Patent Publication Number: US-2023145108-A1

Title: Methods and Systems for Treating Phosphogypsum-Containing Water

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Patent Application Ser. No. 62/720,566 filed on Aug. 21, 2018 and titled “METHOD AND SYSTEM TO TREAT PHOSPHOGYPSUM CONTAINING WASTEWATER,” U.S. Provisional Patent Application Ser. No. 62/770,470 filed on Nov. 21, 2018 and titled “IMPROVED LIMING PROCESS OF ACIDIC WATER FOR PHOSPHATE RECOVERY AND SCALING REDUCTION FOR DOWNSTREAM PROCESSES,” U.S. Provisional Patent Application Ser. No. 62/798,696 filed on Jan. 30, 2019 and titled “AMMONIA/AMMONIUM REDUCTION DURING INDUSTRIAL ACIDIC WASTEWATER TREATMENT,” and U.S. Provisional Patent Application Ser. No. 62/846,952 filed on May 13, 2019 and titled “USING MONO-VALENT CATION SELECTIVE AND ANION ION EXCHANGE MEMBRANES IN ELECTRODIALYSIS TO TREAT DOUBLE LIME TREATED POND WATER,” the entire disclosure of each of which is hereby incorporated herein by reference in its entirety for all purposes. 
    
    
     FIELD OF THE TECHNOLOGY 
     Aspects relate generally to water treatment and, more specifically, to the treatment of water containing phosphogypsum. 
     BACKGROUND 
     Phosphoric acid is a precursor compound in the manufacture of various common fertilizers. Phosphogypsum is a side product from the production of phosphoric acid by treating phosphate ore with sulfuric acid. The reaction produces phosphogypsum sludge, phosphoric acid, and a byproduct liquid stream. The byproduct stream is typically reused for cooling but ultimately stored in large open-air enclosures called phosphogypsum stacks or ponds. 
     This wastewater associated with and produced by phosphate manufacturing operations is typically acidic and typically contains various dissolved constituents such as fluoride, ammonia, silica, sulfate, calcium, heavy metals, phosphate, magnesium, colloidal matter, organic carbon, and, in some instances, radium (a radioactive element). The ponds associated with phosphate processing contain billions of gallons of this wastewater, e.g. 3 billion gallons each. Due to increasingly strict environmental regulations and annual rainfall, the stacks must be treated and closed by the operating companies. The pond water has become one of the largest liabilities of phosphoric acid producers. There is an urgent environmental need to treat this wastewater, particularly in environmentally sensitive areas, or areas where population growth has come into closer contact with phosphate processing sites. Treatment of this wastewater to reduce its toxicity and its volume has been a technological challenge of significant interest. The toxic or harmful contaminants must be either reduced or eliminated before treated water can be discharged into the environment. 
     One conventional approach that may be used to dispose of phosphogypsum wastewater is deep well injection. This process injects the wastewater deep underground between impermeable layers of rocks to avoid polluting fresh water supplies. Proper geology is required for deep well injection sites, and a permit must be obtained prior to injecting the process water underground. Further, phosphate is not recoverable from process water in a deep well injection process. 
     SUMMARY 
     In accordance with one or more aspects, a method of treating phosphogypsum-containing water is disclosed. The method may comprise promoting precipitation of at least one target constituent from the phosphogypsum-containing water to produce a supernatant water, introducing a free metal or salt thereof to the supernatant water to provide a pretreated supernatant water, subjecting the pretreated supernatant water to membrane separation to produce treated water having at least one predetermined discharge requirement and a concentrate stream, removing ammonia from at least one of the pretreated supernatant water and the concentrate stream, and discharging the treated water. 
     In some aspects, precipitation is promoted in a multi-stage process. Calcium and/or magnesium may be precipitated in a first precipitation step. Phosphate may be precipitated in a second precipitation step. The method may further comprise adjusting a pH level of the phosphogypsum-containing water to a first pH level in the first precipitation step. The method may further comprise adjusting the first pH level to a second pH level in the second precipitation step. In some aspects, the method may further comprise a third precipitation step. 
     In some aspects, the method may further comprise recovering calcium fluoride from a precipitation slurry associated with the first precipitation step. Likewise, the method may further comprise recovering phosphate from a precipitation slurry associated with the second precipitation step. 
     In some aspects, the free metal or salt thereof may be introduced to the supernatant water via chemical or electrolytic addition. The free metal or salt thereof may be an aluminum salt or an iron salt. The method may further comprise recovering phosphate from the pretreated supernatant following introduction of the free metal or salt thereof. 
     In some aspects, the membrane separation may involve one or more of nanofiltration, ultrafiltration, and reverse osmosis. The membrane separation may involve reverse osmosis and one of nanofiltration and ultrafiltration. 
     In some aspects, the predetermined discharge requirement pertains to a phosphorous or silica level. The method may further comprise recycling at least one reject stream back to a source of the phosphogypsum-containing water. 
     In some aspects, ammonia may be removed from the concentrate stream. Ammonia may be removed from the pretreated supernatant water. An ammonia concentration at a source of the phosphogypsum-containing water may be maintained or reduced. In at least some aspects, at least 90% of ammonia is recovered. The method may further comprise delivering the recovered ammonia as a fertilizer product. 
     In accordance with one or more embodiments, a system for treating phosphogypsum-containing water is disclosed. The system may comprise a source of phosphogypsum-containing water, a pretreatment subsystem comprising at least one precipitation unit fluidly connected downstream of the phosphogypsum-containing water source, a source of a coagulant comprising a free metal or salt thereof fluidly connected to the pretreatment subsystem, a membrane separation subsystem fluidly connected downstream of the pretreatment subsystem and configured to produce treated water having at least one predetermined discharge requirement, an ammonia removal subsystem in fluid communication with the membrane separation subsystem, and a treated water outlet. 
     In some aspects, the pretreatment subsystem may comprise at least two precipitation units. The source of the coagulant may comprise an electrocoagulation subsystem. 
     In some aspects, the membrane separation subsystem may comprise one or more of a nanofilter, an ultrafilter, and a reverse osmosis unit. The membrane separation subsystem may comprise a reverse osmosis unit and one of a nanofilter and an ultrafilter. 
     In some aspects, the pretreatment subsystem may further comprises at least one clarifier. The pretreatment subsystem may further comprise at least one filter press. The pretreatment subsystem may further comprise a settling pond. 
     In some aspects, the system may further comprise a sensor configured to detect at least one operational parameter associated with the water source, the pretreatment subsystem, the membrane separation subsystem, or the treated water outlet. The sensor may be a flow rate, pH, temperature, conductivity, hardness, or concentration sensor. 
     In some aspects, the system may further comprise a controller in communication with the at least one sensor and configured to adjust at least one operational parameter of the system. The controller may be configured to adjust a flow rate or pH level in response to input from the sensor. The controller may be configured to adjust fractionation among the at least one precipitation unit in order to optimize phosphate recovery. The controller may be configured to adjust an amount of the coagulant introduced in order to optimize phosphate recovery. 
     In some aspects, the ammonia removal subsystem may be configured to remove ammonia from a concentrate stream associated with the membrane separation subsystem. The ammonia removal subsystem may be configured to remove ammonia upstream of the membrane separation subsystem. The ammonia removal subsystem may be configured to maintain or reduce an ammonia concentration at the source of phosphogypsum-containing water. In certain aspects, the ammonia removal subsystem may be configured to recover ammonia at a rate of at least 90%. The ammonia removal subsystem may comprise a gas transfer membrane contactor. 
     The disclosure contemplates all combinations of any one or more of the foregoing aspects and/or embodiments, as well as combinations with any one or more of the embodiments set forth in the detailed description and any examples. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The accompanying drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings: 
         FIG.  1 - 2    present process flow diagrams in accordance with one or more disclosed embodiments; 
         FIG.  3    presents a process flow diagram including an additional solids removal step in accordance with one or more disclosed embodiments; and 
         FIG.  4    presents a process flow diagram including ammonia removal operations in accordance with one or more disclosed embodiments. 
     
    
    
     DETAILED DESCRIPTION 
     In accordance with one or more embodiments, water containing phosphogypsum may be efficiently brought to within preestablished environmental discharge limits. As used herein, the term phosphogypsum-containing water may interchangeably be referred to herein as wastewater or process water. Relevant discharge limits may be established by various local, state, federal, or private agencies. For example, the State of Florida has set a maximum conductivity limit of 1,275 μS/cm for National Pollutant Discharge Elimination System (NPDES) permitting. Conventionally, phosphogypsum wastewater may be treated and diluted by up to five to ten times in order to meet conductivity, concentration, and/or load-based limits for ammonia, fluoride, phosphorous, or other constituents. The water consumed for dilution is typically fresh or treated water that could be used for other purposes. The dilution water may be relatively expensive treated water, such as reverse osmosis product water. In at least some embodiments, a cost competitive alternative to conventional treatment methods is presented. In some embodiments, consumption of fresh water associated with environmental discharge may desirably be reduced. In at least some embodiments, there is no dilution prior to discharge. 
     In accordance with one or more embodiments, various product streams (i.e. phosphoric acid, calcium carbonate, and/or ammonium sulfate) may beneficially be recovered in conjunction with the wastewater treatment. In some embodiments, overall recovery rates may be significantly increased. In certain embodiments, a recovery rate of at least about 30%, 40%, 50%, or more may be achieved. 
     In accordance with one or more embodiments, phosphogypsum wastewater may originate from a phosphate manufacturing operation and be stored in a pond or stack. The phosphogypsum wastewater may be highly acidic, i.e. having a pH level of about 1.5 to about 2 and environmentally hazardous. A non-limiting example of the typical chemical composition of pond water is presented in Table 1. Beyond what is presented, the ammonia concentration may range from a few hundred ppm up to a few thousand ppm. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Parameter* 
                 Range 
               
               
                   
                   
               
             
            
               
                   
                 pH, Standard Units 
                 1.6-2.1 
               
               
                   
                 Total Acidity as CaCO 3   
                 20,000-60,000 
               
               
                   
                 Fluoride, as F 
                  4,000-12,000 
               
               
                   
                 Phosphorus, as P 
                 4,000-9,000 
               
               
                   
                 Silicon, as Si 
                 1,000-3,000 
               
               
                   
                 Total Solids 
                 20,000-50,000 
               
               
                   
                 Total Suspended Solids 
                  50-250 
               
               
                   
                 Conductivity, umhos 
                 15,000-40,000 
               
               
                   
                 Chlorides, as Cl 
                  50-500 
               
               
                   
                 Sulfates, as SO 4   
                  2,000-12,000 
               
               
                   
                 Sodium, as Na 
                   50-3,000 
               
               
                   
                 Calcium, as Ca 
                   50-1,500 
               
               
                   
                 Magnesium, as Mg 
                  50-400 
               
               
                   
                 Aluminum, as Al 
                   50-1.000 
               
               
                   
                 Chrome, as Cr 
                 0.2-5.0 
               
               
                   
                 Zinc, as Zn 
                 1.0-5.0 
               
               
                   
                 Iron, as Fe 
                 100-250 
               
               
                   
                 Manganese, as Mn 
                  5-30 
               
               
                   
                 NH 3 —N, as N 
                    0-1,200 
               
               
                   
                 Total Organic N, as N 
                  3-30 
               
               
                   
                 Color, APHA units 
                   20-4,000 
               
               
                   
                   
               
               
                   
                 *All values expressed as mg/L unless otherwise noted. 
               
            
           
         
       
     
     In accordance with one or more embodiments, wastewater containing phosphogypsum may be pretreated. Pretreatment may promote the removal of at least one target species and/or adjust one or more operational parameters in order to facilitate downstream operations. A pretreated supernatant may be delivered to downstream unit operations for further treatment. 
     In accordance with one or more embodiments, pretreatment may involve precipitation. Precipitation may be strategically staged so as to promote the removal of various target constituents in series. Different target constituents may precipitate out under different conditions. For example, a first target constituent may precipitate out at a first pH condition and a second target constituent may precipitate out at a second pH condition. 
     In accordance with one or more embodiments, pretreatment may involve adjusting a hardness level. In some non-limiting embodiments, magnesium and/or calcium levels may be targeted. The hardness level may be adjusted via precipitation in a first pretreatment stage. 
     In accordance with one or more embodiments, pretreatment may involve phosphate removal. Phosphate removal may be promoted via precipitation in a second pretreatment stage. 
     In accordance with one or more embodiments, pretreatment may involve adjusting a process stream to a first pH level in a first pretreatment stage to promote precipitation of a first target constituent. Pretreatment may subsequently involve adjusting a process stream to a second pH level from the first pH level in a second pretreatment stage to promote precipitation of a second target constituent. 
     In accordance with one or more embodiments, pretreatment may involve further promoting the recovery of one or more constituents, such as phosphorous or silica. In some embodiments, a coagulant may be introduced. In certain embodiments, a free metal or salt thereof may be strategically dosed as a coagulant. In some embodiments, an aluminum salt (i.e. aluminum sulfate) or an iron salt may be dosed as a coagulant. In at least some non-limiting embodiments, a multivalent metal coagulant may be strategically dosed. 
     In accordance with one or more embodiments, the coagulant may be introduced through chemical or electrolytic addition. Since the process water may contain saturated amounts of silica, among other species, addition of the free metals may coagulate and reduce silica levels to acceptable levels for downstream membrane processes. Chemical addition may involve addition of aluminum sulfate, sodium aluminate, iron chloride, or other catalyst. Electrolytic addition may involve electrolysis of anodes consisting of aluminum, other aluminum composites, iron/steel, or other material. As an example, any aluminum or iron salts available on the market (e.g. Al 2 (SO 4 ) 3 , AlCl 3 , NaAlO 2 , Al(NO 3 ) 3  can be possibly utilized as coagulant to reduce the silica content. It is possible to combine the salts that are acidic in aqueous solution and the ones that are basic together to reduce or eliminate the pH adjustment afterwards, e.g. Al(SO 4 ) 3 +NaAlO 2 . 
     In accordance with one or more embodiments, pretreatment may significantly increase the recovery efficiency of downstream unit operations. In some embodiments, pretreatment may be performed upstream of a membrane separation subsystem as further described herein. 
     A process flow diagram in accordance with one or more non-limiting embodiments is presented in  FIG.  1   . A first compound (i.e. limestone) may be introduced to achieve a first target pH level in order to promote a first precipitation. Clarification and filter press or any other related techniques known to those of skill in the art may be used to recover a first precipitate (i.e. calcium fluoride). The first precipitation may generally reduce a hardness level of a process stream entering a second precipitation. A second compound (i.e. slack lime) may be introduced to achieve a second target pH level in order to promote the second precipitation. The second pH level may generally be different than the first pH level. In at least some embodiments, the second pH level may be higher than the first pH level. The second precipitation may generally promote precipitation of a phosphate slurry that may be delivered for further processing and recovery. A coagulant may then be added to further promote phosphate recovery. A coagulant-dosed process stream may be introduced to a settling pond for a predetermined period of time, i.e. several hours. A pH level of a process stream in the settling pond may optionally be readjusted. The settling operation may generally promote precipitation of an additional phosphate slurry that may be delivered for further processing and recovery. A pretreated supernatant may then be delivered downstream for further processing, i.e. via membrane separation. For example, non-limiting membrane separation operations may include one or more of ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO).  FIG.  1    presents an embodiment in which NF and RO are implemented in series.  FIG.  2   . presents an alternative embodiment in which UF and staged RO are implemented in series. 
     In accordance with one or more embodiments, an additional solid waste recovery step may be incorporated as presented in  FIG.  3   . The additional solid waste recovery step may be associated with an intermediate pH level between the first and second pH levels. 
     In accordance with one or more embodiments, various pretreatment stages may be strategically controlled in order to promote recovery of various target compounds. Downstream recovery process may also be optimized. In some embodiments, an amount of coagulant, i.e. aluminum, added may be strategically controlled in order to optimize phosphate recovery and downstream processes. In some embodiments, fractionation (i.e. pH stopping points) associated with pretreatment precipitation may be strategically controlled to optimize recovery and downstream processes. Waiting periods, i.e. within clarifiers and the settling pond time can also be optimized or reduced. 
     Ammonia/ammonium may become increasingly concentrated or enriched over time as various reject streams from membrane processes are recycled back to the pond. In accordance with one or more embodiments, systems and methods may beneficially remove ammonia. 
     In accordance with one or more embodiments, ammonia stripping and/or recovery processes may be strategically integrated. For example, ammonia may be removed downstream of any silica or phosphate reduction process. Alternatively or in addition, ammonia may also be removed from reject streams associated with various membrane processes. A flow rate of an ammonia stripping/recovery process may be strategically adjusted such that an ammonia concentration or content of the pond can be maintained or reduced rather than increased. In some non-limiting embodiments, ammonia removal may be accomplished via membrane degasification, i.e. with a gas transfer membrane contactor. For example, a Liqui-Cel™ gas transfer membrane contactor commercially available from 3M Company may be implemented. In some embodiments, the gas transfer membrane contactor may remove about 90% to about 99% of ammonia from a process stream. In at least some embodiments, ammonia sulfate may be recovered. 
       FIG.  4    presents a process flow diagram in accordance with one or more embodiments implementing an ammonia stripping/recovery process. Alternative positions for ammonia removal are indicated. The ammonia/ammonium concentration can beneficially be maintained relatively stable or reduced. This may make it possible to deal with a simpler stack closure task at a later stage, as well as to recover the value of ammonia/ammonium as ammonium sulfate fertilizer. 
     In accordance with one or more embodiments, a treatment system may include at least one sensor configured to detect an operational parameter. For example, the sensor may be configured to detect an operational parameter associated with the source of pond water, the pretreatment system, i.e. a precipitation subsystem, the membrane subsystem, the ammonia removal subsystem, or the treated water outlet. In some non-limiting embodiments, the sensor may be a flow rate, pH, temperature, conductivity, hardness, or concentration sensor. In some embodiments, two or more sensors, e.g. a plurality of sensors, may be incorporated. The sensors may be strategically positioned throughout the system. The sensors may be interrelated and/or interconnected, for example, with respect to process control. The system may further include a controller in communication with the at least one sensor. The controller may be configured to provide a control signal in response to input from the sensor. For example, the controller may provide a control signal to actuate or adjust a valve of the system or subsystem thereof. In some non-limiting embodiments, the controller may be configured to adjust a flow rate or pH level in response to input from the sensor. The controller may adjust coagulant addition in response to sensor input. In this way, the controller may enable adjustment of one or more process parameters so as to produce one or more desirable product streams. In some non-limiting embodiments, the controller may adjust flow to a membrane contactor, for example, to promote ammonia sulfate recovery as described herein. The controller may be further configured to make a comparison between a measured value and a predetermined value, such as an established discharge requirement and to adjust various control settings accordingly. 
     The function and advantages of these and other embodiments can be better understood from the following examples. The examples are intended to be illustrative in nature and are not considered to be limiting the scope of the invention. 
     Example 1 
     A process flow diagram according to  FIG.  1    was lab tested and modelled. A projected water analysis from modelling is shown in Table 2A. 
     Phosphogypsum-containing sample pond water having a pH of about 2.7 was reacted with limestone to a target pH level of 4-4.5 on a bench-scale. After settling for approximately 20 minutes, the slurry was filtered to recover water to be combined with a supernatant decanted effluent stream (for increased overall water recovery). The solids were projected to have amounts of calcium fluoride, calcium phosphate, silica precipitates, to be further treated as solid waste. Further treatment of the combined supernatant from pH 4-4.5 to a target pH level of 7-7.5 was performed using slack lime (Ca(OH) 2 ) on the lab bench. This second precipitation step yielded a sizable portion of calcium phosphate precipitates. This slurry from the second clarifier is to be pumped to an upstream acid plant for recovery of phosphate. The value of the recovered phosphate to an active plant is considerable and should be noted. The supernatant that has been decanted from the second precipitation step after settling for approximately 20 minutes follows a third precipitation step. To reduce the silica and the phosphate in the second supernatant solution, aluminum was added as aluminum sulfate. Lab results of alum additions are shown in Table 2B for reduction in SiO2 levels. The reduction of the silica facilitates higher water recovery operations upstream. This treated supernatant was then introduced to a settling pond to settle out aluminum phosphate slurry, which may be further treated for recovery of phosphate, or be considered as solid waste. Effluent from the settling pond may be filtered in downstream NF/RO. 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 2A 
               
               
                   
               
               
                   
                   
                 Feed 
                 Supernatant from 
                 Supernatant from 
                 Supernatant from 
               
               
                 Parameter 
                 Unit 
                 (Apr. 10, 2018) 
                 Precipitation#1 
                 Precipitation#2 
                 Precipitation#3 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Volume of sample 
                 mL 
                 50 
                 43 
                 34 
                 35 
               
               
                 Mass of precipitate 
                 g, dry 
                 — 
                 3.53 
                 1.07 
                 0.2 
               
               
                 Calcium 
                 mg/l as CaCO3 
                 3310 
                 4625 
                 320 
                 146 
               
               
                 Magnesium 
                 mg/l as CaCO3 
                 1510 
                 915 
                 43 
                 34 
               
               
                 Sodium 
                 mg/l as CaCO3 
                 5490 
                 6150 
                 6150 
                 6150 
               
               
                 Potassium 
                 mg/l as CaCO3 
                 370 
                 500 
                 500 
                 500 
               
               
                 Iron 
                 mg/l 
                 169 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Manganese 
                 mg/l 
                 25 
                 2.2 
                 2.2 
                 2.2 
               
               
                 Aluminum 
                 mg/l 
                 161 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Barium 
                 mg/l 
                 0 
                 1.9 
                 1.9 
                 1.9 
               
               
                 Strontium 
                 mg/l 
                 48 
                 48 
                 48 
                 48 
               
               
                 Copper 
                 mg/l 
                 0 
                 — 
                 — 
                 — 
               
               
                 Zinc 
                 mg/l 
                 18 
                 — 
                 — 
                 — 
               
               
                 Bicarbonate 
                 mg/l as CaCO3 
                   
                 — 
                 — 
                 — 
               
               
                 Fluoride 
                 mg/l as CaCO3 
                 19500 
                 81 
                 52 
                 0 
               
               
                 Chloride 
                 mg/l as CaCO3 
                 262 
                 262 
                 262 
                 262 
               
               
                 Bromide 
                 mg/l as CaCO3 
                 0 
                 — 
                 — 
                 — 
               
               
                 Nitrate 
                 mg/l as CaCO3 
                 46 
                 12.3 
                 12.3 
                 12.3 
               
               
                 Phosphate 
                 mg/l as CaCO3 
                 51500 
                 22430 
                 4966 
                 2092 
               
               
                 Sulfate 
                 mg/l as CaCO3 
                 7840 
                 5097 
                 4815 
                 4911 
               
               
                 pH 
                   
                 2.7 
                 4.5 
                 7.4 
                 7.1 
               
               
                 Turbidity 
                 NTU 
                 28 
                 — 
                 — 
                 — 
               
               
                 Conductivity 
                 μS/cm 
                 36900 
                 — 
                 — 
                 — 
               
               
                 Total Hardness 
                 mg/l as CaCO3 
                 4631 
                 — 
                 — 
                 — 
               
               
                 TOC 
                 mg/l 
                 192 
                 53 
                 53 
                 53 
               
               
                 Mineral Acidity 
                 mg/l as CaCO3 
                 26864 
                 — 
                 — 
                 — 
               
               
                 Ammonia 
                 mg/l as CaCO3 
                 4531 
                 4531 
                 4531 
                 &lt;4531 
               
               
                 Total Silica 
                 mg/l as CaCO3 
                 3045 
                 451 
                 183 
                 101 
               
               
                 Total Acidity 
                 mg/l as CaCO3 
                 47633 
                 — 
                 — 
                 — 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2B 
               
             
            
               
                   
                   
               
               
                   
                 Ratio Al:SiO2 (mass) 
                   
               
            
           
           
               
               
               
               
               
            
               
                 pH 
                 Time Elapsed (hr) 
                 Al 
                 SiO2 
                 SiO2 (mg/L) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 3.5 
                 4.5 
                 1 
                 2 
                 614 
               
               
                 3.5 
                 20 
                 1 
                 2 
                 379 
               
               
                 3.5 
                 20 
                 1 
                 2 
                 346 
               
               
                 4.5 
                 4.5 
                 1 
                 2 
                 445 
               
               
                 4.5 
                 20 
                 1 
                 2 
                 285 
               
               
                 4.5 
                 20 
                 1 
                 2 
                 281 
               
               
                 5.5 
                 4.5 
                 1 
                 2 
                 330 
               
               
                 5.5 
                 20 
                 1 
                 2 
                 253 
               
               
                 5.5 
                 20 
                 1 
                 2 
                 288 
               
               
                 5.5 
                 16 
                 5 
                 1 
                 609 
               
               
                 5.5 
                 16 
                 5 
                 1 
                 560 
               
               
                 7.3 
                 16 
                 6 
                 1 
                 80 
               
               
                 7.3 
                 16 
                 6 
                 1 
                 86 
               
               
                 7.3 
                 17 
                 2 
                 1 
                 17 
               
               
                 7.3 
                 17 
                 2 
                 1 
                 17 
               
               
                 7.6 
                 17 
                 1 
                 2 
                 19 
               
               
                 7.6 
                 17 
                 1 
                 2 
                 18 
               
               
                 8.9 
                 17 
                 1 
                 8 
                 83 
               
               
                 8.9 
                 17 
                 1 
                 8 
                 86 
               
               
                 7.3 
                 4 
                 N/A 
                 N/A 
                 186 
               
               
                 7.3 
                 4 
                 N/A 
                 N/A 
                 184 
               
               
                 7.3 
                 94 
                 N/A 
                 N/A 
                 155 
               
               
                 7.3 
                 94 
                 N/A 
                 N/A 
                 151 
               
               
                 7.3 
                 18 
                 1 
                 8 
                 131 
               
               
                 7.3 
                 18 
                 1 
                 8 
                 131 
               
               
                 6.7 
                 18 
                 1 
                 8 
                 177 
               
               
                 6.7 
                 18 
                 1 
                 8 
                 175 
               
               
                 7.3 
                 18 
                 1 
                 2 
                 27 
               
               
                 7.3 
                 18 
                 1 
                 2 
                 27 
               
               
                 7.3 
                 18 
                 1 
                 4 
                 78 
               
               
                   
               
            
           
         
       
     
     Example 2 
     A process flow diagram according to  FIG.  2    was lab tested and modelled for scale-up. A summary of scaled-up stream compositions can be seen on Table 3A. Phosphogypsum-containing sample pond water (500 mL) having a pH of about 2.0 was reacted with limestone (20.5 g) at ambient temperature to a target pH level of 3.8. After settling for approximately 30 minutes, the slurry was filtered to recover water to be combined with a supernatant decanted effluent stream (for increased overall water recovery, 90% liquid volume relative to feed). The solids were analyzed to have amounts of fluoride, phosphate, silica, and magnesium, &gt;98%, &gt;40%, 80%, and &gt;25% by wt %, respectively, to be further treated as solid waste. Further treatment of the combined supernatant from pH 3.8 to a target pH level of 7.4 was performed using slack lime (Ca(OH) 2 , 4 g) on the lab bench. This second precipitation step yielded a sizable portion of calcium phosphate precipitates (&gt;45% phosphate wt % relative to feed). This slurry from the second clarifier is to be pumped to an upstream acid plant for recovery of phosphate. The value of the recovered phosphate to an active plant is considerable and would contribute to the overall economics. The supernatant that has been decanted (&gt;75% of liquid volume relative to feed) from the second precipitation step after settling for approximately 30 minutes follows a third precipitation step. To reduce the silica and the phosphate in the second supernatant solution, electrocoagulation (EC) was used. (EC) was evaluated to reduce silica content in phosphogypsum-containing water without increasing the TDS burden. An electrocoagulation reactor was used with 15 mL/min flow of sample water with residence time of 30 minutes at varying current. The data on Table 3B clearly showed that EC can reduce silica in a much shorter time frame and more effective fashion compared to traditional chemical coagulation. Table 3C presents treated data and Table 3D presents control data. 
     In addition, the results further showed that EC (using aluminum electrodes) does not introduce excessive aluminum ions into the treated water which is highly desirable for downstream membrane processes to operate at higher recoveries. This treated supernatant was settled for 30 minutes and decanted. The precipitates from the EC step may be further treated for recovery of phosphate or be considered as solid waste. Effluent from the settling was analyzed via internal laboratory and an industrial projection software was used to model downstream membrane processes. Downstream membrane processes were modelled to be a UF followed by 2-pass RO system. Water recoveries for the UF and the 2-pass RO are 90%, 60%, and 80%, respectively. The 1 st  pass RO uses SH30H-380 membranes and contains 1 stage with 112 pressure vessels (to achieve the scaled-up flowrates). The 2 nd  pass RO uses BW30-400 membranes and contains 2 stages with 48 pressure vessels in each stage. Operating conditions for both passes are ambient 25 C with the first pass being low-pH RO and near neutral pH RO for the second pass. Antiscalant may be required and thus was modelled into the process. Chemtreat antiscalant was used at a dose of 8.7 mg/L going into the 1 st  pass RO. There may be pH adjustment before going to the 1 st  pass RO, thus sulfuric acid may be used to bring down the pH. 2 nd  pass RO permeate is projected to meet NPDES discharge limits, and in some cases only a single pass RO is needed. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 3A 
               
               
                   
               
               
                   
                   
                   
                 Super- 
                 Super- 
                 Super- 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                   
                   
                 natant 
                 natant 
                 natant 
               
               
                   
                   
                 Pond 
                 from 
                 from 
                 from 
                   
                   
                   
                   
                   
                   
                 Slurry 
               
               
                   
                   
                 Feed 
                 Precip- 
                 Precip- 
                 Precip- 
                   
                   
                 RO1 
                 RO2 
                   
                   
                 from 
               
               
                   
                   
                 (Sep. 17, 
                 tiation 
                 tiation 
                 tiation 
                   
                   
                 Perme- 
                 Perme- 
                 RO1 
                 RO2 
                 Precip. 
                 Silica 
               
               
                 Parameter 
                 Unit 
                 2018) 
                 #1 
                 #2 
                 #3 
                 UF 
                 Unit 
                 ate 
                 ate 
                 Reject 
                 Reject 
                 2 
                 Gel 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Volu- 
                 GPM 
                 6959 
                 6207 
                 5559 
                 4460 
                 5000 
                   
                 3375 
                 2160 
                 1800 
                 540 
                 648 
                 1099 
               
               
                 metric 
               
               
                 Flow 
               
               
                 Calcium 
                 mg/L as 
                 3050 
                 4625 
                 320 
                 3.57 
                 3.57 
                 mg/L as 
                 0.02 
                 0.00 
                 71.13 
                 0.10 
                 41552 
                 1604 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Magnesium 
                 mg/L as 
                 1110 
                 916 
                 43 
                 13.9 
                 13.9 
                 mg/L as 
                 0.00 
                 0.00 
                 8.45 
                 0.00 
                 8411 
                 159 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Sodium 
                 mg/L as 
                 5620 
                 6150 
                 6150 
                 5010 
                 5010 
                 mg/L as 
                 3.59 
                 0.04 
                 5791.01 
                 17.80 
                 6150 
                 10777 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Potassium 
                 mg/L as 
                 450 
                 500 
                 500 
                 290 
                 290 
                 mg/L as 
                 1.99 
                 0.08 
                 564.07 
                 9.62 
                 500 
                 1352 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Iron 
                 mg/L as 
                 80 
                 0 
                 0 
                 0.02 
                 0.02 
                 mg/L as 
                 0.00 
                 0.00 
                 0 
                 0.00 
                 0 
                 0 
               
               
                   
                 ion 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Manganese 
                 mg/L as 
                 14 
                 2 
                 2 
                 0.01 
                 0.01 
                   
                 NA 
                 0.00 
                 NA 
                 0.00 
                 2 
                 11 
               
               
                   
                 ion 
               
               
                 Aluminum 
                 mg/L as 
                 108 
                 0 
                 0 
                 0.08 
                 0.08 
                   
                 NA 
                 0.00 
                 NA 
                 0.00 
                 0 
               
               
                   
                 ion 
               
               
                 Strontium 
                 mg/L as 
                 39 
                 2 
                 2 
                 0.03 
                 0.03 
                   
                 0.00 
                 0.00 
                 0.07 
                 0.00 
                 2 
                 9 
               
               
                   
                 ion 
               
               
                 HCO3 
                 mg/L as 
                 &lt;0.5 
                   
                   
                 574.4 
                 574.4 
                 mg/L as 
                 5.52 
                 1.31 
                 1718.62 
                 26.26 
                 0 
                 −2331 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Bromide 
                 mg/L as 
                 &lt;3 
                   
                   
                 6.05 
                 6.05 
                   
                 NA 
                 NA 
                 NA 
                 NA 
                 0 
                 −25 
               
               
                   
                 CaCO3 
               
               
                 Fluoride 
                 mg/L as 
                 19000 
                 81 
                 52 
                 1 
                 1 
                 mg/L as 
                 0.00 
                 0.00 
                 0.95 
                 0.00 
                 327 
                 258 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Chloride 
                 mg/L as 
                 147 
                 262 
                 262 
                 190 
                 190 
                 mg/L as 
                 0.85 
                 0.02 
                 336.27 
                 4.17 
                 262 
                 554 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Nitrate 
                 mg/L as 
                 25 
                 12 
                 12 
                 15.4 
                 15.4 
                 mg/L as 
                 1.15 
                 0.28 
                 45.77 
                 4.64 
                 12 
                 0 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Phosphate 
                 mg/L as 
                 34100 
                 22430 
                 4966 
                 1190 
                 1190 
                 mg/L as 
                 1.08 
                 0.04 
                 2103.34 
                 8.02 
                 172233 
                 20290 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Sulfate 
                 mg/L as 
                 7150 
                 5097 
                 4815 
                 5910 
                 5910 
                 mg/L as 
                 11.56 
                 0.74 
                 15869.9 
                 131.10 
                 7512 
                 373 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 pH 
                 s.u. 
                 2.0 
                 3.8 
                 7.4 
                 8.54 
                 8.54 
                 s.u 
                 5.21 
                 4.63 
                 7.15 
                 5.84 
               
               
                 TDS 
                 mg/L as 
                 49863 
                   
                   
                   
                   
                 mg/L as 
                 28.17 
                 2.81 
                 30773 
                 255.68 
               
               
                   
                 ion 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Ammonia 
                 mg/L as 
                 4089 
                 4089 
                 4089 
                 3325.01 
                 3325.01 
                 mg/L as 
                 9.64 
                 0.34 
                 3001.78 
                 46.83 
                 4089.00 
               
               
                   
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                 Total 
                 mg/L as 
                 2233 
                 451 
                 183 
                 49.29 
                 49.29 
                 mg/L as 
                 0.60 
                 0.01 
                 146.62 
                 2.96 
                 2750.3 
                 723.63 
               
               
                 Silica 
                 CaCO3 
                   
                   
                   
                   
                   
                 ion 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 3B 
               
               
                   
               
               
                   
                 Current 
                 Residence Time 
                 Electrode 
                 Silica In 
                 Silica Out 
                 Silica Reduction 
               
               
                 Trial No. 
                 (A) 
                 (min) 
                 Configuration 
                 (ppm) 
                 (ppm) 
                 (ppm) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.5 
                 31 
                 Al(+) | Al | Al | Al(−) 
                 113 
                 67 
                 46 
               
               
                 2 
                 1.0 
                 31 
                 Al(+) | Al | Al | Al(−) 
                 156 
                 62 
                 94 
               
               
                 3 
                 1.0 
                 31 
                 Fe(+) | Fe | Fe | Fe(−) 
                 156 
                 120 
                 36 
               
               
                 4 
                 0.5 
                 31 
                 Fe(+) | Fe | Fe | Fe(−) 
                 156 
                 123 
                 33 
               
               
                 5 
                 1.0 
                 31 
                 Al(+) | Fe | Al | Fe(−) 
                 147 
                 28 
                 119 
               
               
                 14 
                 1.0 
                 31 
                 Al(+) | Al | Al(−) 
                 142 
                 69 
                 73 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 3C 
               
               
                   
                   
               
               
                   
                 TESTS 
                 RESULT 
                 UNITS 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Aluminum (Al) 
                 0.077 
                 mg/l 
               
               
                   
                 Bicarb (HCO3) 
                 574.4 
                 mg/l CaCO3 
               
               
                   
                 Bromide (Br) 
                 6.05 
                 mg/l CaCO3 
               
               
                   
                 Carbonate (CO3) 
                 232.9 
                 mg/l CaCO3 
               
               
                   
                 Chloride (Cl) 
                 100 
                 mg/l CaCO3 
               
               
                   
                 Fluoride (F) 
                 &lt;1.00 
                 mg/l CaCO3 
               
               
                   
                 Hydroxide (OH) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Nitrate (NO3) 
                 15.4 
                 mg/l CaCO3 
               
               
                   
                 Phosphate (PO4) 
                 1190 
                 mg/l CaCO3 
               
               
                   
                 Sulfate (SO4) 
                 5910 
                 mg/l CaCO3 
               
               
                   
                 Barium (Ba) 
                 &lt;0.050 
                 mg/l 
               
               
                   
                 Calcium (Ca) 
                 3.57 
                 mg/l CaCO3 
               
               
                   
                 Iron (Fe) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Magnesium (Mg) 
                 13.9 
                 mg/l CaCO3 
               
               
                   
                 Manganese (Mn) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Potassium (K) 
                 290 
                 mg/l CaCO3 
               
               
                   
                 Sodium (Na) 
                 5010 
                 mg/l CaCO3 
               
               
                   
                 Free (CO2) 
                 5.3 
                 mg/l CaCO3 
               
               
                   
                 Copper (Cu) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Ammonia (NH3) 
                 2248 
                 mg/l CaCO3 
               
               
                   
                 pH 
                 8.54 
               
               
                   
                 Total Silica (SiO2) 
                 49.29 
                 mg/l CaCO3 
               
               
                   
                 Silicon (Si) 
                 28 
                 mg/l 
               
               
                   
                 Strontium (Sr) 
                 0.031 
                 mg/l 
               
               
                   
                 Zinc (Zn) 
                 0.023 
                 mg/l 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 3D 
               
               
                   
                   
               
               
                   
                 TESTS 
                 RESULT 
                 UNITS 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Aluminum (Al) 
                 0.087 
                 mg/l 
               
               
                   
                 Bicarb (HCO3) 
                 1352.2 
                 mg/l CaCO3 
               
               
                   
                 Bromide (Br) 
                 8.17 
                 mg/l CaCO3 
               
               
                   
                 Carbonate (CO3) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Chloride (Cl) 
                 200 
                 mg/l CaCO3 
               
               
                   
                 Fluoride (F) 
                 &lt;1.00 
                 mg/l CaCO3 
               
               
                   
                 Hydroxide (OH) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Nitrate (NO3) 
                 21.6 
                 mg/l CaCO3 
               
               
                   
                 Phosphate (PO4) 
                 4470 
                 mg/l CaCO3 
               
               
                   
                 Sulfate (SO4) 
                 5890 
                 mg/l CaCO3 
               
               
                   
                 Barium (Ba) 
                 &lt;0.050 
                 mg/l 
               
               
                   
                 Calcium (Ca) 
                 6.27 
                 mg/l CaCO3 
               
               
                   
                 Iron (Fe) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Magnesium (Mg) 
                 11.5 
                 mg/l CaCO3 
               
               
                   
                 Manganese (Mn) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Potassium (K) 
                 310 
                 mg/l CaCO3 
               
               
                   
                 Sodium (Na) 
                 5310 
                 mg/l CaCO3 
               
               
                   
                 Free (CO2) 
                 58.4 
                 mg/l CaCO3 
               
               
                   
                 Copper (Cu) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Ammonia (NH3) 
                 3325 
                 mg/l CaCO3 
               
               
                   
                 pH 
                 7.78 
               
               
                   
                 Total Silica (SiO2) 
                 119.13 
                 mg/l CaCO3 
               
               
                   
                 Silicon (Si) 
                 87 
                 mg/l 
               
               
                   
                 Strontium (Sr) 
                 0.032 
                 mg/l 
               
               
                   
                 Zinc (Zn) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                   
               
            
           
         
       
     
     Table 4 shows the results on silica concentration with a 1:1 ratio of silica to alum as a coagulant. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 TESTS 
                 RESULT 
                 UNITS 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Aluminum (Al) 
                 0.281 
                 mg/l 
               
               
                   
                 Bicarb (HCO3) 
                 474.4 
                 mg/l CaCO3 
               
               
                   
                 Bromide (Br) 
                 6.04 
                 mg/l CaCO3 
               
               
                   
                 Carbonate (CO3) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Chloride (Cl) 
                 169 
                 mg/l CaCO3 
               
               
                   
                 Fluoride (F) 
                 &lt;1.00 
                 mg/l CaCO3 
               
               
                   
                 Hydroxide (OH) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Nitrate (NO3) 
                 18.2 
                 mg/l CaCO3 
               
               
                   
                 Phosphate (PO4) 
                 1770 
                 mg/l CaCO3 
               
               
                   
                 Sulfate (SO4) 
                 6590 
                 mg/l CaCO3 
               
               
                   
                 Barium (Ba) 
                 &lt;0.050 
                 mg/l 
               
               
                   
                 Calcium (Ca) 
                 4.24 
                 mg/l CaCO3 
               
               
                   
                 Iron (Fe) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Magnesium (Mg) 
                 0.858 
                 mg/l CaCO3 
               
               
                   
                 Manganese (Mn) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Potassium (K) 
                 260 
                 mg/l CaCO3 
               
               
                   
                 Sodium (Na) 
                 5080 
                 mg/l CaCO3 
               
               
                   
                 Free (CO2) 
                 62.1 
                 mg/l CaCO3 
               
               
                   
                 Copper (Cu) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Ammonia (NH3) 
                 3005 
                 mg/l CaCO3 
               
               
                   
                 pH 
                 7.24 
               
               
                   
                 Total Silica (SiO2) 
                 45.48 
                 mg/l CaCO3 
               
               
                   
                 Silicon (Si) 
                 26 
                 mg/l 
               
               
                   
                 Strontium (Sr) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Zinc (Zn) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                   
               
            
           
         
       
     
     Table 5 shows the control with no coagulant added. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 5 
               
               
                   
                   
               
               
                   
                 TESTS 
                 RESULT 
                 UNITS 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Aluminum (Al) 
                 0.087 
                 mg/l 
               
               
                   
                 Bicarb (HCO3) 
                 1352.2 
                 mg/l CaCO3 
               
               
                   
                 Bromide (Br) 
                 6.17 
                 mg/l CaCO3 
               
               
                   
                 Carbonate (CO3) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Chloride (Cl) 
                 200 
                 mg/l CaCO3 
               
               
                   
                 Fluoride (F) 
                 &lt;1.00 
                 mg/l CaCO3 
               
               
                   
                 Hydroxide (OH) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Nitrate (NO3) 
                 21.6 
                 mg/l CaCO3 
               
               
                   
                 Phosphate (PO4) 
                 4470 
                 mg/l CaCO3 
               
               
                   
                 Sulfate (SO4) 
                 5890 
                 mg/l CaCO3 
               
               
                   
                 Barium (Ba) 
                 &lt;0.050 
                 mg/l 
               
               
                   
                 Calcium (Ca) 
                 6.27 
                 mg/l CaCO3 
               
               
                   
                 Iron (Fe) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Magnesium (Mg) 
                 11.5 
                 mg/l CaCO3 
               
               
                   
                 Manganese (Mn) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Potassium (K) 
                 310 
                 mg/l CaCO3 
               
               
                   
                 Sodium (a) 
                 5310 
                 mg/l CaCO3 
               
               
                   
                 Free (CO2) 
                 53.4 
                 mg/l CaCO3 
               
               
                   
                 Copper (Cu) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Ammonia (NH3) 
                 3325 
                 mg/l CaCO3 
               
               
                   
                 pH 
                 7.76 
               
               
                   
                 Total Silica (SiO2) 
                 119.13 
                 mg/l CaCO3 
               
               
                   
                 Silicon (Si) 
                 67 
                 mg/l 
               
               
                   
                 Strontium (Sr) 
                 0.032 
                 mg/l 
               
               
                   
                 Zinc (Zn) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                   
               
            
           
         
       
     
     Table 6 shows the results on silica concentration when using an aluminum electrode in an electro-coagulation process. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 6 
               
               
                   
                   
               
               
                   
                 TESTS 
                 RESULT 
                 UNITS 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Aluminum (Al) 
                 0.077 
                 mg/l 
               
               
                   
                 Bicarb (HCO3) 
                 574.4 
                 mg/l CaCO3 
               
               
                   
                 Bromide (Br) 
                 6.05 
                 mg/l CaCO3 
               
               
                   
                 Carbonate (CO3) 
                 232.9 
                 mg/l CaCO3 
               
               
                   
                 Chloride (Cl) 
                 190 
                 mg/l CaCO3 
               
               
                   
                 Fluoride (F) 
                 &lt;1.00 
                 mg/l CaCO3 
               
               
                   
                 Hydroxide (OH) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Nitrate (NO3) 
                 15.4 
                 mg/l CaCO3 
               
               
                   
                 Phosphate (PO4) 
                 1190 
                 mg/l CaCO3 
               
               
                   
                 Sulfate (SO4) 
                 5910 
                 mg/l CaCO3 
               
               
                   
                 Barium (Ba) 
                 &lt;0.050 
                 mg/l 
               
               
                   
                 Calcium (Ca) 
                 3.57 
                 mg/l CaCO3 
               
               
                   
                 Iron (Fe) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Magnesium (Mg) 
                 13.9 
                 mg/l CaCO3 
               
               
                   
                 Manganese (Mn) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Potassium (K) 
                 290 
                 mg/l CaCO3 
               
               
                   
                 Sodium (Na) 
                 5010 
                 mg/l CaCO3 
               
               
                   
                 Free (CO2) 
                 5.3 
                 mg/l CaCO3 
               
               
                   
                 Copper (Cu) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Ammonia (NH3) 
                 2246 
                 mg/l CaCO3 
               
               
                   
                 pH 
                 8.54 
               
               
                   
                 Total Silica (SiO2) 
                 49.29 
                 mg/l CaCO3 
               
               
                   
                 Silicon (Si) 
                 28 
                 mg/l 
               
               
                   
                 Strontium (Sr) 
                 0.031 
                 mg/l 
               
               
                   
                 Zinc (Zn) 
                 0.023 
                 mg/l 
               
               
                   
                   
               
            
           
         
       
     
     Table 7 shows the results on silica concentration when using a 1:1 ratio of silica to ferric salts as a coagulant. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 7 
               
               
                   
                   
               
               
                   
                 TESTS 
                 RESULT 
                 UNITS 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Aluminum (Al) 
                 0.086 
                 mg/l 
               
               
                   
                 Bicarb (HCO3) 
                 863.0 
                 mg/l CaCO3 
               
               
                   
                 Bromide (Br) 
                 6.14 
                 mg/l CaCO3 
               
               
                   
                 Carbonate (CO3) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Chloride (Cl) 
                 938 
                 mg/l CaCO3 
               
               
                   
                 Fluoride (F) 
                 &lt;1.00 
                 mg/l CaCO3 
               
               
                   
                 Hydroxide (OH) 
                 0.0 
                 mg/l CaCO3 
               
               
                   
                 Nitrate (NO3) 
                 24.0 
                 mg/l CaCO3 
               
               
                   
                 Phosphate (PO4) 
                 3180 
                 mg/l CaCO3 
               
               
                   
                 Sulfate (SO4) 
                 5810 
                 mg/l CaCO3 
               
               
                   
                 Barium (Ba) 
                 &lt;0.050 
                 mg/l 
               
               
                   
                 Calcium (Ca) 
                 10.4 
                 mg/l CaCO3 
               
               
                   
                 Iron (Fe) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Magnesium (Mg) 
                 5.15 
                 mg/l CaCO3 
               
               
                   
                 Manganese (Mn) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Potassium (K) 
                 290 
                 mg/l CaCO3 
               
               
                   
                 Sodium (Na) 
                 5140 
                 mg/l CaCO3 
               
               
                   
                 Free (CO2) 
                 55.7 
                 mg/l CaCO3 
               
               
                   
                 Copper (Cu) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                 Ammonia (NH3) 
                 3240 
                 mg/l CaCO3 
               
               
                   
                 pH 
                 7.55 
               
               
                   
                 Total Silica (SiO2) 
                 114.79 
                 mg/l CaCO3 
               
               
                   
                 Silicon (Si) 
                 64 
                 mg/l 
               
               
                   
                 Strontium (Sr) 
                 &lt;0.010 
                 mg/l 
               
               
                   
                 Zinc (Zn) 
                 &lt;0.020 
                 mg/l 
               
               
                   
                   
               
            
           
         
       
     
     Example 3 
     With reference to  FIG.  4   , an ammonia recovery process may be integrated in accordance with one or more embodiments. Due to the high levels of ammonia in certain wastewaters, a dedicated ammonia treatment process may be needed before the membrane systems, as well as to treat concentrate from the membrane systems Ammonia reduction from the wastewater can consist of air stripping and bubbling through concentrated acid, or the use of other technologies such as a membrane contactor. In this example, a membrane contactor utilizing sulfuric acid was considered to treat the ammonia with the stream coming after the EC process. Table 8 presents simulated data of a 1000 gpm Liqui-Cel™ NH 3 —N recovery system at varied recoveries. The ammonia recovery process typically requires higher pH (s.u. 8.5-11) to proceed and 90-99% of ammonia/ammonium can be recovered depending on the operating conditions Ammonium sulfate can be readily reused as fertilizer and resold. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 8 
               
               
                   
               
               
                 Target NH3—N removal and recovery in system: 
                 &gt;90% 
                 &gt;95% 
                 &gt;99% 
               
               
                   
               
             
            
               
                 Contactor size/Membrane Type 
                 14 × 28 × 50 
                 14 × 28 × 50 
                 14 × 28 × 50 
               
               
                 Design ammonia-wastewater flow rate, gpm 
                 1000 
                 1000 
                 1000 
               
               
                 Design ammonia-water temperature, C. 
                 50 
                 50 
                 50 
               
               
                 Recommended acid used for capturing ammonia 
                 Sulfuric Acid 
                 Sulfuric Acid 
                 Sulfuric Acid 
               
               
                 Recommended adjusted pH of ammonia-containing water 
                 10 
                 10 
                 10 
               
               
                 Assumed pH of acid solution entering contactors 
                 &lt;2 
                 &lt;2 
                 &lt;2 
               
               
                 Design Inlet NH3—N concentration, ppm 
                 3,000 
                 3,000 
                 3,000 
               
               
                 Number of contactors in parallel 
                 18 
                 16 
                 24 
               
               
                 Number of contactors in series 
                 2 
                 3 
                 3 
               
               
                 No. of contactors needed, total 
                 36 
                 48 
                 72 
               
               
                 Projected NH3—N conc. after system, ppm 
                 255 
                 117 
                 31 
               
               
                 Projected NH3—N removal in system 
                 91% 
                 96% 
                 99% 
               
               
                 Recommended acid strip CIRCULATION rate (System Total), gpm 
                 637 
                 1021 
                 1096 
               
               
                 Rate of ammonia removal, lbs./hr 
                 1374 
                 1444 
                 1486 
               
               
                 Calculated acid MAKE-UP rate required (System Total), lbs./hr 
                 3961 
                 4161 
                 4284 
               
               
                 Calculated Sulfate production rate, lbs./hr 
                 5335 
                 5604 
                 5770 
               
               
                 Estimated system wastewater DP, psi 
                 5 
                 9 
                 6 
               
               
                 Estimated Acid solution DP, psi 
                 11 
                 16 
                 12 
               
               
                   
               
            
           
         
       
     
     The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of” and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements. 
     Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only. 
     Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and/or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed.