A dilute suspension of phosphatic clays is a waste product of phosphate ore beneficiation where the mineral is separated from the ore during processing. The waste clay suspensions, which can initially contain 3-5 wt % of solids, are pumped to large impoundment areas termed clay settling areas (CSAs) for consolidation. However, increase in the solids content proceeds very slowly. In some cases, settling and self-consolidation of the clay can take 25 years to reach a solids content of 25-40 wt %. In central Florida, CSAs cover over 150 square miles, which represents 30% of the mined land.
Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
Disclosed herein are various examples related to electrokinetic dewatering of suspensions such as, e.g., phosphatic clay suspensions. An example of a device that continually dewaters phosphatic clay (e.g., phosphate mine tailings) through electrokinetic methods. Phosphatic clay suspensions with a solids content of 10 wt % can be continually fed between two belts that allow the clay suspension to come in contact with electrodes that apply an electric field. An expanded-metal anode can be placed on the top, and an expanded-metal cathode can be placed on the bottom, allowing clarified water to drain freely away from the phosphatic clay solids.
The device can produce a dewatered cake with a solids content of 31 to 38 wt % with a residence time of between 1.5 and 3 hours. The disclosed design exhibits surprising results with greatly improved efficiency, as compared to previous designs, allowing a 10-fold reduction in the needed electrode area. The reduction of electrode area is important because the anticipated cost of the operation is driven by capital costs that are scaled by the electrode area. This dewatering scheme can be used for dewatering of phosphate mine tailing. In addition, other mining operations that generate clay-rich suspensions include oil sands and other mineral processing involving use of floatation.
The disclosed continuous electrokinetic dewatering can eliminate the need for land for the long-term storage of phosphatic clay during current separation methods of gravity settling, which takes decades. It can also reduce the risk of dam failures in the long-term storage ponds called clay-settling areas. The recovered water can be recycled into the phosphate ore flotation process. The use of an electric field to cause separation does not require adding polymers to the clay such as is needed for a competitive process that uses flocculation by addition of polymers followed by gravity separation.
Electrokinetic dewatering (EKD) for industrial implementations is presented. The disclosed methods and systems can provide opportunities in reducing the industrial implementation cost of EKD such as, e.g., minimizing the applied potential, increasing throughput, and reducing the cost of construction while maintaining a sufficient solid content to ensure a pseudo-plastic clay cake. These options have been evaluated through the development, fabrication, and testing of various new EKD systems.
Referring to
A dilute feed suspension is delivered to a separation chamber or basin 115 from, e.g., a supply tank or other feed system by a pump 118. For example, the horizontal basin 115 can be filled with a dilute phosphatic clay suspension. A metering valve 121 may be used to control the flow of the dilute feed suspension being supplied to the separation chamber or basin 115. In other implementations, the speed of the pump 118 may be controlled (e.g., by a variable speed drive) to control the suspension flow. The pump 118 and/or the metering valve 121 may be automatically controlled based upon indications from a flow measurement device.
Under an applied potential, clay particles can be collected on a non-conductive conveying belt 109 that passes between the two electrodes 106. The anode 106a and cathode 106c receive DC power from a power supply 124 such as, e.g., a potentiostat. As the clay cake 112 is formed on the horizontal section of the conveying belt 109, the cake 112 is lifted out of the basin 115 onto an inclined section of the conveying belt 109. The conveying belt can be driven forward by an electric motor 127 (e.g., a stepper motor) to move the layer of cake 112 from the cake formation zone 103a to the cake dewatering zone 103b.
The transition of the conveying belt 109 from horizontal to inclined can be facilitated using, e.g., wheels or discs 130 distributed across the width of the conveying belt 109. The inclined section provides the cake dewatering. A second pair of electrodes (anode 116a and cathode 116c) can be used to continue dewatering the cake 112, removing supernatant water that cascades in a counter-current fashion back into the basin 115. The electrodes 106 and/or 116 can be made of iridium-oxide (IrO2) coated titanium or other appropriate corrosion resistant metal in order to minimize electrode corrosion during dewatering. The supernatant liquid 133 can be collected in an overflow weir 136, and the dewatered clay cake 112 can be collected in a bin 139 or other receptacle at the end of the inclined conveying belt 109. Additional details regarding the continuous EDK system comprising a cake formation zone and a cake dewatering zone are provided in PCT application entitled “Continuous Electrokinetic Dewatering of Phosphatic Clay Suspensions” by Orazem et al., International Pub. No. WO 2016/057392, published 14 Apr. 2016, which is hereby incorporated by reference in its entirety.
The single-unit design with separate clay formation and dewatering zones was able to produce clay in excess of 30 wt %, but this was at the expense of throughput.
In order to decrease the capital cost associated with continuous electrokinetic dewatering, throughput may be increased by separating the clay formation and clay dewatering zones into two units: a suspension (or clay) thickening unit and a cake dewatering unit, thereby eliminating the rehydration of the clay. The separation into two unit operations allows for independent mechanism-specific optimization of the zones and reduced rewetting of the separated solids, which can further improve the throughput and efficiency of the EKD. Drag between the clay and the electrodes can be reduced by using two conveying belts that sandwich and transport the clay between the electrodes. In other implementations, a single-stage unit can be used to perform the thickening and dewatering operations in a single cake dewatering unit as will be discussed.
Thickening Unit
The suspension (or clay) thickening unit can be to produce a thickened sludge from the dilute feed. The thickened sludge suspension produced can be collected and transferred to the dewatering unit for further processing. For the most effective operation, the sludge production rate should be sufficiently high to supply the dewatering unit.
In the separation chamber 315, an anode 306a is positioned below a cathode 306c. For instance, the distance between the anode 306a and cathode 306c may be in the range of about 5 cm to about 10 cm, however the distance between the anode 306a and cathode 306c may varied outside of this range. In the example of
The anode 306a and cathode 306c receive DC power from a power supply 324 such as, e.g., a potentiostat. The cathode 306c may be positioned below and adjacent to the surface of the liquid (or dilute feed suspension) within the separation chamber 315, which can be maintained by the position of the overflow 342 within the separation chamber 315. The electrodes 306 may be metallic grids such as, e.g., dimensionally stable mesh electrodes made of titanium with an iridium oxide coating or other material suitable for the environment of the EKD system 300. The IrO2 coated titanium cathode can, for example, be replaced by carbon steel cathodes. The anode 306a can be a solid plate.
The anode 306a can be positioned between the top and bottom portions of the conveying belt 309, and directly below the top portion of the belt. Under the influence of the constant electric field established between the cathode 306c and anode 306a, the dispersed particles in the influent will migrate toward the conveying belt 309, where they settle on an upper portion of the conveying belt 309. As the sludge is deposited on the conveying belt 309, it can be driven forward by an electric motor 327 (e.g., a stepper motor) through gearing or appropriate transmission system. As the thickened sludge is transported to the second end by the conveying belt 309, a dam or weir 345 extending across the separation chamber 315 allows the thickened sludge to build up and flow over the wall of the separation chamber 315 without flowing back onto the cathode 306c. In other implementations, a screw conveyor can be used to remove the thickened sludge from the second end of the separation chamber 315.
The electrodes 306 can be stationary with a moving conveying belt 309 as shown in
A suspension (or clay) thickening unit 300 was fabricated and tested for the production of a sludge from the dilute feed. The dilute feed clay suspension was feed at a first end of the thickening unit 300 of
The phosphatic clay suspension had an initial solids content of 4 wt %, and was left to gravity settle. The supernatant water was decanted, leaving behind 7.5 wt % clay that was used as feed for the thickening unit 300. In a typical experimental run of the thickening unit 300, the separation chamber or basin 315 was filled with the 7.5 wt % clay feed suspension. The electric field was activated, which caused clarified water to form at the top of the tank. The DC-power-supply potential ranged from 4.2 to 8.0 V, which, for a measured line resistance of 1.2Ω, corresponds to a working potential difference of 3.2 V to 5.0 V. The applied potential between the electrodes yielded electric fields between 1.0 and 1.5 V/cm for an electrode separation of 3.4 cm. Prior to activating the conveying belt 309, the suspension was allowed to dewater under the applied electric field for 1 hour. After the initial start-up period, the belt motor 327 and feed pumps 318 were activated which caused clarified water to flow towards the feed side of the unit into the standpipe weir 342. The belt speeds ranged from 0.5 to 1.7 cm/min. The feed volumetric flow rate ranged from 20 to 28 mL/min.
A visible one-inch-thick clear-water layer can be seen in the image of
Specific changes were made to the thickening unit 300 under test to improve performance. The dead space in the basin 315 was reduced with water-filled ziplock bags. Other fillers can also be used to reduce dead spaces. In other implementations, the design of the separation chamber or basin 315 can be adjusted to remove potential dead spaces. A horizontal collection port was converted to the standpipe weir 342 to collect the top layer of supernatant water. A rigid scrapper was added to one end of the conveying belt 309 to remove the accumulated sludge from the conveying belt 309. An edge of the scrapper can be positioned across the belt 309 to scrap off sludge to avoid buildup. A dam 345 was added to partition the collection area from the rest of the separation chamber or basin 315 prevented supernatant water from resuspending the sludge. In addition, one or both of the electrodes 306 can be tilted in the longitudinal axis (e.g., in a range from 1 to 5 degrees) to facilitate escape of the bubbles formed at the anode 306a. For example, a two degree tilt in the longitudinal axis of the electrode frame was added.
The thickening unit 300 was able to produce sludge up to a solids content of 20 wt %.
where V is the volume between the electrodes and qin is the feed volumetric flow rate. The fraction of active electrode surface area γ, estimated by:
which accounted for the electrode surface not blocked by bubbles formed by gas evolution. In equation (2), I is the steady-state current and Imax is the maximum observed current. The electrode area covered by gas bubbles was smaller at lower potentials, due to reduced gas evolution, and was reduced by tilting the electrode assembly, as shown in
The supernatant water was collected using a standpipe overflow weir 342 (
A model was developed to relate the sludge thickening to applied electric field, fraction of active electrode area, and retention time as
where wc is the solids content of the sludge, win is the initial solids content, E is the applied electric field, τt is the retention time and γ is the fraction of active electrode. Equation (3) includes supernatant water density ρ, dielectric constant ϵ, and viscosity μ. The electrode area is A, and the clay-particle zeta potential is ζ. After the electrodes were tilted to facilitate removal of gas bubbles, the average value of γ increased 10% from 0.80 to 0.88. The 10% increase in γ represents a 40% reduction in the area of the electrodes blocked by bubbles.
Dewatering Unit
The sludge output of the thickening unit 300 was fed into a cake dewatering unit implemented as a dual-belt feed-through continuous EKD unit.
The anode 716a and cathode 716c were both expanded metal meshes made of iridium-oxide coated titanium. The anode 716a and cathode 716c receive DC power from a power supply 724 such as, e.g., a potentiostat. The gap between the electrodes 716 was tapered from the inlet end at the sludge infeed to the outlet end at the cake discharge, ensuring adequate clay-electrode contact as the clay cake is moved through the dewatering unit 700. At the outlet end adjacent to the cake discharge, one or both ends of the electrodes 716 may not be fixed in position, but can be supported by a tensioner that applies a compression force on the clay cake. The tensioner allows for movement of the electrodes 716 while maintaining the compression force on the cake. The polarity of the electrodes 716 was reversed with the anode 716a located over the cathode 716c such that the supernatant water moved downward during dewatering. As the cake is moved between the electrodes 716, the supernatant water flows through the false-bottom cathode 716c, collects in the back of a retaining tank 715, and is removed by a pump 718 (e.g., a peristaltic pump) or other appropriate drainage system. This approach was found to reduce the rehydration of the clay by the supernatant water.
The conveying belts 709 encompass expanded metal mesh electrodes 716 with dimensions of 63.5 cm by 38.1 cm. The conveying belts 709 sandwich and transport the clay between the electrodes 706. The feed-side gap between the electrodes 716 was fixed at 6.23 cm. The collection-side end of the anode 716a may not be fixed, allowing a variable collection-side gap. A tensioner can be used to apply sufficient downward force on the anode 716a to ensure electrical contact with the clay suspension, while limiting the collection-side gap to a maximum height. For example, a maximum collection-side gap was 3.4 cm. The lower cathode 716c was an expanded metal mesh that allowed the removed water to drip away from the cake.
The entire assembly was inclined +1.5 degrees on the longitudinal axis and placed in an acrylic tank, which acted as the retaining tank 715 and was inclined +3 degrees in the longitudinal axis. The inclination of the assembly and retaining tank 715, as illustrated in
The electrodes 706 can be stationary with moving conveying belts 709 as shown in
The dewatering unit 700 was typically operated at applied potentials of 15 to 20 V from a DC power supply 724. When the line resistance of 1.0Ω was taken into account, the working potential between the electrodes 716 ranged from 10.6 to 14.2 V. The feed-side gap of the electrodes 716 was set at a constant 6.2 cm. Since the gap between the electrodes 716 was tapered, the electric field increased as the cake progressed down the length of the dewatering unit 700. The feed-side electric field ranged from 1.7 to 2.3 V/cm and was dependent on the working potential. The electrode gap at the discharge ranged from 2.8 to 3.4 cm with an average of 3.4 cm and depended on the working potential, final solids content, and feed rate. The discharge-side electric field ranged from 3.4 to 5.2 V/cm and was a function of the working potential and cake thickness. The belt speed ranged from 0.38 to 0.8 cm/min, and the supernatant water collection rate ranged from 60 to 80 mL/min.
The reversal of the electrode polarities (placing the cathode 716c on the bottom) allowed gravity flow to facilitate the removal of supernatant water. The proof-of-concept for a false-bottom cathode was obtained on the bench-top dewatering cell and resulted in a cake with a solids content of 40 wt. The bench-top test was conducted using expanded-metal meshes for the top and bottom electrodes. The bottom electrode was covered with the nylon-fabric mesh used for the conveying belts 709 to contain the sludge. A potential difference was applied to the electrodes to maintain a constant 4 V/cm. As the clay dewatered, water moved through the false-bottom cathode. The anode was then constantly lowered to ensure electrical contact while the applied potential was reduced to maintain a constant electric field. After an elapsed time of 5 hours, a clay cake with a solids content of 40 wt % was recovered.
The configuration of the anode 716a was modified to improve dewatering. A tensioner was added to the anode 716a that utilized the belt tension to apply a compression force on the cake. It was found that without adequate compression, approximately the last quarter of the electrode area did not contact the clay. The tensioner improved contact and allowed dewatering along the entire length of the electrodes 716.
The dewatering unit 700 was able to produce a dewatered cake with a solids content up to 36 wt % at 3.2 kg/hr which corresponds to a dry-clay production rate of 1.2 kg/hr. A maximum wet-cake production of 6.5 kg/hr was observed. The turbidity of the supernatant water at steady-state was measured at 39 NTU. After 24 hours of settling, the turbidity measurement was reduced to less than 1 NTU.
A model was developed to relate the solids content in the dewatering unit as the clay traveled the length of the belt as:
which is analogous to equation (3). Since the electric field is not constant throughout the length of the belt, an effective electric field Eeff was defined as:
The operational parameters are the applied potential difference Veff, belt speed vbelt, and retention time τd. The retention time in the dewatering unit was defined in terms of the length of the electrodes L and the belt speed as:
The feed-side electrode gap is given by din, and the discharge-side gap is given by dout. If the electrode spacing does not taper, din is equal to dout, and the dewatering model in equation (4) simplifies to equation (3). When the change in solids content divided by the final solids content is plotted as a function of the effective electric field and retention time Eeffτd as shown in
Stand-Alone Dewatering Unit
Experiments were performed to determine whether a stand-alone single-stage dewatering unit 1000 could provide adequate dewatering of an unthickened feed. The dewatering unit 700 of
The electrodes 706 can be stationary with moving conveying belts 709 as shown in
In the initial experimental runs, the dewatering unit 1000 was fed manually. Subsequent experimental runs used a pump to supply feed clay to the dewatering unit 1000. At startup, the dewatering unit 1000 can be manually fed a thickened clay with a solids content of at least 15 wt %. If the dewatering unit 1000 is started with unthickened clay with a lower solids content, the clay may flow freely over the conveyor belt 709c and fail to make electrical contact with the anode 706a, thereby hindering the formation of the dewatered cake. When the dewatering unit 1000 begins producing a dewatered cake, the feed can be switched to an unthickened clay suspension for dewatering. The dewatering unit 1000 can be fed using a pump such as, e.g., a peristaltic pump.
A typical operation in the stand-alone dewatering unit 1000 with unthickened feed produced cake with a final solids content that ranged from 31 to 38 wt % as pictured in
The applied potentials were increased, in comparison to the operation of the dewatering unit 700 of
The turbidity of the supernatant fluid increased in comparison to the dewatering unit 700 of
Carbon Steel Electrodes
Experiments with carbon steel serving as the cathode were completed for the purpose of cost reduction in electrode materials. Dimensionally stable anodes (DSA) made of titanium coated with iridium oxide had been utilized for both the cathode 706c/716c and anode 706a/716a. Benchtop EKD tests were performed utilizing a 1008 carbon-steel expanded-metal cathode on the cell.
A constant electric field of 4 V/cm was maintained in the bench-top test. The low current observed for the carbon-steel electrode during the first hour of operation may be attributed to the removal of the metal-oxide film on the cathode surface. After the film was removed in the first hour of operation, the operating current increased and was similar to the operating current of the DSA cathode. The resulting solids content for the carbon-steel cathode was 2 wt % lower than obtained using the DSA cathode. The reduction in final solids content may be attributed to the initial low current during the removal of the metal-oxide film. These experiments indicate that a carbon-steel cathode did not reduce EKD efficacy.
Economic Analysis
The estimated total energy of the dewatering unit 700 of
where the average steady-state current is I, the working potential is Veff, and mass production rate of wet-cake is m. The final solids content as a function of energy required on a dry solids basis for the single-unit EDK system 100 of
The dry-clay production rate of the designs are compared in
A reduction of the capital costs of industrial EKD can be achieved by increasing the throughput. The capital cost to produce a ton of dry clay in $/tons dry solids, represented by Ccap, can be calculated by:
where the annualized capital cost A is:
The capital cost was calculated assuming a 10% interest rate, represented by i, and a term of 20 years which is represented by n. The present value of the capital investment at installation is P in units of $/m2. The decrease of capital cost with increasing the process throughput is shown in
The experiments with the carbon-steel cathode showed comparable performance when compared to the DSA. The cost of DSAs used in the bench-top experiments is on the order of 4,000 USD/m2; whereas the cost of expanded-mesh carbon-steel electrodes is on the order of 4 USD/m2. The use of carbon-steel cathodes will reduce the capital cost of the dewatering unit.
The installation cost per unit area was estimated at $2000/m2. The cost of electricity was estimated at $0.062/kWh. The estimated electrical cost Cop required to process one metric ton of dry clay can therefore be calculated as:
The primary cost of operation was assumed to be due to cost of electricity. As shown in
The total cost per ton of dry clay Ctotal can be estimated by:
The total cost per ton of dry-clay is represented as function of dry-clay production rate per unit area of electrode in
The viability of industrial EKD has been demonstrated using the disclosed dewatering units. Utilizing a dual conveyor belt design increased throughput at high solids content. The largest dry clay production rate per unit area of electrode of the single-unit design was 3.4 kg/hr m2 at a solids content of 20 wt %; whereas, the stand-alone dewatering unit produced 4.7 kg/hr m2 at a solids content of 31 wt %. The stand-alone dewatering unit can produce cake with a 35 wt % solids content at a production rate of 4 kg/hr m2 on a dry-clay basis; whereas the previous continuous EKD system with two zones could produce only 0.5 kg/hr m2 on a dry-clay basis. This result represents an 8-fold reduction in the electrode area required. The economics were also improved by selecting a cheaper material for the cathode. Carbon-steel cathodes were demonstrated to yield performance comparable to that of more expensive cathodes made of iridium-oxide-coated titanium. The electrical-power required for the stand-alone dewatering unit was similar to that of the continuous EKD system. As a result, the estimated cost for continuous electrokinetic dewatering can be reduced by more than an order of magnitude. At an estimated capital cost of $2000/m2 and an electrical cost of $0.062/kWh, the cost for dewatering is projected to be on the order of $8-9 per ton of dry clay produced. These costs do not include potential savings associated with obviating the need for construction of new clay settling areas.
The efficiency of the clay-water separation was improved by reversing the electrode polarity and by fabricating a false-bottom to facilitate removal of water. These changes yielded an increase of the maximum solids content from 35 wt % in the single unit to 38 wt % in the stand-alone dewatering unit. The increase in solids content was achieved using approximately the same amount of electrical power per dry-clay mass as in the single-unit design. The cost of electrode materials was reduced by almost 50% by demonstrating that an effective clay-water separation was achievable with a carbon-steel cathode. The design improvements yielded an 8 fold increase of the dry-clay production rate per unit area of electrode by resulting in the reduction of cost by a factor of 2-12, depending on the applied electric field.
It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
The term “substantially” is meant to permit deviations from the descriptive term that don't negatively impact the intended purpose. Descriptive terms are implicitly understood to be modified by the word substantially, even if the term is not explicitly modified by the word substantially.
It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt % to about 5 wt %, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. The term “about” can include traditional rounding according to significant figures of numerical values. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”.
This application claims priority to, and the benefit of, U.S. provisional application entitled “Device for Efficient Continuous Electrokinetic Dewatering of Phosphatic Clay Suspensions” having Ser. No. 62/577,967, filed Oct. 27, 2017, which is hereby incorporated by reference in its entirety. This application is a continuation-in-part of U.S. patent application Ser. No. 15/516,989, filed Apr. 5, 2017, now issued as U.S. Pat. No. 10,315,165, which is the National Stage Entry of PCT Application No. PCT/US15/53998, filed Oct. 5, 2015, published as WO 2016/057392, which claims priority to U.S. Provisional Application No. 62/143,303, filed Apr. 6, 2015, and U.S. Provisional Application No. 62/059,930, filed Oct. 5, 2014.
Number | Name | Date | Kind |
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3962069 | Inoue | Jun 1976 | A |
4376022 | Porta | Mar 1983 | A |
4680104 | Kunkle | Jul 1987 | A |
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WO-2016057392 | Apr 2016 | WO |
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20190127256 A1 | May 2019 | US | |
20210206682 A9 | Jul 2021 | US |
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62577967 | Oct 2017 | US | |
62143303 | Apr 2015 | US | |
62059930 | Oct 2014 | US |
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Parent | 15516989 | US | |
Child | 16173184 | US |