WO2021125002A1 - 濃縮システム - Google Patents

濃縮システム Download PDF

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Publication number
WO2021125002A1
WO2021125002A1 PCT/JP2020/045800 JP2020045800W WO2021125002A1 WO 2021125002 A1 WO2021125002 A1 WO 2021125002A1 JP 2020045800 W JP2020045800 W JP 2020045800W WO 2021125002 A1 WO2021125002 A1 WO 2021125002A1
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WO
WIPO (PCT)
Prior art keywords
chamber
liquid
semipermeable membrane
concentrated
target liquid
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PCT/JP2020/045800
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English (en)
French (fr)
Japanese (ja)
Inventor
佑己 三浦
昌平 合田
崇人 中尾
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東洋紡株式会社
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Publication of WO2021125002A1 publication Critical patent/WO2021125002A1/ja

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    • 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
    • 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
    • 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
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

Definitions

  • the present invention relates to a concentration system.
  • a high-pressure target liquid is flowed through the first chamber of the semipermeable membrane module, and a low-pressure target is flowed into the second chamber.
  • a membrane separation method for discharging the target liquid diluted from the above has been studied (see, for example, Patent Document 1: Japanese Patent Application Laid-Open No. 2018-1110).
  • the concentrated liquid discharged from the RO module is flowed to the first chamber of the semipermeable membrane module that can be operated at a higher pressure, and the concentrated liquid is further subjected to the above-mentioned brine concentration (BC) under ultra-high pressure conditions as compared with the RO method.
  • BC brine concentration
  • the scale components are concentrated on the surface of the semipermeable membrane when concentrated by the RO module. It precipitates as scale (carbonate, etc.), causing problems such as clogging of the semipermeable membrane. Therefore, when the stock solution contains a scale component, the stock solution is subjected to a treatment for suppressing or reducing the precipitation of the scale component by adding a scale inhibitor or the like to the extent that the scale does not precipitate in the RO module. ..
  • the level of suppressing or reducing the precipitation of the scale component may be a level at which the scale does not precipitate due to concentration in the RO module, and the scale component is completely removed from the stock solution. There is no need. Therefore, the concentrated liquid discharged from the RO module may have a solution composition at a level at which scale is easily generated when the concentration is further increased.
  • the undiluted solution such as seawater supplied to the RO module may contain turbid components (organic substances, microorganisms, etc.).
  • the turbid component is also usually subjected to a reduction treatment of the turbid component in the stock solution to the extent that the film is not blocked by the turbid component in the RO module.
  • the semipermeable membrane module used for BC may have the same problem as the scale component due to the high concentration of the turbid component. There is.
  • the pressure of the target liquid (concentrated liquid concentrated by BC) discharged from the first chamber 11 of the semipermeable membrane module 1 is reduced to reduce the pressure of the second semipermeable membrane module 1.
  • the target liquid (diluted liquid diluted by BC) that flows into the chamber 12 and is discharged from the second chamber 12 of the semipermeable membrane module 1 is reused as at least a part of the stock solution of the target liquid, this is used. Such problems will continue to occur throughout the enrichment system.
  • the concentrated solution discharged from the first chamber 11 of the semipermeable membrane module 1 is used.
  • the diluted solution that reduces the pressure and flows into the second chamber 12 of the semipermeable membrane module 1 and is discharged from the second chamber 12 of the semipermeable membrane module 1 is reused as at least a part of the stock solution of the target solution.
  • the purpose is to suppress membrane blockage in the semipermeable membrane module and RO module used for BC.
  • a reverse osmosis module that separates and recovers water from a stock solution that has been pressurized to a predetermined pressure via a reverse osmosis membrane, and discharges the concentrated first target solution, which is the stock solution. It has a semipermeable membrane and a first chamber and a second chamber partitioned by the semipermeable membrane, the first target liquid is flowed into the first chamber at a predetermined pressure, and the second target liquid is flown into the predetermined chamber. By flowing the liquid into the second chamber at a pressure lower than the pressure of the above, the water contained in the first target liquid in the first chamber is transferred to the second target liquid in the second chamber via the semipermeable membrane.
  • a semipermeable membrane module which discharges the concentrated liquid from the first chamber and discharges the diluted liquid from the second chamber, is provided. At least a part of the concentrated liquid discharged from the first chamber is flowed into the second chamber as the second target liquid.
  • the diluent is a concentration system that is reused as at least part of the stock solution.
  • a concentration system further comprising a purification device for removing at least one of a hard component and a turbid component from at least one of the first target liquid, the concentrated liquid, the second target liquid, and the diluted liquid.
  • the purification device removes turbid components and hard components from at least one of the first target liquid, the concentrated liquid, the second target liquid, and the diluted liquid in this order, (1) or The concentration system according to (2).
  • the concentrated solution discharged from the first chamber 11 of the semipermeable membrane module 1 is used.
  • the diluted solution that reduces the pressure and flows into the second chamber 12 of the semipermeable membrane module 1 and is discharged from the second chamber 12 of the semipermeable membrane module 1 is reused as at least a part of the stock solution of the target solution.
  • membrane occlusion and the like in the semipermeable membrane module and RO module used for BC can be suppressed.
  • the concentration system of the present embodiment mainly includes a reverse osmosis module 2, a semipermeable membrane module 1, and a purification device 3.
  • the semipermeable membrane module 1 has a semipermeable membrane 10 and a first chamber 11 and a second chamber 12 partitioned by the semipermeable membrane, and the first target liquid is allowed to flow into the first chamber 11 at a predetermined pressure.
  • the second target liquid By flowing the second target liquid through the second chamber 12 at a pressure lower than a predetermined pressure (pressure of the first target liquid), the water contained in the first target liquid in the first chamber 11 is semipermeable membrane.
  • the liquid is transferred to the second target liquid in the second chamber 12 through the chamber 12, the concentrated liquid is discharged from the first chamber 11, and the diluted liquid is discharged from the second chamber 12. At least a part of the concentrated liquid discharged from the first chamber 11 is flowed to the second chamber 12 as the second target liquid, and the diluted liquid discharged from the second chamber 12 is re-used as at least a part of the stock solution. It will be used.
  • the purification device 3 at least one of the hard component and the turbid component is removed from at least one of the first target liquid, the concentrated liquid, the second target liquid, and the diluted liquid.
  • removing at least one of the hard component and the turbid component does not necessarily mean that at least one of the hard component and the turbid component is completely removed, and the hard component and the turbid component do not necessarily have to be completely removed. At least a part of at least one of the components may be removed. That is, it suffices if the amount of at least one of the hard component and the turbid component can be reduced.
  • the enrichment system of this embodiment includes a high pressure pump 2a on the upstream side of the reverse osmosis (RO) module 2.
  • the high-pressure pump 2a boosts the stock solution to a predetermined pressure and supplies it to the first chamber 21 of the RO module 2.
  • the RO module 2 separates water (permeated water) from the undiluted solution pressurized to a predetermined pressure to the second chamber 22 side via the reverse osmosis (RO) membrane 20 to obtain a concentrated undiluted solution (concentrated undiluted solution).
  • the first target solution) is discharged from the first chamber 21, and the water is discharged from the second chamber 22.
  • the "stock solution” is not particularly limited as long as it is a liquid containing water supplied to the RO module 2, and may be either a solution or a suspension.
  • the undiluted solution include seawater, river water, brackish water, wastewater and the like.
  • wastewater include industrial wastewater, domestic wastewater, oil field or gas field wastewater, and the like.
  • a pretreatment device may be provided on the upstream side of the high-pressure pump 2a in order to remove turbid substances (fine particles, microorganisms, scale components, etc.) contained in the stock solution.
  • the pretreatment device include a sand filtration device, a filtration device using a UF (Ultrafiltration) membrane, an MF (Microfiltration) membrane, etc., chlorine, sodium hypochlorite, a flocculant, and scale.
  • Examples include an addition device such as an inhibitor and a pH adjustment device.
  • the scale inhibitor is an additive having an action of preventing or suppressing the precipitation of scale components in the liquid as scale.
  • the anti-scale agent include compounds such as polyphosphoric acid-based, phosphonic acid-based, phosphinic acid-based, and polycarboxylic acid-based compounds.
  • the semipermeable membrane module 1 is connected to the downstream side of the RO module 2 (first chamber 21). Since the concentrated stock solution discharged from the first chamber 21 of the RO module 2 has a high pressure, it is sent to the semipermeable membrane module 1 side by the pressure. That is, the concentrated stock solution discharged from the first chamber 21 of the RO module 2 is the first target liquid supplied to the first chamber 11 of the semipermeable membrane module 1.
  • the semipermeable membrane module 1 has a semipermeable membrane 10 and a first chamber 11 and a second chamber 12 partitioned by the semipermeable membrane 10.
  • the first target liquid (concentrated stock solution) flows into the first chamber 11 at a predetermined pressure, and the second target liquid flows into the second chamber 12 at a pressure lower than the predetermined pressure.
  • the water contained in the first target liquid in the first chamber 11 is transferred to the second target liquid in the second chamber 12 via the semipermeable membrane 10, and is concentrated (concentrated) from the first chamber 11.
  • the first target liquid) is discharged, and the diluted liquid (diluted second target liquid) is discharged from the second chamber 12.
  • At least a part of the concentrated liquid discharged from the first chamber is flowed to the second chamber as the second target liquid.
  • at least a part of the concentrated liquid discharged from the first chamber is flowed to the second chamber as the second target liquid via the purification device 3 described later, but the position of the purification device 3 Is not limited to this position.
  • the target liquids flowing into the first chamber 11 and the second chamber 12 of the semipermeable membrane module 1 are the same liquid, they basically have the same osmotic pressure. Therefore, unlike the RO method, a high pressure for causing reverse osmosis against the high osmotic pressure difference between the target liquid (high osmotic liquid) and fresh water is not required, and pressure is applied at a relatively low pressure. Membrane separation of the target solution can be performed (some target solutions can be diluted and some other target solutions can be concentrated).
  • the second target liquid supplied to the second chamber 12 of the semipermeable membrane module 1 may include a liquid other than the first target liquid supplied to the first chamber 11.
  • the osmotic pressure difference (absolute value) is supplied to the first chamber 11.
  • membrane separation by BC is feasible if the pressure is lower than the pressure of the first target liquid.
  • the difference between the osmotic pressure of the first target liquid flowing into the first chamber 11 (high pressure side) and the osmotic pressure of the second target liquid supplied to the second chamber 12 (low pressure side) is supplied to the first chamber 11. It is preferably 30% or less of the predetermined pressure of the first target liquid.
  • the diluted solution discharged from the second chamber 12 of the semipermeable membrane module 1 is reused as at least a part of the undiluted solution.
  • the liquid discharged to the outside from the concentration system is discharged from the first chamber 11 of the semipermeable membrane module 1 in the most concentrated state and the second chamber 22 of the RO module 2. Only water.
  • the concentrate is further treated and is not discharged into the external environment such as the ocean or river as it is, but only water is discharged into the external environment. Therefore, the second chamber of the semipermeable membrane module 1 is discharged.
  • the solution in a state of being more concentrated than the undiluted solution is not discharged into the external environment, and adverse effects on the environment can be prevented.
  • the BC process may be a one-stage process using one semipermeable membrane module 1 as shown in FIG. 1, but is a multi-stage process using a plurality of semipermeable membrane modules. May be good.
  • BC may be carried out by a multi-step process using a plurality of semipermeable membrane modules for the purpose of stepwise concentration step and reducing the pressure required for BC.
  • BC by such a multi-step process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2018-069198.
  • the semipermeable membrane examples include a semipermeable membrane called a reverse osmosis (RO) membrane, a forward osmosis (FO) membrane, and a nanofiltration (NF) membrane.
  • RO reverse osmosis
  • FO forward osmosis
  • NF nanofiltration
  • the pressure of the first target liquid supplied to the first chamber 11 is preferably 6 to 10 MPa.
  • the pore diameter of the RO membrane and the FO membrane is about 2 nm or less, and the pore diameter of the UF membrane is about 2 to 100 nm.
  • the NF membrane has a relatively low inhibition rate of ions and salts among the RO membranes, and the pore size of the NF membrane is usually about 1 to 2 nm.
  • the salt removal rate of the RO membrane, the FO membrane, or the NF membrane is preferably 90% or more.
  • the material constituting the semipermeable membrane is not particularly limited, and examples thereof include cellulosic resins, polysulfone resins, and polyamide resins.
  • the semipermeable membrane is preferably composed of a material containing at least one of a cellulosic resin and a polysulfone resin.
  • the cellulosic resin is preferably a cellulosic acetate resin.
  • Cellulose acetate-based resins are resistant to chlorine, which is a bactericidal agent, and have the characteristic of being able to suppress the growth of microorganisms.
  • the cellulose acetate-based resin is preferably cellulose acetate, and more preferably tricellulose triacetate from the viewpoint of durability.
  • the polysulfone resin is preferably a polyether sulfone resin.
  • the polyether sulfone-based resin is preferably a sulfonated polyether sulfone.
  • the shape of the semipermeable membrane 10 is not particularly limited, and examples thereof include a flat membrane and a hollow fiber membrane.
  • the semipermeable membrane 10 is a simplified drawing of the flat membrane, but the shape is not particularly limited to such a shape.
  • the hollow fiber membrane (hollow fiber type semipermeable membrane) is advantageous in that the membrane area per module can be increased and the permeation efficiency can be improved as compared with a spiral type semipermeable membrane or the like.
  • the form of the semipermeable membrane module 1 (and the reverse osmosis module 2 described above) is not particularly limited, but when a hollow fiber membrane is used, a module in which the hollow fiber membrane is arranged straight or a hollow fiber membrane is used as a core tube. A cross-wind type module wrapped around the membrane can be mentioned.
  • a flat film examples thereof include a laminated module in which flat films are stacked, and a spiral module in which the flat film is wound around a core tube in an envelope shape.
  • An example of a specific hollow fiber membrane is a single-layered membrane made entirely of cellulosic resin.
  • the monolayer structure referred to here does not have to be a uniform film as a whole, and has, for example, a dense layer in the vicinity of the outer peripheral surface as disclosed in Japanese Patent Application Laid-Open No. 2012-115835. It is preferable that the dense layer is a separation active layer that substantially defines the pore size of the hollow fiber membrane.
  • a two-layer structure having a dense layer made of a polyphenylene resin for example, sulfonated polyether sulfone
  • a support layer for example, a layer made of polyphenylene oxide
  • Membrane is mentioned.
  • a film having a two-layer structure having a dense layer made of a polyamide resin on the outer peripheral surface of a support layer for example, a layer made of polysulfone or polyethersulfone
  • the outside of the hollow fiber membrane is usually the first chamber. This is because even if the fluid flowing inside the hollow fiber membrane (hollow portion) is pressurized, the pressure loss becomes large and it is difficult for the pressurization to work sufficiently.
  • the purification device 3 In the purification device 3, at least one of the hard component and the turbid component is removed from at least one of the first target liquid, the concentrated liquid, the second target liquid, and the diluted liquid.
  • the pressure of the concentrated solution discharged from the first chamber 11 of the semipermeable membrane module 1 is reduced to reduce the pressure of the semipermeable membrane module 1 first.
  • the semipermeable membrane module and the semipermeable membrane module used for BC when the diluted solution that flows into the two chambers 12 and is discharged from the second chamber 12 of the semipermeable membrane module 1 is reused as at least a part of the stock solution of the target solution. It is possible to suppress membrane blockage in the RO module.
  • the removal of the hard component is carried out by, for example, a water softening device described later.
  • the removal of the turbid component is carried out by, for example, a turbidity removing device described later. That is, the purification device 3 includes, for example, these water softening devices, turbidity removing devices, and the like.
  • the purification device 3 either the hard component or the turbid component may be removed, and both the hard component and the turbid component may be removed. That is, the purification device 3 may include only the water softening device, may include only the turbidity removing device, or may include both the water softening device and the turbidity removing device.
  • the turbid component and the hard component are removed from the concentrated stock solution in this order and discharged as the first target solution.
  • the purification device 3 includes both a water softening device and a turbidity removing device, it is preferable that the turbidity removing device and the turbidity removing device are provided in this order from the upstream side of the flow of the concentrated stock solution.
  • a membrane having finer pores such as a nanofiltration membrane is used, and membrane blockage is likely to occur. Therefore, it is better to remove the turbid component first to block the membrane when removing the hard component. This is because problems such as the above are unlikely to occur.
  • the purifying device 3 preferably removes at least one of a hard component and a turbid component from the concentrated liquid discharged from the first chamber 11 of the semipermeable membrane module 1. That is, it is preferable that the purification device 3 is provided on the downstream side of the first chamber 11 of the semipermeable membrane module 1 and on the upstream side of the second chamber 12 of the semipermeable membrane module 1. In this case, the other first target solution (concentrated stock solution), diluted solution, etc. is discharged from the semipermeable membrane module 1 rather than being purified (removing at least one of the hard component and the turbid component). The amount of processing by the purification device is smaller when the purification treatment is performed on the concentrated liquid. This has the advantage that the space required for the equipment is small and the initial investment cost is low.
  • the purifying device 3 since the purifying device 3 often does not have high pressure resistance, the concentrated liquid having a high pressure discharged from the first chamber 11 of the semipermeable membrane module 1 is in a state where the pressure is lowered by, for example, the pressure lowering device 4. Is supplied to the purification device 3. Therefore, a pump 1a for sending the first target liquid to the second chamber 12 of the semipermeable membrane module 1 is provided in the flow path from the purification device 3 to the second chamber 12 of the semipermeable membrane module 1. May be good.
  • the pressure lowering device 4 include a flow dividing valve, a decompressor, an energy recovery device, and the like.
  • the energy recovery device examples include an electric energy recovery device that recovers energy as electricity using a turbine or the like, or a mechanical energy recovery device that mechanically recovers energy from a concentrated liquid.
  • a mechanical energy recovery device a power transmission type energy recovery device that recovers the pressure energy of the concentrate as power by using a turbocharger or a water wheel coaxially coupled to the drive shaft of a high-pressure pump is known.
  • a pressure transfer type energy recovery device that directly recovers the pressure of the concentrated liquid such as a pressure converter (PX) can also be used.
  • PX pressure converter
  • Such an energy recovery device is disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-81913 and Japanese Patent Application Laid-Open No. 1-1236605.
  • the water softening device is a device for obtaining a liquid in which the amount of hard components is reduced by removing hard components (polyvalent ions such as calcium ions and magnesium ions) from the concentrated stock solution discharged from RO module 1.
  • Examples of the water softening device include a filtration device using an NF (Nanofiltration) membrane, a processing device using an ion exchange resin, and the like.
  • NF Nanofiltration
  • Such a water softening device is disclosed in, for example, Nagahisa Sato et al., "Water softening using a modified RO membrane", Membrane (MEMBRANE), 38 (6), 304-309, 2013 and the like.
  • maintenance it is preferable to carry out maintenance of the water softening device during the period when the concentration system is stopped.
  • Examples of maintenance include chemical cleaning in the case of a filtration device using an NF film, and regeneration treatment of an ion exchange resin in the case of a processing device using an ion exchange resin.
  • the turbidity removing device is a device that obtains a liquid in which the amount of turbidity components is reduced by removing turbidity components (insoluble objects such as organic substances and microorganisms) from the concentrated stock solution discharged from RO module 1. ..
  • Examples of the turbidity removing device include a filtration device using a UF (Ultrafiltration) membrane.
  • turbidity removal device It is preferable to carry out maintenance of the turbidity removal device during the period when the concentration system is stopped.
  • maintenance include back pressure cleaning and chemical cleaning in the case of a filtration device using a UF membrane.
  • 1 Semipermeable membrane module 1a pump, 10 Semipermeable membrane, 11 1st chamber, 12 2nd chamber, 2 Reverse osmosis (RO) module, 2a High pressure pump, 20 Reverse osmosis (RO) membrane, 21 1st chamber, 22 2nd room, 3 purification device, 4 pressure reduction device.
  • 1a pump 10 Semipermeable membrane
  • 11 1st chamber 12 2nd chamber
  • 2 Reverse osmosis (RO) module 2a High pressure pump
  • 20 Reverse osmosis (RO) membrane 21 1st chamber, 22 2nd room
  • 3 purification device 4 pressure reduction device.

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  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2020/045800 2019-12-17 2020-12-09 濃縮システム WO2021125002A1 (ja)

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JP2019-227092 2019-12-17
JP2019227092A JP2021094519A (ja) 2019-12-17 2019-12-17 濃縮システム

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10137758A (ja) * 1996-11-14 1998-05-26 Shinko Pantec Co Ltd 水処理方法及び水処理装置
JP2010162527A (ja) * 2008-12-16 2010-07-29 Sekisui Chem Co Ltd 淡水製造方法及び装置
JP2016150308A (ja) * 2015-02-17 2016-08-22 株式会社ササクラ 経口又は外用液体の濃縮装置及び濃縮方法
US20170349465A1 (en) * 2016-06-06 2017-12-07 Battelle Memorial Institute Cross current staged reverse osmosis
JP2018001110A (ja) * 2016-07-05 2018-01-11 東洋紡株式会社 ブラインの処理方法、塩水の淡水化処理方法、ブラインの処理システム、および、塩水の淡水化処理システム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10137758A (ja) * 1996-11-14 1998-05-26 Shinko Pantec Co Ltd 水処理方法及び水処理装置
JP2010162527A (ja) * 2008-12-16 2010-07-29 Sekisui Chem Co Ltd 淡水製造方法及び装置
JP2016150308A (ja) * 2015-02-17 2016-08-22 株式会社ササクラ 経口又は外用液体の濃縮装置及び濃縮方法
US20170349465A1 (en) * 2016-06-06 2017-12-07 Battelle Memorial Institute Cross current staged reverse osmosis
JP2018001110A (ja) * 2016-07-05 2018-01-11 東洋紡株式会社 ブラインの処理方法、塩水の淡水化処理方法、ブラインの処理システム、および、塩水の淡水化処理システム

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