[go: up one dir, main page]

WO2013129111A1 - Procédé de production d'eau - Google Patents

Procédé de production d'eau Download PDF

Info

Publication number
WO2013129111A1
WO2013129111A1 PCT/JP2013/053395 JP2013053395W WO2013129111A1 WO 2013129111 A1 WO2013129111 A1 WO 2013129111A1 JP 2013053395 W JP2013053395 W JP 2013053395W WO 2013129111 A1 WO2013129111 A1 WO 2013129111A1
Authority
WO
WIPO (PCT)
Prior art keywords
filter
amount
water
semipermeable membrane
index
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/053395
Other languages
English (en)
Japanese (ja)
Inventor
千智勲
花田茂久
高畠寛生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Publication of WO2013129111A1 publication Critical patent/WO2013129111A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • 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
    • B01D61/12—Controlling or regulating
    • 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
    • B01D2311/08—Specific process operations in the concentrate stream
    • 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
    • B01D2311/2649—Filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical 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
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • 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
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a fresh water generation method for obtaining fresh water by performing desalination of seawater, brine, or the like using a membrane, or purifying sewage wastewater treated water or industrial wastewater to obtain reused water. .
  • a desalination system using a semipermeable membrane is applied in many industries and water treatment fields, including seawater desalination, and has advantages in terms of separation performance and energy efficiency compared to other separation methods. Has been demonstrated.
  • microorganism growth on the membrane surface, biofilm adhesion on the membrane surface, inorganic scale adhesion on the membrane surface, or organic matter adhesion on the membrane surface that is, fouling. Therefore, there is a problem that the membrane differential pressure rises rapidly and the permeability and separation of the membrane are lowered.
  • the detergent include chelating agents such as citric acid, sodium hydroxide, ethylenediamine-4-acetic acid (EDTA), and surfactants, and these are used alone or in combination.
  • bactericidal agent As a means for suppressing the progress of fouling, when the fouling substance is an inorganic scale, there is a method of adding a scale inhibitor such as sodium hexametaphosphate (SHMP) to the water to be treated.
  • SHMP sodium hexametaphosphate
  • many techniques for adding an agent that suppresses the growth of the biofilm to the water to be treated have been proposed as effective techniques.
  • bactericidal agent containing 2-methyl-4-isothiazolin-3-one or 5-chloro-2-methyl-4-isothiazolin-3-one and a salt thereof as an active ingredient is added to the water to be treated.
  • Patent Document 1 A method for suppressing the growth of biofilm (Patent Document 1) and a method for adding acid or silver ion as a bactericide to water to be treated are disclosed (Patent Documents 2 and 3). If the concentration, frequency, time, and the like at the time of adding these scale inhibitor and bactericidal agent are too small, the progress of fouling cannot be suppressed. On the other hand, if the concentration, frequency, time, and the like of the drug are too high, the progress of fouling can be suppressed, but the drug cost increases. Therefore, it is important to grasp the proper concentration, frequency, and time when adding a drug for suppressing the progress of fouling.
  • a biofilm-forming substrate is placed under the conditions, and the amount of biofilm on the biofilm-forming substrate is measured by the ATP measurement method once a day to 6 months, There is disclosed a technique for determining a film cleaning condition and a disinfectant addition condition so that an ATP amount per unit surface of a material is 200 pg / cm 2 or less.
  • Patent Document 4 can basically deal only with fouling by biofilm (biofouling), and adhesion of inorganic scale to the membrane surface (inorganic fouling), other than biofilm to the membrane surface It is not possible to cope with the adhesion of organic matter (organic matter fouling).
  • the reverse osmosis membrane supply water and / or the reverse osmosis membrane non-permeate water must always be run at a linear velocity equal to the non-permeate water linear velocity in the reverse osmosis membrane module. If the linear velocity deviates greatly, there is a risk that a valid evaluation cannot be performed.
  • the present invention provides a means by which the progress of fouling on the membrane surface can be easily grasped before it appears in membrane operation data such as membrane differential pressure, permeability, and separability.
  • the fresh water generation method of the present invention has any one of the following configurations.
  • a fresh water generation method of treating water to be treated with a semipermeable membrane and separating it into permeated water and concentrated water when cleaning the semipermeable membrane and / or injecting a chemical into the water to be treated,
  • the concentrated water is periodically filtered with a filter capable of trapping solid matter, and is derived from at least one index selected from the group consisting of the performance index of the filter, the amount of deposit on the filter, and the color of the filter when filtered.
  • the operation standard index reaches a predetermined reference value set in advance, the semipermeable membrane is washed or the semipermeable membrane washing condition and / or the chemical injection condition are strengthened Method.
  • the fresh water generation method according to (1) wherein the performance index of the filter is at least one selected from the group consisting of a pressure value during constant flow filtration and a filtration resistance value during constant flow filtration.
  • the performance index of the filter is the reciprocal value of the filtration flow rate value when a constant pressure is applied, the reciprocal value of the amount of water filtered during a predetermined time when the constant pressure is applied, and the constant pressure value.
  • the fresh water generation method according to (1) which is at least one selected from the group consisting of a time required for filtering a predetermined amount of water and a filtration resistance value of the filter when a constant pressure is applied.
  • the fresh water generation method according to (1) wherein the performance index of the filter is an SDI value defined by ASTM D4189-95.
  • a group in which the deposit amount index on the filter is composed of a microorganism amount, an inorganic solid amount, an organic matter amount, a ratio between an inorganic solid matter amount and an organic matter amount, a ratio between an inorganic solid matter amount and a microorganism amount, and a ratio between a microorganism amount and an organic matter amount.
  • the fresh water generation method according to (1) which is at least one selected from: (6) The fresh water generation method according to (5), wherein the amount of the microorganism is a value obtained by an ATP measurement method.
  • the color index of the filter is a color difference defined in JIS Z 8730: 2009 between the filter before filtration and the filter after filtration, and the filter after filtration
  • the fresh water generation method according to (1) which is at least one index selected from the group consisting of reciprocal values of whiteness defined in JIS P 8148: 2001.
  • the semipermeable membrane feed water supplied to the semipermeable membrane is regularly filtered with a filter capable of capturing solid matter, and the performance index of the filter, the amount of deposits on the filter, and the filter when filtered Y is at least one index selected from the group consisting of the following colors: at least one index selected from the group consisting of the performance index of the filter, the amount of deposits on the filter, and the color of the filter when the concentrated water is filtered
  • the fouling progress state on the membrane surface is determined by the operation of the membrane such as membrane differential pressure, permeability and separation. It is possible to grasp before appearing in the data. Moreover, since the operation
  • the fresh water generation method of the present invention is carried out in a fresh water generation system in which treated water 1 is treated by a semipermeable membrane 3 and separated into permeated water 4 and concentrated water 5.
  • the treated water 1 examples include seawater, river water, lake water, ground water, sewage, sewage secondary treated water, and the like.
  • the water 1 to be treated contains solid components such as turbidity, so when the water 1 to be treated is directly filtered through the semipermeable membrane 3, the solid components adhering to the membrane surface increase, and the differential pressure is increased. It soars and it becomes impossible to drive. Therefore, it is common to pre-process the for-treatment water 1 beforehand.
  • the most commonly used pretreatment method is a flocculating sand filtration method in which a flocculant is added to the water 1 to be treated, the solid components are flocked, and filtered with sand or anthracite.
  • a membrane pretreatment for treating the water to be treated 1 with a microfiltration membrane or an ultrafiltration membrane can also be employed as a pretreatment.
  • separate activated sludge after performing activated sludge treatment in order to reduce the organic matter contained in wastewater can also be implemented.
  • the solid-liquid separation method may be precipitation separation using a conventionally used sedimentation basin, or a solid-liquid separation method using a separation membrane such as a microfiltration membrane or an ultrafiltration membrane may be employed.
  • the pretreated water to be treated is supplied to the semipermeable membrane 3 by a high pressure pump 2 at a pressure required for filtration, and separated into permeated water 4 and concentrated water 5.
  • the to-be-processed water before supplying to the semipermeable membrane 3 may be called semipermeable membrane supply water.
  • any material may be used as long as the salt concentration can be lowered so that the treated water 1 can be used for drinking water, industrial water, city water, etc.
  • a cellulose acetate type semipermeable membrane and a polyamide type semipermeable membrane are mentioned.
  • a polyamide-based semipermeable membrane is particularly effective in the method of the present invention.
  • Polyamide-based membranes are less resistant to chlorine, the most commonly used disinfectant to prevent biofilm growth, and even at low concentrations of chlorine, membrane degradation occurs significantly, preventing biofouling Difficult to do. Therefore, the effect by implementing this invention appears notably.
  • the apparatus for adding the drug 10 preferably includes a control mechanism having a valve and a pump that can control the addition amount, the addition time, the addition frequency, and the like in order to control the addition conditions of the drug.
  • the cleaning agent 11 is introduced from a pipe line provided upstream of the semipermeable membrane 3.
  • chemical cleaning is performed.
  • transduces the cleaning agent 11 is not specifically limited, Since there exists a possibility of corroding the high pressure pump 2 depending on the kind of the cleaning agent 11, the downstream is preferable.
  • the cleaning agent 11 is led out from the middle of the pipe of the concentrated water 5 and circulated.
  • Fouling is microbial growth on the membrane surface, biofilm adhesion on the membrane surface, inorganic scale adhesion on the membrane surface, or organic matter adhesion on the membrane surface. Therefore, when the fouling progresses to some extent, the biofilm, inorganic scale, or organic matter adhering to the membrane surface is peeled off by the flow of water on the membrane surface, and these solid matters are mixed into the concentrated water. .
  • the inventors examined whether or not the concentrated water 5 in the fresh water generation system used in the present invention can be regularly used as an index for determining the conditions for membrane cleaning or chemical addition.
  • the concentrated water contains impurities.
  • the concentrated water contains a large amount of salinity.
  • the inventors do not directly measure the concentrated water, but once filter the concentrated water with a filter and measure the characteristics of the filtered filter or the substance collected on the filter.
  • the inventors have found that a highly reliable index can be measured for the progress of fouling by eliminating the influence of impurities in the concentrated water, and the present invention has been achieved.
  • the concentrated water 5 is periodically filtered by a filtering means 6 equipped with a filter capable of capturing solid matter.
  • a filtering means 6 equipped with a filter capable of capturing solid matter.
  • an operation standard index derived from at least one index selected from the group consisting of the performance index of the filter, the amount of deposits on the filter, and the color change value of the filter reaches a predetermined standard value set in advance.
  • the semipermeable membrane 3 is cleaned, or the cleaning conditions for the semipermeable membrane and / or the injection conditions for the drug 10 are strengthened.
  • the solid substance in the present invention represents a suspended component and a colloid component. Therefore, the pore size of the filter provided in the filtering means 6 is not particularly limited as long as the solid matter can be captured, but in consideration of the dimensions of the suspended component and the colloidal component, 0.01 to It is preferably 5 ⁇ m. If a filter with a large pore size is used, the filtration speed is increased and the working time is shortened. However, there is a possibility that the solid matter that cannot be captured increases and the detection of fouling is delayed.
  • the material of the filter is not particularly limited.
  • the filter when the amount of deposit on the filter is evaluated by the amount of inorganic solid or organic matter, the filter is heated to about 600 ° C. to volatilize the organic matter.
  • a filter that can withstand a temperature of about 600 ° C., for example, a glass fiber filter is desirable.
  • the performance index of the filter when the concentrated water is filtered with such a filter, (a) the performance index of the filter, (b) the amount of deposit on the filter, and (c) the operation standard index derived from the index selected from the color of the filter , Grasp the progress of fouling.
  • the indices (a) to (c) will be described below.
  • the performance index of the filter refers to an index selected from various measured values representing the performance of the filter, such as a flow rate value, a pressure value, and a resistance value when concentrated water passes through the filter.
  • the performance index includes pressure value during constant flow filtration, filtration resistance value during constant flow filtration, filtration flow value when constant pressure is applied, amount of water filtered during a predetermined time when constant pressure is applied, constant An index selected from the group consisting of the time required to filter a predetermined amount of water when pressure is applied and the filtration resistance value of the filter when constant pressure is applied is preferred. As long as it shows the performance of passing through.
  • the said value may be used directly and the value (for example, change speed etc.) calculated using the said value may be used.
  • the performance index of the filter is measured as follows, for example. As shown in FIG. 1, after the concentrated water 5 separated by the semipermeable membrane 3 is adjusted to a constant flow rate or pressure by a flow rate adjusting means (or pressure adjusting means) 7, it is applied to a filtering means 6 equipped with a filter. Introduce. The pressure value or flow rate value of the concentrated water when being filtered by the filtering means 6 is measured by the pressure measuring means 8 or the flow rate measuring means 9.
  • a measuring device connected by piping in the order of water tank, pump, valve, pressure gauge and filter, put concentrated water into the water tank, supply it to the filter using the pump, and between the pump and filter Using a certain pressure gauge, it is possible to measure the pressure value or flow rate value of the concentrated water by performing filtration while adjusting the valve so that the concentrated water can be filtered at a constant pressure or a constant flow rate.
  • the filtration resistance value can be obtained from the pressure difference, the viscosity coefficient, and the flow rate by the following equation.
  • R ⁇ P / ( ⁇ ⁇ (Q / A)) here, R: Filtration resistance value [1 / m] ⁇ P: Concentrated water pressure difference [Pa] ⁇ : viscosity coefficient of concentrated water [Pa ⁇ s] Q: Flow rate of concentrated water [m 3 / s] A: The filter area [m 2 ].
  • the reciprocal value of the filtration flow value when a constant pressure is applied the reciprocal value of the amount of water filtered during a predetermined time when a constant pressure is applied, and the predetermined water amount when a constant pressure is applied.
  • the time required, the filter filtration resistance value when a constant pressure is applied, and the like can also be used as indicators.
  • SDI is an abbreviation of Silt Density Index, and is one of values calculated based on the time required to filter a predetermined amount of water when a certain pressure is applied. SDI is specified by ASTM D4189-95 (Standard Test Method for Silt Density Index of Water D4189-95) as a semi-permeable membrane feedwater monitoring index.
  • the SDI value is a value from 0 to 6.66, and the larger the value, the greater the degree of contamination of the sample.
  • the SDI of the water to be treated supplied to the semipermeable membrane is preferably 4 or less.
  • SDI is an index that is generally measured in the operation of a semipermeable membrane, and is an operation that is easy for an operator to learn. Therefore, when SDI is used as an index, the progress of fouling can be easily grasped. It becomes possible.
  • the SDI value can be used as an operation reference index as it is, or the SDI change rate can be calculated and used.
  • the amount of deposits on the filter is the amount of substances deposited on the filter after filtering the concentrated water.
  • the filter after filtering concentrated water is dried, a weight is measured, and the amount of adhering matter can be calculated
  • the filter after filtering can be immersed in pure water etc., and the method of measuring the turbidity, transparency, light absorbency, etc. of the immersed solution can also be used.
  • the index of the amount of deposit is preferably at least one selected from the group consisting of the amount of microorganisms, the amount of inorganic solids, and the amount of organic matter.
  • Biofouling can be grasped by measuring the amount of microorganisms
  • inorganic fouling can be grasped by measuring the amount of inorganic solid matter
  • organic fouling can be grasped by measuring the amount of organic matter.
  • the ratio between the amount of inorganic solids and the amount of organic matter, the ratio between the amount of inorganic solids and the amount of microorganisms, or the ratio between the amount of microorganisms and the amount of organic matter can be used as an indicator of the amount of deposits.
  • the microbial amount represents the amount of bacteria, its metabolite polysaccharides and proteins, its dead bodies, and its constituent nucleic acids. Therefore, various methods for measuring the amount of microorganisms are conceivable, and examples include quantification using protein, sugar, nucleic acid, total bacterial count, viable count, ATP, and the like. Among these, the ATP measurement method is particularly preferable because it is excellent in sensitivity, simplicity, and rapidity, and portable kits and reagents are commercially available.
  • Quantification of proteins, sugars, and nucleic acids requires equipment such as an absorptiometer and a fluorescence analyzer, and uses a strongly alkaline, strongly acidic, or mutagenic reagent. It's hard to say.
  • an agar culture method in which deposits on a filter are suspended in a liquid, and culturable microorganisms are counted as colonies using the suspension.
  • culturable microorganisms can be cultured and counted. Therefore, there is a problem that the total number of microorganisms cannot be evaluated.
  • the ATP measurement method extracts ATP (adenosine-5'-triphosphate), which is an energy substance of life activity of all living organisms, from microbial cells and emits light using luciferase, a firefly luminescent enzyme.
  • the light emission amount (RLU: Relative Light Unit) is measured. Since the amount of luminescence is proportional to the amount of ATP, the amount of microorganisms can be evaluated by measuring the amount of luminescence.
  • the reaction proceeds in the presence of the substrates ATP, luciferin, oxygen, luciferase and coenzyme magnesium ions, and light is generated.
  • the measurement time is as short as a few minutes, and kits for measuring reagents are commercially available.
  • a luminescence photometer device is commercially available that has high detection sensitivity and is portable while being detectable at a concentration of 1 pg / cm 3 .
  • the method for measuring the amount of ATP from the deposit on the filter is not particularly limited as long as it is a quantitative method.
  • the deposit on the filter is collected with a cotton swab and suspended in pure water.
  • a method of measuring the amount of inorganic solid matter for example, a method of measuring the weight of a filter after volatilizing organic matter by heating the filter after filtration to about 600 ° C., and obtaining from the difference from the weight of the filter before filtration There is. It can also be measured by immersing the filter in an acid such as hydrochloric acid or nitric acid or pure water, and analyzing the amount of the inorganic substance in the immersion liquid by ICP or the like. In the analysis by ICP or the like, since it is possible to obtain information on which substances occupy most of the inorganic substances, it is possible to select a drug corresponding to each substance.
  • the filtered filter is dried and weighed, and then the filter is heated to about 600 ° C. to volatilize the organic matter, and then the weight of the filter is measured.
  • There is a method for obtaining the difference by calculating the difference from the weight of the filter before heating to 600 ° C.
  • immerse the filter in sodium hypochlorite, sodium hydroxide or pure water and analyze the total organic carbon content in the immersion liquid with a TOC meter, or analyze the amount of sugar and protein in the immersion liquid. Can also be measured.
  • the whiteness specified in JIS P 8148: 2001 can be used. Also, it is possible to use the whiteness specified by the international standard ISO 2470-1: 2009 or the international standard ISO 2470-2: 2008 corresponding to JIS P 8148.
  • the whiteness is an index indicating the degree of whiteness of the surface color of pulp or paper, and the test piece is irradiated with diffuse illumination using a diffuse reflectance meter having an integrating sphere (diameter 150 mm), and the degree of whiteness is 0 degrees. The reflected light is received at an angle, and the obtained reflectance (percentage) is expressed numerically.
  • the whiteness can be measured with a commercially available whiteness meter. At this time, the filter before filtration is preferably white. Thereby, whiteness can be used as a more effective index.
  • the progress state of fouling is grasped by an operation standard index derived from an index selected from the above three indices (a) to (c), and a predetermined standard set in advance by the operation standard index is set.
  • the operation reference index includes a case where an index selected from the above (a) to (c) is directly used and a case where a value obtained from a value of the index using a predetermined calculation formula is used.
  • the cleaning agent 11 is usually placed in a cleaning tank or the like, introduced into the piping from the downstream side of the high-pressure pump 2 by a pump, led out from the middle of the piping of the concentrated water 5 and circulated.
  • the cleaning condition depends on the degree of fouling. For example, the cleaning agent is circulated for about 1 hour for cleaning, the circulation is stopped, the semipermeable membrane is immersed in the cleaning agent for 2 to 24 hours, and finally rinsed. To complete the cleaning. In some cases, this operation is repeated 2-3 times.
  • the medicine 10 is added from the middle of the supply pipe shown in FIG.
  • the medicine 10 may be added continuously or intermittently at a frequency such as once a day, but it is usually added continuously.
  • means for strengthening the drug injection condition include a method of increasing the concentration of the drug added and a method of increasing the frequency of addition, compared to a preset steady condition.
  • the filter is a semipermeable membrane X and Y, where Y is the value of the index selected from (a ′) the performance index of the filter when the feed water is filtered, (b ′) the amount of deposit on the filter, and (c ′) the color of the filter
  • Y is the value of the index selected from (a ′) the performance index of the filter when the feed water is filtered, (b ′) the amount of deposit on the filter, and (c ′) the color of the filter
  • the progress of fouling can be grasped using the above-mentioned index and a calculated value using the recovery rate of the treatment with the semipermeable membrane as an operation standard index.
  • the filter is a semipermeable membrane Y is the value of the index selected from (a ′) the performance index of the filter when the feed water is filtered, (b ′) the amount of deposits on the filter, and (c ′) the color of the filter.
  • the recovery rate is Re
  • the calculated value obtained from the formula XY / (1-Re) is used as an operation standard index, and when the predetermined standard value is reached, the semipermeable membrane is cleaned. Or cleaning conditions and / or drug injection conditions for the semipermeable membrane can be enhanced.
  • the concentration rate generated by the semi-permeable membrane operation recovery rate can be added to the operation standard index, and the difference between the index obtained from the concentrated water and the index obtained from the semi-permeable membrane feed water can be calculated.
  • the amount of deposit on the filter is used as an index, it is possible to select an appropriate drug or cleaning agent based on the type of deposit on the filter. For example, when a large amount of microorganisms is detected among the deposits on the filter, biofouling is a concern, so it is preferable to select a bactericidal agent as an agent to be injected.
  • a bactericidal agent as an agent to be injected.
  • the fungicide for example, an ingredient selected from 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, salts thereof and mixtures thereof is used as an active ingredient.
  • bactericides such as 2,2-dibromo-3-nitrilopropionamide (DBNPA) and sulfuric acid.
  • the scale inhibitor examples include sodium hexametaphosphate (SHMP).
  • the acid used for the membrane cleaning include 2% citric acid and 0.2% hydrochloric acid.
  • alkali used for the membrane cleaning include a 0.1% sodium hydroxide solution.
  • seawater 12 was processed by the processing method as shown in FIG. First, seawater 12 was taken and stored in a seawater storage tank 14. At the water intake point, a maximum of 15 mg / L sodium hypochlorite 13 was added for 30 minutes once every two days in order to suppress microbial growth in the water intake pipe. In addition, the addition concentration of sodium hypochlorite was adjusted so that the free residual chlorine concentration in the semipermeable membrane feed water storage tank 17 to be described later was about 1 mg / L. Next, seawater is pressurized by the supply pump 15 and supplied from the seawater storage tank 14 to the ultrafiltration membrane 16 (polyvinylidene fluoride hollow fiber ultrafiltration membrane, Toray HFU-1010, membrane area: 28 m 2 ). Pretreatment of seawater was performed by performing filtration. The filtration flux was 2 m / day.
  • Seawater pretreated using the ultrafiltration membrane 16 is once stored in the semipermeable membrane feed water storage tank 17, then sent to the high pressure pump 21 by the water pump 18, and pressurized by the high pressure pump 21. It was filtered through a semipermeable membrane 24 and separated into permeated water 25 and concentrated water 26. Since free residual chlorine was contained in the water to be treated between the water pump 18 and the high-pressure pump 21, about 3 mg / L of sodium bisulfite (SBS) 19 was added to remove chlorine. The purpose of adding SBS is to prevent chlorine degradation of the semipermeable membrane due to free chlorine remaining in the water to be treated.
  • SBS sodium bisulfite
  • a spiral type reverse osmosis membrane (TM810C manufactured by Toray) having a membrane material of polyamide, a desalination rate of 99.75%, and a membrane area of 7.8 m 2 was operated in series.
  • the operation was set to a membrane filtration flux of 14 L / m 2 / hr and a recovery rate of 37%.
  • the recovery rate is calculated by the flow rate of the permeated water 25 / (flow rate of the permeated water 25 + flow rate of the concentrated water 26).
  • operation differential pressure the pressure difference between the semipermeable membrane supply water 22 and the concentrated water 26 (hereinafter referred to as operation differential pressure) was constantly monitored, and changes in the operation differential pressure were observed. Further, between the high-pressure pump 21 and the semipermeable membrane 24, a conduit for introducing a cleaning agent 23 described later is provided so that chemical cleaning can be performed. A conduit for leading the cleaning agent 23 is provided in the middle of the piping of the concentrated water 26 so that the circulation cleaning can be performed.
  • the SDI measuring device 27 includes a filter holder 28 as a membrane separation means, a holder valve 29, a sample tank 30 (18L ⁇ 2 pieces), a compressor 31 as a pressurization means, a pressure adjustment valve 32, a pressure gauge 33, and a filter. It consists of a graduated cylinder 34 for measuring the amount of liquid, a flow meter 35 and the like. The flow meter 35 may or may not be provided as necessary.
  • the filter holder 28 was loaded with a membrane filter (MF-Millipore, HAWP04700F1 manufactured by Millipore) having a pore diameter of 0.45 ⁇ m and a diameter of 47 mm.
  • the sample tank 30 was filled with semipermeable membrane feed water 22 or concentrated water 26, pressurized with a compressor 31, adjusted with a pressure control valve 32 to a filtration pressure of 206 kPa, filtered, and measured for SDI.
  • the SDI calculation method is as described above.
  • the semipermeable membrane was cleaned when the operating differential pressure of the semipermeable membrane reached 150 kPa or more.
  • FIG. 4 shows changes over time in the SDI of the semipermeable membrane feed water 22, the SDI of the concentrated water 26, and the operation differential pressure of the semipermeable membrane.
  • the SDI of the semipermeable membrane feed water 22 hardly changed between 3 and 3.5 during the operation period.
  • the operating differential pressure of the semipermeable membrane hardly changed during the initial 2.5 months, but after 2.5 months, the operating differential pressure increased rapidly, and after that, the operating upper limit differential pressure was reached in 0.5 months.
  • Example 1 After the experiment of Comparative Example 1 was completed and the semipermeable membrane was replaced, the operation was resumed, and the operation of Example 1 was performed under the same conditions as in Comparative Example 1. However, in Example 1, the timing for performing the membrane cleaning was determined using the SDI measurement result of the concentrated water instead of the operation differential pressure. That is, the operation was performed with the operation standard index as SDI of concentrated water and the standard value as 150% of the initial SDI. As in Comparative Example 1, the SDI of the concentrated water 26 was measured twice a week, and the semipermeable membrane was washed when the SDI of the concentrated water reached 150% of the initial SDI. FIG. 5 shows changes over time in the SDI of concentrated water and the operation differential pressure of the semipermeable membrane.
  • the SDI of concentrated water was initially 3.8, but then gradually increased and reached 150% of 3.8, that is, 5.7 in 1.5 months after the start of operation.
  • the semipermeable membrane was washed.
  • the SDI of the concentrated water 26 recovered to almost the same value (3.9) as the initial stage.
  • washing was performed, and the operation was continued for about 10 months.
  • the operation differential pressure of the semipermeable membrane hardly changed and the operation was stable.
  • Example 2 After the operation of Example 1, the operation of Example 2 was performed in the same manner as in Example 1. However, in order to reduce the cleaning frequency of the semipermeable membrane, the addition of the drug 20 was started.
  • a medicine 20 a bactericide 2,2-dibromo-3-nitrilopropionamide (hereinafter DBNPA) is used, and 10 mg / L of DBNPA is provided 1 to 3 times a week between the water pump 18 and the high-pressure pump 21. Added for 1 hour.
  • DBNPA bactericide 2,2-dibromo-3-nitrilopropionamide
  • Example 3 After the operation of Example 2, the addition of the drug 20 was stopped again, and the operation of Example 3 was performed in the same manner as in Example 1. In Example 3, when the SDI of the concentrated water was measured, the amount of ATP on the filter after the SDI measurement was continuously measured twice a week.
  • the ATP amount on the filter was measured according to the following procedure. Three tubes were prepared by dispensing distilled water (Otsuka Pharmaceutical, for injection, 20 mL / piece) into an ATP amount measuring tube ("Lumitube (registered trademark)", manufactured by Kikkoman Co., 3 mL). The adhering matter on the filter was wiped off with one sterilized swab, and the swab from which the adhering matter was wiped was immersed in the water in the first tube for 1-2 minutes, and stirred carefully to obtain a suspension. The swab was sequentially immersed and stirred in the water in the second and third tubes to prepare a three-stage suspension.
  • the amount of concentrated water filtered by the filter was calculated from the difference between the weight before filtration and the weight after filtration of the sample tank 30 used in the SDI measurement. Then, the ATP concentration in the concentrated water was determined by dividing the ATP amount by the filtered concentrated water amount.
  • Example 3 the operation was performed with the ATP concentration in the concentrated water calculated from the ATP amount on the filter as the operation reference index and the reference value as 10 times the initial ATP concentration.
  • the ATP concentration in the concentrated water reached 10 times the initial ATP concentration, the semipermeable membrane was washed in the same manner as in Comparative Example 1, and such operation was continued for about 4 months. In the meantime, the operation differential pressure of the semipermeable membrane hardly changed and the operation was stable.
  • Example 4 In the same manner as in Comparative Example 1, permeated water 25 and concentrated water 26 were obtained from seawater 12. During operation, the amount of deposits on the filter after measuring SDI and SDI of concentrated water was measured twice a week. As the amount of deposits on the filter, the amount of ATP, the amount of inorganic solids, and the amount of organic matter were measured. The SDI of concentrated water and the amount of ATP on the filter were measured by the method described above. The amount of inorganic solid and organic matter on the filter was measured by the following procedure. First, the weight (M 0 ) of the filter before filtration was measured, the filter after filtration was dried, and the weight (M 1 ) was measured.
  • the weight of the filter (M 2 ) after the filter was heated to about 600 ° C. to volatilize the organic matter was measured.
  • Inorganic solid content was determined by subtracting the M 0 from M 2.
  • the amount of organic matter was determined by subtracting M 2 from M 1 .
  • the amount of concentrated water filtered through a filter is obtained, and the amount of inorganic solid matter and the amount of organic matter are divided by the amount of filtered concentrated water, respectively. Solid concentration and organic concentration were calculated.
  • the SDI of concentrated water reached 150% of the initial value in about one month after the start of operation.
  • the amount of deposits on the filter the amount of ATP and the amount of organic matter were almost the same as the initial values, but the amount of inorganic solids increased to a value exceeding 10 times the initial value.
  • ICP emission spectrometry In order to analyze the components of the inorganic solid matter on the filter, separately filter the concentrated water with a filter, soak the filter in 2.0% citric acid overnight, and measure the components of the soaked liquid by ICP emission spectrometry. As a result, it was found that iron accounted for the majority.
  • the ATP amount on the filter increased to 10 times the initial value and the SDI of the concentrated water rose to 150% of the initial value about every three months.
  • the operation differential pressure of the semipermeable membrane hardly changed after about one and a half years of operation, and the operation was stable. That is, in Example 4, SDI is the first operation reference index, the reference value is 150% of the initial SDI, the ATP amount on the filter through which the concentrated water is filtered is the second operation reference index, and the reference value Was operated 10 times the initial value.
  • the amount of microorganisms, the amount of inorganic solids, and the amount of organic matter on the filter through which concentrated water was filtered it was possible to determine the conditions for drug addition and membrane cleaning.
  • Example 5 In the same manner as in Comparative Example 1, permeated water 25 and concentrated water 26 were obtained from seawater 12. Twice a week, 20L of concentrated water is filtered through a membrane filter (MF-Millipore manufactured by Millipore, HAWP04700F1). The color difference ( ⁇ E * ab ) between the filter before filtration and the filter after filtration (Nippon Denshoku Industries Co., Ltd., spectral color difference meter SE 6000).
  • Example 5 the color difference ( ⁇ E * ab ) between the filter before filtration and the filter after filtration was used as an operation reference index, and the operation was performed with a reference value of 3.0.
  • ⁇ E * ab reached 3.0, the semipermeable membrane was washed in the same manner as in Comparative Example 1, and such operation was continued for about 6 months. In the meantime, the operation differential pressure of the semipermeable membrane hardly changed and the operation was stable.
  • MF-Millipore HAWP04700F1 manufactured by Millipore
  • Example 6 the reciprocal of the whiteness of the filter was used as the operation reference index, and when it was 1.3 times the initial value, that is, 1.33 was set as the reference value, the operation was performed.
  • the whiteness of the filter through which the concentrated water was filtered reached 75%
  • the semipermeable membrane was washed in the same manner as in Example 1. Such operation continued for about 4 months. In the meantime, the operation differential pressure of the semipermeable membrane hardly changed and the operation was stable.
  • Example 7 In the same manner as in Comparative Example 1, permeated water 25 and concentrated water 26 were obtained from seawater 12. As in Example 3, the amount of ATP on the filter on which the SDI was measured was measured twice a week for each of the semipermeable membrane feed water and the concentrated water. Further, X is the ATP amount on the filter where the SDI of concentrated water is measured, Y is the ATP amount on the filter where the SDI of semipermeable membrane feed water is measured, and Re is the recovery rate of the semipermeable membrane. The value obtained from the equation 1-Re) was used as the operation standard index.
  • the operation standard index calculated by the above formula increased to 10 times compared with the initial operation.
  • the medicine 20 DBNPA as a bactericidal agent was used, and 10 mg / L DBNPA was added between the water pump 18 and the high-pressure pump 21 1 to 3 times a week for 1 hour. Further, the operation was continued, and after about one month, the operation standard index was reduced to the same level as in the initial operation, so the addition of DBNPA as a disinfectant was stopped.
  • the operation was performed with 10 times the initial value of the operation reference index as the first reference value and 20 times the initial value as the second reference value.
  • the operation differential pressure of the semipermeable membrane hardly changed after about one and a half years of operation, and stable operation was possible.
  • Example 8 In the same manner as in Comparative Example 1, permeated water 25 and concentrated water 26 were obtained from seawater 12. In the operation of the semipermeable membrane, instead of measuring the SDI, the pressure during constant flow filtration was continuously measured twice a week for the semipermeable membrane feed water 22 and the concentrated water 26. The pressure at the time of constant flow filtration was performed by using the same apparatus of FIG. The filter holder 28 was loaded with a membrane filter (MF-Millipore, HAWP04700F1 manufactured by Millipore) having a pore diameter of 0.45 ⁇ m and a diameter of 47 mm.
  • MF-Millipore HAWP04700F1 manufactured by Millipore
  • the value obtained by subtracting the pressure value at the start of filtration from the value is Y
  • the recovery rate of the semipermeable membrane is Re
  • the value obtained from the formula of XY / (1-Re) is used as the operation standard index. Further, the amount of ATP on the filter after measuring the pressure during filtration of the concentrated water at a constant flow rate was measured by the same method as in Example 3.
  • the operation standard index value calculated by the above formula increased by 10 times compared to the initial operation.
  • the amount of ATP on the filter also increased up to 10 times compared to the initial value.
  • the disinfectant DBNPA was added as a medicine 20 between the water pump 18 and the high-pressure pump 21 1 to 3 times a week for 1 hour so as to have a concentration of 10 mg / L. .
  • the operation was continued, and after about 1 month, the operation standard index was reduced to the same level as compared with the initial operation, so the addition of DBNPA as a disinfectant was stopped.
  • the present invention provides a means by which the progress of fouling on the membrane surface can be easily grasped before it appears in membrane operation data such as membrane differential pressure, permeability, and separation. Therefore, the present invention is suitable for obtaining fresh water by performing desalination of seawater, brine, etc. using a membrane, or purifying sewage treated water or industrial wastewater to obtain reused water. Can be used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (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/JP2013/053395 2012-02-29 2013-02-13 Procédé de production d'eau Ceased WO2013129111A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012042963 2012-02-29
JP2012-042963 2012-02-29

Publications (1)

Publication Number Publication Date
WO2013129111A1 true WO2013129111A1 (fr) 2013-09-06

Family

ID=49082313

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/053395 Ceased WO2013129111A1 (fr) 2012-02-29 2013-02-13 Procédé de production d'eau

Country Status (2)

Country Link
JP (1) JPWO2013129111A1 (fr)
WO (1) WO2013129111A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018114472A (ja) * 2017-01-19 2018-07-26 三浦工業株式会社 水処理システム
WO2018199093A1 (fr) * 2017-04-26 2018-11-01 三菱重工エンジニアリング株式会社 Installation à membrane à osmose inverse et procédé de fonctionnement de installation à membrane à osmose inverse
WO2019176825A1 (fr) * 2018-03-12 2019-09-19 栗田工業株式会社 Procédé d'évaluation de l'état de contamination d'une membrane de séparation
SE547261C2 (en) * 2024-02-20 2025-06-17 Helios Innovations AB Method and system for managing process fluid

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11267471A (ja) * 1998-03-20 1999-10-05 Toray Ind Inc 膜濾過装置および運転方法
JP2003275548A (ja) * 2002-03-20 2003-09-30 Hitachi Plant Eng & Constr Co Ltd 膜分離装置
WO2008038575A1 (fr) * 2006-09-25 2008-04-03 Toray Industries, Inc. PROCÉDÉ DE FONCTIONNEMENT D'Une installation DE FILTRATION suR MEMBRANE D'OSMOSE INVERSE, ET installation DE FILTRATION sur MEMBRANE D'OSMOSE INVERSE
WO2008126777A1 (fr) * 2007-04-09 2008-10-23 Nitto Denko Corporation Procédé de séparation de membrane et dispositif de séparation de membrane
JP2012130823A (ja) * 2010-12-18 2012-07-12 Mitsubishi Heavy Ind Ltd 淡水化装置、膜の監視方法および淡水化装置の運転方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11267471A (ja) * 1998-03-20 1999-10-05 Toray Ind Inc 膜濾過装置および運転方法
JP2003275548A (ja) * 2002-03-20 2003-09-30 Hitachi Plant Eng & Constr Co Ltd 膜分離装置
WO2008038575A1 (fr) * 2006-09-25 2008-04-03 Toray Industries, Inc. PROCÉDÉ DE FONCTIONNEMENT D'Une installation DE FILTRATION suR MEMBRANE D'OSMOSE INVERSE, ET installation DE FILTRATION sur MEMBRANE D'OSMOSE INVERSE
WO2008126777A1 (fr) * 2007-04-09 2008-10-23 Nitto Denko Corporation Procédé de séparation de membrane et dispositif de séparation de membrane
JP2012130823A (ja) * 2010-12-18 2012-07-12 Mitsubishi Heavy Ind Ltd 淡水化装置、膜の監視方法および淡水化装置の運転方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018114472A (ja) * 2017-01-19 2018-07-26 三浦工業株式会社 水処理システム
WO2018199093A1 (fr) * 2017-04-26 2018-11-01 三菱重工エンジニアリング株式会社 Installation à membrane à osmose inverse et procédé de fonctionnement de installation à membrane à osmose inverse
JPWO2018199093A1 (ja) * 2017-04-26 2019-11-14 三菱重工エンジニアリング株式会社 逆浸透膜プラント及び逆浸透膜プラントの運転方法
WO2019176825A1 (fr) * 2018-03-12 2019-09-19 栗田工業株式会社 Procédé d'évaluation de l'état de contamination d'une membrane de séparation
JP2019155257A (ja) * 2018-03-12 2019-09-19 栗田工業株式会社 分離膜の汚染状況評価方法
SE547261C2 (en) * 2024-02-20 2025-06-17 Helios Innovations AB Method and system for managing process fluid
SE2450213A1 (en) * 2024-02-20 2025-06-17 Helios Innovations AB Method and system for managing process fluid
WO2025176541A1 (fr) * 2024-02-20 2025-08-28 Helios Innovations AB Procédé et système de gestion de fluide de traitement

Also Published As

Publication number Publication date
JPWO2013129111A1 (ja) 2015-07-30

Similar Documents

Publication Publication Date Title
KR101370689B1 (ko) 역삼투막 여과 플랜트의 운전 방법, 및 역삼투막 여과 플랜트
Jeong et al. Foulant analysis of a reverse osmosis membrane used pretreated seawater
JP4387302B2 (ja) 膜分離システムにおける生物付着の監視方法
Chun et al. A case study of fouling development and flux reversibility of treating actual lake water by forward osmosis process
US20140000346A1 (en) High pressor sensors for detecting membrane fouling
Linares et al. Hybrid SBR–FO system for wastewater treatment and reuse: Operation, fouling and cleaning
Chawla et al. Fouling in gravity driven Point-of-Use drinking water treatment systems
Maliwan et al. Release of microplastics from polymeric ultrafiltration membrane system for drinking water treatment under different operating conditions
Lim et al. Submerged versus side-stream osmotic membrane bioreactors using an outer-selective hollow fiber osmotic membrane for desalination
WO2013129111A1 (fr) Procédé de production d'eau
JP6056869B2 (ja) 逆浸透膜ろ過プラントの運転方法およびバイオフィルム形成モニタリング装置
JP2016221427A (ja) 水処理装置の運転方法
EP3950602B1 (fr) Procédé de séparation membranaire
JP2014193452A (ja) 有機性汚水の処理方法
Kim et al. Potential effects of damaged Pseudomonas aeruginosa PAO1 cells on development of reverse osmosis membrane biofouling
JP2016190212A (ja) 分離膜ろ過プラントにおける分離膜の酸化リスク評価方法
JP2014188385A (ja) 造水方法
JP2014172013A (ja) 造水方法
Wang Assessment of Ozonation and Biofiltration as a Membrane Pre-treatment at a Full-scale Drinking Water Treatment Plant
JP2014171988A (ja) 造水方法
JP2019088219A (ja) バイオフィルム形成ポテンシャル評価法及びプラントの運転方法
Valladares Linares et al. Hybrid SBR–FO system for wastewater treatment and reuse: Operation, fouling and cleaning
Khojah Investigations of the Effects of Biocide Dosing and Chemical Cleaning on the Organic Carbon Removal in an Integrated Ultrafiltration-Nanofiltration Desalination Pilot Plant
Valladares Linares Hybrid membrane system for desalination and wastewater treatment

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2013513463

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13754973

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13754973

Country of ref document: EP

Kind code of ref document: A1