Patent Application
20230052342
This invention relates to processing of per- and poly-fluoroalkyl substances (referred to herein as PFAS). In particular the invention relates to remediation of soils and other substances to separate PFAS and relates to processing PFAS (whether from the remediation system or otherwise) to convert them into safer substances.
Per- and poly-fluoroalkyl substances are chemical compounds with extremely high stability giving them very useful properties for multiple industrial uses, including firefighting foams (‘aqueous film-forming foams’ or AFFFs), non-stick cookware, food packaging, insecticides, and waterproof and fire-resistant fabric. AFFFs have been used on fires at many thousands of emergency and training sites worldwide over the past half-century and the foam can seep into soil and groundwater. PFAS is a hazardous contaminant and due to its stability does not break down easily which means it can accumulate in the environment and eventually move far beyond the source site.
The very properties that have made PFAS industrially and commercially very useful lead to persistency, bio-accumulation and, in some cases, toxicity in the environment. For example, the compound PFOS (perfluoro-octane-sulphonic acid) is very chemically inert and resistant to high temperatures and is therefore very useful in firefighting foam. Complete combustion of PFOS requires combustion temperature of at least 1100° C. PFOS can accumulate in birds, fish and other fauna. The substance is toxic. It accumulates in the liver and in the blood and can cross the placenta. Animal studies have shown liver toxicity, effects related to lipid metabolism, reproduction toxicity and immunological effects.
There are many situations requiring PFAS to be removed from contaminated sources such as water, e.g., groundwater proximate to or downstream in the water migration paths from a contaminated site, or from other sources such as soil, rocks, concrete, paving, asphalt, bitumen, tarmac, etc. where PFAS containing substances have been used.
The processing of PFAS however removed from contaminated sources so as to convert them into safer substances has comprised an incinerating process at temperatures over 1000° C. This requires high energy and specialised high temperature incineration apparatus.
Remediation treatments of soil contaminated with PFAS has been based on some different approaches. For example, addition of chemical reagents to soil so as to chemically react with the PFAS is one known approach currently in use. No known process has been developed to the present inventor's knowledge for separating PFAS from concrete, paving, asphalt, bitumen and tarmac.
US 20190314876 discloses remediation of contaminated soil by conductive heating of soil to raise the temperature to 225° C. to 440° C., break bands of the PFAS to organic carbon in the soil, and enable vaporisation of PFAS said to boil at temperatures from 76° C. to 218° C. The treatment is prolonged from 1-30 days. The PFAS are treated by electro oxidation.
It is an object of the present invention to provide effective methods and apparatus for processing PFAS so as to reduce the risk of exposure to PFAS, whether by humans, fauna, or other living organisms.
It is a first preferred object of a first aspect of the present invention to provide a method and apparatus for processing PFAS to at least partially convert them into safer substances which can be effective and provide at least a useful alternative to existing processing.
It is a second preferred object of a second aspect of the present invention to provide a method for remediating particulate solids such as soils, concrete, asphalt contaminated with PFAS which can be effective and provide at least a useful alternative to existing remediation processes.
It is a further preferred object to provide an apparatus for remediating particulate solids such as soils, concrete, asphalt contaminated with PFAS so as to implement the preferred method.
According to a first aspect of the present invention there is provided a method for processing PFAS to at least partially convert them into safer substances, comprising introducing gaseous or vapour phase PFAS into a treatment zone, and irradiating the treatment zone with microwave radiation of predetermined frequency or frequencies and power level or levels so as to create a plasma in the treatment zone, and whereby the plasma in the treatment zone at least partially dissociates the PFAS and produces safer substances including less toxic atoms, molecules and/or radicals.
The expression “safer substances” used herein, including in the claims, is to be interpreted to encompass not only substances which are less toxic than PFAS but also substances which can be more readily further processed (chemically, thermally, physically or otherwise) than PFAS, e.g. by further processing by condensation, chemical reaction, adsorption, filtration, pyrolysis, incineration or thermal treatment.
Preferably the PFAS are continuously introduced into the treatment zone and dissociation products are continuously withdrawn therefrom with the flow rate and plasma temperature being sufficient to effect substantially complete conversion of the PFAS into safer substances.
The microwave radiation is preferably generated by a microwave generator and a waveguide transfers the microwave radiation to the treatment zone through a microwave transparent wall of, or window in, the treatment zone. The waveguide preferably incorporates a tuner operative to match impedance of the microwave generator and associated waveguide to the impedance of the load consisting of the PFAS (and carries gas or vapour) in the treatment zone so as to thereby improve microwave energy transfer efficiency to the treatment zone and improve the plasma creation.
The first aspect of the invention also provides an apparatus for processing PFAS to at least partially convert them into safer substances, the apparatus comprising means to perform each of the steps of the method according to the first aspect.
According to a second aspect of the invention there is provided a method for remediating particulate solids contaminated with PFAS, the method including the steps of: locating a body of particulate solids contaminated with PFAS in a closed vessel, generating microwave radiation of pre-determined frequency or frequencies and power level or levels, directing microwave radiation generated to the body of particulate solids in the vessel so as to heat the particulate solids and promote vaporisation of PFAS, transferring vapour from the vessel to a treatment stage, and treating in the treatment stage the vapour transferred from the vessel so as to at least partially convert the PFAS into safer substances.
In the method according to the second aspect, the step of treating the vapour in the treatment stage preferably comprises exposing the vapour to a plasma within a treatment zone whereby PFAS in the vapour entering and passing through the treatment zone are subject to at least partial dissociation of the PFAS molecules. Preferably the plasma in the treatment zone is created and/or is maintained by directing to the treatment zone microwave radiation from a secondary microwave generator operatively associated with the treatment zone. Thus the PFAS recovered may be treated using the method according to the first aspect of the invention.
The particulate solids contaminated with PFAS and located in the vessel may be mixed either intermittently or continuously during irradiation by the microwave radiation so as to promote heating of the particulate solids and vaporisation of PFAS.
In a first possible embodiment of the method of the second aspect, particulate solids contaminated with PFAS are progressively fed into the vessel, whether by continuous feeding of particulate solids or by intermittent feeding of charges of particulate solids, and heated particulate solids that have yielded up PFAS by vaporisation are progressively removed from the vessel so that the particulate solids progressively move from a soil feed location of the vessel to a soil removal location of the vessel while being exposed to microwave irradiation. In this embodiment, the chamber in which the particulate solids are irradiated may include (or consist of) a microwave transparent wall or window, e.g. composed of quartz or ceramic or other microwave transparent material, through which the particulate solids are exposed to the irradiation. The enclosure preferably comprises a tube into which particulate solids to be treated are fed, the tube being inclined and either continuously or intermittently vibrated and/or rotated so that the particulate solids progressively travel by gravity down the inclined tube to an exit therefrom.
In a second possible embodiment of the method of the second aspect, a batch of particulate solids contaminated with PFAS is located in the closed vessel, and during irradiation by the microwave radiation, the batch is mixed either intermittently or continuously so as to expose the batch of particulate solids substantially throughout its volume to the microwave irradiation for a vaporisation period during which no further particulate solids are added to the vessel. Vapour containing the PFAS yielded up by the batch may be removed from the closed vessel for downstream treatment prior to opening of the vessel and discharge of the treated particulate solids therein.
In both these first and second possible embodiments, the particulate solids may be subject to a two-stage heating process comprising:
a first preheating stage in which the particulate solids are heated to vaporize water in the particulate solids and thereby dry the particulate solids to a pre-determined moisture content, and
a second higher energy heating stage in which microwave irradiation of the particulate solids having the reduced moisture content occurs to promote vaporization of PFAS.
The first preheating stage may comprise or include conventional heating by conduction or thermal (IR) radiation, (including before introduction into the closed vessel), and induction heating by low power microwave may also or alternatively be used. The microwave generator used for the PFAS vaporization second heating stage can be operated at a lower power level for the first preheating stage.
Preferably vapour containing PFAS yielded by the particulate solids is drawn from the vessel during or after the irradiation of the particulate solids in the vessel. The vapour containing PFAS may be continuously drawn from the vessel and transferred into the treatment stage during the treatment of the particulate solids in the vessel by creating a negative pressure downstream of the treatment stage which thereby draws vapours from the vessel into and through the treatment stage.
The method according to the second aspect of the invention may include the further step of creating a partial vacuum where particulate solids heated by the microwave radiation directed into the closed vessel are located so as to promote vaporization of PFAS from the particulate solids. There are several possible alternative arrangements effecting this suction step.
In a first possible arrangement the suction step of creating a partial vacuum is performed by creating the partial vacuum in the closed vessel while the particulate solids are located therein and the step of directing microwave radiation comprises directing microwave energy into the particulate solids below the surface level of the particulate solids in the closed vessel whereby a significant and preferably major proportion of the available energy is absorbed in the particulate solids before that energy reaches the gas space above the particulate solids level. This reduces the chance of plasma formation in the gas space above the particulate solids which is more likely to occur in a lower vapour pressure space.
In a second possible arrangement having the suction step, the directing of microwave radiation into the vessel is discontinued after a period of heating time, and substantially simultaneously with or after the discontinuation of the step of directing microwave radiation the step of creating the partial vacuum is performed so as to create the partial vacuum in the closed vessel. This also reduces the likelihood of plasma formation and arcing occurring in the gas space when the suction step is performed to lower the vapour pressure.
In a third possible arrangement having the suction step, after the step of directing microwave radiation to heat the particulate solids is ended, the heated particulate solids are then transferred from the closed vessel to an extraction stage, thereby enabling further contaminated particulate solids to be located in the closed vessel for being heated therein, and the suction step of creating the partial vacuum is performed in the extraction stage to promote vaporization of PFAS from the particulate solids. This separates the vaporization under the partial vacuum from the microwave heating so the plasma formation/arcing is not a risk in the suction step.
The method according to the second aspect of the invention may further include a plasma inhibition step performed to inhibit formation of plasma in a gas space above the level of particulate solids during the step of directing microwave radiation into the particulate solids to cause heating thereof. For example, the plasma inhibition step may comprise performing the microwave heating of the particulate solids in two stages consisting of (i) a higher power heating stage during which higher power microwave energy is applied to the particulate solids while simultaneously a pressure within the vessel greater than atmospheric pressure (101 kPa) is maintained, and (ii) a lower power microwave heating stage in which a lower power level of microwave radiation is applied to the particulate solids and simultaneously a partial vacuum is created in the vessel in which the lower power microwave radiation is being applied and during which PFAS are being vaporized for removal from the particulate solids.
In this example, the higher power microwave heating stage and lower power microwave heating stage may be alternated so as to improve the effectiveness of PFAS extraction by higher power heating and higher vacuum extraction.
Alternatively to the two stage heating, or in conjunction therewith, the plasma inhibition step may include substantially increasing the amount of inert gas, particularly helium or neon or argon, in the gas atmosphere mixed with and surrounding the particulate solids undergoing heating by microwave radiation so as to thereby inhibit the creation of a plasma in the gas space above the level of particulate solids in the vessel where microwave irradiation is occurring. The high ionization temperature of helium particularly inhibits the creation of a plasma in the gas.
The method according to the second aspect of the invention may further include a particulate sizing step performed prior to locating the body of particulate solids in the closed vessel to optimize the sizes of the particulate solids to achieve desirable dielectric properties of the particulate solids for their microwave heating. Sizing may be performed by any suitable process such as those used in mineral processing technologies, including crushing and sizing. Such sizing can be most desirable for remediation of PFAS contaminated concrete, paving, asphalt, bitumen, tarmac etc. so as to increase the surface area of the particulate solids and promote extraction of PFAS therefrom.
Preferably the microwave radiation directed to the body of particulate solids is generated by a microwave generator and a waveguide transfers the microwave radiation to the closed vessel through a microwave transparent wall of, or window in, the closed vessel, the waveguide preferably incorporating a tuner operative to match impedance of the microwave generator and associated waveguide to the impedance of the load consisting of the particulate solids in the closed vessel so as to thereby improve microwave energy transfer efficiency to the particulate solids. The tuner may comprise an auto-tuner (such as a three stub tuner) operated under a control system responsive to a dielectric coupler for sensing the reflected power in the waveguide so that the reflected power is minimized.
According to the second aspect of the invention there is also provided an apparatus for use in remediating particulate solids contaminated with PFAS, the apparatus comprising means to perform each of the steps of the method according to the second aspect.
The particularly preferred method and apparatus for remediating particulate solids, particularly soil, contaminated by per- and poly-fluoroalkyl substances (PFAS) comprise the substantially complete removal of PFAS using electromagnetic microwave radiation to effect induction heating to vaporise the contaminants followed by destruction of the PFAS using microwave induced plasma technology.
Possible and preferred features of the present invention will now be described with particular reference to the accompanying drawings. However it is to be understood that the features illustrated in and described with reference to the drawings are not to be construed as limiting on the scope of the invention. In the drawings:
Referring to
The microwave radiation is generated by a microwave generator [7] and a waveguide [21] transfers the microwave radiation to the treatment zone [6] through a microwave transparent wall of, or window in, the treatment zone which is comprised by the quartz tube walls in
It is known that microwave electric fields of sufficient strength can induce an ionised gas, also known as a plasma. Under atmospheric conditions air will break down forming a plasma when the electric field stress is in the vicinity of 30 kV/cm. The specific electric field strength to initiate a plasma will depend on many parameters such is temperature, gas ionisation energy and pressure.
Microwave plasmas are typically initiated in single mode cavities where their resonant nature gives rise to very high field strengths, however plasma can form in non-resonant multimode applicators provided there is sufficient electric field strength. The field strength is proportional to the square root of the applied power level.
The dimensions and configuration of suitable microwave applicators for plasma processing is very much dependent upon the frequency of operation which can be anywhere between 800 MHz to 30 GHz, however the most likely frequencies are 896 MHz, 915 MHz, 922 MHz and 2.45 GHz as these are commercially used in industry.
The power levels required will be dependent upon frequency, gas throughput and pressure and could be as low as 1 kW and as high as 300 kW.
The unique ability of a plasma to cause molecule disassociation into fundamental components is largely due to a combination of the average bulk ion temperature and extremely high individual ion temperatures. Free electrons in the plasma can have very high energy and hence very high individual ion temperatures. The bulk temperatures required are expected to be in the order of 800-1200° C. and the individual ion temperatures may be in the order of 1000 to 10,000° K.
In each of
Referring to
The input [3] and output [4] screw conveyors are lined with microwave chokes [3, 4] to prevent electromagnetic radiation from escaping the treatment chamber.
The treatment chamber [2] rotates to provide mixing of the soil which helps produce a homogeneous heating profile and release vapours (including PFAS). The treatment chamber [2] is angled to allow a gravity assisted flow of product from input to output assisted by the rotation of the chamber and the input [3] and output [4] screw conveyors. The tubular chamber [2] may also be either continuously or intermittently vibrated as well as rotated so that the soil progressively travels by gravity down the inclined tube to the exit [4] therefrom.
Vapours are drawn out of the chamber through the gas output [5] and passed through a microwave plasma treatment stage [6] to destroy the PFAS via thermal oxidation and/or dissociation.
The plasma is produced using a microwave generator [7] operating within the frequency spectrum of 300 MHz to 5 GHz and requires a tuning system [8] in the waveguide [21] for impedance matching.
The neutralised gases and particulates from the gas stream are then filtered [9] or adsorbed or otherwise processed to render them safe.
A pump [10] is used to extract the gasses from the treatment chamber and lower the pressure of the system.
An impedance matching tuner [11] is utilised in the waveguide [22] before the microwave input port, on the generator side, to maximise the amount of electromagnetic energy being absorbed by the soil. Tuning and impedance matching by tuner [11] can help to avoid a need or desirability of using a catalyst (high dielectric loss) in the particulate solids although such use of a catalyst can be possible if desired.
Electromagnetic energy from a microwave generator [12] operating within the frequency spectrum of 300 MHz to 5 GHz, is delivered to the treatment chamber [2] via waveguide [22].
Microwave transparent windows between the tuner [11] and treatment chamber [2] prevents soil and gases from entering the microwave waveguide [22].
Temperature probes [15, 16, 17, 18] are used at both ends of the treatment chamber [2] as well as at each input and output in order monitor the soil and vapour temperatures and enable process control.
The treatment chamber [2] is insulated with TBD material to maintain required internal temperatures.
The remediated soil is removed via the output screw conveyor and choke [4].
Energy levels, heating rates, input and output speed, rotation speed, temperatures and other monitored and controllable inputs and outputs are controlled, monitored and recorded via Touch Screen Computer Control System [19].
In
In the particular apparatus in
The pump [10] which creates suction to draw PFAS out of the treatment chamber [2] and through the treatment stage constituted by the plasma applicator [6] can reduce the vapour pressure in the treatment chamber and hence assist vaporisation of PFAS, although the function of the pump is also to draw the PFAS vapour from the chamber through the treatment stage. Thus the vapour containing PFAS is continuously drawn from the chamber [2] and transferred into the treatment stage [6] during the treatment of the particulate solids in the vessel by creating a negative pressure downstream of the treatment stage which thereby draws vapours from the vessel into and through the treatment stage. However it is also possible that vapour containing PFAS yielded by the soil [30] is drawn from the vessel after the irradiation of the soil in the vessel.
Because removal of water from the soil [30] being treated which occurs under the effects of the microwave irradiation generally increases the permeability of the soil to microwave energy, the process and apparatus may have a two-stage (or more than two-stage) operation. In particular, in a first-stage, the microwave irradiation is primarily conducted using parameters for vaporising water in the soil. This increases the microwave permeability of the progressively drying soil so that, in a second stage, the power of the microwave radiation generated and transmitted into the treatment chamber [2] is increased to more effectively vaporise PFAS in the at least partially dried soil.
In a further possible embodiment of the invention, the chamber [2] in which the soil is irradiated may include (or may consist of) a microwave transparent enclosure, e.g. composed of quartz or ceramic or other microwave transparent material, in which the soil resides during the irradiation. The enclosure may comprise for example a quartz or ceramic tube into which soil to be treated is fed, the tube being inclined and either continuously or intermittently vibrated so that the soil progressively travels by gravity down the inclined tube to an exit therefrom. The vibration will promote penetration of the microwave radiation (and heating effects) and/or direct exposure of the soil surfaces and interstices as the soil particles are agitated and loosened and separated and as they mix and migrate. A suitable apparatus may be a vibrator coupled to the tube and used to promote granular flow e.g. of the type in the mining industry or other industries where flow of particulates in a tube or pipe or the like is required. The vibration frequency and amplitude, and the angle of inclination of the tube, will be parameters that affect the soil movement speed through the irradiation zone, and these parameters may be selectively variable and may be empirically determined to optimise the process.
In both of the particular embodiments of
In both of the particular embodiments of
In a first possible arrangement the means for creating a partial vacuum is performed by creating the partial vacuum in the closed vessel while the soil [30] is located therein and, unlike
In a second possible arrangement having the means for creating a partial vacuum, the directing of microwave radiation into the soil is discontinued after a period of heating time, and substantially simultaneously with or after the discontinuation of the step of directing microwave radiation the partial vacuum is created in the closed vessel. This also reduces the likelihood of plasma formation and arcing occurring in the gas space when the suction step is performed to lower the vapour pressure.
In a third possible arrangement having the means for creating a partial vacuum, and applicable to the batch system of
Also in both of the particular embodiments of
Alternatively, to the two stage heating, or in conjunction therewith, the plasma inhibition may include substantially increasing the amount of inert gas, particularly helium or neon or argon, in the gas atmosphere mixed with and surrounding the soil [30] undergoing heating by microwave radiation so as to thereby inhibit the creation of a plasma in the gas space above the level of soil [30] in the chamber [2] of the vessel where microwave irradiation is occurring. The high ionization temperature of helium particularly inhibits the creation of a plasma in the gas.
In both of the particular embodiments of
The diagram of
In
It will be seen that the particular preferred embodiments of possible apparatus embodying the present invention described and illustrated herein can be used to effectively remediate soil contaminated with PFAS. The processed soil may be of better quality for re-introduction to the environment since lower temperatures are used in the PFAS extraction compared to prior soil heating systems. The apparatus can be sufficiently small scale to be transported to a site where the contaminated soil to be treated is located and the apparatus can be set up and operated at the site by systematically collecting soil throughout the site and processing it according to the method and apparatus of the invention for immediate return.
It is to be understood that various alterations, modifications and/or additions may be made to the features of the possible and preferred embodiment(s) of the invention as herein described without departing from the spirit and scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020900116 | Jan 2020 | AU | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/AU2021/000005 | 1/18/2021 | WO |
