JPH083655A - Method for recovering heavy metals from flying ash - Google Patents
Method for recovering heavy metals from flying ashInfo
- Publication number
- JPH083655A JPH083655A JP23302094A JP23302094A JPH083655A JP H083655 A JPH083655 A JP H083655A JP 23302094 A JP23302094 A JP 23302094A JP 23302094 A JP23302094 A JP 23302094A JP H083655 A JPH083655 A JP H083655A
- Authority
- JP
- Japan
- Prior art keywords
- flotation
- fly ash
- metal
- sulfate
- added
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、廃棄物の再資源化技術
としての焼却飛灰からの重金属類の回収方法に関する。
詳述すると、廃自動車、廃家電製品などをシュレッダー
により破砕して金属を回収した後のシュレッダーダスト
を、焼却減容した際に発生する飛灰からの重金属類の回
収ないしは飛灰の有効利用方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering heavy metals from incinerated fly ash as a technique for recycling waste.
To be more specific, shredder dust after crushing scrapped automobiles and waste home appliances with a shredder to recover metal is used to recover heavy metals from fly ash generated when incinerated and reduced in volume, or how to effectively use fly ash. It is about.
【０００２】[0002]
【従来の技術】近年における消費経済の発達の弊害とし
て、各種廃棄物の増大と、この処分方法が社会的な問題
となっている。現在、廃自動車から有価部品を解体回収
した後のボディ殻、電気洗濯機、電気冷蔵庫などの大型
家電製品等は、シュレッダーにより破砕され、鉄、非鉄
金属類が回収されているが、これらを回収した後のシュ
レッダーダストと呼ばれるプラスチック類を主体とする
分画は、埋立て処分されている。2. Description of the Related Art Increasing amounts of various kinds of waste and this disposal method have become a social problem as an adverse effect on the development of the consumption economy in recent years. At present, large shells such as body shells, electric washing machines, electric refrigerators, etc. after scrapping and collecting valuable parts from scrapped automobiles are crushed by shredders, and iron and non-ferrous metals are collected, but these are collected. The shredder dust, which is mainly made of plastics, is disposed of by landfill.
【０００３】しかしながら、産業廃棄物および一般家庭
からの廃棄物の量は増大傾向にあり、既存の埋立て処分
場の飽和化と環境汚染の問題等から、その処分場の確保
がますます困難となっており、廃棄物の再資源化、減容
化が求められている。上記したシュレッダーダストの再
資源化、減容化の方法としては、焼却発電が検討されて
いる。即ち、シュレッダーダストの主要部を占めるプラ
スチック類の燃焼による熱エネルギーを発電用ボイラー
等での熱交換によって回収利用しようとするものであ
り、また焼却灰として減容化しようとするものである。
このシュレッダーダストを焼却した際に発生する焼却灰
には、炉底灰（ボトムアッシュ）と、燃焼廃ガス中に含
有されておりフィルター等の捕捉手段により回収された
飛灰（フライアッシュ）とがある。However, the amount of industrial waste and household waste is increasing, and it is becoming more and more difficult to secure the landfill site due to the problems of saturation of existing landfill sites and environmental pollution. Therefore, recycling of waste and reduction of volume are required. Incineration power generation is being studied as a method for recycling and reducing the volume of the shredder dust. That is, it aims to recover and utilize the thermal energy generated by the combustion of plastics, which occupy the main part of shredder dust, by heat exchange in a power generation boiler or the like, and also to reduce the volume as incinerated ash.
The incineration ash generated when this shredder dust is incinerated includes bottom ash (bottom ash) and fly ash (fly ash) that is contained in the combustion waste gas and is collected by a capturing means such as a filter. is there.
【０００４】石炭灰等の一般的な飛灰は、骨材、セメン
ト原料化、埋立て処分、安定化処理（ペレット化）とい
った方法で再利用、処分が行なわれているが、上記した
ようなシュレッダーダストなどを焼却して得られる飛灰
中には、ポリ塩化ビニル等のプラスチックに起因する多
くの塩素化合物および金属類が含まれており、骨材、セ
メント原料等としては強度低下、建材の腐蝕、環境性等
の問題から使用できず、また埋立て処分したとしても酸
性雨等により埋立て処分地からの塩素の溶出に伴う塩害
の虞れがあり、また重金属の溶出による環境汚染の虞れ
がある。さらに、資源再利用の見地から、飛灰からの金
属成分の回収が望まれることとなっている。Common fly ash, such as coal ash, is reused and disposed of by aggregates, cement raw materials, landfill disposal, stabilization treatment (pelletization) and the like. Fly ash obtained by incinerating shredder dust, etc. contains many chlorine compounds and metals derived from plastic such as polyvinyl chloride. It cannot be used due to problems such as corrosion and environmental friendliness, and even if it is landfilled, there is a risk of salt damage due to elution of chlorine from the landfill site due to acid rain, etc. There is Furthermore, from the viewpoint of resource reuse, it has been desired to recover metal components from fly ash.
【０００５】特開昭４９−１１３７０３号公報には、焼
却灰の希硫酸溶出液をｐＨ２．０〜３．０に維持しなが
ら、含有金属イオン濃度の当量以上の硫化ソーダを添加
して鉄以外の金属を硫化物として凝析させ、次いで高分
子凝集剤を添加して硫化金属のフロックを形成させ、さ
らにアミン系捕収材及びポリプロピレングリコールエー
テル系起泡剤を添加して送気を行なうことによって硫化
金属フロックをスカムとして浮上させて回収することが
提案されている。しかしながら、焼却灰中に存在する金
属粒子の表面は酸化されており、また焼却灰中には多く
の塩素化合物が存在することから、硫化物の形態として
十分な量の金属を捕捉できず、また、硫化物は浮遊選鉱
によって効率よく回収することが難しいものであった。In Japanese Patent Laid-Open No. 49-113703, while maintaining the diluted sulfuric acid eluate of incinerated ash at pH 2.0 to 3.0, sodium sulfide in an amount equal to or higher than the concentration of metal ions contained is added to make it other than iron. Metal is coagulated as sulfide, then polymer flocculant is added to form metal sulfide floc, and amine collector and polypropylene glycol ether foaming agent are added for air supply. It has been proposed that the metal sulfide flocs are levitated as scum and collected. However, the surface of the metal particles present in the incineration ash is oxidized, and since many chlorine compounds are present in the incineration ash, it is not possible to capture a sufficient amount of metal in the form of sulfide, and , It was difficult to collect sulfide efficiently by flotation.
【０００６】[0006]
【発明が解決しようとする課題】従って本発明は、シュ
レッダーダスト等の廃棄物を焼却した際に発生する飛灰
から、効率よくかつ簡単に各種重金属類を分離回収する
方法を提供することを目的とする。SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for efficiently and easily separating and recovering various heavy metals from fly ash generated when incinerating waste such as shredder dust. And
【０００７】[0007]
【課題を解決しようとするための手段】上記課題を解決
する本発明は、廃棄物を焼却した際に発生する重金属類
およびＣａ固定化塩素を含有する飛灰からの重金属類の
回収方法であって、 ａ）飛灰を炭酸ガスを吹送しながら水を用いて洗浄する
工程と、 ｂ）上記ａ）洗浄工程における洗浄液を濃縮し乾燥して
塩化カルシウムを結晶として得る工程と、 ｃ）前記ａ）洗浄工程における固形残渣にオレイン酸、
１級アミン酢酸塩、アルキル硫酸塩、アルキル又はアリ
ル燐酸塩、トール油、クレゾール酸を捕集剤として使用
し、またパイン油、ＭＩＢＣ、エチレングリコールを起
泡剤として使用し、浮遊選鉱を行ない、フロスとして炭
酸カルシウムを回収する工程と、 ｄ）前記ｃ）浮遊選鉱工程の沈降残渣に硫酸を充分に混
合して沈降残渣中に残存する重金属を硫酸塩とし、この
混合物に水を加えて金属の硫酸塩を溶解すると同時に、
溶解した銅イオンを沈降残渣中に存在していた金属Ａｌ
により金属銅として析出させ、不溶解物と共に瀘滓とし
て分離除去する工程と、 ｅ）前記ｄ）工程で分離した不溶解物を水でリパルプし
て条件槽で硫化剤を加えて金属銅の表面を活性化し、浮
選剤にはザンセート、アルキル又はアリル・ジフォスフ
ェート、ジチォカルバニリド又はジチォカルバメート、
硫化ソーダ、硫化水素、ケロシン、アルキル硫酸エステ
ル、アルキル又はアリル燐酸塩、パイン油、エチレン・
グリコール、メチル・イソブチル・カルビノール、等の
浮選剤を用いて浮選を行い、銅と硫酸鉛を浮遊選鉱の混
合精鉱として回収する工程とを有することを特徴とする
ものである。The present invention for solving the above problems is a method for recovering heavy metals from fly ash containing heavy metals and Ca-immobilized chlorine generated when waste is incinerated. A) a step of washing fly ash with water while blowing carbon dioxide gas, b) a step of concentrating and drying the washing liquid in the above a) washing step to obtain calcium chloride as crystals, and c) the a. ) Oleic acid is added to the solid residue in the washing step,
Using primary amine acetate, alkyl sulfate, alkyl or allyl phosphate, tall oil, cresylic acid as a scavenger, and pine oil, MIBC, ethylene glycol as a foaming agent to perform flotation. A step of recovering calcium carbonate as floss; and d) sulfuric acid is sufficiently mixed with the sedimentation residue of the above-mentioned c) flotation step to make the heavy metal remaining in the sedimentation residue a sulfate, and water is added to this mixture to remove the metal At the same time as dissolving the sulfate
Dissolved copper ions were present in the precipitation residue as metal Al
The step of precipitating as metallic copper by means of the above, and separating and removing it as a slag together with the insoluble matter; And the flotation agent is xanthate, alkyl or allyl diphosphate, dithiocarbanilide or dithiocarbamate,
Sodium sulfide, hydrogen sulfide, kerosene, alkyl sulfates, alkyl or allyl phosphates, pine oil, ethylene
The present invention is characterized by having a step of performing flotation using a flotation agent such as glycol, methyl isobutyl carbinol, etc., and recovering copper and lead sulfate as a mixed concentrate of flotation.
【０００８】また、本発明の前記ｅ）は、好ましくは、
前記ｄ）の濾液に上記ｃ）の浮鉱又は炭酸カルシウムを
加え、ｐＨ５〜６に中和した後、生成したスラリーを加
熱しつつ空気を吹き込み、Ｆｅ（II）をＦｅ（III)に酸
化して水酸化鉄（III)とし水酸化アルミニウムとともに
沈殿し濾別する前記ｅ）第１処理と前記第１段処理で発
生した溶液に消石灰を加えｐＨ６以上にしてＺｎを水酸
化亜鉛として沈殿して濾別し、濾液は原料飛灰の洗浄液
とする前記ｅ）第２段処理とを有することを特徴とする
ものである。The above-mentioned e) of the present invention is preferably
After adding the flotation or calcium carbonate of the above c) to the filtrate of the above d) and neutralizing it to pH 5-6, air is blown in while heating the resulting slurry to oxidize Fe (II) to Fe (III). To elute iron (III) hydroxide with aluminum hydroxide and separate by filtration. E) Slaked lime is added to the solution generated in the first treatment and the first treatment to adjust the pH to 6 or more to precipitate Zn as zinc hydroxide. It is characterized in that it is filtered and the filtrate has the above-mentioned e) second stage treatment which is used as a cleaning liquid for the raw material fly ash.
【０００９】[0009]
【作用】このように本発明は、飛灰中に存在する金属が
多くは酸化物および塩化物として存在するが、Ａｌは微
細な金属粉末として一部存在しているとの新たな知見に
基づき、この金属Ａｌを還元剤として利用することによ
り濃硫酸浸出においてＣｕを沈澱析出させ、溶解する他
の重金属類と分離することで、多種の薬品を使用するこ
となくかつ効率よく重金属類を回収するものである。As described above, the present invention is based on the new finding that Al is present as fine metal powder in part, although most of the metals present in fly ash are present as oxides and chlorides. By utilizing this metallic Al as a reducing agent, Cu is precipitated and precipitated in concentrated sulfuric acid leaching and separated from other heavy metals which are dissolved, so that heavy metals can be efficiently recovered without using various chemicals. It is a thing.
【００１０】以下、本発明に係わる焼却飛灰からの金属
回収方法を取り入れた、廃自動車、廃家電製品からのシ
ュレッダーダストの一連の処理プロセスを例にとり、本
発明を詳細に説明する。まず廃自動車、廃家電製品は、
再使用可能な部品を回収後、常法に基づきシュレッダー
により破砕され、鉄、非鉄金属類が回収される。The present invention will be described in detail below by taking as an example a series of treatment processes of shredder dust from waste automobiles and waste home electric appliances which incorporate the method for recovering metals from incinerated fly ash according to the present invention. First, for abandoned cars and home appliances,
After recovering reusable parts, they are crushed by a shredder according to the usual method to recover ferrous and non-ferrous metals.
【００１１】これらを回収した後の主としてプラスチッ
クからなるシュレッダーダストは、減容化のため燃焼さ
れるが、燃焼によるダイオキシン等の有害成分の発生を
防止するため１０００℃以下、より好ましくは、８００
〜９００℃の温度で焼却できるように、例えば、流動焙
焼炉、火格子炉等を用いて行なわれる。この際発生する
熱エネルギーは、発電用ボイラにおいて熱交換して回収
する。なお、この燃焼の際には、ポリ塩化ビニル等のプ
ラスチックに起因する多くの塩素化合物が発生するが、
焼却時にシュレッダーダスト１００重量部に対し消石灰
または石灰石を２０〜３０重量部程度添加し、塩素化合
物を塩化カルシウム（ＣａＣｌ2 ）として固定化するこ
とで、有害な塩素化合物の放出を防止する。そして、焼
却後に減容化され炉内に残る炉底灰は、含有金属の回収
処理にかけられる。The shredder dust, which is mainly made of plastic after the recovery, is burned to reduce the volume, but in order to prevent the generation of harmful components such as dioxin due to the burning, the temperature is 1000 ° C. or less, more preferably 800.
It is carried out using, for example, a fluidized roasting furnace, a grate furnace or the like so that it can be incinerated at a temperature of up to 900 ° C. The heat energy generated at this time is heat-exchanged and recovered in the power generation boiler. In addition, during this combustion, many chlorine compounds are generated due to plastics such as polyvinyl chloride,
At the time of incineration, about 20 to 30 parts by weight of slaked lime or limestone is added to 100 parts by weight of shredder dust to immobilize the chlorine compound as calcium chloride (CaCl 2 ) to prevent the release of harmful chlorine compounds. Then, the bottom ash, which has been reduced in volume after incineration and remains in the furnace, is subjected to a recovery process of contained metal.
【００１２】一方、燃焼排煙中に含まれる飛灰は、煙道
途中に設けられたフィルター等よりなるダストコレクタ
ーにより捕捉され、回収される。この飛灰の平均粒子径
は５〜２０μｍ程度であり、１０μｍ以下の粒子が全体
の６０〜７０％を占めるものである。そしてこの飛灰中
には前記したように多量のＣａ固定化塩素成分（ＣａＣ
ｌ2 ）と、Ｆｅ、Ｃｕ、Ｚｎ、Ａｌ、Ｐｂ等の重金属類
成分とが珪酸類と共に存在する。これらの金属は、多く
は酸化物および塩化物として存在するが、Ａｌは微細な
金属粉末として一部存在している。従って、重金属類の
回収において、以下に示すように、この金属Ａｌを還元
剤として利用する処理が可能である。On the other hand, the fly ash contained in the combustion flue gas is captured and collected by a dust collector, which is provided in the middle of the flue and is composed of a filter or the like. The fly ash has an average particle size of about 5 to 20 μm, and particles of 10 μm or less account for 60 to 70% of the whole. And in this fly ash, as described above, a large amount of Ca-immobilized chlorine component (CaC
1 2 ) and heavy metal components such as Fe, Cu, Zn, Al and Pb are present together with silicic acids. Most of these metals exist as oxides and chlorides, but Al partially exists as fine metal powder. Therefore, in the recovery of heavy metals, it is possible to perform a process of using this metal Al as a reducing agent, as shown below.
【００１３】本発明においては、まずこの飛灰から塩素
成分を除去するために、ａ）工程として、飛灰を水洗す
る。水洗は、通常、飛灰の１〜４容量倍の水を用い、１
０〜６０分程度の浸出時間を費して行なわれる。このよ
うな処理によりＣａＣｌ2 は、容易に溶解除去可能であ
るが、飛灰中に含まれる金属態様のＡｌを金属のまま他
の金属類とともに固形残渣中に残すために、この洗浄水
に炭酸ガスを溶存添加、例えば洗浄液がｐＨ９以下、好
ましくは６．５〜７．０になるように添加した条件下で
行なう。すなわち、高アルカリ条件下では、アルミニウ
ムが溶解し、水酸化アルミニウムの沈殿が生じてしまう
ためである。In the present invention, first, in order to remove chlorine components from the fly ash, the fly ash is washed with water in step a). Washing with water usually uses 1 to 4 times the volume of fly ash and 1
The leaching time is about 0 to 60 minutes and is performed. Although CaCl2 can be easily dissolved and removed by such a treatment, carbon dioxide gas is added to this washing water in order to leave the metallic form of Al contained in the fly ash as a metal in the solid residue together with other metals. Is dissolved and added, for example, under the condition that the cleaning liquid is added so that the pH is 9 or less, preferably 6.5 to 7.0. That is, under high alkaline conditions, aluminum dissolves and aluminum hydroxide precipitates.
【００１４】この炭酸ガスの添加はまた、塩化カルシウ
ムの浸出を容易にするものであるが、必要に応じてさら
に撹拌を行なって短縮化を図ってもよい。そして、例え
ば沈降槽等における所定の浸出時間経過後、飛灰スラリ
ーの溢流分画と沈降分画を分離する。沈降分画は、含水
率２５〜４０重量％程度の脱塩素飛灰スライムとして得
られる。The addition of this carbon dioxide gas also facilitates the leaching of calcium chloride, but it may be shortened by further stirring if necessary. Then, after elapse of a predetermined leaching time in, for example, a sedimentation tank, the overflow fraction of the fly ash slurry and the sedimentation fraction are separated. The sedimentation fraction is obtained as dechlorinated fly ash slime having a water content of about 25 to 40% by weight.
【００１５】上記洗浄工程において得られた、溶解した
塩化カルシウムを多く含む溢流分画は、次いで、ｂ）工
程において、濃縮処理にかけられ、例えば電気透析、蒸
発缶を用いた蒸発濃縮等の濃縮処理を経て、最終的に噴
霧乾燥により、塩化カルシウム結晶として回収される。
なお、電気透析は、一般的に知られる陰イオン交換膜と
陽イオン交換膜とを組合せた通常の濃縮用の透析槽を有
する装置を用いれば充分であるが、イオン選択性のより
高い交換膜を使用することは可能である。例えば、溢流
分画中の数千ｐｐｍ程度の濃度の塩化カルシウムは、電
気透析により数万ｐｐｍ程度の濃度にまで濃縮され、そ
の後蒸発缶においてさらに４０〜５０％程度にまで濃縮
可能である。The overflow fraction containing a large amount of dissolved calcium chloride obtained in the above washing step is then subjected to a concentration treatment in step b), for example, electrodialysis, concentration such as evaporation concentration using an evaporator. After processing, it is finally spray-dried and recovered as calcium chloride crystals.
For electrodialysis, it is sufficient to use an apparatus having a usual dialysis tank for concentration, which is a combination of a generally known anion exchange membrane and a cation exchange membrane, but an exchange membrane having a higher ion selectivity. It is possible to use For example, calcium chloride having a concentration of about several thousand ppm in the overflow fraction can be concentrated to a concentration of about tens of thousands ppm by electrodialysis, and then can be further concentrated to about 40 to 50% in an evaporator.
【００１６】このようにして回収された塩化カルシウム
は、代表的にはその純度が６０〜７０％程度のものであ
り、例えば、道路の融雪剤として使用可能である。一
方、分離され泥化状態にある脱塩素飛灰スライムは、次
いで、ｃ）工程として、浮遊選鉱にかけられ、炭酸カル
シウムがフロスとして回収される。すなわち、脱塩素飛
灰スライムは、その４〜１０容量倍の水に懸濁され、オ
レイン酸、１級アミン酢酸塩、アルキル硫酸塩、アルキ
ル又はアリル燐酸塩、トール油、クレゾール酸を捕集剤
として、またパイン油、ＭＩＢＣ、エチエン・グリコー
ルを起泡剤として添加し、送気して泡立たせ、炭酸カル
シウムをフロスとして浮上させる。捕集剤および起泡剤
の使用量は、脱塩素飛灰スライム乾燥重量１ｋｇ当り、
それぞれ、１００〜１，０００ｍｇ程度および５〜２０
０ｍｇ程度である。The calcium chloride thus recovered typically has a purity of about 60 to 70% and can be used, for example, as a snow melting agent for roads. On the other hand, the dechlorinated fly ash slime that has been separated and sludge is then subjected to flotation in step c) to recover calcium carbonate as floss. That is, dechlorinated fly ash slime is suspended in 4 to 10 times its volume of water to collect oleic acid, primary amine acetate, alkyl sulfate, alkyl or allyl phosphate, tall oil, and cresylic acid. As a foaming agent, pine oil, MIBC, and ethylene glycol are added, and air is bubbled to make calcium carbonate float up as froth. The amount of scavenger and foaming agent used is 1 kg of dry weight of dechlorinated fly ash slime,
About 100 to 1,000 mg and 5 to 20 respectively
It is about 0 mg.
【００１７】次いで、ｄ）工程において、浮遊選鉱後の
沈降残渣には、硫酸、好ましくは、９０％以上の濃硫酸
が、沈降残渣１ｋｇ（乾燥重量換算）当り１〜２ｋｇ程
度添加され、充分に混合される。この操作により、沈降
残渣に含まれるＦｅ、Ｃｕ、Ｚｎ、Ａｌ等の重金属類が
硫酸塩となる。ここでさらにこの混合物に、水を例え
ば、１〜５程度の割合で添加する。水の添加により、Ｃ
ｕ、Ｚｎ、Ｆｅ等の硫酸塩は溶解するが、この際沈降残
渣に存在していた金属アルミニウムと置換することによ
り、Ｃｕイオンは還元され金属銅となる。そこでこの混
合物を瀘過ないし遠心分離等にかけると、この金属銅は
ＰｂＳＯ4 、ＳｉＯ2 、ＣａＳＯ4 等の不溶解物ととも
に、不溶解物と共に瀘滓として分離除去できる。Next, in step d), sulfuric acid, preferably 90% or more concentrated sulfuric acid, is added to the sedimentation residue after flotation in an amount of about 1 to 2 kg per 1 kg of sedimentation residue (dry weight conversion). Mixed. By this operation, heavy metals such as Fe, Cu, Zn, and Al contained in the sedimentation residue become sulfates. Here, water is further added to this mixture at a rate of, for example, about 1 to 5. With the addition of water, C
Sulfates such as u, Zn, and Fe dissolve, but at this time, Cu ions are reduced to metallic copper by substituting the metallic aluminum present in the precipitation residue. Then, when this mixture is subjected to filtration or centrifugation, the metallic copper can be separated and removed together with the insoluble matter such as PbSO4, SiO2 and CaSO4 together with the insoluble matter as a residue.
【００１８】さらに、ｅ）工程として、前記瀘滓を水に
再懸濁した後、活性化剤を添加して瀘滓中の金属銅を活
性化処理し、浮遊選鉱により金属銅および硫酸鉛を回収
する。活性化剤としては、硫化水素水、硫化ソーダ等が
使用され、また捕集剤として、ザンセート、アルキル又
はアリル・ジフォスフェート、ジチォカルバニリド、ジ
チォカルバメート、アルキル硫酸エステル、アルキル又
はアリル燐酸塩といった公知のものが、また起泡剤とし
てもパイン油、エチレン・グリコール、ＭＩＢＣ、ケロ
シンといったものが使用されるが、もちろんこれらに限
定されるものではない。捕集剤および起泡剤の使用量
は、その種類によっても左右されるが、例えば、前記瀘
滓乾燥重量１ｋｇ当り、それぞれ、５０〜１，０００ｍ
ｇ程度および５〜２００ｍｇ程度である。このようにし
て回収された金属銅の純度は２０〜５０％程度であり、
例えば銅精練原料として使用可能である。Further, in the step e), after resuspending the filtered slag in water, an activator is added to activate the metallic copper in the filtered slag, and metallic copper and lead sulfate are removed by flotation. to recover. As the activator, hydrogen sulfide water, sodium sulfide, etc. are used, and as the scavenger, xanthate, alkyl or allyl diphosphate, dithiocarbanilide, dithiocarbamate, alkyl sulfate ester, alkyl or allyl. Known compounds such as phosphates and pine oil, ethylene glycol, MIBC, kerosene, etc. are used as the foaming agent, but the foaming agent is not limited thereto. The amounts of the scavenger and the foaming agent used depend on the types thereof, but for example, 50 to 1,000 m per 1 kg of the dry weight of the slag, respectively.
It is about g and about 5 to 200 mg. The purity of the metallic copper thus recovered is about 20 to 50%,
For example, it can be used as a copper scouring raw material.
【００１９】なお、前記ｄ）工程において瀘滓と分離さ
れた瀘液中には、Ｆｅ、Ｚｎ、Ａｌ等の重金属類の硫酸
塩が溶解含有されており、また前記ｅ）工程における浮
遊選鉱後の沈降残渣には、Ｃａ等の硫酸塩が不溶物とし
て含有されている。従って、必要に応じ、さらに公知の
析出分離法、浮遊選鉱法等の技術を応用して、これらの
金属類を分離回収してもよい。It should be noted that, in the filtrate separated from the residue in the step d), sulfates of heavy metals such as Fe, Zn and Al are dissolved and contained, and after the flotation in the step e). The sulfate residue such as Ca is contained as an insoluble substance in the sedimentation residue. Therefore, if necessary, a technique such as a known precipitation separation method or a flotation method may be applied to separate and recover these metals.
【００２０】以上は、廃自動車、廃家電製品からのシュ
レッダーダストの焼却により生じた飛灰の場合を例にと
り、本発明の方法を説明したが、本発明の飛灰からの金
属回収方法は、これ以外の廃棄物を焼却した際に生じる
飛灰の処理においても同様に適用可能である。The method of the present invention has been described above by taking as an example the case of fly ash produced by the incineration of shredder dust from waste automobiles and waste home electric appliances. The method for recovering metal from fly ash of the present invention is as follows. The same applies to the treatment of fly ash generated when other wastes are incinerated.
【００２１】[0021]
【実施例】以下、本発明を実施例により具体的に説明す
る。飛灰処理方法について工程別に分け順を追って説明
する。（図１に工程を示す） 本実施例による工程別主要金属成分回収成績を以下の表
１に示す。EXAMPLES The present invention will be specifically described below with reference to examples. The fly ash treatment method will be described step by step according to the order of division. (The process is shown in FIG. 1) The following table 1 shows the main metal component recovery results by process according to this example.
【００２２】[0022]
【表１】 [Table 1]
【００２３】また、本実施例における飛灰成分分析品位
を以下の表２に示す。Table 2 shows the fly ash component analysis grades in this example.
【００２４】[0024]
【表２】 [Table 2]
【００２５】第１工程は脱塩素工程である。飛灰中には
水溶性の塩化カルシウムが含まれて居り、この塩化カル
シウムを除去する。溶出して水溶液になった塩化カルシ
ウム（濃度２，０００〜５，０００ｐｐｍ）は第２工程
において電気透析で濃縮される。塩化カルシウムを除去
した澱物は第３工程で炭酸カルシウムの浮選を行う。飛
灰１００ｇに対し１．５ｌの用水を加え、２ｌのビーカ
内でインペラー撹拌し、１Ｈｒ水洗浄を行った後、ろ過
脱水し、洗浄液と残渣に分けた。Ｃｌ成分の９９．４％
を洗浄液中に回収した。なお水洗を行う際にアルミニウ
ムのアルミン酸化を防ぐため炭酸ガスを注入してｐＨ
６．５〜７．０にｐＨ調整し、アルミニウムの溶解を防
ぎ、水素の発生をおさえる。The first step is a dechlorination step. Fly ash contains water-soluble calcium chloride and removes this calcium chloride. Calcium chloride (concentration 2,000 to 5,000 ppm) that has been eluted to become an aqueous solution is concentrated by electrodialysis in the second step. The precipitate from which calcium chloride has been removed is subjected to flotation of calcium carbonate in the third step. 1.5 liters of water was added to 100 g of fly ash, and the mixture was impeller-stirred in a 2 liter beaker, washed with 1 Hr water, filtered and dehydrated, and separated into a washing liquid and a residue. 99.4% of Cl component
Was recovered in the wash solution. When washing with water, in order to prevent aluminization of aluminum, carbon dioxide gas is injected to
The pH is adjusted to 6.5 to 7.0 to prevent the dissolution of aluminum and suppress the generation of hydrogen.
【００２６】第２工程は塩化カルシウムの精製と濃縮の
ため電気透析を行うもので、塩化カルシウムの濃度を５
万〜７万ｐｐｍまで上げ、蒸発缶で４０〜５０％濃度ま
で濃縮後更に噴霧乾燥して２水塩・塩化カルシウムを粉
末、又は固形化して回収した。（ＣａＣｌ2 品位６０〜
７０％）（電気透析装置はＴＳ−１００−４１０型で透
析槽は２段階方式を採用） 第３工程は塩化カルシウムを除いた飛灰中には炭酸カル
シウムが存在するので、これを分離するため浮遊選鉱法
により炭酸カルシウム浮選を行って回収した。浮遊選鉱
剤にはオレイン酸３００ｇ／ｔ、トール油５０ｇ／ｔ、
クレゾール酸１０ｇ／ｔを用いた。水洗浄残渣（水分３
５％、固体乾量９９ｇ）に３００mlの用水を加え、濃度
調整後、デンバーサブＡ型３００ｇ浮遊機に給鉱し、炭
酸ナトリウムでｐＨを８．５〜９．０に調整し、浮遊剤
添加後１０分条件付与し、１５分の浮選を行い、フロス
として炭酸カルシウム精鉱を回収した。The second step is electrodialysis for purification and concentration of calcium chloride.
The content was raised to 10,000 to 70,000 ppm, concentrated in an evaporator to a concentration of 40 to 50%, and then spray dried to powder or solidify the dihydrate / calcium chloride and collect it. (CaCl 2 grade 60-
(70%) (The electrodialyzer is TS-100-410 type and the dialysis tank is a two-stage system.) In the third step, calcium carbonate is present in the fly ash excluding calcium chloride. The calcium carbonate was collected by flotation by the flotation method. The flotation agent is 300 g / t oleic acid, 50 g / t tall oil,
Cresic acid 10 g / t was used. Water washing residue (water content 3
300 ml of water was added to 5% solid dry weight (99 g), and after adjusting the concentration, it was fed to a Denver Sub A type 300 g floating machine, the pH was adjusted to 8.5-9.0 with sodium carbonate, and a floating agent was added. After that, conditions were applied for 10 minutes, and flotation was performed for 15 minutes to recover calcium carbonate concentrate as floss.
【００２７】ＳｉＯ2 等の抑制のため浮遊選鉱補助剤と
して珪酸ナトリウム、タンニン、澱粉質、を組み合わせ
て使用することにより精鉱品位の上昇を図ることが出来
る。この浮選精鉱中には炭酸カルシウムの他に石膏の浮
遊が見られる。第４工程は硫酸化する工程である。第３
工程で処理をした浮選滓の脱水ケーキに濃硫酸を加える
と硫酸は激しく発熱する。この熱を利用して高温高酸の
好ましい処理条件が得られ且つ短時間で硫酸化ができる
方法である。（本実施例では８０°C 以上の高温条件が
えられ、試料に濃硫酸を加え２時間の処理時間で行っ
た。）硫酸化すると溶液になるものと不溶解物になるも
のに別れる。硫酸化されて溶液になったものは第５工程
に、不溶解物は第６工程でそれぞれ処理する。By using a combination of sodium silicate, tannin, and starch as a flotation auxiliary agent for suppressing SiO 2 etc., the concentrate quality can be increased. In this flotation concentrate, in addition to calcium carbonate, gypsum floats. The fourth step is a step of sulfating. Third
When concentrated sulfuric acid is added to the dehydrated cake of the flotation slag that has been treated in the process, the sulfuric acid vigorously generates heat. It is a method of utilizing this heat to obtain preferable treatment conditions of high temperature and high acid and to perform sulfation in a short time. (In this example, a high temperature condition of 80 ° C. or higher was obtained, and concentrated sulfuric acid was added to the sample for a treatment time of 2 hours.) Sulfation is divided into a solution and an insoluble matter. The solution that is sulphated into a solution is treated in the fifth step, and the insoluble matter is treated in the sixth step.
【００２８】第５工程は硫酸化により溶出した鉄、アル
ミニウムと亜鉛を分離するため炭酸カルシウムで中和を
行う（第３工程で得た炭酸カルシウム浮選精鉱も使用可
能である）。溶液のｐＨを６に調節し加熱しつつ空気に
よる酸化を行って中和澱物として鉄、アルミニウムを分
離した。生成した中和澱物をろ過したろ液をなお更にｐ
Ｈを調節して８．５とし、溶液中の亜鉛を水酸化物とし
て沈殿させる従来技術による亜鉛の回収を行った。In the fifth step, neutralization is carried out with calcium carbonate in order to separate iron, aluminum and zinc eluted by sulfation (the calcium carbonate flotation concentrate obtained in the third step can also be used). The pH of the solution was adjusted to 6 and oxidation was performed with air while heating to separate iron and aluminum as neutralized precipitates. The resulting neutralized precipitate was filtered and the filtrate was
The H was adjusted to 8.5, and the zinc was recovered by a conventional technique in which the zinc in the solution was precipitated as a hydroxide.
【００２９】硫酸浸出のろ液７５０ｃｃを用い、炭カル
によりＦｅＡｌの分離後、その瀘液を消石灰によるＺｕ
の回収を行った。この工程では２段階のｐＨ調節を行っ
て鉄、アルミニウムの混合した沈殿物と亜鉛の沈殿物と
に分けて資源化する方法をとった。After separating FeAl with calcium carbonate using a filtrate 750 cc of sulfuric acid leaching, the filtrate is Zu with slaked lime.
Was recovered. In this process, the pH was adjusted in two steps to separate the precipitate of iron and aluminum and the precipitate of zinc for recycling.
【００３０】第６工程は硫酸化による不溶解物中にアル
ミニウムによって還元された銅粒子および硫酸化ででき
た硫酸鉛があり、これを硫化剤で粒子表面を硫化し、銅
と鉛の混合した状態で浮遊精鉱による回収が可能である
ことが判明したので、浮遊精鉱で銅と硫酸鉛の混合精鉱
を浮鉱として回収した。In the sixth step, copper particles reduced by aluminum and lead sulfate formed by sulfation were present in the insoluble matter by sulfation, and the surface of the particles was sulfurized with a sulfiding agent to mix copper and lead. Since it was revealed that it was possible to recover by a floating concentrate in the state, a mixed concentrate of copper and lead sulfate was recovered as a floating concentrate in the floating concentrate.
【００３１】金属銅粒子の浮選には硫化剤が必要で、硫
化剤に硫化水素、硫化ソーダ、水硫化ソーダ、硫化アン
モン等が使用可能である。この実施例では硫化ソーダ３
００ｇ／ｔを添加した。浮選試薬にはザンセート類、ア
ルキル又はアリルジオフォスフェート、ジチオカルバニ
リド又はジチオカルバメート、アルキル硫酸エステルが
有効である。この実施例ではエチルザンセート１００ｇ
／ｔ、アルキル硫酸エステル３００ｇ／ｔを用いた。A sulphating agent is required for flotation of the metallic copper particles, and hydrogen sulphide, sodium sulphide, sodium hydrosulphide, ammonium sulphide and the like can be used as the sulphating agent. In this embodiment, sodium sulfide 3
00 g / t was added. As the flotation reagent, xanthates, alkyl or allyl diphosphate, dithiocarbanilide or dithiocarbamate, and alkyl sulfate ester are effective. In this example 100 g of ethyl xanthate
/ T, 300 g / t of alkyl sulfate ester were used.
【００３２】起泡剤にはパイン油、ＭＩＢＣ、ケロシン
等通常浮選に使用されているものが適用できる。ここで
は、パイン油を５０ｇ／ｔ用いた。なお脈石類の抑制に
硅酸ナトリウムを使用すると精鉱（フロス）品位の向上
が図れる。浮選で回収した浮鉱は従来の処理方法を適用
して銅製錬、又は鉛製錬の原料とする。浮選尾鉱はセメ
ント原料の１部として利用できる。又は埋立処分も可能
となる。As the foaming agent, those normally used for flotation such as pine oil, MIBC and kerosene can be applied. Here, 50 g / t of pine oil was used. If sodium silicate is used to control gangue, the quality of the concentrate (floss) can be improved. Floating ore collected by flotation is applied as a raw material for copper smelting or lead smelting by applying a conventional treatment method. Flotation tailings can be used as part of a cement raw material. Alternatively, landfill disposal is possible.
【００３３】硫酸浸出工程のろ過脱水残渣（水分３５
％、固体乾量３５ｇ）に用水８５mlを加え、デンバーサ
ブＡ型１００ｇ浮選機に給鉱し、苛性ソーダ（消石灰で
も可）でｐＨを６．５に調整後、硫化ソーダ３００ｇ／
を添加し、５分条件付与し、更にエチルザンセート１０
０ｇ／ｔ、アルキル硫酸エステル３００ｇ／ｔ、パイン
油５０ｇ／ｔを添加し１０分条件付与して、１５分浮選
を行い、フロスとして銅・鉛混合精鉱を回収した。Filtration and dehydration residue in the sulfuric acid leaching step (water content: 35
%, Solid dry weight (35 g) and water (85 ml) were added to a Denver Sub-A type 100 g flotation machine, and the pH was adjusted to 6.5 with caustic soda (slaked lime was acceptable).
Was added for 5 minutes, and ethyl xanthate 10 was added.
0 g / t, 300 g / t of alkyl sulfate ester, and 50 g / t of pine oil were added and the conditions were applied for 10 minutes, followed by flotation for 15 minutes, and a copper / lead mixed concentrate was collected as floss.
【００３４】[0034]
【発明の効果】以上述べたように本発明によれば、飛灰
中から、多種の薬品を使用することなく、比較的簡単な
手法で効率よく、銅等の重金属類を金属の形態として、
また比較的純度の高い安定な塩化カルシウム等の塩類と
して、分離回収することができ、廃棄物中の高度な資源
再利用化が図られると共に、脱塩素、脱重金属による飛
灰の無害化が図られて廃棄に関する環境保全の問題にお
いても著しい進展が期待されるものである。また、この
ように主要な薬品としては硫酸のみを使用することで、
プロセスの閉回路化を図ることができる。As described above, according to the present invention, heavy metals such as copper can be efficiently converted into a metal form from fly ash by a relatively simple method without using various chemicals.
In addition, it can be separated and recovered as stable salts such as calcium chloride with a relatively high degree of purity, which makes it possible to reuse resources in a high degree of waste and to detoxify fly ash by dechlorination and demetalization. As a result, significant progress is expected in the issue of environmental protection related to disposal. Also, by using only sulfuric acid as the main chemical,
The process can be closed circuit.
【図１】本発明の実施例に係わる飛灰処理方法における
工程別を示す図である。FIG. 1 is a diagram showing each step in a fly ash processing method according to an embodiment of the present invention.
Claims (2)
およびＣａ固定化塩素を含有する飛灰からの重金属類の
回収方法であって、 ａ）飛灰を炭酸ガスを吹送しながら水を用いて洗浄する
工程と、 ｂ）上記ａ）洗浄工程における洗浄液を濃縮し乾燥して
塩化カルシウムを結晶として得る工程と、 ｃ）前記ａ）洗浄工程における固形残渣にオレイン酸、
１級アミン酢酸塩、アルキル硫酸塩、アルキル又はアリ
ル燐酸塩、トール油、クレゾール酸を捕集剤として使用
し、またパイン油、ＭＩＢＣ、エチレングリコールを起
泡剤として使用し、浮遊選鉱を行ない、フロスとして炭
酸カルシウムを回収する工程と、 ｄ）前記ｃ）浮遊選鉱工程の沈降残渣に硫酸を充分に混
合して沈降残渣中に残存する重金属を硫酸塩とし、この
混合物に水を加えて金属の硫酸塩を溶解すると同時に、
溶解した銅イオンを沈降残渣中に存在していた金属Ａｌ
により金属銅として析出させ、不溶解物と共に瀘滓とし
て分離除去する工程と、 ｅ）前記ｄ）工程で分離した不溶解物を水でリパルプし
て条件槽で硫化剤を加えて金属銅の表面を活性化し、浮
選剤にはザンセート、アルキル又はアリル・ジフォスフ
ェート、ジチォカルバニリド又はジチォカルバメート、
硫化ソーダ、硫化水素、ケロシン、アルキル硫酸エステ
ル、アルキル又はアリル燐酸塩、パイン油、エチレン・
グリコール、メチル・イソブチル・カルビノール、等の
浮選剤を用いて浮選を行い、銅と硫酸鉛を浮遊選鉱の混
合精鉱として回収する工程とを有することを特徴とする
飛灰からの重金属類の回収方法。1. A method for recovering heavy metals from fly ash containing heavy metals and Ca-immobilized chlorine generated when waste is incinerated, comprising: a) blowing fly ash with carbon dioxide gas to remove water. And b) a step of concentrating and drying the washing liquid in the a) washing step to obtain calcium chloride as crystals, and c) the solid residue in the a) washing step and oleic acid,
Using primary amine acetate, alkyl sulfate, alkyl or allyl phosphate, tall oil, cresylic acid as a scavenger, and pine oil, MIBC, ethylene glycol as a foaming agent to perform flotation. A step of recovering calcium carbonate as floss; and d) sulfuric acid is sufficiently mixed with the sedimentation residue of the above-mentioned c) flotation step to make the heavy metal remaining in the sedimentation residue a sulfate, and water is added to this mixture to remove the metal At the same time as dissolving the sulfate
Dissolved copper ions were present in the precipitation residue as metal Al
The step of precipitating as metallic copper by means of the above, and separating and removing as a slag together with the insoluble matter, e) repulping the insoluble matter separated in step d) with water and adding a sulfiding agent in a condition tank to the surface of the metallic copper And the flotation agent is xanthate, alkyl or allyl diphosphate, dithiocarbanilide or dithiocarbamate,
Sodium sulfide, hydrogen sulfide, kerosene, alkyl sulfates, alkyl or allyl phosphates, pine oil, ethylene
Heavy metal from fly ash, characterized by having a step of performing flotation using a flotation agent such as glycol, methyl isobutyl carbinol, etc., and recovering copper and lead sulfate as a mixed concentrate of the flotation. Method of collecting items.
浮鉱又は炭酸カルシウムを加え、ｐＨ５〜６に中和した
後、生成したスラリーを加熱しつつ空気を吹き込み、Ｆ
ｅ（II）をＦｅ（III)に酸化して水酸化鉄（III)とし水
酸化アルミニウムともに沈殿し濾別する前記ｅ）第１処
理と、 前記第１段処理で発生した溶液に消石灰を加えｐＨ６以
上にしてＺｎを水酸化亜鉛として沈殿して濾別し、濾液
は原料飛灰の洗浄液とする前記ｅ）第２段処理とを有す
る請求項１に記載の飛灰からの重金属類の回収方法。2. In the e), the flotation or calcium carbonate of the above c) is added to the filtrate of the above d) to neutralize it to a pH of 5 to 6, and then the produced slurry is heated and air is blown into the filtrate.
The e) first treatment in which e (II) is oxidized to Fe (III) to form iron (III) hydroxide and aluminum hydroxide is precipitated and filtered, and slaked lime is added to the solution generated in the first stage treatment. 2. Recovery of heavy metals from fly ash according to claim 1, wherein the pH is adjusted to 6 or higher and Zn is precipitated as zinc hydroxide and filtered off, and the filtrate has e) the second stage treatment which is used as a cleaning solution for the raw fly ash. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23302094A JP2792444B2 (en) | 1994-04-22 | 1994-09-28 | Recovery method of heavy metals from fly ash |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-84522 | 1994-04-22 | ||
| JP8452294 | 1994-04-22 | ||
| JP23302094A JP2792444B2 (en) | 1994-04-22 | 1994-09-28 | Recovery method of heavy metals from fly ash |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8024238A Division JPH08323321A (en) | 1994-04-22 | 1996-02-09 | Treatment of fly ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH083655A true JPH083655A (en) | 1996-01-09 |
| JP2792444B2 JP2792444B2 (en) | 1998-09-03 |
Family
ID=26425550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23302094A Expired - Fee Related JP2792444B2 (en) | 1994-04-22 | 1994-09-28 | Recovery method of heavy metals from fly ash |
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| Country | Link |
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| JP (1) | JP2792444B2 (en) |
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| JPH11158562A (en) * | 1997-11-27 | 1999-06-15 | Setsuichi Kasai | Method for separating and recovering useful metal from waste |
| WO2000043557A1 (en) * | 1999-01-21 | 2000-07-27 | Forschungszentrum Karlsruhe Gmbh | Method for processing ashes of incineration plants by desalination and artificial ageing by means of underwater high-voltage discharge |
| WO2004030839A1 (en) * | 2002-10-07 | 2004-04-15 | Taiheiyo Cement Corporation | Method and apparatus for treating calcium-containing powder |
| WO2005028379A1 (en) * | 2003-09-22 | 2005-03-31 | Taiheiyo Cement Corporation | Method and apparatus for treating drain water from step of washing fly ash with water |
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|---|---|---|---|---|
| JPH11158562A (en) * | 1997-11-27 | 1999-06-15 | Setsuichi Kasai | Method for separating and recovering useful metal from waste |
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| WO2004030839A1 (en) * | 2002-10-07 | 2004-04-15 | Taiheiyo Cement Corporation | Method and apparatus for treating calcium-containing powder |
| WO2005028379A1 (en) * | 2003-09-22 | 2005-03-31 | Taiheiyo Cement Corporation | Method and apparatus for treating drain water from step of washing fly ash with water |
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