EP2464609A1 - Procédé à membrane amélioré à récupération d eau élevée - Google Patents

Procédé à membrane amélioré à récupération d eau élevée

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Publication number
EP2464609A1
EP2464609A1 EP10809390A EP10809390A EP2464609A1 EP 2464609 A1 EP2464609 A1 EP 2464609A1 EP 10809390 A EP10809390 A EP 10809390A EP 10809390 A EP10809390 A EP 10809390A EP 2464609 A1 EP2464609 A1 EP 2464609A1
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EP
European Patent Office
Prior art keywords
membrane
inorganic compounds
free
concentrate
stream
Prior art date
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Withdrawn
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EP10809390A
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German (de)
English (en)
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EP2464609A4 (fr
Inventor
Riad Al-Samadi
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Individual
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Individual
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Priority claimed from AU2009210363A external-priority patent/AU2009210363A1/en
Application filed by Individual filed Critical Individual
Publication of EP2464609A1 publication Critical patent/EP2464609A1/fr
Publication of EP2464609A4 publication Critical patent/EP2464609A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • B01D61/04—Feed pretreatment
    • 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
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • 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
    • B01D2311/08—Specific process operations in the concentrate stream
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • 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
    • 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
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/60—Silicon compounds
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C02F1/64—Heavy metal compounds of iron or manganese
    • C02F1/645—Devices for iron precipitation and treatment by air
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/043—Treatment of partial or bypass streams
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/24—Separation of coarse particles, e.g. by using sieves or screens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/083—Mineral agents

Definitions

  • This invention relates to the economical purification of water containing soluble and sparingly or partially soluble inorganic compounds using single-stage or two-stage membrane processes that integrate membrane water purification with chemical precipitation softening and complete hardness and silica removal using ion exchange resins and silica sequestering beds, respectively.
  • Hardness compounds such as barium, calcium, magnesium, iron, carbonate, bi- carbonate, fluoride, sulfate and silica are commonly found in surface water sources such as lakes and rivers, groundwater sources such as water wells and aquifers and in aqueous industrial effluents including cooling tower blow-down, boiler blow-down and landfill leachates.
  • These sparingly soluble contaminants limit the percentage recovery of purified water permeate from reverse osmosis (RO) and nano-filtration (NF) membrane systems, as they tend to form scale compounds upon concentration, which deposit, often irreversibly, on the surface of the membranes and reduce their useful service life.
  • RO reverse osmosis
  • NF nano-filtration
  • the raw water is pre-treated by adding acid to increase the solubility of "temporary" hardness compounds, by using ion exchange softening to remove hardness ions, or by chemical precipitation of the hardness compounds and silica using "cold lime” or “hot lime” softening processes.
  • chemical precipitation softening pretreatment is required, this step is followed by clarification, preferably using solids contact clarifier and filtration using gravity or pressure sand filters, multimedia filters or "fine media” pressure filters.
  • the clarified supernatant can be filtered by ultrafiltration or microfiltration membranes where any entrained suspended solids and fine colloids from the clarifier are completely removed, producing a membrane filtrate with very low 15-minute silt density index (SDI 15 ) of ⁇ 3 which is suitable for purification and desalting using reverse osmosis (RO) membranes or nanofiltration (NF) membranes.
  • SDI 15 15-minute silt density index
  • the pre-concentrated sparingly soluble compounds can be further precipitated by the addition of lime or sodium hydroxide in an inter-stage RO concentrate softening step, followed by additional clarification of the precipitated hardness compounds and silica, filtration of the clarifier supernatant and purification through a second RO or NF membrane stage to achieve further permeate recovery.
  • these processes are limited to achieving overall (i.e. total) 2-stage membrane system recoveries in the range 80% - 85%.
  • U.S. Patent No. 4,000,065 discloses the use of a combination of reverse osmosis (RO) and ultrafiltration (UF) to separate organic material from the aqueous stream.
  • RO reverse osmosis
  • UF ultrafiltration
  • Japanese Patent 57-197085 discloses a filtration apparatus that comprises connecting UF apparatus and RO apparatus in series so as not to deposit scale on the RO membrane.
  • U.S. Patent No. 3,799,806 discloses purification of sugar juices by repeated ultrafiltration and reverse osmosis purification steps.
  • U.S. Patent No. 4,083, 779 discloses a process for treatment of anthocyante extract by ultrafiltration and reverse osmosis treatments.
  • U.S. Patent No. 4,775,477 discloses a process for extraction of cranberry presscake wherein the presscake is ground and subjected to microfiltration to remove colloidal high molecular weight compounds followed by reverse osmosis to recover a red-colored solution.
  • U.S. Patent No. 5, 182,023 discloses a process for removing arsenic from water wherein the water is first filtered to remove solids then passed through an ultrafilter, followed by a chemical treatment to adjust pH to a range from about 6 to 8. Thereafter, scale-inhibitors and anti-fouling materials are added before subjecting the water to reverse osmosis to provide a stream having less than about 50 ppb of arsenic.
  • Japanese Patent 53025-280 discloses the separation of inorganic and organic compounds from a liquid by first using a reverse osmosis membrane and then using a second reverse osmosis membrane having a more permeable membrane such as a microporous or ultrafiltration membrane. Part of the contaminated liquid obtained from the first membrane is processed through the second membrane.
  • U.S. Patent No. 5,501 ,798 discloses a high recovery water purification process involving the use of reverse osmosis followed by chemical precipitation of hardness compounds from the RO concentrate followed by microfiltration to separate precipitated solids and recycling of the "suspended solids' free concentrate" back to the RO.
  • U.S. Patent. No. 6, 1 13,797 discloses a 2-stage high recovey membrane process, where the pre-concentrated hardness and silica in the RO or NF membrane concentrates are removed by chemical precipitation or by ion exchange if silica is not present in limiting concentrations, since silica is not removed by IX resins.
  • This prior art process discloses softening and recycling of the high TDS 2 nd stage membrane concentrate and blending it with the first stage RO membrane concentrate to enable further purification and water recovery from the second stage, thereby achieving overall permeate recoveries > 95% in an economical manner, without resort to using costly multiple, discreet inter-stage softening and membrane stages.
  • U.S. Patent No. 6,461 ,514 discloses a single stage high recovey membrane process, where the pre-concentrated hardness in the RO or NF membrane concentrates is removed by ion exchange.
  • the softened high TDS membrane concentrate is recycled and blended with the raw Influent Water to enable further purification and water recovery, thereby achieving overall permeate recoveries > 95% in an economical manner.
  • the precipitated solids are removed by using a coagulant and/or a polymeric flocculant to enhance settling of the solids, enabling their removal from the bottom of the clarifier, while reducing the concentration of entrained fine particles that may be carried over into the filtration train downstream.
  • an improved membrane process for the treatment of water from natural sources or wastewater containing "sparingly soluble" inorganic scale-forming compounds wherein very high permeate recoveries in the range 67% - 99.9% are achieved in a reliable and consistent manner.
  • the Influent Water, containing the inorganic scale-forming compounds as well as completely soluble inorganic and low concentrations of organic compounds is first pre- treated in order to separate virtually all of the suspended matter including oil and grease by using an oil separation device, followed by chemical coagulation, flocculation, clarification and/or gravity settling, and multi-media filtration.
  • the Influent Water is pre-filtered using micro-media (i.e.
  • the water must be aerated using appropriate in-tank air spargers before coagulation, flocculation and/or filtration.
  • the pre-treated Influent Water in the present invention is purified by a 2-stage or single stage membrane system operating at suitable pressures depending on the concentration of soluble compounds in the Influent Water and the desired overall permeate recovery.
  • the membrane concentrate also known as retentate
  • the membrane concentrate is softened by adding a suitable alkali compound to raise the pH and precipitate the sparingly-soluble hardness compounds, followed by coagulating, flocculating and removing said precipitated compounds in a clarifier or settling tank.
  • the chemically softened membrane concentrate is further softened by using ion exchange (IX) water softening resins, silica sequestering media or a combination of both to ensure almost complete removal of residual cationic scale precursors (i.e. calcium, maagnesium, barium, iron, aluminum, amongst other sparingly soluble multi-valent ions) which will otherwise cause scale formation on the membranes and reduce the process reliability and its ability to consistently achieve the desired permeate recoveries in the range 67% to 99.9%.
  • the completely softened membrane concentrate will contain a high concentration of soluble ions, also known as the total dissolved solids (TDS).
  • the softened membrane concentrate is recycled and blended with the Influent Water in the case of the single-stage process, or blended with the first stage membrane concentrate in the case of the 2-stage pocess to undergo further purification.
  • a small volume of concentrate is removed from the system upstream from the IX water softening resin, combined with a small slurry reject stream from the bottom of the clarifier and disposed of as an overall process reject stream, in order to control the membrane's osmotic pressure, prevent precipitation and control the overall membrane system's permeate recovery in the range 67% - 99.9%.
  • FIG. 1 is a schematic representation of an enhanced high recovery 2-stage membrane process (R01 -CP-IX-R02) which treats high flowrates of Influent Water containing low Total Dissolved Solids (TDS), moderate to high hardness and low to moderate silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • TDS Total Dissolved Solids
  • Fig. 2 is a schematic representation of another embodiment of the enhanced high recovery 2-stage membrane process of FIG. 1 (R01 -CP-IX-SSU-R02) which treats high flow, low TDS, moderate to high hardness and high silica Influent Water and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • Figure 3 is a schematic representation of yet another embodiment of the enhanced high recovery 2-stage membrane process of Figure 1 (CP-R01 -IX-R02) which treats high flowrates of Influent Water containing low TDS, high to very high hardness and moderate silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • CP-R01 -IX-R02 the enhanced high recovery 2-stage membrane process of Figure 1
  • Figure 4 is a schematic representation of another embodiment of the enhanced high recovery 2-stage membrane process of Figure 3 (CP-R01 -IX-SSU-R02) which treats high flowrates of Influent Water containing low TDS, high to very high hardness and high silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds and fouling material on the membrane surface.
  • CP-R01 -IX-SSU-R02 which treats high flowrates of Influent Water containing low TDS, high to very high hardness and high silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds and fouling material on the membrane surface.
  • Figure 5 is a schematic representation of yet another embodiment of the enhanced high recovery 2-stage membrane process of Figure 1 (R01 -IX-R02) which treats high flowrates of Influent Water containing low TDS, moderate to high hardness and very low silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • Fig. 6 is a schematic representation of yet another embodiment of the enhanced high recovery 2-stage membrane process of Fig. 1 (R01 -IX-SSU-R02) which treats high flow Influent Water containing low TDS, moderate hardness and low to moderate silica and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • FIG. 7 is a schematic representation of another enhanced high recovery 2-stage membrane process (R01 -R02-CP-IX) which treats high flowrates of Influent Water containing low TDS, low to moderate hardness and low silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness and silica on the membrane surface.
  • R01 -R02-CP-IX another enhanced high recovery 2-stage membrane process
  • Fig. 8 is a schematic representation of another embodiment of the enhanced 2- stage high recovery membrane process of FIG. 7 (R01 -R02-CP-IX-SSU) with post 2 nd stage membrane concentrate softening and recycling of the softened concentrate, which treats high flowrate Influent Water with low TDS, low to moderate hardness and low to moderate silica and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness and silica on the membrane surface.
  • Fig. 9 is a schematic representation of yet another embodiment of the enhanced high recovery 2-stage membrane process depicted in Fig. 8 (R01 -R02-IX-SSU), which treats high flow Influent Water containing low TDS, low hardness and low to moderate silica and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • Fig. 10 is a schematic representation of another enhanced high recovery single stage membrane process (RO-CP-IX) which treats low flow Influent Water or Influent Water containing a moderate concentration of TDS, low to moderate hardness and low to moderate silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • RO-CP-IX enhanced high recovery single stage membrane process
  • Fig. 11 is a schematic representation of another embodiment of the enhanced high recovery single stage membrane process of Fig. 10 (RO-CP-IX-SSU) which treats low flow Influent Water containing a moderate concentration of total dissolved solids (TDS), low to moderate hardness and moderate to high silica concentrations, and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • RO-CP-IX-SSU which treats low flow Influent Water containing a moderate concentration of total dissolved solids (TDS), low to moderate hardness and moderate to high silica concentrations, and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • Fig. 12 is a schematic representation of yet another embodiment of the enhanced high recovery single stage membrane process depicted in Fig. 10 (RO-IX- SSU), which treats low flow Influent Water containing high TDS, low hardness and low silica and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the surface of membrane unit.
  • RO-IX- SSU enhanced high recovery single stage membrane process depicted in Fig. 10
  • Fig. 13 is a schematic representation of yet another enhanced high recovery single stage membrane process (CP-IX-RO) which treats low flow Influent Water or Influent Water containing a moderate concentration of total dissolved solids (TDS), high to very high hardness and low to moderate silica concentrations and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • CP-IX-RO enhanced high recovery single stage membrane process
  • Fig. 14 is a schematic representation of another embodiment of the enhanced high recovery single stage membrane process of Fig. 13 (CP-IX-SSU-RO) which treats low flow Influent Water containing a moderate concentration of TDS, high to very high hardness and high silica concentrations, and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the membrane surface.
  • CP-IX-SSU-RO the enhanced high recovery single stage membrane process of Fig. 13
  • Fig. 15 is a schematic representation of yet another embodiment of the enhanced high recovery single stage membrane process depicted in Fig. 14 (IX-SSU- RO), which treats low flow Influent Water containing high TDS, moderate hardness and low to moderate silica and recovers 67% to 99.9% of purified water, while eliminating the risk of deposition of hardness, silica and other scale compounds on the surface of membrane unit.
  • IX-SSU- RO enhanced high recovery single stage membrane process depicted in Fig. 14
  • U.S. Pat. 6, 1 13,797 and U.S. Pat. 6,461 , 514B1 U.S. Patent 61 13797 teaches using a 2-stage membrane process with post 2 nd stage membrane concentrate softening that achieves very high purified water recoveries in the range 67% to 99.9%.
  • the high TDS 2 nd stage membrane concentrate containing most of the soluble and sparingly soluble inorganic ions is softened by chemical precipitation at high pH followed by clarification, filtration and pH reduction, and recycling to the low pressure side of the 2 nd stage membrane system to achieve further recovery of purified water.
  • the 2 nd stage membrane concentrate is softened simply by passage through a suitable ion exchange softening resin, followed by recycling to the low pressure side of said 2 nd stage membrane system to achieve further purified water recovery.
  • U.S. Patent 6,461 , 514B1 teaches a single stage high recovery membrane process whereby the membrane concentrate containing high hardness but low silica is softened by passage through a suitable ion exchange softening resin followed by recycling to the low pressure side of said single stage membrane system to achieve further purified water recovery.
  • IX softening When ion exchange (IX) softening is applied on its own to the 2 nd stage membrane concentrate (in U.S. Pat. 6,1 13,797) or is applied to the single stage membrane process concentrate (in U.S. Pat. 6,461 , 514B1) as a simple, low-cost alternative to CP softening, the IX softening step will not be effective in removing silica from the membrane concentrate, thus allowing the silica to further concentrate over the membranes and potentially limit the overall permeate (i.e. purified water) recovery.
  • the addition of anti-scalants will alleviate but not completely eliminate this problem since anti-scalants have an upper silica solubility range of 200-250 mg/L.
  • R01 is first stage reverse osmosis membrane system in a 2-stage high recovery membrane process
  • R02 is second stage reverse osmosis membrane system in a 2-stage high recovery membrane process
  • RO is the reverse osmosis membrane system in a single stage high recovery membrane process
  • CP chemical precipitation softening to remove bulk hardness and silica
  • IX denotes ion exchange softening to completely remove hardness
  • SSU denotes a single or multiple column silica sequestering unit to efficiently and selectively remove silica.
  • the best mode of the invention is the R01-CP-IX-R02 high recovery process configuration represented schematically in FIG. 1.
  • This mode represents enhanced high recovery 2-stage membrane process which treats high flowrates of Influent Water 1 , e.g. > 100 US gallons per minute, containing low to moderate concentrations of total dissolved solids (TDS), e.g. 200 - 4000 mg/L, moderate to high hardness (e.g. 150 - 300 mg/L as calcium carbonate CaC0 3 ) and low to moderate silica (e.g. 5 - 40 mg/L) and produces a good quality low-TDS purified water stream 21 and a small volume of high-TDS reject stream 20, while preventing the precipitation of hardness and silica compounds on the surface of the membranes.
  • TDS total dissolved solids
  • the Influent Water 1 is first pretreated in 2 to remove suspended solids, colloidal matter, oil if present, and other soluble organic and inorganic fouling material by using a suitable pretreatment means including aeration and/or chemical oxidation to oxidize and precipitate iron and manganese if present, biological treatment to remove soluble organic compounds and prevent biological fouling if the chemical oxygen demand (COD) and biological oxygen demand (BOD 5 ) are significant, coagulation, flocculation, clarification, multi-media filtration, ultrafiltration or microfiltration of the suspended solids, chemically or biologically precipitated solids , followed by chemical conditioning of the suspended solids' free water, including the addition of acid and anti-scalant to further reduce the scale potential of the pretreated water 3.
  • a suitable pretreatment means including aeration and/or chemical oxidation to oxidize and precipitate iron and manganese if present, biological treatment to remove soluble organic compounds and prevent biological fouling if the chemical oxygen demand (COD) and biological oxygen demand (BOD 5 )
  • the pretreated water 3 is then introduced into the first stage reverse osmosis (RO) or nanofiltration (NF) membrane system 4, operating at 200 - 300 psig and up to 600 psig, which purifies a large fraction (i.e. 50% to 75% and up to 85%) of the Influent Water 1 , producing a first stage membrane permeate 5 and a smaller first stage membrane concentrate 6 which is normally 20% - 30% of the Influent Water flowrate.
  • the first stage membrane concentrate 6 with TDS in the normal range of 1 ,000-4000 mg/L and up to 10,000 mg/L is blended with recycled high-TDS second stage membrane concentrate 17 to produce a combined membrane concentrate 7 which contains elevated concentrations of TDS (in the range 10,000-20,000 mg/L), elevated hardness and silica.
  • RO reverse osmosis
  • NF nanofiltration
  • Said combined membrane concentrate 7 is treated in the Chemical Precipitation and Clarification unit 8 by the addition of alkali solutions including sodium hydroxide, sodium carbonate, calcium hydroxide and magnesium hydroxide to raise the pH to the range 10-1 1 , chemically precipitate di-valent and tri-valent hardness compounds including calcium, magnesium, iron, manganese and silica and produce a softened and clarified combined membrane concentrate (i.e. clarifier supernatant) 9 that is low in hardness, silica and other chemical and biological fouling compounds.
  • alkali solutions including sodium hydroxide, sodium carbonate, calcium hydroxide and magnesium hydroxide to raise the pH to the range 10-1 1
  • chemically precipitate di-valent and tri-valent hardness compounds including calcium, magnesium, iron, manganese and silica
  • produce a softened and clarified combined membrane concentrate (i.e. clarifier supernatant) 9 that is low in hardness, silica and other chemical and biological fouling compounds.
  • the chemically softened combined membrane concentrate 9 is filtered in 10 by using a suitable, effective filtration means to remove residual, entrained suspended solids and the pH adjusted to the range 6-8 by the addition of a suitable mineral acid to further reduce said combined concentrate stream's temporary hardness and produce a chemically softened, clarified and filtered combined membrane concentrate 11.
  • the said chemically softened, clarified and filtered combined membrane concentrate 11 is further softened in ion exchange softening unit 12 where the residual hardness ions including barium, calcium and magnesium and residual heavy metals including aluminum, iron and manganese are separated efficiently, producing completely softened combined membrane concentrate 13.
  • Said completely softened combined membrane concentrate 13 is introduced into the high pressure second stage RO or NF membrane system 17, normally operating at up to 1 100 psig and possibly up to 2000 or even 3000 psig to produce additional, purified second stage membrane permeate 15 and a high-TDS second stage membrane concentrate 16 with a TDS normally in the range 20,000-40,000 mg/L and up to 80,000 to 100,000 mg/L.
  • the purified second stage membrane permeate 15 is combined with the first stage membrane permeate 5 to produce a combined purified membrane process permeate 21 which is equivalent to 67% to 99.9% of the flowrate of the Influent Water 1.
  • a large fraction of the second stage membrane concentrate 17 is recycled and combined with the first stage membrane concentrate 6 to achieve further softening and water recovery as described earlier.
  • a small stream of high TDS second stage membrane concentrate 18 is combined with clarifier slurry rejects 19 and discharged as a small process reject stream 20 to limit the osmotic pressure.
  • the second stage membrane permeate 15 is combined with the first stage membrane permeate 5 and removed as final recovered product 21.
  • the Influent Water flowrate is small, e.g. ⁇ 100 U.S. gpm, and/or when the Influent Water TDS is high (e.g. in the range 5,000 - 10,000 mg/L)
  • a single stage enhanced high recovery membrane process is used, as illustrated in the embodiments of Figures 10, 13, 1 1 , 14, 12 and 15. In these cases, the single stage membrane process will operate at high pressure of 500-1 100 psig and up to 3000 psig.
  • the Influent Water flowrate is higher (i.e. > 100 gpm) and when the TDS is low (i.e. ⁇ 5000 mg/L)
  • two-stage enhanced high recovery membrane processes are used in order to extract most of the purified water (i.e.
  • the first stage membrane system can operate at up to 600 psig, while the second stage, processing much smaller flowrates, are operated at up to 1 100 psig and possibly up to 3000 psig.
  • the enhanced high recovery process configuration i.e. the relative location of the chemical precipitation unit (CP), the ion exchange softening unit (IX) and the silica sequestering unit (SSU) is dictated by the relative concentrations of hardness ions, especially calcium, magnesium and barium, heavy metal foulants, including iron, manganese and aluminum and by the concentration of silica relative to the hardness.
  • the concentration of hardness and silica are both relatively low, the single stage RO-CP-IX configuration (Fig. 10) and 2-stage R01 -R02-CP-IX (Fig. 7), R01 -R02-CP-IX-SSU (Fig. 8) and R01 -R02-IX-SSU (Fig.
  • the 2-stage R01 -CP-IX-R02 configuration described earlier (Fig. 1 ), the 2-stage R01 -CP-IX-SSU-R02 configuration (Fig. 2) and the 2-stage R01 -IX-SSU-R02 configuration (Fig. 6), as well as the 1 -stage CP-IX-RO configuration (Fig. 13), 1 -stage CP-IX-SSU-RO configuration (Fig. 14) and the 1 -stage IX-SSU-RO configuration (Fig. 15) are utilized.
  • the choice of the softening protocol i.e.
  • CP-IX, CP-IX-SSU or IX-SSU is dictated by the extent of hardness concentration, the extent of silica concentration and their relative magnitudes in the Influent Water, with the CP-IX-SSU train providing the highest removal of both hardness and silica, thus corresponding to Influent Water with high hardness and high silica concentrations.
  • concentration of hardness and silica in the Influent Water is high to very high, the CP-R01 -IX-R02 configuration (Fig. 3) and CP-R01 -IX-SSU-R02 configuration (Fig. 4) are used, respectively as described earlier.
  • the silica concentration in the Influent Water is very low, the R01 -IX-R02 configuration (Fig. 5) is recommended.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (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

La présente invention concerne un procédé économique pour la purification d’eau contenant des composés inorganiques solubles et peu solubles au moyen de procédés à membrane à un étage ou à deux étages qui intègrent la purification d’eau par membrane avec l’adoucissement par précipitation chimique et l’élimination de la dureté et de la silice résiduelles des concentrés de membrane en utilisant des résines d’échange d’ions et des milieux séquestrants de silice, respectivement. La récupération d'eau purifiée selon la présente invention n’est pas affectée de manière indésirable par des déficiences de conception et/ou opérationnelles dans le système d’adoucissement par précipitation chimique qui peuvent conduire à une dureté et une silice résiduelles plus élevées dans le surnageant du clarificateur.
EP10809390.7A 2009-08-15 2010-08-11 Procédé à membrane amélioré à récupération d eau élevée Withdrawn EP2464609A4 (fr)

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AU2009210363A AU2009210363A1 (en) 2008-08-14 2009-08-15 Enhanced High Water Recovery Membrane Process
PCT/CA2010/001240 WO2011020176A1 (fr) 2009-08-15 2010-08-11 Procédé à membrane amélioré à récupération d’eau élevée

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CN103827043B (zh) * 2011-08-17 2016-02-24 R·A·阿尔-萨马迪 高效回收饮用水方法
CN105408007B (zh) * 2013-04-26 2017-08-18 陶氏环球技术有限责任公司 包括超滤模块和可加压储槽的水处理组件
IN2014DE02410A (fr) * 2013-08-23 2015-07-03 Aquatech Int Corp
CN117695848A (zh) * 2014-03-31 2024-03-15 南洋理工大学 反渗透装置和方法
JP7020821B2 (ja) * 2017-08-31 2022-02-16 オルガノ株式会社 硬度成分含有水の処理装置および処理方法
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SG178334A1 (en) 2012-03-29
MX2012001949A (es) 2012-07-25
IN2012DN01222A (fr) 2015-04-10
EP2464609A4 (fr) 2014-10-08
BR112012003296A2 (pt) 2019-09-24
CN102656122B (zh) 2014-05-28
CN102656122A (zh) 2012-09-05
WO2011020176A1 (fr) 2011-02-24

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