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Declaration of Innovation
March 11, 2014 5

By-Product Treatment via Calcium Polysulfide

A method of remediation of potentially toxic Industrial by-products

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Patent Holders: James T. Easton, Jr. & James A. Papp

Contact: flyashcasx@hotmail.com

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Contents

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Introduction Executive Summary EPA news release 2/7/14 - Coal Ash Beneficial Use, Approved Environmental Article 2/19/14 - Coal Ash Recycling Benefits 2 3 6 7 9 23 30

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Patent Document Provisional Patent Document Photos / Exhibits

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Introduction
Toxic waste is an ongoing concern due to potential dangers to human health and the environment. Fly ash (the by-product of coal burning electrical power plants) is at the fore front 5 of this issue. Multiple heavy metals and other toxins are trapped in the ash during coal combustion, and must be disposed of. Challenges occur when these water soluble substance are allowed to come in contact with soils, lakes, rivers and underground water supplies.

We have not only developed a viable, economically feasible solution for the problem of toxic 10 waste, but also a path to generate revenue from creating a superior version of the most widely used commercial product available today, concrete. By utilizing Calcium Polysulfide (lime sulfur) in conjunction with Industrial by-products (i.e. Fly Ash, Blast Furnace Slag, Mining wastes, etc...) we accomplish three things:

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1. Multiple, water soluble, elemental Heavy Metals are chemically reacted to create nonsoluble materials. 2. Further toxic components chemically bind to Hydroxide polymer chains, and are locked into complex molecular structures within a cementitious material. 3. A high strength, high performance version of concrete up to 100 times denser than

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Ordinary Portland Cement is created.

This "Pozzolanic" concrete is: Stronger, denser, more durable, lighter and easier to use than Ordinary Portland Cement. In addition, it is chemically resistant, waterproof, fire retardant, absorbs Carbon Dioxide from the air and provides significant reduction of CO2 emissions by 25 reducing the need for production of Ordinary Portland Cement.

All this translates into a product that can be safely disposed of, or used in the same applications as Ordinary Portland Cement concrete. The process can be safely and quickly performed with existing machinery and knowledge common to local cement contractors around the world 30 costing no more than the production of Ordinary Portland cement.

Executive Summary
By-Product Treatment via Calcium Polysulfide

The enclosed documents outline a potential method for the stabilization of Industrial by-product 5 materials. The method may be employed on existing Fly-Ash storage impoundments, and/or implemented as a proactive, preventative measure mitigating future negative effects of byproduct materials. Treatment via Calcium Polysulfide provides an economically viable, readily available process to mitigate environmental damage and associated costs relating to multiple potentially toxic materials including; Arsenic, Lead, Copper, Cadmium, Molybdenum, 10 Selenium, Mercury, Zinc, Barium, Uranium, Chromium, Cyanide and other materials. The disclosed method combines three known methods of environmental remediation into a single chemical process. First, stabilization of elemental, heavy metal toxins is achieved by creation of insoluble sulfide compounds via ionic/covalent chemical bonding. This process allows for the precipitation of mineral content from aqueous solution similar to the existing processes of in15 situ mining for Uranium, and in-situ chemical fixation utilized in soil remediation. Secondly, further toxic materials are incorporated into complex, Hydroxide polymer chains as Calcium/Silicate content chemically reacts forming a concrete material. The third process regards the encapsulation of potentially toxic content into high performance, Pozzolanic concrete. Pozzolanic cement creates a concrete matrix up to 100 times denser than concrete 20 produced with Ordinary Portland Cement. This characteristic combined with high levels of Alumina and Iron create a waterproof, chemically resistant formulation mimicking the chemical make-up of Roman concrete mixes able to remain unchanged underwater, in Oceanic conditions for over 2,000 years. The final product of this process is a transportable, solidified mass that can be cast into almost shape and size for ease of transportation and potential beneficial re-use. 25 Environmental Benefits: 30 Mitigation of health concerns regarding air and groundwater contamination from untreated Fly-Ash accumulations. Protection to fish and wildlife due to toxic elemental constituents of Fly-Ash storage accumulations.

Long term reductions of atmospheric Carbon Dioxide through absorption into concrete materials as calcium carbonate evolves in produced materials. Protection for public water ways, water supplies, irrigation systems and properties from potential harm from accidental Fly-Ash containment failures.

Reduction in particulate emissions from cement production kilns through reduction in demand for Ordinary Portland Cement.

Economic benefits: 10 20 Significant reduction, if not elimination, of costs associated with clean-up of high volume toxic Coal Ash spills. Protection of Electrical Utilities from government fines, litigation and other financial liability associated with Fly-Ash storage locations. Reduction in costs to concrete production companies through reduction of Ordinary Portland Cement in concrete formulation. 15 Increase in life-cycle of concrete structures due to enhanced performance of Pozzolanic cements when compared with Ordinary Portland Cement. Relief in costs to public funds and government agencies concerning regulation and implementation of Fly-Ash storage policy. Stabilization of Electrical power rates to consumers. Potential for additional profit streams to Electrical Utilities through the sale of concrete products and/or by-product materials. Increase in employment opportunity in localized concrete construction markets. Increase in revenue to local businesses participating in remediation efforts.

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Implementation:

The method of this patent may be readily implemented by commercial means through the use of standard concrete blending equipment. The process may be performed in-situ through the utilization of mobile concrete blending and batch mixing equipment common to the process 30 of road and highway construction in remote locations. Calcium Polysulfide (lime sulfur) and silicate matter from Fly Ash act in direct substitution for the reactive components of Ordinary

Portland Cement. Provision of additional water supplies along with transportation and dry storage of Portland Cement powder are not required. Calcium Polysulfide is readily available in containers ranging in size from chemical totes to railroad tankers as Calcium Polysulfide is currently utilized a fungicide/pesticide in agriculture and in toxic soil remediation efforts across 5 North America. Lime Sulfur has been proven safe and environmentally friendly for use by both the FDA and the EPA.

The procedure of implementation is as follows... 1. Laboratory testing of specific accumulations to finalize ideal mix designs (similar to 10 materials laboratory testing of concrete specified in Architectural construction.) 2. Excavation of Fly Ash storage impoundment ponds and/or landfills. 3. Mixing of Components to stabilize toxic constituents. 4. Placement of mixed embodiments into formwork for curing. 5. Transportation of solidified, non-toxic embodiments to permanent storage locations. 15

http://yosemite.epa.gov/opa/admpress.nsf/0/6A5375FF509189A185257C7800562D51

EPA Evaluation Finds Use of Coal Ash in Concrete and Wallboard Appropriate
5 Release Date: 02/07/2014 Contact Information: Enesta Jones, Jones.enesta@epa.gov, 202-564-7873, 202-564-4355 WASHINGTON Using a newly developed methodology, the U.S. Environmental Protection Agency (EPA) today released its evaluation of the two largest beneficial uses of encapsulated coal combustion residuals (CCR or coal ash): use in concrete as a substitute for portland cement, and the use of flue gas desulfurization gypsum as a substitute for mined gypsum in wallboard. EPAs evaluation concluded that the beneficial use of encapsulated CCRs in concrete and wallboard is appropriate because they are comparable to virgin materials or below the agencys health and environmental benchmarks. These two uses account for nearly half of the total amount of coal ash that is beneficially used. The protective reuse of coal ash advances sustainability by saving valuable resources, reducing costs, and lessening environmental impacts, including reducing greenhouse gas emissions, said Mathy Stanislaus, assistant administrator for EPAs Office of Solid Waste and Emergency Response. In evaluating these two beneficial uses, EPA used its newly developed, Methodology for Evaluating Encapsulated Beneficial Uses of Coal Combustion Residuals. The methodology is intended to assist states and other interested parties with evaluating and making informed determinations about encapsulated beneficial uses of CCRs. Coal ash is formed when coal is burned in boilers that generate steam for power generation and industrial applications. Slightly more than half of coal ash is disposed of in dry landfills and surface impoundments. The remainder of coal ash is used beneficially, as well as in mining applications. More information on the methodology: http://www.epa.gov/epawaste/conserve/imr/ccps/benfuse.htm

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Receive our News Releases Automatically by Email

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http://theenergycollective.com/nrdcswitchboard/340971/coal-ash-why-it-better-recycled-waste

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Coal Ash: Why it is Better Recycled Than as a Waste

Posted February 19, 2014 Keywords: Sustainability, Utilities, Coal, Environmental Policy, Cleantech,Recycling, Public Health, Environment, Water, Risk Management, Energy, Energy and Economy, Fuels, Politics & Legislation, coal ash, governmental regulations, water pollution 15 30 0 45 Scott Slesinger, Legislative Director, Washington, DC EPA has announced that the two primary encapsulated uses of coal ash are safe, so recyclers have no legitimate remaining arguments to support their previous requests for a weak coal ash rule. One of the big issues propagated by the coal burning utility industry, is that regulating coal ash waste as a hazardous waste would hurt the market for recycling of coal ash. Even some in the environmental community believe that if something is hazardous as a waste, it would be hazardous in a product. This sounds logical but happens not always to be the case. There is a reason waste can be much more harmful than the same chemical in a product; it is the same as chemotherapy drugs; important and safe when used correctly, toxic when they are no longer used, so disposal must be done carefully. The key to the safe use of coal ash is encapsulation. Encapsulation is the technology that is used at EPA-regulated hazardous waste landfills to make sure that if the toxic waste gets wet, which it does, it is bound at the molecular level into an insoluble compound that will not allow the toxics elements to leach to contaminate underground water sources or surface waters. This is the same technology used in encapsulating fly ash and FGD sludge in concrete and wallboard. Therefore, it was not a surprise to me that EPA found that the use of fly ash in concrete and wallboard is no more a threat than the raw materials it replaces. Even if coal ash used in construction is demolished, it still will not leach toxics, because even if pulverized, it is not broken down below the molecular level. The EPA study, released February 7, 2014 is entitled "Methodology for Evaluating Encapsulated Beneficial Uses of Coal Combustion Residuals" and an accompanying document, "Coal Combustion Residual Beneficial Use Evaluation: Fly Ash Concrete and [flue gas desulfurization (FGD) Gypsum Wallboard," applies the new methodology to those practices. The risk evaluation document concludes that "environmental releases of constituents of potential concern (COPC) from CCR fly ash concrete and FGD gypsum wallboard during use by the consumer are comparable to or lower than those from analogous non-CCR products, or are at or below relevant regulatory and health-based benchmarks for human and ecological receptors."

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Based on the conclusion of the analysis in this document stated above, and the available environmental and economic benefits, EPA supports the beneficial use of coal fly ash in concrete and FGD gypsum in wallboard." 5 NRDC, as well as the Green Building Council, agree that recycled fly ash in building materials is superior to alternatives. Regulating the disposal of fly ash should raise the price of disposal and therefore encourage more companies to recycle fly ash. Such reuse will protect our air and water and lower greenhouse emissions by lowering the carbon inputs into cement. The coal ash recyclers should support EPAs regulation of coal ash disposal instead of continuing down the road with the utilities. The utilities are very happy with the present weak standards which, not surprisingly, led to the recent spill in North Carolina in the Dan River. It is time these companies spent their money upgrading their facilities rather than lobbying Congress to keep Americans at risk from their unsafe practices.

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By-product Treatment Via Calcium Polysulfide Patent Document

Filing Date: 03/13/2013 Notice of Allowance Date: 02/13/2014 Attorney Docket Number COGC.005PA Confirmation Number: 9363

Application/Control Number: 13/801,887

Art Unit: 1731

Patent Attorney: Crawford Maunu PLLC, 1150 Northland Dr., Suite 100, St. Paul, MN 55120

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Aspects of various embodiments are directed to the treatment of by-products using calcium polysulfide. This application claims the benefit of U.S. Provisional Application No. 61/610,428, filed March 13, 2012 which is incorporated herein by reference in its entirety.

BACKGROUND 15 A variety of processes are generated by-products that are harmful or otherwise undesirable. For example, the production of electricity by coal fired production plants creates by-product materials containing toxic waste. As coal is burned, toxic heavy metals such as Mercury, Arsenic, Cadmium, Lead and other substances become gases. Molecules of these gases cool in exhaust systems and collect with fine ash particles to make fly ash. Heavy ashes 20 fall during coal combustion to create bottom ash. These materials are often stored in piles or in ponds at production facilities. The presence of these sites creates a potential hazard to human populations, at least in part due to the ability of toxins to dissolve in water supplies. Once in water supplies, the toxins can become a threat. As another example, slag piles and other by-products of industrial processes such as 25 mining, metal smelting and refining can pose potential problems. For instance, toxic lead, arsenic, copper, selenium and other contamination may be generated from such processes. These and other matters have presented challenges to managing by-products of a variety of applications.

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SUMMARY Various example embodiments are directed to methods and apparatuses for treating waste by-products.

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In accordance with one or more example embodiments, negatively-charged calcium polysulfide is reacted with toxins to create non-soluble sulfide-based crystals. In some implementations, these non-soluble crystals are locked in a material as hydration is completed. The crystals effectively render the toxins insoluble in water, mitigating issues relating to water5 borne contamination. Another example embodiment is directed to a method as follows. A by-product type substance is rendered insoluble in water by mixing the by-product in water with calcium polysulfide, forming negatively-charged sulfur and positively-charged ions, the positivelycharged ions including a material from the by-product substance, and creating non-soluble sulfide crystals by reacting the negatively-charged sulfur with the positively-charged ions. A calcium silicate hydrate is formed with the non-soluble sulfide crystals, and the calcium silicate hydrate is used to form the concrete-based material. The above discussion/summary is not intended to describe each embodiment or every implementation of the present disclosure. The figures and detailed description that follow also exemplify various embodiments.

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BRIEF DESCRIPTION OF THE FIGURES Various example embodiments may be more completely understood in consideration of the following detailed description in connection with the accompanying drawings, in which: FIG. 1 shows a method for treating a by-product, in accordance with an example embodiment; and

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FIG. 2 shows a method for forming a concrete-based material, in accordance with another example embodiment. While various embodiments discussed herein are amenable to modifications and alternative forms, aspects thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the

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invention to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure including aspects defined in the claims. In addition, the term example as used throughout this application is only by way of illustration, and not limitation.

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DETAILED DESCRIPTION Aspects of the present disclosure are believed to be applicable to a variety of different types of apparatuses, systems and methods involving the treatment of toxins and/or other types of components desirably rendered insoluble, and the generation of building materials using 5 resulting treated products. While not necessarily so limited, various aspects may be appreciated through a discussion of examples using this context. Various example embodiments are directed to manufacturing building materials such as concrete building materials by recycling industrial waste by-products utilizing calcium polysulfide. In accordance with one or more embodiments, it has been discovered/recognized 10 that toxins are rendered non-viable as human pathogens by reacting the toxins to create nonsoluble sulfide crystals locked in a hydrate material as hydration is completed, and further that the resulting material can be used in concrete-type products. The sulfides are not soluble in water and are locked into position within the hydrate material without the ability to readily escape or change in state. This approach may, for example, be used to mitigate or eliminate the 15 ability of the toxin to dissolve into water and travel into ground water supplies. The resulting crystals are implemented in a building product. In some embodiments, a building product is generated as follows from a coal-fired electricity production plant. As the coal is burned, toxic heavy metals such as Mercury, Arsenic, Cadmium, Lead and other substances become gases, which collect with fine ash 20 particles to make fly ash upon cooling. Heavy ashes fall during coal combustion to create bottom ash. These materials may, for example, be stored in piles or in ponds at production facilities. The bottom ash is reacted with a negatively charged dianion of sulfur, S (2-), in a highly alkaline solution, Calcium Polysulfide, and locked in a resulting crystal. In other embodiments, a building product is generated from one or more of slag piles 25 and other by-products, as may be formed during mining, metal smelting and refining. The slag and/or other by-products is/are reacted with a negatively charged dianion of sulfur, S (2-), in a highly alkaline solution, Calcium Polysulfide, and locked in a resulting crystal. Such approaches can be used to render heavy metals insoluble in water. These heavy metals can be bonded with negatively-charged Sulfur ions in an alkaline solution using calcium polysulfide, 30 yielding non-toxic metal sulfides.

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Turning now to the figures, Figure 1 shows a method for treating a by-product, in accordance with another example embodiment. At block 110, a by-product such as described herein is rendered insoluble in water as follows. The by-product is mixed with calcium polysulfide in water at block 112. At block 114, negatively-charged sulfur and positively5 charged by-product ions are formed. Non-soluble sulfide crystals are formed at block 116, using the respective ions. After the by-product is rendered insoluble, the process continues at block 120, in which calcium silicate hydrate is formed from the sulfide crystals. Further, in accordance with one or more embodiments, the calcium silicate hydrate is then used at block 130 by forming a concrete-based material therefrom. 10 FIG. 2 shows a method for forming a concrete-based material, in accordance with another example embodiment. At block 210, components are assembled for making a concretebased product, such as by forming a water-insoluble material as described herein or shown in Figure 1. At block 220, dry components from block 210 are combined in a container, and the components are blended at block 230 (with or without glass reinforcement). Calcium 15 Polysulfide is added at block 240. If the Calcium Polysulfide is wet at block 240, the solution with calcium polysulfide is blended with the components at block 250, and placed in a form (e.g., with or without reinforcement) at block 252. The material is then cast in the form and removed at block 254. If the calcium polysulfide is not wet at block 240, powdered lime (CaO) and powdered 20 sulfur (S) are added at block 260. The dry components are blended at block 262, and water is added with all components being blended completely at block 264. The process then continues as described above, at block 252. In one or more embodiments such as those described above, Calcium Polysulfide is degraded to create Calcium Hydroxide and elemental Sulfur in aqueous solution. Negatively25 charged Sulfur ions are bonded to positively-charged ions of toxic substances (e.g., in highly alkaline aqueous solution) to create sulfides. Sulfides may, for example, be similar to sulfide ores that are commercially mined for use in extracting or smelting metals for industrial use. By way of example, one such approach involves reacting elemental Mercury with sulfide to create Mercury Sulfide, Cinnabar: 30 Hg + S -> HgS,

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in which positive Mercury ions bond to negative Sulfur ions. In the Sulfide form, the Mercury rendered insoluble in water and does not pose a threat to biological organisms. In other embodiments, a reaction similar to that discussed above is carried out with other toxic or potentially toxic substance that presents itself as a positively charged ion in an oxidated 5 state (such as when placed in hydroxide solution). The toxic substances are reacted to form Sulfides, and the crystallized substance is locked into Calcium Silicate Hydrate. In some embodiments, the Calcium Silicate Hydrate can then be implemented in a concrete-based construction component (e.g., with mobile concrete production facilities, concrete production plants or on construction sites). 10 Various embodiments are directed to a high strength, light weight material with water and chemical resistance properties. The material is made from industrial by-products such as toxic waste that has been remediated or rendered non-viable as a human pathogen. In some implementations, the material is molded into and/or otherwise used in building materials such as concrete masonry units, precast concrete structural systems, landscape accents, highways, roads, 15 bridges, traffic barriers, concrete safety liners for fracking wells, steel reinforcement, foundations, cold weather materials with mitigated expansion and contraction characteristics, and other concrete-type products. Such materials can be used in lieu of cement, mitigating cement-based production and use matters. In various embodiments, a Calcium Silicate Hydrate as produced herein is formed into 20 concrete building materials, poured as slabs and used in detailed casting and form work. The material can create buildings, stadiums, highways, bridges, roads, curbs, sidewalks, foundations, walls, fences, traffic barriers, statues, monuments, modular construction systems, chemically resistant applications such as slabs in oil refineries and chemical production plants, and other products such as discussed herein and in the underlying provisional application to which benefit 25 is claimed. In accordance with such concrete-type product manufacturing embodiments, one or more of the following components are mixed in various proportions to create concrete mix designs of various strengths and consistencies for use in construction materials: 1. Calcium Polysulfide, CaSx, in aqueous solution 30 2. Class F Fly Ash (a pozzalan) 3. Class C Fly Ash (a pozzolan)

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4. Sand 5. Volcanic Rock (a pozzolan also known as cinders, pumice) 6. Pulverized Slag (a pozzolan) 7. Cement 5 8. Crushed Aggregate Calcium Polysulfide solutions are substituted for water to present a negatively charged ion of Sulfur in a highly alkaline solution, which is used to facilitate the bonding of toxins with Sulfur and the creation of non-soluble Sulfides. Calcium Polysulfide is added in various amounts and with various proportions of water added to the solution, to suit particular 10 applications. The Calcium Polysulfide is degraded to create Calcium Hydroxide and Sulfur. The Calcium Hydroxide becomes an integral part of Calcium Silicate Hydrate through reaction with Silicate Hydroxide. The class F Fly Ash is a by-product of coal fired electrical production and is high in silicates. The class C Fly Ash is also a by-product of coal fired electrical production. Class C 15 Fly Ash provides lime, CaO, and silicates. Fly Ash can be added in various amounts. This is a pozzolanic material that reacts with Calcium in Hydroxide solution to create Calcium Silicate Hydrate. The lime, CaO, present in the Class C Fly Ash slakes with water in the Calcium Polysulfide solution to create Calcium Hydroxide from the water molecules. In some implementations, most or all water is eliminated from the mix during this reaction. The 20 remaining silicate content of the Class C Fly Ash is bonded to form Calcium Silicate Hydrate as described above. Class F Fly Ash can be used to improve the workability of the material in form work by adding glassy silicates. The sand provides a fine aggregate and is high in silicates. The sand is used as a filler in the mix to increase bonding properties. Sand can be added in various amounts to effect strength 25 and consistency of the mix design. The volcanic rock is a natural by-product of high temperature reactions and is high is silicates. Volcanic rock is a pozzolanic material with the ability to chemically bond to Calcium Silicate Hydrate (e.g., rather than just be encased in cementitous material). Pulverized slag is a by-product (e.g., potentially toxic) of industrial metal smelting and is high in silicates. Slag can also be high in lime depending on the type of 30 ore that was smelted to create the specific slag accumulation. Slag is a pozzolanic material that facilitates reactions to create Calcium Silicate Hydrate. The cement may, for example, be

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Ordinary Portland Cement, which includes a powder that can be mixed with water, sand and crushed rock to form concrete. Crushed aggregate is used in concrete mix designs as filler and to increase the compressive strength by including high strength materials with the cementing agents. Crushed aggregate may be of various sizes and various types in various amounts. 5 Different types of volcanic rock and slag aggregate can be added in different sizes to effect strength, texture, color and final weight of the material. In certain embodiments, the components of the method come together to supply Sulfur in a negatively charged ion to bond with positively charged toxic ions turning them into nonharmful sulfides. The Sulfides are locked in a concrete-like material, such as by a pozzolanic 10 reaction and/or as follows: CH + SH -> CSH, in which Calcium Hydroxide reacts with Silicate Hydroxide to form Calcium Silicate Hydrate. The silicates mix with hydroxide to create silicate hydroxide. The Calcium Hydroxide from the Calcium Polysulfide solution reacts with the Silicate Hydroxide to create Calcium Silicate 15 Hydrate. Accordingly, various embodiments are directed to rendering toxins harmless as human pathogens with the use of Calcium Polysulfide, and bonding resulting components together to create practical construction materials. Different materials can be mixed in different amounts with Calcium Polysulfide to eliminate heavy metal toxins and create building materials of 20 various strengths, sizes, uses, colors, textures and other characteristics. The resulting concrete-based materials can be implemented in a variety of manners, such as by mixing the components with water and placing the wet material into form work similar to normal concrete construction methods. In some embodiments, dry components can also be packed into forms and liquid Calcium Polysulfide applied to the packed material to cause a 25 chemical reaction. In certain embodiments, all components are mixed in dry form including powdered Calcium Oxide and powdered Sulfur in a premixed form, and water is added to facilitate reactions such as described above. The dry Calcium Oxide and Sulfur together with water constitute Calcium Polysulfide, and the negatively charged ion of Sulfur will be presented in highly alkaline aqueous solution.

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In some embodiments, calcium polysulfide is injected in-situ into ground containing high levels of silicate materials and used to create concrete, such as to provide barriers to block the movement of underground insects such as termites. In certain embodiments, structures using variations of lime concrete that is based upon a 5 pozzolanic reaction are strengthened using approaches as described herein to form a cement-like material. The materials mimic characteristics of and adhere to pozzolanic mixtures, using a pozzolanic reaction as described herein. In other embodiments, concrete-type products are formed underwater using approaches as described herein. Waterproof-type and chemical resistant-type properties of calcium silicate 10 hydrate facilitate the underwater formation. Water is pulled into the mass until all lime has slaked to create Calcium Hydroxide. The Calcium Hydroxide is used to bond silicates to create Calcium Silicate Hydrate, with the resulting material being insoluble in (and/or not affected by) water. Based upon the above discussion and illustrations, those skilled in the art will readily 15 recognize that various modifications and changes may be made to the various embodiments without strictly following the exemplary embodiments and applications illustrated and described herein. For example, a variety of different types of toxins can be reacted with calcium polysulfide, and used to lock in and render a substance non-soluble in water. Still other embodiments are directed to one or more aspects as described or shown in the figures in the 20 U.S. Provisional Patent Application Serial No. 61/610,428, to which priority is claimed and which is fully incorporated herein by reference. Such modifications do not depart from the true spirit and scope of various aspects of the invention, including aspects set forth in the claims.

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WHAT IS CLAIMED:

1.

(Original) A method comprising: rendering a by-product substance insoluble in water by

mixing the by-product in water with calcium polysulfide, forming negatively-charged sulfur and positively-charged ions, the positively-charged ions including a material from the by-product substance, creating non-soluble sulfide crystals by reacting the negatively-charged sulfur with the positively-charged ions; forming a calcium silicate hydrate with the non-soluble sulfide crystals; and forming a concrete-based material with the calcium silicate hydrate.

2.

The method of claim 1, wherein the by-product includes fly ash.

3.

The method of claim 2, wherein forming a concrete-based material includes forming a

concrete-based material that is substantially devoid of Portland cement.

4.

The method of claim 2, wherein creating non-soluble sulfide crystals includes utilizing

the fly ash and forming non-soluble Selenium.

5.

The method of claim 2, wherein the fly ash includes class F and class C fly ash.

6.

The method of claim 2, wherein the fly ash includes aluminum oxide.

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The method of claim 1, wherein forming a concrete-based material includes utilizing at

least one of volcanic rock, pumice and a pozzolan.

8.

The method of claim 1, wherein forming negatively-charged sulfur and positively-

charged ions includes forming calcium hydroxide utilizing the calcium polysulfide and bonding hydrogen ions from the calcium hydroxide with the negatively-charged sulfur to create 15 hydrogen sulfide.

9.

The method of claim 8, wherein forming a calcium silicate hydrate includes utilizing the

hydrogen sulfide with heavy metal ions to produce non-soluble sulfide compounds.

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10.

The method of claim 1, wherein the by-product includes fly ash, and forming the

calcium silicate hydrate includes reacting material from the fly ash with calcium in a hydroxide.

11.

The method of claim 10, wherein mixing the by-product in water with calcium

polysulfide includes forming a calcium polysulfide solution, further including slaking the fly ash with water in the calcium polysulfide solution to create calcium hydroxide, and after the slaking, bonding remaining fly ash to form the calcium silicate hydrate.

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The method of claim 11, wherein slaking the fly ash with water includes eliminating

about all water is eliminated from the solution via reaction with the fly ash.

13.

The method of claim 1, wherein the by-product includes fly-ash having lime, and

wherein forming the concrete based material includes slaking about all the lime in the by15 product material with water.

14.

The method of claim 1, wherein the by-product includes at least one of: human

pathogens and slag.

15.

The method of claim 1, further including, after forming the concrete-based material, in

response to water introduced to a crack in the concrete-based material, interact the concretebased material with the water to form the concrete-based material in the crack.

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A method for forming structural concrete, the method comprising:

mixing fly ash with a solution including calcium polysulfide and water; forming negativelycharged sulfur and positively-charged hydrogen ions from the mixed fly ash and solution; creating non-soluble sulfide crystals by reacting the negatively-charged sulfur with the positively-charged ions; forming a calcium silicate hydrate with the non-soluble sulfide crystals; and forming a concrete-based material with the calcium silicate hydrate.

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The method of claim 16, wherein forming the calcium silicate hydrate includes reacting

calcium hydroxide with silicate hydroxide.

18.

The method of claim 17, further including forming the calcium hydroxide by slaking the

fly ash with water in the calcium polysulfide solution.

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The method of claim 16, wherein the steps of forming negatively-charged sulfur and

positively-charged hydrogen ions and creating the non-soluble sulfide crystals include forming calcium hydroxide utilizing the calcium polysulfide, and bonding hydrogen ions from the calcium hydroxide with the negatively-charged sulfur to create hydrogen sulfide.

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An intermediate article of manufacture for use in forming a concrete-based material, the

article of manufacture comprising: negatively-charged sulfur and positively-charged hydrogen ions in a mixture of fly ash with a solution including calcium polysulfide and water; non-soluble sulfide crystals including components of the negatively-charged sulfur reacted with the positively-charged ions; and a calcium silicate hydrate including the non-soluble sulfide crystals, the calcium silicate hydrate being configured and arranged provide structural support

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by forming a concrete-based material.

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ABSTRACT By-product materials are processed to mitigate undesirable effects. In some embodiments, industrial waste by-products are recycled using calcium polysulfide and used in building materials. In certain implementations, toxins are rendered non-viable as human 5 pathogens by reaction with calcium polysulfide to create non-soluble sulfide crystals locked in the material as hydration is completed. The sulfides are not soluble in water and are locked into position within the resulting hydrate material, which mitigates escape of or changes of state in the toxins.

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PROVISIONAL APPLICATION FOR PATENT

INVENTION TITLE A means to create clean concrete building materials by recycling industrial waste by-products utilizing Calcium Polysulfide.

BACKGROUND OF THE INVENTION Problem Solved: The production of electricity by coal fired production plants creates by-product materials containing toxic waste. As coal is burned toxic heavy metals such as Mercury, Arsenic, Cadmium, Lead and other substances become gases. The molecules of these gases cool in the exhaust systems and collect with fine ash particles to make fly ash. Heavy ashes fall during coal combustion to create bottom ash. These materials are often stored in piles or in ponds at production facilities. The presence of these sites creates a dangerous hazard to human populations due to the ability of toxins to dissolve in water supplies. Once in water supplies the toxins become a threat to human health. One example, is the Tennessee Valley Authority Kingston Ash Slide of 2008. On December 23, 2008 1.1 billion gallons of toxic coal ash spilled into the Emory River containing high levels of Mercury and other toxins. A similar problem exists in the form of slag piles and other by-products of industrial processes such as mining, metal smelting and refining. The East Helena, MT, ASARCO smelting site is one such example. The site was responsible for toxic lead, arsenic, copper, selenium and other contamination in the surrounding environment. Cancer rates had increased to 1 in 50 people at one time. This is 2000 times the normal level of cancer occurrence in human beings. High lead levels in children living areas surrounding the site were first recorded in blood tests as far back as the 1960s and 70s. Currently remediation efforts are under way to eliminate toxic levels of Arsenic and Selenium on the site. Other methods of creating concrete from industrial wastes do not react toxic substances within the industrial by-products to render them harmless to human beings. Other products do not present sulfur in a negatively charged form to create sulfides as calcium silicate hydrate is formed. Our method renders toxins non-viable as human pathogens by reacting the toxins to create non-soluble sulfide crystals locked in the material as hydration is completed. The Sulfides are not soluble in water and are locked into position within the hydrate material without ability to readily escape or change in state. The ability of the toxin to dissolve into water and travel into ground water supplies has been eliminated. The final result of our method is a practical building product with the ability to be mass produced by industrial, mechanized methods. DETAILED DESCRIPTION OF THE INVENTION As stated above, the production of electricity by coal fired production plants creates by-product materials containing toxic waste. As coal is burned toxic heavy metals such as Mercury, Arsenic, Cadmium, Lead and other substances become gases. The molecules of these gases cool in the exhaust systems and collect with fine ash particles to make fly ash. Heavy ashes fall during coal combustion to create bottom ash. These materials are often stored in piles or in ponds at production facilities. The presence of these sites creates a dangerous hazard to human populations due to the ability of toxins to dissolve in water supplies. Once in water supplies the toxins become a threat to human health. One example, is the Tennessee Valley Authority Kingston Ash Slide of 2008. On December 23, 2008 1.1 billion gallons of toxic coal ash spilled into the Emory River containing high levels of Mercury and other toxins. A similar problem exists in the form of slag piles and other by-products of industrial processes such as mining, metal smelting and refining. The East Helena, MT, ASARCO smelting site is one such example.

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The site was responsible for toxic lead, arsenic, copper, selenium and other contamination in the surrounding environment. Cancer rates had increased to 1 in 50 people at one time. This is 2000 times the normal level of cancer occurrence in human beings. High lead levels in children living areas surrounding the site were first recorded in blood tests as far back as the 1960s and 70s. Currently remediation efforts are under way to eliminate toxic levels of Arsenic and Selenium on the site. The invention claimed here solves this problem. Calcium Polysulfide degrades to create Calcium Hydroxide and elemental Sulfur in aqueous solution. Our invention presents the negatively charged dianion of sulfur, S (2-), in a highly alkaline solution, Calcium Polysulfide.

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Many toxic substances present themselves as positive ions in highly alkaline aqueous solutions. The negatively charged Sulfur ions will bond to positively charged ions to create sulfides. Sulfides are commonly known as ores, and are commercially mined for use in extracting or smelting metals for industrial use.

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i.e. Elemental Mercury will react to create Mercury Sulfide, Cinnabar.

Hg + S -> HgS (positive Mercury ions bond to negative Sulfur ions)

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In the Sulfide form Mercury is not soluble in water and does not pose a threat to biological organisms. This same reaction takes place with any potentially toxic substance that presents itself as a positively charged ion in an oxidated state (such as when placed in hydroxide solution).

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Our method allows the reaction of toxic substances to form Sulfides, then, locks the crystallized substance into Calcium Silicate Hydrate. Calcium Silicate Hydrate is a material similar to Portland Cement concrete with the ability to gain high compressive strengths for use a construction material. The claimed invention differs from what currently exists. Our invention is a high strength, light weight material with water and chemical resistance properties. The product is made from industrial byproducts or "toxic waste" that has been remediated or rendered non-viable as a human pathogen. Our material can be molded into usable building materials such as concrete masonry units, precast concrete structural systems, landscape accents, highways, roads, bridges, traffic barriers and other common concrete products. Our process minimizes or eliminates the need for Portland cement reducing carbon dioxide emissions and resultant air pollution. This invention is an improvement on what currently exists. Our invention is a high strength, light weight material with water and chemical resistance properties. The product is made from industrial byproducts or "toxic waste" that has been remediated or rendered non-viable as a human pathogen. Our material can be molded into usable building materials such as concrete masonry units, precast concrete structural systems, landscape accents, highways, roads, bridges, traffic barriers and other common concrete products. Our process minimizes or eliminates the need for Portland cement reducing carbon dioxide emissions and resultant air pollution. Other methods can allow the leaching of toxic materials into ground water supplies or allow potentially dangerous human contact as water penetrates into the material to contact toxic substances. The toxins

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will dissolve into water and travel out of the materials with water, potentially causing illness in biological organisms. Our method renders toxins non-viable as human pathogens by reacting the toxins to create non-soluble sulfide crystals locked in the material as hydration is completed. The Sulfides are not soluble in water and are locked into position within the hydrate material without ability to readily escape or change in state. The ability of the toxin to dissolve into water and travel into ground water supplies has been eliminated. The final result of our method is a practical building product with the ability to be mass produced by industrial, mechanized methods. Also, it can produce The Calcium Silicate Hydrate can be formed into concrete building materials, poured as slabs and used in detailed casting and form work. The material can create buildings, stadiums, highways, bridges, roads, curbs, sidewalks, foundations, walls, fences, traffic barriers, statues, monuments, modular construction systems and other similar products including, but not limited to those listed above. The Version of The Invention Discussed Here Includes:

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1. Calcium Polysulfide, CaSx, in aqueous solution 2. Class F Fly Ash (a pozzalan) 3. Class C Fly Ash (a pozzolan) 4. All Purpose Sand 5. Volcanic Rock (a pozzolan also known as cinders, pumice)

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6. Pulverized Slag (a pozzolan) 7. Ordinary Portland Cement 8. Crushed Aggregate Relationship Between The Components:

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The components are mixed in various proportions to create concrete mix designs of various strengths and consistencies for use in construction materials.

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1 - Calcium Polysulfide solutions are substituted for ordinary water to present the negatively charged ion of Sulfur in a highly alkaline solution to facilitate the bonding of toxins with sulfur to create nonsoluble Sulfides. Calcium Polysulfide can be added in various amounts and with various proportions of water added to the solution. Calcium Polysulfide will quickly degrade to create Calcium Hydroxide and sulfur. The Calcium Hydroxide becomes an integral part of Calcium Silicate Hydrate through reaction with Silicate Hydroxide. Calcium Polysulfide must be used in this method of invention.

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2 - Class F Fly Ash is a by-product of coal fired electrical production and is high in silicates. Fly Ash can be added in various amounts. This is a pozzolanic material known to react with Calcium in Hydroxide solution to create Calcium Silicate Hydrate.

3 - Class C Fly Ash is also a by-product of coal fired electrical production. Class C Fly Ash provides lime, CaO, and silicates. Fly Ash can be added in various amounts. This is a pozzolanic material known to

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react with Calcium in Hydroxide solution to create Calcium Silicate Hydrate. The lime, CaO, present in the Class C Fly Ash quickly "slakes" with water in the Calcium Polysulfide solution to create Calcium Hydroxide from the water molecules. All water is eliminated from the mix during this reaction. The remaining silicate content of the Class C Fly Ash, then, bonds to form Calcium Silicate Hydrate as described above.

4 - All Purpose Sand provides a fine aggregate and is high in silicates. Sand provides a filler in the mix to increase bonding properties. Sand can be added in various amounts to effect strength and consistency of the mix design.

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5 - Volcanic Rock is a natural by-product of high temperature reactions and is high is silicates. Volcanic Rock is a pozzolanic material with the ability to chemically bond to Calcium Silicate Hydrate rather than just be encased in cementitious material. Volcanic rock may or may not be used in various amounts in mix designs.

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6 - Pulverized Slag is a by-product of industrial metal smelting and is high in silicates. Slag can also be high in lime depending on the type of ore that was smelted to create the specific slag accumulation. Slag is a pozzolanic material that facilitates the reactions needed to created Calcium Silicate Hydrate. Slag is commonly known as a potentially toxic waste product. Slag may or may not be used in various amounts in mix designs.

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7 - Ordinary Portland Cement - A readily available powder that can be mixed with water, sand and crushed rock to form concrete. Portland cement may or may not be added to Calcium Silicate Hydrate as a method of increasing strength of the final material.

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8 - Crushed Aggregate is used in concrete mix designs as filler and to increase the compressive strength by including high strength materials with the cementing agents. Crushed aggregate may be a various size and various types in various amounts. Crushed aggregate may or may not be added to any mix design.

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How The Invention Works: The components of the method come together to supply sulfur in a negatively charged ion to bond with positively charged toxic ions turning them into non-harmful sulfides. The sulfides are, then, locked in a concrete-like material based on the following chemical reaction. Also known as the "pozzolanic reaction".

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CH + SH -> CSH (simplified)

calcium hydroxide + silicate hydroxide -> calcium silicate hydrate

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The silicates mix with hydroxide to create silicate hydroxide. The Calcium Hydroxide from the Calcium Polysulfide solution reacts with the Silicate Hydroxide to create Calcium Silicate Hydrate. Calcium Silicate Hydrate can be used as a substitute for Ordinary Portland Cement Concrete.

The components of the method come together to first react toxins to render them harmless as human pathogens with the use of Calcium Polysulfide. Then, the components bond together to create practical construction materials. Our method provides the ability for different materials to be mixed in different amounts with Calcium Polysulfide to eliminate heavy metal toxins and create building materials of various strengths, sizes, uses, colors, textures and other characteristics. Including, but not limited to those listed above. How To Make The Invention: The invention can be made by mixing the components and placing the wet material into form work similar to normal concrete construction methods. Dry components can also be packed into forms and the liquid, Calcium Polysulfide, applied to the packed material to cause a chemical reaction. It is also possible to mix all components in dry form including powdered Calcium Oxide and powdered Sulfur in a premixed form. Then, water added to facilitate all chemical reactions listed above. The dry Calcium Oxide and Sulfur together with water constitute Calcium Polysulfide for the purpose this invention as the negatively charged ion of Sulfur will be presented in highly alkaline aqueous solution. Calcium Polysulfide, Class C Fly Ash and Sand are necessary for the invention to form into a solid concrete material. Class F Fly Ash improves the workability of the material in form work by adding glassy silicates. Different types of volcanic rock and slag aggregate can be added in different sizes to effect strength, texture, color and final weight of the material. Ordinary Portland cement is optional to increase strength and speed setting time of the material. Crushed aggregate is optional, but can be used to effect strength, consistency, texture and color of the final product. The components can be interchanged in that Ordinary Portland Cement can be used in greater amounts or increased to effect strength of the material. If used in conjunction with Calcium Polysulfide rather than ordinary water for the purpose of rendering a toxic substance non-viable as a pathogen the method is reconfigured for similar results with a slightly different product. How To Use The Invention:

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The invention is a method of solution for potentially toxic ash by-products of coal fired electrical facilities, and potentially toxic slag piles from industrial smelting operations by removing the potentially toxic materials. The removed materials are, then, mixed with chemical agents to facilitate the reactions needed to render toxins non-viable as human pathogens. The agents, then, continue reactions to create Calcium Silicate Hydrate. A material capable of being cast into almost shape. The shapes can be used to create modular construction materials of high compressive strength. Steel reinforcing can be used in conjunction with the material as is done in common construction practices with Ordinary Portland Cement. Toxic wastes are used in conjunction with Calcium Polysulfide and common materials to produce inert, harmless building materials. Additionally: The method of invention can be used to create Calcium Silicate Hydrate for use in restoration of historic and ancient buildings. Prior to the invention of Ordinary Portland Cement concrete structures were built using variations of the Lime concrete based on the pozzolanic reaction. Materials made from our method will be able to more readily mimic characteristics of and adhere to pozzolanic mixtures than materials made of Ordinary Portland Cement.

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The product resulting from this method of invention can be used for creation of concrete underwater. The waterproof and chemical resistant properties of Calcium Silicate hydrate make it an ideal solution for underwater concrete work. Water will simply be pulled into the mass until all lime has slaked to create Calcium Hydroxide. The Calcium Hydroxide will bond will Silicates to create Calcium Silicate Hydrate a material not soluble in or effected by water.

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Also, it can create: The Calcium Silicate Hydrate can be formed into concrete building materials, poured as slabs and used in detailed casting and form work. The material can create buildings, stadiums, highways, bridges, roads, curbs, sidewalks, foundations, walls, fences, traffic barriers, statues, monuments, modular construction systems and other similar products including, but not limited to those listed above.

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ABSTRACT A means to create clean concrete building materials by recycling industrial waste by-products utilizing Calcium Polysulfide is disclosed. Our method renders toxins non-viable as human pathogens by reacting the toxins to create non-soluble sulfide crystals locked in the material as hydration is completed. The Sulfides are not soluble in water and are locked into position within the hydrate material without ability to readily escape or change in state. The ability of the toxin to dissolve into water and travel into ground water supplies has been eliminated. The final result of our method is a practical building product with the ability to be mass produced by industrial, mechanized methods.

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