The present invention relates to sewage and wastewater treatment and in particular to an improved method and apparatus for dewatering sewage sludge.
Most existing dewatering systems (i.e. separating water from solid waste) are designed for large scale and high throughput wastewater treatment. Conventional systems are generally available as standalone units that can be integrated into industrial site processes. Many of these units have been in operation for decades and are purchased as off-the-shelf equipment. Generic dewatering equipment such as centrifuge, belt and plate filters, vacuum filtration are available for large scale applications, while thermal systems for drying sludge have been known in the prior art for a long time.
Attempts have been made to scale down some of the existing units for use on smaller industrial sites. However, in most cases there is always a resulting decrease in processing energy efficiency. Large scale systems typically use between 6 to 98 kWh per tonne of sludge for dewatering, while it is found that the energy consumption per tonne increases as the system is scaled down. Recently, especially on the small to medium scale, some conventional dewatering systems have been adapted to use electrokinetic (EK) processes, which utilise the polar nature of water and particulate molecules to facilitate separation by inducing an electric field across the sewage sludge.
However, although dewatering systems based on EK processes have produced beneficial effects, the throughput and energy efficiency have not been particularly satisfactory. Hence, conventional EK systems do not have sufficient dewatering rates to enable them to be functional units for industrial applications.
It is therefore an object of the present invention to mitigate or overcome the above drawbacks and problems in the art and to provide a reliable and energy efficient method and apparatus for dewatering sewage sludge.
According to an aspect of the present invention there is provided a dewatering method for treating sewage sludge, the method comprising:
The provision of a dewatering method comprising the application of ultrafine bubbles to a sludge together with the application of acoustic energy to agitate at least a portion of the ultrafine bubbles is found to be particularly advantageous as high dewatering rates can be achieved at relatively low energy input as compared to conventional sludge dewatering systems.
The present invention is intended to dewater sewage sludge by separating solid waste in particulate or floc (small, loosely aggregated mass of flocculent material suspended in or precipitated from a liquid) from the retaining water which includes free water, interstitial water held by physical and chemical forces within colloidal and particulate suspensions together with water retained within the internal cell walls. The method can be applied to all sludges that relate to and contain organic matter such as, but not limited to, sewage sludge treatment (e.g. raw, primary, SAS etc.), biomass slurries, COD/BOD (Chemical Oxygen Demand/Biochemical Oxygen Demand) wastewaters, digestate from anaerobic digestion plants, raw and prepared food processing and manufacturing waste waters, paper and pulp processing waste water, tanning, mineral, mining industrial waste waters, etc.
The present method utilises a number of techniques to perform the dewatering process.
As a pre-treatment step, the sewage sludge may be passed through a maceration unit or macerator to ensure that all relatively large extraneous materials or solids are broken up or crushed via comminution to a size at least <12 mm, and most preferably, <2 mm.
In an exemplary embodiment, the sludge is collected in a holding tank. The sludge is then subjected to the application of ultrafine bubbles (UFB), which are injected into, or otherwise permeated through, the volume of the sludge.
By “ultrafine bubbles” or “UFB”, we mean any bubbles that have a bubble diameter of less than about 50 μm. UFB have certain characteristic properties. For example, unlike bubbles with diameters>50 microns, UFB are not strictly limited by Stokes' law and thus generally do not rise to the surface of the sludge.
The ultrafine bubbles preferably have a diameter of less than about 40 μm, for example, less than 30 μm, or less than 20 μm. Particularly preferably, the ultrafine bubbles have a diameter of less than about 10 μm. It may alternatively be said that the ultrafine bubbles have a diameter of up to about 50 μm. Preferably the ultrafine bubbles have a diameter of up to about 40 μm, for example up to about 30 μm, or up to about 20 μm. Particularly preferably the ultrafine bubbles have a diameter of up to about 10 μm.
When the generated bubbles have a bubble diameter of less than 10 μm, the UFBs may reduce in size. It is hypothesised that this is because the internal gas phase pressure of the bubble is positive relative to the pressure of the external liquid, causing dissolution of gas in the liquid phase. Because of this difference in phases, the UFBs are gravitationally stable and decrease in size to a nanometre scale. This enables a high concentration of UFBs to be maintained in the medium of the sludge, without loss of UFBs.
In some embodiments, the UFBs reduce in size to have a diameter of less than about 400 nm. In particularly preferred embodiments, the UFBs reduce in size to have a diameter of less than about 300 nm.
The reduction in diameter of the bubbles affects the volume of the bubbles in that the surface area (A) of a volume of bubbles increases proportionally to the reduction in bubbles diameter (D). Ultrafine bubbles therefore have a higher surface area to volume ratio compared to larger bubbles.
Various methodologies and proprietary equipment are available to generate UFB in liquids and sludges. Some utilise mechanical liquid shearing using turbo mixers or other mechanical motive devices, while others generate UFB using compressed air injected through specially designed ceramics or metal grills.
The size of the UFBs and the size distribution may be varied depending on the method used to generate the UFBs. For example, where the UFBs are generated using compressed air injected through specially designed ceramics, the size of the UFBs and the size distribution may be varied by varying the pore size of the ceramic nozzle from which the bubble is generated.
If UFBs are being generated in clean water, it is possible to get up to 90% of the inlet gas volume converted to UFBs. However, in the present invention, UFBs are being generated in sewage sludge may therefore have a reduced conversion. The % conversion depends upon the % total solids. In some embodiments, the conversion is between about 20% and about 50%.
Any conventional ultrafine bubble generator may be used in conjunction with the present invention, without sacrificing any of its benefits or advantages.
Therefore, as used herein, the term “aerated sludge” is intended to refer to a sludge that has been subjected to a dose of UFB and in which a high concentration of the bubbles have been retained within the sludge.
It is to be appreciated that the step of applying UFB to the sludge can preferably be repeated as many times as required, so that any degree of dosing or concentration of UFB can be built up in the sludge, depending on the particular treatment and processing requirements. In preferred embodiments, the effective dosing of UFB is >0.05% of the sludge volume, and preferably up to about 20% volume. In particularly preferred embodiments, the effective dosing of UFB is up to about 5% of the sludge volume. Although it is to be appreciated the percentage dosing is not limited to this range and may vary to suit the sludge being treated and/or the configuration of the apparatus etc.
After dosing the sludge with UFB, the aerated sludge is subjected to the application of acoustic energy. In exemplary embodiments, the acoustic energy comprises ultrasound waves, with frequencies in the range of preferably about 10 kHz to about 50 MHz, and most preferably, about 16 kHz to about 20 kHz.
In preferred embodiments, the aerated sludge is pumped into an ultrasound flow reactor or similar vessel, which are available from proprietary suppliers. Any suitable ultrasound generator may be used in conjunction with the present invention. The function of the ultrasound generator is to agitate at least a portion of the UFB in the sludge to thereby produce cavitation and other secondary effects.
In the process of acoustic cavitation, the UFB expand and undergo radial motion as acoustic waves propagate through the sludge. The resulting bubbles can range in size from microns down to 4-300 nm in diameter. When the UFB bubbles (i.e. “cavitation bubbles”) are exposed to sinusoidal ultrasound waves, they naturally undergo contraction (negative) and expansion (positive) wave cycles. When the cavitation bubbles expand, more gas diffuses into them because of their larger surface area; while when the bubbles are compressed, less gas diffuses out because of the reduced surface area. With each cycle, the bubbles grow in size. Eventually, the bubbles reach a resonant size, whereupon at this point, there are two possible outcomes: either the bubble collapses violently (transient cavitation) or the bubble breaks apart gently and the bubble fragments are then exposed to the ultrasound waves triggering a new growth cycle (stable cavitation). UFB cavitation processes can cause physical and/or chemical effects, which may enhance thermochemical/biochemical reactions etc.
It is found in the present invention, that an unsymmetrical collapse of cavitation bubbles preferably produces micro-jets at high speed, which propagate toward the walls of the ultrasound flow reactor. The collapse of the bubbles also produces relatively strong shockwaves within the sludge, while the resulting impulsive movement of liquid toward or away from the collapsing bubbles leads to micro-convection. It is known that bubble collapse also leads to calculated localised adiabatic temperatures in excess of 5000K. This micro-convection preferably enhances the transport of liquid and solid particles within the sludge, which may also lead to forces that can cause emulsification or dispersion depending on the particular conditions within the ultrasound flow reactor. The emulsification or dispersion is caused by cavitation induced collapse at or near the interface leading to disruption and mixing, thereby resulting in the formation of very fine emulsions. Powerful mechanical disruption of phase boundaries within the liquid can occur caused by the cavitating bubbles.
The strong shockwaves and micro-jets generate significant shear forces that are able to scatter liquid within the sludge into tiny droplets and/or crush solid particles into finer material, such as powder (which remains in solution).
It is found that the degree of cell disruption/damage of the solid matter in the sludge is proportional to the number of bubble collapses with sufficient energy to overcome the minimum (activation energy) required for cell damage, and is related to collision frequency, number of bubbles and cell concentration per unit volume of sludge.
The addition of UFB to the sludge prior to the ultrasonification greatly enhances the above effects. The solid matter is composed of dissolved organic solids, insoluble solids and biomass cell matter. Removing free water is relatively easy, but energy use and complexity increase when removing interstitial, colloidal and intercellular water. Therefore, the combined application of UFB dosing and ultrasound to the sludge breaks through the cell structure and enables the water bound up in the cells to be recovered as free water, without significantly increasing the energy input to the system.
Moreover, an additional advantage of the present method is that it also enhances the destruction, or otherwise weakens, the cell walls of any pathogens in the sludge—resulting in the waste solid and released effluent water being virtually pathogen free.
In preferred embodiments, the frequency of the ultrasound applied to the sludge is varied during the treatment in the ultrasound flow reactor. The varying of the frequency is found to maximise the impact of the sonification and further enhance the cavitation effect on the UFB, since it causes the bubbles to undergo enhanced agitation leading to a greater number of bubble collapses per unit volume of sludge. In exemplary embodiments, the frequency is varied from about 10 kHz to about 20 kHz, for example from about 12 kHz to about 18 kHz. Most preferably, the optimum frequency is centred on about 16 kHz. However, a wider range of frequencies may be used depending on the sludge being treated, and therefore other optimum frequencies may be higher or lower than about 16 kHz subject to the particular arrangement being used. For example, in some embodiments, the frequency is varied from about 16 kHz to about 20 kHz.
In another preferred embodiment, the ultrasound generator may comprise at least two transducers, each generating an acoustic wave of the same or different frequency but propagating in opposing directions.
In embodiments where at least two transducers each generate an acoustic wave of the same frequency, an ultrasound standing wave may be created in the sludge. In preferred embodiments the two transducers each generate an acoustic wave of a frequency between about 10 kHz and about 20 kHz. In particularly preferred embodiments, the two transducers each generate an acoustic wave of a frequency of about 16 kHz.
The standing wave may enhance the cavitation and secondary effects on the UFB. The process of cavitation collapse is propagated through the sludge by the resonant expansion and contraction of the UFB. It is found that this process may be further enhanced when standing waves are established over the frequency range used, thereby utilising the nodes and anti-nodes of the standing waves to enhance dispersion and disruption of cell, floc and aggregated materials in the sludge. Of course, it is to be appreciated that any number of standing waves may be created within the ultrasound flow reactor at the same or different frequencies, depending on the particular conditions and/or sludge to be treated.
In some embodiments, it may be preferable not to generate a standing wave. For example, if particles are getting stuck at the nodes and anti-nodes of the standing waves. In these embodiments, it is preferable to use at least two transducers each generating an acoustic wave of different frequencies. In preferred embodiments one transducer generates an acoustic wave of a frequency between about 10 kHz and about 20 kHz and the other transducer generates an acoustic wave of a different frequency between about 10 kHz and about 20 kHz. For example, one transducer may generate an acoustic wave of a frequency of about 16 kHz and the other transducer may generate an acoustic wave of a frequency of about 18 kHz. In another example, one transducer may generate an acoustic wave of a frequency of about 19 kHz and the other transducer may generate an acoustic wave of a frequency of about 20 kHz.
In yet another embodiment, four transducers each generating an acoustic wave of a different frequency, for example, at frequencies of about 16 kHz, about 18 kHz, about 19 kHz and about 20 kHz.
The relative geometry of the transducers, which may comprise separate transducer plates, may be square, hexagonal, octagonal or any other suitable configuration depending on the setup of the treatment apparatus.
The process leads to a reduction in floc length and fractal particle dimension. By the term “floc length”, we mean the average length of the small, loosely aggregated mass of flocculent material. By the term “fractal particle”, we mean geometric particles of varying fractal dimension having Hausdorff-Besicovitch dimensions greater than their topological dimensions. The process preferably reduces the floc length/fractal particle dimension to less than 3.0 mm. For example, the process may reduce the floc length/fractal particle dimension to less than 2.95 mm. In particularly preferred embodiments, the process may reduce the floc length/fractal particle dimension to less than 2.8 mm.
In preferred embodiments, the sludge is then transferred to another vessel enabling an electric field to be applied to the sludge. Preferably, the vessel is in the form of an electrokinetic reactor (EKR). The construction of the EKR is described in more detail below in relation to the second aspect of the present invention. However, in summary, the EKR is most preferably constructed from inert and/or electrically conductive materials, such as sand, zeolite or other semi-conductive materials.
By the term “zeolite” we mean aluminosilicate minerals comprising sodium, potassium, calcium and barium. Examples of zeolites that could be used to construct the EKR include, but are not limited to gonnardite, natrolite, mesolite, paranatrolite, scolecite, tetranatrolite, edingtonite, kalborsite, thomsonite-series, analcime, leucite, pollucite, wairakite, laumontite, yugawaralite, goosecreekite, montesommaite, harmotome, phillipsite-series, amicite, gismondine, garronite, gobbinsite, boggsite, merlinoite, mazzite-series, paulingite-series, perlialite, chabazite-series, herschelite, willhendersonite, faujasite-series, linde type, maricopaite, mordenite, offretite, wenkite, bellbergite, bikitaite, erionite-series, ferrierite, gmelinite, levyne-series, darchiadite-series, epistilbite, clinoptilolite, heulandite-series, barrerite, stellerite, stilbite-series, brewsterite-series, cowlesite, pentasil, and tschernichite, or any combination of the above.
In one embodiment, the zeolite is a clinoptilolite. In a preferred embodiment, the zeolite is a hydrated sodium-potassium-calcium-alumino-silicate having a chemical formula of (Na0.5K2.5)(Ca1.0Mg0.5)(Al6Si30)O72.24H2O.
In preferred embodiments, the walls of the EKR act as a porous cathode electrode. The effect of the porous cathode is that it can absorb water molecules that have stuck to the UFBs and been transported towards the cathode of the EKR. In some embodiments, the recovered effluent water from the cathode may be collected in a retaining tank or other suitable vessel.
The walls of the EKR preferably comprise zeolite and the conductivity of the walls may be further enhanced by the addition of one or more carbonaceous materials such as graphite particles, ultra pure graphite (UPG) or nuclear graphite (NG), graphite felt (GFe), carbon felt (CFe), graphite foil (GFo), carbon foil (CFo), flake graphite (FG) or ultra pure flake graphite (UP-FG), expanded graphite (EG) or expanded flake graphite (EFG), carbon black (CB), activated carbon black (ACB), carbon nanoplatelets (CN) or nanocarbon platelets (NCP), carbon nanotubes (CNT), and graphene (GR) etc.
Graphite is a crystalline form of the element carbon with its atoms arranged in a hexagonal structure. Graphite flakes or flake graphite may be isolated, flat, plate like particles which may have hexagonal edges if unbroken. Graphite felt is a rayon based material which may have a thickness of about 6 mm to about 12 mm. Carbon felt is a lower chemical purity alternative to graphite felt. Graphite foil is natural graphite flakes which have been processed into continuous foil by an acid. Carbon foil is a lower chemical purity alternative to graphite foil. Expanded graphite, or expanded flake graphite (EFG) is a synthesized intercalation compound of graphite that expands or exfoliates when heated. Carbon black is a form of paracrystalline carbon that has a high surface-area-to-volume ratio. Activated carbon black has a higher surface-area-to-volume ratio than carbon black. Carbon nanoplatelets, or nanocarbon platelets, consist of small stacks of graphene (for example 1-4 layers) that are 1-15 nanometres thick with diameters ranging from sub-micrometre to 100 micrometres. Carbon nanotubes are an allotrope of carbon taking the form of cylindrical carbon molecules. Graphene is an allotrope of carbon consisting of a single layer of carbon atoms arranged in a hexagonal lattice.
The carbonaceous material may comprise between about 1% and about 60% of the composition of the walls. For example, the carbonaceous material may comprise between about 5% and about 50% of the composition of the walls. In some embodiments, the carbonaceous material comprises up to about 20% of the composition of the walls. For example, the carbonaceous material may comprise up to about 15% of the composition of the walls. In particularly preferred embodiments, the carbonaceous material comprises up to about 10% of the composition of the walls.
The conductivity of the EKR walls may be further enhanced by the application of an additional fine layer of a mixture of a carbonaceous powder and zeolite or zeolite powder alone.
The anode of the EKR is most preferably disposed towards the centre of the reactor to ensure a symmetrical electric field within the EKR. However, additional anodes may be located at other specific locations within the EKR to create any desired electric field topography depending on the particular EKR geometry and/or the treatment conditions to be adopted for the sludge. Hence, it is to be appreciated that the geometry of the EKR and/or the number of anodes used (including their relative positions within the EKR) are not intended to be limiting. An example of a suitable geometry of the EKR is shown in
The anode may be fabricated from the same material as the cathode or may be made from carbon, metal or a metal composite.
When an electric voltage is applied to the EKR, the aerated sludge is then subjected to an electric field. Preferably, the applied voltage is in the range of between 5V-100V, and most preferably, in the range of 30V-70V. The action of the electric field on the UFB causes a negative electrophoretic mobility due a preferential adsorption of hydroxyl (OH−) ions, arising from the orientation of the water dipoles near the interphase with their positive poles directed towards the liquid in the sludge. This effect causes the water molecules in the sludge to effectively “stick” to the UFB, which essentially act as transport carriers (i.e. transport medium) for the water as they migrate towards the cathode of the EKR. In this way, water molecules are then dragged along with the bubbles towards the porous cathode, whereupon they are then absorbed by the cathode.
In addition, the UFB may also act as carriers for other particles (e.g. charged particles and dipole molecules etc.) and enable those particles to migrate through the sludge under the effect of the electric field. Moreover, the presence of the UFB also advantageously reduces the effective viscosity of the sludge by providing porosity, thereby enhancing the transport of water molecules through the EKR to the cathode.
Any solid matter or solid particulates in the sludge are transported to the anode or anodes under a corresponding electrophoretic mobility. Therefore, applying an electric field to the aerated sludge facilitates separation and transport of water molecules from solid matter within the sludge.
In the present invention, there are two main electrokinetic phenomena operating to dewater the sludge, namely electro-osmosis and electrophoresis. As is known in the art, electro-osmosis is the motion of liquid induced by an applied potential across a porous material; while electrophoresis is the motion of dispersed particles relative to a fluid under the influence of a uniform electric field. Although water molecules possess an overall neutral charge, they are polar molecules. This means that they are attracted to cations (positively charged ions) in a solution and become oriented around these ions. If sludge is saturated with liquid containing ions in solution and an electric field is set up within the sludge, the positive ions tend to move towards the negative electrode (the cathode). As the ions move, the surrounding water molecules are effectively dragged along and hence water moves towards the cathode.
The electrode reactions can be summarised as follows:
At the Anode:
2H2O→O2+4H+ (1)
Ma→Min++ne− (2)
At the Cathode
2H2O+2e−→H2+2OH− (3)
Min++ne−→Mi (4)
Min++OH−→Mi(OH)n (5)
where Ma represents the anode metal and Mi is the dissolved cation species, i, in solution. Equation (1) states that the anode hydrolysis generates oxygen and reduces the solution pH value. As a result, a metallic anode will corrode, as shown in Equation (2). The solution pH will increase at the cathode and hydrogen will be generated, as shown in Equation (3). Cations are driven to the cathode by the electric field where they may reduce to element metals, as shown in Equation (4), or, more likely, form hydroxides, as shown in Equation (5). During the electrokinetic process, the movement of H+ and OH− will change the sludge pH drastically. A pH gradient will be generated across the sludge as a result of the electrode reactions. The acid front at the anode will advance across the sludge suspensions toward the cathode by advection and diffusion effects. The net effect is the decrease of cathode pH in the later stage of treatment stabilising the pH of the sludge.
It is known that the surface of a bubble can adsorb alcohol molecules, ions and other impurities or particles in the immersed liquid. Equation (2) indicates that indicates that the cations will be attracted to the anode. The movement of charged particles is always opposite to the electro-osmotic flow of water. It is found that pH levels<3 around the cathode will typically make these cations insoluble. Therefore, solid particles will accumulate on the anode.
In preferred embodiments, the mobility of the UFB under the action of the electric field may be further increased by subjecting the EKR to a vacuum of preferably about 300 Pa-5 kPa, and most preferably, about 500 Pa-1.5 KPa.
The dewatering rate may be further enhanced by the application of jet mixing within the EKR. Therefore, one or more jets or jet injectors may be provided in the EKR, and most preferably at the base, to allow a jet of air or additional UFB to be injected into the sludge to promote improved mobility. The jets prevent the occurrence of any initial sludge compaction or build up of a static layer of solid matter in the sludge, thereby assisting with sludge mobility and rapid dewatering rates.
The recovered effluent water from the cathode may be collected in a retaining tank or other suitable vessel. The solid waste may be mechanically removed from the EKR after treatment and both the effluent water and solid waste may be used for agricultural, livestock or similar purposes due to being virtually or completely pathogen free. Alternatively, the effluent water and solids may be further treated to meet specific environmental discharge levels and can be additionally processed for edible crop use and, in the case of the water, for drinking standards.
It is to be appreciated that the present method may be operated as a single one-off process or may be operated cyclically or continuously, depending on the particular site of operation, treatment conditions an/or sludge.
According to a second aspect of the present invention there is provided a dewatering apparatus for treating sewage sludge, comprising:
The apparatus according to the second aspect of the present invention is intended to be used with the method according to the first aspect of the present invention, but us not intended to be solely limited by that use.
The means for generating and injecting a plurality of ultrafine bubbles (UFB) into a sludge preferably comprises a bubble generator, and most preferably an ultrafine bubble generator. Any conventional ultrafine bubble generator may be used in conjunction with the present invention, without sacrificing any of its benefits or advantages.
The means for applying acoustic energy preferably comprises an ultrasound generator, wherein the ultrasound generator is preferably operable to vary the frequency of the ultrasound during treatment. Any suitable ultrasound generator may be used in conjunction with the present invention. The function of the ultrasound generator is to agitate at least a portion of the UFB in the sludge to thereby produce cavitation and other secondary effects, as described above in relation to the first aspect of the invention.
In preferred embodiments, the ultrasound generator is operable to generate standing waves within the aerated sludge.
The means for applying an electric field to the aerated sludge preferably comprises an electrokinetic reactor (EKR). The EKR is preferably structurally and functionally the same as that described in relation to the first aspect of the invention. However, in addition, the EKR is preferably constructed as individual plates or panels (e.g. forming the walls) that are assembled into the specific EKR geometry for that particular application. In preferred embodiments, the EKR may adopt a cubic structure or rectangular form analogous to a long rectangular tank. Of course, it is to be understood that any suitable shape may be used in conjunction with the present invention.
The EKR is most preferably constructed from inert and/or electrically conductive materials, such as sand, zeolite or other semi-conductive materials. In preferred embodiments, the walls of the EKR act as a porous cathode electrode. The walls of the EKR preferably comprise zeolite and the conductivity of the walls may be further enhanced by the addition of one or more carbonaceous materials such as graphite particles, ultra pure graphite or nuclear graphite (NG), graphite felt, carbon felt, graphite foil, carbon foil, flake graphite or ultra pure flake graphite (UP-FG), expanded graphite or expanded flake graphite (EFG), carbon black, activated carbon black (ACB), carbon nanoplatelets or nanocarbon platelets (NCP), carbon nanotubes, and graphene etc. The carbonaceous material may comprise between about 1% and about 60% of the composition of the walls.
The conductivity of the EKR walls may be further enhanced by the application of an additional fine layer of a mixture of a carbonaceous powder and zeolite or zeolite powder alone.
The anode of the EKR is most preferably disposed towards the centre of the reactor to ensure a symmetrical electric field within the EKR. However, alternative and/or additional anodes may be located at other specific locations within the EKR to create any desired electric field topography depending on the particular EKR geometry and/or the treatment conditions to be adopted for the sludge.
Hence, it is to be appreciated that the geometry of the EKR and/or the number of anodes used (including their relative positions within the EKR) are not intended to be limiting. An example of a suitable geometry of the EKR is shown in
The anode may be fabricated from the same material as the cathode or may be made from carbon, metal or a metal composite.
The walls of the EKR are preferably cast and moulded into a required form using a particulate media of preferably a zeolite/carbonaceous mixture and a composition epoxy, or other non-corrosive resin/binder that will not dissolve or corrode in use. Examples of suitable resin/binders include, but are not limited to, carbon nanotube epoxy composite, conductive nanotube composite additives and two component epoxy based adhesives. Where the resin/binder is a two component epoxy based adhesive, one component may comprise bisphenol A-epichlorohydrin epoxy resin and the other component may comprise butanedioldiglycidyl ether. Such a resin/binder may be referred to herein as Araldite®.
The resin binder composition may range between about 10-50% by weight of the overall zeolite/carbonaceous mixture. The properties of this resin binder may be further enhanced by the addition of carbon based powders and/or particulates, as described above in relation to the cathode.
The EKR may be assembled by binding the edges of the walls using a conductive adhesive or the resin binder.
In preferred embodiments, the electrical supply to the EKR can be AC or DC, and may be continuous or pulsed at set intervals. Preferably the electrical supply to the EKR is DC. The electrical supply to the EKR walls is preferably connected to respective sides of the EKR. However, in other embodiments, this arrangement may be replaced with a single electrical connection comprising respective cathode and anode connections.
The applied voltage is preferably in the range of between 5V-100V AC/DC, and most preferably, between 30V-70V AC/DC. Of course, it is to be appreciated that the particular voltage range will depend on factors such as the EKR geometry and/or the sludge to be treated.
In preferred embodiments, the mobility of the UFB under the action of the electric field may be further increased by subjecting the EKR to a vacuum of preferably about 300 Pa-5 kPa, and most preferably, about 500 Pa-1.5 KPa. In preferred embodiments, the EKR comprises at least one jet injector to promote sludge mobility. Therefore, one or more jets or jet injectors may be provided in the EKR, and most preferably at the base, to allow a jet of air or additional UFB to be injected into the sludge to promote improved mobility. The jets prevent the occurrence of any initial sludge compaction or build up of a static layer of solid matter in the sludge, thereby assisting with sludge mobility and rapid dewatering rates.
It should be understood that the present apparatus is inherently scalable and as such the apparatus may comprise a single EKR, or alternatively, the apparatus may comprise an array of electrokinetic reactors, depending on the particular installation and required treatment conditions. Any suitable configuration for the array may be used in conjunction with the present invention, without sacrificing any of its benefits or advantages.
It is to be appreciated that none of the aspects, embodiments or examples described in relation to the present invention are mutually exclusive, and therefore the features and functionality of one embodiment or example may be used interchangeably or additionally with the features and functionality of any other embodiment or example without limitation.
Embodiments of the present invention will now be described in detail by way of example and with reference to the accompanying drawings in which:
Referring to
As an initial pre-treatment step, the sewage sludge 102, in this case a primary sludge, is passed through a maceration unit 104 to ensure that all relatively large extraneous materials or solids are broken up or crushed via comminution to a size at least <12 mm, and ideally <2 mm. The maceration unit 104 comprises a pre-treatment tank 104a and a maceration pump 104b.
The sludge is then subjected to the application of ultrafine bubbles (UFB), which are injected into the sludge via an ultrafine bubble generator 106. By “ultrafine bubbles” or “UFB”, we mean any bubbles that have a bubble diameter generally in the range of <10-50 microns. The step of applying UFB to the sludge can be repeated as many times as required, so that any degree of concentration of UFB can be built up in the sludge, depending on the particular treatment and processing requirements.
After dosing the sludge with UFB, the “aerated sludge” is pumped into an ultrasound flow reactor 108, whereupon the sludge is subjected to the application of ultrasound waves. The ultrasound waves are applied with frequencies in the range of about 10 kHz to about 50 MHz.
As shown in
The function of the ultrasound is to agitate at least a portion of the UFB in the sludge to thereby produce cavitation and other secondary effects. In the process of cavitation, the UFB grow, expand and undergo radial motion as acoustic energy propagates through the sludge. The resulting bubbles range in size from microns down to 4-300 nm in diameter, and are found to be generally stable. During stable cavitation, the radii of the UFB undergo radial oscillation by periodically expanding and shrinking within several acoustic cycles. However, when the bubbles reach their resonant size, at least some will undergo transient cavitation and others will break apart gently, whereby the resulting fragments will start a new cycle of stable cavitation. The collapse of the bubbles produces physical and/or chemical effects. These effects can enhance thermochemical/biochemical reactions etc. according to one or more of the following mechanisms:
Cavitating bubbles are sufficient to cause rupture of the O—H bond itself. This is because the collapse of the cavitation bubbles is also near adiabatic and generates temperatures of thousands of degrees within the bubbles for a short period of time. Under these temperature conditions, highly reactive radicals are generated. In water, H and OH radicals are generated by the homolysis of water. This results in the formation of radical species and the production of oxygen gas and hydrogen peroxide
H2O→H++OH−
OH−+OH−→H2O2
OH−+OH−→H2O+O
OH−+OH−→H2+O2
H++O2→HO2−
HO2−+H+→H2O2
HO2−+HO2−→H2O2+O2
OH−+H2O→H2O2+H+
H++H+→H2
H++OH−→H2O
In the presence of a metal ion present, an alternative mechanism may be
M2++H+→M++H+
H++O2→HO2−
M2++HO2−→M++H++O2
OH−+H2O2→HO2−+H2O
OH−+OH−→H2O2
HO2−+HO2−→H2O2+O2
These resulting free radicals may then participate in chemical reactions within the sludge. The formation of hydroxyl radicals during sonification, enhances the negative electrophoretic movement of the UFB towards the cathode.
It is found in the present invention, that an unsymmetrical collapse of bubbles typically produces micro-jets at high speed, which propagate toward the walls of the ultrasound flow reactor 108. The collapse of the bubbles also produces relatively strong shockwaves within the sludge, while the resulting impulsive movement of liquid toward or away from the collapsing bubbles leads to micro-convection. This micro-convention enhances the transport of liquid and solid particles within the sludge, which may also lead to forces that can cause emulsification or dispersion depending on the particular conditions within the ultrasound flow reactor.
The strong shockwaves and micro-jets generate significant shear forces that are able to scatter liquid within the sludge into tiny droplets and/or crush solid particles into finer material, such as powder (which remains in solution).
It is found that the degree of cell disruption/damage of the solid matter in the sludge is proportional to the number of bubble collapses with sufficient energy to overcome the minimum (activation energy) required for cell damage, and is related to collision frequency, number of bubbles and cell concentration per unit volume of sludge.
The addition of UFB to the sludge prior to the ultrasonication greatly enhances the above effects. The solid matter is composed of dissolved organic solids, insoluble solids and biomass cell matter. Removing free water is relatively easy, but energy use and complexity increase when removing interstitial, colloidal and intercellular water. Therefore, the combined application of UFB dosing and ultrasound to the sludge breaks through the cell structure and enables the water bound up in the cells to be recovered as free water, without significantly increasing the energy input to the system.
Referring now to
The cavitation effect on the UFB via the application of ultrasound leads to a reduction in sludge particle size, together with a breakup of flocculated particles and a reduction in floc and particle fractal dimension. Due to the resulting rupturing of the particle, bound up water is released into the sludge medium. This effect leads to a reduction in sludge viscosity, which thereby reduces the measured CST. The impact of increasing the dosage of UFB within the sludge media causes an increase in global cavitation activity, which in turn promotes greater sludge disintegration. As a result, the measured CST is further reduced and consequently the CST value provides a direct indictor of the effectiveness of the dewaterability of the sludge.
As shown in
Moreover, an additional advantage of the present method is that it also enhances the destruction, or otherwise weakens, the cell walls of any pathogens in the sludge—resulting in the waste solid and released effluent water being virtually pathogen free.
The frequency of the ultrasound applied to the sludge is varied during the treatment in the ultrasound flow reactor 108. The varying of the frequency is found to maximise the impact of the sonification and further enhance the cavitation effect on the UFB, since it causes the bubbles to undergo enhanced agitation leading to a greater number of bubble collapses per unit volume of sludge.
Although not shown in
Alternatively, the ultrasound flow reactor 108 may include an ultrasound generator that comprises at least two transducers, each generating an acoustic wave of a different frequency.
As an example, there is shown in each of
The sludge is then transferred to another unit 112 comprising an electrokinetic reactor (EKR) 114, which enables an electric field to be applied to the sludge. As shown in
The EKR 114 is constructed from inert and/or electrically conductive materials, such as sand, zeolite or other semi-conductive materials, while the walls of the EKR act as a porous cathode electrode.
The walls of the EKR 114 are cast and moulded into a required form using a particulate media of a zeolite/carbonaceous mixture and a composition epoxy, or other non-corrosive resin/binder that will not dissolve or corrode in use. The resin binder composition may range between about 10-50% by weight of the overall zeolite/carbonaceous mixture. The properties of this resin binder can be further enhanced by the addition of carbon based powders and/or particulates, such as graphite particles, expanded graphite, carbon black, carbon nanoplatelets and graphene etc.
The conductivity of the EKR walls can be further enhanced by the application of an additional fine layer of a mixture of a carbonaceous powder and zeolite or zeolite powder alone or by the addition of a carbonaceous material such as graphite particles, expanded graphite, carbon black, carbon nanoplatelets and graphene etc. The carbonaceous material may comprise between about 1%-60% of the composition of the walls.
The anode may be fabricated from the same material as the cathode or may be made from carbon, (sacrificial) metal or a metal composite. The anode can have any suitable shape or configuration depending on the geometry of the EKR etc. As shown in
Examples of possible compositions for the material of the EKR 114 are presented in Table 1 below. This list is intended to be illustrative and not exhaustive. The type of zeolite used in the present apparatus is a Clinoptilolite. However, it is to be understood that other types of materials may alternatively be used.
For ease of reference, the following acronyms are used in Table 1:
dpavg—Average particle diameter
N/A—Not applicable
NCP—Nanocarbon platelets
NG-92—Nuclear graphite (ultrapure flake graphite)
EFG—Expanded flake graphite
ACB—Activated carbon Black
FG-92—Flake graphite
UP-FG—Ultrapure flake graphite
CNT—Carbon nanotube
To fabricate the EKR cathode and anode, the constituent particulates are mixed with 10-15% of an adhesive binder and left to set for a period of time that can range from a minimum of 3-25 minutes. The mixed material is cast in a mould and allowed to set. This technique allows for any shape or geometry of EKR 114 to be created. If the cathode and/or the anode are cast as individual walls/plates, then the EKR 114 can be assembled by binding the edges of the walls using a conductive adhesive or the resin binder. The conductivity of the EKR walls may be further enhanced by the application of an additional fine layer of a mixture of a carbonaceous powder and zeolite or zeolite powder alone.
The anode of the EKR 114 is located towards the centre of the reactor to ensure a symmetrical electric field within the EKR. However, alternative and/or additional anodes can be located at other specific locations within the EKR to create any desired electric field topography depending on the particular EKR geometry and/or the treatment conditions to be adopted for the sludge.
Hence, it is to be appreciated that the geometry of the EKR and/or the number of anodes used (including their relative positions within the EKR) are not intended to be limiting. An example of a suitable geometry of the EKR is shown in
The electrical supply to the EKR 114 can be AC or DC, and can be continuous or pulsed at set intervals. Preferably the electrical supply to the EKR is DC. The electrical supply to the EKR walls is generally connected to respective sides of the EKR 114. However, in other arrangements this can be replaced with a single cathode/anode electrical connection. The applied voltage is in the range of between 5V-100V AC/DC, and typically between 30V-70V. Of course, it is to be appreciated that the particular voltage range will depend on factors such as the EKR geometry and/or the sludge to be treated.
When an electric voltage is applied to the EKR 114, the aerated sludge is then subjected to an electric field. The action of the electric field on the UFB causes a negative electrophoretic mobility due a preferential adsorption of hydroxyl (OH−) ions, arising from the orientation of the water dipoles near the interphase with their positive poles directed towards the liquid in the sludge. This effect causes the water molecules in the sludge to effectively “stick” to the UFB, which essentially act as transport carriers (i.e. transport medium) for the water as they migrate towards the cathode of the EKR 114. In this way, water molecules are then dragged along with the bubbles towards the porous cathode, whereupon they are then absorbed by the cathode.
In addition, the UFB may also act as carriers for other particles (e.g. charged particles and dipole molecules etc.) and enable those particles to migrate through the sludge under the effect of the electric field. Moreover, the presence of the UFB also advantageously reduces the effective viscosity of the sludge by providing porosity, there enhancing the transport of water molecules through the EKR 114 to the cathode.
Any solid matter or solid particulates in the sludge are transported to the anode or anodes under a corresponding electrophoretic mobility. Therefore, applying an electric field to the aerated sludge facilitates separation and transport of water molecules from solid matter within the sludge.
Referring now to
It is found that there is a limit to enhancing the electrophoretic effect with increasing voltage due, for example, to steric effects and changes to the zeta potential (arising from the pH gradient within the EKR). In an example setup, the optimum dewatering voltage was found to be around 50V DC. However, the range of effective voltages that could be applied was between 15V and 80V, but could be between 10V and 100V, depending on the particular sludge/wastewater being treated.
The effect of the combined UFB and ultrasonication of the sludge according to the present invention can be seen in Table 2 below for two test ultrasound frequencies of 16 kHz and 20 kHz.
Hence, it is clear that the application of the UFB to the sludge not only increases the percentage total solids remaining, and thus recovered water, but it also leads to significantly lower energy input (i.e. power consumption) as compared to the absence of UFB in the sludge. Therefore, the combination of UFB and ultrasonication according to the present invention provides a method and apparatus, which gives increased dewatering rates and lower power requirements than conventional dewatering systems.
The mobility of the UFB under the action of the electric field is found to be further increased by subjecting the EKR 114 to a vacuum of about 300 Pa-5 kPa, and typically about 500 Pa-1.5 KPa.
Although not shown in
The recovered effluent water 118 from the cathode may be collected in a retaining tank or other suitable vessel (not shown). The solid waste 120 may be mechanically removed from the EKR 114 after treatment and both the effluent water 118 and solid waste 120 can be used for agricultural, livestock or similar purposes due to being virtually or completely pathogen free. Indeed, the dewatered sludge can be used as a valuable fertiliser or as a feedstock to a combustion system. The dewatered sludge is virtually or completely pathogen free, while the claimed invention may also be applied to sanitation purposes. The effluent water may be processed to drinking water standards.
Of course, it is to be understood that the method and apparatus of the present invention are inherently scalable, and therefore the apparatus, and in turn, the electrokinetic reactor, can be sized to treat a sludge or slurry according to any particular requirement depending on the desired use and/or implementation. Hence, none of the embodiments or examples disclosed herein are to be taken to be limiting on the size of the apparatus.
Indeed, a typical laboratory EKR as used herein can be scaled up to a full-scale plant reactor by utilising the ratio of the internal laboratory EKR volume to the full scale EKR dewatering unit. In one example, the ratio of this scale-up can be 244 (i.e. numerical multiplying factor), but in other arrangements can range between 30 and 300. The scale up between laboratory EKR and full-scale plant reactor may also be based on surface area ratio between the laboratory EKR and full-scale reactor. In one example, the ratio of this scale-up is 39.06, but in other arrangements can range between 10 and 50.
Thus, the above embodiments are described by way of example only. Many variations are possible without departing from the invention.
Number | Date | Country | Kind |
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1804034.5 | Mar 2018 | GB | national |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2019/056265 | 3/13/2019 | WO | 00 |