FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENT RULES, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
Title of Invention:
A BIOACTIVE MATERIAL
Applicant:
CALIX LTD
a company incorporated in Australia having address as:
Level 1, 9 Bridge Street Pymble,
New South Wales 2073, Australia
The following specification particularly describes the invention and the manner in which it is to
be performed.
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Technical Field
[0001] The present invention relates broadly to the production of a material product that is a
contact biocide for use in agriculture, aquaculture and other applications, and which is
produced from calcined powders using flash calcination of materials. This invention is a
further development of a generic bioactive material, and its method of manufacture, described
by Sceats (AU2014374829) and Sceats and Hodgson (A U2015904534), included herein in
their entireties, in which the general method of manufacture described therein is further
adapted for the production of material by optimising the bio-activity, by extending the range
of the materials that can be used to manufacture the product and thereby extending the range
of applications of the product.
Background
[0002] Sceats, and Sceats and Hodgson, focussed on the application of the product to
agriculture, but there is a broader range of potential applications. For example, in 2016,
aquaculture farming production, especially for fish, molluscs and crustaceans, exceeded that
from wild capture commercial fishing. This transition has been driven by demand from
growing human populations and the stagnation of wild capture. The Food and Agriculture
Organisation (FAO) of the United Nations has reported that in 2015 the world aquaculture
production reached 97.2 million tonnes (live weight) with an estimated value of USD157
billion in 2013 with a growth rate of 5.6%. The FAO reports that its Global Aquaculture
Production statistics database shows that 575 aquatic species grown in freshwater, seawater
and brackish water have been registered.
[0003] Intensive aquaculture farming practices are rapidly evolving, compared to those of
agriculture, which have evolved over thousands of years. The very high population density of
the cultivated species in farming compared to the wild leads to the occurrence, severity and
spread of diseases within and between aquaculture populations in ways that are similar to those
associated with diseases in dense human and terrestrial animal populations. Factors that impact
on the development and severity of a disease following exposure of the cultivated species to a
pathogen include the virulence of the pathogen, the immune, genetic and physiological
condition of the cultivated species; and its stress and population density; as well as the general
environmental conditions of both the aquatic and benthic ecosystems of an aquaculture pond
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or pen. The cultivated species population density is the most important factor in the spread of
diseases in aquaculture, because of the increased rate of infection. This dense population in the
aquatic environment, and the limited water flow, facilitates the spread of pathogens, and the
benthic environment is often a source of such pathogens. The development of a disease and the
relevant severity of that disease within the cultivated species population is influenced by a
complex interaction of these variables associated with the pathogen, the cultivated species and
these two environments.
[0004] There is a third ecosystem in aquaculture systems, which is the pond or pen
infrastructure that may comprise the wall structure of the pens, the bottom of boats, and
equipment used to manage the farm such as feeders and boats. These surfaces are subject to
the growth of biofilms, and the impact of these films on this critical infrastructure has a
significant economic impact. Biofilm growth suppression had previously been prevented by
the use of very toxic materials, such as tri-butyl tin. However, this material leached the toxic
materials into the aqueous ecosystems, and many such compounds have been subsequently
banned in most countries. Other systemic biocides have been deployed that have a reduced
impact but there are concerns about the potential for such systems to leach, as well as the
growth of resistance. There is a need for a non-taxi c coating material of marine infrastructure
such as wharves, piles, nets, ships and boats that can suppress the growth of biofiIms, and in
the context of aquaculture, this includes all the surfaces of the aquaculture pens and systems.
The ability of pathogens to move between the aquatic ecosystem, the benthic ecosystem and
this infrastructure ecosystem means that all three ecosystems need to be managed in
aquaculture.
[0005] The ecosystems in aquaculture comprise the aquatic, benthic and infrastructure zones.
The pathogen are may first incubate in the benthic zone and then progress to the aquatic zone,
because the benthic zone often becomes polluted more quickly. In addition, systemic biocides
are often applied to the aquaculture systems just to prevent biofiIm generation, and these can
find their way into the aquatic and benthic ecosystems. Therefore, aquaculture is therefore
difficult to target with systemic biocides. There is a search for materials that can mitigate the
development and spread of diseases so that costly intervention with systemic biocides is rarely
required and prudently applied. Such a material would likely be a contact biocide to ensure that
it is active against a wide spectrum of diseases.
[0006] Just as for agriculture, there is a need for methods of infectious disease controls that
preferably impacts positively against the pathogen, while benefiting the cultivated species and
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the environment. However, the same sets of issues arise in aquaculture as in agriculture and
human health, whereby diseases in the cultivated species rapidly become tolerant to systemic
biocides through adaptation. Such biocides are generally neurotoxic compounds, which are
toxic to both humans and animals. In aquaculture, the use of such compounds is limited because
the cost of chemicals generally exceeds the benefits. For a contact biocide application in
aquaculture, the contact requirement is met by a material that is largely insoluble, and an
additional challenge would then be to find a means of application in which contact can be made
in each of the aquatic, benthic and infrastructure ecosystems.
[0007] There has been an extensive development of nano-materials with biocide properties,
and in particular, of nano-magnesia MgO and nano-zinc oxide ZnO. An example of a biocide
is “Antibacterial characteristics of magnesium oxide powder”, J. Sawei et. al. WorldJ ournal
of Microbiology and Biotechnology, 16, Issue 2, pp 187- 194 (2000) and T.Y in and Y. He,
“Antibacterial activities of magnesium oxide nanoparticles against foodborne pathogens” J.
Nanopart. Res. 13, 6877-6885. In the study by Sawai et al, the objective was to make high
surface area MgO with particle sizes below about 50 nm. In trials of these materials, the MgO
particles rapidly react with water to form nano-magnesium hydroxide Mg(OH)2. Prior art
references to nano-MgO are ascribed herein to nano- Mg(OH)2. These hydrated nano-materials
exhibit broad spectrum bioactivity response to viruses, bacteria and fungi. However, the cost
of production of nano-materials is such that they are rarely deployed in aquaculture.
Furthermore, there are concerns about the toxicity of nanomaterials in general because they are
readily entrained in breaths of air, and fast diffusion through the skin.
[0008] The process for production development of nano-active Mg(OH)2 from carbonate
minerals such magnesite and dolomite has been described, for example, by Sceats and Sceats
and Hodgson. In that approach, Mg(OH)2 particles in the range of about 0.4-100 microns are
produced which are composites of nano-seal e crystalIites in an aqueous solution. Tests of the
effectiveness in agriculture have demonstrated that these materials have the same bio-active
responses to bacteria, fungi and viruses as the Mg(OH)2 nano-particles, and they are therefore
deemed to be nano-active. The larger particles are in an aqueous solution, and are not entrained
in air for breathing, and the particles are too large to diffuse through the pores in the skin. The
toxicity to humans is the same as large Mg(OH)2 particles, as in Milk of Magnesia, but the
material retains the nano-activity to pathogens through their nano-crystalline structure. In this
invention, that approach to production is extended to the use of brucite as a source of MgO,
with the brucite being either a mineral or a synthetic material produced from brine.
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[0009] In agricultural applications, the bio-activity is generally realised by diluting the slurry
in water, and applying it to leaves of plants as a foliar spray. Without being bound by theory,
the bio-activity observed in agricultural tests as a spray is ascribed to the release of Reactive
Oxygen Species, such as peroxide and superoxide radicals that are produced on the high energy
edges of the MgO nano-crystallites that are formed during flash calcination of Magnesium
Carbonate, for example in the calciner described by Sceats and Horely (PCT Patent Application
No. WO2007045048) and included herein in its entirety. These chemical species survive
hydration, for example, in the process described by Sceats and Vincent (AU2014339743) and
included herein in its entirety, to make a stable magnesium hydroxide slurry, with up to 60%
of the active ingredient as Mg(OH)2. It has been observed that the particles adhere to the plant
leaf, and the particles gradually degrade as the magnesium is ingested through the leaves as a
fertiliser, to assist the production of chlorophyll. It is believed that in this prior art, the bioactivity is achieved through the gradual release of ROS, which prevents the leaf ecosystem
from becoming anaerobic, and thereby preventing disease. A common feature of many diseases
is that the pathogens initially grow in anaerobic conditions. In that sense, the nano-active
materials are disease preventative contact biocides, and the diseases do not develop immunity.
The concentration of ROS is generally not sufficiently high that it has an adverse impact on
aerobic bio-organisms. Specifically, the ROS and the alkali, Mg(OH)2, in the particles both
promote an oxygenated ecosystem, and in such systems pathogenic microbes do not thrive. No
substantial persistent bioactivity has been observed in Mg(OH)2 produced from MgO produced
from conventional calciners, and this loss is attributed to the sintering of the nano-crystalline
surfaces, which is correlated with the recombination of the ROS species with the trapped
electrons.
[0010] In aquaculture, the cultivated species are animals that are generally very sensitive to
stress, and are intolerant to toxic chemicals that might be tolerated by plants. Therefore, the
broad spectrum toxic disease preventatives that are used in agriculture for plants generally
cannot be used in aquaculture. Most generally, products that are toxic to humans are also toxic
to animals such fish and shellfish. Moreover, the use of drugs developed as disease
preventatives for humans, such as antibiotics, show the same evolution as observed in humans,
namely the loss of bio- activity overtime as the diseases develop strains that are resistant to the
drugs. There is a need in aquaculture for disease preventative products that are non-toxic to the
cultivated species and to humans, and which are broad based in their activity so that the
pathogens do not become resistant to the use of the product.
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[0011] In aquaculture, the cultivated species are fish, molluscs and crustaceans. The primary
method of disease prevention in the cultivated species has been to use successful treatments
from land based animal husbandry. In aquaculture, the most common treatments involve
adding bioactive materials to food that is fed to the cultivated species and ingested. These
treatments often use systemic drugs. However, the quantity of bioactive materials required to
achieve disease prevention are very large, and the costs are very high. The poor performance
is a result of the aqueous environment. Soluble compounds may dissolve in the water before
the cultivated species eat the food, and there are large losses of the bioactive materials.
Furthermore, such compounds are taken up by alI the species in the water, from plants,
plankton, other aquatic animals, as well as the cultivated species. If compounds are stabilised
in particles, any uneaten particles fall to the bottom of the pond, then the bioactive materials
are taken up by the benthic ecosystem on the pen or pond floor. These practices are generally
deemed to be unstainable, and the resistance to diseases in all the biota has the propensity for
significant undesirable long term effects in the whole ecosystems. There is a need for a nontoxic disease preventive that is non-toxic to the cultivated species, but is also beneficial to the
environment of the pond, and specifically to the long term healthy ecosystem of the water.
Most generally, there is a need for a product for aquaculture that is a disease preventive that
has no toxicity impact on the cultivated species or the other animal species that inhabit a healthy
aquaculture system, including both the aqueous, the benthic and infrastructure ecosystems. The
nature of the ecosystems in aquaculture vary significantly throughout the world because they
are dictated by the cultivated species natural habitat and farming practices. The abiIity to
prevent disease depends on maintaining healthy aquatic, benthic and infrastructure ecosystems.
[0012] For example, a particular problem arises in aquaculture ponds that are constructed from,
or located near, acid-sulphate soils. Such soils are often found in areas surrounding mangrove
swamps. In mangroves, the conditions are anaerobic and reducing, and iron is deposited as
pyrites (ferrous sulphide), which accumulate and persist over geological timescales. When
aquaculture ponds are produced from such soils, or the soils are disturbed, for example, from
water run-off and flooding, the pyrites is released into the water and in such oxidising
conditions, the pyrites is sequentially oxidised, firstly releasing ferrous and sulphide ions,
followed by further oxidation to ferric ions and sulphuric acid, such that the pH falls, releasing
aluminium ions into solution. The iron and aluminium ions are toxic to species such as prawns,
resulting in significant kills of cultivated species. Eventually, the ions are removed through the
formation of insoluble iron oxide particles, which are fall into the sludge. On a long timescale,
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the reducing conditions in the mud form pyrites, and the cycle will continue when the mud is
disturbed and exposed to oxygen. There is a need for a material that can be added to the water
in a new aquaculture pond, or a pond that has been disturbed by flooding, that not only prevents
pathological disease from microbes for such cultivated species, but which also rapidly removes
the toxic iron and aluminium ions from solution.
[0013] The heavy metals, such as cadmium, copper, lead, chromium, arsenic, barium, cobalt,
manganese and vanadium are toxic to most cultivated species in aquaculture. The bigger
problem is that these metals may be concentrated by accumulation, such as in the gills of fish,
through the use of recirculated water, or by natural events (floods and the like). The major issue
is generally not the toxic effects on the cultivated species because the concentrations are
normally low, but the health impact on humans arising from the accumulated Ievels of heavy
metals in the human body over a Iong time from eating such cultivated species. There is a need
for a material that can remove heavy metal ions from aquaculture ponds.
[0014] A more general issue arises from the water contamination from excretions which cannot
disperse because of the dense population, the high food consumption, and low water flow. Of
particular concern is the high concentrations of phosphorous, as phosphate ion, and nitrogen,
as urea and ammonia. These may cause eutrophication and hypoxia, in the pond or in
downstream water. Increasingly, aquaculture farmers are under pressure to reduce the leakage
of these materials from aquaculture pens and ponds. There is a need to remove phosphorous,
as phosphate, and nitrogen, generally as ammonia, from aquaculture pens and ponds on the
basis that excess amounts of these cause stress on the cultivated species, but also adversely
impact on the environment in and around the aquaculture ponds. There is need to remove
excess phosphorous and nitrogen from the water in aquaculture pens.
[0015] The prior art of Sceats, and Sceats and Hodgson, cited above, discloses the production
and use of nano-active materials from carbonate compounds to produce a biocide for
application in agriculture and aquaculture, and other applications such as protection of food to
infestation of microbes that induce diseases in humans. The carbonate precursor identified in
that patent is the mineral magnesite, MgCO3. Magnesite is a relatively rare mineral, and is
usually characterised by a significant amounts of impurities including sand, dolomite, talc and
clay. Beneficiating the mineral to achieve high purity mineral feedstock is costly. There is a
need to extend the range of precursors that can be used to produce nano-active Mg(OH)2.
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[0016] Any discussion of the prior art throughout the specification should in no way be
considered as an admission that such prior art is widely known or forms part of common
general knowledge in the field.
Summary
Problems To Be Solved
[0017] It is an object of the present invention to provide a process to optimise the product for
the specific use in aquaculture, where the product is to be bio-active in both the aquatic and
benthic ecosystems, and to be a non-toxic food additive for ingestion by the cultured species.
[0018] It is an alternative object of the present invention to provide a process to manufacture a
product or a product for the restoration the aqueous ecosystem in aquaculture which may be
adversely impacted by heavy metals, by eutrophication from phosphorous and nitrogen, and
excess turbidity from solid particulates such as clays and iron oxide.
[0019] It is another alternative object of the present invention to provide a process to
manufacture a product or a product for the restoration of the benthic ecosystem in aquaculture
which may be adversely impacted by septic conditions.
[0020] It is yet another alternative object of the present invention to provide The prior art of
Sceats and Hodgson claimed the application in aquaculture, and subsequent tests demonstrated
that the performance may be enhanced by more specific specifications, now claimed in this
invention.
[0021] It is an alternative object of the present invention to reduce the adverse impact of
biofilms on the infrastructure of the aquaculture pond or pen, and more generally for all marine
infrastructure, such as ships, boats, buoys, and wharves.
Means For Solving The Problem
[0022] A first aspect of the present invention provides a process for producing a biocide
powder, comprising the steps of:
 Selecting one or more carbonate compounds with a predetermined
calcium/magnesium ratio;
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 Grinding the carbonate compounds to produce a carbonate powder with a first
predetermined particle size distribution;
 Selecting a magnesium hydroxide compound;
 Grinding the hydroxide compound to produce a hydroxide powder with a
second particle size distribution;
 Calcining the carbonate powder in an externally heated counterflow flash
calciner at a first temperature to produce a calcined mixture having a surface
area sufficiently high enough to exhibit bioactivity;
 Calcining the hydroxide powder in an externally heated counterflow flash
calciner at a second temperature to produce a calcined oxide with a surface area
sufficiently high enough to exhibit bioactivity; and
 Blending the calcined mixture and the calcined oxide in a predetermined
proportions.
[0023] Preferably, the process further comprises the step of adding ground limestone, or lime
or hydrated lime to the form the biocide powder.
[0024] Preferably, the carbonate compounds comprising Magnesite and Dolomite.
[0025] Preferably, the degree of calcination of the magnesium carbonate in the magnesite and
dolomite is in the vicinity of 95% or more, and the degree of calcination of the calcium
carbonate is in the vicinity of 5% or less.
[0026] Preferably, wherein the calcined mixture and calcined oxide comprises magnesium
oxide (MgO).
[0027] Preferably, the surface area of the magnesium oxide is ranged from 200 m2/gm to 300
m2/gm.
[0028] Preferably, the magnesium hydroxide compound comprises mineral brucite or
magnesium hydroxide powder produced from seawater or brine in which the degree of
calcination of the magnesium hydroxide is around 95% or more.
[0029] Preferably, the surface area of the oxide from the hydroxide powder is above 200 m2
/gm
of MgO, and preferably above 250 m2
/gm of MgO and most preferably above 300 m2
/gm of
MgO.
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[0030] Preferably, the particle size distribution of the ground carbonate compounds is in the
range of about 1 to 100 microns, with the particle fraction in the range of 1 to 10 microns.
[0031] Preferably, the particle size distribution of the ground magnesium hydroxide compound
is in the range of about 1 to 100 microns with the distribution in the range of 1 to 10 microns.
[0032] Preferably, the particle size of the ground limestone or lime is in the range of about 1
to 100 microns.
[0033] Preferably, the blend of the powder produced from carbonate; the powder produced
from hydroxide depends on the availability of the carbonate and hydroxide input materials and
the specification to achieve a predetermined Ca/Mg ratio.
[0034] Preferably, the proportion of limestone, lime or hydrated lime depends on the
specification to achieve a desirable Ca/Mg ratio for the application and to achieve a desirable
viscosity and stability of the slurry in conjunction with the amount of carboxylic acid added in
the slurry production process.
[0035] Preferably, the first temperature is different to the second temperature.
[0036] Preferably, the first temperature is about 750°C.
[0037] Preferably, the second temperature is about 450°C.
[0038] Preferably, the process further comprises the step of:
 Hydrating the biocide powder with water at or near the boiling point of water until
the hydration is completed;
 Applying a shear mixing, and
 Adding a carboxylic acid or salt as the thinning agent,
in order to form a stable, readily thinned, slurry of the hydrated oxide with about
60% solids in the final product.
[0039] Preferably, the process further comprises the step of quenching the slurry to below
60°C.
[0040] Preferably, the process further comprises the step of cooling the slurry to ambient.
[0041] Preferably, the process further comprises the step of adding additives to the slurry
[0042] Preferably, the additive is an aqueous solution of hydrogen peroxide.
[0043] Preferably, the additive is ozone, which is sparged into the slurry.
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[0044] Preferably, the biocide powder is adapted to use in agriculture, food, water treatment,
chemical detoxifier, and industrial applications such as rubber production, the Ca/Mg ratio
being around 5% to less than 2%.
[0045] Preferably, the biocide powder is adapted to use in aquaculture, the Ca/Mg ratio being
around more than 5% to 15%.
[0046] Preferably, the biocide powder is adapted for an application as a biocide spray, a foam
or a fog wherein the slurry or powder is mixed with oil to form an emulsion if required, and
processed into a foam or fog.
[0047] Preferably, the biocide powder or slurry product for application as a biocide paint,
including a marine paint to prevent biofiIm growth wherein the slurry of powder is mixed as a
filler into a paint formulation that may be either water or oil based.
[0048] Preferably, the carboxylic acid is acetic acid, and the carboxylic salt is magnesium or
calcium acetate.
[0049] In another aspect of the present invention, there is provided a reaction apparatus for
producing biocide powder or a chemical detoxifier powder or a catalyst support from a
carbonate mineral, comprising:
 a grinder for carbonate compounds
 a grinder for hydroxide compounds
 an externally heated counter flow flash calciner that produces high surface area
oxides from the ground carbonate;
 an externally heated counter flow flash calciner that produces high surface area
oxides from the ground carbonate; and
 a blender in which the calcined solid powders are mixed together, and or with other
ground solids for the production of a biocide powder.
[0050] Preferably, the reaction apparatus further comprises a hydration reaction vessel for
the production of the slurry product having an inlet for the blended powder and a water
inlet; and a shearing apparatus for shearing the reaction mixture; and a steam outlet for
release of steam from the reaction vessel, such that in use the reaction is controlIed by
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alIowing heat of hydration to raise the temperature of the reaction mixture, allowing water
to boil off from the reaction mixture as hydration proceeds, and removing steam via the
steam outlet to remove excess heat and control reaction temperature at boiling point; and
a means of quenching the slurry to below 60°C, preferably by transfer of the slurry to a
cooled container and a means of cooling the slurry to ambient temperature; and a means
of adding solid or liquid additives to the slurry.
[0051] Preferably, the reaction apparatus for post-processing the bioactive power or slurry
from the apparatus by one or more of the folIowing steps:
 sparging the powder or slurry with a gas adjuvent such as ozone to enhance
bioactivity; or
 adding and mixing liquid adjuvent compounds to the powder or slurry to enhance
bioactivity; or
 adding and mixing materials to the powder or slurry to make a biocidal coating
product or
 adding and mixing materials to the powder or slurry to make a biocidal emulsion
or foam.
[0052] In another aspect of the present invention, there is provided a chemical composition
as a powder adapted for use as a biocide, wherein the composition comprises: a powder of
micron scale calcined particles which are formed from a mixture of carbonate compounds
and hydroxide compounds, and which have additives to boost the biocide impact such as
ozone, hydrogen peroxide wherein the particles have a porosity of greater than 0.5 and
wherein the pore surface is largely composed of nano-crystalline structures.
[0053] Preferably, the chemical composition is presented as a slurry adapted for use as a
biocide, wherein the composition comprises a slurry produced by hydrating the powder
with additives that stabilise the slurry.
[0054] Preferably, the chemical composition is presented as a coating material slurry
adapted for use as a biocide, wherein the composition comprises a coating material
produced by mixing the powder or the slurry with additives that set the material when
applied to a surface.
[0055] Prefer the chemical composition is presented as a foam, spray or emulsion material
slurry adapted for use as a biocide, wherein the composition comprises a foam, spray or
13
emuIsion material produced by mixing the powder or the slurry with additives that form a
foam, spray or emulsion when processed.
[0056] In the context of the present invention, the words “comprise”, “comprising”, and
the like are to be construed in their inclusive, as opposed to their exclusive, sense, that is
in the sense of “including, but not limited to”.
[0057] The invention is to be interpreted with reference to the at least one of the technical
problems described or affiliated with the background art. The present aims to solve or
ameliorate at least one of the technical problems and this may result in one or more
advantageous effects as defined by this specification and described in detail with reference
to the preferred embodiments of the present invention.
Brief Description Of The Figures
[0058] Figure 1 depicts a schematic drawing of a process for production of a powder or a
slurry from powders of mineral magnesite, dolomite or brucite in which the powder
particle size, porosity and surface area are optimised by calcination to form a biocide.
Description Of The Invention
[0059] Preferred embodiments of the invention will now be described with reference to
the accompanying drawings and non-limiting examples.
[0060] Figure 1 depicts a schematic drawing of a process for production of a powder or a
slurry from powders of mineral magnesite, dolomite or brucite in which the powder
particle size, porosity and surface area are optimised by calcination to form a biocide.
[0061] One example form of manufacture of the product which can be described by
consideration of the process flow of Figure 1 for the mineral precursors of magnesite and
dolomite as carbonate compounds and brucite as a hydroxide compound. Other minerals
particulate impurities in a mined mineral may include sand, talcs, and clays. The desired
material product is either a bioactive powder or a bioactive slurry. The desired solid
product may be made solely from the carbonate materials, or the hydroxide materials, or a
combination of either, and a by-product from the carbonate compound processing may be
a pure carbon dioxide gas.
[0062] The hydroxide compound may be a mineral brucite or a synthetic brucite for
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example, produced from sea water or brines in the known art by precipitating the hydroxide
from sea water or brines by the addition of limestone. The synthetic material is called
herein brucite, although it may have a different crystalline structure from the mineral.
[0063] In this embodiment, the 10 comprises the following steps:-
 Grinding the feedstocks (steps 12a, 12b);
 Calcining the ground materials (steps 14a, 14b);
 Blending the calcined materials (steps 16);
[0064] In another embodiment the process 10 may comprise a further step of adding
ground limestone, or lime or hydrated lime to the form the biocide powder.
[0065] In yet another embodiment, the process 10 may comprise a further step of hydrating
the blended powder to form a slurry product (step 18).
[0066] In yet another embodiment, the process 10 may further comprise a step of
enhancing the bioactivity of the slurry with adjuvents as an option (step 20).
[0067] In one embodiment of the present invention, the first step of process 10 is one in
which the desired particle size distribution is achieved by crushing and grinding the
compounds (steps 12a, 12b). The magnesite and brucite are the primary sources of nanoactive Mg(OH)2 in the final product, whereas the dolomite is the primary source of
calcium. These minerals may be found within a mine site and are selectively mined, or in
the case of brucite, synthesised. In this embodiment the hydroxide compound are ground
separately from the carbonate compound. It is known in the art that the brucite grinds very
differently to the other minerals by virtue of its different crystal structure, which is such
that the mineral rapidly flakes to during grinding give small particles in the range of 0.4-
15 microns. In this embodiment, the process for production of brucite is taken to be
unchanged from that used to make, for example, brucite for the manufacture of
refractories, in which the process is optimised to facilitate ease of filtering, drying and
compacting for subsequent calcination in a kiln. That is, the particle size distribution
exceeds the preferred distribution of say 0.4-100 microns. In this embodiment, the dried
particles are ground. This may preferably be done by first sieving the particles to remove
the fraction above 100 microns, and then grinding the oversized fraction to produce
particle with sizes in the range of 0.4-15 microns. A number of sieving and grinding stages
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can be performed to give the desired particle size distribution for the application.
[0068] In this embodiment, the desired particle size distribution of the ground carbonate
compound may be achieved in a number of grinding stages, folIowed by mixing. For
example, a single grinding process may not provide a sufficient number density of small
particles, such that a fraction of the coarsely ground material may be finely ground, and
remixed with the residual coarsely ground fraction. The art of obtaining a desired particle
size distribution by such comminution processes is a known art per se. The desired particle
size distribution is typically in the range of 0.4- 100 microns.
[0069] In this embodiment, the fraction of dolomite in the ground material is set to give
the desired calcium/magnesium ratio for the desired application. For example, in
aquaculture, For aquaculture, a typical desirable Mg/Ca ratio on a molar basis is in the
range of about 6:1-4:1. While it is possible to use ground limestone as the source of the
calcium, the availability of the calcium carbonate from limestone is lower than that which
is available from the calcined dolomite, described below, by virtue of the higher porosity
and surface area of the calcined dolomite compared to ground limestone.
[0070] The second step of the sample embodiment is calcination. The ground carbonate
compound is processed by calcination, as described by Sceats and Hodgson to create the
nano-scale crystallites that are believed to be the source of the bioactivity. This step of the
process is that of calcination of the carbonate in which the MgCO3 in the magnesite and
dolomite is calcined. It is important that the processed particles exhibit minimal sintering
during the calcination process, and achieve a degree of calcination of the MgCO3 sites, in
the magnesite and dolomite, that is preferably in excess of 95%. The most fundamental
measure of the deleterious impact of sintering is the specific surface area. The
experimental results show that the calcination of the dolomite MgO site does not generate
nano-scale crystallites of MgO with super-oxide formation to create a biocide. Without
being limited by theory, it is reasonable to assume that the uncalcined CaCO3 moeities in
the dolomite prevents the formation of MgO nano-crystallites because there is insufficient
time during flash calcination for diffusion and aggregation of nano-structured MgO to
occur, as reasoned by Sceats and Horley in AU2006904553. Extending the time Ieads to
sintering and phase separation with no nano-scale crystallites. The surface area that
provides the bio-activity of the calcined product is that of the MgO from magnesite alone.
This can be deduced from surface area and calcination measurement, and should be 200
m2
/gm of MgO from magnesite, and preferably greater than 250m2
/gm of MgO and more
16
preferably greater than 300 m2
/gm of MgO. The type of calciner is critical to achieving the
properties described above. The basic requirement is that the process is very fast to
eliminate the effect of sintering, and this should be preferably several seconds. This means
that the process is flash calcination. The second requirement is that the particles experience
the lowest possible temperature during this time. Conventional flash calciners drop the
particles into a very hot combustion gas, and from that time, the temperature of the gas
decreases as the reaction extract energy from the gas stream. Further, not all particles
experience the same conditions. The net result is that the outer surfaces of the particles are
extensively sintered, and it is difficult to achieve surface areas in excess of 50m2
/gm of
MgO. The small particles are most extensively sintered. The preferred calciner is that
described by Sceats and Horely, for example in WO2007/112496 (incorporated herein by
reference). In this case, the temperature of the particles flowing through the calciner
steadily increases for all particles, and the maximum temperature they experience is the
exhaust temperature. During the calcination, there is generally some decrepitation of the
input particles, and often a shoulder appears on the particle size distribution in the region
of 0.1-1 microns. C antral of the external burners along the calciner provides the desired
heat transfer to the particles, and the degree of calcination and surface area can be
controlled. This system is known per se, and is capable of operating at production Ievels
of about 5 tonnes per hour for particles that are 95% calcined for the Mg site, with a surface
area of greater than 200 m2
/gm of MgO from magnesite. The important factor which
determines the biocidal impact is the high surface area of the MgO from the magnesite in
the calcined powder. For the calcination of magnesite and dolomite the exhaust
temperature from the calciner is preferably about 750°C, at which temperature about 95%
calcination of the MgCO3 is achieved, less than about 3% calcination of the CaCO3 is
achieved.
[0071] The calcination process for the ground hydroxide compound is similar to that
described above for the ground carbonate compounds, except that the temperature of the
exhaust of the calciner is preferably lower than about 450°C, at which temperature 95%
calcination of the Mg(OH)2 to nano-active MgO is achieved with a surface area greater
than 120 m2
/gm of MgO. This process has not previously be described.
Generally, multiple hearth furnaces can produce MgO from magnesium hydroxide with a
surface area of typically 50-100 m2
/gm, and such MgO does not display the required nanoactive properties required for biocidal activity. At higher exhaust temperatures of above
17
about 450°C, for a given calciner, the sintering of the particles dramatically reduces the
surface area.
[0072] It highly desirable that the calciner design, of the type, for example, described by
Sceats and Horely, is its capability for processing either the hydroxide compound at about
450°C or the carbonate compound at about 760°C. That is, in the embodiment of Figure
1, the two calciners shown can mean the same equipment operating under different settings
at different times.
[0073] The third stage of the embodiment of Figure 1 shows that the powder streams from
the two calcination processes being mixed to form the biocide powder product. This
product has the desired particle size distribution and the Ca/Mg ratio to suit the application.
This powder is a biocide, and can be used in application where a powder form is used,
either directly or indirectly as a feed for the manufacture of products such as coatings.
[0074] Where a slurry product is desirable, the fourth stage of the process is to hydrate the
slurry. This process is well described by Sceats and Vincent for example in AU
2013904096 (incorporated herein by reference), as a process that can produce tonnes of
slurry per hour to match the production rate of the calciner described above. The high
surface area of the particles is such that the hydration reaction, when mixed vigorously,
liberates a large amount of heat and boils the water. This establishes a set point and the
thermally activated hydration occurs at the boiling point, and the excess heat is liberated
by boiling. The application of a shear mixer provides the agitation required for a uniform
controlIed process. During the course of the reaction, acetic acid is added to the slurry to
provide thinning necessary for the shear mixer to operate. The reaction is complete when
the temperature starts to drop from the heat I asses. It is preferred to quench the slurry
quickly below 60°C, and then let the slurry cool to ambient for the next processing step.
The net result is a slurry that has hydrated, and which is stable over many months with
regard to sedimentation, and which is readily shear thinned to allow pouring and
processing. This slurry has the same intrinsic biocide activity as has nano-particles when
diluted in water for application as a foliar spray. Importantly, there is no significant loss
of biocide activity during over the slurry lifetime of several months.
[0075] The fifth stage is the option, if required, to add adjuvants to either the powder or
the intrinsic slurry product described in order to increase the biocide properties above that
of the intrinsic biocide response considered below. There are many such adjuvants.
18
Examples are hydrogen peroxide, or ozone, which can be added to saturate the crystalline
binding sites on the Mg(OH)2 surfaces with the radical species being the superoxide ion,
the hydroperoxide anion, and oxygen radical, and the hydroxyl radical. Magnesium
peroxide MgO2 is a stable compound. In addition, the acetate ions may be further
converted to the peroxyacetate ion, which is stable at the pH of the slurry, at about 10.4.
Impurity ions, such as Fe2+ and Fe3+ are removed from the slurry as particles for ferric
oxide. The use of hydrogen peroxide or ozone supplements the intrinsic radicals developed
during calcination and hydration. Ozone is added by sparging the slurry with ozonated air.
Other adjuvents include a large number of established biocides, including all those listed
in US 6,827,766 B2 or nano-particles such as AgO and ZnO. Depending on the specific
adjuvant and the amount added, the stability of the slurry may have to be re-established by
the addition of dispersion agents. The use of adjuvants is not generally preferred because
it may make the product toxic to humans, and increase the cost of production compared to
the intrinsic biocide developed in the previous stages.
[0076] If required, impurities in the mineral such as sand, talc and magnetic particles are
extracted during this process at any stage. The process to be used depends on the mineral
source, whether macrocrystalline or cryptocrystalline, the impurities, the grinder and the
grinder settings. Generally, for aquaculture applications, no such separation step is
required.
[0077] Most importantly, it is noted that there is an expectation that there are no
nanocrystal Ii ne particles present (i.e. with a diameter Iess than 0.1 microns) in the powder
or slurry, and generally such particles are undesirable because, as fines, they are difficult
to filter from the grinder air, and also to process in the steps described below, and to meet
customer and community concerns about the toxicity of nanoparticles in general. The
grinders are preferably grinding mills that entrains the ground particles in air, and which
removes particles above about 0.5-1 micron before they can be further ground. This is a
known art per se.
[0078] The intrinsic biocidefor aquaculture produced using steps 1-5 described above
produces either a powder or a 60% solids slurry of particles with a range of particle sizes
from 0.1 microns to 100 microns as measured by a particle size analyser, and a Mg/Ca
ratio in the range of 4-6.
[0079] The biocide activity of the intrinsic powder and slurry in aquaculture has been
19
established in preliminary aquaculture trials on crayfish, prawns, salmon, tilapia, sea bass,
silver perch, trout and milkfish.
[0080] The milkfish trials were conducted on fingerlings over 13 weeks in a 4 ha pond of
0.85 ML stocked with 250,00 fingerlings that are fed 3 times per day. The water is drained
every 2 weeks. Weekly doses of 60 kg of the slurry were used. The pH was about 8.0-8.5.
The odour of H2S was not present, compared to the control, and samples of the pond
bottom were more solid, had Iess odour, and were Ii ghter in colour. The fingerling
mortality was 55% compared to 65% in the control, and the weight of the fingerlings was
34.9 g, compared to 22.4 g in the control. Thus the yield improvement was 84%. The
fingerlings were transferred to sea pens (without further treatment), and at the harvest, the
average fish weight was 7.3 kg, compared to 6.6 kg for the control. The quantity of
premium fish, with the highest weight, increased by a factor of 4. The economic impact
was estimated to be ten times higher than the cost of dosing.
[0081] The biocide activity of the instrinsic powder slurry for agriculture and other
applications has also been established, and are the same as described by Sceats, and Sceats
and Hodgson.
[0082] In one embodiment of the present invention, the nano-activity is demonstrated
when brucite is used as a starting material. Brucite is the mineral of Mg(OH)2 which is
formed in a slow process where the grain size or crystallite size is in the region of microns
and larger, and when ground, the particles exhibit no bioactivity. Brucite may be
synthesised from sea water or brines by treating such with lime of hydrated lime to
precipitate the Brucite. This brucite also exhibits no substantial bioactivity. When the
brucite is flash calcined to give a very high surface area MgO, the MgO is formed as nanoscale crystallites within the particle, and hydration creates nano-scale Mg(OH)2 within the
particles. There is no observable change in the particle size, so that the process has
transformed the structure of the brucite from macrocrystalline to nanocrystalline, and the
defect density is accordingly very high, and the nano-activity is accordingly high.
[0083] The sprayed slurry of the hydrated nano-active Mg(OH)2 has the effect of a disease
preventative contact biocide, and is not a systemic biocide. The implication is that it has a
broad spectrum response, typical of other biocides such as sulphur and copper compounds,
and hydrogen peroxide, but without the toxic effects on all the biota on the leaf ecosystem.
An advantage of the nano-active particles is that the potentially adverse toxic impact of
20
nano-particles on humans is mitigated because the particles cannot be breathed into the
lung, and cannot diffuse through the skin into the human blood and lymph systems because
the particles are too large. If ingested into the human gut, the particles are rapidly dissolved
by the acids in the stomach. At high concentrations, the release of magnesium ions in the
human or animal gut has the mild muscle relaxant effect of Milk of Magnesia.
[0084] In one embodiment of this invention, the materials described by Sceats and
Hodgson are extended to include marine applications generally, in combination with other
materials to form a setting material that, as a biocide, inhibits the formation of biofilms.
[0085] A first aspect of this invention may include the extension of the precursors that can
be used for the production of the nano-active Mg(OH)2 biocide described by Sceats and
Hodgson, and the variation of the process conditions to achieve the biocidal properties.
The prior art of Sceats and Hodgson claims a production process of carbonate minerals
with the first step being grinding the precursor to produce a powder with a broad particle
size distribution. The specification of the nano- active Mg(OH)2 material was a particle
size in the range of 0.5-100 microns. The feedstock for this prior art was generally
magnesite, which is not abundant and is usually found with mineral impurities. In this
invention, the range of preferred mineral precursors is increased from carbonatates such
as magnesite MgCO3 and dolomite MgCO3.CaCO3 to include brucite, Mg(OH)2, where
brucite include the mineral as well as synthetic magnesium hydroxide produced from
brine, as a known art per se. Subsequent experiments have shown that magnesium
hydroxide crystals made from brine itself are not nano-active because their surface area is
too low. However, nano-activity can be induced by flash calcination of brucite to a nanoactive MgO, followed by rehydration to form a nano-active Mg(OH)2 material in the
process described herein. The invention requires significantly different processing
conditions that are disclosed herein. The synthetic brucite typically has a broad distribution
of crystal sizes with a significant fraction above 100 microns, such that further grinding,
wet or dry, is required to give a preferred distribution. The synthetic brucite material has
been developed for ease of processing and for applications such as refractory manufacture
in which the crystal size is generally as large as possible. For this invention, smaller crystal
sizes are required, and the invention recognises that the synthetic process for brucite can
be modified to yield a crystal size distribution that meets the requirements for this
invention. Therefore, the first step in this modified process is one in which the size
distribution may be achieved by either grinding or synthesising the precursors to give the
21
desired particle size distribution. The first step can include grinding different fractions of
the raw materials in a number of fractions to a number of different degrees of grinding and
remixing the fractions to give the desired distribution, or including within a grinder
segmentation of the materials to achieve the desired particle size distribution. The first step
can include synthesising the precursor in a number of stages to give the desired
distribution. For example, with synthetic brucite, boron can be used to control the
crystallite distribution as described by Chisholm in US 3,232,768.
[0086] A second aspect of the present invention may include the production of a nanoactive product that can simultaneously provide bioactivity in the aqueous and the benthic
ecosystems of an aquaculture pen or pond. In order to achieve a simultaneous impact, the
product must be provided to both these ecosystems in doses that enable them to
respectively impact on pathogenic species in each ecosystem.
The general means of dosing used in aquaculture ponds is to deliver the product from a
spray in a liquid form, or a metered spray of the liquid form or a powder form on the
surface of the pond or pen. It has been found that the most advantageous distribution
between ecosystems can be achieved by controlling the particle size distribution. It has
been observed that very small particles, say below 10 microns in diameter have a very Iong
residence time in the aqueous ecosystem. This is because their settling hydrodynamics is
dominated by Brownian motion from the water, such that the settling velocity of such fine
particles from the aqueous ecosystem is very low. This gives a prolonged residence time,
so that the encounter of the particles with a pathogen is sufficiently probable that the
bioactivity of the particles can exert themselves in this ecosystem. The fine nano-active
particles can adhere onto the pathogen for direct bio-impact, or the cultured species or
algae for indirect bio- impact. It has been observed that larger particles, say above 50
microns, have a shorter residence time in the aqueous environment because their
hydrodynamics is dominated by gravitation, offset by turbulence of the water, such that
they quickly fall into the benthic environment where they can exert their bio-impact.
Intermediate sized particles have intermediate residence time. The most desired residence
time depends on the location of the pathogen and the life-cycle of the pathogen. For
example, some pathogens initially grow in benthic layer, before making an impact on the
cultivated species. Therefore, the most effective means of controlling the residence time
is to control the particle size distribution of the particles so that a sufficient fraction of the
particles fall directly into the benthic ecosystem. Thus there is a preferred fraction of fines
22
in the range of 0.4-10 microns that have a Iong residence time in the aqueous ecosystem,
and course larger particles in the range of 50-100 microns that have a short residence time
in that ecosystem, so that they act to improve the benthic ecosystem.
[0087] The specification of 0.5-100 microns was developed by Sceats and Hodgson to be
such that the calcination process and the formation of a stable slurry could be readily
achieved. For aquaculture, experiments have shown that the particle size distribution is
preferably further specified to meet the residence time distribution of the particles in the
aqueous ecosystem and the benthic ecosystem so as to have maximum bio-impact for the
health of the cultivated species, as well as meeting the requirements for calcination and
slurry stability. The preferred range of the particle size for aquaculture applications is
within the 0.5-100 micron range claimed by Sceats and Hodgson, and is herein further
specified for use in aquaculture. Thus key feature of this innovation is that the particIe size
distribution has become a parameter to optimise the biocidal impact of the nano-structured
particles, rather than just a specification for the ease of calcination and stable slurry
production. For example, for controlling the parasite vibrio in prawns, for an aquaculture
pond that was 2 metres deep, the desirable particle size was such that at least 30% of the
particles were less than 5 microns.
[0088] A third aspect of the invention is associated with the ingestion of the particles by
the cultivated species. The prior art described by Sceats and Hodgson is focussed on the
use of nano-structured particles in agricultural crops, where the ingestion of the particles
through the leaf stomata provides an additional benefit of enhancing the growth of the
plant by the adsorption of magnesium for the production of chlorophyll. However, by
analogy, the ingestion of the particles by the cultivated species in aquaculture provides a
means of providing minerals for growth. The cultivated species have specific requirements
for calcium for the growth of bones or shells, and the aqueous ecosystem may not be able
to supply the required amounts. Further, calcium is also important in fish hatchery water
supplies, because eggs tend to hydrate at low calcium concentrations and may not develop
or hatch if the calcium concentration is too low. The cultivated species may ingest the
calcium from the ions in the water (ie through the calcium hardness, which varies from
lakes, rivers, estuaries and the sea) and from food, either directly or from algae that grow
in the pond, or from additives such as calcium sulphate. The nano-active material is
generally Mg(OH)2 produced from hydration of MgO from calcining magnesite ores. Most
magnesite ore, dominantly MgCO3 contains some dolomite MgCO3.CaCO3.
23
When the dolomite ore is processed, the product is a semidolime MgO.CaCO3, and the
formation of dolime MgO.CaO is suppressed at low calcination temperatures by the high
partial pressure of CO2. This process is described by Sceats and Horely (AU 2006904553),
incorporated herein for reference. The dolomite crystallites are often found within the
ground mineral feedstock particles along with magnesite and silica. Experiments have
shown that the high porosity and surface area of the semidolime produced in the flash
calciner is such that the hydrated material, Mg(OH)2.CaCO3 exhibits a very fast acid
decomposition which releases the calcium ions. In the gut of the fish, the acids in the
stomach quickly release the calcium which can be ingested and can assist in the growth of
the fish. It is preferable that the conditions of the calcination is such that the CaCO3 is not
calcined to lime. The absence of lime CaO, as dolime MgO.CaO, is such that the pH within
the particle is maintained at about 10.4, and experiments have shown that the intake of the
hydrated semi dolime in the hydrated product has no adverse effects from stress that
otherwise may have occurred had quicklime been formed. The desirable Mg/Ca balance in
the product can be optimised to meet the requirements of the cultivated species, taking into
account the calcium and magnesium in the water and in the food. Generally, the use of a
mixture of Magnesite and dolomite as feed into the calciner can be varied so as to deliver
the required Ca/Mg dose for growth of the cultivated species. More generally, mineral
deposits of magnesite are found in layers, usually accompanied with dolomite layers, and
the magnesite rich layers have some Dolomite as granular impurities and substitutional
impurities. This benefit of specifying a Ca/Mg ratio is an important feature for aquaculture,
but relatively unimportant for plants. Thus the specification for the production of the
bioactive material by Sceats, and Sceats and Hodgson, failed to teach the benefits of
controlling the input mineral to provide the desired bioactivity, and the desired Mg/Ca ratio
in aquaculture applications to promote the health of the cultivated species, specifically with
respect to the growth of bones and the hatching of eggs. This capability relies on the lack of
toxicity of the nano-active species for ingested particle's because the acids in the stomach
dissolve the particles and the released ROS is at sufficiently low doses that they are rapidly
reduced in the digestive tract. The animal cells are capable of handling intense bursts of ROS
because the release of ROS is a primary mechanism developed to combat infection. Thus
nano- active particles have no toxicity to the cultivated species when ingested, and it is
desirable that the calcium required for bones and shells is provided as CaCO3, in particles
with a high surface area so that ingestion is rapid. Thus calcined dolomite is preferable to
the addition of ground limestone because the calcium is more accessible from semidolime
24
because of the higher surface area arising from calcination of the magnesium site.
[0089] A fourth aspect of the invention relates to the ability of the particles that are
suspended for a short time to remove heavy metals, and excess phosphate and nitrogen,
from the aquatic ecosystem. The specification provided by Sceats and Hodgson uses the
surface area and porosity of the magnesium oxide as indicators of the nano-crystallinity of
the powder, and therefore as indicators of the propensity of the particles to generate ROS at
the nano-grain boundaries, and to retain these species as oxidants after hydration. However,
experiments in aquaculture have revealed that the surface area of the magnesium hydroxide
itself enables the controlled removal of heavy metals and phosphorous and nitrogen from
the aquatic ecosystem during their passage to the floor of the pen. The accumulation of
heavy metals, such as cadmium, copper, lead, chromium, arsenic, barium, cobalt,
manganese and vanadium in the cultivated species may make the product unsuitable for
human consumption. Very high concentrations of iron, from pyrites oxidation, are toxic to
the fish. Magnesium hydroxide is well established as a product for removing iron and heavy
metals from soils and water, where the metals precipitate to form insoluble hydroxides.
Experiments have shown that the extraction efficiency is enhanced by the high porosity and
surface area of the Mg(OH)2 particles. Without being bound by theory, the reason for this is
two-fold. Firstly, the reaction kinetics for the precipitation of insoluble hydroxides scales with
the surface area of the Mg(OH)2, and secondly, within the pores of the particle, the
concentration of hydroxide ions is that of water saturated by the dissolution of Mg(OH)2 at the
pH of 10.4, rather than the pH of the water itself, which is preferably in the range of 7.0-7.6
for aquaculture. Thus the particles, falling through the water, efficiently extract the heavy
metals from the aqueous ecosystem without the need for the particles to raise the pH to the
levels required for heavy metal precipitation. These larger particles, having accumulated the
metals, fall into the sludge of the benthic ecosystem. It is now current practice to extract the
sludge from the pen after a number of days, and in this case, the heavy metals ions are removed
from the pen. In the sludge, the larger particles sequester the heavy metals in the same way as
Mg(OH)2 is used to sequester heavy meals in soiIs, with a very low rate of leaching. It is
preferable that there is a sufficient fraction of particles move through the aqueous ecosystem
and fall into the benthic ecosystem to remove heavy metals from the aqueous system, and that
there is a sufficient amount of such particles in the sludge, when removed, such that the heavy
metals are extracted from the benthic ecosystem. Experiments have shown that the use of low
surface area, low porosity Mg(OH)2 is not as efficient for heavy metal extraction. The invention
25
is that the high porosity and surface area increases the yield of heavy metal ions that would be
expected on the basis of the pH of the aqueous ecosystem.
[0090] In a similar manner, excess phosphorus, as the phosphate ion, and nitrogen as the
ammonium ion, precipitate magnesium phosphate and magnesium ammonium phosphate in
the particle pores at the pH of 10.4 and at a concentration of magnesium that is or order unity
(directly from a surface site), and these materials are collected in the sludge. It is preferable
that there is a sufficient fraction of particles move through the aqueous ecosystem and fall into
the benthic ecosystem to remove excess phosphorous and nitrogen from the aqueous system,
and that there is a sufficient amount of such particles in the sludge, when removed, such that
the excess phosphorous nitrogen are extracted from the benthic ecosystem. It is noted that
excess nitrogen is extracted when there is excess phosphate. In the case that the heavy metal
ions are sufficiently low, the sludge is a useful plant fertilizer. Experiments have shown that
the use of low surface area, low porosity Mg(OH)2 is not as efficient for excess phosphorous
and nitrogen extraction. The invention is that the high porosity and surface are increases the
yield of excess phosphorus and nitrogen that would be expected on the basis of the pH and
magnesium concentration in the aqueous ecosystem.
[0091] Therefore, in this innovation, the high surface area and porosity of the Mg(OH)2
particles have been shown to control the extraction of heavy metal ions, phosphorous and
nitrogen from the aqueous ecosystem, such that the cultivated species can grow healthily in
a clean ecosystem, and the cultivated species can be consumed without adverse health
impacts to humans.
[0092] A fifth aspect of the invention is associated with the capability of the Mg(OH)2
particles to induce the flocculation of the particles in the aqueous phase. These particles
may be suspended clays from soiIs folIowing run off or disturbance, or organic matter such
as faeces or uneaten food. In aquaculture practice, the optimum turbidity of the pond is
dependent on the needs of the cultivated species, and generally it should not be too high to
induce health problems, or too low to facilitate the capture by predators, such as birds.
Magnesium hydroxide is an established flocculant because its high charge density causes
the collapse of ionic boundary layers which others keeps the particles in suspension.
Without being bound by theory, the Mg(OH)2 particle have a point of zero charge at a pH
of 10.4, and are thus negatively charged in an aqueous ecosystem with a pH in the ideal
range of 7.5-7.0, whereas the particles that cause the turbidity and health problems have a
point of zero charge below a pH of 7.0 and are charged positively. This is the basis of why
26
Mg(OH)2 is an excellent flocculant. However, the high surface area is such that the local
response of these particles is fast, and the floe forms quickly through the charge
neutralisation. Experiments have shown that the efficiency and rate of flocculation of a high
porosity high surface area Mg(OH)2 particle is larger than a comparable Mg(OH)2 particles
that have a lower surface area and lower porosity. Generally, this process removes the
Mg(OH)2 particles as well as the target particles, and they fall to the floor of the pen and
are removed from the aqueous ecosystem. The larger particles trap a large number of smaller
suspended particles that cause the turbidity. The flocculated particles are part of the sludge
removed from the pens on a regular basis in many aquaculture practices.
[0093] It follows that the first and second aspects are optimised for small particles that have
a long residence time, while the third and fourth aspects are optimised by larger particles
that are sufficiently large that they pass through the aqueous ecosystems. The control of the
particle size allows for such control.
[0094] The aspects considered above are concerned with the health of the aqueous
ecosystem. Experiments have shown that the larger particles that move into then benthic
ecosystem play a significant role in the health of that ecosystem, whether or not the particles
have sequestered heavy metal ions or have deposited other particles. A sixth aspect is
associated with the benefits of a healthy benthic ecosystem arising from the presence of
nano-active Mg(OH)2. It is often observed that the sludge at the base of an untreated
aquaculture pen is septic, with a characteristic small of H2S, it is acidic and anaerobic. This
generally arises from the anaerobic bacterial decomposition of organic matter, from faeces
and uneaten food, as a result of the high population density of the cultivated species. It is a
known art that the dosing of sewage systems by Mg(OH)2 is a means of raising the pH to a
level that the decomposition is suppressed. Further, the use of nano-active Mg(OH)2 may
suppress the growth of pathogenic organisms in this benthic ecosystem, and mitigate their
growth such that they do not significantly move into the aquatic ecosystem and infect the
cultivated species. Experiments have shown that the sludge that is removed from the base
of the pond or pen in which the nano-active Mg(OH)2 has been added has very little sulphide
smell, and is more compact compared to an untreated sludge. The degree of compaction is
related to the same factors as flocculation, so that high surface area, and high porosity lead
to more compact sludge. The practices in agriculture associated with sludge vary widely. In
some cases, the sludge is decomposed in anaerobic digesters to produce a fuel, and
experiments have shown that the presence of nano-active Mg(OH)2 decreases the H2S, and
27
increases the methane content. In one practice, the sludge is sold as a fertilizer, and the
absence of the H2S odour is benefit. In another practice, the water is drained before being
refilled and restocked, alIowing a time for regeneration of the pond bed in aerobic
conditions. The time for regeneration is signifi candy reduced if the anaerobic conditions of
the sludge have previously been reduced and the sludge is compact, as a result of dosing
with nano-active Mg(OH)2.
[0095] A seventh aspect of the invention is the use of the nano- Mg(OH)2 application in
aquaculture is as a coating on aquaculture infrastructure. Experiments have shown the nanoactive Mg(OH)2 minimises the formation of biofilms. The result is that secondary growth
of barnacles is also supressed. Without being bound by theory, the mode of action of the
nano- Mg(OH)2 is believed to arise from the encapsulation of the particles by the
extracelIular extrusions of biofiIm forming organisms, and the subsequent release of ROS
and increase of the pH in the biofilms degrades the films, and leads to the disruption of the
colonies of the biofiIm forming organisms. This aspect is applicable to the maritime
industry, as well as the aquaculture industry. For shipping, the presence of a biofilm causes
a roughness on the hull, and the higher expenditure of energy. For aquaculture, the biofilm
causes destruction of the pond enclosures, and fouling of equipment used to manage the
cultivation. Depending on the application, the strength of the nano-Mg(OH)2 coating can be
enhanced by using additives. These include acrylic materials used in paints, and other
stabilising materials. For example, the use of graphene fibres is particularly useful in such
applications.
[0096] In this specification, the word “comprising” is to be understood in its “open” sense,
that is, in the sense of “including”, and thus not limited to its “closed” sense, that is the
sense of “consisting only of”. A corresponding meaning is to be attributed to the
corresponding words “comprise”, “comprised” and “comprises” where they appear.
[0097] While particular embodiments of this invention have been described, it will be
evident to those skilled in the art that the present invention may be embodied in other
specific forms without departing from the essential characteristics thereof. The present
embodiments and examples are therefore to be considered in alI respects as illustrative and
not restrictive, with all changes which come within the meaning and range of equivalency
therefore intended to be embraced therein. It will further be understood that any reference
herein to known prior art does not, unless the contrary indication appears, constitute an
admission that such prior art is commonly known by those skilled in the art to which the
28
invention relates.
[0098] In one embodiment of the present invention, there is provided a reaction apparatus
for producing biocide powder or a chemical detoxifier powder or a catalyst support from a
carbonate mineral, comprising: a first grinder for carbonate compounds and a second
grinder for hydroxide compounds; an externally heated counter flow flash calciner that
produces high surface area oxides from the ground carbonate; an externally heated counter
flow flash calciner that produces high surface area oxides from the ground carbonate; and a
blender in which the calcined solid powders are mixed together, and or with other ground
solids for the production of a biocide powder.
[0099] In another embodiment the reaction apparatus further comprising a hydration
reaction vessel for the production of the slurry product having an inlet for the blended
powder and a water inlet; and a shearing apparatus for shearing the reaction mixture; and a
steam outlet for release of steam from the reaction vessel, such that in use the reaction is
controlled by allowing heat of hydration to raise the temperature of the reaction mixture,
allowing water to boil off from the reaction mixture as hydration proceeds, and removing
steam via the steam outlet to remove excess heat and control reaction temperature at boiling
point and a means of quenching the slurry to below 60°C, preferably by transfer of the slurry
to a cooled container and a means of cooling the slurry to ambient temperature; and a means
of adding solid or liquid additives to the slurry.
[00100] In a further embodiment, the reaction apparatus is adapted for post- processing the
bioactive power or slurry from the apparatus by one or more of the folIowing steps:
 sparging the powder or slurry with a gas adjuvent such as ozone to enhance
bioactivity;
 adding and mixing liquid adjuvent compounds to the powder or slurry to enhance
bioactivity;
 adding and mixing materials to the powder or slurry to make a biocidal coating
product or
 adding and mixing materials to the powder or slurry to make a biocidal
emulsion or foam.
[00101] In one embodiment of the present invention, there is provided a chemical
composition as a powder adapted for use as a biocide, wherein the composition comprises:
29
a powder of micron scale calcined particles which are formed from a mixture of carbonate
compounds and hydroxide compounds, and which have additives to boost the biocide
impact such as ozone, hydrogen peroxide wherein the particles have a porosity of greater
than 0.5 and wherein the pore surface is largely composed of nano-crystalline structures.
[00102] The chemical composition as a slurry is adapted for use as a biocide, wherein the
composition comprises a slurry produced by hydrating the powder of mentioned above with
additives that stabilise the slurry.
[00103] In another embodiment the chemical composition is presented as a coating material
slurry adapted for use as a biocide, wherein the composition comprises a coating material
produced by mixing the powder or the slurry mentioned above with additives that set the
material when applied to a surface.
[00104] In another embodiment the chemical composition is presented as a foam, spray or
emulsion material slurry adapted for use as a biocide, biofilm inhibitor, or plant root
repellant,, wherein the composition comprises a foam, spray or emulsion material produced
by mixing the powder or the slurry mentioned above with additives that form a foam, spray
or emulsion when processed.
[00105] Although the invention has been described with reference to specific examples, it
will be appreciated by those skilled in the art that the invention may be embodied in many
other forms, in keeping with the broad principles and the spirit of the invention described
herein.
[00106] The present invention and the described preferred embodiments specifically
include at least one feature that is industrial applicable.
30
We Claim:
1. A process for producing a biocide powder, comprising the steps of:
a. Selecting one or more carbonate compounds with a predetermined calcium/magnesium
ratio;
b. Grinding the carbonate compounds to produce a carbonate powder with a first
predetermined particle size distribution;
c. Selecting a magnesium hydroxide compound;
d. Grinding the hydroxide compound to produce a hydroxide powder with a second
particle size distribution;
e. Calcining the carbonate powder in an externally heated counterflow flash calciner at a
first temperature to produce a calcined mixture having a surface area sufficiently high
enough to exhibit bioactivity;
f. Calcining the hydroxide powder in an externally heated counterflow flash calciner at a
second temperature to produce a calcined oxide with a surface area sufficiently high
enough to exhibit bioactivity; and
g. Blending the calcined mixture and the calcined oxide in a predetermined proportions.
2. The process of claim 1 further comprising the step of adding ground limestone, or
lime or hydrated lime to the form the biocide powder.
3. The process of claim 1 or claim 2, wherein the carbonate compounds comprising
Magnesite and Dolomite.
4. The process of claim 3, wherein the degree of calcination of the magnesium carbonate
in the magnesite and dolomite is in the vicinity of 95% or more, and the degree of calcination
of the calcium carbonate is in the vicinity of 5% or less.
5. The process of any one of claims 1 to 4, wherein the calcined mixture and calcined
oxide comprises magnesium oxide (MgO).
6. The process of claim 5 wherein the surface area of the magnesium oxide is ranged from
200 m2
/gm to 300 m2
/gm.
7. The process of any one of claims 1 to 6, wherein the magnesium hydroxide compound
comprises mineral brucite or magnesium hydroxide powder produced from seawater or brine
in which the degree of calcination of the magnesium hydroxide is around 95% or more.
31
8. The process of claim 5, wherein the surface area of the oxide from the hydroxide
powder is above 200 m2
/gm of MgO, and preferably above 250 m2
/gm of MgO and most
preferably above 300 m2
/gm of MgO.
9. The process of any one of claims 1 to 8, wherein the particle size distribution of the
ground carbonate compounds is in the range of about 1 to 100 microns, with the particle
fraction in the range of 1 to 10 microns.
10. The process of any one of claims 1 to 9, wherein the particle size distribution of the
ground magnesium hydroxide compound is in the range of about 1 to 100 microns with the
distribution in the range of 1 to 10 microns.
11. The process of any one of claims 1 to 10, wherein the particle size of the ground
limestone or lime is in the range of about 1 to 100 microns.
12. The process of any one of claims 1 to 11, wherein the blend of the powder produced
from carbonate; the powder produced from hydroxide depends on the availability of the
carbonate and hydroxide input materials and the specification to achieve a predetermined
Ca/Mg ratio.
13. The process of claim 2, wherein the proportion of limestone, lime or hydrated lime
depends on the specification to achieve a desirable Ca/Mg ratio for the application and to
achieve a desirable viscosity and stability of the slurry in conjunction with an amount of
carboxylic acid added in the slurry production process.
14. The process of any one of claims 1 to 13, wherein the first temperature is different to
the second temperature.
15. The process of any one of claims 1 to 14, wherein the first temperature is about 750oC.
16. The process of any one of claims 1 to 15, wherein the second temperature is about
450oC.
17. The process of any one of claims 1 to 16 further comprising the step of:
a. hydrating the biocide powder with water at or near the boiling point of water until the
hydration is completed;
b. Applying a shear mixing, and
c. Adding a carboxylic acid or salt as the thinning agent,
32
in order to form a stable, readily thinned, slurry of the hydrated oxide with about 60% solids
in the final product.
18. The process of any one of claims 17, further comprising the step of quenching the slurry
to below 60oC.
19. The process of claim 18 further comprising the step of cooling the slurry to ambient.
20. The process any one of claims 17 to 19, further comprising the step of adding additives
to the slurry
21. The process of any one of claim 20, wherein the additive is an aqueous solution of
hydrogen peroxide.
22. The process of any one of claim 20, wherein the additive is ozone, which is sparged
into the slurry.
23. The process of any one of claims 1 to 16, wherein the biocide powder is adapted to use
in agriculture, food, water treatment, chemical detoxifier, and industrial applications such as
rubber production, the Ca/Mg ratio being around 5% to less than 2%.
24. The process of any one of claims 1 to 16, wherein the biocide powder is adapted to use
in aquaculture, the Ca/Mg ratio being around more than 5% to 15%.
25. The process of any one of claims 1 to 16, wherein the biocide powder is adapted for an
application as a biocide spray, a foam or a fog wherein the slurry or powder is mixed with oil
to form an emulsion if required, and processed into a foam or fog.
26. The process of any one of claims 1 to 25, wherein the biocide powder or slurry product
for application as a biocide paint, including a marine paint to prevent biofilm growth wherein
the slurry of powder is mixed as a filler into a paint formulation that may be either water or oil
based.
27. The process of claim 13, wherein the carboxylic acid is acetic acid, and the carboxylic
salt is magnesium or calcium acetate.
28. The process of any one claim of 17 to 27, wherein the slurry is mixed with one or more
viscosity modifier and setting additives for manufacturing a coating to sewage pipes and
manholes.
29. A reaction apparatus for producing biocide powder or a chemical detoxifier powder or
a catalyst support from a carbonate mineral, comprising:
33
a. a grinder for carbonate compounds
b. a grinder for hydroxide compounds
c. an externally heated counter flow flash calciner that produces high surface area oxides
from the ground carbonate;
d. an externally heated counter flow flash calciner that produces high surface area oxides
from the ground hydroxide; and
e. a blender in which the calcined solid powders are mixed together, and or with other
ground solids for the production of a biocide powder.
30. A reaction apparatus of claim 28, further comprising a hydration reaction vessel for the
production of the slurry product having an inlet for the blended powder and a water inlet; and
a shearing apparatus for shearing the reaction mixture; and a steam outlet for release of steam
from the reaction vessel, such that in use the reaction is controlled by allowing heat of hydration
to raise the temperature of the reaction mixture, allowing water to boil off from the reaction
mixture as hydration proceeds, and removing steam via the steam outlet to remove excess heat
and control reaction temperature at boiling point; and a means of quenching the slurry to below
60oC, preferably by transfer of the slurry to a cooled container and a means of cooling the
slurry to ambient temperature; and a means of adding solid or liquid additives to the slurry.
31. A reaction apparatus for post-processing the bioactive power or slurry from the
apparatus of Claim 29 which is adapted to carrying out one or more steps of:
 sparging the powder or slurry with a gas adjuvent such as ozone to enhance bioactivity;
 adding and mixing liquid adjuvent compounds to the powder or slurry to enhance
bioactivity;
 adding and mixing materials to the powder or slurry to make a biocidal coating product; or
 adding and mixing materials to the powder or slurry to make a biocidal emulsion or foam.
32. A chemical composition as a powder adapted for use as a biocide, wherein the
composition comprises: a powder of micron scale calcined particles which are formed from a
mixture of carbonate compounds and hydroxide compounds, and which have additives to boost
the biocide impact such as ozone, hydrogen peroxide wherein the particles have a porosity of
greater than 0.5 and wherein the pore surface is largely composed of nano-crystalline
structures.
34
33. A chemical composition as a slurry adapted for use as a biocide, wherein the
composition comprises a slurry produced by hydrating the powder of Claim 31 with additives
that stabilise the slurry.
34. A chemical composition as a coating material slurry adapted for use as a biocide,
wherein the composition comprises a coating material produced by mixing the powder of
Claim 31 or the slurry of Claim 32 with additives that set the material when applied to a surface.
35. A chemical composition as a foam, spray or emulsion material slurry adapted for use
as a biocide, biofilm inhibitor, or plant root repellant, wherein the composition comprises a
foam, spray or emulsion material produced by mixing the powder of Claim 31 or the slurry of
Claim 32 with additives that form a foam, spray or emulsion when processed.