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Chemical Treatment of Coal Ash for Beneficial Use
Applications / By‐Product Treatment Via Calcium
Polysulfide
CONFERENCE: 2015 World of Coal Ash – (www.worldofcoalash.org)
KEYWORDS: coal ash, concrete, encapsulation, remediation, calcium polysulfide
Written: March 16, 2015
Primary author: James T. Easton1
Additional Authors: James Papp1, Guy Wojtowicz1
1JJG Environmental Solutions, llc
PO Box 882191
Steamboat Springs, Colorado, USA 80488
ABSTRACT
An explanation of US patent #8,741,058 B1 involving chemical treatment of the Coal Fired
Electrical by‐product, Coal Ash, via Calcium Polysulfide. This method, first, provides a system to
immobilize potentially toxic elements found in residual Coal Ash. A highly alkaline aqueous
solution is generated to force the ionic charge of heavy metal elements to positive states in the
presence of the Sulfur atom in a negative state. Elemental atoms are, then, bonded into non‐
soluble Sulfide molecules diminishing the ability of toxic constituents to leach into water
supplies. Secondly, this process leads to the encapsulation of toxins in concrete materials.
These materials are formed by the pozzolanic reaction of Calcium Hydroxide with Silicates
present in Coal Ash. The chemicals present in this reaction are similar to those found in the
composition of Roman concrete. Resultant material is comparable and arguably superior in
physical properties and compressive strength to materials formed with Ordinary Portland
cement. This secondary reaction is capable of forming market ready raw material for use as
road base and aggregate specified for Portland cement based concrete construction purposes.
This material is required to meet the ASTM standard abrasion test for aggregate use, and is not
limited by the measure of Carbon content indicated by the loss on ignition value stipulated in
typical concrete Engineering specifications. This process presents an opportunity for safe,
profitable beneficial use of mass accumulations of Coal Ash residuals with relatively minimal on‐
site processing.
2015 World of Coal Ash (WOCA) Conference in Nasvhille, TN - May 5-7, 2015http://www.flyash.info/
I. Introduction
Coal Fired Electrical power production has been used in the United States for well over a
century. The process involves burning coal to boil water and create steam. Steam, then,
creates positive pressure that is directed to spin turbines generating electricity. This method of
power production provides electrical service to roughly 40%, or over 42 million households
spread across the United States. Electrical production based on Coal is economical and reliable.
Power companies rely on the availability of Coal to maintain steady service to homes and
businesses in all weather conditions, times of day, seasonal climates and socio‐political
environments.
Coal is an important resource providing stability and security to the United States. However,
the use of Coal has proven to create serious Environmental threats to human health as proven
by recent accidents including the Dan River spill in North Carolina and the Kingston Coal Ash
spill in Tennessee. The by‐products of Coal do contain potentially toxic materials, and when
irresponsibly handled do negatively impact human beings. Although 45% of Coal Ash by‐
products are safely and responsibly recycled into beneficial use applications the remainder is
often discarded as trash with little regard to the potential effects on nearby populations.
Countless instances of Ground Water pollution have now been documented as the direct result
of Coal Ash residual by‐products. Our society is reaching a critical point where irresponsible
handling of Coal Ash accumulations has begun to cause obvious, negative impacts to our
Environment.
Coal Fired Power provides the majority of Electricity in the United States
This paper is written with the intention of presenting a problem solving approach to mitigate
the negative effects of the by‐products of Coal combustion. Our intention is to propose
solutions for problems associated with the 55% of Coal Ash by‐product material that does not
make it into beneficial use under current standards. We believe it is possible to beneficially
reuse up to 100% of Coal Ash by‐product material in safe, productive applications. Through this
analysis the reader will come to understand that Coal combustion can be used both as a clean,
reliable source of Electrical production, and as a method to create harmless, beneficial raw
material for public use.
II. Background Explanation and Description
Science has proven Coal is formed from the Carbon remnants of old growth forests. Carbon
from organic life collects and is compressed over thousands of years by natural forces.
However, Coal is not purely Carbon, nor is organic life able to sustain without multiple chemical
constituents. The Carbon component is what readily burns making Coal useful for the purpose
of Electrical power generation. However, as Coal is burned molecular chains are broken and
traces of elemental substances are released. When released, these substances can be caught
by pollution control devices, or trapped in by‐product Coal Ash at production facilities. In small
amounts, most of these substances are not harmful, and many are required by living organisms
to complete biological processes. Yet, in large accumulations many of these substances
become toxic, and are known to cause cancers, birth defects, deformities and other serious
illnesses in human beings and wildlife.
Efforts to beneficially use by‐products from Coal combustion are ongoing. Up to 45% of Coal
Ash is beneficially reused each year. Most of the reused Ash is in the form of Fly Ash. It is
important to note that Fly Ash is divided into several "classes" depending on the chemical
makeup of the Ash. This material is used in certain cosmetics and other products, however, the
main avenue for beneficial reuse is the construction industry. The smaller particles of Ash
collected in bagging systems used to filter emissions from combustion are termed Fly Ash.
These particles are sold to concrete companies as an additive to Ordinary Portland Cement. Fly
Ash particles are up to 100 times smaller than the reactive particles found in Ordinary Portland
Cement. The addition of Fly Ash has multiple effects on, and does greatly increase the overall
quality of Portland cement concrete. The material reduces the heat of hydration in concrete,
provides increased workability, reduces overall costs and improves water resistance protecting
steel reinforcement in concrete structures. The fact is, concrete containing Fly Ash is all around
us, everyday. Parking garages, highways, bridges, building foundations and bagged ready mix
concrete available at local home improvement centers all contain amounts of Fly Ash.
Spherical Particles of Fly Ash in relation to Ordinary Portland cement
The concrete industry is regulated under Engineering Specifications written to assist in
controlling the end product of concrete used in construction. The American Concrete Institute
is the main body controlling these specifications. Historically, specifications have been based
on the recipe of components that are used. In this manner, the results can be reliably
predicted. The process is rather simple. Fly Ash meeting the standard is brokered and sold to
concrete companies. Ash not meeting the standard is generally discarded, or used as a form of
structural fill when possible.
Specified criteria dictates the size of particles, and the amount of Carbon present in the Ash;
measured as the LOI or Loss on Ignition. In the 1990s, a different method of specification was
created. This method is based on laboratory testing of the final product of concrete. The
newer method allows for greater flexibility in the materials used to create concrete, but has not
yet gained wide‐spread industry acceptance. As our understanding of the chemistry of
concrete has improved our abilities to create blended cements has improved as well. Although
the recipe based standard has served the construction industry well in providing predictable
results in strength and material properties technology has surpassed the aging, main stream
specification procedure.
The building code dictates basic structural requirements for use by Architects and Engineers.
The specification system assists in ensuring that formulations of concrete will meet these
requirements. The most basic notion is that certain structural components must meet specific
strength requirements measured in resistance by pounds per square inch or PSI. For example,
residential footings are typically 3,500 PSI concrete, a podium deck for a wood framed multi‐
family residential project will be 5,000 PSI footings for a steel framed skyscraper can be as
much as 10,000 PSI and a common sidewalk 1,500 PSI.
Additional requirements can also effect concrete selection. Chemical resistance, workability,
fluidity, formability, water resistance, heat resistance and other specific material qualities are
recognized as significant factors in many construction projects. Steel reinforcing must be
protected from oxidation and/or chemical attack as steel will expand as it rusts destroying
structural concrete from the inside out. In order to protect projects from failure, and loss of
human life it is extremely important to carefully specify materials in their best use scenario.
Professionals in the construction industry must study and identify the proper use of materials
used in construction. This is the underlying function of the specification system, and the most
obvious explanation for the selective process for the beneficial use of Fly Ash. Much of the
remaining 55% of Coal Ash contains excess amounts of Carbon, and is not of a size determined
appropriate for use in Portland cement, the adhesive portion of ordinary concrete.
III. Chemical Composition of Coal Ash
Coal Ash shares a chemical formulation similar to Ordinary Portland Cement and to that of
naturally occurring Volcanic Ash in many aspects. The main body of Chemical constituents is
identical. The differences lie in the amounts of these chemicals that are present. The basic
ingredients are Calcium Oxide (Lime) and Silicon Dioxide (Silicate, also known as Quartz). Other
materials such as Aluminum Oxide, Iron Oxide, Manganese Oxide and Sulfur are also present.
The following table illustrates the differences in composition of Class "F" Fly Ash, Class "C" Fly
Ash and Ordinary Portland Cement.
Chemical Portland Cement
(OPC) Fly Ash Fly Ash
Component (%) Ordinary Portland
Cement Class "C" Class "F"
CaO 64.4 24.3 8.7 SiO2 22.6 39.9 52 Al2O3 4.3 16.7 25.8 MgO 2.1 4.6 1.8 Fe2O3 2.4 5.8 6.9 SO3 2.3 3.3 0.6
Na2O/K2O 0.6 1.3 0.6
SUB‐TOTAL 98.7 95.9 96.4
TRACE ELEMENTS 1.3 4.1 3.6
TOTAL 100% 100% 100%
Review of the above table indicates a significant difference in the amount of Calcium Oxide
(CaO or Lime), Silicon Dioxide (Si2O) and Aluminum Oxide (Al2O3) present in Ordinary Portland
Cement vs. that of Fly Ash. These differences are significant for the following reasons. First,
Calcium Oxide mixes or "slakes" with water (H2O) to create Calcium Hydroxide. Calcium Oxide
is not reactive with Silicon Dioxide. It is the reaction of Calcium Hydroxide with Silicon Dioxide
that creates concrete. Second, Silicon Dioxide reacted with Calcium Hydroxide creates what is
termed Calcium Silicate Hydrate or C‐S‐H in concrete chemistry notation. Third, Ordinary
Portland Cement contains a minimal amount of Aluminum Oxide (Al2O3). The level of
Aluminum Oxide present in Fly Ash is significantly greater than that of Ordinary Portland
Cement.
Silicone Oxide Crystals (Left), Microscopic Calcium Hydroxide (Right)
Recent International studies involving researchers from the University of California at Berkeley
and the King Abdullah University in Saudi Arabia have identified the exact composition of
Roman concrete using advanced light source technology. Their results show the presence of
Aluminum Tobermorite crystals in the Calcium Silicate Hydrate formation, and have been
termed Calcium Aluminum Silicate Hydrate or C‐A‐S‐H. These studies were performed to
evaluate and identify how Roman concrete, under sea water for over 2000 years was able to
out‐perform our best modern, Ordinary Portland Cement concrete. The final hypothesis is that
the presence of Aluminum Oxide in Volcanic Ash used by the Romans led to a far superior
product as modern Ordinary Portland Cement concrete is completely devoid of the Aluminum
Tobermorite compound.
The Aqueducts and Pantheon Constructed of Roman Volcanic Ash Concrete
This hypothesis follows the basic, available knowledge of Aluminum Oxide. Aluminum Oxide is
completely insoluble in water, highly resistant to damage from heat and is purposely limited in
Ordinary Portland Cement formulation due to the fact it causes a flash set in C‐S‐H. Sulfur is
purposefully added to Ordinary Portland Cement to slow the effect of flash setting due to
Aluminum Oxide. Sulfur is commonly found in Volcanic Ash and was referred to in history as
brimstone due to it being commonly found at the brim of Volcanoes. Logical deduction would
indicate that the Sulfur content of Roman concrete would have been high enough to counter
flash setting of Aluminum Oxide, and would have supplied acidic forms of Sulfur capable of
breaking the Aluminum Oxide molecular chains allowing their inclusion in the Calcium Silicate
Hydrate molecular formation. Thereby creating Calcium Aluminum Silicate Hydrate.
IV. Concrete Chemistry at the Molecular Level
The presence of trace elements as listed in the table in section (III) is an important facet of this
report. Trace elements can be almost anything found in the materials used in the production of
Ordinary Portland Cement (OPC). OPC is a dry powder made from heating specific types of
rock, brick and/or other materials in a high temperature kiln to form what is referred to as
clinker. Clinker is, then, ground to a fine powder known as Portland cement. Trace elements
found in Coal Ash are similar in nature. Often those trace elements are potentially toxic
substances such as Mercury, Arsenic, Lead and other materials.
Portland cement Clinker (Left), Ground Portland cement (Right)
As mentioned above, the Lime (Calcium Oxide) present in the Portland cement powder will mix
with water to form Calcium Hydroxide. The chemical reaction forming concrete is achieved by
the action of a highly alkaline (basic pH) material, Calcium Hydroxide, coming into contact with
a slightly acidic material, Silicon Dioxide. To the visible eye concrete is an ordinary material
surrounding us every day. Photos taken of concrete by Electron Microscopes depict something
completely different; a uniquely beautiful fabric of crystalline formations, referred to as the
matrix of concrete.
Microscopic images of Ordinary Concrete
It is these Hydroxide based formations that have the ability to encapsulate or "lock in place"
traces of multiple molecular compounds. Different elements combine to create different
shapes that embed themselves securely into the concrete matrix. In this manner, potentially
toxic trace elements are held in place within concrete. Effectively mitigating the potential
leaching of toxic materials into our environment. For this reason, the United States
Environmental Protection Agency has identified encapsulation in concrete as an acceptable
method of Environmental remediation of toxic materials.
Natural Calcium Carbonate, Limestone, formation created by Calcium Hydroxide
Steamboat Springs, Colorado.
V. Calcium Polysulfide
Calcium Polysulfide (CaSx) is a highly alkaline aqueous solution created by boiling Lime (CaO) in
water with Sulfur. The solution has been widely used in agriculture since the 1840s as a
fungicide and insecticide. Extensive research has been completed on the Environmental effects
of the chemical by the US EPA, the FDA and countless other organizations. The solution has
been granted a GRAS (Generally Recognized as Safe) designation by the FDA, and was approved
for Reregistration for use by the US EPA in a 2005 Reregistration Eligibility Decision (RED).
The solution is economical, commercially produced and able to be transported by railroad,
tanker truck and in totes through the US mail. The chemical has gained acceptance as a
reducing agent used for In‐Situ Geochemical Fixation of multiple toxins found in ground water.
As a highly basic liquid, Calcium Polysulfide will present the negatively charged dianion (2‐) of
Sulfur. This negatively charged form of Sulfur is only found in highly alkaline aqueous solutions.
This specific presentation of Sulfur is important in that most potentially toxic heavy metals will
present themselves as positively charged ions in their respective oxidation state. Negatively
charged Sulfur will easily bond to positively charged heavy metals to form Sulfide molecular
structures. Most Sulfides are commonly known mineralized Ores, and are often sought after by
commercial mining interests as Sulfur can be removed from the Ore through the smelting
process to isolate specific metals.
Mercury Sulfide (Left), Copper Sulfide (Right)
Uranium is commonly mined through the use of Calcium Polysulfide. Mines can be flooded
with water to allow Uranium to dissolve directly into water. This water is, then, removed from
the mine and mixed with Calcium Polysulfide. The Sulfur in solution bonds to positively charged
Uranium atoms creating Uranium Sulfide, or "Yellow Cake." The Uranium Sulfide, then,
precipitates from the solution and is extracted. Further processing of the Uranium Sulfur
releases the bonded Sulfur isolating the pure Uranium material. Similar processes can be
directed to most, if not all potentially toxic heavy metals.
Calcium Polysulfide quickly degrades to Calcium Hydroxide and Sulfur. This specific chemistry
makes the liquid ideal for use in the production of high quality concrete. Lower levels of
Calcium Oxide (CaO) in Fly Ash can be off‐set by direct liquid application of Calcium hydroxide in
the chemical reaction creating concrete. This allows significant reduction, and potential
elimination of Ordinary Portland Cement to create high strength, highly workable material that
is resistant to both water and chemical attack. The increase in Sulfur allows an increase in
Aluminum Oxide as increased Sulfur acts to inhibit the flash setting properties of Aluminum
Oxide. Acidic Sulfur compounds capable of breaking apart the Aluminum Oxide molecule will
be present allowing the creation of Calcium Aluminum Silicate Hydrate. The same compound
identified as responsible for the superior quality of Roman cement.
VI. Coal Ash Storage Impoundments
There are over 1,500 Coal Ash storage locations in the United States, and many have been in
operation for close to or more than 100 years. These areas serve as dumping grounds for the
majority of the 55% of Coal Ash that does not meet current standards for beneficial use. A
typical Ash impoundment, or basin is a large hole measuring anywhere from 20 to 50 feet deep,
covers several acres of land, and is capable of containing millions of tons of Coal Ash. Studies
concerning the contents of Ash impoundments have shown that sand, silt, gravel and Coal Ash
are present in various amounts across the ponds. Unburned Carbon is typically present as well,
but seems to reside mostly in the largest particles present. If constructed properly, Coal Ash
impoundments will serve their purpose without causing Environmental risk. However, many
impoundments are poorly constructed and located in areas where minor failures can become
significant Environmental disasters. Unlined impoundments pose the greatest pollution risk.
The Dan River Steam Station (Left) and Kingston TVA Ash Impoundments (Right)
Toxic substances within Coal Ash tend to be highly water soluble. As water enters the
impoundment area either from movement above or below ground these toxins will move freely
with water sources. Once movement into the ground has occurred Ground Water pollution has
begun. This is a significant Environmental danger as pollutants can enter waterways, irrigation
supplies and water used for public consumption. Most municipalities do treat water before it
enters public supplies, however, many people do rely on wells as sources of water for livestock,
commercial crops and homes. In addition, aquatic wildlife residing in affected Rivers, Lakes and
Streams can be contaminated. These toxic contaminations can travel to human beings through
food consumption, contact with or ingestion of contaminated water supplies.
Protective liners being installed at a new Dry Coal Ash Landfill
The trace elements causing contamination are usually a very small percentage of the total
volume of material accumulated on site. However, mass accumulations of discarded Ash
multiply concentrations of toxic material. If one Ash basin is capable of containing 2 million
tons of Coal Ash, 1% of that amount can be assumed to be toxic material. In percentages, the
amount of potential toxin can seem very low. Yet, after a quick calculation it is apparent that
1% of 1million tons equates to 20 million pounds of toxic material. Material that at one time
was bound into unburned Coal posing no threat to our Environment.
Coal Ash Storage locations spread across the United States – US EPA Map
VII. Remediation Solutions for Ash Impoundments
Ground Water pollution is not unique to Coals Ash Impoundments. Factories, mining
operations, dry cleaning facilities, lumber treatment yards and a multitude of other locations
have been the source of significant Environmental pollution in the United States. Chemical
injections, pump and treat operations and the construction of permeable reactive barriers
(PRBs) have been successful in remediating multiple types of pollution. In the case of Coal Ash
by‐products it would seem logical to utilize technology that can benefit from the inherent
chemistry of the Ash itself.
Calcium Polysulfide has the ability to act a reducing agent for a wide range of toxins typically
found in Coal Ash. Once the hydrological patterns of water movement are understood at a
specific site, Calcium Polysulfide can be directly injected into problem areas. The chemical will
react with free flowing, elemental toxins to create insoluble molecular compounds. Effectively
stopping these compounds in place, reducing or eliminating their ability to effect water
supplies. Traditional vertical drilling can deliver injections to specifically targeted area of high
toxic concentrations. Reactive Barriers can be created by placing trenches perpendicular to the
flow of ground water. These systems treat polluted water as it passed from one side of the
permeable barrier to the other. Horizontal drilling equipment can be used to install piping
systems across wide areas that can be connecting to pumping systems to repeatedly deliver
remediating chemicals. In order to reach maximum effectiveness, each specific site must be
analyzed to understand underground water movement, and to know exactly which toxins are
the greatest threat in any given area. These methods are effective, and can be used to reverse
Environmental threats of toxins that have already leached into Ground Water Supplies.
Horizontal or “Directional Drilling” Diagram and Equipment
In addition, Calcium Polysulfide can be used to stop toxic contaminants at their source within
the surface impoundments. As previously discussed, Calcium Polysulfide will react with
elemental toxins to create non‐soluble Sulfides. Also, Calcium Polysulfide will supply the
Calcium Hydroxide and Sulfur needed to react with Coal Ash to create concrete materials.
These characteristics can be used to treat Coal Ash accumulations while creating material
suitable for beneficial reuse. Horizontal drilling equipment can be fitting with 24" diameter
augers to move laterally through Coal Ash deposits with ease. Our basic process involves, first,
drilling through the material to loosen compacted Ash. The second step is to pull the auger
back through the material while injecting Calcium Polysulfide under pressure into the path of
drilling. Calcium Polysulfide can, then, simultaneously bind toxic material into Sulfide forms
and supply Calcium Hydroxide to react with Silicate material in the Ash creating a hardened
concrete.
Mobile Concrete Equipment deployed to a remote location
Typical ¾” gravel used as aggregate in concrete
The hardened concrete can then be excavated and tested for resistance to abrasion. If the
material does not pass ASTM testing on the first attempt, it can be reprocessed with Ordinary
Portland added to increase strength. Once the material has achieved suitable hardness it can
be ground to the size of ordinary gravel, and used as synthetic aggregate in concrete
construction. By directing this material to use as aggregate only the abrasion test is needed to
qualify the material for use. Loss on Ignition and fineness standards specific to use in Ordinary
Portland cement are no longer factors. The material is simply a replacement for aggregate
added to Ordinary Portland cement to create concrete. This material can, then, be sold in
competition with gravel to create revenue for Electrical Power Companies. In the end, Ground
Water pollution is reversed protecting the environment and up to 100% of Coal Ash by‐product
material is recycled into beneficial use. The United States Patent #8,741,058 B1 discloses a
method of production of concrete utilizing a direct liquid application of Calcium Polysulfide.
Calcium Polysulfide is a readily available, commercially produced formulation of Calcium
Hydroxide and Sulfur. Concrete Core samples have been made and tested in accordance with
ASTM standards achieving strengths of over 4000 PSI in samples substantially devoid of
Ordinary Portland Cement and containing only pumice as aggregate. Both the above
referenced patent document and Provisional patent document are attached to this paper as
addendums.
The United States can readily utilize Billions of tons of
Aggregate in concrete Road and Highway construction
VIII. Conclusion
Coal not only provides a reliable means of producing electricity, it is a valuable resource used extensively
in the construction industry. However, the use of Coal Ash has been limited by practical application as
an additive to only the adhesive portion of concrete, Ordinary Portland cement. Portland cement is in
fact less than twenty percent of the volume of concrete. Specifications allow no more than 35% of that
Portland cement component to be replaced with suitable Coal Ash. The bulk of concrete is made up of
aggregate rock held in place by the Portland cement binder. The use of Coal Ash in concrete can
increase exponentially by the utilization of technology to process discarded Coal Ash into synthetic
aggregate ready for wide‐spread use. Chemical treatment of the by‐product Ash can be used to
chemically bind potential toxins rendering Coal Ash environmentally safe while also reversing existing
contamination of Ground Water supplies. These processes can take place on‐site at existing
impoundment locations, reducing further Environmental impact, limiting resources required for
remediation efforts and can be completed with processes already full accepted by the United States
Environmental Protection Agency.
PROVISIONAL APPLICATION FOR PATENT
Application No. 61/610,428 filed March 13, 2012
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. 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.
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.
i.e. Elemental Mercury will react to create Mercury Sulfide, Cinnabar.
Hg + S ‐> HgS
(positive Mercury ions bond to negative Sulfur ions)
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).
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 by‐products 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 by‐products 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 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:
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)
6. Pulverized Slag (a pozzolan)
7. Ordinary Portland Cement
8. Crushed Aggregate
Relationship Between The Components:
The components are mixed in various proportions to create concrete mix designs of various
strengths and consistencies for use in construction materials.
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 non‐soluble 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.
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 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.
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 cementitous material. Volcanic rock may or may not be
used in various amounts in mix designs.
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.
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.
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.
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".
CH + SH ‐> CSH (simplified)
calcium hydroxide + silicate hydroxide ‐> 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
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:
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.
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.
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.
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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