WO2017086252A1 - 水処理装置、超純水製造装置及び水処理方法 - Google Patents

水処理装置、超純水製造装置及び水処理方法 Download PDF

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WO2017086252A1
WO2017086252A1 PCT/JP2016/083563 JP2016083563W WO2017086252A1 WO 2017086252 A1 WO2017086252 A1 WO 2017086252A1 JP 2016083563 W JP2016083563 W JP 2016083563W WO 2017086252 A1 WO2017086252 A1 WO 2017086252A1
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water
activated carbon
water treatment
quaternary ammonium
group
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PCT/JP2016/083563
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English (en)
French (fr)
Japanese (ja)
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聖哲 塚越
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野村マイクロ・サイエンス株式会社
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Priority to CN201680066592.4A priority Critical patent/CN108349764B/zh
Priority to KR1020187012824A priority patent/KR102678703B1/ko
Publication of WO2017086252A1 publication Critical patent/WO2017086252A1/ja

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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • 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
    • C02F3/06—Aerobic processes using submerged 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
    • C02F3/10—Packings; Fillings; Grids
    • 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 water treatment apparatus, an ultrapure water production apparatus, and a water treatment method.
  • an ultrapure water production apparatus that produces ultrapure water from raw water such as city water, well water, groundwater, and industrial water is often composed of a pretreatment device, a primary pure water system, and a secondary pure water system.
  • the pretreatment device is composed of, for example, a coagulation sedimentation device, a pressurized flotation device, a filtration device, and the like, and removes turbid components from the raw water to obtain pretreatment water.
  • the primary pure water system is configured by combining, for example, a degassing device, a reverse osmosis membrane device, an ion exchange device, an ultraviolet oxidation device, and the like, and organic substances, ionic components in pretreated water obtained by treatment with the pretreatment device, Dissolved gas etc. are removed to produce primary pure water.
  • the secondary pure water system is composed of, for example, an ultraviolet oxidizer, a mixed bed ion exchange device, an ultrafiltration device, and the like, and processes trace impurities in the primary pure water produced by the primary pure water system. Produces high purity ultrapure water.
  • Patent Document 1 discloses a urea removal method in which biological treatment is performed after adding urea or a urea derivative and / or an ammoniacal nitrogen source to raw water.
  • the present invention has been made to solve the above-described problems, and an object thereof is to provide a water treatment apparatus and a water treatment method capable of easily and highly removing urea in water. Another object of the present invention is to provide an ultrapure water production apparatus capable of easily obtaining high purity ultrapure water having a very low TOC concentration by highly removing urea.
  • the water treatment device of the present invention is a water treatment device for biologically treating raw water, wherein the raw water is in contact with the water-insoluble polymer having an amino group or quaternary ammonium group immobilized thereon and the water-insoluble polymer. And biological activated carbon for treating.
  • the water-insoluble polymer is preferably a water-insoluble polymer in which a quaternary ammonium group is immobilized.
  • the water-insoluble polymer and the biological activated carbon may be provided in a mixed bed type or a multi-bed type in which the water-insoluble polymer is laminated on the upstream side of the biological activated carbon. preferable.
  • the amount of the water-insoluble polymer and the biological activated carbon used is 1/99 to 99/1 in a volume ratio represented by the water-insoluble polymer / the biological activated carbon. It is preferable.
  • the water-insoluble polymer is preferably an ion exchange fiber or an ion exchange resin having the amino group or the quaternary ammonium group as an ion exchange group.
  • the ultrapure water production apparatus of the present invention includes the water treatment apparatus of the present invention, and a primary pure water system and a secondary pure water system provided on the downstream side thereof.
  • the water treatment method of the present invention comprises a step of bringing raw water into contact with a water-insoluble polymer having an amino group or quaternary ammonium group immobilized thereon, and the raw water in contact with the water-insoluble polymer by biological activated carbon. And a step of processing.
  • the raw water preferably has a pH of 4 to 9.
  • urea in water can be easily and highly removed.
  • urea is highly removed, so that high purity ultrapure water having a very low TOC concentration can be easily obtained.
  • FIG. 1 is a block diagram schematically showing a water treatment apparatus 1 of the present embodiment.
  • the water treatment apparatus 1 includes a storage tank 10 that stores and supplies raw water W and a biological treatment apparatus 20 that performs biological treatment.
  • the biological treatment apparatus 20 includes a mixed bed in which a water-insoluble polymer having an amino group or quaternary ammonium group immobilized (amino group or quaternary ammonium group-immobilized polymer) (AP) and biological activated carbon (BAC) are mixed. Is filled.
  • the raw water W stored in the storage tank 10 is processed by the biological treatment apparatus 20, and then supplied to, for example, a primary pure water system or a secondary pure water system to produce pure water or ultrapure water.
  • the raw water W stored in the storage tank 10 is processed by the biological treatment apparatus 20, and then supplied to, for example, a primary pure water system or a secondary pure water system to produce pure water or ultrapure water.
  • the raw water W stored in the storage tank 10 is processed by the biological treatment apparatus 20,
  • Biological activated carbon is obtained by carrying microorganisms on activated carbon and is used for biological treatment.
  • organic substances are decomposed by microorganisms (bacteria) that perform biological treatment in oxygen respiration, nitric acid respiration, fermentation processes, etc., and are gasified or taken into the body of microorganisms and removed as sludge.
  • nitrogen nitrification denitrification method
  • phosphorus biological phosphorus removal method
  • Biological activated carbon is prepared as follows, for example. Carbon sources, phosphorus, trace metals, and inorganic salts, which are microorganism nutrients, are added to sludge containing microorganisms. Further, if necessary, oxygen is blown to perform an aerobic treatment. Thereby, microorganisms can be cultured. Activated carbon is immersed in the activated sludge in which microorganisms are cultured. As a result, the microorganism is supported in the pores of the activated carbon to produce the biological activated carbon. Normally, when water containing a TOC component is passed through this biological activated carbon, biological treatment is performed by the above action of the microorganisms supported on the biological activated carbon, and the TOC component in the water is removed. In such a biological treatment, in order to maintain the activity of the microorganism, it is added to water supplying the nutrient source of the microorganism as necessary.
  • nitrifying bacteria sludge in which the nitrifying bacteria group (ammonia oxidizing bacteria group) is dominant can be obtained. This is thought to be because microorganisms other than the nitrifying bacteria group are difficult to grow in the presence of ammoniacal nitrogen, while the nitrifying bacteria group having ammonia resistance grows. About the substance and quantity of additives other than urea or ammonia nitrogen, the substance and quantity normally used for nitrifying bacteria culture may be sufficient.
  • biological activated carbon carrying nitrifying bacteria can be obtained by immersing activated carbon in the nitrifying sludge obtained above. Since the nitrifying bacteria group metabolizes urea, urea in the water is removed by biological treatment with biological activated carbon carrying nitrifying bacteria.
  • the total amount of biological activated carbon used in the biological treatment apparatus 20 may be obtained by immersing activated carbon in activated sludge, biological activated carbon obtained by immersing in activated sludge, and activated carbon that has not been subjected to immersion treatment.
  • the present invention is not limited to these methods.
  • the amount of nitrifying bacteria supported on biological activated carbon can be expressed by using the urea removal rate as an index.
  • the biological activated carbon those capable of reducing urea to 0.02 ⁇ g / L or less, more preferably 0.005 ⁇ g / L or less are suitable.
  • the activated carbon used for the biological activated carbon is not particularly limited, and examples thereof include those manufactured using coal, coconut shells, charcoal and the like as raw materials.
  • shape of the activated carbon there is no particular limitation on the shape of the activated carbon, and for example, a fibrous shape, a honeycomb shape, a columnar shape, a crushed shape, a granular shape, a powder shape, a pellet shape, or the like can be used.
  • granular or crushed activated carbon is preferable in that it easily supports microorganisms.
  • the particle size is preferably 0.35 to 2.0 mm, more preferably 0.42 to 1.7 mm.
  • the particle size of the activated carbon can be measured by, for example, a JIS standard sieve.
  • the amino group or quaternary ammonium group-immobilized polymer is a water-insoluble polymer in which an amino group or quaternary ammonium group is immobilized.
  • the amino group means an amino group constituting a primary to tertiary amine, and further includes a group that is ionized to form an ammonium ion.
  • the polymer used as the amino group or quaternary ammonium group-immobilized polymer is not particularly limited as long as it can immobilize the amino group or quaternary ammonium group and is a water-insoluble polymer.
  • this polymer examples include styrene / divinylbenzene copolymer, polyvinyl alcohol, cellulose such as acetate, acrylic such as polymethacrylonitrile and polyacrylonitrile, vinyl chloride such as polyvinyl chloride and polyvinylidene chloride, nylon Various types of urethane-based polymers such as polyamide-based and polyurethane can be used.
  • the form of the polymer is not particularly limited, and the polymer can be used in various forms such as a resin form, a fiber form, a film form, and a block form.
  • the amino group or quaternary ammonium group-immobilized polymer one type may be used alone, or two or more types may be used in combination.
  • the amino group may be either an amino group constituting a primary to tertiary amine or a quaternary ammonium group.
  • the amino group or quaternary ammonium group of the amino group or quaternary ammonium group-immobilized polymer may be one kind or plural kinds.
  • the amino groups constituting the primary to tertiary amines are groups represented by —NH 2 , —NHR, and —NR 2 , respectively, and the quaternary ammonium group is represented by —N + R 3.
  • R is a substituted or unsubstituted alkyl group or a substituted or unsubstituted hydroxyalkyl group, each of which may be the same or different.
  • a quaternary ammonium group is particularly excellent in improving the ability of nitrifying bacteria to remove urea, followed by —NR 2 , —NHR and —NH 2 in this order.
  • Examples of the method for immobilizing an amino group or quaternary ammonium group in an amino group or quaternary ammonium group-immobilized polymer include a method in which an amino group or quaternary ammonium group is bonded to a polymer skeleton.
  • a compound in which an amino group or a quaternary ammonium group is bonded to a carbon atom or the like constituting a main chain or a branch of is preferable.
  • those in which an amino group or a quaternary ammonium group is bonded to a carbon atom or the like constituting a branch are more preferable.
  • Examples of the substituent R in the amino group and the quaternary ammonium group include alkyl groups such as a methyl group, an ethyl group, and a butyl group, and hydroxyalkyl groups such as a hydroxymethyl group, a hydroxyethyl group, and a hydroxybutyl group. .
  • an ion exchange fiber or ion exchange resin having the amino group or quaternary ammonium group as an ion exchange group is preferably used as the polymer for immobilizing the amino group or quaternary ammonium group. Since these have a large surface area inside, the contact area with the water to be treated can be increased. In addition, the amount of amino groups or quaternary ammonium groups per unit volume is large. By these, the removal efficiency of urea can be improved. Furthermore, since there are few effluents, the quality of treated water is not adversely affected. Therefore, it is preferably used for the purpose of highly removing impurities such as in the production of ultrapure water.
  • the amount of the amino group or quaternary ammonium group contained in the amino group or quaternary ammonium group-immobilized polymer is 0 in terms of the functional group amount (total exchange capacity) per unit capacity of the amino group or quaternary ammonium group-immobilized polymer. 0.01 equivalent / L (eq / L) to 10 equivalent / L (eq / L) is preferable, and 0.5 equivalent / L (eq / L) to 5 equivalent / L (eq / L) is more preferable.
  • the amount of the amino group or the quaternary ammonium group is 0.01 equivalent / L (eq / L) or more, the microflora of the nitrifying bacteria group is maintained well, and the urea removal ability can be improved.
  • the amount of the amino group or quaternary ammonium group is 10 equivalents / L (eq / L) or less, the stability of the amino group or quaternary ammonium group-immobilized polymer is excellent.
  • the ion exchange resin examples include a gel type ion exchange resin, a porous type ion exchange resin in which a macropore having a pore diameter of 100 to 1000 angstroms is formed on the gel type ion exchange resin, and a highly porous high ion having finer pores than the porous type ion exchange resin.
  • examples thereof include porous ion exchange resins. Since the amount of amino groups per unit capacity can be increased, a porous or high porous ion exchange resin is more preferable.
  • ion exchange resin a styrene / divinylbenzene copolymer or an acrylic polymer is used as a resin skeleton, and a trimethylammonium group (—N + (CH 3 ) 3 ) or a dimethylhydroxyethylammonium group (—N + (CH 3 )
  • an ion exchange fiber the basic anion exchange fiber etc. which the said amino group or the quaternary ammonium group couple
  • the water content is preferably 35 to 65% by mass, and 40 to 50% by mass. % Is more preferable. This makes it easier to retain microorganisms when mixed with biological activated carbon.
  • Diaion series (WA20, WA21J, etc.) manufactured by Mitsubishi Chemical Corporation, Levacit series manufactured by LANXESS, Duolite series manufactured by DOW, etc. can be used.
  • the strongly basic anion exchange resin for example, Diaion series (SA10A, SA20A) manufactured by Mitsubishi Chemical Corporation, Levachit series manufactured by LANXESS, Duolite series manufactured by DOW, or the like can be used.
  • the weak base ion exchange fiber for example, EF-SA-WA manufactured by NICHIBI, and as the strong base ion exchange fiber, IEF-SA manufactured by NICHIBI can be used.
  • usable ion exchange resins and ion exchange fibers are not limited to the types described above.
  • the ion exchange resin may be a new ion exchange resin or a used one, for example, an ion exchange resin that has been used for a long time in a pure water production apparatus.
  • a strong basic anion exchange resin having a quaternary ammonium group as an ion exchange group is particularly preferable.
  • the method for obtaining the mixed bed of amino group or quaternary ammonium group-immobilized polymer and biological activated carbon is not particularly limited. After the biological activated carbon and amino group or quaternary ammonium group-immobilized polymer prepared above are accommodated in a container, It can be produced by a method of mixing by passing water in an upward flow or a method of mixing by a mixer or the like. Moreover, it can produce by the method of carrying
  • the ratio between the amino group or quaternary ammonium group-immobilized polymer and the biological activated carbon is such that, for example, the volume ratio expressed by amino group or quaternary ammonium group-immobilized polymer / biological activated carbon is in the range of 1/99 to 99/1.
  • the effects of the invention can be obtained, 1/9 to 9/1 is more preferable, and 3/7 to 7/3 is more preferable in terms of increasing the urea removal rate.
  • a biological treatment apparatus is prepared by filling a mixed bed of biological activated carbon and an amino group or quaternary ammonium group-immobilized polymer into, for example, a water treatment tower having a water supply pipe for supplying water to be treated and a discharge pipe for discharging treated water. 20 can be configured.
  • the raw water W to be treated ground water, river water, city water, other industrial water, or recovered water obtained by collecting used ultrapure water such as a semiconductor factory or a liquid crystal factory is used.
  • recovered water it is preferable to use it by ion-exchange treatment or neutralization treatment to adjust the pH to a range described below, for example.
  • the water to be treated may be one obtained by treating the raw water W with a pretreatment system or an apparatus similar to this.
  • the pretreatment system includes, for example, a coagulation sedimentation device, a pressure levitation device, a filtration device, and the like, and removes turbid components in the raw water.
  • the urea concentration in the raw water W is preferably about 5 to 200 ⁇ g / L, particularly about 5 to 100 ⁇ g / L.
  • the dissolved oxygen concentration (DO) of the raw water W is preferably 5 to 8 mg / L.
  • Raw water W is supplied to the biological treatment apparatus 20 where urea is removed.
  • urea is removed.
  • Either an upward flow system or a downward flow system may be sufficient.
  • the upward flow method is preferable in that clogging due to bacteria is unlikely to occur.
  • Water flow rate into the biological treatment apparatus 20 may preferably be about SV5 ⁇ 50 hr -1, more preferably SV5 ⁇ 20 hr -1.
  • the temperature of the water to be treated supplied to the biological treatment apparatus 20 is preferably around normal temperature, for example, 10 to 35 ° C., more preferably about 20 to 35 ° C., from the viewpoint of improving the activity of microorganisms. Therefore, it is preferable to provide a heat exchanger before the biological treatment apparatus 20 as necessary.
  • the pH of the water to be treated supplied to the biological treatment apparatus 20 is preferably neutral to weakly alkaline, for example, pH 4 to 9, preferably pH 5 to 8, in order to predominate the nitrifying bacteria group among microorganisms. It is more preferable.
  • an ammonia nitrogen source has been added to the feed water in order to maintain the flora of the nitrifying bacteria group that decomposes urea and to sterilize other bacteria.
  • the ammonia nitrogen contained in the amino group or quaternary ammonium group of the amino group or quaternary ammonium group-immobilized polymer acts in the same manner as ammonia nitrogen added to water.
  • the water contacted with the amino group or quaternary ammonium group-immobilized polymer is continuously passed through the biological activated carbon, so that nitrification can be achieved by the action of the ammonia nitrogen of the amino group or quaternary ammonium group-immobilized polymer. It is considered that the bacteria group of the fungus group is maintained, the nitrifying bacteria group is dominant, and urea is removed.
  • the amino group or quaternary ammonium group-immobilized polymer and the biological activated carbon do not necessarily have to be mixed as in the biological treatment apparatus 20, and the raw water W in contact with the amino group or quaternary ammonium group-immobilized polymer is biological. If treated with activated carbon, the same effect as using the water treatment apparatus 1 can be obtained.
  • a water treatment apparatus other than the water treatment apparatus 1 a water treatment apparatus 2 having a multiple bed in which an amino group or quaternary ammonium group-immobilized polymer and biological activated carbon are laminated as shown in FIG. And a water treatment apparatus 3 having a single bed of amino group or quaternary ammonium group-immobilized polymer and a single bed of biological activated carbon, as shown in FIG.
  • the water treatment device 2 includes a biological treatment device 21 having a laminated structure in which an amino group or quaternary ammonium group-immobilized polymer and biological activated carbon are laminated in this order from the upstream side to the downstream side.
  • the water treatment device 3 is sequentially provided in a device 22 having an amino group or quaternary ammonium group-immobilized polymer and a biological activated carbon device 23.
  • the same effects as the water treatment apparatus 1 can be obtained for the water treatment apparatuses 2 and 3.
  • biological activated carbon and an amino group or a quaternary ammonium group fixed polymer biological activated carbon each other, an amino group, or a quaternary Ammonium group-immobilized polymers may adhere to each other to form a lump.
  • backwashing with water is performed.
  • an ion exchange apparatus using an ion exchange resin or an ion exchange fiber is used. Thus, it is not necessary to regenerate with chemicals such as acid and alkali.
  • urea in water can be highly removed without adding chemicals such as an ammoniacal nitrogen source. Further, in the method of treating the water added with the ammoniacal nitrogen source with biological activated carbon, it takes a long time to start up from the start of water passage to the biological activated carbon until the urea removal rate is stabilized. According to the water treatment apparatus, the start-up period can be shortened.
  • FIG. 4 is a block diagram schematically showing the ultrapure water production apparatus 4 of the embodiment.
  • the ultrapure water production apparatus 4 includes a primary pure water system 41 and a secondary pure water system 42 on the downstream side of the water treatment apparatus 1 (which may be the water treatment apparatus 2 or the water treatment apparatus 3).
  • the primary pure water system 41 is configured by combining, for example, an ion exchange device, a reverse osmosis membrane device, a deaeration device, an ultraviolet oxidation device, and a regenerative mixed bed ion exchange device.
  • impurity ions are removed from the treated water from which urea has been removed by the water treatment device 1 of the above embodiment by a combination of an anion exchange device and a cation exchange device as an ion exchange device, and reverse osmosis.
  • Inorganic ions, organic substances, fine particles and the like are removed by the membrane device.
  • dissolved gas such as dissolved oxygen and dissolved carbonic acid is removed by the deaeration device.
  • the primary pure water has, for example, a TOC concentration of 10 ⁇ g C / L or less and a specific resistivity of 17 M ⁇ ⁇ cm or more.
  • the secondary pure water system 42 is an apparatus for removing trace organic substances and trace fine particles in the primary pure water, and combines an ultraviolet oxidation apparatus, a membrane deaeration apparatus, a non-regenerative mixed bed ion exchange apparatus, and an ultrafiltration apparatus. Configured.
  • the ultrapure water obtained in this way is reduced, for example, to a TOC concentration of 5 ⁇ g C / L or less, a specific resistivity of 17.5 M ⁇ ⁇ cm or more, and a urea concentration of 5 ⁇ g / L or less.
  • urea in water can be highly removed without adding chemicals such as an ammonia nitrogen source to the water to be treated, and therefore the TOC concentration is extremely low. Ultrapure water can be obtained easily. Further, since the upstream side of the primary pure water system 41 can add a ammonia nitrogen source to the water to be treated and then treat with biological activated carbon, the start-up period of the biological treatment apparatus can be shortened. In addition, there is no waste of raw water, and ultrapure water can be produced efficiently.
  • Example 1 2 mg / L of urea and 50 mg / L of ammonia were added to the activated sludge and allowed to stand for 30 days to acclimatize the nitrifying sludge. When the urea removal ability of the obtained nitrifying bacteria sludge was measured using urea-containing water, urea could be removed to 0.02 mg / L.
  • the urea concentration in the treated water obtained from the column was measured, and the change over time of the urea removal rate was examined with the start of water flow as 0 day. The results are shown by a solid line in the graph of FIG.
  • the urea removal rate was calculated by the following formula.
  • the water temperature passed without any adjustment.
  • the water temperature during the water flow test was 24 to 26 ° C. The same applies to the water temperatures of Examples and Comparative Examples described later.
  • Urea removal rate [1 ⁇ (urea concentration in treated water / urea concentration in treated water)] ⁇ 100 (%)
  • Example 1 when the strong base anion exchange resin after use was taken out of the column after 350 days of water flow and the exchange capacity was measured, it was 95% of the initial exchange capacity. From this, it was confirmed that the ion exchange resin was not a supply source of ammonium ions. In addition, since ammonium groups are not reduced, it can be predicted that a high urea removal rate is continuously maintained even when water flow is continued.
  • Example 1 The column is filled with biological activated carbon produced in the same manner as in Example 1 except that the strongly basic anion exchange resin is not mixed and the amount of biological activated carbon used is increased. Ammonia was added to a concentration of 0.5 mg / L, and water was passed through the column under the same conditions as in Example 1. Similar to Example 1, the change with time in the urea removal rate was examined. The results are shown in broken lines in the graph of FIG.
  • Example 2 A mixed bed was prepared in the same manner as in Example 1 except that the amount of the activated carbon remained at 300 mL and the volume ratio represented by strong basic anion exchange resin / biological activated carbon was set to 1/1. Using this mixed bed, the urea removal rate was measured under the same conditions as in Example 1. In this example, the urea removal rate exceeded 85% after 30 days of water flow and became 100% after 50 days.
  • Example 3 A mixed bed was prepared in the same manner as in Example 1 except that the amount of the activated carbon remained at 300 mL and the volume ratio represented by strongly basic anion exchange resin / biological activated carbon was set to 1/8. Using this mixed bed, the urea removal rate was measured under the same conditions as in Example 1. In this example, the urea removal rate exceeded 80% after 30 days of water flow and became 90% after 50 days, and thereafter, the urea removal rate remained stable.
  • Example 4 A mixed bed was prepared in the same manner as in Example 1 except that the amount of the activated carbon remained at 300 mL and the volume ratio represented by strong basic anion exchange resin / biological activated carbon was set to 1/99. Using this mixed bed, the urea removal rate was measured under the same conditions as in Example 1. In this example, the urea removal rate exceeded 75% after 30 days of water flow and reached 88% after 50 days, and thereafter, the urea removal rate remained stable.
  • Example 5 Similar to Example 1 except that weakly basic anion exchange resin (Diaion WA30, manufactured by Mitsubishi Chemical Corporation, amino group content 1.5 mol / L or more) was used instead of strong basic anion exchange resin. Thus, a mixed bed was prepared. Using this mixed bed, the urea removal rate was measured under the same conditions as in Example 1. In this example, the urea removal rate exceeded 95% after 30 days of water flow and became 99% after 50 days, and thereafter, the urea removal rate remained stable.
  • weakly basic anion exchange resin Diaion WA30, manufactured by Mitsubishi Chemical Corporation, amino group content 1.5 mol / L or more
  • Example 6 The same basic anion exchange resin and biological activated carbon as in Example 1 were used. The amount of biological activated carbon remained 300 mL, and the mixing ratio was strong basic anion exchange resin / biological activated carbon (volume ratio). A mixed bed was prepared in the same manner as in Example 1 except that the ratio was 3/1. Using this mixed bed, the urea removal rate was measured under the same conditions as in Example 1. In this example, the transition of the urea removal rate was the same as in Example 1 (solid line in FIG. 5).
  • Example 7 The strong basic anion exchange resin and the biological activated carbon as in Example 1 were not mixed, and the biological activated carbon was laminated above the strong basic anion exchange resin (strongly basic anion with respect to the water to be treated).
  • a double bed was prepared in the same manner as in Example 1 except that the exchange resin was upstream and the biological activated carbon was downstream).
  • the removal rate of urea was measured under the same conditions as in Example 1 except that the water to be treated was passed upward through this multiple bed. In this example, the transition of the urea removal rate was the same as in Example 1 (solid line in FIG. 5).
  • Example 2 100 mL of a strongly basic anion exchange resin similar to that in Example 1 was immersed in nitrifying sludge for 7 days, then taken out, filled in a column, and the urea removal rate was measured under the same conditions as in Example 1. It was. In this example, the urea removal rate exceeded 30% after 30 days of water flow and became 45% after 50 days, and thereafter, the urea removal rate remained stable.
  • urea in water can be highly removed without adding a chemical such as an ammoniacal nitrogen source.
  • the removal rate of urea is stabilized from the start of water flow to biological activated carbon. It can be seen that the start-up period can be shortened.

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JPS6168198A (ja) * 1984-09-11 1986-04-08 Hitachi Plant Eng & Constr Co Ltd 廃水処理剤
JPH0839058A (ja) * 1994-07-28 1996-02-13 Kurita Water Ind Ltd 半導体洗浄排水の処理方法
JPH08150400A (ja) * 1994-11-29 1996-06-11 Japan Organo Co Ltd 有機物含有酸性排水処理装置
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