JP3315650B2 - Method for recovering by-produced salt and apparatus for recovering the by-produced salt - Google Patents
Method for recovering by-produced salt and apparatus for recovering the by-produced saltInfo
- Publication number
- JP3315650B2 JP3315650B2 JP23608898A JP23608898A JP3315650B2 JP 3315650 B2 JP3315650 B2 JP 3315650B2 JP 23608898 A JP23608898 A JP 23608898A JP 23608898 A JP23608898 A JP 23608898A JP 3315650 B2 JP3315650 B2 JP 3315650B2
- Authority
- JP
- Japan
- Prior art keywords
- concentrated water
- drying
- recovering
- exhaust gas
- product salt
- 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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- Processing Of Solid Wastes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、処分場から流出す
る浸出水等の排水中に含まれる塩分を効率的に回収する
副生塩の回収方法及びその副生塩の回収装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a by-product salt recovery method and a by-product salt recovery apparatus for efficiently recovering salt contained in wastewater such as leachate flowing out of a disposal site.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】従
来、ゴミ焼却場や、工場から排出される各種産業廃棄物
の焼却場等の焼却炉から排出される多量の灰の埋立地
（処分場）から流出する浸出水には、多くの塩分や有機
物が含まれており、そのまま河川等に放流することはで
きないため、環境汚染を防止するために、種々の方法が
提案されている。2. Description of the Related Art Conventionally, landfills (disposal sites) for large amounts of ash discharged from incinerators such as garbage incineration plants and various industrial waste incineration plants discharged from factories. The leachate flowing out of the lake contains many salts and organic substances and cannot be discharged to rivers and the like as it is. Therefore, various methods have been proposed to prevent environmental pollution.
【０００３】例えば、図６に示すように、処分場５１か
らの浸出水は流量調整設備５２にて流量を調整された
後、カルシウム除去設備５３に供給され、炭酸ソーダ、
ポリマー、凝集剤およびアルカリなどが浸出水に添加さ
れてカルシウムが除去され、さらに、その水は生物処理
設備５４において、微生物により有機物が分解され、凝
集・沈殿設備５５において、ポリマー、凝集剤、酸、ア
ルカリなどが添加されて凝集・沈殿化が図られ、さら
に、ｐＨ調整のために必要に応じて酸、アルカリなどが
被処理水に添加され、砂濾過設備５６で濾過された後、
活性炭吸着設備５７において、有機物は活性炭に吸着・
除去され、キレート吸着処理５８を経て濃縮設備５９で
濃縮水と透過水に分離され、透過水は経路６０を経て河
川等に放流されていた。For example, as shown in FIG. 6, the leachate from a disposal site 51 is supplied to a calcium removal facility 53 after a flow rate is regulated by a flow regulation facility 52, and is supplied to sodium carbonate,
A polymer, a flocculant, an alkali and the like are added to the leachate to remove calcium, and the water is used to decompose organic matter by microorganisms in a biological treatment facility 54, and a polymer, a flocculant, an acid , An alkali or the like is added to achieve coagulation / precipitation, and further, if necessary, an acid or an alkali is added to the water to be treated for pH adjustment.
In the activated carbon adsorption equipment 57, organic matter is adsorbed on activated carbon.
It was removed, separated into concentrated water and permeated water by the concentration equipment 59 through the chelate adsorption treatment 58, and the permeated water was discharged to the river or the like via the route 60.
【０００４】ところが、図６に示す方法では、浸出水中
の塩分濃度が高い場合には、微生物による有機物の分解
は困難であった。さらに、難分解性の有機物は微生物で
分解することはできず、また一部の有機物については活
性炭で吸着することができないという欠点がある。さら
に、図６に示す方法では、濃縮設備５９で濃縮された濃
縮水６１には多量の塩分が含まれているが、再利用され
ずに、乾燥後に袋詰にして埋め立てられるか、焼却炉で
焼却されていた。However, in the method shown in FIG. 6, when the salt concentration in the leachate is high, it is difficult for microorganisms to decompose organic substances. Furthermore, there is a drawback that hardly decomposable organic substances cannot be decomposed by microorganisms, and some organic substances cannot be adsorbed by activated carbon. Further, in the method shown in FIG. 6, although the concentrated water 61 concentrated in the concentration equipment 59 contains a large amount of salt, it is not reused and is filled in a bag after drying or filled in an incinerator. Had been incinerated.
【０００５】また、焼却炉の焼却灰中にダイオキシンが
含まれている場合、処分場からの浸出水にダイオキシン
が含まれるので、このダイオキシンが自然環境を破壊し
ないように、浸出水を何らかの方法で処理し、ダイオキ
シンを除去する必要がある。しかし、ダイオキシンは化
学的に安定な物質であるため、図６に示すような、生物
処理と活性炭吸着処理を組み合わせるだけでは、その完
全な除去は困難である。[0005] Further, when dioxin is contained in the incineration ash of the incinerator, dioxin is contained in the leachate from the disposal site. Treatment to remove dioxins. However, since dioxin is a chemically stable substance, it is difficult to completely remove dioxin only by combining biological treatment and activated carbon adsorption treatment as shown in FIG.
【０００６】そこで、水に含まれるダイオキシン濃度を
低減させるための方法として、これに紫外線を照射して
ダイオキシンを分解処理する装置が提案されている。し
かし、この装置では、水によって紫外線が遮られるので
紫外線ランプから離れた位置にあるダイオキシンには紫
外線が届きにくいので、ダイオキシンを完全に処理する
のは困難である。巨大な紫外線ランプを用いれば処理能
力を高めることはできるが、設備コストおよびランニン
グコストの上昇を招くので、実用的に問題である。Accordingly, as a method for reducing the concentration of dioxin contained in water, there has been proposed an apparatus for irradiating ultraviolet light onto the dioxin to decompose dioxin. However, in this apparatus, it is difficult to completely treat dioxin because ultraviolet rays are hard to reach dioxin located at a position distant from the ultraviolet lamp since ultraviolet rays are blocked by water. If a huge ultraviolet lamp is used, the processing capacity can be increased, but this raises equipment costs and running costs, which is a practical problem.
【０００７】本発明は従来の技術の有するこのような問
題点に鑑みてなされたものであって、その目的は、塩分
を含む被処理水から有機物およびダイオキシンを除去し
て処理水質を向上し、高品位の塩分を有効に回収して工
業的に再利用することができる副生塩の回収方法を提供
することにある。また、本発明の目的は、そのような副
生塩を回収するための低コストの回収装置を提供するこ
とにある。The present invention has been made in view of such problems of the prior art, and has as its object to improve the quality of treated water by removing organic substances and dioxins from treated water containing salts. It is an object of the present invention to provide a method for recovering by-product salt that can effectively recover high-grade salt and reuse it industrially. Another object of the present invention is to provide a low-cost recovery device for recovering such by-product salt.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
に本発明によれば、塩分を含む被処理水を濃縮し、その
濃縮水を乾燥した後、その乾燥物を代表的には以下の３
つの方法により処理することとしている。According to the present invention, in order to achieve the above object, the water to be treated containing salt is concentrated, and the concentrated water is dried. 3
It is to be processed in two ways.
【０００９】すなわち、「その乾燥物を不活性ガス雰囲
気下で３００〜５５０℃に加熱し、次いで、間接冷却方
式で急冷し、且つ上記加熱時の燃焼排ガスを濃縮水に吸
収させる排ガス循環システムを形成する方法」か、「そ
の乾燥物を酸化雰囲気下で８００℃以上で焼成し、次い
で、間接冷却方式で急冷し、且つ上記焼成時の燃焼排ガ
スを濃縮水に吸収させる排ガス循環システムを形成する
方法」か、または「その乾燥物を酸化雰囲気下で３００
〜７５０℃で焼成し、さらに、不活性ガス雰囲気下で３
００〜５５０℃に加熱し、次いで、間接冷却方式で急冷
する方法」を採用することにより、被処理水中の有機物
とダイオキシンを効率的に分解することができる。That is, “the dried product is heated to 300 to 550 ° C. in an inert gas atmosphere ,
Quenched by the formula , and the combustion exhaust gas from the above heating is absorbed into the concentrated water.
A method of forming an exhaust gas circulation system to be collected ”or“ The dried product is fired at 800 ° C. or more in an oxidizing atmosphere, then quenched by an indirect cooling method , and the combustion exhaust gas during the firing is fired.
An exhaust gas circulation system that absorbs wastewater into concentrated water
Method "or" drying the dried product in an oxidizing atmosphere for 300
で 750 ° C., and under an inert gas atmosphere for 3 hours.
By heating to 00 to 550 ° C. and then quenching by indirect cooling, the organic matter and dioxin in the water to be treated can be efficiently decomposed.
【００１０】このようにして本発明によれば、高品位の
副生塩を回収することができる。As described above, according to the present invention, high-grade by-product salts can be recovered.
【００１１】そのための回収装置としては、濃縮水を蓄
えた濃縮水槽と乾燥・焼成炉と冷却容器を主たる構成要
素とする回収装置が好ましい。As a recovery device for this purpose, a recovery device having a concentrated water tank storing concentrated water, a drying / firing furnace, and a cooling vessel as main components is preferable.
【００１２】[0012]
【発明の実施の形態】すなわち、本願は、第一の発明と
して、塩分を含む被処理水を濃縮し、その濃縮水を乾燥
した後、不活性ガス雰囲気下で３００〜５５０℃に加熱
し、次いで、間接冷却方式で急冷し、且つ上記加熱時の
燃焼排ガスを濃縮水に吸収させる排ガス循環システムを
形成したことを特徴する副生塩の回収方法を提供する。
この第一の発明によれば、酸素欠乏状態の特定雰囲気で
３００〜５５０℃に加熱することによりダイオキシンを
分解し、且つ微生物による分解が困難な有機物を除去
し、その後、間接冷却方式で急冷し、且つ上記加熱時の
燃焼排ガスを濃縮水に吸収させる排ガス循環システムを
形成したことによりダイオキシンが再生されることはな
く、高品位の副生塩（ＮａＣｌ等）を回収することがで
きる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, as a first invention, water to be treated containing salt is concentrated, the concentrated water is dried, and then heated to 300 to 550 ° C. in an inert gas atmosphere. then quenched with indirect cooling method, and when the heating
An exhaust gas circulation system that absorbs flue gas into concentrated water
Provided is a method for recovering a by-product salt, which is characterized by being formed .
According to the first invention, decomposing dioxins by heating to 300 to 550 ° C. in particular an atmosphere of oxygen deficiency, and degradation by microorganisms to remove difficult organics, then quenched with indirect cooling method At the time of heating
An exhaust gas circulation system that absorbs flue gas into concentrated water
Dioxin is not regenerated by the formation , and high-grade by-product salts (NaCl and the like) can be recovered.
【００１３】また、第二の発明として、塩分を含む被処
理水を濃縮し、その濃縮水を乾燥した後、酸化雰囲気下
で８００℃以上で焼成し、次いで、間接冷却方式で急冷
し、且つ上記焼成時の燃焼排ガスを濃縮水に吸収させる
排ガス循環システムを形成したことを特徴とする副生塩
の回収方法を提供する。この第二の発明によれば、酸化
雰囲気下で８００℃以上の高温焼成によりダイオキシン
を分解し、且つ微生物による分解が困難な有機物を酸化
分解し、その後、間接冷却方式で急冷し、且つ上記焼成
時の燃焼排ガスを濃縮水に吸収させる排ガス循環システ
ムを形成したことによりダイオキシンが再生されること
はなく、高品位の副生塩を回収することができる。According to a second aspect of the present invention, the water to be treated containing salt is concentrated, and the concentrated water is dried, fired at 800 ° C. or more in an oxidizing atmosphere, and then quenched by an indirect cooling method.
And absorb the combustion exhaust gas from the above calcination into concentrated water
Provides a method of recovering by-product salt, characterized in that the formation of the exhaust gas circulation system. According to the second invention, decomposing dioxins by high-temperature calcination above 800 ° C. in an oxidizing atmosphere, and oxidative decomposition difficult organic matter decomposition by microorganisms, then quenched with indirect cooling method, and the firing
Exhaust gas circulation system that absorbs flue gas from flue gas into concentrated water
As a result , dioxin is not regenerated, and high-grade by-product salts can be recovered.
【００１４】また、第三の発明として、塩分を含む被処
理水を濃縮し、その濃縮水を乾燥した後、酸化雰囲気下
で３００〜７５０℃で焼成し、さらに、不活性ガス雰囲
気下で３００〜５５０℃に加熱し、次いで、間接冷却方
式で急冷することを特徴とする副生塩の回収方法を提供
する。この第三の発明によれば、酸化雰囲気下で３００
〜７５０℃の焼成により、微生物による分解が困難な有
機物を酸化分解し、酸素欠乏状態の特定雰囲気で３００
〜５５０℃に加熱することによりダイオキシンを分解
し、その後、間接冷却方式で急冷することによりダイオ
キシンが再生されることはなく、高品位の副生塩を回収
することができる。According to a third aspect of the present invention, the water to be treated containing salt is concentrated, and the concentrated water is dried, fired at 300 to 750 ° C. in an oxidizing atmosphere, and further dried under an inert gas atmosphere. ~ 550 ° C, then indirect cooling
Provided is a method for recovering by-product salt, which is characterized by rapidly cooling by a formula . According to the third invention, 300 in an oxidizing atmosphere.
By calcination at ~ 750 ° C, organic substances that are difficult to decompose by microorganisms are oxidatively decomposed, and are oxidized and decomposed in a specific atmosphere in an oxygen-deficient state.
Dioxin is decomposed by heating to ５550 ° C., and then quenched by an indirect cooling method, so that dioxin is not regenerated, and high-grade by-product salts can be recovered.
【００１５】また、第四の発明として、第一、第二また
は第三の発明において、濃縮の前または後で被処理水中
のカルシウムを除去することを特徴とする副生塩の回収
方法を提供する。この第四の発明によれば、被処理水の
濃縮の前または後において、例えば、被処理水に、Ｎａ
2ＣＯ3、ＣＯ2 等を添加すれば、被処理水中に存在する
ＣａはＣａＣＯ3 として析出し、沈殿分離、膜分離等の
手段により固液分離することにより被処理水から除去さ
れ、副生塩中に潮解性のあるＣａＣｌ2 が含まれず、副
生塩の品位が向上する。According to a fourth aspect of the present invention, there is provided the method for recovering by-product salt according to the first, second or third aspect, wherein calcium in the water to be treated is removed before or after concentration. I do. According to the fourth aspect, before or after the concentration of the water to be treated, for example, Na is added to the water to be treated.
If 2 CO 3 , CO 2, etc. are added, Ca present in the water to be treated is precipitated as CaCO 3 , and is removed from the water to be treated by solid-liquid separation by means of precipitation separation, membrane separation, etc. Since deliquescent CaCl 2 is not contained in the salt, the quality of the by-product salt is improved.
【００１６】また、第五の発明として、第一、第二、第
三または第四の発明において、濃縮の前または後で被処
理水中の遷移元素を除去することを特徴とする副生塩の
回収方法を提供する。例えば、この遷移元素としてＭｎ
やＦｅを除去する場合には、被処理水を酸化剤（ＮａＣ
ｌＯ、Ｏ3、 Ｈ2Ｏ2）で酸化し、マンガン砂でＭｎやＦ
ｅの酸化物を吸着することにより白色の高品位の副生塩
を回収することができる。According to a fifth aspect of the present invention, there is provided the first, second, third or fourth aspect of the invention, wherein the transition element in the water to be treated is removed before or after the concentration. Provide a recovery method. For example, as this transition element, Mn
To remove Fe and Fe, the water to be treated is treated with an oxidizing agent (NaC
10 O, O 3 , H 2 O 2 ) and manganese sand to oxidize Mn and F
By adsorbing the oxide of e, a white high-grade by-product salt can be recovered.
【００１７】また、第六の発明として、濃縮水を蓄えた
濃縮水槽と乾燥・焼成炉と冷却容器を有する副生塩の回
収装置であって、濃縮水槽の濃縮水を乾燥・焼成炉にお
いて乾燥後に不活性ガス雰囲気下で３００〜５５０℃に
加熱し、加熱によって得られた物質を間接冷却方式の冷
却容器で冷却し、乾燥・焼成炉の燃焼排ガスを濃縮水槽
に導入する経路を設けたことを特徴とする副生塩の回収
装置を提供し、第七の発明として、濃縮水を蓄えた濃縮
水槽と乾燥・焼成炉と冷却容器を有する副生塩の回収装
置であって、濃縮水槽の濃縮水を乾燥・焼成炉において
乾燥後に酸化雰囲気下で８００℃以上で焼成し、焼成に
よって得られた物質を間接冷却方式の冷却容器で冷却
し、乾燥・焼成炉の燃焼排ガスを濃縮水槽に導入する経
路を設けたことを特徴とする副生塩の回収装置を提供
し、第八の発明として、濃縮水を蓄えた濃縮水槽と乾燥
・焼成炉と冷却容器を有する副生塩の回収装置であっ
て、濃縮水槽の濃縮水を乾燥・焼成炉において乾燥後に
酸化雰囲気下で３００〜７５０℃で焼成し、さらに、不
活性ガス雰囲気下で３００〜５５０℃に加熱し、加熱に
よって得られた物質を間接冷却方式の冷却容器で冷却す
ることを特徴とする副生塩の回収装置を提供する。これ
ら第六、第七、第八の発明によれば、一つの乾燥・焼成
炉において、上記した特定条件下で有機物とダイオキシ
ンの分解を行うことができるので効率的である。なお、
乾燥・焼成炉と冷却容器を一つの設備内に納めることも
できる。According to a sixth aspect of the present invention, there is provided an apparatus for recovering by-product salt having a concentrated water tank storing concentrated water, a drying / firing furnace, and a cooling vessel, wherein the concentrated water in the concentrated water tank is dried in a drying / firing furnace. Thereafter, the mixture is heated to 300 to 550 ° C. in an inert gas atmosphere, the substance obtained by heating is cooled in a cooling vessel of an indirect cooling system , and the combustion exhaust gas from the drying / firing furnace is concentrated in a concentrated water tank.
A seventh aspect of the present invention is to provide a device for collecting by-produced salt, wherein a device for introducing by- product salt is provided, wherein a concentrated water tank storing concentrated water, a drying / firing furnace, and a cooling vessel are provided. An apparatus in which concentrated water in a concentrated water tank is dried in a drying / firing furnace and then fired in an oxidizing atmosphere at 800 ° C. or higher, and a substance obtained by firing is cooled in a cooling vessel of an indirect cooling method.
Through which the flue gas from the drying and firing furnace is introduced into the retentate tank.
Provides recovery apparatus byproduct salt, characterized in that a road, as the eighth invention, there the recovery device of by-product salts with a concentrated water tank accumulated concentrated water and drying and sintering furnace cooling vessel The concentrated water in the concentrated water tank is dried in a drying / sintering furnace, and then calcined at 300 to 750 ° C. in an oxidizing atmosphere, and further heated to 300 to 550 ° C. in an inert gas atmosphere to obtain a substance obtained by heating. Provided is a device for collecting by-product salt, which is cooled by a cooling vessel of an indirect cooling system. According to the sixth, seventh and eighth aspects of the present invention, the organic matter and the dioxin can be decomposed under the above-mentioned specific conditions in one drying / firing furnace, so that it is efficient. In addition,
The drying / firing furnace and cooling vessel can be housed in one facility.
【００１８】また、第六または第七の発明ように、乾燥
・焼成炉の排ガスを濃縮水槽に導入する経路を設けたこ
とにより、乾燥・焼成炉の排ガス中のダイオキシン等の
有機物は濃縮水に吸収され、外部へダイオキシン等の有
機物が放出されないので好ましい。しかも、排ガスの保
有熱により濃縮水を予熱することができ、乾燥工程にお
ける加熱量を抑えることができるので経済的である。Further, in the sixth or seventh invention so, this provided a path for introducing the exhaust gas of the drying and baking furnace concentrated water tank
And the organic matter such as dioxins in the exhaust gas drying and firing furnace is absorbed by the concentrated water is preferable because organic substances such as dioxin to the outside not released. Moreover, the concentrated water can be preheated by the retained heat of the exhaust gas, and the amount of heating in the drying step can be suppressed, which is economical.
【００１９】また、第九の発明として、第六、第七また
は第八の発明において、濃縮水槽と乾燥焼成炉とを接続
する経路にスクラバーを設け、乾燥・焼成炉の排ガスを
上記スクラバーに導入する経路を設けたことを特徴とす
る副生塩の回収装置を提供する。この第九の発明によれ
ば、第六または第七の発明と同様にして、乾燥・焼成炉
の排ガス中のダイオキシン等の有機物は濃縮水に吸収さ
れ、また、排ガスの保有熱により濃縮水を予熱すること
ができるという利点がある。Also, as a ninth invention , the sixth, seventh and
In the eighth aspect , a scrubber is provided in a path connecting the concentrated water tank and the drying and firing furnace, and a path for introducing exhaust gas from the drying and firing furnace into the scrubber is provided. I will provide a. According to the ninth invention , in the same manner as the sixth or seventh invention , organic substances such as dioxin in the exhaust gas of the drying / firing furnace are absorbed by the concentrated water, and the concentrated water is removed by the retained heat of the exhaust gas. It has the advantage that it can be preheated.
【００２０】また、第十の発明として、第六、第七、第
八または第九の発明において、乾燥焼成炉の排ガスを酸
化処理するための触媒酸化装置を設け、乾燥焼成炉の排
ガスを上記触媒酸化装置を経て濃縮水槽に導入する経路
を設けたことを特徴とする副生塩の回収装置を提供す
る。この第十の発明によれば、酸化触媒を用いた酸化処
理により排ガス中のダイオキシン等の有機物を分解除去
することができるとともに、排ガスの保有熱により濃縮
水を予熱することができるという利点がある。[0020] In a tenth aspect , the sixth, seventh, and seventh aspects are described.
In the eighth or ninth aspect, a catalyst oxidizing device for oxidizing exhaust gas from the drying and firing furnace is provided, and a route for introducing the exhaust gas from the drying and firing furnace into the concentrated water tank through the catalytic oxidizing device.
It was provided to provide a recovery system for by-product salt, wherein. According to the tenth aspect, the oxidation treatment using the oxidation catalyst can decompose and remove organic substances such as dioxin in the exhaust gas, and can be concentrated by the retained heat of the exhaust gas.
There is the advantage that it is possible to preheat the water.
【００２１】そして、第十一の発明として、第九または
第十の発明において、活性炭充填塔を設け、濃縮水槽ま
たはスクラバーから排出されるガスを上記活性炭充填塔
に導入する経路を設けたことを特徴とする副生塩の回収
装置を提供する。この第十一の発明によれば、濃縮水槽
またはスクラバー内の濃縮水に吸着されなかった排ガス
中のダイオキシン等の有機物は活性炭に吸着され、排ガ
スの清浄化が図れるので好ましい。And, as an eleventh invention , a ninth or
In the tenth invention , there is provided an apparatus for recovering by-product salt, wherein an activated carbon packed tower is provided, and a path for introducing gas discharged from a concentrated water tank or a scrubber into the activated carbon packed tower is provided. According to the eleventh aspect , organic substances such as dioxin in the exhaust gas not adsorbed by the concentrated water in the concentrated water tank or the scrubber are adsorbed by the activated carbon, and the exhaust gas can be purified, which is preferable.
【００２２】[0022]
【実施例】以下に本発明の実施例を図面を参照しながら
説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００２３】図１は、本発明の方法を実施するに好適で
ある装置の概略構成を示すフロー図である。図１におい
て、１は各種産業廃棄物の焼却場等の焼却炉から排出さ
れる多量の灰の埋立地（処分場）であり、この処分場１
から降雨等により浸出する浸出水は調整槽２に送られ、
次いで、Ｃａおよび遷移元素除去装置３に送られ、後述
するようなプロセスを経て浸出水中のＭｎおよびＦｅ等
の遷移元素とＣａが除去される。そして、Ｃａおよび遷
移元素除去装置３から所定量の浸出水が濃縮装置４に送
られる。そして、濃縮装置４において濃縮された濃縮水
は副生塩回収・精製システム５に送られ、後ほど詳細に
説明するようなプロセスを経て副生塩６が回収される。
また、透過水は経路７を経て河川等に放流される。濃縮
装置としては、例えば、逆浸透膜を使用した装置、電気
透析装置、蒸発缶等を使用することができる。FIG. 1 is a flowchart showing a schematic configuration of an apparatus suitable for carrying out the method of the present invention. In FIG. 1, reference numeral 1 denotes a landfill (disposal site) for a large amount of ash discharged from an incinerator such as an incinerator for various industrial wastes.
Leachate leached from the rain due to rain etc. is sent to the adjustment tank 2,
Next, it is sent to the Ca and transition element removal device 3, and the transition elements such as Mn and Fe and Ca in the leachate are removed through the process described below. Then, a predetermined amount of leachate is sent from the Ca and transition element removal device 3 to the concentration device 4. Then, the concentrated water concentrated in the concentration device 4 is sent to the by-product salt recovery / purification system 5, and the by-product salt 6 is recovered through a process described in detail later.
Further, the permeated water is discharged to a river or the like via a route 7. As the concentration device, for example, a device using a reverse osmosis membrane, an electrodialysis device, an evaporator, or the like can be used.
【００２４】次に、図２に基づいて、Ｃａおよび遷移元
素除去装置について説明する。８は成分調整槽であり、
この成分調整槽８にＣａの析出剤としてのＮａ2ＣＯ3、
凝集剤としてのポリ塩化アルミニウム、ｐＨ調整剤とし
てのＮａＯＨが添加される。Ｎａ2ＣＯ3／Ｃａのモル比
は、１．０〜１．５が好ましく、沈殿槽９に送られる被
処理水のｐＨは９．５〜１１．５が好ましい。沈殿槽９
の底部からはＣａＣＯ3 が適宜除去される。沈殿槽９上
部の被処理水は調整タンク１０を経てポンプ１１により
濾過槽１２に送られる。また、濾過槽１２に送られる被
処理水には、酸化剤槽１３から適宜酸化剤として、Ｎａ
ＣｌＯ、Ｏ3 あるいはＨ2Ｏ2が注入され、被処理水のｐ
Ｈが６．８〜７．２となるように、中和剤槽１４からＨ
Ｃｌ等の酸またはＮａＯＨ等のアルカリが添加される。
濾過槽１２は、マンガン砂（マンガンの高級酸化物をコ
ーティングした砂）の充填された充填部１５を有してい
る。Next, an apparatus for removing Ca and transition elements will be described with reference to FIG. 8 is a component adjusting tank,
Na 2 CO 3 as a precipitation agent for Ca
Polyaluminum chloride as a flocculant and NaOH as a pH adjuster are added. The molar ratio of Na 2 CO 3 / Ca is preferably 1.0 to 1.5, and the pH of the water to be sent to the precipitation tank 9 is preferably 9.5 to 11.5. Settling tank 9
CaCO 3 is removed as appropriate from the bottom of the. The water to be treated in the upper part of the sedimentation tank 9 is sent to the filtration tank 12 by the pump 11 via the adjustment tank 10. In addition, the water to be treated sent to the filtration tank 12 is appropriately oxidized from the oxidant tank 13 as Na.
ClO, O 3 or H 2 O 2 is injected, the water to be treated p
H is supplied from the neutralizing agent tank 14 so that H becomes 6.8 to 7.2.
An acid such as Cl or an alkali such as NaOH is added.
The filtration tank 12 has a filling portion 15 filled with manganese sand (sand coated with a higher oxide of manganese).
【００２５】次に、図３に基づいて副生塩の回収・精製
システムについて詳細に説明する。図３において、１６
は、濃縮水を蓄えた濃縮水槽であり、この濃縮水槽１６
内の水はポンプ１７によりスクラバー１８に送られ、ス
クラバー１８の下部には後記する乾燥・焼成炉の排ガス
を送給する経路１９が接続されており、スクラバー１８
の上方には活性炭充填塔２０が配置されている。スクラ
バー１８の下部から経路１９ａを経てポンプ２１により
濃縮水がフィーダー２２まで送られ、フィーダ２２から
所定量の濃縮水が円筒状の乾燥・焼成炉２３に供給され
る。乾燥・焼成炉２３の外周側には電気ヒータ２４が配
設されている。なお、電気ヒータに代えてバーナーを使
用することも可能である。また、乾燥時に限ってはスチ
ームの使用も可能である。乾燥・焼成炉２３は、モータ
２５により所定の速度で回転可能であり、そのために、
フィーダー２２と乾燥・焼成炉２３とを接続する経路２
６、空気を供給するコンプレッサー２７と乾燥・焼成炉
２３とを接続する経路２８、窒素を供給する窒素ボンベ
２９と乾燥・焼成炉２３とを接続する経路３０、冷却容
器３１と乾燥・焼成炉２３とを接続する経路３２、炉頂
部からスクラバー１８まで排ガスを供給する経路３３か
らなる各経路（２６、２８、３０、３２、３３）と乾燥
・焼成炉２３とは係合・離脱が可能なように接続されて
いる。また、乾燥・焼成炉２３の内部には、平板状の攪
拌翼３４が複数枚配置されており、この攪拌翼３４はモ
ータ３５により所定の速度で回転可能である。さらに、
冷却容器３１は円筒状であり、外周側に冷却水の通入さ
れるジャケット３６が配設されている。冷却容器３１も
モータ３７により所定の速度で回転可能であり、そのた
めに、乾燥・焼成炉２３と冷却容器３１とを接続する経
路３２および冷却容器３１から副生塩を排出する経路３
８の各経路（３２、３８）と冷却容器３１とは係合・離
脱が可能なように接続されている。Next, a system for collecting and purifying by-product salts will be described in detail with reference to FIG. In FIG. 3, 16
Is a concentrated water tank in which concentrated water is stored.
The water in the inside is sent to a scrubber 18 by a pump 17, and a lower part of the scrubber 18 is connected to a path 19 for supplying exhaust gas from a drying / firing furnace which will be described later.
Activated carbon packed tower 20 is arranged above. The concentrated water is sent from the lower part of the scrubber 18 to the feeder 22 by the pump 21 via the path 19a, and a predetermined amount of the concentrated water is supplied from the feeder 22 to the cylindrical drying / firing furnace 23. An electric heater 24 is provided on the outer peripheral side of the drying / firing furnace 23. Note that a burner can be used instead of the electric heater. In addition, steam can be used only during drying. The drying / sintering furnace 23 can be rotated at a predetermined speed by a motor 25.
Path 2 connecting feeder 22 and drying / firing furnace 23
6. A path 28 connecting the compressor 27 for supplying air and the drying and firing furnace 23, a path 30 for connecting a nitrogen cylinder 29 for supplying nitrogen and the drying and firing furnace 23, a cooling vessel 31 and the drying and firing furnace 23. And the drying / firing furnace 23 can be engaged and disengaged from each other (26, 28, 30, 32, 33) composed of a path 32 for connecting exhaust gas and a path 33 for supplying exhaust gas from the furnace top to the scrubber 18. It is connected to the. A plurality of plate-like stirring blades 34 are arranged inside the drying / firing furnace 23, and the stirring blades 34 can be rotated at a predetermined speed by a motor 35. further,
The cooling vessel 31 has a cylindrical shape, and a jacket 36 through which cooling water flows is provided on the outer peripheral side. The cooling vessel 31 is also rotatable at a predetermined speed by the motor 37. Therefore, a path 32 for connecting the drying / sintering furnace 23 and the cooling vessel 31 and a path 3 for discharging by-product salt from the cooling vessel 31 are provided.
8 are connected to the cooling vessel 31 so that they can be engaged and disengaged.
【００２６】以上のように構成されるシステムにより副
生塩を回収して精製する方法の一例について、図１〜３
に基づいて説明する。An example of a method for recovering and purifying by-product salts using the system configured as described above is shown in FIGS.
It will be described based on.
【００２７】図１の処分場１から調整槽２を経てＣａお
よび遷移元素除去装置３に達した浸出水は、図２に示す
成分調整槽８において、Ｎａ2ＣＯ3、ポリ塩化アルミニ
ウムおよびＮａＯＨを添加することによって、そのｐＨ
は９．５〜１１．５に調整され、沈殿槽９において、浸
出水中のＣａはＣａＣＯ3 として析出して凝集化し、沈
殿槽９の底部からを適宜除去される。調整タンク１０を
経てポンプ１１により濾過槽１２に送られる沈殿槽９上
部の被処理水には、酸化剤槽１３から適宜酸化剤とし
て、ＮａＣｌＯ、Ｏ3 あるいはＨ2Ｏ2が注入され、中和
剤槽１４から適宜中和剤として、ＨＣｌ等の酸またはＮ
ａＯＨ等のアルカリが添加される。そして、濾過槽１２
において、浸出水中のＭｎやＦｅ等の遷移元素の酸化物
は充填部１５のマンガン砂に吸着除去される。なお、Ｍ
ｎやＦｅは沈殿槽９においても一部除去される。次に、
このようにして処理された浸出水は濃縮装置４に送られ
て濃縮される。The leachate reaching the disposal site 1 of Fig. 1 via the adjusting tank 2 Ca and transition element removal apparatus 3, the component adjustment tank 8 shown in FIG. 2, Na 2 CO 3, polyaluminum chloride and NaOH By adding, its pH
Is adjusted to 9.5 to 11.5, and in the precipitation tank 9, Ca in the leachate precipitates as CaCO 3 and agglomerates, and is appropriately removed from the bottom of the precipitation tank 9. NaClO, O 3 or H 2 O 2 as an oxidizing agent is appropriately injected from an oxidizing agent tank 13 into the water to be treated above the sedimentation tank 9 sent to the filtration tank 12 by the pump 11 via the adjusting tank 10, and neutralized. An acid such as HCl or N
An alkali such as aOH is added. And the filtration tank 12
In the above, oxides of transition elements such as Mn and Fe in the leachate are adsorbed and removed by the manganese sand in the filling section 15. Note that M
n and Fe are also partially removed in the precipitation tank 9. next,
The leachate thus treated is sent to the concentration device 4 and concentrated.
【００２８】以上のようにして、Ｃａ、ＭｎおよびＦｅ
を除去されて濃縮された水は、図３の濃縮水槽１６に達
し、濃縮水槽１６内の濃縮水はポンプ１７によりスクラ
バー１８まで送られる。そして、スクラバー１８におい
て、経路１９を経て送られる乾燥・焼成炉２３の排ガス
と濃縮水が接触することにより排ガス中のダイオキシン
等の有機物は濃縮水に吸収される。同時に排ガスの保有
熱により濃縮水は所定量加熱されるので、後記する乾燥
工程における濃縮水の加熱量を節減することができる。
また、経路１９から分岐した経路３９により乾燥・焼成
炉２３の排ガスを濃縮水槽１６に送ることもできる。こ
の場合も上記と同様にして、排ガス中のダイオキシン等
の有機物は濃縮水に吸収され、排ガスの保有熱により濃
縮水は所定量加熱される。スクラバーにおける排ガス洗
浄ではダイオキシン等の有機物の除去が不充分の場合
は、活性炭充填塔２０において排ガス中のダイオキシン
等の有機物を活性炭に吸収させた後、外部に放出するこ
ともできる。また、図４に示すように、濃縮水槽１６の
上方にも活性炭充填塔２０を配置してもよく、濃縮水槽
１６から出てくる排ガス中のダイオキシン等の有機物を
活性炭に吸着させた後外部に放出すれば、排ガスの清浄
化が図れるので好ましい。As described above, Ca, Mn and Fe
The water that has been removed and concentrated reaches the concentrated water tank 16 in FIG. 3, and the concentrated water in the concentrated water tank 16 is sent to the scrubber 18 by the pump 17. Then, in the scrubber 18, when the exhaust gas from the drying / firing furnace 23 sent through the path 19 comes into contact with the concentrated water, organic substances such as dioxin in the exhaust gas are absorbed by the concentrated water. At the same time, the concentrated water is heated by a predetermined amount by the retained heat of the exhaust gas, so that the amount of concentrated water to be heated in the drying step described later can be reduced.
Further, the exhaust gas from the drying / firing furnace 23 can be sent to the concentrated water tank 16 via a path 39 branched from the path 19. Also in this case, similarly to the above, organic substances such as dioxin in the exhaust gas are absorbed by the concentrated water, and the concentrated water is heated by a predetermined amount by the retained heat of the exhaust gas. When the removal of organic substances such as dioxins is not sufficient in the exhaust gas cleaning in the scrubber, the organic substances such as dioxins in the exhaust gas can be absorbed by activated carbon in the activated carbon packed tower 20 and then released to the outside. Further, as shown in FIG. 4, an activated carbon packed tower 20 may be disposed above the concentrated water tank 16, and after adsorbing organic substances such as dioxin in the exhaust gas coming out of the concentrated water tank 16 onto the activated carbon, the activated carbon is externally provided. Emission is preferable because the exhaust gas can be purified.
【００２９】以上のようにして、ダイオキシン等の有機
物を含有し、且つ所定量加熱された濃縮水はポンプ２１
によりフィーダー２２まで圧送される。そして、フィー
ダー２２から所定量の濃縮水が乾燥・焼成炉２３に供給
され、電気ヒータ２４に通電して乾燥・焼成炉２３内を
１００〜１５０℃に加熱し、濃縮水を乾燥する。このと
きの炉内排ガスを、図１に示す調整槽２に戻せば、調整
槽内の水の加温に使用することができる。As described above, the concentrated water containing an organic substance such as dioxin and heated to a predetermined amount is supplied to the pump 21.
To feeder 22. Then, a predetermined amount of concentrated water is supplied from the feeder 22 to the drying and firing furnace 23, and the electric heater 24 is energized to heat the inside of the drying and firing furnace 23 to 100 to 150 ° C. to dry the concentrated water. If the exhaust gas in the furnace at this time is returned to the adjustment tank 2 shown in FIG. 1, it can be used for heating water in the adjustment tank.
【００３０】次に、コンプレッサー２７から乾燥・焼成
炉２３内に空気を送り、同時に電気ヒーター２４により
乾燥・焼成炉２３内を３００〜７５０℃に加熱し、また
モータ２５と３５により炉２３と攪拌翼３４をそれぞれ
所定の速度で回転させつつ炉内の乾燥物を焼成し、有機
物を燃焼させて除去する。このときの炉内排ガスを、経
路１９または３９を経て、スクラバー１８または濃縮水
槽１６に送り、上記のようにしてガス中のダイオキシン
等の有機物を除去し、濃縮水の予熱に利用することがで
きる。また、乾燥・焼成炉２３の排ガスをスクラバー１
８または濃縮水槽１６に送らずに、図５に示すように、
経路４０を経て、酸化触媒４１（例えば、ハニカム状の
チタン系金属酸化物触媒）を充填した触媒酸化装置４２
に送ることもできる。乾燥・焼成炉２３から排出された
ガス中のダイオキシン等の有機物は、上記酸化触媒によ
って分解される。酸化触媒の充填量は排ガス量によって
異なるが、例えば、１時間当たり１００ｍ3 の排ガスを
処理する場合、約５０リットルの触媒を使用するのが好
ましい。というのは、その程度の使用量が酸化処理効率
の点で優れており、それ以上に触媒を増量しても経済的
に不利を招くだけだからである。さらに、触媒酸化装置
４２から排出されるガスを経路４３を経て濃縮水槽１６
に送り、濃縮水の予熱に利用することができる。Next, air is sent from the compressor 27 into the drying / firing furnace 23, and at the same time, the inside of the drying / firing furnace 23 is heated to 300 to 750 ° C. by the electric heater 24, and is stirred with the furnace 23 by the motors 25 and 35. While rotating the blades 34 at a predetermined speed, the dried matter in the furnace is fired, and the organic matter is burned and removed. The exhaust gas in the furnace at this time is sent to the scrubber 18 or the concentrated water tank 16 via the path 19 or 39 to remove organic substances such as dioxin in the gas as described above, and can be used for preheating the concentrated water. . Further, the exhaust gas from the drying / firing furnace 23 is supplied to the scrubber 1.
8 or without being sent to the retentate tank 16, as shown in FIG.
Through a path 40, a catalytic oxidation device 42 filled with an oxidation catalyst 41 (for example, a honeycomb-shaped titanium-based metal oxide catalyst)
Can also be sent to Organic substances such as dioxin in the gas discharged from the drying / firing furnace 23 are decomposed by the oxidation catalyst. Although the amount of the oxidation catalyst varies depending on the amount of exhaust gas, for example, when treating 100 m 3 of exhaust gas per hour, it is preferable to use about 50 liters of the catalyst. This is because such an amount of use is excellent in terms of the oxidation treatment efficiency, and even if the amount of the catalyst is increased beyond that, it only causes economic disadvantage. Further, the gas discharged from the catalytic oxidation device 42 is passed through the path 43 to the concentrated water tank 16.
To be used for preheating concentrated water.
【００３１】約２〜５時間後にコンプレッサー２７の運
転を止め、窒素ボンベ２９から乾燥・焼成炉２３内に窒
素を供給し、炉内の雰囲気を完全に窒素に置換する。こ
のように炉内を酸素欠乏状態にして、電気ヒーター２４
により乾燥・焼成炉２３内の温度を３００〜５５０℃に
加熱し、モータ２５とモータ３５により炉２３と攪拌翼
３４をそれぞれ所定の速度で回転させつつ炉内に存在す
るダイオキシンを酸素欠乏状態で分解する。このときの
炉内排ガスを、経路１９または３９を経て、スクラバー
１８または濃縮水槽１６に送り、上記のようにしてガス
中のダイオキシンを除去し、濃縮水の予熱に利用するこ
とができる。After about 2 to 5 hours, the operation of the compressor 27 is stopped, nitrogen is supplied from the nitrogen cylinder 29 into the drying / firing furnace 23, and the atmosphere in the furnace is completely replaced with nitrogen. Thus, the inside of the furnace is depleted of oxygen, and the electric heater 24 is turned off.
The temperature in the drying / firing furnace 23 is heated to 300 to 550 ° C., and the dioxin present in the furnace is reduced in an oxygen-deficient state while rotating the furnace 23 and the stirring blade 34 at predetermined speeds by the motors 25 and 35, respectively. Decompose. The exhaust gas in the furnace at this time is sent to the scrubber 18 or the concentrated water tank 16 via the path 19 or 39, and dioxin in the gas is removed as described above, and can be used for preheating the concentrated water.
【００３２】約１時間後に窒素ボンベ２７からの窒素の
供給と電気ヒーター２４の通電とモータ２５と３５の駆
動を停止し、乾燥・焼成炉２３内に残留する塩（ＮａＣ
ｌ等）を冷却容器３１に移してジャケット３６に水を通
入してモータ３７により容器３１を所定の速度で回転さ
せつつ容器内の塩を４０〜６０℃まで急冷する。以上の
ような工程を経て、高品位の副生塩を回収することがで
きる。After about one hour, the supply of nitrogen from the nitrogen cylinder 27, the energization of the electric heater 24, the driving of the motors 25 and 35 are stopped, and the salt (NaC
1) is transferred to the cooling container 31, water is passed through the jacket 36, and the salt in the container is rapidly cooled to 40 to 60 ° C. while rotating the container 31 at a predetermined speed by the motor 37. Through the above steps, high-grade by-product salts can be recovered.
【００３３】以上の実施例は、主として第三の発明に従
った方法で副生塩を回収する場合を説明したが、第一の
発明のように、濃縮水を乾燥した後、不活性ガス雰囲気
下で３００〜５５０℃に加熱し、次いで、急冷すること
により副生塩を回収することもできるし、第二の発明の
ように、濃縮水を乾燥した後、酸化雰囲気下で８００℃
以上で焼成し、次いで、急冷することにより副生塩を回
収することもできる。In the above embodiment, the case where the by-product salt is recovered mainly by the method according to the third invention has been described. However, as in the first invention, after the concentrated water is dried, the inert gas atmosphere is recovered. The by-product salt can be recovered by heating to 300 to 550 ° C. and then rapidly quenching, or, as in the second invention, after drying the concentrated water, 800 ° C. in an oxidizing atmosphere.
By calcination as described above, and then quenched, the by-product salt can be recovered.
【００３４】実際に処分場の浸出水の濃縮水を用いて、
その濃縮水を乾燥した後、第三の発明に従った方法によ
り高品位の副生塩を回収することができたので、説明す
る。Actually, using concentrated water of leachate at the disposal site,
After drying the concentrated water, a high-grade by-product salt could be recovered by the method according to the third invention, which will be described.
【００３５】すなわち、乾燥・焼成炉内を空気雰囲気と
し、６００℃で３時間焼成し、さらに、炉内を窒素雰囲
気に代えて４００℃で６０分間加熱し、次いで、急冷し
たところ、有機物１００ｍｇ／ｋｇ以下、水分０．１％
以下の副生塩を得、その塩中のダイオキシン濃度は０．
００８ｎｇ・ＴＥＱ／ｇであることを確認した。なお、
第一の発明や第二の発明に従った方法でも、有機物およ
びダイオキシン濃度が同程度である高品位の副生塩を回
収することができた。That is, the inside of the drying / firing furnace was baked at 600 ° C. for 3 hours in an air atmosphere, and the furnace was heated at 400 ° C. for 60 minutes in place of a nitrogen atmosphere. kg or less, moisture 0.1%
The following by-product salt was obtained, and the dioxin concentration in the salt was 0.1.
008 ng · TEQ / g. In addition,
The method according to the first invention or the second invention was able to recover high-grade by-product salts having the same concentration of organic substances and dioxins.
【００３６】以上のようにして得た副生塩は、化学工
業、金属精錬業等に使用できる高品位のものである。The by-product salt obtained as described above is a high-grade salt that can be used in the chemical industry, metal refining industry and the like.
【００３７】また、Ｃａおよび遷移元素除去装置３にお
けるＣａ、ＭｎおよびＦｅの具体的な除去条件の一例に
ついて説明すると、次の通りである。 （１）Ｃａの除去 被処理水５００ミリリットルに適量のＮａ2ＣＯ3と、適量のポ
リ塩化アルミニウムを添加し、ＮａＯＨでｐＨを１０．
５に調整した。そして、沈殿槽９内の攪拌翼９ａを１５
０ｒｐｍで３０分間回転させた後、３０ｒｐｍで１５分
間回転させ、攪拌を停止して１５分間放置した。放置後
に沈殿槽１９の上澄液を採取して成分を測定すると、Ｃ
ａ濃度は、５５０ｍｇ／Ｌ（原水）が１０ｍｇ／Ｌに激
減していた。なお、Ｍｎ濃度も減少していた。 （２）ＭｎおよびＦｅの除去 濾過槽１２のマンガン砂の充填部１５にはマンガン砂を
２リットル充填し、酸化剤槽１３から被処理水にＮａＣ
ｌＯを適量添加し、中和剤槽１４から被処理水にＨＣｌ
を適量添加して被処理水のｐＨを７．０に調整し、空間
速度（流量／容積）１５（1／hr）、 線速度（流量／断
面積）１５ｍ／hrの条件で被処理水を下向流にて濾過槽
１２に通水した結果、Ｍｎ濃度は、１．０ｍｇ／Ｌ（原
水）が０．０２ｍｇ／Ｌに激減し、Ｆｅ濃度は０．２１
ｍｇ／Ｌ（原水）が０．０５ｍｇ／Ｌに激減したことが
成分測定により分かった。An example of specific conditions for removing Ca, Mn, and Fe in the Ca and transition element removing device 3 will be described below. (1) Removal of Ca An appropriate amount of Na 2 CO 3 and an appropriate amount of polyaluminum chloride are added to 500 ml of the water to be treated, and the pH is adjusted to 10 with NaOH.
Adjusted to 5. Then, the stirring blade 9a in the settling tank 9 is
After rotating at 0 rpm for 30 minutes, it was rotated at 30 rpm for 15 minutes, stirring was stopped, and the mixture was allowed to stand for 15 minutes. After the standing, the supernatant of the sedimentation tank 19 was collected to measure the components.
The concentration a was drastically reduced from 550 mg / L (raw water) to 10 mg / L. Note that the Mn concentration also decreased. (2) Removal of Mn and Fe The manganese sand filling section 15 of the filtration tank 12 is filled with 2 liters of manganese sand, and NaC is added to the water to be treated from the oxidizing tank 13.
10 to the water to be treated from the neutralizer tank 14 with HCl.
The pH of the water to be treated is adjusted to 7.0 by adding an appropriate amount of water, and the water is treated under the conditions of a space velocity (flow rate / volume) of 15 (1 / hr) and a linear velocity (flow rate / cross-sectional area) of 15 m / hr. As a result of passing water through the filtration tank 12 in a downward flow, the Mn concentration was sharply reduced from 1.0 mg / L (raw water) to 0.02 mg / L, and the Fe concentration was reduced to 0.21 mg / L (raw water).
It was found from the component measurement that the mg / L (raw water) was drastically reduced to 0.05 mg / L.
【００３８】さらに、実際に処分場の浸出水から上記方
法によりＣａ、ＭｎおよびＦｅを除去した後、その浸出
水を濃縮・乾燥し、以下の３つの方法により高品位の副
生塩を回収することができたので、順次説明する。 ａ．乾燥・焼成炉内を窒素雰囲気とし、４００℃で６０
分間加熱し、次いで、急冷したところ、Ｃａ０．０５重
量％以下、有機物８０ｍｇ／ｋｇ以下、水分０．１％以
下の白色の副生塩を得、その塩中のダイオキシン濃度は
０．００１ｎｇ・ＴＥＱ／ｇであることを確認した。 ｂ．乾燥・焼成炉内を空気雰囲気とし、９００℃で６０
分間焼成し、次いで、急冷したところ、Ｃａ０．０５重
量％以下、有機物８０ｍｇ／ｋｇ以下、水分０．１％以
下の白色の副生塩を得、その塩中のダイオキシン濃度は
０．００１ｎｇ・ＴＥＱ／ｇであることを確認した。 ｃ，乾燥・焼成炉内を空気雰囲気とし、６００℃で６０
分間焼成し、さらに、炉内雰囲気を窒素雰囲気に代えて
４５０℃で６０分間加熱し、次いで、急冷したところ、
Ｃａ０．０５重量％以下、有機物８０ｍｇ／ｋｇ以下、
水分０．１％以下の白色の副生塩を得、その塩中のダイ
オキシン濃度は０．００１ｎｇ・ＴＥＱ／ｇであること
を確認した。Further, after actually removing Ca, Mn and Fe from the leachate at the disposal site by the above-mentioned method, the leachate is concentrated and dried, and high-grade by-product salts are recovered by the following three methods. Since it was able to do, it explains sequentially. a. The drying and firing furnace is set to a nitrogen atmosphere,
After heating for 1 minute and then quenching, a white by-product salt having a Ca content of 0.05% by weight or less, an organic substance of 80 mg / kg or less and a water content of 0.1% or less was obtained, and the dioxin concentration in the salt was 0.001 ng · TEQ. / G. b. The inside of the drying / firing furnace is air atmosphere,
And then quenched to obtain a white by-product salt of 0.05% by weight or less of Ca, 80 mg / kg or less of organic matter, and 0.1% or less of water. The dioxin concentration in the salt is 0.001 ng · TEQ. / G. c. The inside of the drying / firing furnace was set to an air atmosphere,
After calcination for 450 minutes, the furnace atmosphere was replaced with a nitrogen atmosphere and heated at 450 ° C. for 60 minutes, and then quenched.
Ca 0.05% by weight or less, organic matter 80 mg / kg or less,
A white by-product salt having a water content of 0.1% or less was obtained, and it was confirmed that the dioxin concentration in the salt was 0.001 ng · TEQ / g.
【００３９】以上のようにして得た副生塩は、化学工
業、金属精錬業等に使用できる高品位のものである。The by-product salt obtained as described above is a high-grade salt that can be used in the chemical industry, metal refining industry and the like.
【００４０】[0040]
【発明の効果】本発明は上記のとおり構成されているの
で、次の効果を奏する。 請求項１、２、３記載の発
明によれば、塩分を含む被処理水から有機物およびダイ
オキシンを除去して処理水質を向上し、ダイオキシンが
再合成されることなく、高品位の塩分を有効に回収して
工業的に再利用することができる。特に、請求項１、２
記載の発明によれば、処理対象濃縮水の予熱を行うこと
ができるという効果もある。 請求項４記載の発明に
よれば、潮解性のあるＣａＣｌ2 を含まない高品位の副
生塩を回収することができる。 請求項５記載の発明
によれば、白色の高品位の副生塩を回収することができ
る。 請求項６、７、８記載の発明によれば、有機物
の分解とダイオキシンの分解を一つの炉で行うことがで
きる効率的な副生塩の回収装置を提供することができ
る。 請求項９記載の発明によれば、さらなるダイオ
キシン等の有機物の除去と処理対象濃縮水の予熱を行う
ことができるので、回収装置のランニングコストを低減
することができる。 請求項１０記載の発明によれ
ば、排ガス中のダイオキシン等の有機物の除去を行うこ
とができるとともに処理対象濃縮水の予熱を行うことが
できるので、回収装置のランニングコストをさらに低減
することができる。 請求項１１記載の発明によれ
ば、排ガス中のダイオキシン等の有機物の除去を行うこ
とができる。Since the present invention is configured as described above, the following effects can be obtained. According to the invention of claim 1, 2, 3, wherein, to improve to remove organics and dioxins from the for-treatment water treated water containing salt, dioxin
Without being resynthesized, high-grade salt can be effectively recovered and reused industrially . In particular, Claims 1 and 2
According to the described invention, preheating of the concentrated water to be treated is performed.
There is also an effect that can be done . According to the fourth aspect of the present invention, a high-grade by-product salt that does not contain deliquescent CaCl 2 can be recovered. According to the fifth aspect of the present invention, a white high-grade by-product salt can be recovered. According to the sixth, seventh, and eighth aspects of the present invention, it is possible to provide an efficient by-product salt recovery apparatus capable of decomposing organic matter and dioxin in a single furnace. According to the ninth aspect of the present invention, it is possible to further remove organic substances such as dioxin and preheat the concentrated water to be treated, so that the running cost of the recovery device can be reduced. According to the invention of claim 10
For example, it is necessary to remove organic substances such as dioxin in exhaust gas.
It is possible to preheat concentrated water to be treated
Possible, further reducing the running cost of the recovery device
can do. According to the invention of claim 11, it can be removed organic materials such as dioxins in exhaust gas.
【図１】本発明の方法を実施するに好適である装置の概
略構成を示すフロー図である。FIG. 1 is a flowchart showing a schematic configuration of an apparatus suitable for carrying out a method of the present invention.
【図２】Ｃａおよび遷移元素除去装置の概略構成図であ
る。FIG. 2 is a schematic configuration diagram of an apparatus for removing Ca and transition elements.
【図３】副生塩の回収・精製システムの全体図である。FIG. 3 is an overall view of a by-product salt recovery / purification system.
【図４】副生塩の回収・精製システムの別の実施例の全
体図である。FIG. 4 is an overall view of another embodiment of the by-product salt recovery / purification system.
【図５】副生塩の回収・精製システムの別の実施例の全
体図である。FIG. 5 is an overall view of another embodiment of the by-product salt recovery / purification system.
【図６】従来の排水の処理フローの概略構成を示す図で
ある。FIG. 6 is a diagram showing a schematic configuration of a conventional wastewater treatment flow.
１…処分場 ２…調整槽 ３…Ｃａおよび遷移元素除去装置 ４…濃縮装置 ５…副生塩回収・精製システム ６…副生塩 ９…沈殿槽 １２…濾過槽 １６…濃縮水槽 １８…スクラバー ２０…活性炭充填塔 ２３…乾燥・焼成炉 ３１…冷却容器 ４２…触媒酸化装置 DESCRIPTION OF SYMBOLS 1 ... Disposal site 2 ... Adjustment tank 3 ... Ca and transition element removal apparatus 4 ... Concentrator 5 ... By-product salt collection / purification system 6 ... By-product salt 9 ... Precipitation tank 12 ... Filtration tank 16 ... Concentrated water tank 18 ... Scrubber 20 ... activated carbon packed tower 23 ... drying / firing furnace 31 ... cooling vessel 42 ... catalytic oxidation device
───────────────────────────────────────────────────── フロントページの続き (72)発明者 桂 健治 兵庫県神戸市垂水区高丸７丁目４番 Ａ −103号 (56)参考文献 特開 昭55−22359（ＪＰ，Ａ) 特開 昭53−65262（ＪＰ，Ａ) 特開 昭57−19079（ＪＰ，Ａ) 特開 昭54−90868（ＪＰ，Ａ) 特開 昭53−137869（ＪＰ，Ａ) 特公 昭54−19717（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) F23G 7/04 C02F 1/04 B09B 1/00 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kenji Katsura 7-4 A-103 Takamaru, Tarumizu-ku, Kobe-shi, Hyogo (56) References JP-A-55-22359 (JP, A) JP-A-53- 65262 (JP, A) JP-A-57-19079 (JP, A) JP-A-54-90868 (JP, A) JP-A-53-137869 (JP, A) JP-B-54-19717 (JP, B1) (58) Field surveyed (Int. Cl. 7 , DB name) F23G 7/04 C02F 1/04 B09B 1/00
Claims (11)
水を乾燥した後、不活性ガス雰囲気下で３００〜５５０
℃に加熱し、次いで、間接冷却方式で急冷し、且つ上記
加熱時の燃焼排ガスを濃縮水に吸収させる排ガス循環シ
ステムを形成したことを特徴とする副生塩の回収方法。1. Concentrated water to be treated containing a salt is dried, and then the concentrated water is dried.
℃, then quenched by indirect cooling , and
Exhaust gas circulation system that absorbs combustion exhaust gas during heating into concentrated water
A method for recovering by-product salt, comprising forming a stem .
水を乾燥した後、酸化雰囲気下で８００℃以上で焼成
し、次いで、間接冷却方式で急冷し、且つ上記焼成時の
燃焼排ガスを濃縮水に吸収させる排ガス循環システムを
形成したことを特徴とする副生塩の回収方法。2. The water to be treated containing salt is concentrated, and after the concentrated water is dried, it is calcined at 800 ° C. or more in an oxidizing atmosphere, and then quenched by an indirect cooling method .
An exhaust gas circulation system that absorbs flue gas into concentrated water
A method for recovering by-product salt, which is formed .
水を乾燥した後、酸化雰囲気下で３００〜７５０℃で焼
成し、さらに、不活性ガス雰囲気下で３００〜５５０℃
に加熱し、次いで、間接冷却方式で急冷することを特徴
とする副生塩の回収方法。3. The water to be treated containing salt is concentrated, the concentrated water is dried, and then calcined at 300 to 750 ° C. in an oxidizing atmosphere, and further, at 300 to 550 ° C. in an inert gas atmosphere.
, And then rapidly cooled by an indirect cooling method.
ウムを除去することを特徴とする請求項１、２または３
記載の副生塩の回収方法。4. The method according to claim 1, wherein calcium in the water to be treated is removed before or after the concentration.
The method for recovering the by-produced salt according to the above.
素を除去することを特徴とする請求項１、２、３または
４記載の副生塩の回収方法。5. The method for recovering by-product salt according to claim 1, wherein the transition element in the water to be treated is removed before or after the concentration.
と冷却容器を有する副生塩の回収装置であって、濃縮水
槽の濃縮水を乾燥・焼成炉において乾燥後に不活性ガス
雰囲気下で３００〜５５０℃に加熱し、加熱によって得
られた物質を間接冷却方式の冷却容器で冷却し、乾燥・
焼成炉の燃焼排ガスを濃縮水槽に導入する経路を設けた
ことを特徴とする副生塩の回収装置。6. An apparatus for recovering by-product salt having a concentrated water tank storing concentrated water, a drying / firing furnace and a cooling vessel, wherein the concentrated water in the concentrated water tank is dried in a drying / firing furnace and then subjected to an inert gas atmosphere. To 300 to 550 ° C., and the substance obtained by heating is cooled in a cooling vessel of an indirect cooling system , and dried.
A path was provided to introduce the combustion exhaust gas from the firing furnace into the concentrated water tank
An apparatus for collecting by-product salt, characterized in that:
と冷却容器を有する副生塩の回収装置であって、濃縮水
槽の濃縮水を乾燥・焼成炉において乾燥後に酸化雰囲気
下で８００℃以上で焼成し、焼成によって得られた物質
を間接冷却方式の冷却容器で冷却し、乾燥・焼成炉の燃
焼排ガスを濃縮水槽に導入する経路を設けたことを特徴
とする副生塩の回収装置。7. An apparatus for recovering by-product salt having a concentrated water tank storing concentrated water, a drying / sintering furnace, and a cooling vessel, wherein the concentrated water in the concentrated water tank is dried in a drying / sintering furnace and then dried under an oxidizing atmosphere. で 焼 成 で 以上 以上 以上 以上 以上 以上 、 以上 以上 、 、
An apparatus for recovering by-product salt, comprising a path for introducing flue gas into a concentrated water tank .
と冷却容器を有する副生塩の回収装置であって、濃縮水
槽の濃縮水を乾燥・焼成炉において乾燥後に酸化雰囲気
下で３００〜７５０℃で焼成し、さらに、不活性ガス雰
囲気下で３００〜５５０℃に加熱し、加熱によって得ら
れた物質を間接冷却方式の冷却容器で冷却することを特
徴とする副生塩の回収装置。8. An apparatus for recovering by-product salt having a concentrated water tank storing concentrated water, a drying / sintering furnace, and a cooling container, wherein the concentrated water in the concentrated water tank is dried in a drying / sintering furnace and then dried under an oxidizing atmosphere. A by-product salt recovery apparatus, wherein the apparatus is baked at about 750 ° C., further heated to 300 to 550 ° C. in an inert gas atmosphere, and the substance obtained by heating is cooled in a cooling vessel of an indirect cooling method. .
にスクラバーを設け、乾燥・焼成炉の排ガスを上記スク
ラバーに導入する経路を設けたことを特徴とする請求項
６、７または８記載の副生塩の回収装置。 9. A scrubber is provided in a path connecting the concentrated water tank and the drying and firing furnace, and a path for introducing exhaust gas from the drying and firing furnace into the scrubber is provided.
The apparatus for recovering by-product salt according to 6, 7, or 8 .
めの触媒酸化装置を設け、乾燥焼成炉の排ガスを上記触
媒酸化装置を経て濃縮水槽に導入する経路を設けたこと
を特徴とする請求項６、７、８または９記載の副生塩の
回収装置。 10. A catalyst oxidizing apparatus for oxidizing exhaust gas from a drying and firing furnace, wherein the exhaust gas from the drying and firing furnace is subjected to the above-mentioned catalytic oxidation.
The device for recovering by-product salt according to claim 6, 7, 8 or 9, further comprising a path for introducing the concentrated water tank through the medium oxidation device.
スクラバーから排出されるガスを上記活性炭充填塔に導
入する経路を設けたことを特徴とする請求項９または１
０記載の副生塩の回収装置。 11. The activated carbon packed column is provided, the gas discharged from the concentrated water bath or scrubber, characterized in that a path to be introduced into the active carbon packed column according to claim 9 or 1
0. A device for recovering by-product salt according to 0 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23608898A JP3315650B2 (en) | 1998-02-20 | 1998-08-21 | Method for recovering by-produced salt and apparatus for recovering the by-produced salt |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3897598 | 1998-02-20 | ||
| JP10-38975 | 1998-02-20 | ||
| JP23608898A JP3315650B2 (en) | 1998-02-20 | 1998-08-21 | Method for recovering by-produced salt and apparatus for recovering the by-produced salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11304131A JPH11304131A (en) | 1999-11-05 |
| JP3315650B2 true JP3315650B2 (en) | 2002-08-19 |
Family
ID=26378292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23608898A Expired - Fee Related JP3315650B2 (en) | 1998-02-20 | 1998-08-21 | Method for recovering by-produced salt and apparatus for recovering the by-produced salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3315650B2 (en) |
-
1998
- 1998-08-21 JP JP23608898A patent/JP3315650B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11304131A (en) | 1999-11-05 |
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