JPH0368757B2 - - Google Patents
Info
- Publication number
- JPH0368757B2 JPH0368757B2 JP7370384A JP7370384A JPH0368757B2 JP H0368757 B2 JPH0368757 B2 JP H0368757B2 JP 7370384 A JP7370384 A JP 7370384A JP 7370384 A JP7370384 A JP 7370384A JP H0368757 B2 JPH0368757 B2 JP H0368757B2
- Authority
- JP
- Japan
- Prior art keywords
- ion exchange
- ions
- water
- boron
- exchange layer
- 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.)
- Expired
Links
- -1 tetrafluoroborate ions Chemical class 0.000 claims description 74
- 238000005342 ion exchange Methods 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 229910052796 boron Inorganic materials 0.000 claims description 42
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 38
- 239000003456 ion exchange resin Substances 0.000 claims description 37
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 37
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002699 waste material Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000005349 anion exchange Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- YAWNFGAHEUCLNJ-UHFFFAOYSA-N [B].OB(O)O Chemical group [B].OB(O)O YAWNFGAHEUCLNJ-UHFFFAOYSA-N 0.000 description 3
- 229940063013 borate ion Drugs 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明はホウ素含有廃水の処理方法にかかり、
被処理水のホウ素をあらかじめ沈殿性化合物とし
て除去したのち、イオン交換樹脂を用いて残存す
るホウ素を除去する構成に関する。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for treating boron-containing wastewater,
The present invention relates to a configuration in which boron in water to be treated is previously removed as a precipitable compound, and then remaining boron is removed using an ion exchange resin.
ホウ素は石灰焚ボイラーの排脱廃水、ゴミ生焼
却炉洗煙廃水中に含まれホウ酸イオン（BO3 3-）、
またはフツ素と鎖体を形成してテトラフルオロホ
ウ酸イオン（BF4 -）の形で存在する。このよう
なホウ素は植物にとつては必須元素ではあるが、
その必要量は極くわずかであり、過剰摂取はその
生育に悪影響を及ぼすため、排水中のホウ素濃度
は１mg／以下、２mg／以下等と条例によつて
厳しく規制されている。
Boron is contained in wastewater discharged from lime-fired boilers and smoke washing wastewater from garbage incinerators, and contains boric acid ions (BO 3 3- ).
Alternatively, it forms a chain with fluorine and exists in the form of tetrafluoroborate ion (BF 4 - ). Although boron is an essential element for plants,
The required amount is extremely small, and excessive intake has a negative effect on its growth, so the concentration of boron in wastewater is strictly regulated by local ordinances, such as 1 mg/or less, 2 mg/or less, etc.
従来のホウ素を含む廃水の処理方法としては、
イオン交換樹脂により吸着させるものと、硫酸ア
ルミニウムにより不溶性沈殿物として固液分離す
るものとがあるが、何れも効果的な除去方法では
ない。 Conventional methods for treating wastewater containing boron include:
There are two methods: adsorption using an ion exchange resin and solid-liquid separation using aluminum sulfate as an insoluble precipitate, but neither method is effective for removal.
イオン交換樹脂でホウ素を吸着する場合は、被
処理水中のホウ素の形態によりホウ素の吸着能力
が異なることが多い。例えばホウ酸イオンとテト
ラフルオロホウ酸イオンの両イオンが存在する被
処理水の場合、ホウ酸イオンを選択的に吸着する
イオン交換樹脂を用いてテトラフルオロホウ酸イ
オンを吸着させて処理水中のホウ素濃度を１mg／
以下にすることはむずかしい。同様にテトラフ
ルオロホウ酸イオンのようなフツ素鎖体を形成し
ているイオンを選択的に吸着するイオン交換樹脂
を用いてホウ酸イオンを吸着させ、処理水中のホ
ウ素濃度を１mg／以下にすることはむずかし
い。 When adsorbing boron with an ion exchange resin, the adsorption capacity for boron often differs depending on the form of boron in the water to be treated. For example, in the case of water to be treated that contains both borate ions and tetrafluoroborate ions, an ion exchange resin that selectively adsorbs borate ions is used to adsorb the tetrafluoroborate ions to eliminate boron in the treated water. Concentration 1mg/
It is difficult to do the following. Similarly, borate ions are adsorbed using an ion exchange resin that selectively adsorbs ions forming fluorine chains such as tetrafluoroborate ions, and the boron concentration in the treated water is reduced to 1 mg/or less. That's difficult.
このように、単一のイオン交換樹脂を用いてホ
ウ酸イオンやテトラフルオロホウ酸イオンの両イ
オンが存在する液を処理して処理水のホウ素濃度
を１mg／以下にすることはむずかしい。 As described above, it is difficult to reduce the boron concentration of the treated water to 1 mg/min or less by treating a liquid containing both borate ions and tetrafluoroborate ions using a single ion exchange resin.
また、一般にホウ素を吸着するイオン交換樹脂
は吸着能力が小さく、このため再生頻度が多く多
量の再生剤を必要とする欠点があつた。 In addition, ion exchange resins that adsorb boron generally have a low adsorption capacity, and therefore have the drawback of requiring a large amount of regenerating agent.
一方、硫酸アルミニウムにより不溶性沈殿物と
して固液分離する方法は、多量の硫酸アルミニウ
ムを添加し、かつPHの中和のために硫酸アルミニ
ウムと同量かあるいはそれ以上の消石灰を必要と
し、多量の汚泥が発生するという欠点があつた。 On the other hand, the method of solid-liquid separation as an insoluble precipitate using aluminum sulfate requires the addition of a large amount of aluminum sulfate and the same amount of slaked lime as the aluminum sulfate or more to neutralize the pH, resulting in a large amount of sludge. There was a drawback that this occurred.
特に、高濃度のホウ素を数10〜100mg／まで
低減させる場合と異なり、処理水のホウ素濃度を
１mg／以下にしようとする場合には、更に多量
の硫酸アルミニウムまたは消石灰を必要とし経済
的な処理方法とはいえない。 In particular, unlike the case of reducing high concentrations of boron to several tens to 100 mg/d, when attempting to reduce the boron concentration of treated water to 1 mg/d or less, a larger amount of aluminum sulfate or slaked lime is required, making the treatment economical. It cannot be called a method.
また、被処理水中のホウ素の形態によつて、固
液分離しやすい場合と、固液分離しにくい場合と
がある。ホウ素の形態にかかわらず安定して処理
水のホウ素濃度を１mg／以下にすることはむず
かしい。 Further, depending on the form of boron in the water to be treated, there are cases where solid-liquid separation is easy and cases where solid-liquid separation is difficult. Regardless of the form of boron, it is difficult to stably reduce the boron concentration in treated water to 1 mg/or less.
本発明は上述の問題に鑑み、被処理水をOH型
塩基性アニオン交換樹脂と、OH型弱塩基性アニ
オン交換樹脂とに通水してテトラフルオロホウ酸
イオンと、ホウ酸イオンを可及的に除去するとと
もにイオン交換樹脂の再生に際して苛性ソーダを
通液した第１のイオン交換層の廃液を予め流酸を
通液した第２のイオン交換層に通液することによ
り再生剤の使用量を少なくしようとするものであ
る。
In view of the above-mentioned problems, the present invention passes the water to be treated through an OH type basic anion exchange resin and an OH type weakly basic anion exchange resin to remove tetrafluoroborate ions and borate ions as much as possible. At the same time, when regenerating the ion exchange resin, the waste liquid from the first ion exchange layer through which caustic soda was passed is passed through the second ion exchange layer through which flowing acid has been passed in advance, thereby reducing the amount of regenerating agent used. This is what I am trying to do.
本発明は、テトラフルオロホウ酸イオン
（BF4 -）とホウ酸イオン（BO3 3-）を含む被処理
水のホウ素を沈殿性化合物として分離し上澄水を
OH型塩基性アニオン交換樹脂を充填した第１の
イオン交換層に通水して残存するテトラフルオロ
ホウ酸イオンを除去し流出水を続いてOH型弱塩
基性アニオン交換樹脂を充填した第２のイオン交
換層に通水して残存するホウ酸イオンを除去する
工程と、前記第１のイオン交換層が吸着したテト
ラフルオロホウ酸イオンを苛性ソーダの通液によ
り離脱させこの廃液を硫酸の通液により吸着した
ホウ酸イオンを離脱した後の第２のイオン交換層
に通液させ夫々前記イオン交換樹脂を再生する工
程とよりなり、ホウ素を含む被処理水より大部分
のホウ素を沈殿性化合物として除去し、夫々２種
のイオン交換樹脂を用いて残存するテトラフルオ
ロホウ酸イオンとホウ酸イオンてを除去し、これ
らのイオンを除去した第１、第２のイオン交換層
を再生するとともに再生廃液を再利用するもので
ある。
The present invention separates boron from treated water containing tetrafluoroborate ions (BF 4 - ) and borate ions (BO 3 3- ) as a precipitating compound, and extracts supernatant water.
Water is passed through a first ion exchange layer filled with an OH type basic anion exchange resin to remove remaining tetrafluoroborate ions, and the effluent water is passed through a second ion exchange layer filled with an OH type weakly basic anion exchange resin. A step of removing remaining borate ions by passing water through the ion exchange layer, and removing the tetrafluoroborate ions adsorbed by the first ion exchange layer by passing caustic soda through the layer, and removing this waste liquid by passing sulfuric acid through the ion exchange layer. After removing the adsorbed borate ions, the liquid is passed through the second ion exchange layer to regenerate the ion exchange resin, and most of the boron is removed from the boron-containing water to be treated as a precipitable compound. Then, the remaining tetrafluoroborate ions and borate ions are removed using two types of ion exchange resins, and the first and second ion exchange layers from which these ions have been removed are regenerated, and the recycled waste liquid is recycled. It is meant to be reused.
次に本発明の実施例を添附図面について説明す
る。
Next, embodiments of the present invention will be described with reference to the accompanying drawings.
排脱廃水、ゴミ焼却炉洗煙廃水等よりなる被処
理水ａを酸性反応槽１に導入する。次にこの反応
槽１に硫酸アルミニウムｂを注入し、酸性下で撹
拌機２で撹拌処理を行なう。反応槽１の滞留時間
は３時間以上にするのが好ましく、また被処理水
ａ中に多量のテトラフルオロホウ酸イオンを含む
場合は、反応槽１内に硫酸ｃの注入によつてPHを
４以下にする。硫酸アルミニウムｂの存在下にPH
を４以下に調整することにより、テトラフルオロ
ホウ酸イオン（BF4 -）は次の反応式によつてフ
ツ化物とホウ酸とに分解され次工程以下のテトラ
フルオロホウ酸イオンの負荷を減少することがで
きる。 Water to be treated a consisting of discharged wastewater, garbage incinerator smoke washing wastewater, etc. is introduced into the acidic reaction tank 1. Next, aluminum sulfate b is injected into this reaction tank 1, and stirred with a stirrer 2 under acidic conditions. The residence time in the reaction tank 1 is preferably 3 hours or more, and if the water to be treated a contains a large amount of tetrafluoroborate ions, the pH is reduced to 4 by injecting sulfuric acid c into the reaction tank 1. Do the following. PH in the presence of aluminum sulfate b
By adjusting the ion to 4 or less, tetrafluoroborate ion (BF 4 - ) is decomposed into fluoride and boric acid according to the following reaction formula, reducing the load of tetrafluoroborate ion in the next process and below. be able to.
2Al（SO4）3＋3HBF4＋9H2O→
4AlF3＋6H2SO4＋3H3BO3
酸性反応槽１から流出した流出水ｄはアルカリ
性反応槽３に導入されこの反応槽３に消石灰ｅが
注入されアルカリ性下で撹拌機４で撹拌される。
アルカリ性反応槽３内の滞留時間は0.5時間以上
が好ましい。さらにアルカリ性反応槽３内のPHは
10以上、望ましくは12以上にするのがよい。この
アルカリ性反応槽３内で生成される水酸化物の形
態は明らかでないが、不溶性で沈降性もよく、次
工程の固液分離槽５における固液分離を容易にす
る。2Al(SO 4 ) 3 +3HBF 4 +9H 2 O→ 4AlF 3 +6H 2 SO 4 +3H 3 BO 3The effluent water d flowing out from the acidic reaction tank 1 is introduced into the alkaline reaction tank 3, and slaked lime e is injected into this reaction tank 3. The mixture is stirred with a stirrer 4 under alkaline conditions.
The residence time in the alkaline reaction tank 3 is preferably 0.5 hours or more. Furthermore, the pH in alkaline reaction tank 3 is
The number should be 10 or more, preferably 12 or more. Although the form of the hydroxide produced in the alkaline reaction tank 3 is not clear, it is insoluble and has good sedimentation properties, facilitating solid-liquid separation in the solid-liquid separation tank 5 in the next step.
アルカリ性反応槽流出水ｆは固液分離槽５に導
入され上澄水ｇと凝集沈殿物ｈとに分離される。 The alkaline reaction tank effluent water f is introduced into the solid-liquid separation tank 5 and separated into supernatant water g and coagulated precipitate h.
以上の工程によつて、被処理水ａは、遊離のフ
ツ素イオンが除去される他、テトラフルオロホウ
酸イオンの一部を不溶性沈殿物としホウ酸イオン
の一部も不溶性沈殿物とし上澄水ｇ中のホウ素濃
度は低下される。 Through the above steps, in the treated water a, free fluorine ions are removed, some of the tetrafluoroborate ions are converted into insoluble precipitates, some of the boric acid ions are also converted into insoluble precipitates, and the supernatant water The boron concentration in g is reduced.
得られた上澄水ｇはOH型アニオン交換樹脂を
充填した第１のイオン交換層６を有する１段イオ
ン交換樹脂塔７に導入される。１段イオン交換樹
脂塔７で用いられるイオン交換樹脂は、OH型塩
基性アニオン交換樹脂であり、弱塩基性または強
塩基性の何れの形でも使用できるが、特にテトラ
フルオロホウ酸イオンを選択的に吸着する樹脂で
あることが望ましい。 The obtained supernatant water g is introduced into a one-stage ion exchange resin column 7 having a first ion exchange layer 6 filled with an OH type anion exchange resin. The ion exchange resin used in the first-stage ion exchange resin column 7 is an OH type basic anion exchange resin, and can be used in either weakly basic or strongly basic form, but it is particularly selective for tetrafluoroborate ions. It is desirable that the resin be adsorbed to.
上澄水ｇと第１のイオン交換層６との接触滞留
時間は、５分以上で、通常SV＝６〔１／ｈ〕で通
液するのが望ましい。 It is desirable that the contact residence time between the supernatant water g and the first ion exchange layer 6 is 5 minutes or more, and that the liquid is passed normally at SV=6 [1/h].
１段イオン交換樹脂塔７から流出した流出水ｉ
はOH型弱塩基性アニオン交換樹脂よりなる第２
のイオン交換層８を有する２段イオン交換樹脂塔
９に導入される。２段イオン交換樹脂塔９で用い
られるイオン交換樹脂は、OH型弱塩基性アニオ
ン交換樹脂のうち、特にホウ酸イオンを選択的に
吸着する樹脂が望ましい。１段イオン交換樹脂塔
７からの流出水ｉと第２のイオン交換層８との接
触滞留時間は５分以上で、通常SV＝６〔１／ｈ〕
で通液するのが望ましい。 Outflow water i flowing out from the first stage ion exchange resin tower 7
is a second compound made of an OH type weakly basic anion exchange resin.
is introduced into a two-stage ion-exchange resin column 9 having an ion-exchange layer 8 . The ion exchange resin used in the two-stage ion exchange resin column 9 is desirably a resin that selectively adsorbs boric acid ions among OH type weakly basic anion exchange resins. The contact residence time between the outflow water i from the first stage ion exchange resin column 7 and the second ion exchange layer 8 is 5 minutes or more, and usually SV = 6 [1/h]
It is desirable to pass the liquid through.
以上の１段、２段のイオン交換処理によつて上
澄水ｇに含まれるテトラフルオロホウ酸イオン
（BF4 -）およびホウ酸イオン（BO3 3-）は夫々の
イオン交換層６，８に吸着され、ホウ素濃度とし
て１mg／以下の清澄な処理水ｊが得られる。 Through the above 1-stage and 2-stage ion exchange treatments, the tetrafluoroborate ions (BF 4 - ) and borate ions (BO 3 3- ) contained in the supernatant water g are transferred to the ion exchange layers 6 and 8, respectively. It is adsorbed and clear treated water j with a boron concentration of 1 mg/or less is obtained.
尚、上澄水ｇの通水の順序は第１のイオン交換
層６、第２のイオン交換層８の順に通水する必要
がある。何故ならば、第１のイオン交換層６に充
填されたイオン交換樹脂はテトラフルオロホウ酸
イオンを選択的に吸着し、ホウ酸イオンは殆ど吸
着しない。また第２のイオン交換層８のイオン交
換樹脂は、ホウ酸イオンを吸着するがテトラフル
オロホウ酸イオンも吸着する。このため第２のイ
オン交換層８に上澄水ｇを通液するとホウ酸イオ
ンとテトラフルオロホウ酸イオンが同時に吸着さ
れ吸着能を急速に低下するからである。また第
１、第２のイオン交換層６，８の順に通水すれば
第１のイオン交換層６で吸着されなかつた微量の
テトラフルオロホウ酸イオンを第２のイオン交換
層８で吸着させることができる。 Note that the supernatant water g must be passed through the first ion exchange layer 6 and the second ion exchange layer 8 in this order. This is because the ion exchange resin filled in the first ion exchange layer 6 selectively adsorbs tetrafluoroborate ions and hardly adsorbs borate ions. Further, the ion exchange resin of the second ion exchange layer 8 adsorbs borate ions, but also tetrafluoroborate ions. For this reason, when supernatant water g is passed through the second ion exchange layer 8, borate ions and tetrafluoroborate ions are simultaneously adsorbed, rapidly reducing the adsorption capacity. Furthermore, if water is passed through the first and second ion exchange layers 6 and 8 in this order, the trace amount of tetrafluoroborate ions that were not adsorbed by the first ion exchange layer 6 can be adsorbed by the second ion exchange layer 8. I can do it.
イオン交換によつてテトラフルオロホウ酸イオ
ンまたはホウ酸イオンを交換吸着した夫々のイオ
ン交換樹脂は、吸着濃度が低下次第その再生を行
なう。 The respective ion exchange resins that have exchanged and adsorbed tetrafluoroborate ions or borate ions through ion exchange are regenerated as soon as the adsorption concentration decreases.
テトラフルオロホウ酸イオンを吸着した第１の
イオン交換層６には苛性ソーダ水溶液ｋを、ホウ
酸イオンを吸着した第２のイオン交換層８には硫
酸水溶液ｌを通液し、夫々再生廃液ｍ、ｎを得
る。次に、第２のイオン交換層８をSO4型から
OH型に戻すために、１段イオン交換樹脂塔７の
再生廃液ｍを第２のイオン交換層８に通液する。 A caustic soda aqueous solution K is passed through the first ion exchange layer 6 that has adsorbed tetrafluoroborate ions, and a sulfuric acid aqueous solution L is passed through the second ion exchange layer 8 that has adsorbed borate ions, and the regenerated waste liquid m, Get n. Next, the second ion exchange layer 8 is made from SO 4 type.
In order to return to the OH type, the recycled waste liquid m from the first stage ion exchange resin tower 7 is passed through the second ion exchange layer 8.
テトラフルオロホウ酸イオンを交換吸着した第
１のイオン交換層６の樹脂は、苛性ソーダで再生
を行うだけでも再生効率を低下させるこはない
が、ホウ酸イオンを交換吸着した第２のイオン交
換層８の樹脂は、苛性ソーダで再生を行うだけで
は単に樹脂をOH型に整えるだけで再生効率が悪
い。このため第２のイオン交換層８は苛性ソーダ
よりも再生効率の高い硫酸を用いて再生を行う。
しかしながら硫酸再生のみでは、被処理水の通水
再開時に処理水中へホウ素がリークするため、第
２のイオン交換層８をSO4型からOH型に戻す必
要がある。そこで第２のイオン交換層８の再生工
程では硫酸再生を行つたのち、苛性ソーダを多量
に含む１段イオン交換樹脂塔７からの再生廃液ｍ
を第２のイオン交換層８に通液し、このイオン交
換層８の樹脂をSO4型からOH型に戻し再々生廃
液ｐを得る。この際、１段イオン交換樹脂塔７の
再生廃液ｍに含まれるテトラフルオロホウ酸イオ
ン（第１のイオン交換層６の再生の際脱着された
テトラフルオロホウ酸イオンが多量に存在する。）
は、第２のイオン交換層８に交換吸着されること
はない。 The resin of the first ion exchange layer 6 that has exchanged and adsorbed tetrafluoroborate ions will not reduce the regeneration efficiency even if it is simply regenerated with caustic soda, but the resin of the second ion exchange layer 6 that has exchanged and adsorbed borate ions will not reduce the regeneration efficiency. Regenerating the resin No. 8 with caustic soda simply converts the resin into an OH type, which results in poor regeneration efficiency. Therefore, the second ion exchange layer 8 is regenerated using sulfuric acid, which has higher regeneration efficiency than caustic soda.
However, if only sulfuric acid regeneration is performed, boron will leak into the treated water when the flow of the water to be treated is restarted, so it is necessary to change the second ion exchange layer 8 from the SO 4 type to the OH type. Therefore, in the regeneration step of the second ion exchange layer 8, after performing sulfuric acid regeneration, the regenerated waste liquid m from the first stage ion exchange resin tower 7 containing a large amount of caustic soda is
is passed through the second ion exchange layer 8, and the resin in the ion exchange layer 8 is returned from the SO 4 type to the OH type to obtain a recycled waste liquid p. At this time, tetrafluoroborate ions contained in the recycled waste liquid m of the first-stage ion exchange resin tower 7 (a large amount of tetrafluoroborate ions desorbed during the regeneration of the first ion exchange layer 6 are present).
is not exchanged and adsorbed by the second ion exchange layer 8.
再生工程において最終的に生ずる廃液は、硫酸
イオンとホウ酸イオンを高濃度に含む２段イオン
交換樹脂塔９の再生廃液ｎと、苛性ソーダとテト
ラフルオロホウ酸イオンを高濃度に含む再々生廃
液ｐとである。これらの両廃液ｎ、ｐは混合して
酸性反応槽１に戻すか、混合せずに夫々を酸性反
応槽１またはアルカリ性反応槽３に戻す。その何
れかは、被処理水ａの性状あるいは装置の運転状
況に応じて決定する。 The waste liquid finally generated in the regeneration process is a regenerated waste liquid n from the two-stage ion exchange resin column 9 containing high concentrations of sulfate ions and borate ions, and a regenerated waste liquid p containing high concentrations of caustic soda and tetrafluoroborate ions. That is. These two waste liquids n and p are either mixed and returned to the acidic reaction tank 1, or returned to the acidic reaction tank 1 or the alkaline reaction tank 3, respectively, without being mixed. Either one is determined depending on the properties of the water to be treated a or the operating conditions of the apparatus.
被処理水ａのテトラフルオロホウ酸イオン濃度
が高く、あるいは、第１のイオン交換層６のテト
ラフルオロホウ酸イオン交換吸着能が小さい場合
には、再々生廃液ｐを酸性反応槽１に戻し、この
再々生廃液ｐに含まれるテトラフルオロホウ酸イ
オンをフツ化物とホウ酸イオンに分解するとよ
い。その結果テトラフルオロホウ酸イオン濃度が
減少し、第１イオン交換層６の樹脂の負荷が減少
される。この場合は、２段イオン交換樹脂塔９か
らの再生廃液ｎはアルカリ性反応槽３へ戻す。 When the tetrafluoroborate ion concentration of the water to be treated a is high, or when the tetrafluoroborate ion exchange adsorption capacity of the first ion exchange layer 6 is small, the recycled waste liquid p is returned to the acidic reaction tank 1, It is preferable to decompose the tetrafluoroborate ions contained in this recycled waste liquid p into fluoride and borate ions. As a result, the tetrafluoroborate ion concentration decreases, and the resin load on the first ion exchange layer 6 is reduced. In this case, the regenerated waste liquid n from the two-stage ion exchange resin tower 9 is returned to the alkaline reaction tank 3.
また、被処理水ａのテトラフルオロホウ酸イオ
ン濃度およびホウ酸イオン濃度が低い場合で、か
つ、前処理における薬剤量を軽減する必要がある
ときは、硫酸イオンを多量に含む２段イオン交換
樹脂塔９の再生廃液ｎを、酸性反応槽１に戻し、
苛性ソーダを多量に含む再々生廃液ｐをアルカリ
性反応槽３に戻すことができる。この場合は、酸
性反応槽１またはアルカリ性反応槽３への硫酸ｃ
や消石灰ｅの添加量が軽減されることになる。 In addition, when the tetrafluoroborate ion concentration and borate ion concentration of water to be treated a are low, and when it is necessary to reduce the amount of chemicals in pretreatment, a two-stage ion exchange resin containing a large amount of sulfate ions can be used. The recycled waste liquid n from the tower 9 is returned to the acidic reaction tank 1,
The recycled waste liquid p containing a large amount of caustic soda can be returned to the alkaline reaction tank 3. In this case, sulfuric acid c is added to acidic reaction tank 1 or alkaline reaction tank 3.
The amount of addition of slaked lime and slaked lime e will be reduced.
最終的に生じた凝集沈殿物ｈは、アルミニウム
を含む水産化物およびこれら水産化物に吸着され
たホウ素化合物等からなる汚泥で、固液分離槽５
の下端から引出され、必要に応じて脱水処理や固
化処理が施される。 The final coagulated precipitate h is sludge consisting of aluminum-containing aquatic products and boron compounds adsorbed to these aquatic products, and is collected in the solid-liquid separation tank 5.
It is pulled out from the bottom end and subjected to dehydration and solidification treatments as necessary.
本発明によれば、テトラフルオロホウ酸イオン
とホウ酸イオンを含む被処理水のホウ素を沈殿性
化合物として分離し上澄水をOH型塩基性アニオ
ン交換樹脂を充填した第１のイオン交換層に通水
して残存するテトラフルオロホウ酸イオンを吸着
させ、続いてOH型弱塩基性アニオン交換樹脂を
充填した第２のイオン交換層に通水して残存する
ホウ酸イオンを吸着させるため、被処理水中の大
部分のホウ素は沈殿性化合物として予め分離さ
れ、第１、第２のイオン交換樹脂層の通水される
上澄水には小量のテトラフルオロホウ酸イオンと
小量のホウ酸イオンが残存するのみであるから、
夫々のイオン交換樹脂の負荷を軽減し吸着性能を
高めるとともに長期間吸着性能を保持させること
ができる。また、第１、第２のイオン交換層に通
水しテトラフルオロホウ酸イオンとホウ酸イオン
を別個に夫々に適したイオン交換樹脂を用いて吸
着除去したから除去率が高く、処理水中のホウ素
濃度を１mg／以下にすることができる。さらに
テトラフルオロホウ酸イオンを吸着した第１のイ
オン交換層に苛性ソーダを通液し、ホウ酸イオン
を吸着した第２のイオン交換層に硫酸を通液し次
に苛性ソーダを通液した第１のイオン交換層の廃
液を第２のイオン交換層に通液するから、樹脂に
吸着したテトラフルオロホウ酸イオンまたはホウ
酸イオンが離脱してイオン交換性能を再生するこ
とができ、また硫酸を通液した第１のイオン交換
層には苛性ソーダを含む第１のイオン交換層の廃
液を更に通液してOH型にすることによりホウ酸
イオンの吸着性能を付与させるとともに再生用薬
剤を節約することができる。
According to the present invention, boron in the water to be treated containing tetrafluoroborate ions and borate ions is separated as a precipitable compound, and the supernatant water is passed through the first ion exchange layer filled with an OH type basic anion exchange resin. Water is applied to adsorb the remaining tetrafluoroborate ions, and then the water is passed through the second ion exchange layer filled with an OH type weakly basic anion exchange resin to adsorb the remaining borate ions. Most of the boron in the water is separated in advance as precipitable compounds, and the supernatant water that is passed through the first and second ion exchange resin layers contains a small amount of tetrafluoroborate ion and a small amount of borate ion. Since it only remains,
It is possible to reduce the load on each ion exchange resin, improve adsorption performance, and maintain adsorption performance for a long period of time. In addition, since water is passed through the first and second ion exchange layers and tetrafluoroborate ions and borate ions are adsorbed and removed separately using ion exchange resins suitable for each, the removal rate is high, and boron in the treated water is removed. The concentration can be lower than 1 mg/ml. Furthermore, caustic soda was passed through the first ion exchange layer that adsorbed tetrafluoroborate ions, sulfuric acid was passed through the second ion exchange layer that adsorbed borate ions, and then caustic soda was passed through the first ion exchange layer. Since the waste liquid from the ion exchange layer is passed through the second ion exchange layer, the tetrafluoroborate ions or borate ions adsorbed on the resin can be released and the ion exchange performance can be regenerated. The waste liquid of the first ion exchange layer containing caustic soda is further passed through the first ion exchange layer to convert it into an OH type, thereby imparting borate ion adsorption performance and saving regeneration chemicals. can.
前述の実施例の装置を用いて排脱排水処理の実
験を行つた。
An experiment on drainage and wastewater treatment was conducted using the apparatus of the above-mentioned example.
排脱排水（PH7.1〜7.3、ホウ素濃度330〜360mg
−Ｂ／、蒸発残留物1.2％）に硫酸アルミニウ
ムを４ｇ／添加したのち、３時間撹拌を行い、
そのあと消石灰を６ｇ／加え30分撹拌ののち約
１時間放置して固液分離を行つた。凝集沈殿上澄
水のホウ素濃度はホウ酸性ホウ素（BO3−Ｂ）
120mg／、テトラフルオロホウ酸ホウ素（BF4
−Ｂ）５mg／であつた。 Drainage wastewater (PH7.1-7.3, boron concentration 330-360mg
-B/, evaporation residue 1.2%) was added with 4 g of aluminum sulfate, and stirred for 3 hours.
Thereafter, 6 g/slaked lime was added, stirred for 30 minutes, and then left to stand for about 1 hour to perform solid-liquid separation. The boron concentration in the flocculation sedimentation supernatant water is boric acid boron (BO 3 -B)
120mg/Boron Tetrafluoroborate (BF 4
-B) It was 5 mg/.
この上澄水を１段イオン交換樹脂塔７に通水し
たところ、流出水のテトラフルオロホウ酸性ホウ
素濃度は200B、Ｖで平均0.5mg−Ｂ／以下であ
つた。なお、この時のホウ酸性ホウ素濃度は、
108mg−Ｂ／であつた。さらに、この１段イオ
ン交換樹脂塔７の流出水を２段イオン交換樹脂塔
９に通水したところ、処理水のホウ酸性ホウ素濃
度は20B、Ｖで平均0.5mg−Ｂ／以下であり、
全ホウ素濃度は１mg−Ｂ／以下となつた。 When this supernatant water was passed through the first-stage ion exchange resin column 7, the tetrafluoroboric acid boron concentration of the effluent was 200 B, V, and was less than 0.5 mg-B/ on average. In addition, the boric acid boron concentration at this time is
It was 108 mg-B/. Furthermore, when the effluent water from the first-stage ion-exchange resin tower 7 was passed through the second-stage ion-exchange resin tower 9, the boric acidic boron concentration of the treated water was 20B, V, and the average was less than 0.5 mg-B/,
The total boron concentration was less than 1 mg-B/.
次に処理水のホウ素濃度が１mg−Ｂ／を越え
た時点で、原水の供給をやめ再生を行つた。 Next, when the boron concentration of the treated water exceeded 1 mg-B/, the supply of raw water was stopped and regeneration was performed.
第１のイオン交換層６の再生は苛性ソーダを用
い、再生レベル65ｇNaOH／−樹脂、SV2
〔１／ｈ〕で通液した。その結果このイオン交換
層６からテトラフルオロホウ酸イオン（BF4−
Ｂ）の濃度が300mg／の液が得られ、ほぼホウ
素脱着率は100％であつた。 The first ion exchange layer 6 is regenerated using caustic soda, regeneration level 65g NaOH/-resin, SV2
The solution was passed at a rate of [1/h]. As a result, tetrafluoroborate ions (BF 4 −
A solution with a concentration of B) of 300 mg/W was obtained, and the boron desorption rate was almost 100%.
また、２段イオン交換樹脂塔９の再生は硫酸を
用い、再生レベル48ｇH2SO4／−樹脂、SV2
〔１／ｈ〕で通液した。この結果、イオン交換層
８からホウ酸性ホウ素（BO3−Ｂ）の濃度717
mg／の液が得られ、ほぼホウ素脱着率100％で
あつた。 In addition, the second stage ion exchange resin column 9 is regenerated using sulfuric acid, and the regeneration level is 48 g H 2 SO 4 /-resin, SV2
The solution was passed at a rate of [1/h]. As a result, the concentration of boric acid boron (BO 3 −B) from the ion exchange layer 8 was 717
mg of liquid was obtained, and the boron desorption rate was almost 100%.
さらに、１段イオン交換樹脂塔７の再生廃液を
全量SV2〔１／ｈ〕で第２のイオン交換層８に通
液した。その結果、この第２イオン交換層８から
テトラフルオロホウ酸ホウ素（BF4−Ｂ）の濃度
として300mg／の液が得られた。この結果より、
１段イオン交換樹脂塔７の再生廃液に含まれるテ
トラフルオロホウ酸ホウ素は第２イオン交換層８
には吸着されないことが分つた。 Further, the recycled waste liquid from the first stage ion exchange resin column 7 was passed through the second ion exchange layer 8 at a total rate of SV2 [1/h]. As a result, a liquid with a concentration of boron tetrafluoroborate (BF 4 -B) of 300 mg was obtained from the second ion exchange layer 8. From this result,
Boron tetrafluoroborate contained in the recycled waste liquid from the first stage ion exchange resin column 7 is transferred to the second ion exchange layer 8.
It was found that it was not adsorbed by
図は本発明の一実施例を示す処理方法の工程説
明図である。
６……第１のイオン交換層、８……第２のイオ
ン交換層。
The figure is a process explanatory diagram of a treatment method showing an embodiment of the present invention. 6...First ion exchange layer, 8...Second ion exchange layer.
Claims (1)
ウ酸イオン（BO3 3-）を含む被処理水のホウ素を
沈殿性化合物として分離し上澄水をOH型塩基性
アニオン交換樹脂を充填した第１のイオン交換層
に通水して残存するテトラフルオロホウ酸イオン
を除去し流出水を続いてOH型弱塩基性アニオン
交換樹脂を充填した第２のイオン交換層に通水し
て残存するホウ酸イオンを除去する工程と、前記
第１のイオン交換層が吸着したテトラフルオロホ
ウ酸イオンを苛性ソーダの通液により離脱させこ
の廃液を硫酸の通液により吸着したホウ酸イオン
を離脱した後の第２のイオン交換層に通液させ
夫々前記イオン交換樹脂を再生する工程とよりな
ることを特徴とするホウ素含有廃水の処理方法。 ２ 被処理水に硫酸アルミニウムを加えて撹拌し
次に消石灰を加えて撹拌しホウ素を含む沈殿性化
合物を生成することを特徴とする特許請求の範囲
第１項に記載のホウ素含有廃水の処理方法。[Claims] 1. Boron in the water to be treated containing tetrafluoroborate ions (BF 4 - ) and borate ions (BO 3 3- ) is separated as a precipitating compound, and the supernatant water is subjected to OH-type basic anion exchange. Water is passed through a first ion exchange layer filled with resin to remove remaining tetrafluoroborate ions, and the effluent is then passed through a second ion exchange layer filled with an OH type weakly basic anion exchange resin. the first ion exchange layer to remove the remaining borate ions; and the step of removing the tetrafluoroborate ions adsorbed by the first ion exchange layer by passing caustic soda through the waste solution, and removing the adsorbed borate ions by passing sulfuric acid through the waste liquid. A method for treating boron-containing wastewater, comprising the step of passing the liquid through a second ion-exchange layer after separation to regenerate the ion-exchange resin. 2. The method for treating boron-containing wastewater according to claim 1, which comprises adding aluminum sulfate to the water to be treated and stirring, and then adding slaked lime and stirring to generate a precipitable compound containing boron. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7370384A JPS60216882A (en) | 1984-04-12 | 1984-04-12 | Treatment of waste water containing boron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7370384A JPS60216882A (en) | 1984-04-12 | 1984-04-12 | Treatment of waste water containing boron |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60216882A JPS60216882A (en) | 1985-10-30 |
| JPH0368757B2 true JPH0368757B2 (en) | 1991-10-29 |
Family
ID=13525835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7370384A Granted JPS60216882A (en) | 1984-04-12 | 1984-04-12 | Treatment of waste water containing boron |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60216882A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4813106B2 (en) * | 2004-08-10 | 2011-11-09 | 株式会社神鋼環境ソリューション | Waste water treatment method and waste water treatment equipment |
| EP2735546B1 (en) * | 2012-11-21 | 2018-02-07 | Ovivo Inc. | Treatment of water, particularly for obtaining ultrapure water |
-
1984
- 1984-04-12 JP JP7370384A patent/JPS60216882A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60216882A (en) | 1985-10-30 |
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