TW201841837A - Ultrapure water production system and ultrapure water production method - Google Patents
Ultrapure water production system and ultrapure water production method Download PDFInfo
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- TW201841837A TW201841837A TW107112998A TW107112998A TW201841837A TW 201841837 A TW201841837 A TW 201841837A TW 107112998 A TW107112998 A TW 107112998A TW 107112998 A TW107112998 A TW 107112998A TW 201841837 A TW201841837 A TW 201841837A
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- 229910021642 ultra pure water Inorganic materials 0.000 title claims abstract description 78
- 239000012498 ultrapure water Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 59
- 229910052796 boron Inorganic materials 0.000 claims abstract description 177
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 176
- 239000011347 resin Substances 0.000 claims abstract description 163
- 229920005989 resin Polymers 0.000 claims abstract description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 145
- 238000001179 sorption measurement Methods 0.000 claims abstract description 128
- 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 abstract description 91
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 71
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 71
- 238000005349 anion exchange Methods 0.000 claims abstract description 46
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 42
- 230000001172 regenerating effect Effects 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 69
- 238000005342 ion exchange Methods 0.000 claims description 47
- 230000001590 oxidative effect Effects 0.000 claims description 42
- 238000001223 reverse osmosis Methods 0.000 claims description 37
- 238000005341 cation exchange Methods 0.000 claims description 29
- 239000003729 cation exchange resin Substances 0.000 claims description 22
- 238000002242 deionisation method Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 38
- 238000000354 decomposition reaction Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical group CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- -1 carboxylic acid compound Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009296 electrodeionization Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- OBSLWIKITOYASJ-YDEIVXIUSA-N (3r,4r,5s,6r)-6-(hydroxymethyl)-3-(methylamino)oxane-2,4,5-triol Chemical group CN[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O OBSLWIKITOYASJ-YDEIVXIUSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 102100035925 DNA methyltransferase 1-associated protein 1 Human genes 0.000 description 2
- 101000930289 Homo sapiens DNA methyltransferase 1-associated protein 1 Proteins 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002349 well water Substances 0.000 description 2
- 235000020681 well water Nutrition 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—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
- 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
- B01J41/08—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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
本發明係關於超純水製造系統及超純水製造方法。The invention relates to an ultrapure water production system and an ultrapure water production method.
以往，在半導體製造製程所使用的超純水係使用超純水製造系統來製造。超純水製造系統，係以一次純水系統及二次純水系統所構成，該一次純水系統是使用去除例如原水中的懸浮物質的前處理裝置、使用逆滲透膜裝置、離子交裝置等去除前處理水中的總有機碳(TOC)成分、離子成分等者，該二次純水系統是去除一次純水中的極微量之雜質者。作為原水，除了可使用自來水、井水、地下水、工業用水等以外，還能使用在點置系統(POU：Point Of Use)被回收的使用完畢的超純水(以下稱為[回收水])。Conventionally, ultrapure water systems used in semiconductor manufacturing processes have been manufactured using ultrapure water manufacturing systems. The ultrapure water manufacturing system is composed of a primary pure water system and a secondary pure water system. The primary pure water system is a pretreatment device that removes, for example, suspended substances in raw water, a reverse osmosis membrane device, and an ion exchange device. Those who remove total organic carbon (TOC) components, ionic components, etc. in the pre-treated water, and this secondary pure water system is one which removes a very small amount of impurities in the primary pure water. As raw water, in addition to tap water, well water, groundwater, industrial water, etc., it is also possible to use ultra-pure water (hereinafter referred to as [recycled water]) that has been recycled in a Point of Use (POU) system. .
關於超純水，對於高純度化的要求逐年提高，關於各種雜質濃度，也逐漸被要求去除到例如ng/L(ppt)目。因此，例如，在減低TOC的目的上，進行以下的情事，亦即，將分解TOC成分的紫外線氧化裝置(TOC-UV)與吸附去除殘留於紫外線氧化裝置的處理水中的低分子量之有機酸、二氧化碳等之混床式離子交換樹脂裝置之組合分別設在一次純水系統及二次純水系統(例如，參照專利文獻1)。With regard to ultrapure water, the requirements for high purity have been increasing year by year, and various impurity concentrations have also been required to be removed to, for example, the ng / L (ppt) mesh. Therefore, for the purpose of reducing TOC, for example, the following cases have been performed, that is, the ultraviolet oxidation device (TOC-UV) that decomposes TOC components and the adsorption and removal of low molecular weight organic acids remaining in the treated water of the ultraviolet oxidation device, The combination of a mixed bed type ion exchange resin device such as carbon dioxide is provided in a primary pure water system and a secondary pure water system (for example, refer to Patent Document 1).
又，被要求減低作為極微量的雜質例如硼。因此，在提升去除硼能力的目的上，提案有採用硼選擇性離子交換樹脂與混床式離子交換樹脂層積或混合而填充的離子交換樹脂塔之超純水製造系統(例如，參照專利文獻2)。In addition, it is required to reduce impurities such as boron as a very small amount. Therefore, for the purpose of improving the boron removal capability, an ultrapure water production system using an ion exchange resin column that is laminated or filled with a boron selective ion exchange resin and a mixed-bed ion exchange resin has been proposed (for example, refer to Patent Literature) 2).
又，含於紫外線氧化裝置的處理水中之低分子量的有機酸等會阻礙在硼選擇性離子交換樹脂的硼之吸附，造成硼去除能力早期降低。為了防止這種的缺失，在維持長期間優良的硼去除能力的目的上，亦提案有將硼選擇性離子交換樹脂與陰離子交換樹脂混合的混床式離子交換樹脂(以下亦稱為[硼吸附樹脂混合離子交換樹脂])之超純水製造系統(例如參照專利文獻3)。 [先前技術文獻] [專利文獻]In addition, low molecular weight organic acids and the like contained in the treated water of the ultraviolet oxidation device hinder the adsorption of boron in the boron selective ion exchange resin, resulting in an early reduction in boron removal ability. In order to prevent this deficiency, a mixed-bed ion exchange resin (hereinafter also referred to as "boron adsorption" Resin mixed ion exchange resin]) ultra-pure water production system (see, for example, Patent Document 3). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開2004-025184號公報 [專利文獻2]日本特開平8-84986號公報 [專利文獻3]日本特開2016-047496號公報[Patent Document 1] Japanese Patent Application Publication No. 2004-025184 [Patent Document 2] Japanese Patent Application Publication No. 8-84986-[Patent Document 3] Japanese Patent Application Publication No. 2016-047496
[發明所欲解決的課題][Problems to be Solved by the Invention]
但，依據本發明者們的研究檢討發現，在將硼吸附樹脂混合離子交換樹脂配置於紫外線氧化裝置的後段之情況，在紫外線氧化裝置因過量的紫外線照射所產生的過氧化氫會分解硼吸附樹脂混合離子交換樹脂，造成低分子量的有機物大量溶出，下游側的水處理裝置之TOC去除負載變高。且，亦得知在此情況，設置於硼吸附樹脂混合離子交換樹脂的下游之非再生型混床式離子交換樹脂的劣化早期進行，造成超純水的長期製造極為困難。However, according to a research review conducted by the present inventors, it was found that when a boron adsorption resin mixed ion exchange resin is disposed at the rear stage of the ultraviolet oxidation device, the hydrogen peroxide generated by the ultraviolet oxidation device due to excessive ultraviolet irradiation will decompose the boron adsorption. Resin mixed with ion exchange resin causes a large amount of low-molecular-weight organic substances to dissolve, and the TOC removal load of the downstream water treatment device becomes high. In addition, it was also found that in this case, the degradation of the non-regenerating mixed-bed ion exchange resin provided downstream of the boron adsorption resin mixed ion exchange resin proceeds early, making long-term production of ultrapure water extremely difficult.
本發明係為了解決前述課題而開發完成之發明，其目的係在於提供針對具備有硼吸附樹脂混合離子交換樹脂之超純水製造系統，能夠長期間獲得高水質的超純水之超純水製造系統及超純水製造方法。 [用以解決課題之手段]The present invention was developed to solve the aforementioned problems, and an object thereof is to provide an ultrapure water production system for an ultrapure water production system including a boron adsorption resin and a mixed ion exchange resin, which can obtain high water quality ultrapure water for a long period of time. System and method for manufacturing ultrapure water. [Means to solve the problem]
本發明的超純水製造系統，係將包含有硼成分與總有機碳成分之被處理水進行處理來製造超純水的超純水製造系統，其特徵為依序具備有：第1紫外線氧化裝置，其係對前述被處理水，以紫外線照射量為0.05kWh/m3 以上0.2kWh/m3 以下的方式照射紫外線；具有將硼吸附樹脂及陰離子交換樹脂混合所構成的硼吸附陰離子交換混床樹脂，將在前述第1紫外線氧化裝置照射了紫外線的被處理水進行處理之硼吸附樹脂混合離子交換裝置；對藉由前述硼吸附樹脂混合離子交換裝置進行了處理之前述被處理水照射紫外線之第2紫外線氧化裝置；及將藉由前述第2紫外線氧化裝置照射了紫外線的前述被處理水進行處理之非再生型混床式離子交換樹脂裝置。The ultra-pure water production system of the present invention is an ultra-pure water production system for producing ultra-pure water by treating to-be-treated water containing a boron component and a total organic carbon component, and is characterized in that it includes: first ultraviolet oxidation A device for irradiating ultraviolet rays on the water to be treated such that the amount of ultraviolet radiation is 0.05 kWh / m 3 or more and 0.2 kWh / m 3 or less; and has a boron adsorption anion exchange mixture composed of a boron adsorption resin and an anion exchange resin. Bed resin, a boron-adsorbed resin mixed ion exchange device that treats water to be treated with ultraviolet light irradiated by the first ultraviolet oxidizing device; the treated water that has been treated with the boron-adsorbed resin mixed ion-exchange device irradiates ultraviolet light A second ultraviolet oxidizing device; and a non-regenerating type mixed-bed ion-exchange resin device that treats the water to be treated irradiated with ultraviolet rays by the second ultraviolet oxidizing device.
在本發明的超純水製造系統，其中，前述硼吸附陰離子交換混床樹脂中之前述硼吸附樹脂及前述陰離子交換樹脂之混合比例係當將前述陰離子交換樹脂的交換容量設為「CA 」、將前述硼吸附樹脂的交換容量設為「CB 」時，CA /CB 為0.2以上5以下。In the ultrapure water production system of the present invention, the mixing ratio of the boron adsorption resin and the anion exchange resin in the boron adsorption anion exchange mixed bed resin is such that the exchange capacity of the anion exchange resin is set to "C A " When the exchange capacity of the boron adsorption resin is "C B ", C A / C B is 0.2 or more and 5 or less.
在本發明的超純水製造系統，其中，前述硼吸附樹脂混合離子交換裝置，係具有對前述硼吸附陰離子交換混床樹脂進一步混合陽離子交換樹脂所構成之硼吸附陽離子交換陰離子交換混床樹脂。In the ultrapure water production system of the present invention, the boron adsorption resin mixed ion exchange device includes a boron adsorption cation exchange anion exchange mixed bed resin composed of further mixing the boron adsorption anion exchange mixed bed resin with a cation exchange resin.
在本發明的超純水製造系統，其中，前述硼吸附陽離子交換陰離子交換混床樹脂中之硼吸附樹脂、陰離子交換樹脂及陽離子交換樹脂之混合比例，係當前述陰離子交換樹脂的交換容量設為「CA 」、前述硼吸附樹脂的交換容量設為「CB 」、前述陽離子交換樹脂的交換容量設為「CC 」時，CC /(CA ＋CB )為0.3以上1.3以下。In the ultrapure water production system of the present invention, the mixing ratio of the boron adsorption resin, anion exchange resin, and cation exchange resin in the boron adsorption cation exchange anion exchange mixed bed resin is when the exchange capacity of the anion exchange resin is set to When "C A ", the exchange capacity of the boron adsorption resin is "C B ", and the exchange capacity of the cation exchange resin is "C C ", C C / (C A + C B ) is 0.3 or more and 1.3 or less.
在本發明的超純水製造系統，其中，在前述第1紫外線氧化裝置之上游側，依序具備有逆滲透膜裝置和電去離子裝置。In the ultrapure water production system of the present invention, a reverse osmosis membrane device and an electric deionization device are sequentially provided on the upstream side of the first ultraviolet oxidation device.
在本發明的超純水製造系統，其中，前述電去離子裝置之每1電池對處理流量之電流值係30A/(m3 /h)以上。In the ultrapure water production system of the present invention, the current value of the treatment flow rate per battery of the aforementioned electric deionization device is 30 A / (m 3 / h) or more.
在本發明的超純水製造系統，其中，前述逆滲透膜裝置之膜阻抗為45MPa/(m/h)以上。In the ultrapure water production system of the present invention, the membrane impedance of the reverse osmosis membrane device is 45 MPa / (m / h) or more.
在本發明的超純水製造系統，其中，前述硼吸附樹脂混合離子交換裝置之處理水中之總有機碳濃度為5μg/L(as C)以下。In the ultrapure water production system of the present invention, the total organic carbon concentration in the treated water of the boron adsorption resin mixed ion exchange device is 5 μg / L (as C) or less.
在本發明的超純水製造系統，其中，前述非再生型混床式離子交換樹脂裝置之處理水中之總有機碳濃度為未滿0.5μg/L(as C)、硼濃度為未滿0.5ng/L。In the ultrapure water production system of the present invention, the total organic carbon concentration in the treated water of the non-renewable mixed-bed ion exchange resin device is less than 0.5 μg / L (as C), and the boron concentration is less than 0.5 ng. / L.
本發明的超純水製造方法，係將包含硼成分與總有機碳成分的被處理水進行處理來製造超純水之超純水製造方法，其特徵為具備有以下製程：藉由第1紫外線氧化裝置，以紫外線照射量為0.05kWh/m3 以上0.2kWh/m3 以下的方式，將前述被處理水進行處理之製程；以具有將硼吸附樹脂及陰離子交換樹脂混合所構成的硼吸附陰離子交換混床樹脂之硼吸附樹脂混合離子交換裝置，對前述第1紫外線氧化裝置的處理水進行處理之製程；以第2紫外線氧化裝置，將硼吸附樹脂混合離子交換裝置的處理水進行處理之製程；及以非再生型混床式離子交換樹脂裝置，將前述第2紫外線氧化裝置的處理水進行處理之製程。 [發明效果]The method for producing ultrapure water of the present invention is a method for producing ultrapure water by treating treated water containing a boron component and a total organic carbon component to produce ultrapure water, and is characterized by having the following process: by a first ultraviolet The oxidation device is a process for treating the water to be treated such that the amount of ultraviolet radiation is 0.05 kWh / m 3 or more and 0.2 kWh / m 3 or less; it has a boron adsorption anion formed by mixing a boron adsorption resin and an anion exchange resin Process for processing mixed water of boron adsorption resin mixed ion exchange device for exchanging mixed bed resin to process the treated water of the first ultraviolet oxidation device; process for processing water of boron adsorption resin mixed ion exchange device by the second ultraviolet oxidation device ; And a process of treating the treated water of the second ultraviolet oxidizing device with a non-regenerating mixed-bed ion exchange resin device. [Inventive effect]
若依據本發明的超純水製造系統及超純水製造方法的話，在具備有硼吸附樹脂混合離子交換樹脂之超純水製造系統，能夠長期間製造硼濃度及TOC濃度低之高水質的超純水。According to the ultrapure water production system and the ultrapure water production method according to the present invention, an ultrapure water production system provided with a boron adsorption resin mixed with an ion exchange resin can produce ultrahigh-quality ultrahigh water with low boron concentration and TOC concentration for a long period of time. Pure water.
以下，參照圖面詳細地說明實施形態。 (第1實施形態) 如圖1所示，第1實施形態之超純水製造系統1的結構，係將前處理裝置11、第1紫外線氧化裝置(TOC-UV1)12、硼吸附樹脂混合離子交換裝置13、第2紫外線氧化裝置(TOC-UV2)14、及非再生型混床式離子交換樹脂裝置(Polisher)15依序連接。在超純水製造系統1，原水係藉由經過前處理裝置11、第1紫外線氧化裝置12、硼吸附樹脂混合離子交換裝置13、第2紫外線氧化裝置14及非再生型混床式離子交換樹脂裝置15來進行處理，再將非再生型混床式離子交換樹脂裝置15的處理水(末端水)供給至點置系統(POU)16。在超純水製造系統1，第1紫外線氧化裝置12之紫外線照射量係為0.05～0.2kWh/m3 。Hereinafter, embodiments will be described in detail with reference to the drawings. (First Embodiment) As shown in FIG. 1, the structure of the ultrapure water production system 1 of the first embodiment is a pretreatment device 11, a first ultraviolet oxidation device (TOC-UV1) 12, and a boron adsorption resin mixed ion. The exchange device 13, the second ultraviolet oxidation device (TOC-UV2) 14, and the non-regenerating mixed-bed ion exchange resin device (Polisher) 15 are sequentially connected. In the ultrapure water production system 1, raw water is passed through a pretreatment device 11, a first ultraviolet oxidation device 12, a boron adsorption resin mixed ion exchange device 13, a second ultraviolet oxidation device 14, and a non-renewable mixed bed type ion exchange resin. The device 15 performs processing, and then the treated water (terminal water) of the non-regenerating mixed-bed ion exchange resin device 15 is supplied to a point setting system (POU) 16. In ultrapure water production system 1, the first amount of ultraviolet radiation-based ultraviolet oxidation device 12 is of 0.05 ~ 0.2kWh / m 3.
在超純水製造系統1，作為原水，可使用自來水、井水、工業用水等。原水中，含有5～100μg/L左右之硼(B)。前處理裝置11係具有以下功能，亦即，去除原水中的懸浮物質，將原水處理成可適合供給至硼吸附樹脂混合離子交換裝置13的水質之功能。原水中的硼中，未被前處理裝置11去除之硼會殘留於水中。In the ultrapure water production system 1, as raw water, tap water, well water, industrial water, and the like can be used. Raw water contains about 5 to 100 μg / L of boron (B). The pretreatment device 11 has a function of removing suspended matter in raw water and processing the raw water into a water quality suitable for supplying to the boron adsorption resin mixed ion exchange device 13. Of the boron in the raw water, boron that has not been removed by the pretreatment device 11 remains in the water.
前處理裝置11係可適宜選擇例如用來去除原水中的懸浮物質之砂過濾裝置、精密過濾裝置等來構成，且可因應需要，具備進行被處理水的溫度調節之熱交換器等來構成。再者，依據原水的水質，亦可省略前處理裝置11。The pre-treatment device 11 can be configured by suitably selecting, for example, a sand filter device or a precision filter device for removing suspended matter in raw water, and can be configured with a heat exchanger or the like to adjust the temperature of the water to be treated as required. Moreover, depending on the water quality of the raw water, the pre-processing device 11 may be omitted.
第1紫外線氧化裝置(TOC-UV1)12係具有可照射具有185nm附近的波長之紫外線的紫外線燈，利用以此紫外線燈對被處理水照射紫外線，將被處理水中的TOC進行氧化分解。使用於第1紫外線氧化裝置12之紫外線燈，可使用例如可放射185nm的紫外線與254nm附近的紫外線之低壓水銀燈。作為這種低壓水銀燈之市面販賣品，理想為例如JPW-2、AUV-8000TOC、SUV-TOC系列等(皆為日本Photoscience公司製)。The first ultraviolet oxidizing device (TOC-UV1) 12 has an ultraviolet lamp that can irradiate ultraviolet rays with a wavelength around 185 nm. The ultraviolet lamp is used to irradiate ultraviolet rays to the treated water to oxidize and decompose TOC in the treated water. As the ultraviolet lamp used in the first ultraviolet oxidizing device 12, for example, a low-pressure mercury lamp that can emit ultraviolet rays at 185 nm and ultraviolet rays near 254 nm can be used. As a commercially available product of such a low-pressure mercury lamp, for example, JPW-2, AUV-8000TOC, and SUV-TOC series (all manufactured by Japan Photoscience Corporation) are desirable.
第1紫外線氧化裝置12係藉由波長185nm左右的紫外線，將水分解而產生OH自由基，此OH自由基具有將含於被處理水中的有機物進行氧化分解的功能。在第1紫外線氧化裝置12進行了過剩的紫外線照射之情況，未有助於有機物的氧化分解之OH自由基彼此產生反應而產生過氧化氫。此所產生的過氧化氫，會有將設在下游側的離子交換樹脂塔內的樹脂分解之情況。The first ultraviolet oxidizing device 12 decomposes water by ultraviolet rays having a wavelength of about 185 nm to generate OH radicals. The OH radicals have the function of oxidizing and decomposing organic substances contained in the water to be treated. When the first ultraviolet oxidizing device 12 is subjected to excessive ultraviolet irradiation, OH radicals that do not contribute to the oxidative decomposition of organic substances react with each other to generate hydrogen peroxide. The generated hydrogen peroxide may decompose the resin in the ion exchange resin tower provided on the downstream side.
為了減低前述過氧化氫，抑制下游側的硼吸附樹脂混合離子交換樹脂之分解，第1紫外線氧化裝置12之紫外線照射量為0.05～0.2kWh/m3 。In order to reduce the aforementioned hydrogen peroxide and suppress the decomposition of the boron adsorption resin mixed ion exchange resin on the downstream side, the ultraviolet irradiation amount of the first ultraviolet oxidation device 12 is 0.05 to 0.2 kWh / m 3 .
在此，前述紫外線照射量係為處理流量(m3 /h)除紫外線氧化裝置之每1支光源(紫外線燈)的消耗電力(kW)×紫外線燈的支數(支)所算出的值。在第1紫外線氧化裝置，在被處理水流通的處理室內部設置攪拌葉片等，藉由該攪拌葉片，將被處理水進行攪拌為佳。藉此，可抑制因來自光源的距離的差異所引起之紫外線照射量的差異，對紫外線氧化裝置內的被處理水造成之影響。Here, the aforementioned ultraviolet irradiation amount is a value calculated by dividing the processing flow rate (m 3 / h) by the power consumption (kW) per one light source (ultraviolet lamp) of the ultraviolet oxidation device x the number of ultraviolet lamps (branch). In the first ultraviolet oxidizing device, a stirring blade or the like is provided inside the processing chamber in which the water to be treated flows, and the water to be treated is preferably stirred by the stirring blade. Thereby, the difference in the amount of ultraviolet irradiation caused by the difference in the distance from the light source can be suppressed, and the effect on the treated water in the ultraviolet oxidation device can be suppressed.
又，若後段的硼吸附樹脂混合離子交換裝置13的被處理水中，含有二氧化碳、羧酸化合物等的話，會有因該等物質吸附於硼吸附樹脂，造成硼吸附樹脂的硼之吸附能力降低。Further, if the treated water of the boron adsorption resin mixed ion exchange device 13 in the subsequent stage contains carbon dioxide, a carboxylic acid compound, and the like, these substances may be adsorbed on the boron adsorption resin, thereby reducing the boron adsorption capacity of the boron adsorption resin.
在此所稱的羧酸化合物係指例如分子內具有1或2以上的羧基且碳數為0或1以上的脂肪族羧酸，典型為碳數為0~5之脂肪族羧酸。作為羧酸化合物，具體而言，可舉出蟻酸、醋酸、草酸等。The carboxylic acid compound referred to herein means, for example, an aliphatic carboxylic acid having 1 or 2 or more carboxyl groups in the molecule and having a carbon number of 0 or 1 or more, and typically an aliphatic carboxylic acid having 0 to 5 carbon numbers. Specific examples of the carboxylic acid compound include formic acid, acetic acid, and oxalic acid.
藉由前述第1紫外線氧化裝置12之紫外線照射量為0.05～0.2kWh/m3 ，能夠減低處理水中的二氧化碳及羧酸化合物。且，藉由將紫外線照射量設成0.05kWh/m3 以上且未滿0.1kWh/m3 ，則可抑制紫外線照射裝置的消耗電力，因此更為理想。在前述範圍，亦可獲得硼吸附樹脂混合離子交換裝置13之硼吸附能力提升效果。流通於前述第1紫外線氧化裝置12後的水中之二氧化碳及羧酸化合物的總和濃度，理想為當以TOC進行換算時為1～20μg/L(as C)。When the ultraviolet irradiation amount of the first ultraviolet oxidizing device 12 is 0.05 to 0.2 kWh / m 3 , carbon dioxide and carboxylic acid compounds in the treated water can be reduced. In addition, by setting the amount of ultraviolet irradiation to 0.05 kWh / m 3 or more and less than 0.1 kWh / m 3 , the power consumption of the ultraviolet irradiation device can be suppressed, which is more desirable. Within the aforementioned range, the boron adsorption capacity improvement effect of the boron adsorption resin mixed ion exchange device 13 can also be obtained. The total concentration of carbon dioxide and carboxylic acid compounds in the water flowing through the first ultraviolet oxidizing device 12 is preferably 1 to 20 μg / L (as C) when converted into TOC.
在超純水製造系統1，硼吸附樹脂混合離子交換裝置13係具備有作為硼吸附樹脂混合離子交換樹脂之將硼吸附樹脂及陰離子交換樹脂混合所構成的硼吸附陰離子交換混床樹脂。In the ultrapure water production system 1, a boron adsorption resin mixed ion exchange device 13 is provided with a boron adsorption anion exchange mixed bed resin composed of a boron adsorption resin and an anion exchange resin as a boron adsorption resin mixed ion exchange resin.
硼吸附樹脂混合離子交換裝置13係具有將流通於第1紫外線氧化裝置12後的水中之硼予以捕捉並去除之功能。硼吸附樹脂混合離子交換裝置13為例如對圓筒狀的樹脂塔內部填充硼吸附樹脂及陰離子交換樹脂之混合物所構成。The boron adsorption resin mixed ion exchange device 13 has a function of capturing and removing boron flowing through the water after the first ultraviolet oxidation device 12. The boron adsorption resin mixed ion exchange device 13 is configured by, for example, filling a mixture of a boron adsorption resin and an anion exchange resin into a cylindrical resin tower.
由硼吸附樹脂及陰離子交換樹脂的混合物所構成之硼吸附陰離子交換混床樹脂中的硼吸附樹脂及陰離子交換樹脂之混合比例，係當將硼吸附樹脂的交換容量設為CB 、陰離子交換樹脂的交換容量設為CA 時，CA /CB 為0.2～5為佳，1～5為更佳。藉由將CA /CB 作成為5以下，能夠充分地發揮藉由硼吸附樹脂之硼吸附能力。藉由將CA /CB 作成為0.2以上，能夠抑制阻礙硼吸附樹脂之硼吸附能力的有機酸的影響，因此能夠充分地發揮藉由硼吸附樹脂之硼吸附能力。The mixing ratio of boron adsorption resin and anion exchange resin in a boron adsorption anion exchange mixed bed resin composed of a mixture of boron adsorption resin and anion exchange resin is when the exchange capacity of boron adsorption resin is set to C B , anion exchange resin When the exchange capacity is set to C A , C A / C B is preferably from 0.2 to 5, and more preferably from 1 to 5. By setting C A / C B to 5 or less, the boron adsorption ability of the boron adsorption resin can be fully exhibited. By setting C A / C B to be 0.2 or more, the influence of the organic acid that inhibits the boron adsorption ability of the boron adsorption resin can be suppressed, and thus the boron adsorption ability of the boron adsorption resin can be fully exerted.
作為硼吸附陰離子交換混床樹脂之硼吸附樹脂，可使用在聚苯乙烯樹脂、酚樹脂等附加具有作為硼吸附基之多元醇基的官能基之樹脂。作為硼吸附樹脂，包含具有高度的硼吸附能力之N-甲基葡糖胺基的離子交換樹脂尤佳。又，從硼去除能力的觀點來看，硼吸附樹脂的交換容量，理想為0.15~1.5meq/mL。硼吸附樹脂之比重，理想為1.05～1.15g/cm3 。As the boron adsorption resin for the boron adsorption anion exchange mixed bed resin, a resin having a functional group having a polyhydric alcohol group as a boron adsorption group can be added to a polystyrene resin, a phenol resin, or the like. As the boron adsorption resin, an ion exchange resin containing an N-methylglucamine group having a high boron adsorption ability is particularly preferable. From the viewpoint of boron removal ability, the exchange capacity of the boron adsorption resin is preferably 0.15 to 1.5 meq / mL. The specific gravity of the boron adsorption resin is preferably 1.05 to 1.15 g / cm 3 .
作為硼吸附樹脂的市面販賣品，可舉出例如Amberlite(登錄商標；羅門哈斯公司(Rohm and Haas Company)製)，IRA-743T、DIAION CRB02、DIAION CRB03(皆為三菱化學(股)公司製)等。Examples of commercially available boron adsorption resins include Amberlite (registered trademark; manufactured by Rohm and Haas Company), IRA-743T, DIAION CRB02, and DIAION CRB03 (all manufactured by Mitsubishi Chemical Corporation) )Wait.
又，硼吸附樹脂混合離子交換裝置13，除了前述硼吸附樹脂及陰離子交換樹脂，還可具備混合了陽離子交換樹脂之硼吸附陽離子交換陰離子交換混床樹脂。The boron adsorption resin mixed ion exchange device 13 may include a boron adsorption cation exchange anion exchange mixed bed resin mixed with a cation exchange resin in addition to the boron adsorption resin and the anion exchange resin.
在此情況，可抑制來自於硼吸附陽離子交換陰離子交換混床樹脂的脫離基作為有機物漏出。In this case, the leaving group from the boron-adsorbed cation exchange anion exchange mixed bed resin can be suppressed from leaking out as an organic substance.
硼吸附陽離子交換陰離子交換混床樹脂中之硼吸附樹脂、陽離子交換樹脂及陰離子交換樹脂的混合比例，在當將前述硼吸附樹脂的交換容量設為CB 、陽離子交換樹脂的交換容量設為CC 、陰離子交換樹脂的交換容量設為CA 的情況時之交換容量比，理想為CC /(CA ＋CB )係0.3～1.3，更理想為0.4～1.0。When the mixing ratio of boron adsorption resin, cation exchange resin, and anion exchange resin in boron adsorption cation exchange anion exchange mixed bed resin is set as the exchange capacity of the boron adsorption resin as C B and the exchange capacity of the cation exchange resin as C The exchange capacity ratio when the exchange capacity of C and anion exchange resin is set to C A is preferably C C / (C A + C B ) 0.3 to 1.3, and more preferably 0.4 to 1.0.
若CC /(CA ＋CB )為1.3以下的話，硼吸附陽離子交換陰離子交換混床樹脂不易變成酸性環境，能夠充分地發揮硼吸附能力。藉由CC /(CA ＋CB )為0.3以上，能夠充分地發揮作為被混合的陽離子交換樹脂及陰離子交換樹脂之混床式離子交換樹脂的效果，可使處理水的純度提升。If C C / (C A + C B ) is 1.3 or less, the boron-adsorbing cation-exchange anion-exchange mixed-bed resin is unlikely to become an acidic environment, and the boron-adsorbing ability can be fully exerted. When C C / (C A + C B ) is 0.3 or more, the effect of being a mixed-bed ion exchange resin that is a mixed cation exchange resin and anion exchange resin can be fully exerted, and the purity of the treated water can be improved.
作為陰離子交換樹脂，理想為強鹼性陰離子交換樹脂，由於離子交換樹脂的加水分解少、有機系陰離子成分朝超純水的溶出少，故，具有作為離子交換基之第4級銨基的苯乙烯系樹脂等為佳。作為強鹼性陰離子交換樹脂，交換容量理想為0.7～1.5meq/mL、更理想為1～1.5meq/mL者。As the anion exchange resin, a strongly basic anion exchange resin is preferred. Since the ion exchange resin has less hydrolyzation and less elution of the organic anion component into ultrapure water, it has a fourth-order ammonium group benzene as an ion exchange group. Vinyl-based resins are preferred. As the strongly basic anion exchange resin, the exchange capacity is preferably 0.7 to 1.5 meq / mL, and more preferably 1 to 1.5 meq / mL.
又，陰離子交換樹脂，由於要能夠去除離子選擇性低之陰離子成分，故，OH型為佳。作為OH型轉換率，理想使用99.95%以上者。陰離子交換樹脂之比重，理想為1.0～1.1g/cm3 。In addition, since the anion exchange resin needs to be able to remove anion components with low ion selectivity, the OH type is preferred. As the OH conversion rate, it is desirable to use one having 99.95% or more. The specific gravity of the anion exchange resin is preferably 1.0 to 1.1 g / cm 3 .
作為強鹼性陰離子交換樹脂，可舉出Duolite AGP(羅門哈斯公司(Rohm and Haas Company)製)、DIAION SAT20L(三菱化學(股)公司製)等。Examples of the strongly basic anion exchange resin include Duolite AGP (manufactured by Rohm and Haas Company), DIAION SAT20L (manufactured by Mitsubishi Chemical Corporation), and the like.
作為陽離子交換樹脂，理想為強酸性陽離子交換樹脂，由於離子交換樹脂的加水分解少、有機陽離子成分朝超純水的溶出少，故，具有作為離子交換基之磺酸基的苯乙烯系樹脂等為佳。強酸性陽離子交換樹脂，係交換容量理想為1.5～2.5meq/mL、更理想為2～2.5meq/mL者。As the cation exchange resin, a strongly acidic cation exchange resin is preferred. Since the ion exchange resin has less hydrolysis and less elution of organic cation components into ultrapure water, it is a styrene resin having a sulfonic acid group as an ion exchange group. Better. The strongly acidic cation exchange resin is preferably one having an exchange capacity of 1.5 to 2.5 meq / mL, and more preferably 2 to 2.5 meq / mL.
作為陽離子交換樹脂，由於要能夠去除離子選擇性低之陽離子成分，故，H型為佳。作為H型轉換率，理想使用99.95%以上者。陽離子交換樹脂之比重，理想為1.2～1.3g/cm3 。As a cation exchange resin, since it is necessary to be able to remove cation components with low ion selectivity, the H type is preferred. As the H-type conversion rate, it is desirable to use one having 99.95% or more. The specific gravity of the cation exchange resin is preferably 1.2 to 1.3 g / cm 3 .
作為強酸性陽離子交換樹脂，可舉出Duolite CGP(羅門哈斯公司(Rohm and Haas Company)製)、DIAION SKT20L(三菱化學(股)公司製)等。Examples of the strongly acidic cation exchange resin include Duolite CGP (manufactured by Rohm and Haas Company), DIAION SKT20L (manufactured by Mitsubishi Chemical Corporation), and the like.
硼吸附樹脂混合離子交換裝置13之通水速度，從長時間可高度地去除硼的觀點來看，空間速度SV理想為1～100(1/h)，特別理想為3～50(1/h)。藉由使通水速度為前述上限值以下，能夠使硼之去除率提升。另外，藉由使其為前述下限值以上，能夠抑制有機物等從混床樹脂溶出，可進一步減低處理水的TOC濃度。From the viewpoint that boron adsorption resin mixed ion exchange device 13 can pass water for a long period of time, the space velocity SV is preferably 1 to 100 (1 / h), and particularly preferably 3 to 50 (1 / h). ). By setting the water flow rate to be equal to or less than the aforementioned upper limit value, the removal rate of boron can be improved. Moreover, by making it into the said lower limit or more, elution of organic substances etc. from a mixed bed resin can be suppressed, and the TOC concentration of a treated water can be reduced further.
作為硼吸附樹脂混合離子交換裝置13之硼去除率，例如能夠獲得97%以上，在使用前述水質的原水之情況，能夠獲得硼濃度為1ng/L以下之處理水。又，硼吸附樹脂混合離子交換裝置13的處理水中之TOC濃度，理想為維持在5μg/L(as C)以下，更理想為3μg/L(as C)以下，更加理想為1μg/L(as C)以下。As the boron removal rate of the boron adsorption resin mixed ion exchange device 13, for example, 97% or more can be obtained. When using the raw water of the aforementioned water quality, treated water having a boron concentration of 1 ng / L or less can be obtained. The TOC concentration in the treated water of the boron adsorption resin mixed ion exchange device 13 is preferably maintained at 5 μg / L (as C) or less, more preferably 3 μg / L (as C) or less, and even more preferably 1 μg / L (as C) The following.
第2紫外線氧化裝置(TOC-UV2)14係對硼吸附樹脂混合離子交換裝置13的處理水照射紫外線，將水中的TOC成分分解。作為硼吸附樹脂混合離子交換裝置13的處理水中之TOC成分，主要為硼吸附樹脂混合離子交換裝置13內的混床樹脂分解所產生之有機物成分、微量殘留的來自於原水的有機物成分、及來自於配管等的有機物成分等。在第2紫外線氧化裝置14，藉由分解這種的有機物成分，在末端能夠獲得TOC濃度更低的超純水。The second ultraviolet oxidizing device (TOC-UV2) 14 irradiates ultraviolet rays to the treated water of the boron adsorption resin mixed ion exchange device 13 to decompose the TOC components in the water. The TOC components in the treated water of the boron adsorption resin mixed ion exchange device 13 are mainly organic components produced by decomposition of the mixed bed resin in the boron adsorption resin mixed ion exchange device 13 and trace amounts of organic components derived from raw water and from For organic components such as piping. In the second ultraviolet oxidizing device 14, by decomposing such an organic component, ultrapure water having a lower TOC concentration can be obtained at the end.
作為第2紫外線氧化裝置14，能夠使用與第1紫外線氧化裝置12相同的裝置。第2紫外線氧化裝置14之紫外線照射量係為0.1～0.5kWh/m3 。如此，藉由設置第2紫外線氧化裝置14，能夠減少第1紫外線氧化裝置12及第2紫外線氧化裝置14之消耗電力的總合。又，由於第1紫外線氧化裝置12及第2紫外線氧化裝置14之消耗電力變小，故，能夠減低過氧化氫的產生量。因此，能夠抑制硼吸附樹脂混合離子交換裝置13、非再生型混床式離子交換樹脂裝置15等之離子交換樹脂尤其是硼吸附樹脂之分解。As the second ultraviolet oxidizing device 14, the same device as the first ultraviolet oxidizing device 12 can be used. The ultraviolet irradiation amount of the second ultraviolet oxidizing device 14 is 0.1 to 0.5 kWh / m 3 . As described above, by providing the second ultraviolet oxidizing device 14, the total power consumption of the first ultraviolet oxidizing device 12 and the second ultraviolet oxidizing device 14 can be reduced. In addition, since the power consumption of the first ultraviolet oxidizing device 12 and the second ultraviolet oxidizing device 14 is reduced, the amount of generated hydrogen peroxide can be reduced. Therefore, decomposition of the ion exchange resin, especially the boron adsorption resin, such as the boron adsorption resin mixed ion exchange device 13 and the non-regenerable mixed bed type ion exchange resin device 15 can be suppressed.
非再生型混床式離子交換樹脂裝置(Polisher)15係以因應各交換容量將陽離子交換樹脂與陰離子交換樹脂混合後之陽離子交換陰離子交換混床樹脂被填充於樹脂塔等的裝置內的方式構成。Non-regenerating mixed-bed type ion exchange resin device (Polisher) 15 is configured such that a cation exchange anion exchange mixed bed resin in which a cation exchange resin is mixed with an anion exchange resin in accordance with each exchange capacity is filled in a device such as a resin tower .
非再生型混床式離子交換樹脂裝置15係設置於超純水製造系統1的末端，亦即，點置系統(POU)16前的附近位置。非再生型混床式離子交換樹脂裝置15，主要是去除在第2紫外線氧化裝置14水中的有機物成分分解而產生之微量的有機酸成分，使TOC濃度降低。The non-regenerating type mixed-bed ion exchange resin device 15 is installed at the end of the ultrapure water production system 1, that is, in the vicinity of the point placement system (POU) 16. The non-regenerating mixed bed type ion exchange resin device 15 mainly removes a trace amount of organic acid components generated by decomposition of organic components in the water of the second ultraviolet oxidation device 14 to reduce the TOC concentration.
非再生型混床式離子交換樹脂裝置15係當被填充於內部的陽離子交換陰離子交換混床樹脂劣化乃至穿透之際，整個裝置更換，或取出填充於內部的樹脂並更換成新的樹脂。在此，若供給至第2紫外線氧化裝置14的水中之TOC成分的量多的話，在此處被分解所產生的有機酸之量會變多，造成非再生型混床式離子交換樹脂裝置15的負載增大，使得更換頻率增大。The non-regenerating mixed bed type ion exchange resin device 15 is used when the cation exchange anion exchange mixed bed resin filled in the interior deteriorates or even penetrates, the entire device is replaced, or the resin filled in the interior is taken out and replaced with a new resin. Here, if the amount of TOC components in the water supplied to the second ultraviolet oxidizing device 14 is large, the amount of organic acids generated by being decomposed here will increase, resulting in a non-regenerating mixed-bed ion exchange resin device 15 The increase in load increases the frequency of replacement.
在本實施形態的超純水製造系統1，藉由將第1紫外線氧化裝置12的紫外線照射量設在前述範圍內，可抑制硼吸附樹脂混合離子交換裝置13內的樹脂之分解。因此，可抑制有機物成分自硼吸附樹脂混合離子交換裝置13漏出，可極力地減輕非再生型混床式離子交換樹脂裝置15之負載。藉此，不需要更換非再生型混床式離子交換樹脂裝置15，能夠長期間製造硼濃度及TOC濃度極低的超純水。In the ultrapure water production system 1 of this embodiment, by setting the ultraviolet irradiation amount of the first ultraviolet oxidizing device 12 within the aforementioned range, decomposition of the resin in the boron-adsorbing resin mixed ion exchange device 13 can be suppressed. Therefore, leakage of organic components from the boron adsorption resin mixed ion exchange device 13 can be suppressed, and the load on the non-regenerating mixed bed type ion exchange resin device 15 can be reduced as much as possible. Thereby, it is not necessary to replace the non-regenerating mixed bed type ion exchange resin device 15, and ultrapure water with extremely low boron concentration and TOC concentration can be produced for a long period of time.
再者，在超純水製造系統1，除前述裝置以外，亦可設置去除離子成分的逆滲透膜裝置、電去離子裝置、去除溶解氣體的真空脫氣裝置、膜脫氣裝置、及其他去除微粒子、非離子成分等的超過濾裝置(UF)、精密過濾裝置(MF)等。In addition, in the ultrapure water production system 1, in addition to the aforementioned devices, a reverse osmosis membrane device for removing ionic components, an electric deionization device, a vacuum degassing device for removing dissolved gas, a membrane degassing device, and other removals may be provided. Ultrafiltration device (UF), fine filtration device (MF), etc. for fine particles and non-ionic components.
如前述般，本發明者們發現，在將硼吸附陰離子交換混床樹脂配置於紫外線氧化裝置的後段之情況，在紫外線氧化裝置因過量的紫外線照射所產生的過氧化氫會分解硼吸附陰離子交換混床樹脂，造成低分子量的有機物大量溶出，因該低分子量的有機物，造成下游側的水處理裝置之TOC去除負載變高。其理由可推測如下。As mentioned above, the present inventors have found that when a boron-adsorbing anion exchange mixed bed resin is disposed at the rear stage of an ultraviolet oxidation device, hydrogen peroxide generated by the ultraviolet oxidation device due to excessive ultraviolet irradiation decomposes the boron-adsorbing anion exchange. Mixed-bed resins cause a large amount of low-molecular-weight organics to dissolve. Due to the low-molecular-weight organics, the TOC removal load of the downstream water treatment device becomes high. The reason can be presumed as follows.
在含有過氧化氫的水與具有作為官能基之前述這種多元醇基之硼吸附樹脂接觸之情況，會有硼吸附樹脂被分解的狀況。在以下的說明，針對此硼吸附樹脂的分解，參照下述式子(I)，以在樹脂骨架具有作為離子交換基之N-甲基葡糖胺基的硼吸附樹脂為例進行說明。When the water containing hydrogen peroxide is in contact with a boron adsorption resin having the aforementioned polyhydric alcohol group as a functional group, the boron adsorption resin may be decomposed. In the following description, the decomposition of this boron adsorption resin will be described with reference to the following formula (I), and a boron adsorption resin having an N-methylglucosamine group as an ion exchange group in the resin skeleton will be described as an example.
【化學式1】 [Chemical Formula 1]
如前述式子(I)所示，在為具有N-甲基葡糖胺基之硼吸附樹脂的情況，因過氧化氫造成結合斷裂，會有以下的4種情況，亦即(1)構成聚苯乙烯樹脂、酚樹脂等的樹脂骨架之烴鏈 與苯環之結合斷裂的情況、(2)N-甲基葡糖胺基脫離的情況、(3)N-甲基葡糖胺基之與氮原子結合的甲基脫離的情況、(4)N-甲基葡糖胺基之與氮原子結合的多元醇基脫離的情況。又，在(4)N-甲基葡糖胺基之與氮原子結合的多元醇基脫離的情況，亦可考量為該多元醇所含的複數個碳-碳間之結合斷裂。As shown in the aforementioned formula (I), in the case of a boron adsorption resin having an N-methylglucamine group, the bond may be broken due to hydrogen peroxide, and the following four cases may occur, namely, the structure of (1) Polystyrene resins, phenol resins, and other resin backbones, such as when the bond between the benzene ring is broken, (2) when the N-methylglucamine group is detached, and (3) when the N-methylglucamine group is broken. When a methyl group bonded to a nitrogen atom is detached, and (4) when a polyhydric alcohol group bonded to a nitrogen atom of the N-methylglucamine group is detached. When the (4) N-methylglucosamine group is detached from a polyvalent alcohol group bonded to a nitrogen atom, it is also possible to consider the cleavage of a plurality of carbon-carbon bonds contained in the polyhydric alcohol.
在此，在硼吸附陰離子交換混床樹脂，在(1)～(4)中的其中之一，結合斷裂之情況，已經脫離的有機物成分也會從離子交換樹脂層漏出。此漏出的有機物成分，能在紫外線氧化裝置藉由進行紫外線照射而分解成有機酸後，進一步藉由非再生型混床式離子交換樹脂捕捉有機酸，藉此加以去除。Here, in the case of the boron-adsorbed anion exchange mixed bed resin, in one of (1) to (4), the detached organic components may also leak out of the ion exchange resin layer in the case of cleavage. This leaked organic component can be removed after being decomposed into an organic acid by ultraviolet irradiation in an ultraviolet oxidizing device, and then the organic acid can be captured by a non-regenerating mixed-bed ion exchange resin, thereby being removed.
但，在前述(4)斷裂而產生之有機物成分的情況，藉由在紫外線氧化裝置的紫外線照射，對已經脫離的多元醇基，可能產生最大5倍當量的蟻酸。因此，配置於下游側之非再生型混床式離子交換樹脂裝置的負載也相應地增加，造成使非再生型混床式離子交換樹脂極早期劣化。However, in the case of the organic component generated by the rupture (4), the ultraviolet radiation in the ultraviolet oxidizing device may generate a maximum of 5 times equivalents of formic acid to the detached polyol group. Therefore, the load of the non-regenerating mixed-bed type ion exchange resin device disposed on the downstream side is correspondingly increased, resulting in extremely early deterioration of the non-regenerating mixed-bed type ion exchange resin.
又，在硼吸附陽離子交換陰離子交換混床樹脂，硼吸附樹脂之在前述(1)、(2)的脫離所產生的脫離基，係具備具有＋的電荷之氮原子%(N＋ )，因此，已經脫離的有機物成分會藉由硼吸附陽離子交換陰離子交換混床樹脂中所含有的陽離子交換樹脂進行離子交換，不會有從離子交換樹脂層漏出之情況。另外，如前述(3)、(4)，結合斷裂之情況，已經脫離的有機物成分未被硼吸附陽離子交換陰離子交換混床樹脂進行離子交換，會從離子交換樹脂層漏出。Furthermore, the cation exchange anion exchange mixed bed resin adsorbed on boron, and the leaving group generated by the dissociation of boron adsorption resin from (1) and (2) mentioned above has a nitrogen atom% (N + ) having a charge of + . Therefore, The detached organic components will be ion-exchanged by the cation-exchange resin contained in the cation-exchange anion-exchange mixed bed resin adsorbed by boron, and there will be no leakage from the ion-exchange resin layer. In addition, as described in (3) and (4) above, in the case of rupture, the separated organic components are not ion-exchanged by the boron-adsorbed cation-exchange anion-exchange mixed-bed resin, and may leak out of the ion-exchange resin layer.
再者，硼吸附樹脂以外，陰離子交換樹脂也會有被過氧化氫分解之情況，例如，具有作為離子交換基之一級胺基、二級胺基、三級胺基等之陰離子交換樹脂，也會產生有機物成分之脫離。又，前述陰離子交換樹脂的分解是在硼吸附陰離子交換混床樹脂內產生之情況，脫離所產生之有機物成分會直接從離子交換樹脂漏出。Furthermore, in addition to boron adsorption resins, anion exchange resins may be decomposed by hydrogen peroxide. For example, anion exchange resins having primary amine groups, secondary amine groups, and tertiary amine groups as ion exchange groups may also Release of organic components will occur. In addition, the decomposition of the anion exchange resin is generated in the boron-adsorbed anion exchange mixed bed resin, and the organic components generated by the detachment will leak out directly from the ion exchange resin.
但，即使在前述硼吸附陰離子交換混床樹脂內，前述陰離子交換樹脂被分解而產生之有機物成分從離子交換樹脂層漏出的情況，因該漏出的有機物成分所引起之對後段的非再生型混床式離子交換樹脂之影響也極小。這是因為陰離子交換樹脂所具有的離子交換基之分子量較硼吸附樹脂所具有的離子交換基的分子量小，碳-碳結合數也少，因此，這些因分解所產生的有機分成分之當量形成較因前述硼吸附樹脂的分解所產生之量大幅少之故。However, even in the boron-adsorbed anion exchange mixed bed resin, if the organic component generated by the decomposition of the anion exchange resin leaks out of the ion exchange resin layer, the non-renewable type mixing in the latter stage due to the leaked organic component The effect of bed-type ion exchange resins is also minimal. This is because the molecular weight of the ion-exchange group of the anion exchange resin is smaller than that of the ion-exchange group of the boron adsorption resin, and the number of carbon-carbon bonds is also small. Therefore, the equivalent amount of these organic components produced by the decomposition is formed. The amount is significantly smaller than that due to the decomposition of the boron adsorption resin.
另外，前述陰離子交換樹脂的分解是在硼吸附陽離子交換陰離子交換混床樹脂內產生之情況，有機物成分係離子交換基直接脫離，而具備具有＋電荷的氮原子(N＋ )者為大部分，因此，被離子交換樹脂層內的陽離子交換樹脂捕捉，幾乎不會從離子交換樹脂層漏出。在陽離子交換樹脂的分解是在硼吸附陽離子交換陰離子交換混床樹脂內產生之情況，有機物成分係離子交換基直接脫離，而具備具有負(-)電荷者為大部分，因此，被離子交換樹脂層內的陰離子交換樹脂捕捉，幾乎不會從離子交換樹脂層漏出。In addition, the decomposition of the aforementioned anion exchange resin occurs in a boron-adsorbed cation exchange anion exchange mixed bed resin, and the ion exchange group of the organic component component is directly detached, and those having a nitrogen atom (N + ) having a charge are the majority. Therefore, it is captured by the cation exchange resin in the ion exchange resin layer, and it hardly leaks from the ion exchange resin layer. When the decomposition of cation exchange resin occurs in boron-adsorbed cation exchange anion exchange mixed bed resin, the organic component ion exchange group is directly detached, and those with negative (-) charge are the majority. The anion exchange resin in the layer is trapped and hardly leaks from the ion exchange resin layer.
依據前述推測，本發明者們發現，藉由調整第1紫外線氧化裝置12之紫外線照射量，抑制第1紫外線氧化裝置12之過氧化氫的產生量，可達到硼吸附陰離子交換混床樹脂之高硼去除率，並且可更有效率地減低設在下游側的非再生型混床式離子交換樹脂裝置15之負載，能夠長期間製造使硼濃度及TOC濃度顯著降低之超純水。Based on the foregoing speculations, the inventors have found that by adjusting the amount of ultraviolet radiation in the first ultraviolet oxidizing device 12 to suppress the amount of hydrogen peroxide generated in the first ultraviolet oxidizing device 12, the boron adsorption anion exchange mixed bed resin can be achieved at a high level. The boron removal rate can reduce the load of the non-regenerating mixed-bed ion exchange resin device 15 provided on the downstream side more efficiently, and it is possible to produce ultrapure water that significantly reduces the boron concentration and the TOC concentration for a long period of time.
(第2實施形態) 其次，參照圖2，說明關於第2實施形態之超純水製造系統2。超純水製造系統2，係在前述第1實施形態之超純水製造系統1中的第1紫外線氧化裝置(TOC-UV1)的上游側，具備逆滲透膜裝置(RO)21及電去離子裝置(EDI)22而構成。在圖2中，對於具有與圖1所示的超純水製造系統1相同功能之結構，賦予相同的圖號並省略重複之說明。(Second Embodiment) Next, an ultrapure water production system 2 according to a second embodiment will be described with reference to Fig. 2. The ultrapure water production system 2 is an upstream side of the first ultraviolet oxidizing device (TOC-UV1) in the ultrapure water production system 1 of the first embodiment, and includes a reverse osmosis membrane device (RO) 21 and electric deionization. Device (EDI) 22. In FIG. 2, structures having the same functions as those of the ultrapure water production system 1 shown in FIG. 1 are given the same reference numerals, and redundant descriptions are omitted.
逆滲透膜裝置(RO)21係將前處理水中的鹽類、及離子性、膠體性的有機物等去除而生成濃縮水及透過水。作為逆滲透膜裝置21，可使用三醋酸纖維素系非對稱膜、使用聚醯胺系複合膜作為薄片平膜、螺旋膜、管狀膜、中空絲膜之膜模組。其中，從提高雜質的去除率的觀點來看，聚醯胺系的複合膜為佳，膜形狀係螺旋膜為佳。The reverse osmosis membrane device (RO) 21 removes salts, ionic and colloidal organic substances in the pre-treated water, and generates concentrated water and permeated water. As the reverse osmosis membrane device 21, a cellulose triacetate-based asymmetric membrane and a polyamide-based composite membrane can be used as a membrane module of a flat sheet membrane, a spiral membrane, a tubular membrane, and a hollow fiber membrane. Among them, from the viewpoint of improving the removal rate of impurities, a polyamide-based composite film is preferable, and a film shape-based spiral film is preferable.
逆滲透膜裝置21的水回收率，理想為50~95%，更理想為60~90%，更加理想為65~85%。從長期間獲得硼濃度極低之超純水的觀點來看，逆滲透膜裝置21的硼去除率，理想為85%以上，更理想為90%以上。The water recovery rate of the reverse osmosis membrane device 21 is preferably 50 to 95%, more preferably 60 to 90%, and even more preferably 65 to 85%. From the viewpoint of obtaining ultrapure water with extremely low boron concentration over a long period of time, the boron removal rate of the reverse osmosis membrane device 21 is preferably 85% or more, and more preferably 90% or more.
逆滲透膜裝置21的膜阻抗，理想為45MPa/(m/h)，更理想為53MPa/(m/h)以上，更加理想為60MPa/(m/h)以上。若逆滲透膜裝置21的膜阻抗為45MPa/(m/h)以上的話，在末端，能夠更長期間維持極低的硼濃度。膜阻抗係200MPa/(m/h)以下為佳。若膜阻抗為200MPa/(m/h)以下的話，設在逆滲透膜裝置21的逆滲透膜模組的數量不會變得過大，可正確地進行運轉。在此，膜阻抗係當使預定的供給壓之純水通水於逆滲透膜裝置21時之該壓力對通量之值(壓力/通量)。通量係在常溫(20℃±5℃)、逆滲透膜模組的設計最大運轉壓以下且該逆滲透膜模組的設計運轉壓的1/4以上之壓力，使純水通水而實際測到的值。The membrane impedance of the reverse osmosis membrane device 21 is preferably 45 MPa / (m / h), more preferably 53 MPa / (m / h) or more, and even more preferably 60 MPa / (m / h) or more. If the membrane impedance of the reverse osmosis membrane device 21 is 45 MPa / (m / h) or more, it is possible to maintain a very low boron concentration at the end for a longer period. The film impedance is preferably 200 MPa / (m / h) or less. If the membrane impedance is 200 MPa / (m / h) or less, the number of reverse osmosis membrane modules provided in the reverse osmosis membrane device 21 does not become excessively large, and the operation can be performed accurately. Here, the membrane impedance is a value (pressure / flux) of the pressure versus the flux when pure water of a predetermined supply pressure is passed through the reverse osmosis membrane device 21. The flux is a pressure at room temperature (20 ° C ± 5 ° C) below the design maximum operating pressure of the reverse osmosis membrane module and at least 1/4 of the design operating pressure of the reverse osmosis membrane module. Measured value.
作為這樣的逆滲透膜裝置21，可舉出例如TM820K(膜阻抗120MPa/(m/h))、TM820M(膜阻抗94MPa/(m/h))、TM820V(膜阻抗65MPa/(m/h))、TM820(膜阻抗55MPa/(m/h))、SU720RB(膜阻抗50MPa/(m/h))(皆為東麗公司製)、SWC4 MAX(膜阻抗72MPa/(m/h)、日東電工公司製)。Examples of such a reverse osmosis membrane device 21 include TM820K (membrane impedance 120 MPa / (m / h)), TM820M (membrane impedance 94 MPa / (m / h)), and TM820V (membrane impedance 65 MPa / (m / h)) ), TM820 (membrane impedance 55MPa / (m / h)), SU720RB (membrane impedance 50MPa / (m / h)) (all manufactured by Toray), SWC4 MAX (membrane impedance 72MPa / (m / h), Nitto Made by an electric company).
逆滲透膜裝置21，亦可將2台以上的逆滲透膜裝置以串聯方式連接而作成為複數段所構成。在此情況，提高在逆滲透膜裝置21之脫鹽率，其結果，在硼吸附樹脂混合離子交換裝置13，可縮小硼吸附陰離子交換混床樹脂、或硼吸附陽離子交換陰離子交換混床樹脂之負載，因此能夠提高硼去除能力。再者，在將逆滲透膜裝置21作成為複數段而構成之情況，使用2段逆滲透膜裝置為佳。The reverse osmosis membrane device 21 may be configured by connecting two or more reverse osmosis membrane devices in series to form a plurality of stages. In this case, the desalination rate in the reverse osmosis membrane device 21 is increased. As a result, the boron adsorption resin mixed ion exchange device 13 can reduce the load of boron adsorption anion exchange mixed bed resin or boron adsorption cation exchange anion exchange mixed bed resin. Therefore, the boron removal ability can be improved. When the reverse osmosis membrane device 21 is configured in a plurality of stages, a two-stage reverse osmosis membrane device is preferably used.
電去離子裝置(EDI)22係將逆滲透膜裝置21的透過水進行離子交換處理，將水中的離子成分去除。電去離子裝置22係對以陰離子交換膜與陽離子交換膜所形成的空隙填充離子交換體，形成脫鹽室、濃縮室，再施加直流電流而去除被處理水中的離子。作為電去離子裝置22，可使用MK-3系列(E-Cell公司製)、VNX系列(IONPURE公司製)等的市面販賣品。再者，電去離子裝置22之水回收率係80～98%為佳。電去離子裝置22，能以單段的方式使用1台，亦可將2台以上以串聯方式連接而作為複數段使用。The electric deionization device (EDI) 22 is configured to perform ion exchange treatment on the permeated water of the reverse osmosis membrane device 21 to remove ionic components in the water. The electric deionization device 22 fills an ion exchanger with a gap formed by an anion exchange membrane and a cation exchange membrane to form a desalination chamber and a concentration chamber, and then applies a direct current to remove ions in the water to be treated. As the electric deionization device 22, commercially available products such as the MK-3 series (manufactured by E-Cell Corporation) and the VNX series (manufactured by IONPURE Corporation) can be used. In addition, the water recovery rate of the electric deionization device 22 is preferably 80 to 98%. The electric deionization device 22 can be used in a single stage, or two or more can be connected in series and used as a plurality of stages.
在本實施形態的超純水製造系統2，可調節電去離子裝置(EDI)22之電流值，使末端水質提升。電去離子裝置22之每1電池對處理流量的電流值(A值)，理想為30A/(m3 /h)以上，更理想為40A/(m3 /h)以上，更加理想為60A/(m3 /h)以上。藉由使電去離子裝置22之每1電池對處理流量的電流值為30A/(m3 /h)以上，使得能夠在末端更長期間維持較低的硼濃度。從消耗電力不會變得過大的點來看，A值係300A/(m3 /h)以下為佳。再者，1電池對處理流量係每1電池對的處理流量，可藉由電去離子裝置22所具有的陰離子交換膜與陽離子交換膜的組合(對)之數量(電池數)除被處理水朝電去離子裝置22之供給流量(m3 /h)來求取。In the ultrapure water production system 2 of this embodiment, the current value of the electric deionization device (EDI) 22 can be adjusted to improve the water quality at the end. The current value (A value) of the processing flow per battery of the electric deionization device 22 is preferably 30 A / (m 3 / h) or more, more preferably 40 A / (m 3 / h) or more, and 60 A / (m 3 / h) or more. By making the current value of the processing flow rate per cell of the electric deionization device 22 to 30 A / (m 3 / h) or more, it is possible to maintain a lower boron concentration for a longer period of time. From the point that the power consumption does not become excessively large, the A value is preferably 300 A / (m 3 / h) or less. In addition, the processing flow rate of one battery pair is the processing flow rate of one battery pair, and the treated water can be divided by the number (battery) of the combination (pairs) of anion exchange membrane and cation exchange membrane included in the electric deionization device 22. The supply flow rate (m 3 / h) to the electrodeionization device 22 was obtained.
從長期間獲得硼濃度極低之超純水的觀點來看，電去離子裝置22之硼去除率，理想為90%以上，更理想為95%以上。From the viewpoint of obtaining ultrapure water with extremely low boron concentration for a long period of time, the boron removal rate of the electrodeionization device 22 is preferably 90% or more, and more preferably 95% or more.
如此，在逆滲透膜裝置21及電去離子裝置22被處理過的水，依序通水於硼吸附樹脂混合離子交換裝置13、第2紫外線氧化裝置14及非再生型混床式離子交換樹脂裝置15，將殘留於水中之硼及TOC成分去除。硼吸附樹脂混合離子交換裝置13、第2紫外線氧化裝置14及非再生型混床式離子交換樹脂裝置15之理想態樣及及通水條件等是與前述第1實施形態相同。In this way, the water treated in the reverse osmosis membrane device 21 and the electric deionization device 22 is passed through the boron adsorption resin mixed ion exchange device 13, the second ultraviolet oxidation device 14, and the non-renewable mixed bed ion exchange resin in this order. The device 15 removes boron and TOC components remaining in the water. The boron adsorption resin mixed ion exchange device 13, the second ultraviolet oxidation device 14, and the non-regenerating mixed bed type ion exchange resin device 15 are the same as those in the first embodiment.
在超純水製造系統2，由於對經過了前述逆滲透膜裝置21及電去離子裝置22之水，藉由第1紫外線氧化裝置，以紫外線量0.05～0.2kWh/m3 照射紫外線，故，可抑制填充於硼吸附樹脂混合離子交換裝置13之混床樹脂的分解，硼吸附樹脂混合離子交換裝置13的處理水中之TOC濃度係可獲得例如0.6μg/L(as C)以下。藉此，能夠在1個月更佳為1年的長期間內，製造例如TOC濃度為0.5μg/L(as C)以下、硼濃度為1ng/L以下的超純水，作為非再生型混床式離子交換樹脂裝置15的處理水。更理想為能夠長期間製造TOC濃度為0.4μg/L(as C)以下、更加理想為TOC濃度為0.2μg/L(as C)以下的超純水。又，更理想為能夠長期間製造硼濃度為0.7ng/L以下、更加理想為硼濃度為0.5ng/L以下的超純水。 [實施例]In the ultrapure water production system 2, since the water that has passed through the aforementioned reverse osmosis membrane device 21 and the electric deionization device 22 is irradiated with ultraviolet rays at an ultraviolet amount of 0.05 to 0.2 kWh / m 3 through the first ultraviolet oxidation device, Decomposition of the mixed bed resin filled in the boron adsorption resin mixed ion exchange device 13 can be suppressed, and the TOC concentration in the treated water of the boron adsorption resin mixed ion exchange device 13 can be, for example, 0.6 μg / L (as C) or less. This makes it possible to produce, for example, ultrapure water having a TOC concentration of 0.5 μg / L (as C) or less and a boron concentration of 1 ng / L or less over a long period of one month to one year. The treated water of the bed-type ion exchange resin device 15. It is more desirable to be able to produce ultrapure water having a TOC concentration of 0.4 μg / L (as C) or less for a long period of time, and it is more desirable to have a TOC concentration of 0.2 μg / L (as C) or less. Furthermore, it is more desirable to be able to produce ultrapure water having a boron concentration of 0.7 ng / L or less over a long period of time, and even more preferably a boron concentration of 0.5 ng / L or less. [Example]
其次，說明關於實施例。Next, examples will be described.
(實驗例) 針對硼吸附樹脂(B)、陰離子交換樹脂(A)、陽離子交換陰離子交換混床樹脂(MB)、硼吸附陽離子交換陰離子交換混床樹脂(BMB)，確認到因TOC成分的漏出所引起之對後段的非再生型混床式離子交換樹脂裝置之負載的差異。(Experimental example) The leakage of TOC components was confirmed for boron adsorption resin (B), anion exchange resin (A), cation exchange anion exchange mixed bed resin (MB), and boron adsorption cation exchange anion exchange mixed bed resin (BMB). The difference in load caused by the non-regenerating mixed-bed ion exchange resin device in the latter stage.
在填充有硼吸附樹脂的裝置之下游側，依據配置紫外線氧化裝置(TOC-UV)與非再生型混床式離子交換樹脂裝置(Polisher)，作為加速試驗，以空間速度SV＝13(1/h)將過氧化氫濃度設為200μg/L之試驗水供給至硼吸附樹脂。試驗水係對純水添加了過氧化氫加以調製。On the downstream side of the device filled with boron adsorption resin, an ultraviolet oxidation device (TOC-UV) and a non-regenerating mixed-bed ion exchange resin device (Polisher) are installed as an acceleration test at a space velocity of SV = 13 (1 / h) Test water having a hydrogen peroxide concentration of 200 μg / L was supplied to the boron adsorption resin. The test water system was prepared by adding hydrogen peroxide to pure water.
針對試驗水經過通水後的非再生型混床式離子交換樹脂裝置之處理水的TOC濃度(末端TOC濃度)之經過時間的變化進行調查。其結果如圖3所示。The change in the elapsed time of the TOC concentration (terminal TOC concentration) of the treated water of the non-regenerating mixed-bed ion exchange resin device after the test water was passed through the water was investigated. The results are shown in Fig. 3.
針對將前述硼吸附樹脂分別變更成陰離子交換樹脂、陽離子交換陰離子交換混床樹脂、硼吸附陽離子交換陰離子交換混床樹脂之情況，與前述同樣地將試驗水進行通水，調查非再生型混床式離子交換樹脂裝置的處理水之TOC濃度(末端TOC濃度)的經過時間的變化。其結果如圖3所示。Regarding the case where the boron adsorption resin was changed to an anion exchange resin, a cation exchange anion exchange mixed bed resin, and a boron adsorption cation exchange anion exchange mixed bed resin, the test water was permeated in the same manner as described above to investigate the non-regenerating mixed bed. The change in the TOC concentration (terminal TOC concentration) of the treated water of the ion exchange resin device over time. The results are shown in Fig. 3.
再者，在本試驗例所使用的各裝置(樹脂)的規格及通水條件是如以下所述。 硼吸附樹脂(B)：使用DIAION CRB03(三菱化學(股)社製、交換容量：0.8eq/L)3.8L、空間速度SV＝13.2(1/h)、流量50L/h。 陰離子交換樹脂(A)：使用強鹼性陰離子交換樹脂(Duolite AGP、羅門哈斯公司(Rohm and Haas Company)製、交換容量：1.1eq/L)2.8L、空間速度SV＝18(1/h)、流量50L/h。The specifications and water flow conditions of each device (resin) used in this test example are as follows. Boron adsorption resin (B): DIAION CRB03 (manufactured by Mitsubishi Chemical Corporation, exchange capacity: 0.8 eq / L) 3.8 L, space velocity SV = 13.2 (1 / h), flow rate 50 L / h. Anion exchange resin (A): Strongly basic anion exchange resin (Duolite AGP, manufactured by Rohm and Haas Company, exchange capacity: 1.1 eq / L) 2.8 L, space velocity SV = 18 (1 / h ), Flow 50L / h.
陽離子交換陰離子交換混床樹脂(MB)：使用將強酸性陽離子交換樹脂(Duolite CGP、羅門哈斯公司(Rohm and Haas Company)製、交換容量：2.0eq/L)0.8L與強鹼性陰離子交換樹脂(Duolite AGP、羅門哈斯公司(Rohm and Haas Company)製、交換容量：1.1eq/L)2.8L予以混合者、空間速度SV＝14(1/h)、流量50L/h。Cation exchange anion exchange mixed bed resin (MB): Use a strong acidic cation exchange resin (Duolite CGP, manufactured by Rohm and Haas Company, exchange capacity: 2.0eq / L) 0.8L and strong basic anion exchange A resin (Duolite AGP, manufactured by Rohm and Haas Company, exchange capacity: 1.1 eq / L), 2.8 L was mixed, a space velocity SV = 14 (1 / h), and a flow rate of 50 L / h.
硼吸附陽離子交換陰離子交換混床樹脂(BMB)：使用將前述硼吸附樹脂、強鹼性陰離子交換樹脂及強鹼性陰離子交換樹脂，以硼吸附樹脂/強鹼性陰離子交換樹脂/強鹼性陰離子交換樹脂所表示的交換容量比(CC /CA /CB )為5.6/10.6/3.0進行混合者16.2L、空間速度SV＝3.2(1/h)、流量50L/h。 非再生型混床式離子交換樹脂裝置：使用將Duolite CGP、羅門哈斯公司(Rohm and Haas Company)製與Duolite AGP羅門哈斯公司(Rohm and Haas Company)製以交換容量為等量進行混合者，其樹脂量1L、空間速度SV＝50(1/h)、流量50L/h。Boron adsorption cation exchange anion exchange mixed bed resin (BMB): using the aforementioned boron adsorption resin, strong basic anion exchange resin and strong basic anion exchange resin, boron adsorption resin / strong basic anion exchange resin / strong basic anion The exchange capacity ratio (C C / C A / C B ) indicated by the exchange resin was 5.6 / 10.6 / 3.0, and 16.2 L was mixed, the space velocity SV was 3.2 (1 / h), and the flow rate was 50 L / h. Non-regenerating mixed bed type ion exchange resin device: A mixture of Duolite CGP, Rohm and Haas Company and Duolite AGP Rohm and Haas Company is used to mix the exchange capacity as the same amount. , Its resin volume is 1L, space velocity SV = 50 (1 / h), and flow rate is 50L / h.
如圖3所示，可得知若使含有過氧化氫之試驗水通水於硼吸附樹脂的話，比起陰離子交換樹脂、陽離子交換陰離子交換混床樹脂等，下游側的非再生型混床式離子交換樹脂裝置之劣化較早期行進。As shown in FIG. 3, it can be seen that if the test water containing hydrogen peroxide is allowed to pass through the boron adsorption resin, compared with anion exchange resin, cation exchange anion exchange mixed bed resin, etc., the downstream non-regenerating mixed bed type Deterioration of ion exchange resin devices progressed earlier.
(例1~6) 在例1~6，使用與圖1相同的結構，調查第1紫外線氧化裝置(TOC-UV1)之紫外線照射量與末端TOC濃度之關係。例2～5為實施例，例1、6為比較例。(Examples 1 to 6) In Examples 1 to 6, the relationship between the ultraviolet irradiation amount of the first ultraviolet oxidation device (TOC-UV1) and the terminal TOC concentration was investigated using the same structure as in FIG. 1. Examples 2 to 5 are examples, and examples 1 and 6 are comparative examples.
依序配置第1紫外線氧化裝置、硼吸附陽離子交換陰離子交換混床樹脂裝置、第2紫外線氧化裝置、非再生型混床式離子交換樹脂裝置。各裝置係使用以下的裝置。A first ultraviolet oxidation device, a boron-adsorbed cation exchange anion exchange mixed bed resin device, a second ultraviolet oxidation device, and a non-renewable mixed bed type ion exchange resin device were sequentially arranged. Each device uses the following devices.
硼吸附陽離子交換陰離子交換混床樹脂裝置：將與前述試驗例使用過者相同的樹脂，以相同比率混合者25L填充至樹脂塔內的裝置、SV＝30(1/h)。 第1紫外線氧化裝置、第2紫外線氧化裝置：日本Photoscience公司製 JPW-2。 非再生型混床式離子交換樹脂裝置：與前述實驗例相同者、SV＝30(1/h)。Boron adsorption cation exchange anion exchange mixed bed resin device: A device that fills the resin column with 25L of the same resin as the one used in the previous test example at the same ratio, and SV = 30 (1 / h). The first ultraviolet oxidation device and the second ultraviolet oxidation device: JPW-2 manufactured by Japan Photoscience. Non-regenerable mixed bed ion exchange resin device: The same as the previous experimental example, SV = 30 (1 / h).
將第1紫外線氧化裝置之紫外線照射量如表1所示進行變更，調查將被處理水通水1年時的非再生型混床式離子交換樹脂裝置的處理水之TOC濃度(末端TOC濃度)。其結果顯示於表1及圖4。被處理水的水質係TOC濃度100μg/L(as C)、硼濃度60μg/L、導電率70μS/cm。The UV irradiation amount of the first ultraviolet oxidation device was changed as shown in Table 1. The TOC concentration (terminal TOC concentration) of the treated water in the non-regenerating mixed-bed ion-exchange resin device when the treated water was passed for one year was investigated. . The results are shown in Table 1 and Fig. 4. The water quality of the treated water is TOC concentration of 100 μg / L (as C), boron concentration of 60 μg / L, and electrical conductivity of 70 μS / cm.
以與前述同樣地，調查將被處理水通水1個月的非再生型混床式離子交換樹脂裝置的處理水之TOC濃度(末端TOC濃度)。其結果顯示於表1及圖5。In the same manner as described above, the TOC concentration (terminal TOC concentration) of the treated water of the non-regenerating mixed-bed ion-exchange resin device in which the treated water was allowed to pass through for one month was investigated. The results are shown in Table 1 and FIG. 5.
又，測定通水初期的第1紫外線氧化裝置的處理水之過氧化氫濃度，調查第1紫外線氧化裝置之紫外線照射量與過氧化氫的產生量之關係。其結果顯示於表1及圖6。In addition, the hydrogen peroxide concentration of the treated water in the first ultraviolet oxidizing device at the initial stage of the water flow was measured, and the relationship between the amount of ultraviolet radiation and the amount of hydrogen peroxide generated in the first ultraviolet oxidizing device was examined. The results are shown in Table 1 and FIG. 6.
(例7~16(實施例)) 在例7~16，使用與圖2相同的結構，調查逆滲透膜裝置(RO)及電去離子裝置(EDI)之處理條件與非再生型混床式離子交換樹脂裝置的處理水之水質(末端水質)的關係。在前述例所使用的結構之第1紫外線氧化裝置之上游側，依序配置逆滲透膜裝置和電去離子裝置。原水的水質係TOC濃度200μg/L(as C)、硼濃度100μg/L、導電率150μS/cm。(Examples 7 to 16 (Examples)) In Examples 7 to 16, using the same structure as in FIG. 2, investigated the processing conditions of the reverse osmosis membrane device (RO) and the electric deionization device (EDI) and the non-regenerating mixed bed type. Relationship between the water quality (terminal water quality) of the treated water in the ion exchange resin device. On the upstream side of the first ultraviolet oxidizing device having the structure used in the foregoing example, a reverse osmosis membrane device and an electrodeionization device were sequentially arranged. The water quality of the raw water is a TOC concentration of 200 μg / L (as C), a boron concentration of 100 μg / L, and a conductivity of 150 μS / cm.
將第1紫外線氧化裝置(TOC-UV1)之紫外線照射量設為0.09kW・h/m3 ，再將被處理水供給至逆滲透膜裝置(TM820K、東麗公司製)。將此逆滲透膜裝置之透過水依據通水於電去離子裝置(VNX、IONPURE公司製)、硼吸附樹脂混合離子交換裝置、非再生型混床式離子交換樹脂裝置。The ultraviolet irradiation amount of the first ultraviolet oxidation device (TOC-UV1) was set to 0.09 kW · h / m 3 , and the treated water was supplied to a reverse osmosis membrane device (TM820K, manufactured by Toray Corporation). The permeated water of this reverse osmosis membrane device was passed through an electric deionization device (manufactured by VNX, IONPURE), a boron adsorption resin mixed ion exchange device, and a non-renewable mixed bed type ion exchange resin device.
作為硼吸附樹脂混合離子交換裝置，樹脂塔內部填充30L之硼吸附陽離子交換陰離子交換混床樹脂，其是將在前述實驗例使用過的樹脂同樣的硼吸附樹脂、強鹼性陰離子交換樹脂及強酸性陽離子交換樹脂以交換容量比CC /CA /CB ＝5.6/10.6/3.0(CC /(CA ＋CB )＝0.41)進行混合所獲得之硼吸附陽離子交換陰離子交換混床樹脂。As a boron adsorption resin mixed ion exchange device, the resin tower is filled with 30 L of boron adsorption cation exchange anion exchange mixed bed resin, which is the same boron adsorption resin, strong basic anion exchange resin, and strong acid as the resin used in the previous experimental example. A boron-adsorbed cation exchange anion exchange mixed bed resin obtained by mixing a basic cation exchange resin with an exchange capacity ratio C C / C A / C B = 5.6 / 10.6 / 3.0 (C C / (C A + C B ) = 0.41).
此時，變更供給至電去離子裝置的電流，將A值調節成表2所示，分別將被處理水進行通水，再調查1個月後、1年後之非再生型混床式離子交換樹脂裝置的處理水之TOC濃度及硼(B)濃度。其結果顯示於表2。At this time, the current supplied to the electric deionization device was changed, and the A value was adjusted as shown in Table 2. The treated water was passed through the water, and the non-regenerating mixed-bed type ions after 1 month and 1 year were investigated. The TOC concentration and boron (B) concentration of the treated water of the resin device are exchanged. The results are shown in Table 2.
又，測定被處理水之通水初期的第1紫外線氧化裝置的處理水之過氧化氫濃度、逆滲透膜裝置之膜阻抗及硼(B)去除率、電去離子裝置之硼(B)去除率。硼(B)去除率係以{1-(透過水中的硼濃度/供給水中的硼濃度)}×100(%)所算出之值。其結果顯示於表2。In addition, the hydrogen peroxide concentration of the treated water in the first ultraviolet oxidizing device at the initial stage of the water passing through the treated water, the membrane impedance of the reverse osmosis membrane device, and the boron (B) removal rate, and the boron (B) removal of the electrodeionization device were measured. rate. The removal rate of boron (B) is a value calculated by {1- (the concentration of boron in the permeate water / the concentration of boron in the supply water)} × 100 (%). The results are shown in Table 2.
接著，將第1紫外線氧化裝置之紫外線照射量設為0.09kW・h/m3 ，將電去離子裝置的A值設為80A/(m3 /h)，以前述相同的方式將被處理水供給至逆滲透膜裝置。Next, the ultraviolet irradiation amount of the first ultraviolet oxidation device was set to 0.09 kW · h / m 3 , and the A value of the electric deionization device was set to 80 A / (m 3 / h). The treated water was treated in the same manner as described above. It is supplied to a reverse osmosis membrane device.
作為逆滲透膜裝置，使用膜阻抗不同者，通水被處理水，分別調查1個月後、1年後之非再生型混床式離子交換樹脂裝置的處理水之TOC濃度及硼(B)濃度。其結果顯示於表3。As a reverse osmosis membrane device, use the water with different membrane resistance to pass through the treated water. Investigate the TOC concentration and boron (B) of the treated water of the non-regenerating mixed-bed ion exchange resin device one month and one year later. concentration. The results are shown in Table 3.
又，測定被處理水之通水初期的第1紫外線氧化裝置的處理水之過氧化氫濃度、逆滲透膜裝置之膜阻抗及硼(B)去除率、電去離子裝置之硼(B)去除率，其結果顯示於表3。In addition, the hydrogen peroxide concentration of the treated water in the first ultraviolet oxidizing device at the initial stage of the water passing through the treated water, the membrane impedance of the reverse osmosis membrane device, and the boron (B) removal rate, and the boron (B) removal of the electrodeionization device were measured. The results are shown in Table 3.
再者，所使用的逆滲透膜裝置為下述的裝置。 TM820K(膜阻抗120MPa/(m/h))、TM820M(膜阻抗94MPa/(m/h))、TM820V(膜阻抗65MPa/(m/h))、TM820(膜阻抗55MPa/(m/h))、SU720RB(膜阻抗50MPa/(m/h))、SUL-G20P(膜阻抗40MPa/(m/h))(皆為東麗公司製)、SWC4 MAX(膜阻抗72MPa/(m/h)、日東電工公司製)。The reverse osmosis membrane device used was the following device. TM820K (membrane impedance 120MPa / (m / h)), TM820M (membrane impedance 94MPa / (m / h)), TM820V (membrane impedance 65MPa / (m / h)), TM820 (membrane impedance 55MPa / (m / h) ), SU720RB (membrane impedance 50MPa / (m / h)), SUL-G20P (membrane impedance 40MPa / (m / h)) (all manufactured by Toray), SWC4 MAX (membrane impedance 72MPa / (m / h) , Manufactured by Nitto Denko Corporation).
又，在個別例，TOC濃度係藉由TOC濃度計(Anatel社製、Anatel A1000 XP)進行測定，硼濃度係藉由誘導結合電漿質量分析(ICP-MS)裝置進行測定，而過氧化氫濃度係藉由Noxia(野村微科學(Nomura Micro Science)(股)公司製)進行測定。In some cases, the TOC concentration was measured by a TOC concentration meter (Anatel A1000 XP, manufactured by Anatel), and the boron concentration was measured by an inductively coupled plasma mass analysis (ICP-MS) device, and hydrogen peroxide was measured. The concentration was measured by Noxia (manufactured by Nomura Micro Science Co., Ltd.).
1、2‧‧‧超純水製造系統1, 2‧‧‧ ultrapure water manufacturing system
11‧‧‧前處理裝置11‧‧‧ pre-processing device
12‧‧‧第1紫外線氧化裝置(TOC-UV1)12‧‧‧The first ultraviolet oxidation device (TOC-UV1)
13‧‧‧硼吸附樹脂混合離子交換裝置13‧‧‧ Boron adsorption resin mixed ion exchange device
14‧‧‧第2紫外線氧化裝置(TOC-UV2)14‧‧‧The second ultraviolet oxidation device (TOC-UV2)
15‧‧‧非再生型混床式離子交換樹脂裝置(Polisher)15‧‧‧Non-regenerate mixed bed ion exchange resin device (Polisher)
16‧‧‧點置系統(POU)16‧‧‧point system (POU)
21‧‧‧逆滲透膜裝置(RO)21‧‧‧ reverse osmosis membrane device (RO)
22‧‧‧電去離子裝置(EDI)22‧‧‧Electric Deionization Device (EDI)
圖1係顯示第1實施形態之超純水製造系統的方塊圖。 圖2係顯示第2實施形態之超純水製造系統的方塊圖。 圖3係顯示使過氧化氫水通水於各種離子交換樹脂時的通水時間與處理水TOC濃度的關係之圖表。 圖4係顯示對實施例的超純水製造系統進行通水1年後之第1紫外線氧化裝置的紫外線照射量與末端TOC濃度的關係之圖表。 圖5係顯示對實施例的超純水製造系統進行通水1個月後之第1紫外線氧化裝置的紫外線照射量與末端TOC濃度的關係之圖表。 圖6係顯示第1紫外線氧化裝置的紫外線照射量與過氧化氫的產生量的關係之圖表。FIG. 1 is a block diagram showing an ultrapure water production system according to the first embodiment. FIG. 2 is a block diagram showing an ultrapure water production system according to a second embodiment. FIG. 3 is a graph showing the relationship between the water passing time when hydrogen peroxide water is passed through various ion exchange resins and the TOC concentration of the treated water. FIG. 4 is a graph showing the relationship between the ultraviolet irradiation amount and the terminal TOC concentration of the first ultraviolet oxidizing device in the ultrapure water production system according to the example after one year of water flow. FIG. 5 is a graph showing the relationship between the ultraviolet irradiation amount of the first ultraviolet oxidizing device and the terminal TOC concentration of the first ultraviolet oxidizing device after the water was passed through the ultrapure water production system of the example for one month. FIG. 6 is a graph showing the relationship between the amount of ultraviolet radiation and the amount of hydrogen peroxide generated in the first ultraviolet oxidizing device.
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| JP4294731B2 (en) * | 1996-02-20 | 2009-07-15 | 野村マイクロ・サイエンス株式会社 | Ultrapure water production method and ultrapure water production apparatus |
| JP5211414B2 (en) * | 2001-03-12 | 2013-06-12 | 栗田工業株式会社 | Ultrapure water production equipment |
| JP3852926B2 (en) * | 2002-08-08 | 2006-12-06 | オルガノ株式会社 | Organic porous body having selective boron adsorption capacity, boron removal module and ultrapure water production apparatus using the same |
| JP3853776B2 (en) * | 2003-10-06 | 2006-12-06 | 野村マイクロ・サイエンス株式会社 | Ultrapure water production equipment |
| JP5454468B2 (en) * | 2008-03-31 | 2014-03-26 | 栗田工業株式会社 | Pure water production method and pure water production apparatus |
| JP6029948B2 (en) * | 2012-11-21 | 2016-11-24 | 野村マイクロ・サイエンス株式会社 | Pure water production method and pure water production system |
| JP6310819B2 (en) * | 2014-08-27 | 2018-04-11 | 野村マイクロ・サイエンス株式会社 | Pure water production apparatus, ultrapure water production system, and pure water production method |
| CZ2014627A3 (en) * | 2014-09-12 | 2016-05-04 | Centrum Výzkumu Řež S.R.O. | Installation for reducing organic carbon in boric acid solution |
-
2017
- 2017-04-27 JP JP2017088793A patent/JP2018183761A/en active Pending
-
2018
- 2018-04-06 KR KR1020197034201A patent/KR20190141208A/en not_active Application Discontinuation
- 2018-04-06 CN CN201880027433.2A patent/CN110678420A/en active Pending
- 2018-04-06 WO PCT/JP2018/014702 patent/WO2018198723A1/en active Application Filing
- 2018-04-17 TW TW110134392A patent/TW202200508A/en unknown
- 2018-04-17 TW TW107112998A patent/TWI754042B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190141208A (en) | 2019-12-23 |
| JP2018183761A (en) | 2018-11-22 |
| TWI754042B (en) | 2022-02-01 |
| WO2018198723A1 (en) | 2018-11-01 |
| CN110678420A (en) | 2020-01-10 |
| TW202200508A (en) | 2022-01-01 |
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