Reactive filtration
Claim Score by NHIP
Abstract
In one embodiment, a reactive filtration method includes continuously regenerating a reactive filter media while simultaneously filtering contaminants from fluid flowing through the filter media. In one embodiment, regenerating the reactive filter media comprises mixing metal granules with the filter media and agitating the mixture. In another embodiment, regenerating the reactive filter media comprises introducing a metal in the fluid flowing through the filter media and agitating the filter media. In one embodiment, a method for removing phosphorus, arsenic or a heavy metal from water includes introducing a metal salt reagent into the water at a molar ratio of 5:1 to 200:1 to the phosphorous or the arsenic in the water and passing the water through a bed of moving sand.

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Expired 3 December 2023, 2.8 years ago.
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10 claims: 3 independent, 7 dependent
- 1A method, comprising:adding a metal salt reagent to water in sufficient quantity and concentration to allow precipitation reactions between the metal salt reagent and a dissolved contaminant in the water to go to at least near completion and to leave unreacted metal salt reagent in the water;flowing the water through a serpentine pipe configured to produce more turbulent flow through bends in the pipe and less turbulent flow through straight-aways in the pipe inducing turbulence in the water ;and then flowing the water through a bed of moving filter media, wherein unreacted metal salt reagent in the water reacts with the filter media to generate a reactive metal oxide or hydroxide coating on the filter media to adsorb dissolved contaminants remaining in the water.
- 7Broadest claimClaim Score 90, very broad(NHIP)A method comprising continuously regenerating a filter media by abrading the filter media sufficient to allow surface sites on the filter media to be available for reacting with a chemical reagent, while simultaneously filtering contaminants from fluid flowing through the filter media and continuously adding the chemical reagent to the fluid supplied to the filter media for reaction with the surface sites.
- 9A method comprising:introducing iron oxides into water supplied to a moving bed media filter effective to precipitate contaminants from the water and to form iron oxide coated media surfaces in the moving bed media filter;simultaneously filtering the precipitated contaminants with the moving bed media filter and sorbing other contaminants to the iron oxide coated media surfaces;abrading sorbed contaminant-iron solids from the iron oxide coated media surfaces;separating the precipitated and sorbed contaminants from the iron oxide coated media surfaces;and, continuously introducing additional iron oxides to the moving bed media filter sufficient to regenerate the iron oxide coated media surfaces.
Independent claims3
41 paragraphs in 7 sections, as filed
CROSS
id="REI-00001" date="20131105"
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id="REI-00001"
REFERENCE TO RELATED
id="REI-00002" date="20131105"
APPLICATION
id="REI-00002"
id="REI-00003" date="20131105"
APPLICATIONS
id="REI-00003"
0001The present patent application is a reissue application of commonly assigned U.S. Pat. No. 7,713,423, issued May 11, 2010, which is a divisional of, and claims priority from, U.S. patent application Ser. No. 10/727,963, filed Dec. 3, 2003 now U.S. Pat. No. 7,399,416 and entitled “Reactive Filtration” which claims the benefit of U.S. Provisional Patent Application 60/430,756, filed Dec. 4, 2002. The disclosuresdisclosure of the above mentioned patent applications are incorporated herein by reference in their entireties.
STATEMENT OF RIGHTS TO INVENTIONS MADE UNDER FEDERALLY FUNDED RESEARCH AND DEVELOPMENT
0002Part of the work performed during the development of embodiments of the invention was funded by the United states Environmental Protection Agency under contract no. EPA-EPSCoR GR827683-01-0. The United States government may have certain rights in the invention.
BACKGROUND
0003Phosphorus exists in waters as dissolved ortho-phosphate, polyphosphate, and complex organo-phosphorus compounds. In typical phosphorus-containing waste waters, such as the secondary or tertiary effluents of municipal waste water treatment plants, there is a dissolved fraction of phosphorus compounds, primarily in the form of ortho-phosphate and poly-phosphates, and a suspended fraction of micro-particulate phosphorus-containing solids. Trace levels of arsenic are sometimes found in some sources of drinking water and in higher concentrations in some waste waters. Arsenic can occur in natural waters as reduced arsenite, As(III), or oxidized arsenate, As(V).
0004Several methods are currently utilized for the removal of phosphorus compounds, arsenic, and other contaminants from waste water. Micro-particulate and other solid contaminants are typically removed by filtration using a solid media such as sand, and sedimentation, where solid contaminants with higher densities than water are allowed to settle. Dissolved contaminants are typically removed by flocculation and sorption. In flocculation, metal salt solutions are mixed with waste water to precipitate the contaminant out of solution, where it can then be removed through filtration or sedimentation. In sorption, contaminated waste water is passed through a stationary filtration media, typically iron oxide coated sand, having a partially charged cationic boundary layer that is reactive with a target contaminant dissolved in the waste water.
0005In conventional fixed-bed filtration systems, filtration media can quickly lose its filtration efficiency as the interstitial spaces between the particles of the filtration media become saturated with micro-particulate and solid contaminants. Thus, the filtration media must be flushed or replaced, which tends to be costly and time intensive. Additionally, the filtration process must be stopped while the filtration media is being flushed or replaced.
0006Moving-bed filtration devices seek to mitigate these limitations by utilizing processes that remove micro-particulate and solid contaminants from the filtration media while simultaneously filtering water. These moving-bed filtration devices still have a disadvantage in that they do not remove dissolved contaminants from waste water.
0007U.S. Pat. No. 5,369,072 to Benjamin et al. describes methods of preparing iron-oxide coated sand to be used as a filtration media in either fixed-bed or moving-bed systems to remove both solid and dissolved contaminants from waste water. When such a filtration media is used in a fixed-bed system, there remains the disadvantage of having to flush or replace the filter media on a regular basis to remove the solid contaminant waste. Although the use of this media in a moving-bed system may overcome these disadvantages, it does not overcome a disadvantage common to the use of the described iron oxide coated sand in either system. That is, the reactive surface of the iron oxide coated sand becomes saturated with adsorbed contaminants, and therefore needs to be either replaced or regenerated. Benjamin states that the adsorbed contaminant can be desorbed by treating the saturated filtration media with a solution with a pH range that is known to desorb the specific contaminant ion from the specific adsorbing surface. Therefore, in either a fixed-bed or moving-bed system, filtration of water must stop to allow the filtration media to be rinsed with pH solution.
0008Environmental concerns and increasingly stricter government regulations have many industries searching for cost-effective and efficient water-treatment solutions. Additionally, there is a recognized need to be able to filter out water contaminants that exist in what may be considered trace amounts. For example, the removal capability of conventional coagulation-precipitation methods drop off significantly at contaminant levels lower than 500 parts per billion (ppb). However, science has recognized that ambient phosphorus levels in water greater than 10-20 ppb can lead to eutrophication. The U.S. Environmental Protection Agency is pushing for lower limits of phosphorus in effluents. Currently, the EPA estuarine water criteria for total phosphorus is 0.10 mg/L. High volume dischargers are experiencing a reduction in the levels allowed in their regulatory permits.
DESCRIPTION OF THE DRAWINGS
<figref idref="DRAWINGS">FIG. 1</figref> illustrates a moving bed particle filtration system that may be used to implement various embodiments of the invention.
<figref idref="DRAWINGS">FIG. 2</figref> illustrates a moving bed filtration system constructed according to one embodiment of the invention in which the waste water is pre-treated with a reagent.
DETAILED DESCRIPTION
0011Embodiments of the invention were developed in an effort to more efficiently remove contaminants from waste water by increasing flows through a filtration system, even when contaminants are present in relatively small amounts. “Waste water” as used in this Description and in the Claims means any water to be treated—it is not necessarily highly contaminated water and may contain only trace amounts of phosphorus, arsenic, or other contaminants (organic or inorganic and in single or mixed solution).
0012<figref idref="DRAWINGS">FIG. 1</figref> illustrates a moving-bed particle radial filtration system <b>10</b> that may be used to implement various embodiments of the invention. Referring to <figref idref="DRAWINGS">FIG. 1</figref>, waste water flows into a vertically oriented cylindrical treatment vessel <b>12</b> through an inlet pipe <b>14</b>. Vessel <b>12</b> includes a filter chamber <b>16</b>, a stem <b>18</b> and an expansion gravity settling chamber <b>20</b>. Filter chamber <b>16</b> contains a bed of sand <b>22</b>, iron oxide coated sand, sand and iron granules or another suitable filter media. Inlet pipe <b>14</b> extends down into filter chamber <b>16</b>. Waste water is discharged into sand <b>22</b> along the perforated lower part <b>24</b> of inlet pipe <b>14</b>. Treated water flows out of filter chamber <b>16</b> through a perforated outer perimeter <b>26</b> into a sleeve <b>28</b> and is removed from vessel <b>12</b> through an outlet pipe <b>30</b>. The perforations in the lower part <b>24</b> of inlet pipe <b>14</b> and the outer perimeter <b>26</b> of filter chamber <b>16</b> are screened as necessary to prevent sand from passing through the perforations.
0013The comparatively narrow stem <b>18</b> of vessel <b>12</b> connects filter chamber <b>16</b> with expansion chamber <b>20</b>. A sludge removal port <b>32</b> is positioned near the bottom of expansion chamber <b>20</b>. A recirculation pipe <b>34</b> extends from the bottom of filter chamber <b>16</b> to the top of expansion chamber <b>20</b>. An air compressor <b>36</b> pumps air into recirculation pipe <b>34</b> at the bottom of filter chamber <b>16</b> causing a counterclockwise motion of air, water, sand and filtered particulates through vessel <b>12</b>. A back flow preventer <b>38</b>, such as a flapper valve, prevents materials in recirculation pipe <b>34</b> from flowing back into compressor <b>36</b>. A flow control valve <b>39</b>, sampling tube <b>40</b>, sampling valve <b>42</b> and clean-out <b>43</b> on recirculation pipe <b>34</b>, and a sight glass <b>44</b> in stem <b>18</b>, may be provided if necessary or desirable.
0014In operation, waste water pumped into filter chamber <b>16</b> through inlet pipe <b>14</b> passes radially through sand <b>22</b> into sleeve <b>28</b> and flows out outlet pipe <b>30</b> as treated water. Sand <b>22</b> moves continuously down through vessel <b>12</b> under the influence of gravity. An aerated mixture of used sand and water flows from the bottom of filter chamber <b>16</b> back up to expansion chamber <b>20</b> through recirculation pipe <b>34</b> along with contaminants removed from the waste water. Air is vented to the atmosphere at the top of expansion chamber <b>20</b> to prevent pressurization of the system. The pressure head of water in sand <b>22</b> is kept such that some of the treated water flows from filter chamber <b>16</b> up through stem <b>18</b> into expansion chamber <b>20</b> to rinse contaminants from the used sand particles returning to expansion chamber <b>20</b>. This rinse water, now carrying a high concentration of contaminants less dense than sand, is removed from chamber <b>22</b> and flows out through sludge removal port <b>32</b>. In a preferred operation, the top of the sand bed for filtration is three fourths the height of filter chamber <b>16</b>. Expansion chamber <b>20</b> and narrow stem <b>18</b> contain a dilute sand and water mixture that contains filtered particles that have been moved first to the bottom of sand <b>22</b> and circulated via pipe <b>34</b> into the water residing in expansion chamber <b>20</b>. Water flow at inlet pipe <b>14</b>, outlets <b>30</b> and <b>32</b> and recirculation pipe <b>34</b> can be balanced so that a preferred rate of 5-10% of the inlet water carrying contaminants is discharged through sludge removal port <b>32</b>.
0015The system of <figref idref="DRAWINGS">FIG. 1</figref> may be used to implement a process for continuously regenerating an iron oxide coated sand bed while simultaneously filtering contaminants from the incoming flow of waste water. The process creates and utilizes a reactive filter media that removes contaminants by filtering and by adsorption. A reactive filter media is any filter media with the additional capability of removing contaminants from waste water through chemical processes such as adsorption. The iron oxide coated sand bed, a reactive filter media, screens contaminants from the water and the reactive surfaces of the granules of sand adsorb contaminants from the water. In one embodiment, iron metal granules in proportions of 10-30% by volume in sand bed <b>22</b> provide a solid phase reactive surface of corroding iron metal as well as a source of dissolved iron such as salts of Fe (II) and Fe(III) that react with the sand in the filter bed to create reactive iron oxide coated sand. The strongly reducing nature of water solutions with iron metal and sand mixtures can be useful for chemical reactions, such as the reductive degradation of organic solvents dissolved in contaminated water. Reduction potentials lower than −200 mV versus the standard hydrogen electrode can be observed with 30% iron:sand mixtures.
0016In an alternative embodiment, a reagent capable of creating a reactive surface on the filter media is added to the incoming flow of waste water at molar ratios such as 5:1 to 200:1 with the target contaminant. While it is expected that soluble forms of manganese, aluminum or other metals such as zinc and copper will provide suitable reagents, iron will typically be used as the reagent due to its proven reactivity with a variety of contaminants and its current widespread use in water treatment. Ferric chloride, for example, is a preferred reagent when phosphorus or arsenic is the target contaminant. In any particular water targeted for treatment, their may be alternate and competitive reactive pathways for the added active reagents. These pathways will be the result of the specific water chemistry in the waste water. For example, waste water with high levels of dissolved carbonate or phosphate can react with added iron salts in competition to the target contaminant such as arsenic. Molar ratios of Fe(III) to water arsenic in field studies have been in excess of 100:1. In these studies, inlet concentrations of arsenic in source water for drinking were reduced from approximately 40 parts per billion to less than 5 parts per billion treating at a rate of 10 gallon per minute in a pilot scale operation. However, other water types may have less alternate, competitive reactive pathways. It is preferred to field test to determine the optimal molar ratio for any particular treatment environment to ensure sufficient excess reagent is delivered to the reactive sand surface to form iron oxide coated sand. Additional considerations in reagent balancing direct efforts to minimizing reagent addition to ensure that the process effluents are not overly high in dissolved iron or other reagent, thereby creating an additional treatment or discharge concern. Excess reagent consumption will also undesirably increase the cost of operation of the process.
0017In the removal of dissolved and suspended phosphorus, field studies have demonstrated that successful high flow, low concentration removal occurs in this process in iron to phosphorous molar rations of 5:1 to 40:1. It is preferred that the actual reagent dose is optimized to ensure near complete solution reaction and saturation of all of the competing reactive pathways and allowing for residual iron in the solution to react with the sand bed. In some phosphorus contaminated test waste waters, optimizing the correct balance of conditions yields a preferred ratio of iron to phosphorus at 8:1. The metal salt reagent, ferric chloride in this example, reacts with the surface of the sand to form iron oxide coated sand (IOCS). IOCS provides a stationary phase removal pathway for water borne contaminants such as phosphorus and arsenic. Contaminants in the waste water are exposed as a “mobile” phase over the “stationary” (slowly moving) IOCS bed for high efficiency sorptive and ion exchange removal. The physical action of the moving sand abrades the surface of the sand granules, regenerating active sites for additional iron salt and water contaminant reactions. Hence, regenerated reactive sites for contaminant binding are continually presented to the flowing water. Abraded sand-iron-contaminant solids are removed by the screen filtering action of the sand bed. The treated water exits the sand filter bed with contaminants substantially removed, ready for discharge or post-treatment processing.
0018Sorption is the removal of undersaturated solutes from solution onto minerals. Sorbate is the species removed from solution and the sorbent is the solid onto which solution species are sorbed. There are three types of sorption: adsorption wherein solutes are held at the mineral surface as a hydrated species; absorption wherein solute is incorporated into the mineral structure at the surface; and ion exchange wherein an ion becomes sorbed to a surface by changing places with a similarly charged ion previously residing on the sorbent. Mineral surfaces, such as the silicates in sand, have fixed or acquired surface charges that can be modified by water chemistry such as pH and dissolved solutes such as iron salts that can complex with the surface charges of sand. As a result of fixed surface charges, a property of the mineral, and pH, a property of the water, mineral surfaces develop a point of zero net proton charge (PZNPC). The PZNPC is the pH at which net surface charge is zero. At lower pH than PZNPC, the net surface charge is positive and at higher pH, the net surface charge is negative. These surface charges allow attraction of oppositely charged anions or cations, respectively, from solution. Larger amounts of dissolved constituents, such as positively charged Fe(III) can be attracted to a negatively charged surface such as the silicates in sand to such a degree that the surface becomes overall positively charged and therefore attractive to anions such as phosphate and arsenate. Silica, SiO<sub>2 </sub>has a low PZNPC of 2, whereas iron oxyhydroxide, α-FeOOH has a PZNPC of 7.8, and iron hydroxide, Fe(OH)<sub>3 </sub>has a PZNPC of 8.5. Increasing quantities of iron oxide forming on a sand surface will increase the PZNCP of the sand grains such that net surface charge is positive and thereby attractive to anions such as phosphate and arsenate at higher pH levels of about 6-8. Most environmental waters, including drinking water and wastewaters exist at these circum-neutral pH levels. Hence, the selective addition of iron oxides to the sand creates a useful sorbent.
0019In a moving sand bed system such as the one shown in <figref idref="DRAWINGS">FIG. 1</figref>, concentrated contaminants, now in the form of filterable solid waste, are removed from the system through sludge removal port <b>32</b> via continuous rinsing in expansion chamber <b>18</b>. This continuous rinsing and waste removal process is particularly important in the case of a hazardous material such as arsenic in drinking water. Rinse/waste water outflow, typically 5-10% of the incoming water, can be recycled and put back into the process following separation of the suspended solids by settling or clarification. In a fixed-bed system, in which the particulate filtrate remains on the sand and in the sand, the sand bed is periodically flushed or changed out to remove the concentrated contaminant waste.
0020<figref idref="DRAWINGS">FIG. 2</figref> illustrates a novel moving bed filtration system <b>50</b> constructed according to one embodiment of the invention in which the waste water is pre-treated with a metal salt reagent. Referring to <figref idref="DRAWINGS">FIG. 2</figref>, filtration system <b>50</b> includes a pre-reactor system <b>52</b> and a reactive filter system <b>54</b>. Waste water is pumped into the serpentine piping <b>56</b> of pre-reactor <b>52</b> through an inlet pipe <b>58</b> and flow control valve <b>60</b>. A metal salt or other suitable reagent is introduced into serpentine piping <b>56</b> through a reagent inlet port <b>62</b> immediately downstream from inlet pipe <b>58</b>. Preferably, serpentine piping <b>56</b> is substantially larger than inlet pipe <b>58</b> to slow the flow through piping <b>56</b> compared to inlet pipe <b>58</b>. A slower flow increases the time available for the reagent to mix with the waste water and react with contaminants in the waste water. The waste water flow will be more turbulent near the transition from the smaller inlet pipe <b>58</b> to the larger serpentine piping <b>56</b>. Introducing the reagent into this turbulent flow also helps mixing.
0021The waste water/reagent mix flows through straight-aways <b>64</b> and gentle bends <b>66</b> of serpentine piping <b>56</b>. The waste water/reagent mix exits serpentine piping <b>56</b> into an outlet pipe <b>68</b> that takes the mix into reactive filter system <b>54</b>. Prescribed overdosing introduces the reagent in sufficient quantities and concentrations to (1) allow for the co-precipitation and flocculation reactions between the reagent and the dissolved contaminants in pre-reactor system <b>52</b> to go to near completion to dilute levels where equilibrium and diffusion limited processes limit further reaction, (2) saturate competing reactive pathways with natural waters with reagent, and (3) leave enough excess reagent in the mix to activate the filter media in reactive filter system <b>54</b>. The amount of excess reagent is determined by the reactive capacity of the influent solution and the desire to deliver excess reagent to the sand filtration bed for the continuous formation of iron oxide coated sand.
0022The comparatively slow flow through serpentine piping <b>56</b> allows for better coagulation of precipitates. The straight-aways <b>64</b> allow for less turbulent flow to enhance coagulation. Periodic gentle bends <b>66</b> introduce and maintain additional turbulent flow and introduce flow vortices to periodically mix the flowing solution. Preferably, the serpentine mixing array allows for a decrease in flow velocity for 2-8 minutes to allow for sufficient pre-reaction time. Design of the array needs to consider maintaining sufficient flow to prevent deposition of precipitation solids in the pre-reactor assembly. The actual length and diameter of serpentine piping <b>56</b> for most applications will result for an optimization of the required reaction time (usually 1-5 minutes), the desired flow rate, the space available at the site of deployment, and the presence of competing reactions in the treatment water.
0023The pre-treated waste water flows into the vertically oriented cylindrical treatment vessel <b>70</b> of reactive filtration system <b>54</b> through an inlet pipe <b>72</b>. Inlet pipe <b>72</b> is positioned at the center of vessel <b>70</b>. Vessel <b>70</b> includes a filter chamber <b>74</b> that contains a bed of sand <b>76</b> or another suitable filter media. Inlet pipe <b>72</b> extends down into filter chamber <b>74</b> to discharge the waste water into the lower portion of sand bed <b>76</b> through a perforated manifold <b>78</b>. Waste water pumped into filter chamber <b>74</b> passes up through sand <b>76</b>, over a baffle <b>80</b> near the top of filter chamber <b>74</b> as fully treated water, into a basin <b>82</b> and is removed from vessel <b>70</b> through an outlet pipe <b>84</b>.
0024A recirculation tube <b>86</b> extends from the bottom to the top of filter chamber <b>74</b> at the center of vessel <b>70</b>. Inlet pipe <b>72</b> extends down the center of recirculation tube <b>86</b>. Inlet flow discharge manifold <b>78</b> extends out through openings in recirculation tube <b>86</b>. An air compressor <b>88</b> pumps air into used sand and water at the bottom of vessel <b>70</b> through an air inlet pipe <b>89</b>. The aerated mixture of used sand and water rises through recirculation tube <b>86</b> along with contaminants removed from the waste water up to a sand and particulate/water separator <b>90</b>. Separator <b>90</b> represents generally any suitable separation device that may use, for example, physical separation, gravity separation, particle size separation, magnetic separation, membrane separation, or cyclonic separation. The sand removed from the mix by separator <b>90</b> is recycled back to filter chamber <b>74</b>. The now highly contaminated waste water is removed through a sludge removal port <b>94</b>. Sand <b>76</b> moves continuously down through vessel <b>70</b> under the influence of gravity.
0025Phosphorus exists in waters and waste waters as dissolved ortho-phosphate, polyphosphate and complex organo-phosphorus compounds. In typical phosphorus containing waste waters, such as the secondary or tertiary effluents of municipal waste water treatment plants, there is a dissolved fraction, primarily as ortho-phosphate (PO<sub>4</sub><sup>3−</sup>) and poly-phosphates and as a micro-particulate or suspended fraction of phosphorous containing solids. Trace levels of arsenic are sometimes found in some sources of drinking water and in higher concentrations in some waste waters. Arsenic can occur in natural waters in the reduced arsenite, As(III) or oxidized arsenate, As(V) forms. Arsenate reacts with iron and aluminum salts to form insoluble compounds. Waters with arsenite contamination can be treated with an oxidizer such as chlorine to allow for further reaction with reactive metal salts. Ferric chloride or sulfate is typically used as a metal salt reagent to remove phosphorus and arsenic from water, although other salts and ferrous compounds can be used.
0026In the system described above, excess ferric iron enters sand bed <b>76</b> along with the particulate Fe—As or Fe—P solids and residual As or P in solution in the waste water. Ferric ions react with sand surfaces to form iron oxide coated sand (IOCS). IOCS sorbs residual solution As/P out of solution. The physical action of the moving sand abrades the surface of the sand granules, refreshing active sites for additional IOCS formation and Fe—As or Fe—P reactions. Hence, fresh reactive sites for As/P binding are continually presented to the flowing water via microscopic erosion of the sand surface.
0027For phosphorus, ferric chloride is added at a preferred molar ratio of 5:1 to 40:1 with the phosphorus in the waste water. The pre-reactor system allows for a pre-reaction to form metal phosphate salts such as FePO<sub>4</sub>, Vivianite and humic-fulvic organic phosphorus solids that are amenable to filtration in the sand bed reactive filter system. Vivianite is a very thermodynamically stable compound that is rapidly formed in solutions of iron cations and phosphate. Excess iron salt reagent is passed unreacted into the sand bed where it binds to the surface of the sand to form iron coated sand, a phosphate and polyphosphate reactive surface. Metal cations will selectively bind to the silicate and other negatively charged groups on the solid sand surface. This binding will yield a partially charged cationic boundary layer on the iron coated sand surface that will be reactive with soluble ortho-phosphate and poly-phosphate. The mobile phase (treatment water) and stationary phase (iron coated sand) configuration of this process allows for near quantitative removal of phosphorus because diffusion processes are nearly eliminated in the dilute solution reactive pathway of this process. Testing has shown that this process can remove ortho-phosphate to less than detection limits (10 parts per billion) at efficiencies greater than 99% and total phosphorus to less than 40 parts per billion at greater than 90% efficiency of removal from the original concentration.
0028The processes described above have been shown to produce iron arsenic solids that are classified non-hazardous by the Toxicity Characteristic Leaching Procedure (TCLP) directed by the Resource Conservation and Recovery Act (RCRA 42 U.S.C. s/s 6901 et seq.) and can be disposed in a landfill, and iron phosphate solids that may be used in agricultural applications as a low grade slow release fertilizer.
0029The reactive filter media are deployed in a moving bed to assist in continuous renewal of the reactive iron oxide layer. Movement may be accomplished, for example, by fluidizing or moving the bed using the fluid flow, by mechanical action such as augers or mixing bars, by acoustic action such as the application of ultrasonic waves or by physical transport using compressed air.
0030Other embodiments are possible. For example, the filter media can be any natural or synthetic, organic or inorganic substrate that can react with dissolved iron to form a reactive oxide surface. The particle size of the filter media will be a size suitable for the level of filtration and flow desired. It is expected that the following inorganic materials will provide suitable filtration media: sand; silica beads or granules; high silicate glass; glass beads; glass sand; zeolite; mineral sands such as olivine, hematite, goethite; diatomaceous earth; iron oxyhydroxide granules; iron oxide granules; ceramic beads or granules; iron metal granules or beads; iron metal coated beads or granules; and synthetic or natural iron coated sand. It is expected that the following organic materials will provide suitable filtration media: polystyrene beads; polyethylene beads; modified cationic surface polymer beads; modified anionic surface polymer beads; mixed or pure polymer beads or granules; and polymer coated inorganic beads or granules. Some of these materials can have naturally occurring reactive sites that can be maintained or supplemented by the addition of active reagents such as ferric chloride solution. Because of the well known filtration properties of sand, its inexpensive use, its routine application in water treatment, its natural reactive silicate surface for inner sphere and outer sphere metal oxide binding to form iron oxide coated sand, and its abrasion properties, it is the preferred embodiment of an active filtration media in a moving bed process.
0031Suitable filtration media include corroding iron metal granules or ion exchange resins with the ability to bind iron compounds. Corroding iron metal granules allow for reductive processes that can be used to remove trace amounts of chlorinated solvents in water. Testing has shown that a 30% by volume iron-sand bed deployed in the system of <figref idref="DRAWINGS">FIG. 1</figref> has a solution oxidation-reduction potential of −200 mV versus the standard hydrogen electrode. Typical deployments of static beds of iron granules or iron granules and sand suffer from loss of porosity or passivation of the reactive iron metal surface. The motion of a moving bed deployment allows for a continual refreshing of the iron metal surface and its associated chemically reactive sites as well as maintenance of filtration ability. A 98% efficiency has been demonstrated for removing phosphorus from contaminated discharge water originally containing 2 to 3 parts per million phosphorus.
0032In some circumstances, removing arsenic for example, it may be desirable to pre-oxidize the waste water to convert arsenite to the iron reactive arsenate. Arsenite in natural solutions at circumneutral pH is non-ionic and therefore typically non-reactive in most treatment deployments. Pre-oxidation can be accomplished using conventional water oxidation operations such as chlorination, sonication or ozonation. The pre-oxidation operation can be part of a full water treatment process train and may be preceded or followed by other conventional water treatment processes such as filtration, aeration, chemical treatment, flocculation, clarification and others that may be required in the normal processing and disinfection of drinking water.
0033The present invention has been shown and described with reference to the foregoing exemplary embodiments. It is to be understood, however, that other forms, details, and embodiments may be made without departing from the spirit and scope of the invention which is defined in the following claims.
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| US4366128A | Cites | United States of America | Applicant |
| US4689154A | Cites | United States of America | Applicant |
| GB471277A | Cites | United Kingdom | Applicant |
| US4842744A | Cites | United States of America | Applicant |
| US5087374A | Cites | United States of America | Applicant |
| US5173194A | Cites | United States of America | Applicant |
| US5190659A | Cites | United States of America | Applicant |
| US5236595A | Cites | United States of America | Applicant |
| US5302356A | Cites | United States of America | Applicant |
| US5369072A | Cites | United States of America | Applicant |
| US5372720A | Cites | United States of America | Applicant |
| US5439595A | Cites | United States of America | Applicant |
| US5443729A | Cites | United States of America | Applicant |
| US5454959A | Cites | United States of America | Applicant |
| US5534153A | Cites | United States of America | Applicant |
| US5573666A | Cites | United States of America | Applicant |
| US5670046A | Cites | United States of America | Applicant |
| US5679257A | Cites | United States of America | Applicant |
| US5707528A | Cites | United States of America | Applicant |
| US5746913A | Cites | United States of America | Search report |
| US5755977A | Cites | United States of America | Applicant |
| US5843308A | Cites | United States of America | Applicant |
| US5855787A | Cites | United States of America | Applicant |
| US5876606A | Cites | United States of America | Applicant |
| US5904855A | Cites | United States of America | Applicant |
| US5911882A | Cites | United States of America | Applicant |
| US6077446A | Cites | United States of America | Applicant |
| US6132623A | Cites | United States of America | Applicant |
| US6143186A | Cites | United States of America | Applicant |
| US6200482B1 | Cites | United States of America | Applicant |
| US6217765B1 | Cites | United States of America | Applicant |
| US6334956B1 | Cites | United States of America | Applicant |
| US6426005B1 | Cites | United States of America | Applicant |
| US6432312B1 | Cites | United States of America | Applicant |
| US6464877B1 | Cites | United States of America | Applicant |
| US6468942B1 | Cites | United States of America | Applicant |
| US6471857B1 | Cites | United States of America | Applicant |
| US6630071B1 | Cites | United States of America | Applicant |
| US6663781B1 | Cites | United States of America | Applicant |
| US6716344B1 | Cites | United States of America | Applicant |
| US6942786B1 | Cites | United States of America | Applicant |
| US6942807B1 | Cites | United States of America | Applicant |
| US7029589B2 | Cites | United States of America | Applicant |
| US7399416B2 | Cites | United States of America | Applicant |
| US7445721B2 | Cites | United States of America | Applicant |
| JPH03137990A | Cites | Japan | Applicant |
| JPH07232161A | Cites | Japan | Applicant |
| US20010052495A1 | Cites | United States of America | Applicant |
| US20020003116A1 | Cites | United States of America | Applicant |
| US20040144728A1 | Cites | United States of America | Applicant |
| US20050127003A1 | Cites | United States of America | Applicant |
| US20050173348A1 | Cites | United States of America | Applicant |
| US20050263447A1 | Cites | United States of America | Applicant |
| US20060000784A1 | Cites | United States of America | Applicant |
| US20060000785A1 | Cites | United States of America | Applicant |
| US20070136919P1 | Cites | United States of America | Applicant |
| US20070187329A1 | Cites | United States of America | Applicant |
| GB471277 | Cites | United Kingdom | Applicant |
| GB1596205 | Cites | United Kingdom | Applicant |
| JP3137990 | Cites | Japan | Applicant |
| JP3137990 | Cites | Japan | Applicant |
| JP7232161 | Cites | Japan | Applicant |
| JP20010070954 | Cites | Japan | Applicant |
| JP2002159977 | Cites | Japan | Applicant |
| WO0110786 | Cites | World Intellectual Property Organization (WIPO) | Applicant |
| WO0110786 | Cites | World Intellectual Property Organization (WIPO) | Applicant |
| WO0110786A1 | Cites | World Intellectual Property Organization (WIPO) | Search report |
22 members in 5 offices
Priority claims14
| Document | Office | Kind | Date |
|---|---|---|---|
| 43075602 | United States of America | P | |
| 43075602 | United States of America | P | |
| 72796303 | United States of America | A | |
| 72796303 | United States of America | A | |
| 2519408 | United States of America | A | |
| 2519408 | United States of America | A | |
| 201213470185 | United States of America | A | |
| 10727963 | – | – | – |
| 12025194 | – | – | – |
| 60430756 | – | – | – |
| US20020430756P | – | – | – |
| US20030727963 | – | – | – |
| US20080025194 | – | – | – |
| US201213470185 | – | – | – |
Members22
| Document | Office | Kind | |
|---|---|---|---|
| WO2004050561A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2003299642A1 | Australia | A1 | |
| US2004144728A1 | United States of America | A1 | |
| EP1567453A1 | European Patent Office (EPO) | A1 | |
| US2006000785A1 | United States of America | A1 | |
| JP2006508791A | Japan | A | |
| US2007163958A1 | United States of America | A1 | |
| EP1813578A1 | European Patent Office (EPO) | A1 | |
| EP1813579A1 | European Patent Office (EPO) | A1 | |
| JP2007203291A | Japan | A | |
| JP2007203292A | Japan | A | |
| US2007187329A1 | United States of America | A1 | |
| US7399416B2 | United States of America | B2 | |
| US7445721B2 | United States of America | B2 | |
| US2008277349A1 | United States of America | A1 | |
| US2008302726A1 | United States of America | A1 | |
| US7713423B2 | United States of America | B2 | |
| US7744764B2 | United States of America | B2 | |
| US8071055B2 | United States of America | B2 | |
| US8080163B2 | United States of America | B2 | |
| USRE44570EThis record | United States of America | E | |
| US2013341278A1 | United States of America | A1 |
47 transactions on the USPTO file
Allowed without a rejection on record.
- Non-final rejections
- 0
- Final rejections
- 0
- RCEs
- 0
- Appeals
- 0
Over time
Point at a mark for the transactionTransactions
| Event | Code | |
|---|---|---|
| Payment of Maintenance Fee, 12th Yr, Small EntityM2553 | M2553 | |
| Payment of Maintenance Fee, 8th Yr, Small EntityM2552 | M2552 | |
| Recordation of Patent Grant MailedPGM/ | PGM/ | |
| Email NotificationEML_NTR | EML_NTR | |
| Issue Notification MailedAllowedWPIR | WPIR | |
| Dispatch to FDCD1935 | D1935 | |
| Application Is Considered Ready for IssuePILS | PILS | |
| Email NotificationEML_NTR | EML_NTR | |
| Change in Power of Attorney (May Include Associate POA)PA.. | PA.. | |
| Correspondence Address ChangeC.AD | C.AD | |
| Miscellaneous Incoming LetterLET. | LET. | |
| Issue Fee Payment VerifiedN084 | N084 | |
| Issue Fee Payment ReceivedIFEE | IFEE | |
| Electronic ReviewELC_RVW | ELC_RVW | |
| Email NotificationEML_NTF | EML_NTF | |
| Mail Notice of AllowanceAllowedMN/=. | MN/=. | |
| Information Disclosure Statement consideredIDSC | IDSC | |
| Reference capture on IDSRCAP | RCAP | |
| Information Disclosure Statement (IDS) FiledM844 | M844 | |
| Information Disclosure Statement (IDS) FiledWIDS | WIDS | |
| Notice of Allowance Data Verification CompletedAllowedN/=. | N/=. | |
| Interview Summary - Examiner InitiatedEXIE | EXIE | |
| Reasons for AllowanceEX.R | EX.R | |
| Examiner's Amendment CommunicationEX.A | EX.A | |
| Case Docketed to Examiner in GAUDOCK | DOCK | |
| Case Docketed to Examiner in GAUDOCK | DOCK | |
| Case Docketed to Examiner in GAUDOCK | DOCK | |
| Notice of Reissue Published in Official GazetteNRE. | NRE. | |
| Application Is Now CompleteCOMP | COMP | |
| Email NotificationEML_NTR | EML_NTR | |
| Filing Receipt - UpdatedFLRCPT.U | FLRCPT.U | |
| Application Dispatched from OIPEOIPE | OIPE | |
| Payment of additional filing fee/PreexamFLFEE | FLFEE | |
| The identification of one or more legal entities other than the inventor(s), each such legal entityASGMT | ASGMT | |
| Small Entity Statement (37 CFR 1.27)SES | SES | |
| A statement by one or more inventors satisfying the requirement under 35 USC 115, Oath of the ApplicOATHDECL | OATHDECL | |
| Electronic ReviewELC_RVW | ELC_RVW | |
| Email NotificationEML_NTR | EML_NTR | |
| Email NotificationEML_NTF | EML_NTF | |
| Filing ReceiptFLRCPT.O | FLRCPT.O | |
| Notice Mailed--Application Incomplete--Filing Date AssignedINCD | INCD | |
| Cleared by L&R (LARS)L128 | L128 | |
| Referred to Level 2 (LARS) by OIPE CSRL198 | L198 | |
| Miscellaneous Incoming LetterLET. | LET. | |
| Preliminary AmendmentA.PE | A.PE | |
| IFW Scan & PACR Auto Security ReviewSCAN | SCAN | |
| Initial Exam Team nnIEXX | IEXX |
8 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Maintenance fee paymentMAFP | MAFP | |
| Maintenance fee paymentMAFP | MAFP | |
| Fee paymentFPAY | FPAY | |
| Surcharge for late paymentSULP | SULP | |
| Maintenance fee reminder mailedREMI | REMI | |
| AssignmentAS | AS | |
| AssignmentAS | AS | |
| Fee payment procedurePAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITYFEPP | FEPP |
Numbers
- Publication
- RE044570
- Publication, DOCDB
- RE44570
- Publication, EPODOC
- USRE44570E
- Application
- 13470185
- Application, DOCDB
- 201213470185
- Application, EPODOC
- US201213470185
Titles
- English
- Reactive filtration
Classification
- CPC, 28
- C02F1/281
- B01D21/01
- B01D24/105
- B01D41/02
- B01J20/06
- B01J20/3236
- C02F1/004
- C02F1/288
- C02F1/42
- C02F1/5236
- C02F1/76
- C02F2101/103
- C02F2101/105
- C02F2101/20
- C02F2209/40
- C02F2301/024
- C02F2303/16
- Y10S210/912
- Y10S210/906
- Y10S210/911
- B01J20/3204
- B01J20/3433
- B01J20/3475
- B01J2220/56
- B01J20/0229
- B01D24/30
- B01D24/4684
- B01D24/4689
- IPC, 12
- C02F1 28
- B01D21 01
- B01D24 10
- B01D41 02
- B01J20 06
- B01J20 32
- B01J20 34
- C02F1 00
- C02F1 42
- C02F1 52
- C02F1 62
- C02F1 76
- USPC, 10
- 210667000
- 210669000
- 210673000
- 210676000
- 210683000
- 210716000
- 210738000
- 210906000
- 210911000
- 210912000