Patent Grant
7625492
Generally, filtration systems, layered double hydroxide (LDH) compounds and methods of sorbing inorganic or organic material(s) onto such LDH compounds, including biological agents such as bacteria or viruses present in liquids or gases.
Numerous species of biological agents, including, but not limited to, protozoans parasites, bacteria, fungi, or viruses enter water systems or enter the atmosphere from sources such as solid waste material, commercial processing wastes, sewage effluent, septic tanks effluents, sewage sludge, garbage disposal, urban runoff, medical facilities, agricultural runoff, human beings sneezing or coughing and the like.
Bacteria are well adapted to and are common biological agents in water systems. Bacteria may have ranges in size from about 1000 nanometers (nm) to about 10,000 nm in size and include species such as Aeromonas, campylobacter, Escherichia coli, Helicobacter pylori, Legionella, Nontuberculosis mycobacteria, Psedomonas aeruginosa, salmonella, shigella, Vibrio vholerae, Yersinia enterocolitica, and the like bacteria.
Major bacteria identified in ambient air include species such as: Acinetobacter, Ordetella perfussis, Corynebacteria diphtheria, Mycobacterium avium, Pseudomonas aeruginosa, Staphylococcus aureus, and the like bacteria.
Viruses have been detected in all environments including water systems as described by Gerba, C. P. and Rose, J. B., “Viruses in Source and Drinking Water”, Drinking Water Microbiology (1990), incorporated by reference herein, and in ambient air. Most viruses are small (about 20 nm to about 200 nm) and consist of nucleic acid encapsulated in protein molecules. In municipal sewage, more than 100 different viruses may be identified, and viruses such as poliovirus, hepatitis A, echo, coxsackie, rota, adeno, or Norwalk-like viruses are virulently hazardous at very low concentrations. In ambient air, viruses such as adenovirus, coronavirus, echovirus, influenza, and rhinovirus have been widely detected.
Because the occurrence of pathogenic biological agents in water and air systems constitutes a serious threat to human health and can be the source of a variety of diseases, such as gastroenteritis, cholera, hepatitis, typhoid fever, giardiasis, or the like, the United States Environmental Protection Agency is in the process of addressing the public health risk resulting from pathogenic contamination of water systems.
However, the use of conventional large-scale water purification technologies such as ultraviolet irradiation or chlorination may allow concentrations of pathogenic biological agents to survive. As such, secondary treatment of conventionally treated water may be necessary to completely capture or remove biological agents in water systems. In addition, these technologies are largely not available in rural areas, military operations, tourism sites, etc. Under such circumstances, portable apparatus with low or no power requirements are in need to remove bioagents from the water systems.
To meet the demand for secondary treatment technology, including, but not limited to, commercial or residential secondary water treatment, a variety of distillation, reverse osmosis, and filtration systems have been developed which utilize evaporation, activated carbon, ion exchange resins, or reverse osmosis membranes to further purify water. However, even though these conventional technologies can be effective in the removal of certain organic compounds, and certain metals, such as lead and mercury, a variety of problems remain yet to be addressed with respect to both primary and secondary treatment methods.
A significant problem with conventional water treatment technology can be that loading capacity of activated carbon or ion exchange resins, or the like, can be low requiring frequent changes or requiring the frequent use of reactivation procedures to maintain water quality. Similarly, reverse osmosis membranes may not be suitable for purification of water with high levels of dissolved solids because the reverse osmosis membrane can become saturated or clogged with solids resulting in reduced efficiency.
Another significant problem with conventional water treatment technology can be that the amount of water processed may be low. Conventional evaporation technology and reverse osmosis technology are typically suitable only for those applications in which small volumes of water are to be purified, such as in the residential setting to purify drinking water. In addition, the energy and pressurizing requirements of reverse osmosis treatment further limit its use.
Another significant problem with conventional water treatment technology can be that sorbent materials used in conventional water treatment may possess a neutral or negatively charged surface. While some biological agents may nonspecifically interact with neutral or negatively charged sorbents, the low binding efficiency excludes the use of these sorbents to attract, capture, collect, or remove biological-agents from water systems.
These problems with conventional water treatment technology coupled with the increasing concerns over pathogenic microbial contamination of drinking water, and especially in view of recent concerns over the use of biological agents as weapons, warrant the imminent development of a cost-effective water treatment technology that can be readily applied to remove biological agents from water systems.
Moreover significant problems remain unresolved with regard to conventional air or gas treatment technology. Prominent among these problems may be that conventional gas filtration systems may only remove relatively large particulates such as pollen while allowing pathogenic agents such as viruses to pass through without retention to the filter material.
The instant invention addresses each of these concerns with respect to attracting, capturing, inactivating, or removing metal ions, inorganic and organic compounds, or biological agents from aqueous systems or gas systems whether the treatment is primary or secondary.
On the basis of their structure and properties, specific applications for layered double hydroxide (LDH) compounds and compositions have been previously identified. These include the use of LDH compounds as catalysts and catalyst precursors, as antacids, as solid ionic conductors, in preparation of pigments, to interact with anionic contaminants such as Cr2O72−, trichlorophenol (TCP), and to interact with radioactive anionic pollutants TcO4−, ReO4− and I−.
Accordingly, a significant objective of the invention is to provide materials that, individually or in combination, interact with, capture, sorb, inactivate, or exchange a wide variety of materials in water or gas such as metal ions, inorganic compounds, organic compounds, biological agents, or the like materials.
Another significant object of the invention can be to provide layered double hydroxide compounds to treat water or gas by sorbing, absorbing, adsorbing, interacting with, attracting, sequestering, capturing, deactivating, or removing bacteria, including, but not limited to bacteria in the group consisting of: Acinetobacter, Aeromonas, Campylobacter, Corynebacteria diphtheria, Escherichia coli, Helicobacter pylori, Legionella, Mycobacterium avium, Nontuberculosis mycobacteria, Ordetella perfussis, Psedomonas aeruginosa, Salmonella, Sshigella, Staphylococcus aureus, Vibrio vholerae, and Yersinia and other opportunistic bacteria.
Another significant object of the invention can be to provide layered double hydroxide compounds to treat water or gas by sorbing, absorbing, adsorbing, interacting with, attracting, sequestering, capturing, deactivating, or removing viruses, including, but not limited to viruses in the group consisting of: Adenovirus, Coronavirus, Coxsackievirus, Echovirus, Enteroviruses, Hepatitis virus, Influenza, Norwalk-like virus, Poliovirus, Reovirus, Rotovirus, Toravirus, and the like viruses.
Another significant object of the invention can be to provide layered double hydroxide compounds that exhibit positively charged surface areas or regions which can interact with negatively charged surface areas or regions of biological agents to attract, sorb, absorb, adsorb, sequester, capture, or remove them from water or air systems.
Another significant object of the invention can be to provide layered double hydroxide compounds having intercalated ions of sufficient size to maintain or orient the sheets of the layered double hydroxide compounds a sufficient distance apart to allow or optimize interaction of the positively charged surfaces of layered double hydroxide compound with the numerous and varied biological agents, or materials, to be attracted, sorbed, absorbed, adsorbed, captured, sequestered, or removed from water or air systems.
Another significant object of the invention can be to provide layered double hydroxide compounds for the removal of, both pathogenic biological agents and toxic anionic trace elements, including, but not limited to, arsenic or selenium, independently or at the same time.
Another significant object of the invention can be to provide layered double hydroxide compounds which attract, sorb, absorb, adsorb, sequester, capture, or remove pathogenic biological agents and toxic anionic compounds from water systems at same time.
Another significant object of the invention can be to provide layered double hydroxide compounds for the removal of, both pathogenic and nonpathogenic biological agents and anions, including, but not limited to, phosphate, sulfate, and carbonate.
Another significant object of the invention can be to provide layered double hydroxide compounds (which exhibit positively charged surface areas or regions) attached to materials having negatively charged surface areas or regions whereby the presentation of both the positively charged surface of the layered double hydroxide in combination with the negatively charged surface of the attached material can attract, sorb, absorb, adsorb, capture, sequester, exchange, or remove materials (including mixtures of metal oxides and biological agents) in fluids that have either positively charged surface areas or regions or negatively charged surface areas or regions, or both.
Another significant object of the invention can be to provide layered double hydroxide-lignin compounds for the removal of, individually or in combination, biological agents or metals from liquids.
Another significant object of the invention can be to provide layered double hydroxide-lignin compounds for the removal of, individually or in combination, biological agents or metals from gases.
Another significant object of the invention can be to provide layered double hydroxide compounds that can be calcined to reactivate the layered double hydroxide compound, or destroy or deactivate the sorbed biological agents after use.
Another significant object of the invention can be to provide layered double hydroxide compounds that can be dissolved in acid solution and resynthesized by coprecipitation method(s) for recycle use after being first used for removing biological agents from water systems or gas systems.
Another significant object of the invention can be to provide water treatment apparatus including, but not limited to, batch process containers, flow through containers, columns, bags, tubes, or the like, whether disposable or reusable, filled with one or more layered double hydroxide compounds or one or more layered double hydroxides bound, attached, or coating support or carrier materials such as filters, membranes, or particles, to be used as water treatment apparatus for the removal of particulate, metals, inorganic compounds, organic compounds, or biological agents from water. The water treatment apparatus can be sized or configured to the particular application, the amount of water to be processed, and the location at which the water is processed.
Another significant object of the invention can be to provide water treatment apparatus for residential use configured to attach to or adapt to existing residential plumbing or water inlet or outlet fixtures to treat residential water by removal of metal, inorganic compounds, organic compounds, or biological agents.
Another significant object of the invention can be to provide easy-carry water treatment apparatus for United States army or military in the field to treat field water by removal of metal, inorganic compounds, organic compounds, or biological agents and obtain potable water.
Another significant object of the invention can be to provide fluid filtration systems that can be used for emergency response efforts to treat contaminated water or air.
Another significant object of the invention can be to provide layered double hydroxide compounds to biological scientists and environmental engineers to concentrate biological agents, including, but not limited to, bacteria and viruses, from liquid and gas samples.
Another significant object of the invention is to provide portable water or air treatment apparatus for military or other purposes which is discrete or can be combined with existing water or air treatment apparatus for use in the field.
Another significant object of the invention can be to provide layered double hydroxide compounds connected, attached or otherwise coated to a membrane or filter surface to collect or concentrate biological agents, such as bacteria, viruses, prions, proteins, nucleic acids, or other biological agents, components, or molecules in liquids. The biological agents collected or concentrated by the layered double hydroxide compound can serve as samples for qualification or quantification or otherwise analyzed to detect, identify, and characterize the collected biological agents.
Yet another object of the invention can be to provide gas treatment apparatus in batch process containers, flow through containers, columns, tubes, or the like, whether disposable or reusable, filled with one or more layered double hydroxide compounds or one or more layered double hydroxides bound, attached, or coating support or carrier materials such as filters, membranes, or particles, to be used to purify gases, or purify air or other partial pressures of gases, or otherwise treat gas by removal of particulate, metals, inorganic compounds, organic compounds, or biological agents. Specifically, layered double hydroxide compounds, including, but not limited to, layered double hydroxide-lignin compounds can be used to remove potential pathogens in the air delivered to residential or commercial buildings.
Naturally, further independent objects of the invention are disclosed throughout other areas of the specification.
As mentioned earlier, the present invention includes a variety of aspects, which may be combined in different ways. The following descriptions are provided to list elements and describe some of the embodiments of the present invention. These elements are listed with initial embodiments, however it should be understood that they may be combined in any manner and in any number to create additional embodiments. The variously described examples and preferred embodiments should not be construed to limit the present invention to only the explicitly described systems, techniques, and applications. Further, this description should further be understood to support and encompass descriptions and claims of all the various embodiments, systems, techniques, methods, devices, and applications with any number of the disclosed elements, with each element alone, and also with any and all various permutations and combinations of all elements in this or any subsequent application.
Generally, the present invention may provide a system for removal of impurities from any type of fluid. Impurities may include contaminants, pollutants, or any type of undesired component that may be found in fluids. A fluid (40) may include any substance that is capable flowing, such as but not limited to liquid, gas, water, air, or the like. In some embodiments, the present invention may include establishing a fluid (40) which may include containing air or water in some sort of container, providing some type of indoor or enclosed area for air or water, providing air or water from outdoors, among others.
Water may be used from a stream, any type of plumbing system, faucet, or any water source and air may be used from the outdoors, indoors, buildings, vehicles, and the like. Water may include raw water or even primarily treated water. Raw water is to be understood as any water that is in a natural, uncultivated, or even unrefined state, it may be untreated water, or may be water from a river, ocean, stream, rain, and the like water sources. Primarily treated water may include water which may have been previously filtered, for example, water as received in a home or office, which may have gone through a municipal filtration system, such as water found in a residential or commercial building or the like.
A fluid (40) may contain impurities that may be desired to be removed before a human, animal or the like consumes or may be exposed to those contaminants—possibly for the prevention of an illness. In some embodiments, the present invention may include the removal of nanostructural components from fluids. A nanostructural component may be any structure that is very small, minute, not visible or detectable by the eye, or the like.
In fluids, different types of impurities or contaminants may exist. For example, fluids may contain a first, second and third components, among others. A first component (4) may include any substance, chemical, or compound found in a fluid and may even include an anionic substance, such as but not limited to, an anionic contaminant (8), a biological agent, arsenic, selenium, dicamba, anionic surfactant, virus, bacteria, hormone, fungi, prions, proteins, nucleic acids, phosphate, sulfate, carbonate, MS2 virus, Phi-X 174, Escherichia coli strains, Pseudomonas arugenosa, and the like contaminants. A second component (5) may include any substance, chemical, or compound found in a fluid and may even include a cationic contaminant, lead, chromium, zinc, mercury, ammonium, sodium, calcium, iron, copper, and the like contaminants. A third component (6) may include any substance, chemical, or compound found in a fluid and may even include substances that are not anionic nor cationic that may exist in a fluid, such as but not limited to non-ionic organic contaminants (20), 1,2,4-trichlorobenzene, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and the like contaminants. A bioagent may include any type of living organism, such as but not limited to virus, bacteria, hormone, fungi, MS2 virus, Phi-X 174, Escherichia coli strains, Pseudomonas arugenosa, and the like bioagents.
To remove various impurities or contaminants from fluids, the present invention may include providing an unpowered charged sorbent medium (3), shown in
A medium may include an intervening substance and may even include any type of porous support mediums which may be permeable by fluid, water, air, and the like and which holds or bears some sort of sorbent element. Mediums may include any substance that can be used for filtration or purification of fluids, such as but not limited to filter paper, plan paper, special paper fibers, cloth, fabric, water insoluble substances, coated particles, coating support, carrier materials and the like.
An unpowered charged sorbent medium (3) may include a layered double hydroxide (“LDH”) composition (1) which may contain a net positive charge as shown in
[MII1-xMIIIx(OH)2]z+An−z/n.yH2O,
wherein MII and MIII are bivalent and trivalent cations in octahedral positions and An− are anions intercalcated with the octahedral sheets or anions bound in an intermediate layer. The interlayer spacing of the octahedral sheets can vary depending on the size and geometrical structure of the intercalated anions. The net positive charge on the surface of LDH compounds may be due to the isomorphic substitution of trivalent metals by divalent metals and this positive charge on the surface of LDH compound may be balanced by the intercalated anions. Due to their structure, LDH compounds can exhibit relatively large surface areas (0.02-0.12 km2/kg) and high anion exchange capacities (200-500 cmol/kg). LDH compounds also can exhibit high pH buffering capacities and are relatively stable under a wide range of pH values. Thermal stability of LDH compounds may be dependent on the intercalcated anions and LDH compounds can may maintain their layered structure at temperatures under about 250° C.
As shown in
Referring to
Lignin compounds generally carry negative charges on its surface, which offer numerous binding sites for cationic contaminants (9), positively charged compounds or even metals or the like. For example, toxic metals having ionic forms with positive charges are often present in water systems. Lignin compounds can remove about 99.9% of these metals from the aqueous phase. The combination of lignin (2) with LDH compounds can possess the affinity to both negatively charged contaminants as discussed above and to positively charged contaminants. Understandably, a lignin and LDH compound can be useful in attracting, collecting, sequestering, retaining, or removing either positively charged ions or negatively charged contaminants, individually or simultaneously.
In embodiments, the present invention may include moving at least some of a fluid in the vicinity of a sorbent or a medium having sorbents. Sorbents may include an anionic contaminant sorbent, a cationic contaminant sorbent (11), LDH composition, anionic compositions (13), cationic compositions (12), lignin, or any substance capable of sorbing. A movement may include a flow or current of any type including but not limited to physically moving a fluid, osmosis, mechanically moving a fluid, or the like fluid flow. A circulation element (50) may be used for a mechanical movement and may even be used to drive or force fluid movement, such as but not limited to an air blower, air conditioner, water or air pump, fan, an electronic apparatus, or any device for producing a current of fluid by movement of the device. Physically moving a fluid may include any type of movement made by a user or occurring naturally such as but not limited to stirring, breathing, wind, pouring water, river flow and the like.
As a fluid is moving, it may be near or in the proximity of a sorbent. Of course, not all of a fluid may be in the vicinity of a sorbent, but at least some of a fluid may get close enough to allow attraction of certain types of molecules to the sorbent. A fluid may pass through a medium and some fluid components may be prevented from moving through a medium due to the porous nature of a medium. For example, even without attraction, relatively larger substances may not pass through pores in a medium because of their size. Yet, smaller substances may fit through the pores and pass through a medium.
Accordingly, to remove a variety of impurities from fluids, the present invention, in embodiments, may provide attracting impurities to a charged component or sorbent. As previously discussed, impurities or contaminants may include first, second and third components, anionic contaminants, cationic contaminants, non-ionic organic contaminants and even biological agents. Anionic components having a net negative charge and even cationic compositions (12) having a net positive charge may be provided. By attraction, an impurity may be drawn by a physical force causing or tending to cause an impurity to approach, adhere, or unite to a charged component. This may include, but is not limited to the interactions between oppositely charged substances such as ionic interactions between a cation and an anion.
In embodiments, a dual sorbent medium may be provided in which any type of medium may sorb at least two types of contaminants. This may include an anionic component (13) and a cationic composition (12). Cationic composition (12) may include layered double hydroxide compositions. Layered double hydroxides may include an anionic contaminant sorbent (10) due to the attraction of anions. Anionic components (13) may include lignin. Lignin may include a cationic contaminant sorbent due to the attraction of cations.
In other embodiments, the present invention may include sorbing at least some impurities to a component or sorbent. This may include, in various embodiments and as shown in
After a fluid has been in some contact with a sorbent component, the present invention may provide moving a fluid with at least some reduction (42) of an impurity. This may be further illustrated in
In certain embodiments, the present invention may include providing layered double hydroxide composition and containing an amount of LDH. This may include containing LDH in any way, and even a filtering device whether it be for air or water filtration. The present invention may even include any type of medium that can hold LDH particles or solutions. Depending on how much fluid that may be desired to be filtered, an amount of LDH may be contained.
In embodiments, the present invention may include an anionic contaminant sorbent (10) which may include any type of sorbent that can sorb anionic contaminants (8). Accordingly, an anionic contaminant sorbent may include sorbing of inorganic and organic anionic contaminants. Some inorganic contaminants may include Cl−, NO3−, ClO4−, CO32−, SO42−, CrO42−, I−, SeO32−, SeO42−, As(III) as well as other anionic inorganic substances. Some organic contaminants may include trichlorophenol (TCP), trinitrophenol (TNP), 2,4-dichlorophenoxyacetic acid (2,4-D), 3,6 dichloro-2-methoxy benzoic acid (dicamba), octylsulfate (SOS), sodium dodecylsulfate (SDS), sodium 4-octylbenzenesulfonate (SOBS), sodium dodecylbenzenesulfonate (SDBS), as well as other cationic organic substances. Anionic contaminant sorbents (10) may also sorb biological agents (7) such as viruses, bacteria, and the like. Some examples of these may include MS2, Phi-x 174, E coli, SO2, NOx, H2S, phenolic compounds, and other anionic organic vapors. Due to the number of different bacteria, any type of bacteria may be included and thus may be sorbed onto an anionic contaminant sorbent.
Certain embodiments of the invention comprise LDH compounds that can remove inorganic and organic material(s) from aqueous systems. For example, various LDH compounds and calcined-LDH compounds in accordance with the invention can be synthesized and used to sorb anionic selenium, arsenic, or dicamba (3,6 dichloro-2-methoxy benzoic acid), and other inorganic and organic materials.
In embodiments, biological agents may be substantially sorbed on a surface of layered double hydroxide composition, as shown in
By substantially sorbed it is to be understood that LDH has a certain number of sites that it can sorb various anionic contaminants. At some point, the LDH surface may become full or mostly full of anionic contaminants and can no longer attract and sorb additional biological agents (7). A filter having LDH may be saturated when all or most of the LDH sorbing sites may be occupied by bioagents therefore no further sorption could occur. At this point, the LDH may need to be removed from a filtration system and replaced with either new unsorbed LDH or even re-activated LDH. The lifespan for a filter may be calculated by the per unit sorbing capacity of LDH to certain bioagents. For example, for bacteria, typically 1 gram of LDH can sorb 10^8 bacteria. If it is determined that there are 10^16 bacteria in certain volume of pretreated medium, 2 grams of LDH could be the minimal requirement. To be conservative, a filter may be changed at about 60% to about 75% full. A percentage sorbent value may represent the amount of bioagents sorbed on a medium such as a filter having LDH. While this may include any percentage value, such possibilities may include:
The present invention may include, in embodiments, chemically associating LDH and lignin. In embodiments, a chemical mixture (16) may include an anionic component (11) and a cationic component (12) and may even include LDH (1) and lignin (2). A chemical mixture (16) may include an aggregate of two or more substances that are chemically united. A chemical association may include, but is not limited to ionic bonding, covalent bonding, tether molecule, hydrophobic interaction, and the like as known to those skilled in the art. In other embodiments, LDH and lignin may be mixed where they are not chemically united and may even exist in no fixed proportion to each other.
LDH compounds, as described above, or otherwise described or synthesized, can be associated directly with lignin through ion bonding, or can be associated with lignin through a tether molecule attached to lignin that presents a region sufficiently negatively charged to generate an ionic bond or covalent bond with LDH compound(s). LDH may be tethered to lignin with a variety of tether or linking molecules that may generate covalent bonds between the tether and lignin or between the tether and LDH compound(s) or both, or LDH compounds may become associated with lignin by hydrophobic interaction, or the like. A wide variety of linking or tether molecules could be used to associate LDH compounds with lignin. The tether molecules could be selected on the basis of length, reactive groups, hydrophilicity, resistance to degradation, or the like. Understandably, numerous permutations and combinations of lignin-LDH, or lignin-tether-LDH, can be generated. Each LDH, organo-LDH, lignin-LDH, or lignin-tether-LDH can be used in accordance with the invention to interact with, sequester, sorb, inactive, or remove biological agents from various types of aqueous systems.
The present invention may provide, in embodiments, functionally situating unpowered charged sorbent medium (3) with lignin or even functionally situating an amount of LDH with an amount of lignin. This may include moving at least some of a fluid near or through LDH and some fluid may be moved near or through lignin. Depending on the type of environment, a fluid may be desired to first be filtered through LDH and then through lignin. Or it may be desirable to first filter a fluid through lignin then through LDH. This may include stacking or layering LDH and lignin. In
In embodiments, the present invention may include a cationic contaminant (9). A cationic contaminant (9) may be any cation and may include lead, chromium, zinc, mercury, ammonium, sodium, calcium, iron, copper, and the like. Lignin may include a cationic contaminant sorbent in which cationic contaminants may be attracted and sorbed on lignin.
In embodiments the present invention may include containing an amount of organic composition (17). Referring to
In embodiments, the present invention may provide for moving a fluid in the vicinity of an organic composition (17). Impurities in the fluid may be attracted and may even be sorbed by the organic composition (17). Particularly, organic compositions may sorb non-ionic organic contaminants (20). For example, non-ionic organic contaminants may include benzene, ethybenzene, toluene, xylenes, other aromatic compounds, perchloroethene, trichloroethene, dichloroethene and the like. In embodiments, the present invention may include moving a fluid with a reduction of non-ionic organic contaminants (20).
In other embodiments, a percentage non-ionic organic contaminant reduction amount may be removed from a fluid. While any percentage of removal is possible, such possibilities may include:
In embodiments, the present invention may provide removing harmful biological agents from fluids such as air and water. Some harmful biological agents may include coronavirus, influenze, bacillus anthracis, measles, smallpox virus, among any disease that may cause a severe illness, perhaps even death.
In an embodiment, the present invention may include providing an amount of LDH functionally situated with lignin and organic compositions (17), as previously discussed. An organic composition may be mixed with lignin and LDH. In embodiments, the present invention may provide an organic composition layer, an LDH composition layer and even a lignin layer.
Unknown prior to the invention, was that the positive charges on the surface of LDH compounds make them ideal sorbents with respect to removing a wide range of biological agents, which as a whole or as regions, present negative charge. Although biological agents, such as bacteria, viruses and fungi, may also present some localized positive charges at specific pH values, LDH compounds, organo-LDH compounds, lignin-LDH compositions and even surfactant modified LDH in accordance with the invention are capable of sorption of such bacteria and viruses to capture, to collect, to retain, to sequester, to inactivate, or to remove, them from aqueous liquids or aqueous process systems.
In other embodiments, a percentage biological agent reduction amount may be removed from a fluid. While any percentage of removal is possible, such possibilities may include:
The biological agent removal may be dependent on the contamination type, concentration, LDH type, competition anions and solution pH, among other factors. At a low anion concentration, the reduction rate may be about 100%. At a high concentration, the reduction rate may be about 60%. Accordingly, such removal rates may vary.
In other embodiments, a percentage cationic contaminant reduction amount may be removed from a fluid. While any percentage of removal is possible, such possibilities may include:
As a non-limiting example, certain LDH compounds in accordance with the invention can be used to retain, sequester, or remove, MS2 (an indicator bacterial phage) virus, Phi-X 174, Escherichia coli strains (an indicator bacterium) or Pseudomonas arugenosa from deionised water, tap water, or ground water having a pH range of 6.3-7.5, a residence time of 0 min to 3.0 hr, and temperature at 4-30° C. Viral adsorption efficiency of LDH compounds in such aqueous systems can be 100% and 99.9% at viral concentrations of 2×106 plaque forming unit (PFU)/L and 2×108 PFU/L, respectively. The loading ratio in the case of MS2 adsorption is approximately 1.5×1011 to 8.0×1012 PFU/kg of LDHs. Bacterial adsorption efficiency can be 99.9% at an E. coli concentration of 3.7×108 colony forming unit (CFU)/L. The loading ratio in E. Coli adsorption can be approximately 2.2×1011 CFU/kg of LDHs.
As another non-limiting example, certain LDH compounds in accordance with the invention can be used to retain, sequester, or remove general bacteria from tap water and raw river and creek water having a pH range of 7.0-8.5, a residence time of 15 min to 45 min, and temperature at 20-30° C. Bacterial adsorption efficiency of LDH compounds in such aqueous systems can be 75-100% at background bacterial concentrations of 5×105-2×107 CFU/ml.
In embodiments, LDH and even lignin can be packed or coated to carrier materials to make water filtration units. The filtered water, under this design, may be drinkable or potable. This type of apparatuses may be made as disposable tubes, pumps, columns, and other tools to produce drinkable water in the field where no potable water may be available.
In other embodiments, LDHs and even lignin can be packed into a unit that connects to a tap water faucet directly or even through an adaptor. The filtered water may be free or very low in metals and potential pathogenic agents.
In an embodiment, LDHs or even lignin may be used in a large scale column or vessel filter, which can be added to conventional drinking water or wastewater treatment process as a polishing step for disinfection.
In an embodiment, LDH can be coated to a membrane surface and used to concentrate bio-agents, such as viruses, bacteria, and other biological molecules. The collected LDH-bioagents may serve as samples for detection, identification, characterization and other applications. The LDH containing collector may highly concentrate bioagents present in water bodies; therefore it may increase the sensitivity of early detection of bioagents in waters.
In embodiments, LDH and even lignin can be used as air filters that possess high affinity to potential pathogens in the air. The filters can be used for both residential and commercial buildings.
In embodiments, the present invention may include a water treatment apparatus. A water treatment apparatus may include any type of device or apparatus or system that can be used to remove impurities from water. This may include, but is not limited to batch process containers, flow through containers, coated sand columns, columns, bags, tubes, coating support, and filters. The present invention may include establishing an amount of water desired to be filtered. LDH, lignin, organic composition, individually or in any combination may be contained in a water treatment apparatus or even on a water filter. As previously discussed, different types of impurities may be attracted and even sorbed onto a water filter having various sorbents.
A water treatment apparatus may be attached to any type of plumbing system and may even be attached to a water outlet attachment. In other embodiments, the present invention may include attaching a water treatment apparatus to any type of plumbing such as a water inlet, outlet fixture, or the like. After attachment, the present invention may include running water through the water treatment apparatus to remove any impurities or contaminants that may be in the water. A water outlet attachment may include any type of attachment configured to attach to a conduit, a sink faucet, outdoor conduit, and the like. Water treatment apparatus may be used to treat different quantities of water. Some water treatment apparatus may include a high volume water filter in which large amounts of water may be treated. This may be useful for municipal applications.
In some embodiments, the water treatment apparatus may be portably used for any type of water use perhaps even outdoor use. In other embodiments, the present invention may include a disposable semipermeable unit (27) as shown in
In embodiments, the present invention may include removing impurities with re-activated cationic composition or even re-activated LDH. In an embodiment, the present invention provides for a reactivation element (51). Once an cationic composition or even LDH has sorbed anionic contaminants, such as bioagents, they can be calcinated (e.g., heated) to convert the LDH compound retaining such collected biological agents back to the original structural configuration which can then again be used to collect bio-agents. This makes LDH compounds in accordance with the invention ideal candidates for industrial applications. LDH compounds, along with the sorbed biological agents, can be incinerated at between about 400° C. to about 450° C. for a duration of between about one hour to about three hours depending on the LDH compound (two hours typically being sufficient) to affect complete decomposition of retained organic materials, including bio-agents, and convert the structural configuration of the used LDH compound to the activated structural configuration capable again of attracting, collecting, retaining, or otherwise having an affinity for biological agents or organic compounds. The impurity, contaminant, and even biological agent that was sorbed on LDH may be removed by this process. After removal of the impurities, LDH may be rehydrated and used to sorb other impurities. The ability to regenerate, reactivate, or restore used LDH compounds allows LDH compositions and even organo and LDH compounds, in accordance with the invention, to be repeatedly regenerated and used over and over to attract or collect bio-agents or organic compounds.
After LDH compounds are used to collect bio-agents, they can be dissolved in acid solution and the collected bio-agents can be inactivated in acid solution. Then the LDH compounds can be resynthesized by coprecipitation of an acid solution with base, for example, sodium hydroxide or potassium hydroxide. The ability to regenerate, reactivate, or restore used LDH compounds allows LDH compounds, in accordance with the invention, to be repeatedly regenerated and used over and over to attract or collect bio-agents or organic compounds.
In other embodiments the present invention may include detecting any impurities that may have been sorbed on a sorbent, identifying an impurity or even a biological agent. A biological agent identification element (52) may include some type of sensor that may respond in some fashion when biological agents may be detected.
In an embodiment, the present invention may provide moving at least some of a fluid through a primary medium or even a primary filter. A primary filter (45) may be any kind of filter that is known in the art or even as discussed in this application that can be included in addition to a medium or filter as discussed above. Here, one could simply add a filter as discussed in this invention to a previous existing filtration system. The primary filter may be used as a first filtration system and may prevent at least some of certain impurities, contaminants, components, such as but not limited to dust, dirt, and the like from moving through said primary filter. Then the fluid can pass through an unpowered charged sorbent medium, such as an LDH filter, a lignin filter, or even a combination of the two. This may provide extended use of such unpowered charged sorbent medium. It may be desirable to replace the primary filter more often than the LDH filter, as an example.
In other embodiments, the present invention may include providing an air filter. A filter (43) may be represented in
As shown in
In embodiments, the present invention may include electrostatically sorbing contaminants. This may include creating any type of medium with electric charges or even currents in which impurities or contaminants may be sorbed.
The present invention may include establishing respiratory air in a confined community gathering location. Air or even respiratory air may include air that is intended or may be breathed by an animal or human being. A confined community gathering location may include any location in which a few or even several people may meet and which contaminants may exist in the air. This may include a building, school, home, and the like. An air filter may include LDH so that when air may be moved near or through the air filter, anionic contaminants may be attracted and may even be sorbed to the LDH, as discussed above. The air may be moved and circulated in a confined community gathering location with a reduction in anionic contaminants, for example, bioagents. As such, the present invention may provide for circulating purified air in an aircraft, commercial building, residential structure, vehicle or the like. Further, in embodiments, an air filter may contain lignin which may attract and sorb cationic contaminants, also discussed previously. Air filters may be used in a number of different applications. For example, but not limited to, an air filter may be configured for an airplane, commercial building, a residential structure, a vehicle, and the like.
An individual may be contaminated with a communicable illness, such as the flu, severe acute respiratory syndrome (SARS), or the like. That individual may want to prevent others from catching the illness, or even an individual may desire to protect themselves from breathing in contaminants. In embodiments, the present invention may provide for a wearable mask (37) having an amount of LDH composition on it. In
After using a wearable mask, the mask may have biological agents substantially sorbed on the surface of the LDH composition, as discussed above. In other embodiments, the wearable respirable mask may include providing lignin on a mask and the mask may even include other organic compositions. The wearable mask may include individually or in combination lignin, LDH or an organic compositions for the removal of cationic contaminants, anionic contaminants and non-ionic organic contaminants. As discussed above the lignin may be layered on the mask with LDH or may even be chemically associated with LDH. Any or even all of the sorbents may be sprayed on paper. Of course, any way to attach the sorbents to some sort of filter is meant to be included in this disclosure.
In embodiments, the present invention may provide attracting a first component to a vehicle air filter. In embodiments, an air filter may include a vehicle air filter in which a LDH composition may be provided on an air filter. In other embodiments, an air filter used in a vehicle may contain, but is not limited to a cationic composition, an anionic composition, LDH, lignin, organic compositions, individually or in any combination. A vehicle air filter may be placed in a vehicle possibly near the air vents, or at any place in the car. A vehicle air filter may even include a mechanical device which may be plugged into a cigarette lighter for power. A vehicle may have an enclosed space in which air may be established in the vehicle. Of course, a window or door may be opened in which air flow from the outside may occur. The air in a vehicle or even respiratory air in a vehicle may interact with a vehicle air filter. Any contaminants may be attracted and sorbed on the vehicle air filter. Of course, such contaminants may include anionic contaminants, cationic contaminants, biological agents, and even non-ionic contaminants, as previously discussed. The air can be circulated in the vehicle with a reduction in contaminants and even a reduction in bioagents. Occupants of a vehicle may release contaminants when sneezing or coughing, or even simply breathing creating air which may need to be re-filtered and then re-circulated. In other embodiments, the vehicle air filter may include lignin and may even include other organic compositions to remove anionic contaminants and non-ionic organic contaminants.
The present invention can be used in a wide variety of applications. For example, using an unpowered charged sorbent medium, LDH composition, lignin composition and even organic compositions for commercial use, residential use, personal use, and the like.
Virus stocks were diluted in artificial groundwater (CaCl2 0.075 mM, MgCl2 0.082 mM, KCl 0.051 mM and NaHCO3 1.5 mM) having pH 7.5. A 5 ml aliquot of LDH stock solution (ultrasonically dispersed) was transferred to sterilized 25 ml Screw-top Corex glass centrifuge tubes. To avoid generation of an air-water interface (AWI), 25 ml of virus solutions were transferred into such tubes to form a meniscus at the tube opening and capped. Tubes containing the mixture of LDH solution and virus solution were mixed in an end-over-end shaker at 20 rpm for 3 hr at between 4-7° C. and then centrifuged at 9,000 g for 15 min. Virus concentration in LDH suspensions was determined by plaque assay. All experiments were conducted with three replicates and using control blanks. Data results can be found in Tables 1-10.
LDH-coated sand was generated by transferring 1000 g oxide-removed sand to a plastic beaker and 2 L 5% LDH solution was added. The mixture was autoclaved for 1 hr and oven dried at 80° C. with occasionally stirring. The LDH-coated sand was then washed extensively with distilled water to remove unbound LDH and oven-dried. Acrylate columns having top and bottom plates sealed with O-rings were fitted with a stainless steel screen on the bottom plate. LDH-coated sand was transferred in 1-cm increments into the column prefilled with deaerated water and stirred to prevent layering and air entrapment. Around 100 pore volumes (PV) of buffer solution (AGW) are pumped into the sealed columns with a peristaltic pump to establish a steady-state flow condition. Virus solutions were pumped into separate corresponding columns and outflow samples were collected in 4 ml glass tubes using a fraction collector. The concentrations of viruses in the various samples were determined by plaque assay.
Sand LDH-lignin columns were prepared and equilibrated as described in Example II. Bacteria solutions were pumped into separate columns prepared and outflow samples were collected in 4 ml glass tubes using a fraction collector. The concentrations of bacteria in the various samples were determined by plaque assay.
Sand LDH-lignin columns were prepared and equilibrated as described in Example II and III. Mixtures of virus and bacteria solutions were pumped into separate columns prepared and outflow samples were collected in 4 ml glass tubes using a fraction collector. The concentrations of bacteria in the various samples were determined by plaque assay.
LDH was made in granular form with particle sizes (e.g., 0.3 mm-3 mm diameter) that facilitate reasonable water flow rate. One to five grams of LDH was packed into a 10 ml syringe sized column with glass wool at the outflow port. Bacteria/virus containing water flow into the column and the effluent concentrations were determined by colony/plaque assay. Approximately 200 mls of raw river water (98200 CFU/ml bacteria or 1.8×107 total bacteria) may be filtered with 5 g of LDH material. Effluent water from such a filtration system may be potable with sufficient removal of bioagents. An expanded example of this application is to increase the amount of LDH and column size proportionally to treat larger quantity of raw or partially treated bacteria/virus containing water.
LDH was made in granular form with particle sizes (e.g., 0.3 mm-3 mm diameter) that facilitate reasonable water flow rate. LDH was packed into a sizable column with glass wool at the outflow port. The column may be attached to a pump. Bacteria/virus containing water flew into the column and the effluent concentrations were determined by colony/plaque assay. Approximately 200 mls of raw water (98200 CFU/ml bacteria or 1.8×107 total bacteria) may be filtered with 5 g of LDH column. Effluent water from such a filtration system may be potable with sufficient removal of bioagents. The sizes of the column and pump are flexible based on the amount and quality of water to be filtered. Such a system may be used for military personnel, field travelers, small municipality, rural farms, etc.
LDH was made in granular form with particle sizes (e.g., 0.3 mm-3 mm diameter) that prevents its leakage from a porous wrap such as double layered cheese cloth. Five grams of LDH was packed into a doubled layered cheese cloth and put into a cup of 200 ml of raw river water (8200 CFU/ml bacteria or 1.8×107 total bacteria). The bagged LDH was placed in the water for 30 min with or without stirring. Treated water from such a system may be potable with sufficient removal of bioagents. An expanded example of this application is to increase the amount of LDH material proportionally to treat larger quantity of raw or partially treated bacteria/virus containing water.
LDH was made in powder or granular form and packed in a treatment tank, vessel or similar containers. Amount of LDH is determined based on the quality of the water to be treated. This system may be added to an existing water treatment process as a bioagent removal step. Applications include residential and industrial water treatment facilities.
Air-filter devices were prepared using acrylate columns as described in Example II. Air or other partial pressures of gases are passed through a liquid solution to collect the bacteria or virus, or both, in the volume of gases. The liquid solutions were then pumped into separate columns prepared and outflow samples were collected in 4 ml glass tubes using a fraction collector. The concentrations of bacteria in the various samples were determined by plaque assay. Control blanks were run in a substantially identical fashion to provide a baseline for comparison.
Gas filter devices can be prepared using a carrier material such as ceramic or fabric material. LDH compounds can be used to coat a variety of carrier materials with an amount of LDH compound sufficient to afford nano-structural exclusion or electrostatic sorption of biological agents present in ambient air. Air flow through the gas filter devices can be facilitated with pressure differential generation devices such as pumps or fans. Air or other partial pressure of gases are passed through the gas filter device to collect the bacteria or virus, or both, in the volume of gases. The concentrations of bacteria in various samples can be determined by plaque assay. Control blanks can be run in substantially identical fashion to provide a baseline for comparison. The LDH coated fabrics and particles can be used in one embodiment as an additional filter layer in a respirator canister or in household air purifiers, or the like.
The data gathered may show that LDH in a bag can sorb bacteria such as Pseudomonas aeruginosa and extrapolately other bacteria in water samples (see Tables 6-10). In most of the tests, the LDH bag (ranging from 1 g of LDH to 4 g) removed 90 percent of bacteria from the 500 mL bottle of water (250 mL in Table 6) in 30 min or less (see Tables 6-10 excluding 9, the Zn—Al LDH).
Make LDH bags by sewing a 5×10 cm piece of cloth with fishing wire with a measured amount of LDH inside (size 2.36-4.75 mm). When finished, autoclave the bags at 122 degrees C. for 15 min to sterilize. Prepare dilution test tubes by putting 9 mL of sterile tap water in each one. Centrifuge the bacterial TSB solution for 15 min at 3400 rpm, decant the broth, add sterile water in its place. Dilute the bacterial solution with 1/10 dilutions until desired concentration is obtained. (For this case, 500 mL of ˜10^2 CFU/mL is desired for each bottle so take 5 mL of 10^4 solution in 495 mL of sterile tap water). Take reference samples of the solutions in each of the 500 mL bottles before the LDH bag is added. Plate 100 uL of each bottle (usually do triplicates) onto TSA petri dishes. Place the LDH bags inside of the bottles and start timing. Collect and plate 100 uL of each at desired times. Dip a glass spreader into alcohol, flame, let cool, and use to spread the 100 uL solution on each of the TSA petri dishes. Seal with parafilm, set aside until later to put in an incubator overnight at 35 degrees C. Count the colonies in the morning.
As can be easily understood from the foregoing, the basic concepts of the present invention may be embodied in a variety of ways. It involves both water and air purification techniques as well as devices to accomplish the appropriate filter. In this application, the water and air purification techniques are disclosed as part of the results shown to be achieved by the various devices described and as steps which are inherent to utilization. They are simply the natural result of utilizing the devices as intended and described. In addition, while some devices are disclosed, it should be understood that these not only accomplish certain methods but also can be varied in a number of ways. Importantly, as to all of the foregoing, all of these facets should be understood to be encompassed by this disclosure.
The discussion included in this application is intended to serve as a basic description. The reader should be aware that the specific discussion may not explicitly describe all embodiments possible; many alternatives are implicit. It also may not fully explain the generic nature of the invention and may not explicitly show how each feature or element can actually be representative of a broader function or of a great variety of alternative or equivalent elements. Again, these are implicitly included in this disclosure. Where the invention is described in device-oriented terminology, each element of the device implicitly performs a function. Apparatus claims may not only be included for the device described, but also method or process claims may be included to address the functions the invention and each element performs. Neither the description nor the terminology is intended to limit the scope of the claims.
It should also be understood that a variety of changes may be made without departing from the essence of the invention. Such changes are also implicitly included in the description. They still fall within the scope of this invention. A broad disclosure encompassing both the explicit embodiment(s) shown, the great variety of implicit alternative embodiments, and the broad methods or processes and the like are encompassed by this disclosure. This application seeks examination of as broad a base of claims as deemed within the applicant's right and will be designed to yield a patent covering numerous aspects of the invention both independently and as an overall system.
Further, each of the various elements of the invention and claims may also be achieved in a variety of manners. This disclosure should be understood to encompass each such variation, be it a variation of an embodiment of any apparatus embodiment, a method or process embodiment, or even merely a variation of any element of these. Particularly, it should be understood that as the disclosure relates to elements of the invention, the words for each element may be expressed by equivalent apparatus terms or method terms—even if only the function or result is the same. Such equivalent, broader, or even more generic terms should be considered to be encompassed in the description of each element or action. Such terms can be substituted where desired to make explicit the implicitly broad coverage to which this invention is entitled. As but one example, it should be understood that all actions may be expressed as a means for taking that action or as an element which causes that action. Similarly, each physical element disclosed should be understood to encompass a disclosure of the action which that physical element facilitates. Regarding this last aspect, as but one example, the disclosure of a “sorbent” should be understood to encompass disclosure of the act of “sorbing”—whether explicitly discussed or not—and, conversely, were there effectively disclosure of the act of “sorbing”, such a disclosure should be understood to encompass disclosure of a “sorbent” and even a “means for sorbing” Such changes and alternative terms are to be understood to be explicitly included in the description.
All patents, publications, or other references mentioned in this application for patent or listed in the above listing are hereby incorporated by reference. In addition, as to each term used it should be understood that unless its utilization in this application is inconsistent with such interpretation, common dictionary definitions should be understood as incorporated for each term and all definitions, alternative terms, and synonyms such as contained in the Random House Webster's Unabridged Dictionary, second edition are hereby incorporated by reference. Finally, as to all references listed or specifically mentioned, each is hereby appended and hereby incorporated by reference, however, as to each of the above, to the extent that such information or statements incorporated by reference might be considered inconsistent with the patenting of this/these invention(s) such statements are expressly not to be considered as made by the applicant(s).
Thus, the applicant(s) should be understood to claim at least: i) each of the LDH, lignan-LDH or modified LDH compositions as herein disclosed and described, ii) the related utilities, processes, or methods disclosed and described, iii) similar, equivalent, and even implicit variations of each of these devices and methods, iv) those alternative designs which accomplish each of the functions shown as are disclosed and described, v) those alternative designs and methods which accomplish each of the functions shown as are implicit to accomplish that which is disclosed and described, vi) each feature, component, and step shown as separate and independent inventions, vii) the applications enhanced by the various systems or components disclosed, viii) the resulting products produced by such systems or components, and ix) methods and apparatuses substantially as described hereinbefore and with reference to any of the accompanying examples, x) the various combinations and permutations of each of the elements disclosed, and xi) each potentially dependent claim or concept as a dependency on each and every one of the independent claims or concepts presented.
E. coli
E. coli
E. coli
E. coli
Experiment conditions: Temperature: 20° C.
Background solution: Artificial Ground Water (CaCl2 0.075 mM, MgCl2 0.082 mM, KCl 0.051 mM and NaHCO3 1.5 mM)
pH: 7.5
Sorption time: instaneously flow through
E. coli
E. coli
Pseudomonas aeruginosa) starting bacterial conc. 96 CFU/mL
This application is the United States National Stage of international application no. PCT/US2004/002373, filed 28 Jan. 2004 which claims the benefit of U.S. Provisional Application No. 60/443,548, filed 28 Jan. 2003, each hereby incorporated by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US2004/002373 | 1/28/2004 | WO | 00 | 7/28/2005 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2005/012194 | 2/10/2005 | WO | A |
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| 60443548 | Jan 2003 | US |
