Note: Descriptions are shown in the official language in which they were submitted.
CA 02609651 2007-11-07
METHODS AND COMPOSITIONS FOR FILTRATION MEDIA
Related U.S. Application Data
[0001] The present application claims priority to the November 7, 2005 U.S.
Provisional Application No. 60/734õ240, which is incorporated herein by
reference.
Field Of The Invention
[0002] The present invention is directed to filtration media with
antimicrobial
properties. In particular, the present invention is directed to making and
using
filtration media with aqueous antimicrobial compositions comprising
organosiloxane quaternary ammonium compounds. The filtration media of the
present invention may be used for filtration of water to remove or kill
microorganisms in the water.
Background Of The Invention
[0003] The treatment of "non-point source" water pollution such as
stormwater and industrial runoff is a growing concern for urban centers,
industrial sites, and residential property owners. Increasingly, government
entities are instituting strict regulations for treatment and disposal of
stormwater
and industrial runoff. Despite increasing public concern and government issues
surrounding this issue, current technology does not adequately meet the
current
needs. Stormwater and industrial runoff can be highly contaminated with a
highly variable mix of particulate ar-d dissolved contaminants. In many
circumstances, runoff flow occurs intermittently and in high volume requiring
rapid, but effective, treatment and rerr-oval of the various contaminants,
which
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may include human and animal waste, organic chemicals, pesticides, oils,
solids
(particulates and dissolved), heavy metals, and fertilizers.
[0004] Microbial contaminants from sewage, human waste and animal waste,
including bacteria, viruses, fungi, and other disease organisms, are of
particular
concern. Although urban runoff has been found to contain Salmonella, the
occurrence of Salmonella in urban runoff is generally low. Of greater concern
are pathogenic organisms which are infective at a low organism concentration
or whose mode-of-entry is not oral ingestion. These pathogens include, but are
not limited to Pseudomonas aeruginosa, Staphyloccus aureus, Escherichia coli,
Shigella, or enteroviruses. Pseudomonas is reported to be the most abundant
pathogenic bacteria present in urban runoff and streams, with several thousand
P. aeruginosa organisms per 100 rnL being common. Relatively small
populations of P. aeruginosa may cause health problems simply through water
contact, and such bacteria are typically resistant to antibiotics. The
presence of
enteroviruses in urban runoff is of concern since very small virus
concentrations
are capable of producing infections or diseases. Recent studies have shown,
for
example, that swimmers at beaches located near stormwater outfall show an
increased risk of a variety of health problems.
[0005] Despite the health concerns surrounding stormwater and industrial
runoff, particularly related to microbial contamination, there exists a need
for
economic and effective methods to treat runoff for microbial contamination.
Currently, if runoff is treated at all, it is handled by filtration, typically
using
filtration media such as sand, compost, fibers, fabrics, peat and other
elaborate
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filtration systems. While these filtration media may often be effective in
handling many target pollutants such as total suspended solids, soluble heavy
metals, oil and grease, these media are less effective for removing microbial
contaminants. Microbial contaminants may be removed from aqueous solutions
by filtration through filters with very small pore sizes, typically 0.4
microns or
less. However, the use of such filter media for stormwater runoff is not
desirable
because of the poor flow characteristics such media are too slow and prone to
fouling by larger particulates.
[0006] What is needed are methods and compositions for treatment of water
sources that are capable of controlling or killing a broad spectrum of
biological
agents, including viruses, bacteria and other microbial agents. The treatments
should also be stable, have good flow characteristics, be durable with a long
lasting effect, safe and non-toxic.
Detailed Description
[0007] The present invention corriprises methods and compositions for
treatment of water including but not limited to storm water runoff, industrial
liquid discharge, sewer water discharge, catch basins, livestock water holding
ponds, and livestock waste lagoons. T'he compositions of the present invention
comprise compositions comprising organosilane quaternary amine compounds
and quatemary ammonium compounds, admixed with perlite. The present
invention comprises treating perlite filtration media with biocidal or
antimicrobial compositions of the present invention to make a biocidal or
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antimicrobial filtration media and methods for using the biocidal or
antimicrobial filtration media.
[0008] The present invention comprises biocidal compositions comprising an
organosilane quaternary amine compound and at least one additional biocidal
active compound. The at least one additional biocidal active compound is one
or more compounds includes, but is not limited to, quaternary ammonium
compounds, such as chloride and saccharinate quatemary ammonium
compounds from Lonza or Stepan Co., antibiotics, antivirals, antifungals, and
antimicrobials.
[0009] Compositions of the present invention may further comprise stabilizer
compounds. Several compounds and methods of stabilizing organosilane
quaternary compounds are known in the art, and include methods described in
U.S. Patent Nos. 5,954,869; 5,959,014; 6,120,587; 6,113,815; 6,469,120; and
6,762,172. In one embodiment, the organosilane quaternary compound may be
stabilized by the reaction in propylene carbonate. An advantage of stabilized
organosilane quaternary compounds is the ability to deliver silanes in an
aqueous solution to commonly encountered surfaces. Compositions used in
methods of the present invention may also comprise an organosilane quaternary
ammonium compound and an organos:ilane provided in emulsions such as those
taught in US Patent Nos. 4,908,355 and 6,607,717, which are incorporated
herein by reference.
[00010] Compositions of the present invention may comprise an organosilane
quatemary compound and a quaternary ammonium compound, which when
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combined can provide contact disinfection and residual antimicrobial activity;
and may further comprise an oxidizing agent and a chelating agent, and water
or
other solvent. Examples include, but are not limited to, compositions wherein
the oxidizing agent is hydrogen peroxide and the chelating agent is EDTA.
[00011] The present invention comprises compositions comprising an
organosilane quatemary compound and a quatemary ammonium compound, and
may further comprise an oxidizing agent or a chelating agent, and may
optionally comprise a surfactant; a wetting agent; an antibiotic compound,
antifungal agent, or an antiviral agent. Compositions of the present invention
also comprise an organosilane quatemary compound and may further comprise
one or more of, a surfactant; a wetting agent; an antibiotic compound,
antifungal
agent, an antiviral agent, an oxidizing agent or a chelating agent.
[000121 The compositions of the present invention comprise a ratio of
organosilane quatemary compound to one or more quatemary ammonium
compounds in a weight range of 1:100 to 100:1 or in a weight range of 1:10 to
10:1. The ratio of organosi lane quatemary compound to one or more quatemary
ammonium compounds may be determined by the particular use of the
composition or final product or the surface or material to which the
composition
is to be applied, as well as the specific nature of the microbial
contamination or
potential microbial contamination.
[00013] Compositions may comprise water, an aqueous or non aqueous
solvent, or combinations or aqueous and nonaqueous solvents in a range
between about 50% to about 80%i, by weight; organosilane quatemary
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compound in a concentration range of' about 0.001% to about 85%; one or more
quaternary ammonium compounds in a concentration range of about 0.001 % to
about 10%; and optionally, chelating agent such as EDTA in a concentration
range of about 0% to about 5%; reducing agent such as hydrogen peroxide in a
concentration range of about 0% to about 5%; solubility enhancing agents or
other formulation agents such as isopropyl alcohol in a concentration range of
about 0% to about 10%, solvent enhancers such as glycol ether in a
concentration range of about 0% to about 10%; and wetting agents such as NP-9
(Nanophenol Ethoxylate-9) in a concentration range of about 0% to about 10%.
[000141 A composition may comprise about 60-90% water; an organosilane
quaternary compound in a concentration range of about 0.001% to about 6%;
one or more quaternary ammonium compounds in a concentration range of
about 0.001% to about 5%; EDTA at a concentration of range of about 0.1% to
about 3%; hydrogen peroxide at a concentration range of about 0.01% to about
3%; isopropyl alcohol at a concentration range of about 5% to about 7%; Glycol
Ether DB at a concentration range oi' about 0.1 % to about 7%; and NP-9 at a
concentration range of about 0.1% to about 4%.
[00015] Organosilane quatemary compounds of the present invention include
compounds taught by US Patent Nos. 5,954,869; 5,959,014; 6,120,587;
6,113,815; 6,469,120; and 6,762,172, all of which are incorporated herein by
reference, and include the AM500 product line of BioShield Technology, Inc.,
the antimicrobial products of Nova Biogenetics, Inc. and SiShield, Inc. of
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Norcross, Georgia, and the Aem5700 antimicrobial products of Aegis
Environmental.
[00016] As used herein, the term surfactant (or surface-active agent) refers
to
any compound which, when dissolvecl in water or a water-containing solution,
reduces surface tension of the solution or the interfacial tension between
water
or the water-containing solution and another liquid, or between water, a water-
containing solution, or another liquid and a solid. Surfactants can be
classified
as anionic, zwitterionic or non-ionic, depending on the overall charge that
the
molecule carries.
[00017] The surfactant can optionally be present in the composition of the
present invention in amounts of from about 0% to about 30% by weight, or from
about 0.1% to 15% by weight or frorn about 2% to about 10%, or from about
1.0% to about 5.0% by weight.
[00018] Chelating agents of the present invention include inorganic and
organic compounds. The chelating agent used may depend upon the specific
application. Application specific conc.erns include cost, nature of the metal
ions
to be chelated, compatibility with the components of the composition, and
solubility in the composition. Chelating agents of the present invention are
generally non-toxic to animals and humans in the amounts described herein.
One skilled in the art would be able to appreciate these parameters and select
the appropriate chelating agent without undo experimentation.
[00019] In one embodiment, chelating agents of the present invention would
have a complex formation equilibrium constant of about 107 to about 1027. In
8
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another embodiment, the chelating agent used in the composition has a complex
formation constant of about 107, 108, 109, 1010, 1011, 1012, 1013, 1014, 1015,
1016,
1017, 1018, 1019, 1020, I021, 1023, 1024, 1025, 1026, and 1027.
[00020] A safe and effective amount of one or more chelating agents may be
added to the compositions of the present invention, and when present
comprising about 0.1% to about 10% by weight of the composition. In another
aspect, the composition comprises from about 1% to about 5% by weight of
each of at least one chelating agents. In yet another aspect, the biocidal
composition comprises from about 1% to about 5% by weight of a single
chelating agent. In one embodimentõ the biocidal composition comprises, by
weight, about 0.50%, 0.75%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%,
1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2o/i, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4 /i, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%,
4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.69'/o, 4.7%, 4.8%, 4.9%, and 5.0% of one
chelating agent. In a further aspect, the biocidal composition comprises, by
weight, about 0.50%, 0.75%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%,
1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2o/i, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%,
4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, and 5.0% of the
combination of all chelating agents, wherein the composition comprises two or
more chelating agents.
[00021] In one aspect, exemplary chelating agents of the present invention
include, but are not limited to, ethylenediamine tetraacetic acid (EDTA) or
its
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salts (e.g. EDTA, sodium salt), and may comprise a composition comprising, by
weight, about 0.50%, 0.75%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%,
1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.40/0, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%,
4.1%,4.2%,4.3%,4.4%,4.5%,4.6%,4.7%,4.8%,4.9%, and 5.0% of EDTA.
[00022] In general, a reducing agent is a chemical which can provide an
electron, or be an electron donor. Reducing agents in the present invention
include, but are not limited to, hydrogen peroxide.
[00023] Solid or filter media suitable for use in the present invention
include,
but are not limited to, siliceous materials such as perlite, ceramic
spheroids,
hollow glass spheres, polymeric type media, sand, zeolites and thermoset
coated glass spheres. Perlite is a generic name for a naturally occurring
volcanic glass that when heated, expands from four to twenty times its
original
volume. Perlite is generally referred to as course (grain size 1.5mm-6.Omm),
normal/medium (0.1-3.0mm), and fine/very fine(0.0-0.2mm). It is composed
primarily of silicon(Si02), 72-76%, free moisture-0.5%, aluminum(A1203): 11-
17%, calcium(CaO): 0,5-2.0%, Magnesium(MgO), Iron (Fe203): 0.5-1.5%,
Potassium 4-5%, Sodium: 3-4%.
[00024] In general, an antimicrobial or biocidal filtration media is made by
admixing a composition comprising an aqueous solution of at least an
organosilane compound and a solid material, such as perlite, for an amount of
time sufficient for the solid to contact the organosilane compound. Any of the
compositions taught herein can be used in the methods for treating the solid
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filtration media. The filtration media may be pretreated or may not be
pretreated. Dyes may be added to the compositions for visual confirmation of
presence of the composition on the solid media. Initial treatments may be
applied by one method, such as complete immersion of the solid in a solution,
and subsequent treatments may be by spraying, or running solution through the
solid media while in situ.. Multiple or repeated treatments in the field or by
its
removal and retreatment treatments of filtration media over many years of use
of the media are contemplated by the present invention.
[000251 For example, expanded perlite siliceous rock (coarse type) was mixed
in an aqueous solution containing a stabilized organosilane quaternary
compound for a time sufficient to allow the compound to contact the perlite
material, part A. Part A was prepared to form an antimicrobial effective
complex comprising (0.75% TMSQ& 99.25% D.I. water solution by weight,
which makes this solution 3/4 % active by w/v). A second composition that has
both disinfectant (contact efficacy) and residual antimicrobial efficacy, and
which comprises about 1% active by weight (part B), was added to part A while
contacting the perlite. In general, this second solution is added at a ratio
of 2
parts A to 1 part B. The perlite was mixed and agitated in the combined
aqueous solution for at least several minutes to allow contact. Other methods
for contacting the solid material and the solutions are contemplated by the
present invention and include, but are not limited to, spraying, forced
immersion, and centrifugal inundation. The treated perlite then was drained
and
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removed to dry at room temperature. Other drying methods can also be
employed.
[00026] Methods of the present invention comprise using the treated filtration
media to treat waters of any kind to render the water substantially free of
microbial contamination. The compositions of the present invention may be
used to treat solid filtration media to render such media antimicrobial or
biocidal so that such antimicrobial or biocidal filtration media may be used
in
treatment of water. Treatment of water includes use of the solid media to
remove particulates from the water and also includes antimicrobial and
biocidal
activity whereby microbial lifeforms are killed or inhibited from growing. Any
channeled or contained waters are contemplated by the present invention,
including but not limited to; contained water for swimming pools, spas,
cooling
towers; storm water runoff, industrial liquid discharge, sewer water
discharge,
catch basins, livestock water holding ponds, and livestock waste lagoons.
[00027] Uses of antimicrobial treated solid media or other surface for any
physical, chemical and mechanical tneans of eliminating bacteria and other
microorganisms from water including but not limited to: storm waters. stagnant
or low flow water conditions in catch basins, storm water pipes. pools, spas,
waste lagoons, such as those used in agriculture in the cattle, poultry,
aquarium,
fish farms; industrial liquid discharge; municipal waste water reprocessing
plants; raw water before and after treatment; sewer discharge; food and
beverage processing plants discharge; cooling towers and hot water systems in
buildings; drinking water pipes and water distribution system; water
filtration
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systems of any size; bottled waters; waters used in the healthcare area;
waters
for research or high purity requirements; treatment of leachate or hazardous
waste water; marine desalinization, marine graywater; military applications of
all of these types; drinking and potable water; surface water treatment; and
cleanup after flooding. Examples of uses of the antimicrobial perlite
filtration
media of the present invention include use in the Aqua-FilterTM Filtration
System (AquaShield, Inc.), a two component in-line treatment train, for
removal
of gross contaminants, very fine sediments, water-borne hydrocarbons, heavy
metals and nutrients such as phosphcirous and nitrogen; and, the Aqua-GuardTM
Catch Basin Insert (AquaShield, Inc.), which removes gross contaminants, oil
and sediment at the source. Other commercial applications in which the
present invention could be employed include, but is not limited to, filtration
systems of Stormwater Management; Vortechnics (Stormwater 360 under
ConTech) CDS media filtration system, The Schundler Co.; General Filtration;
Lenntech Water Treatment; Filtrox AG; Aqua-Perl; and Pall Corporation.
(00028) The present invention comprises methods of treating water, by
contacting the water with a solid surface having a composition taught herein
adhered thereto. For example, the water is storm water runoff and the solid
surfaces are in treatment systems are canisters, containers, tins, flasks,
cylinders,
cartridges, bags, beds, layers, fabric, textile, sheets, capsules, baskets,
socks,
booms, pillows, pipes, screens, panel, guard, shield, patrician, barrier,
dividers,
weirs, baffles, drip trays, packet, tablets, wafers, sachets, pocket, or
tubes. For
example, the water treated is industrial runoff and discharge from drain
piping
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to point discharge such as sheet flow to open swales, ditches, or conveyances.
For example, the water is agricultural runoff and discharge, and involves
drain
piping to point discharge, or sheet flow to open swales, ditches, or
conveyances.
[000291 The methods of the preser.it invention comprise treatment of water.
Compositions of the present invention comprise filtration media comprising
solid materials such as perlite, and organosilane quaternary compound and
quaternary ammonium compound compositions taught herein, referred to as
treated filter media that is antimicrobial or biocidal, for rendering the
water free
of microbial contamination. Such treated filter media may be used in known
commercial filters and under a wide variety of filtering conditions. For
example,
the methods include filtering water at flow rates of greater than 5, 10, 15,
20,
25, or 30 gal/sq.ft. per minute. These ilow rates are achievable with gravity
flow
and do not require pressurization or rnechanical pumping through the
filtration
step. The water that is filtered over or through the treated perlite is
capable of
rendering the water free of a degree of microbial contamination for a period
time. For example, the treated perlite rnay be capable of rendering the water
free
of at least 50% of the microbial contamination, at least 60%, at least 80%, at
least 90% or at least 95% of the microbial contamination of the water. A
filter
comprising the treated perlite may be effective at rendering the water free of
microbial contamination to such a degree for a period of time of at least one
month, two months, three months, four months, five months or longer without
being retreated or contacting the perlite with an organosilane composition
again.
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[00030] Additional examples include water treatment of sanitary discharge
from on site or extended septic treatrnent systems including but not limited
to
single family homes; large multi-unit dwellings; industrial (rural plants and
factories, schools);commercial sites, combined Sewer Overflow (CSO)
Municipalities (these "combine" or carry stormwater runoff into the sanitary
system which often overflows when large storm events overwhelm the piping
structure thus sending raw sewage into receiving waters);and Municipal
Sanitary Sewer Discharges (sanitize before release into receiving water body).
Other methods of water treatment include treatments of water used in food
processing such as washing food, meats, vegetables, misting of food at
groceries, and includes treating the water before and after washing the food
items. Other uses include treatment of water that may be contaminated by
microorganisms removed from water by bodily contact such as by contact from
oral hygiene treatments at the dentist offices or in home uses; physician or
other
medical offices and hospitals, field and emergency response and other health
care situations. Both in providing water to such sites and water discharged
from
procedures that clean or irrigate wounds, or other body surfaces. This
prevents
health care workers from handling and disposing of bacteria contaminated water
reducing their risks of infection or spread of the virus.
[00031] Additionally, the present invention is useful in providing clean
water,
or in cleaning water to provide potable water at disaster sites or for
providing
sanitary water treatment systems. For example, the methods and compositions
of the present invention can be used by emergency response and disaster relief
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sanitary water treatment teams with a mobile or transportable system to aid
FEMA, State EMA's, Civil Defense, and other first responders. Such systems
may be mobile and can be flown or driven to sites or air dropped for emergency
situations.
[00032] The present invention is also useful for controlling microbial growth
and treatment of standing water in heating and cooling systems. Such
treatments include heat and air conditioning systems; cooling towers in
industrial, commercial, or office complexes; home HVAC units that are
currently using UV light to disinfect mold, bacterial slim, mildew from
condensate/drip pans, boiler/heat energy re-processed water. Other
applications
include treatment of water wells including wells that are private; public;
drinking; agricultural; industrial. The;re are also recreational uses for the
present
invention such as treatment of water for use in recreational vehicles, house
boats, and water for camping and hiking,
[00033] The antimicrobial filter media of the present invention is effective
for
deactivating, killing, inhibiting, destroying and/or removing from a liquid,
such
as water, microbial lifeforms including but not limited to bacteria, fungi,
viruses, parasites, eubacteria, rotifers, phytoplankton, plankton, and spores,
from species such as Escherichia coli, Salmonella choleraesuis,
Staphylococcus, Aspergillus, Klebisiella, Listeria clostridium, rotavirus,
cysts
and other microorganisms. Moreover, the filter media can be used repeatedly
without a decrease in antimicrobial and biocidal effectiveness.
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[00034] As used herein, the terms antimicrobial and biocidal are overlapping
and interchangeable terms, and are intended to encompass both the ability to
kill
and inhibit the growth of microbial lifeforms.
[00035] As used herein, optional or optionally means that the subsequently
described event or circumstance may or may not occur, and that the description
includes instances where said event or circumstance occurs and instances where
it does not. For example, the phrase optionally substituted lower alkyl means
that the lower alkyl group may or may not be substituted and that the
description includes both unsubstituted lower alkyl and lower alkyl where
there
is substitution.
[00036] By the term effective amount of a compound, product, or composition
as provided herein is meant a sufficient amount of the compound, product or
composition to provide the desired result. As will be pointed out below, the
exact amount required will vary from substrate to substrate, depending on the
particular compound, product or composition used, its mode of administration,
and the like. Thus, it is not always possible to specify an exact effective
amount.
However, an appropriate effective amount may be determined by one of
ordinary skill in the art using only routine experimentation.
[00037] As used herein, the term suitable is used to refer a moiety which is
compatible with the compounds, proclucts, or compositions as provided herein
for the stated purpose. Suitability for the stated purpose may be determined
by
one of ordinary skill in the art using only routine experimentation.
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[00038] As used herein, substrate: refers to any article, product, or other
surface that can be treated with the inventive compounds. Suitable substrates
are generally characterized in preferably having a negatively charged surface
of
oxygen atoms, or any surface capable of electrostatically, ionically or
covalently
adhering or binding to the compounds, products, or compositions of the present
invention. The adhering or binding may occur at the silicon atom of the
organosilane portion of the compounds, products, or compositions of the
present
invention, but such binding is not a requirement. Therefore, as used herein,
the
term adhere is meant to refer to ionic, covalent, electrostatic, or other
chemical
attachment of a compound, product or composition to a substrate.
[00039] As used herein, the term biocidal is used in its general sense to
refer
to the property of the described compound, product, composition or article to
kill, prevent or reduce the growth, spread, formation or other livelihood of
organisms such as bacteria, viruses, protozoa, fungi, molds, algae, or other
organisms likely to cause spoilage, disease or infection.
[00040] As used herein, the term stabilizer is used to refer to the class of
polyols as specified herein wherein any two of the at least three hydroxy
groups
are separated by at least three atorris. Such compounds have been found to
stabilize the organosilanes by preventing self-condensation or other
inactivation
of the resulting compounds and products.
[00041] It is to be understood that the terminology used herein is for the
purpose of describing particular embodiments only and is not intended to be
limiting. It must be noted that, as used in the specification and the appended
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claims, the singular forms a, an and the include plural referents unless the
context clearly dictates otherwise.
[00042] Throughout this application, where publications are referenced, the
disclosures of these publications in t:heir entireties are hereby incorporated
by
reference into this application in ordeir to more fully describe the state of
the art
to which this invention pertains.
[00043] The following Examples are provided as illustrative of the uses and
applications of the present invention to add one skilled in the art. The
Examples
are not to be considered limiting or restricting to the uses of the present
invention.
EXAMPLES
[00044] EXAMPLE 1. Preparation of Perlite Antimicrobial Filtration
Media with Antimicrobial Properties
[00045] 350 grams of expanded coarse perlite (8.0 - 12.0 pounds per cubic
foot) was mixed with stirring solution. comprising 0.75% (w/v) water-
stabilized
3-(trimethoxysilyl)propyl- dimethyloctadecyl ammonium chloride (TMSAC).
The pH of the treatment solution was about 6.5. The amount of perlite used was
about 1 liter, and the amount of TMSAC used was about 1 gallon. Initially, the
perlite was manually submerged. The temperature of the solution was about 70-
75 C.
[00046] After stirring the perlite and TMSAC solution for 15-30 minutes, an
equal volume of a second solution was added and stirring was allowed to
continue for an additional 15-30 minutes. The second solution was:
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Component Percent (w/w)
3-(trihydroxysilyl) propyldimethyl octadecyl ammonium chloride 0.50
N,NDiakyl(C8-C10)-N,N-dimethylammonium chloride 0.75
N-Alkyl(50%C 14,40%C 12,10%C 16) dimethylbenzylammonium chloride 0.75
Isopropyl alcohol 0.75
Glycol Ether EB 0.75
Barlox 0.67
EDTA 0.25
T-NP-9.5 Surfactant 0.38
Water 95.20
[000471 The perlite was then removed from the solution and was dried at
room temperature.
[00048] EXAMPLE 2. Evaluation of Antimicrobial Perlite Filtration Media
of E. coli.
[000491 Antimicrobial filtration media was prepared as described in Example
1. The antimicrobial filtration media filled a 1.5 inch diameter media
cartridge
12 inches in length. The volume of the cartridge, 21.24 square inches,
contained 82 grams of antimicrobial filtration media. Prior to testing, the
cartridge was flushed with 42 gallons of laboratory reagent grade water. The
42
gallons of water flushed through the cartridge roughly translates to what
would
pass a 24 square foot system, 12 inches deep over a three month period at a
flow
rate of 407,300 gallons per year. For this test, an E. coli stock was prepared
from a KWIK-STIK pellet, traceable to authentic references collections such as
the American Type Culture Collection.. The pellet was reconstituted in water
in
a volume of 10 ml, from which a 1.0 ml sample was removed and placed into
one gallon HDPE containers. The containers were filled with sterile water to a
volume of 1 gallon and gently shakeil for 10 minutes. The resulting solution
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constitutes the E. coli simulation solution. A 100 ml sample of the E. coli
simulation solution was removed and analyzed for E. coli concentration.
[00050] The E coli samples were tested as per "Methods for the Examination
of Water and Wastewater", 18th Edition, (1992). Test Method Number: 9260F.
Samples were analyzed within appropriate holding times for each method.
Internal blanks and standards were analyzed with the simulations as part of a
standard QAQC program. A finding of <1 colony E. coli per 100 ml is
essentially considered "None Detected" as I is the method detection limit for
method 9260F.
[00051] The test apparatus used for this experiment consists of five basic
components. A 2 gallon, conical bottom, polypropylene tank contained the
influent. Discharge from the holding tank into the media cartridge was a
direct
gravity feed regulated by a flow valve at the bottom of the holding tank. The
media cartridge was a PVC cylinder, 1.5 inches diameter and 12 inches in
length. A flexible nylon screen (1 mm square openings) held in place with open
PVC end caps retained the encased perlite media. The effluent was collected
from the cartridge in a 2 gallon polypropylene container. The E. coli
simulation
solution was delivered into the media cartridge at a flow rate that maintained
a 3
inch headspace. A control sample was removed from the E. coli simulation
solution to passing the solution through the cartridge media. The collected
post-
cartridge effluent sample, along with the control sample, was immediately
analyzed for E Coli.
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[00052] Previous testing indicated that E. coli coliforms were being killed
and
not physically removed or filtered during the described simulation sample
testing. Standard E. coli bacteria are approximately 1 to 2 microns in length
and
0.5 to 1 microns in length and would easily pass the perlite cartridge. The
control taken from the E. coli simulation solution prior to testing contained
approximately 1180 colonies per 100 ml. The post-cartridge effluent sample
contained <1 colony per 100 ml. The simulation roughly estimates a three
month period based on a flow of 407,300 gallons a year through a 24 square
foot system, 12 inches deep. The actual gallon simulation passed the filter at
approximately 30 gallons per minute per square foot.
[00053] The results indicate that filt.ration of water containing E. coli
through
a cartridge containing antimicrobial filtration media effectively suppressed
>99% E Coli at a flow rate approximately 30 gallons per minute per square
foot.
[00054] EXAMPLE 3. Evaluatioit of Antimicrobial Perlite Filtration Media
for the Removal of E. coli.
[00055] Independent laboratory berich scale tests assessed the efficacy of a
treated coarse perlite filter media cartridge to remove TSS (Total Suspended
Solids) and E. coli from simulated stormwater standard. Ten runoff simulations
were performed using 100 mg/L of TSS with an average particle size of - 20
microns and a stock E. coli was selected as product microorganism, repeatable
and reproducible solution containing 150 colonies per 100m1 and gravity fed at
a flow rate approximately 18 to 19 gpm/ft2 maintaining a headspace at 3
inches.
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[00056] The results indicated that the antimicrobial filtration media
effectively removed or suppressed >80% TSS and > 99% E. coli.
[00057] EXAMPLE 4. Evaluatiori of Antimicrobial Perlite Filtration Media
for the Removal of E. coli.
[00058] An additional test to evaluate the efficacy of the coarse perlite
filter
media cartridge with a higher concentration of E. coli at a higher flow rate
over
a longer period of time was performed. Prior to testing, an additional 42
gallons
of laboratory reagent grade water was flushed the over the already tested 10
gallons of simulation from Example 3. These 42 gallons represent
approximately 3 months of rainfall over a 1-acre site receiving an annual rain
event of 15 inches or 407,300 gallons passing a 24ft2 filtration treatment
system
12 inches deep over 12 months. A stock E. coli was selected as a product
microorganism, in a repeatable and reproducible solution containing 1180
colonies per 100m1 and was gravity fed at a flow rate of about 30 gpm/ft2
maintaining a headspace of less than 3 inches.
[00059] Tests concluded that the E.coli removal efficiency was >99%.
[00060] EXAMPLE 5. Evaluatiori of Antimicrobial Perlite Filtration
Media.
[00061] Independent laboratory bench scale tests assessed the efficacy of an
antimicrobial coarse perlite filter media cartridge to remove 42 gallons of E.
coli
from a simulated stormwater event. A stock E. coli was selected as product
microorganism, and a repeatable and reproducible solution containing 4300
colonies per 100ml was gravity fed at a flow rate approximately 15 to 18
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CA 02609651 2007-11-07
gpm/ft2, maintaining a headspace < 3 inches. Pre- and post-cartridge samples
were taken every 1, 10, 21, 32, and 42 gallons. This represents - 2.4 months
of
rainfall over a 1-acre site that would receive an annual rain of 15 inches or
407,300 gallons passing a 24 ft2 treatment system 12 inches deep over 12
months. The results indicated that the treated coarse perlite effectively
removed
99.9% E. coli.
[00062] EXAMPLE 6. Evaluation of Antimicrobial Perlite Filtration Media
for the Removal of E. coli.
[00063] For this laboratory bench test, 42 gallons of a stock solution having
an E. coli concentration of 2,120 colonies per 100 ml was gravity fed from top
to bottom through a perlite filter nledia cartridge of the type described in
Example 2, the perlite filter media being treated with an antimicrobial
composition as described herein. The solution was fed at a flow rate of 9
gpm/ft2. Samples were analyzed frorn the 15t, 10'h and 42"d gallons of
solution
and over 99.9% of the E. coli were eliminated from the stock solution in each
test sample. Since the same filter media cartridge configuration was used as
in
Example 5, the 42 gallon test represents - 2.4 months of rainfall over a 1-
acre
site that would receive an annual rainfall of 15 inches or 407,300 gallons
passing a 24 ft2 treatment system 12 irlches deep over 12 months.
[00064] EXAMPLE 7. Evaluation of Antimicrobial Perlite Filtration Media
for the Removal of High Concentration E. coli in Upflow Filtration.
[00065] A laboratory bench test was devised to test for removal of E. coli at
concentrations representative of sanitary applications utilizing upflow
filtration.
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For this test, perlite filtration media was treated with an antimicrobial
composition and used to fill a 6 inch diameter filter cartridge, of
approximately
0.75 inches in depth, for a total volume of 21.24 inches. The is the same
volume as utilized in examples 2 through 6, although in a flatter
configuration.
A stock solution was prepared having a E. coli concentration of 2,950 colony
forming units per 100 ml. The stock solution was gravity fed from a holding
tank into the media cartridge at its base. The solution flowed from bottom to
top through the perlite filter media cartridge. The perlite was held in place
by
flexible nylon fabric, while a delivery nozzle atop the cartridge allowed the
filtered solution to exit the top of the cartridge for collection. The 5'h,
10th, 20th
and 41 St gallons were analyzed for E. coli. The flow rate for this test was
approximately 9.5 gpm//ft2- Testing determined that E. coli removal was
greater
than 99.9% efficient in the fifth and tenth gallons. Samples from these
gallons
contained less than 1 colony forming unit per 100 ml in gallon 5 and about 2
colony forming units per 100 ml in gallon 10. Efficiency of removal
deteriorated slightly, as at gallon 20 there were 3 colony forming units per
100
ml for approximately 99.9% removal efficiency and while the sample from
gallon 41 contained 8 colony forming units per 100 ml for approximately 99.7%
efficiency.
[000661 . These tests are summarized in Table 1.
Table 1
Test Data Summary
E. Coli Concentration Flow Rate Test Gallons Media Cartridge Media Cartridge
Example No. cfu/100 ml Efficacy Gpm/ft, gm Dimensions -
[nches
3 150 >99.9 19 10 122 1.5 d x l2 h
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4 1,180 >99.9 30 42/1* 82 1.5dx12h
4,300 >99.9 18 42 78.6 1.5 d x 12 h
6 2,120 >99.9 9 42 66.3 1.5 d x 12 h
7 3,000 99.9 to 99.7 10 42 66.3 6 d x 0.75 h Upflow
[00067] EXAMPLE 8. Preparation of Perlite Antimicrobial Filtration
Media.
[00068] Perlite was saturated and mixed in plastic jars with AM 500
antimicrobial composition from SiShield. Afterwards, the plastic jars were
drained using a nylon screen with 1 mm openings. Perlite in the jars were held
in draining position for approximately 24 to 26 hours with temperature between
25 and 30 C. Then to prepare filter imedia, the perlite was allowed to gravity
pack or settle by gently tapping sides of the jars. A test cartridge was
prepared
with a 4 inch diameter and 2 inch thickness filled with the treated and dried
perlite.
[00069] EXAMPLE 9. Evaluation of Antimicrobial Perlite Filtration Media
AM 500 1:5 (1% active).
[00070] The cartridge was prepared as in Example 8 with using AM 500
1:5 (1% active) antimicrobial from SiShield. Then a 42 gallon stock solution
was prepared with 2800 colony forming units of E. coli per 100 ml. The stock
solution was delivered by gravity feed to the base of the test cartridge
providing
for an upflow test. The flow rate of the solution was approximately 10.4
gpm/ft2. The efficacy of the E. coli removal was tested at the second gallon
(99.8% efficacy), 10th gallon (99.6 /) removal efficacy), 20 th gallon (97.9%
removal efficacy) and 40th gallon (90.4% removal efficiency). Removal
26
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CA 02609651 2007-11-07
efficacy began to decrease after the 20'h gallon to approximately 90% efficacy
at
the 40'h gallon.
[00071] EXAMPLE 10. Evaluation of Antimicrobial Perlite Filtration Media
AM 500 1:5 (0.5% active).
[00072] The cartridge was prepared as in Example 8 with AM 500 1:10
(0.5% active) antimicrobial from SiShield. Then a 42 gallon stock solution was
prepared with 3500 colony forming units of E. coli per 100 ml. The stock
solution was delivered by gravity feed to the base of the test cartridge
providing
for an upflow test. The flow rate of the solution was approximately 10.4
gpm/ft2. The efficacy of the E. coli removal was tested at the second gallon
(99.8% efficacy), 10t" gallon (98.80,% removal efficacy), 20t" gallon (99.3%
removal efficacy) and 401" gallon (89.8% removal efficiency). Removal
efficacy began to decrease after the 20'' gallon to approximately 90% efficacy
at
the 40" gallon as was the case in Example 9.
[00073] EXAMPLE 11. Preparation of Antimicrobial Perlite Filtration
Media.
[000741 A known weight of perlite was mixed with SiShield AM 500
(1:10) to create a saturated slurry with excess AM 500. The slurry was flipped
end over end at 32 rpm for 60 minutes in a glass vessel. The vessel was
inverted and allowed to gravity drain through a 2.0 mm nylon screen for 24 to
26 hours at a temperature between 25 and 30 C. There was a 21.6% loss in
fines or particles less than 2 mm in size. Of the perlite retained by the
screen,
1.43 ml of am 500 was used to treat each gram of perlite. The treated perlite
27
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CA 02609651 2007-11-07
media was then placed in a 6 inch diameter media cartridge 0.75 inches in
depth. The volume of the cartridge, 21.24 square inches, contained 70.4 grams
of treated perlite.
[00075] EXAMPLE 12. Evaluation of Antimicrobial Perlite Filtration Media.
[00076] A stock solution of 43 gallons of water was treated with E. coli
pellets to create a liquid 3,800 colony forming units per 100 ml. The test
cartridge was connected to a 1,000 gallon tank filled with water that tested
negative for both chlorine and E. coli. At a flow rate of approximately 10
gallons per minute per square foot, 100 gallons of rinse water passed the test
cartridge. At the 100 gallon mark, the flow was stopped, the cartridge
disconnected and attached to the tank containing E. coli stock solution. At an
approximately flow rate of 10 gallons per minute, three gallons of E. coli
stock
solution passed the cartridge. A sample was collected from the third gallon
and
tested for E. coli suppression. The test cartridge was then reattached to the
1,000 gallon rise tank and the process repeated at the 200, 400 and 800 gallon
marks. Both tanks delivered all the stock solution and rise into the cartridge
base providing an upflow delivery through the filter. At 100 gallon testing,
less
than 1 E. coli cfm per 100 ml was detected indicating that greater than 99%
efficiency in E. coli reduction. At the 200 gallon test, 740 E. coli cfu per
100 ml
was detected indicating approximate:ly 80% removal efficiency. At the 400
gallon test, 3,630 E. coli cfu per 100 ml were detected and at the 800 gallon
point 3,800 cfu per 100 ml were detected, indicating little if any suppressive
effect.
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[00077] The upflow delivery of water filtration is generally better
controllable in practice, providing more even and uniform media contract than
systems using gravity percolation. In addition, because upflow filtration
causes
perlite filter media to move upward within the filtration canister when water
is
flowing, and at the conclusion of the flow gravity returns the perlite to a
lower
position within the canister, the movement prevents channeling in the filter
media from continuing between water treatment events.
[00078] Whereas this invention has been described in detail with particular
reference to specific embodiments, it will be apparent to those skilled in the
art
that various modifications and variations can be made in the present invention
in light of the above teachings without departing from the scope or spirit of
the
invention. Other embodiments of the invention will be apparent to those
skilled
in the art from consideration of the specification and practice of the
invention
disclosed herein. It is intended that the specification and examples be
considered exemplary only, with a true scope and spirit of the invention being
indicated by the following claims.
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