Patent Grant
10377651
This invention relates to the generation of fine bubbles and their application in two processes, one being airlift loop bioreactors and the other being particle, in particular, algal floc, separators.
Bubbles of gas in liquid are frequently required in many different applications and usually, but not exclusively, for the purpose of dissolving the gas in the liquid. Like any industrial process, it is generally desired that this be done in the most efficient manner possible. It is widely recognised that one way to achieve efficiency is to reduce the size of the bubbles. The surface area to volume ratio of a smaller bubble is higher. Moreover, the surface tension of a small bubble means that the gas pressure inside the bubble is relatively much higher than in a large bubble. Also small bubbles rise more slowly than large bubbles and they coalesce less quickly so that larger bubbles, that rise to the surface faster, are less quickly formed.
Applications that do not involve gas dissolution exist in oil wells where bubbles rising can transport oil to the surface in certain types of well. Here small bubbles are also advantageous because it takes them longer to coalesce and form the big slugs of gas that are not effective in raising oil. The reason large slugs are not effective is because they have a small surface area compared with small bubbles and it is the surface of bubbles to which articles adhere. It has also been discovered that in the case of particles being lifted by bubbles there is a correlation between bubble size and particle size, in the sense that approximately equal sized bubbles and particles results in good collision efficiency and thus floc formation.
The corollary problem connected with fine bubbles, however, is that they are harder to produce. Reducing the size of the aperture through which the bubble is injected into the liquid is a first step, since it is difficult to form small bubbles through a large aperture. But, even so, a bubble may reach a large size by growing while attached even to a small gas-supplying aperture. Bubble separation is a dynamic process. In any event, such reduction in aperture size is not without cost, because the friction resisting flow of the gas through such a fine aperture, and through the passage leading to the aperture, means that a greater pressure drop is required. The bubble forms once the size of the bubble goes beyond hemispherical and necking-off of the bubble can occur. However, more energy needs to be applied at this stage to finally detach the bubble and generally this is simply achieved by pressing more gas into it increasing its size.
Indeed, generally, bubbles can be no smaller in diameter than the diameter of the aperture through which they are injected, and reducing the size of the bubble increases the energy needed to produce them so that a limit is reached beyond which the efficiency of the system is not improved any further. In fact, getting bubbles anywhere near the size of the aperture (i.e., less than double) would be a significant advancement.
A further problem is that, as bubbles grow beyond hemispherical, the pressure inside them drops. Consequently, two or more bubbles grown in parallel from a common source tend to be unstable beyond hemispherical. What occurs is that, beyond the hemispherical stage, one bubble grows rather more rapidly than an adjacent one (for any of a number of reasons, eg perhaps one is closer to the pressure source and so there is correspondingly less drag and greater pressure to drive the bubble formation). Once there is a size differential there is also a pressure differential with the greater pressure being in the smaller bubble. Consequently, since the bubbles are connected, the smaller bubble inflates the larger one at the expense of its own growth. The result is that, where multiple conduits are connected to a common pressure source, only a few of them end up producing overly large bubbles.
This instability of bubble formation may lead to one of the bubbles growing out of proportion to the aperture size. The necking-off and separation is a dynamic phenomenon and if the unstable bubble grows fast, it may reach a big size before it separates.
Another problem with uncontrolled bubble formation is that colliding bubbles frequently coalesce, so that the extra effort of forming small bubbles is immediately wasted. Ideally, monodisperse bubbles should be provided with sufficient gap between them to prevent coalescing. Indeed, the conditions that lead to coalescing may be dependent on a number of factors connected with a particular site and application, and that, desirably tuning of a bubble generation system should be possible so that the most efficient bubble generation can be arranged.
WO99/31019 and WO99/30812 both solve the problem of fine bubble generation using relatively large apertures by injecting the gas into a stream of the liquid being driven through a small aperture directly in front of the gas exit aperture. The stream of liquid draws the gas into a fine stream, much narrower than the exit aperture for the gas, and fine bubbles ultimately form beyond the small aperture. However, the physical arrangement is quite complex, although bubbles of 0.1 to 100 microns are said to be produced. Furthermore, although the gas exit aperture is large, the liquid into which the gas is injected is necessarily under pressure to drive it through the small aperture which therefore implies that the gas pressure is necessarily also higher, which must mitigate some of the advantage.
Numerous publications recognise that vibration can assist detachment of a bubble or, in the case of EP1092541, a liquid drop. That patent suggests oscillating one side of an annular discharge orifice. The production of liquid drops in a gas matrix can sometimes be regarded as a similar problem to the production of gas bubbles in a liquid matrix.
SU1616561 is concerned with aeration of a fish tank which comprises forcing air through a pipe where apertures open between flaps that vibrate under the influence of the gas motion and produce fine bubbles.
GB1281630 employs a similar arrangement, but also relies on the resonance of a cavity associated with a steel flap to increase frequency of oscillation of the flap and thereby further reduce the size of the bubbles.
U.S. Pat. No. 4,793,714 pressurises the far side of a perforated membrane through which the gas is forced into the liquid, the membrane being vibrated whereby smaller bubbles are produced.
U.S. Pat. No. 5,674,433 employs a different tack by stripping bubbles from hydrophobic hollow fibre membranes using volume flow of water over the fibres.
GB2273700 discloses an arrangement in which sonic vibrations are applied to the air in a sewage aeration device comprising a porous “organ pipe” arrangement, in which the pipe is vibrated sonically by the air flow. The invention relies on vibration of the aerator by virtue of the organ pipe arrangement, losing much of the energy input through inevitable damping by the surrounding water.
DE4405961 also vibrates the air in an aeration device for sewage treatment by mounting a motor driving the air pump on the aeration grid employed, and so that the grid vibrates with the natural vibration of the motor and smaller bubbles result. DE19530625 shows a similar arrangement, other than that the grid is oscillated by a reciprocating arrangement.
JP2003-265939 suggests ultrasonically vibrating the surface of a porous substrate through which a gas is passed into a liquid flowing over the surface.
From the above it is apparent that small bubble generation has application in the sewage treatment industry, in which it is desired to dissolve oxygen in the water being treated. This is to supply respiring bacteria that are digesting the sewage. The more oxygen they have, the more efficient the digestion process. However, a similar requirement exists in bioreactors and fermenters generally where they are sparged for aeration or other purposes. Specifically, the yeast manufacturing industry has this requirement, where growing and reproducing yeast bacteria need constant oxygen replenishment for respiration purposes. Another application is in the carbonisation of beverages, where it is desired to dissolve carbon dioxide into the beverage. A process not looking to dissolve the gas but nevertheless benefiting from small bubbles is in the extraction of hard-to-lift oil reserves in some fields which either have little oil left, or have the oil locked in sand. Indeed, much of the oil in Canada's oil reserves is in the form of oil sand. Bubbling gas up through such oil-bearing reserves has the effect of lifting the oil as the bubbles rise under gravity and bring the oil with them. The bubbles are formed in water and pumped into the well or reserve and the oil is carried at the interface between the gas and water of each bubble as it passes through the reserves. The smaller the bubble, the greater is the relative surface area for transport of the oil.
Another application of bubbles is in particle separation from a liquid suspension of the particles, of which an example application is algal separation. This might be desired for one or both of two reasons. A first reason is to clarify water contaminated with algae. A second reason is to harvest algae grown in water. The process is not limited to algal separation; any mixer comprising solid particles can comprise the use of bubbles which attach to suspended particles and carry them to the surface from which they may be scraped, either to recover the particles or clarify the water. However, attachment of the bubbles to the particles is problematic, particularly if the particles are charged when they may simply bounce off bubbles and not attach to them. Dissolved air flotation (DAF) is a known technique where air is dissolved under substantial pressure into water which, when released into the separation tank immediately releases large quantities of small bubbles. However, there are two issues. The first is the substantial energy requirements to compress and dissolve air in water. The second is the turbulence of the bubbles released into the tank.
It is an object of the present invention to improve upon the prior art arrangements. It is also an object to provide process applications using small bubbles.
In accordance with a first aspect of the present invention there is provided an airlift bioreactor comprising a liquid fermenter tank for microorganisms. The tank has sides and a base. The liquid in the tank has a top surface above which is a header space. The tank may be divided by a divider into a riser section and a downcomer section. The sections are interconnected at the top and bottom of each section. A diffuser of a microbubble generator is disposed at the base of the riser section and is arranged to inject bubbles of gas into the riser section, whereby the apparent density of the fluid in the riser section and downcomer zone is changed, causing a circulating flow of the fluid: up the riser section; over a divider at the top of the riser section; down the downcomer section: and back into the riser section under the bottom of the divider. Said flow, at least in the riser section, is non-turbulent laminar flow, having a Reynolds number less than 2000. Preferably, the Reynolds number is less than 200. In this connection, the Reynolds number is based on the liquid flow velocity, its constitutive properties and the pore diameter of the diffuser. Throughout this specification, including the claims, the term “airlift” should be understood to include “gaslift” where gas other than air is injected.
Indeed, while a physical divider is possible, comprising, for example, a draft tube in a cylindrical tank, a physical divider is not, in fact, absolutely necessary because the requisite circulation occurs naturally, when the flow is entirely laminar. The divider is simply the boundary separating the rising flow from the returning downcomer flow, which separate effectively from one another without turbulence or significant mixing in these conditions.
By arranging for laminar flow, which is achieved by taking into account a number of different factors including the density and viscosity of the liquid as well as the rate of injection and size of the bubbles introduced, the energy required for the gasification and circulation of the fermenter can be reduced to very low levels. A most important aspect is the size of the bubbles that must have such a slow terminal velocity in the liquid that, to all intents and purposes, they are stationary in the liquid and primarily generate movement of the liquid through the apparent density change of the liquid and which results in mass transport of the liquid including the bubbles. Absolutely stationary bubbles (with respect to the liquid) are of course impossible because of the density difference between the gas injected and the liquid which will always cause some movement, however small the bubble. However, because the frictional resistance of a rising bubble is proportional to its surface area, whereas the gravitational force causing it to rise is proportional to bubble volume, the smaller the bubble the slower its rise in any given liquid. In an aqueous environment, a bubble of less than 100 μm diameter rises sufficiently slowly not to create significant turbulence. Nevertheless, with sufficient number of such small bubbles per unit volume, the apparent density of the bubble-containing-liquid can be reduced to such an extent that the density difference can drive an entire column of liquid to rise, possibly at a much greater rate than the rise of the bubble with respect to the liquid. Indeed, the rate of injection of one bubble followed by a succeeding bubble can be close to the rate of rise of the liquid so that the injection itself generates little or no turbulence.
Depending on the particular fermentation taking place, preferably a proportion of the bubbles are carried over the divider into the downcomer section whereby gas transport across the bubble surface also takes place in the downcomer section.
This only occurs once the rate of fall of the liquid in the downcomer exceeds the rate of rise of the bubble in the liquid. Again this reduces wastage (of bubbles reaching the surface), if the object is the dissolve all the gas of the bubble in the liquid, which is frequently the case in fermenters. In aqueous fermenters, bubble size needs to be less than about 100 μm in diameter.
Conveniently, more than 90% of the bubbles having a size in the range 10 to 100 μm diameter (preferably 20 to 40) and a bubble density of at least 50 million per cubic meter, optionally at least 100 million.
Preferably, the gas holdup is less than 2%, optionally less than 1%. Holdup is the overall volume of gas in bubbles per unit volume of liquid.
In accordance with another aspect of the present invention there is provided a suspended particle separation tank, comprising: a floor having a floor area; liquid in the tank having suspended particles; and a diffuser of a microbubble generator, which diffuser is disposed at the base of the tank and is arranged to inject bubbles of gas into the tank to reduce the apparent density of the liquid above the diffuser, thereby creating a flow of the liquid and gas bubbles that is a non-turbulent laminar flow having a Reynolds number less than 2000, wherein more than 90% of the bubbles have a size in the range 10 to 100 μm diameter and a bubble density of at least 50 million per cubic meter, the Reynolds number being based on the liquid flow velocity, its constitutive properties and the pore diameter of the diffuser.
The Reynolds number may be less than 200. Optionally, more than 90% of the bubbles have a size in the range 20 to 50 μm diameter. The bubble density may be at least 100 million per cubic meter.
Preferably, the gas holdup is less than 2%, optionally less than 1%. The diffuser may be disposed across substantially the entire floor area of the tank. A specific example of a suspended particle separation tank is an algal separation tank.
The suspended particle separation tank may take the same form as the airlift bioreactor described above.
In this aspect, the invention also provides a method of particle separation comprising the steps of providing a separation tank as defined above comprising an aqueous mixture of suspended particles to be separated from the water, adding a flocculant to cause the particles to coagulate in flocs and adjusting the acidity of the mixture to a predetermined pH appropriate for the selected flocculant, and injecting bubbles into the tank, optionally across substantially the entire area of the floor of the tank, wherein more than 90% of the bubbles have a size in the range 10 to 100 μm diameter (preferably 20 to 40) and a bubble density of at least 50 million per cubic meter and wherein the flow created by the bubbles injected is a non-turbulent laminar flow having a Reynolds number less than 2000. Again, the Reynolds number is based on the liquid flow velocity, its constitutive properties and the pore diameter of the diffuser.
The foregoing separation technique has application also in the minerals sector and for oil water emulsions. It is also feasible to separate yeast or, indeed, any microorganism.
Preferably, the bubbles introduced create non-turbulent laminar flow having a Reynolds number less than 200. Preferably, the Reynolds number is less than 20. The benefit of a non-turbulent introduction of the bubbles is two-fold. Firstly, little energy is employed, so that the cost of the process is minimised, and secondly the flux rate of the bubbles is such that they gently approach flocs of coagulated material without disturbing them. Indeed, the problem of attachment is avoided because the particles (flocs) are much larger and so the bubbles can gently lift from underneath the floc rather than having to chemically attach and connect. This is not to suggest that chemical attachment does not occur, but rather that time is permitted for the attachment to occur through the gentle pressure caused by the constant, albeit small, force of gravity. The tendency of bubbles to bounce off or slip by particles is reduced.
The method is continued until a desired level of clarity of the water remains and at least until the sludge layer on the surface of the water comprising the particles separated from the water has thickened and thinned.
By “thickened and thinned” is meant that the solids density of the sludge layer has increased through compression from below by accumulated gas bubbles lifting the sludge against the surface and consequential squeezing out of water from the sludge layer, and whereby the thickness of the sludge layer reduces.
In some embodiments, certainly in the case of algal separation, the flocculant may be a metallic inorganic coagulant, such as iron or aluminium salts, added in solution. Coagulation is achieved with the coagulants dissociating into Fe3+ and Al3+ respectively as well as other soluble complexes having varying high positive charges. Essentially, the rate and extent to which these trivalent ions and other complexing species adsorb onto colloidal surfaces is pH dependent. At room temperature, under acidic pH, trivalent species-Fe3+ and Al3+. are the dominant species in the continuous phase. These predominant trivalent species are the most effective in colloidal charge neutralization and attach to the negatively charged algal cell. The excess H+ present under low pH react with hydroxides of these metals to further release the trivalent metal species. As a consequence, more Al3+ and Fe3+ species become available again for charge neutralization, but the amount of hydroxide species is reduced. As pH shifts away from acidity however, H+ concentration becomes less than OH− and the amount of trivalent ions present in solution reduces. These prevalent OH− react freely with the available trivalent metallic species to form the corresponding metallic hydroxide species. As such, hydroxide species become predominant under alkaline conditions attaching to algal cells and precipitating as large gelatinous flocs. Increased concentrations of hydroxide species for aluminium and ferric salts respectively has been reported as pH moves beyond pH 7 at room temperature. This explains the large flocs generated under alkaline condition. It is for these reasons the recovery efficiency is observed to increase again under alkaline pH. Consequently, either acidic or alkaline conditions may be selected to enhance the flocculant effect. (Note that flocculation and coagulation are used interchangeably for the same effect). Nevertheless, despite the above, acidic conditions are preferred. Despite large flocs being good vehicles for sweep flocculation, the overall efficiency under alkaline conditions for aluminium and ferric sulphate coagulants is lower than under acidic conditions.
This observation can be explained by the difference in charge density of species. The higher the size and charge of the species, the more effective the coagulation process will be. Because these charges increase with increasing acidity, recovery efficiency is highest under acidic pH. In addition, relatively larger flocs are developed under alkaline state and given that as particle size increases the residence time of the rising microbubble-floc agglomerate also increases leading to a prolonged flotation time. Moreover, the lifting force of microbubbles diminishes with increased particle size.
By contrast, the condition is quite different for FeCl3 however. Whilst a similar tendency occurs under acidic condition, FeCl3 exhibits a rather different behaviour under basic pH. It is note-worthy to reiterate that ferric chloride produced the overall best recovery result so far discovered. This is because ferric salts are relatively less soluble than aluminium salts. In addition, hydroxides of aluminium are amphoteric—containing both basic and acidic functional groups. Furthermore, the addition of ferric salts decreases the solution pH and the closer the pH tends towards acidity, the concentration of trivalent species in the solution increases. Thus the optimum pH for algal separation ranges from 5-7 for ferric chloride but for aluminium and ferric sulphate, two ranges are effective-5-6 and 8-9. Overall, the process governing these reactions is very complex and by no means easy to fully detail especially also as the growth medium itself may contain vital and very reactive chemical constituents.
Preferably, said separation tank is also a fermenter tank as defined above, comprising algae, which are grown through photosynthesis. The algae are harvested when required by introducing the flocculant into the acidity-regulated liquid so as to causes the algae to coagulate together in flocs which are lifted to the surface by the microbubbles. With a laminar flow of the fermenter liquid, the bubbles do not disrupt the flocs and effective clarification of the liquid can be achieved and the algae subsequently harvested by scraping from the surface.
Other kinds of fermenters are anaerobic digesters. An anaerobic digester is a processing unit in a wastewater treatment plant where organic matter is broken down via anaerobic bacteria in the absence of oxygen. The biodegradation of organic matter in an anaerobic digester takes place through four steps. The first step is an hydrolysis stage which converts the complex organic matter in to a simple state. The second step is the acidogenesis stage. In this stage, the product of the first stage converts into volatile fatty acids. Volatile fatty acids are converted into acetate in the third step by acetatogenic stage. Finally the acetate and carbon dioxide with hydrogen produced in second step convents into methane and carbon dioxide in the methanogenesis stage. Each stage is mediated by specific type of bacteria. Each bacteria requires a specific environment. Methanogenesic bacteria are more sensitive to change of operating conditions. However, there are general operating conditions, such as temperature, pH, Carbon-nitrogen ratio, and ammonia etc, appropriate for all the bacterial consortia.
The hydraulic retention time of a mesophilic anaerobic digester is approximately 20 days. Then the sludge discharges as effluent. The digested sludge (effluent) contains organic matters (biodegradable), anaerobic bacteria and some dissolved gases, for instance carbon dioxide and hydrogen sulphide. The presence of these dissolved gases has negative impact on piping and the downstream processing units. Corrosion is one potential problem in piping metals. In addition, the generation of biogas continuously in digested sludge during transfer creates a gas-liquid mixture. Even if a small phase fraction of gas, it degrades the performance of pumps due to cavitation phenomena.
Anaerobic digestion is an important source of methane in the search for green energy. It is UK Government policy to recycle 50% and recover energy from 25% of human waste by 2020. Anaerobic digestion breaks down food and plant waste to produce biogas, a mixture of methane and carbon dioxide which is burnt to produce electricity and a residual material which can be used as a soil improver.
Thus, in another aspect of the present invention there is provided an anaerobic digester comprising a liquid fermenter tank for anaerobic microorganisms and a diffuser of a microbubble generator to introduce bubbles of non-oxygen containing gas into the digester whereby methane and acid gases produced by the digestion are exchanged across the bubble surface to strip such gases from the liquid.
The anaerobic digester may take the same form as the airlift bioreactor described above.
In one embodiment, at a commencement phase of said digestion, said gas is nitrogen or another inert gas that merely strips the fermenter of oxygen to promote the onset of anaerobic digestion.
In another embodiment, during a growth phase of the microorganisms in the digester, said gas is or comprises the biogas generated and released into a head space of the fermenter tank. This typically comprises approximately 60% methane and 40% carbon dioxide. While reintroduction of bubbles of such gas into the fermenter does little to change the equilibrium of such gases in the liquid, it provides an escape route for the methane which in physical terms should be gaseous at room temperatures and the temperature of anaerobic digestion (typically 35° C.) it typically clings to particles such as the microorganisms themselves. Locally positioned bubbles permit methane to escape the liquid phase. Inside the bubbles, which thus grow in this environment, the balance of carbon dioxide remains so that it is also stripped from the liquid, along with acid gases.
Conventional anaerobic digestion does not need a nutrient gas. However, in yet another embodiment, during a growth phase of digester, said gas is or comprises carbon dioxide. Not only does this preferentially extract methane and hydrogen sulphide, but also provides “food” for the methanogenesic bacteria.
In another embodiment, at an endphase of said digestion, said gas is also is nitrogen or another inert gas that serves in this event to strip methane and hydrogen sulphide. Not only does this reduce the acidity of the remaining liquid but also it promotes further growth of the methanogenesic bacteria enhancing the methane output.
Thus, microbubbles introduced into the reactor increases methane yields, while at the same time ‘sinking’ waste CO2.
Such a process has the possibility to increase or even double the amount of methane extracted through anaerobic digestion. Methane tends to adhere to the microorganisms and biomass in the reactor, rather than be released to the gas headspace. By using carbon dioxide microbubbles, it is found that, in addition to removing the methane already produced more effectively, the production rate of methane increases. The dissolved carbon dioxide is taken up as food by methanogenesic bacteria, thus increasing their production of methane. Microbubbles speed up gas exchange by providing more food to the bioculture, but also by removing the methane, which has an inhibitory effect on metabolism.
Preferably, the carbon dioxide is sourced from power production from the methane, or from sequestered carbon dioxide from other sources.
Also, fertilizer recovered from anaerobic digestion has hitherto been dried and trucked to farms, despite the fact that the digestate is about 90% water and would benefit from other transport mechanisms such as piping. This is necessary because the digestate is highly acidic and corrosive. By stripping out the acid gases, leaving the digestate substantially neutral, this barrier to transport via pumps and pipes is removed, improving the attraction of the anaerobic digestion process and the production of more environmentally sustainable electricity. It also supports sustainable agriculture by recovering the nutrients, particularly phosphates and potassium, which are not renewable without recycling.
This is better explained by reference to the reactions taking place. There are two competing reactions, the desirable methanogenesis reactions and the competing sulphide reduction reactions (see equations (10)-(13) below). From these equations, it can be seen that the sulphide-reduction reactions have greater thermodynamic driving force than methanogenesis, so that methane production is adversely impacted by sulphide concentration. Moreover of H2S has a negative impact on the methane production bacteria. The concentration of H2S can be taken as an indicator of inhibition of methanogenesic bacteria.
Thus removal of dissolved H2S from sludge prevents inhibition of methanogenesic bacteria and reduces odour from digested sludge. Normally, the removal of CO2 and H2S take place through displacement of biogas generated (CH4 and CO2) or by contact with head space in the top of sludge. But this is insufficient to remove the dissolved gases. Mixing of the digested sludge provides intimate contact between sludge and bubbles of biogas or headspace.
Thus a method of operating an anaerobic digester as defined above comprises the steps of:
The flow generated by the bubbles may be non-turbulent laminar, having a Reynolds number less than 2000, the Reynolds number being based on the liquid flow velocity, its constitutive properties and the pore diameter of the diffuser. Sufficient bubbles must be introduced, of course, and sufficient proportion of them must be small enough (in the range 10 to 30 μm) to be retained in suspension to provide a site for microorganisms to attach and enable the transfer of methane from their surface into the bubble. There will be sufficient number of bubbles introduced, and sufficiently small, if the gas holdup of the bubbles in the tank one hour after at the end of the period provided in step d) is at least of 0.05%, preferably at least 0.5%.
During the digestion, step d) may be repeated daily and the period of time in step d) may be between 30 and 120 mins. the bubbles introduced in step d) may comprise carbon dioxide, indeed, more than 90% carbon dioxide, or essentially pure carbon dioxide. When the yield of biogas from the digester falls below a predetermined amount, step d) may be repeated a final occasion with said bubbles comprising substantially only nitrogen gas, whereby remaining methane, carbon dioxide and hydrogen sulphide is stripped from the digestate to neutralise the pH of the digestate. After this step, the digestate can be pumped from the tank and transported by pipeline to an irrigation array for land fertilisation. This is much less energy consuming than drying the digestate and transporting it by road.
While the anaerobic reactor has application in the digestion of waste, it also has application in yeast fermentation to (bio) ethanol and in anaerobic ammonium oxidation (anammox).
In accordance with another aspect of the present invention there is provided a method of producing small bubbles of gas in a liquid comprising the steps of:
Thus the entire energy of the system is in oscillating the gas, and not the conduit through which it is passed, whereby the efficiency of the system can be maximised. Energy is not wasted in oscillating the conduit that will have a much greater mass and consequently will require more energy to oscillate. Despite any resonance, friction still accounts for a proportion of the energy employed.
Sonic and ultrasonic vibrations, as suggested in GB2273700 and JP2003-265939 respectively, are high frequency and may not be as effective in generating bubbles. Although high energies can be imparted, the most effective detachment of bubbles is with longer stroke (higher amplitude) oscillations, rather than higher frequencies.
Preferably, said oscillations effected by the fluidic oscillator are effected at said frequency between 1 and 100 Hz, preferably between 5 and 50 Hz, more preferably between 10 and 30 Hz.
Preferably, the bubbles formed are between 0.1 μm and 100 μm in diameter, more preferably between 30 and 80 μm.
Preferably, said oscillation is of the type that has between 10% and than 30% backflow of gas from an emerging bubble. Indeed, said oscillation preferably is of the type that has between 10% and 20% backflow of gas from an emerging bubble. This is preferably provided by an arrangement in which a fluidic oscillator divides flow between two paths, at least one of said paths forming said source.
Backflow here means that, of a net gas flow rate from said conduit of x m3s−1, (x+y) m3s−1 is in the positive direction while (−y) m3s−1 is in the negative direction, 100(y/(y+x)) being defined as the percentage backflow. Some backflow is largely inevitable, particularly with the arrangement where flow splits between paths, since there will always be some rebound. Indeed, such is also a tendency with bubble generation since, with the removal of pressure, back pressure inside the bubble will tend to cause some backflow. Indeed, backflow here means at the conduit opening, because backflow may vary by virtue of the compressibility of the gas.
Preferably, said means to oscillate flow from one output port to the other comprises each output port being controlled by respective control ports. Preferably, the control ports are interconnected by a closed control loop. Alternatively, a branch of each output port may supply each respective control port, whereby part of the flow in an output port becomes a control flow, switching the supply flow from that output port to the other output port.
When a control loop is employed, the control ports are arranged so that each has reduced pressure when the gas flows through its respective output, and increased pressure when there is no flow through its respective output. Consequently, when gas flows out of a control port, it detaches the main supply flow of the gas from the wall in which said control port is formed and switches that flow from the output port associated with that wall to the other output port, attaching the main flow from supply port to the wall associated with the other control port, and so the situation reverses with the main flow from the supply port oscillating between said output ports with a frequency determined by a number of factors including the length of the control loop.
Preferably, there are at least two of said conduits, each output port being connected to one or the other of said conduits.
The frequency of the oscillations may be adjusted by changing the length of said closed loop.
Preferably, the volumetric flow rate for each cycle of oscillation is sufficient to fill a bubble at the opening of each conduit to at least hemispherical size before the oscillation is switched, so that all the bubbles have substantially the same size before being separated from the conduit opening by the break in pressure.
Without wishing to be bound by any particular theory, it is believed that initial growth of a bubble from flat across the mouth of the conduit towards hemispherical accelerates and gives momentum to the liquid being displaced away from the mouth. Normally, as more gas is supplied, the bubble simply grows and the momentum of the retreating liquid continues, albeit decelerating, since the rate of growth of bubble radius is proportional to the cubed root of the volume of gas in the bubble. However, if the supply of gas to the bubble is cut off suddenly, a dynamic separation regime is observed whereby the bubble is “torn-off” the conduit. The bubble therefore forms at a much smaller size than would otherwise occur with a steady state fill pressure. Some backflow assists the necking of the bubble and the subsequent break-off of it.
Preferably, the conduit opens in the liquid at a surface of the material in which the conduit is formed, said surface being in a plane which is substantially vertical with respect to gravity. It is found that the tendency of the bubble to rise transversely with respect to the conduit by virtue of the disposition of the material surface surrounding the conduit serves to cause a pinching-off effect as the bubble rebounds at the end of each oscillation. Indeed, in one experiment, where the surface containing the conduit was horizontal, bubbles of diameter 500 microns in diameter were produced and yet, by turning the surface through 90 degrees with all other things being equal, bubbles of diameter one tenth of that were achieved.
In one arrangement, said conduit comprises a membrane having a slit which is closed, gas pressure behind the membrane serving to distend the slit to permit a bubble of gas to form through the slit, the slit closing behind the bubble, wherein the oscillation of the gas flow is synchronised in terms of pressure, flow rate, amplitude and frequency with the elastic properties of the membrane to encourage small bubble formation. In this respect, with a constant gas pressure, the mode of operation of such a membrane diffuser is oscillatory and consequently the oscillations of the gas can be synchronised so that, as the pressure behind the slit drops, sufficient gas has already exited the slit that the bubble cannot be squeezed back through the slit by its own surface tension before the slit closes.
In this respect, the material of the surface through which the conduit is formed is preferably non-wettable by the gas, so that the bubble does not tend to stick to it. Glass is a suitable material in this respect, although other materials such as Teflon® are also suitable.
The invention permits retro-fitting in existing installations that comprise a supply of gas under pressure and one or more bubble generators supplied by said supply and comprising a plurality of conduits opening into the liquid. In this event, the gas oscillator is interposed between the supply and bubble generator. Preferably, said bubble generator comprises a chamber connected to said gas supply and a porous wall of said chamber separating said chamber from the liquid and comprising said plurality of conduits. Said conduits may be apertures formed in said wall. The wall may be metal, for example sintered metal in which said conduits are pores in said metal. Alternatively, the wall may be a porous ceramic and the conduits being the pores of said ceramic.
Such methods of bubble production as described above may be employed in the fermenters and separators as defined above.
In connection with the algal separator, as well as in anaerobic and other digesters, such methods of bubble production as described herein are especially beneficial because of their low energy consumption. To introduce bubbles into a tank, the pressure of the gas supply need only be about half a bar higher than the hydrostatic pressure of the liquid at the point of introduction. In a typical tank with a three meter height of liquid, traditional DAF (dissolved air flotation) injects liquid saturated with gas at about 6 bar pressure into the ˜1.3 bar clarifying tank. The turbulence caused by the liquid injection and release of the bubbles, despite their small size, is significant. The bubble production of the present invention injects at ˜2 bar into the ˜1.3 bar tank, and it is gas, not liquid, that is injected so there is no liquid turbulence. The present invention achieves the onset of the bubble creation with little more than the energy to create the bubble and the momentum needed to overcome the head of liquid above it. Consequently, each bubble can be injected at not much more than its terminal rise velocity.
While turbulent flow has been seen as beneficial with regard to attachment in flocculation processes (because it increases the collision rates of bubbles and generalized particles (droplets included)), the shear instability of turbulent flows also produces strong eddies that destroy flocs.
The present invention produces bubbles that rise in laminar flow. Moreover, at low gas flow rates, the gas phase holdup can be less than about 1%. Given that the traditional levels of gas phase holdup in dissolved air flotation is in the order of 10-12%, there is no comparison with the bubble flux; that is, there is much less kinetic energy/momentum injected with the present invention, so that, on the face of it, there is much less lift force as well. It is therefore unexpected that the present invention achieves comparable separation performance and rates to traditional DAF.
Without being bound to a particular hypothesis, one theory is that the flocs that form with a laminar flow of few small bubbles do not break up because of the lack of the turbulence destruction mechanism, and achieve comparable separation performance and rates. Additionally, because energy dissipation rates are typically proportional to the Reynolds number of the liquid flow, based on the diameter of the exit pore/nozzle, the present invention provides a Reynolds number in the range of 10-100, whereas conventional DAF has exit-nozzle Reynolds numbers of 10000-100000. It is therefore expected that the present invention dissipates ˜1000-fold less energy. The capital cost of equipment, due to working at pressures less than 2 bar, is substantially less than working at pressures of 6 bar for DAF.
Embodiments of the invention are further described hereinafter, by way of example, with reference to the accompanying drawings, in which:
a and b are respectively a schematic perspective view of a diffuser employed in a method according to the present invention and a side section showing bubble pinch-off;
a and b are respectively side sections, (a) to (e), through an elastic membrane showing the development of a bubble, and a graph of differential gas/liquid pressure ΔP across the membrane at each of the stages of bubble formation shown in
a and b are histograms of (a) bubble size distributions and (b) bubble density from a stainless steel mesh diffuser used in the set up of
i a to c are photographs of the flotation unit of the set up of
ii is a graph over the three stages referred to in
a to c are graphs of recovery efficiency at 150 mg/L coagulant dose against time at varying pH levels for all three metallic coagulants mentioned with respect to
a to c are plots of algae recovery efficiency as a function of pH at different coagulant concentrations;
a to c are graphs of algae recovery efficiency at pH 5 as a function of time at varying coagulant concentrations for the three metallic coagulant types;
a to c are snapshots of simulated gas concentration in the tank (across a half section thereof) at (a) diameter 20 μm and (b) after 100 μm over a development period from 0, 40, 80 and 120 sec after commencement, and (c) after 120 sec for different bubble diameters (20, 60, 100, 120 and 140 μm);
a and b are graphs showing (a) methane production from the digesters of
a and b are graphs showing (a) carbon dioxide produced from the digester, with and without nitrogen injection, and (b) hydrogen sulphide produced from anaerobic digestion, again with and without nitrogen sparging.
In
If the flow is predominantly into outlet passage 14b, for example, then the flow of fluid follows closely wall 14g of the inlet passage 14a and across the mouth of control passage 14d, reducing the pressure in the passage accordingly by virtue of the venturi effect. Conversely, there is not so much flow adjacent control passage 14e. Consequently, a pressure difference is created in the control loop 22 and fluid flows from control port 20f, around control loop 22, and enters control port 20d. Eventually, the flow out of the control passage 14d becomes so strong that the flow from inlet passage 14a to outlet passage 14b detaches from the wall 14g containing the mouth of control passage 14d, and instead attaches on the opposite wall 14h, whereupon such flow is switched to passage 14c. Then, the opposite condition pertains, and the pressure in control port 14e is reduced, and grows in control port 14d, whereupon the flow in control loop 22 reverses also. The arrangement therefore oscillates, in known manner, dependent on several factors including the length of loop 22, which length affects the inertia of the control flow and the speed with which it switches. Other factors including the geometry of the system, back pressure from the outlets and the flow through the diverter 10 also affect the frequency.
The arrangement shown in
When the outputs A,B of diverter 10 are connected to bubble diffusers 30 in an arrangement 100 such as illustrated schematically in
A suitable diffuser 30 is shown in
Indeed, as regards
While described above with reference to sewage treatment, as mentioned above, the present invention may have application in numerous other fields in which a gas needs diffusing into a liquid. In the sewage treatment regime, other than in the search for efficiency, the equality of the bubble size or their absolute minimisation in size may not be imperative. Rather, the capacity to retro-fit the arrangement may be more important. However, in new installations, or in other applications where, for particular reasons, a very small bubble size, and very even bubble size distribution, is desired, the arrangement illustrated in
Referring first to
In
Passage 62 may be larger than passage 64, but the ports 62a are certainly larger than the ports 62b. The reason for this is that the passage 62 is arranged to carry liquid, the liquid in which the diffuser 50 is sited. The passage 64, on the other hand, carries gas. The arrangement is such that the diameter of the gas port 62b is small, according to the desired size of bubble to be formed, and possibly as small as 0.5 mm or less depending on the technique employed to form the port 64a. In Perspex™-type material, the holes can be drilled mechanically to about 0.5 mm, but other methods exist to make smaller holes if desired.
Turning to
However, when the air supply 16 is turned on the pressure in branch A grows, albeit oscillatingly, to half the supply pressure, and this is arranged to be greater than the hydrostatic pressure at the bottom of the tank 80 so that air ultimately passes along the passage 64 and exits the ports 64a forming bubbles 90 in the liquid 82. When a pulse of pressure arrives in outlet B, the level of liquid in the line 88 drops, since the bleed 84 is controlled by a valve 94 transmitting the pressure pulse into a flow of liquid into the passage 62 and out of respective ports 62a. However, when the diverter switches flow back to outlet A, the hydrostatic pressure in the tank 82 returns the liquid through ports 62a refilling the line 88. Whether the line 88 is refilled entirely, so that the pressure outlet 88 is ambient by the time flow is switched again to outlet B is purely a design matter. It can be arranged that only when the pressure in the line 88 is substantially at the hydrostatic pressure near the bottom of the tank 80 is there sufficient pressure in the line 88 to bleed enough gas through the valve 94. In any event, the liquid level in the line 88 must be arranged at some point between the top and bottom of the tanks, and to oscillate above and below that level as gas supply is switched to and from the output B.
The ports 62a are larger simply because of the increased resistance of the liquid to flow, but also because a large flow pulse, rather than a narrow flow jet, is better at knocking off bubbles.
The back pressure regime in outputs A,B is arranged such that it does not adversely interfere with the oscillation of diverter 10, and each pulse into output A is arranged such that a hemispherical bubble forms at the mouth of each port 64a. When the pulse switches to output B, a jet of water issues from the mouth of each port 62a and is directed against the side of the bubble on the ports 64a and knocks them off. The bubbles 90 so formed are therefore very small, or at least much smaller than they would otherwise be, and of very even size distribution.
When the arrangement described above is employed with a liquid of relatively low viscosity such as water, it works very well. However, when it is employed with more viscous liquids, such as oil, a different mechanism is observed which gives rise to an alternative arrangement of the present invention (shown in
With high viscosity liquids such as motor oil as the liquid 82, the oscillations can be seen to permit introduction of some of the liquid into the conduit 64′ through some of the ports 95. The exact mechanism is not yet explained, although could be through the venturi effect of high flow of gas periodically through the conduit 64′ drawing liquid through certain of the ports (eg ports 95a), or it may be due to the low pressure phase of the oscillations and the relatively higher pressure in the liquid at this point in the gas pressure cycle. In any event, despite there being a net flow of gas through the conduit 64′ and out of the ports 64a′, nevertheless, plugs 97 of liquid appear in the conduit and progress along it, driven by the net flow of gas. As they travel along the conduit, they progressively close off mouths 98 of the ports (eg port 95b) and liquid enters the ports behind the gas already in the port. When the plug liquid contacts the main body of liquid 82 at the open end 99 of the port, the gas/liquid interface in the port completes the gas/liquid interface of bubble 101 presently being formed by the gas. Consequently it is easily detached from the port 95b and released into the liquid body 82.
With this mechanism, an inclined series of bubbles rise from the ports 64a′; and possibly several such streams, if several plugs 97 form (as shown for example at 103 where the plug is almost exhausted having pushed off a series of bubbles 105 and losing some of its volume to the main body of liquid 82). Also a new plug 107 is shown being drawn into the conduit 64′.
If such a mechanism is working with lower viscosity systems, (where the mechanism is more difficult to observe by virtue inter alia of the greater frequency of operation of such systems), then the above described mode of operation of the knock off system shown in
In
Turning to
By matching the oscillation of the gas flow to the elastic resonance of the membrane the formation of small bubbles is possible with little energy expenditure.
1. Application in Algal Separation
Flotation has become the mainstay for colloidal particle separation from an aqueous solution. In essence, the key subprocess is the generation of microbubbles that attach to hydrophobic particles, resulting in buoyant aggregates which then rise to the surface of the flotation cell, where following bubble rupture, the particles are recovered (Dai et al., 2000). Recovery of valuable end-products has been the centre of attraction in flotation separation. A large body of experimental evidence show the reclamation of products such as oil (Al-Shamrani et al., 2002b, Al-Shamrani et al., 2002a, Hosny, 1996, Li et al., 2007, Zouboulis and Avranas, 2000), minerals (Englert et al., 2009), algae (Teixeira and Rosa, 2006, Teixeira et al., 2010) and in cases where water scarcity is the challenge, potable water (Kitchener and Gochin, 1981, Edzwald, 1995) can be achieved by flotation separation.
Algae, in particular, are a reasonable target for flotation separations for biomass processing, but as yet untried with the dense solutions produced from algal cultivation. Pienkos and Darzins (2009) highlight harvesting and dewatering operations as a key challenge for economic algal biofuels processing. The density can reach 10 g/L of dry biomass, which is substantially higher than DAF removal of fine particles in water purification. Gudin and Thepenier (1986) estimated that harvesting can account for 20-30% of the total production cost. Molina et al. (2003) present possibly the closest technique to microflotation for algal harvesting—flocculation and bioflocculation followed by sedimentation. Flotation is often viewed as “inverted” sedimentation. The Jameson Cell (Yan and Jameson, 2004) is an induced air flotation process which also achieves high separation performance for microalgae (98%) and phosphorus. When present in effluent water, algae could be a pernicious contaminant in potable water treatment otherwise, but could be regarded as a raw material given the numerous products obtainable from the unicellular organism such as β-carotene (Borowitzka, 1992) glycerol, biomass and in particular, biofuel from lipid (Chisti, 2007). While most previous works have focused on the production of biomass from algae (Zimmerman et al., 2011b), only few researchers have been concerned with harvesting biomass and lipid from algae. Whether it is for potable water treatment or recovery of algae for biofuel, flotation separation is a viable means for harvesting algae.
However for flotation to be successful, it is vital for particles to be hydrophobic (Gochin and Solari, 1983) and ultimately attach to gas bubbles. Chemical coagulation is employed to aid this process. Through the suppression of the electrical double layer of particles, particle-particle interaction is facilitated, leading to the formation of larger colloidal structures or flocs. Following collision particles adhere to the surface of gas bubbles forming a strong stable particle-bubble union (Dai et al., 2000). Removal of flocs is hugely dependent on the coagulation pH but another important factor is the bubble size and flux. Bubbles enhance particle recovery by providing the lifting force necessary for transport and separation. Separation efficiency varies inversely with bubble size (Dai et al., 1998, Dai et al., 2000).
Application of gas bubbles in liquid is gaining extensive application across many fields. Generally, these processes entail efficient ways of facilitating bubble-particle interaction in the liquid rather than merely passing the bubbles through the liquid without it actually adhering and lifting the particles out of solution. Best practices however, require that the particles in the aqueous solution attain optimum collision, attachment and stability efficiencies respectively (Derjaguin and Dukhin, 1993) with the gas bubble for complete capture prior to reaching the liquid surface. As such, one of the most efficient ways of achieving this is miniaturising the bubbles. Due largely to their high surface area to volume ratio, particle flotation by small bubbles occur more rapidly and efficiently. Ahmed and Jameson (1985) estimate a 100-fold enhancement in separation performance for fine particles with bubble size reduction from approximately 700 to 70 microns. Further, small bubbles have gentle convective force relative to large bubbles by reason of their low rise velocity (Schulze, 1992), resulting in tender contact with fragile flocs. To this end, several microbubble generation techniques have been thus developed for flotation applications. Examples include: turbulent microflotation (Miettinen et al., 2010), Induced Air Flotation (IAF) (El-Kayar et al., 1993), Dissolved Air flotation (Edzwald, 2010), and Electroflotation (Hosny, 1996). Of the several techniques available, dissolved air flotation and dispersed air flotation are the most widely developed. Specialist microbubble separations have been achieved in minerals processing with colloid gas aphrons, which are charged microbubbles (Cilliers and Bradshaw, 1996; Waters et al. 2008).
1.1 Dissolved Air Flotation
Dissolved air flotation (DAF) in particular is the most efficient and widely employed flotation option. According to Henry's law, the process essentially requires dissolving air in water at very high pressure. By so doing, the solution becomes supersaturated; leading to nucleation of microbubbles as soon as pressure is reduces at the nozzle. Unfortunately, this process is energy intensive, due to the high pressure required for air dissolution in water as well as the work done by the pump in feeding the saturator with clarified water.
1.2 Dispersed Air Flotation
Traditional dispersed air flotation involves the supply of continuous air stream directly into a porous material (usually a nozzle or a diffuser) from where bubbles are generated. By comparison with other microbubble generation methods, this technique is less energy consumptive. However, the natural problem associated with this method is the difficulty in small bubble production.
1.3 Example of the Invention in Use
A schematic representation of the bench scale dispersed air flotation unit is shown in
Three inorganic metallic coagulants were used: aluminium sulphate, ferric III chloride and ferric sulphate (Sigma Aldrich, UK), while hydrochloric acid and sodium hydroxide (Sigma Aldrich, UK) were used for pH adjustment. The tests were conducted across five pH ranges and five coagulant concentrations.
Dunaliella salina 19/30 obtained from the Culture Centre of Algae and Protozoa (CCAP), Oban, Scotland was previously pre-cultured in a 250 L airlift Loop Bioreactor containing 248 L of Dunaliella salina growth medium (Zimmerman et al., 2011b) for 2 weeks. Following that, the microalgae from the laboratory scale 250 L airlift loop bioreactor was transferred to an outdoor 2200 liter ALB for field trials at Scunthorpe, UK. The microalgae were grown with waste CO2 from steel plant exhaust gas. After ˜17 days, the cultured microalgae from the ALB were emptied into several drums and delivered back to the laboratory for harvesting. Several months after growth the microalgae culture was taken for further processing. Two liters of microalgae sample at room temperature (20° C.) was mixed to break lumps and disperse the cells homogenously in solution following sedimentation and clustering of cells as a result of prolonged storage. Coagulation and flocculation followed for 4 mins and 10 mins respectively following pH adjustment. Immediately after flocculating with a mechanical stirrer at 70 rpm, the broth was gradually introduced into the flotation column to a height of 30 cm above diffuser before the microbubble generator was turned on. The diffuser used in this study was made of Perspex material and measures 40 mm in diameter and overlaid with a stainless steel mesh (Plastok, UK) with pore size of 38 μm and an open area of 36%. Broth samples were collected every three (3) minutes from sample ports SP1,2,3 and 4, and measured with the calibrated spectrophotometer DR 2800 (HACH Lange) to assay absorbance at 663 and 640 nm wavelength. Recovery efficiency (R) was determined using the formulae:
where Ci and Cf are the initial and final algae concentrations respectively.
1.4 Bubble size Distribution Measurement
There are two main methods for measuring the size of bubbles generated in a liquid: namely optical and acoustical techniques.
The acoustic bubble sizer (Dynaflow, Inc.) was developed to meet challenges in the optical method caused by cloudy liquid. By exploiting the ability of bubbles to affect acoustic propagated waves, bubble size and population can be extracted at varying frequencies (Wu and Chahine, 2010). The device consists of a pair of transducer hydrophones 177, made of piezoelectric materials inserted in a polyurethane material to prevent contact with water. Both hydrophones are connected to a computer 175 via a control box. The transmitting hydrophone generates short bursts of sound signals within a set frequency which are then received by the second hydrophone after travelling through the liquid. The signals are then analysed by special in-built software for processing the phase velocity and attenuation within the desired frequency range to estimate the size distribution of bubbles. The acoustic bubble sizer (ABS) was used in this study for bubble characterisation. The two sets of flat hydrophones 177 used (measuring: 7.5×7.5×2.5 cm, optimal operating frequency range from 70˜200 kHz and corresponding bubble size of 34-100 μm) were mounted vertically (9 cm apart) on either side of the flotation column 170. Three (3) runs were undertaken to determine bubble size distribution under oscillatory conditions.
1.5 Bubble Size Distribution
Microbubble generation is an essential part of flotation separation.
The bubble density graph presented in
The difference in bubble size is simply attributable to the fluidic oscillator. The bistable device facilitates microbubble production by oscillating a stream of the continuous air supply. The pulse generated due to the oscillation helps to knock-off bubbles at the developmental stage. Without oscillation, bubbles tend to move irregularly, leading to increased bubble-bubble interaction and coalescence leading to larger bubbles. Regular detachment results in less coalescence because the bubbles are more uniformly spaced and sized. The level of inertial force in the pulse can be tuned so that bubbles emerge with little excess kinetic energy over the terminal rise velocity (Parkinson et al., 2008).
1.6 Algal Recovery
Understanding the step-wise processes prevalent in a multi-floc system between particle-bubble interaction in a flotation column is both interesting and informative. See
Stage 1 is simply attributable to the large surfaces of flocs which readily render them susceptible to bubble collision and adhesion, bubble formation at particle surface, microbubble entrapment in aggregates and bubble entrainment by aggregates. (Edzwald, 2010) reported these bubble-particle interaction mechanisms in the review of flotation as a wastewater treatment. These large flocs also engage in sweep flocculation as they travel upwards under the lift of microbubbles; hence the exponential biomass recovery efficiency recorded at the early stage.
After half the separation time (being the sum of Stages 1 and 2 together), the amount of large flocs decreases markedly. During the next, straight-line, phase (Stage 2), smaller flocs become prevalent in the flotation unit. Biomass concentration only reduces slightly and as such recovery efficiency hardly changes. In the second stage, surface sludge build-up continues, thickening the sludge blanket. As more bubbles rise to the top, these bubbles compress the sludge layer from underneath, reducing the water content of the sludge.
The third key stage is primarily characterised by intensive sludge thickening and thinning. By that is meant increasing density of the sludge layer, and hence reducing depth, which makes separation of the sludge easier to achieve. At this stage, the majority of the particles have been separated, ending the separation phase, whereby microbubble rise velocity is increased, since very few particles are present to cause rise retardation. The rate of water removal from the sludge is thus high as it is compressed. The sludge layer is reduced to almost a quarter of the initial size.
1.7 Coagulant and Effect of pH
Chemical pre-treatment is essential in decreasing the effect of repulsive charge between bubbles and flocs. The success of chemical pre-treatment depends on pH, because pH determines the solubility of chemical constituents of nutrient and metals in solution and influences the form and quantity of ions produced. Optimum pH and coagulant dosing reduces the charge on particles to about zero causing particles to be more hydrophobic (Edzwald, 2010). To investigate the effect of pH on separation, trials were conducted across different pH levels and results reported in
From the graphs in
In general, the optimum cell recovery result in these experiments was found at the lowest pH studied.
Considering that large flocs are good vehicles for sweep flocculation, one might wonder why, despite the relatively large flocs formed at pH greater than 7, the overall efficiency under alkaline condition recorded for aluminium and ferric sulphate coagulant was still lower than results under acidic state. Under the same operating conditions of flowrate, bubble size and flux, this observation can be explained by the difference in charge density of species. The higher the size and charge of the species, the more effective the coagulation process will be. Because these charges increase with increasing acidity, recovery efficiency is highest under acidic pH. In addition, relatively larger flocs are developed under alkaline state and given that as particle size increases the residence time of the rising microbubble-floc agglomerate also increases leading to prolonged flotation time. Moreover, the lifting force of microbubbles diminishes with increased particle size (Miettinen et al., 2010).
By contrast, the condition is quite different for FeCl3 though. Whilst a similar tendency occurs under acidic condition, FeCl3 exhibits a rather different behaviour under basic pH. It is noteworthy to reiterate that ferric chloride produced the overall best recovery result. The justification for this is that ferric salts are relatively less soluble than aluminium salts. This observation corresponds with the findings of Chow et al. (1998) on the concentration of iron speciation in solution. Their results showed that the soluble ion concentrations were less than 1% of the total iron chloride amount initially added. In addition, hydroxides of aluminium are amphoteric—containing both basic and acidic functional groups. Furthermore, the addition of ferric salts decreases the solution pH and the closer the pH tends towards acidity, concentration of trivalent species in the solution increases. Wyatt et al. (2011) observed the same occurrence in their study of critical conditions for ferric chloride-induced flocculation of freshwater algae. The optimum pH for algal separation ranges from 5-7 for ferric chloride but for aluminium and ferric sulphate, two ranges are effective-5-6 and 8-9. Overall, the process governing these reactions is very complex and by no means easy to fully detail especially also as the growth medium contains vital and very reactive chemical constituents.
2. Application in Gaslift Bioreactor
Airlift bioreactors have many advantages over stirred tanks. For instance, there are no moving parts inside the reactor, low cost of installation and maintenance, and low energy consumption. However, bio-reactors would benefit from increased efficiency of mass and heat transfer rate in gas-liquid processes. Enhancement of mass transfer rate in gas-liquid interface has been traditionally dependent on increasing interfacial area between gas and liquid phases. The use of microbubbles not only increases surface area to volume ratio, but, also, increases mixing efficiency through increase in the liquid velocity circulation around a reactor. The mixing process in bioreactors is an important and critical factor in determining the efficiency of fermentation process and the nature of design which plays an active role in providing a suitable environment for micro-organisms. The traditional mixing method (i.e., stirred tanks) may yield better performance in the degradation process, yet when the process energy requirement is weighed against the energy obtained from biogas produced, these processes become economically unviable. Therefore, the reduction of the energy required for mixing is one the most challenging targets that is faced by advanced developments of bioprocess applications.
2.1 Bioreactor
The airlift reactor (ALR) has been used in several industrial applications, and it has been the most appealing option for any gas-liquid contacting process. It has been noticed that using airlift reactor intensifies the efficiency the process compared to stirred tanks. According to their structure, airlift reactors can be classified into two main types: airlift external loop reactor, in which the circulation takes place in separate conduits; and, airlift internal loop reactor, which is provided with a tube or a plate to create the conduit (channel) inside a single reactor for circulating the liquid inside the reactor. The latter is shown in
The tank may be circular cylindrical, with a diameter D, and the draft tube may be likewise circular cylindrical with a diameter d, each centred on the axis A of the tank at which the diffuser is also positioned. The draft tube has a top edge 198, spaced from the surface 200 of the biological liquid medium 182, and a bottom edge 202 spaced from the diffuser 186 and bottom 188 of the tank. A toroidal path is thus established comprising the riser section 194, over the top edge 198 of the draft tube, down the downcomer section 196, and under the bottom edge 202 of the draft tube back into the riser section.
Bioreactor design requires accuracy in choosing the dimensions and materials required for manufacturing due to the complexity of the medium. The biological medium is a multiphase mixture, which consists of solid, liquid and gas, as well as having different microorganisms that need suitable environmental conditions. It is conceivable under such situations to provide reliable control systems for pH and temperature monitoring, in addition to maintain the process under anaerobic conditions (if required). A cylindrical bioreactor shape as airlift gas injection was used in the current study. The ratio (D/d) of the diameter (D) of the bioreactor to the draught tube diameter (d) was 0.7. The volume of reactor was 15 liters, while 8-9 liters were working volume leaving 6-7 liters in the head space.
2.2 Flow Modelling of the Gaslift Digester
A simulation process of an airlift bioreactor was carried out using COMSOL Multiphysics software (Version 4.1). The properties of the process are:
A laminar bubbly flow model interface was used for modelling of the two-fluid flow regimes (e.g. mixture from gas bubbles and liquid), driven by gravitation through the density difference between gas-bubble-containing liquid in the riser section 194 and depleted-gas-bubble-containing liquid in the downcomer section 196.
A laminar bubble flow model interface was used for modelling of the two-fluid flow regimes (e.g. mixture from gas bubbles and liquid). Thus, the momentum transport equation is given by:
Where Øl is liquid volume fraction (m3/m3), ρl is density of liquid, ul the velocity of liquid phase (m/s), t is time (sec), P is pressure (Pa), ηl is dynamic viscosity of liquid phase (Pa·s) and g the gravity (m/s2).
For low gas concentration, the liquid holdup coefficient (Øl) is about unity. Therefore, the change of Øl can be neglected in the following equation.
The equation of the gas phase is illustrated as follows:
Where ρØ is the density of gas phase (kg/m3), gas volume fraction (m3/m3), uØ is velocity of gas and −mgl the mass transfer rate (kg/m3·s).
For the purposes of approximation, there is considered no mass transfer between gas and liquid phases. Thus the mgl=0. Therefore, the continuity equation can be arranged for two phases (e.g. gas and liquid) but without mass-transfer terms as follows:
The ideal gas law was used to calculate the density of gas (ρg):
Where Mw is the molecular weight of the gas bubble, R is the ideal gas constant (8.314 J/(mol·K) and T the temperature of gas (K)
The gas volume fraction is estimated by the following equation
Øg−1−Øl (6)
The gas velocity can be determined as ug=ul+uslip, since uslip is relative velocity between two-phases fluid (gas and liquid).
Pressure-drag balance, obtained from slip model, was used to calculate the uslip. The assumption of this model suggests that there is momentum balance state between viscous drag and pressure forces on the gas microbubble:
where Cd is the viscous drag coefficient (dimensionless), db is bubble diameter (m). Given that the microbubble diameters used in the simulation are equal to or less than 1000 μm, the Hadamard-Rybczynski drag law was used, and hence:
where:
and where Reh is Reynolds number
On the draft tube 192 and internal airlift bioreactor walls, no slip (u=0) was used in boundary conditions (BCs) for the liquid phase, whilst no gas flux values were used for the gas bubble phase, hence the values of ul and n(ugØg) equal to zero. On the other hand, the “Gas outlet” and the slip (n,u=0) BCs were used at the top of liquid phase for both liquid phase and gas phase, respectively. On the top of the diffuser 186, no slip boundary conditions were used for liquid phase and the “gas flux” boundary conditions for the gas phase.
The gas concentration and arrows streamlines of the liquid velocity at different bubble diameters (20, 100, 200, 400, 600, 800, and 1000 μm) over 120 seconds were determined. The results for 20 and 100 μm bubbles are shown in
This situation was different when the produced micro-bubbles diameter was less than 200 μm.
Therefore, the retention time of the gas bubbles increases dramatically (e.g. doubled, if it is assumed that the rotation of these bubbles has only been for one cycle). Moreover, the residence time of gas micro-bubbles in the “downcomer” zone would be longer than that for the riser zone, if the gravity force is considered. In addition, in certain areas in the downcomer zone, the buoyancy force of the gas bubbles is balanced with their drag force caused by flowing liquid; thus, leading to stationary states of the bubbles velocity, which cause the residence time of these bubbles to increase. Hence, the controllable size of micro-bubbles generated by fluidic oscillation would add another advantage to gaslift bioreactor system by increasing the mass and heat transfer not only in the riser region but also in the downcomer region.
2.3 Liquid and Gas Velocity Profile
The goals of the mixing system in biological processes include prevention of the formation of thermal stratification, maintaining uniformity of the pH, increase of contact between feed and microbial culture, and preventing fouling and foaming. As described earlier, some of biological media are viscous liquids, of high density, and contain solids, grits etc, thus, mixing of these materials thoroughly in order to achieve the desired objectives requires a great effort and energy. In fact, using a bubbling system for mixing of such media is inefficient at certain flow rates. Owing to generation of foams at the top of the culture surface, an increase of induced gas flow rate becomes necessary, perhaps rendering the entire bioprocess uneconomical.
Changing this scenario is possible, however, if micro-bubbles are used in this process, because, the rising velocity of gas bubbles is dependent on the pressure drag-coefficient and bubble diameter. For example, a decrease of bubble diameter causes a corresponding decrease in the Reynolds number, and the pressure drag-coefficient also increases. Consequently, a rise in velocity of the microbubbles decreases the drag coefficient.
The simulation data showed that below a certain constant flow rate (e.g. 300 l/min), the gas velocity decreases with decrease in bubble size, due to increased drag force against the buoyancy force as shown in the
2.4 Penetration of the Microbubbles
Penetration depth (hp) of the micro-bubble into the downcomer zone was also investigated in the present study. Depth of penetration represents, and can be an indicator, of enhanced efficiency of the mixing system in an airlift bioreactor as a result of the increased residence time in this region. Greater transfer rates of heat and mass would be achieved by higher residence times. The simulation data illustrated that the depth of penetration of the microbubbles increases with decreasing the bubbles size due to a bigger downward drag force compared to the buoyancy force. As mentioned above, that gas volume fraction increases in the downcomer zone with decreasing the bubbles size.
Microbubbles of smaller sizes penetrate deeper; however, the position of the gas diffuser in reactor has applied an important role in this situation. The gaslift bioreactor was simulated with four different locations of gas sparger 186. Dead zones were experienced with reduced circulation as the gas sparger was raised in the tank. Hence it is better to locate it low in the tank. Likewise the diameter d of the draft tube 192 in the gaslift bioreactor is relevant to circulation. The ratio of draft tube diameter to bioreactor diameter (d/D) was varied from 0.6 to 0.9. The effect of varying d/D ratio on velocity of gas and liquid was investigated. Two bubble diameters (20 μm, 400 μm) were used for investigating effect the draft parameter on mixing efficiency. The simulation data showed a maximum velocity of liquid in Y-axis (along axis A) that could be achieved with a ratio of 0.6 (m/m) is higher than that observed with ratio of 0.7, 0.8, and 0.9 (m/m). A narrow entrance between the diffuser and draft tube also contributed in increasing the velocity of liquid phase in the riser region.
The above considerations apply to any bioreactor including the anaerobic digester discussed below. However, different circumstances call for different requirements and while the above has purely considered the mixing and circulating effects of microbubbles, there is also the case of mass and heat transfer in the contribution of nutrients as well as the exhaustion of waste or product. In the case of algal growth, access to light is essential and, again the circulation and mixing of the tank contents reduces dead and stagnant zones and ensures access of all the entire algal population to light, as well as reducing the tendancy of adhesion to the tank surfaces.
3. Application in Anaerobic Digestion
Anaerobic digestion of already digested sludge by processing in an airlift bioreactor is used for nutrient and energy recovery from biomass. It is used to breakdown organic matter into methane (CH4), carbon dioxide (CO2), hydrogen sulphide (H2S). Digested sludge is dried and used for fertilizer. There are four biodegradation stages. The rate of gas generation through mesophilic anaerobic digestion is generally high, yet the remaining dissolved gases in a digested sludge have a pejorative effect on the environment when they are eventually released, as well as causing operational difficulties. The generation of biogas in an already digested sludge causes cavitation phenomena in pumps. An airlift bioreactor (ALR) is used as anaerobic digester in the present invention to remove the produced gases from digested sludge, with a resultant reduction in pathogens and odour, as well as improvement digested sludge for fertilizer. As already discussed above, ALRs have many valuable benefits in comparison with stirred tanks for instance: there are no moving parts inside the reactor, low cost of installation and maintenance, and low energy required. In addition, using an airlift reactor enhances the mixing efficiency. The process is preferable to agitation by stirring in conventional tanks on power consumption grounds. The experimental data discussed below shows that the cumulative methane production of an airlift anaerobic digester is about 30% more than the observed in the conventional anaerobic digester, and even greater efficiency is achieved, as discussed further below, by nutrient supply.
3.1 Penetration of the Microbubbles
In a duplicate procedure, two reactors D1,D2 as shown in
Fresh sludge, taken from a wastewater treatment plant, has physical, chemical and biological properties. These properties change for several reasons, for instance, the type of wastewater, time of sampling and storage, handling and transfer from the wastewater treatment plant to the laboratory, weather conditions and seasonal variation of water treatment equipment design and operating conditions. Biologically, there are many types of anaerobic bacteria exist in wastewater. The activity, type and number of these bacteria depend on the characteristics of the wastewater and weather conditions at the time of collection. This will affect strongly the production of biogas and the efficiency of biodegradation of the organic matter. Since chemical and physical properties for the sewage sludge are variable, this may cause difficulties in linking the results of experiments that are carried out with different sludge batches. Therefore, the present study used samples of the same sludge, which was taken from the same wastewater treatment plant and distributed it to both reactors D1,D2 at the same time with the same operating conditions.
The introduction of nutrients or trace metals into sludge is usually not required because wastewater generally comprises lipids, polysaccharides, protein and nucleic acids which are bio-degraded by anaerobic bacteria to produce biogas and effluent, which used as fertilizer.
For the successful operation of anaerobic digestion, facultative anaerobes, including methanogenic bacteria and organic particulates should be present in the sludge. The primary clarifier in waste treatment provides particulates and many anaerobes including methane-produce bacteria, whilst the secondary clarifier provides many facultative anaerobes. In the present research, the digested sludge was collected from the outlet stream of a full-scale mesosphilic digester from a wastewater treatment plant in Sheffield city, UK. Digested sludge has methanogenesic bacteria but with low concentration of substrates.
3.2 Results and Discussion
After sparging, the overall Gibbs free energy becomes more negative, and hence the reaction becomes thermodynamically favourable and moves towards the formation of more products. However, due to the use of digested sludge in this experiment, the substrate composition was minimal and limiting for the methanogenesic bacteria. Thus, during the hydraulic retention time, the production of methane decreased each day as illustrated in the
The essential ingredient in the biological medium is water with a composition of 90-95% depending on the type of bioprocess. For instance, water content in sludge is around 95%, while 5% consists of micro-organisms, organic matters, elements and suspended solids. Micro-organisms feed on the organic matter and elements to produce gases by metabolic processes. Carbon dioxide, methane, and hydrogen are highest composition gases produced from fermentation process. The ability of these gases to stay in the liquid phase is related to their relatively solubility, which is 1.45 g gas/kg water in the case of carbon dioxide, 0.0215 g gas/kg water in the case of methane and 0.00155 g gas/kg water in the case of hydrogen. It can be seen that CO2 is relatively highly soluble compared with CH4 and H2. Thus, it will be stay in the liquid phase longer as dissolved aqueous gas (CO2(aq)). Released carbon dioxide reacts with water to produce carbonic acid. Kinetically, the conversion to carbonic acid is very slow, just 0.2% of carbon dioxide converts to carbonic acid and its ions, while 99.8% remains as dissolved gas. Carbonic acid is a diprotic acid, dissociating into bicarbonate and carbonate ions, and producing two hydrogen atoms ionisable in water.
From the above, it can be noted that the presence of dissolved carbon dioxide in the liquid phase will produce a hydrogen ion that would be expected to lead to a lowering of the pH. However the pH observed in the airlift anaerobic digester 280 and the conventional anaerobic digester 282 approximately stabilized during the experimental work, (except that a slight change in the airlift digester was observed during sparging of nitrogen). This means that the carbonic acid produced from dissolved carbon dioxide is treated immediately by ammonia produced from biodegradation of protein. The low solubility of the methane contributes to its transfer from the liquid phase to the gas phase. Most of the carbon dioxide remains in the sludge as “dissolved gas” until a suitable opportunity for it to transfer is provided through the driving force of sparging with nitrogen.
The same thing happens with H2S. The high solubility of hydrogen sulphide contributes to remaining in the sludge as H2S(aq). When H2S dissolves in sludge, the pH, also, would drop due to releasing a hydrogen ion and forming a weak acid. Indeed, the behaviour of the solubility of hydrogen sulphide is very similar to carbon dioxide because both gases form a diprotic acid in water.
Sulphate dissolved with a high concentration, can inhibit generation of biogas produced from the anaerobic digestion of wastewater. The most important reason leading to this inhibition is that the sulphate dissolved in wastewater encourages growth of sulphate-reducing bacteria, which consume acetic acid and hydrogen that would otherwise be consumed by methanogenesic bacteria. This competition between the sulphate-reducing bacteria and the methane-producing bacteria for the consumption of the hydrogen and acetic acid can be illustrated thermodynamically through the equations:
Methanogensis:
CO2+4H2→CH4+2H2O ΔG=−135 kJ (10)
CH3COOH+4H2→CH4+CO2 ΔG=−28.5 kJ (11)
Sulphate Reduction:
SO42−+4H2→2H2O+2OH− ΔG=−154 kJ (12)
SO42−+CH3COOH→H2S+2HCO3− ΔG=−43 kJ (13)
From above equations, it can be seen that the sulphate-reduction reactions have greater thermodynamic driving force than methanogenesis. Therefore methane production is inversely related to sulphate concentration. It has also been discovered that H2S has a negative impact on the methane production bacteria. It is also suggested that the concentration of H2S can be taken as an indicator of inhibition of methanogenesic bacteria (GERARDI M. H., 2003).
Removal of dissolved H2S from sludge prevents inhibition of methanogenesic bacteria and is desirable also to reduce odour from digested sludge. Normally, the removal of CO2 and H2S take place by biogas generated (CH4 and CO2) or by contact with the head space in the top of sludge. But this is insufficient to remove the dissolved gases. Mixing of the digested sludge provides intimate contact between sludge and bubbles of biogas and headspace. However; the characteristics of digested sludge require high energy to make it. Using an airlift digester with low energy requirement helps to remove most of hydrogen sulphide generated.
The benefits of the airlift bioreactor are illustrated through the above results. Low energy, good mixing, and enhancement of stripping gases are the most important of the characteristics of airlift bioreactor that were utilized in this study. More methane and more stripping of carbon dioxide and hydrogen sulphide were obtained from this utilization.
However, while bubbling nitrogen during the initial, growth and end phases of anaerobic digestion enhance methane production for the reasons explained above, a further development is in recycling biogas produced by the digestion during the growth phase. This appears counterproductive, because biogas has a composition of approximately 60% carbon dioxide and 40% methane, which broadly balances the concentrations in solution. Consequently, bubbles of gas with this constitution do not alter the composition of the digester through chemical imbalance, (where the bubble surface acts as a membrane across which a concentration gradient exists). Nevertheless, it is found that bubbles of biogas increase in size and volume following injection. The reason for this is that methane is “strongly” gaseous at room and warmer temperatures (anaerobic digestion is exothermic and can elevate temperatures of digesters to circa 35° C.). However, methane is also “sticky”, with respect to particles and bacteria surfaces, and therefore does not easily escape the liquid phase after its release by the producing bacteria. Collisions with biogas bubbles however provide an opportunity for methane to escape the liquid environment and return to the gas phase and thus enlarge the bubbles cycling through the digester. As a result, the concentration of carbon dioxide, and other gases such as hydrogen sulphide, therefore inevitably also decreases within the bubbles as methane is absorbed. By that means, a concentration gradient is restored across the bubble surface driving more dissolved gases into the bubble. This saves having to employ nitrogen.
In a final development, it is found that pure carbon dioxide can be injected during the growth phase. This also has the counterintuitive effect, not of affecting methane extraction, but of course of adding to the carbon dioxide loading of the digester. However, it is found that the reaction-limiting factor of methanogensis is not a lack of hydrogen in equations (10) and (11) above (and (10) in particular), but firstly the inhibiting effect of retained methane AND a lack of appropriate fuel (carbon dioxide) for the bacteria. The bubbles have therefore also comprised pure carbon dioxide (optionally exhaust carbon dioxide from other processes, for example, the combustion of biogas already produced and used in the generation of electricity). Consequently, in this context “pure” carbon dioxide may well contain impurities. Nevertheless, not only do the bubbles of such gas extract the methane, just as biogas or nitrogen does, but also they provide additional fuel to encourage growth of the methanogenesic bacteria. Consequently, the yield of methane is yet further enhanced.
At the end of the growth phase, it is still preferred to return to nitrogen purging, for the purposes explained above, to both remove vestigial dissolved gases and neutralise the final digestate. The result is a digestate that does not require drying, but instead can be distributed in liquid form without damaging pumps (through cavitation problems) or unprotected pipelines (through corrosive acid attack). Indeed, in appropriate situations, the digestate can be pumped from the digester through pipelines directly to irrigation arrays and ditches on agricultural land for fertilisation purposes. This saves significant energy costs in otherwise drying and transporting digestate by road.
The bubbling of gas into the anaerobic digester may be undertaken once or twice daily over a period of perhaps one hour on each occasion. If the bubbles are small, in the order of 10-30 μm then they have such a slow rise rate in the tank that they will remain in place for up to 24 hours. During that period they are resident in the digester and, if sufficient quantity of bubbles are injected, and the bubbles are small enough, microorganisms throughout the digester can access bubbles to shed themselves of the inhibiting methane.
Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, means “including but not limited to”, and is not intended to (and does not) exclude other moieties, additives, components, integers or steps.
Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise. Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.
The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0621561.0 | Oct 2006 | GB | national |
This application claims priority to and is a continuation-in-part of co-pending U.S. patent application Ser. No. 12/447,629, filed Apr. 28, 2009, entitled, “Bubble Generation For Aeration And Other Purposes,” which is a national stage application, filed under 35 U.S.C. § 371, of International Application Number PCT/GB2007/004101, filed Oct. 29, 2007, entitled, “Bubble Generation For Aeration And Other Purposes,” which claims priority to Great Britain Patent Application No. 0621561.0, filed Oct. 30, 2006, entitled, “Bubble Generation For Aeration And Other Purposes,” all of which are hereby incorporated by reference herein in their entirety.
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| Number | Date | Country | |
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| Number | Date | Country | |
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| Parent | 12447629 | US | |
| Child | 13652004 | US |
