JP2944939B2 - Desulfurization wastewater treatment method and apparatus - Google Patents

Desulfurization wastewater treatment method and apparatus

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Publication number
JP2944939B2
JP2944939B2 JP8263482A JP26348296A JP2944939B2 JP 2944939 B2 JP2944939 B2 JP 2944939B2 JP 8263482 A JP8263482 A JP 8263482A JP 26348296 A JP26348296 A JP 26348296A JP 2944939 B2 JP2944939 B2 JP 2944939B2
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JP
Japan
Prior art keywords
reverse osmosis
osmosis membrane
desulfurization
treatment
concentrated
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.)
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JP8263482A
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Japanese (ja)
Other versions
JPH1085742A (en
Inventor
文雄 上村
邦臣 蓑島
直樹 政
紀宏 川島
勝 伊藤
慎一 平岩
浩人 舞田
Original Assignee
川崎重工業株式会社
中国電力株式会社
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【0001】[0001]
【発明の属する技術分野】本発明は、発電所等に設置さ
れている石灰石膏法/石灰石石膏法(マグネシウムを添
加する方式も含む)による排煙脱硫装置から排出される
排水を処理して、減容化された固形物と工業用水レベル
の清浄水とを得る方法及び装置に関するものである。
The present invention relates to a method for treating wastewater discharged from a flue gas desulfurization apparatus installed in a power plant or the like by a lime gypsum method / limestone gypsum method (including a method of adding magnesium) . to a method and apparatus to obtain the clean water of reduced iodide are solid and industrial water level.
【0002】[0002]
【従来の技術】排煙脱硫装置から排出される排水(以
下、「脱硫排水」という。)は、多量の溶存塩類を含ん
でおり、所定の処理を施してから隣接水域に放流されて
いる。しかしながら、脱硫排水が周囲の環境に及ぼす影
響を鑑みたとき、その影響を可能な限り最低限に抑える
ことが要求されるのは当然であり、特にその負荷が内
海、湖沼といった閉鎖系水域にもたらされる場合は、特
にその成分中のN分、COD、BODの負荷による影響
の度合を限りなくゼロに近づけることが要求される。ま
た、環境保護装置とはいえ、脱硫装置では大量の用水が
消費されており、地域社会に与える影響は無視できず、
できる限りの必要水量の削減が望まれる。脱硫排水の処
理に逆浸透膜法を採用することは従来から行われていた
が、脱硫排水をトータルで無排水化することを目的とし
て行われたことはなく、これまでは逆浸透膜による透過
液か濃縮液のどちらか一方にのみ着目するにとどまって
いた。
2. Description of the Related Art Wastewater discharged from a flue gas desulfurization apparatus (hereinafter referred to as "desulfurization wastewater") contains a large amount of dissolved salts and is discharged to an adjacent water area after a predetermined treatment. However, considering the effects of desulfurization effluent on the surrounding environment, it is naturally necessary to minimize the effects, especially when the load is brought to closed water bodies such as inland seas and lakes. In such a case, it is particularly required that the degree of the influence of the load of N, COD, and BOD in the component be as close to zero as possible. In addition, although it is an environmental protection device, a large amount of water is consumed by the desulfurization device, and its impact on local communities cannot be ignored.
It is desirable to reduce the required water volume as much as possible. The use of the reverse osmosis membrane method for the treatment of desulfurization effluent has been conventionally carried out, but it has not been carried out for the purpose of eliminating the total desulfurization effluent without drainage. They focused only on either the liquid or the concentrate.
【0003】特開昭52−39963号公報には、燃焼
ガス排煙脱硫装置等から排出された廃水を浄化する際、
活性炭によるCOD成分の吸着を阻害する原因となる溶
存塩類及び重金属を除去する目的で逆浸透膜による脱塩
処理を行うことが記載されており、逆浸透膜としてはセ
ルロースアセテート製内圧式チューブラー型が一例に挙
げられている。特開昭53−125966号公報には、
湿式法の排煙脱硫装置からの排水を非加熱手段で濃縮
し、得られた濃縮液中のCOD成分を熱分解処理する方
法が記載されており、排水を濃縮する非加熱手段の一例
として逆浸透膜法が挙げられている。特開昭61−22
2524号公報では、水酸化マグネシウム(Mg(O
H)2)を用いる湿式排煙脱硫法において、硫酸マグネ
シウム(MgSO4)を含有する排水に水酸化カルシウ
ム(Ca(OH)2)又は酸化カルシウム(CaO)を
添加することにより、硫酸カルシウム(CaSO4)と
水酸化マグネシウム(Mg(OH)2)の形で沈殿処理
を行う一連の工程の中で、塩化カルシウム(CaC
2)含有水の濃縮に逆浸透膜が利用されている。特開
平7−8750号公報には、湿式排煙脱硫設備から排出
される排水を電気透析装置、蒸発缶及び固化装置を用い
て処理する方法が記載されており、その制御手段に特徴
を有している。
[0003] Japanese Patent Application Laid-Open No. 52-39963 discloses that when purifying wastewater discharged from a combustion gas flue gas desulfurization apparatus or the like,
It is described that a desalination treatment using a reverse osmosis membrane is performed for the purpose of removing dissolved salts and heavy metals that cause inhibition of adsorption of COD components by activated carbon, and the reverse osmosis membrane is an internal pressure tubular type made of cellulose acetate. Is cited as an example. JP-A-53-125966 discloses that
A method is described in which wastewater from a flue gas desulfurization apparatus of the wet method is concentrated by a non-heating means, and a COD component in the obtained concentrate is subjected to thermal decomposition treatment. The osmosis membrane method is mentioned. JP-A-61-22
No. 2524 discloses magnesium hydroxide (Mg (O
H) 2 ), in a wet flue gas desulfurization method, calcium sulfate (Ca (OH) 2 ) or calcium oxide (CaO) is added to waste water containing magnesium sulfate (MgSO 4 ) to form calcium sulfate (CaSO 4). 4 ) and magnesium hydroxide (Mg (OH) 2 ) in a series of steps of precipitation treatment, calcium chloride (CaC
l 2 ) A reverse osmosis membrane is used to concentrate the contained water. Japanese Patent Application Laid-Open No. 7-8750 describes a method of treating wastewater discharged from a wet-type flue gas desulfurization facility using an electrodialyzer, an evaporator, and a solidifier, and has a feature in its control means. ing.
【0004】[0004]
【発明が解決しようとする課題】上述したように、脱硫
排水に関してその無排水化を目的として逆浸透膜による
濃縮技術を利用した方法及び装置は、これまでに開発さ
れていない。逆浸透膜による濃縮では、相変化を伴わな
いため、所要エネルギーが小さくて済み、効率的な運転
が可能となるが、これまで脱硫排水の無排水化処理に適
用されてこなかった理由は、排水そのものが多成分から
構成されているために、複雑な前処理を行う必要があ
り、特にその含有成分であるカルシウムイオン(C
2+)、硫酸イオン(SO4 2-)及び酸化珪素(Si
2)が濃縮過程で膜面にスケールとして析出し安定運
転が困難となるのを防止する必要があったからである。
As described above, a method and an apparatus utilizing a reverse osmosis membrane concentration technique for the purpose of eliminating the desulfurization wastewater from drainage have not been developed so far. Concentration using a reverse osmosis membrane does not involve a phase change, and therefore requires less energy and enables efficient operation.However, it has not been applied to desulfurization wastewater treatment to date. Since it itself is composed of multiple components, it is necessary to perform a complicated pretreatment, and in particular, calcium ion (C
a 2+ ), sulfate ions (SO 4 2− ) and silicon oxide (Si
This is because it was necessary to prevent O 2 ) from depositing as a scale on the membrane surface during the concentration process and making stable operation difficult.
【0005】特開昭52−39963号公報の処理方法
では、具体的な廃水の処理性能に関して言及されておら
ず、また、逆浸透膜処理で得られた濃縮液に着目した記
載は何もなされていない。特開昭53−125966号
公報では、上述したように、排水を濃縮する非加熱手段
の一例として、単に逆浸透膜法が挙げられているにとど
まり、排水を逆浸透膜に通して濃縮するとともに清浄水
を得るという逆浸透膜処理の具体的な記載は何もなされ
ていない。特開昭61−222524号公報では、塩化
カルシウム(CaCl2)含有水タンクでの液の濃度を
調整することを目的として逆浸透膜が用いられており、
排水の無排水化を目的として排水の濃縮に逆浸透膜を採
用したものではない。また、処理の対象となる液は塩化
カルシウム(CaCl2)含有水にとどまり、他の多種
類の成分を含有する排水の処理に適用できるものではな
い。特開平7−8750号公報の処理方法は、逆浸透膜
による濃縮手段を利用して脱硫排水を処理する方法では
ない。また、電気透析装置は定期的にメンテナンス作業
が必要であり、またスケールによるトラブルが発生した
場合、装置を分解し手作業による洗浄作業が必要となる
など維持管理が煩雑となる。
[0005] In the treatment method of Japanese Patent Application Laid-Open No. 52-39963, no specific reference is made to the treatment performance of wastewater, and there is no description focusing on the concentrated solution obtained by the reverse osmosis membrane treatment. Not. JP-A-53-125966, as described above, merely mentions the reverse osmosis membrane method as an example of the non-heating means for condensing waste water, and concentrates waste water by passing it through a reverse osmosis membrane. There is no specific description of reverse osmosis membrane treatment for obtaining clean water. In JP-A-61-222524, a reverse osmosis membrane is used for the purpose of adjusting the concentration of a liquid in a water tank containing calcium chloride (CaCl 2 ).
It does not use reverse osmosis membranes to concentrate wastewater for the purpose of eliminating wastewater. Further, the liquid to be treated is only water containing calcium chloride (CaCl 2 ), and is not applicable to the treatment of wastewater containing other various components. The treatment method disclosed in Japanese Patent Application Laid-Open No. 7-8750 is not a method of treating desulfurization wastewater using a concentration means using a reverse osmosis membrane. In addition, maintenance work is required for the electrodialysis apparatus, such as periodic maintenance work, and when troubles due to scale occur, the apparatus is disassembled and manual cleaning work is required.
【0006】本発明は上記の諸点に鑑みなされたもの
で、本発明の目的は、脱硫排水に関してその無排水化を
実現するために逆浸透膜による濃縮技術を利用した方法
及び装置を提供することにある。そして、脱硫排水を逆
浸透膜に通して濃縮し、さらに蒸発及び乾燥又は固化さ
ることにより、減容化された固形物と清浄水(工業用
水)とに分離する方法及び装置を提供することを目的と
している
SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and an object of the present invention is to provide a method and an apparatus utilizing a concentration technology by a reverse osmosis membrane in order to realize desulfurization wastewater without drainage. It is in. Then, the desulfurization wastewater is passed through a reverse osmosis membrane and concentrated , and then evaporated and dried or solidified.
By so Rukoto, it is an object to provide a method and apparatus for separating the the volume-reduced is solid with clean water (industrial water).
【0007】[0007]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明の脱硫排水の処理方法は、脱硫排水に凝集
剤を添加し凝集沈殿させて凝集沈殿物を除去した後、濾
過処理を行い、得られた処理液を逆浸透膜に通して濃縮
するとともに清浄水を得、逆浸透膜に通して得られた濃
縮水を、脱硫排水に凝集剤を添加し凝集沈殿させて得ら
れた凝集沈殿物とともに、蒸発器を用いてさらに濃縮し
た後、乾燥させて乾燥固形物とすることを特徴としてい
る。また、本発明の方法は、脱硫排水に凝集剤を添加し
凝集沈殿させて凝集沈殿物を除去した後、濾過処理を行
い、得られた処理液を逆浸透膜に通して濃縮するととも
に清浄水を得、逆浸透膜に通して得られた濃縮水を、脱
硫排水に凝集剤を添加し凝集沈殿させて得られた凝集沈
殿物とともに、蒸発器を用いてさらに濃縮した後、固化
剤を用いて固化固形物とすることを特徴としている。
れらの方法において、逆浸透膜に通す前の処理液にスケ
ール防止剤を添加することが望ましい。また、スケール
発生を回避するため、排水性状にあわせて脱塩性能に注
目した逆浸透膜の選定を行うことが望ましい
To achieve the above object SUMMARY OF THE INVENTION The processing method of the desulfurization effluent of the present invention, after removal of the flocculation precipitate added to aggregate precipitate flocculant de硫排water, filtered After performing the treatment, the obtained treatment liquid is concentrated through a reverse osmosis membrane, and at the same time, purified water is obtained .
Compressed water is obtained by adding a flocculant to the desulfurization
Further concentrate using an evaporator together with the coagulated sediment
And then dried to obtain a dry solid . Further, the method of the present invention comprises adding a flocculant to the desulfurization wastewater.
After coagulation and sedimentation to remove coagulation sediment, filtration is performed.
The resulting treatment solution is concentrated through a reverse osmosis membrane.
The concentrated water obtained by passing through a reverse osmosis membrane
Coagulation sedimentation obtained by adding coagulant to sulfuric acid wastewater and coagulating sedimentation
After further concentration using an evaporator together with the residue, solidification
It is characterized by using an agent to make a solidified solid. In these methods, it is desirable to add a scale inhibitor to the processing solution before passing through the reverse osmosis membrane. In addition, in order to avoid the generation of scale, it is desirable to select a reverse osmosis membrane focusing on the desalination performance according to the drainage properties .
【0008】本発明の脱硫排水の処理装置は、脱硫排水
に凝集剤を添加して凝集沈殿物を除去するための凝集沈
殿槽と、得られた清澄液中の懸濁物を除去するための濾
過装置と、得られた処理液を濃縮するとともに清浄水を
得るための逆浸透膜装置と、逆浸透膜に通して得られた
濃縮水を、脱硫排水に凝集剤を添加し凝集沈殿させて得
られた凝集沈殿物とともに、さらに濃縮するための逆浸
透膜装置及び凝集沈殿槽に接続された蒸発器と、濃縮さ
れた固形物を乾燥させるための乾燥装置と、を備えたこ
とを特徴としている。また、本発明の装置は、脱硫排水
に凝集剤を添加して凝集沈殿物を除去するための凝集沈
殿槽と、得られた清澄液中の懸濁物を除去するための濾
過装置と、得られた処理液を濃縮するとともに清浄水を
得るための逆浸透膜装置と、逆浸透膜に通して得られた
濃縮水を、脱硫排水に凝集剤を添加し凝集沈殿させて得
られた凝集沈殿物とともに、さらに濃縮するための逆浸
透膜装置及び凝集沈殿槽に接続された蒸発器と、濃縮さ
れた固形物を固化剤を用いて固化させるための固化装置
と、を備えたことを特徴としている。
[0008] processor of the desulfurization effluent of the present invention is to eliminate the coagulation-sedimentation tank to remove aggregates precipitate by adding a coagulant in de硫排water, the suspension in the resulting clear solution A filtration device, a reverse osmosis membrane device for concentrating the obtained treatment liquid and obtaining clean water, and a concentrated water obtained by passing through the reverse osmosis membrane are subjected to coagulation sedimentation by adding a coagulant to desulfurization wastewater. Get
Reverse immersion for further concentration with the aggregated sediment
It is characterized by comprising an evaporator connected to the membrane permeable device and the coagulation sedimentation tank, and a drying device for drying the concentrated solid matter. Also, equipment of the present invention, a filtration device for removing the coagulating sedimentation tank to remove aggregates precipitate by adding a coagulant to the desulfurization effluent, the suspension in the resulting clear solution, A reverse osmosis membrane device for concentrating the obtained treatment liquid and obtaining clean water, and the concentrated water obtained through the reverse osmosis membrane are obtained by adding a coagulant to the desulfurization wastewater to cause coagulation sedimentation.
Reverse immersion for further concentration with the aggregated sediment
It is characterized by comprising an evaporator connected to the membrane permeable device and the coagulating sedimentation tank, and a solidifying device for solidifying the concentrated solid using a solidifying agent.
【0009】[0009]
【発明の実施の形態】図1は本発明の脱硫排水の処理方
法の一例を示すフローシートである。図1において、脱
硫排水に適切な凝集剤を添加してから、凝集沈殿槽10
にて凝集沈殿物の沈殿除去を行う。沈殿除去方法として
は、その他、遠心沈降法、自然沈降法がある。得られた
清澄液は濾過装置12にて濾過処理が行われ懸濁物が除
去される。濾過装置12としては、一例として三層圧力
濾過装置やプレコートフィルターが挙げられる。このよ
うな簡単な前処理操作を行うだけで、逆浸透膜に供給し
ても問題のない良好な水質の処理液を得ることができ
る。また、濾過装置12は、凝集沈殿槽10で得られた
清澄液を用いて定期的に洗浄し、その際に発生する排水
は再び凝集沈殿槽10に送られ処理される。そして、こ
の処理液に適切なスケール防止剤を添加しておけば、逆
浸透膜による安定した濃縮処理が可能となり、その含有
成分であるカルシウムイオン(Ca2+)、硫酸イオン
(SO4 2-)及び酸化珪素(SiO2)が次の逆浸透膜に
よる濃縮過程で膜面にスケールとして析出することはな
い。凝集剤としては、弱アニオン系高分子凝集剤やノニ
オン系高分子凝集剤が用いられ、その注入量の範囲は、
0.1〜5ppm程度、好ましくは0.5〜1.0ppmの範
囲である。スケール防止剤としては、液体高分子系結晶
成長抑制剤やSHMP(ヘキサメタリン酸ソーダ)が用
いられ、その注入量の範囲は、0.1〜100ppm程
度、好ましくは10〜50ppmの範囲である。添加され
るこれらの薬品類は、濃縮液に残留しても蒸発工程や乾
燥工程で無害化されるため、周囲の環境(特に内海や湖
沼といった閉鎖系水域)に与える悪影響は全くない。
FIG. 1 is a flow sheet showing an example of a method for treating desulfurized waste water according to the present invention. In FIG. 1, after adding an appropriate coagulant to the desulfurization wastewater, the coagulation sedimentation tank 10
To remove the aggregated precipitate. Other methods for removing sediment include centrifugal sedimentation and natural sedimentation. The obtained clarified liquid is subjected to a filtration treatment in a filtration device 12 to remove suspended matter. Examples of the filtration device 12 include a three-layer pressure filtration device and a precoat filter. By simply performing such a simple pretreatment operation, it is possible to obtain a treatment liquid of good water quality that does not cause any problem even when supplied to the reverse osmosis membrane. In addition, the filtration device 12 is periodically cleaned using the clarified liquid obtained in the coagulation / sedimentation tank 10, and the wastewater generated at that time is sent to the coagulation / sedimentation tank 10 again for processing. If an appropriate scale inhibitor is added to the treatment liquid, a stable concentration treatment using a reverse osmosis membrane can be performed, and the contained components such as calcium ion (Ca 2+ ) and sulfate ion (SO 4 2- ) And silicon oxide (SiO 2 ) do not deposit as scale on the membrane surface during the subsequent concentration process by the reverse osmosis membrane. As the coagulant, a weak anionic polymer coagulant or a nonionic polymer coagulant is used.
The range is about 0.1 to 5 ppm, preferably 0.5 to 1.0 ppm. As the scale inhibitor, a liquid polymer-based crystal growth inhibitor or SHMP (sodium hexametaphosphate) is used, and the injection amount is about 0.1 to 100 ppm, preferably 10 to 50 ppm. Even if these added chemicals remain in the concentrated solution, they are detoxified in the evaporation step and the drying step, and therefore have no adverse effect on the surrounding environment (particularly in closed water bodies such as inland seas and lakes).
【0010】上記の前処理操作を行い適切なスケール防
止剤を添加した処理液は、逆浸透膜装置14に通されて
濃縮工程に入り、ここで濃縮水と工業用水レベルの清浄
水(回収水)とに分離される。逆浸透膜としては、その
性能が0.1〜1wt%程度の塩水に対して脱塩率が95
%以下程度のものであり、好ましくは脱塩率が90〜9
3%のものであり、例えば、ポリアミド系合成高分子系
低圧逆浸透膜が用いられる。得られた濃縮水は、先ほど
の凝集沈殿で得られた凝集沈殿物とともに、蒸発器16
に導入されてさらに濃縮された後、乾燥装置18にて乾
燥処理されて乾燥固形物となる。この乾燥固形物は、産
業廃棄物として処理することができ、フライアッシュ、
石膏等に混合して処理することもできる。一方、得られ
た清浄水(回収水)は、蒸発工程で得られた水分ととも
に、脱硫設備における工業用水として再利用することが
でき、これにより脱硫排水の無排水化が実現できる。
The treatment solution to which the above-mentioned pretreatment operation and an appropriate scale inhibitor have been added is passed through a reverse osmosis membrane device 14 to enter a concentration step, in which concentrated water and industrial-grade clean water (recovered water) ) And separated into The reverse osmosis membrane has a desalination rate of 95 to 0.1 to 1 wt% of salt water.
% Or less, preferably having a desalination rate of 90 to 9%.
For example, a polyamide-based synthetic polymer-based low-pressure reverse osmosis membrane is used. The obtained concentrated water is combined with the coagulated sediment obtained by the coagulation sedimentation and the evaporator 16.
And further concentrated, and then dried in a drying device 18 to become a dry solid. This dried solid can be treated as industrial waste, fly ash,
It can also be mixed with gypsum or the like for treatment. On the other hand, the obtained clean water (recovered water) can be reused as industrial water in a desulfurization facility together with the water obtained in the evaporation step, thereby making it possible to eliminate desulfurization wastewater.
【0011】図2は本発明の脱硫排水の処理方法の他の
例を示している。本例の方法は、蒸発器16からの濃縮
物を固化剤とともに固化装置20に導入し固化させて固
化固形物とするものである。固化剤としては、重金属固
定剤〔エポルバ500、NEWエポルバ500(ミヨシ
油脂製)〕が用いられ、その添加量は0.1〜10wt
%、望ましくは0.1〜3wt%である。他の構成及び作
用は図1の場合と同様である。
FIG. 2 shows another example of the method for treating desulfurized effluent of the present invention. In the method of the present embodiment, the concentrate from the evaporator 16 is introduced into a solidifying device 20 together with a solidifying agent and solidified to form a solidified solid. As the solidifying agent, a heavy metal fixing agent [Epolva 500, NEW Epolva 500 (manufactured by Miyoshi Oil & Fats)] is used, and the added amount is 0.1 to 10 wt.
%, Desirably 0.1 to 3% by weight. Other configurations and operations are the same as those in FIG.
【0012】図3は本発明の脱硫排水の処理装置の一例
を示している。図3において、10は凝集沈殿槽であ
り、適切な凝集剤を添加した脱硫排水が導入され、凝集
沈殿物の沈殿除去が行われる。12は濾過装置であり、
凝集沈殿物を除去して得られた清澄液中の懸濁物の除去
が行われる。濾過装置12としては、例えば、三層圧力
濾過装置等が挙げられる。凝集沈殿槽10及び濾過装置
12による前処理工程を経ることにより、次の逆浸透膜
装置14に供給しても問題のない良好な水質の処理液を
得ることができる。そして、この処理液に適切なスケー
ル防止剤を添加しておけば、その含有成分であるカルシ
ウムイオン(Ca2+)、硫酸イオン(SO4 2-)及び酸
化珪素(SiO2)が次の逆浸透膜による濃縮過程で膜
面にスケールとして析出することはない。
FIG. 3 shows an example of a desulfurization wastewater treatment apparatus according to the present invention. In FIG. 3, reference numeral 10 denotes a coagulation sedimentation tank, into which desulfurization wastewater to which an appropriate coagulant is added is introduced, and sedimentation of the coagulated sediment is performed. 12 is a filtration device,
The suspension in the clarified liquid obtained by removing the aggregated precipitate is removed. Examples of the filtering device 12 include a three-layer pressure filtering device. By passing through the pretreatment step by the coagulation sedimentation tank 10 and the filtration device 12, even if it is supplied to the next reverse osmosis membrane device 14, it is possible to obtain a treatment liquid of good water quality without any problem. Then, if an appropriate scale inhibitor is added to this treatment liquid, its components, ie, calcium ion (Ca 2+ ), sulfate ion (SO 4 2− ), and silicon oxide (SiO 2 ) are reversed in the following manner. It does not precipitate as scale on the membrane surface during the concentration process by the permeable membrane.
【0013】14は逆浸透膜装置であり、前記の前処理
工程を経て得られた処理液を濃縮することにより、濃縮
水と清浄水(回収水)とが得られる。この場合、膜モジ
ュールは容積効率が良く、装置全体がコンパクトにまと
まる。また、膜のメンテナンスは通常のフラッシング操
作のみであり、それは自動運転であり、他の電気透析等
に比べても非常に簡易な装置となる。16は蒸発器であ
り、逆浸透膜装置14に通して得られた濃縮水を、先ほ
どの凝集沈殿槽10で得られた凝集沈殿物とともに、さ
らに濃縮する。18は乾燥装置であり、蒸発器16でさ
らに濃縮された固形物を乾燥させて乾燥固形物とする。
この乾燥固形物は、産業廃棄物として処理することがで
き、フライアッシュ、石膏等に混合して処理することも
できる。蒸発器16としては、水蒸気加熱蒸発器、液膜
式蒸発器、多重効用式蒸発器などが用いられ、乾燥装置
18としては、ドラムドライヤー、スプレードライヤ
ー、薄膜式乾燥機、流動層乾燥機、ベルト式乾燥機、真
空式乾燥機などが用いられる。一方、得られた清浄水
(回収水)は、蒸発器16で得られた水分とともに、脱
硫設備における工業用水として再利用することができ
る。逆浸透膜装置14による濃縮は相変化を伴わず、本
発明の装置の運転エネルギーは、10〜30kg/cm2G程
度の加圧用のエネルギーのみであり、運転費用がきわめ
て少額である。
Reference numeral 14 denotes a reverse osmosis membrane device, which concentrates the treatment liquid obtained through the pretreatment step to obtain concentrated water and clean water (recovered water). In this case, the membrane module has good volumetric efficiency, and the entire apparatus is compact. Further, maintenance of the membrane is only a normal flushing operation, which is an automatic operation, and is a very simple apparatus as compared with other electrodialysis and the like. Reference numeral 16 denotes an evaporator, which further concentrates the concentrated water obtained through the reverse osmosis membrane device 14 together with the coagulated sediment obtained in the coagulated sedimentation tank 10 described above. Numeral 18 denotes a drying device which dries the solid matter further concentrated in the evaporator 16 to a dry solid matter.
This dried solid can be treated as industrial waste, and can also be treated by mixing it with fly ash, gypsum or the like. As the evaporator 16, a steam heating evaporator, a liquid film evaporator, a multi-effect evaporator, or the like is used. As the drying device 18, a drum dryer, a spray dryer, a thin film dryer, a fluidized bed dryer, a belt Dryers, vacuum dryers and the like are used. On the other hand, the obtained clean water (recovered water) can be reused together with the water obtained in the evaporator 16 as industrial water in a desulfurization facility. The concentration by the reverse osmosis membrane device 14 does not involve a phase change, and the operation energy of the device of the present invention is only energy for pressurization of about 10 to 30 kg / cm 2 G, and the operation cost is extremely small.
【0014】図4は本発明の脱硫排水の処理装置の他の
例を示している。本例の装置は、蒸発器16からの濃縮
物を固化剤とともに固化装置20に導入し固化させて固
化固形物とするものである。固化装置20としては、混
合造粒機、混練機を挙げることができる。他の構成及び
作用は図3の場合と同様である。
FIG. 4 shows another example of a desulfurization wastewater treatment apparatus according to the present invention. The apparatus of this example is to introduce the concentrate from the evaporator 16 together with the solidifying agent into the solidifying device 20 and solidify it to form a solidified solid. Examples of the solidifying device 20 include a mixing granulator and a kneader. Other configurations and operations are the same as those in FIG.
【0015】[0015]
【実施例】つぎに、本発明の実施例について説明する。 実施例1 図1及び図3に示すフローに従って、SS(Suspe
nded Solid、浮遊固形物)190mg/lを含
む脱硫排水原水を凝集沈殿槽で処理し、ついで三層圧力
濾過装置で濾過した。濾過装置の濾液(膜供給水)のS
Sは2mg/l、FI(Fouling Index)値
は4以下であった。膜供給水の性状は表1に示す如くで
あった。ついで、この膜供給水をポリアミド系合成高分
子系低圧逆浸透膜を用いた逆浸透膜装置に導入して処理
した。供給圧力は28kg/cm2G、回収率は70%であっ
た。この結果、濃縮水及び清浄水(透過水)の性状は表
1に示す如くであった。
Next, an embodiment of the present invention will be described. Example 1 According to the flow shown in FIG. 1 and FIG.
ND solid (suspended solids) (190 mg / l) was treated in a coagulation sedimentation tank, and then filtered with a three-layer pressure filter. S of filtrate (membrane supply water) of filtration device
S was 2 mg / l, and FI (Fouling Index) value was 4 or less. The properties of the membrane feed water were as shown in Table 1. Subsequently, the membrane feed water was introduced into a reverse osmosis membrane apparatus using a polyamide-based synthetic polymer-based low-pressure reverse osmosis membrane for treatment. The supply pressure was 28 kg / cm 2 G, and the recovery was 70%. As a result, the properties of the concentrated water and the clean water (permeated water) were as shown in Table 1.
【0016】[0016]
【表1】 [Table 1]
【0017】[0017]
【発明の効果】本発明は上記のように構成されているの
で、つぎのような効果を奏する。 (1) 脱硫排水を逆浸透膜に通して濃縮するととも
に、逆浸透膜による濃縮物を蒸発器を用いてさらに濃縮
を行い、乾燥装置にて乾燥させるか、又は固化装置にて
固化させることにより、減容化された固形物と清浄水
(回収水)とに分離することができ、脱硫設備からの排
水をゼロ、すなわち無排水化することができ、周囲の環
境(特に内海や湖沼といった閉鎖系水域)への負荷をな
くすことができる。また、得られた清浄水は脱硫設備で
工業用水として再利用できるので、脱硫設備全体の用水
量を大幅に削減することができる。 (2) 逆浸透膜による濃縮では、相変化を伴わないた
め、所要エネルギーが小さくて済み、効率的な運転が可
能となる。具体的には、装置の運転動力は10〜30kg
/cm2G程度の加圧用のエネルギーのみであり、運転費用
はきわめて少額であり、設備運転経費が削減できる。 (3) 逆浸透膜における膜モジュールは容積効率が良
く、装置全体がコンパクトにまとまる。また、膜のメン
テナンスは通常のフラッシング操作のみであり、それは
自動運転であり、他の電気透析等に比べても非常に簡易
な装置となる。 (4) 適切な凝集剤を添加することによる凝集物の沈
殿除去、及び濾過操作を行うことにより、簡単な前処理
操作により、逆浸透膜に供給しても問題のない良好な水
質の処理液を得ることができる。 (5) 適切なスケール防止剤を添加する場合は、逆浸
透膜による安定した濃縮処理が可能となり、その含有成
分であるカルシウムイオン(Ca2+)、硫酸イオン(S
4 2-)及び酸化珪素(SiO2)が次の逆浸透膜による
濃縮過程で膜面にスケールとして析出することはない。 (6) 添加される凝集剤やスケール防止剤の薬品類
は、濃縮液に残留しても蒸発工程や乾燥工程で無害化さ
れるため、周囲の環境に与える悪影響はない。 (7) 逆浸透膜による濃縮物を蒸発器を用いてさらに
濃縮を行い、乾燥装置にて乾燥させるか、又は固化装置
にて固化させることにより、乾燥固形物又は固化固形物
が得られるので、固形状の産業廃棄物として処理するこ
とができ、フライアッシュ、石膏等に混合して処理する
こともできる。 (8) 凝集沈殿で得られた凝集沈殿物は、後流の蒸発
工程及び乾燥工程又は固化工程で処理できるので、追加
の処理装置を設ける必要がなく効率的である。
As described above, the present invention has the following effects. (1) together and concentrated through a desulfurization effluent reverse osmosis membrane
The concentrate from the reverse osmosis membrane is further concentrated using an evaporator.
And dry it with a drying device, or use a solidifying device
By solidifying, it is possible to separate the reduced solid matter and clean water (recovered water), and to eliminate the wastewater from the desulfurization equipment, that is, to eliminate the wastewater, and to remove the surrounding environment (especially inland seas). And the impact on closed water bodies such as lakes and marshes. Further, the obtained clean water can be reused as industrial water in the desulfurization facility, so that the amount of water used in the entire desulfurization facility can be significantly reduced. (2) Since the concentration by the reverse osmosis membrane does not involve a phase change, the required energy is small and efficient operation is possible. Specifically, the operation power of the device is 10 to 30 kg.
Only pressurizing energy of about / cm 2 G, the operation cost is extremely small, and the equipment operation cost can be reduced. (3) The membrane module in the reverse osmosis membrane has good volumetric efficiency, and the whole apparatus is compact. Further, maintenance of the membrane is only a normal flushing operation, which is an automatic operation, and is a very simple apparatus as compared with other electrodialysis and the like. (4) A treatment liquid with good water quality that can be supplied to a reverse osmosis membrane by a simple pretreatment operation by performing precipitation operation of removing aggregates by adding an appropriate coagulant and filtering operation. Can be obtained. (5) When an appropriate scale inhibitor is added, a stable concentration treatment using a reverse osmosis membrane becomes possible, and calcium ion (Ca 2+ ) and sulfate ion (S
O 4 2- ) and silicon oxide (SiO 2 ) do not precipitate as scale on the membrane surface during the subsequent concentration process by the reverse osmosis membrane. (6) Even if the added coagulant or scale preventive chemicals remain in the concentrated solution, they are rendered harmless in the evaporation step and the drying step, and therefore have no adverse effect on the surrounding environment. The concentrate according to (7) reverse osmosis membrane performed further concentrated using an evaporator, or dried in a drying apparatus, or by solidifying by solidifying device, because dry solid or solidified solid is obtained, It can be treated as solid industrial waste and can also be mixed with fly ash, gypsum, etc. for treatment. (8) Since the coagulated sediment obtained by coagulated sedimentation can be treated in the downstream evaporation step, drying step, or solidification step, it is efficient without providing an additional processing device.
【図面の簡単な説明】[Brief description of the drawings]
【図1】本発明の脱硫排水の処理方法の一例を示すフロ
ーシートである。
FIG. 1 is a flow sheet showing an example of a method for treating desulfurization wastewater of the present invention.
【図2】本発明の脱硫排水の処理方法の他の例を示すフ
ローシートである。
FIG. 2 is a flow sheet showing another example of the method for treating desulfurization wastewater of the present invention.
【図3】本発明の脱硫排水の処理装置の一例を示す概略
図である。
FIG. 3 is a schematic view showing an example of a desulfurization wastewater treatment device of the present invention.
【図4】本発明の脱硫排水の処理装置の他の例を示す概
略図である。
FIG. 4 is a schematic view showing another example of the desulfurization wastewater treatment apparatus of the present invention.
【符号の説明】[Explanation of symbols]
10 凝集沈殿槽 12 濾過装置 14 逆浸透膜装置 16 蒸発器 18 乾燥装置 20 固化装置 DESCRIPTION OF SYMBOLS 10 Coagulation sedimentation tank 12 Filtration apparatus 14 Reverse osmosis membrane apparatus 16 Evaporator 18 Drying apparatus 20 Solidification apparatus
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C02F 1/04 ZAB C02F 5/00 610F 1/52 B01D 53/34 125R 5/00 610 125E (72)発明者 政 直樹 神戸市中央区東川崎町3丁目1番1号 川崎重工業株式会社 神戸工場内 (72)発明者 川島 紀宏 神戸市中央区東川崎町1丁目1番3号 川崎重工業株式会社 神戸本社内 (72)発明者 伊藤 勝 広島県広島市中区小町4番33号 中国電 力株式会社内 (72)発明者 平岩 慎一 広島県広島市中区小町4番33号 中国電 力株式会社内 (72)発明者 舞田 浩人 広島県広島市中区小町4番33号 中国電 力株式会社内 (56)参考文献 特開 昭51−93789(JP,A) 特開 昭53−102271(JP,A) 特開 昭53−125966(JP,A) 特開 平7−8750(JP,A) 特開 昭61−222524(JP,A) 特開 昭63−28485(JP,A) 特開 昭58−11094(JP,A) 実開 昭63−193600(JP,U) (58)調査した分野(Int.Cl.6,DB名) C02F 1/44 B01D 53/50 B01D 53/77 B01D 61/02 B01D 61/04 C02F 1/04 C02F 1/52 C02F 5/00 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification symbol FI C02F 1/04 ZAB C02F 5/00 610F 1/52 B01D 53/34 125R 5/00 610 125E (72) Inventor Naoki Kobe Kobe City 3-1-1 Higashi-Kawasaki-cho, Chuo-ku Kawasaki Heavy Industries, Ltd. Kobe Plant (72) Inventor Norihiro Kawashima 1-3-1, Higashi-Kawasaki-cho, Chuo-ku, Kobe Kawasaki Heavy Industries, Ltd.Kobe Main Office (72) Inventor Masaru Ito 4-33 Komachi, Naka-ku, Hiroshima-shi, Hiroshima Prefecture Inside Chugoku Electric Power Company (72) Inventor Shinichi Hiraiwa 4-33 Komachi, Naka-ku, Hiroshima City, Hiroshima Prefecture Inside Chugoku Electric Power Company (72) Inventor Hiroto Maita Hiroshima No. 4-33, Komachi, Naka-ku, Hiroshima-shi, Japan (56) References JP-A-51-93789 (JP, A) JP-A-53-102271 (JP, A) JP-A-53-125966 (JP, A) JP-A-7-8750 (JP, A) JP-A-61-222524 (JP, A) JP-A-63-28485 (JP, A) JP-A-58-11094 (JP, A) 63-193600 (JP, U) (58) Fields investigated (Int. Cl. 6 , DB name) C02F 1/44 B01D 53/50 B01D 53/77 B01D 61/02 B01D 61/04 C02F 1/04 C02F 1/52 C02F 5/00

Claims (5)

    (57)【特許請求の範囲】(57) [Claims]
  1. 【請求項1】 脱硫排水に凝集剤を添加し凝集沈殿させ
    て凝集沈殿物を除去した後、濾過処理を行い、得られた
    処理液を逆浸透膜に通して濃縮するとともに清浄水を
    、逆浸透膜に通して得られた濃縮水を、脱硫排水に凝
    集剤を添加し凝集沈殿させて得られた凝集沈殿物ととも
    に、蒸発器を用いてさらに濃縮した後、乾燥させて乾燥
    固形物とすることを特徴とする脱硫排水の処理方法。
    1. A desulfurization effluent, to which a flocculant is added to cause coagulation sedimentation to remove coagulation sediment, followed by filtration treatment, and the obtained treatment liquid is concentrated through a reverse osmosis membrane and clean water is obtained . The concentrated water obtained through the reverse osmosis membrane is condensed into desulfurization wastewater.
    With the aggregated precipitate obtained by adding the flocculant and coagulating and sedimenting
    After further concentration using an evaporator, dry and dry
    A method for treating desulfurization effluent, which is a solid .
  2. 【請求項2】 脱硫排水に凝集剤を添加し凝集沈殿させ
    て凝集沈殿物を除去した後、濾過処理を行い、得られた
    処理液を逆浸透膜に通して濃縮するとともに清浄水を
    得、逆浸透膜に通して得られた濃縮水を、脱硫排水に凝
    集剤を添加し凝集沈殿させて得られた凝集沈殿物ととも
    に、蒸発器を用いてさらに濃縮した後、固化剤を用いて
    固化固形物とすることを特徴とする脱硫排水の処理方
    法。
    2. A coagulant is added to desulfurization effluent to cause coagulation sedimentation.
    After removing the aggregated precipitate by filtration, a filtration treatment was performed to obtain
    Concentrate the processing solution through a reverse osmosis membrane and clean water
    And the concentrated water obtained through the reverse osmosis membrane is condensed into desulfurization wastewater.
    With the aggregated precipitate obtained by adding the flocculant and coagulating and sedimenting
    Then, after further concentrating using an evaporator, using a solidifying agent
    Treatment of desulfurization effluent characterized by solidification solids
    Law.
  3. 【請求項3】 逆浸透膜に通す前の処理液にスケール防
    止剤を添加する請求項1又は2記載の脱硫排水の処理方
    3. A process according to claim 1 or 2 processing method desulfurization effluent according adding scale inhibitor before the processing solution through the reverse osmosis membrane.
  4. 【請求項4】 脱硫排水に凝集剤を添加して凝集沈殿物
    を除去するための凝集沈殿槽と、 得られた清澄液中の懸濁物を除去するための濾過装置
    と、 得られた処理液を濃縮するとともに清浄水を得るための
    逆浸透膜装置と、 逆浸透膜に通して得られた濃縮水を、脱硫排水に凝集剤
    を添加し凝集沈殿させて得られた凝集沈殿物とともに、
    さらに濃縮するための逆浸透膜装置及び凝集沈殿槽に接
    続された蒸発器と、 濃縮された固形物を乾燥させるための乾燥装置と、 を備えたことを特徴とする脱硫排水の処理装置。
    4. A coagulation sedimentation tank for adding a coagulant to desulfurization effluent to remove coagulation sediment, a filtration device for removing a suspension in the obtained clear liquid, and a treatment obtained. a reverse osmosis unit for obtaining clean water as well as concentrated liquid, the concentrated water obtained through reverse osmosis membrane, flocculant desulfurization effluent
    Together with the coagulated precipitate obtained by coagulation and sedimentation,
    Contact with reverse osmosis membrane device and coagulation sedimentation tank for further concentration
    A desulfurization wastewater treatment device, comprising: a continuous evaporator; and a drying device for drying the concentrated solid matter.
  5. 【請求項5】 脱硫排水に凝集剤を添加して凝集沈殿物
    を除去するための凝集沈殿槽と、 得られた清澄液中の懸濁物を除去するための濾過装置
    と、 得られた処理液を濃縮するとともに清浄水を得るための
    逆浸透膜装置と、 逆浸透膜に通して得られた濃縮水を、脱硫排水に凝集剤
    を添加し凝集沈殿させて得られた凝集沈殿物とともに、
    さらに濃縮するための逆浸透膜装置及び凝集沈殿槽に接
    続された蒸発器と、 濃縮された固形物を固化剤を用いて固化させるための固
    化装置と、 を備えたことを特徴とする脱硫排水の処理装置。
    5. A coagulation sedimentation tank for adding a coagulant to desulfurization effluent to remove coagulation sediment, a filtration device for removing a suspension in the obtained clear liquid, and a treatment obtained. a reverse osmosis unit for obtaining clean water as well as concentrated liquid, the concentrated water obtained through reverse osmosis membrane, flocculant desulfurization effluent
    Together with the coagulated precipitate obtained by coagulation and sedimentation,
    Contact with reverse osmosis membrane device and coagulation sedimentation tank for further concentration
    A desulfurization wastewater treatment device, comprising: a continuous evaporator; and a solidifying device for solidifying the concentrated solid using a solidifying agent.
JP8263482A 1996-09-12 1996-09-12 Desulfurization wastewater treatment method and apparatus Expired - Fee Related JP2944939B2 (en)

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