WO2005049501A1 - Procede de traitement d'eaux usees contenant des substances organiques et appareil de traitement - Google Patents

Procede de traitement d'eaux usees contenant des substances organiques et appareil de traitement Download PDF

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Publication number
WO2005049501A1
WO2005049501A1 PCT/JP2004/015688 JP2004015688W WO2005049501A1 WO 2005049501 A1 WO2005049501 A1 WO 2005049501A1 JP 2004015688 W JP2004015688 W JP 2004015688W WO 2005049501 A1 WO2005049501 A1 WO 2005049501A1
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Prior art keywords
wastewater
treatment
scale inhibitor
organic matter
membrane separation
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PCT/JP2004/015688
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English (en)
Japanese (ja)
Inventor
Nozomu Ikuno
Koichi Nagata
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Kurita Water Industries Ltd.
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Publication date
Priority claimed from JP2004026961A external-priority patent/JP4496795B2/ja
Priority claimed from JP2004232977A external-priority patent/JP3906855B2/ja
Application filed by Kurita Water Industries Ltd. filed Critical Kurita Water Industries Ltd.
Priority to KR1020067011801A priority Critical patent/KR101098679B1/ko
Publication of WO2005049501A1 publication Critical patent/WO2005049501A1/fr

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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
    • 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
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/04—Feed pretreatment
    • 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
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • 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
    • 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
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/164—Use of bases
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
    • 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

Definitions

  • the present invention relates to a method and an apparatus for treating wastewater containing organic matter (TOC) discharged from an electronic device manufacturing plant or the like using a reverse osmosis (RO) membrane separation apparatus.
  • TOC wastewater containing organic matter
  • RO reverse osmosis
  • RO membrane separation treatment can effectively remove impurities (ions, organic substances, fine particles, etc.) in water.
  • impurities ions, organic substances, fine particles, etc.
  • this is firstly biologically treated to remove the TOC component, and then to biologically treated water. Is described in Japanese Patent Application Laid-Open No. 2002-336886.
  • Wastewater that is also discharged from the electronic device manufacturing plant may contain a nonionic surfactant that may adhere to the membrane surface of the RO membrane separation device and reduce the flux.
  • the RO membrane separation treatment could not be applied to such non-ionic surfactant-containing wastewater.
  • wastewater from an electronic device factory contains an oxidizing agent such as hydrogen peroxide in addition to the organic substances described above. If the wastewater contains an oxidizing agent, an activated carbon tower is generally installed in front of the RO membrane separator. Since organic matter is contained in these wastewaters, the inside of the activated carbon tower tends to be a hotbed of microorganisms. When microorganisms grow in the activated carbon tower, the pressure difference in the activated carbon tower rises, and the microorganisms leak, raising the SDI value of the activated carbon treated water.
  • an oxidizing agent such as hydrogen peroxide in addition to the organic substances described above.
  • the present invention provides a method for treating and recovering an organic matter-containing wastewater using an RO membrane separation apparatus for a long period of time by preventing a decrease in flux due to the organic substance adhering to the membrane surface in the RO membrane separation apparatus and preventing biofouling. It is an object of the present invention to provide a method and an apparatus for treating organic matter-containing wastewater, which performs high-quality treated water by efficiently reducing the TOC concentration in water while performing stable treatment for a long time.
  • the method for treating wastewater of the present invention comprises a step of adding a scale inhibitor to an organic matter-containing wastewater in an amount of at least 5 times the weight of calcium ions in the organic matter-containing wastewater; Before, after or simultaneously, add alkali to the wastewater containing organic matter to adjust the pH to 9.5 or more.Reverse osmosis membrane separation of wastewater containing organic matter that has passed through the pH control step with the scale inhibitor added and the pH adjustment step. And a membrane separation step for processing.
  • the wastewater treatment apparatus of the present invention includes a scale inhibitor adding means for adding a scale inhibitor at least 5 times the weight of calcium ions in the organic matter-containing wastewater to the organic matter-containing wastewater; Before, after, or simultaneously, an alkali is added to the organic matter-containing wastewater to adjust the pH to 9.5 or more, and a reverse flow in which the organic matter-containing wastewater that has passed through the scale inhibitor addition means and the pH adjustment means is introduced.
  • a permeable membrane separation treatment device for adding a scale inhibitor at least 5 times the weight of calcium ions in the organic matter-containing wastewater to the organic matter-containing wastewater.
  • the amount of the scale inhibitor added is a value converted into an acid even when the scale inhibitor is a salt such as a sodium salt.
  • FIG. 1 is a system diagram showing a method and apparatus for treating organic matter-containing wastewater according to an embodiment of the present invention.
  • Fig. 2 is a graph showing the time-dependent change of the membrane flux of the RO membrane separation device in Example 1 and Comparative Examples 1 and 2.
  • FIG. 3 is a time-dependent change in the viable cell count of the RO membrane separation device in Example 1 and Comparative Examples 1 and 2.
  • FIG. 3 is a time-dependent change in the viable cell count of the RO membrane separation device in Example 1 and Comparative Examples 1 and 2.
  • Fig. 4 is a graph showing the change over time of the membrane flux of the RO membrane separation device in Example 2 and Comparative Examples 3-5.
  • Fig. 5 is a graph showing the change over time of the membrane flux of the RO membrane separator in Examples 1 and 3 and Comparative Examples 6 and 7.
  • FIG. 6 is a graph showing the time-dependent changes in the membrane flux of the RO membrane separator in Examples 4, 5 and Comparative Example 8.
  • FIG. 7 is a graph showing the results of Example 6.
  • FIG. 8 is a graph showing the results of Example 7.
  • FIG. 9 is a system diagram showing a method and apparatus for treating wastewater containing organic matter and oxidizing agent according to another embodiment of the present invention.
  • FIG. 10 is a graph showing the change over time in the viable cell count of activated carbon-treated water in Example 8 and Comparative Example 9.
  • FIG. 11 is a graph showing the time-dependent change of the membrane flux of the RO membrane separator in Example 8 and Comparative Example 9.
  • FIG. 12 is a graph showing the time-dependent changes in membrane flux of the RO membrane separator in Example 9 and Comparative Examples 10-12.
  • FIG. 13 is a graph showing the time-dependent change of membrane flux of the RO membrane separation apparatus in Examples 8 and 10 and Comparative Examples 13 and 14.
  • the water to be treated (hereinafter referred to as “RO feed water”) introduced into the RO membrane separation device
  • a salt rejection rate when a 1500 mg ZL saline solution is subjected to RO membrane separation treatment under the conditions of 1.47 MPa, 25 ° C, and pH 7 as the RO membrane (hereinafter, simply referred to as “salt rejection rate”). It is preferable to perform the RO membrane separation treatment using a polybutyl alcohol-based low-filing RO membrane having a desalination performance of 95% or more. It is preferable to use such a low-filing RO film for the following reason.
  • the above-mentioned RO film for low fouling is very excellent in stain resistance because it loses the chargeability of the film surface and improves the hydrophilicity as compared with the aromatic polyamide film that is usually used.
  • the effect of the stain resistance is reduced, and the flux decreases with time.
  • a polybuil alcohol-based low-filing RO membrane having the above-mentioned specific desalination performance and a pH of the RO feedwater are set to 9.5 or more.
  • the pH of the RO feed water is preferably 10.5 or more, particularly 10.5-12.
  • the addition amount of the scale inhibitor is 5 to 50 times the calcium ion concentration. If the calcium ion concentration in the RO feedwater is high, a cation exchange treatment is performed as a pretreatment before the addition of the scale inhibitor to remove calcium.
  • the wastewater treatment method and treatment apparatus of this aspect high-density and / or low-concentration organic matter-containing wastewater discharged from an electronic device manufacturing plant and various other fields, particularly non-ferrous water.
  • the flux is prevented from adhering to the membrane surface of organic substances in the RO membrane separator, and biofouling is prevented to stabilize for a long time.
  • high-quality treated water can be obtained by efficiently reducing the TOC concentration in water.
  • the treated water obtained by the treatment according to the present invention can be used as raw water for producing ultrapure water, boiler water, or cooling water.
  • FIG. 1 is a system diagram showing a method and an apparatus for treating organic matter-containing wastewater according to one embodiment.
  • Fig. 1 after adding a scale inhibitor to the raw water (organic matter-containing wastewater) introduced through the tank 1, the alkali is added to adjust the pH to 9.5 or more, and then introduced into the RO membrane separation device. Perform RO membrane separation.
  • a chelate-based scale such as ethylenediaminetetraacetic acid (EDTA) or nitric acid triacetic acid (NTA) is easily dissociated in an alkaline region to form a complex with a metal ion.
  • Inhibitors are preferably used.
  • low molecular weight polymers such as (meth) acrylic acid polymer and its salt, maleic acid polymer and its salt, and ethylenediamine Phosphonic acids and phosphonates such as tramethylenephosphonic acid and its salts, hydroxyethylidene diphosphonic acid and its salts, nitrilotrimethylenephosphonic acid and its salts, phosphonobutanetricarboxylic acid and its salts, hexametaphosphoric acid and its Salts, inorganic polymerized phosphoric acid such as tripolyphosphoric acid and salts thereof, and inorganic polymerized phosphates can be used.
  • acrylic acid polymer and its salt such as (meth) acrylic acid polymer and its salt, maleic acid polymer and its salt, and ethylenediamine Phosphonic acids and phosphonates
  • tramethylenephosphonic acid and its salts such as tramethylenephosphonic acid and its salts, hydroxyethylidene diphosphonic acid and its salts, nitrilotrim
  • the amount of the scale inhibitor added is at least 5 times the weight of the calcium ion concentration in the raw water (water to which the scale inhibitor is added). If the amount of the scale inhibitor added is less than 5 times the weight of the calcium ion concentration in the raw water, the effect of adding the scale inhibitor cannot be sufficiently obtained. Even if an excessively large amount of the scale inhibitor is added, it is not preferable in terms of drug cost. Therefore, it is preferable to set the calcium ion concentration in the raw water to 5 to 50 times by weight.
  • the raw water to which the scale inhibitor has been added is then adjusted to pH 9.5 or more, preferably 10 or more, more preferably 10.5-12, for example, ⁇ .5-11 by adding an alkaline agent. Introduce into RO membrane separator 2.
  • the alkali agent used here is not particularly limited as long as it is an inorganic alkali agent such as sodium hydroxide and potassium hydroxide which can adjust the pH of raw water to 9.5 or more.
  • the RO membrane of the RO membrane separation apparatus includes one having alkali resistance, for example, a polyether amide composite membrane, a polybutyl alcohol composite membrane, an aromatic polyamide membrane, and the like.
  • a polyether amide composite membrane for example, a polyether amide composite membrane, a polybutyl alcohol composite membrane, an aromatic polyamide membrane, and the like.
  • salt rejection rate for low-filling polybutyl alcohol with a salt rejection rate of 95% or more when subjected to RO membrane separation at 25 ° C and pH 7 (hereinafter simply referred to as “salt rejection rate”).
  • An RO film may be used. The reason why it is preferable to use such a low-filling RO film is as follows.
  • the above-mentioned RO film for low fouling is extremely excellent in stain resistance because it loses the chargeability of the film surface and improves hydrophilicity as compared with an aromatic polyamide film that is usually used.
  • the effect of the stain resistance is reduced, and the flux decreases with time.
  • the RO membrane may be of any type, such as a spiral type, a hollow fiber type, and a tubular type.
  • the concentrated water of the RO membrane separation device 2 is adjusted to neutral pH by adding an acid as necessary, and then discharged out of the system.
  • the permeated water of the RO membrane separator 2 is then adjusted to pH 4-8 by adding an acid, and further subjected to an activated carbon treatment or the like, if necessary, and then reused or discharged.
  • the acid used here include mineral acids such as hydrochloric acid and sulfuric acid, which are not particularly limited.
  • FIG. 1 shows an example of the present invention, and the present invention is not limited to the illustrated one.
  • Fig. 1 after adjusting the pH by adding a scale inhibitor to the raw water and then adding an alkali to adjust the pH, the pH is adjusted by adding the alkali to the raw water, and then the scale inhibitor is added.
  • the pH adjustment and the addition of the scale inhibitor may be performed simultaneously.
  • the treatment by the RO membrane separation apparatus is not limited to one-stage treatment, but may be a multi-stage treatment of two or more stages.
  • a cation exchange tower for removing calcium ions may be provided prior to the addition of the agent to remove calcium.
  • a mixing tank for adding the pH adjusting / scale preventing agent may be provided.
  • Example 1 The wastewater from an electronic device manufacturing plant containing a nonionic surfactant (pH 7.2, TOClOmg, calcium ion concentration lmgZL) is used as raw water, and after adding 10 mg / L of ethylenediaminetetraacetic acid sodium salt as a scale inhibitor to the raw water, After adding NaOH to make ⁇ .5, RO membrane separation treatment was performed using a RO membrane separation apparatus (Nitto Denko's low-pressure aromatic polyamide type RO membrane “NTR-759”) at a recovery rate of 90%.
  • a nonionic surfactant pH 7.2, TOClOmg, calcium ion concentration lmgZL
  • the TOC concentration of the RO permeate was 50 ⁇ g ZL, and TOC was highly removed.
  • the treatment was performed under the same conditions as in Example 1 except that the pH of the RO feedwater was set to 7 without adding a scale inhibitor to the raw water, and the time of the membrane flux of the RO membrane separator and the viable cell count in the RO concentrated water The changes are shown in Figures 2 and 3, respectively.
  • Example 1 no decrease in flux was observed even after 500 hours from the start of water supply, whereas in Comparative Example 1, 300 hours after the start of water supply, the flux was already higher than the initial flux. It decreased by about half. Also, in Comparative Example 2 in which the slime control agent was added, the flux decreased to about 60% of the initial flux at 300 hours after the start of water flow.
  • Example 1 the flux decreased due to the synergistic effect of the growth of microorganisms in the RO membrane and the adhesion of the nonionic surfactant to the membrane surface, and in Comparative Example 2, the slime control Although the growth of microorganisms can be suppressed by the addition of the detergent, the flux decreases due to the nonionic surfactant adhering to the membrane surface.
  • Example 1 according to the present invention the RO membrane separation device was used. It is clear that both the growth of microorganisms in the device and the adhesion of the nonionic surfactant to the membrane surface can be simultaneously suppressed.
  • Example 2 Same conditions as in Example 1 except that the pH of the RO feedwater was 9.5 (Example 2), 9.2 (Comparative Example 3), 9 (Comparative Example 4), or 8.5 (Comparative Example 5).
  • Example 3 Same conditions as in Example 1 except that the pH of the RO feedwater was 9.5 (Example 2), 9.2 (Comparative Example 3), 9 (Comparative Example 4), or 8.5 (Comparative Example 5).
  • the time-dependent changes in the membrane flux of the RO membrane separator were examined, and the results are shown in FIG.
  • Example 7 The treatment was performed under the same conditions as in Example 1 except that ZL (Comparative Example 7) was used, and the change with time of the membrane flux of the RO membrane separation apparatus was examined.
  • FIG. 5 also shows the results of Example 1 in which the amount of the scale inhibitor added was lOmgZL.
  • FIG. 5 shows that the decrease in membrane flux of the RO membrane separation apparatus can be suppressed by setting the amount of the scale inhibitor to 5 times or more the calcium ion concentration. At this time, when the RO membrane surface of the RO membrane separation device with reduced membrane flux was examined, it was confirmed that the scan was made of calcium carbonate.
  • the wastewater from an electronic device manufacturing plant containing a nonionic surfactant (PH7.2, TOC30mg, calcium ion concentration lmgZL) was used as raw water, and after adding 10mg / L of ethylenediaminetetraacetic acid sodium salt as a scale inhibitor to the raw water, With NaOH added to make ⁇ .5, RO membrane separator (Nitto Denko's polyvinyl alcohol-based low-filing RO membrane “LF-10” (salt rejection 99.5%)) with a recovery rate of 90% RO membrane separation was performed.
  • RO membrane separator Naitto Denko's polyvinyl alcohol-based low-filing RO membrane “LF-10” (salt rejection 99.5%)
  • the RO permeated water had a TOC concentration of 100 ⁇ g ZL, and TOC was highly removable.
  • the treatment was carried out under the same conditions as in Example 4 except that the pH of the RO feed water was set to 7, and the change over time of the membrane flux of the RO membrane separation device is shown in FIG.
  • the addition amount of the acrylic acid polymer was lmgZL, 3mg / L, 5mg / L, lOmgZL.
  • NTA Sodium triacetate
  • the dispersing capacity of the disodium ditrisodium triacetate-based scale inhibitor was 1.23 mg / L, 3.7 mg / L, 6.2 mg / L, 12.3 mgZL (in terms of acid, lmgZL, 3 mg / L L, 5 mg / L, lOmg / L), and the treatment was carried out under the same conditions as in Example 1.
  • the time-dependent changes in the membrane flux of the RO membrane separation apparatus were examined. The results are shown in FIG. [0062] As shown in Fig. 8, it was found that a decrease in the flux can be suppressed by adding the amount of the scale inhibitor at least 5 times the Ca concentration in the feedwater. When the surface of the membrane with reduced flux was prayed, precipitation of calcium carbonate scale was observed.
  • an activated carbon treatment step of treating organic matter and oxidant-containing wastewater with activated carbon, and a reverse osmosis membrane separation treatment of the wastewater that has passed through the activated carbon treatment step In a method for treating organic matter and oxidizing agent-containing wastewater comprising a membrane separation step, in a stage prior to the activated carbon treatment step, an alkali is added to the wastewater to adjust the pH to 9.5 or more. And a step of adding a scale inhibitor to the wastewater at a stage prior to the membrane separation step, which is at least 5 times the weight of calcium ions in the wastewater.
  • a wastewater treatment apparatus includes activated carbon treatment means for treating organic matter and oxidant-containing wastewater with activated carbon, and reverse osmosis membrane separation of the wastewater that has passed through the activated carbon treatment means.
  • an apparatus for treating wastewater containing organic matter and oxidizing agent comprising a membrane separation means
  • the pH is adjusted to 9.5 or more by adding an alkali to the wastewater, which is provided before the activated carbon treatment means.
  • AC water supply the water to be subjected to the activated carbon treatment.
  • the reason why the AC water supply is adjusted to pH 9.5 or more and a predetermined amount of the scale inhibitor is added to the RO water supply is as follows.
  • the pH of the activated carbon treated water flowing out of the activated carbon tower is also alkaline at pH 9.5 or more.
  • Alkaline activated carbon-treated hydropower is supplied to the unit, which can similarly suppress the growth of microorganisms in the RO membrane separation unit, and eliminates the need for the addition of expensive slime control agents as in the past. Biofouling in the membrane separation device can be prevented.
  • the pH of the AC water supply is preferably 10.5 or more, particularly preferably 10.5 to 12.
  • calcium ion or the like which is a source of scale
  • a high-concentration and low-concentration organic substance and an oxidizing agent discharged from an electronic device manufacturing plant and various other fields are provided.
  • the wastewater containing wastewater is treated and recovered using an activated carbon tower and an RO membrane separator, the flux decreases due to the organic substance adhering to the membrane surface in the RO membrane separator, and the biofilling occurs in the activated carbon tower and the RO membrane separator.
  • Fig. 9 is a system diagram for performing processing in the above-mentioned (0) mode. However, it is needless to say that this one mode can also adopt the above-mentioned GO or the mode (iii) or (iv).
  • activated carbon towers are shown as activated carbon treatment means.However, the activated carbon treatment means is not limited to activated carbon towers at all, provided that activated carbon can be brought into contact with wastewater to remove the oxidizing agent in the wastewater.
  • the activated carbon treatment means is not limited to activated carbon towers at all, provided that activated carbon can be brought into contact with wastewater to remove the oxidizing agent in the wastewater.
  • the activated carbon treatment means is not limited to activated carbon towers at all, provided that activated carbon can be brought into contact with wastewater to remove the oxidizing agent in the wastewater.
  • alkali is added to adjust the pH to 9.5 or higher.
  • the treated water is introduced into the RO membrane separator 13 via the tank 12 to perform the RO membrane separation process.
  • the amount of the scale inhibitor to be added is preferably 5 to 50 times the calcium ion concentration in the raw water. The reason for this is described above.
  • the raw water to which the scale inhibitor has been added is then adjusted to pH 9.5 or more, preferably 10 or more, more preferably 10.5-12, for example, ⁇ .5-11 by adding an alkaline agent. Introduced into activated carbon tower 11.
  • the alkaline agent used here is not particularly limited as long as it is an inorganic alkaline agent such as sodium hydroxide and sodium hydroxide which can adjust the pH of raw water to 9.5 or more.
  • the type of activated carbon used in activated carbon tower 11 is not particularly limited, as long as it can remove an oxidizing agent, such as coal or coconut shell.
  • the flow method may be either upward flow or downward flow, and the flow SV is not particularly limited, but the flow is preferably performed at 140 hr- 1 .
  • the activated carbon treated water from which the oxidizing agent has been removed in the activated carbon tower 11 is introduced into the RO membrane separation device 13 by the pump P via the tank 12 in the next step.
  • Suitable RO membranes for the RO device 13 have been described above.
  • the concentrated water in the RO membrane separation device 13 is adjusted to neutral pH by adding an acid as necessary, and then discharged out of the system.
  • the permeated water of the RO membrane separation device 13 is then adjusted to pH 4-8 by adding an acid, and further subjected to an activated carbon treatment or the like as necessary, and then reused or discharged.
  • the acid used here include mineral acids such as hydrochloric acid and sulfuric acid, which are not particularly limited.
  • a predetermined amount of a scale inhibitor is added to the raw water, the pH is adjusted to 9.5 or more, and then the activated carbon treatment and the RO membrane separation treatment are performed. It does not cause a decrease in the flux, prevents the carbon dioxide from the activated carbon tower and the RO membrane separator, and performs a long-term stable treatment to obtain high-quality treated water with high TOC removal. .
  • FIG. 9 shows an example of the embodiment of the present invention as described above, and the present invention The present invention is not limited to those shown in the drawings unless the gist of the present invention is exceeded.
  • the alkali is added to adjust the pH, but the alkali is added to the raw water to adjust the pH, and then the scale inhibitor is added.
  • the pH adjustment and the addition of the scale inhibitor may be performed simultaneously.
  • the raw water may be supplied to an activated carbon tower, and a scale inhibitor may be added to the water that has flowed out of the activated carbon tower.
  • a scale inhibitor may be added to any of the above-mentioned positions.However, when a low molecular weight polymer is used, it may be adsorbed by activated carbon. U, preferably added to the effluent from the (RO feed).
  • the processing by the RO membrane separation apparatus is not limited to one-stage processing, and may be multi-stage processing of two or more stages.
  • Example 8 Treatment was carried out under the same conditions as in Example 8 except that the pH of the AC feedwater was 7.2 without adding NaOH to the raw water, and the aging of live bacterial water in the activated carbon treated water and the membrane flux of the RO membrane separator was performed. The changes are shown in FIGS.
  • Example 8 no decrease in the flux was observed even after 500 hours from the start of water supply, whereas in Comparative Example 9, the decrease in the membrane flux was caused by the organic substance adsorption action of the activated carbon for 300 hours after the start of water supply. Unseen power After about 300 hours, the flatness of the power was extremely reduced.
  • Example 9 Same as Example 9 except that the pH of the AC water was 9.5 (Example 9), 9.2 (Comparative Example 10), 9 (Comparative Example 11), or 8.5 (Comparative Example 12).
  • the treatment was performed under the conditions described above, and the change over time in the membrane fatters of the RO membrane separation device was examined. The results are shown in FIG.
  • RO membrane separation was performed under the same conditions as in Example 10 except that the amount of addition of scale inhibitor was 5 mg ZL (Example 10), 3 mg ZL (Comparative Example 13), or lm gZL (Comparative Example 14).
  • the time course of the membrane flux of the equipment was examined and the results are shown in FIG. FIG. 13 also shows the results of Example 1 in which the amount of the scale inhibitor added was 10 mg / L.

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Dans l'exécution d'un traitement/une récupération au moyen d'un séparateur à membrane d'osmose inverse (OI) d'eaux usées contenant des substances organiques à forte concentration ou à faible concentration, déchargées d'usines de production de dispositifs électroniques ou d'autres installations dans divers secteurs, non seulement il est possible d'effectuer un traitement stable pendant une durée prolongée tout en empêchant le bioencrassage et la chute de flux imputables à la fixation de substances organiques à la surface de la membrane dans un séparateur à membrane (OI), mais également la concentration de matières organiques totales dans l'eau peut être réduite efficacement afin d'obtenir ainsi une eau traitée de haute qualité. L'eau usée contenant les substances organiques est chargée d'un inhibiteur de tartre représentant jusqu'à au moins cinq fois en poids la concentration d'ions calcium dans l'eau et elle est également chargée d'un alcali de manière à ajuster la valeur du pH à 9,5 ou davantage, et ensuite elle est passée à travers un séparateur (2) à membrane OI. Grâce à l'ajustement de la valeur du pH de l'eau fournie à l'OI à 9,5 ou davantage, un éventuel bioencrassement du séparateur à membrane OI peut être empêché et également toute fixation d'un tensioactif non ionique à la surface de la membrane peut être empêché afin d'éviter ainsi toute chute de flux. Du fait de l'addition de l'inhibiteur de tartre, il est possible d'empêcher un éventuel encrassement de la surface de la membrane par le tartre contenant du carbonate de calcium sous des conditions de pH élevé.
PCT/JP2004/015688 2003-11-18 2004-10-22 Procede de traitement d'eaux usees contenant des substances organiques et appareil de traitement WO2005049501A1 (fr)

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JP2004026961A JP4496795B2 (ja) 2003-11-18 2004-02-03 有機物含有排水の処理方法及び処理装置
JP2004-026961 2004-02-03
JP2004232977A JP3906855B2 (ja) 2004-08-10 2004-08-10 有機物及び酸化剤含有排水の処理方法及び処理装置
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JP2007253115A (ja) * 2006-03-24 2007-10-04 Kurita Water Ind Ltd 有機物含有排水の処理方法及び処理装置
JP5135697B2 (ja) * 2006-03-27 2013-02-06 栗田工業株式会社 界面活性剤含有排水の処理方法
JP5608988B2 (ja) 2009-02-27 2014-10-22 栗田工業株式会社 活性炭用スライムコントロール剤、活性炭装置への通水方法、有機物含有水の処理方法及び処理装置
KR101427797B1 (ko) * 2013-05-20 2014-10-07 엘지전자 주식회사 수처리용 여과막의 유지세정 방법 및 그 수처리 시스템

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JPH0739871A (ja) * 1993-07-28 1995-02-10 Kurita Water Ind Ltd 純水製造装置
JP2002066259A (ja) * 2000-08-29 2002-03-05 Kurita Water Ind Ltd 純水の製造方法
JP2002186835A (ja) * 2000-12-20 2002-07-02 Japan Organo Co Ltd 逆浸透膜装置の運転方法
JP2003300069A (ja) * 2002-04-09 2003-10-21 Toray Ind Inc 造水方法及び造水装置

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JPH0739871A (ja) * 1993-07-28 1995-02-10 Kurita Water Ind Ltd 純水製造装置
JP2002066259A (ja) * 2000-08-29 2002-03-05 Kurita Water Ind Ltd 純水の製造方法
JP2002186835A (ja) * 2000-12-20 2002-07-02 Japan Organo Co Ltd 逆浸透膜装置の運転方法
JP2003300069A (ja) * 2002-04-09 2003-10-21 Toray Ind Inc 造水方法及び造水装置

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