Various water treatment technologies exist. Membrane distillation is one type of water treatment technology that removes a distillate from a feed solution. Membrane distillation can be used in the treatment of wastewater and salty or brine solutions. During membrane distillation, a feed solution is typically preheated to generate a temperature differential across a membrane. This temperature differential creates a vapor pressure differential between a feed side and a distillate side of the membrane, which causes a portion of the feed solution to evaporate near the pore entrance on the feed side and the vapor to transmit through the membrane. The transmitted vapor then condenses at a gas/liquid interface near the pore entrance of the membrane on the distillate side, thereby providing the desired distillate. Because the vaporization of a liquid is involved in the separation process, a large amount of thermal energy can be transferred from the feed solution to the distillate.
The thermal efficiencies of membrane distillation units have been a concern as membrane distillation competes with other water treatment technologies. The gained output ratio (GOR) of a membrane distillation system is the ratio of the latent energy of the distillate to the energy spent to produce the distillate. For a membrane distillation system utilizing direct contact membrane distillation (DCMD) having a design configuration of a membrane distillation module and a heat exchanger, the GOR plateaus around 3. Until now, reaching this GOR level required investment in specialized equipment, such as titanium heat exchangers, which increased the overall cost of the membrane distillation system. The present invention provides a membrane distillation system capable of providing a GOR greater than that of prior systems in addition to providing a design that can be scaled up for large scale applications.
A membrane distillation system includes a distillation vessel defining a distillation volume with generally opposite first and second portions. The system also includes an array of hollow fiber membranes, which are pervious to distillate vapor but impervious to feed solution, and an array of hollow tubes, which are impervious to distillate vapor and feed solution but allow transmission of thermal energy to heat feed solution flowing through the hollow tubes using thermal energy from feed solution flowing through the hollow fiber membranes. Both arrays extend through the distillation volume and are spaced from each other. The system further includes a pump for delivering a feed solution to the array of hollow tubes, a heat exchanger for heating the feed solution after it exits the hollow tubes and before it enters the hollow fiber membranes and an outlet for removing distillate from the distillation vessel.
A circuitous membrane distillation system includes a feed solution source, a pump for delivering a feed solution to a distillation vessel, a distillation vessel and first and second heat exchangers. The distillation vessel includes vessel walls defining a distillation volume, a first manifold located in a first portion of the distillation vessel for receiving the feed solution, a second manifold located in a second portion of the distillation vessel, and a plurality of hollow tubes extending from the first manifold to the second manifold where the hollow tubes are impervious to distillate vapor and feed solution but allow transmission of thermal energy. The distillation vessel also includes a third manifold located in the second portion of the distillation vessel and spaced from the second manifold for receiving heated feed solution, a fourth manifold located in the first portion of the distillation vessel and spaced from the first manifold, a plurality of hollow fiber membranes extending from the third manifold to the fourth manifold where the hollow fiber membranes are pervious to distillate vapor but impervious to feed solution, allowing distillate vapor to cross the membrane into the distillation volume, and an outlet for removing distillate from the distillation volume. The first heat exchanger heats the feed solution after it exits the second manifold and before it enters the third manifold. The second heat exchanger cools the feed solution after it exits the fourth manifold and before it returns to the feed solution source.
A method for removing distillate from a feed solution includes delivering a feed solution through hollow tubes spanning a distillation vessel to preheat the feed solution, heating the feed solution after it exits the hollow tubes, delivering the feed solution through bores of hollow fiber membranes spanning the distillation vessel to create a vapor pressure differential between the bores of the hollow fiber membranes and a distillation volume within the distillation vessel, and removing distillate from the distillation volume of the distillation vessel. The vapor pressure differential causes vapor from the feed solution to transmit across the hollow fiber membranes and condense as distillate within the distillation vessel. Thermal energy from the feed solution flowing through the bores of the hollow fiber membranes is transferred to the feed solution flowing through the hollow tubes.
The present invention provides a membrane distillation system and method capable of operating with increased thermal efficiency. High thermal efficiency can be obtained without the use of expensive recuperating heat exchangers. The present invention allows for a single vessel membrane distillation system suitable for water treatment at various scales. This membrane distillation system obviates the need for more expensive cartridge-based membrane modules and reduces the overall complexity of the membrane distillation system.
Feed source 12 is a tank, vessel, conduit or other container or location for supplying feed solution to membrane distillation system 10. Feed source 12 includes an inlet 24 for introducing new feed solution to feed solution source 12 and an outlet 26 for removing feed solution from feed source 12. Suitable feed solutions for use in membrane distillation system 10 include wastewater, seawater, brines or other aqueous solutions containing salts, other solutes or contaminants.
Pump 14 is connected to feed source 12 by line 22a of feed conveyance network 22. Pump 14 delivers low temperature feed solution from feed source 12 to membrane distillation vessel 16 and the rest of membrane distillation system 10. Pump 14 pressurizes the low temperature feed solution to provide the necessary pressure to circulate the feed solution throughout membrane distillation system 10. From pump 14, the low temperature feed solution travels to membrane distillation vessel 16. Pump 14 is connected to distillation vessel 16 by one or more lines 22b of feed conveyance network 22.
Distillation vessel 16 includes arrays of hollow fiber membranes and arrays of hollow tubes. Distillate, as vapor, crosses the hollow fiber membranes and collects within distillation vessel 16. The hollow tubes are used for heat recuperation (preheating the low temperature feed) to improve efficiency of membrane distillation system 10. The configuration and operation of distillation vessel 16 and the contained arrays of hollow fiber membranes and hollow tubes are described in further detail below. The low temperature feed solution enters distillation vessel 16 and passes through the hollow tubes where it is preheated by distillate flowing through distillation vessel 16. The preheated feed solution exits distillation vessel 16 and is delivered to heat exchanger 18. Distillation vessel 16 is connected to heat exchanger 18 by one or more lines 22c of feed conveyance network 22. Distillation vessel 16 also includes distillate outlet 27 for removing distillate from distillation vessel 16. Optionally, distillate is recirculated through distillation vessel 16 during operation. Recirculation loop 29 includes pump 31 for recirculating distillate through distillation vessel 16. The direction of distillate flow through recirculation loop 29 can vary depending on the distillation application. Recirculation loop 29 can pump distillate from the bottom of distillation vessel 16 to the top of distillation vessel 16, as shown in
Heat exchanger 18 is a heating heat exchanger. In one embodiment, heat exchanger 18 is a solar powered heat exchanger. In other embodiments, heat exchanger 18 utilizes steam or industrial plant waste heat streams. Heat exchanger 18 heats the preheated feed solution to an elevated temperature (producing a high temperature feed solution) before it is delivered to the hollow fiber membranes within distillation vessel 16. The high temperature feed solution is typically heated to a temperature between about 50° C. and about 100° C., with particularly suitable temperatures being between about 70° C. and about 95° C. These ranges of feed solution temperatures allow vapor pressure differentials to form so that feed solution vapor can pass across membranes and collect as distillate. Once heated, the high temperature feed solution is delivered back to distillation vessel 16. Heat exchanger 18 is connected to distillation vessel 16 by one or more lines 22d of feed conveyance network 22. The high temperature feed solution reenters distillation vessel 16 and passes through the hollow fiber membranes. Heating the preheated feed solution allows the resulting high temperature feed solution to enter distillation vessel 16 and the hollow fiber membranes at an elevated temperature to increase the distillation rate within distillation vessel 16. A portion of the high temperature feed solution is converted to distillate and passes across the hollow fiber membranes, and a portion of the feed solution continues through the hollow fiber membranes as retentate feed solution. The retentate feed solution that continues through the hollow fiber membranes exits distillation vessel 16 and is delivered to heat exchanger 20. Distillation vessel 16 is connected to heat exchanger 20 by one or more lines 22e of feed conveyance network 22.
Heat exchanger 20 is a cooling heat exchanger. Heat exchanger 20 cools the retentate feed solution that exits distillation vessel 16 to a reduced temperature before it is delivered back to feed source 12. The retentate feed solution is typically cooled to a temperature between about 5° C. and about 75° C., with particularly suitable temperatures being between about 20° C. and about 55° C. Once cooled, the retentate feed solution is delivered back through line 22f of feed conveyance network 22 to feed source 12, where it can continue through membrane distillation system 10 additional times or be removed from membrane distillation system 10. At this point, the feed solution has been concentrated as some distillate from the feed solution has been removed during distillation. The feed solution can be removed from feed source 12 at outlet 26 or mixed with additional incoming feed solution provided through inlet 24.
As shown in
The low temperature feed solution travelling through hollow tubes 32 is pre-heated in distillation vessel 16 by the high temperature feed solution travelling through hollow fiber membranes 34 and the vapor crossing hollow fiber membranes 34. This heating of the low temperature feed solution reduces the amount of energy needed to heat the low temperature feed solution at heat exchanger 18. The high temperature feed solution travelling through the bores of hollow fiber membranes 34 is pre-cooled in distillation vessel 16 by the vapor crossing hollow fiber membranes 34 (the vapor taking thermal energy away from the hot feed solution) and the low temperature feed solution travelling through hollow tubes 32. This cooling of the high temperature feed solution reduces the amount of energy needed to cool the high temperature feed solution at heat exchanger 20.
Examples of suitable materials for membrane wall 36 include hydrophobic polymeric materials, such as polypropylenes, polyethylenes, polytetrafluoroethylenes, polyvinylidene difluorides, Halar® ECTFE (ethylene chlorotrifluoroethylene, available from Solvay Solexis, Brussels, Belgium) and combinations thereof. Hydrophobic materials help prevent distillate in distillation volume 28 from crossing membrane wall 36 into inner hollow region 38 of hollow fiber membranes 34. Other suitable materials include non-hydrophobic polymer materials, such as polysulfones, polyethersulfones, and polyimides that are coated with hydrophobic material(s). Examples of particularly suitable materials for membrane wall 36 include thermally-resistant polymeric materials, such as polytetrafluoroethylenes, polyvinylidene difluorides, and combinations thereof. Examples of suitable wall thicknesses for membrane wall 36 range from about 50 micrometers to about 500 micrometers, with particularly suitable wall thicknesses ranging from about 100 micrometers to about 250 micrometers. Examples of suitable average pore sizes for membrane wall 36 range from about 0.01 micrometers to about 0.6 micrometers, with particularly suitable average pore sizes ranging from about 0.1 micrometers to about 0.4 micrometers.
Membrane distillation system 10 is configured to operate in liquid gap mode. In this configuration, vapor distillate crosses membrane wall 36 through pores 40 and condenses on an outer surface 42 of membrane wall 36. Outer surface 42 is located within distillation volume 28 of distillation vessel 16. Liquid (distillate) is present or flows through distillation volume 28. The liquid present or flowing through distillation volume 28 is generally cooler than the vapor passing across membrane wall 36. When the vapor encounters the liquid at outer surface 42, the vapor transfers thermal energy to the liquid and the vapor cools. As the vapor cools it condenses on outer surface 42 and joins with the liquid (distillate) in distillation volume 28.
In one embodiment of membrane distillation system 10, arrays of hollow fiber membranes 34 and arrays of hollow tubes 32 are arranged in distillation volume 28 of distillation vessel 16. Thermal energy is recuperated within distillation vessel 16 as heat is transferred from the high temperature feed solution in hollow fiber membranes 34 to the distillate in distillation volume 28 to the low temperature feed solution in hollow tubes 32. In another embodiment of membrane distillation system 10, distillation volume 28 is packed with a heat exchange material to improve heat conductivity within distillation volume 28.
In
Heat exchange material 50 aids in the transfer of thermal energy within distillation volume 28 by virtue of its thermal conductivity (i.e. its ability to conduct heat). Heat exchange material 50 can contain metals, alloys, ceramics, zeolites, compounds and other matter having thermal conductivity greater than the thermal conductivity of the distillate. Table 1 indicates various heat exchange materials 50 and the approximate thermal conductivity values at 25° C. associated with those heat exchange materials 50. Each of these heat exchange materials 50 are suitable for use in distillation vessels 16 according to the present invention. The heat exchange materials 50 listed in Table 1 are by no means exclusive of other materials having a thermal conductivity greater than the thermal conductivity of the distillate (about 0.6 W/m·° C. for water in desalination applications).
Due to the presence of the distillate within distillation volume 28, any heat exchange material 50 present within distillation vessel 16 should be both free of contaminants and inert with respect to the distillate. Distillate passing over and around heat exchange material 50 should not absorb contaminants in or on heat exchange material 50. Thus, heat exchange material 50 should be free of contaminants that could contaminate the distillate. Heat exchange material 50 is contacted with distillate throughout most, if not all, of the membrane distillation operation. Since the presence of distillate within distillation volume 28 is essentially continuous, heat exchange material 50 should be resistant to any chemical changes (e.g., oxidation) that may be initiated by the presence of warm distillate.
Heat exchange material 50 can be coated with another material to prevent reactions between heat exchange material 50 and the distillate. Typically, metallic particles (metals and alloys) are more likely to be coated than other heat exchange materials 50, but any matter suitable for coating can be coated. Suitable coatings for heat exchange material 50 include polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate and hydrophilic plastic materials. Coatings for heat exchange material 50 should be stable in water at the operating temperatures of distillation vessel 16.
Heat recovery of membrane distillation system 10 can be expressed as gained output ratio (GOR). GOR is the ratio of the latent energy of the distillate to the energy spent to produce the distillate. The higher the GOR, the more efficient the membrane distillation system. Higher GORs lead to reduced operating costs. Systems utilizing cartridge-based membrane distillation units for direct contact membrane distillation can reach GORs around 3 but require expensive special equipment like titanium heat exchangers. Aside from the GOR limitation, cartridge type membrane distillation units have other disadvantages when compared to membrane distillation system 10 of the present invention. Cartridge-based membrane distillation units can be expensive to produce, having membranes and modules with high costs. Scaling up operations using cartridge units can be costly as changes to the overall assembly can be complex. Membrane distillation system 10 offers the potential to reach GORs of greater than 3 while also keeping system manufacturing, replacement and maintenance costs low and providing a design that allows for adaptation to large scale applications.
Modeling of membrane distillation system 10 indicates that a GOR of about 3.8 or greater can be reached. In one modeled embodiment, membrane distillation system 10 includes the components indicated in
Membrane distillation system 10 provides for a method for producing distillate from a feed solution.
Embodiments of the present invention allow for membrane distillation with high thermal efficiency, simple designs and the ability to adapt to large scale operations. A distillation vessel having arrays of hollow fiber membranes and hollow tubes offers lower manufacturing, replacement and maintenance costs when compared to prior art membrane systems. Placing a heat exchange material between the hollow fiber membranes and hollow tubes of a distillation vessel also provides for increased thermal efficiency. The heat exchange material offers greater thermal conductivity than the distillate alone.
While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.