the splitting of water molecules in the presence of electrical energy.
Nano catalysts may be attached to current collecting surfaces of the electrode. By electroplating the surface with a metallic material, nano particles are entrapped within the electroplated metallic layer to permanently adhere the particles to that surface. The catalysts may include metals, metal oxides, or a mixture of metals, alloys and/or their oxides. Noble metals may also be included to catalyze or enhance the reaction. The resulting electrode can be arranged to produce an apparatus with a very high rate and high efficiency of water electrolysis. A method for the coating of an electrode is described in “Electrochemical Devices, Systems and Methods” (U.S. Patent App. Pub. 2011/0114496, published May 19, 2011, and PCT Pub. WO 2010/009058, published Jan. 21, 2010), both of which are hereby incorporated by reference in their entirety.
One way to coat an electrode with nano catalysts is where the particles exhibit very low impedance while allowing them to freely interact with the liquid boundary layer for electrochemical activity. The nano catalytic powders are entrapped within a plating substrate such as, e.g., nickel, copper, tin, silver and/or gold. The coating may be applied on all surfaces inside and outside of a complex porous shape such as, e.g., a foam surface. A uniform coating on all internal and external surfaces of the porous structure can extend the reactive surface area, leaving the particles well exposed with very low impedance at the reaction sites. The foam surface may be welded to a solid base plate prior to coating. The loading of nano powders may be increased from 1% of the bath weight to 5% to 10% of the plating solution weight. The pH may also be lowered from a pH of 4 to a pH of 2. The plating is first applied with a short burst of current in a forward direction, entrapping the powders under the coating. A rest period allows for ionic diffusion to rebalance the ionic concentrations. A reverse pulse is than applied to strip the plated metal from the top of each nano particle. The sequence may be repeated to increase the amount of nano catalytic powder coating the electrode. For example, in one implementation a 14 cm2 foam electrode was coated by applying +30 Amps for about 0.5 mSec; 0.0 Amps for about 9.5 mSec; −10 Amps for about 0.75 mSec; 0.0 Amps for about 0.25 mSec; and repeating the cycle for about 48.88 minutes to give 2000 ASec of coating. The short forward pulses attach the powders to the external and internal surfaces and the reverse pulses strip the nickel off of the nano powders, leaving them exposed to the boundary layer.
The coated electrode may be used for electrolysis of water to produce hydrogen and/or oxygen at an efficient and high rate. The electrode may function as an anode or a cathode. The singlet oxygen produced on the anode of the electrolyzer may be used to degrade and digest organic molecules and the hydrogen produced at the cathode of the cell hydrolyzes any lipids present in the electrolyte fluid. The energy to do this is low as compared to the previous methods. Other examples of electrode designs include, but are not limited to, platinum particles adhered to a titanium plate, nano catalyst(s) adhered to stainless steel plate, a flat metallic surface of transition metal(s), nano catalyst(s) adhered to a two-dimensional surface or to a three-dimensional surface such as e.g., a metallic foam or a metallic sheet or foam that is corrugated, folded, or patterned.
Referring to
Organic molecules may be decomposed within the reaction vessel 200. With an electrolyte including the organic molecules disposed within the cell 224 of the reaction vessel 200, a varying voltage can be applied between the inner and outer electrodes 204 and 202 to produce the singlet oxygen to decompose the organic molecules.
Various experiments were performed using cornstarch to verify the digestion of organic molecules. The electrolyte can be produced using an easily ionized compound such as, e.g., sodium chloride (NaCl), potassium hydroxide (KOH), sodium hydroxide (NaOH), hydrochloric acid (HCl), among many others. In some implementations, concentrations of the ionized compound may be in the range of about 5% or less, in the range of about 2% or less, in the range of about 1% or less, in the range of about 0.75% or less, or in the range of about 0.5% or less. The electrolyte may be prepared by mixing the ionized compound solution, followed by a slow heating to about 100° C. and subsequent cooling while continuously stirring the solution. If glucose is added, it may be added to the hot electrolyte before cooling. The electrolyte fluid allows the charge to be carried between the electrodes. In some implementations, the reaction vessel 200 of
The concentration of starch in solution was determined based upon the colorimetric method using the well-known starch iodine reaction. The electrolyte was used as a detector solution consisting of 0.35 cc of 1% Iodine (I) and 0.35 cc 1% potassium iodide (KI) in water. The maximum absorption wavelength was found to be 620 nm. A calibration curve was developed using serial dilutions from the 1% starting point giving the relationship of:
Percent starch=−0.0065*LN(%T)−0.0001
where LN(%T) is the natural logarithm of the percent of 620 nm light transmitted through a tube of fluid within the spectrophotometer.
Using the 50 Hz, 50% duty square wave of
As the amount of digestion increased, the lower the temperature rise of the reaction vessel 200 (
The effect of the formation of singlet oxygen on the electrode material was examined using its reaction with iron from the SS316. Referring to
At DC, the singlet oxygen never sees the neutralizing hydrogen, so it attacks the iron vigorously. As the applied frequency is increased, hydrogen is delivered more quickly to the singlet site where it reacts, reforming a water molecule. As can be seen in
As shown in
Experiments were run using a 1% KOH electrolyte solution including 1% starch at room temperature. The experiments were carried out at various frequencies with a 100% duty cycle.
Referring now to
Referring back to
Referring now to
As can be seen from
Electrochemical Impedance Spectroscopy (EIS) is a very useful technique to evaluate the activity of electrodes. An impedance scan provides a measurement of the total AC impedance as a function of the frequency applied. The lower the impedance, the higher the activity of the electrode.
Notice that the horizontal axis is logarithmic, so the cathodic current density is two decades (100×) higher with the nano coating.
The effectiveness of the reaction vessel may be improved by utilizing a plurality of cells to increase the total electrode surface area.
The monofunctional electrodes 812/814 can include a porous metal component 616 spot welded to one side of the substrate 614 and the bifunctional electrodes 816 can include porous metal components 616 spot welded to both sides of the substrate 614.
The example of
During operation, electrolyte including the organic molecules may be passed through the reaction vessel via the inlet and outlet connections 804/806 and the electrodes 812/814/816 are energized to digest the organic molecules. During the cycle in which electrode 812 is negatively charged, hydrogen gas and hydroxyl ions are evolved from that electrode while consuming two water molecules and two electrons (2H2O+2e−→2OH+H2). That hydroxyl molecule diffuses to the first bifunctional plate 816 where that hydroxyl liberates its electron into the plate while creating a singlet oxygen (or nascent or atomic oxygen) and one water molecule (2OH−→½O2H2O+2e−). The electrons pass through the bifunctional plate 816 where it behaves as it did on the initial monofunctional plate 812, producing an H2 and two hydroxyl ions. The process continues until reaching the last monofunctional plate 814 where the electrons exit to this positive plate. The polarity of the plates 812/814 is alternated when driven by a 100% duty cycle illustrated in
Referring next to
The fluid 1006 can be pumped using a small piston or other suitable pump 1004, which may be driven by, e.g., a DC motor 1014. The flow rate of the fluid 1006 may be adjusted to provide an optimum dwell time within the reaction chamber 1002 for digestion of the organic molecules. The fluid 1006 flows from a fluid reservoir 1016 through an inlet manifold 1008 into the cells of the reaction vessel 1002, before passing through the output manifold 1010 (which may comprise a reducing manifold) back to the fluid reservoir 1016. Adjustment of the flow rate of the fluid 1006 may be provided by adjusting the speed of the pump 1004 or by throttling the output of the pump 1004 using, e.g., a valve (not shown). In some implementations, turbulence may be induced at the outlet(s) of the reaction vessel 1002 to improve digestion of the organic molecules by the generated singlet oxygen that my still be present in the fluid 1006. In some cases, a discharge chamber may be included at the outlet(s) of the reaction vessel 1002 or the outlet of the outlet manifold 1010 to promote effective utilization of any singlet oxygen leaving the reaction vessel 1002. In other implementations, turbulence may be induced within the cells of the reaction vessel 1002 to aid in the breakdown of the organic molecules.
Ozone may be added to the fluid 1006 to enhance the electrochemistry and assist in the degradation of the organic molecules. The addition of air (or other gas) bubbles may also influence the reaction by saturating the fluid 1006 with non-reactive gases such as, e.g., nitrogen. The fluid flow rate through the reaction vessel 1002 may also be adjusted to improve or maximize efficiency. For example, a flow that is too high may hinder the reaction by limiting or reducing the time the electrolyte solution (or fluid) is adjacent to an electrode of the reaction vessel 1002. In some implementations, product of the digestion process is separated from the electrolyte solution (or fluid) by centrifuge and/or drying. In other implementations, the product may naturally separate from the electrolyte through buoyancy. The product may then be siphoned off the electrolyte before further processing.
Various experiments were performed using an embodiment of the electrochemical digestion system 1000 of
In each experiment, a total of 500 ml of electrolyte solution 1006 was circulated through the three necked beaker 1016 at about 5 liters/minute flow rate with the four cells of the reaction vessel 1002 electrically connected in series and the electrolyte flowing through an inlet manifold 1008 and outlet manifold 1010. Each cell of the reaction vessel 1002 contained a volume of about 28.5 cm3, so the total reaction chamber volume is about 74 cm3. The electrodes were coated with nano nickel, nano tin and nano cobalt according to the teachings of U.S. Patent App. Pub. 2011/0114496 as described above. The coated electrodes are very effective as water electrolysis electrodes when run in near eutectic KOH or NaOH electrolyte. The electrolyte solution 1006 used in the experiments included 1% organics (e.g., Starch or Cellulose) and 1% ion carrier (e.g., sodium chloride (NaCl), potassium hydroxide (KOH), or sodium hydroxide (NaOH)) in water depending on the particular experiment. Repeated circulation of the electrolyte solution 1006 through the reaction vessel 1002 during excitation of the electrodes by the power source 1012 breaks down the organic molecule chains (e.g., starch) in electrolyte solution 1006.
In a first example of the digestion process, an electrolyte solution 1006 including 1% KOH and 1% corn starch was utilized to study the effect on soluble organic molecules. The organic molecules in the electrolyte solution 1006 were digested using a corrugated coated expanded metal electrode for 24 hours, running at 340 mA (25 mA/cm2). The volume of electrolyte solution 1006 was 500 cc and the total electrode surface area was about 112 cm2. The resulting fluid 1006, after processing through the reactive vessel 1002, was much clearer than the milky appearance of the starting fluid. Evaluation was performed using a colorimetric method using the well known iodine reaction with starch, which produces a deep blue color. Using a spectrophotometer, the colorimetric method was developed, which proved to be reliably quantitative. First, a series of absorption readings were taken, at one low starch concentration, to find the maximum absorption for that blue color. The wavelength was shown to be 620 nm for the iodine-starch complex. Then a series of starch concentrations were run at that wavelength giving a calibration curve. It was recognized that the iodine is actually staining only the amylose portion of starch (about 15%), not the amylopectin (about 85%), but a loss of one strongly suggests that both are being digested.
Samples of the fluid 1006 were drawn frequently during the digestion process and during subsequent digestion experiments using potato starch. The results are given in TABLE 1. The rates shown are the slope at the beginning of digestion, since it finds an asymptote as the supply of starch is lost to digestion.
In a second example of the digestion process, an electrolyte solution 1006 including 1% KOH and 1% wood flour such as, e.g., pine flour, oak flour and micro crystalline cellulose (MCC) was used to study the effect on insoluble organic molecules. The electrolyte solution 1006 including 1% Pine Flour in 1% KOH was digested using a corrugated coated expanded metal electrode running at 340 mA (25 mA/cm2) for 24 hours. The volume of the electrolyte solution 1006 was 500 cc and the total electrode surface area is about 112 cm2. The resulting material appearance was very different from the original appearance with all color being removed and a much lower volume of settled matter.
The samples were vigorously mixed, and 50 milliliters were passed through dried and weighed filter paper in a 55 mm Buchner funnel. The resulting filtrate was collected in a clean, dry and pre-weighed filtration beaker, and 20 milliliter of this was transferred to a ceramic weighing vessel. Both the filter paper and the vessel were then transferred to a 105 degrees Celsius (° C.) drying oven for about 16 hours. All materials had been pre-dried and weighed, so the weights reflected the new weight added from the insoluble material (on the filter papers) and the soluble materials (in the solution). The results are shown in TABLE 2.
A common method to break down organic molecules is to heat the solution to 350° C. at which temperature the molecules spontaneously break down. The energy it takes to heat 500 cc of water from 21 to 350° C. is 688 BTU or 202 Wh. In the 24 hours under electrochemical digestion, essentially all of the starch (1% of 500=5 grams=5000 mg) is consumed. To thermally break down that amount of organic material, the rate is 25 mg/WHr is calculated. The last column in Tables 1 and 2 show the ratio of the power efficiency improvement using the electrochemical method to break down organic molecules.
Other organic molecules such as, but not limited to, cellulose, hemicellulose, lignin, lignite coal slurry, algae (e.g., for lipid extraction), viruses and bacterium for decontamination, wastewater, etc. may be digested using the disclosed system and method. For example, cellulose concentrations in the range from about 0.1% to about 20%, from about 0.5% to about 10%, and from about 0.75% to about 2.5%, may be digested. The concentration of organic molecules may be based upon the viscosity of the electrolyte.
Heating can improve the digestion of the organic molecules in the fluid. The digestive processes, such as those in a continuous flow reaction vessel using fluid that is heated directly, can be enhanced by using heat-producing electrode elements that are coated with nano catalysts such as those previously described. When properly formulated, the catalytic surface can enhance the electrolysis of water on the heat-producing electrodes, making them electrochemically active. Water electrolysis occurring at the plates produces singlet oxygen's during the heating process. The neutral singlet oxygen atoms react with oxygen atoms within the organic molecules resident in the fluid, thereby liberating diatomic oxygen and reducing the overall oxygen content of the organic material. This reduction in oxygen content increases the energy density of the resulting organic. It also would increase the liberation of buoyant lipids through the lysing of cell walls and vacuoles. The hydrogen produced may well hydrogenate the lipids on the catalytic surface, thus increasing their energy content.
The present disclosure discusses controlled heating and electrochemical degradation of electrically conductive fluids e.g. gases, pastes, suspensions, plasmas, slurries and liquids, as we let such a fluid flow (or rest) in a pipe/reservoir/chamber/reactor, or similar vessel. As discussed herein, the term pipe may be used interchangeably with any of the terms discussed above as the particular device/embodiment requires. A multi-frequency (MF) heating concept may be applied to power one or more elements of the system that are electrically insulated from other elements of the system. The applied power can be direct current (DC) or alternating current (AC) and/or electromagnetic frequencies making use of any and all frequencies that are permitted and available including, but not limited to, those in the RF range. Various elements that are part of the insulating system or added as part of the internal components may provide direct and indirect heating of the fluid contained in the system. Insulators, seals, and mechanical supports may be required to hold the device together and in alignment under high fluid pressure. Dimensional changes in materials caused by increasing or decreasing temperatures can be accounted for in the design of the system.
A power source causes electric current to flow through the fluid and heat it to high temperatures. Heating can occur by the direct interaction of applied electric fields with the fluid. The frequency may be selected based upon, e.g., the conductivity and/or dielectric property of the fluid and/or the effect on digestion of the organic molecules. The desired power for the source can depend on, e.g., the diameter of the pipe, shape and dimensions of the electric conductors and insulators, and the dielectric properties of the fluid, as well as other factors. The power required for the source may also depend on the specific heat of the fluid, its flow rate, the thermal insulation used around the pipes and the desired temperature of the fluid.
The electric insulators 1110 electrically isolate the inner pipe section 1108 from the adjacent outer pipe sections 1106a and 1106b. The material used for electric insulators 1110 can be chosen to withstand the temperatures and pressures of fluid 1102 being heated. Such materials include, but are not limited to, high temperature polymers and ceramics. The length of the electric insulators 1110 may be adjusted to alter the heating pattern over the cross section of pipe sections 1106/1108. Shorter insulators 1110 cause greater heating near the walls of the pipe outer pipe sections 1106a and 1106b and longer insulators 1110 cause the heating to extend more towards the center of the pipe outer pipe sections 1106a and 1106b to provide more uniform heating of fluid 1102.
The seals 1112 can be made of ceramics, high temperature polymers or high temperature polymer composites incorporating inorganic fibers to add strength, as well as other materials, and are chosen so that they may not be easily corroded by fluid 1102. The seals 1112 can be any shape, such as washer-shaped or toroidal-shaped, appropriate for the configuration of the heating system 1100. They can be at the ends of insulators 1110, on the outer surface of insulators 1110 or on the inner surface of insulators 1110 depending on whether the insulators 1110 are in line with the pipe sections 1106/1108, inside the pipe sections 1106/1108, or outside the pipe sections 1106/1108.
An electrical power source 1114 may be connected between the inner pipe section 1108 and the two outer pipe sections 1106a and 1106b. In
To aid in the following description, five regions are defined for later reference. Region 50R is before the upstream insulator 1110a. Region 60R is at upstream insulator 1110a. Region 70R is between the upstream insulator 1110a and the downstream insulator 1110b. Region 80R is at the downstream insulator 1110b. Region 90R is after the downstream insulator 1110b. The electric power source 1114 causes electric current to flow through the fluid 1102 between regions 50R and 70R and also between regions 70R and 90R. This electric current heats fluid 1102 directly because of the fluid's electrical conductivity or equivalently its dielectric loss properties. The specifications for electric power source 1114 depend upon the type of fluid 1102 being heated, its flow rate and the temperature to which it is to be heated as well as other factors. For highly conductive fluids 1102, such as salt water, a low frequency alternating current source can be used. Less conductive fluids can use higher frequency alternating current sources. A number of commercial power sources are available that can be used.
The optimum frequency depends on various factors including, but not limited to, the dielectric properties of the fluid 1102. The optimum voltage for electric power source 1114 can depend on, e.g., the diameter of the pipe sections 1106/1108, length of electric insulators 1110 as well as the dielectric properties of fluid 1102. The power required for electric power source 1114 depends on the specific heat of fluid 1102, its flow rate, the thermal insulation used around the heating system 1100, and the desired fluid 1102 temperatures. The power needs for the digestion of the organic molecules may also be considered when evaluating capabilities of the electric power source 1114. If the power required exceeds the power levels of any single commercially available electric source, two or more heating systems 1100 and their associated electric power sources can be installed along the pipe to achieve the required power level.
Thermocouple 1120 allows measurement of the fluid's temperature immediately after it has been heated. The temperature of the fluid 1102 may be kept at the desired value by using this measured temperature to control the power level of electric source 1114 using, e.g., a standard commercially-available controller 1122.
The electric current flow pattern is now discussed. When insulators 1110 are short, the current flow occurs mostly close to the pipe walls in regions 60R and 80R and only a short distance upstream and downstream of these regions. This results in the greatest heating occurring near the pipe walls close to insulators 1110. For turbulent fluid flows, mixing occurs, which produces a more uniform heating of the fluid 1102. For laminar flow, where the fluid flow is slow at the walls of the pipe sections 1106/1108 and rapid near the center of the pipe sections 1106/1108. Because little or no mixing occurs, the fluid 1102 may become overheated at the pipe wall. This overheating at the pipe wall can be reduced by increasing the length of insulators 1110 to cause the electric current flow to move more towards the center of the pipe sections 1106/1108. However, because of the velocity profile for laminar flow of the fluid 1102, the heating can still be excessive at the pipe wall.
A number of different current distribution parts may be added to the heating system 1100 to produce a more uniform heating of the fluid 1102 by improving the electric current flow pattern and by physically mixing of the fluid 1102 before, during and/or after it is heated, as will be described. Referring to
A first current distribution part 1202 includes two flat metal plates intersecting at right angles about their center lines. The size of the part may be such that it may snuggly fit into pipe sections 1106/1108 (
A second current distribution part 1204 may include two intersecting flat metal plates that have been deformed so that their outer edges form four helices. The helices shown in
A third current distribution part 1206 includes a plurality of parallel metal plates. In
Another current distribution part 1208 is similar to part 1206 except that the metal plates are not parallel to the axis of pipe sections 1106/1108. The reason for their not being parallel to the axis of pipe sections 1106/1108 is to alter the direction of the fluid flow to cause physical mixing of fluid 1102 (
Other current distribution parts 1212a and 1212b may be described as auger-shaped metal disks. Current distribution part 1212a is right handed and current distribution part 1212b is left handed. The pitch of the auger can be selected for best physical mixing of fluid 1102 (
Current distribution part 1214 is a metal cylinder that could be placed along the axis, or other location, of pipe sections 1106/1108 and held in place in a variety of means. In some embodiments, the cylinder of current distribution part 1214 may be combined with one of the above-mentioned parts by welding or other means. For example, the cylinder could be combined with either current distribution part 1202 or 1204 with the cylinder axis along the intersection of the metal plates forming parts 1202 or 1204. The cylinder may also be combined with one or more of the auger-shaped current distribution parts 1212. In these embodiments, the cylinder could run through the center of one or more of the current distribution parts 1212. The ends of the cylinder of current distribution part 1214 can be of any suitable configuration and geometry including, but not limited to, flat, pointed or curved. Its purpose is to improve uniformity of heating as well as promote physical mixing of fluid 1102 (
Other current distribution parts 1216 may be shaped as a frustum of a conical cone. As with current distribution part 1214, current distribution part 1216 may be held in place by combining it with other current distribution parts. The ends of current distribution part 1216 can be of any suitable configuration and geometry including, but not limited to, flat, pointed or curved. Its purpose is to improve uniformity of heating as well as promote physical mixing of fluid 1102.
At the bottom of
Shown in the middle of
Referring to
A continuously circulating heating system can be constructed including a coaxial electromagnetic heating apparatus (or heating element) to efficiently heat a fluid contained in a pipe and/or piping system. The system may operate with or without a circulating pump. For example, the fluid may be circulated without a circulating pump by using thermal density gradients. A vertical system circuit orientation can be used to heat a fluid to super critical temperatures yet safely and efficiently contain the fluids at the increased temperatures and pressures. The basic principle of operation is based on the change in density of fluids with temperature, i.e., the fluid density decreasing when it is heated and the fluid density increasing as it cools.
In the example of
In the embodiment of
As discussed above, various embodiments may include one or more pumps to aid in circulating the fluid(s). Such pumps may be present in various locations along the flow path. Such pumps can increase flow rates over embodiments without circulating pumps. In some embodiments, additional reservoirs may be included in the system to accommodate the influence of the circulating pumps.
A flow through heating system can be constructed including a coaxial heating apparatus (or heating element) to efficiently heat a fluid that continuously flows through a pipe and/or piping system. Referring to
The design illustrated in
Although the flow through system 1800 of
As noted above, the heated flow through system 1800 can be replicated based on the production rate sought and the capacity of the power supplied to the systems 1800. The flow through system 1800 illustrated in
Various embodiments may employ one or more coaxial applicators. Each applicator can include two electrodes with the electric current passing from one electrode to the other electrode directly heating the fluid between them. In the example of
The inner radius (R) of the pipe, the radius (r) of the of the central coaxial electrode, and the length (L), along with the electrical properties of the fluid 1908 determine the electrical impedance of the flow through heating system 1900, which must be within certain ranges to obtain good coupling of power from the RF generator or AC power line to the electrode 1904. Electrical matching networks for RF can provide some compensation, but by careful design using optimum dimensions, efficient coupling of power can be achieved. Optimum dimensions vary with frequency and thus are different for 13.56 MHz RF and 60 Hz AC power input.
Digestion of organic molecules can be improved by including a catalytic coating to the current distribution parts of
-
- A first component may be, substantially, a substrate such as a plate or other structure having a regular or complex geometry and having a smooth or rough surface and consisting of transition metals including among others, nickel, iron, stainless steel, or silver. The first component may be defined by a reticular structure, a plate, a random textile, channeled, dendritic, foam, or self-similar patterned or unpatterned structure with internal channels or external grooves or pits, spines, fins, or any kind of structure that permit fluids or fluid components to reach a surface or surfaces thereof, including a surface of a material layered on the substrate, either by convection, advection or diffusion.
- A second component may be, substantially, a component of transition metals including among others, nickel, gold or silver attached to the first component, for example by electroplating.
- A third component may be, substantially, metal particles; preferably nano-sized metal particles and/or mixed nano-micron sized particles of transition metals including among others iron, tin, nickel, silver, manganese, cobalt and alloys and oxides of these metals.
- The third component may be partially embedded in the second component and may be principally of nano and/or micron sized particles partially embedded in the second component but exposed such that when the completed electrode is immersed in electrolyte, the third component is in intimate contact with the electrolyte. The third component may be partially covered by the second component but, due to the second component's overlying the third component closely, so conforming to the third component size and shape that the third component imparts a roughness to the surface of the second component that is responsive to the size and shape of the third component.
Nano catalysts may also be coated onto a porous current collector, as described with respect toFIGS. 6A, 6B and/or 9 , and then tack welded to the current distribution parts such as the examples shown inFIG. 12 .
Referring now to
As power is applied to the plates 2004 for resistive heating, electrolysis will occur on the plates. As previously described, the electrolysis will produce singlet oxygen atoms, which are very reactive and will attack the organic molecules in the surrounding fluid. The nano catalysts 2002 can enhance the electrolysis on the heat-producing plates 2004 of the current distribution parts, making them electrochemically active. The likely target is oxygen molecules within the organic molecules, forming diatomic oxygen, which then bubbles off by buoyancy. An example of such an organic molecule is shown in
The nano catalysts can be included in the heating systems of
Referring next to
Referring now to
Teflon, among others.
Disclosed herein are various embodiments related to electrochemical digestion of organic molecules. In an aspect, a method can comprise, for example, providing a fluid mixture including organic molecules to a reaction vessel including at least one current distribution part suspended within the fluid mixture and controlling an electrical potential applied to the at least one current distribution part to control current flow through the fluid mixture to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders. In one or more aspects, the fluid mixture can be pumped continuously through the reaction vessel and/or the fluid mixture can be circulated through a holding tank and the reaction vessel. In various implementations, the nano catalytic powders can be less than 50 nm in diameter. The electrical potential can be applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz, at a frequency below 0.1 Hz, or at a frequency below 0.01 Hz. In some aspects, the method can further comprise sparging ozone into the fluid mixture. The fluid mixture can contain charge-carrying ions and/or the fluid mixture can include an ion source of the charge-carrying ions. For example, the ion source can be potassium hydroxide (KOH). In various embodiments, at least a portion of the fluid mixture can be selected from water, biomass, fossil fuels, seawater, contaminated fluids, slurries, emulsions, pastes, liquids, gases, plasmas, and combinations thereof and/or at least a portion of the fluid mixture can contains at least one of woody crops, herbaceous crops, the seeds of oil crops, and brown coal.
In other aspects, a device can comprise a pipe section distributed along a longitudinal axis of the device and surrounding a fluid mixture including organic molecules, a current distribution part positioned within the pipe section and suspended in the fluid mixture, and an electrical coupling assembly configured to provide an electrical potential to the current distribution part for heating and electrolysis of the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders. In one or more aspects, the fluid mixture can be pumped continuously through the pipe section. The electrical potential can be applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz, at a frequency below 0.1 Hz, or at a frequency below 0.01 Hz. In various implementations, at least a portion of the pipe section is coated with nano catalytic powders. In some aspects, the current distribution part can comprise an inner conductive element extending along the longitudinal axis of the device and at least one intermediate conductive tube concentric with the inner conductive element and the pipe section. In various embodiments, an inner side and an outer side of the one intermediate conductive tube can be coated with nano catalytic powders. In various aspects, the current distribution part cab comprise an inner conductive element extending along the longitudinal axis of the device, where the inner conductive element including plates extending radially outward towards the pipe section. In some embodiments, the pipe section can include plates extending inward towards the longitudinal axis of the device, where the plates of the pipe section are interleaved with the plates of the current distribution part. In various implementations, the nano catalytic powders can be less than 50 nm in diameter.
In other aspects, a system can comprise a reaction vessel comprising conductive elements suspended in a fluid mixture including organic molecules, and a power source configured to supply an electrical potential to at least a portion of the conductive elements to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture. At least a portion of the conductive elements include a coating of nano catalytic powders. In various aspects, the system can further comprise a pump configured to continuously pump the fluid mixture through the reaction vessel and/or an ozone sparge configured to add ozone into the fluid mixture. In some implementations, the fluid mixture can be pumped continuously through the reaction vessel and/or the fluid mixture can be continuously circulated through a holding tank and the reaction vessel. The fluid mixture can contain charge-carrying ions and/or a source of the charge-carrying ions can be potassium hydroxide (KOH). The electrical potential can be applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz, at a frequency below 0.1 Hz, or at a frequency below 0.01 Hz. In various embodiments, at least a portion of the fluid mixture can be selected from water, biomass, fossil fuels, seawater, contaminated fluids, slurries, emulsions, pastes, liquids, gases, plasmas, and combinations thereof and/or at least a portion of the fluid mixture can contains at least one of woody crops, herbaceous crops, the seeds of oil crops, and brown coal. In various implementations, the nano catalytic powders can be less than 50 nm in diameter.
It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt % to about 5 wt %, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. The term “about” can include traditional rounding according to significant figures of numerical values. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”. therefore, at least the following is claimed:
Claims
1. A method, comprising:
- providing a fluid mixture including organic molecules to a reaction vessel including at least one current distribution part suspended within the fluid mixture, where at least a portion of the current distribution part is coated with nano catalytic powders; and
- controlling an electrical potential applied to the at least one current distribution part to control current flow through the fluid mixture to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture.
2. The method of claim 1, wherein the fluid mixture is pumped continuously through the reaction vessel.
3. The method of claim 1, wherein the nano catalytic powders are less than 50 nm in diameter.
4. The method of claim 1, wherein the electrical potential is applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz.
5. The method of claim 4, wherein the electrical potential is applied to the at least one current distribution part in a square wave shape at a frequency below 0.1 Hz.
6. The method of claim 5, wherein the electrical potential is applied to the at least one current distribution part in a square wave shape at a frequency below 0.01 Hz.
7. The method of claim 1, further comprising sparging ozone into the fluid mixture.
8. The method of claim 1, wherein the fluid mixture contains charge-carrying ions.
9. The method of claim 8, wherein the fluid mixture includes an ion source of the charge-carrying ions.
10. The method of claim 1, wherein at least a portion of the fluid mixture is selected from the group consisting of water, biomass, fossil fuels, seawater, contaminated fluids, slurries, emulsions, pastes, liquids, gases, plasmas, and combinations thereof.
11. The method of claim 1, wherein at least a portion of the fluid mixture contains at least one member of a group consisting of woody crops, herbaceous crops, the seeds of oil crops, and brown coal.
12. A device, comprising:
- a pipe section distributed along a longitudinal axis of the device, the pipe section surrounding a fluid mixture including organic molecules;
- a current distribution part positioned within the pipe section, at least a portion of the current distribution part coated with nano catalytic powders, the current distribution part suspended in the fluid mixture; and
- an electrical coupling assembly configured to provide an electrical potential to the current distribution part for heating and electrolysis of the fluid mixture.
13. The device of claim 12, wherein the fluid mixture is pumped continuously through the pipe section.
14. The device of claim 12, wherein the electrical potential is applied to the current distribution part in a square wave shape at a frequency below 0.1 Hz.
15. The device of claim 14, wherein the potential is applied in a square wave shape at a frequency below 0.01 Hz.
16. The device of claim 12, wherein at least a portion of the pipe section is coated with nano catalytic powders.
17. The device of claim 12, wherein the current distribution part comprises an inner conductive element extending along the longitudinal axis of the device and at least one intermediate conductive tube concentric with the inner conductive element and the pipe section.
18. The device of claim 17, wherein an inner side and an outer side of the one intermediate conductive tube is coated with nano catalytic powders.
19. The device of claim 12, wherein the current distribution part comprises an inner conductive element extending along the longitudinal axis of the device, the inner conductive element including plates extending radially outward towards the pipe section; and
- where the pipe section includes plates extending inward towards the longitudinal axis of the device, the plates of the pipe section interleaved with the plates of the current distribution part.
20. The device of claim 12, wherein the nano catalytic powders are less than 50 nm in diameter.
Type: Application
Filed: Jan 3, 2019
Publication Date: May 9, 2019
Inventor: Robert Brian Dopp (Marietta, GA)
Application Number: 16/238,993