WO2017086252A1 - Water treatment device, ultrapure water manufacturing device, and water treatment method - Google Patents
Water treatment device, ultrapure water manufacturing device, and water treatment method Download PDFInfo
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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
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910021642 ultra pure water Inorganic materials 0.000 title claims abstract description 34
- 239000012498 ultrapure water Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 167
- 125000003277 amino group Chemical group 0.000 claims abstract description 65
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 65
- 229920003176 water-insoluble polymer Polymers 0.000 claims description 25
- 238000005342 ion exchange Methods 0.000 claims description 22
- 239000003456 ion exchange resin Substances 0.000 claims description 18
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 68
- 239000004202 carbamide Substances 0.000 abstract description 68
- 229920003169 water-soluble polymer Polymers 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 description 40
- 241000894006 Bacteria Species 0.000 description 24
- 230000001546 nitrifying effect Effects 0.000 description 24
- 239000003957 anion exchange resin Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 244000005700 microbiome Species 0.000 description 19
- 239000010802 sludge Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- -1 hydroxyethyl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001453382 Nitrosomonadales Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 244000005706 microflora Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Images
Classifications
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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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Abstract
To provide a water treatment device and a water treatment method able to easily and effectively remove urea from water, and to provide an ultrapure water manufacturing device able to easily obtain high-purity ultrapure water that has an extremely low TOC concentration. The water treatment device and the water treatment method, which are provided with: a non-water-soluble polymer onto which is fixed an amino group or a quaternary ammonium group; and a biological activated carbon for treating raw water that has been contacted by the non-water-soluble polymer. The ultrapure water manufacturing device, which has the water treatment device, and a primary pure water system and a secondary pure water system provided downstream from the water treatment device.
Description
本発明は、水処理装置、超純水製造装置及び水処理方法に関する。
The present invention relates to a water treatment apparatus, an ultrapure water production apparatus, and a water treatment method.
一般に、市水、井水、地下水、工業用水等の原水から超純水を製造する超純水製造装置は、前処理装置、一次純水システム及び二次純水システムから構成されることが多い。このうち、前処理装置は、例えば、凝集沈殿装置、加圧浮上装置、ろ過装置等で構成され、原水中の濁質分を除去して前処理水とする。一次純水システムは、例えば、脱気装置、逆浸透膜装置、イオン交換装置、紫外線酸化装置等を組み合わせて構成され、前処理装置で処理して得られた前処理水中の有機物、イオン成分、溶存ガス等を除去して一次純水を製造する。また、二次純水システムは、例えば、紫外線酸化装置、混床式イオン交換装置及び限外ろ過装置等で構成され、一次純水システムで製造された一次純水中の微量不純物を処理して高純度の超純水を製造する。
In general, 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. . Among these, 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. In addition, 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.
近年、超純水に対しては、その純度の向上への要求が極めて高くなってきており、これに伴い全有機炭素(TOC)成分の除去が求められている。超純水中のTOC成分のうち、特に尿素は、分子量が小さくイオン化しにくいため、これを除去することが困難である。そのため、超純水中のTOC成分を低減するほど、TOC成分中における尿素の含有率が高くなる。そこで、超純水中のTOCを高度に低減するために、超純水製造装置に供給される水中から可能な限り尿素を除去することが求められる。
In recent years, there has been an extremely high demand for ultrapure water to improve its purity, and accordingly, removal of all organic carbon (TOC) components has been demanded. Of the TOC components in ultrapure water, urea is particularly difficult to remove because it has a low molecular weight and is difficult to ionize. Therefore, the urea content in the TOC component increases as the TOC component in the ultrapure water is reduced. Therefore, in order to reduce the TOC in ultrapure water to a high degree, it is required to remove urea as much as possible from the water supplied to the ultrapure water production apparatus.
特許文献1には、原水に尿素若しくは尿素誘導体、及び/又はアンモニア性の窒素源を添加した後、生物処理を行う尿素の除去方法が開示されている。
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.
しかしながら、尿素を添加して生物処理を行う方法では、その添加量の制御が困難なために、尿素が残留する場合がある。また、アンモニア性の窒素源を添加すると、このアンモニア性窒素が除去されないことがあり、超純水製造装置の下流側に配置される膜や樹脂の劣化を招くおそれがある。また、下流側にアンモニア性の窒素を除去するための装置を配置する必要が生じる等の理由で、超純水を製造するのに適さない場合がある。
However, in the method of performing biological treatment by adding urea, it may be difficult to control the amount added, so urea may remain. In addition, when an ammoniacal nitrogen source is added, this ammoniacal nitrogen may not be removed, and there is a risk of deteriorating a film or resin disposed on the downstream side of the ultrapure water production apparatus. Moreover, it may not be suitable for producing ultrapure water because, for example, an apparatus for removing ammonia nitrogen needs to be arranged on the downstream side.
本発明は、上記した課題を解決するためになされたものであって、水中の尿素を簡易かつ高度に除去することのできる水処理装置及び水処理方法を提供することを目的とする。
また、尿素を高度に除去して、TOC濃度の極めて低い高純度の超純水を簡易に得ることのできる超純水製造装置を提供することを目的とする。 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.
また、尿素を高度に除去して、TOC濃度の極めて低い高純度の超純水を簡易に得ることのできる超純水製造装置を提供することを目的とする。 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.
本発明の水処理装置は、原水を生物処理する水処理装置であって、アミノ基又は4級アンモニウム基が固定化された非水溶性のポリマーと、前記非水溶性のポリマーに接触した前記原水を処理するための生物活性炭とを備えることを特徴とする。
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.
本発明の水処理装置において、前記非水溶性ポリマーが4級アンモニウム基が固定化された非水溶性ポリマーであることが好ましい。
In the water treatment apparatus of the present invention, the water-insoluble polymer is preferably a water-insoluble polymer in which a quaternary ammonium group is immobilized.
本発明の水処理装置において、前記非水溶性のポリマーと前記生物活性炭は、混床式、又は前記生物活性炭の上流側に前記非水溶性のポリマーが積層された複床式で設けられることが好ましい。
In the water treatment apparatus of the present invention, 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.
本発明の水処理装置において、前記非水溶性のポリマーと前記生物活性炭の使用量は、前記非水溶性のポリマー/前記生物活性炭で表される体積比で、1/99~99/1であることが好ましい。
In the water treatment apparatus of the present invention, 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.
本発明の水処理装置において、前記非水溶性のポリマーが、前記アミノ基又は前記4級アンモニウム基をイオン交換基として有する、イオン交換繊維又はイオン交換樹脂であることが好ましい。
In the water treatment apparatus of the present invention, 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.
本発明の超純水製造装置は、本発明の水処理装置と、その下流側に設けられた、一次純水システム及び二次純水システムと、を備えることを特徴とする。
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.
本発明の水処理方法は、原水を、アミノ基又は4級アンモニウム基が固定化された非水溶性のポリマーに接触させる工程と、前記非水溶性のポリマーに接触された前記原水を生物活性炭によって処理する工程と、を備えることを特徴とする。
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.
本発明の水処理方法において、前記原水のpHが4~9であることが好ましい。
In the water treatment method of the present invention, the raw water preferably has a pH of 4 to 9.
本発明の水処理装置及び水処理方法によれば、水中の尿素を簡易かつ高度に除去することができる。
本発明の超純水製造装置によれば、尿素が高度に除去されるため、TOC濃度の極めて低い高純度の超純水を簡易に得ることができる。 According to the water treatment apparatus and the water treatment method of the present invention, urea in water can be easily and highly removed.
According to the ultrapure water production apparatus of the present invention, urea is highly removed, so that high purity ultrapure water having a very low TOC concentration can be easily obtained.
本発明の超純水製造装置によれば、尿素が高度に除去されるため、TOC濃度の極めて低い高純度の超純水を簡易に得ることができる。 According to the water treatment apparatus and the water treatment method of the present invention, urea in water can be easily and highly removed.
According to the ultrapure water production apparatus of the present invention, urea is highly removed, so that high purity ultrapure water having a very low TOC concentration can be easily obtained.
以下、図面を参照して、本発明の実施形態を詳細に説明する。
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(水処理装置)
図1は、本実施形態の水処理装置1を概略的に示すブロック図である。水処理装置1は、原水Wを貯留して供給する貯留槽10と、生物処理を行う生物処理装置20を備えている。生物処理装置20には、アミノ基又は4級アンモニウム基を固定化した非水溶性のポリマー(アミノ基又は4級アンモニウム基固定化ポリマー)(AP)と生物活性炭(BAC)の混合された混床が充填されている。この貯留槽10に貯留された原水Wは、生物処理装置20で処理されて、その後、例えば、一次純水システム、さらには二次純水システムに供給されて純水又は超純水が製造される。 (Water treatment equipment)
FIG. 1 is a block diagram schematically showing awater 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
図1は、本実施形態の水処理装置1を概略的に示すブロック図である。水処理装置1は、原水Wを貯留して供給する貯留槽10と、生物処理を行う生物処理装置20を備えている。生物処理装置20には、アミノ基又は4級アンモニウム基を固定化した非水溶性のポリマー(アミノ基又は4級アンモニウム基固定化ポリマー)(AP)と生物活性炭(BAC)の混合された混床が充填されている。この貯留槽10に貯留された原水Wは、生物処理装置20で処理されて、その後、例えば、一次純水システム、さらには二次純水システムに供給されて純水又は超純水が製造される。 (Water treatment equipment)
FIG. 1 is a block diagram schematically showing a
生物活性炭は、活性炭に微生物を担持させたものであり、生物処理を行うために用いられる。一般的に有機物は、生物処理を行う微生物(菌体)により酸素呼吸・硝酸呼吸・発酵過程等で分解されて、ガス化されるか、微生物の体内に取り込まれ、汚泥として除去される。また、生物処理によって、窒素(硝化脱窒法)やりん(生物学的リン除去法)の除去処理もできる。このような微生物による水処理を一般に生物処理という。
Biological activated carbon is obtained by carrying microorganisms on activated carbon and is used for biological treatment. In general, 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. Furthermore, nitrogen (nitrification denitrification method) and phosphorus (biological phosphorus removal method) can be removed by biological treatment. Such water treatment with microorganisms is generally called biological treatment.
生物活性炭は、例えば、次のように準備される。微生物を含む汚泥に、微生物の栄養源となる、炭素源、リン、微量金属、無機塩を添加する。さらに必要に応じて、酸素を吹き込み、好気処理を行う。これにより、微生物を培養することができる。この、微生物の培養された活性汚泥に、活性炭を浸漬する。これにより、微生物が活性炭の有する細孔内に担持されて生物活性炭が作製される。通常、この生物活性炭にTOC成分を含有する水を通水すると、生物活性炭に担持された微生物の上記作用で生物処理が行われて、水中のTOC成分が除去される。このような生物処理に際しては、微生物の活性を維持するため、必要に応じて上記微生物の栄養源を供給する水に添加することが行われる。
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.
この際、活性汚泥に栄養源としてアンモニア性窒素を添加することで、硝化菌群(アンモニア酸化菌群)を優占化させた硝化菌汚泥を得ることができる。これは、硝化菌群以外の微生物がアンモニア性窒素の存在下で増殖しにくい一方で、アンモニア耐性を有する硝化菌群が増殖するためであると考えられる。尿素またはアンモニア性窒素以外の添加物の物質および量については、通常硝化菌培養に使用される物質および量でよい。
At this time, by adding ammoniacal nitrogen as a nutrient source to the activated sludge, a 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.
例えば、上記で得られる硝化菌汚泥に活性炭を浸漬することで、硝化菌群を担持させた生物活性炭を得ることができる。硝化菌群は、尿素を代謝するため、硝化菌を担持させた生物活性炭により生物処理を行うことで水中の尿素が除去される。
For example, 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.
生物処理装置20において使用される生物活性炭は、その全量が、活性炭を活性汚泥に浸漬して得られたものでもよく、活性汚泥に浸漬して得られた生物活性炭と、浸漬処理していない活性炭とが混合されたものでもよいが、これらの方法に限定されるものではない。
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. However, the present invention is not limited to these methods.
生物活性炭における硝化菌群の担持量は、尿素の除去率を指標として表わすことができる。生物活性炭としては、尿素を好ましくは0.02μg/L以下、より好ましくは0.005μg/L以下まで低減可能なものが好適である。
The amount of nitrifying bacteria supported on biological activated carbon can be expressed by using the urea removal rate as an index. As the biological activated carbon, those capable of reducing urea to 0.02 μg / L or less, more preferably 0.005 μg / L or less are suitable.
生物活性炭に用いられる活性炭としては、特に限定されず、石炭、ヤシ殻、木炭等を原料として製造されたものが挙げられる。活性炭の形状についても特に限定されず、例えば、繊維状、ハニカム状、円柱状、破砕状、粒状、粉末状、ペレット状等のものを使用することができる。なかでも、微生物を担持し易い点で、粒状又は破砕状の活性炭が好ましい。粒状又は破砕状の活性炭の活性炭を用いる場合、その粒度は、0.35~2.0mmが好ましく、0.42~1.7mmがより好ましい。活性炭の粒度は、例えば、JIS標準篩等によって測定することができる。
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. 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. Of these, granular or crushed activated carbon is preferable in that it easily supports microorganisms. In the case of using granular or crushed activated carbon, 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.
アミノ基又は4級アンモニウム基固定化ポリマーは、アミノ基又は4級アンモニウム基を固定化した非水溶性のポリマーである。本発明のアミノ基又は4級アンモニウム基固定化ポリマーにおいて、アミノ基とは、1級~3級アミンを構成するアミノ基を意味し、さらにこれらがイオン化してアンモニウムイオンを形成した基を含むものとする。アミノ基又は4級アンモニウム基固定化ポリマーとして使用されるポリマーは、アミノ基又は4級アンモニウム基を固定化可能であるとともに、非水溶性のポリマーであれば特に限定されない。このポリマーとして、例えば、スチレン・ジビニルベンゼン共重合体やポリビニルアルコール系、アセテート等のセルロース系、ポリメタクリロニトリルやポリアクリロニトリル等のアクリル系、ポリ塩化ビニルやポリ塩化ビニリデン等の塩化ビニル系、ナイロン等のポリアミド系、ポリウレタンなどウレタン系の各種のポリマーを使用することができる。ポリマーの形態についても特に限定されず、樹脂状、繊維状、膜状、ブロック状等の種々の形態で使用することができる。アミノ基又は4級アンモニウム基固定化ポリマーは1種を単独で用いてもよく2種以上を併用してもよい。
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. In the amino group or quaternary ammonium group-immobilized polymer of the present invention, 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. Examples of this polymer 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. As 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.
アミノ基としては1級~3級アミンを構成するアミノ基又は4級アンモニウム基のいずれであってもよい。アミノ基又は4級アンモニウム基固定化ポリマーの有するアミノ基又は4級アンモニウム基は1種であってもよく、複数種であってもよい。ここで、1級~3級アミンを構成するアミノ基は、それぞれ、-NH2、-NHR、-NR2で表される基であり、4級アンモニウム基は、-N+R3で表される基である(式中、Rはそれぞれ同一であっても異なってもよい、置換または非置換のアルキル基又は置換または非置換のヒドロキシアルキル基である。)。
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. Here, 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. Wherein R is a substituted or unsubstituted alkyl group or a substituted or unsubstituted hydroxyalkyl group, each of which may be the same or different.
硝化菌による尿素除去能を向上させる点では、4級アンモニウム基が特に優れており、次いで、-NR2、-NHR、-NH2の順である。アミノ基又は4級アンモニウム基固定化ポリマーにおけるアミノ基又は4級アンモニウム基の固定化方法は、例えば、ポリマー骨格上にアミノ基又は4級アンモニウム基が結合したものが挙げられ、具体的にはポリマーの主鎖又は分岐を構成する炭素原子等にアミノ基又は4級アンモニウム基が結合したものが好ましい。尿素除去性能をより向上させるために、分岐を構成する炭素原子等にアミノ基又は4級アンモニウム基が結合したものが、より好ましい。
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. In order to further improve the urea removal performance, 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.
上記したアミノ基及び4級アンモニウム基における置換基Rとしては、例えば、メチル基、エチル基、ブチル基等のアルキル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシブチル基等のヒドロキシアルキル基が挙げられる。
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. .
アミノ基又は4級アンモニウム基を固定化するポリマーとして具体的には、上記アミノ基又は4級アンモニウム基をイオン交換基として有するイオン交換繊維やイオン交換樹脂を使用することが好ましい。これらは、内部に広い表面積を持つため、処理対象水との接触面積を大きくすることができる。また、単位容量あたりのアミノ基又は4級アンモニウム基の量が多い。これらにより尿素の除去効率を向上させることができる。さらに、溶出物が少ないため、処理水の水質に悪影響を与えない。したがって、超純水の製造等、不純物を高度に除去する目的で好適に使用される。
Specifically, 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.
アミノ基又は4級アンモニウム基固定化ポリマーが有する上記アミノ基又は4級アンモニウム基の量は、アミノ基又は4級アンモニウム基固定化ポリマーの単位容量当たりの官能基量(総交換容量)で、0.01当量/L(eq/L)~10当量/L(eq/L)が好ましく、0.5当量/L(eq/L)~5当量/L(eq/L)がより好ましい。アミノ基又は4級アンモニウム基の量が0.01当量/L(eq/L)以上であれば、硝化菌群の菌相が良好に維持されて、尿素除去能を向上させることができる。アミノ基又は4級アンモニウム基の量が10当量/L(eq/L)以下であることで、アミノ基又は4級アンモニウム基固定化ポリマーの安定性に優れる。
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. If 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. When 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.
イオン交換樹脂としては、ゲル型イオン交換樹脂、ゲル型イオン交換樹脂に孔径100~1000オングストロームのマクロポアーを形成したポーラス型イオン交換樹脂、ポーラス型イオン交換樹脂より微細な孔を持つ高多孔性のハイポーラス型イオン交換樹脂が挙げられる。単位容量あたりのアミノ基の量を多くできるので、ポーラス型あるはハイポーラス型のイオン交換樹脂であることがより好ましい。
Examples of the ion exchange resin 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.
また、イオン交換樹脂としては、スチレン・ジビニルベンゼン共重合体又はアクリル系のポリマーを樹脂骨格として、トリメチルアンモニウム基(-N+(CH3)3)、ジメチルヒドロキシエチルアンモニウム基(-N+(CH3)2(C2H5OH))等の4級アンモニウム基をイオン交換基として有する強塩基性陰イオン交換樹脂、及びメチルアミノ基、ジメチルアミノ基等のアミノ基や-NH-(C2H4NH)nHで表されるポリアミン型イオン交換基などを有する弱塩基性陰イオン交換樹脂が挙げられる。イオン交換繊維としては、ポリビニルアルコール系の繊維に上記アミノ基又は4級アンモニウム基の結合した塩基性陰イオン交換繊維等を使用することができる。
As the 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 ) A strongly basic anion exchange resin having a quaternary ammonium group as an ion exchange group such as 2 (C 2 H 5 OH)), an amino group such as a methylamino group or a dimethylamino group, and —NH— (C 2 Examples include weakly basic anion exchange resins having a polyamine type ion exchange group represented by H 4 NH) n H. As an ion exchange fiber, the basic anion exchange fiber etc. which the said amino group or the quaternary ammonium group couple | bonded with the fiber of polyvinyl alcohol can be used.
アミノ基又は4級アンモニウム基固定化ポリマーとして弱塩基性陰イオン交換樹脂又は強塩基性陰イオン交換樹脂を用いる場合、その水分含有量は35~65質量%であることが好ましく、40~50質量%であることがより好ましい。これにより、生物活性炭と混合して用いる場合に、微生物を保持し易くなる。
When a weakly basic anion exchange resin or a strongly basic anion exchange resin is used as the amino group or quaternary ammonium group-immobilized polymer, 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.
弱塩基性陰イオン交換樹脂としては、例えば、三菱化学株式会社製のダイヤイオンシリーズ(WA20、WA21J等)、ランクセス社製のレバチットシリーズ、DOW社製のデュオライトシリーズ等を使用することができる。強塩基性陰イオン交換樹脂としては、例えば、三菱化学株式会社製のダイヤイオンシリーズ(SA10A、SA20A)、ランクセス社製のレバチットシリーズ、DOW社製のデュオライトシリーズ等を使用することができる。
As the weakly basic anion exchange resin, for example, Diaion series (WA20, WA21J, etc.) manufactured by Mitsubishi Chemical Corporation, Levacit series manufactured by LANXESS, Duolite series manufactured by DOW, etc. can be used. . As 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.
弱塩基イオン交換繊維としては、例えば、ニチビ社製のEF-SA-WA、強塩基イオン交換繊維としては、ニチビ社製のIEF-SA等を使用することができる。
As 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.
なお、使用可能なイオン交換樹脂やイオン交換繊維は、上記に記載された種類に限定されない。また、イオン交換樹脂を用いる場合、イオン交換樹脂は、新品のイオン交換樹脂でもよく、使用済みのもの、例えば、純水製造装置内で長期間使用したイオン交換樹脂を使用してもよい。
Note that usable ion exchange resins and ion exchange fibers are not limited to the types described above. When using an ion exchange resin, 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.
アミノ基又は4級アンモニウム基固定化ポリマーとしては、なかでも、イオン交換基として4級アンモニウム基を有する強塩基性陰イオン交換樹脂が好ましい。
As the amino group or quaternary ammonium group-immobilized polymer, a strong basic anion exchange resin having a quaternary ammonium group as an ion exchange group is particularly preferable.
アミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭の混床を得る方法は特に限定されず、上記で準備された生物活性炭とアミノ基又は4級アンモニウム基固定化ポリマーを容器に収容した後、上向流で通水して混合する方法や、ミキサー等によって混合する方法で作製することができる。また、活性炭とアミノ基又は4級アンモニウム基固定化ポリマーを混合した混床に、活性汚泥を用いて微生物を担持させる方法で作製することができる。硝化菌の優占化は、上記したように微生物に栄養源としてのアンモニア性窒素源を添加して行うが、これは、生物活性炭をアミノ基又は4級アンモニウム基固定化ポリマーと混合する前に行ってもよく、アミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭を混合した後に行ってもよい。また、あらかじめ硝化菌群の優占化された生物活性炭を用いてもよく、混床を作成してから硝化菌群を優占化させてもよい。
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 | supporting microorganisms using the activated sludge in the mixed bed which mixed activated carbon and the amino group or quaternary ammonium group fixed polymer. As described above, nitrifying bacteria are dominant by adding an ammoniacal nitrogen source as a nutrient source to microorganisms. This is done before mixing biological activated carbon with an amino group or quaternary ammonium group-immobilized polymer. It may be performed after mixing the amino group or quaternary ammonium group-immobilized polymer and the biological activated carbon. Moreover, you may use the biological activated carbon in which the nitrifying bacteria group was predominated previously, and after making a mixed bed, you may make the nitrifying bacteria group dominant.
アミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭の割合は、例えば、アミノ基又は4級アンモニウム基固定化ポリマー/生物活性炭で表される体積比が1/99~99/1の範囲で本発明の効果を得ることができるが、尿素の除去率をより高くする点では、1/9~9/1がより好ましく、3/7~7/3がさらに好ましい。
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. Although 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.
生物活性炭とアミノ基又は4級アンモニウム基固定化ポリマーの混床を例えば、処理対象水を供給する給水管及び処理水を排出する排出管を備えた水処理塔等に充填して、生物処理装置20を構成することができる。
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.
処理対象の原水Wとしては、地下水、河川水、市水、その他の工業用水、又は半導体工場や液晶工場等の使用済み超純水を回収した回収水が用いられる。回収水を用いる場合、これを、イオン交換処理又は中和処理して、pHを例えば後述する範囲に調製して用いることが好ましい。また、処理対象水は、これらの原水Wを、前処理システム又はこれと同様の装置で処理したものであってもよい。前処理システムは、例えば、凝集沈殿装置、加圧浮上装置、ろ過装置等により構成され、原水中の濁質分を除去する。
As 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. In the case of using 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. Further, 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.
原水W(処理対象水)中の尿素濃度は5~200μg/L、特に5~100μg/L程度が好適である。また、硝化菌群を優占化して尿素の除去率を上げるため、原水Wの溶存酸素濃度(DO)は5~8mg/Lであることが好ましい。
The urea concentration in the raw water W (treatment target water) is preferably about 5 to 200 μg / L, particularly about 5 to 100 μg / L. Further, in order to predominate the nitrifying bacteria group and increase the urea removal rate, the dissolved oxygen concentration (DO) of the raw water W is preferably 5 to 8 mg / L.
原水Wは、生物処理装置20に供給されて、ここで、尿素が除去される。生物処理装置20への通水方法に特に制限はなく、上向流方式、下向流方式のいずれであってもよい。菌による目詰まりが起こりにくい点では、上向流方式が好ましい。
Raw water W is supplied to the biological treatment apparatus 20 where urea is removed. There is no restriction | limiting in particular in the water flow method to the biological treatment apparatus 20, 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.
生物処理装置20への通水速度は、SV5~50hr-1程度とするのが好ましく、SV5~20hr-1がより好ましい。この生物処理装置20へ供給される処理対象水の水温は、微生物の活性を向上させる点で、常温付近、例えば10~35℃であることが好ましく、20~35℃程度がより好ましい。したがって、必要に応じて、生物処理装置20の前段に熱交換機を設けるのが好ましい。
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.
生物処理装置20へ供給される処理対象水のpHは、微生物の中でも硝化菌群を優占化させる点で、中性~弱アルカリ性、例えばpH4~9であることが好ましく、pH5~8であることがより好ましい。
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.
本実施形態の水処理装置1において、アミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭によって水中の尿素が低減される理由は次のように推測される。
In the water treatment apparatus 1 of the present embodiment, the reason why urea in water is reduced by the amino group or quaternary ammonium group-immobilized polymer and biological activated carbon is presumed as follows.
従来、硝化菌群により生物処理を行う場合、尿素を分解する硝化菌群の菌相を維持し、その他の菌を殺菌するために給水にアンモニア性窒素源を添加することが行われていた。生物処理装置20では、アミノ基又は4級アンモニウム基固定化ポリマーのアミノ基又は4級アンモニウム基が有するアンモニア性窒素が、水中に添加されるアンモニア性窒素と同様に作用すると考えられる。すなわち、アミノ基又は4級アンモニウム基固定化ポリマーに接触された水を生物活性炭に連続的に通水することで、アミノ基又は4級アンモニウム基固定化ポリマーの有するアンモニア性窒素の作用で、硝化菌群の菌相が維持されるとともに硝化菌群が優占化され、尿素の除去が行われると考えられる。
Conventionally, when biological treatment is performed with a nitrifying bacteria group, 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. In the biological treatment apparatus 20, it is considered that 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. That is, 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.
したがって、アミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭は必ずしも生物処理装置20のように混合されている必要はなく、アミノ基又は4級アンモニウム基固定化ポリマーに接触された原水Wが生物活性炭によって処理されれば、水処理装置1を用いるのと同様の効果を得ることができる。このような、水処理装置1以外の構成の水処理装置の例として、図2に示すようなアミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭を積層した複床を有する水処理装置2、及び図3に示すような、アミノ基又は4級アンモニウム基固定化ポリマーの単床と生物活性炭の単床をそれぞれ有する水処理装置3が挙げられる。
Therefore, 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. As an example of such 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.
水処理装置2は、アミノ基又は4級アンモニウム基固定化ポリマーと生物活性炭を上流側から下流側へこの順に積層した積層構造を有する生物処理装置21を備えている。水処理装置3は、アミノ基又は4級アンモニウム基固定化ポリマーを備える装置22と生物活性炭装置23に順に備えている。例えば、水処理装置2、3についても水処理装置1と同様の効果を得ることができる。
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. For example, the same effects as the water treatment apparatus 1 can be obtained for the water treatment apparatuses 2 and 3.
なお、上記で説明した各実施形態の水処理装置は、これにより長期間水処理を行った場合に、生物活性炭とアミノ基又は4級アンモニウム基固定化ポリマー、生物活性炭同士又はアミノ基又は4級アンモニウム基固定化ポリマー同士が相互に付着して塊が生じることがあり、この場合には、水による逆洗が行われるが、例えば、イオン交換樹脂やイオン交換繊維等を用いたイオン交換装置のように、酸やアルカリ等の薬剤によって再生する必要はない。
In addition, when the water treatment apparatus of each embodiment demonstrated above performs long-term water treatment by this, 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. In this case, backwashing with water is performed. For example, 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.
以上説明した実施形態の水処理装置によれば、アンモニア性窒素源等の薬剤を添加することなく、水中の尿素を高度に除去することができる。また、アンモニア性窒素源を添加した水を生物活性炭で処理する方法では、生物活性炭への通水開始から尿素の除去率が安定するまでの立ち上げに長期間が必要であるが、実施形態の水処理装置によれば、立ち上げ期間を短縮することができる。
According to the water treatment apparatus of the embodiment described above, 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.
(超純水製造装置)
次に、上記した実施形態の水処理装置を備える超純水製造装置について説明する。図4は、実施形態の超純水製造装置4を概略的に示すブロック図である。超純水製造装置4は、水処理装置1(水処理装置2又は水処理装置3でもよい。)の下流側に、一次純水システム41と二次純水システム42を備えている。 (Ultra pure water production equipment)
Next, an ultrapure water production apparatus provided with the water treatment apparatus of the above-described embodiment will be described. 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 primarypure 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).
次に、上記した実施形態の水処理装置を備える超純水製造装置について説明する。図4は、実施形態の超純水製造装置4を概略的に示すブロック図である。超純水製造装置4は、水処理装置1(水処理装置2又は水処理装置3でもよい。)の下流側に、一次純水システム41と二次純水システム42を備えている。 (Ultra pure water production equipment)
Next, an ultrapure water production apparatus provided with the water treatment apparatus of the above-described embodiment will be described. 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
一次純水システム41は、例えば、イオン交換装置、逆浸透膜装置、脱気装置、紫外線酸化装置、再生型混床式イオン交換装置を組み合わせて構成される。一次純水システム41では、上記実施形態の水処理装置1で尿素が除去された処理水から、イオン交換装置としての陰イオン交換装置及び陽イオン交換装置の組合せによって不純物イオンが除去され、逆浸透膜装置によって無機イオン、有機物、微粒子等が除去される。さらに、脱気装置により溶存酸素や溶存炭酸などの溶存ガスが除去される。残存する有機物が紫外線酸化装置で分解除去された後、再生型混床式イオン交換装置によって微量のイオン成分が除去されて一次純水が製造される。一次純水は、例えば、TOC濃度は10μgC/L以下、比抵抗率が17MΩ・cm以上である。
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. In the primary pure water system 41, 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. Further, dissolved gas such as dissolved oxygen and dissolved carbonic acid is removed by the deaeration device. After the remaining organic matter is decomposed and removed by the ultraviolet oxidizer, a trace amount of ion components are removed by the regenerative mixed bed ion exchanger to produce primary pure water. The primary pure water has, for example, a TOC concentration of 10 μg C / L or less and a specific resistivity of 17 MΩ · cm or more.
二次純水システム42は、一次純水中の微量有機物や微量微粒子を除去する装置であり、紫外線酸化装置、膜脱気装置、非再生型混床式イオン交換装置、限外ろ過装置を組み合わせて構成される。これにより得られる超純水は、例えば、TOC濃度が5μgC/L以下、比抵抗率が17.5MΩ・cm以上、尿素濃度が5μg/L以下まで低減される。
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 μg C / L or less, a specific resistivity of 17.5 MΩ · cm or more, and a urea concentration of 5 μg / L or less.
以上説明した実施形態の超純水製造装置によれば、処理対象水にアンモニア性窒素源等の薬剤を添加することなく、水中の尿素を高度に除去することができるため、TOC濃度の極めて低い超純水を簡易に得ることができる。また、一次純水システム41の上流側において、処理対象水にアンモニア性窒素源を添加し、その後、生物活性炭で処理する方法に比べて、生物処理装置の立ち上げ期間を短縮することができるため、原水の無駄がなく、効率的に超純水を製造することができる。
According to the ultrapure water production apparatus of the embodiment described above, 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.
(実施例1)
活性汚泥に、尿素を2mg/L、アンモニア50mg/Lを添加し、30日間静置して、硝化菌汚泥を馴養した。得られた硝化菌汚泥の尿素除去能を、尿素含有水を用いて測定したところ、尿素を0.02mg/Lまで除去可能であった。 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.
活性汚泥に、尿素を2mg/L、アンモニア50mg/Lを添加し、30日間静置して、硝化菌汚泥を馴養した。得られた硝化菌汚泥の尿素除去能を、尿素含有水を用いて測定したところ、尿素を0.02mg/Lまで除去可能であった。 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.
この硝化菌汚泥に、活性炭(ダイヤホープM006、カルゴンカーボンジャパン社製、粒状活性炭、粒径0.425~1.7mm)の300mLを7日間浸漬して、その後取り出し、生物活性炭を得た。この生物活性炭の300mLに、強塩基性陰イオン交換樹脂(ダイヤイオンSA10A、三菱化学株式会社製、4級アンモニウム基量1.3モル/L以上)の100mLを混合して混床を作製した。混合比は、[強塩基性陰イオン交換樹脂/生物活性炭]で示される体積比で、1/3である。
In this nitrifying sludge, 300 mL of activated carbon (Diahope M006, Calgon Carbon Japan, granular activated carbon, particle size 0.425 to 1.7 mm) was immersed for 7 days, and then taken out to obtain biological activated carbon. To 300 mL of this biological activated carbon, 100 mL of strongly basic anion exchange resin (Diaion SA10A, manufactured by Mitsubishi Chemical Corporation, quaternary ammonium group amount 1.3 mol / L or more) was mixed to prepare a mixed bed. The mixing ratio is 1/3 in volume ratio shown by [strongly basic anion exchange resin / biological activated carbon].
得られた混床を内径25mmのカラムに充填し、処理対象水として厚木市市水から塩素を除去して尿素を添加した水(溶存酸素濃度5~6mg/L、pH=6~7、尿素濃度10~20μg/L)を、SV=10h-1で通水した。
The obtained mixed bed was packed in a column with an inner diameter of 25 mm, and water was removed from the water of Atsugi City as the water to be treated, and urea was added (dissolved oxygen concentration 5-6 mg / L, pH = 6-7, urea Concentration 10-20 μg / L) was passed through with SV = 10 h −1 .
カラムから得られた処理水中の尿素濃度を測定し、通水開始時を0日として、尿素除去率の経時変化を調べた。結果を図5のグラフに実線で示す。なお、尿素除去率は、下記式によって算出した。水温は、調節せず成り行きで通水した。通水試験の間の水温は24~26℃であった。後述の各実施例及び比較例の水温についても同様である。
尿素除去率=[1-(処理水中の尿素濃度/処理対象水中の尿素濃度)]×100(%) 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 (%)
尿素除去率=[1-(処理水中の尿素濃度/処理対象水中の尿素濃度)]×100(%) 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 (%)
また、実施例1において、350日通水後にカラムから、使用後の強塩基性陰イオン交換樹脂を取出し、交換容量を測定したところ、初期の交換容量の95%であった。このことから、イオン交換樹脂がアンモニウムイオンの供給源となっていないことが確認された。また、アンモニウム基が減少していないことから、さらに通水を継続した場合にも、継続的に高い尿素除去率が維持されると予測できる。
Further, in 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.
(比較例1)
強塩基性陰イオン交換樹脂を混合しない点、生物活性炭の使用量を増やした点以外は実施例1と同様に作製した生物活性炭をカラムに充填し、実施例1と同様の処理対象水に、アンモニアを濃度が0.5mg/Lとなるように添加して、実施例1と同様の条件でカラムに通水した。実施例1と同様に、尿素除去率の経時変化を調べた。結果を実施例1とあわせて図5のグラフに破線で示す。 (Comparative 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.
強塩基性陰イオン交換樹脂を混合しない点、生物活性炭の使用量を増やした点以外は実施例1と同様に作製した生物活性炭をカラムに充填し、実施例1と同様の処理対象水に、アンモニアを濃度が0.5mg/Lとなるように添加して、実施例1と同様の条件でカラムに通水した。実施例1と同様に、尿素除去率の経時変化を調べた。結果を実施例1とあわせて図5のグラフに破線で示す。 (Comparative 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.
(実施例2)
活性炭の使用量は300mLのままで、強塩基性陰イオン交換樹脂/生物活性炭で示される体積比を1/1とした他は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に85%を超え、50日後には100%となった。 (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.
活性炭の使用量は300mLのままで、強塩基性陰イオン交換樹脂/生物活性炭で示される体積比を1/1とした他は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に85%を超え、50日後には100%となった。 (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.
(実施例3)
活性炭の使用量は300mLのままで、強塩基性陰イオン交換樹脂/生物活性炭で示される体積比を1/8とした他は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に80%を超え、50日後には90%となり、以降、尿素の除去率は安定して推移した。 (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.
活性炭の使用量は300mLのままで、強塩基性陰イオン交換樹脂/生物活性炭で示される体積比を1/8とした他は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に80%を超え、50日後には90%となり、以降、尿素の除去率は安定して推移した。 (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.
(実施例4)
活性炭の使用量は300mLのままで、強塩基性陰イオン交換樹脂/生物活性炭で示される体積比を1/99とした他は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に75%を超え、50日後には88%となり、以降、尿素の除去率は安定して推移した。 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.
活性炭の使用量は300mLのままで、強塩基性陰イオン交換樹脂/生物活性炭で示される体積比を1/99とした他は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に75%を超え、50日後には88%となり、以降、尿素の除去率は安定して推移した。 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.
(実施例5)
強塩基性陰イオン交換樹脂の代わりに弱塩基性陰イオン交換樹脂(ダイヤイオンWA30、三菱化学株式会社製、アミノ基量1.5モル/L以上)を使用した以外は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に95%を超え、50日後には99%となり、以降、尿素の除去率は安定して推移した。 (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.
強塩基性陰イオン交換樹脂の代わりに弱塩基性陰イオン交換樹脂(ダイヤイオンWA30、三菱化学株式会社製、アミノ基量1.5モル/L以上)を使用した以外は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に95%を超え、50日後には99%となり、以降、尿素の除去率は安定して推移した。 (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.
(実施例6)
実施例1と同様の強塩基性陰イオン交換樹脂と生物活性炭を用い、生物活性炭の使用量は300mLのままで、混合比を、強塩基性陰イオン交換樹脂/生物活性炭(体積比)で、3/1にした以外は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率の推移は、実施例1(図5の実線)と同様であった。 (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).
実施例1と同様の強塩基性陰イオン交換樹脂と生物活性炭を用い、生物活性炭の使用量は300mLのままで、混合比を、強塩基性陰イオン交換樹脂/生物活性炭(体積比)で、3/1にした以外は、実施例1と同様にして、混床を作製した。この混床を用いて、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率の推移は、実施例1(図5の実線)と同様であった。 (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).
(実施例7)
実施例1と同様の強塩基性陰イオン交換樹脂と生物活性炭を、混合せずに、強塩基性陰イオン交換樹脂の上方に生物活性炭を積層した(処理対象水に対して強塩基性陰イオン交換樹脂が上流側、生物活性炭が下流側)他は実施例1と同様にして複床を作製した。この複床に、処理対象水を上向流で通水した以外は、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率の推移は、実施例1(図5の実線)と同様であった。 (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).
実施例1と同様の強塩基性陰イオン交換樹脂と生物活性炭を、混合せずに、強塩基性陰イオン交換樹脂の上方に生物活性炭を積層した(処理対象水に対して強塩基性陰イオン交換樹脂が上流側、生物活性炭が下流側)他は実施例1と同様にして複床を作製した。この複床に、処理対象水を上向流で通水した以外は、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率の推移は、実施例1(図5の実線)と同様であった。 (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).
(比較例2)
実施例1と同様の強塩基性陰イオン交換樹脂100mLを硝化菌汚泥に7日間浸漬した後、取出して、カラムに充填し、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に30%を超え、50日後には45%となり、以降、尿素の除去率は安定して推移した。 (Comparative 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.
実施例1と同様の強塩基性陰イオン交換樹脂100mLを硝化菌汚泥に7日間浸漬した後、取出して、カラムに充填し、実施例1と同様の条件で、尿素の除去率の測定を行った。本例では、尿素除去率が、通水30日後に30%を超え、50日後には45%となり、以降、尿素の除去率は安定して推移した。 (Comparative 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.
各実施例及び比較例の結果より、実施形態の水処理装置によれば、アンモニア性窒素源等の薬剤を添加することなく、水中の尿素を高度に除去することができることが分かる。また、図5より、実施形態の水処理装置によれば、アンモニア性窒素源を添加した水を生物活性炭で処理する方法に比べて、生物活性炭への通水開始から尿素の除去率が安定するまでの立ち上げ期間を短縮することができることが分かる。
From the results of the examples and comparative examples, it can be seen that according to the water treatment apparatus of the embodiment, urea in water can be highly removed without adding a chemical such as an ammoniacal nitrogen source. Moreover, according to the water treatment apparatus of embodiment from FIG. 5, compared with the method of processing the water which added ammonia nitrogen source with biological activated carbon, 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.
1,2,3…水処理装置、4…超純水製造装置、10…貯留槽、20,21…生物処理装置、22…アミノ基又は4級アンモニウム基固定化ポリマーを備える装置、23…生物活性炭装置、41…一次純水システム、42…二次純水システム。
DESCRIPTION OF SYMBOLS 1, 2, 3 ... Water treatment apparatus, 4 ... Ultrapure water manufacturing apparatus, 10 ... Reservoir, 20, 21 ... Biological treatment apparatus, 22 ... Apparatus provided with an amino group or quaternary ammonium group fixed polymer, 23 ... Biology Activated carbon device, 41 ... primary pure water system, 42 ... secondary pure water system.
Claims (8)
- 原水を生物処理するための水処理装置であって、
アミノ基又は4級アンモニウム基が固定化された非水溶性のポリマーと、
前記非水溶性のポリマーに接触した前記原水を処理するための生物活性炭と、
を備えることを特徴とする水処理装置。 A water treatment device for biologically treating raw water,
A water-insoluble polymer having an amino group or quaternary ammonium group immobilized thereon;
Biological activated carbon for treating the raw water in contact with the water-insoluble polymer;
A water treatment apparatus comprising: - 前記非水溶性ポリマーが4級アンモニウム基が固定化された非水溶性のポリマーであることを特徴とする請求項1記載の水処理装置。 2. The water treatment apparatus according to claim 1, wherein the water-insoluble polymer is a water-insoluble polymer having a quaternary ammonium group immobilized thereon.
- 前記非水溶性のポリマーと前記生物活性炭は、
混床式、又は前記生物活性炭の上流側に前記非水溶性のポリマーが積層された複床式で設けられることを特徴とする請求項1又は2に記載の水処理装置。 The water-insoluble polymer and the biological activated carbon are
3. The water treatment apparatus according to claim 1, wherein the water treatment apparatus is provided in a mixed bed type or a double bed type in which the water-insoluble polymer is laminated on the upstream side of the biological activated carbon. - 前記非水溶性のポリマーと前記生物活性炭の使用量は、前記非水溶性のポリマー/前記生物活性炭で表される体積比で、1/99~99/1であることを特徴とする請求項1乃至3のいずれか1項に記載の水処理装置。 2. The use amount of the water-insoluble polymer and the biological activated carbon is 1/99 to 99/1 in a volume ratio represented by the water-insoluble polymer / the biological activated carbon. The water treatment apparatus of any one of thru | or 3.
- 前記非水溶性のポリマーが、前記アミノ基又は前記4級アンモニウム基をイオン交換基として有する、イオン交換繊維又はイオン交換樹脂であることを特徴とする請求項1乃至4のいずれか1項に記載の水処理装置。 The water-insoluble polymer is an ion exchange fiber or an ion exchange resin having the amino group or the quaternary ammonium group as an ion exchange group. Water treatment equipment.
- 請求項1乃至5のいずれか1項に記載の水処理装置と、
その下流側に設けられた、一次純水システム及び二次純水システムと、を備えることを特徴とする超純水製造装置。 The water treatment device according to any one of claims 1 to 5,
An ultrapure water production apparatus comprising a primary pure water system and a secondary pure water system provided on the downstream side thereof. - 原水を、アミノ基又は4級アンモニウム基が固定化された非水溶性のポリマーに接触させる工程と、
前記非水溶性のポリマーに接触された前記原水を、生物活性炭によって処理する工程と、
を備えることを特徴とする水処理方法。 Contacting the raw water with a water-insoluble polymer having an amino group or quaternary ammonium group immobilized thereon;
Treating the raw water contacted with the water-insoluble polymer with biological activated carbon;
A water treatment method comprising: - 前記原水のpHが4~9であることを特徴とする請求項7に記載の水処理方法。 The water treatment method according to claim 7, wherein the pH of the raw water is 4 to 9.
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