WO2020165594A1

WO2020165594A1 - A method for remediating contaminated water and apparatus for the same

Info

Publication number: WO2020165594A1
Application number: PCT/GB2020/050340
Authority: WO
Inventors: William Alexander BEVERIDGE; Leigh Cassidy
Original assignee: SEM Energy Limited
Priority date: 2019-02-14
Filing date: 2020-02-13
Publication date: 2020-08-20
Also published as: GB2581365A; GB201902026D0

Abstract

The present invention relates to methods of remediating contaminated water, for example frac flowback water and/or produced water such that it is suitable for re-use or environmental discharge, and to apparatuses for the same.

Description

A METHOD FOR REMEDIATING CONTAMINATED WATER AND APPARATUS FOR THE SAME Field of the Invention

Background

Many industrial fields have a problem with water contamination, and require methods/apparatuses for removing organic and inorganic contaminants from a variety of different effluent streams. Such industrials fields include, industrial interceptor waste, contaminated ground water, agriculturally contaminated water, animal processing plants, distillation water streams, ballast water, bilge water and sea-going vessel wash-down water, effluents contaminated with heavy metals, conventional and unconventional produced water from hydrocarbon and water / geothermal wells and fracking.

Taking fracking as an example, fracking is a well stimulation process whereby high-pressure liquids are pumped / injected downhole in order to fracture formation rock, thereby increasing the flow of formation fluids into the wellbore. Fracking may be applied to water wells but is more commonly applied to hydrocarbon wells, and unconventional hydrocarbon wells such as shale oil, shale gas, gas and coal-based methane wells.

The most commonly used fracking liquid is water-based fluid, which primarily contains freshwater.

Following fracking of a hydrocarbon well, water is typically produced along with the recovered hydrocarbons. This water is known as produced water . The initial produced water production phase comprises what is deemed frac flowback water .

Frac flowback water and produced water contain a variety of organic and inorganic contaminants. The main contaminants are generally categorised as oil/grease, total suspended solids (TSS) (particles > 1 to 2pm in size), bacteria/viruses, and total dissolved solids (TDS). TSS include proppant, sand, shale and scale. TDS include, salts, dissolved heavy metals, other dissolved chemicals, colloidal solids and dissolved naturally occurring radioactive material (NORM). Dissolved BTEX hydrocarbons, gasses including hydrogen sulphide (H2S) can also be present. In order for frac flowback water and/or produced water to be re-used as fracking liquid or discharged into the environment, these contaminants must be removed or at least significantly reduced. This is generally conducted in two stages - a primary treatment process to remove oil/grease, TSS and bacteria/virus, and a second treatment process to remove TDS.

Removal of TSS is typically achieved by filtration / separation, chemical precipitation and/or oxidation, the latter of which is also used to remove bacteria/viruses. Removal of TDS is typically achieved by desalination technologies, for example reverse/forward osmosis (RO),

distillation/evaporation, and crystallisation.

Fracking operators commonly set maximum levels for TDS and TSS for use in fracking at around <100,000ppm and <50 ppm respectively. For discharge purposes, water must be treated not only to remove almost all TSS, bacteria/viruses and heavy metals, but TDS levels must also be reduced to about <500 ppm.

Produced water that is not re-used or treated for surface discharge is generally injected into class two disposal wells. This often involves energy intensive trucking of the contaminated fluids to disposal well sites and high-pressure injection into isolated subsurface formations. Energy intensive trucking of huge volumes of fresh water is also required to allow drilling and fracking of new wells.

Thus, frac flowback and/or produced water remediation is a growing area, with increasing regulatory requirements and public concern, primarily due to the large amounts of water required during the fracking process and increasing water stress in many fracking areas.

It therefore stands that if a simple, cost effective technology to reduce TDS (and other

contaminants) could be deployed in-line with standard technologies to remove oil/grease, TSS and bacteria/viruses, then this would both maximise re-use and minimise fresh water requirements. In so doing, regional water stress and costs to the operator are lowered. Additionally, less produced water requires disposal via injection wells, thus reducing disposal / logistical costs and carbon footprint.

Moreover, enhanced reduction of TDS and other contaminants in a primary treatment process / method will either increase applications where more cost-effective desalination technologies can be employed as a secondary treatment for surface discharge (i.e. RO over distillation), or even negate the requirement all together.

Restoration of water systems to maximum contaminant levels (MCLs) or consent to discharge (CTD) levels remains a difficult challenge. Traditional reductive water remediation treatments have included the use of simple electron donor compounds such as lactose, alcohols, milk fat, Hydrogen Release Compound (HRC ) , or complex electron donors such as molasses, corn syrup, zero valent iron (ZVI), organic mulch, yeast extract, edible oils, and Biogeochemical Reductive Dechlorination (BIRD). However, such treatments are expensive (HRC), require repeated applications (sodium lactate, whey), require complex storage techniques (whey), or have reduced permeability / water flux (ZVI, some mulches).

Other remediation technologies have included treating contaminated water with draff, which is a solid waste product of the fermentation of cereals, such as those discussed in GB0718989.7.

This present invention provides enhanced methods and apparatuses for remediating contaminated water, both in situ and ex situ, which are effective, sustainable and cheap. The present invention particularly provides enhanced primary treatment of frac flowback water and produced water for re-use, negates/reduces the extent/cost of secondary treatment of frac flowback water and produced water for environmental discharge, and enhances the treatment of alternative effluent streams.

It is important to note that although the invention is generally described in relation to the treatment of frac flowback water and produced water, it is equally applicable to other effluent streams where contaminant removal is enhanced.

Summary

According to a first aspect, the present invention provides a method of remediating contaminated water, the method comprising treating the water with draff, said draff comprising a solid by product of grain alcohol manufacture, and oxidising the draff treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof. The present invention also provides an apparatus suitable for use /for use in the method of the first aspect of the invention, the apparatus comprising a container containing the draff and a module configured to allow water to contact the draff on passing through the container, and an oxidising module configured to treat the draff treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof.

According to a second aspect, the present invention provides a method of remediating

contaminated water, the method comprising treating the water with fresh hops and/or hops that have been used in brewing.

The present invention also provides an apparatus suitable for use / for use in a method of the second aspect of the invention, the apparatus comprising a container containing the hops and a module configured to allow water to contact the hops on passing through the container.

Figures

Figure 1 shows a schematic representation of a treatment method/apparatus according to any aspect of the invention. (Method 2)

Figure 2 shows a schematic representation of a first embodiment according to any aspect of the invention. (Method 3)

Figure 3 shows a schematic representation of a second embodiment according to any aspect of the invention. (Method 4)

Figure 4 shows a schematic representation of a third embodiment according to any aspect of the invention. (Method 5)

Figure 5 shows a schematic representation of a fourth embodiment according to any aspect of the invention. (Method 6)

Figure 6 shows a schematic representation of a fifth embodiment according to any aspect of the invention. (Method 7) Figure 7 shows a schematic representation of a sixth embodiment according to any aspect of the invention. (Method 8)

Figure 8 shows a schematic representation of a seventh embodiment according to any aspect of the invention. (Method 9)

Figure 9 shows a schematic representation of a treatment method/apparatus according to the second or third aspect of the invention. (Method 1)

Figure 10 shows various configurations of the main filter apparatus 10 of any aspect of the invention.

Detailed Description

The present invention provides methods and apparatuses for remediating contaminated water using a filtrate material.

In summary, contaminated water is passed through a container comprising filtrate material, and contact with the filtrate material removes and/or reduces various different contaminants by virtue of the filtrate material chemistry. The filtrate operates via sorption; contaminates are removed by a combination of adsorption, absorption, and ion and cation exchange. The exact mechanism depends on the contaminant. Several additional treatment steps/modules may be added to the method/apparatus, to further enhance the removal and/or reduction of the contaminants.

In a first aspect, remediation is achieved by treating the contaminated water with draff.

Draff is a solid waste product of the fermentation of cereals, such as from the fermentation of barley during whisky or beer- production. For example, during whisky production the barley is firstly soaked to induce germination of the grain, which is then halted by heating ("malting"), following which the grain is ground and heated in a mash tun with water ("mashing") . After mashing, the liquids (the "wort") are taken for distillation to produce the whisky, whereas the solids (the "draff") are removed as a waste product, traditionally used as animal feed. Whilst a preferred draff for use in the present invention comprises a solid .waste product of the fermentation process of barley, and in particular a solid waste product from whisky manufacture, the term "draff" as used herein encompasses all solid waste products of the for example maize, fermentation process of any cereal, wheat, rice, barley, sorghum, millet, oats, rye, triticale, and buckwheat.

As a waste product from fermentation processes of cereals draff is thus cheap and readily available. Draff may be refrigerated, for example for up to four months, without significant inhibition of performance, and may be frozen.

The biological/physical/chemical make-up of draff is a complex mixture of different constituents, the content of which will vary between different cereals and fermentation processes. An example of the content of whisky draff is shown below:

Whilst not being bound by theory, draff is believed to be useful for water remediation through a combination of factors resulting from it s chemical, biochemical and physical make-up. Thus, it is thought that draff maintains favourable redox conditions, provides electron donor compounds, a carbon source for the bacterial community, and catalytic compounds, and enforces a positive feedback cycle utilising biotic, abiotic and synergistic pathways. The chemical properties of draff are believed to maintain the reductive environment, malt and yeast provide sugars and trace nutrients and also facilitate the breakdown of cellulose within grain husks, alcohol, oil and protein are believed to act as surfactants altering the interfacial tension at the contaminant-water interface, and draff also provides fermentative organisms.

In a second aspect, remediation is achieved by treating contaminated water with fresh hops and/or hops that have been used in brewing. Hops are the flowers of the hop plant Humulus lupulus. Spent hops are hops from the beer brewing industry, which are a true waste product, i.e. they do not get used for cattle feed or any other secondary monetised application. The present inventors have surprisingly found that fresh hops and hops that have been used in brewing, also function well in removal of a variety of

contaminants, as discussed above.

In a third aspect, remediation is achieved by treating contaminated water with any filtrate medium that is able to remove and/or reduce contaminants from contaminated water. Examples of such filtrate medium include, but are not limited to, any one of sake kasu (the lees left over from sake production), rice husks, coconut fibre, wood chips, cider residues, seaweed residues, crushed seashells, and nut shells.

In the methods according to any aspect of the present invention, the filtrate may be used to treat water in-situ, for example in 'treatment walls, permeable reactive barriers (PRB), or within a borehole using a borehole deployable delivery system.

Alternatively, the filtrate may be used to treat water ex-situ, for example in bioreactors, fluidised bed reactors or sediment tanks. The water' may be treated passively, for example by initiating and/or augmenting natural and sustainable decontamination and attenuation mechanisms. For example, filtrate may be placed into the ground for groundwater to pass through, e.g. by drilling a borehole and dropping a borehole deployable delivery system, such as a canister or chain of linked canisters containing filtrate, down the borehole. Alternatively, a trench may be dug into which the filtrate is placed. Water may alternatively be treated actively, for example by capturing or funnelling groundwater to be treated into a treatment zone containing the filtrate. The filtrate may be used alone or bulked with non-active materials such as sand or woodchips. For example, in a trench or a borehole deployable delivery system the filtrate may be sandwiched between layers of sand, woodchips or other non-active material.

The apparatus according to any aspect of the invention comprises at least a container containing the filtrate material, and a module configured to allow water to contact the filtrate material on passing though the container. In any aspect of the invention, the container may comprise an elongate canister, and may be made from a material which is substantially inert and non-corroding in the intended environment of use, such as stainless steel.

The container may comprise a mesh, the mesh size being sufficiently small, for example from 2 to 4mm, so as to substantially prevent egress of the filtrate from the container whilst allowing groundwater to pass through the mesh and the filtrate within the container.

The apparatus may comprise a plurality of containers linked together in a chain. The apparatus may comprise two or more filters linked together in series for increased retention time (i.e. multiple passes). The apparatus may comprise two or more filters linked together in parallel for increased flowrate.

The apparatus may be for use down a borehole, i.e. it may be borehole deployable.

The methods and apparatuses according to any aspect of the invention preferably require / are suitable for achieving zero energy input in operation. The filtrate material is environmentally friendly - spent filtrate material can be used as a fuel to produce heat as it has a very high calorific value (dependent on the nature of the contaminant and possible treatment of exhaust gasses). Alternatively, where spent filtrate material is not burnt as fuel, the volume of the spent filtrate material for disposal can be greatly reduced by simply decomposing it under atmospheric conditions.

In many cases, the removed contaminants are completely broken down by the methods and apparatuses according to any aspect of the invention, with only inert by-products produced.

The contaminants in the spent filtrate can be recovered by simply composting the spent filtrate or, in some cases, by blending the filtrate into manufacturing processes for new materials. This is particularly important for the filtration of contaminants that represent a finite resource, for example phosphates. This is also important where the filtered contaminant is dangerous, harmful to the environment or difficult to dispose of, because composting vastly reduces the volume of contaminated material.

The methods and apparatus of the invention operates like a fluidised bed reactor, and therefore has a negligible pressure drop across the filter when in operation. This means that it can be gravity fed or fed by low-pressure systems. Thus, the methods and apparatus of the invention is an order of magnitude more efficient and cost effective in operation than alternative filtration methods such as microfiltration, ultrafiltration and nanofiltration.

Thus, the methods and apparatuses according to any aspect of the invention, offer a sustainable, long-life and cost-effective method of significantly reducing/ removing contaminants from any contaminated water sources.

Further details of each aspect of the invention are described below in more detail:

First Aspect

In a first aspect, the present invention provides a method of remediating contaminated water, the method comprising treating the water with draff, said draff comprising a solid by product of grain alcohol manufacture, and oxidising the draff treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

In one embodiment, the draff comprises a solid by-product of whisky manufacture.

In the method of the invention, the method may further comprise passing the water through a strainer filter to remove or reduce total suspended solids (TSS) particles greater than 40pm in size, before treating the water with draff.

In one embodiment, the method may further comprise passing the water through a hydrocyclonic separation unit and then a balance tank to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff.

In one aspect, the method may also comprise passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the balance tank and before treating the water with the draff. In one aspect, the bag or cartridge filtration may be pressurised by a pump.

In another embodiment, the method may further comprise passing the water through a

hydrocyclonic separation unit to remove TSS particles greater than 25-5pm in size and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, after passing the water through the strainer filter and before treating the water with the draff, and passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the draff.

In one aspect, ultrasonic waves may be applied to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. In one aspect, the bag or cartridge filtration may be pressurised by a pump.

In another aspect, the water may also be treated with ozone combined with UV, after passing the water through the hydrocyclonic separation unit and before passing the water into the

chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

In a further embodiment, the method may further comprise passing the water through a three phase centrifuge to remove or reduce free oil and/or grease and then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff, and passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the draff, and treating the water with ozone combined with UV, after passing the water through the three phase centrifuge and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

In one aspect, ultrasonic waves may be applied to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. In one aspect, the bag or cartridge filtration may be pressurised by a pump. In another aspect, the water may be treated with CIO2 after treatment with ozone combined with UV and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

In a further aspect, after the oxidation, the water may be desalinated. The water may be

desalinated by reverse osmosis, forward osmosis, distillation or crystallisation. The water may be desalinated by reverse or forward osmosis when total dissolved solids (TDS) in the water is 45,000- 50,000ppm. The water may be desalinated by distillation when total dissolved solids (TDS) in the water is 40, 000-260, OOOppm. The water may be desalinated by crystallisation when total dissolved solids (TDS) in the water is greater than 260, OOOppm.

In the method of the invention, the water may be contaminated with one or more of chlorinated hydrocarbons, dissolved and free product phase hydrocarbons, metals, BTEX, chromium, uranium including its decay products including Radium 226, Radium 228 and Lead 210, perchlorate, and RDX.

In the method of the invention, the contaminated water may comprise frac flowback and/or produced water, optionally wherein the water may be contaminated with one or more of free and dispersed oil and grease; soluble BTEX hydrocarbons; dissolved gas including hydrogen sulphate; suspended solids including proppant, sand, shale and colloidal solids; dissolved solids including salts and heavy metals; and other dissolved chemicals, scale and naturally occurring radioactive material (NORM).

In the method of the invention, the method may reduce or eliminate microbial action.

In this embodiment, the method may kill bacteria and viruses in the contaminated water, for example, through oxidation.

In the method of the invention, the method may reduce chemical oxygen demand and/or biological oxygen demand from organic and/or non-organic sources.

In the method of the invention, the draff may comprise a solid by-product of the fermentation process of maize, wheat, barley or rye, preferably barley. In the method of the invention, the method may comprise groundwater remediation through enhanced natural attenuation.

Natural attenuation describes a variety of physical, chemical, or biological processes that, under favourable conditions, act without human intervention to reduce the mass, toxicity, mobility, volume, or concentration of contaminants in soil or groundwater.

In the method of the invention, the water may be groundwater, and the method may comprise groundwater remediation through reductive dechlorination of the chlorinated hydrocarbons.

In one embodiment, the reductive dechlorination may proceed via biotic pathways and/or abiotic pathways.

In another embodiment, the reductive dechlorination may proceeds via a combination of biotic and abiotic pathways.

In the method of the invention, the water may be groundwater and may be treated in situ.

In one embodiment, the in situ treatment may comprise the use of a treatment wall, a permeable reactive barrier, or a borehole using a borehole deployable delivery system.

In the method of the invention, the water may be groundwater and may be treated ex-situ.

In one embodiment, the ex situ treatment may comprise the use of a bioreactor, a fluidised bed reactor or a sediment tank.

In the method of the invention, the water may be treated passively by initiating and/or augmenting natural decontamination and attenuation mechanisms.

In the method of the invention, the water may be treated actively by capturing and/or funnelling the water into a treatment zone.

In the method of the invention, the draff may be used alone as an active material. In the method of the invention, the draff may be combined with non-active materials.

The present invention also provides an apparatus for use in a method of the first aspect of the invention, as described above, the apparatus comprising a container containing the draff and a module configured to allow water to contact the draff on passing through the container, and an oxidising module configured to treat the draff treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof.

In the apparatus of the invention, the container may comprise an elongate canister.

In the apparatus of the invention, the container may be made from a material which is substantially inert and non-corroding in the intended environment of use.

In the apparatus of the invention, the container may be made from stainless steel or nickel alloy.

In the apparatus of the invention, the apparatus may comprise a plurality of containers linked together in a chain.

In the apparatus of the invention, the apparatus may be for deployment down a borehole.

In the apparatus of the invention, the apparatus may further comprise a strainer filter configured to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with draff.

In one embodiment, the apparatus may further comprise a hydrocyclonic separation unit and then a balance tank configured to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the draff.

In an aspect, the apparatus may further comprise a bag or cartridge filter between the balance tank and the container containing the draff, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size. In another aspect, the bag or cartridge filtration may be pressurised by a pump. In another embodiment, the apparatus may further comprise a hydrocyclonic separation unit configured to remove or reduce TSS particles greater than 25-5pm in size and then a

chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, between the strainer filter and the container containing the draff.

In one aspect, the apparatus further comprises an ultrasonic wave module configured to apply ultrasonic waves to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process.

In another aspect, the apparatus further comprises a bag or cartridge filter between the

chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the draff, configured to remove or reduce TSS particles greater than lpm- O.OOOlpm in size. In a further aspect, the bag or cartridge filtration is pressurised by a pump.

In one aspect of this embodiment, the apparatus may further comprise a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

In a further embodiment, the apparatus may further comprise a three phase centrifuge configured to remove or reduce free oil and/or grease. Emulsion breakers may be added to enhance splitting of free oil and/or grease prior to the three phase centrifuge. Then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system configured to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the draff, and the apparatus further comprises a bag or cartridge filter between the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the draff, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size, and the apparatus further comprises a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the

In one aspect, the apparatus further comprises an ultrasonic wave module configured to apply ultrasonic waves to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. In another aspect, the bag or cartridge filtration is pressurised by a pump,

In one aspect of this embodiment, the apparatus may further comprise a second treatment module configured to treat the water with CIO2 between the first treatment module and the

In a further aspect, the apparatus may comprise a desalination module after the oxidation module.

Second Aspect

In a second aspect, the present invention provides a method of remediating contaminated water, the method comprising treating the water with fresh hops and/or hops that have been used in brewing.

In the method of the invention, the method may further comprise oxidising the hop treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

In one embodiment, the method may further comprise passing the water through a strainer filter to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with the hops.

In one aspect, the method may further comprise passing the water through a hydrocyclonic separation unit and then a balance tank to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the hops. The water may be passed through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the balance tank and before treating the water with the hops. The bag or cartridge filtration may be pressurised by a pump.

In another aspect, the method may further comprise passing the water through a hydrocyclonic separation unit to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, after passing the water through the strainer filter and before treating the water with the hops, and the method further comprises passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the hops. Ultrasonic waves may be applied to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. The bag or cartridge filtration may be pressurised by a pump.

The water may be treated with ozone combined with UV, after passing the water through the hydrocyclonic separation unit and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

In a further aspect, the method may further comprise passing the water through a three phase centrifuge to remove or reduce free oil and/or grease. Emulsion breakers may be added to enhance splitting of free oil and/or grease prior to the three phase centrifuge. Then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the hops, and the method further comprises passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the hops, and wherein the water is treated with ozone combined with UV, after passing the water through the three phase centrifuge and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system. Ultrasonic waves may be applied to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. The bag or cartridge filtration may be pressurised by a pump

In addition, the water may be treated with CIO2 after treatment with ozone combined with UV and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

After the oxidation, the water may also be desalinated, optionally wherein the water may be desalinated by reverse osmosis, forward osmosis, distillation or crystallisation. The water may be desalinated by reverse or forward osmosis when total dissolved solids (TDS) in the water is 45,000- 50, OOOppm. The water may be desalinated by distillation when total dissolved solids (TDS) in the water is 40, 000-260, OOOppm. The water may be desalinated by crystallisation when total dissolved solids (TDS) in the water is greater than 260, OOOppm.

In the method of the invention, the water may be contaminated with one or more of chlorinated hydrocarbons, dissolved and free product phase hydrocarbons, metals, BTEX, chromium, uranium and it s decay products including Radium 226, Radium 228 and Lead 210, perchlorate, and RDX.

In the method of the invention, the contaminated water may be frac flowback and/or produced water remediation.

In one embodiment, the water may be contaminated with one or more of free and dispersed oil and grease; soluble BTEX hydrocarbons; dissolved gas including hydrogen sulphate; suspended solids including proppant, sand, shale and colloidal solids; dissolved solids including salts and heavy metals; and other dissolved chemicals, scale and naturally occurring radioactive material (NORM),

In the method of the invention, the method may reduce or eliminate microbial action. In this embodiment, the method may kill bacteria and viruses in the contaminated water, for example, through oxidation.

The invention also provides an apparatus for use in a method according to the method of the second aspect of the invention, as described above, the apparatus may comprise a container containing the hops and a module configured to allow water to contact the hops on passing through the container.

In the apparatus of the invention, the apparatus may further comprise an oxidising module configured to treat the hop treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof. In one embodiment, the apparatus may further comprise a strainer filter configured to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with the hops.

In one aspect, the apparatus may further comprise a hydrocyclonic separation unit and then a balance tank configured to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the hops. The apparatus further may comprise a bag or cartridge filter between the balance tank and the container containing the hops, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size. The bag or cartridge filtration may be pressurised by a pump.

In another aspect, the apparatus may further comprise a hydrocyclonic separation unit configured to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance TSS particle removal/reduction, between the strainer filter and the container containing the hops, and the apparatus further comprises a bag or cartridge filter between the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the hops, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size, optionally wherein the bag or cartridge filtration is pressurised by a pump. The apparatus may further comprise an ultrasonic wave module configured to apply ultrasonic waves to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system. The bag or cartridge filtration may be pressurised by a pump.

The apparatus may further comprise a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system.

In a further aspect, the apparatus may further comprise a three phase centrifuge configured to remove or reduce free oil and/or grease. Emulsion breakers may be added to enhance splitting of free oil and/or grease prior to the three phase centrifuge. Then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the hops, and the apparatus further comprises a bag or cartridge filter between the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the hops, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size, and the apparatus further comprises a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system. The apparatus may further comprise an ultrasonic wave module configured to apply ultrasonic waves to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. The bag or cartridge filtration may be pressurised by a pump.

In addition, the apparatus may further comprise a second treatment module configured to treat the water with CIO2 between the first treatment module and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

Further, the apparatus may also comprise a desalination module after the oxidation module.

Third Aspect

In a third aspect, the present invention provides a method of remediating contaminated water, the method comprising treating the water with any filtrate medium that is able to remove and/or reduce contaminants from contaminated water.

In one embodiment, the filtrate medium comprises sake kasu (the lees left over from sake production), rice husks, coconut fibre, wood chips, cider residues, seaweed residues, crushed seashells, or nut shells.

In one embodiment, the method may further comprise any embodiment according to the second aspect of the invention.

The invention also provides an apparatus for use in a method according to the method of the third aspect of the invention, as described above, the apparatus may comprise a container containing the filtrate medium and a module configured to allow water to contact the filtrate medium on passing through the container.

In one embodiment, the apparatus may further comprise any embodiment according to the second aspect of the invention. Water sources

In any aspect of the invention, the contaminated water may be from any contaminated source in need of remediation, for example frac flowback water and produced water from fracking processes, industrial interceptor waste, contaminated ground water, agriculturally contaminated water, animal processing plant water, distillation waste streams, ballast water, bilge water and sea-going vessel wash-down water, and effluent contaminated with heavy metals.

Contaminants

In any aspect of the invention, the methods and apparatuses may be suitable to remove or reduce any water contaminants.

The methods and apparatuses according to any aspect of the invention reduce the level

contaminants in contaminated water to a concentration such that the water can be re-used in industry and/or safely discharged into the environment, compared to the pre-treated water. For example, in the case of produced water and frac flowback water, the methods and apparatuses according to any aspect of the invention reduce the level contaminants in the frac flowback and/or produced water to a concentration such that the water can be re-used in the fracking process and/or surface discharged, compared to the pre-treated water.

The methods and apparatuses according to any aspect of the invention reduce the level of contaminants in contaminated water compared to the pre-treated water by at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, at least 99.9%. For example, the methods and apparatuses according to any aspect of the invention reduce the level of BTEX hydrocarbons in produced water compared to the pre-treated water, by at least 99.9%.

It will be understood that references to removing or reducing contaminants, or otherwise, includes substantially reducing the contaminant, for example reducing the contaminant by at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, at least 99.9%, at least 99.99%, and removing 100% of the contaminant, compared to the contaminated water. A selection of specific contaminants that may be removed or reduced by the methods and apparatuses according to any aspect of the invention are selected from Cu, Cd, Zn, Cr(lll), Cr(VI), Pb, As, Ni, Hg, Sn, U, Co, 2,4 D, 2,4 DB, MCPB, MCPA, RDX, TNT, diesel, petrol, benzene, toluene, ethyl benzene, Xylene, Napthalene, PCE, TCE and DCE

The methods and apparatuses according to any aspect of the invention preferably remove or reduce water contaminants including, but not limited to, chlorinated hydrocarbons, dissolved and free product phase hydrocarbons, metals, BTEX, chromium, uranium, perchlorate, and RDX.

Preferably, the methods of the invention remove or reduce chlorinated hydrocarbons.

The methods and apparatuses according to any aspect of the invention preferably remove or reduce free and dispersed oil and grease, soluble BTEX hydrocarbons, dissolved gas including H2S, suspended solids including proppant, sand, shale and colloidal solids, dissolved solids including salts and heavy metals, other dissolved chemicals, scale and naturally occurring radioactive material (NORM). Preferably, the methods of the invention remove or reduce one or more of the contaminants selected from bromide, hydrogen sulphide, Uranium decay products, for example Radium 226, Radium 228 and/or Lead 210, and heavy metals.

Examples of produced water chemistry from different fracking plays are shown below. The methods of any aspect of the invention preferably remove or reduce one or more of these water

contaminants compared to the pre-treated water:

The methods and apparatuses according to any aspect of the invention also preferably reduce chemical oxygen demand (COD) and biological oxygen demand (BOD) in contaminated water, from both organic and in-organic sources, especially when combined with oxidation.

COD is a measurement of the oxygen required to oxidize soluble and particulate organic matter in water, i.e. is a measure of the amount of organics in water. It can be used to quantify the amount of oxidisable contaminants in water. BOD is a measurement of the amount of dissolved oxygen (DO) that is used by aerobic microorganisms when decomposing organic matter in water. It can be used to quantify the amount of organic contaminants in water.

The following table shows the results of COD and BOD contaminant concentration before (Initial cone.) and after (post DRAM) treatment according to the methods and apparatus of the first aspect of the invention:

The methods and apparatuses according to any aspect of the invention also preferably remove or reduce bacteria and viruses in contaminated water, when combined with oxidation, for example by ozone (O3) and/or chlorine dioxide (CIO2).

Organic substances in bacterial cells react with CI02 including amino acids and the RNA in the cell. The production of proteins is prevented. Chlorine dioxide affects the cell membrane by changing membrane proteins and fats and by prevention of inhalation. 03 interferes with the metabolism of bacterium-cells through inhibiting and blocking the operation of the enzymatic control system. 03 breaks through the cell membrane, and this leads to the destruction of the bacteria.

When bacteria are eliminated, the cell wall is penetrated by CI02. Viruses are eliminated in a different way; CI02 reacts with peptone, a water-soluble substance that originates from hydrolysis of proteins to amino acids. CI02 kills viruses by prevention of protein formation. Chlorine dioxide is more effective against viruses than chlorine or ozone. Ozone destroys viruses by diffusing through the protein coat into the nucleic acid core, resulting in damage of the viral RNA. At higher concentrations, ozone destroys the capsid, or exterior protein shell by oxidation so DNA

(deoxyribonucleic acid), or RNA (ribonucleic acid) structures of the microorganism are affected.

Chlorine dioxide is one of a number of disinfectants that are effective against Giardia Lambia and Cryptosporidium parasites, which are found in drinking water and induce diseases called 'giardiasis' and 'cryptosporidiosis'. The best protection against protozoan parasites such as these is disinfection by a combination of ozone and chlorine dioxide.

Exemplary Methods and Apparatus of the First, Second and Third Aspects

The methods and apparatus according to the aspects of the invention are described in more detail below, in relation to Figures 1-9.

Figure 1 is according to any aspect of the present invention, and demonstrates a method of remediating contaminated water. The method comprises treating the water in a DRAM container 10 comprising a filtrate 12 of either draff 14, said draff 14 comprising a solid by product of grain alcohol manufacture, or fresh hops and/or hops that have been used in brewing, and oxidising the draff/hop treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

Oxidation takes place in an oxidiser unit 16.

Oxidising post treatment kills any residual bacteria.

This method is particularly suitable for the primary and possibly secondary treatment of

produced / flowback water with for example the following characteristics:

Low free / emulsified oil content

Low to negligible dissolved H2S

Low to medium BTEX hydrocarbon content

Low to negligible TSS

Low to medium TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination Figure 2 is according to any aspect of the present invention, and demonstrates the method shown in Figure 1, further comprising passing the water through a strainer filter 18 to remove total suspended solids (TSS) particles greater than 40pm in size, before treating the water with draff/hops.

This method is particularly suitable for the primary and possibly secondary treatment of produced / flowback water with for example the following characteristics:

Low free / emulsified oil content

Low to negligible dissolved H2S

Low to medium BTEX hydrocarbon content

Low to high TSS; particle sizes > ~ 40 m

Low to medium TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination

Figure 3 is according to any aspect of the present invention, and demonstrates the method shown in Figure 2, further comprising passing the water through a hydrocyclonic separation unit 20 and then a balance tank 22 to remove TSS particles greater than 25-5pm in size, after passing the water through the strainer filter 18 and before treating the water with the draff/hops. Optionally, the water is passed through a bag or cartridge filter 24 to remove TSS particles greater than lpm- O.OOOlpm in size after passing the water through the balance tank 22 and before treating the water with the draff. Optionally, the bag or cartridge filtration is pressurised by a pump 25. The hydrocyclonic separation unit 20 may discharge solids/sludge 26 into a suitable container 28.

Enhancement of TSS particle removal/reduction is possible with microfiltration, ultrafiltration and nanofiltration, removing particles as small as 0.05pm, 0.0025pm and O.OOlpm respectively.

Low free / emulsified oil content

Low to negligible dissolved H2S

Low to medium BTEX hydrocarbon content

Low to high TSS; particle sizes > ~ 5 m

Low to medium TDS / salinity High bacteria count

Low to high heavy metal / NORM contamination

Figure 4 is according to any of the present invention, and demonstrates the method shown in Figure 2, further comprising passing the water through a hydrocyclonic separation 20 unit to remove TSS particles greater than 25-5pm in size and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30 to further enhance TSS particle removal, after passing the water through the strainer filter 18 and before treating the water with the draff/hops. Optionally, ultrasonic waves 32 are applied to the water in the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process. The method further comprises passing the water through a bag or cartridge filter to remove TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the draff. Optionally, the bag or cartridge filtration 24 is pressurised by a pump.

The combination of a hydrocyclonic separation unit 20, chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30, and optionally ultrasonic waves, can remove even colloidal particles.

Low to medium free / emulsified oil content

Low to negligible dissolved H2S

Low to medium BTEX hydrocarbon content

Low to high TSS; particle sizes down to colloidal particles

Low to medium TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination

Figure 5 is according to any aspect of the present invention, and demonstrates the method shown in Figure 4, wherein the water is treated with ozone combined with UV, after passing the water through the hydrocyclonic separation unit 20 and before passing the water into the

chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30. Ozone dosing combined with UV light treatment will oxidise and remove/reduce hydrogen sulphide. It can also enhance removal of bacteria, certain metals such as iron and manganese (reducing TDS) and reduce total organic carbon (TOC).

The ozone dosing is achieved with an in-line UV / ozone injection device 34.

Ozone/UV dosing can also enhance removal of BTEX hydrocarbons, and heavy metals.

produced / flowback water with for example the following characteristics:

Low to medium free / emulsified oil content

Low to high dissolved H2S

Medium to high BTEX hydrocarbon content

Low to high TSS; particle sizes down to colloidal particles

Low to medium TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination

Figure 6 is according the any aspect of the present invention, and demonstrates the method shown in Figure 2, further comprising passing the water through a three phase centrifuge 120 to remove free oil and/or grease and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30 to remove TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff/hops. Optionally, ultrasonic waves 32 are applied to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30 to enhance the coagulation, flocculation or separation process. The method further comprises passing the water through a bag or cartridge filter 24 to remove TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30 and before treating the water with the draff 14. Optionally, the bag or cartridge filtration is pressurised by a pump. The method further comprises treating the water with ozone combined with UV, after passing the water through the three phase centrifuge and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system. The addition of a three-phase centrifuge 120 removes far higher levels of free oil where applicable.

It can also separate the majority of suspended solids present and discharge the heavy liquid phase (water) for further treatment.

Medium to high free / emulsified oil content

Low to high dissolved H2S

Medium to high BTEX hydrocarbon content

Low to high TSS; particle sizes down to colloidal particles

Low to medium TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination

Figure 7 is according to any aspect of the present invention, and demonstrates the method shown in Figure 6, wherein the water is treated with CIO2 38 after treatment with ozone combined with UV and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system 30.

The addition of in-line CIO2 injection 38 further enhances removal of BTEX hydrocarbons. It also removes any carcinogenic chemicals, for example, produced via the breakdown of any bromide contaminants in the water into bromate, by the ozone/UV dosing.

This two-stage oxidation process (ozone/UV dosing followed by in-line CIO2 injection), may be applied as part of any of the methods of the invention, to remove bromide where required.

Medium to high free / emulsified oil content

Low to high dissolved H2S

High BTEX hydrocarbon content

Bromide contamination

Low to high TSS; particle sizes down to colloidal particles Low to medium TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination

Figure 8 is according to the any aspect of the present invention, and demonstrates the method shown in Figure 7, wherein, after the oxidation, the water is desalinated, optionally wherein the water is desalinated by reverse osmosis, forward osmosis, distillation or crystallisation 40 by a distillation unit 42.

The desalination process reduces TDS levels in the contaminated water, and can be applied at as part of any of the methods if the invention, where TDS levels of the treated water remains too high for environmental discharge.

A summary of each of the desalination processes is as follows:

Reverse / Forward osmosis (RO/FO); TDS< 40,000 ppm;

Requires relatively high energy costs in comparison to standard filtration

Least expensive TDS removal / desalination technology

Requires moderate operator skill level

If TDS levels are higher or SS / colloidal solids are present membranes will

quickly block and require immediate and expensive remedial action

Requires water softening

Distillation / evaporation; TDS 40,000 ppm < 260,000 ppm

Very high energy and CAPEX costs

High operator skill

Crystallization; TDS > 260,000 ppm

Very high energy and CAPEX costs

High operator skill

Can be cost effective with sale of commodity chemical by-products

This method is particularly suitable for the primary and secondary treatment of produced / flowback water with for example the following characteristics:

Medium to high free / emulsified oil content

Low to high dissolved H2S High BTEX hydrocarbon content

Bromide contamination

Low to high TSS; particle sizes down to colloidal particles

High TDS / salinity

High bacteria count

Low to high heavy metal / NORM contamination

Figure 9 is according to the second aspect of the present invention, and demonstrates a method of remediating contaminated water, the method comprising treating the water with fresh hops and/or hops 112 that have been used in brewing.

Low free / emulsified oil content

Low to negligible dissolved H2S

Low to medium BTEX hydrocarbon content

Low to negligible TSS

Low to medium TDS / salinity

Low to negligible bacteria count

Low to medium heavy metal / NORM contamination

Figure 10 shows various configurations of the main filter apparatus 10 of any aspect of the invention. Inlet manifolds 200 and outlet manifolds 202 may be provided to control and direct fluid flow.

In relation to the above examples, the following levels apply:

Free / emulsified oil content

Low 0 to 300 ppm (mg/I)

Medium 300 ppm to 1,000 ppm (mg/I)

High 1,000 ppm (mg/I) or more

Dissolved H2S Low 0 to 20 ppm (mg/I)

Medium 21 to 99 ppm (mg/I)

High - 100 to 1,000 ppm (mg/I)

BTEX hydrocarbon content

Benzene up to ~ 400 ppb (pg/L)

Toluene up to ~ 3,500 ppb (pg/L)

Ethylbenzene - up to ~ 2,000 ppb (pg/L) Xylenes - up to ~ 1,500 ppb (pg/L)

Bromide contamination

Up to l g/L

TSS

Low - <50ppm

Medium 50-200ppm

High - >200ppm

Colloidal particles - 1 to 2.5 pm

TDS / salinity

Low - <15,000ppm

Medium 15,000 to 40, OOOppm

High - >40,000 to ~300, OOOppm

Colloidal particles - <1 pm

Bacteria count

Low - <100ppm

High - >100ppm

Heavy metal / NORM contamination

Low - <10 Bq/L

Medium/High - >10 Bq/L The following table shows maximum sorption rates achieved per kg of filtrate material comprising draff, against various contaminants in groundwater and wastewater effluents. Note - the filter apparatus as a whole contains about 400kg of filtrate material, and lg/kg = lOOOppm:

It will be understood that the illustrated embodiment described herein shows an application of the invention in one form only for the purposes of illustration. In practice, the invention may be applied to many different configurations the detailed embodiments being straightforward to those skilled in the art to implement.

It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine study, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims. All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. The use of the word "a" or "an" when used in conjunction with the term "comprising" in the claims and/or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one." The use of the term "or" in the claims is used to mean "and/or" unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and "and/or." Throughout this application, the term "about" is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.

As used in this specification and claim(s), the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps

The term "or combinations thereof" as used herein refers to all permutations and combinations of the listed items preceding the term. For example, "A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. Any part of this disclosure may be read in combination with any other part of the disclosure, unless otherwise apparent from the context.

All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Statements of the Invention

51. A method of remediating contaminated water, the method comprising treating the water with draff, said draff comprising a solid by product of grain alcohol manufacture, for example whisky manufacture, and oxidising the draff treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

52. The method of SI, further comprising passing the water through a strainer filter to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with draff.

53. The method of S2, further comprising passing the water through a hydrocyclonic separation unit and then a balance tank to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff,

optionally wherein the water is passed through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the balance tank and before treating the water with the draff,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

54. The method of S2, further comprising passing the water through a hydrocyclonic separation unit to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, after passing the water through the strainer filter and before treating the water with the draff,

optionally wherein ultrasonic waves are applied to the water in the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process,

and the method further comprises passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the draff,

optionally wherein the bag or cartridge filtration is pressurised by a pump. 55. The method of S4, wherein the water is treated with ozone combined with UV, after passing the water through the hydrocyclonic separation unit and before passing the water into the

56. The method of S2, further comprising passing the water through a three phase centrifuge to remove or reduce free oil and/or grease and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff,

optionally wherein the bag or cartridge filtration is pressurised by a pump,

and the method further comprises treating the water with ozone combined with UV, after passing the water through the three phase centrifuge and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

57. The method of S6, wherein the water is treated with CIO2 after treatment with ozone combined with UV and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

58. The method of S7, wherein, after the oxidation, the water is desalinated,

optionally wherein the water is desalinated by reverse osmosis, forward osmosis, distillation or crystallisation.

59. The method of S8, wherein the water is desalinated by reverse or forward osmosis when total dissolved solids (TDS) in the water is 45, 000-50, OOOppm,

or the water is desalinated by distillation when total dissolved solids (TDS) in the water is 40, 000-260, OOOppm, or the water is desalinated by crystallisation when total dissolved solids (TDS) in the water is greater than 260,000ppm.

S10. The method according to Sl-9 wherein the water is contaminated with one or more of chlorinated hydrocarbons, dissolved and free product phase hydrocarbons, metals, BTEX, chromium, uranium including its decay products including Radium 226, Radium 228 and Iron 210, perchlorate, and RDX.

Sll The method according to Sl-10 wherein the contaminated water comprises frac flowback and/or produced water, optionally wherein the water is contaminated with one or more of free and dispersed oil and grease; soluble BTEX hydrocarbons; dissolved gas including hydrogen sulphate; suspended solids including proppant, sand, shale and colloidal solids; dissolved solids including salts and heavy metals; and other dissolved chemicals, scale and naturally occurring radioactive material (NORM),

512. The method according to Sl-11 wherein the method reduces or eliminates microbial action.

513. The method according to Sl-12 wherein the method reduces chemical oxygen demand and/or biological oxygen demand from organic and/or non-organic sources.

514. The method according to Sl-13 wherein the draff comprises a solid by-product of the fermentation process of maize, wheat, barley or rye.

515. The method according to any preceding statement wherein the draff comprises a solid waste product of the fermentation process of barley.

516. The method according to any preceding statement which comprises groundwater remediation through enhanced natural attenuation.

517. The method according to any preceding statement wherein the water is groundwater and the method comprises groundwater remediation through reductive dechlorination of the chlorinated hydrocarbons.

518. The method according to S17 wherein the reductive dechlorination proceeds via biotic pathways and/or abiotic pathways.

519. The method according to S18 wherein the reductive dechlorination proceeds via a combination of biotic and abiotic pathways.

520. The method according to any preceding statement in which the water is groundwater which is treated in situ.

521. The method according to S20 wherein the in situ treatment comprises the use of a treatment wall, a permeable reactive barrier, or a borehole using a borehole deployable delivery system.

522. The method according to any one of SI to 21 in which the water is groundwater which is treated ex-situ.

523. The method according to S22 wherein the ex situ treatment comprises the use of a bioreactor, a fluidised bed reactor or a sediment tank.

524. The method according to any preceding statement wherein the water is treated passively by initiating and/or augmenting natural decontamination and attenuation mechanisms.

525. The method according to any one of SI to 23 wherein the water is treated actively by capturing and/or funnelling the water into a treatment zone.

526. The method according to any preceding statement wherein the draff is used alone as an active material.

527. The method according to any preceding statement wherein the draff is bulked with non-active materials.

528. Apparatus for use in a method according to SI, the apparatus comprising a container containing the draff and a module configured to allow water to contact the draff on passing through the container, and an oxidising module configured to treat the draff treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof. 529. Apparatus according to S28 wherein the container comprises an elongate canister.

530. Apparatus according to S28 or 29 wherein the container is made from a material which is substantially inert and non-corroding in the intended environment of use.

531. Apparatus according to any one of S28 to 30 wherein the container is made from stainless steel.

532. Apparatus according, to any one of S28 to 31 which comprises a plurality of containers linked together in a chain.

533. Apparatus according to any one of S28 to 32 for deployment down a borehole.

534. The apparatus of S28, further comprising a strainer filter configured to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with draff.

535. The apparatus of S34, further comprising a hydrocyclonic separation unit and then a balance tank configured to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the draff,

optionally wherein the apparatus further comprises a bag or cartridge filter between the balance tank and the container containing the draff, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

536. The apparatus of S34, further comprising a hydrocyclonic separation unit configured to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, between the strainer filter and the container containing the draff,

optionally wherein the apparatus further comprises an ultrasonic wave module configured to apply ultrasonic waves to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process,

and the apparatus further comprises a bag or cartridge filter between the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the draff, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

537. The apparatus of S36, further comprising a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

538. The apparatus of S34, further comprising a three phase centrifuge configured to remove or reduce free oil and/or grease, and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system configured to remove or reduce TSS particles greater than 25- 5pm in size, between the strainer filter and the container containing the draff,

optionally wherein the bag or cartridge filtration is pressurised by a pump,

and the apparatus further comprises a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system.

539. The apparatus of S38, further comprising a second treatment module configured to treat the water with CIO2 between the first treatment module and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

540. The apparatus of S39, further comprising a desalination module after the oxidation module.

S41 A method of remediating contaminated water, the method comprising treating the water with fresh hops and/or hops that have been used in brewing 542. The method of S41, further comprising oxidising the hop treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

543. The method of S42, further comprising passing the water through a strainer filter to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with the hops.

544. The method of S43, further comprising passing the water through a hydrocyclonic separation unit and then a balance tank to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the hops,

optionally wherein the water is passed through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the balance tank and before treating the water with the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

545. The method of S43, further comprising passing the water through a hydrocyclonic separation unit to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, after passing the water through the strainer filter and before treating the water with the hops,

optionally wherein ultrasonic waves are applied to the water in the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process ,

and the method further comprises passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

546. The method of S45, wherein the water is treated with ozone combined with UV, after passing the water through the hydrocyclonic separation unit and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system. 547. The method of S43, further comprising passing the water through a three phase centrifuge to remove or reduce free oil and/or grease, and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump

and wherein the water is treated with ozone combined with UV, after passing the water through the three phase centrifuge and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

548. The method of S47, wherein the water is treated with CIO2 after treatment with ozone combined with UV and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

549. The method of S48, wherein, after the oxidation, the water is desalinated,

550. The method of S49, wherein the water is desalinated by reverse or forward osmosis when total dissolved solids (TDS) in the water is 45000-5000ppm, or the water is desalinated by distillation or crystallisation when total dissolved solids (TDS) in the water is greater than 5000ppm.

551. The method according to S41-50 wherein the water is contaminated with one or more of chlorinated hydrocarbons, dissolved and free product phase hydrocarbons, metals, BTEX, chromium, uranium and it s decay products including Radium 226, Radium 228 and Iron 210, perchlorate, and RDX. 552. The method according to S41-51 wherein the contaminated water is frac flowback and/or produced water remediation, optionally wherein the water is contaminated with one or more of free and dispersed oil and grease; soluble BTEX hydrocarbons; dissolved gas including hydrogen sulphate; suspended solids including proppant, sand, shale and colloidal solids; dissolved solids including salts and heavy metals; and other dissolved chemicals, scale and naturally occurring radioactive material (NORM),

553. The method according to S41-52 wherein the method reduces or eliminates microbial action.

554. The method according to S41-53 wherein the method reduces chemical oxygen demand and/or biological oxygen demand from organic and non-organic sources.

555. Apparatus for use in a method according to S41, the apparatus comprising a container containing the hops and a module configured to allow water to contact the hops on passing through the container.

S56 The apparatus of S55, further comprising an oxidising module configured to treat the hop treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof.

557. The apparatus of S56, further comprising a strainer filter configured to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with the hops.

558. The apparatus of S57, further comprising a hydrocyclonic separation unit and then a balance tank configured to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the hops,

optionally wherein the apparatus further comprises a bag or cartridge filter between the balance tank and the container containing the hops, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

559. The apparatus of S57, further comprising a hydrocyclonic separation unit configured to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance TSS particle

removal/reduction, between the strainer filter and the container containing the hops, optionally wherein the apparatus further comprises an ultrasonic wave module configured to apply ultrasonic waves to the water in the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system,

and the apparatus further comprises a bag or cartridge filter between the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the hops, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

560. The apparatus of S59, further comprising a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

561. The apparatus of S57, further comprising a three phase centrifuge configured to remove or reduce free oil and/or grease, and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump,

and the apparatus further comprises a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system

562. The apparatus of S61, further comprising a second treatment module configured to treat the water with CIO2 between the first treatment module and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system. S63. The apparatus of S62, further comprising a desalination module after the oxidation module.

Claims

1. A method of remediating contaminated water, the method comprising treating the water with draff, said draff comprising a solid by product of grain alcohol manufacture, for example whisky manufacture, and oxidising the draff treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

2. A method of remediating contaminated water, the method comprising treating the water with fresh hops and/or hops that have been used in brewing.

3. The method of claim 1, further comprising oxidising the hop treated water with ozone, CIO2 or ultraviolet light (UV) or a combination thereof.

4. The method of claim 1 or 3, further comprising passing the water through a strainer filter to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with the draff or the hops.

5. The method of claim 4, further comprising passing the water through a hydrocyclonic separation unit and then a balance tank to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff or the hops,

optionally wherein the water is passed through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the balance tank and before treating the water with the draff or hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

6. The method of claim 4, further comprising passing the water through a hydrocyclonic separation unit to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, after passing the water through the strainer filter and before treating the water with the draff or the hops,

optionally wherein ultrasonic waves are applied to the water in the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to enhance the coagulation, flocculation or separation process, and the method further comprises passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the draff or the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

7. The method of claim 6, wherein the water is treated with ozone combined with UV, after passing the water through the hydrocyclonic separation unit and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

8. The method of claim 4, further comprising passing the water through a three phase centrifuge to remove or reduce free oil and/or grease and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system to remove or reduce TSS particles greater than 25-5pm in size, after passing the water through the strainer filter and before treating the water with the draff or the hops,

and the method further comprises passing the water through a bag or cartridge filter to remove or reduce TSS particles greater than lpm-O.OOOlpm in size after passing the water through the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system and before treating the water with the draff or the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump,

9. The method of claim 8, wherein the water is treated with CIO2 after treatment with ozone combined with UV and before passing the water into the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

10. The method of claim 9, wherein, after the oxidation, the water is desalinated,

11. The method of claim 10, wherein the water is desalinated by reverse or forward osmosis when total dissolved solids (TDS) in the water is 45, 000-50, OOOppm,

or the water is desalinated by distillation when total dissolved solids (TDS) in the water is 40, 000-260, OOOppm,

or the water is desalinated by crystallisation when total dissolved solids (TDS) in the water is greater than 260, OOOppm.

12. The method according to claims 1-11 wherein the water is contaminated with one or more of chlorinated hydrocarbons, dissolved and free product phase hydrocarbons, metals, BTEX, chromium, uranium including its decay products including Radium 226, Radium 228 and Iron 210, perchlorate, and RDX.

13 The method according to claims 1-12 wherein the contaminated water comprises frac flowback and/or produced water, optionally wherein the water is contaminated with one or more of free and dispersed oil and grease; soluble BTEX hydrocarbons; dissolved gas including hydrogen sulphate; suspended solids including proppant, sand, shale and colloidal solids; dissolved solids including salts and heavy metals; and other dissolved chemicals, scale and naturally occurring radioactive material (NORM),

14. The method according to claims 1-13 wherein the method reduces or eliminates microbial action.

15. The method according to claim 1-14 wherein the method reduces chemical oxygen demand and/or biological oxygen demand from organic and/or non-organic sources.

16. Apparatus for use in a method according to claim 1, the apparatus comprising a container containing the draff and a module configured to allow water to contact the draff on passing through the container, and an oxidising module configured to treat the draff treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof.

17. Apparatus for use in a method according to claim 2, the apparatus comprising a container containing the hops and a module configured to allow water to contact the hops on passing through the container.

18 The apparatus of claim 17, further comprising an oxidising module configured to treat the hop treated water with an oxidiser, wherein the oxidiser is ozone, CIO2 or UV or a combination thereof.

19. The apparatus of claim 16 or 18, further comprising a strainer filter configured to remove or reduce total suspended solids (TSS) particles greater than 40pm in size before treating the water with the draff or the hops.

20. The apparatus of claim 19, further comprising a hydrocyclonic separation unit and then a balance tank configured to remove or reduce TSS particles greater than 25-5pm in size, between the strainer filter and the container containing the draff or the hops,

optionally wherein the apparatus further comprises a bag or cartridge filter between the balance tank and the container containing the draff or the hops, configured to remove or reduce TSS particles greater than lpm-O.OOOlpm in size,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

21. The apparatus of claim 19, further comprising a hydrocyclonic separation unit configured to remove or reduce TSS particles greater than 25-5pm in size and then a chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system to further enhance TSS particle removal/reduction, between the strainer filter and the container containing the draff or the hops,

and the apparatus further comprises a bag or cartridge filter between the chemical/electro coagulation, flocculation, dissolved air flotation (DAF) or separation system and the container containing the draff or the hops, configured to remove or reduce TSS particles greater than lpm- O.OOOlpm in size,

optionally wherein the bag or cartridge filtration is pressurised by a pump.

22. The apparatus of claim 21, further comprising a first treatment module configured to treat the water with ozone combined with UV, between the hydrocyclonic separation unit and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

23. The apparatus of claim 19, further comprising a three phase centrifuge configured to remove or reduce free oil and/or grease, and then a chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system configured to remove or reduce TSS particles greater than 25- 5pm in size, between the strainer filter and the container containing the draff or the hops,

optionally wherein the bag or cartridge filtration is pressurised by a pump,

24. The apparatus of claim 23, further comprising a second treatment module configured to treat the water with CIO2 between the first treatment module and the chemical/electro-coagulation, flocculation, dissolved air flotation (DAF) or separation system.

25. The apparatus of claim 24, further comprising a desalination module after the oxidation module.