JPH08173755A - Method for removing fluorine in drainage of flue gas desulfurization - Google Patents
Method for removing fluorine in drainage of flue gas desulfurizationInfo
- Publication number
- JPH08173755A JPH08173755A JP6322446A JP32244694A JPH08173755A JP H08173755 A JPH08173755 A JP H08173755A JP 6322446 A JP6322446 A JP 6322446A JP 32244694 A JP32244694 A JP 32244694A JP H08173755 A JPH08173755 A JP H08173755A
- Authority
- JP
- Japan
- Prior art keywords
- flue gas
- solid
- gas desulfurization
- discharged
- fluorine
- 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.)
- Pending
Links
Landscapes
- Treating Waste Gases (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は燃焼排ガス中の酸化硫黄
ガスを石灰−石膏法による湿式排煙脱硫処理するときに
排出される排水を、無害化処理する方法に関し、特に燃
焼排ガスの冷却工程と吸収工程とが一体となったスート
混合型の脱硫装置から排出される排水中のフッ素の除去
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for detoxifying waste water discharged during a wet flue gas desulfurization process by a lime-gypsum method for sulfur oxide gas in combustion exhaust gas, and particularly to a combustion exhaust gas cooling step. The present invention relates to a method for removing fluorine in wastewater discharged from a soot-mixing type desulfurization device in which an absorption step and an absorption step are integrated.
【０００２】[0002]
【従来の技術】石炭などを燃料とする燃焼排ガスは石灰
−石膏法などによる脱硫装置で処理されて、フッ素を含
む排水が排出される。フッ素を含む排水の処理方法とし
て、フッ素イオンに対し２〜３倍当量のカルシウムイオ
ンを添加してフッ化カルシウムとして除去する方法が一
般的である。しかし、この方法では、処理水中のフッ素
濃度が高く、全国一律の規制基準（１５ｍｇ／リットル
以下）を達成することが困難である。2. Description of the Related Art Combustion exhaust gas using coal or the like as a fuel is treated by a desulfurization device by the lime-gypsum method or the like, and waste water containing fluorine is discharged. As a method of treating wastewater containing fluorine, a method of adding calcium ions in an amount of 2 to 3 times the amount of fluorine ions to remove it as calcium fluoride is generally used. However, with this method, the concentration of fluorine in the treated water is high, and it is difficult to achieve a nationally uniform regulation standard (15 mg / liter or less).
【０００３】この処理方法を改良して、図４に示す２段
凝集沈殿法が一般に知られている。以下、この方法につ
いて説明する。燃焼排ガス１０ａは排煙脱硫装置１にて
冷却、除塵並びに硫黄酸化物を吸収除去された後、清浄
ガス１０ｂとして放出される。なお図中１１は硫黄酸化
物の吸収剤として供給される石灰石スラリである。排煙
脱硫装置１からは燃料成分に起因するフッ素化合物を含
む脱硫排水３１と冷却吸収工程スラリ１２が排出され
る。この脱硫排水３１を溶解槽２１に導入し、酸３２を
添加してｐＨ４以下にし、排水中の酸溶解成分及び後の
第２沈殿槽から返送される沈殿物４２を溶解する（溶解
槽２１の作用については後述する）。As a modification of this processing method, a two-stage coagulating sedimentation method shown in FIG. 4 is generally known. Hereinafter, this method will be described. The combustion exhaust gas 10a is cooled, dust-removed, and sulfur oxides are absorbed and removed by the flue gas desulfurization apparatus 1, and then discharged as clean gas 10b. Reference numeral 11 in the figure is a limestone slurry supplied as a sulfur oxide absorbent. From the flue gas desulfurization device 1, desulfurization wastewater 31 containing a fluorine compound derived from a fuel component and the cooling absorption process slurry 12 are discharged. This desulfurization wastewater 31 is introduced into the dissolution tank 21, an acid 32 is added to adjust the pH to 4 or less, and the acid-dissolved component in the wastewater and the precipitate 42 returned from the second precipitation tank later are dissolved (in the dissolution tank 21). The action will be described later).
【０００４】この溶解液３３を第１ｐＨ調整槽２２に導
入し、消石灰３４を添加してｐＨ８〜９に調整すること
により、重金属の水酸化物、石膏及びフッ化カルシウム
を含有する沈殿物を生成させる。次いで、この反応液３
５に高分子凝集剤３６を添加して、沈殿物を沈降しやす
くしたのち、第１沈殿槽２３で重力沈降による固液分離
をする。その上澄液３８は第２ｐＨ調整槽２５に流入さ
せる一方、沈殿物３７は脱水機２４で脱水する。脱水ろ
液３７ｂは第２ｐＨ調整槽２５に導入し、脱水ケーキ３
７ａは系外へ排出する。The solution 33 is introduced into the first pH adjusting tank 22 and slaked lime 34 is added to adjust the pH to 8 to 9 to form a precipitate containing heavy metal hydroxide, gypsum and calcium fluoride. Let Then, this reaction liquid 3
Polymer coagulant 36 is added to 5 to facilitate sedimentation of the precipitate, and then solid-liquid separation by gravity sedimentation is performed in the first sedimentation tank 23. The supernatant liquid 38 is caused to flow into the second pH adjusting tank 25, while the precipitate 37 is dehydrated by the dehydrator 24. The dehydrated filtrate 37b was introduced into the second pH adjusting tank 25, and the dehydrated cake 3
7a is discharged out of the system.
【０００５】第２ｐＨ調整槽２５では、第１沈殿槽２３
で固液分離した上澄液３８を主とする液にアルカリ剤３
９を添加し、ｐＨ１０以上に調整する。アルカリ剤３９
としては水酸化ナトリウム、水酸化カリウム、炭酸ナト
リウム、炭酸カリウムなどが使用できるが、運転費など
の面から、好ましくは水酸化ナトリウム、炭酸ナトリウ
ムを使用する。 水酸化ナトリウムを添加した場合は水
酸化マグネシウムの沈殿物が生じ、炭酸ナトリウムを添
加した場合は炭酸カルシウムの沈殿物が生じる。第２ｐ
Ｈ調整槽の反応液４０中の大部分のフッ素イオンは、こ
れらの沈殿物と錯塩を形成している。なおマグネシウム
化合物は前記排ガス成分に由来するもので、通常マグネ
シウムイオンとして５００〜１，０００ｍｇ／リットル
程度含有する場合が多い。In the second pH adjusting tank 25, the first precipitation tank 23
Alkaline agent 3 is added to the liquid mainly containing the supernatant liquid 38 solid-liquid separated by
9 is added and pH is adjusted to 10 or more. Alkaline agent 39
Although sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like can be used, sodium hydroxide and sodium carbonate are preferably used from the viewpoint of operating cost. A precipitate of magnesium hydroxide is formed when sodium hydroxide is added, and a precipitate of calcium carbonate is formed when sodium carbonate is added. 2nd p
Most of the fluorine ions in the reaction solution 40 in the H adjustment tank form a complex salt with these precipitates. The magnesium compound is derived from the exhaust gas component and usually contains magnesium ions in an amount of about 500 to 1,000 mg / liter in many cases.
【０００６】第２ＰＨ調整槽２５の反応液４０には高分
子凝集剤３６を添加して、沈殿物を沈降しやすくしたの
ち、第２沈殿槽２６で重力沈降による固液分離をし、処
理水４１は必要に応じて酸により中和処理をした後、系
外へ排出する。沈殿物４２は前記溶解槽２１に返送し、
新たな脱硫排水３１と共に溶解槽２１に入る。A polymer flocculant 36 is added to the reaction liquid 40 in the second pH adjusting tank 25 to facilitate sedimentation of the precipitate, and then solid-liquid separation by gravity sedimentation is carried out in the second sedimentation tank 26 to obtain treated water. If necessary, 41 is neutralized with an acid and then discharged out of the system. The precipitate 42 is returned to the dissolution tank 21,
It enters the dissolution tank 21 together with new desulfurization wastewater 31.
【０００７】溶解槽２１では、沈殿物４２及び新たな脱
硫排水３１に酸３２を添加し、再びｐＨ４以下にして酸
可溶成分、例えば水酸化マグネシウム、炭酸カルシウム
などを溶解させる。このとき、これらの沈殿物と錯塩を
形成していたフッ素イオンは、沈殿物の溶解に伴い液中
に再溶解する。さらに、この溶解液３３は第１ｐＨ調整
槽２２に流入させ、消石灰３４を添加してｐＨ８〜９に
調整することにより、再溶解した液中のフッ素化合物が
溶離したカルシウムイオンと反応してフッ化カルシウム
の沈殿となり、第１沈殿槽２３で固液分離して排出す
る。以下第２ｐＨ調整槽２５以降の工程は、前記と同様
である。なお、冷却吸収工程スラリ１２は脱水機２で脱
水されて脱水ケーキ１２ａとして系外へ排出され、脱水
ろ液１２ｂは別途処理するか排煙脱硫装置１の補給水の
１部などに利用される。In the dissolution tank 21, the acid 32 is added to the precipitate 42 and the new desulfurization wastewater 31, and the pH is adjusted to 4 or less again to dissolve acid-soluble components such as magnesium hydroxide and calcium carbonate. At this time, the fluoride ions forming a complex salt with these precipitates are redissolved in the liquid as the precipitates are dissolved. Further, the solution 33 is caused to flow into the first pH adjusting tank 22 and slaked lime 34 is added to adjust the pH to 8 to 9, whereby the fluorine compound in the re-dissolved solution reacts with the eluted calcium ions and fluorinated. Calcium precipitates, which is solid-liquid separated in the first precipitation tank 23 and discharged. The steps after the second pH adjusting tank 25 are the same as described above. The cooling and absorption process slurry 12 is dehydrated by the dehydrator 2 and discharged as a dehydrated cake 12a to the outside of the system, and the dehydrated filtrate 12b is treated separately or used as a part of makeup water for the flue gas desulfurization apparatus 1. .
【０００８】[0008]
【発明が解決しようとする課題】しかし前記の従来の処
理方法には次のような問題点かあった。 （１）排煙脱硫装置で発生する脱硫石膏（図４の１２
ａ）以外に、前記の凝集沈殿による汚泥が大量に発生す
る。脱硫石膏は高純度であるため、回収石膏としてセメ
ントや石膏ボードなどの工業原料として利用できるが、
凝集沈殿汚泥（図４の３７ａ）は石膏以外に水酸化マグ
ネシウム，フッ化カルシウム及びその他の重金属水酸化
物などの不純物を多く含むため、通常廃棄物として扱わ
れている。したがって凝集沈殿汚泥をできるだけ減らす
ことによって、脱硫石膏の回収率が向上するが、前記従
来法ではそれを実現することはできないHowever, the conventional processing method described above has the following problems. (1) Desulfurization gypsum generated in the flue gas desulfurization device (12 in FIG. 4)
In addition to a), a large amount of sludge is generated due to the coagulation and sedimentation. Since desulfurized gypsum has a high purity, it can be used as an industrial raw material such as cement and gypsum board as recovered gypsum.
Coagulated sediment sludge (37a in FIG. 4) contains a large amount of impurities such as magnesium hydroxide, calcium fluoride and other heavy metal hydroxides in addition to gypsum, and is therefore usually treated as waste. Therefore, the recovery rate of desulfurized gypsum is improved by reducing the coagulation sedimentation sludge as much as possible, but it cannot be realized by the conventional method.
【０００９】（２）排煙脱硫装置で発生する脱硫石膏
（図４の１２ａ）の脱水処理装置以外に、凝集沈殿汚泥
（図４の３７ａ）のための脱水処理装置が必要であり、
設備費と運転費が高くなるだけでなく、運転管理に要す
る負担がさらに増大する。 （３）フッ素を除去するために多数の処理工程が必要
で、設備費と薬品などの運転費が高くなるうえ運転管理
が複雑となる。 （４）多量の消石灰を使用するため、装置のスケーリン
グの問題が常につきまとう。(2) In addition to the dehydration treatment device for desulfurization gypsum (12a in FIG. 4) generated in the flue gas desulfurization device, a dehydration treatment device for coagulating sedimentation sludge (37a in FIG. 4) is required,
Not only will the equipment and operating costs increase, but the operational management burden will increase further. (3) A large number of processing steps are required to remove fluorine, which increases equipment costs, operating costs for chemicals, and complicates operation management. (4) Since a large amount of slaked lime is used, there is always the problem of device scaling.
【００１０】[0010]
【課題を解決するための手段】本発明は前記従来法にお
ける問題点を解消するために完成されたものである。す
なわち、石灰石あるいは消石灰スラリ等のアルカリ吸収
液を用いた燃焼排ガスの湿式排煙脱硫処理装置から排出
する排水中のフッ素の処理方法において、該排水にアル
カリ剤を添加してフッ素錯化合物を含有する固形物を析
出させたのち固液分離し、分離した水は系外へ排出し、
該固形物は前記脱硫装置に返送して吸収剤として再利用
することを特徴とする排煙脱硫排水中のフッ素の除去方
法である。本発明の好ましい態様として、前記固液分離
の方法が中空糸膜またはセラミック膜によりろ過する方
法である前記排煙脱硫排水中のフッ素の除去方法があ
る。The present invention has been completed to solve the problems in the conventional method. That is, in a method of treating fluorine in wastewater discharged from a wet flue gas desulfurization treatment apparatus for combustion exhaust gas using an alkaline absorbent such as limestone or slaked lime slurry, an alkaline agent is added to the wastewater to contain a fluorine complex compound. After solid matter is precipitated, solid-liquid separation is performed, and the separated water is discharged out of the system,
The method for removing fluorine in flue gas desulfurization wastewater is characterized in that the solid matter is returned to the desulfurization apparatus and reused as an absorbent. As a preferred embodiment of the present invention, there is a method of removing fluorine in the flue gas desulfurization wastewater, wherein the solid-liquid separation method is a method of filtering with a hollow fiber membrane or a ceramic membrane.
【００１１】本発明の一実施例であるスート混合方式脱
硫排水の処理方法を図１に示し、以下にさらに詳述す
る。石炭などの燃焼排ガス１０ａは排煙脱硫装置１の冷
却吸収工程（図示せず）で冷却、除塵並びに硫黄酸化物
等を吸収、除去した後、清浄ガス１０ｂとして放出され
る。なお図中１１は吸収剤として供給される石灰石スラ
リである。その際、排煙脱硫装置１から燃料成分に起因
するばい塵、重金属、硫黄酸化物のカルシウム塩等のほ
かに、フッ素化合物を含有する中性付近の冷却吸収工程
排水１３が放出される。この冷却吸収工程排水１３をｐ
Ｈ調整槽３に導入し、アルカリ剤１４を添加してｐＨ９
以上、好ましくはｐＨ１０．５〜１２に調整する。アル
カリ剤１４としては水酸化ナトリウム、炭酸ナトリウ
ム、水酸化カリウム、炭酸カリウムなどが適用できる
が、コストなどから水酸化ナトリウムあるいは炭酸ナト
リウムが好ましい。A method for treating soot-mixing type desulfurization effluent which is an embodiment of the present invention is shown in FIG. 1 and will be described in more detail below. The combustion exhaust gas 10a such as coal is cooled and absorbed in a cooling and absorption process (not shown) of the flue gas desulfurization apparatus 1 and after absorbing and removing sulfur oxides and the like, it is released as a clean gas 10b. In the figure, 11 is a limestone slurry supplied as an absorbent. At that time, in addition to dust, heavy metals, calcium salts of sulfur oxides, and the like due to the fuel components, the flue gas desulfurization device 1 discharges the near neutral neutral cooling absorption process wastewater 13. This cooling absorption process wastewater 13
It is introduced into the H adjusting tank 3 and the alkaline agent 14 is added to adjust the pH to 9
As described above, the pH is preferably adjusted to 10.5 to 12. As the alkali agent 14, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate or the like can be applied, but sodium hydroxide or sodium carbonate is preferable from the viewpoint of cost.
【００１２】該ｐＨ領域において、冷却吸収工程排水１
３中の共存成分から不溶物質が析出するが、その物質の
主成分は次式に示すようにアルカリ剤１４の種類によっ
て異なる。In the pH range, the cooling absorption process wastewater 1
An insoluble substance is precipitated from the coexisting components in 3, but the main component of the substance differs depending on the type of the alkaline agent 14 as shown in the following formula.
【化１】・水酸化ナトリウムを使用した場合： 2 Mg2+＋ 2 F- ＋ 2 NaOH → Mg(OH)2 *- MgF2＋ 2 Na + (1)## STR1 ## when using sodium hydroxide: 2 Mg 2+ + 2 F - + 2 NaOH → Mg (OH) 2 * - MgF 2 + 2 Na + (1)
【化２】・炭酸ナトリウムを使用した場合： 2 Ca2+＋ 2 F- ＋ Na2CO3 → CaCO3 * - CaF2＋ 2 Na + (2)Embedded image when using sodium carbonate: 2 Ca 2+ + 2 F - + Na 2 CO 3 → CaCO 3 * - CaF 2 + 2 Na + (2)
【００１３】上記反応式において、析出した水酸化マグ
ネシウム〔Ｍｇ（ＯＨ）2 * 〕または炭酸カルシウム
〔ＣａＣＯ3 * 〕の表面は何れも活性化しており、液中
のフッ化カルシウム〔ＣａＦ2 〕は、それぞれの表面で
フッ素錯化合物〔Ｍｇ（ＯＨ） 2 * −ＭｇＦ2 ↓、Ｃａ
ＣＯ3 * −ＣａＦ2 ↓〕を形成して不溶化し、その結果
液中の濃度が減少する。なお、予め析出させた水酸化マ
グネシウムまたは炭酸カルシウムの固形粉末を添加して
も前記（１）〜（２）式のようなフッ素錯化合物はほと
んど生成されないか、されても極めて少ない。ｐＨ調整
槽３の反応液１５は次に固液分離装置４で固液分離し、
処理水１６は必要に応じて酸を加え、中和処理をした後
系外へ排出する（図示せず）。一方、固形物スラリ１７
は排煙脱硫装置１に返送する。この固液分離装置４の方
法として、反応液１５の固形物濃度が高く（約１０重量
％以上）アルカリ性沈殿物を脱硫装置で再利用するため
には、中空糸膜またはセラミック膜による固液分離が適
している。In the above reaction formula, the deposited hydroxide hydroxide
Nesium [Mg (OH)2 *] Or calcium carbonate
[CaCO3 *], All surfaces are activated, and
Calcium fluoride [CaF2] On each surface
Fluorine complex compound [Mg (OH) 2 *-MgF2↓, Ca
CO3 *-CaF2↓] is formed and insolubilized, and as a result
The concentration in the liquid decreases. In addition, pre-precipitated hydroxide
Add solid powder of gnesium or calcium carbonate
Also, the fluorine complex compound represented by the above formulas (1) to (2) is
It is not generated or very little is generated. pH adjustment
The reaction liquid 15 in the tank 3 is then solid-liquid separated by the solid-liquid separation device 4,
Treated water 16 is added with an acid as necessary and neutralized.
Discharge to the outside of the system (not shown). On the other hand, solid slurry 17
Is returned to the flue gas desulfurization apparatus 1. This solid-liquid separator 4
As a method, the solid concentration of the reaction liquid 15 is high (about 10 wt.
% Or more) To reuse alkaline precipitate in desulfurization equipment
For this, solid-liquid separation using a hollow fiber membrane or ceramic membrane is suitable.
are doing.
【００１４】中空糸膜の材料としては、例えばポリエチ
レン、ポリスルフォン、ポリアクリルなどがあり、ま
た、セラミック膜の材料の例としてはムライト、シリコ
ンカーバイト、ケイ酸塩類、無灰純粋炭素などがあげら
れる。Examples of the material of the hollow fiber membrane include polyethylene, polysulfone, polyacrylic and the like, and examples of the material of the ceramic membrane include mullite, silicon carbide, silicates and ashless pure carbon. To be
【００１５】中空糸膜による固液分離装置４ａの概略構
造の一例を図２に示し、さらに詳述する。図２において
反応液１５が固液分離装置４ａに供給される。固液分離
装置４ａには中空糸膜６が配備され、ろ過ポンプ５で中
空糸膜６を吸引して透過液１６ａ（処理水１６）とな
る。中空糸膜６は直径３００μｍのポリエチレン製の繊
維状の中空糸（細孔径０．１μｍ）を束ねたもので、高
い固形物濃度の排水に直接浸漬して吸引（減圧）ろ過
し、その透過液の固形物濃度を０．２ｍｇ／リットル以
下にすることができる。中空糸膜６の下部には散気装置
７を設けて、常時空気１８などの気体を噴出させること
により中空糸膜６を振動させるとともに、反応液１５の
混合を行う。これによって中空糸膜６の固形物の付着蓄
積が防止できる。空気１８の流量は固形物濃度によって
変わるが、固液分離装置４ａの横断面積１ｍ2 に対して
０．０２ｍ3 ／ｍｉｎ以上であればよい。この中空糸膜
６によってろ過が阻止された析出物は固液分離装置４ａ
内で濃縮され、固形物スラリ１７として排煙脱硫装置１
に返送される。なお、この中空糸膜６は、ろ過を継続し
ても、ろ過差圧の上昇は比較的少なく、長時間逆洗は不
要である。逆洗を行う場合は、処理水１６でろ過と逆方
向に加圧水を供給して、中空糸膜６の細孔を閉塞させた
粒子を除去すればよい。An example of the schematic structure of the solid-liquid separation device 4a using a hollow fiber membrane is shown in FIG. 2 and will be described in more detail. In FIG. 2, the reaction liquid 15 is supplied to the solid-liquid separation device 4a. A hollow fiber membrane 6 is provided in the solid-liquid separation device 4a, and the hollow fiber membrane 6 is sucked by a filtration pump 5 to form a permeate 16a (treated water 16). The hollow fiber membrane 6 is a bundle of polyethylene fibrous hollow fibers (pore diameter: 0.1 μm) with a diameter of 300 μm, and is directly immersed in wastewater having a high solid concentration and suction (pressure reduction) filtered to obtain a permeated liquid. The solid concentration of can be 0.2 mg / liter or less. An air diffuser 7 is provided below the hollow fiber membrane 6 to vibrate the hollow fiber membrane 6 by constantly ejecting a gas such as air 18 and mix the reaction liquid 15. This can prevent the solid matter from adhering and accumulating on the hollow fiber membrane 6. The flow rate of the air 18 varies depending on the solid concentration, but may be 0.02 m 3 / min or more per 1 m 2 of the cross-sectional area of the solid-liquid separation device 4a. The precipitate whose filtration is blocked by the hollow fiber membrane 6 is a solid-liquid separator 4a.
Flue gas desulfurization equipment 1 which is concentrated inside and is converted into solid slurry 17
Will be returned to. It should be noted that the hollow fiber membrane 6 does not require backwashing for a long period of time even if the filtration is continued, because the increase in the filtration differential pressure is relatively small. When backwashing is performed, pressurized water is supplied in the direction opposite to the filtration with the treated water 16 to remove particles that have clogged the pores of the hollow fiber membrane 6.
【００１６】またセラミック膜による固液分離装置４ｂ
の概略構造の一例を図３に詳述する。図３において反応
液１５がろ過ポンプ５で固液分離装置４ｂに定流量で供
給される。固液分離装置４ｂには複数のセラミック膜８
が配備されており、反応液１５はろ過ポンプ５によって
加圧され、セラミック膜８でろ過され、透過液１６ａを
得て処理水１６となる。一方、固形物が濃縮された液は
固形物スラリ１７として排煙脱硫装置１に戻される。セ
ラミック膜８は外径３０ｍｍの円筒形セラミック（細孔
径は０．２μｍ）で、高い固形物濃度の排水を直接加圧
ろ過することができ、その透過液の固形物濃度を０．４
ｍｇ／リットル以下にすることができる。排水のろ過を
継続すると、セラミック膜８のろ過差圧が上昇する。そ
のため圧縮空気１８ａで、ろ過と逆方向に短時間加圧し
てろ過液を逆流させ、その際生じた逆洗スラリ１７ａは
固形物スラリ１７とともに排煙脱硫装置１に戻される。
この逆洗操作は間欠的に行えばよい。Further, a solid-liquid separation device 4b using a ceramic membrane
An example of the schematic structure of is detailed in FIG. In FIG. 3, the reaction liquid 15 is supplied to the solid-liquid separation device 4b by the filtration pump 5 at a constant flow rate. The solid-liquid separator 4b has a plurality of ceramic membranes 8
The reaction liquid 15 is pressurized by the filtration pump 5 and filtered by the ceramic membrane 8 to obtain the permeated liquid 16a and become the treated water 16. On the other hand, the liquid in which the solid matter is concentrated is returned to the flue gas desulfurization apparatus 1 as the solid matter slurry 17. The ceramic membrane 8 is a cylindrical ceramic having an outer diameter of 30 mm (pore diameter is 0.2 μm), and wastewater having a high solid content concentration can be directly pressure-filtered, and the solid content concentration of the permeated liquid is 0.4.
It can be less than or equal to mg / liter. When the filtration of the waste water is continued, the filtration differential pressure of the ceramic membrane 8 increases. Therefore, the compressed air 18a is pressurized for a short time in the direction opposite to the filtration to reversely flow the filtrate, and the backwash slurry 17a generated at that time is returned to the flue gas desulfurization apparatus 1 together with the solid matter slurry 17.
This backwashing operation may be performed intermittently.
【００１７】排煙脱硫装置１に返送された固形物スラリ
１７は同装置内の冷却・吸収工程（図示せず）液と混合
される。排煙脱硫装置１の冷却・吸収工程（図示せず）
では、次式のように排ガス１０ａ中の酸化硫黄ガスの吸
収・酸化反応が進行し、石膏が生成される。その際冷却
・吸収工程（図示せず）の液は中性付近に保たれてい
る。The solid matter slurry 17 returned to the flue gas desulfurization apparatus 1 is mixed with a cooling / absorption process (not shown) liquid in the apparatus. Cooling / absorption process of flue gas desulfurization device 1 (not shown)
Then, as shown in the following equation, the absorption / oxidation reaction of the sulfur oxide gas in the exhaust gas 10a proceeds, and gypsum is generated. At that time, the liquid in the cooling / absorption process (not shown) is kept near neutral.
【化３】 SO2 ＋ H2O → H+ ＋ HSO3 - (3) H +＋ HSO3 - ＋ 1/2 O2 → H2SO4 (4) H2SO4 ＋ CaCO 3 ＋ H2O → CaSO4・2H2O↓＋ CO2↑ (5) Embedded image SO 2 + H 2 O → H + + HSO 3 - (3) H + + HSO 3 - + 1/2 O 2 → H 2 SO 4 (4) H 2 SO 4 + CaCO 3 + H 2 O → CaSO 4・ 2H 2 O ↓ + CO 2 ↑ (5)
【００１８】固形物スラリ１７中のフッ素の錯化合物が
水酸化マグネシウム・フッ素錯化合物の場合、これらの
反応に並行して、水酸化マグネシウムが溶解し、過剰に
存在するカルシウムイオンとフッ素イオンが次式のよう
に反応して、フッ化カルシウムが生成される。When the complex compound of fluorine in the solid slurry 17 is magnesium hydroxide / fluorine complex compound, in parallel with these reactions, magnesium hydroxide is dissolved and the excess calcium ion and fluorine ion are Calcium fluoride is produced by reacting according to the formula.
【化４】 Mg(OH)2 * −MgF2＋ Ca2+ ＋ 2H + → 2Mg2+＋ CaF2 ↓＋ 2H2O (6)[Chemical 4] Mg (OH) 2 * -MgF 2 + Ca 2+ + 2H + → 2Mg 2+ + CaF 2 ↓ + 2H 2 O (6)
【００１９】また固形物スラリ１７中のフッ素の錯化合
物が炭酸カルシウム・フッ素錯化合物の場合、前記
（３）〜（５）式の反応と並行して、次式によりフッ化
カルシウムが生成される。When the fluorine complex compound in the solid slurry 17 is calcium carbonate / fluorine complex compound, calcium fluoride is produced by the following equation in parallel with the reactions of the equations (3) to (5). .
【化５】 CaCO3 * −CaF2＋H2SO 4＋H2O → CaSO 4・2H2O↓＋CaF2↓＋ CO2↑ (5) [Chemical formula 5] CaCO 3 * -CaF 2 + H 2 SO 4 + H 2 O → CaSO 4・ 2H 2 O ↓ + CaF 2 ↓ + CO 2 ↑ (5)
【００２０】こうして排煙脱硫装置１から排出された冷
却吸収工程スラリ１２は脱水機２で脱水されて、脱水ケ
ーキ１２ａとして系外へ排出するとともに、脱水ろ液１
２ｂは排煙脱硫装置１の補給水（図示せず）の一部とし
て利用する。以下、冷却吸収工程排水１３はｐＨ調整槽
３へ導入し、前記と同様に処理し排ガス成分に起因する
マグネシウム化合物を循環利用し、残存するフッ素化合
物を再び捕捉して排煙脱硫装置１に戻し、フッ化カルシ
ウムに変換して除去する。The cooling and absorption process slurry 12 thus discharged from the flue gas desulfurization apparatus 1 is dehydrated by the dehydrator 2 and discharged as a dehydrated cake 12a to the outside of the system, and the dehydrated filtrate 1
2b is used as a part of makeup water (not shown) of the flue gas desulfurization apparatus 1. In the following, the cooling / absorption process wastewater 13 is introduced into the pH adjusting tank 3, treated in the same manner as described above, and the magnesium compound originating from the exhaust gas component is circulated and used, and the remaining fluorine compound is captured again and returned to the flue gas desulfurization apparatus 1. , Converted to calcium fluoride and removed.
【００２１】[0021]
（１）活性化した水酸化マグネシウムまたは炭酸カルシ
ウムを形成させることにより、それらとのフッ素錯化合
物が生成され、フッ化カルシウムのみを生成させた場合
に比べて、溶解性のフッ素イオンが大幅に低下する。 （２）アルカリ剤１４として水酸化ナトリウムを使用し
た場合は水酸化マグネシウムを、炭酸ナトリウムを使用
した場合は炭酸カルシウムを含む固形物スラリ１７が得
られるがこのスラリは、ｐＨが何れも９以上のアルカリ
性であり、排煙脱硫装置１の冷却・吸収工程において、
吸収剤として再使用することができる。(1) By forming activated magnesium hydroxide or calcium carbonate, a fluorine complex compound with them is generated, and the soluble fluorine ion is significantly reduced as compared with the case where only calcium fluoride is generated. To do. (2) When sodium hydroxide is used as the alkaline agent 14, magnesium hydroxide is used, and when sodium carbonate is used, a solid slurry 17 containing calcium carbonate is obtained. This slurry has a pH of 9 or more. Alkaline, in the cooling and absorption process of the flue gas desulfurization device 1,
It can be reused as an absorbent.
【００２２】[0022]
【実施例】以下に実施例及び比較例を挙げて、本発明を
さらに具体的に説明する。 （実施例１）石炭を燃料とするボイラからの排ガスを、
図１及び図２に示すプロセスによって処理し、本発明の
排煙脱硫方法の試験を行った。このときの排ガス及び排
煙脱硫排水の水質を表１に示す。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. (Example 1) Exhaust gas from a boiler using coal as a fuel,
The flue gas desulfurization method of the present invention was tested by treatment by the process shown in FIGS. 1 and 2. Table 1 shows the water quality of the exhaust gas and the flue gas desulfurization wastewater at this time.
【００２３】[0023]
【表１】 [Table 1]
【００２４】前記排煙脱硫排水に、アルカリ剤として水
酸化ナトリウムを添加し、ｐＨを９、１０、１１、１２
の四段階に調整した液を、ポリエチレン中空糸膜（三菱
レーヨン製、細孔径０．１μｍ）でろ過速度３０リット
ル／ｍ2 ・ｈの連続吸引ろ過をした。その間の散気用の
空気量は、装置断面積１ｍ2 に対して０．０２ｍ3 ／ｍ
ｉｎを供給した。何れのｐＨにおいても、ろ過差圧は、
ろ過開始１４日後でも当初の８ｋＰａと変わらなかっ
た。この透過液（処理水）の水質を表２に示す。また何
れのｐＨのときも、清浄ガスＳＯ2 濃度は３０ｐｐｍ、
脱硫率は９１％であった。また脱水ケーキ（副生石膏）
の固形物量は、約５ｔ／ｈ（乾物ベース）であり、その
組成は大略２水石膏（ＣａＳＯ4 ・２Ｈ2 Ｏ）が９６．
５％、フッ化カルシウム（ＣａＦ2 ）が１％、その他
２．５％であった。Sodium hydroxide as an alkaline agent was added to the flue gas desulfurization wastewater to adjust the pH to 9, 10, 11, 12
The liquid prepared in four stages was subjected to continuous suction filtration with a polyethylene hollow fiber membrane (manufactured by Mitsubishi Rayon, pore size 0.1 μm) at a filtration rate of 30 liter / m 2 · h. The amount of air for aeration during that time is 0.02 m 3 / m for 1 m 2 of the device cross-sectional area.
supplied in. At any pH, the filtration pressure difference is
Even after 14 days from the start of filtration, the initial value was 8 kPa. The water quality of this permeate (treated water) is shown in Table 2. Also, at any pH, the clean gas SO 2 concentration is 30 ppm,
The desulfurization rate was 91%. Also dehydrated cake (by-product gypsum)
Has a solid content of about 5 t / h (on a dry matter basis) and its composition is approximately 96 g of dihydrate gypsum (CaSO 4 .2H 2 O).
5%, calcium fluoride (CaF 2 ) 1%, and other 2.5%.
【００２５】[0025]
【表２】 [Table 2]
【００２６】（実施例２）実施例１に示す表１の排煙脱
硫排水に、アルカリ剤として炭酸ナトリウム５００、１
０００、１５００ｍｇ／リットルとなるように添加し
て、実施例１と同様の条件で、中空糸膜による連続吸引
ろ過をした。何れの炭酸ナトリウム注入濃度において
も、ろ過差圧は、ろ過開始２０日後で当初の８ｋＰａと
変わらなかった。この透過液（処理水）の水質を表３に
示す。何れのｐＨのときも、清浄ガスＳＯ2 濃度は３０
ｐｐｍ、脱硫率は９１％で、脱水ケーキ（副生石膏）の
固形物量は、約５ｔ／ｈ（乾物ベース）であり、その組
成は大略２水石膏（ＣａＳＯ4 ・２Ｈ2 Ｏ）が９６．５
％、フッ化カルシウム（ＣａＦ2 ）が１％、その他２．
５％であった。(Example 2) In the flue gas desulfurization waste water of Table 1 shown in Example 1, sodium carbonate 500, 1 as an alkali agent
000 and 1500 mg / liter were added, and continuous suction filtration with a hollow fiber membrane was performed under the same conditions as in Example 1. The filtration pressure difference did not change from the initial value of 8 kPa 20 days after the start of filtration at any sodium carbonate injection concentration. Table 3 shows the water quality of the permeated liquid (treated water). At any pH, the clean gas SO 2 concentration is 30
ppm, desulfurization rate is 91%, the solid content of the dehydrated cake (by-product gypsum) is about 5 t / h (dry matter base), and its composition is approximately 96.5 gypsum dihydrate (CaSO 4 .2H 2 O).
%, Calcium fluoride (CaF 2 ) 1%, other 2.
5%.
【００２７】[0027]
【表３】 [Table 3]
【００２８】（実施例３）実施例１と同様に、アルカリ
剤として水酸化ナトリウムを添加し、ｐＨを９、１０、
１１、１２の４段階に調整した液を、図３に示すチュー
ブラ型セラミック膜（日本碍子製、細孔径０．１μｍ）
を用いて、ろ過速度０．５ｍ3 ／ｍ2 ・ｈの定流量加圧
ろ過をした。ろ過差圧が一定となるように、５分毎に一
回、１秒間逆洗を行った。逆洗圧力は２ｋｇ／ｃｍ2 と
した。その結果、ろ過差圧は、ろ過開始２０日後でも当
初の０．４ｋｇ／ｃｍ2 と変わらなかった。このときの
透過液（処理水）水質は表２と同じ結果が得られ、排煙
脱硫装置の脱硫率は実施例１と同じ結果が得られた。ま
た脱水ケーキ（副生石膏）の固形物量も実施例１とまっ
たく同じ結果が得られた。(Example 3) As in Example 1, sodium hydroxide was added as an alkaline agent to adjust the pH to 9, 10,
The liquid prepared in four stages of 11 and 12 was used as a tubular ceramic membrane shown in FIG. 3 (manufactured by Nippon Insulators, pore diameter 0.1 μm).
Was used for constant flow rate pressure filtration at a filtration rate of 0.5 m 3 / m 2 · h. Backwashing was performed once every 5 minutes for 1 second so that the filtration pressure difference became constant. The backwash pressure was 2 kg / cm 2 . As a result, the filtration pressure difference did not change from the initial 0.4 kg / cm 2 even after 20 days from the start of filtration. The permeated liquid (treated water) water quality obtained at this time was the same as in Table 2, and the desulfurization rate of the flue gas desulfurization apparatus was the same as in Example 1. Further, the same amount of solid matter as in the dehydrated cake (by-product gypsum) was obtained as in Example 1.
【００２９】（実施例４）実施例２と同様に、アルカリ
剤として炭酸ナトリウム５００、１０００、１５００ｍ
ｇ／リットルとなるように添加して、実施例３と同じ運
転条件で、セラミック膜を用いた定流量加圧ろ過をし
た。ろ過速度、逆洗頻度及び逆洗圧力も実施例３と同様
にした。このときの透過液（処理水）の水質は表３と同
じ結果が得られ、排煙脱硫装置の脱硫率はともに実施例
２と同じ結果が得られた。また脱水ケーキ（副生石膏）
の生成量も実施例２と同じ結果が得られた。(Example 4) As in Example 2, sodium carbonate 500, 1000, 1500 m was used as an alkaline agent.
It was added so as to be g / liter and subjected to constant flow rate pressure filtration using a ceramic membrane under the same operating conditions as in Example 3. The filtration rate, backwash frequency and backwash pressure were also the same as in Example 3. The water quality of the permeated liquid (treated water) at this time was the same as that in Table 3, and the desulfurization rate of the flue gas desulfurization device was the same as that in Example 2. Also dehydrated cake (by-product gypsum)
The same results as in Example 2 were obtained with respect to the production amount of.
【００３０】（比較例１）実施例１と同じ石炭を燃料と
するボイラからの排ガスを、図４に示す従来方法によっ
て脱硫試験を行った。このときのボイラ排ガス及び排煙
脱硫排水の水質は、表１と同じであった。この排水を、
酸３２として塩酸を添加して、溶解槽２１のｐＨを３、
第１ｐＨ調整槽のｐＨを消石灰３４で９とし、アルカリ
剤３９として水酸化ナトリウムを添加して、第２ｐＨ調
整槽のｐＨを１１に設定して処理した。このときの処理
水水質はｐＨ１１．０、ＳＳ２０ｍｇ／リットル、溶解
性Ｆ１０ｍｇ／リットルであった。また清浄ガスＳＯ2
濃度は３０ｐｐｍ、脱硫率は９１％で、脱硫装置石膏と
凝集沈殿汚泥の脱水ケーキ３７ａの合計量は約５ｔ／ｈ
（乾物ベース）であった。Comparative Example 1 Exhaust gas from a boiler using the same coal as in Example 1 as a fuel was subjected to a desulfurization test by the conventional method shown in FIG. At this time, the water quality of the boiler exhaust gas and the flue gas desulfurization wastewater was the same as in Table 1. This drainage,
Hydrochloric acid is added as the acid 32 to adjust the pH of the dissolution tank 21 to 3,
The pH of the first pH adjusting tank was adjusted to 9 with slaked lime 34, sodium hydroxide was added as an alkaline agent 39, and the pH of the second pH adjusting tank was set to 11, and the treatment was performed. At this time, the treated water quality was pH 11.0, SS 20 mg / liter, and solubility F 10 mg / liter. Also clean gas SO 2
The concentration is 30 ppm, the desulfurization rate is 91%, and the total amount of the desulfurization unit gypsum and the dehydrated cake 37a of the coagulation sludge is about 5 t / h.
(Dry matter base).
【００３１】（比較例２）アルカリ剤３９として炭酸ナ
トリウムを１５００ｍｇ／リットル添加して、比較例１
と同様に処理試験を行った。このときの処理水水質はｐ
Ｈ１０．０、ＳＳ２０ｍｇ／リットル、溶解性Ｆ１０ｍ
ｇ／リットルであった。また清浄ガスＳＯ2 濃度は３０
ｐｐｍ、脱硫率は９１％で、脱硫装置石膏と凝集沈殿汚
泥の脱水ケーキ３７ａの合計量は、約５ｔ／ｈ（乾物ベ
ース）であった。(Comparative Example 2) 1500 mg / liter of sodium carbonate was added as an alkali agent 39, and Comparative Example 1
A treatment test was conducted in the same manner as in. The treated water quality at this time is p
H10.0, SS20mg / l, Solubility F10m
g / liter. The clean gas SO 2 concentration is 30
ppm, the desulfurization rate was 91%, and the total amount of the desulfurization unit gypsum and the dehydrated cake 37a of the coagulation sedimentation sludge was about 5 t / h (on a dry matter basis).
【００３２】[0032]
（１）排水処理工程では、生成するフッ化カルシウム、
水酸化マグネシウム及び炭酸カルシウムの凝集沈殿汚泥
を沈降しやすくするために、高分子凝集剤を添加しなけ
ればならない。高分子凝集剤は、排煙脱硫装置での吸収
剤の脱硫性能を悪化させる恐れがあるため、従来方法で
は、それを含む沈殿物またはその上澄水を、脱硫装置で
の吸収剤と混合することを避けなければならなかった。
本発明によれば、中空糸やセラミック膜を用いた固液分
離装置によりろ過するため、固形物を粗大化する必要性
が小さいので前記汚泥を沈殿させるための、高分子凝集
剤を添加する必要がないため、排煙脱硫装置の脱硫率を
低下させずに、前記析出物またはその上澄水を脱硫装置
での吸収剤と混合することが始めて可能となった。(1) Calcium fluoride produced in the wastewater treatment step,
Aggregation of Magnesium Hydroxide and Calcium Carbonate A polymeric flocculant must be added to facilitate sludge settling. Since the polymer flocculant may deteriorate the desulfurization performance of the absorbent in the flue gas desulfurization equipment, the conventional method is to mix the precipitate containing it or the supernatant water with the absorbent in the desulfurization equipment. Had to avoid.
According to the present invention, since filtration is performed by a solid-liquid separation device using a hollow fiber or a ceramic membrane, it is less necessary to coarsen the solid matter, and therefore it is necessary to add a polymer flocculant for precipitating the sludge. Therefore, it became possible for the first time to mix the precipitate or its supernatant water with the absorbent in the desulfurization device without lowering the desulfurization rate of the flue gas desulfurization device.
【００３３】（２）排水処理工程において発生する汚泥
を、排煙脱硫装置へ返送することが可能となることによ
って、排ガスの吸収剤として再利用することができるよ
うになる。そのため排水処理工程の汚泥処理が不要とな
り、設備費及び薬品費を節減することができる。また排
水処理工程が簡素となり、運転管理が極めて容易とな
る。（３）本発明では、排煙脱硫装置の排水のフッ素及
び重金属等の濃度は、従来方法と同じまたはそれ以下の
水質レベルが得られるため、必要ならばｐＨ調整をして
直接放流することが可能となる。(2) The sludge generated in the wastewater treatment process can be returned to the flue gas desulfurization device, and can be reused as an exhaust gas absorbent. Therefore, sludge treatment in the wastewater treatment process is not required, and equipment costs and chemical costs can be saved. In addition, the wastewater treatment process is simplified, and operation management becomes extremely easy. (3) In the present invention, the concentration of fluorine, heavy metals, etc. in the wastewater of the flue gas desulfurization device can be the same as or lower than that of the conventional method, so that the pH can be adjusted and discharged directly if necessary. It will be possible.
【図１】本発明に係る排煙脱硫排水処理の工程説明図。FIG. 1 is a process explanatory view of a flue gas desulfurization wastewater treatment according to the present invention.
【図２】本発明の実施例１及び実施例２に係わる中空糸
膜による固液分離装置。FIG. 2 is a solid-liquid separation device using hollow fiber membranes according to Examples 1 and 2 of the present invention.
【図３】本発明の実施例３及び実施例４に係わるセラミ
ック膜による固液分離装置。FIG. 3 is a solid-liquid separation device using a ceramic membrane according to Examples 3 and 4 of the present invention.
【図４】従来の技術に係る排煙脱硫排水処理の工程説明
図を示す。FIG. 4 is a process explanatory view of a flue gas desulfurization wastewater treatment according to a conventional technique.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０２Ｆ 1/58 ＣＤＧ ＺＡＢ Ｍ Ｂ０１Ｄ 53/34 １２５ Ｒ Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location C02F 1/58 CDG ZAB M B01D 53/34 125 R
Claims (3)
液により吸収、分離する湿式排煙脱硫処理装置から排出
される排水中のフッ素処理方法において、該排水にアル
カリ剤を添加してフッ素錯化合物を含有する固形物を析
出させたのち固液分離し、分離した水は系外へ排出し、
該固形物は前記脱硫装置に返送して吸収剤として再利用
することを特徴とする排煙脱硫排水中のフッ素の除去方
法。1. A method for treating fluorine in wastewater discharged from a wet flue gas desulfurization treatment apparatus in which sulfur oxide in combustion exhaust gas is absorbed and separated by an alkali absorption liquid, and a fluorine complex compound is added to the wastewater by adding an alkali agent. After solid matter containing is precipitated, solid-liquid separation is performed, and the separated water is discharged out of the system,
A method for removing fluorine in flue gas desulfurization wastewater, wherein the solid matter is returned to the desulfurization apparatus and reused as an absorbent.
る請求項１に記載の排煙脱硫排水中のフッ素の除去方
法。2. The method for removing fluorine in flue gas desulfurization wastewater according to claim 1, wherein the solid-liquid separation is a method of filtering with a hollow fiber membrane.
である請求項１に記載の排煙脱硫排水中のフッ素の除去
方法。3. The method for removing fluorine in flue gas desulfurization wastewater according to claim 1, wherein the solid-liquid separation is a method of filtering with a ceramic membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6322446A JPH08173755A (en) | 1994-12-26 | 1994-12-26 | Method for removing fluorine in drainage of flue gas desulfurization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6322446A JPH08173755A (en) | 1994-12-26 | 1994-12-26 | Method for removing fluorine in drainage of flue gas desulfurization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08173755A true JPH08173755A (en) | 1996-07-09 |
Family
ID=18143763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6322446A Pending JPH08173755A (en) | 1994-12-26 | 1994-12-26 | Method for removing fluorine in drainage of flue gas desulfurization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08173755A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008073690A (en) * | 2007-10-24 | 2008-04-03 | Matsushita Environment Airconditioning Eng Co Ltd | Treatment method and apparatus of fluorine-containing waste water |
| CN108726772A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of advanced treatment and reclamation method of sodium alkali desulfurization liquid |
| CN108726769A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of advanced treatment and reclamation method of flue gas desulfurization liquid |
| JP2021505386A (en) * | 2017-12-06 | 2021-02-18 | オビボ インコーポレイテッド | Treatment of fluoride-containing wastewater |
-
1994
- 1994-12-26 JP JP6322446A patent/JPH08173755A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008073690A (en) * | 2007-10-24 | 2008-04-03 | Matsushita Environment Airconditioning Eng Co Ltd | Treatment method and apparatus of fluorine-containing waste water |
| JP4485562B2 (en) * | 2007-10-24 | 2010-06-23 | パナソニック環境エンジニアリング株式会社 | Method and apparatus for treating fluorine-containing wastewater |
| CN108726772A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of advanced treatment and reclamation method of sodium alkali desulfurization liquid |
| CN108726769A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of advanced treatment and reclamation method of flue gas desulfurization liquid |
| JP2021505386A (en) * | 2017-12-06 | 2021-02-18 | オビボ インコーポレイテッド | Treatment of fluoride-containing wastewater |
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