WO2019163174A1 - ホウ素の除去方法、及び純水又は超純水の製造方法 - Google Patents

ホウ素の除去方法、及び純水又は超純水の製造方法 Download PDF

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Publication number
WO2019163174A1
WO2019163174A1 PCT/JP2018/033811 JP2018033811W WO2019163174A1 WO 2019163174 A1 WO2019163174 A1 WO 2019163174A1 JP 2018033811 W JP2018033811 W JP 2018033811W WO 2019163174 A1 WO2019163174 A1 WO 2019163174A1
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Prior art keywords
boron
water
adsorption tower
product
concentration
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PCT/JP2018/033811
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English (en)
French (fr)
Japanese (ja)
Inventor
中馬　高明
後藤　秀樹
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栗田工業株式会社
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Application filed by 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to CN201880066892.1A priority Critical patent/CN111225880A/zh
Priority to KR1020207011157A priority patent/KR20200121279A/ko
Publication of WO2019163174A1 publication Critical patent/WO2019163174A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/108—Boron compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a method for removing boron by passing boron-containing water through a boron adsorption tower filled with a boron selective adsorbent.
  • the present invention also relates to a method for producing pure water or ultrapure water using this boron removal method.
  • BTC Bit through capacity
  • BTP Bit through point
  • the ultrapure water production system is composed of a pretreatment system, a primary pure water system, and subsystems.
  • the role of the primary pure water system is to remove most of the ionic components and TOC in the pretreated water, and it is composed of RO device (reverse osmosis membrane device), deaeration membrane device, deionization device and the like.
  • a deionization apparatus is selected from a multiple bed type ion exchange apparatus, a mixed bed type ion exchange apparatus, an electrodeionization apparatus, etc. using an ion exchange resin according to needs such as the amount of water and non-chemical.
  • the sub-system is a system that polishes the pure water obtained in the primary pure water system according to the purpose to obtain a predetermined ultrapure water quality. It is a UV device (ultraviolet oxidation device), a non-regenerative ion exchanger, It is composed of an air membrane device, a UF device (ultrafiltration membrane device), and the like.
  • the role of the subsystem is to remove trace amounts of ions, TOC, and fine particles that could not be achieved with the primary pure water system.
  • boron chelate resin boron selective ion exchange resin
  • anion exchange resin is a resin that immobilizes and removes boron in water by a reaction between N-methylglucamine group (NMG) inside the resin and boron.
  • Patent Document 1 describes that boron is removed by bringing pretreated water into contact with a boron chelate resin at any position in pure water or ultrapure water production equipment.
  • Patent Document 2 describes that a non-chemical regeneration type desalination apparatus (two-stage RO, electric regeneration type desalination apparatus, distillation apparatus) is brought into contact with a boron chelate resin at a subsequent stage.
  • a non-chemical regeneration type desalination apparatus two-stage RO, electric regeneration type desalination apparatus, distillation apparatus
  • Patent Document 3 describes that in removing boron by an anion exchange resin, the temperature of water to be treated is lowered to raise boron BTC.
  • Patent Document 4 describes that boron BTC is increased by passing warm pure water through an anion exchange resin adsorbing boron to desorb and regenerate boron.
  • boron-selective adsorbents such as boron chelate resins are expensive, it is desired to make the most of their boron adsorption capacity, that is, to sufficiently increase the boron BTC of the boron adsorption tower.
  • Patent Document 4 it is possible to newly remove boron by the amount of boron desorption, but this method does not provide a sufficient adsorption capacity improvement effect and also costs hot water.
  • the present invention increases the boron BTC of a boron adsorption tower packed with a boron selective adsorbent without using special equipment, chemicals, energy, etc., and maximizes the adsorption capacity of the boron selective adsorbent.
  • An object of the present invention is to provide a method for removing boron that makes it possible to remove more boron with a smaller amount of resin, and a method for producing pure water or ultrapure water using this boron removal method. .
  • the present inventor installed the same boron BTP in a process of removing boron by passing boron-containing water through a boron adsorption tower packed with a boron selective adsorbent. Even so, the present inventors have found that the boron BTC is different depending on the water flow SV, and that the boron BTC can be increased by lowering the water supply load and the water flow SV, thereby completing the present invention.
  • the gist of the present invention is as follows.
  • the boron adsorption tower is set in accordance with the boron BTP of the boron adsorption tower set in advance.
  • a method for removing boron wherein the boron-containing water is passed under a condition that the product of the boron concentration of the feed water and the boron-containing water flow SV to the boron adsorption tower is a predetermined value or less.
  • the boron adsorption tower is set in accordance with the boron BTP of the boron adsorption tower set in advance. Passing the boron-containing water under the condition that the product of the boron concentration of the feed water and the boron-containing water flow SV to the boron adsorption tower and the boron-containing water flow time is a predetermined value or less.
  • a method for producing pure water or ultrapure water comprising a step of removing boron by the boron removing method according to any one of [1] to [6].
  • the boron adsorption capacity of a boron-selective adsorbent such as a boron chelate resin is effectively utilized to the maximum to reduce the regeneration frequency or exchange frequency, and to remove more boron with a smaller amount of resin. Therefore, desired treated water or pure water or ultrapure water having a low boron concentration can be stably obtained.
  • FIG. 1 is a graph showing the relationship between water flow SV and boron BTC in Experimental Example 1.
  • 2a, 2b, and 2c are graphs showing the relationship between the product of the water flow SV and the feed water boron concentration in Example 2 and the boron BTC.
  • the boron BTC can be increased by setting the product of the feed water boron concentration and the water flow SV or the product of the feed water boron concentration, the water flow SV and the water flow time to a predetermined value or less according to the boron BTP. Is considered as follows.
  • boron selective adsorbents such as boron chelate resins
  • examples of general physical properties of boron selective adsorbents such as boron chelate resins include the following.
  • the boron BTC differs greatly depending on the water flow SV (FIG. 1 of Experimental Example 1), and depending on the boron BTP, The boron BTC can be increased by setting the product of the feed water boron concentration and the water flow SV to a predetermined value or less (FIG. 2 of Experimental Example 2).
  • the feed water contains boron-containing water (boron adsorption water) according to the preset boron BTP.
  • Treatment is performed under such a condition that the product of the boron concentration of the water flowing into the tower) and the water flow SV or the product of the feed water boron concentration, the water flow SV, and the water flow time is a predetermined value or less.
  • the boron BTC differs greatly when the water flow SV is different. Therefore, in the present invention, for example, in order to obtain a boron BTC by setting a desired boron BTC with respect to a preset boron BTP (this value is the boron concentration of the target boron removal treated water).
  • the product (load per hour) of the water flow SV and the feed water boron concentration is set, and the water selective SV and the boron selective adsorbent amount to be filled in the boron adsorption tower so as to satisfy this set value (the boron selectivity used) Adsorbent amount) is determined.
  • a plurality of ion exchange towers are connected in series. Regenerate the ion exchange column at the front stage to be introduced and install the regenerated ion exchange tower at the last stage, or remove the ion exchange tower at the front stage and perform a new ion exchange further downstream from the ion exchange tower at the last stage.
  • a so-called merry-go-round regeneration or exchange system with a tower is known.
  • the present invention is applied to such a merry-go-round system, a plurality of boron adsorption towers are provided in series, and the boron adsorption towers that sequentially stop the water flow are changed, and each of the boron adsorption towers does not conduct water for a certain period of time. You may do it. If it does in this way, water flow SV during operation will remain as it is, water flow SV per unit time (time average load amount) can be lowered, boron penetration time into the resin can be secured, and boron BTC can be raised.
  • Such reduction of the water flow SV (time average load) by stopping water flow is particularly effective when the concentration of boron in the water to be treated is high.
  • ⁇ Specific condition setting> how to set the product of the feed water boron concentration and the water flow SV or the product of the feed water boron concentration, the water flow SV and the water flow time according to the boron BTP depends on the boron selective adsorbent used. It is determined according to the boron adsorption capacity and the desired boron BTC. An example of setting conditions is given below.
  • the product of the water flow SV (1 / h) and the water supply boron concentration ( ⁇ g / L) is 120 or less
  • the water flow SV (1 / h) and the water supply Conditions are set so that the product of the boron concentration ( ⁇ g / L) and the operation time (h) is 2880 or less.
  • the product of the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) is 100 or less
  • the product is 2400 or less, more preferably, the product of the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) is 60 or less, the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) and operation.
  • the product of time (h) is set to 1440 or less.
  • the product of the water flow SV (1 / h) and the water supply boron concentration ( ⁇ g / L) is 80 or less
  • the water flow SV (1 / h) Conditions are set so that the product of the feed water boron concentration ( ⁇ g / L) and the operation time (h) is 1920 or less.
  • the product of the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) is 60 or less, and the water flow SV (1 / h), the feed water boron concentration ( ⁇ g / L), and the operation time (h).
  • the product is 1440 or less, more desirably, the product of the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) is 45 or less, and the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) are operated.
  • the product of time (h) is set to 1080 or less.
  • the boron selective adsorbent used in the present invention may be a granular material such as a boron chelate resin (boron selective chelate resin) or a fibrous material.
  • boron selective adsorbent various types such as those that adsorb boron by ion exchange action and those that adsorb boron by chelation action can be used.
  • commercially available boron selective chelate resin “ Diaion CRB "(Mitsubishi Chemical Co., Ltd.), boron-selective chelate fiber” Chirest Fiber GRY “(Chillest Co., Ltd.), and the like can be used.
  • Diaion CRB02 has a chemical structure in which an N-glucamine group is introduced as a chelate-forming group having high boron selectivity into the styrene-divinylbenzene skeleton as shown below.
  • This N-glucamine group is a tertiary amine type similar to the weakly basic anion exchange resin, and adsorbs boric acid boron by the following reaction.
  • the boron selective adsorbent that has been broken through by adsorbing boron can be regenerated by any method using an acid such as HCl or H 2 SO 4 or an alkali agent such as NaOH or KOH.
  • the boron adsorption tower according to the present invention is provided on the inlet side of the subsystem (the last stage of the primary pure water system) and is operated by sufficiently lowering the water flow SV so that the boron BTC is raised and the boron concentration is 1 High-quality pure water or ultrapure water of ⁇ 10 ng / L can be stably produced.
  • This boron adsorption tower can be continuously operated by replacing the boron selective adsorbent usually every 3 years, preferably every 5 years.
  • Boron BTP is set to 50 ng / L when treated by supplying water with a boron concentration of 1 ⁇ g / L to a boron adsorption tower packed with 600 mL-R of boron chelate resin “CRBT03” manufactured by Mitsubishi Chemical Corporation. Then, an experiment for examining boron BTC was conducted by changing the water flow SV in various ways.
  • the relationship between the water flow SV and the boron BTC is as shown in Table 1 below.
  • Table 1 the relationship between the water flow SV and the boron BTC is as shown in Table 1 below.
  • Example 2 In Experimental Example 1, the experiment was performed in the same manner except that boron BTP was set to 1 ng / L, 10 ng / L, or 100 ng / L, and the water flow SV (1 / h) and the feed water boron concentration ( ⁇ g / L) The relationship between the product and boron BTC was examined, and the results are shown in FIGS. 2a, 2b and 2c.
  • the boron BTC can be increased by setting the product of the water flow SV and the feed water boron concentration to a predetermined value or less.
  • the product of the water flow SV and the feed water boron concentration is 80 ⁇ g / L / h or less
  • the product of the water flow SV and the feed water boron concentration is 120 ⁇ g. It can be seen that it is preferable to set the conditions so that the product of the water flow SV and the feed water boron concentration is 200 ⁇ g / L / h or less in the case of boron BTP of 100 ng / L below / L / h.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Water Treatment By Sorption (AREA)
  • Removal Of Specific Substances (AREA)
PCT/JP2018/033811 2018-02-20 2018-09-12 ホウ素の除去方法、及び純水又は超純水の製造方法 WO2019163174A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880066892.1A CN111225880A (zh) 2018-02-20 2018-09-12 硼的去除方法、及纯水或超纯水的制造方法
KR1020207011157A KR20200121279A (ko) 2018-02-20 2018-09-12 붕소의 제거 방법, 및 순수 또는 초순수의 제조 방법

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JP2018027933A JP7225544B2 (ja) 2018-02-20 2018-02-20 純水又は超純水の製造方法
JP2018-027933 2018-02-20

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KR102498578B1 (ko) * 2022-02-22 2023-02-13 삼성전자주식회사 초순수 제조 시스템의 관리 방법

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JPS632619A (ja) * 1986-06-18 1988-01-07 Satake Eng Co Ltd 放電加工装置
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54131340A (en) * 1978-03-31 1979-10-12 Mitsubishi Chem Ind Ltd Water treatment device
JPS632619A (ja) * 1986-06-18 1988-01-07 Satake Eng Co Ltd 放電加工装置
JP2001340851A (ja) * 2000-06-02 2001-12-11 Nippon Denko Kk ホウ素含有排水の処理方法及び処理装置
JP2004066153A (ja) * 2002-08-08 2004-03-04 Japan Organo Co Ltd ホウ素選択吸着能を有する有機多孔質体、これを用いたホウ素除去モジュールおよび超純水製造装置
JP2004195457A (ja) * 2002-12-18 2004-07-15 Rohm & Haas Co 低廃棄物量の水処理系
JP2004275948A (ja) * 2003-03-18 2004-10-07 Sumitomo Chem Co Ltd 硼素除去方法および硼素除去装置
JP2011167606A (ja) * 2010-02-17 2011-09-01 Nippon Rensui Co Ltd キレート形成基含有吸着材料の製造方法
JP2012205996A (ja) * 2011-03-29 2012-10-25 Kurita Water Ind Ltd イオン交換装置の運転方法及びイオン交換システム
JP2014176794A (ja) * 2013-03-14 2014-09-25 Japan Organo Co Ltd 重金属含有溶液の処理方法
JP2015136685A (ja) * 2014-01-24 2015-07-30 三菱レイヨンアクア・ソリューションズ株式会社 被処理水の処理装置、純水の製造装置および被処理水の処理方法

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JP7225544B2 (ja) 2023-02-21
TW201934495A (zh) 2019-09-01
KR20200121279A (ko) 2020-10-23
TWI781227B (zh) 2022-10-21
CN111225880A (zh) 2020-06-02
JP2019141775A (ja) 2019-08-29

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