Renewable smart materials for selectively removing pollutants from water and wastewater

Abstract

The present disclosure relates to a system and regenerable molecular media for wastewater purification treatment, and a method for preparing the same. The molecular filter media of the present invention are filter granules and pellets that have a very high surface area and are supplied loose or formed into blocks. They are used in industry for filtration in flow-through filter devices. The disclosed regenerant effectively breaks the bonds and prepares the molecular filter for the next cycle of use.

Description

[Technical field]

[0001] The present invention relates to the technical field of wastewater treatment. More particularly, the present invention relates to a system for wastewater purification treatment and a renewable molecular media and a method for preparing the same. [Background technology]

[0002] In water treatment, the use of activated carbon is considered one of the most economical methods to remove various pollutants. Activated carbon is used in drinking water treatment to remove organic pollutants. Activated carbon can adsorb inorganic molecules such as phosphates and chromates, but the adsorption sites for these components are very limited. The term "refractory compounds" refers to organic polymeric pollutants derived from various industries that have complex aromatic ring structures. Microorganisms, especially fungi, are used to decompose such compounds. The industries where the removal of these pollutants is a challenge are mainly the resin production industry, the pulp and paper industry, and the bleaching industry. The decolorization of wastewater discharged from bleaching and pulp mills is also important as well as the treatment of persistent organic pollutants. Therefore, an integrated approach consisting of all these technologies is a promising solution to treat the compounds. The most commonly used physicochemical methods for the treatment of industrial wastewater are coagulation-flocculation, chemical precipitation, chemical oxidation, membrane filtration, and adsorption. These methods are very effective in removing BOD and COD, but are ineffective in removing persistent compounds. In addition, the chemicals used in the treatment can cause toxicity, and the cost of the chemicals is expensive. Therefore, economical and safe treatment is required for the treatment and removal of persistent compounds. Please see the following literature: CN115057507A relates to a wastewater purification treatment agent and its preparation method, the wastewater purification treatment agent is made of activated carbon, polymeric ferric sulfate and polymeric aluminum chloride as raw materials. The powdered wastewater purification treatment agent is obtained by uniformly mixing activated carbon, polymeric ferric sulfate and polymeric aluminum chloride powder in a specific ratio. In particular, the treatment agent obtained when the mass fraction of the total iron in the polymeric ferric sulfate is 21% or more, the treatment agent obtained when the content of aluminum oxide in the polymeric aluminum chloride powder is 29wt% or more and the basicity is 40-55%, has excellent adsorption and flocculation performance, fast reaction rate, can significantly reduce the COD concentration and turbidity in industrial wastewater, and has obvious decolorization effect. In addition, the preparation method is simple, convenient to use, safe ingredients, and no secondary pollution. Chinese patent CN106517467A discloses a flocculant suitable for polymeric ferric sulfate and containing activated carbon and its preparation method, in which the flocculant obtained by mixing activated carbon, zeolite, ferric sulfate waste liquor, Thiobacillus ferrooxidans, hydrogen peroxide, Agrobacterium tumefaciens, silver nitrate, polyacrylamide, attapulgite, ethylene glycol and water in a certain weight ratio has obviously improved efficiency and stable quality, but the preparation ingredients and preparation method are more complicated, and the cost increases to a certain extent. WO-2011016038-A1 relates to the treatment of an aqueous fluid contaminated with selenium contaminants by mixing or passing the same with an adsorbent material selected from: (i) transition metal oxides or hydroxides, or aluminium nanoparticles or colloids, or mixtures thereof; or (ii) granular, particulate or powdered forms of porous carbon, activated carbon, aluminium oxide or hydroxide, activated alumina, mineral clay, zeolite, or mixtures thereof, on which nanoparticles or colloids of transition metal or aluminium oxide or hydroxide, or mixtures thereof, are supported, to obtain an aqueous fluid purified from selenium. JP5244867B2 relates to a filter medium having a microbial blocking function, a filtration system including such a filter medium, and a method for producing and using the same. JP6728133B2 relates to a composite particulate filtration medium consisting of a mixture of particulate filtration media and nanofibers for removing contaminants from water sources such as drinking water for water purification applications. Despite the widespread use of activated carbon and zeolites in the treatment of polluted liquids, industrial waste, and sewage, it is clear that their durability is limited. To counter such claims, reusable and robust platforms and materials for reducing contaminants and lowering COD in wastewater are the need of the hour. The molecular filter media of the present invention are extremely high surface area filter powders and pellets for lowering COD and removing contaminants. The technology is based on basic filtration foundations such as sand beds, activated carbon, etc., and is a cost-effective technology that performs well against difficult-to-remove contaminants. The information disclosed in the Background section of this disclosure is intended to enhance the understanding of the general background of the present invention and should not be construed as an admission or in any way suggesting that this information forms prior art already known to those of ordinary skill in the art. Summary of the Invention

[0003] The present invention seeks to overcome the problems faced by the prior art, and discloses a system and a renewable molecular media for wastewater purification treatment, as well as a method for preparing the same. In one embodiment of the present invention, the present invention discloses a filter medium for removing contaminants from a polluted liquid, comprising about 70-100% by weight of microporous activated ceramic powder beads; about 0% to about 20% by weight of a binder, and at least excipients (Fe, C). Excipients are active substances added to absorb specific contaminants. To prepare the filter medium, the activated ceramic beads are mixed with the binder, the mixture is processed in an extruder to produce a dense extrudate, the extrudate is further spheronized and converted to green beads by cold working, and finally the green beads are sintered to remove all or part of the binder and provide a stable filter medium. The sintering is performed at a temperature of at least 350°C or higher. In another embodiment of the present invention, the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolite, metal oxides, complex metal oxides such as mica, aluminosilicate oxides, and combinations thereof. Further, the ratio of alumina to silica in the bead material is 1:20 to 20:1, and the shape of the beads is at least one selected from, but not limited to, spherical, thread-like, star-like, snowflake-like, and combinations thereof. In yet another embodiment of the present invention, the beads are activated by an active agent in the fusion, extrusion, molding, slip casting, powder coating, wet molding or dry molding of active particles.Furthermore, the binder is at least a powder converted into liquid and liquid form selected from the group consisting of sucrose, gelatin and starch, cellulose derivatives and polyvinylpyrrolidone, which have improved adhesive properties, crosslinked polyvinylpyrrolidone and microcrystalline cellulose.The excipient is made of a material selected from the group consisting of activated carbon powder, activated carbon granules, activated carbon fiber, zeolite, activated alumina, activated magnesia, diatomaceous earth, sponge iron, activated silica, hydrotalcite, glass, polyethylene fiber, polypropylene fiber, ethylene maleic anhydride copolymer fiber, sand, clay and combinations thereof, but is not limited to these. In a preferred embodiment of the invention, the pore size of the filter media ranges from 0.02 nm to about 2 nm. In an embodiment, the filter media for removing aluminum contamination from a contaminated liquid comprises at least 3% silica beads, alumina and other oxides. In an embodiment, the filter media for removing cyanide contamination from a contaminated liquid comprises filament beads having 30% binder, 30% ferrous sulfate and 30% zeolite. In a preferred embodiment of the present invention, the present invention discloses a regenerant for recharging the filter media in a filter, the regenerant being at least 20% by volume of the molecular filter media. In one embodiment, the regenerant is at least one selected from the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an aqueous composition of at least 90%. Furthermore, the regenerant is selected according to the contaminants to be filtered from the filter media and the contaminated liquid. In one embodiment, the regenerant for recharging the alumina filter media after removing heavy metals and silica contaminated liquid includes 4% acid, plus FeCl3, NaOCl, H2O2, or combinations thereof. In an exemplary embodiment, the present invention provides a method for removing trihalomethanes, heavy metals, aluminum, hardness, bacteria and fungi by providing a filter including a filter media and a pump; then feeding a contaminated liquid to the filter including the molecular filter media; further, once the liquid is purified and the filter media is saturated, the filter media is soaked in a regenerant to effectively regenerate the filter media; and finally, reintroducing the effluent liquid for the next filtration cycle. According to the present invention there is provided a filtering device for purifying a contaminated liquid, said filtering device comprising: (a) at least one frame having an inlet and an outlet; (b) at least one molecular filter media comprising: (i) about 70-100% by weight of a plurality of filter core components comprising microporous activated granules; (ii) about 0-20% by weight of a plurality of extruded filter activator components including a binder; (iii) about 0.5-15% by weight of the plurality of filter components consisting of an active agent; (c) a regenerant in the frame, the regenerant being an aqueous liquid added at least to recharge the filter media; and (d) A pump configured within the housing for transporting the filtered purified liquid therefrom, the pump maintaining pressure within the housing to cause the liquid to flow under or against gravity. In at least one embodiment, the molecular filter media is in the form of a cartridge within a frame for filtering contaminated liquids. In at least one embodiment, a filter media for removing contaminants from a contaminated liquid comprises: - a plurality of filter particles consisting of about 70-100% by weight of microporous active ceramic powder granules; - about 0-20% by weight of the plurality of filter particles consisting of a binder; - at least an active substance added to absorb specific pollutants, a) mixing ceramic beads infused with an active agent with a binder; b) processing the mixture of beads and binder from step (a) in an extruder to produce a high density extrudate; c) spheronizing the extrudates and converting them into green beads by cold process; d) sintering the green beads from step (c) to remove all or a portion of the binder and provide a stable filter media, the sintering being carried out at a temperature of at least 350°C or greater. In at least one embodiment, the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides, and combinations thereof. In at least one embodiment, the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides, and combinations thereof, wherein the ratio of alumina to silica in the bead material is from 1:20 to 20:1. In at least one embodiment, the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides, and combinations thereof, wherein the bead shape is at least one selected from, but not limited to, spherical, thread-like, star-shaped, snowflake-like, and combinations thereof. In at least one embodiment, the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides and combinations thereof, in which the beads are infused with an active agent consisting of a metal salt (which imparts selective absorption properties to the beads) using a process selected from extrusion, molding, slip casting, powder coating, wet molding or dry molding of the active particles. In at least one embodiment, the binder is at least a liquid selected from the group consisting of PEG, polyvinyl acetate, sucrose, gelatin and starch, cellulose derivatives and polyvinylpyrrolidone, cross-linked polyvinylpyrrolidone and microcrystalline cellulose, which have improved adhesive properties. In at least one embodiment, the excipient comprises a material selected from the group consisting of, but not limited to, activated carbon powder, activated carbon granules, activated carbon fiber, graphene, zeolite, activated alumina, activated magnesia, diatomaceous earth, sponge iron, activated silica, hydrotalcite, glass, polyethylene fiber, polypropylene fiber, ethylene maleic anhydride copolymer fiber, sand, clay, and combinations thereof. In at least one embodiment, the pore size of the filter media is within the range of 0.02 nm to about 2 nm, as defined by the particular ions used in the preparation of the material. In at least one embodiment, the filter media comprises: a. Sintered ceramic beads consisting of 70% alumina and 30% binder, spheroidized, dried, treated with 6% KMnO4, and heated to 350°C; and b. Treating at least 20% of the ceramic beads from step a) with at least 80% of a core component, the core component being a high quality carbon for effectively adsorbing recalcitrant organic and inorganic matter to reduce the chemical oxygen demand of the contaminated liquid. In at least one embodiment, the filter media is composed of at least 94% alumina and other oxides to remove silica contamination from the contaminated liquid. In at least one embodiment, the filter media is comprised of filament beads having 30% binder, 30% ferrous sulfate, and 40% zeolite to remove cyanide contamination of the contaminated liquid. In at least one embodiment, the regenerant for recharging the filter media in a filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an at least 90% aqueous composition. In at least one embodiment, the regenerant for recharging the filter media in a filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an at least 90% aqueous composition, where the regenerant is at least 20% by volume of the molecular filter media. In at least one embodiment, the regenerant for recharging the filter media in the filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an at least 90% aqueous composition, wherein the regenerant is selected according to the filter media and the contaminants to be filtered from the contaminated liquid. In at least one embodiment, the regenerant for recharging the filter media in the filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizer, and combinations thereof, in an at least 90% aqueous composition, wherein the regenerant comprises FeCl3, NaOCl, and H2O2, or combinations thereof, in addition to 4% acid, for recharging the alumina filter media after removing heavy metal and silica contaminated liquids. According to the present invention, there is provided the following method for removing trihalomethanes, heavy metals, aluminum, hardness, bacteria and fungi: - Providing a filter including a filter medium and a pump; - feeding the contaminated liquid to a filter containing a molecular filter media; - Once the liquid has been clarified and the filter media is saturated, the filter media is soaked in a regenerant to effectively regenerate the filter media; and - Reintroduce the effluent for the next filtration cycle. Description of the Preferred Embodiments

[0004] Since this is a patent document, general broad rules of interpretation should be applied when reading it. Everything described and shown in this document is an example of the subject matter of the claims appended below. The specific structural and functional details disclosed herein are merely for the purpose of illustrating how to make and use the examples. Several different embodiments and methods not specifically disclosed herein may be included within the scope of the claims. Thus, the claims may be embodied in many alternative forms and should not be interpreted as being limited to only the examples described herein. The terms "comprises," "comprising," or other variations thereof, as used in this disclosure, are intended to cover a non-exclusive inclusion, such that a device, apparatus, system, assembly, or method consisting of a list of components or a sequence of steps, does not include only those components or steps, but may include other components or steps not expressly listed or inherent to such apparatus, assembly, or device. In other words, one or more elements or steps in a system or device or process proceeded by "comprises a" or "comprising" does not, without more constraints, exclude the presence of other elements or additional elements or additional steps in the system or device or process, as the case may be. Rather, an exclusive modifier such as "only" or "single" may preclude the presence or addition of other subjects in the modifier. The use of permissive terms such as "may" or "can" reflects optionality such that the modifier is not necessarily present, while the absence of a permissive term does not reflect compulsion. In listing items in the exemplary embodiments, conjunctions and inclusive terms such as "and," "together," and "or" include, without excluding, all combinations of one or more of the listed items. The use of "etc." is defined as "et cetera" and indicates the inclusion of all other elements belonging to the same group of the preceding item in any "and / or" combination(s). The modifiers "first," "second," "another," and the like may be used herein to describe various items, but do not limit the modified items to any order. These terms are used only to distinguish one element from another. When there is an ordinal number such as "second" or higher, there must simply be that many elements, without necessarily any difference or other relationship between those elements. When an element is referred to as being "connected," "coupled," "on," "attached," "fixed," or otherwise related to another element, it may be directly connected to the other element, or there may be intervening elements present. In contrast, when an element is referred to as being "directly connected" or "directly coupled" to another element, there are no intervening elements present. Other words used to describe the relationship between elements should be interpreted similarly (e.g., "between" vs. "directly between," "adjacent" vs. "directly adjacent," etc.). As used herein, singular forms such as "a", "an" and "the" are intended to include both the singular and the plural unless the context expressly dictates otherwise. An indefinite article such as "a" or "an" introduces or refers to any modified term, whether previously introduced or not, and a definite article such as "the" refers to the same term previously introduced. Relative terms such as "approximately", "more than" and terms of degree such as "approximately" or "substantially" reflect a 10% variation in the modified value or the full range of imprecision that achieves the functionality of the modified term when understood by one of ordinary skill in the art in the technical context. Precision and non-variation are expressed by opposing terms such as "exactly". The structures and operations described below may occur out of the order described and / or depicted in the figures. For example, two operations and / or figures shown in succession may in fact be performed simultaneously or in the reverse order depending on the functionality / acts involved. Similarly, individual operations within the exemplary methods described below may be performed iteratively, individually, or sequentially to provide a loop or other sequence of operations apart from the exact operations described below. Any embodiment or method having the features and functionality described below, in any workable combination, should be presumed to be within the scope of the exemplary embodiments. The inventors have recognized that, despite the widespread use of available treatments to reduce pollutants, persistent COD is not reduced sufficiently and operating costs are very high. Furthermore, operating costs are high because the filter media is used up during the treatment. Thus, there remains a need for a novel method of regenerating filter media in such applications that is not only environmentally friendly but also economical and provides excellent results for removing pollutants and reducing persistent COD. To overcome these problems, the inventors have developed the exemplary embodiments and methods described below to address these and other problems recognized by the inventors with unique solutions enabled by the exemplary embodiments. In one embodiment, the present invention relates to a system and method for reducing persistent chemical oxygen demand, herein referred to as COD, which is inorganic and organic contaminants in wastewater, sewage, medical wastewater, and industrial wastewater. The molecular filter media of the present invention are extremely high surface area filter powders and pellets that are supplied as standalones for industry to use in stacks and existing filter equipment. The technology is based on basic filtration infrastructure such as sand beds, activated carbon, etc., and is a cost-effective technology that performs well against difficult to remove contaminants. In a preferred embodiment, the present invention relates to a filtration device for purifying a contaminated liquid, comprising: (a) at least one frame having an inlet and an outlet; and (b) at least one molecular filter media comprising (i) about 70-80% by weight of a plurality of filter core components made of microporous activated beads, (ii) about 0-20% by weight of a plurality of filter activation components that are extruded and may include a binder, and (iii) about 0.5%-about 5% by weight of a plurality of filter particle components made of excipients; (c) a regenerant in the frame, the regenerant being at least an aqueous liquid that is added to recharge the filter media; and (d) a pump in the frame for transporting the liquid after filtration, the pump for maintaining pressure in the frame to flow the liquid under or against gravity. In another embodiment of the present invention, the molecular filter media of the present invention is in the form of a cartridge within a frame for filtering contaminated liquids. In an exemplary embodiment of the present invention, the present invention discloses a filter medium for removing contaminants from a contaminated liquid, the filter medium comprises a plurality of filter particles of about 70-about 100% by weight of microporous activated ceramic powder beads; about 0%-about 20% by weight of the plurality of filter particles of a binder, at least excipients (Fe, C), the excipients being active materials added to absorb specific contaminants. To prepare the filter medium, a) the activated ceramic beads are mixed with the binder; (b) the mixture of beads and binder from step a) is then processed in an extruder to produce a dense extrudate; (c) the extrudate is spheronized and converted into green beads by cold working; and finally (d) the green beads from step (c) are sintered to remove all or part of the binder and provide a stable filter medium, wherein the sintering is performed at a temperature of at least 350 OC or higher. In another embodiment of the present invention, the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolite, metal oxides, complex metal oxides such as mica, aluminosilicate oxides, and combinations thereof. Further, the ratio of alumina to silica in the bead material is 1:20 to 20:1, and the shape of the beads is at least one selected from, but not limited to, spherical, thread-like, star-like, snowflake-like, and combinations thereof. In yet another embodiment of the invention, the beads are activated by KMNO4 infusion, extrusion, molding, slip casting, powder coating, wet molding or dry molding of the active particles. In yet another embodiment of the present invention, the binder is at least a liquid and a powder converted into liquid form selected from the group consisting of PEG, polyvinyl acetate, sucrose, gelatin and starch, cellulose derivatives and polyvinylpyrrolidone, which have improved adhesive properties, crosslinked polyvinylpyrrolidone and microcrystalline cellulose. In another embodiment of the present invention, the excipient comprises a material selected from the group consisting of, but not limited to, activated carbon powder, activated carbon granules, activated carbon fiber, zeolite, activated alumina, activated magnesia, diatomaceous earth, sponge iron, activated silica, hydrotalcite, glass, porcelain, polyethylene fiber, polypropylene fiber, ethylene maleic anhydride copolymer fiber, sand, clay, and combinations thereof. In one embodiment, the excipient is high quality carbon, with activated carbon being about 79% of various mesh sizes. 75% of the excipient is 30 / 60 mesh size, which is in the range of 400-500 microns, mixed with 4 / 8 mesh size to give the necessary structure. In a preferred embodiment of the invention, the pore size of the filter media ranges from 0.02 nm to about 2 nm and is defined by the specific ions used in the preparation of the material. In one embodiment of the present invention, the filter media for reducing the chemical oxygen demand of the contaminated liquid comprises: 70% alumina and 30% binder, which after spheronization and drying is treated with 6% KMnO4 to provide ceramic beads and heated to 350 for sintering; and at least 20% of the ceramic beads from step a) are treated with at least 80% excipient, which is high quality carbon for effectively adsorbing recalcitrant organic and inorganic matter. In yet another embodiment of the present invention, a filter medium for removing aluminum contamination from a contaminated liquid comprises at least 35% silica beads, alumina and other oxides. In one embodiment, a filter medium for removing cyanide contamination from a contaminated liquid comprises filament beads having 30% binder, 30% ferrous sulfate, and 30% zeolite. In a preferred embodiment of the present invention, the present invention discloses a regenerant for recharging a filter medium in a filter, the regenerant being at least 20% by volume of the molecular filter medium. In an embodiment, the regenerant is at least one selected from the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof in at least 90% aqueous composition. Furthermore, the regenerant is selected according to the filter medium and the contaminants to be filtered from the contaminated liquid. In another embodiment of the present invention, a regenerant for recharging alumina filter media after removing heavy metal and silica contaminated liquids includes 4% acid plus FeCl3, NaOCl and H2O2, or a combination thereof. In an exemplary embodiment, the present invention relates to a method for removing trihalomethanes, heavy metals, aluminum, hardness, bacteria, and fungi by providing a filter comprised of a filter media and a pump; then feeding the contaminated liquid to a filter containing a molecular filter media; further, once the liquid has been purified and the filter media is saturated, soaking the filter media in a regenerant, effectively regenerating the filter media; and finally, reintroducing the effluent for the next filtration cycle. In one embodiment, the material has excellent absorptive and redox capabilities to break down organic matter into simpler molecules. It also has excellent antibacterial properties to resist biofouling. (Table 1a, Table 1b) [Table 1(a)] [Table 1(b)] In one embodiment, the oxidizer and media work together to oxidize dissolved solids into suspended solids that are filtered. The media drives the chemical reaction, removes the solids produced by oxidation, and is periodically backwashed from the filter vessel. Chlorine, supplied as sodium hypochlorite or bleach (12.5% ​​NaOCl or greater), is the preferred oxidizer because it is relatively inexpensive, readily available worldwide, and effective. Other oxidizers, such as hydrogen peroxide (H2O2), chlorine dioxide (ClO2), and ozone, may also be used as long as residual amounts can be measured and maintained. In one embodiment, the regenerant is introduced into the medium (about 10-20% by volume relative to the weight) and allowed to dwell for at least 1 hour, preferably overnight, after which the medium is rinsed with water and the leachate is either reused or neutralized and appropriately disposed of. In one embodiment, the concept of oxidation-reduction beads is introduced, where special resistant zirconia beads are impregnated with oxidizing and reducing agents. For example, peroxide / oxidizing agents can be impregnated to harden scrubber water with sulfite / bisulfite, which is then oxidized to sodium sulfate and water. Sodium sulfate can be used for industrial purposes such as cement production. The treated water can be reused depending on the application. Ultimately, such an approach will be used to oxidize and reduce chemical species in the water scrubber, converting the molecules into industrially relevant chemical species that can be reused. Organic acids such as sodium metabisulfite, ascorbic acid, oxalic acid, phosphorous acid, hypophosphorous acid, etc. can be used for the reduction treatment. EXAMPLES

[0005] Example 1: To reduce COD: The filter media was produced according to a scheme that included 70% alumina powder and 30% binder, which after spheronization and drying was treated with power mixed with 4-10% KMnO4, and then heated to 350-750°C to obtain ceramic beads. At least 20% of the produced beads, obtained in this previous step, were treated with at least 80% excipient, which is high-quality carbon to effectively adsorb pollutant molecules. Moreover, the regenerant of this COD-reducing filter media was 4% HCl + 4% H2SO4 with 0.1% FeCl3 by weight in water. Example 2: For removal of silica and heavy metals (Mn, Fe, As, Pb, H2S, etc.): The filter media was produced according to the scheme containing more than 94% alumina and the remaining binder, which after spheronization and drying was treated with <1% KMnO4 and then sintered by heating to 750 °C to obtain ceramic beads. These beads were directly used as silica concentration reducing molecular filters. Furthermore, regenerants containing 4% acid and FeCl3, NaOCl and H2O2, NaOH or their combinations were added to recharge the alumina filter media after removing heavy metals and silica from the wastewater. For silica removal: To remove silica, a molecular filter with excellent adsorption power was used. Bases such as sodium hydroxide and dilute amine solutions were used as regenerants, and the silica underwent an ion exchange reaction with the hydroxide on the surface (Table 2). [Table 2] To reduce the amount of lead contamination in your sample: For lead removal, a highly adsorptive molecular filter media was used according to the scheme of Example 2. The regenerant used was an acid, and the lead underwent a ceramic ion exchange reaction in which the hydrogen ions of the acid regenerant were replaced with metal ions (Table 3). [Table 3] Example 3: For hardness removal: The filter media, which consisted of more than 94% alumina, 3-4% silica, the remaining 2-3% binder and traces of exchangeable ions such as sodium and potassium, was spheronized, dried, and then sintered at 250°C to produce ceramic beads. The beads were directly used as hardness reduction molecular filters. In addition, a regenerant containing 0-50% NaOH, amines, or a combination thereof was added to recharge the filter media after filtering the wastewater. The ratio of sodium:silica:alumina in the ion exchange process was in the range of 1:1:2. For removing water hardness: First, the amount of hardness contained in a given water sample was identified in the same manner as in Example (3) above using different media and molecular filters. Observations showed that the hardness of the blank sample solution and the sample solution soaked overnight was successfully reduced (Table 4). [Table 4] When the filter media became saturated, a regenerant was added to regenerate the filter media and reuse it. During the treatment process, the Na ions in the molecular filter media were replaced by Ca / Mg, and after treatment with the regenerant, the Ca / Mg were removed, freeing up more sites for filtration (Table 5). [Table 5] Removal of calcium ions: First, the amount of hardness in water samples collected from four different water sources was identified using different media and molecular filters in the same manner as in Example (3) above. Observations showed that the hardness of the blank sample solution and the sample solution soaked overnight was successfully reduced (Table 6). [Table 6] Example 4: For orthophosphate removal: The filter media was produced according to the scheme, containing more than 94% alumina and the remaining binder, which, after spheronization and drying, was treated with 15% KMnO4, then heated to 350 °C and sintered into ceramic beads. The beads were used as they were for orthophosphate removal. In addition, a regenerant containing a combination of NaOCl and H2O2, or other oxidizing agents, was added to reload the filter media after wastewater treatment. Other oxidizing agents, such as chromate or ceria, could be used instead of KMnO4. Reduction of Sodium Orthophosphite in Electroless Nickel Plating Baths: The orthophosphite level in the bath must be kept below 100 g / L for the bath to function well. It was observed that treatment of the wastewater with certain filter media resulted in the decomposition of sodium orthophosphite, allowing the bath to be used for longer and with greater metal recovery. It was concluded that in an aged bath, the amount of sodium orthophosphite was reduced from 153.92 gm / L to about 44.4 g / L after passing through the filter media. (Table 7) [Table 7] Example 5: For bisulfite removal: The filter media was manufactured according to a scheme containing about 60% alumina, 2-10% zirconia, 35% silica, and the rest binder, which was spheroidized, dried, and then sintered at 350-750 °C to obtain tough ceramic beads. These beads are a strong substrate for effectively absorbing and donating oxidizing and reducing agents to transform wastewater. For example, to recharge filter media for treating bisulfate wastewater, regenerants containing NaOCl and H2O2 or their combinations were used along with other oxidizing agents such as aeration with air. Example 6: For removing cyanide: The filter media was fabricated according to a scheme in which the active materials were encapsulated in the matrix by drawing into filaments containing 10-30% binder, 10-30% ferrous sulfate, and 30-50% zeolite, drying, and then heating to 350°C for sintering. In addition, a regenerant containing ferrous sulfate and a reducing agent or a combination thereof was added to recharge the filter media after effluent treatment. Example 7: For aluminum decontamination: The filter media was manufactured as planned with 30% binder, 20-30% silica, and the rest metal oxides and exchangeable ions such as sodium, lithium, and zirconium, which were then spheronized, dried, and sintered at 750°C to obtain glassy ceramic beads. In addition, regenerants containing more than 10% NaOH, amines, HCl, and their combinations were added to recharge the filter media after wastewater treatment. In order to control the amount of aluminum in the anodizing bath, the bath was treated with molecular filter media as described in the above scheme (Example 7), and the amount of aluminum before and after treatment was calculated. As a result, it was observed that the molecular filter media can effectively reduce the total Al amount from 12.42 g / L to 5.94 g / L (Table 8). [Table 8] Example 8: Conversion of scrubber water containing a mixture of sulfite and bisulfite to sulfate: The filter media was manufactured according to a scheme containing about 60% alumina, 2-10% zirconia, 35% silica, and the remainder binder, which was spheroidized, dried, and then sintered at 350-750 °C to provide tough ceramic beads. These beads are a strong substrate for effectively absorbing and donating oxidizing and reducing agents to transform wastewater. For example, to recharge filter media for treating bisulfite wastewater, regenerants containing NaOCl and H2O2 or their combinations were used along with other oxidizing agents such as aeration with air. To study the conversion of sulfate from bisulfite and sulfite, the concept of oxidation-reduction beads was introduced, where special resistant zirconia beads were impregnated with oxidizing and reducing agents. For example, peroxide / oxidizing agents were impregnated to harden scrubber water with sulfite / bisulfite, which was then oxidized to sodium sulfate and water. Sodium sulfate can be further used for industrial applications such as cement production. The blank value was 68.0 cm 3 (Table 9) [Table 9] Since sulfite was still present in the above experiment, further experiments were carried out as follows (Table 10). [Table 10] The end result was that the molecules in the scrubber water were uniformly converted to oxidized species, namely sulfates. Example 9: Flow mode experiments for industrial wastewater treatment: Industrial wastewater was passed through the cartridge in flow mode, and the flow rate was maintained at 10 liters per hour. The amount of COD reduction media in the column was ~180g. After repeated filtration, the filter medium became saturated, and to regenerate the filter medium, a regenerant was introduced into the filter medium and allowed to interact with the filter medium overnight. After the regenerant treatment, the filtration capacity of the treated filter medium was restored. (Table 11) [Table 11] According to the advantages of the present invention compared to existing formulations, the present invention is to provide a major change in the field of wastewater treatment with a cost-effective, reusable and energy-efficient process that reduces pollutants and lowers COD for wastewater treatment. In industrial wastewater treatment applications, there is often no functional COD lowering mechanism, e.g. metal finishing, oil and gas produced water for food and beverages, fractionated flowback, production and industrial wastewater from metal finishing and textile dyeing industries. There is also a need to find a cost-effective way to recycle the filter media to lower operating costs. The first treatment step consists of the oxidizing agent and filter media working together to oxidize the dissolved solids into suspended solids that are filtered. The second stage of the integrated process is to treat the saturated filter media with a regenerant to recharge the filter media, further removing dissolved organic and inorganic compounds, and finally making the purified wastewater suitable for discharge or reuse. Ultimately, approaches such as conversion of sulfate from bisulfite and sulfite will be used to oxidize and reduce species in water scrubbers to industrially relevant ones that can reuse the molecules. Organic acids such as ascorbic acid, oxalic acid, phosphorous acid, and hypophosphorous acid can be used for the sodium metabisulfite reduction process. Technical Advantages

[0006] Advanced wastewater treatment molecular filters (media) remove / reduce persistent COD / turbidity and color, improving the efficiency of wastewater treatment plants (ETP's). Customizable filter media that can be designed to remove selective molecules from wastewater streams, depending on the wastewater and the respective contaminants, such as persistent organics, silica, persistent COD, cyanides, heavy metals, sulfides, etc. · Renewable media, with on-site refurbishment processes allowing for multiple cycles of use. Molecular filters are very high surface area filter powders or pellets that can be supplied singly by industry for use in stacks or existing filter equipment, or can be formed into blocks for the same purpose. The technology is based on a plug-and-play flow-mode filtration setup and basic filtration infrastructure such as sand beds and activated carbon. A cost-effective technology that performs well against hard-to-remove contaminants. Molecular filters are designed to remove selective molecules from wastewater streams, such as refractory organics, silica, COD, cyanide, heavy metals and sulfides, allowing them to be treated without the cumbersome processes and chemicals used in wastewater treatment plants (ETPs). · Filter media can be introduced into an FRP (fiber reinforced plastic, a plastic type material that packs molecular filters) case system at the outlet of the problem wastewater. The filter media captures the problem in the wastewater and delivers colorless, odorless, purified water (in most cases, cased) that can be recycled or further treated in the plant ETP. Generally, filter media is used in tertiary treatment, but it can also be used as primary treatment before RO water treatment, extending the life of the membrane filter by simply removing ions first. This pretreatment helps reduce the usage of expensive chemicals in the ETP. It will be further understood that the functions or structures of multiple components or steps may be combined into a single component or step, or that the functions or structures of one step or component may be split into multiple steps or components. The present invention contemplates all of these combinations. Unless otherwise stated, the dimensions and shapes of the various structures depicted herein are not intended to limit the present invention, and other dimensions and shapes are possible. In addition, while a feature of the present invention may be described in the context of only one of the illustrated embodiments, such feature may be combined with one or more other features of other embodiments for any given application. It will also be understood from the above that the creation of the unique structures herein and their operation also constitute methods in accordance with the present invention. The present invention also encompasses intermediate and final products resulting from the practice of the methods herein. The use of "comprising" or "including" also contemplates embodiments that "consist essentially of" or "cosist of" the recited features. Although embodiments of the present invention have been described in terms that are specific to structural features, it should be understood that the present invention is not necessarily limited to the particular features described. Rather, specific features and methods are disclosed as embodiments for the present invention. Numerous modifications and adaptations of the systems / components of the present invention will be apparent to those skilled in the art, and it is therefore intended by the appended claims to cover all such modifications and adaptations that fall within the scope of the present invention.

Claims

1. 1. A filtration device for purifying a contaminated liquid, comprising: (a) at least one frame having an inlet and an outlet (b) at least one molecular filter medium; (i) about 70-100% by weight of a plurality of filter core components comprising microporous activated granules; (ii) about 0-20% by weight of a plurality of extruded filter active ingredients, including a binder. (iii) about 0.5-15% by weight of the plurality of filter components consisting of an active agent; (c) a regenerant in the frame, the regenerant being at least an aqueous liquid added to recharge the filter media; and (d) a pump configured within said frame for pumping therefrom the purified filtered liquid, said pump maintaining pressure within the frame to drive the liquid under or against gravity.

2. 2. The filtration device of claim 1, wherein the molecular filter media is in the form of a cartridge within the frame for filtering contaminated liquids.

3. 10. The filtration device of claim 1, comprising a filter media for removing contaminants from a contaminated liquid, the filter media comprising: - a plurality of filter particles consisting of about 70-100% by weight of microporous active ceramic powder granules; - about 0-20% by weight of the plurality of filter particles consisting of a binder; - at least an active substance added to absorb specific pollutants, where a) mixing ceramic beads infused with an active agent with a binder; b) processing the mixture of beads and binder from step (a) in an extruder to produce a high density extrudate; c) spheronizing the extrudates and converting them into green beads in a cold process; d) sintering the green beads from step (c) to remove all or a portion of the binder to provide a stable filter media, wherein the sintering is performed at a temperature of at least 350° C. or greater.

4. 4. The filter media of claim 3, wherein the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides, and combinations thereof.

5. 4. The filter media of claim 3, wherein the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides, and combinations thereof, wherein the ratio of alumina to silica in the bead material is from 1:20 to 20:

1.

6. The filter media according to claim 3, wherein the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolite, metal oxides, composite metal oxides such as zirconia, mica, alumino-silico-oxides, and combinations thereof, and the shape of the beads is at least one selected from the group consisting of spherical, filamentous, star-shaped, snowflake-shaped, and combinations thereof.

7. 4. The filter media of claim 3, wherein the bead material is at least a porous ceramic powder selected from the group consisting of alumina, carbon, silica, zeolites, metal oxides, complex metal oxides such as zirconia, mica, aluminosilico-oxides, and combinations thereof, and wherein the beads are impregnated with an active agent consisting of a metal salt (to impart selective absorption properties to the beads) using a process selected from extrusion, molding, slip casting, powder coating, wet molding, or dry molding of active particles.

8. 4. The filter media of claim 3, wherein the binder is at least one selected from the group consisting of PEG, polyvinyl acetate, sucrose, gelatin and starch, cellulose derivatives and polyvinylpyrrolidone, polyvinylpyrrolidone with improved adhesion properties, cross-linked polyvinylpyrrolidone and microcrystalline cellulose.

9. 4. The filter media of claim 3, wherein the filler is comprised of a material selected from the group consisting of activated carbon powder, activated carbon granules, activated carbon fiber, graphene, zeolite, activated alumina, activated magnesia, diatomaceous earth, sponge iron, activated silica, hydrotalcite, glass, polyethylene fiber, polypropylene fiber, ethylene maleic anhydride copolymer fiber, sand, clay, and combinations thereof.

10. 4. The filter media of claim 3, wherein the pore size of the filter media is within the range of 0.02 nm to about 2 nm and is defined by the specific ions used in the preparation of the material.

11. 4. The filter media of claim 3, a. 70% alumina and 30% binder, which after spheroidization and drying is 6% KMnO 4 and heated to 350° C.; and b. Treating at least 20% of the ceramic beads from step a) with at least 80% of a core component, the core component being a high quality carbon for effectively adsorbing refractory organic and inorganic matter so as to reduce the chemical oxygen demand of the contaminated liquid.

12. 4. The filter media of claim 3 comprising at least 94% alumina and other oxides for removing silica contamination of contaminated liquids.

13. 4. The filter media of claim 3, comprising filament beads containing 30% binder, 30% ferrous sulfate, and 40% zeolite for removing cyanide contamination of contaminated liquids.

14. 2. The filtration apparatus of claim 1, wherein the regenerant for recharging a filter media in the filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an at least 90% aqueous composition.

15. 10. The filtration device of claim 1, wherein the regenerant for recharging the filter media in the filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an aqueous composition of at least 90%, wherein the regenerant is at least 20% by volume of the molecular filter media.

16. 2. The filtration apparatus of claim 1, wherein the regenerant for recharging the filter media in the filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an at least 90% aqueous composition, wherein the regenerant is selected according to the filter media and contaminants to be filtered from the contaminated liquid.

17. 10. The filtration apparatus of claim 1, wherein the regenerant for recharging the filter media in the filter comprises at least one of the group consisting of an acid, an alkali, a ferrous salt, a zinc salt, an oxidizing agent, and combinations thereof, in an aqueous composition of at least 90%, wherein the regenerant comprises, in addition to 4% acid, FeCl 2 , 4% ferrous salt ... 3 , NaOCl and H 2 O 2 or a combination thereof.

18. 1. A method for removing trihalomethanes, heavy metals, aluminum, hardness, bacteria, and fungi, comprising: - providing a filter including a filter medium and a pump; - feeding the contaminated liquid to a filter containing a molecular filter media; - once the liquid has been clarified and the filter media has been saturated, the filter media is soaked in a regenerant to effectively regenerate the filter media; and - Reintroduce the effluent for the next filtration cycle.

Images