Embodiments of the present invention relate to wastewater treatment, to membrane biofilm reactors, and to assemblies of gas permeable membranes for supporting a biofilm.
In a membrane biofilm reactor (MBfR), a membrane is used to both support a biofilm and to transport a gas to the biofilm. Membrane biofilm reactors were recently reviewed by Martin and Nerenberg in “The membrane biofilm reactor (MBfR) for water and wastewater treatment: Principles, applications, and recent developments” (Bioresour. Technol. 2012). Membrane-aerated biofilm reactors (MABR) are a subset of MBfRs in which an oxygen containing gas is used. MABRs were reviewed by Syron and Casey in “Membrane-Aerated Biofilms for High Rate Biotreatment: Performance Appraisal, Engineering Principles, Scale-up, and Development Requirements” (Environmental Science and Technology, 42(6): 1833-1844, 2008).
U.S. Pat. No. 7,169,295 describes a membrane supported biofilm reactor with modules having fine hollow fiber membranes. The membranes are made from dense wall polymethyl pentene (PMP) used in tows or formed into a fabric. The membranes are potted in a header of a module to enable oxygen containing gas to be supplied to the lumens of the hollow fibers. The reactor may be used to treat wastewater. Mechanical, chemical and biological methods are used to control the thickness of the biofilm.
This specification describes an assembly, alternatively called a cord, which may be used for supporting a biofilm. The cord comprises a plurality of hollow fiber gas transfer membranes. The cord may optionally also comprise one or more reinforcing filaments.
The cord may comprise a plurality of yarns. At least one of the yarns comprises a plurality of gas transfer membranes. At least one of the yarns extends along the length of the cord generally in the shape of a spiral. In some cases, the cord has a core and one or more wrap yarns. In some other cases, the cord comprises a set of braided yarns.
In an embodiment, the cord has an outside diameter in the range of about 0.3 mm to 2.0 mm. In an embodiment, the gas transfer membranes have an outside diameter that is less than 200 microns. In an embodiment, the sum of the circumferences of the gas transfer membranes is at least 1.5 times the circumference of the smallest circle that can surround the cord. In use, a biofilm covers the cord and the outer surface of the biofilm is substantially round.
A module may be made by potting a plurality of cords in at least one header. The cords are generally independent of each other except in the header. A reactor may be made by placing the module in a tank adapted to hold water to be treated and providing a gas delivery system. A process for treating wastewater comprises steps of feeding water to the tank and supplying a gas to the module. In use, a biofilm may cover a cord to form a membrane biofilm assembly.
The cord, module, reactor and process may be used to treat water, for example in, or in the manner of, an MBfR.
At least one of the yarns 8 extends along the length of the cord 10 generally in the shape of a spiral and may be referred to as a spiral yarn. In an embodiment, at least one spiral yarn 8 is wrapped at least partially around the outside of the other yarn or yarns 8 of the cord 10.
In the cords 10 of
Each cord 10 has a plurality of hollow fiber gas transfer membranes 14. The gas transfer membranes 14 may be located in a core 12, in one or more wraps 18, or in another yarn 8. In an embodiment, the gas transfer membranes 14 are provided in the form of a multi-filament yarn having a plurality of gas transfer membranes which may be called a gas transfer membrane yarn 15. Optionally, a cord may also have a reinforcing yarn 16. The reinforcing yarn has one or more reinforcing filaments 34. A yarn 8 having both a plurality of gas transfer membranes 14 and at least one reinforcing filament 34 may be called both a gas transfer membrane yarn 15 and a reinforcing yarn 16.
In an embodiment, the outside diameter of a cord 10 is in a range of about 0.3 to 2.0 mm. The outside diameter of the cord 10 may be measured as the largest width of a cord measured through its longitudinal axis or as the diameter of the smallest hole that the cord 10 will pass through. Anomalies, defects or non-repeating bumps are ignored in these measurements.
Generally speaking, a core 12 provides mechanical strength, defines a longitudinal axis of the cord 10, supports any wraps 18, and may also comprise gas transfer membranes 14. A wrap 18, or other yarn outside of the core 12, may do one or more of: protect the core 12 or another underlying yarn 8, comprise gas transfer membranes 14, or contribute to the mechanical strength of the cord 10.
A core 12 can be made of one or more monofilament yarns or multi-filament yarns. A Multi-filament yarn may comprise filaments that are braided, twisted or otherwise united, or filaments that are merely collected together in a bundle or tow. Multiple yarns may be arranged as parallel warp yarns or twisted, braided or otherwise united. For example a core 12 may consist essentially of a single monofilament yarn; a single multi-filament yarn; or, an assembly of about 2 to 6 monofilament or multi-filament yarns arranged in parallel or twisted or braided together. In an embodiment, an assembly of twisted or braided yarns will be more flexible than a single monofilament of the same outer diameter. A core 12 typically, but not necessarily, comprises at least one reinforcing yarn 16. A core 12 may optionally comprise one or more gas transfer membrane yarns 15.
A wrap 18 is typically a multi-filament yarn. A multi-filament yarn may comprise filaments that are twisted or otherwise united or filaments that are merely collected together in a bundle or tow. A wrap 18 can be wrapped around a core 12 in a clockwise spiral or a counterclockwise spiral. Alternatively, a cord 10 may have at least one wrap 18 in each direction or no wrap 18. A wrap 18 can be a gas transfer membrane yarn 15, a reinforcing yarn 16, or both.
A reinforcing filament 34 can be made of any water-resistant and non-biodegradable polymer such as polyethylene, nylon or polyester, more particularly nylon or polyester. A reinforcing filament 34 is typically solid. Gas transfer membranes 14 tend to be expensive and weak relative to reinforcing filaments 34 made of common textile polymers such as nylon or polyester. A reinforcing yarn 16 can be a monofilament or multi-filament yarn. In the case of a multi-filament yarn, the reinforcing filaments 34 may be braided, twisted or otherwise united, or filaments that are merely collected together in a bundle or tow. Optionally, a yarn 8 may comprise one or more reinforcing filaments 34 mixed with the gas transfer membranes 14.
In an embodiment, the gas transfer membranes 14 have an outside diameter of 500 microns or less, more particularly 200 microns or less, optionally 100 microns or less. In an embodiment, the hollow area of a hollow fiber (meaning the cross sectional area of the lumen of a fiber as a percentage of its total cross sectional area) is at least 20%, for example in the range of 20-50%. For example, a gas transfer membrane 14 may have an outside diameter in the range of about 30-70 microns and an inside diameter of about 15-50 microns. The wall thickness of a gas transfer membrane 14 may be 20 microns or less.
In an embodiment, the gas transfer membranes 14 are handled in a multi-filament gas transfer membrane yarn 15. A gas transfer membrane yarn 15 may have between 2 and 200, between 12 and 96, or between 10 and 60 individual filaments of gas transfer membrane 14. A gas transfer membrane yarn 15 used as a wrap 18 is not tightly twisted, braided or crimped according to an embodiment to allow the individual gas transfer membranes 14 to spread out over an underlying yarn 8. A gas transfer membrane yarn 15 may be made by re-winding gas transfer membranes 14 from multiple take up spools in combination onto another spool.
A gas transfer membrane yarn 15 may be provided, in a core 12, either as a central yarn or as a warp parallel to a central reinforcing yarn 16; in one or more wraps 18; or, in another spiral yarn 8. It is desirable for gas transfer efficiency to have the gas transfer membranes 14 near the outer surface of the cord 10. However, the gas transfer membranes 14 are typically fragile and they are more likely can be damaged if they form the outer surface of a cord 10. Accordingly, in an embodiment, a reinforcing yarn 16 is used as an outer wrap 18. In this case, a gas transfer membrane yarn 15 may be used in the core 12 or in an inner wrap 18.
The gas transfer membranes 14 may be porous, non-porous or semi-porous. Composite membranes, for example having a non-porous membrane layer, and a semi-porous or porous support layer, may also be used. Asymmetric membranes, for example having a non-porous region and an integral semi-porous or porous region, may also be used.
Porous gas transfer membranes 14 may have pores up to the microfiltration range. Wetting is avoided by choosing hydrophobic materials or treating the hollow fibers 14 to make them hydrophobic. Porous hollow fibers 14 may be made, for example, using polyethylene, polyvinylchloride, polypropylene or polysulfone.
Non-porous gas transfer membranes 14, including dense wall gas transfer membranes 14, may be made from a thermoplastic polymer, for example a polyolefin such as polymethyl pentene (Poly (4-methylpentene-1) or PMP), polyethylene (PE) or polypropylene (PP). PMP is sold, for example, by Mitsui Petrochemical under the trade mark TPX. The polymer may be melt spun into a hollow fiber. The gas transfer membranes 14 may be called non-porous if water does not flow through the fiber walls by bulk or advective flow of liquid even though there are small openings through the wall, typically in the range of 4 or 5 Angstroms in the case of melt spun PMP. However, oxygen or other gases may permeate or travel through the fiber walls. In a dense walled hollow fiber 14, gas travel is primarily by molecular diffusion or dissolution-diffusion which occurs when openings in the fiber walls are generally less than 30 Angstroms. Gas transfer membranes 14 as described in U.S. Pat. No. 7,169,295, which is incorporated by reference, may be used.
The term porous has been used to refer to any structure having openings larger than in a dense wall, for example having openings of 30 or 40 Angstroms or more, but without openings large enough to be wetted or transport liquid water by advective, Poiseuille or bulk flow. In this specification, membranes with openings in this size range are referred to as semi-porous.
Gas transfer membranes 14 may alternatively be made by mechanically or thermally treating a melt spun thermoplastic polymer after spinning to increase its permeability to oxygen without making the fiber wettable or capable of permitting advective flow of liquid water. Spinning or post-treatment steps that can be used or controlled to increase permeability include the spinning speed or drawing ratio, the quenching conditions such as temperature or air flow rate, post annealing, if any, stretching and heat setting. The resulting fibers may have a dense layer, with openings ranging from the size of openings in the raw polymer to 30 or 40 Angstroms, on either the inside of the fiber, the outside of the fiber or both, with the remaining parts of the fiber being porous or semi-porous. For example, U.S. Pat. No. 4,664,681, issued on May 12, 1997, to Anazawa et al. describes, in examples 4 and 6, processes for melt-spinning and post-processing PE and PP to produce acceptable fibres while other fibers are made from PMP or polyoxymethylene. Processes described in “Melt-spun Asymmetric Poly (4-methyl-1-pentene) Hollow Fibre Membranes”, Journal of Membrane Science, 137 (1997) 55-61, Twarowska-Shmidt et al., also produce acceptable fibres of PMP and may be adopted to produce fibres of other polyolefins such as PE or PP. In one example, the mean pore size of the fibers produced is just over 40 Angstroms. In U.S. Pat. No. 4,664,681, membranes are melt spun, stretched (by producing the membrane at a high draft ratio) under weak cooling and then heat treated. The resulting membranes are asymmetric containing a dense layer with substantially no pore with a diameter of 30 Angstroms or more and a microporous layer having larger pores. The non-porous layer is the outer surface of the fiber and so the fiber is non-wetting.
Another alternative process for making gas transfer membranes 14 is to make an asymmetric outside dense skin membrane with a spongy substructure by the non-solvent induced phase separation (NIPS) process. Polymers typically used for this process are polysulfone, cellulose acetate and polyimide. Other alternative methods of making gas transfer membranes 14 may include, for example, meltblown extrusion, flash spinning, and electrospinning.
In general, silicon rubber or PDMS have very high oxygen permeability but cannot be processed using many textile techniques and are not available in small diameter fibers. PMP has higher oxygen permeability than PE or PP, but it is more expensive. Porous membranes have high oxygen permeability but they are prone to wetting in use. Accordingly, dense wall polymeric gas transfer membranes 14, for example of PE. PP or PMP, with a wall thickness of 50 microns or less, more particularly 20 microns or less, or polymeric membranes that are not entirely dense walled but have a nonporous or semi-porous layer, are applied but not essential.
A yarn 8 in a core 12, whether it is a gas transfer yarn 15 or a reinforcing yarn 16, may be called a warp 26. In an embodiment, a wrap 18 is applied around a core 12 or another underlying yarn 8 with some tension to cause its filaments to spread on the surface of the core 12. Wrapping may be done with a pitch ratio (pitch divided by the diameter of the core) of between 1 and 5. Wrapping can be in one direction only, but is more particularly done in both directions. There may be 1 or more, for example between 1 and 3, wraps 18 in one direction. In an embodiment, gas transfer membranes 14 are directly exposed over at least 25% of the surface of the core 12 although oxygen can also travel from a gas transfer membrane 14 through an overlying yarn 8.
A cord 10 may consist of only a set of twisted yarns 8. However, merely twisted yarns 8 may tend to partially untwist and separate in use. Accordingly, in an embodiment, twisted yarns 8 are used as a core 12 with at least one wrap 18 wrapped around the core 12 in the direction opposite to the twist of the core 12. A braided core 12 is more stable. Spiral yarns 8 may be added as a braid around a core 12, but a wrap 18 can be made at a faster line speed with a less complicated machine. A cord structure using one or more wraps 18 also allows for a reinforcing yarn 16 to be used as an outer wrap 18 to help protect an interior gas transfer membrane yarn 15.
In the examples of
In
In
In
In
One or more spindles 30, or other yarn wrapping devices, are located below the distributor 28. Each spindle 30 is loaded with a yarn and wraps the yarn around the one or more warps 26 of the core 12 as they pass through the spindle 30. Due to the downward movement of the core 12, each wrapped yarn forms a spiral wrap 18. The machine 20 may also have alignment guides (not shown) to keep the core 12 aligned with the central axis of the spindles 30 and to reduce vibration of the core 12.
An example of a suitable spindle 30 is a Temco™ spindle model MSE150 by Oerlikon Textile. Each spindle 30 has an electrical motor and a hollow core and holds a bobbin of wrap yarn. The spindle 30 is positioned so that its central axis coincides with the core 12. In the machine 20 of
A plurality of cords 10, for example 100 or more, may be made into a module generally in the manner of making an immersed hollow fiber membrane filtration module. At least one end of each of the cords 10 is potted in a block of a potting material such as thermoplastic or thermosetting resin which is sealed to a pan to form a header. The ends of the gas transfer membranes 14 are made open to the inside of the header, for example by cutting them open after potting. The other ends of the cords 10 may be potted in another header with the ends of the gas transfer membranes 14 open or closed, closed individually, or looped back and potted in the first header. A port in the header allows a gas to be fed to the lumens of the gas transfer membranes 14. The gas may be fed to the gas transfer membranes 14 in a dead end manner or with exhaust through a second header.
As one example, the composite fibers 10 may be assembled into modules and cassettes according to the configuration of ZeeWeed 500™ immersed membrane filtration units sold by GE Water & Process Technologies. Sheets of cords 10 are prepared with the composite fibers 10 generally evenly spaced in the sheet. Multiple sheets are stacked on top of each other to form a bundle with adjacent sheets spaced apart from each other. The bundle is potted. After the potting material cures, it is cut to expose the open ends of the gas transfer membranes and sealed to a header pan. Several such modules may be attached to a common frame with their ports manifolded together to form a cassette. Various useful techniques that may be used or adapted for making a module are described in U.S. Pat. Nos. 7,169,295, 7,300,571, 7,303,676, US Publication 2003/01737006 A1 and International Publication Number WO 02/094421, all of which are incorporated by reference. Alternatively, other known techniques for making a hollow fiber membrane module may be used.
Referring to
Referring to
Referring to
Referring to
When used for wastewater treatment, the cords 10 are immersed in a bioreactor and a gas, for example air, oxygen, hydrogen or another gas, is fed through the lumen of the gas transfer membranes 14. A biofilm develops on the outside surface of the cords 10, and anchors itself by filling the gaps between filaments. The resulting membrane biofilm assembly has a generally circular cross section. The cross section of the membrane biofilm assembly has a diameter of about 0.5 to 3 mm determined assuming that the biofilm forms a film extending no more than 0.5 mm beyond the outer diameter of the core 12. A more typical biofilm thickness is in the range of 0.05 to 0.2 mm. The sum of the circumferences of the gas transfer membranes 14 multiplied by the length of the cord approximates the active gas transfer surface area while the circumference of the outside of the biofilm multiplied by the length of the cord 10 gives the biofilm area. In an embodiment, the sum of the circumferences of the gas transfer membranes 14 is at least 1.5 times the circumference of a circle having the outside diameter of the cord 10. In an embodiment, the sum of the circumferences of the gas transfer membranes 14 is also at least 1.5 times the circumference of the attached biofilm when in use.
Modules of the cords 10 may be deployed in a membrane biofilm reactor (MBfR) by immersing them in an open tank in manner similar to the use of ZeeWeed 500 immersed hollow fibre filtering membranes. Although the cords 10 will be used to support and transport gas to a biofilm and not for filtration, various system design and operating features of the ZeeWeed 500 system can be adapted. As mentioned above, the cords 10 may be potted with an orderly spacing between them. The module configuration with two headers may be used but modified to use one header of each element for introducing the fresh gas and one header for venting exhausted gas. ZeeWeed cassette frames may be used to facilitate deploying multiple modules with the cords 10 oriented vertically into open tanks Gas sparging by way of bubbles produced below or near the bottom of the modules can be provided at a low rate to renew the liquid around the cords 10. Gas sparging at a higher rate may be used to help control biofilm thickness either by the direct action of bubbles, bubble wakes or bubble pressure effects on the biofilm, or by causing cords 10 mounted with slack between the headers to sway in the water to produce turbulence or contact between cords 10. Optionally, gas exhausted from the cords may be recycled for use in gas sparging.
Referring to
Optionally, the aerator 68 may comprise a supply pipe 82 and a transducer 84. The transducer 84 collects gas ejected from the supply pipe in a pocket below a shell 86. The pocket of gas grows larger as gas is accumulated as shown in the first two compartments of the shell 86, counting from the left side of the shell 86. When the pocket of gas extends to the bottom of J shaped tube, as in the third compartment of the shell 86, the gas is released through the J shaped tube as shown in the last compartment of the shell 86. In this way, large bursts of bubbles are released periodically without requiring a large volume of gas to be continuously pumped into the tank 70. Excessive scouring gas consumes energy and may disturb desirable anoxic or anaerobic conditions in the tank 70. Periodic large bursts of bubbles can be more effective for renewing the water around the cords 10 or removing biofilm from the cords 10 than the same amount of gas supplied as a continuous stream of bubbles.
In some prior MBfRs, silicon rubber or polydimethylsiloxane (PDMS) are coated over a flat substrate to make a flat sheet membrane. While silicon and PDMS are highly permeable to oxygen, such a flat sheet membrane can provide a surface area for oxygen transfer to surface area of biofilm ratio of only about 1. Further, with reasonably large sheets it is difficult to renew water to be treated along the edges of the sheet or remove excess biofilm from the edges of the sheet. Accordingly, the sheets are often separation by a substantial spacing and the total biofilm area in a tank may be low.
In U.S. Pat. No. 7,169,295 a membrane supported biofilm reactor has modules made with fine hollow fiber membranes. The fine hollow fibers have a thin wall which allows for good gas transfer efficiency even when heat spun polymers are used. However, the fine hollow fibers are also easily damaged. A tow module described in U.S. Pat. No. 7,169,295, although useful in some applications, has loose and exposed hollow fibers which are prone to damage and to being clumped together by biofilm in other applications. Sheet modules described in U.S. Pat. No. 7,169,295 are more resilient and can provide a surface area for oxygen transfer to surface area of biofilm ratio of more than 1. However, like silicon flat sheet module, these sheet modules are still subject to total biofilm area limitations.
The cords 10 described above provide a useful alternative gas transfer module configuration. The use of fine hollow fiber gas transfer membranes 14 allows for good gas transfer efficiencies even when using melt spun polymers and a surface area for oxygen transfer to surface area of biofilm ratio of more than 1. The fine hollow fiber membranes are not loose and exposed. Yet since the cords 10 can move generally independently and do not form a solid sheet, fresh liquid and bubbles used to scour the biofilm to control its thickness can reach cords 10 located in the interior of a module. Movement of the cords 10, or contact between cords 10, may also help control biofilm thickness. Further, the total biofilm surface area can be increased relative to a sheet form module.
In a calculated example, a cord 10 comprises a core 12 and two wraps 18, one in each direction, of gas transfer membrane yarns 15. The outside diameter of the cord is 1 mm. The wrapping pitch is 5 core diameters resulting in a wrap 18 helix length of 1.18 times the cord length. The cord 10 has 57 meters of 70 micron outside diameter PMP gas transfer membrane 14 per meter of cord 10 length. The surface area of the gas transfer membranes per unit length of cord is 3.04 times the outer surface area of the cord, calculated based on the circumference of a 1 mm circle.
A biofilm on the cord 10 is assumed to have a thickness of 0.2 mm giving a membrane biofilm assembly diameter of 1.4. The cords 10 are potted in a module in a rectilinear grid with a 0.7 mm gap between their outside surfaces. With biofilm attached, the gap between adjacent cords in a line is 0.4 mm. Using ZeeWeed module moldings, a module 66 has 16 rows of 340 cords 10 each, or 5440 cords 10. The exposed length of each cord is 1.9 m giving a biofilm area per module of 45.5 square meters. Using a ZeeWeed frame, a cassette with a 3.7 square meter footprint and 2.5 meter height has 64 modules 66 and a total biofilm surface area of 2910 square meters. The biofilm surface area is 315 square meters per cubic meter of cassette volume and 786 square meters per square meter of cassette footprint.
In comparison, a comparable sheet form module made with similar gas transfer membranes 14 can have a 1 mm thick fabric with a similar gas transfer surface area to biofilm surface area of 3.34. The sheets are made into a module with horizontally apposed vertical headers. The module is 2 m long with 1.8 m of exposed membrane length. The sheets and module are 1 m high. The module is 0.3 m wide and can be operated in a 1.5 m deep tank. The centre-to-centre spacing between adjacent sheets is 8 mm. The biofilm surface area is 250 square meters per cubic meter of cassette volume and 250 square meters per square meter of cassette footprint.
As illustrated by the comparison above, the cord 10 module can have more biofilm area per unit volume of module than a sheet form module. Further, tall sheet modules that rely on bubbles for liquid renewal or scouring have been known in the context of filtering membranes to be prone to a chimney effect whereby bubbles and liquid flow are concentrate near the vertical midline of the sheets. This limits the height of sheet modules. It is expected that a cord 10 module can be higher without a similar chimney effect which allows for an additional decrease in tank footprint and land consumption per unit biofilm area.
This written description uses examples to disclose the invention and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art.
Filing Document | Filing Date | Country | Kind |
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PCT/US2013/027435 | 2/22/2013 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2014/130043 | 8/28/2014 | WO | A |
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Number | Date | Country | |
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20160009578 A1 | Jan 2016 | US |