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WO2010131251A2 - Séparation d'ions mg2+ à partir d'eau de mer et saumâtre à des fins de reminéralisation d'eau et d'eau résiduaire - Google Patents

Séparation d'ions mg2+ à partir d'eau de mer et saumâtre à des fins de reminéralisation d'eau et d'eau résiduaire Download PDF

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Publication number
WO2010131251A2
WO2010131251A2 PCT/IL2010/000383 IL2010000383W WO2010131251A2 WO 2010131251 A2 WO2010131251 A2 WO 2010131251A2 IL 2010000383 W IL2010000383 W IL 2010000383W WO 2010131251 A2 WO2010131251 A2 WO 2010131251A2
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water
line
junction
fed
unit
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WO2010131251A3 (fr
Inventor
Ori Lahav
Liat Birnhack
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RENEWED WATER MINERALS Ltd
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RENEWED WATER MINERALS Ltd
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Priority to SG2011083854A priority Critical patent/SG176061A1/en
Priority to AU2010246959A priority patent/AU2010246959A1/en
Publication of WO2010131251A2 publication Critical patent/WO2010131251A2/fr
Publication of WO2010131251A3 publication Critical patent/WO2010131251A3/fr
Priority to IL216240A priority patent/IL216240A0/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/029—Multistep processes comprising different kinds of membrane processes selected from reverse osmosis, hyperfiltration or nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2623—Ion-Exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to addition of Mg 2+ from the reject of nanofiltration (NF) or low salt-rejection reverse osmosis (RO) membranes to desalinated water and wastewater.
  • NF nanofiltration
  • RO reverse osmosis
  • the WHO recommends in its recent publications the inclusion of magnesium and calcium ions in desalinated and naturally soft waters (WHO, 2008; WHO, 2009) because of their acknowledged public health beneficial effects. Both ions are also welcome in desalinated water designated for irrigation.
  • magnesium ions are recommended by the WHO at a concentration higher than 10 mg Mg/I and calcium ions at a concentration higher than 20-30 mg/l (WHO, 2005; WHO, 2009).
  • calcium ions are added as part of the treatment since calcium (and bicarbonate) ions are also required for "chemical stability" purposes, i.e. to reduce the aggressiveness of soft waters to water distribution systems.
  • Calcium ions are added to desalinated waters in the "post treatment” step, typically through the dissolution of solid CaCOs (quarry limestone), which releases to the water both Ca 2+ ions and carbonate alkalinity.
  • Mg 2+ ions can potentially be carried out using one of the following processes: (1) Direct dosage of magnesium salts, such as MgCI 2 or MgSO 4 , to the water; (2) dissolution of quarry dolomite (MgCa(CO 3 ) 2 ) rocks (Bimhack et al., 2009); or (3) extraction of Mg 2+ from seawater by a cation exchange resin and subsequent release of the Mg 2+ to the desalinated water in exchange for Ca 2+ , which originates from CaCO 3 dissolution (PCT Patent application no. PCT/IL2007/001261 by Lahav et al.).
  • Direct dosage of magnesium salts such as MgCI 2 or MgSO 4
  • Another option that has been proposed in seawater desalination operations is to blend the desalinated water with -1% seawater (volume to volume basis) to attain Mg 2+ concentration of ⁇ 13 mg/l.
  • This option suffers from a major disadvantage which is that in addition to Mg 2+ and other welcome elements, the water is enriched with a very high concentration of unwanted Na + and Cl " ions.
  • a system for production of divalent ion supplemented water comprising: a system inlet line; a system outlet line; a DU (desalination unit), a DU inlet line fluidly connected to the system inlet line, a DU outlet line fluidly connected to the system outlet line, a first and a second junction on the DU line, a third junction on the DU outlet line, the second junction positioned between the first junction and the DU, the DU capable of: desalinating DU salty water fed to the DU via the DU inlet line, and releasing desalinated water from the DU into the DU outlet line; at least one divalent ion separation unit (SU) inlet line, at least one SU outlet line and at least one SU reject line, and at least one SU, wherein at least one SU is capable of: receiving SU salty water fed from a SU inlet line, rejecting brine to a SU reject line, wherein the brine comprises
  • said divalent ions comprise magnesium ions.
  • Said divalent ions preferably further comprise calcium ions.
  • Said monovalent ions preferably comprise sodium ions and chloride.
  • the at least one SU reject line is a SU inlet line, such that brine from a first SU is SU salty water fed to a second SU, whereby brine from the second SU comprises a higher concentration of divalent ions and a lower concentration of monovalent ions than the brine from the first SU.
  • the system may further comprise means for evaluating the pH of the divalent ion supplemented water and for adjusting the pH level of the supplemented water.
  • the DU unit is a RO unit and the SU units are selected from one or more of the group comprising: RO, UF, ion exchange resin and ion exchange column.
  • system further comprises a pretreatment unit capable of making the DU salty water essentially free of bacteria.
  • the system may further comprise a post-treatment unit capable of supplementing the divalent ion supplemented water with calcium ions.
  • the SU units comprise an ion exchange unit and at least one UF unit, wherein the ion exchange unit SU inlet line is the SU reject line of a first UF unit, and the first UF unit is capable of rejecting Mg 2+ and calcium ions at over 70% and Cl " at under 30%.
  • the first UF unit is capable of rejecting Mg 2+ at approximately 98%, calcium ions at approximately 92%, sulfate at approximately 99%, Cl " at approximately 24% and HCO 3 " at approximately 44%.
  • first UF unit may comprises an NF array capable of rejecting Mg 2+ at approximately 95%, calcium ions at approximately 82%, sulfate at approximately 99%, Cl " at approximately 17% and HCO 3 " at approximately 45%.
  • the SU units of the system may comprise a ion exchange unit and two UF units, the ion exchange unit SU characterized by a high affinity towards SO 4 2" ions and a low (but not very low) affinity towards Cl " ions, the system being configured so that: at a load step the SU inlet line of the ion exchange unit comprises the SU reject line of a first UF unit, and the eluate of the ion exchange unit and the permeate of first UF unit are fed to the DU, and at a Cl " absorbance step the first UF unit is bypassed so that the ion exchange unit is fed with salty water fed via the first junction, and the eluate of the ion exchange unit is fed to the SU inlet line of the second UF unit, the brine of the second UF unit being fed to the third junction and the permeate of the second UF unit being fed to the second junction, whereby the divalent ion supplemented water has reduced chloride ion concentration.
  • the ion exchange unit may be for example Purolite A-850 or Amberlite IRA-67.
  • a method for production of divalent ion supplemented water comprising: providing: a system inlet line, a system outlet line; a DU (desalination unit), a DU inlet line fluidly connected to the system inlet line, a DU outlet line fluidly connected to the system outlet line, a first and a second junction on the DU line, a third junction on the DU outlet line, the second junction positioned between the first junction and the DU; at least one divalent ion separation unit (SU) inlet line, at least one SU outlet line and at least one SU reject line, and at least one SU; desalinating DU salty water fed to the DU via the DU inlet line; releasing desalinated water from the DU into the DU outlet line; receiving SU salty water fed from a SU inlet line; rejecting brine to a SU reject line, wherein the brine comprises a higher concentration of divalent ions and a lower
  • a method of intentional struvite precipitation for phosphate recovery from wastewater comprising adding brine produced from a SU according to claim 14 to the wastewater.
  • Figure 1 illustrates a schematic drawing of an embodiment for addition of Mg 2+ from the reject of nanofiltration (NF) or low salt-rejection reverse osmosis (RO) membranes to desalinated water.
  • NF nanofiltration
  • RO reverse osmosis
  • Figure 2 shows a schematic drawing of another embodiment for addition of Mg 2+ from the reject of nanofiltration (NF) or low salt-rejection reverse osmosis (RO) membranes to desalinated water, wherein the reject is further treated before the addition.
  • NF nanofiltration
  • RO reverse osmosis
  • Figure 3 is graph of chloride rejection vs. sulfate levels in feed to NF membranes
  • Figure 4 shows an ion exchange-aided novel configuration used for increasing the
  • Figure 5 schematically illustrates recovery of phosphorus from excess sludge of wastewater
  • Figure 6 shows in schematic form a system embodiment for production of a struvite precipitation factor
  • Figure 7 shows a collection of data from use of a membrane that is provided in the embodiment described in Example 5, and
  • Figure shows shows a collection of data from use of a membrane that is provided in the embodiment described in Example 6.
  • a new method is presented to add magnesium ions to desalinated water and wastewater streams in a simple and cost effective way.
  • Brine that contains a high Mg 2+ concentration (along with proportional Ca 2+ and SO 4 2" concentrations) can be used to enrich the product water of a desalination plant with Mg 2+ ions.
  • Two options are suggested for the use of the brine:
  • the first option is to blend the Mg-rich brine with the product water of the desalination plant.
  • the blending ratio is designed to result in the required magnesium concentration in the water.
  • the byproduct of this action is that the water in also enriched by other ions present in the brine. While Ca 2+ and SO 4 2' are typically welcome, Cl " and Na + are usually not. Thus, a membrane would be selected so that the rejection of Cl " and Na + will result in minimum addition of these ions due to the blending action.
  • a second option may be based on the first option, further including reducing the Cl " and Na + content of the brine by for example passing the brine through further NF membranes with identical characteristics (2 nd pass, 3 rd pass etc., as required or loading specific ion exchange resins with Mg 2+ and thereafter releasing the magnesium ions held in the resin to the desalinated water as described in PCT Patent application no. PCT/IL2007/001261.
  • This option allows enriching the product water with magnesium ions without the concurrent addition of other ions present in the brine.
  • Magnesium ions can be largely separated from solution by passing pretreated (UF) inlet water (seawater or brackish water) through a membrane characterized by a high rejection (>70%) toward divalent ions (Mg 2+ , Ca 2+ , SO 4 2" , etc) and a low rejection (typically ⁇ 30%) toward monovalent ions (Cl “ , Na + , K + , HCO 3 " , etc).
  • Such membranes can be defined as nanofiltration (NF) membranes or low salt-rejection reverse osmosis (RO) membranes.
  • NF nanofiltration
  • RO reverse osmosis
  • the brine of such operation will be rich in Mg 2+ , Ca 2+ and SO 4 2" and relatively poor in Na + and Cl " .
  • a membrane can be chosen so that the ratio between Mg 2+ and Ca 2+ in the brine is higher than the original ratio in the inlet water (seawater or brine, see examples below).
  • the Mg 2+ rich brine can be utilized in two ways: (1) If water quality criteria of the desalination plant do not allow the addition of Na + and Cl " to the product water, the brine can be used to load a specific ion exchange resin with Mg 2+ and thereafter release it to the product water using the process described in PCT Patent application no.
  • the brine can be blended with the permeate of the desalination plant (after this has been subjected to the post treatment step, i.e. blending of the brine will be done with water that already contains the required Ca 2+ and alkalinity concentrations) to attain a required Mg 2+ concentration.
  • the pH may be elevated using concentrated NaOH to attain a required stability index (LSI or CCPP).
  • the membrane should be selected due to its specific rejection properties to both Mg 2+ and Cl " and Na + to result in minimum addition of the unwanted ions due to the blending action.
  • the process and system 100 in accordance with a preferred embodiment is depicted schematically in Fig. 1.
  • the system 100 for production of divalent ion supplemented water includes: a system inlet line 112A; a system outlet line 112B;
  • a DU (desalination unit) 126 a DU inlet line 122A fluidly connected to the system inlet line 112A, a DU outlet line 122B fluidly connected to the system outlet line 112B, a first 114A and a second 114B junction on the DU line 122A, a third junction 114C on the DU outlet line 122B, the second junction 114B positioned between the first junction 114A and the DU 126, the DU 126 capable of: desalinating DU salty water fed to the DU 126 via the DU inlet line 122A, and releasing desalinated water from the DU 126 into the DU outlet line 122B; a divalent ion separation unit (SU) inlet line 132A, a SU outlet line 132B and a SU reject line 132C, and a SU 136, the SU 136 being capable of: receiving SU salty water fed from the SU inlet line 132A, rejecting
  • FIG. 2 shows one such embodiment, a system 200 in which one SU reject line 232C is a SU inlet line 242A, such that brine from the first SU 236 is SU salty water fed to a second SU 246, whereby brine from the second SU 246 comprises a higher concentration of divalent ions and a lower concentration of monovalent ions than the brine from the first SU 236.
  • the systems further include means 250 for evaluating the pH of the divalent ion supplemented water and for adjusting the pH level of the supplemented water.
  • the systems may further include a pretreatment unit 260 capable of making the DU salty water essentially free of bacteria and larger microorganisms.
  • the systems may further include a post- treatment unit 270 capable of supplementing the divalent ion supplemented water with calcium ions.
  • NF NF membranes
  • low salt-rejection RO membranes alike.
  • passing the brine of the first membrane pass through further passes is optional and will be carried out when Cl " and Na + concentrations are to be reduced prior to blending with the product water.
  • the desalination plant is provided with an adjunct system that comprises a separation unit.
  • Pretreated seawater typically 1.0% to 2.0% of the overall flow rate of the plant
  • UF filtration units to remove microorganisms.
  • the water flows to the magnesium separation unit (NF or low rejection RO membranes).
  • the permeate of the magnesium separation unit flows back to the entrance of the desalination RO whereas the brine is blended with the post-treated RO permeate to attain the required Mg 2+ concentration.
  • the pH is raised to adjust CaCO 3 stability indices by the addition of concentrated NaOH solution or by aeration for CO 2 stripping.
  • the option of loading ion exchange resins with the brine is not covered in Fig. 1.
  • the brine blending process can be implemented in both brackish water and seawater desalination plants.
  • the major differences will be (1) in the blending ratio of brine to the salty water fed via the first junction, that will typically be lower in brackish water operations because of the lower Mg 2+ concentration in the brackish water and (2) the ratio of Ca 2+ to Mg 2+ and alkalinity to Mg 2+ in the brine may be higher in brackish water, a fact that should be taken into consideration in the design of the post treatment processes of the desalination plant, and may reduce the cost of adding Ca 2+ and alkalinity to the water in the post treatment stage, and (3) In seawater the ratio between the combined concentration of Ca 2+ + Mg 2+ (in meq/l) and the SO 4 2" concentration is approximately constant. In brackish water, in contrast, it may vary significantly. In case this ratio is low, chloride rejection may have to be relatively high, in order to maintain electro- neutrality in the reject solution.
  • treatment of the water involves additional equipment and actions.
  • embodiments such as the systems 100 and 200 shown in Figures 1 and 2 may be modified by additional treatment of salty water supplied to US 136, 236, respectively, at units 180 and 190 respectively, for example.
  • the new large seawater desalination plants (Ashkelon, Hadera, Soreq, etc.) are required to supply water with Cl “ and Na + concentrations lower than 20 mg/l and 30 mg/l.
  • Cl " and Na + concentrations lower than 20 mg/l and 30 mg/l.
  • Chloride rejection of NF 2540 (circles) and NE 2540-70 (triangles) is shown vs. SO 4 2" : (Mg 2+ + Ca 2+ ) in seawater (the SO 4 2" concentration in seawater was elevated by dissolution of weighed Na 2 SO 4 ).
  • the system 300 used for increasing the SO 4 2' :(Mg 2+ + Ca 2+ ) ratio in the NF feed is depicted in Fig. 4.
  • the process combines the use of two NF units 336A, 336B and an ion exchanger (IX) 346, and thus denoted NF - IX- NF.
  • a specific anion exchange resin is used.
  • the resin is characterized by a high affinity towards SO 4 2" ions and a low (but not very low) affinity towards Cl " ions.
  • the resin used in this step may be Purolite A-850 or Amberlite IRA-67 or equivalent (Purolite A-850 was shown to have a separation factor (a SOi/a ) of 0.54, at
  • Such resins can exchange SO 4 2" with Cl " .
  • the resin is "loaded” with SO 4 2" by passing through it brine generated when seawater is passed through a NF membrane.
  • the Cl “ : SO 4 2' ratio in the NF brine in this step may be approximately 3 to 1 (equivalent to equivalent) up to 5 to 1 depending on the membrane used, but in any event the ratio is much lower than the typical ⁇ 10 to 1 ratio in seawater.
  • the mass of SO 4 2" absorbed to the resin might be between 70% and 40% depending on the affinity of the resin towards the relevant anions, and the SO 4 2" : Cl " ratio in the NF brine, which is used as the load solution.
  • UF filtered seawater (seawater from which bacteria and larger microorganisms are removed) is passed through the SO 4 2" loaded resin.
  • the seawater contacted with the ion exchange column at this step can be regarded as untreated seawater since its chemical composition is not changed by the UF pretreatment.
  • NF - IX - NF process In places where the proposed process is used in the context of BW and seawater is available (e.g. Ma'agan Michael, Israel), a slightly modified NF - IX - NF process can be used: At the start up of the process the resin is loaded with sulfate using seawater (the seawater leaving the IX column flows back to the sea).
  • the absorbed sulfate is recycled over and over again (see Sarkar and SenGupta, 2008).
  • the process comprises of the following steps: first, sulfate is unloaded from the resin into the BW and thus the BWs sulfate concentration is increased and its Cl " concentration decreased.
  • the chemically modified BW is passed through a NF membrane.
  • the brine of this NF operation is then used for two purposes: a fraction of it is contacted with the resin, in order to reload it with sulfate; the remaining reject is blended with the post treated desalinated water, to enrich it with Mg 2+ .
  • NF brine rich in Mg 2+ can be used for improving the precipitation of solids from water and wastewater streams, for example, to precipitate and remove struvite (MgNH 4 PO 4 »6H 2 O) from wastewater, as explained herein.
  • Struvite a white crystalline compound consisting of Mg 2+ , NH 4 + and PO 4 3" at equal molar concentrations (MgNH 4 PO 4 «6H 2 O), is known to precipitate and clog pipes and pumps, causing operational difficulties and increased maintenance costs in wastewater treatment plants (WWTP) around the world.
  • WWTP wastewater treatment plants
  • struvite may be used separately as a cheap replacement to slow-release fertilizers or as a component in other commercial fertilizers (Hu et al., 1996; Gaterell et al., 2000; Battistoni et al., 2002). Struvite precipitation occurs only at relatively high concentrations of magnesium (Mg 2+ ), ammonium (NH 4 + ) and phosphate (PO 4 3" ). Such concentration combination is encountered in WWTP only in the anaerobic sludge treatment line.
  • Mg 2+ magnesium
  • NH 4 + ammonium
  • PO 4 3 phosphate
  • the dosage of external magnesium salts (MgCI 2 , MgSO 4 , Mg(OH) 2 ) is typically required in order to precipitate a significant mass of struvite solids (Munch and Barr, 2001; Lee et al., 2003; Chimenos et al., 2003; Nelson et al., 2003; van Rensburg et al., 2003
  • Figure 5 shows in schematic form an embodiment 400 in which brine from the NF-IX-NF Mg 2+ separation process is used to recover struvite from dewatering supernatant from excess sludge of wastewater.
  • Figure 6 illustrates an embodiment 500 for provision of Mg 2+ enriched brine as a struvite precipitation factor.
  • Hassan (2002, quoted in Eriksson et al., 2005), incorporated in its entirety by reference, reported on a NF membrane with the following salt rejection characteristics for seawater application: Mg 2+ was rejected by this membrane at 98%, calcium at 92% and sulfate at 99%.
  • the concentration of Mg 2+ in the reject of such operation would be approximately 3600 mg/l; similarly, Ca 2+ will be present at app. 1083 mg/l; SO 4 2' at 7948 mg/l, Na + at 15862 mg/l, HCO3- at -265 mg/l and Cl " at 27398 mg/l.
  • HCO 3 bicarbonate, or alkalinity
  • the mass ratio Mg 2+ to Ca 2+ in the brine is 3.32 to 1 relative to 3.2 in seawater. This fact, along with the high Mg 2+ concentration, makes the brine ideal for loading of the ion exchange resin that allows essentially complete separation of Mg 2+ from the unwanted Cl " and Na + , as explained in PCT Patent application no. PCT/IL2007/001261 to the applicant.
  • the second option is to blend the brine directly with the post treated RO permeate (assuming that the addition of Cl " and Na + is acceptable):
  • the dilution ratio between brine and permeate needs to be approximately 360 to 1.
  • the additional concentration of Ca 2+ , SO 4 2" Na + and Cl " in the water, as a result of the blending, would be 3.0, 22.0, 43.9 and 75.9 mg/l, respectively.
  • the recovery ratio in the membrane application is of low importance. If a recovery ratio lower than 65% is used, this will result in requiring a different blending ratio to obtain the same magnesium ion concentration, however the product water composition will be identical and water will not be lost, since both streams (permeate and reject) will be further used in the process to make up the product water.
  • Mg 2+ 146 mg/l
  • Ca 2+ 195 mg/l
  • Na + 1014 mg/l
  • Cl ' 1970 mg/l
  • SO 4 2" 251 mg/l
  • HCO 3 - 372 mg/l
  • Mg 2+ 479.8 mg/l
  • Ca 2+ 613.6 mg/l
  • Na + 1577 mg/l
  • Cl " 3064 mg/l
  • SO 4 2" 830 mg/l
  • HCO 3 " 753 mg/l.
  • This brine may be used for loading resins with magnesium since the ratio of Mg 2+ to Ca 2+ is 1.29 to 1 (equivalent per equivalent), in case a strict restriction is posed on the addition of Cl " , Na + , or both, or, alternatively, it can be blended directly with the post-treated permeate. In the case of direct blending, the blending ratio for attaining Mg 2+ concentration of 10 mg Mg/l is app. 48 to 1.
  • the paper concentrates on different treatment arrangements, and, among other things, reports on the rejection of the various ions, as a function of such parameters as temperature, recovery rate, NF array, etc.
  • the mass ratio of Mg 2+ to Ca 2+ in the brine is 3.6 to 1 relative to 3.2 in seawater. This fact, along with the high Mg 2+ concentration, makes the brine suitable for loading of the ion exchange resin that allows essentially complete separation of Mg 2+ from the unwanted Cl " and Na + , as explained in PCT Patent application no. PCT/IL2007/001261 to Technion - Research & Development Foundation Ltd.
  • a second option is to blend the brine directly with the post treated RO permeate (assuming that the addition of Cl " and Na + to the product water is acceptable):
  • This brine may be used for loading resins with Mg 2+ since the ratio of Mg 2+ to Ca 2+ is 4.7 to 1 (mass per mass, i.e. 7.7 equivalent per equivalent), in case a strict restriction is posed on the addition of Cl " , Na + , or both, or, alternatively, it can be blended directly with the post-treated permeate.
  • the blending ratio for attaining Mg 2+ concentration of 10 mg Mg/l is app. 421 to 1.
  • the additional concentration of Ca 2+ , Na + , and Cl " in the water, as a result of the blending, would be approximately 2.1 , 36.2 and 81.1 mg/l, respectively.
  • the Dow NF45 membrane is used in the oil industry for pre-treating seawater used for re-injection.
  • Mg 2+ 5010 mg/l
  • Ca 2+ 673 mg/l
  • Na + 12,736 mg/l
  • Cl " 22,000 mg/l
  • SO 4 2" 10,456 mg/l
  • HCO 3 " 500 mg/l.
  • the blending ratio for attaining Mg 2+ concentration of 10 mg /I is app. 501 to 1.
  • the additional concentration of Ca 2+ , Na + , and Cl " in the water, as a result of the blending would be 1.34, 25.4 and 43.9 mg/l, respectively.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention porte sur un système comprenant : une DU (unité de dessalement); une unité de séparation (SU) fournissant de la saumure enrichie en ions divalents et un perméat enrichi en ions monovalents, et conçu pour : répartir l'eau salée entre la DU et la SU, ajouter le perméat à la DU et ajouter la saumure à l'eau dessalée provenant de la DU.
PCT/IL2010/000383 2009-05-13 2010-05-13 Séparation d'ions mg2+ à partir d'eau de mer et saumâtre à des fins de reminéralisation d'eau et d'eau résiduaire Ceased WO2010131251A2 (fr)

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SG2011083854A SG176061A1 (en) 2009-05-13 2010-05-13 Separation of mg2+ ions from sea-and brackish water for the purpose of re-mineralization of water and wastewater
AU2010246959A AU2010246959A1 (en) 2009-05-13 2010-05-13 Separation of Mg2+ ions from sea-and brackish water for the purpose of re-mineralization of water and wastewater
IL216240A IL216240A0 (en) 2009-05-13 2011-11-09 Separation of mg2+ions from sea and brackish water for the purpose of re-mineralization of water and wastewater

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