JP2012213730A - Desalination apparatus and desalination method - Google Patents

Desalination apparatus and desalination method Download PDF

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JP2012213730A
JP2012213730A JP2011081252A JP2011081252A JP2012213730A JP 2012213730 A JP2012213730 A JP 2012213730A JP 2011081252 A JP2011081252 A JP 2011081252A JP 2011081252 A JP2011081252 A JP 2011081252A JP 2012213730 A JP2012213730 A JP 2012213730A
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reducing agent
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JP5669651B2 (en
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Katsunori Matsui
克憲 松井
Kazuhisa Takeuchi
和久 竹内
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Mitsubishi Heavy Industries Ltd
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    • 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
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Abstract

PROBLEM TO BE SOLVED: To provide a desalination apparatus and a desalination method capable of controlling excessive injection of SBS solution and surely completing neutralization treatment when carrying out the neutralization treatment using a reducing agent to raw water after chlorination treatment.SOLUTION: The desalination apparatus 10 includes: a desalting treatment apparatus 17 and a reducing agent feeder 18 which includes a chlorine adding part 31 for taking out raw water obtained by adding chlorine-containing water from an upstream side of the desalting treatment apparatus 17 and quantitatively adding chlorine components to the raw water which has been taken out, a chlorine determining quantity part 32 for determining quantity of chlorine amount in the raw water obtained by adding chlorine components, a reducing agent feeding amount determination part 33 for calculating reducing agent amount corresponding to the difference between the chlorine amount determined by the chlorine determining quantity part 32 and the quantitatively added chlorine amount and determining feeding amount of the reducing agent, and a reducing agent feeding part 34 for feeding the determined feeding amount of the reducing agent to the raw water obtained by adding chlorine-containing water at the upstream side of the desalting treatment apparatus 17.

Description

本発明は、海水を淡水化するための淡水化装置及び淡水化処理方法に関する。   The present invention relates to a desalination apparatus and a desalination treatment method for desalinating seawater.

海水を淡水化するための設備として、逆浸透膜（ＲＯ膜、Ｒｅｖｅｒｓｅ Ｏｓｍｏｓｉｓ Ｍｅｍｂｒａｎｅ）を用いて海水（原水）を脱塩処理して淡水化する海水淡水化装置（以下、淡水化装置という）がある。ＲＯ膜としては、酢酸セルロース膜やポリアミド膜などが使用される。   As equipment for desalinating seawater, there is a seawater desalination apparatus (hereinafter referred to as a desalination apparatus) that desalinates seawater (raw water) using a reverse osmosis membrane (RO membrane, Reverse Osmosis Membrane). is there. As the RO membrane, a cellulose acetate membrane or a polyamide membrane is used.

淡水化装置では、一般的に、原水を脱塩処理する前に、殺菌などを目的として原水に塩素剤を添加する前処理が行われる。ＲＯ膜としてポリアミド膜などの塩素耐性を有しない材料からなる膜を使用した場合、ＲＯ膜に塩素が接触すると、ＲＯ膜が劣化する。そのため、ＲＯ膜の前段側において、還元剤を用いて原水中の塩素を中和処理する必要がある。還元剤としては、例えば重亜硫酸ソーダ（ＳＢＳ、Ｓｏｄｉｕｍ ｂｉｓｕｌｆａｔｅ ｓｏｄａ）が用いられる（特許文献１〜３）。   In the desalination apparatus, generally, before desalting the raw water, a pretreatment for adding a chlorine agent to the raw water for the purpose of sterilization or the like is performed. When a film made of a material having no chlorine resistance, such as a polyamide film, is used as the RO film, the RO film deteriorates when chlorine contacts the RO film. Therefore, it is necessary to neutralize the chlorine in the raw water using a reducing agent on the upstream side of the RO membrane. For example, sodium bisulfite (SBS) is used as the reducing agent (Patent Documents 1 to 3).

特開平７−３０８６７１号公報JP-A-7-308671 特開平７−１７１５６５号公報JP 7-171565 A 特開平９−５７０７６号公報JP-A-9-57076

塩素を含む原水をＳＢＳ溶液で中和する際には、中和処理した原水中の酸化還元電位を計測して、中和の終了を確認する。酸化還元電位（ＯＲＰ）はＯＲＰ計により計測する。該ＯＲＰ計は、原水の性状（ｐＨ等）、ＯＲＰ電極の連続使用による電極汚れ、及びＯＲＰ計自体の製造要因のぶれ等により絶対値が変動することがある。このため、ＳＢＳを添加した原水のＯＲＰの絶対値を直接測定し、これを目標値としてＳＢＳ溶液の供給量を制御しようとすると、ＳＢＳ溶液の注入量が不足、または過剰となる可能性がある。ＳＢＳ溶液の注入量が不足した場合には、原水が十分に中和されないため、ＲＯ膜の損傷要因となる。ＳＢＳ溶液の注入量が過剰の場合には、ランニングコストが嵩む上、ＳＢＳ由来の硫黄化合物が逆浸透膜に付着し、閉塞等の問題を引き起こす可能性がある。   When neutralizing raw water containing chlorine with the SBS solution, the oxidation-reduction potential in the neutralized raw water is measured to confirm the end of neutralization. The oxidation-reduction potential (ORP) is measured with an ORP meter. The absolute value of the ORP meter may fluctuate due to the properties of raw water (pH, etc.), electrode contamination due to continuous use of the ORP electrode, and fluctuations in manufacturing factors of the ORP meter itself. For this reason, if the absolute value of the ORP of the raw water added with SBS is directly measured and the supply amount of the SBS solution is controlled using this value as a target value, the injection amount of the SBS solution may be insufficient or excessive. . When the injection amount of the SBS solution is insufficient, the raw water is not sufficiently neutralized, which causes damage to the RO membrane. When the injection amount of the SBS solution is excessive, the running cost increases and the SBS-derived sulfur compound adheres to the reverse osmosis membrane, which may cause problems such as blockage.

本発明は、このような事情に鑑みてなされたものであって、塩素処理した後の原水に対して還元剤を用いて中和処理する際に、ＳＢＳ溶液の過剰注入を抑制しつつ、より確実に中和処理を完了することのできる淡水化装置及び淡水化方法の提供を目的とする。   The present invention has been made in view of such circumstances, and when neutralizing the raw water after chlorination using a reducing agent, while suppressing excessive injection of the SBS solution, An object of the present invention is to provide a desalination apparatus and a desalination method capable of reliably completing the neutralization treatment.

上記課題を解決するために、本発明は、塩素含有水を添加した原水から塩類を分離するための逆浸透膜を有する脱塩処理装置と、前記脱塩処理装置の前流側で、前記塩素含有水を添加した原水に、塩素を中和可能な還元剤を供給する還元剤供給装置と、を備えた淡水化装置であって、前記還元剤供給装置が、前記脱塩処理装置の前流側から前記塩素含有水を添加した原水を抜き出して、該抜き出した原水に塩素成分を定量的に添加する塩素添加部と、前記塩素成分を添加した原水の塩素量を定量する塩素定量部と、前記塩素定量部で定量した塩素量と、前記定量的に添加した塩素量との差分の塩素量に対応する還元剤量を算出して、還元剤の供給量を決定する還元剤供給量決定部と、前記決定した供給量の還元剤を脱塩処理装置の前流側で前記塩素含有水を添加した原水に供給する還元剤供給部とを含む淡水化装置を提供する。   In order to solve the above problems, the present invention provides a desalination treatment apparatus having a reverse osmosis membrane for separating salts from raw water to which chlorine-containing water is added, and the chlorine on the upstream side of the desalination treatment apparatus. A desalination apparatus comprising a reducing agent supply apparatus that supplies a reducing agent capable of neutralizing chlorine to the raw water to which the contained water has been added, wherein the reducing agent supply apparatus is upstream of the desalination treatment apparatus. Extracting the raw water to which the chlorine-containing water has been added from the side, adding a chlorine component quantitatively to the extracted raw water, and a chlorine quantitative unit for determining the chlorine content of the raw water to which the chlorine component has been added, A reducing agent supply amount determination unit that determines a supply amount of the reducing agent by calculating a reducing agent amount corresponding to a difference between the chlorine amount quantified by the chlorine determination unit and the quantitatively added chlorine amount. And the determined supply amount of the reducing agent in front of the desalination apparatus Providing desalination device that includes a reducing agent supply unit for supplying the raw water with the addition of chlorine-containing water.

上記発明によれば、塩素含有水を添加した原水に、更に定量的に塩素成分を加えることで、塩素濃度が高くなるため、より正確に塩素量を定量することが可能となる。添加前後の差分の塩素量は、塩素含有水を添加した原水に含まれる塩素量に相当するため、上記差分の塩素量を中和するために必要な還元剤量を算出することで、還元剤の供給量を決定できる。   According to the above invention, the chlorine concentration is increased by adding the chlorine component quantitatively to the raw water to which the chlorine-containing water is added, so that the amount of chlorine can be more accurately quantified. Since the difference chlorine amount before and after the addition corresponds to the chlorine amount contained in the raw water to which the chlorine-containing water is added, by calculating the amount of reducing agent necessary to neutralize the difference chlorine amount, the reducing agent is calculated. Can be determined.

上記発明の一態様において、前記還元剤供給装置が、前記塩素含有水を添加した原水の一部を抜き出して、定量用の還元剤溶液を添加しつつ、還元剤と塩素との酸化還元電位の最大変化部を求め、この当量点に対応する還元剤添加濃度を求め、該還元剤添加濃度を前記還元剤供給量決定部で決定した還元剤の供給量と比較し、前記還元剤供給量を適宜補正する補正部を備えても良い。
補正部を備えることで、より正確に適量の還元剤を注入することが可能となる。 In one aspect of the invention, the reducing agent supply device extracts a portion of the raw water to which the chlorine-containing water has been added, and adds a reducing agent solution for quantification, while reducing the redox potential of the reducing agent and chlorine. The maximum change part is obtained, the reducing agent addition concentration corresponding to the equivalence point is obtained, the reducing agent addition concentration is compared with the reducing agent supply amount determined by the reducing agent supply amount determination unit, and the reducing agent supply amount is determined. You may provide the correction | amendment part which correct | amends suitably.
By providing the correction unit, it is possible to inject an appropriate amount of the reducing agent more accurately.

また、本発明は、逆浸透膜を有する脱塩処理装置を用いて塩素含有水を添加した原水から塩類を分離する方法であって、前記脱塩処理装置の前流側から前記塩素含有水を添加した原水を抜き出して、該抜き出した原水に塩素成分を定量的に添加し、前記塩素成分を添加した原水の塩素量を定量し、前記定量した塩素量と、前記定量的に添加した塩素量との差分の塩素量に対応する還元剤量を算出して、還元剤の供給量を決定し、前記脱塩処理装置の前流側で、前記塩素含有水を添加した原水に、前記決定した供給量の還元剤を供給し、前記塩素含有水を添加した原水に含まれる塩素を中和する淡水化方法を提供する。   The present invention is also a method for separating salts from raw water to which chlorine-containing water has been added using a desalination treatment apparatus having a reverse osmosis membrane, wherein the chlorine-containing water is removed from the upstream side of the desalination treatment apparatus. Extracting the added raw water, quantitatively adding a chlorine component to the extracted raw water, quantifying the amount of chlorine in the raw water to which the chlorine component has been added, and determining the amount of chlorine and the amount of chlorine added quantitatively The amount of reducing agent corresponding to the difference between the amount of chlorine and the amount of reducing agent supplied is determined, and the raw water to which the chlorine-containing water is added is determined on the upstream side of the desalting apparatus. Provided is a desalination method for supplying a supply amount of a reducing agent and neutralizing chlorine contained in raw water to which the chlorine-containing water is added.

上記発明の一態様において、前記塩素含有水を添加した原水の一部を抜き出して、定量用の還元剤溶液を添加しつつ、還元剤と塩素との酸化還元電位の最大変化部である当量点を求め、この当量点に対応する還元剤添加濃度を求め、該還元剤添加濃度を前記還元剤供給量決定部で決定した還元剤の供給量と比較し、前記還元剤供給量を適宜補正しても良い。   In one aspect of the invention, an equivalent point that is a maximum change portion of the oxidation-reduction potential between the reducing agent and chlorine while extracting a part of the raw water to which the chlorine-containing water is added and adding the reducing agent solution for quantification. The reducing agent addition concentration corresponding to the equivalence point is obtained, the reducing agent addition concentration is compared with the reducing agent supply amount determined by the reducing agent supply amount determination unit, and the reducing agent supply amount is appropriately corrected. May be.

本発明によれば、間接的に還元剤の必要量を定量できるため、還元剤の過剰注入を防止しつつ、塩素をより確実に中和することが可能となる。   According to the present invention, since the necessary amount of the reducing agent can be indirectly determined, it is possible to more reliably neutralize chlorine while preventing excessive injection of the reducing agent.

第１実施形態に係る淡水化装置の概略図である。It is the schematic of the desalination apparatus which concerns on 1st Embodiment. 第２実施形態に係る補正部の概略図である。It is the schematic of the correction | amendment part which concerns on 2nd Embodiment. サンプル水基準ＳＢＳ濃度とＯＲＰ計測値との関係を示す図である。It is a figure which shows the relationship between sample water reference | standard SBS density | concentration and ORP measured value.

（第１実施形態）
以下に、本発明に係る淡水化装置及び淡水化方法の一実施形態について、図面を参照して説明する。
図１は、本実施形態に係る淡水化装置１０の概略図である。淡水化装置１０は、前処理装置１３、脱塩処理装置１７、及び還元剤供給装置１８を具備してなる、海水（原水）から塩類を分離して淡水とする装置である。なお、図１中、符号２０は濃縮水、２１ａ、２１ｂは送液ポンプ、２２は原水ライン、２３は濾過水ライン、２４は濃縮水ライン、２５は透過水ラインを各々図示する。 (First embodiment)
Hereinafter, an embodiment of a desalination apparatus and a desalination method according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view of a desalination apparatus 10 according to the present embodiment. The desalination apparatus 10 is an apparatus comprising a pretreatment device 13, a desalination treatment device 17, and a reducing agent supply device 18, which separates salts from seawater (raw water) to produce fresh water. In FIG. 1, reference numeral 20 is concentrated water, 21a and 21b are liquid feed pumps, 22 is a raw water line, 23 is a filtered water line, 24 is a concentrated water line, and 25 is a permeate line.

前処理装置１３は、前処理膜１３ａを備えており、該前処理膜１３ａに原水（海水）１１を透過させることで、原水１１から濁質分を除去する役割を果たす。   The pretreatment device 13 includes a pretreatment membrane 13a and plays a role of removing turbid components from the raw water 11 by allowing the raw water (seawater) 11 to pass through the pretreatment membrane 13a.

脱塩処理装置１７は、濾過水ライン２３を介して前処理装置１３の後流側に接続されている。脱塩処理装置１７は、逆浸透膜（ＲＯ膜）１６を備えており、原水から塩類を分離することができる。逆浸透膜１６は、塩類を透過させない半透膜とされる。逆浸透膜１６は、酢酸セルロース系ポリマー、ポリアミド、ポリイミド、ビニルポリマーなどの高分子素材などからなる。逆浸透膜１６は、逆浸透法により使用される既存の膜から選択され得る。   The desalting apparatus 17 is connected to the downstream side of the pretreatment apparatus 13 via the filtered water line 23. The desalting apparatus 17 includes a reverse osmosis membrane (RO membrane) 16 and can separate salts from raw water. The reverse osmosis membrane 16 is a semipermeable membrane that does not allow salt to permeate. The reverse osmosis membrane 16 is made of a polymer material such as cellulose acetate polymer, polyamide, polyimide, vinyl polymer or the like. The reverse osmosis membrane 16 can be selected from existing membranes used by the reverse osmosis method.

還元剤供給装置１８は、前処理装置１３と脱塩処理装置１７との間の濾過水ライン２３に接続されており、塩素添加部３１、塩素定量部３２、還元剤供給量決定部３３、及び還元剤供給部３４を備えている。
塩素添加部３１は、脱塩処理装置１７の前流側の濾過水ライン２３から、前処理装置１３で濁質分が除去された原水（濾過水１４Ａ）の一部を抜き出して、該抜き出した濾過水１４Ａに塩素成分を定量的に添加することができる。 The reducing agent supply device 18 is connected to the filtered water line 23 between the pretreatment device 13 and the desalting treatment device 17, and includes a chlorine addition unit 31, a chlorine determination unit 32, a reducing agent supply amount determination unit 33, and A reducing agent supply unit 34 is provided.
The chlorine addition unit 31 extracts a part of the raw water (filtered water 14A) from which the turbid components have been removed by the pretreatment device 13 from the filtrate water line 23 on the upstream side of the desalination treatment device 17 and extracts it. A chlorine component can be quantitatively added to the filtered water 14A.

塩素定量部３２は、塩素添加部３１により塩素成分を添加された濾過水１４Ｂの塩素量を定量することができる。塩素量の定量は、比色法（ＤＰＤ法、オルトトリジン法）、電流法などによって実施され得る。本実施形態では、ジエチル−ｐ−フェニレンジアンモニウム（ＤＰＤ）を用いた比色法（ＤＰＤ法）を例示する。   The chlorine determination unit 32 can determine the amount of chlorine in the filtered water 14B to which the chlorine component is added by the chlorine addition unit 31. The determination of the amount of chlorine can be carried out by a colorimetric method (DPD method, orthotolidine method), current method or the like. In this embodiment, a colorimetric method (DPD method) using diethyl-p-phenylenediammonium (DPD) is exemplified.

ＤＰＤ法では、塩素添加部３１により塩素成分を添加された濾過水にＤＰＤを加え、残留塩素との反応で生じる桃色から桃赤色を、残留塩素標準比色液と比較して定量する。残留塩素とは、遊離残留塩素と結合性残留塩素の合計量を指す。ＤＰＤと塩素による定色は５１３ｎｍ及び５５３ｎｍ付近に極大吸収波長を有する。ＤＰＤは遊離残留塩素と速やかに反応するが、結合性残留塩素との反応は遅く、試薬添加後１分以内に比色すると、遊離残留塩素のみが定量される。その後、ヨウ化カリウムを加えることでヨウ化物イオンが触媒となり、結合性残留塩素によっても発色が起こる。   In the DPD method, DPD is added to the filtered water to which the chlorine component is added by the chlorine addition unit 31, and the pink to pink color generated by the reaction with residual chlorine is quantified in comparison with the residual chlorine standard colorimetric solution. Residual chlorine refers to the total amount of free residual chlorine and bound residual chlorine. The constant color by DPD and chlorine has maximum absorption wavelengths around 513 nm and 553 nm. DPD reacts rapidly with free residual chlorine, but the reaction with bound residual chlorine is slow, and if the color is compared within 1 minute after addition of the reagent, only free residual chlorine is quantified. Thereafter, by adding potassium iodide, iodide ion becomes a catalyst, and color development also occurs due to binding residual chlorine.

還元剤供給量決定部３３は、塩素定量部３２で定量した濾過水１４Ｂの塩素量と、濾過水１４Ａに定量的に添加した塩素量との差分の塩素量に対応する還元剤量を算出して、還元剤の供給量を決定することができる。   The reducing agent supply amount determination unit 33 calculates the reducing agent amount corresponding to the chlorine amount which is the difference between the chlorine amount of the filtered water 14B quantified by the chlorine quantifying unit 32 and the chlorine amount quantitatively added to the filtered water 14A. Thus, the supply amount of the reducing agent can be determined.

還元剤供給部３４は、還元剤供給量決定部３３で決定された量の還元剤を、脱塩処理装置１７の前流側にある濾過水ライン２３に供給することができる。   The reducing agent supply unit 34 can supply the amount of reducing agent determined by the reducing agent supply amount determination unit 33 to the filtered water line 23 on the upstream side of the desalting apparatus 17.

次に、淡水化装置１０を用いて海水を淡水化する方法を説明する。
海水（原水）１１を淡水化装置１０に供給すると、まず、塩素含有水１２が原水１１に添加される。塩素含有水１２は、次亜塩素酸ナトリウムの水溶液などとされ、１ｐｐｍ程度添加される。 Next, a method for desalinating seawater using the desalination apparatus 10 will be described.
When seawater (raw water) 11 is supplied to the desalination apparatus 10, first, chlorine-containing water 12 is added to the raw water 11. The chlorine-containing water 12 is an aqueous solution of sodium hypochlorite or the like, and about 1 ppm is added.

塩素含有水１２が添加された原水１１は、前処理装置１３に送られ、前処理膜１３ａによって濾過されて濾過水１４Ａとなる。濾過水１４Ａは濾過水ライン２３を通り、還元剤で中和された後、脱塩処理装置１７へと供給される。   The raw water 11 to which the chlorine-containing water 12 is added is sent to the pretreatment device 13 and filtered by the pretreatment membrane 13a to become filtered water 14A. The filtered water 14 </ b> A passes through the filtered water line 23, is neutralized with a reducing agent, and then supplied to the desalting apparatus 17.

濾過水１４Ａの中和は、還元剤供給装置１８によって行われる。まず、塩素添加部３１によって濾過水ライン２３から濾過水１４Ａの一部を抜き出す。次に、抜き出した濾過水１４Ａに、塩素成分を定量的に添加し、濾過水１４Ｂとする。塩素成分は、次亜塩素酸ナトリウムの水溶液などの形態で添加されて良く、塩素含有水１２と同じ組成であることが好ましい。塩素成分の添加量は、０．５〜１．０ｐｐｍ程度とすると良い。   The neutralization of the filtered water 14 </ b> A is performed by the reducing agent supply device 18. First, a part of the filtered water 14 </ b> A is extracted from the filtered water line 23 by the chlorine addition unit 31. Next, a chlorine component is quantitatively added to the extracted filtered water 14A to obtain filtered water 14B. The chlorine component may be added in the form of an aqueous solution of sodium hypochlorite or the like, and preferably has the same composition as the chlorine-containing water 12. The addition amount of the chlorine component is preferably about 0.5 to 1.0 ppm.

次に、塩素定量部３２により、濾過水１４Ｂに含まれる塩素量（Ｘ）を定量する。次に、定量した濾過水１４Ｂに含まれる塩素量（Ｘ）から、濾過水１４Ａに定量的に添加した塩素量（Ｙ）を除算し、濾過水１４Ａにもともと含まれる塩素量（Ｚ）を算出する。   Next, the amount of chlorine (X) contained in the filtered water 14B is quantified by the chlorine quantification unit 32. Next, the amount of chlorine (Y) quantitatively added to the filtered water 14A is divided from the amount of chlorine (X) contained in the quantified filtered water 14B to calculate the amount of chlorine (Z) originally contained in the filtered water 14A. To do.

次に、還元剤供給量決定部３３により還元剤の供給量を決定する。例えば、塩素含有水として次亜塩素酸ナトリウム（ＮａＣｌＯ）溶液を使用し、還元剤としてＳＢＳ（ＮａＨＳＯ３）溶液を使用した場合の酸化還元反応は次の式で示される。
ＮａＣｌＯ＋ＮａＨＳＯ３→ＮａＨＳＯ４＋ＮａＣｌ
上記反応式に基づき、ＮａＣｌＯ １ｍｏｌに対して、ＮａＨＳＯ３ １ｍｏｌとなるようにＳＢＳ溶液の供給量を決定すると良い。 Next, the reducing agent supply amount determination unit 33 determines the supply amount of the reducing agent. For example, the oxidation-reduction reaction when a sodium hypochlorite (NaClO) solution is used as the chlorine-containing water and an SBS (NaHSO 3 ) solution is used as the reducing agent is represented by the following formula.
NaClO + NaHSO 3 → NaHSO 4 + NaCl
Based on the above reaction formula, the supply amount of the SBS solution may be determined so as to be 1 mol of NaHSO 3 with respect to 1 mol of NaClO.

上記で決定した還元剤の供給量の情報は、還元剤供給部３４に提供される。還元剤供給部３４は、提供された情報に基づき、濾過水ライン２３に還元剤を供給する。これによって、還元剤を過剰注入することをなく、濾過水ライン２３を流れる濾過水１４を中和することができる。なお、濾過水ライン２３から濾過水１４の一部を抜き出してから還元剤を濾過水ライン２３へと供給するまでを一連の中和処理工程とし、該中和処理工程は脱塩処理装置１７へ塩素成分が混入しないよう繰り返し実施される。   Information on the supply amount of the reducing agent determined above is provided to the reducing agent supply unit 34. The reducing agent supply unit 34 supplies the reducing agent to the filtered water line 23 based on the provided information. As a result, the filtered water 14 flowing through the filtered water line 23 can be neutralized without excessive injection of the reducing agent. It should be noted that a series of steps from extracting a portion of the filtered water 14 from the filtered water line 23 to supplying the reducing agent to the filtered water line 23 is a series of neutralizing treatment steps, and the neutralizing treatment steps are directed to the desalination treatment apparatus 17. It repeats so that a chlorine component may not mix.

中和された濾過水１４は、脱塩処理装置１７へと供給され、逆浸透膜１６にて塩類が分離される。   The neutralized filtered water 14 is supplied to the desalting apparatus 17, and the salts are separated by the reverse osmosis membrane 16.

（第２実施形態）
本実施形態では、還元剤注入装置が補正部を備える以外は第１実施形態と同様の構成とされる。
図２に、本実施形態に係る還元剤供給装置の補正部１００の一例を示す。補正部１００は、前処理装置（図示せず）からの濾過水ライン２３を流れる濾過水１４の一部抜出水１０４ａをサンプル水として抜出す抜出ライン１０１と、抜出された一部抜出水１０４ａに定量用の還元剤溶液であるＳＢＳ溶液１０８ａを供給する定量用還元剤供給部である定量用ＳＢＳ供給タンク１０２と、定量用ＳＢＳ溶液１０８ａが添加された混合液１０４ｂの酸化還元電位を計測する電極１０３ａ及び測定部３３ｂを有する酸化還元電位（ＯＲＰ）計１０３とを具備する。 (Second Embodiment)
In this embodiment, it is set as the structure similar to 1st Embodiment except a reducing agent injection apparatus being provided with the correction | amendment part.
In FIG. 2, an example of the correction | amendment part 100 of the reducing agent supply apparatus which concerns on this embodiment is shown. The correction unit 100 includes a withdrawal line 101 that draws out a part of the drained water 104a of the filtrate 14 that flows through the filtrate line 23 from the pretreatment device (not shown) as sample water, and a part of the drained water that is extracted. Measures the redox potential of the quantitative SBS supply tank 102, which is a quantitative reducing agent supply unit that supplies the quantitatively reducing agent solution 108a to 104a, and the mixed liquid 104b, to which the quantitative SBS solution 108a is added. And an oxidation-reduction potential (ORP) meter 103 having an electrode 103a and a measurement unit 33b.

補正部１００は、定量用ＳＢＳ溶液１０８ａを一部抜出水１０４ａに供給しつつ、ＯＲＰ計１０３により両者の最大変化部である当量点を求め、求めた当量点に対応する定量用ＳＢＳ溶液１０８ａの還元剤添加濃度（Ｃｓｍ）を求め、この還元剤添加濃度（Ｃｓｍ）を中和可能なＳＢＳ溶液の流量を算出する演算装置１０４を備えている。
図２中、符号１０５は一部抜出水１０４ａを測定部１０３ｂに供給する定量ポンプ、１０６は定量用ＳＢＳ溶液１０８ａを供給する流量可変定量ポンプ、１０７はシーケンサー、１０９は排水を各々図示する。 The correction unit 100 obtains the equivalent point which is the maximum change part of the two by using the ORP meter 103 while supplying a part of the quantitative SBS solution 108a to the extracted water 104a, and determines the equivalent SBS solution 108a corresponding to the obtained equivalent point. An arithmetic unit 104 is provided that calculates the reducing agent addition concentration (Csm) and calculates the flow rate of the SBS solution that can neutralize the reducing agent addition concentration (Csm).
In FIG. 2, reference numeral 105 is a metering pump that supplies partially extracted water 104 a to the measuring unit 103 b, 106 is a variable flow rate metering pump that supplies the SBS solution 108 a for metering, 107 is a sequencer, and 109 is drainage.

前処理装置で前処理された濾過水１４には塩素が含有されているので、塩素含有水１２を含む濾過水１４の一部抜出水１０４ａをサンプル水として定量ポンプにて連続的に酸化還元電位（ＯＲＰ）計の測定部１０３ｂに供給する。
シーケンサー１０７からの信号を受けた流量可変定量ポンプ１０６によりサンプル水である一部抜出水１０４ａに定量用ＳＢＳ溶液１０８ａの供給流量を変えながら一定パターンで供給混合する。 Since the filtered water 14 pretreated by the pretreatment apparatus contains chlorine, the redox potential is continuously obtained by a metering pump using the partially extracted water 104a of the filtered water 14 containing the chlorine-containing water 12 as sample water. (ORP) Supply to the measuring unit 103b of the meter.
The variable flow rate metering pump 106 that receives the signal from the sequencer 107 supplies and mixes the sampled water 104a, which is sample water, in a constant pattern while changing the supply flow rate of the SBS solution 108a for metering.

次いで、混合液１０４ｂの酸化還元電位（ＯＲＰ）を測定部１０３ｂで計測し、ＯＲＰ計１０３とシーケンサー１０７とからの信号により、還元剤と塩素との酸化還元電位の最大変化部（当量点）を求め、この当量点に対応する還元剤添加濃度（Ｃｓｍ）を求め、この濃度に対応したＳＢＳ溶液の量を算出する。   Next, the redox potential (ORP) of the mixed liquid 104b is measured by the measuring unit 103b, and the maximum change portion (equivalent point) of the redox potential of the reducing agent and chlorine is determined by a signal from the ORP meter 103 and the sequencer 107. The reducing agent addition concentration (Csm) corresponding to this equivalence point is determined, and the amount of the SBS solution corresponding to this concentration is calculated.

ここで、前記操作において、ＯＲＰ計１０３の測定部１０３ｂに供給される基準ＳＢＳ濃度（Ｃｓ）を（１）式にて算出することができる。
また、基準ＳＢＳ（Ｃｓ）の変化に対するＯＲＰ値の最大変化を与える還元剤添加濃度（Ｃｓｍ）になるよう、逆浸透膜装置に供給する濾過水１４に添加するＳＢＳ溶液の流量（Ｆ３）を（２）式にて算出することができる。
Ｃｓ＝（Ｆ１×Ｃ１）／Ｆ２ …（１）
ここで、
Ｃｓ：サンプル水基準ＳＢＳ濃度（ｍｏｌ／ｌ）
Ｃ１：定量用ＳＢＳ溶液濃度（ｍｏｌ／ｌ）
Ｆ１：定量用ＳＢＳ溶液流量（１／ｈ）
Ｆ２：サンプル水流量（１／ｈ）
Ｆ３＝（Ｆ４×Ｃｓｍ）／Ｃ３ …（２）
Ｆ３：ＳＢＳ溶液１８の供給流量（１／ｈ）
Ｆ４：ＲＯ供給水流量（１／ｈ）
Ｃ３：ＳＢＳ溶液濃度（ｍｏｌ／ｌ）
Ｃｓｍ：当量点に対応する還元剤添加濃度（ｍｏｌ／ｌ） Here, in the above-described operation, the reference SBS concentration (Cs) supplied to the measuring unit 103b of the ORP meter 103 can be calculated by the equation (1).
Further, the flow rate (F3) of the SBS solution added to the filtered water 14 supplied to the reverse osmosis membrane device is set so that the reducing agent addition concentration (Csm) that gives the maximum change in the ORP value with respect to the change in the reference SBS (Cs) is ( 2) It can be calculated by the equation.
Cs = (F1 × C1) / F2 (1)
here,
Cs: Sample water reference SBS concentration (mol / l)
C1: SBS solution concentration for determination (mol / l)
F1: SBS solution flow rate for quantification (1 / h)
F2: Sample water flow rate (1 / h)
F3 = (F4 × Csm) / C3 (2)
F3: Supply flow rate of SBS solution 18 (1 / h)
F4: RO supply water flow rate (1 / h)
C3: SBS solution concentration (mol / l)
Csm: Reducing agent addition concentration corresponding to the equivalence point (mol / l)

ここで、演算装置１０４での演算内容について説明する。
１）一定流量のサンプル水１０４ａに定量用ＳＢＳ溶液１０８ａを、供給流量を変えながら混合し、混合後の混合液１０４ｂの酸化還元電位（ＯＲＰ）を、測定部１０３ｂの電極１０３ａで測定し、ＯＲＰ計１０３でその結果を求める。
ここで、定量用ＳＢＳ溶液１０８ａの供給流量は、あらかじめ変化パターンをプログラミングしたシーケンサー１０７からの信号により、流量可変定量ポンプ１０６を変化させることで行う。
２）流量可変定量ポンプ１０６からＯＲＰ測定部１０３ｂにいたる液の滞留時間および電極１０３ａの検出遅れ等を考慮し、上記供給流量はステップ状に変化させ、一定時間、定量用ＳＢＳ溶液１０８ａの供給量を維持する変化パターンとする。
３）シーケンサー１０７からの定量用ＳＢＳ溶液１０８ａの供給流量信号は、同時に演算装置１０４にも送られ、ここでまず、ＯＲＰ計１０３からのＯＲＰ信号値と、サンプル水基準ＳＢＳ濃度の関係を得る。
図３は、サンプル水基準ＳＢＳ濃度（ｍｏｌ／ｌ）と、ＯＲＰ計測値（ｍＶ）との関係図である。なお、図３の上段の横軸には、ＳＢＳ／Ｃｌモル比についても示している。
図３に示すとおり、横軸にＯＲＰの測定部１０３ｂに供給するサンプル水基準ＳＢＳ濃度（Ｃｓ）を前出（１）式により算出して示し、縦軸には検出されたＯＲＰ値の関係をプロットする。
上記（１）式にて、Ｃ１、Ｆ２の変数はあらかじめ演算装置１０４に入力しておき、Ｆ１は供給流量変化ごとにシーケンサー１０７から自動入力される。
４）次に、演算装置１０４では図３よりＳＢＳ濃度変化に対し、ＯＲＰの変化が最大となるサンプル水基準ＳＢＳ当量濃度が求められる。これが、当量点に対応する還元剤添加濃度（Ｃｓｍ）となる。
実測値を結んだスムージングカーブをＳＢＳ濃度（Ｃｓ）に対して微分することで自動的に求めることが可能である。
５）さらに、演算装置１０４にて上記当量点に対応する還元剤添加濃度（Ｃｓｍ）となるＳＢＳ溶液の流量（Ｆ３）を（２）式により算出する。
なお、（２）式にてＦ４、Ｃ３の変数はあらかじめ演算装置１０４に入力しておく。 Here, the calculation contents in the calculation device 104 will be described.
1) The SBS solution 108a for quantification is mixed with the sample water 104a having a constant flow rate while changing the supply flow rate, and the oxidation-reduction potential (ORP) of the mixed solution 104b after the mixing is measured with the electrode 103a of the measurement unit 103b. The result is obtained in total 103.
Here, the supply flow rate of the quantitative SBS solution 108a is changed by changing the variable flow rate quantitative pump 106 in accordance with a signal from the sequencer 107 programmed in advance with a change pattern.
2) Considering the liquid residence time from the variable flow rate metering pump 106 to the ORP measuring unit 103b, the detection delay of the electrode 103a, and the like, the supply flow rate is changed stepwise, and the supply amount of the SBS solution 108a for quantification for a certain time. Change pattern to maintain
3) The supply flow rate signal of the quantitative SBS solution 108a from the sequencer 107 is also sent to the arithmetic unit 104 at the same time. First, the relationship between the ORP signal value from the ORP meter 103 and the sample water reference SBS concentration is obtained.
FIG. 3 is a relationship diagram between the sample water reference SBS concentration (mol / l) and the ORP measurement value (mV). Note that the horizontal axis in the upper part of FIG. 3 also shows the SBS / Cl molar ratio.
As shown in FIG. 3, the horizontal axis represents the sample water reference SBS concentration (Cs) supplied to the ORP measuring unit 103b by the above equation (1), and the vertical axis represents the relationship between the detected ORP values. Plot.
In the above equation (1), variables C1 and F2 are input to the arithmetic unit 104 in advance, and F1 is automatically input from the sequencer 107 every time the supply flow rate changes.
4) Next, the arithmetic unit 104 obtains the sample water reference SBS equivalent concentration that maximizes the change in ORP with respect to the change in SBS concentration, as shown in FIG. This is the reducing agent addition concentration (Csm) corresponding to the equivalence point.
It can be automatically obtained by differentiating the smoothing curve connecting the measured values with respect to the SBS concentration (Cs).
5) Further, the arithmetic unit 104 calculates the flow rate (F3) of the SBS solution at the reducing agent addition concentration (Csm) corresponding to the equivalence point by the equation (2).
Note that the variables F4 and C3 in equation (2) are input to the arithmetic unit 104 in advance.

演算装置１０４で算出された還元剤添加濃度（Ｃｓｍ）を中和可能なＳＢＳ溶液の流量は、比較部還元剤定量部で定量した塩素量（Ｚ）と比較される。塩素量（Ｚ）が演算装置１０４で算出したＳＢＳの流量と大きく異なる場合、濾過水ライン２３に供給される還元剤量は適宜補正される。   The flow rate of the SBS solution capable of neutralizing the reducing agent addition concentration (Csm) calculated by the arithmetic unit 104 is compared with the chlorine amount (Z) quantified by the reducing agent quantification unit of the comparison unit. When the amount of chlorine (Z) is significantly different from the SBS flow rate calculated by the arithmetic unit 104, the amount of reducing agent supplied to the filtrate line 23 is corrected as appropriate.

１０ 淡水化装置
１１ 原水（海水）
１２ 塩素含有水
１３ 前処理装置
１３ａ 前処理膜
１４ 濾過水
１５ 透過水
１６ 逆浸透膜（ＲＯ膜）
１７ 脱塩処理装置
１８ 還元剤供給装置
２０ 濃縮水
２１ａ、２１ｂ 送液ポンプ
２２ 原水ライン
２３ 濾過水ライン
２４ 濃縮水ライン
２５ 透過水ライン
３１ 塩素添加部
３２ 塩素定量部
３３ 還元剤供給量決定部
３４ 還元剤供給部
１００ 補正部
１０１ 抜出ライン
１０２ 定量用ＳＢＳ供給タンク
１０３ ＯＲＰ計
１０３ａ ＯＲＰ電極
１０３ｂ ＯＲＰ測定部
１０４ 演算装置
１０４ａ サンプル水
１０４ｂ 混合液
１０５ 定量ポンプ
１０６ 流量可変定量ポンプ
１０７ シーケンサー
１０８ａ 定量用ＳＢＳ溶液
１０９ 排水
10 Desalination equipment 11 Raw water (seawater)
12 Chlorine-containing water 13 Pretreatment device 13a Pretreatment membrane 14 Filtered water 15 Permeated water 16 Reverse osmosis membrane (RO membrane)
DESCRIPTION OF SYMBOLS 17 Desalination processing apparatus 18 Reducing agent supply apparatus 20 Concentrated water 21a, 21b Liquid feed pump 22 Raw water line 23 Filtrated water line 24 Concentrated water line 25 Permeated water line 31 Chlorine addition part 32 Chlorine determination part 33 Reductant supply amount determination part 34 Reducing agent supply unit 100 Correction unit 101 Extraction line 102 SBS supply tank for determination 103 ORP meter 103a ORP electrode 103b ORP measurement unit 104 Arithmetic device 104a Sample water 104b Mixed solution 105 Metering pump 106 Flow variable metering pump 107 Sequencer 108a Metering SBS Solution 109 drainage

Claims (4)

塩素含有水を添加した原水から塩類を分離するための逆浸透膜を有する脱塩処理装置と、前記脱塩処理装置の前流側で、前記塩素含有水を添加した原水に、塩素を中和可能な還元剤を供給する還元剤供給装置と、を備えた淡水化装置であって、
前記還元剤供給装置が、
前記脱塩処理装置の前流側から前記塩素含有水を添加した原水を抜き出して、該抜き出した原水に塩素成分を定量的に添加する塩素添加部と、
前記塩素成分を添加した原水の塩素量を定量する塩素定量部と、
前記塩素定量部で定量した塩素量と、前記定量的に添加した塩素量との差分の塩素量に対応する還元剤量を算出して、還元剤の供給量を決定する還元剤供給量決定部と、
前記決定した供給量の還元剤を脱塩処理装置の前流側で前記塩素含有水を添加した原水に供給する還元剤供給部と、
を含む淡水化装置。 Chlorine is neutralized in the desalination treatment device having a reverse osmosis membrane for separating salts from the raw water to which chlorine-containing water is added, and the raw water to which the chlorine-containing water is added on the upstream side of the desalination treatment device. A desalination apparatus comprising a reducing agent supply device for supplying a possible reducing agent,
The reducing agent supply device comprises:
A chlorine addition unit for extracting the raw water to which the chlorine-containing water has been added from the upstream side of the desalination treatment apparatus, and quantitatively adding a chlorine component to the extracted raw water;
A chlorine determination unit for determining the amount of chlorine in the raw water to which the chlorine component is added;
A reducing agent supply amount determination unit that determines a supply amount of the reducing agent by calculating a reducing agent amount corresponding to a difference between the chlorine amount quantified by the chlorine determination unit and the quantitatively added chlorine amount. When,
A reducing agent supply unit that supplies the determined supply amount of the reducing agent to the raw water to which the chlorine-containing water is added on the upstream side of the desalination treatment apparatus;
Including desalination equipment. 前記還元剤供給装置が、
前記塩素含有水を添加した原水の一部を抜き出して、定量用の還元剤溶液を添加しつつ、還元剤と塩素との酸化還元電位の最大変化部を求め、この当量点に対応する還元剤添加濃度を求め、該還元剤添加濃度を前記還元剤供給量決定部で決定した還元剤の供給量と比較し、前記還元剤供給量を適宜補正する補正部を備える請求項１に記載の淡水化装置。 The reducing agent supply device comprises:
Extracting a portion of the raw water to which the chlorine-containing water has been added, adding a reducing agent solution for determination, obtaining the maximum change portion of the redox potential of the reducing agent and chlorine, and reducing agent corresponding to this equivalent point 2. The fresh water according to claim 1, further comprising a correction unit that obtains an addition concentration, compares the reducing agent addition concentration with the reducing agent supply amount determined by the reducing agent supply amount determination unit, and appropriately corrects the reducing agent supply amount. Device. 逆浸透膜を有する脱塩処理装置を用いて塩素含有水を添加した原水から塩類を分離する方法であって、
前記脱塩処理装置の前流側から前記塩素含有水を添加した原水を抜き出して、該抜き出した原水に塩素成分を定量的に添加し、
前記塩素成分を添加した原水の塩素量を定量し、
前記定量した塩素量と、前記定量的に添加した塩素量との差分の塩素量に対応する還元剤量を算出して、還元剤の供給量を決定し、
前記脱塩処理装置の前流側で、前記塩素含有水を添加した原水に、前記決定した供給量の還元剤を供給し、前記塩素含有水を添加した原水に含まれる塩素を中和する淡水化方法。 A method for separating salts from raw water to which chlorine-containing water has been added using a desalination treatment apparatus having a reverse osmosis membrane,
The raw water to which the chlorine-containing water is added is extracted from the upstream side of the desalination treatment apparatus, and a chlorine component is quantitatively added to the extracted raw water,
Quantifying the amount of chlorine in the raw water to which the chlorine component is added,
Calculate the amount of reducing agent corresponding to the amount of chlorine that is the difference between the amount of chlorine quantified and the amount of chlorine added quantitatively, and determine the amount of reducing agent supplied,
Fresh water that supplies the determined supply amount of the reducing agent to the raw water to which the chlorine-containing water has been added and neutralizes the chlorine contained in the raw water to which the chlorine-containing water has been added on the upstream side of the desalination treatment apparatus. Method. 前記塩素含有水を添加した原水の一部を抜き出して、定量用の還元剤溶液を添加しつつ、還元剤と塩素との酸化還元電位の最大変化部である当量点を求め、この当量点に対応する還元剤添加濃度を求め、該還元剤添加濃度を前記還元剤供給量決定部で決定した還元剤の供給量と比較し、前記還元剤供給量を適宜補正する請求項３に記載の淡水化方法。
While extracting a part of the raw water to which the chlorine-containing water has been added and adding a reducing agent solution for quantification, an equivalent point that is the maximum change portion of the redox potential of the reducing agent and chlorine is obtained, and this equivalent point is obtained. The fresh water according to claim 3, wherein a corresponding reducing agent addition concentration is obtained, the reducing agent addition concentration is compared with the reducing agent supply amount determined by the reducing agent supply amount determination unit, and the reducing agent supply amount is corrected as appropriate. Method.
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