WO2011163656A1

WO2011163656A1 - Method of treating organic material

Info

Publication number: WO2011163656A1
Application number: PCT/US2011/041960
Authority: WO
Inventors: Christian Gollmann
Original assignee: Gold Holdings, Llc
Priority date: 2010-06-25
Filing date: 2011-06-27
Publication date: 2011-12-29

Abstract

A method of treating a liquid-form organic material is performed by contacting the liquid-form organic material with an aqueous oxidative treatment fluid prepared in a treatment system comprising a vessel (3, 11 ) containing an aqueous fluid and a pair of electrodes (1, 2, 21, 22) positioned within the aqueous fluid. At least one of the electrodes (1, 2, 21, 22) is a doped electrode that facilitates the treatment system providing the oxidative treatment fluid from the aqueous fluid when an electric potential is applied across the pair of electrodes at a selected voltage and current so that the aqueous oxidative treatment fluid is suitable for oxidatively degrading the organic material.

Description

METHOD OF TREATING ORGANIC MATERIAL

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 61/398,496, filed June 25, 2010, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[0002] This invention relates to processes and devices for treating organic matter and other materials.

BACKGROUND OF THE INVENTION

[0003] Current commercial processes designed to destroy bacteria, algae and fungus include subjecting the bacteria to aqueous solutions of hydrogen peroxide, ozone, and halogens such as fluorine, chlorine, bromine, and iodine. Ultraviolet radiation is also used to destroy bacteria as well as electrolyzed water. While many of these processes are effective in destroying bacteria, only high concentrations of catalyzed hydrogen peroxide has been chemically affective in breaking down unwanted organic material. Bacterial breakdown of organic material in the sewage industry has become the standard worldwide as a relatively inexpensive and successful alternative to chemical treatment. The use of bacteria, however, has created expensive challenges to prepare the treated wastewater to reenter the environment.

[0004] Accordingly a need exists for other methods for economically and effectively degrading or destroying organic material to more desirable products.

SUMMARY

[0005] A method of treating a liquid-form organic material is performed by contacting the liquid-form organic material with an aqueous oxidative treatment fluid prepared in a treatment system. The treatment system comprises a vessel containing an aqueous fluid and a pair of electrodes positioned within the aqueous fluid. At least one of the electrodes is a doped electrode that facilitates the treatment system providing the oxidative treatment fluid from the aqueous fluid when an electric potential is applied across the pair of electrodes at a selected voltage and current so that the aqueous oxidative treatment fluid is suitable for oxidatively degrading the organic material.

[0006] In certain embodiments, the organic material is contacted with the treatment fluid while the treatment fluid is within the treatment system. In other embodiments, the organic material is contacted with the treatment fluid after the treatment fluid is removed from the treatment system.

[0007] The liquid-form organic material may be an organic material dispersed in an aqueous fluid and wherein the aqueous fluid of the liquid-form organic material forms the aqueous fluid of the treatment fluid. In certain applications, contacting of the organic material with the treatment fluid may degrades all of the organic material so that substantially no organic material remains.

[0008] The electrode may be constructed in various forms. In certain embodiments each of the electrodes to which the electric potential is applied is a doped electrode. The dopant may have at least one of sodium, sodium alkoxide, metal alkoxide, titanium, a conductive metal, a conductive metal oxide, tantalum, tantalum oxide, ruthenium, ruthenium oxide, iridium, iridium oxide, sodium carbonate, carbon, chloride, titanium dioxide, titanium tetrachloride, manganese, molybdenum, manganese-molybdenum oxide and NaRu0₂. In certain embodiments the electrodes is a titanium electrode. The electrode may be doped with sodium in certain embodiments.

[0009] The organic material that is treated may be selected from at least one of biological material, bacteria, algae, fungus, fecal matter, sewage, industrial waste, hydrocarbons, crude oil, tar, petroleum products, an aliphatic hydrocarbon, an aromatic hydrocarbon, an alkene, an alkyne, and a heteroatom-containing hydrocarbon.

[0010] In another aspect of the invention, a method of treating a material is peformed by contacting the material with a treatment fluid. The treatment fluid is prepared by introducing an aqueous fluid into a system comprising a vessel containing a pair of electrodes. At least one of the electrodes is a doped electrode that facilitates the treatment system providing the treatment fluid when an electric potential is applied across the pair of electrodes at a selected voltage and current so that the treatment fluid is sufficient for at least one of (1) oxidatively degrading the material, and (2) precipitating salts and increasing the solubility of the treatment fluid for oxygen.

[0011] In certain embodiments, the organic material is contacted with the treatment fluid while the treatment fluid is within the treatment system. In other embodiments, the organic material is contacted with the treatment fluid after the treatment fluid is removed from the treatment system.

[0012] The material may be an organic material. The organic material may be dispersed in an aqueous fluid and wherein the aqueous fluid of the liquid-form organic material forms the aqueous fluid of the treatment fluid. In certain applications, contacting of the organic material with the treatment fluid may degrades all of the organic material so that substantially no organic material remains. The material may also be a salt.

[0013] The electrode may be constructed in various forms. In certain embodiments each of the electrodes to which the electric potential is applied is a doped electrode. The dopant may have at least one of sodium, sodium alkoxide, metal alkoxide, titanium, a conductive metal, a conductive metal oxide, tantalum, tantalum oxide, ruthenium, ruthenium oxide, iridium, iridium oxide, sodium carbonate, carbon, chloride, titanium dioxide, titanium tetrachloride, manganese, molybdenum, manganese-molybdenum oxide and NaRu0₂. In certain embodiments the electrodes is a titanium electrode. The electrode may be doped with sodium in certain embodiments.

[0014] The material that is treated may be selected from at least one of biological material, bacteria, algae, fungus, fecal matter, sewage, industrial waste, hydrocarbons, crude oil, tar, petroleum products, an aliphatic hydrocarbon, an aromatic hydrocarbon, an alkene, an alkyne, and a heteroatom-containing hydrocarbon.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying figures, in which:

[0016] FIGURE 1 is a schematic representation of a treatment system for use in a treatment method in accordance with the invention; [0017] FIGURE 2 is a schematic representation of a treatment system employing helically configured electrodes for use in a treatment method in accordance with the invention; and

[0018] FIGURE 3 is a schematic representation of a treatment system employing a treating system having a baffled treating chamber for use in a treatment method in accordance with the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0019] A need persists for a process to economically and efficiently treat unwanted organic matter to either partially break these organics down into wanted derivatives, or completely break them down into inorganic compounds such as carbon dioxide (C0₂), water (H₂0), ammonia (NH₃), and/or inorganic acids and/or salts. There is also a need to economically destroy bacteria, algae, fungus and other undesirable materials into more desirable forms of material.

[0020] The present invention is directed to methods and devices for treating such organic materials so that it can be converted or degraded into a desired form or forms. This may involve degrading such materials to organic materials of lower molecular weight (such as methanol) or into inorganic materials, such as C0₂, H₂0, NH₃, and/or inorganic acids and/or salts, etc. The invention makes use of a system that facilitates the preparation of an oxidative treatment fluid. The oxidative treatment fluid is an aqueous fluid that has a unique metastable water chemistry that efficiently breaks down organic material through oxidation into degradation products that may include constituent components of the organic material into other forms. These may include degrading the organic material to C0₂, H₂0, NH₃, and/or inorganic acids and/or salts, etc. The types of degradation products produced depend upon the composition of the treated organic material, which may be organic materials or hydrocarbons that contain or do not contain heteroatoms.

[0021] The organic material may be living and nonliving biological material, including bacteria, algae, fungus, animal and human fecal matter, organic compounds derived from biological materials, such as fats, oils (e.g. vegetable oil), etc. The organic matter may include sewage, industrial waste, hydrocarbons, refined and unrefined petroleum products, crude oil, tar, aliphatic hydrocarbons, aromatic hydrocarbons, alkenes, alkynes, etc. The organic materials may also include those organic materials and hydrocarbons containing heteroatoms. The organic material may be materials that constitute product waste and spills. The organic materials that may be treated in accordance with the invention may include those that increase biological and chemical oxygen demand (BOD and COD). The organic materials may also include those that create highly offensive odorous organic compounds, such as organo sulfur s, amines, and other organic heterocyclic compounds.

[0022] The organic material treated in accordance with the invention may be a liquid- form organic material. As used herein, the expression "liquid-form organic material" is meant to encompass organic material that is either in liquid form or is dispersed or suspended in a liquid. The liquid of the liquid-form organic material may be aqueous or non-aqueous (e.g. crude oil). In many applications, the liquid will be an aqueous fluid. The liquid form organic material may include both aqueous and non-aqueous liquids that are mixed together, such as an emulsion. Additionally, the liquid-form organic material may include solids that are suspended in the liquid, such as sewage that may constitute an aqueous liquid with suspended solids. Where the liquid-form organic material includes aqueous liquids with organics dispersed or suspended in the aqueous liquid, the aqueous liquids of the liquid-form organic material may form an oxidative treatment fluid when treated in accordance with the invention.

[0023] The treatment of organic materials in accordance with the invention makes use of a unique treatment system and/or treatment fluid prepared by the treatment system. The treatment may use no additional chemicals or bacteria to accomplish the breakdown of the unwanted organic material and requires extraordinarily low energy to accomplish the breakdown or degradation of the organic material. The treatment system constitutes a low voltage electrochemical device that causes a metastable chemical change within water or aqueous liquids when subjected to an electric field generated by specially designed electrodes. The prepared water oxidizes contained organics as it passes through the device within an electrical field generated by the electrodes. Furthermore, water or aqueous fluids without the organic material to be treated that have been subjected to the electric field in the treatment system can be used as treatment fluids to treat organic material even after the electric field has been removed or the treatment fluids have been removed from the treatment system. This may be used as a treatment fluid to sanitize water, food, hospital equipment, restaurant equipment, etc.

[0024] By using the treatment system with the specially designed electrodes, when a low voltage current is applied to water or aqueous liquid containing organic material or inorganic salts through the electrodes, the electrodes generate a concentration of metastable hydronium (H₃0⁺) and hydroxyl ions (OH ) in the water or aqueous liquid. The metastable hydroxyl ions are generated at or around the negative-biased electrode, whereas the metastable hydronium ions may be generated at or around the positive-biased electrode. The treatment system thus forms a water or aqueous liquid that is oxidative in nature and forms a treatment fluid that facilitates the degrading or destruction of organic material. The degradation of the organic material by the treatment system and/or treatment fluid can be to lower molecular weight organic compounds (e.g. methanol) or into inorganic materials, such as C0₂, H₂0, NH , and/or inorganic acids and/or salts, etc. The degree of degradation may vary depending upon the length of treatment or the amount of treatment fluid used in treating the organic material.

[0025] The degradation takes place primarily through oxidation, although some degradation may take place through acid- and base-catalyzed mechanisms. Possible oxidants formed by salt water in the treatment system may include hydrogen peroxide, hypochlorous acid, sodium hypochlorite, chlorine, ozone, and oxygen. Hydrogen peroxide, ozone and oxygen may also be formed in fresh water where small concentrations of salt are present. In large enough quantities, any one of the oxidants above are known to destroy bacteria, algae, and fungus. From a purely chemical standpoint, only an extremely high concentration of catalyzed hydrogen peroxide is known to completely decompose organic material. Hydrogen peroxide concentrations produced by the treatment system do not appear to reach such high levels, yet unwanted organic materials are quickly and efficiently removed from solutions and suspensions treated by the treatment system.

[0026] Although the specific oxidants produced by the treatment system within the treated water have not yet been identified, oxidation reduction potential (ORP) measurements of treated water using a platinum probe indicate that the ORP millivolt (mv) increase from input to output ranges from approximately 200 to 450 millivolts. This suggests that the produced oxidants are relatively mild. Oxidative mildness of treated fresh water is further verified by the lack of corrosiveness to even the most sensitive parts of human tissue (eyes and nose), with no obvious bleaching of clothes or hair, and no strong bleach odor, or taste.

[0027] In contrast to the statement above concerning a weak oxidant, the treated solution (fresh or saltwater), however, performs as an extremely powerful oxidant completely breaking down many liquid-form organic compounds to C0₂, H₂0, NH₃, and/or inorganic acids and/or salts, etc. within a short time frame.

[0028] The oxidative or degrading characteristics of the water or aqueous liquid treated with the treatment system to form a treatment fluid does not necessarily diminish or stop immediately after treatment with treatment system wherein current to the electrodes has been cut off. Through experiments it was discovered that the reactive oxidant of the treated water or aqueous liquid has a limited lifespan, in other words, it is metastable. If the oxidant is metastable it is possible that a solution gas such as dissolved oxygen may exist in the fluid and thus provides the oxidative properties. Although the oxidative lifespan of the liquid may be limited, in certain cases, water treated with the treatment system retained its oxidative or degrading properties for significant periods of days, weeks, and in some cases even months at a time after treatment with the treatment system.

[0029] In addition to the degradation of organic materials, new salts are formed during the electrolysis process, thus precipitating some of the new salts and existing salts. It is believed that the formation of these new salts and metastable hydroxyl and hydronium ions may saturate the solution and cause salt precipitation. Research has demonstrated that where these ions are the most concentrated the greatest salt precipitation occurs. These may include inorganic salts that are typically highly soluble in water, such as metal halide salts, including chlorine-containing salts of NaCl, KC1, etc. A decrease in solubility for less soluble salts is also expected. These salts precipitate as new salts are being formed by electrolysis.

[0030] Furthermore, while salts are precipitated, an increase in the solubility of the water or aqueous liquid for oxygen has been observed. This oxygen solubility has been demonstrated through measurement of evolved oxygen from the anode of the treatment system. Dissolved oxygen measured from treated water was at greater than about 30 mg/L. Such quantities of dissolved oxygen within the treated water remained for days, weeks, and even months in some cases. In contrast, the highest predicted dissolved oxygen levels found in the environment are approximately 14 mg/L, and they occur in fresh water, at near freezing temperature at sea level. These levels decrease with increased temperature, lower atmospheric pressure, and higher salinity.

[0031] The treatment system makes use of specialized electrodes that have been described in U.S. Pat. App. Pub. No. US2011/0011749A1, which is herein incorporated by reference in its entirety for all purposes. U.S. Patent Application No. 61/384,509, filed September 20, 2010, also describes such electrodes and is herein incorporated by reference in its entirety for all purposes. The electrode substrate is typically formed of titanium, although other metals may be used for the metal substrate of the electrodes. The electrodes are doped or treated with certain materials that provide the unique treating effect or treatment fluid with the previously described characteristics. Such dopant or treatment materials may include sodium, sodium isopropoxide, sodium alkoxide, metal alkoxide, titanium, a conductive metal, a conductive metal oxide, tantalum, tantalum oxide, ruthenium, ruthenium oxide, iridium, iridium oxide, sodium carbonate, carbon, chloride, titanium dioxide, titanium tetrachloride, manganese, molybdenum, manganese-molybdenum oxide, tungsten and NaRu0₂. Combinations of such materials may also be used. Examples of other electrode substrates, dopant and/or electrode treatment materials may include those described in U.S. Patent No. 3,948,751, which is herein incorporated by reference in its entirety for all purposes.

[0032] As used herein, the expression "doped," "dopant" or similar expressions, unless explicitly stated or is otherwise apparent from its context, is meant to be construed as those materials that are deposited or otherwise incorporated into the electrode substrate. Such terms are meant to refer both to each material by themselves individually and together as a whole. Such materials individually may or may not provide any exhibited effect when used by themselves or may only provide spectator materials once deposited or incorporated into the electrode substrate but may, however, provide the necessary actions, interactions or form reaction products with other materials that provide the necessary dopant coating or deposit on the electrode substrate used to provide the desired treatment or formation of treatment fluid when used as described herein. Such materials may still exist and be incorporated into the electrodes, however, regardless of any temporary or permanent function they may have with respect to the treatment or doping of the electrodes.

[0033] Although described in more detail in the above patent publication, the following is a brief description of the preparation of the electrodes. One electrode of the treatment system may be formed by treating or contacting the electrode substrate with a solution of tantalum oxide dissolved in isopropyl alcohol. This is then spun to provide a uniform coating and then baked or sintered at high temperature (e.g. 600 °F (316 °C)). The tantalum oxide coated electrode is then treated or contacted with a solution of raw sodium dissolved in isopropyl alcohol. This is then spun to provide a uniform coating and then baked at a relatively lower temperature (e.g. 300 degrees °F (149 °C)) until the alcohol is evaporated. This provides a sodium dopant on the electrode, which may be deposited as a sodium isopropoxide. Sodium in combination with other alcohols or alkyl alcohols may also be used, which may provide a sodium alkoxide coating or deposit. The above-described process may be repeated several times. Finally, the electrode is treated or contacted with ruthenium oxide or iridium oxide in a similar manner, spun and baked or sintered at a high temperature (e.g. 1,200 to 1,600 °F (649 to 982 °Q) to provide the final electrode. This electrode may be used as a negative electrode in many applications, however, in certain embodiments a sodium-doped or sodium-alkoxide-doped electrode prepared in the above manner may be used as either or both the negative and positive electrode.

[0034] Another electrode of the treatment system may be formed by treating the electrode substrate with a solution of tantalum oxide in isopropyl alcohol, spun and baked or sintered at relatively high temperature (e.g. 600 °F (316 °C)). This is followed by treating or contacting the electrode with a solution of titanium tetrachloride dissolved in isopropyl alcohol, spinning and baking or sintering of the material at a relatively lower temperature (e.g. 300 degrees °F (149 °C)) until the alcohol is evaporated. The above-described process may be repeated several times. Finally, the electrode is treated or contacted with ruthenium oxide in a similar manner, spun and baked or sintered at a high temperature (e.g. 1,200 to 1,600 °F (649 to 982 °C)) to provide the final electrode. This electrode may be used as a positive electrode in many applications, however, in certain embodiments it may be used as either or both the positive or negative electrode.

[0035] Referring to Figure 1, a basic schematic of a treatment system is shown. The treatment system includes the doped negative and positive electrodes 1, 2, respectively, prepared in the manner described above or similar to those described in U.S. Pat. App. Pub. No. US2011/0011749A1. The electrodes 1, 2 are spaced apart a distance and disposed in a vessel 3 that defines a non-electrically-conductive treatment chamber 4. The chamber 4 may be cylindrical or may have other configurations. The spacing between the electrodes 1, 2 may vary depending upon conductivity of the liquid being treated, with higher conductive liquids requiring a greater distance between the electrodes 1, 2. [0036] The electrodes can have various configurations. They may be in the form of flat plates, cylinders or other configurations. The electrodes can be formed from a flexible wire mesh or other flexible form that can be molded into various shapes or forms. In certain embodiments, the electrodes may each be formed from a wire mesh or other flexible material, which may increase surface area of the electrode, that is helically or spirally wound into a generally cylindrical coil shape, with one electrode being concentrically positioned within the interior of the other. Such helical or spiral configuration allows the electrodes to be narrowly spaced apart while providing an increased surface area for contact with the fluid being treated. Additionally, the electrodes may be the same or different sizes and shapes. In certain applications, the anode or positive electrode may have a surface area that is greater than that of the cathode or negative electrode, or vice versa. For example, the surface area of the positive electrode may be 2, 3, 4, 5 times or more than the surface area of the negative electrode, or vice versa. The concentric helical or spiral configurations may help accommodate such differences in surface area, with the outer electrode having a greater surface area than the inner electrode. In addition, neutral or non-biased electrodes or conductive structures can be positioned within the chamber. Such neutral electrodes or structures may be configured the same or differently than the electrically biased electrodes. The neutral electrodes may be positioned between the oppositely biased electrodes or elsewhere.

[0037] In certain applications, only a single doped electrode may be used with the other being a non-doped electrode, which may be formed solely from the substrate electrode material. In such cases, the negative electrode may constitute the doped electrode. It has also been discovered that what has been referred to herein as the "positive" electrode prepared from the titanium tetrachloride described previously, may also be used as a negative-biased electrode to produce the metastable hydroxyl ions. When used this way, however, the titanium tetrachloride treated electrode cannot be polarity reversed to help limit scaling of calcium and magnesium. The described negative electrode with the sodium dopant can be reversed in polarity, however, to retard scale buildup. Furthermore, the sodium doped electrode can be used as both the negative- and positive-biased electrode within the same treatment system.

[0038] An inlet 5 may be provided in the lower section of the vessel 3. The inlet 5 communicates with the chamber 4 and allows the introduction of liquid to be treated within the chamber 4 of the treating system. With a cylindrical chamber 4, the incoming liquid can impinge upon the wall of the chamber 4 to flow in a swirl or provide a slight turbulence to facilitate a stirring action of the fluid and keeping sediment off the bottom of the chamber 4.

[0039] Mixing plates or structures 6 may also be provided within the vessel 3 at the upper end or outlet of the chamber 4. The mixing plates 6 are nonconductive and facilitate agitation or mixing of the liquid and generally define a mixing chamber 7 where the ionic liquid streams coming off the electrodes 1, 2 are mixed. Studies have shown that mixing of the streams coming off each electrode improves the oxidative properties of the liquid. The liquids are discharged from the mixing chamber 7 through outlet 8 of the vessel 3.

[0040] A lower outlet 9 provided with a valve or selectively openable closure may also be provided with the vessel 3 for removal of any liquids or sediment and may facilitate cleaning and servicing of the treatment system. Although not shown in the embodiment of Figure 1, sleeves, shrouds or other devices may be positioned around at least a portion of any of the electrodes, including the neutral electrodes, to facilitate collection of precipitate or concentrated liquid ion streams from around the electrodes.

[0041] The treatment system is provided with a power supply 10 to the electrodes 1, 2. The power supply may be a variable voltage direct current (DC) power supply that can be adjusted to account for the conductivity of the entering liquid and the surface area of the electrodes. The variable power supply may be constructed to supply 1 to approximately 50 volts, although other voltages may be used. In the examples described later on, the treatment systems typically drew 1 to 8 amps at approximately 6 to 20 volts, depending upon the design.

[0042] When an electric potential or current is applied across the electrodes at selected voltage and current, the negatively-biased electrode facilitates reduction by reacting water and electrons to evolve hydrogen gas and produce metastable hydroxyl ions in the aqueous liquid. Reduction takes place at the negative -biased electrode as in Equation (1) below:

2 H₂0(Z) + 2e^"→ U₂(gas) + 2 OW(aq) ( 1 )

The positively-biased electrode facilitates oxidation by converting water into oxygen, metastable hydronium ions, and electrons as in Equation (2) below: 2H₂O( → 0₂(gas) + 4 H⁺(aq) + 4e (2)

[0043] In a highly saline solution, depending upon the content of the dopant provided or incorporated into the surface of the positive-biased electrode, chlorine evolution may replace oxygen evolution. Tests suggest that the sodium- or s odium- alkoxide- doped electrodes of the present invention may evolve some oxygen in addition to chlorine in high saline environments. Observations from treated ultrahigh chloride water (e.g. 150,000 to 175,000 ppm chloride) indicate that the treated product is very efficient at oxidizing organic material and even crude oil. Research has also indicated that it may be helpful to dope the outer coating of the electrodes and particularly the positive-biased electrode with manganese-molybdenum oxide or some other metal oxide that has been demonstrated to promote oxygen instead of chlorine evolution at the positive electrode when treating high chloride solutions.

[0044] The following examples serve to further illustrate the invention.

EXAMPLES

Experimental

[0045] In the following examples different treatment systems were used. Two of the treatment systems had configurations similar to that illustrated in Figure 2, with one being larger than the other. As shown in Figure 2, the treatment systems were each comprised of a vessel 11 formed from a cylindrical nonconductive material having an inlet 16 that communicates with an interior chamber 18 of a nonconductive vessel 11. The inlet 16 may be tangentially located to the vessel wall so that liquid is introduced along the sides of the chamber 16 to provide a turbulent swirling effect.

[0046] Within the interior of the chamber 18 were disposed electrodes 21, 22. The electrodes in each case were formed from 1-inch (2.54-cm) wide titanium wire mesh that had been treated in accordance with the procedures outlined above and described in U.S. Pat. App. Pub. No. US2011/0011749A1 to provide the positive and negative electrodes. The initial process steps of each electrode were only repeated three times before the final treatment with ruthenium oxide. For those examples directed to oxidative reduction of organic materials, both electrodes 21, 22 were those formed using raw sodium in isopropyl alcohol, as described in U.S. Pat. App. Pub. No. US2011/0011749A1. [0047] In the configuration of Figure 2, electrode 21 is a positive biased electrode and electrode 22 is a negative-biased electrode. The electrodes 21, 22 are helical or spirally configured. Electrode 22 is wound around a nonconductive tubular member and secured thereto by small tungsten rods or fasteners 30 bent at ninety degree angles. The tungsten may be beneficial in bacteria eradication and may reduce gas evolution. The electrode 21 is wound around circumferentially-spaced-apart nonconductive support rods or structures 32 within the chamber 18. In this way, the electrode 22 is radially spaced apart but located concentrically within the coiled electrode 21. A variable power supply 40 is connected to the electrodes for supplying variable voltage DC power. Liquid 42 to be treated is introduced into the system through lower inlet 16, with treated liquid 44 passing over nonconductive mixing plates 46 into mixing chamber 48 and discharged through outlet 50.

[0048] In the larger treatment system (referred to as System 1) configured as in Figure 2, the treatment system was configured to treat approximately 10,000 barrels (1590 m ) per day of fluid. The treatment system chamber 18 was approximately 40 inches (1.02 meters) long, 14 inches (0.36 meter) in diameter. The outer electrode 21 was 1-inch (2.54-cm) wide mesh that had a total linear length of 39 ft (11.9 meters) with a wound coil height of 40 inches (1.02 meters) and a coil diameter of approximately 12 inches (0.30 meter). The inner electrode 22 was also 1-inch (2.54- cm) wide mesh with a total linear length of 13 feet (3.96 meters), a coil height of 40 inches (1.02 meters) and a coil diameter of 5.6 inches (0.14 meter). The radial spacing between the electrodes 21, 22 was approximately 3.2 inches (0.08 meter), which is a suitable spacing when treating salt water with chloride measurements between approximately 100,000 ppm and 180,000 ppm. The total surface area of the outer positive-biased electrode 21 was approximately three (3) times that of the inner negative-biased electrode 22. When used to treat oil field salt water, the larger system was set to approximately 4 or 8 volts and controlled to draw about 5 to 6 amps depending upon the conductivity of the treated solution.

[0049] In the smaller of the treatment systems (referred to as System 2) configured as in Figure 2, the treatment system was configured to treat approximately 23 barrels (3.66 m ) of fluid. The treatment system had a treatment chamber 18 that was 12 inches (0.30 meter) long and 4 inches (0.1 meter) in diameter. The electrodes 21, 22 were 1-inch (2.54-cm) wide mesh. The outer helical electrode had a total linear length of 4.75 feet (1.45 meters) with a coil height of 12 inches (0.30 meter) and a coil diameter of 3 inches (7.6 cm). The inner helical electrode had a total linear length of 1.6 feet (0.49 meter) with a coil height of 12 inches (0.30 meter) and a coil diameter of 1.5 inches (3.8 cm). The radial spacing between the electrodes was 0.75 inches (1.9 cm) for treating fresh water with total dissolved solids of less than 1,000 ppm. The system was set to use approximately 9 to 15 volts and draw 1 amp.

[0050] Either of the above-described systems (System 1 and 2) can be scaled up or down depending upon treatment requirements.

[0051] A third treatment system (referred to as System 3) was used in treating sewage. The system is shown schematically in Figure 3. The treatment system was configured with a box-shaped treatment chamber that was about 4-feet (1.22-meter) long, about 1.5-feet (0.46-meter) wide and 8-inches (0.20-meter) deep. The electrodes were each about 8-feet (2.44-meters) long formed of 1-inch (2.54-cm) wide titanium wire mesh treated as described above with both electrodes being sodium- or s odium- alkoxide doped electrodes used in a side-by-side fashion. The electrodes were spaced about 1.5 inches (3.81 cm) apart, but could be adjusted within the treating chamber to accommodate changes in conductivity. Tungsten was applied to the negative electrode. The interior of the treatment chamber was provided with a center baffle along its length with the wire mesh electrodes generally following the flow path defined by the center baffle. A DC power supply provided current to the electrodes hold an approximately 1 amp current, with the voltage being varied depending upon the conductivity of the fluid being treated.

Example 1

[0052] Sewage water from East Texas was oxidatively treated in the treatment system System 3 described above. After treatment the DO levels were measured with a DO meter. The treated sewage had an extraordinarily high DO in the relatively warm (summer) East Texas effluent. It took over one week for the DO levels to decrease to 28 mg/L, which was the upper limit of the electronic dissolved oxygen meter used to determine DO.

Example 2

[0053] East Texas formation water having approximately 175,500 ppm chlorides from the Cotton Valley Formation was treated with the treatment system System 1. The formation water was light orange from high levels of emulsified oil and was slightly acidic. In this example, the positive and negative electrodes were shielded or sheathed to facilitate collection of materials drawn from around each electrode. A hydroxyl ion dominated stream (pH greater than 13) of saltwater was drawn off the negative electrode side of the device and a hydronium ion dominated stream (pH 1) was harvested from the positive electrode side. The two outputs were collected in separate chambers and analyzed for anion and cation content, pH, and mineral content of the precipitate that formed only within the hydroxyl ion chamber. Water and precipitate analysis was performed at the Baker Hughes' Houston Technical Services Laboratory.

[0054] The pH tests were conducted on both the negative- and positive-electrode water samples on the day of collection. The hydroxyl side (from the negative electrode) was highly basic with a pH greater than 13 and the hydronium side (from the positive electrode) was very acidic at approximately a pH of 1. Notably, neither water sample was corrosive to human hands as would be expected at a pH of 1 and 13. Six days later when the pH of the samples was tested again by Baker Hughes, the pH of both samples had changed significantly and both were measured in the acidic range. The side that was originally at a pH of 13 had lowered to a pH of 5.3 (5 meq/L). And the side that was originally at a pH of 1 had risen to a pH of 4.7 (340 meq/L). The hydroxyl ions depleted significantly over the six-day period, and of the two electrode products, the basic side carried the reactive oxidant. The results are presented in Table 1 below.

Table 1

[0055] The visually apparent emulsified crude oil of the input water appeared to be absent on the hydroxyl side. Consequently, the hydroxyl side may have become acidic in part by breakdown of the emulsified crude oil into sodium carbonate, which ultimately converts into carbon dioxide and water. Aqueous carbon dioxide may have reacted with water supplying weak carbonic acid and thus increasing the acidity of the hydroxyl side.

[0056] The Cotton Valley Formation input saltwater treated had a chloride level of 175,500 ppm chloride. The output water decreased remarkably to 24,000 ppm chloride. The difference was 151,500 ppm chloride found mainly as a crystalline precipitate. The precipitate was calcium hydroxide (portlandite), sodium chloride (halite) and a trace of magnesium hydroxide at the bottom of the hydroxyl chamber. There was no precipitate at the bottom of the acid separation chamber. Analysis of the precipitate was conducted by x-ray diffraction (XRD) and x-ray fluorescence (XRF). Notably, the chloride content in the hydroxyl and hydronium chambers was 121,100 ppm and 125,500 ppm, respectively, and both were well below the input sample of 175,500 ppm chloride.

[0057] It was determined from this study that separated hydroxyl and hydronium ionic concentrations from the negative (basic) and positive (acidic) electrodes have a relatively short lifespan (fewer than 6 days), that the basic side appears to produce the reactive oxidant, and that the peculiar basic and acidic solutions are uncharacteristically noncorrosive to human tissue. It was further observed that new salts are formed during the electrolysis process thus precipitating some of the new and existing salts from the treated input Cotton Valley Formation water in the hydroxyl chamber.

Example 3

[0058] Swimming pool water was treated in System 2 and indicated that the solubility of chlorine gas may decrease in treated fresh water. It is apparent that new salts are formed during the electrolysis process thus precipitating some of the new and existing salts.

Example 4

[0059] One gallon of raw sewage was placed into 550 gallons (2.08 m³) of high bacteria/algae-laden fresh water and let set for 24 hours. The water was sampled and tested for bacteria before treatment and then treated by System 2. Bacteria levels including E-coli were too numerous to count before treatment, and virtually absent (less than 1) after treatment. The 550 gallons (2.08 m ) tank of treated water was left open during the month of November to the atmosphere for 21 days and then tested for bacteria again. After 21 days the tank remained bacteria free.

Example 5

[0060] Fresh tap water was treated by using System 3, removed from the system and contained for 41 days (Sample 1). Another sample of fresh tap water was treated by System 3 for immediate use (Sample 2). Both Samples 1 and 2 were used to treat organic material within equine fecal remains. Sample 2 broke down the fecal remains more quickly than Sample 1, however after several minutes the 41 -day-old water did begin to degrade the fecal remains. These experiments illustrate that whereas 41 -day old treated tap water (sample 1) still degrades organics, the freshly prepared treated tap water degrades organics at a faster rate.

Example 6

[0061] Oxidative treatment of 25,000 gallon (94.64 m³) swimming pool water was treated using System 1. Bacterial analysis before treatment showed an HDT of 738 bacteria colonies, a count of 1,732.9 PN, E. coli, Colilert-18-DW, and 2,419.6 PN, total Coliform, Colilert-18 bacteria. Within two hours of treatment of the pool water circulation most if not all of the algae and bacteria formed a thin biofilm on the surface of the pool. In the sample collected after 2 hours of circulation the respective numbers dropped from 738 bacteria colonies to 0.2, from 1,732.9 PN, E. coli, Colilert-18-DW to 1 and from 2,419 PN, total coliform, Colilert-18 bacteria to 1, respectively. After approximately one week of 8 hour per day treatment all of the algae stains on the walls of the pool were gone suggesting that even the older algae within the fabric of the plaster walls of the pool was broken down. The same bacteria test was duplicated 21 days after installation and it recorded 0.2, <1, and <1 in respect to the initial numbers. After six months of treatment with the pool water, the pool had crystal clear water and all of the algal stain on the walls and floor of the pool were completely absent, indicating at least visibly the pool was bacteria and algal free. Over that six month period the pH of the pool was constant at 7.8.

Example 7

[0062] A small 40 gal/min (151.4 L/min) treatment system System 2 was installed on a water well at a ranch in East Texas. Sewage and all other water waste using the well water from the house were collected within a cesspool tank. After approximately 6 weeks the cesspool tank was pumped out. The liquid pumped from the tank was almost completely free of sludge and consisted primarily of odorless water. Most of the organic waste was converted to C0₂, H₂0, NH₃, and inorganic acids or salts.

Example 8

[0063] Multiple tests were conducted on treating raw sewage with System 3. From these tests it was determined that the sulfur-, nitrogen-, oxygen-, and other heteroatoms found in organic compounds (odor producing molecules) were immediately broken down to C0₂, H₂0, NH₃, and inorganic acids or salts upon contact with the treatment system. It was also determined that the treatment system broke down most of the organic material in sewage to C0₂, H₂0, NH₃, and inorganic acids or salts over a period of approximately 72 hours at ambient temperature. It was also determined that the bacteria was destroyed and broken down within treated sewage. It was also determined that total organic content (TOC), can be reduced, or in some cases eliminated bringing COD and BOD to environmentally safe levels such that treated sewage water may be safely returned to the aqueous environment. Bovine, equine and other animal fecal waste was also converted to C0₂, H₂0, NH , and inorganic acids or salts over a period of approximately 72 hours at ambient temperature.

Example 9

[0064] A bovine fecal slurry was treated within an electric field of System 3 for approximately 30 minutes converted to 96% pure methanol (CH₃OH). Laboratory analysis of the converted bovine fecal slurry was as follows: 96% methanol, 1.6% MTBE, 0.35% isopropyl alcohol, 0.89% m- and p-xylene, 0.18% o-xylene, 0.49% ethyl benzene, 0.06% naphthalene, 0.03% benzene, and 0.43% miscellaneous hydrocarbons.

Example 10

[0065] Both fresh water and saltwater treated by System 1 were successful for use as an oxidative treatment fluid used in breaking down crude oil to carbon dioxide and water. Thus crude oil, tar, and refined crude oil can be treated within or outside using the aqueous oxidative treatment fluid. Tests indicate that heat helps speed the breakdown, but all crude oil is generally broken completely down within approximately 72 hours of exposure to oxidative treatment water.

Example 11

[0066] System 1 was used to treat oil field formation saltwater to form an oxidative treatment fluid from the salt water that was then pumped down a water disposal well into a sandstone reservoir through casing perforations at approximately 10,000 feet (3048 meters) to degrade oil, tar, and bacteria that had partially plugged the permeability of the sandstone reservoir in the near vicinity of the wellbore. From pressure information, it was determined that much of the organic material plugging the pore spaces was degraded allowing a significant increase of permeability and resulting decreases in entry pressure for pumped saltwater disposal. It is apparent from this that the treatment system can remove organic material, including bacteria and crude oil from produced, formation, and pit water, allowing these valuable waters to be reused in the fracturing process and other processes and eliminating the cost of disposal of these fluids.

Example 12

[0067] Broiler chickens were fed water on a broiler farm in East Texas treated by System 2. The farm raised 96,000 broilers from hatch to slaughter (40-50 days) and prior to installing System 2 to treat the broiler's drinking water experienced a mortality rate of 3%. The water source was laden with significant bacteria prior to treatment. After installation of System 2 the average mortality rate for the last six generation of broiler chickens dropped to 1%. The mortality drop was directly attributed to complete elimination of bacteria in the water treated with System 2.

[0068] While the invention has been shown in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes and modifications without departing from the scope of the invention. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention.

Claims

CLAIMS I claim:

1. A method of treating a liquid-form organic material comprising: contacting the liquid-form organic material with an aqueous oxidative treatment fluid prepared in a treatment system comprising a vessel containing an aqueous fluid and a pair of electrodes positioned within the aqueous fluid, at least one of the electrodes being a doped electrode that facilitates the treatment system providing the oxidative treatment fluid from the aqueous fluid when an electric potential is applied across the pair of electrodes at a selected voltage and current so that the aqueous oxidative treatment fluid is suitable for oxidatively degrading the organic material.

2. The method of claim 1, wherein: the organic material is contacted with the treatment fluid while the treatment fluid is within the treatment system.

3. The method of claim 1, wherein: the organic material is contacted with the treatment fluid after the treatment fluid is removed from the treatment system.

4. The method of claim 1, wherein: the liquid-form organic material is an organic material dispersed in an aqueous fluid and wherein the aqueous fluid of the liquid-form organic material forms the aqueous fluid of the treatment fluid.

5. The method of claim 1, wherein: contacting of the organic material with the treatment fluid degrades all of the organic material so that substantially no organic material remains.

6. The method of claim 1, wherein: the dopant is at least one of sodium, sodium alkoxide, metal alkoxide, titanium, a conductive metal, a conductive metal oxide, tantalum, tantalum oxide, ruthenium, ruthenium oxide, iridium, iridium oxide, sodium carbonate, carbon, chloride, titanium dioxide, titanium tetrachloride, manganese, molybdenum, manganese-molybdenum oxide and NaRu0₂.

7. The method of claim 1, wherein: said at least one of the electrodes is a titanium electrode.

8. The method of claim 1, wherein: the organic material is selected from at least one of biological material, bacteria, algae, fungus, fecal matter, sewage, industrial waste, hydrocarbons, crude oil, tar, petroleum products, an aliphatic hydrocarbon, an aromatic hydrocarbon, an alkene, an alkyne, and a heteroatom-containing hydrocarbon.

9. The method of claim 1, wherein: each of electrodes of the pair of electrodes is a doped electrode.

10. The method of claim 1, wherein: the electrode is doped with sodium.

11. A method of treating a material comprising: contacting the material with a treatment fluid, the treatment fluid being prepared by introducing an aqueous fluid into a system comprising a vessel containing a pair of electrodes, at least one of the electrodes being a doped electrode that facilitates the treatment system providing the treatment fluid when an electric potential is applied across the pair of electrodes at a selected voltage and current so that the treatment fluid is sufficient for at least one of (1) oxidatively degrading the material, and (2) precipitating salts and increasing the solubility of the treatment fluid for oxygen.

12. The method of claim 11, wherein: the material is contacted with the treatment fluid while the treatment fluid is within the system.

13. The method of claim 11, wherein: the material is contacted with the treatment fluid after the treatment fluid is removed from the system.

14. The method of claim 11, wherein: the material is an organic material.

15. The method of claim 11, wherein: the material is a salt or salt solution.

16. The method of claim 11, wherein: the material is a liquid-form organic material dispersed in an aqueous fluid and wherein the aqueous fluid of the liquid-form organic material forms the aqueous fluid of the treatment fluid.

17. The method of claim 11, wherein: the dopant is at least one of sodium, sodium alkoxide, metal alkoxide, titanium, a conductive metal, a conductive metal oxide, tantalum, tantalum oxide, ruthenium, ruthenium oxide, iridium, iridium oxide, sodium carbonate, carbon, chloride, titanium dioxide, titanium tetrachloride, manganese, molybdenum, manganese-molybdenum oxide and NaRu0₂.

18. The method of claim 11, wherein: said at least one of the electrodes is a titanium electrode.

19. The method of claim 11, wherein: the material is an organic material selected from at least one of biological material, bacteria, algae, fungus, fecal matter, sewage, industrial waste, hydrocarbons, crude oil, tar, petroleum products, an aliphatic hydrocarbon, an aromatic hydrocarbon, an alkene, an alkyne, and a heteroatom-containing hydrocarbon.

20. The method of claim 11, wherein: each of electrodes of the pair of electrodes is a doped electrode. The method of claim 11, wherein: the electrode is doped with sodium.