Patent Application
20110114567
The invention relates generally to liquid treatment devices, methods, and associated systems. More particularly, this invention relates to precipitation devices, methods and associated systems for decreasing the salinity of saline liquids.
Saline liquids such as concentrate water from wastewater/brackish water desalination devices, e.g., supercapacitor desalination devices or electrodialysis reversal devices, generally need to be processed before recycle to decrease their salinity by removing or reducing salts which include, but are not limited to, sodium chloride, magnesium and calcium sulfates, and bicarbonates.
Precipitation is an approach to decrease the salinity of saline liquid. However, currently available precipitation devices are often designed primarily for obtaining crystals with desired qualities and either are complex in their construction or operate at high temperatures or low pressures, which leads to high capital and/or operating costs.
Therefore, there is a need to develop a precipitation device, method, and associated system to decrease the salinity of the liquid at lower cost.
In one aspect, a precipitation device is provided. The precipitation device comprises: a precipitation element disposed within a vessel and configured to define a precipitation zone and a solid-liquid separation zone between the precipitation element and the vessel, the precipitation zone configured to receive a first stream of saline liquid and to precipitate solids from the saline liquid, the solid-liquid separation zone configured to settle the solids by gravity, and an exit port located in an upper portion of the vessel and configured for exit of a second stream of liquid of lower salinity than the first stream, wherein a ratio of a diameter of the vessel to a diameter of the precipitation element ranges from about 1.5 to about 2.8.
In another aspect, a system is provided. The system comprises the precipitation device, and a desalination device providing the first stream to the precipitation device and receiving the second stream from the precipitation device.
In yet another aspect, a method is provided. The method comprises: providing a precipitation device comprising: a precipitation element disposed within a vessel and configured to define a precipitation zone and a solid-liquid separation zone between the precipitation element and the vessel, and an exit port located in an upper portion of the vessel, wherein a ratio of a diameter of the vessel to a diameter of the precipitation element ranges from about 1.5 to about 2.8, providing a first stream of saline liquid into the precipitation zone to precipitate solids from the saline liquid, settling the solids by gravity in the solid-liquid separation zone, and releasing a second stream of liquid of lower salinity than the first stream through the exit port.
These and other advantages and features will be better understood from the following detailed description of preferred embodiments of the invention that is provided in connection with the accompanying drawings.
Preferred embodiments of the present disclosure will be described hereinbelow with reference to the accompanying drawings. The same numerals in
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” or “substantially”, is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Moreover, the suffix “(s)” as used herein is usually intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term.
The salinity of the second stream 17 of liquid is affected by many factors, e.g., construction of the precipitation device 12. The precipitation element 21 and the upper portion 45 of the vessel 20 have hollow cylindrical shapes. The precipitation element 21 comprises a lower opening 201 in communication with the vessel 20. Additionally, an upper opening 202 in communication with the lower opening 201 of the precipitation element 21 may or may not be provided to communicate with the vessel 20. In some embodiments, a flow rate per unit cross-sectional area in the solid-liquid separation zone is about 0.12 to about 0.48 gallons per minute per square foot cross-sectional area (gpm/ft2), or about 8.2×10−5 to about 3.3×10−4 cubic meter per second per square meter cross-sectional area (meter/sec). A ratio of a diameter D of the upper portion 45 of the vessel 20 to a diameter D1 of the precipitation element 21 ranges from about 1.5 to about 2.8, or preferably from about 1.6 to about 2.2. In the illustrated embodiment, the lower portion of the vessel 20 is cone-shaped having a taper angle α of from about 60 to about 120 degrees. A ratio of a height H to the diameter D of the vessel 20 is not less than 0.2.
In some non-limiting examples, the vessel 20 may have other shapes, such as whole cylindrical shapes. Similarly, the precipitation element 21 may also comprise other shapes, such as cone shapes.
For the illustrated embodiment, a confining element 22 is provided to define a confinement zone 220 with at least a portion thereof disposed within the precipitation zone 24 and in communication with the precipitation zone 24 and the solid-liquid separation zone 200. As one example, the confining element 22 may comprise two open ends and have a hollow cylindrical shape having a uniform diameter.
Additionally, an agitation device 23 may be provided to extend into the confinement zone 220 so as to facilitate the flow of the liquid (or solid-liquid mixture) in the precipitation zone 24 and the confinement zone 220. The flow direction of the liquid (or solid-liquid mixture) agitated by the agitation device 23 may be from top to bottom or from bottom to top.
The ratio of the diameter D2 of an impeller 230 of the agitation device 23 to the diameter D of the vessel 20 ranges from about 0.2 to about 0.4. The ratio of the diameter Dc of the confining element 22 to the diameter D2 of the impeller 230 of the agitation device 23 ranges from about 1.0 to about 2.0. In some embodiments, the impeller 230 is a marine impeller having a diameter of about ¼ of the diameter of the vessel 20. In some embodiments, the impeller 230 is a straight pitched blade impeller having a diameter of about ⅓ of the diameter of the vessel 20. In some embodiments, the impeller 230 is an axial flow impeller comprising from about 2 to about 6 blades.
In certain applications, the supercapacitor desalination device may comprise one or more supercapacitor desalination cells (not shown). As is known, in non-limiting examples, each supercapacitor desalination cell may at least comprise a pair of electrodes, a spacer, and a pair of current collectors attached to the respective electrodes. A plurality of insulating separators may be disposed between each pair of adjacent SCD cells when more than one supercapacitor desalination cell stacked together is employed.
In embodiments of the invention, the current collectors may be connected to positive and negative terminals of a power source (not shown), respectively. Since the electrodes are in contact with the respective current collectors, the electrodes may act as anodes and cathodes, respectively.
For the illustrated arrangement, during the charging state of the supercapacitor desalination device 100, an input stream 13 from a liquid source (not shown) passes through a valve 110 and enters into the SCD device 100 for desalination. In this state, the flow path of an input stream 17 to the SCD device 100 is closed by valve 110. Positive and negative electrical charges from the power source accumulate on surfaces of the anode(s) and the cathode(s), respectively and attract anions and cations from the ionized input stream 13, which causes them to be adsorbed on the surfaces of the anode(s) and the cathode(s), respectively. As a result of the charge accumulation on the anode(s) and the cathode(s), an outflow stream, such as an output stream 14 from the SCD device 100 passing through valve 111 may have a lower salinity (concentration of salts or other ionic impurities) as compared to the input stream 13. In certain examples, the dilute outflow stream 14 may be subjected to de-ionization again by being fed through another desalination device or being redirected into the SCD device 100.
In the discharging state of the supercapacitor desalination device 100, the adsorbed anions and cations dissociate from the surfaces of the anode(s) and the cathode(s), respectively. The input stream 17 is pumped by pump 18 from the precipitation device 12, and passes through filter 19 and valve 110 to enter the SCD device 100 to carry ions (anions and cations) therefrom. An outflow stream 16 flowing from the SCD device 100 and passing through the valve 111 has a higher salinity (concentration of the salt or other ionic impurities) as compared with the input stream 17. In this state, the flow path of the input stream 13 to the SCD device 100 is closed by the valve 110. The filter 19 is configured to filter some particles to avoid clogging the SCD device 100. In certain applications, filter 19 may not be provided.
After discharging of the SCD device is complete, the SCD device is placed in the charging state for a period of time for preparation of a subsequent discharging. That is, the charging and the discharging of the SCD device are alternated for treating input streams 13 and 17, respectively.
In certain applications, the initial (input) stream 13 and the initial (input) stream 17 may or may not comprise the same salts or impurities, and may or may not have the same concentration of the salts or the impurities. In other examples, the concentration of the salts or impurities in the input stream 17 may or may not be saturated or supersaturated.
As the liquid is circulated through the SCD device in the discharging state, the concentration of salts or other ionic impurities in the liquid increases so as to produce precipitate. The precipitation device 12 is configured to precipitate solids from the first stream 16 and separate a part of the precipitate particles (solids) of the salts or other impurities by settling them into the lower portion of the vessel 20 by gravity before the liquid 17 is circulated into the SCD device 100 from the precipitation device 12.
As illustrated in
When the precipitation rate plus a blow down rate of stream 27 equals the charged species removal rate from the input stream 13, where the rates are averaged over one or more charging-discharging cycles, the degree of saturation or supersaturation (saturation and supersaturation are interchangeable throughout this application) of the streams circulating between the SCD device and the precipitation device may stabilize and a dynamic equilibrium may be established.
In some embodiments, device 25 including a pump may also be provided to direct a portion of the liquid (recirculation stream) from a recirculation port 46 of the bottom portion of the vessel 20 to pass through a valve 26 and to enter into the precipitation zone so as to facilitate the flow of the liquid in the precipitation zone 24 and the confinement zone 220. After particle attrition, a portion of the precipitate particles in the recirculation stream may be sent back to be re-suspended in the liquid and to act as seed particles to thereby induce more precipitation in the precipitation zone 24. Normally, valve 26 blocks a flow path of discharge (waste) stream 27 pumped through the device 25.
In some embodiments, the confining element 22 may not be employed. Similarly, in particular embodiments, agitation device 23 and/or the pump 25 may not be provided.
In certain examples, the energy released in the discharging state may be used to drive an electrical device (not shown), such as a light bulb, or may be recovered using an energy recovery cell, such as a bi-directional DC-DC converter.
In other non-limiting examples, similar to the SCD cells stacked together, the supercapacitor desalination device 100 may comprise a pair of electrodes, a pair of current collectors attached to the respective electrodes, one or more bipolar electrodes disposed between the pair of electrodes, and a plurality of spacers disposed between each of the pairs of adjacent electrodes for processing input stream 13 in a charging state and second stream 17 in a discharging state. Each bipolar electrode has a positive side and a negative side, separated by an ion-impermeable layer.
In some embodiments, the current collectors may be configured as a plate, a mesh, a foil, or a sheet and formed from a metal or metal alloy. The metal may include titanium, platinum, iridium, or rhodium, for example. The metal alloys may include stainless steel, for example. In other embodiments, the current collectors may comprise graphite or plastic material, such as polyolefin, which may include polyethylene. In certain applications, the plastic current collectors may be mixed with conductive carbon blacks or metallic particles to achieve a certain level of conductivity.
The electrodes and/or bipolar electrodes may include electrically conductive materials, which may or may not be thermally conductive, and may have particles with small sizes and large surface areas. In some examples, the electrically conductive material may include one or more carbon materials. Non-limiting examples of the carbon materials include activated carbon particles, porous carbon particles, carbon fibers, carbon aerogels, porous mesocarbon microbeads, or combinations thereof. In other examples, the electrically conductive materials may include a conductive composite, such as oxides of manganese, or iron, or both, or carbides of titanium, zirconium, vanadium, tungsten, or combinations thereof.
Additionally, the spacer may comprise any ion-permeable, electronically nonconductive material, including membranes and porous and nonporous materials to separate the pair of electrodes. In non-limiting examples, the spacer may have or itself may be space to form flow channels through which a liquid for processing passes between the pair of electrodes.
In certain examples, the electrodes, the current collectors, and/or the bipolar electrodes may be in the form of plates that are disposed parallel to each other to form a stacked structure. In other examples, the electrodes, the current collectors, and/or the bipolar electrodes may have varied shapes, such as a sheet, a block, or a cylinder. Further, the electrodes, the current collectors, and/or the bipolar electrodes may be arranged in varying configurations. For example, the electrodes, the current collectors, and/or the bipolar electrodes may be disposed concentrically with a spiral and continuous space therebetween.
For certain arrangements, the precipitation device 12 may be used together with an electrodialysis reversal (EDR) device 11 as is shown in
As is known, in some non-limiting examples, the EDR device comprises a pair of electrodes configured to act as an anode and a cathode, respectively. A plurality of alternating anion- and cation-permeable membranes are disposed between the anode and the cathode to form a plurality of alternating dilute and concentrate channels therebetween. The anion-permeable membrane(s) are configured to be passable for anions. The cation-permeable membrane(s) are configured to be passable for cations. Additionally, the EDR device may further comprise a plurality of spacers disposed between each pair of the membranes, and between the electrodes and the adjacent membranes.
Accordingly, while an electrical current is applied to the EDR device 11, liquids, such as the streams 13 and 17 (as shown in
As a result, the second stream 17 passes through the concentrate channels to carry the concentrated anions and cations out of the EDR device 11 so that the outflow stream 16 may be have a higher salinity than the input stream 17. After the circulation of the liquid in the EDR device 11, the precipitation of the salts or other impurities may occur in the precipitation device 12.
In some examples, the polarities of the electrodes of the EDR device 11 may be reversed, for example, every 15-50 minutes so as to reduce the fouling tendency of the anions and cations in the concentrate channels. Thus, in the reversed polarity state, the dilute channels from the normal polarity state may act as the concentrate channels for the second stream 17, and the concentrate channels from the normal polarity state may function as the dilution channels for the input stream 13.
Thus, in a state when the EDR device is at a normal polarity state, stream 13 from a liquid source (not shown) and stream 17 from a vessel 20, respectively, pass through first valves 31 and 32 along respective first input pipes, as indicated by solid lines 33 and 34 to enter into the EDR device 11. A dilute stream 14 and an outflow stream 16 pass through second valves 35 and 36 and enter into respective first output pipes, as indicated by solid lines 37 and 38.
When the EDR device is in a reversed polarity state, the streams 13 and 17 may enter the EDR device 11 along respective second input pipes, as indicated by broken lines 39 and 40. The dilute stream 14 and the outflow stream 16 may flow along respective second output pipes, as indicated by broken lines 41 and 42. Thus, the input streams and the output stream may be alternately entered into respective pipes to minimize the scaling tendency.
When the precipitation rate plus the blow down rate of stream 27 equals the removal rate of the charged species from stream 13, the degree of saturation or supersaturation of the liquid circulating between the EDR device and the precipitation device may stabilize and a dynamic equilibrium may be established.
In some EDR applications, the electrodes may include electrically conductive materials, which may or may not be thermally conductive, and may have particles with small sizes and large surface areas. The spacers may comprise any ion-permeable, electronically nonconductive material, including membranes and porous and nonporous materials. In non-limiting examples, the cation permeable membrane may comprise a quaternary amine group. The anion permeable membrane may comprise a sulfonic acid group or a carboxylic acid group.
In some embodiments, the precipitation of the salts or other impurities may not occur until the degree of saturation or supersaturation thereof is very high. For example, calcium sulfate (CaSO4) often reaches a degree of supersaturation of 500% before precipitation occurs, which may be disadvantageous to the precipitation system. Accordingly, in certain examples, seed particles (not shown) may be added into the vessel 20 to induce precipitation on surfaces thereof at a lower degree of supersaturation of the salts or other ionic impurities. Additionally, the agitation device 23 and/or the pump 25 may be provided to facilitate suspension of the seed particles in the vessel 20.
In non-limiting examples, the seed particles may have an average diameter range from about 1 to about 500 microns, and may have a concentration range of from about 0.1 weight percent (wt %) to about 30 wt % of the weight of the liquid in the precipitation zone. In some examples, the seed particles may have an average diameter range from about 5 to about 100 microns, and may have a concentration range of from about 1.0 wt % to about 20 wt % of the weight of the liquid in the precipitation zone. In certain applications, the seed particles may comprise solid particles including, but not limited to CaSO4 particles and their hydrates to induce the precipitation. The CaSO4 particles may have an average diameter range from about 10 microns to about 200 microns. In some examples, the CaSO4 seed particle concentration may be in a range of from about 0.1 wt % to about 2.0 wt % of the weight of the liquid in the precipitation zone, so that the concentration of CaSO4 in the solution leaving precipitation device 12 may be controlled in a range of from about 100% to about 150% of saturation.
In other examples, one or more additives may be added into outflow stream 16 to reduce the degree of saturation or supersaturation of some species. For example, an acidic additive may be added into the EDR or SCD outflow stream 16 to reduce the degree of saturation or supersaturation of calcium carbonate (CaCO3). In certain examples, the additives may or may not be added into the first stream 16.
It should be noted that seed particles and additives are not limited to any particular seed particles or additives, and may be selected based on specific applications.
In certain examples, a stream 29 may be discharged to remove a certain amount of the liquid to maintain a constant volume and/or to reduce the degree of saturation or supersaturation of some species in the vessel 20. The stream 29 may be mixed with a stream 30, which is removed from the bottom portion of the vessel 20 using pump 25 to form discharge (waste) stream 27.
In some examples, stream 30 may comprise ten or more weight percent of the precipitate. For these examples, valve 26 blocks the flow path for recirculation of the liquid to the vessel 20. Additionally, a valve 204 may be disposed on the lower portion of vessel 20 to facilitate evacuating the vessel 20.
It should be noted that precipitation device 12 is not limited to be used together with any particular supercapacitor desalination (SCD) device or any particular electrodialysis reversal (EDR) device.
In addition, as depicted in
In another aspect, the present invention relates to a method, comprising: providing a precipitation device comprising: a precipitation element disposed within a vessel and configured to define a precipitation zone and a solid-liquid separation zone between the precipitation element and the vessel; and an exit port located in an upper portion of the vessel; wherein a ratio of a diameter of the vessel to a diameter of the precipitation element ranges from about 1.5 to about 2.8; providing a first stream of saline liquid into the precipitation zone to precipitate solids from the saline liquid; settling the solids by gravity in the solid-liquid separation zone; and releasing a second stream of liquid of lower salinity than the first stream through the exit port.
Referring to
Referring to
Referring to
In some embodiments, the first stream comprises calcium sulfate having a saturation or supersaturation degree of about 120% to 140%. The second stream comprises calcium sulfate having a saturation or supersaturation degree of about 100% to 120%.
Design features of various embodiments described herein can be replaced, interchanged or combined according to specific applications. The precipitation device yields liquid with desired quality at low cost and simple mechanism.
The following example is included to provide additional guidance to those of ordinary skill in the art in practicing the claimed invention. Accordingly, this example does not limit the invention as defined in the appended claims.
The tops of the vessel 121 and precipitation element 124 are flush. Cover 126 covers the tops of the vessel and the precipitation element to protect from dust and has a diameter of 350 mm. There are two sample ports 127 and one product stream exit port 128. The vessel 121 supports the precipitation element 124 by engagement structures 129 and the precipitation element supports the confining element 125 by connecting structures 130. In the confining element 125, bearings 131 are provided for supporting the shaft of the agitation device. The precipitation device 120 is mounted on a base 132 in such a way that the lower portion 123 is located below the base. The lower portion comprises two outlets 133 extending upward from the bottom of the lower portion, one as a recirculation port, the other one for backup in case the first one becomes plugged, and one valve 134 extending downward from the bottom of the lower portion for slurry discharge.
The input stream (stream 1,
The water flow rate of inlet stream 1 and outlet stream 2 in and out of the vessel 122, respectively, was controlled at 500 ml/min, which corresponds to 8.6 cm/sec linear velocity. The flow rate per unit cross-sectional area in the solid-liquid separation zone is about 0.25 gpm per square foot (gallons per minute per square foot) or 1.7×10−4 cubic meter per second per square meter. Since the seeds have a tendency to continue to grow during each 45-minute cycle, a recirculation stream (stream 3) at a flow rate of 6000 ml/min operates for 4 minutes during each 30-minute feed portion of the 45-minute cycle to keep the particle size and distribution stable. The water volume in the precipitation device was kept constant by using an overflow stream (stream 4). To maintain a stable seed inventory, there was a 2-second blowdown step in the 30-minute feed during each 45-minute cycle. During the blowdown step, 75 ml of slurry (in stream 5) was discharged. About 6-7 gram of particles were filtered out from the blowdown slurry. During the blowdown step, the overflow stream 4 feeds into the stream 5.
The particle concentration in the outlet stream 2 was measured by filtration to be about 11 ppm. Optical microscopy images from a Nikon ECLIPSE Ti microscope showed that the water quality of outlet (stream 2) was comparable to deionized water. The turbidity of stream 2 was measured daily with a HACH 2100AN TURBIDMETER. Table 2 shows the turbidity data.
In summary, the saturation degree of CaSO4 was decreased by the precipitation device and the system operation is very stable.
While the disclosure has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present disclosure. As such, further modifications and equivalents of the disclosure herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the disclosure as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010101105019.4 | Jan 2010 | CN | national |
This application is a continuation-in-part of U.S. patent application Ser. No. 12/512,324 filed on Jul. 30, 2009 and titled as DESALINATION SYSTEM AND METHOD.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12512324 | Jul 2009 | US |
| Child | 13015466 | US |
