Processing post-industrial and post-consumer waste streams and preparation of post-industrial and post-consumer products therefrom
11359152 · 2022-06-14
Assignee
Inventors
Cpc classification
B29B17/02
PERFORMING OPERATIONS; TRANSPORTING
B09B3/20
PERFORMING OPERATIONS; TRANSPORTING
Y02P40/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02W30/62
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B09B3/00
PERFORMING OPERATIONS; TRANSPORTING
C08J11/02
CHEMISTRY; METALLURGY
B09B3/40
PERFORMING OPERATIONS; TRANSPORTING
B01J20/043
PERFORMING OPERATIONS; TRANSPORTING
C08L2023/42
CHEMISTRY; METALLURGY
Y02E50/30
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C10L5/40
CHEMISTRY; METALLURGY
B29B17/04
PERFORMING OPERATIONS; TRANSPORTING
B29B17/02
PERFORMING OPERATIONS; TRANSPORTING
C08J11/02
CHEMISTRY; METALLURGY
B01J20/04
PERFORMING OPERATIONS; TRANSPORTING
B09B3/00
PERFORMING OPERATIONS; TRANSPORTING
C02F1/52
CHEMISTRY; METALLURGY
B09B3/40
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A system for and method of, processing post-consumer and post-industrial waste streams, producing active ingredients for waste stream processing, processing aqueous waste streams, preparing and collecting a multi-purpose chemical precursor, removing phosphates, nitrates, heavy metals, and other contaminants from aqueous waste streams, collecting and processing a post-consumer and post-industrial product from aqueous waste streams, administering and positioning assets and processes associated with waste stream processing, and scheduling operations for sub-systems of the system.
Claims
1. A method of producing a composite ash from paper and/or carpet exothermic processing waste, the composite ash reactive with a pH greater than about 7.0, the method comprising the steps of: a) receiving a paper or carpet exothermic processing waste stream; b) adding a mineral product to the exothermic processing waste stream as a catalyst and thermally processing the paper or carpet exothermic processing waste stream, for a period of about 30.0 minutes to about 12.0 hours, at an average process bed temperature of about 600 to about 1000 degrees C., to remove organics, for yielding the composite ash, of common crystalline and amorphous non-crystalline composition, the composite ash comprising metakaolin and at least one of a group consisting of mineral oxide and mineral carbonate, wherein the mineral product is yielded from a previously-run thermal processing of a paper or carpet exothermic processing waste stream and the mineral product is essentially the same as the composite ash; and c) recovering and collecting the composite ash.
2. The method of producing the composite ash of claim 1, wherein receiving the paper or carpet exothermic processing waste stream comprises at least one of a group of steps consisting of dewatering the paper or carpet exothermic processing waste stream, de-lumping the paper or carpet exothermic processing waste stream, and comminuting the paper or carpet exothermic processing waste stream.
3. The method of producing the composite ash of claim 1, wherein thermally processing the paper or carpet exothermic processing waste stream comprises removing organics without essentially decomposing calcium carbonate present in the composite ash.
4. The method of producing the composite ash of claim 1, wherein thermally processing the paper or carpet exothermic processing waste stream comprises allowing combustion gases to flow in co-current direction with any of the composite ash produced.
5. The method of producing the composite ash of claim 1, wherein thermally processing the paper or carpet exothermic processing waste stream comprises recovering energy to recycle for use anywhere in the method of producing the composite ash.
6. The method of producing the composite ash of claim 1, wherein thermally processing the paper or carpet exothermic processing waste stream comprises thermally processing, for a period of about 30.0 minutes to about 2.0 hours, at an average process bed temperature in the range of about 600 to about to 825 degrees C.
7. The method of producing the composite ash of claim 1, wherein thermally processing the paper or carpet exothermic processing waste stream comprises thermally processing, for a period of about 30.0 minutes to about 1.0 hours, at an average process bed temperature in the range of about 600 to about to 800 degrees C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) In the figures, like reference numerals refer to like parts throughout the various views unless otherwise indicated. For reference numerals with letter character designations such as “102A” or “102B”, the letter character designations may differentiate two like parts or elements present in the same figure. Letter character designations for reference numerals may be omitted when it is intended that a reference numeral to encompass all parts having the same reference numeral in all figures.
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(14) The drawings constitute a part of this specification and include exemplary embodiments of the present invention, which may be embodied in various forms. It is to be understood that in some instances various aspects of the invention may be shown as exaggerated, reduced, enlarged, or otherwise distorted to facilitate an understanding of the present invention. In the drawings, like elements are given the same or analogous references when convenient or helpful for clarity. The same or analogous reference to these elements will be made in the body of the specification, but other names and terminology may also be employed to further explain the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
(15) For a further understanding of the nature, function, and objects of the present invention, reference should now be made to the following detailed description taken in conjunction with the accompanying drawings. While detailed descriptions of the preferred embodiments are provided herein, as well as the best mode of carrying out and employing the present invention, it is to be understood that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system, structure, or manner. The practice of the present invention is illustrated by the included Examples, which are deemed illustrative of both the process taught by the present invention and of the results yielded in accordance with the present invention.
(16) An exemplary embodiment of the present invention provides a system for and a method of (1) sustainable waste management, (2) PC and PI product management, (3) water management, (4) sustainably producing a chemical precursor, platform, or active ingredient, (5) sustainably producing a PC or PI agricultural fertilizer product from an exothermic processing waste stream and a municipal aqueous wastewater stream, via, at least, the produced chemical precursor, platform, or active ingredient, and (6) open water treatment for lakes, reservoirs, oceans, rivers, ponds, and streams, as well as various other open water applications. An exemplary exothermic processing waste stream has at least about 15.0% inorganics and at least about 20.0% organics, hydrous and/or anhydrous. An exemplary exothermic processing waste stream also is defined by an energy value element of at least about 2000.0 BTUs/lb. Further, an exemplary exothermic processing waste stream is derived from a paper mill sludge or deinking sludge (DIR) and/or a carpet third stream.
(17) More specifically, the paper mill sludge or deinking sludge or the carpet third stream processing waste stream, generally, may be characterized by the following information provided in Table 1.
(18) TABLE-US-00001 TABLE 1 PAPER MILL SLUGE Water . . . 40%-60% Organics . . . cellulose fiber . . . 20%-40% Inorganics . . . minerals and fillers . . . fly-ash, calcium carbonates, glass . . . 50% Btu value . . . 2000-5000 btus/lb. RECYCLED CARPET AND RECYCLED CARPET WASTE Organic polymers . . . 50% Inorganics . . . minerals and fillers . . . kaolins and calcium carbonates . . . 15%-30% Btu value . . . 8000-12000 btus/lb. FLY ASH Organic . . . carbon . . . 1%-10% Inorganics . . . minerals and oxides . . . 90%-99% Btu value . . . 200-2000 btus/lb.
(19) The information in Table 1 illustrates the chemical compositions and physical characteristics of each portion, segment, or flow of the exothermic waste streams, or blends thereof, to which this exemplary embodiment may pertain.
(20) Separately, the municipal aqueous wastewater stream, relevant to this exemplary embodiment, has contamination from phosphates and nitrates, primarily, and is derived from a municipal water treatment source. The municipal wastewater stream, from the municipal water treatment source, or from any other intermediary entity, system, or process, which may preemptively process or prepare the waste water for future processing, for example, also is independent in terms of source, location, etc., from the paper mill sludge/deinking sludge or the carpet third stream processing waste stream previously described. In fact, it is a feature of the present invention, and a solution to a problem in the prior art, that the inventive concept is more efficiently and effectively practiced than the prior art.
(21) A person of ordinary skill in the art understands that this embodiment is applicable to a wide variety of PC or PI waste streams and aqueous waste streams and wastewaters (e.g., agricultural run-off, retention ponds, animal farm run-off, animal park run-off, streams, lakes, canals, reservoirs, residential and commercial storm-water run-off, wastewater treatment plant discharge, food processing discharge, industrial wastewater discharge, residential wastewater discharge, meat processing residuals, toilet water, and aquarium water), regardless of source or type, so long as they have similar or equivalent defining characteristics, or similar chemical compositions, chemical interaction, and/or chemical processes. A person of ordinary skill in the art also understands that the paper mill sludge or deinking sludge or the carpet third stream processing waste stream may have various stages of preliminary processing (e.g., air drying of hydrous waste streams, physical shredding, de-lumping), and that the municipal aqueous wastewater stream may have various stages of preliminary processing (e.g., to remove biological particulates and non-biological debris), prior to becoming an “input” for this exemplary embodiment. Further, a person of ordinary skill in the art understands that, in the case of carpet third stream processing waste streams, or other similar or equivalent waste streams, no drying or dewatering is necessary. Further, a person of ordinary skill in the art understands that recent developments in the art (see the Prior Art Section for a more detailed explanation) has, to some extent, changed the expected composition of the relevant waste streams or wastewaters (i.e., changed some of the expected and commonly-used mineral additives for color and texture, for example), which may also change the expected results from applying seemingly common processes and methods to the relevant waste streams/wastewaters.
(22) Returning, generally, to this exemplary embodiment, and with reference to a front-end grouping of processes and related systems, the paper mill sludge or deinking sludge or the carpet third stream processing waste stream has its latent energy liberated, separated, and/or recovered, and its minerals recycled and reused, as a function of controlled thermal reactions within a thermal reactor, that is, a rotary kiln, vertical kiln, calciner, flash calciner, etc. The front end of this exemplary embodiment provides a process in which the paper mill sludge or deinking sludge or the carpet third stream, with its constituent organics and mineral content, is subjected to thermal separation permitting energy recovery from the organics.
(23) Next, with reference to a back-end grouping of processes and related systems, this exemplary embodiment also is directed generally to a system for, and method of, recycling and recovering phosphates or nitrates from the municipal wastewater stream. The municipal wastewater is independent and separately situated and sourced when compared to the paper mill sludge or deinking sludge, or the carpet third stream waste stream, and the municipal wastewater may be alkaline, acidic, or neutral as it leaves the source and enters the inventive concept described herein. As is briefly mentioned above, and as is described in greater detail herein, this exemplary embodiment also discloses a method for evaluation, and preparation, of a useful and economically valuable, PC or PI agricultural fertilizer product carrying these phosphorous or nitrogen groups from the aqueous waste, either in slurry or out of slurry. The aqueous waste, however, does not require any pH adjustment, prior to becoming an “input” for the back-end grouping of processes, or after becoming an “input”, in order for the inventive concept to operate as intended. The precipitated PC or PI agricultural fertilizer product output operates as a mild and sustainable platform for domestic, commercial, and agriculture uses, or as a mild soil additive or soil conditioner.
(24) A person of ordinary skill in the art understands that this embodiment is applicable to the production of a wide variety of PC or PI “recycled” products, regardless of their end-state or how they are marketed or named, so long as they have similar or equivalent defining characteristics, or similar chemical compositions and/or chemical interactions. A person of ordinary skill in the art also understands that the produced composite ash, from the front-end, may be utilized as an ionic chemical precursor or platform, for example, for the secondary, and possibly entirely independent, production of various useful and economically valuable PC or PI products separate and distinct from the produced chemical fertilizer of the present invention. A person of ordinary skill in the art may see this use as a chemical precursor or platform as distinct from its use as an intermediate capture material, the differences primarily being whether the composite ash is immediately incorporated into a related, back-end grouping of process, or whether the composite ash is collected, sold, and marketed to independent, out-side entities for use in their own independent production operations. A person of ordinary skill in the art also understands that the PC or PI agricultural fertilizer produced from an integrated back-end grouping of processes, for example, may have various stages of preliminary processing prior to becoming an “output” (described in greater detail herein) of this exemplary embodiment.
(25) Returning, generally, to this exemplary embodiment, and with reference to the back-end grouping of processes and related systems, the composite ash and energy outputs of the front end are used as post-consumer or recycled inputs for the back-end process grouping, and can be looped into the front-end processing group to facilitate operations as well. The composite ash is catalyzed via oxidation/combustion, and the ash is a non-limiting example of an active ingredient for sustainable waste stream processing of various sorts, including wastewater processing, for example. The composite ash is primarily a mineral, crystalline, multi-component product comprising calcium oxide, partially converted calcium carbonate, and meta-kaolin, containing calcium components of about 60.0% and meta-kaolin components of about 30.0%. The composite ash exhibits unique and synergistic molecular attraction forces, including chemical bonding and chemisorption forces. The composite ash, therefore, has the necessary structure and attractive forces and affinity to operate as a collector or precipitation agent ideally suited for the collection and removal of phosphates and nitrates from municipal wastewaters.
(26) A person having ordinary skill in the art understands that, like the outputs of the front end, the outputs of the back end of this exemplary embodiment—fresh or decontaminated water and the post-consumer agricultural fertilizer, for example—also may be used as post-consumer or recycled inputs for the inventive concept itself, whether the front end and/or the back end, or may be used as post-consumer or recycled inputs for another, entirely separate, process.
(27) Turning now to
(28) In the Front End Grouping
(29) receiving and preliminarily processing a paper or carpet exothermic processing waste stream (102);
(30) thermally processing a paper or carpet exothermic processing waste stream (104);
(31) producing and recovering energy from the thermal processing of the paper or carpet exothermic processing waste stream (106); and
(32) recovering minerals from the waste and producing a composite ash, as a PC or PI collecting or precipitating agent (108).
(33) In the Back End Grouping
(34) processing wastewater (110);
(35) removing phosphates and nitrates from the wastewater and pH adjusting the effluent slurry or the resulting water output (112); and
(36) precipitating, collecting, and processing a post-consumer product from the ash slurry with the wastewater (114).
(37) In some exemplary embodiments, the method 10 efficiently and effectively consumes the substantial majority of the paper or carpet exothermic processing waste stream, with limited emissions, bi-products, and residues that cannot be captured, filtered, or reused and/or recycled.
(38) The receiving and preliminarily processing step 102 of the method 10 relates to a paper or carpet exothermic processing waste stream (EWS). The EWS could be in a hydrous (water/moisture>air dried material) or anhydrous state (air dried or bone dry). If they are in a hydrous state, drying is performed prior to the thermal processing step 104. In the paper mill sludge example, the material is in a hydrous state and may require some dewatering and physical shredding and/or de-lumping, as preliminary processing, prior to the thermal processing step 104. In the case of carpet, if it is an anhydrous state, then it generally requires no dewatering or drying prior to thermal processing step 104. Instead, preliminary processing involves comminuting the carpet into pieces, such as shredding, chopping, grinding, shaving, cutting, tearing, and/or shearing the carpet to produce pieces a smaller size.
(39) Next, the thermal separation step 104 of the method 10 on the paper or carpet exothermic processing waste stream occurs at an average process bed temperature in the range of about 600° C. to about 1000° C. The EWS is passed to the thermal separation stage 104, where various thermal separators (reactors) are employed including kilns, rotary kilns, grate furnaces, moving grate furnaces, fluidized beds, vertical or horizontal calciners, and the like. This controlled thermal separation step 104 is carried out to remove organics from the EWS materials. It is, in general, desirable to remove the organics from the minerals without decomposing the calcium carbonate present; however, other special products may be produced by allowing at least a temporary decomposition of the calcium carbonate. For example, the carbon dioxide in calcium carbonate flashes off above 800° C., more specifically at about 825° C., the organics decompose below 700° C., and the calcium carbonate decomposes before 900° C. These facts may be used in tailoring the products of the thermal separation step 104.
(40) An exemplary temperature range for the thermal separation process 104 is 600° C. to 1000° C. average bed process temperature for a period of 30 minutes to 12 hours, preferably at 600° C. to 825° C. average bed process temperature for a period of 30 minutes to 2 hours, and more preferably at 600° C. to 800° C. average bed process temperature for a period of 30 minutes to 1 hour. In another exemplary embodiment of the present invention, the thermal separation may be carried out in an indirectly heated rotary kiln at approximately 700° C. average bed process temperature for approximately a 30 minute resident time with adequate air flow to assure proper combustion. Two or more thermal separation steps 104 can be included depending on the efficiency of the thermal separation step 104, such as the reactors or reaction parameters used in the thermal separation step 104, or if a certain end product is desired. In another exemplary embodiment, the thermal separation step 104 is carried out at an average bed process temperature in the ranges of from 600° C. to 800° C., 800° C. to 1000° C., and 825° C. to 1000° C.
(41) Optionally, in some exemplary embodiments of the invention, at least a portion of the composite ash (the produced collecting or precipitating agent at step 108) is recycled into the thermal separation step 104. The EWS feed into feed step 102 can be polymer-based and if subjected to the thermal separation step, as is, may not oxidize (combust) efficiently. It has been found that adding some of the composite ash to the EWS feed, the composite ash preferably being mineral product previously having been subjected to the thermal separation step 104, increases the efficiency of the thermal separation step and the quality of the resulting mineral product. It has also been found that adding some of the composite ash to the EWS feed may help to obtain the proper dryness or moisture content prior to any thermal separation step 104.
(42) The thermal processing step 104 of the EWS is the most crucial step in the method 10. The controlled processing parameters include combustion, temperature, time, combustion atmosphere, etc. The thermokinetics of the process is contingent on the EWS, and the operational and design elements of the thermal processing system used, and the desired quality or material characteristics of the energy and mineral or material products desired. The primary purpose of the thermal processing step 104 is to separate and remove the organics from the inorganics through combustion and to create a sterile, bright, and reactive mineral oxide material. Critical processing parameters (CPP) for thermally processing paper mill sludge are as follows:
(43) Kiln or Calciner Material Bed Temperatures Range from 700° C.-1000° C., specifically in the range of 750° C.-900° C.;
(44) The dwell or retention time for combustion, liberation, separation, and recovery of the energy and minerals or material elements within the reactor is in the range of 30 minutes to 4 hours specifically in the range of 30 minutes to 2 hours. The actual time parameter is a function of the chemical and thermokinetics of the system including specific product qualities desired; and
(45) The combustion atmosphere is oxidizing to slightly oxidizing.
(46) Several types of thermal reactors can be used for the thermal processing step 104 of the method 10. These reactors include but are not limited to: Direct and indirect fired rotary kilns Direct and indirect fired rotary calciners Vertical multi-hearth calciners and kilns Flash calciners Fluidized bed calciners and kilns
(47) Turning briefly to
(48) More specifically, the exemplary embodiment of
(49) Turning back to
(50) In the thermal separation step 104, energy from the combustion or oxidation of the EWS is recovered in the recovering energy step 106. During the thermal processing step 104, energy is released in the form of heat. The renewable energy is generated from the combustion process and is recovered in an energy-recovery-heat-exchanger (waste heat recovery boiler). The energy recovery is then converted into both steam and/or power as valuable renewable energy products. A person of ordinary skill in the art understands that each EWS contains various energy values, and energy efficient systems are designed for maximum energy recovery. The recovered energy is used as is or the heat may be used as is. High and low pressure steam also may be produced, which may be used for electricity or other purposes.
(51) Next, the recovering and producing the composite ash step 108 of the method 10 is related directly the thermal processing step 104. The chemical composition and physical characteristics of the ash product are functions of the EWS resources processed. The products are considered energy+ (e.g., 20× to 40× more energy generated than consumed), post-consumer, recycled, renewable, etc., which are in demand for life cycle-based companies. By controlling the EWS and chemical compositions, unique and valuable physical and chemical products are created for a range of applications, such as wastewater treatments, and as the building-blocks or precursors for other products.
(52) For example, when paper mill sludge or deinking sludge is thermally processed as in step 104 under carefully controlled CPPs and properly designed reactors (such as kiln 2 and/or calciner 4 of
(53) In this way, for the back-end wastewater processing portion (see steps 110-114), the composite ash is used as a post-consumer active ingredient or input for the method 10 itself, whether in feedback with the front end and/or as a direct input, and as a substitute for less sustainable materials and chemical reagents. Additionally, the composite ash can be used as a post-consumer treatment material, chemical reagent, building material, filler, etc., for another, entirely separate system or process.
(54) Further, the composite ash of the front-end (see steps 102-108) is specifically designed as nutrient removal collector, collection, or precipitation agent in wastewater streams including but not limited to municipal and industrial streams along with open-water applications such as lakes, oceans, and rivers. The derived ash has a significant CaO component as is described herein. The meta-kaolin component, alongside any multivalent metal ions that might be present as constituents, may act as a primary collector, as the reactivity and surface area of meta-kaolin create a double-layer surface attraction to specific phosphate and nitrate ion species in aqueous solution. In this way, and as is described in greater detail herein, the collection and precipitation synergy between the meta-kaolin and the metal ions, specifically but not limited to certain metal oxides, may drive the phosphate and nitrate separation in the wastewater treatment processing portion of the inventive concept. Further, in this way, and as is described in greater detail herein, the derived ash with its significant CaO component, and with its produced hydroxide chemical intermediates, inherently increases the pH in any treated municipal wastestream (whether coming-in as acid, alkaline, or neutral) to above about 10, as is usually required for efficient contaminant removal or precipitation, without need for any secondary pH adustment treatment step, as is understood in the art.
(55) As such, the composite ash outputs of the front end are used as post-consumer or recycled inputs for the back end, as is the energy output. Therefore, the method 10 produces or reduces the “fresh” inputs (i.e., fresh or currently-uncontaminated inputs, like water, etc., as is described in steps 110-114) necessary for paper mill sludge, deinking sludge, or the carpet third stream waste stream processing, and also related to reducing the non-useful, or potentially toxic, outputs therefrom. The system and method of this exemplary embodiment achieves sustainable elimination of pollution streams that, even when recycled/treated, as taught in the prior art, would produce (1) residues, (2) new wastes or pollutants, and/or (3) secondary waste or pollution streams. Method 10 solves these problems when compared to the prior art as shown and disclosed in the following Examples including experimental results.
(56) Returning, generally, to the recovering and producing the composite ash step 108 of the method 10, this step involves subjecting the produced product through a milling processing, for example, or another process for reducing the structure of the composite ash, if desired and/or if necessary for producing a desired end product for a particular use.
(57) Once the mineral product ash is obtained through the present invention, it can be further treated if desired to produce other valuable products. For example, the composite ash produced in the thermal separation step 104 can be milled and pulverized using any of various known suitable dry milling techniques such as hammer mill pulverizers, ball mills, and the like. This pulverization, milling, or grinding is employed to expose as many distinct particle surfaces as possible for reaction in the following steps and stages of the process. The dried mineral product material may be further milled or pulverized in other substeps to assure uniformity and better dispersion and to give the desired oil absorption properties, if necessary. If oil absorption values are in excess of 40 or if lower oil absorption values are otherwise desired, ball milling may be employed.
(58) Milling the mineral product of the present invention alters the morphology or crystalline structure of the mineral product by creating or destroying or reducing the structure to provide the desired degree of structure to yield, for example, the desired oil absorption and density for the desired end use.
(59) Turning briefly to
(60) More specifically, the exemplary embodiment of
(61) Turning back to
Ca(HCO.sub.3).sub.2+Ca(OH).sub.2.fwdarw.2CaCO.sub.3↓+2H.sub.2O (8)
(62) As the pH value of the wastewater increases beyond about 10, excess calcium ions will then react with the phosphate to precipitate a hydroxylapatite, as is generally characterized by the following Formula 9.
10 Ca.sup.2++6 PO.sub.4.sup.3−+2 OH.sup.−.Math.Ca.sub.10(PO.sub.4)*6(OH).sub.2↓ (9)
(63) The meta-kaolin acts as the primary Ca in the process. The reactivity and surface area of the meta-kaolin creates a double layer surface attraction to specific phosphorous and nitrate ion species. The collection and precipitation synergy between the meta-kaolin and the metal ions specifically but not limited to CaO drive the phosphorous and nitrate separation process. It is understand by a person of ordinary skill in the art that, as the reaction is between the lime and the alkalinity of the wastewater (after introduction of the derived ash with the municipal wastewater to be treated), the quantity required will be, in general, independent of the amount of phosphate present. Instead, it will primarily depend on the alkalinity of the wastewater. The lime dose required can be approximated at 1-2 times the alkalinity as CaCO.sub.3.
(64) The mixing process usually requires that the composite ash is slaked prior to mixing with the wastewater effluent for better mixing; however, dry applications are also envisioned. Once the mixing is complete and thorough, reaction times range from 0.25-2 hours. Mixing is completed with inline mixers, agitated tanks, etc. In addition to the recovered composite ash product, other metal compounds and coagulants may be added to the slurry to further enhance separation and improve the separation kinetics of the process. ZnO and HMW separation polymers are two examples of the separation enhancers.
(65) Next, the removing phosphates and nitrates from the wastewater step 112, and the associated pH adjusting the effluent slurry or the resulting clean water output step, of the method 10 is directly related to the processing the wastewater step 110. In some cases, but not required, the pH may be adjusted prior to the separation step 114 to create additional valuable and enriched compounds within the recovered solids i.e., pH adjustment with phosphoric, sulfuric, and/or stearic acid to add or enhance valuable components to the recovered solids. In this way, the outputs of the front end steps 102-108 may be used as post-consumer or recycled inputs for another, entirely separate, process; a process that would otherwise use fresh inputs or comparatively unsustainable inputs, or for the back-end steps 110-114.
(66) Next, the precipitating, collecting, and processing a post-consumer product from the ash-effluent slurry step 114 of the method 10 is directly related to the removing phosphates and nitrates from the wastewater step 112. Once the reaction of step 112 is complete, the precipitated and collected phosphate and/or nitrate compounds are separated from the effluent slurry using a range of separation techniques including but not limited to clarifiers, centrifuges, filters, etc. Of course, it is also envisioned that, instead of strict separation techniques, other known techniques for targeting and collecting the desired product may be implemented, including but not limited to flocculation, agglomeration, etc.
(67) Once the precipitate or solids are separated, the material is filtered and/or dried into a dry product or left in a liquid depending on various product applications. Further, once the phosphate and nitrate separation is complete, the pH adjusted/decontaminated water may be discharged into the watershed via river, ocean, lake, etc., or may be cycled back into the municipal system. At this point, optionally, the purified effluent may be pH adjusted using weak and/or strong acids including but not limited to phosphoric, sulfuric, hydrochloric, and stearic acid. Again, any secondary pH adjustment is optional before or after the separation processes.
(68) The final product generated from the removing phosphates and nitrates from the wastewater step 112 contains valuable and unique forms of chemical and minerals. The wastewater treatment process increased valuable phosphate and nitrate compounds by 1%-30%. Chemical compounds that contain calcium, kaolin, phosphates, nitrates, and sulfates are excellent platforms for agricultural uses such as fertilizers, soil modifiers, soil enrichers, and soil enhancers. The unique materials and products recovered from the removing phosphates and nitrates from the wastewater step 112 contain valuable minerals and compounds. The materials and products also inherently retain reactive chemical complexes that are also unique and valuable in some product applications.
(69) These applications include products designed and recovered for applications in the following industries: Agricultural, including fertilizers Building and construction, including pozzolans Paper, including pigments and fillers Municipalities, including wastewater treatment.
(70) In this way, the outputs of the back-end process grouping of steps 108-114, may be used as post-consumer or recycled inputs for the inventive concept itself, or may be used as post-consumer or recycled inputs for another, entirely separate, process. The outputs of the back-end process grouping of steps 108-114 may also be useful in various different delivery methods. In one exemplary embodiment, the composite ash may exhibit broadcast delivery or non-point source applications, e.g., aerial applications, barge and boat spreading systems (even broadcast or below-surface injection), and global positioning orientated systems. In another exemplary embodiment, the composite ash may exhibit point-source application. This may be especially useful for meat processing customer segments, where excess nutrient-laden wastewater is directly attributable to one source. A person of ordinary skill in the art understands that point-source treatment plants are highly-engineered facilities with multi-step treatment vessels and mixing tanks, where the tanks are arranged in treatment sequences, well suited for direct injection of carefully calibrated amounts of the composite ash product, for example.
EXAMPLES 1-6
(71) The following are six (6) illustrative examples of the process of the present invention when applied under experimental conditions.
Example 1
Controlled Experiment #1
(72) A phosphate standard solution was prepared from 1000 mg/L phosphorous standard solution and distilled water to a concentration of 5 mg/L. A 0.2 mg sample of collection material was mixed with 200 mL of the 5 mg/L phosphate standard solution in a plastic beaker with a bench-top mixer set at 400 rpm. After 30 minutes of mixing, the solution was transferred to a centrifuge vessel and centrifuged for 7 minutes. A post treatment sample was collected with a pipette from the top half inch of post treatment solution. The post-centrifuged solution was analyzed for orthophosphate concentration using a Hach colorimeter. The post-treatment phosphate concentration was 0.08 mg/I representing a 98.4% removal of phosphate.
Example 2
Controlled Experiment #2
(73) A phosphate standard solution was prepared from 1000 mg/L phosphorous standard solution and distilled water to a concentration of 20 mg/L. A 0.1 mg sample of collection material was mixed with 200 mL of the 20 mg/L phosphate standard solution in a plastic beaker with a bench-top mixer set at 400 rpm. After 30 minutes of mixing, the solution was transferred to a centrifuge vessel and centrifuged for 7 minutes. A post treatment sample was collected with a pipette from the top half inch of post treatment solution. The post-centrifuged solution was analyzed for orthophosphate concentration using a Hach colorimeter. The post-treatment phosphate concentration was 0.55 mg/L representing a 97.25% removal of phosphate.
Example 3
Municipal Wastewater #1
(74) A 2 g sample of collection material was mixed with 300 mL of effluent obtained from the Sandersville, Ga., US wastewater treatment facility having an initial phosphate concentration of 1.46 mg/L. The sample and effluent was mixed in a plastic beaker with a bench-top mixer set at 400 rpm. After 30 minutes of mixing, the solution was transferred to a centrifuge vessel and centrifuged for 7 minutes. A post treatment sample was collected with a pipette from the top half inch of the post treatment solution. A post treatment sample was collected with a pipette from the top half inch of post treatment solution. The post-centrifuged solution was analyzed for phosphate concentration using a Hach colorimeter. The post-treatment phosphate concentration was 0.1 mg/L representing a 93.2% removal of phosphate.
Example 4
Municipal Wastewater #2
(75) A 40 g sample of collection material was mixed with 80 liters of effluent obtained from the Milledgeville, Ga., US wastewater treatment facility having a phosphate concentration of 1.25 mg/L. The sample and effluent was mixed in a plastic barrel with a barrel mixer. After 30 minutes of mixing, the solution was transferred to a centrifuge vessel and centrifuged for 7 minutes. A post treatment sample was collected with a pipette from the top half inch of post treatment solution. The post-centrifuged solution was analyzed for phosphate concentration using a Hach colorimeter. The post-treatment phosphate concentration was 0.12 mg/L representing a 90.4% removal of phosphate.
Example 5
Industrial Waste Stream #1
(76) A 1 g sample of collection material was mixed with 1 L of industrial wastewater obtained from XYZ Inc. having an initial phosphate concentration of 4.2 mg/L. The sample and effluent was mixed in a plastic beaker with a bench-top mixer set at 400 rpm. After 30 minutes of mixing, the solution was transferred to a centrifuge vessel and centrifuged for 7 minutes. A post treatment sample was collected within pipette from the top half inch of post treatment solution. The post-centrifuged solution was analyzed for phosphate concentration using a Hach colorimeter. The post-treatment phosphate concentration was 0.51 mg/L representing an 88.09% removal of phosphate.
Example 6
Industrial Waste Stream #2
(77) A 2 g sample of collection material was mixed with 1 L of industrial wastewater obtained from XYZ Inc. having an initial phosphate concentration of 14 mg/L. The sample and effluent was mixed in a plastic beaker with a bench-top mixer set at 400 rpm. After 30 minutes of mixing, the solution was transferred to a centrifuge vessel and centrifuged for 7 minutes. A post treatment sample was collected with a pipette from the top half inch of the post treatment solution. A post treatment sample was collected with a pipette from the top half inch of post treatment solution. The post-centrifuged solution was analyzed for phosphate concentration using a Hach colorimeter. The post-treatment phosphate concentration was 0.89 mg/L representing a 93.6% removal of phosphate.
EXAMPLES 7-14
(78) The following are seven (7) illustrative examples of the process of the present invention, specifically performed for purpose of optimizing and refining the inventive concept for application to various conditions.
Example 7
(79) This experiment was performed to evaluate the effect, if any, of calcination temperature and setting time on final [PO.sub.4] after use of the composite ash/capture material on contaminated water. When compared to the centrifuge trial (see Example 8 below), it was determine that centrifugation gave better results, and that settling-only techniques were not necessarily worth pursuing. Some of the experimental results obtained are represented by the following information provided in Tables 2A and 2B.
(80) TABLE-US-00002 TABLE 2A Initial Vol. Mass Conc. Initial Initial Init. pH Mix Test Sol'n Material So'ln Temp pH Sol'n + Time ID Material (ml) (g) (mg/l) Sol'n Sol'n material (min) 003 Meta Kaolin 100 1 2.43 18 5.8 5.83 30 004 Calitza LS 100 1 2.43 18 5.8 9.86 30 001 R1000 100 1 2.43 18.7 3.7 13.02 30 005 R1000 100 1 2.43 16.2 6.26 13.67 30 007 R1000 100 1 2.43 16.9 6.55 13.69 30 009 R1000 100 1 2.48 18.5 6.49 13.69 30 011 R1000 200 2 2.48 22 6.24 12.89 30 002 R800 100 1 2.43 18.7 4.4 13.23 30 006 R800 100 1 2.43 16.2 6.23 13.65 30 008 R800 100 1 2.43 16.9 6.53 13.81 30 010 R800 100 1 2.48 18.5 6.51 13.76 30 012 R800 200 2 2.48 22 6.23 12.92 30 013 R850 100 1 2.48 19.5 6.2 13.28 30 014 R900 100 1 2.48 19.5 6.2 13.3 30 015 R950 100 1 2.48 19.5 6.2 13.35 30 016 R800 300 3 2.48 20.9 6.76 13.53 30 017 R800 300 3 2.48 20.9 6.76 13.53 30 018 R Calc 100 1 2.48 21.6 6.91 13.13 30 019 R calc. Pulv 100 1 2.48 21.6 6.91 13.24 30
(81) TABLE-US-00003 TABLE 2B pH Temp Post Settle Post Test Post post screen Time settle ID screen Screen ° C. conc. (min) Conc. notes 003 7.95 17 — 1440 2.21 colorimeter test fault- 004 8.72 17 — 105 1.39 colorimeter test fault- 001 13.36 17.3 1.38 60 post settle test fault 005 13.71 16.4 1.3 30 0.59 007 13.62 17.1 1.14 30 0.78 009 13.76 18.4 1.01 90 0.5 heat added settle final temp. 45.2 011 12.87 19.7 2.19 30 post settle test fault- no screening 002 16.65 17.3 0.27 60 post settle test fault 006 13.87 16.7 0.18 30 0.61 008 13.74 17.2 0.55 30 0.21 010 13.81 18.4 0.72 15 0.35 heat added settle final temp. 45.2 012 12.84 19.6 1.08 5 0.5 no screening 013 13.48 21 0.68 30 post settle test fault- no screening 014 13.56 21.1 1.1 30 0.36 no screening 015 13.11 21.1 1.12 30 0.81 no screening 016 13.49 21.1 1.16 20 0.98 no screening 017 13.51 21 1.03 20 0.98 no screening 018 13.09 21.1 0.97 40 0.38 no screening 019 13.22 21.1 2.39 40 0.42 no screening
(82) The information in Table 2A and 2B illustrates individual trials (Test IDs) and their results, based on the use of the composite ash and various other prior art products. The composite ash trials are specifically labeled using “R Calcined”, “R calc. pulv”, “R###”, wherein the “###” portion is indicative of the applied calcination temperature for production of that trial's composite ash.
Example 8
(83) This experiment was performed to evaluate the effect of centrifugation time on the final [PO.sub.4] after use of the composite ash/capture material on contaminated water. Some of the experimental results obtained are represented by the following information provided in Table 3A and 3B.
(84) TABLE-US-00004 TABLE 3A Vol- Initial ume Mass Conc. Initial Initial Init. pH Test Sol'n Material Solution Temp pH Solution + ID Material (ml) (g) (mg/l) Sol'n Sol'n material 020 R Calc 200 10 ml @ 2.43 21.3 7.67 13.52 Pulv 20% 021 R Calc 200 10 ml @ 2.43 21.3 7.59 13.22 Pulv 20% 022 R Calc 200 10 ml @ 2.43 19.6 7.31 13.27 15% 023 R Calc 300 2 1.46 16.6 6.34 13.47 024 R Calc 300 2 1.46 16.6 6.34 13.51 025 R Calc 300 2 1.46 16.6 6.34 13.51 026 R Calc 300 2 1.46 15.2 6.34 Pulv 027 R Calc 300 2 1.46 15.2 6.34 Pulv 028 R Calc 300 2 1.46 15.2 6.34 Pulv 029 Ranier 250 2 2.43 030 CaO 250 2 2.43 Calitza 031 N—C 250 2 2.43
(85) TABLE-US-00005 TABLE 3B pH Centri- Post Post fuge centri- Test Mix Centri- Duration fuge ID Time fuge (min) Conc. notes 020 30 13.1 8 0.16 Slake by hand mixing 2 min 021 30 13.22 8 0.07 Slake by hand mixing 2 min 022 30 13.25 8 0.09 Slake by hand mixing 2 min 023 30 7 0.26 Sandersville Effluent used 024 30 7 0.06 Sandersville Effluent used 025 30 7 0.19 Sandersville Effluent used 026 30 7 0.39 Sandersville Effluent used 027 30 7 0.41 Sandersville Effluent used 028 30 7 0.1 Sandersville Effluent used 029 30 7 0.15 030 30 7 0.24 031 30 7 0.02
(86) The information in Tables 3A and 3B illustrates individual trials (Test IDs) and their results, based on the use of the composite ash and various other prior art products. The composite ash trials are specifically labeled using “R Calc Pulv” and “R Calc”.
Example 9
(87) This experiment was performed to evaluate the effect of total mix time/retention time on the final [PO.sub.4] after use of the composite ash/capture material on contaminated water. From a production or WWTP standpoint, less mix time/retention time is preferred. Some of the experimental results obtained are represented by the following information provided in Table 4.
(88) TABLE-US-00006 TABLE 4 Retention Time Trials Vol- Mass Initial Centri- Post ume Ma- Conc. Mix fuge centrifuge Test Sol'n terial Sol'n Time Time Conc. ID Material (ml) (g) (mg/l) (mins) (min) (mg/l) 041 R Cal 200 0.3 2.45 30 7 0.07 Pulv 042 R Cal 200 0.3 2.45 30 7 0.13 Pulv 043 R Cal 200 0.3 2.45 30 7 0.08 Pulv 044 R Cal 200 0.3 2.45 20 7 0.15 Pulv 045 R Cal 200 0.3 2.45 20 7 0.13 Pulv 046 R Cal 200 0.3 2.45 20 7 0.15 Pulv 047 R Cal 200 0.3 2.44 10 7 0.28 Pulv 048 R Cal 200 0.3 2.44 10 7 0.24 Pulv 049 R Cal 200 0.3 2.44 10 7 0.15 Pulv 050 R Cal 200 0.3 2.43 5 7 0.19 Pulv 051 R Cal 200 0.3 2.43 5 7 0.25 Pulv 052 R Cal 200 0.3 2.43 5 7 0.21 Pulv 053 R Cal 200 0.3 2.43 3 7 0.51 Pulv 054 R Cal 200 0.3 2.43 3 7 0.41 Pulv 055 R Cal 200 0.3 2.43 3 7 0.48 Pulv 056 R Cal 200 0.3 2.43 1 7 0.79 Pulv 057 R Cal 200 0.3 2.43 1 7 1.23 Pulv 058 R Cal 200 0.3 2.43 1 7 0.97 Pulv
(89) The information in Table 4 illustrates individual trials (Test IDs) and their results, based on the use of the composite ash. The composite ash trials are specifically labeled using “R Cal Pulv”.
Example 10
(90) This experiment was performed to evaluate the effect of different relative amounts/material dosage of added composite-ash/capture material on the final [PO.sub.4] after use on contaminated water. From a cost standpoint, it is preferred to use relatively less than more. Some of the experimental results obtained are represented by the following information provided in Tables 5 and 6.
(91) TABLE-US-00007 TABLE 5 Material Dosage Trials Initial Mix Centrifuge Post Test Vol. Mass Conc. Sol'n Time Duration centrifuge ID Material Sol'n (ml) Material (g) (mg/l) (mins) (min) Conc. (mg/l) 032 R cal pulv 200 0.7 2.45 30 7 0.15 035 R cal pulv 200 0.7 2.45 30 7 0.16 033 R cal pulv 200 0.5 2.45 30 7 0.11 036 R cal pulv 200 0.5 2.45 30 7 0.14 034 R cal pulv 200 0.3 2.45 30 7 0.13 037 R cal pulv 200 0.3 2.45 30 7 0.09 038 R cal pulv 200 0.2 2.45 30 7 0.73 039 R cal pulv 200 0.1 2.45 30 7 0.4 040 R cal pulv 200 0.05 2.45 30 7 0.41
(92) TABLE-US-00008 TABLE 6 Initial Mix Centrifuge Post Test Vol. Sol'n Mass Conc. Sol'n Time Duration centrifuge ID Material (ml) Material (g) (mg/l) (min) (min) Conc. (mg/l) 108 R Cal Pulv 200 0.1 5 30 7 0.32 109 R Cal Pulv 200 0.2 5 30 7 0.09 110 R Cal Pulv 200 0.4 5 30 7 0.19 111 R Cal Pulv 200 0.1 10 30 7 0.5 112 R Cal Pulv 200 0.2 10 30 7 0.24 113 R Cal Pulv 200 0.4 10 30 7 0.1 114 R Cal Pulv 200 0.1 20 30 7 0.82 115 R Cal Pulv 200 0.2 20 30 7 0.54 R Cal Pulv 200 0.4 20 30 7 0.16
(93) The information in Tables 5 and 6 illustrate individual trials (Test IDs) and their results, based on the use of the composite ash. The composite ash trials are specifically labeled using “R Calc Pulv” and “R cal pulv”.
Example 11
(94) This experiment was performed to evaluate the effects of the process of the present invention, as optimized and refined via the results presented in Examples 7-10, on the final [NO.sub.3] after use of the composite ash/capture material on contaminated water. Some of the experimental results obtained are represented by the following information provided in Table 7.
(95) TABLE-US-00009 TABLE 7 Nitrate adsorption Trials Post Mass Initial Centri- centri- Vol. Ma- Conc. Mix fuge fuge Test Ma- Soln terial Sol'n Time Duration Conc. ID terial (ml) (g) (mg/l) (mins) (min) (mg/l) notes 059 R Cal 200 0.3 3.4 30 7 1.1 no3 Pulv 060 R Cal 200 0.3 3.4 30 7 1 no3 Pulv 061 R Cal 200 0.3 3.4 30 7 1.1 no3 Pulv 062 R Cal 100 0.3 3.4 30 7 0.9 NO3 Pulv Sol'n used 062 R Cal 100 2.43 30 7 0.25 PO4 Pulv Sol'n used 062 R Cal 100 0.3 3.5 30 7 1 NO3 Pulv Sol'n used 062 R Cal 100 2.43 30 7 0.12 PO4 Pulv Sol'n used 064 R Cal 100 0.3 3.4 30 7 0.9 NO3 Pulv Sol'n used 064 R Cal 100 2.43 30 7 0.17 PO4 Pulv Sol'n used
(96) The information in Table 7 illustrates individual trials (Test IDs) and their results, based on the use of the composite ash. The composite ash trials are specifically labeled using “R Calc Pulv”.
Example 12
(97) This experiment was performed to evaluate the effects of the process of the present invention, as optimized and refined via the results presented in Examples 7-11, on the final [PO.sub.4] and/or final [NO.sub.3] after use of the composite ash/capture material on high initial [PO.sub.4] and/or high initial [PO.sub.4], indicative of industrial waste waters. Some of the experimental results obtained are represented by the following information provided in Tables 8A, 8B, 9A, and 9B.
(98) TABLE-US-00010 TABLE 8A High Concentration Trials Initial Post Vol Mass Conc. Mix Centrifuge centrifuge Test Sol'n Material Sol'n Time Time Conc. ID Material (ml) (g) (mg/l) min (min) (mg/l) Notes 041 R Cal Pulv 200 0.3 2.45 30 7 0.07 042 R Cal Pulv 200 0.3 2.45 30 7 0.13 043 R Cal Pulv 200 0.3 2.45 30 7 0.08 065 r cal pulv 200 0.3 17.1 30 7 1 High Con. PO4- low accuracy 066 r cal pulv 200 0.3 17.1 30 7 0.5 High Con. PO4- low accuracy 067 r cal pulv 200 0.3 17.1 30 7 1.2 High Con. PO4- low accuracy 068 R Cal Pulv 200 0.3 24.5 30 7 1.2 High Con. PO4- low accuracy 069 R Cal Pulv 200 0.3 24.5 30 7 0.5 High Con. PO4- low accuracy 070 R Cal Pulv 200 0.3 24.5 30 7 0.8 High Con. PO4- low accuracy 071 R Cal Pulv 200 0.3 11.1 30 7 0.2 High Con. PO4- low accuracy 072 R Cal Pulv 200 0.3 11.1 30 7 0.4 High Con. PO4- low accuracy
(99) TABLE-US-00011 TABLE 8B Initial Post Vol Mass Conc. Mix Centrifuge centrifuge Test Sol'n Material Sol'n Time Time Conc. ID Material (ml) (g) (mg/l) min (min) (mg/l) Notes 073 R Cal 200 0.3 11.1 30 7 0.2 High Con. PO4- Pulv low accuracy 074 R Cal 500 0.75 26.6 30 settle 1.8 Settle time 40 Pulv mins 075 NaOH 200 ph 11.17 26.6 30 7 25.2 ph adjust only w/NaOH 076 NaOH 200 ph 11.28 26.6 30 7 25 ph adjust only w/NaOH 077 NaOH 200 ph 11.31 26.6 30 7 25.4 ph adjust only w/NaOH
(100) TABLE-US-00012 TABLE 9A Vol. Mass Initial Conc. Test Sol'n Material Sol'n ID Material (ml) (g) (mg/l) NO3 078 r1000 pulv 200 0.3 17.4 079 r1000 pulv 200 0.3 7.7 080 r1000 pulv 200 0.3 3.8 081 r1000 pulv 200 0.3 16.5 082 r1000 pulv 200 0.3 16.5 083 r cal pulv 200 0.3 16.5 084 r1000 pulv 200 0.3 5.8 085 r1000 pulv 200 0.3 5.8 086 r cal pulv 200 0.3 5.8 087 r1000 pulv 200 0.3 21.1 088 r1000 pulv 200 0.3 21.1 089 r cal pulv 200 0.3 21.1 090 Cao 200 0.3 5.3 091 Cao 200 0.3 13.4 092 Cao 200 0.3 21.1 093 Ray 200 0.3 5.3 094 ray 200 0.3 13.4 095 ray 200 0.3 21.1 096 Metakaolin 200 0.3 5.3 097 metakaolin 200 0.3 13.4 098 Metakaolin 200 0.3 21.1
(101) TABLE-US-00013 TABLE 9B Post Mix Centrifuge centrifuge Test Time Duration Conc. ID (min) (min) (mg/l) notes 078 30 7 0.35 079 30 7 0.2 080 30 7 0.08 081 30 7 0.44 082 30 7 0.46 083 30 7 0.59 084 30 7 0.22 085 30 7 0.14 086 30 7 0.05 087 30 7 0.36 088 30 7 0.51 089 30 7 0.19 090 30 7 0.17 091 30 7 0.23 092 30 7 0.24 093 30 7 0.42 094 30 7 2.09 095 30 7 6.9 096 30 7 5 ph adjust to 12 w/ NaOH 097 30 7 13.2 ph adjust to 12 w/ NaOH 098 30 7 20.8 ph adjust to 12 w/ NaOH
(102) The information in Tables 8A, 8B, 9A, and 9C illustrate individual trials (Test IDs) and their results, based on the use of the composite ash and various other prior art products. The composite ash trials are specifically labeled using “R Cal Pulv” and “r cal pulv”.
Example 13
(103) This experiment was performed to evaluate the effects of certain prior art products/substances on the final [NO.sub.3] after use on contaminated water. Some of the experimental results obtained are represented by the following information provided in Table 10.
(104) TABLE-US-00014 TABLE 10 Additive Trials Initial Conc. Post Vol Mass Sol′n Mix Centrifuge centrifuge Test Sol′n Material (mg/l) Time Duration Conc. ID Material (ml) (g) NO3 min (min) (mg/l) Notes 090 Cao 200 0.3 5.3 30 7 0.17 091 Cao 200 0.3 13.4 30 7 0.23 092 Cao 200 0.3 21.1 30 7 0.24 096 Metakaolin 200 0.3 5.3 30 7 5 ph adjust to 12 w/NaOH 097 metakaolin 200 0.3 13.4 30 7 13.2 ph adjust to 12 w/NaOH 098 Metakaolin 200 0.3 21.1 30 7 20.8 ph adjust to 12 w/NaOH 099 MK + 200 0.3 5.3 30 7 0.02 66.6% CaO CaO 33.3% Meetakaolin 100 MK + 200 0.3 13.4 30 7 0.03 66.6% CaO CaO 33.3% Meetakaolin 101 MK + 200 0.3 21.1 30 7 0.12 66.6% CaO CaO 33.3% Meetakaolin 102 MK + Cao + 200 0.3 5.3 30 7 0.02 66.25% Cao Zno 33.25% Metakaolin 0.5% Zno 103 MK + Cao + 200 0.3 13.4 30 7 0.02 66.25% Cao Zno 33.25% Metakaolin 0.5% Zno 104 MK + Cao + 200 0.3 21.1 30 7 0.02 66.25% Cao Zno 33.25% Metakaolin 0.5% Zno 105 ZnO 200 0.3 5.3 30 7 4.5 106 ZnO 200 0.3 13.4 30 7 11.6 107 ZnO 200 0.3 21.1 30 7 18.6
Example 14
(105) This experiment was performed to show the effect of calcination temperature on the composition of the composite ash/capture agent, and the reactivity of calcined product. Some of the experimental results obtained are represented by the following information provided in Tables 11 and 12.
(106) TABLE-US-00015 TABLE 11 CaO SiO2 Al2O3 TiO2 MgO Fe2O3 K2O SO3 Cl La2O3 SrO R_1000 65.8 23.00 4.09 2.23 1.6 1.57 0.391 0.323 0.14 0.0549 0.0548 R_800 61.8 24.60 5.37 2.69 1.67 1.92 0.388 0.34 0.11 0.0967 0.0392 post process Sm2O5 ZrO CeO2 CuO MnO Na2O P2O5 ZnO R_1000 0.0424 0.037 0.0367 0.0321 0.0316 0.218 0.187 0.168 R_800 0.0543 0.0439 0.0547 0.037 0.0352 0 0.27 0.4 post process
(107) TABLE-US-00016 TABLE 12 Reactivity pH (Δ° C. in LOI @ (reactivity 3 min) 1000° C. t = 0) R_800 3.7 1.78% 13.04 R_850 4.5 0.99% 13.33 R_900 3.2 2.48% 13.54 R_950 4.4 0.65% 13.44 R_1000 4.2 0.57% 13.57 R_850 Cal. 1.09%
(108) The information in Tables 11 and 12 illustrate individual trials, wherein the “###” portion is indicative of the applied calcination temperature for production of that trial's composite ash.
Example 15
(109) This experiment was performed to establish a dose curve for [PO.sub.4]. Some of the experimental results obtained are represented by the following information provided in
EXAMPLES 16-19
(110) The following are four (4) illustrative examples of the process of the present invention, specifically performed to determine how slurry-dosing effects compared to dry-dosing effects for waste water treatment. It was expected that the slurried form had large scale production advantages. These experiments also sought to determine the highest % solid that would give good results without having the inherent problems of mixing. Conductivity was also monitored to give some indication of the salt content remaining in the water after treatment.
Example 16
5% Slurry
(111) Some of the experimental results obtained are represented by the following information provided in Tables 13-17.
(112) TABLE-US-00017 TABLE 13 Slurry Slaking Time (min) pH Temp (° C.) 0 11 27.7 5 11.05 39.2 10 11.08 49.1 15 11.25 46.8 20 11.66 53.7 25 11.51 54.4 30 11.42 51.1 35 11.6 54.52 40 11.17 56.7 42 11.79 61.3 45 10.94 55.3 47 10.86 57.1 50 10.85 53.8 60 10.78 55.7 84.5 na8.8 38.9 89.8 10.13 37.6 120 10.08 26.3
(113) TABLE-US-00018 TABLE 14 SAMPLES - 5% slurry Low [PO4] mg/L PO4 Cal Method 8048 reduction check Sample (<2.5 mg/L) stdev (%) stdev 2.53 Slurry 5L1 0.06 97.628 2.53 Slurry 5L2 0.01 99.605 2.53 Slurry 5L3 0.07 97.233 Slurry AVG 0.047 0.032 98.155 1.271 2.5 Dry 2.5 mg/L + 0.29 88.371 dry 900 C. comparison Avg Slurry % 11.07 increase over dry
(114) TABLE-US-00019 TABLE 15 Conductivity mS/cm @ t (min) post % Cond Sample 0 5 10 15 20 25 30 centrifuge loss stdev 5L1 2.67 2.79 2.79 2.77 2.73 2.72 2.69 2.53 5.24 5L2 2.81 2.81 2.79 2.77 2.74 2.72 2.69 2.47 12.10 5L3 2.74 2.74 2.73 2.69 2.67 2.65 2.63 2.37 13.50 AVG 10.28 4.419835
(115) TABLE-US-00020 TABLE 16 SAMPLES - 5% slurry High [PO4] mg/L PO4 Cal Method 8048 reduction check Sample (<2.5 mg/L) stdev (%) stdev 20.5 Slurry 5H1 0.08 99.610 20.5 Slurry 5H2 0.04 99.805 20.5 Slurry 5H3 0.03 99.854 Slurry Average 0.050 0.0265 99.756 0.129061 20 20 mg/L + 900 C. 0.34 98.283 dry comparison Avg Slurry % increase over dry 1.50
(116) TABLE-US-00021 TABLE 17 Conductivity mS/cm @ t (min) post % Cond Sample 0 5 10 15 20 25 30 centrifuge loss stdev 5H1 2.78 2.78 2.77 2.75 2.73 2.69 2.69 2.36 15.11 5H2 2.75 2.75 2.73 2.72 2.69 2.67 2.65 2.46 10.55 5H3 2.75 2.75 2.73 2.71 2.69 2.67 2.65 2.43 11.64 avg cond 12.43 2.38 loss
Example 17
10% Slurry
(117) Some of the experimental results obtained are represented by the following information provided in Tables 18-22.
(118) TABLE-US-00022 TABLE 18 Slurry Slaking Time temp (min) pH (° C.) 0 12.16 25.8 5 11.34 33.7 10 11.33 36.2 15 11.35 41.2 20 11.28 42.7 25 11.28 44.4 30 11.3 45.3 35 11.32 46.6 40 11.33 47.4 45 11.35 48.7 50 11.41 49.3 55 11.44 50.6 60 11.49 49.9 65 11.54 49.2
(119) TABLE-US-00023 TABLE 19 SAMPLES - 10% slurry Low [PO4] mg/L PO4 Cal Method 8048 reduction check Sample (<2.5 mg/L) stdev (%) stdev 2.48 10L1 0.05 97.984 2.48 10L2 0.18 92.742 2.48 10L3 0.05 97.984 Slurry Average 0.093 0.075 96.237 3.026 2.5 Dry 2.5 mg/L + 0.29 88.371 dry 900 C. compare Avg Slurry % 8.90 increase over dry
(120) TABLE-US-00024 TABLE 20 Conductivity mS/cm @ T (min) pre- post % Cond Name add 0 5 10 15 20 25 30 centrifuge loss stdev 10L1 0.029 2.67 2.69 2.68 2.67 2.66 2.64 2.62 2.47 7.49 10L2 0.0054 2.65 2.67 2.66 2.65 2.63 2.61 2.58 2.42 8.6792 10L3 0.0052 2.58 2.61 2.6 2.59 2.57 2.56 2.53 2.36 8.5271 AVG 8.23 0.646
(121) TABLE-US-00025 TABLE 21 SAMPLES - 10% slurry High [PO4] mg/L PO4 Cal Method 8048 reduction check Sample (<2.5 mg/L) stdev (%) stdev 20.5 10H1 0.06 99.707 20.5 10H2 0.19 99.073 20.5 10H3 0.14 99.317 Slurry Average 0.130 0.066 99.366 0.3199 20 mg/L + 0.34 98.283 dry 900 C. comparison Avg Slurry % 1.10 increase over dry
(122) TABLE-US-00026 TABLE 22 Conductivity mS/cm @ post pre- centri- % Cond ame add 0 5 10 15 20 25 30 fuge loss stdev 10H1 0.0024 2.6 2.62 2.61 2.61 2.59 2.58 2.56 2.46 5.38 10H2 0.0023 2.61 2.62 2.61 2.61 2.59 2.58 2.56 2.35 9.96 10H3 0.0023 2.59 2.61 2.6 2.6 2.58 2.56 2.54 2.31 10.81 AVG 8.719 2.919
Example 18
15% Slurry
(123) Some of the experimental results obtained are represented by the following information provided in Tables 23-27.
(124) TABLE-US-00027 TABLE 23 Slurry Slaking Time (min) pH Temp (° C.) 0 11.89 30.5 5 12.03 34 10 12.01 38 15 12.05 41.9 20 12.05 44.6 25 12.05 47.5 30 12.03 49 35 12.02 49.9 40 11.96 48 45 11.9 50 50 11.83 50.8 55 11.79 51.8 60 11.78 53.4 65 11.81 54 70 11.83 53.5 75 11.81 54.4
(125) TABLE-US-00028 TABLE 24 SAMPLES-15% slurry Low Cal [PO4] mg/L Method 8048 PO4 reduction check Sample (<2.5 mg/L) stdev (%) stdev 2.47 15L1 0.02 99.190 2.47 15L2 0.09 96.356 2.47 15L3 0.06 97.571 Slurry Average 0.057 0.035 97.706 1.42 2.5 Dry 2.5 mg/L + 900 C. 0.29 88.371 dry comparison Avg Slurry % increase 10.56 over dry
(126) TABLE-US-00029 TABLE 25 Conductivity mS/cm @ t (min) post pre- centri % Cond Name add 0 5 10 15 20 25 30 fuge loss stdev 15L1 0.0148 2.71 2.74 2.72 2.71 2.69 2.67 2.65 2.41 11.07 15L2 0.0052 2.67 2.69 2.67 2.65 2.64 2.62 2.59 2.32 13.11 15L3 0.0057 2.72 2.73 2.72 2.7 2.68 2.66 2.64 2.38 12.5 AVG 12.23 1.046
(127) TABLE-US-00030 TABLE 26 SAMPLES-15% slurry High Cal [PO4] mg/L Method 8048 PO4 reduction check Sample (<2.5 mg/L) stdev (%) stdev 20.5 15H1 0.09 99.561 20.5 15H2 0.09 99.561 20.5 15H3 0.05 99.756 Slurry Average 0.077 0.023 99.626 0.112 20 20 mg/L + 900 C. 0.34 98.283 dry comparison Avg Slurry % increase over 1.37 dry
(128) TABLE-US-00031 TABLE 27 Conductivity mS/cm @ t (min) post pre- centri- % Cond Name add 0 5 10 15 20 25 30 fuge loss stdev 15H1 0.0251 2.69 2.73 2.72 2.7 2.68 2.66 2.65 2.47 8.18 15H2 0.0252 2.65 2.69 2.67 2.65 2.63 2.61 2.6 2.39 9.81 15H3 0.0248 2.64 2.66 2.65 2.63 2.62 2.6 2.59 2.43 7.95 AVG 8.65 1.014
Example 19
20% Slurry
(129) Some of the experimental results obtained are represented by the following information provided in Tables 28-32.
(130) TABLE-US-00032 TABLE 28 20% Slurry Slaking Time (min) pH Temp (° C.) 0 12.74 29.2 5 12.51 36.7 10 12.41 39.5 15 12.36 43.1 20 12.32 46 25 12.31 47.4 30 12.24 49.6 35 12.19 51.5 40 12.21 52.3 45 12.19 52.8 50 12.16 53.3 55 12.12 54.1 60 12.24 53.3 65 12.18 52.1
(131) TABLE-US-00033 TABLE 29 SAMPLES-20% slurry Low Cal [PO4] mg/L Method 8048 PO4 reduction check Sample (<2.5 mg/L) stdev (%) stdev 2.43 20L1 0.08 96.708 2.43 20L2 0.01 99.588 2.43 20L3 0.04 98.354 Slurry Avg 0.043 0.035 98.217 1.445 2.5 2.5 mg/L + 900 C. 0.29 88.371 dry comparison Avg Slurry % increase over 11.14 dry
(132) TABLE-US-00034 TABLE 30 Conductivity mS/cm @ t min) post centri- % Cond Sample pre-add 0 5 10 15 20 25 30 fuge loss stdev 20L1 0.00747 2.43 2.48 2.48 2.45 2.45 2.44 2.43 2.22 8.6 20L2 0.00758 2.4 2.43 2.43 2.41 2.4 2.38 2.36 2.22 7.5 20L3 0.00703 2.44 2.47 2.47 2.45 2.43 2.41 2.4 2.21 9.4 AVG 8.5 0.969
(133) TABLE-US-00035 TABLE 31 SAMPLES-20% slurry High Cal [PO4] mg/L Method 8048 PO4 reduction check Sample (<2.5 mg/L) stdev (%) stdev 20.4 20H1 0.08 99.608 20.4 20H2 0.1 99.510 20.4 20H3 0.03 99.853 Slurry Avg 0.070 0.036 99.657 0.177 20 mg/L + 900 C. 0.34 98.283 dry comparison Avg Slurry % increase over 1.40 dry
(134) TABLE-US-00036 TABLE 32 Conductivity mS/cm @ t (min) post centri- % Cond Sample pre-add 0 5 10 15 20 25 30 fuge loss stdev 20H1 0.0306 2.44 2.48 2.47 2.45 2.43 2.41 2.4 2.3 5.74 20H2 0.0263 2.44 2.48 2.47 2.45 2.43 2.41 2.39 2.25 7.79 20H3 0.0256 2.38 2.41 2.4 2.38 2.36 2.34 2.33 2.19 7.98 AVG 7.17 1.24
EXAMPLES 20-21
(135) The following are two illustrative examples of the process of the present invention, specifically performed for three objectives: (1) to determine which specific acid was most effective at neutralization; (2) to determine what effect combining the composite-ash/capture-material dosage, and the acid neutralization, into the same step (before centrifugation), had on final [PO.sub.4]; and (3) to determine if significantly-improved reduction was seen at pH 7 than pH 8.
Example 20
2.5 mg/L Initial [PO.SUB.4.]
(136) Some of the experimental results obtained are represented by the following information provided in Tables 33-36.
(137) TABLE-US-00037 TABLE 33 10% HNO3 Total mL added pH post cent pH 0 12.44 0.5 12.41 1.5 12.27 2.5 12.02 3.5 11.43 4.5 10.72 5 10.57 6 9.33 6.5 8.41 9.11 7 7.7 7.1 7.87 7.3 6.9 8.03
(138) TABLE-US-00038 TABLE 34 10% H2SO4 total mL added pH post cent pH 0 12.47 0.5 12.37 1.5 11.99 2.5 10.83 3 10.79 3.5 9.35 4 8.59 4.5 8.25 4.7 5.59 4.75 8.33 4.8 7.81 8.4 4.9 6.16 4.95 8.61 5 7.69 5.025 7.21 7.16
(139) TABLE-US-00039 TABLE 35 10% H3PO4 total mL added pH post cent pH 0 12.46 0.5 12.32 1.5 11.64 2.5 8.55 2.6 8.87 2.8 8.4 2.9 8.34 3.1 8.24 3.3 7.84 7.63 3.4 7.92 3.5 7.78 3.6 7.64 3.7 7.32 3.75 7.23 7.29
(140) TABLE-US-00040 TABLE 36 [PO4] PO4 PO4 PO4 Acid re- re- re- Addition duction duction duction post (%) (%) (%) centrifuge control control pH 8 pH 8 pH 7 pH 7 2.47 control 0.05 99.980 2.47 HNO3 0.9 99.636 0.12 99.951 2.47 H3PO4 30 0.000 30 0.000 2.47 H2SO4 0.19 99.923 0.15 99.939
Example 21
20 mg/L Initial [PO.SUB.4.]
(141) Some of the experimental results obtained are represented by the following information provided in Tables 37-42.
(142) TABLE-US-00041 TABLE 37 10% HNO3 #1 total mL added pH post cent pH 0 12.48 1 12.33 2 11.82 2.5 10.73 3 8.72 3.025 8.87 3.05 8.93 3.075 8.82 3.1 8.73 3.125 8.97 3.15 8.67 3.175 9.26 3.275 8.83 8.83 3.375 8.73 3.475 8.24 3.575 8.14 3.6 8.03 3.625 8.81 3.675 7.78 3.7 7.49 3.725 7.48 3.75 7.44 3.775 7.47 3.8 7.32 3.825 7.18 5.78
(143) TABLE-US-00042 TABLE 38 10% HNO3 #2 total mL added pH post cent pH 0 12.53 1 12.36 2 11.82 2.5 10.75 3 8.76 3.025 9.09 3.05 8.91 3.075 8.79 3.1 8.99 3.125 8.98 3.15 8.97 3.175 9.29 3.275 8.76 8.82 3.275 8.76 8.82 3.375 8.68 3.475 8.48 3.575 8.15 3.6 8.31 3.625 8.79 3.675 8.18 3.7 7.48 3.725 7.45 3.75 7.4 3.775 7.4 3.8 7.24 3.825 7.14 6.78
(144) TABLE-US-00043 TABLE 39 10% H3PO4 #1 total mL post added H cent pH 0 2.56 1 1.57 2 .59 7.9 2.1 .78 2.2 .5 2.225 .34 2.25 .32 2.275 .28 2.325 .08 7.15
(145) TABLE-US-00044 TABLE 40 10% H3PO4 #2 total mL post added H cent pH 0 2.56 1 1.5 2 .63 7.88 2.1 .8 2.2 .48 2.225 .33 2.25 .2 2.275 .2 2.325 7 7.08
(146) TABLE-US-00045 TABLE 41 H2SO4 total mL added pH post cent pH 0 12.13 1 11.32 2 7.22 NaOH 2.025 8.27 2.125 7.43 NaOH 2.15 9.03 2.175 8.21 7.79 2.2 7.34 2.225 7.22 7.25
(147) TABLE-US-00046 TABLE 42 (Initial [PO4] = 20.4 mg/L) Final [PO4] Final [PO4] (mg/L) PO4 (mg/L) PO4 reduction (%) pH 8 Avg reduction Sample con- control control control final (%) Name trol stdev control avg stdev pH 8 [PO4] stdev pH 8 control 0.05 0.028 99.998 99.999 0.001 Avg 0.01 100.000 HNO3 1.5 1.530 0.042 99.926 Avg 1.56 99.924 H3PO4 30 30.000 0.000 0.000 Avg 30 0.000 H2SO4 1.04 0.970 0.099 99.949 Avg 0.9 99.956 Final [PO4] (mg/L) pH 7 Avg Sample PO4 reduction (%) final PO4 reduction (%) Name pH 8 Avg stdev pH 7 [PO4] stdev pH 7 pH 8 Avg stdev control Avg HNO3 99.925 0.002 0.42 0.420 0 99.979 99.979 0 Avg 0.42 99.979 H3PO4 0.000 0 30 30.000 0 0.000 0.000 0 Avg 30 0.000 H2SO4 99.952 0.0048 0.51 0.490 0.0283 99.975 99.976 0.0014 Avg 0.47 99.977
(148) Returning to
(149) As such, the system and method of method 10 is also related to administering and positioning the assets and processes associated with the waste stream processing of the EWS and the municipal wastewaters.
(150) Turning back again to
(151) More specifically, the exemplary embodiment of
(152) More specifically, the regional system 20 and its sub-systems and equipments, etc. are spread out over a vast, operational network. The operational network may link various sub-process stations and locations that are intended to handle specific portions of method 10. For example, the FRONT END GROUPING of method 10 (receiving and preliminarily processing a paper or carpet exothermic processing waste stream 102, thermally processing a paper or carpet exothermic processing waste stream 104, producing and recovering energy from the thermal processing of the paper or carpet exothermic processing waste stream 106, and recovering minerals from the waste and producing a composite ash, as a PC or PI collecting/precipitating agent 108) may be primarily handled at the high-concentration DIR processing center, while secondary efforts may be handled at the regional centers within proximity to the high-concentration DIR processing center. A person of ordinary skill in the art understands that this allows efficiencies and efficacies to facilitate regional waste-management, without having to implement multiple redundant operations in one region or municipality. Similarly, a person of ordinary skill in the art understands that the efficiencies of the inventive concept allow for this type of regional set-up, to avoid redundancies.
(153) As such, it is envisioned that certain sub-process stations and locations of the regional system 20 may be entirely separate, in term of locations and operations and personnel and equipment, while others may be adaptable and movable to have the same location and operations infrastructure (at least partially) as another sub-process station or location, as needed or as required. In the most general sense, the network links may interconnect, via supply chains and continuous/interdependent processes, for example, various stages of the waste stream processing.
(154) Next, the exemplary embodiment of FIG. also may be an integration system 40 comprising various sub-systems, equipment, means of communication, conduits, etc., exhibiting strategic, relative positioning, readily understood by a person of ordinary skill in the art interpreting the schematic diagram, for applying the inventive method 10, for example. The system 40 is integrative in the sense that the sub-systems and equipment responsible for the production of the composite ash, may be fully integrated into the operations and infrastructure of a high-concentration DIR processing center (no regional and geographically-distant operations needed). The system 40 is further characterized as integrated, in the holistic regional/municipal waste stream processing sense, as the system 40, with integrated composite ash/chemical precursor operations like system 20, is also fully integrated with nearby, municipal WWTP operations, for example. As such, the system 40 inherently comprises cooperative and coordinated operations-managements and a sharing of physical space, land, equipment, technical personnel, and/or management to facilitate the efficiencies and efficacies of the present invention.
(155) More specifically, the integration system 40 and its sub-systems and equipment, etc. are, unlike the regional system 20 of
(156) A person of ordinary skill in the art understands that this may allow efficiencies and efficacies to facilitate integrative, multi-purpose, waste-management, all in one place, without having to taint or burden another location or municipality with the downsides of another integrated system 40 and/or a regional system 20. Similarly, a person of ordinary skill in the art understands that the efficiencies of the inventive concept allow for the integrated set-up, to make production of the active ingredients and geopolymer precursors for municipal wasterwater treatment, for example, “in house”, “a la carte”, and “to specific need and quantity” without wastes or inefficiencies. As such, it is envisioned that certain sub-process stations or locations of the integrated system 40 facilitate administering and positioning the assets and processes associated with various, distinct waste stream processing operations, all in one place. This may include: coordinating, including strategically positioning and situating, the sub-systems and equipment associated with any reduction of the output waste from the processing of paper or carpet exothermic waste stream. Further, it may include establishing and maintaining a grid for the introduction of the produced-energy (steam powered or direct thermal-reactor powered), including looping the energy back into the overall integrated system 40, for use at any of the near-by or on-site sub-systems. Further, it may include coordinating, including strategically positioning and situating, the sub-systems and equipment associated with any production of the active ingredient or composite ash for the waste stream processing. Further, it may include coordinating, including strategically positioning and situating, the sub-systems and equipment associated with any processing of the wastewater, to make use of the output clean water available to the entire integrated system 40. Further, it may include establishing and maintaining a grid for the introduction of the produced-clean water output, including looping the clean water back into the overall integrated system 40. Further, it may include coordinating, including strategically positioning and situating, the sub-systems and equipment associated with any collection of the excess composite ash or geopolymer precursor, and/or any utilization of the excess composite ash to form a final PC or PI agricultural fertilizer product, or to collect, market, or sell to independent third-party PC or PI producers the precursor. Further, it may include coordinating, including strategically positioning and situating, the sub-systems and equipment associated with any reduction, collection, and/or capturing of phosphates, nitrates, and heavy metals, and other contaminants, from the wastewater, and/or any collection and processing of any precipitated phosphate- or nitrate-rich compounds. Further, it may include scheduling operations for sub-systems of the overall integrated system 40 such that the process are performed in conjunction, and with the purpose of facilitating efficiencies, amongst the various components of the inventive concept described herein.
(157) Turning back again to
(158) The illustrative integrated system 60 practically implements the present invention in the Dalton, Ga. municipality. The integrated system 60 represents the possible construction plans for a grassroots facility in Dalton system, on free- and available- land immediately adjacent to a pre-existing regional DIR processing plant. The DIR processing plant in the Dalton system has incoming DIR waste flows characterized as 150,000 lbs/year on PC carpet and PC carpet waste. The DIR processing plant specifically comprises whole carpet processing, PC carpet waste, fluff, and carcass processing, and evergreen type carpet processing. The integrated system 60 is expected to recover energy in estimates of 4 to 6 MWe, plus spent steam of 110,000 to 120,000 lbs/hr at 20 psig and 340° F. The integrated system 60 also is expected to recover energy in estimates of 130,000 to 150,000 lbs/hr at 100 psig and 340° F. The integrated system 60 also is expected to recover composite ash product/precursor/capture material in estimates of 55,000,000-70,000,000 lbs/year. Construction times for an integrated system 60 in the Dalton system is expected to take 15-18 months with a capital cost (+/−30% estimate error) of about $22,000,000 to $26,000,000.
(159) Turning now to
(160) providing waste water (1010);
(161) blunging, liberating, mixing, and/or contacting the waste water with a chemically reactive amount/concentration of the inventive composite ash as described herein (1012);
(162) providing time and/or conditions for the composite ash to react and/or collect the phosphates and nitrates in the waste water, such that the resultant product precipitates out of solution, and provides the structure for chemisorption of the phosphates and nitrates (1014);
(163) separating and dewatering the nutrient-enriched precipitated and resultant products from the purified water (1016); and
(164) drying, agglomerating, pulverizing, and/or granulating the separated and dewatered, nutrient-enriched precipitated and resultant product (1018).
(165) In some exemplary embodiments, the method 1000 efficiently and effectively consumes the substantial majority of the phosphates and nitrates in the waste water, with limited emissions, bi-products, and residues that cannot be captured, filtered, or reused and/or recycled. Further, the method 1000 may be similar to the back end grouping of process of method 10 of
(166) processing wastewater (110);
(167) removing phosphates and nitrates from the wastewater and pH adjusting the effluent slurry or the resulting water output (112); and
(168) precipitating, collecting, and processing a post-consumer product from the ash slurry with the wastewater (114).
(169) Like method 10 of
(170) The blunging, liberating, mixing, and/or contacting the waste water with a chemically reactive amount/concentration of the inventive composite ash step (1012) usually requires that the composite ash be slaked prior to mixing with the waste water; however, dry applications are also envisioned. The composite ash may be added, dry or wet, at specific ratios, as functions of the nutrient concentration, as is shown and described herein. Mixing is completed with inline mixers, agitated tanks, etc. High to medium shear mixing may increase reactivity, surface area contact, and therefore collection performance.
(171) Next, the reacting and/or collecting the phosphates and nitrates in the waste water, such that the resultant product precipitates out of solution, and provides the structure for chemisorption of the phosphates and nitrates, step (1014) may be similar to the removing phosphates and nitrates from the wastewater step 112, and the associated pH adjusting the effluent slurry or the resulting clean water output step, and the precipitating, collecting, and processing a post-consumer product from the ash-effluent slurry step 114, of the method 10 of
(172) In some cases, but not required, the pH may be adjusted during to the reacting and/or collecting step (1014) to create additional valuable and enriched compounds within the recovered solids i.e., pH adjustment with phosphoric, sulfuric, and/or stearic acid to add or enhance valuable components to the recovered solids. Further, an exemplary embodiment envisions the reacting and collecting step (1014) occuring in either a static or dynamic system with reaction time of about 30.0 minutes up to about 2.0 hrs.
(173) Next in the process is the separating and dewatering the precipitated/resultant products step (1016). Once the reacting and/or collecting the phosphates and nitrates in the waste water step (1014) is complete, the resultant products are separated from the effluent slurry using a range of separation techniques including but not limited to clarifiers, centrifuges, filters, rotary vacuum filtration, belt filters, etc. Of course, it is also envisioned that, instead of strict separation techniques, other known techniques for targeting and collecting the desired product may be implemented, including but not limited to flocculation, agglomeration, etc.
(174) Once the separating and dewatering step (1016) is complete, the material undergoes the drying, agglomerating, pulverizing, and/or granulating the separated and dewatered precipitated and resultant product step (1018). In other exemplary embodiments, the resultant nutrient-enriched product may be left in a liquid depending on the intended product application. It is appreciated that the final resultant product may be dried using conventional dryers, i.e., rotary dryers, spray dryer, cage mills, etc.
EXAMPLES 22-24
(175) Returning to the illustrative examples, the following are three (3) illustrative examples of the process of the present invention. Example 22 specifically is performed for two objectives: (1) to determine if re-using the composite-ash/capture-material is capable of continued PO.sub.4 removal; and (2) to determine if approximate max capacity can be approximated. The recycled composite-ash/capture-material was collected from dosage trials similar to those described in detail in this disclosure, post PO.sub.4 collection. The recycled composite-ash/capture-material was then dried. The results shows that using recycled composite-ash/capture-material continues to remove PO.sub.4. Next, cycles of re-use were studied until the resultant did not meet 1 mg/L [PO.sub.4] (see Examples 23 and 24).
Example 22
2.5 mg/L Initial [PO.SUB.4.] and 2.0 mg/L Initial [PO.SUB.4.] at First Cycle
(176) Some of the experimental results obtained are represented by the following information provided in Table 43 and illustrated in
(177) TABLE-US-00047 TABLE 43 Round Round 1 Round 2 Round 2 Round 2 Sample 1 PO4 Final final Avg Final [PO4] Orig [PO4] Name uptake stdev [PO4] [PO4] [PO4] stdev uptake 2.66 2.5-2.5-1 2.6025 0.059 0.039 0.27 0.275 0.007 2.39 2.66 2.5-2.5-2 0.28 2.38 20.5 2.5-20-1 2.6025 0.059 0.039 0.23 0.355 0.177 20.27 20.5 2.5-20-2 0.48 20.02 2.66 20-2.5-1 20.9308 0.105 0.101 0.3 0.325 0.035 2.36 2.66 20-2.5-2 0.35 2.31 20.5 20-20-1 20.9308 0.105 0.101 0.34 0.365 0.035 20.16 20.5 20-20-2 0.39 20.11 Avg Round Total PO4 Average 2 [PO4] removal (mg/L) % Final Avg % Orig [PO4] uptake stdev (Round 1 + 2) reduction [PO4] stdev reduction stdev 2.66 2.385 0.007 4.993 89.85 0.275 0.007 89.66 0.265 2.66 2.380 89.47 20.5 20.145 0.177 22.873 98.88 0.355 0.176 98.27 0.862 20.5 20.020 97.66 2.66 2.335 0.035 23.291 88.72 0.325 0.035 87.78 1.33 2.66 2.310 86.84 20.5 20.135 0.035 41.091 98.34 0.365 0.035 98.22 0.172 20.5 20.110 98.10
Example 23
2.5 mg/L Initial [PO.SUB.4.] and 2.0 mg/L Initial [PO.SUB.4.] at First Cycle
(178) Example 23 specifically is performed to repeat Example 22 and to determine if approximate end-point can be approximated. The recycled composite-ash/capture-material was collected from dosage trials similar to those described in detail in this disclosure, post PO.sub.4 collection. The recycled composite-ash/capture-material was then dried. The results shows that using recycled composite-ash/capture-material continues to remove PO.sub.4 to below 1 mg/L [PO.sub.4]. Some of the experimental results obtained are represented by the following information provided in Table 44 and illustrated in
(179) TABLE-US-00048 TABLE 44 Total PO4 G3 Round Round 3 Round Avg Round uptake/removal orig Sample 3 final Avg Final 3 [PO4] 3 [PO4] (mg/L) (Round R2 % R3 % [PO4] Name [PO4} [PO4] stdev uptake uptake stdev 1 + 2 + 3) reduction reduction 2.62 5-2.5-1 0.28 0.305 0.035 2.34 2.315 0.035 7.3325 89.85 89.31 2.62 5-2.5-2 0.33 2.29 7.2725 89.47 87.40 2.62 22.5-2.5-1 0.51 0.42 0.127 2.11 2.2 0.127 24.9825 98.88 80.53 2.62 22.5-2.5-2 0.33 2.29 24.9125 97.66 87.40 20.5 22.5-20-1 0.68 0.99 0.438 19.82 19.51 0.438 43.1108 88.72 96.68 20.5 22.5-20-2 1.3 19.2 42.4408 86.84 93.66 20.5 40-20-1 0.56 0.56 0 19.94 19.94 0 61.0308 98.34 97.27 20.5 40-20-2 0.56 19.94 60.9808 98.10 97.27
Example 24
2.5 mg/L Initial [PO.SUB.4.] and 2.0 mg/L Initial [PO.SUB.4.] at First Cycle
(180) Example 24 specifically is performed to repeat Example 23 and to determine if approximate end-point can be better approximated and better methodology performed. The recycled composite-ash/capture-material was collected from dosage trials similar to those described in detail in this disclosure, post PO.sub.4 collection. The recycled composite-ash/capture-material was then dried. The results shows that using recycled composite-ash/capture-material continues to remove PO.sub.4 to below 1 mg/L [PO.sub.4]. Some of the experimental results obtained are represented by the following information provided in Table 45 and illustrated in
(181) TABLE-US-00049 TABLE 45 Total PO4 uptake/removal (mg/L) G4 starting Round 4 final Round 4 Avg Round 4 Avg Round 4 (Round 1 + R4 % [PO4] Sample name [PO4} Final [PO4] stdev [PO4] uptake [PO4] uptake stdev 2 + 3 + 4) reduction 2.62 2.5-2.5-2.5-2.5 1.15 1.115 0.0495 1.47 1.505 0.0495 8.8025 56.12 2.62 1.08 1.54 8.8125 58.78 20.2 2.5-20-2.5-20 10.5 12.95 3.4648 9.7 7.25 3.4648 34.6825 48.02 20.2 15.4 4.8 29.7125 23.76 2.62 20-2.5-20-2.5 1.2 3.05 2.6162 1.42 −0.43 2.6163 44.5308 54.20 2.62 4.9 −2.28 40.160 −87.02 20.2 20-20-20-20 15.7 15.95 0.3535 4.5 4.25 0.3536 65.5308 22.28 20.2 16.2 4 64.9808 19.80
EXAMPLE 25
(182) The following is illustrative examples of the process of the present invention. Example 25 specifically is performed to determine how the use of fly-ash for PO.sub.4-removal compares to the use of the composite-ash/capture-material for PO.sub.4-removal. The fly ash was tested from different sources (e.g., Boral class ash—coal-fired/coal-sourced, Dublid/Butch ash—wood-fired/wood-sourced) and was used in dosage trials similar to those described in detail in this disclosure. The used solids were dried, and a portion of the samples were calcined at 1000 degrees C., and a chapelle test was performed. XRF Asis Chemistry analysis was performed on a portion of the calcined sample. Some of the analytical results obtained are represented by the following information provided in
Example 25
2.5 mg/L Initial [PO.SUB.4.] and 20.0 mg/L Initial [PO.SUB.4.] at First Cycle
(183) The results show that fly ash, of various types and sources, show good results for nutrient removal; however, heavy metal leaching is possible. The results also show that wood-fired or wood-sourced fly ash is more efficient at PO.sub.4-removal, and this is perhaps due to the higher carbon content from the wood process rather than the coal burning process. The results also show that wood-fired or wood-sourced fly ash showed less leaching than the coal-fired or coal-sourced flyash. Some of the experimental results obtained are represented by the following information provided in
(184) The various embodiments are provided by way of example and are not intended to limit the scope of the disclosure. The described embodiments comprise different features, not all of which are required in all embodiments of the disclosure. Some embodiments of the present disclosure utilize only some of the features or possible combinations of the features. Variations of embodiments of the present disclosure that are described, and embodiments of the present disclosure comprising different combinations of features as noted in the described embodiments, will occur to persons with ordinary skill in the art. It will be appreciated by persons with ordinary skill in the art that the present disclosure is not limited by what has been particularly shown and described herein above. Rather the scope of the invention is defined by the appended claims.