JP7225544B2 - Method for producing pure water or ultrapure water - Google Patents
Method for producing pure water or ultrapure water Download PDFInfo
- Publication number
- JP7225544B2 JP7225544B2 JP2018027933A JP2018027933A JP7225544B2 JP 7225544 B2 JP7225544 B2 JP 7225544B2 JP 2018027933 A JP2018027933 A JP 2018027933A JP 2018027933 A JP2018027933 A JP 2018027933A JP 7225544 B2 JP7225544 B2 JP 7225544B2
- Authority
- JP
- Japan
- Prior art keywords
- boron
- water
- concentration
- adsorption tower
- flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C02F1/28—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
Description
本発明は、ホウ素含有水をホウ素選択性吸着体が充填されたホウ素吸着塔に通水してホウ素を除去する方法に関する。本発明はまた、このホウ素の除去方法を用いた純水又は超純水の製造方法に関する。
なお、本明細書において、ＢＴＣ（Break through capacity）とは、ホウ素吸着塔の貫流交換容量をさし、ＢＴＰ（Break through point）とは、その貫流点（破過点）をさす。
TECHNICAL FIELD The present invention relates to a method for removing boron by passing boron-containing water through a boron adsorption tower packed with a boron-selective adsorbent. The present invention also relates to a method for producing pure water or ultrapure water using this method for removing boron.
In the present specification, BTC (Break through capacity) refers to the cross-flow exchange capacity of the boron adsorption tower, and BTP (Break through point) refers to its flow-through point.
超純水製造システムは、前処理システム、一次純水システム、サブシステムにより構成される。
一次純水システムの役割は前処理水中のイオン成分やＴＯＣの大部分を除去することにあり、ＲＯ装置（逆浸透膜装置）、脱気膜装置、脱イオン装置などによって構成される。このうち、脱イオン装置は水量やノンケミカルなどのニーズに応じてイオン交換樹脂による複数床式イオン交換装置、混床式イオン交換装置、電気脱イオン装置などから選択される。
The ultrapure water production system consists 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 is composed of an RO device (reverse osmosis membrane device), a degassing membrane device, a deionization device, and the like. Among them, the deionization device is selected from a multi-bed ion exchange device using ion exchange resin, a mixed bed ion exchange device, an electrodeionization device, etc. according to needs such as the amount of water and non-chemicals.
サブシステムは一次純水システムで得られた純水を目的に応じてポリッシュアップし、所定の超純水水質とするシステムであり、ＵＶ装置（紫外線酸化装置）、非再生型イオン交換装置、脱気膜装置、ＵＦ装置（限外濾過膜装置）などで構成される。
サブシステムの役割は、一次純水システムでなし得なかった微量のイオンやＴＯＣ及び微粒子の除去にある。
The sub-system polishes the pure water obtained in the primary pure water system according to the purpose and makes it into the specified ultrapure water quality. It consists 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 particulates that could not be done in the primary pure water system.
近年、最先端の電子産業分野では、ホウ素濃度１ｎｇ／Ｌ以下の超純水が要求されるようになってきている。
従来、水中のホウ素濃度を低減する手段の一つに、ホウ素キレート樹脂（ホウ素選択性イオン交換樹脂）又はアニオン交換樹脂の利用が挙げられる。ホウ素キレート樹脂は、樹脂内部のＮ－メチルグルカミン基（ＮＭＧ）とホウ素との反応によって、水中のホウ素を固定化して除去する樹脂である。
In recent years, ultrapure water with a boron concentration of 1 ng/L or less has been required in the cutting-edge electronics industry.
Conventionally, use of a boron chelate resin (boron-selective ion exchange resin) or an anion exchange resin is mentioned as one of means for reducing the boron concentration in water. The boron chelate resin is a resin that fixes and removes boron in water through a reaction between the N-methylglucamine group (NMG) inside the resin and boron.
例えば、特許文献１には、純水又は超純水製造設備内のいずれかの位置で、前処理水をホウ素キレート樹脂に接触させてホウ素を除去することが記載されている。
特許文献２には、非薬品再生型脱塩装置（２段ＲＯ、電気再生式脱塩装置、蒸留装置）の後段でホウ素キレート樹脂に接触させることが記載されている。
特許文献３には、アニオン交換樹脂によるホウ素の除去に当たり、被処理水の水温を低下させてホウ素ＢＴＣを上げることが記載されている。
特許文献４には、ホウ素を吸着したアニオン交換樹脂に温純水を通水してホウ素を脱着させて再生することでホウ素ＢＴＣを上げることが記載されている。
For example,
Patent Literature 2 describes contacting a boron chelate resin in the latter stage of a non-chemically regenerated desalting device (two-stage RO, electrically regenerating desalting device, distillation device).
Patent Document 3 describes that when removing boron by an anion exchange resin, the water temperature of the water to be treated is lowered to raise the boron BTC.
Patent Document 4 describes increasing boron BTC by passing warm pure water through an anion exchange resin that adsorbs boron to desorb and regenerate the resin.
ホウ素キレート樹脂等のホウ素選択性吸着体は高価なものであるため、そのホウ素吸着容量を最大限に活用すること、即ち、ホウ素吸着塔のホウ素ＢＴＣを十分に高めることが望まれる。
このような技術的要求において、従来技術は十分ではなく、例えば、前述の特許文献１，２の方法では、単純な配置でホウ素を除去することは可能であるが、ホウ素キレート樹脂に合わせた最適な運転制御を行っておらず、適正化を図ることができない。
特許文献３の方法は、水温調整によってリークしやすいホウ素を樹脂内に留まらせ、樹脂の吸着容量を有効利用するものであるが、水温調整のために、熱交換器の設置が必要なうえに、その効果は十分なものとは言えない。
特許文献４の方法では、ホウ素の脱離分だけ新たにホウ素除去が見込めるが、この方法でも十分な吸着容量の向上効果は得られず、また、温水のコストもかかる。
Since boron-selective adsorbents such as boron chelating resins are expensive, it is desirable to maximize their boron adsorption capacity, ie, to sufficiently increase the boron BTC of the boron adsorption tower.
In terms of such technical requirements, the prior art is not sufficient. For example, the methods of
The method of Patent Document 3 makes effective use of the adsorption capacity of the resin by allowing boron, which tends to leak, to remain in the resin by adjusting the water temperature. , the effect is not sufficient.
In the method of Patent Literature 4, it is expected that only the amount of desorbed boron will be newly removed.
本発明は、特別な装置設備や薬品、エネルギー等を必要とすることなく、ホウ素選択性吸着体を充填したホウ素吸着塔のホウ素ＢＴＣを高め、ホウ素選択性吸着体の吸着容量を最大限に活用し、より少ない樹脂量でより多くのホウ素を除去することを可能とするホウ素の除去方法と、このホウ素の除去方法を用いた純水又は超純水の製造方法を提供することを課題とする。 The present invention increases the boron BTC of a boron adsorption tower filled with a boron-selective adsorbent and makes maximum use of the adsorption capacity of the boron-selective adsorbent without requiring special equipment, chemicals, energy, etc. An object of the present invention is to provide a method for removing boron that can remove more boron with a smaller amount of resin, and a method for producing pure water or ultrapure water using this method for removing boron. .
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、ホウ素選択性吸着体を充填したホウ素吸着塔にホウ素含有水を通水してホウ素を除去する処理において、同じホウ素ＢＴＰを設置しても、通水ＳＶによって、ホウ素ＢＴＣが異なるものとなること、給水負荷や通水ＳＶを下げることで、ホウ素ＢＴＣを高めることができることを見出し、本発明を完成させた。
即ち、本発明は以下を要旨とする。
As a result of intensive studies to solve the above problems, the present inventors installed the same boron BTP in the process of removing boron by passing boron-containing water through a boron adsorption tower filled with a boron-selective adsorbent. However, it was found that the boron BTC differs depending on the water flow SV, and that the boron BTC can be increased by reducing the water supply load and the water flow SV, and completed the present invention.
That is, the gist of the present invention is as follows.
［１］ ホウ素含有水をホウ素選択性吸着体が充填されたホウ素吸着塔に通水してホウ素を除去する方法において、予め設定された該ホウ素吸着塔のホウ素ＢＴＰに応じて、該ホウ素吸着塔の給水のホウ素濃度と該ホウ素吸着塔への該ホウ素含有水の通水ＳＶとの積が所定値以下となる条件で該ホウ素含有水を通水することを特徴とするホウ素の除去方法。 [1] In a method of removing boron by passing boron-containing water through a boron adsorption tower filled with a boron-selective adsorbent, the boron adsorption tower is adjusted in accordance with a preset boron BTP of the boron adsorption tower. and passing the boron-containing water under the condition that the product of the boron concentration of the feed water and the flow SV of the boron-containing water to the boron adsorption tower is equal to or less than a predetermined value.
［２］ ［１］において、前記通水ＳＶと給水ホウ素濃度との積が所定値以下となるように、該通水ＳＶ、及び／又は、前記ホウ素吸着塔に充填するホウ素選択性吸着体量を設定することを特徴とするホウ素の除去方法。 [2] In [1], the water flow SV and/or the amount of boron-selective adsorbent to be filled in the boron adsorption tower so that the product of the water flow SV and the boron concentration in the feed water is equal to or less than a predetermined value. A method for removing boron, characterized by setting
［３］ ホウ素含有水をホウ素選択性吸着体が充填されたホウ素吸着塔に通水してホウ素を除去する方法において、予め設定された該ホウ素吸着塔のホウ素ＢＴＰに応じて、該ホウ素吸着塔の給水のホウ素濃度と該ホウ素吸着塔への該ホウ素含有水の通水ＳＶと該ホウ素含有水の通水時間との積が所定値以下となる条件で該ホウ素含有水を通水することを特徴とするホウ素の除去方法。 [3] In the method of removing boron by passing boron-containing water through a boron adsorption tower filled with a boron-selective adsorbent, the boron adsorption tower is adjusted in accordance with the preset boron BTP of the boron adsorption tower. The boron-containing water is passed under the condition that the product of the boron concentration of the feed water, the flow time SV of the boron-containing water to the boron adsorption tower, and the flow time of the boron-containing water is a predetermined value or less. A method for removing boron.
［４］ ［３］において、前記通水ＳＶと給水ホウ素濃度と通水時間との積が所定値以下となるように、該通水ＳＶの設定、前記ホウ素吸着塔に充填するホウ素選択性吸着体量の設定、及び通水時間の制御のいずれかを行うことを特徴とするホウ素の除去方法。 [4] In [3], the water flow SV is set so that the product of the water flow SV, the boron concentration of the feed water, and the water flow time is equal to or less than a predetermined value, and the boron adsorption tower is filled with selective adsorption of boron. A method for removing boron, characterized by either setting a body weight or controlling a water flow time.
［５］ ［３］において、複数の前記ホウ素吸着塔を用い、該複数のホウ素吸着塔のうちの一部のホウ素吸着塔に前記給水の通水を継続しながら、前記通水ＳＶと給水ホウ素濃度と通水時間との積が所定値以下となるように、他のホウ素吸着塔に通水の停止期間を設定することを特徴とするホウ素の除去方法。 [5] In [3], using a plurality of the boron adsorption towers, while continuing to flow the feed water to some of the boron adsorption towers, the water flow SV and the feed water boron A method for removing boron, characterized by setting a period during which water supply to another boron adsorption tower is stopped such that the product of concentration and water supply time is equal to or less than a predetermined value.
［６］ ［５］において、前記複数のホウ素吸着塔が並列に接続されており、該複数のホウ素吸着塔のうちの一部のホウ素吸着塔に前記給水の通水を継続しながら、他のホウ素吸着塔に通水の停止期間を設定することを特徴とするホウ素の除去方法。 [6] In [5], the plurality of boron adsorption towers are connected in parallel, and while continuing to pass the feed water to some boron adsorption towers of the plurality of boron adsorption towers, the other A method for removing boron, characterized by setting a period during which water supply to a boron adsorption tower is stopped.
［７］ ［１］ないし［６］のいずれかに記載のホウ素の除去方法によりホウ素を除去する工程を有する純水又は超純水の製造方法。 [7] A method for producing pure water or ultrapure water, comprising a step of removing boron by the method for removing boron according to any one of [1] to [6].
本発明によれば、ホウ素キレート樹脂等のホウ素選択性吸着体のホウ素吸着容量を最大限に有効利用して再生頻度又は交換頻度を低減し、より少ない樹脂量でより多くのホウ素を除去することができ、所望の低ホウ素濃度の処理水ないしは純水又は超純水を安定して得ることができる。 According to the present invention, the boron adsorption capacity of a boron-selective adsorbent such as a boron chelate resin is maximally utilized to reduce the frequency of regeneration or replacement, thereby removing more boron with a smaller amount of resin. Thus, it is possible to stably obtain treated water or pure water or ultrapure water having a desired low boron concentration.
以下に本発明の実施の形態を詳細に説明する。 Embodiments of the present invention will be described in detail below.
＜メカニズム＞
本発明により、ホウ素ＢＴＰに応じて、給水ホウ素濃度と通水ＳＶの積或いは給水ホウ素濃度と通水ＳＶと通水時間の積を所定値以下とすることで、ホウ素ＢＴＣを上げることができるメカニズムは以下の通り考えられる。
<Mechanism>
According to the present invention, depending on the boron BTP, the product of the boron concentration of the feed water and the water flow SV or the product of the boron concentration of the feed water, the water flow SV and the water flow time is set to a predetermined value or less. A mechanism that can increase the boron BTC. is considered as follows.
ホウ素キレート樹脂等のホウ素選択性吸着体の一般的な物性として、次のようなことが挙げられる。
即ち、例えば、吸着容量０．７ｅｑ／Ｌ－Ｒの樹脂を１Ｌ用いた場合、理論上は７．５ｇ程度のホウ素を吸着除去できるはずであるが、超純水として求められるホウ素濃度１～１０ｎｇ／Ｌの処理水を得るべくホウ素ＢＴＰを１～１０ｎｇ／Ｌに設定した場合、ホウ素は５０～３００ｍｇ程度しか除去できない（即ち、吸着容量５０～３００ｍｇ／Ｌ－Ｒ）。
これは、ホウ素の反応が遅いので、樹脂であれば外周部に吸着したホウ素が樹脂内に拡散する速度が非常に遅くなることから、樹脂内部をホウ素の吸着除去に活用できていないためである。
給水負荷を極端に下げたり、非常にゆっくり通水すると、ホウ素が樹脂内を拡散し、樹脂の内部を効率的にホウ素の吸着に使うことができるようになり、ホウ素ＢＴＣを高くすることができるようになる。
General physical properties of boron-selective adsorbents such as boron chelate resins are as follows.
That is, for example, when using 1 L of resin with an adsorption capacity of 0.7 eq/LR, theoretically about 7.5 g of boron should be able to be adsorbed and removed, but the boron concentration required for ultrapure water is 1 to 10 ng. When boron BTP is set to 1-10 ng/L to obtain treated water of 1/L, only about 50-300 mg of boron can be removed (that is, adsorption capacity of 50-300 mg/L−R).
This is because the reaction of boron is slow, and if it is a resin, the speed at which boron adsorbed on the outer periphery diffuses into the resin is extremely slow, so the inside of the resin cannot be used to adsorb and remove boron. .
When the water supply load is extremely lowered or the water is passed very slowly, boron diffuses inside the resin, and the inside of the resin can be efficiently used for boron adsorption, and the boron BTC can be increased. become.
このことは後掲の実験例１，２の結果からも明らかであり、同じホウ素ＢＴＰであっても通水ＳＶによってホウ素ＢＴＣは大きく異なり（実験例１の図１）、ホウ素ＢＴＰに応じて、給水ホウ素濃度と通水ＳＶの積を所定値以下とすることで、ホウ素ＢＴＣを大きくすることができる（実験例２の図２）。
給水ホウ素濃度と通水ＳＶと通水時間の積についても同様である。
This is also clear from the results of Experimental Examples 1 and 2 below. Even with the same boron BTP, the boron BTC differs greatly depending on the water flow SV (Fig. 1 of Experimental Example 1). By setting the product of the feed water boron concentration and the water flow SV to a predetermined value or less, the boron BTC can be increased (Fig. 2 of Experimental Example 2).
The same applies to the product of the feed water boron concentration, the water flow SV, and the water flow time.
＜ホウ素吸着塔の運転方法＞
本発明では、ホウ素選択性吸着体を充填したホウ素吸着塔にホウ素含有水を通水してホウ素含有水中のホウ素を除去するに当たり、予め設定したホウ素ＢＴＰに応じて、給水ホウ素含有水（ホウ素吸着塔に流入する水）のホウ素濃度と通水ＳＶとの積、或いは給水ホウ素濃度と通水ＳＶと通水時間との積が、所定値以下となるような条件で処理を行う。
<How to operate the boron adsorption tower>
In the present invention, when removing boron in the boron-containing water by passing the boron-containing water through a boron adsorption tower filled with a boron-selective adsorbent, the boron-containing water (boron adsorption The treatment is performed under conditions such that the product of the boron concentration in 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 less than or equal to a predetermined value.
前述の通り、ホウ素選択性吸着体は、同じホウ素ＢＴＰ、同じ給水ホウ素濃度であっても、通水ＳＶが異なるとホウ素ＢＴＣが大幅に異なるものとなる。そこで、本発明では、例えば、予め設定されたホウ素ＢＴＰ（この値は目的とするホウ素除去処理水のホウ素濃度となる。）に対して所望のホウ素ＢＴＣを設定し、このホウ素ＢＴＣを得るために、通水ＳＶと給水ホウ素濃度との積（時間あたり負荷量）を設定し、この設定値を満たすように通水ＳＶや、ホウ素吸着塔に充填するホウ素選択性吸着体量（用いるホウ素選択性吸着体量）を決定する。 As described above, the boron-selective adsorbent has the same boron-BTP and the same feed-water boron concentration, but the boron-BTC is significantly different when the water flow SV is different. Therefore, in the present invention, for example, a desired boron BTC is set with respect to a preset boron BTP (this value is the boron concentration of the target boron removal treated water), and to obtain this boron BTC , Set the product of the water flow SV and the feed water boron concentration (load amount per hour), and set the water flow SV and the amount of boron selective adsorbent filled in the boron adsorption tower (boron selectivity to be used) so as to satisfy this set value Determine the amount of adsorbent).
一方、通水ＳＶを下げられない場合は、例えば、一定量通水後に休止時間を設けることで、休止時間も含めて単位時間当たりの通水ＳＶを下げることで、対応することができる。
例えば、医薬用、食品用、飲料用、半導体用水として用いられる超純水の製造装置において、複数のイオン交換塔を直列に接続し、イオン交換塔の再生又は交換に当たり、最もイオン成分濃度の高い水が導入される最前段のイオン交換塔を再生し、再生したイオン交換塔を最後段に設置するか、或いは、最前段のイオン交換塔を取り外し、最後段のイオン交換塔の更に後段に新しいイオン交換塔を設置する、所謂メリーゴーランド方式の再生又は交換方式が知られているが、本発明をこのようなメリーゴーランド方式に適用し、複数のホウ素吸着塔を直列に設け、順次通水を停止するホウ素吸着塔を変えてゆき、各々のホウ素吸着塔において、一定期間通水を行わないようにすることで、運転中の通水ＳＶはそのままで単位時間当たりの通水ＳＶ（時間平均負荷量）を下げ、樹脂内部へのホウ素の浸透時間を確保してホウ素ＢＴＣを上げることができる。
また、複数のホウ素吸着塔を並列に接続し、順次通水を行うホウ素吸着塔と通水を停止するホウ素吸着塔を変えてゆき、各々のホウ素吸着塔において、一定時間通水を行わないようにすることで、運転中の通水ＳＶはそのままで、単位時間当たりの通水ＳＶ（時間平均負荷）を下げ、樹脂内部へのホウ素の浸透時間を確保してホウ素ＢＴＣを上げることができる。
このような通水の停止による通水ＳＶ（時間平均負荷）の低減は、被処理水中のホウ素濃度が高い場合に特に有効である。
On the other hand, when the water flow SV cannot be lowered, for example, by providing a rest time after a certain amount of water flow, it is possible to reduce the water flow SV per unit time including the rest time.
For example, in ultrapure water production equipment used for pharmaceuticals, food, beverages, and semiconductors, a plurality of ion exchange towers are connected in series, and when the ion exchange towers are regenerated or replaced, the ion component concentration is the highest. Regenerate the foremost ion exchange tower into which water is introduced and install the regenerated ion exchange tower at the last stage, or remove the forefront ion exchange tower and install a new one after the last ion exchange tower. A so-called merry-go-round type regeneration or exchange system is known in which an ion exchange tower is installed, but the present invention is applied to such a merry-go-round system, a plurality of boron adsorption towers are installed in series, and water flow is stopped sequentially. By changing the boron adsorption tower and preventing water flow for a certain period of time in each boron adsorption tower, the water flow SV per unit time (time average load) remains the same as the water flow SV during operation. can be lowered, and boron BTC can be increased by ensuring the penetration time of boron into the inside of the resin.
In addition, a plurality of boron adsorption towers are connected in parallel, and the boron adsorption towers in which the water flow is sequentially switched and the boron adsorption towers in which the water flow is stopped are changed so that the water flow is not performed for a certain period of time in each boron adsorption tower. By doing so, the water flow SV (time average load) per unit time can be lowered while the water flow SV during operation remains the same, and the boron BTC can be increased by ensuring the penetration time of boron into the resin.
Reduction of the water flow SV (time average load) by stopping the water flow is particularly effective when the boron concentration in the water to be treated is high.
＜具体的な条件設定＞
本発明において、ホウ素ＢＴＰに応じて給水ホウ素濃度と通水ＳＶの積、或いは、給水ホウ素濃度と通水ＳＶと通水時間の積をどのように設定するかは、用いるホウ素選択性吸着体のホウ素吸着能と所望とするホウ素ＢＴＣに応じて決定されるものであるが、例えば、次のように条件設定することが好ましい。
<Specific condition settings>
In the present invention, how to set the product of the feedwater boron concentration and the water flow SV or the product of the feedwater boron concentration, the water flow SV and the water flow time depending on the boron BTP depends on the boron-selective adsorbent used. Although it is determined according to the boron adsorption capacity and the desired boron BTC, it is preferable to set the conditions as follows, for example.
具体的には、処理水ホウ素濃度即ちホウ素ＢＴＰを１０ｎｇ／Ｌに設定したい時は、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積を１２０以下、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）と運転時間（ｈ）の積を２８８０以下となるように条件設定する。
望ましくは、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積を１００以下、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）と運転時間（ｈ）の積は２４００以下、さらに望ましくは通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積を６０以下、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）と運転時間（ｈ）の積は１４４０以下に設定する。
Specifically, when you want to set the boron concentration in the treated water, that is, the boron BTP to 10 ng / L, the product of the water flow SV (1 / h) and the feed water boron concentration (μg / L) is 120 or less, and the water flow SV (1 /h), the feed-water boron concentration (μg/L) and the operating time (h) are set to 2880 or less.
Desirably, the product of the water flow SV (1/h) and the feedwater boron concentration (μg/L) is 100 or less, and the water flow SV (1/h), the feedwater boron concentration (μg/L) and the operating time (h) The product is 2400 or less, more preferably the product of water flow SV (1/h) and feedwater boron concentration (μg/L) is 60 or less, water flow SV (1/h) and feedwater boron concentration (μg/L) and operation The time (h) product is set to 1440 or less.
また、処理水ホウ素濃度即ち、ホウ素ＢＴＰを１ｎｇ／Ｌに設定したい時は、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積を８０以下、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）と運転時間（ｈ）の積を１９２０以下になるように条件設定する。望ましくは、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積を６０以下、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）と運転時間（ｈ）の積は１４４０以下、さらに望ましくは通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積を４５以下、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）と運転時間（ｈ）の積は１０８０以下に設定する。 Also, when you want to set the boron concentration in the treated water, that is, the boron BTP to 1 ng / L, the product of the water flow SV (1 / h) and the feed water boron concentration (μg / L) is 80 or less, and the water flow SV (1 / h ), the feed-water boron concentration (μg/L), and the operating time (h) are set to 1920 or less. Desirably, the product of the water flow SV (1/h) and the feedwater boron concentration (μg/L) is 60 or less, and the water flow SV (1/h), the feedwater boron concentration (μg/L) and the operating time (h) The product is 1440 or less, more preferably the product of water flow SV (1/h) and feedwater boron concentration (μg/L) is 45 or less, water flow SV (1/h) and feedwater boron concentration (μg/L) and operation The time (h) product is set to 1080 or less.
＜ホウ素選択性吸着体＞
本発明で用いるホウ素選択性吸着体としては、ホウ素キレート樹脂（ホウ素選択性キレート樹脂）のような粒状物でも良く、繊維状物でも良い。
ホウ素選択性吸着体としては、イオン交換作用でホウ素を吸着するものや、キレート作用でホウ素を吸着するものなど、各種のものを用いることができるが、例えば、市販のホウ素選択性キレート樹脂の「ダイヤイオンＣＲＢ」（三菱ケミカル（株））、ホウ素選択性キレート繊維の「キレストファイバーＧＲＹ」（キレスト（株））等を用いることができる。
例えば、「ダイヤイオンＣＲＢ０２」は、以下に示す如く、スチレン・ジビニルベンゼンの骨格にホウ素選択性の高いキレート形成基としてＮグルカミン基を導入した化学構造を有している。
<Boron-selective adsorbent>
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.
Various types of boron-selective adsorbents can be used, such as those that adsorb boron by ion exchange action and those that adsorb boron by chelate action. "Diaion CRB" (Mitsubishi Chemical Co., Ltd.), boron-selective chelate fiber "Chelast Fiber GRY" (Cherest Co., Ltd.), and the like can be used.
For example, "Diaion CRB02" has a chemical structure in which an N-glucamine group as a chelate-forming group with high boron selectivity is introduced into the skeleton of styrene-divinylbenzene, as shown below.
このＮグルカミン基は、弱塩基性アニオン交換樹脂と同様の３級アミン型になっており、次のような反応でホウ酸性ホウ素を吸着する。 This N-glucamine group is of a tertiary amine type similar to that of the weakly basic anion exchange resin, and adsorbs boron borate in the following reaction.
ホウ素を吸着して破過したホウ素選択性吸着体は、ＨＣｌ、Ｈ２ＳＯ４等の酸、又はＮａＯＨ、ＫＯＨ等のアルカリ剤を用いて任意の方法で再生することができる。 The boron-selective adsorbent that adsorbs and breaks through boron can be regenerated by any method using an acid such as HCl or H2SO4 or an alkaline agent such as NaOH or KOH.
＜純水又は超純水の製造への適用＞
本発明のホウ素の除去方法を純水又は超純水の製造方法に適用することで、ホウ素濃度が十分に低減された純水又は超純水を安定かつ効率的に得ることができる。
この場合、本発明によるホウ素吸着塔は、サブシステムの入口側（一次純水システムの最後段）に設け、十分に通水ＳＶを下げて運転を行うことで、ホウ素ＢＴＣを上げた上で、ホウ素濃度１～１０ｎｇ／Ｌというような高水質の純水又は超純水を安定に製造することができ、通常３年毎、好ましくは５年毎のホウ素選択性吸着体の交換で運転を継続することが可能となる。
<Application to production of pure water or ultrapure water>
By applying the method for removing boron of the present invention to a method for producing pure water or ultrapure water, pure water or ultrapure water in which the boron concentration is sufficiently reduced can be stably and efficiently obtained.
In this case, 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 with the water flow SV sufficiently lowered to raise the boron BTC, High-quality pure water or ultrapure water with a boron concentration of 1 to 10 ng / L can be stably produced, and operation is continued by replacing the boron-selective adsorbent usually every 3 years, preferably every 5 years. It becomes possible to
以下に実施例に代わる実験例を挙げる。 Experimental examples in place of the examples are given below.
［実験例１］
三菱ケミカル（株）製ホウ素キレート樹脂「ＣＲＢＴ０３」を樹脂量として６００ｍＬ－Ｒ充填したホウ素吸着塔に、ホウ素濃度１μｇ／Ｌの給水を通水して処理するときのホウ素ＢＴＰを５０ｎｇ／Ｌに設定し、通水ＳＶを種々に変えて、ホウ素ＢＴＣを調べる実験を行った。
その結果、通水ＳＶとホウ素ＢＴＣとの関係は、下記表１の通りであり、これをグラフ化すると図１の通り、同じホウ素ＢＴＰであっても通水ＳＶにより、ホウ素ＢＴＣは大きく異なること、通水ＳＶを低くすることで、ホウ素ＢＴＣを大きくすることができることが判明した。
[Experimental example 1]
Boron BTP is set to 50 ng/L when water is passed through a boron adsorption tower filled with 600 mL-R of Mitsubishi Chemical Corporation's boron chelate resin "CRBT03" as a resin amount and treated with feed water having a boron concentration of 1 μg / L. Then, an experiment was conducted to check the boron BTC by changing the water flow SV variously.
As a result, the relationship between the water flow SV and boron BTC is as shown in Table 1 below, and when graphed, as shown in FIG. , it was found that the boron BTC can be increased by lowering the water flow SV.
［実験例２］
実験例１において、ホウ素ＢＴＰを１ｎｇ／Ｌ、１０ｎｇ／Ｌ又は１００ｎｇ／Ｌに設定したこと以外は同様にして実験を行い、通水ＳＶ（１／ｈ）と給水ホウ素濃度（μｇ／Ｌ）の積と、ホウ素ＢＴＣとの関係を調べ、結果を図２（ａ），（ｂ），（ｃ）に示した。
図２（ａ），（ｂ），（ｃ）より、いずれのホウ素ＢＴＰの場合も、通水ＳＶと給水ホウ素濃度との積を所定値以下とすることで、ホウ素ＢＴＣを大きくすることができることが分かる。
具体的には、ホウ素ＢＴＰ１ｎｇ／Ｌの場合は通水ＳＶと給水ホウ素濃度との積は８０μｇ／Ｌ／ｈ以下に、ホウ素ＢＴＰ１０ｎｇ／Ｌの場合は通水ＳＶと給水ホウ素濃度との積は１２０μｇ／Ｌ／ｈ以下に、ホウ素ＢＴＰ１００ｎｇ／Ｌの場合には通水ＳＶと給水ホウ素濃度との積は２００μｇ／Ｌ／ｈ以下となるように条件設定することが好ましいことが分かる。
[Experimental 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. The relationship between the product and boron BTC was investigated, and the results are shown in FIGS.
2(a), (b), and (c), in the case of any boron BTP, the boron BTC can be increased by setting the product of the water flow SV and the boron concentration in the feed water to a predetermined value or less. I understand.
Specifically, when boron BTP is 1 ng/L, the product of water flow SV and feed-water boron concentration is 80 μg/L/h or less, and when boron BTP is 10 ng/L, the product of water flow SV and feed-water boron concentration is 120 μg. /L/h or less, and in the case of 100 ng/L of boron BTP, the product of the water flow SV and the feed-water boron concentration is preferably set to 200 µg/L/h or less.
Claims (6)
該ホウ素を除去する工程において、該ホウ素吸着塔の給水のホウ素濃度と該ホウ素吸着塔への該ホウ素含有水の通水ＳＶとの積が所定値以下となる条件で該ホウ素含有水を通水し、
予め設定された該ホウ素吸着塔のホウ素ＢＴＰに応じて、該所定値を設定することにより、ホウ素濃度１～１０ｎｇ／Ｌの純水又は超純水を製造することを特徴とする純水又は超純水の製造方法。 A method for producing pure water or ultrapure water, comprising a step of removing boron by a boron removal method of removing boron by passing boron-containing water through a boron adsorption tower filled with a boron-selective adsorbent,
In the step of removing boron, the boron-containing water is passed under the condition that the product of the boron concentration in the feed water of the boron adsorption tower and the flow SV of the boron-containing water to the boron adsorption tower is a predetermined value or less. death,
By setting the predetermined value according to the boron BTP of the boron adsorption tower set in advance, pure water or ultrapure water having a boron concentration of 1 to 10 ng / L is produced . A method for producing pure water .
該ホウ素を除去する工程において、該ホウ素吸着塔の給水のホウ素濃度と該ホウ素吸着塔への該ホウ素含有水の通水ＳＶと該ホウ素含有水の通水時間との積が所定値以下となる条件で該ホウ素含有水を通水し、
予め設定された該ホウ素吸着塔のホウ素ＢＴＰに応じて、該所定値を設定することにより、ホウ素濃度１～１０ｎｇ／Ｌの純水又は超純水を製造することを特徴とする純水又は超純水の製造方法。 A method for producing pure water or ultrapure water, comprising a step of removing boron by a boron removal method of removing boron by passing boron-containing water through a boron adsorption tower filled with a boron-selective adsorbent,
In the step of removing boron, the product of the concentration of boron in the feed water of the boron adsorption tower, the flow time SV of the boron-containing water to the boron absorption tower, and the flow time of the boron-containing water becomes equal to or less than a predetermined value. passing the boron-containing water under conditions,
By setting the predetermined value according to the boron BTP of the boron adsorption tower set in advance, pure water or ultrapure water having a boron concentration of 1 to 10 ng / L is produced . A method for producing pure water .
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018027933A JP7225544B2 (en) | 2018-02-20 | 2018-02-20 | Method for producing pure water or ultrapure water |
| KR1020207011157A KR20200121279A (en) | 2018-02-20 | 2018-09-12 | Method for removing boron, and method for producing pure or ultrapure water |
| CN201880066892.1A CN111225880A (en) | 2018-02-20 | 2018-09-12 | Method for removing boron and method for producing pure water or ultrapure water |
| PCT/JP2018/033811 WO2019163174A1 (en) | 2018-02-20 | 2018-09-12 | Method for removing boron and method for manufacturing pure water or ultrapure water |
| TW107133323A TWI781227B (en) | 2018-02-20 | 2018-09-21 | Method for removing boron, and method for producing pure water or ultrapure water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018027933A JP7225544B2 (en) | 2018-02-20 | 2018-02-20 | Method for producing pure water or ultrapure water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019141775A JP2019141775A (en) | 2019-08-29 |
| JP7225544B2 true JP7225544B2 (en) | 2023-02-21 |
Family
ID=67687527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018027933A Active JP7225544B2 (en) | 2018-02-20 | 2018-02-20 | Method for producing pure water or ultrapure water |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7225544B2 (en) |
| KR (1) | KR20200121279A (en) |
| CN (1) | CN111225880A (en) |
| TW (1) | TWI781227B (en) |
| WO (1) | WO2019163174A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102498578B1 (en) * | 2022-02-22 | 2023-02-13 | 삼성전자주식회사 | Management method of ultra pure water manufacturing system |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001017866A (en) | 1999-07-07 | 2001-01-23 | Kurita Water Ind Ltd | Preparation of boron adsorbing resin |
| JP2001340851A (en) | 2000-06-02 | 2001-12-11 | Nippon Denko Kk | Method and apparatus for treating boron-containing wastewater |
| JP2004066153A (en) | 2002-08-08 | 2004-03-04 | Japan Organo Co Ltd | Organic porous body having selective boron adsorption capability and boron removal module and ultrapure water production apparatus using the same |
| JP2004195457A (en) | 2002-12-18 | 2004-07-15 | Rohm & Haas Co | Water treatment system generating small waste quantity |
| JP2004275948A (en) | 2003-03-18 | 2004-10-07 | Sumitomo Chem Co Ltd | Boron removal process and boron removal apparatus |
| JP2012205996A (en) | 2011-03-29 | 2012-10-25 | Kurita Water Ind Ltd | Operation method of ion exchange apparatus and ion exchange system |
| JP2011167606A5 (en) | 2010-02-17 | 2013-03-28 | ||
| JP2014176794A (en) | 2013-03-14 | 2014-09-25 | Japan Organo Co Ltd | Treatment method of heavy metal-containing solution |
| JP2014188444A (en) | 2013-03-27 | 2014-10-06 | Chiyoda Corp | Method for treating boron-containing effluent |
| JP2015136685A (en) | 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 | Device for treating water to be treated, device for producing purified water, and method for treating water to be treated |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54131340A (en) * | 1978-03-31 | 1979-10-12 | Mitsubishi Chem Ind Ltd | Water treatment device |
| JPS632619A (en) * | 1986-06-18 | 1988-01-07 | Satake Eng Co Ltd | Electric discharge machine |
| JP3200301B2 (en) | 1994-07-22 | 2001-08-20 | オルガノ株式会社 | Method and apparatus for producing pure or ultrapure water |
| JP3426072B2 (en) | 1996-01-17 | 2003-07-14 | オルガノ株式会社 | Ultrapure water production equipment |
| JP3489650B2 (en) * | 1997-03-13 | 2004-01-26 | オルガノ株式会社 | Treatment method of boron-containing wastewater |
| JP2004330012A (en) * | 2003-05-01 | 2004-11-25 | Shin Nihon Salt Co Ltd | Boron adsorbing agent and manufacturing method therefor |
| CN1894029B (en) * | 2003-12-15 | 2011-05-11 | 旭化成化学株式会社 | Porous formed article and method for production thereof |
| JP2005177564A (en) | 2003-12-17 | 2005-07-07 | Nomura Micro Sci Co Ltd | Ultrapure water production method and apparatus |
| JP5081690B2 (en) | 2008-03-31 | 2012-11-28 | オルガノ株式会社 | Production method of ultra pure water |
| JP2011167606A (en) | 2010-02-17 | 2011-09-01 | Nippon Rensui Co Ltd | Method for producing chelate forming group-containing adsorbing material |
| CN106629975A (en) * | 2016-12-27 | 2017-05-10 | 南京慧城水处理设备有限公司 | Method used for removing trace boron in desalination seawater with boron selective chelating resin |
-
2018
- 2018-02-20 JP JP2018027933A patent/JP7225544B2/en active Active
- 2018-09-12 KR KR1020207011157A patent/KR20200121279A/en not_active Application Discontinuation
- 2018-09-12 WO PCT/JP2018/033811 patent/WO2019163174A1/en active Application Filing
- 2018-09-12 CN CN201880066892.1A patent/CN111225880A/en active Pending
- 2018-09-21 TW TW107133323A patent/TWI781227B/en active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001017866A (en) | 1999-07-07 | 2001-01-23 | Kurita Water Ind Ltd | Preparation of boron adsorbing resin |
| JP2001340851A (en) | 2000-06-02 | 2001-12-11 | Nippon Denko Kk | Method and apparatus for treating boron-containing wastewater |
| JP2004066153A (en) | 2002-08-08 | 2004-03-04 | Japan Organo Co Ltd | Organic porous body having selective boron adsorption capability and boron removal module and ultrapure water production apparatus using the same |
| JP2004195457A (en) | 2002-12-18 | 2004-07-15 | Rohm & Haas Co | Water treatment system generating small waste quantity |
| JP2004275948A (en) | 2003-03-18 | 2004-10-07 | Sumitomo Chem Co Ltd | Boron removal process and boron removal apparatus |
| JP2011167606A5 (en) | 2010-02-17 | 2013-03-28 | ||
| JP2012205996A (en) | 2011-03-29 | 2012-10-25 | Kurita Water Ind Ltd | Operation method of ion exchange apparatus and ion exchange system |
| JP2014176794A (en) | 2013-03-14 | 2014-09-25 | Japan Organo Co Ltd | Treatment method of heavy metal-containing solution |
| JP2014188444A (en) | 2013-03-27 | 2014-10-06 | Chiyoda Corp | Method for treating boron-containing effluent |
| JP2015136685A (en) | 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 | Device for treating water to be treated, device for producing purified water, and method for treating water to be treated |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201934495A (en) | 2019-09-01 |
| CN111225880A (en) | 2020-06-02 |
| KR20200121279A (en) | 2020-10-23 |
| WO2019163174A1 (en) | 2019-08-29 |
| TWI781227B (en) | 2022-10-21 |
| JP2019141775A (en) | 2019-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8771522B2 (en) | Method and apparatus for treating organic matter-containing water | |
| JP6298275B2 (en) | Water treatment especially to obtain ultrapure water | |
| CN105517957A (en) | Method and apparatus for manufacturing pure water | |
| JP4599803B2 (en) | Demineralized water production equipment | |
| JPH09278418A (en) | Purification of hydrogen peroxide solution | |
| TWI808053B (en) | Ultrapure water production system and ultrapure water production method | |
| JP7225544B2 (en) | Method for producing pure water or ultrapure water | |
| JP5584043B2 (en) | Pretreatment device for membrane separation and membrane separation method using the same | |
| KR20150048866A (en) | Method of desalinating boron-containing solution | |
| JP2013023442A (en) | Method and apparatus for purifying alcohol | |
| JP6437874B2 (en) | Method and apparatus for regenerating ion exchange resin | |
| JP6310819B2 (en) | Pure water production apparatus, ultrapure water production system, and pure water production method | |
| JPS62110795A (en) | Device for producing high-purity water | |
| JP5739687B2 (en) | Alcohol purification method, apparatus and system | |
| JP2016150275A (en) | Method and device for producing purified water | |
| KR102489442B1 (en) | Anion exchange resin and water treatment method using the same | |
| JP7313262B2 (en) | Reverse osmosis membrane device | |
| JP2005246126A (en) | Device and method for manufacturing pure water or ultra pure water | |
| JP2015199050A (en) | Method of removing metal ion in saturated salt water | |
| JPH0251672B2 (en) | ||
| JPH04271848A (en) | Recovery method for anion exchange resin | |
| JP2006254794A (en) | Method for regenerating phenolic absorbing resin in sugar solution refining system and sugar solution refining apparatus | |
| JP5564817B2 (en) | Ion exchange resin regeneration method and ultrapure water production apparatus | |
| JP2023077744A (en) | Regeneration process for pure water production apparatus and pure water production apparatus | |
| JP2001219163A (en) | Treating method of boron-containing water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201105 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20211116 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220117 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220510 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220707 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220906 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230110 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230123 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7225544 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |