JPH09174015A - Stabilizing process of waste containing antimony - Google Patents
Stabilizing process of waste containing antimonyInfo
- Publication number
- JPH09174015A JPH09174015A JP7342523A JP34252395A JPH09174015A JP H09174015 A JPH09174015 A JP H09174015A JP 7342523 A JP7342523 A JP 7342523A JP 34252395 A JP34252395 A JP 34252395A JP H09174015 A JPH09174015 A JP H09174015A
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- JP
- Japan
- Prior art keywords
- treating agent
- fly ash
- sulfide
- sulfide treating
- waste
- 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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Links
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- Processing Of Solid Wastes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ゴミ焼却飛灰等の
一般廃棄物や各種産業廃棄物に含まれるアンチモン（元
素記号Ｓｂ）およびその他の有害重金属を、難溶性の固
体化合物に転化する安定化処理方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a stable method for converting antimony (elemental symbol Sb) and other harmful heavy metals contained in general waste such as refuse incineration fly ash and various industrial wastes into a sparingly soluble solid compound. The present invention relates to a chemical treatment method.
【０００２】[0002]
【従来の技術】ゴミの焼却灰や焼却飛灰（フライアッシ
ュ）には、有害な重金属が含まれている場合があるの
で、該重金属を難溶性の固体化合物に転化し安定化する
処理を行って、埋立て用等に廃棄されている。安定化処
理法の従来技術として、特公平５−７７４７７号公報に
は、ゴミ焼却飛灰に硫化剤と水を加え、含水量１８〜３
０％として混練し、飛灰中に含まれる重金属を難溶性の
硫化物に転化せしめ安定化する方法が示されている。2. Description of the Related Art Since incinerated ash and fly ash of refuse may contain harmful heavy metals, it is necessary to convert the heavy metals into insoluble solid compounds for stabilization. It has been discarded for landfills. As a conventional technique of the stabilization treatment method, Japanese Patent Publication No. 5-77477 discloses a waste incineration fly ash to which a sulfidizing agent and water are added to obtain a water content of 18 to 3
A method is disclosed in which kneading is performed at 0% to convert the heavy metal contained in the fly ash into a sparingly soluble sulfide for stabilization.
【０００３】また、本発明者等は、特開平２−２０３９
８１号公報により、有害重金属を含有する鉱滓、ばいじ
ん、汚泥等の産業破棄物に水を加えてペースト状とし、
これを撹拌しながら、硫黄イオンを含有する薬剤および
カルボン酸基を含む有機高分子の水溶液を添加、混練し
て無害化処理を行い、有害重金属イオンの溶出を防止し
て廃棄処理する方法を提案している。The inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 2039/1990.
According to No. 81 publication, water is added to industrial waste such as slag, dust and sludge containing harmful heavy metals to form a paste,
While stirring this, we propose a method of adding chemicals containing sulfur ions and aqueous solutions of organic polymers containing carboxylic acid groups, kneading them to perform detoxification treatment, and preventing the elution of harmful heavy metal ions to dispose of them. doing.
【０００４】[0004]
【発明が解決しようとする課題】ところで、ゴミの中に
は、難燃材、特殊インク、合金類、火薬等に使用される
Ｓｂが含まれている場合があり、焼却灰や飛灰にもＳｂ
が含まれることになる。また、その他の一般廃棄物や産
業廃棄物にもＳｂが含まれる場合がある。そして、Ｓｂ
の溶出量は、極微量のｐｐｂ単位で管理されるべきもの
であり、上記のような従来技術では、十分な安定化処理
を行うことが困難であった。本発明は、ゴミ焼却灰や焼
却飛灰等の一般廃棄物や、各種産業廃棄物に含まれるＳ
ｂおよびその他の重金属を、簡便な手段で、難溶性の固
体化合物に転化するための安定化処理方法を提供するこ
とを目的とする。By the way, dust may contain Sb used in flame-retardant materials, special inks, alloys, explosives, etc., and also in incineration ash and fly ash. Sb
Will be included. Further, Sb may be contained in other general wastes and industrial wastes. And Sb
The amount of elution of the syrup should be controlled in an extremely small amount of ppb, and it was difficult to perform sufficient stabilization treatment by the above-mentioned conventional techniques. INDUSTRIAL APPLICABILITY The present invention includes S contained in general waste such as refuse incineration ash and incineration fly ash, and various industrial wastes.
It is an object of the present invention to provide a stabilizing treatment method for converting b and other heavy metals into a hardly soluble solid compound by a simple means.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
の本発明は、重金属を含有する廃棄物に硫化物処理剤と
水を添加する処理法において、硫黄イオンを遊離する薬
剤にカルボン酸基を含む有機高分子を配合してなる硫化
物処理剤を添加した後の工程で、鉄化合物を添加するこ
とにより前記廃棄物中のアンチモンを難溶性の固体化合
物に転化することを特徴とする含Ｓｂ廃棄物の安定化処
理方法である。Means for Solving the Problems The present invention for achieving the above object is to provide a method for adding a sulfide treating agent and water to a waste containing a heavy metal, wherein a carboxylic acid group is added to a sulfur ion releasing agent. In a step after adding a sulfide treating agent prepared by blending an organic polymer containing, the antimony in the waste is converted into a hardly soluble solid compound by adding an iron compound. This is a method for stabilizing Sb waste.
【０００６】[0006]
【発明の実施の形態】本発明法において、対象とする廃
棄物は、ゴミ焼却灰やゴミ焼却飛灰等の一般廃棄物、お
よび、ばいじん、汚泥、鉱滓等の産業廃棄物であり、粉
状のものである。塊状のものは粉砕した後、本発明法に
より処理することができる。硫化物処理剤としては、硫
黄イオンを遊離する薬剤にカルボン酸基を含む有機高分
子を配合してなるもの（以下、硫化物処理剤Ｒと記す）
を使用する。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, the target wastes are general wastes such as refuse incineration ash and refuse incineration fly ash, and industrial wastes such as dust, sludge and slag, which are powdered. belongs to. The lumps can be crushed and then processed by the method of the present invention. As the sulfide treating agent, one obtained by blending a sulfur ion-releasing agent with an organic polymer containing a carboxylic acid group (hereinafter referred to as a sulfide treating agent R)
Use
【０００７】硫黄イオンを遊離する薬剤とは、水に溶か
したときに硫黄イオンを形成するものをいい、具体的に
は硫化ナトリウム（Ｎａ2 Ｓ）、水硫化ソーダ（ＮａＨ
Ｓ）、多硫化ソーダ（Ｎａ2 Ｓn ）、チオ尿素、ソジウ
ムメルカプチッド等をいう。カルボン酸基を含む有機高
分子とは、１分子中に多数のカルボン酸またはその誘導
体、すなわち塩、アミド、エステルなどを含有する水溶
性の合成樹脂を指し、硫化物の微結晶と化学的吸着を行
うものをいい、作用としては、多くの微粒子を結合して
強固な粗大粒子を形成するもので、単なる荷電や物理吸
着による凝集効果とは異なるものである。具体的には、
ポリアクリル酸ナトリウムが主体をなし、一部アミド、
エステルを含有するもので、分子量としては（１０〜１
５００）×１０4 の範囲のものが好ましい。本発明法で
使用するこのような硫化物処理剤Ｒの例としては、重金
属不溶出化飛灰処理剤ＲＨＦ（甲陽化成株式会社製商品
名）がある。The agent that releases sulfur ions is one that forms sulfur ions when dissolved in water. Specifically, sodium sulfide (Na 2 S) and sodium hydrosulfide (NaH) are used.
S), sodium polysulfide (Na 2 S n), thiourea, it refers to sodium Melka Puchi' de like. An organic polymer containing a carboxylic acid group refers to a water-soluble synthetic resin containing a large number of carboxylic acids or derivatives thereof in one molecule, that is, salts, amides, esters, etc. The effect is to combine many fine particles to form strong coarse particles, which is different from the agglomeration effect due to simple charge or physical adsorption. In particular,
Mainly made of sodium polyacrylate, partly amide,
It contains an ester and its molecular weight is (10-1).
It is preferably in the range of 500) × 10 4 . An example of such a sulfide treating agent R used in the method of the present invention is a heavy metal non-eluting fly ash treating agent RHF (trade name, manufactured by Koyo Kasei Co., Ltd.).
【０００８】本発明法は、上記のような廃棄物に硫化物
処理剤と水を添加して混練する方法において、上記のよ
うな硫化物処理剤Ｒを添加した後、鉄化合物を添加する
ことを特徴とする。すなわち、硫化物処理剤Ｒの添加
後、鉄化合物を添加し、ついで水を添加して混練しても
よく、水を添加し、ついで鉄化合物を添加して混練して
もよい。また、廃棄物に水を添加した後、硫化物処理剤
Ｒを添加し、ついで鉄化合物を添加して混練してもよ
い。鉄化合物としては、鉄鋼の製造工程で発生する電炉
ダスト、スケール粉等の酸化鉄、あるいは酸洗スラジ等
の塩化鉄などを採用することができる。In the method of the present invention, a sulfide treating agent and water are added to a waste as described above and kneading is performed. After adding the sulfide treating agent R as described above, an iron compound is added. Is characterized by. That is, after adding the sulfide treating agent R, an iron compound may be added and then water may be added and kneaded, or water may be added and then an iron compound may be added and kneaded. Alternatively, after adding water to the waste, the sulfide treating agent R may be added, and then the iron compound may be added and kneaded. As the iron compound, electric furnace dust generated in the steel manufacturing process, iron oxide such as scale powder, or iron chloride such as pickling sludge can be used.
【０００９】本発明法によるゴミ焼却飛灰の処理工程例
を図１に示す。ゴミ収集ピット１からゴミが焼却炉２に
投入され、燃焼したガスは、排熱利用の温水ボイラー３
の熱交換器をとおり、排ガス処理装置４内で、ガス処理
用のアルカリ剤タンク５より供給されたアルカリ剤で処
理される。燃焼熱で舞い上がった煤塵やガスに含まれる
酸性物質などが、集塵装置７によって捕集され焼却飛灰
となり、清浄となったガスは、煙突８から排出される。
集塵装置７で捕集された焼却飛灰は、混合機９に導かれ
る。FIG. 1 shows an example of the steps of treating refuse incinerated fly ash according to the method of the present invention. Waste gas is put into the incinerator 2 from the waste collection pit 1, and the burned gas is a hot water boiler 3 that uses waste heat.
In the exhaust gas treatment device 4, the heat treatment is performed with the alkaline agent supplied from the alkaline agent tank 5 for gas treatment. The soot dust and the acidic substances contained in the gas, which are soared by the combustion heat, are collected by the dust collector 7 to be incinerated fly ash, and the cleaned gas is discharged from the chimney 8.
The incineration fly ash collected by the dust collector 7 is guided to the mixer 9.
【００１０】一方、希釈タンク１０に、硫化物処理剤タ
ンク１１から硫化物処理剤Ｒが一定量毎供給され、焼却
飛灰に対して適正な水分量となるよう、また適正な硫化
物処理剤Ｒの添加量となるように水で希釈される。希釈
された硫化物処理剤Ｒの希釈水が混合機９に注入され、
乾燥した粉末状の焼却飛灰と混合される。そして、ダス
トタンク１２から鉄化合物の粉末が混合機９に投入され
て、混合処理される。混合機９で混合された処理物は、
焼却炉２で発生し、灰冷却装置６で冷却された焼却灰を
運ぶ灰排出コンベア１３に導かれて、灰ピット１４に溜
められる。On the other hand, a fixed amount of the sulfide treating agent R is supplied from the sulfide treating agent tank 11 to the diluting tank 10 so that an appropriate amount of water can be obtained for incineration fly ash. It is diluted with water to the amount of R added. Diluted water of the diluted sulfide treating agent R is injected into the mixer 9,
It is mixed with dry powdery incineration fly ash. Then, the iron compound powder is put into the mixer 9 from the dust tank 12 and mixed. The processed products mixed by the mixer 9 are
The incineration ash generated in the incinerator 2 and cooled by the ash cooling device 6 is guided to the ash discharge conveyor 13 and is accumulated in the ash pit 14.
【００１１】本例において、混合機９では、焼却飛灰と
硫化物処理剤Ｒを水で希釈した液とを混合し、その後に
鉄化合物の粉末を注入する方式をとっているが、この
他、水と硫化物処理剤Ｒと鉄化合物を、それぞれ別の経
路、３経路から注入する方式でもかまわず、また、最終
処理物の含水率が適正量になるよう、硫化物処理剤Ｒの
希釈水を充分に飛灰と混合させたうえで、鉄化合物の粉
末を水でスラリー状としたものを注入して混合する方式
でもかまわない。処理しようとする飛灰は、乾燥した粉
末であるため、液状の硫化物処理剤Ｒを混合するために
必要な水分は多いほうが望ましくなる。In this example, the mixer 9 employs a system in which incineration fly ash and a liquid obtained by diluting the sulfide treating agent R with water are mixed, and then the iron compound powder is injected. Alternatively, the method of injecting water, the sulfide treating agent R, and the iron compound from different routes and 3 routes may be used, and the sulfide treating agent R may be diluted so that the water content of the final treated product becomes an appropriate amount. A method may be used in which water is sufficiently mixed with fly ash, and then a powder of iron compound is slurried with water and then mixed. Since the fly ash to be treated is a dry powder, it is desirable that the water content necessary for mixing the liquid sulfide treating agent R is large.
【００１２】混合機９は、粉体と水分を充分に混合でき
るものであればよく、混合不良を起こし粉末が継粉（ま
まこ）を作るような、未反応の粉体がある状態の機械は
使用できない。反応時の温度条件としては、温度が高い
ほど反応速度は速くなるものの、硫化物処理剤Ｒが液体
であるため、処理対象とするものが水分の沸点以上の温
度であれば、急激な水分の蒸発が起こり、ミストの発生
やガスの発生などが起こり得ることがあり、作業環境上
の難点が発生することもあり、理想的には、対象物温度
が常温時に処理をするのは望ましく、水分蒸発を考慮す
れば８０℃以下が好ましい。The mixer 9 may be any machine as long as it can sufficiently mix the powder and the water, and is a machine in a state where there is unreacted powder such that mixing failure occurs and the powder forms a continuous powder (mamako). Cannot be used. As the temperature condition during the reaction, the higher the temperature is, the faster the reaction rate becomes. However, since the sulfide treating agent R is a liquid, if the object to be treated is at a temperature equal to or higher than the boiling point of the moisture, abrupt moisture Evaporation may occur, and mist or gas may be generated, which may cause difficulties in the working environment. Ideally, it is desirable to perform the treatment when the temperature of the object is room temperature. Considering evaporation, the temperature is preferably 80 ° C or lower.
【００１３】[0013]
【実施例】都市ゴミ焼却炉で発生した飛灰で、ｐＨ＝１
２．２６、Ｓｂ溶出量＝８４．２ｐｐｂ、Ｐｂ溶出量＝
７．７ｐｐｍのものをサンプルとして実験を行った。飛
灰に硫化物処理剤と水と鉄化合物の調整剤を、この順に
添加して混練した。硫化物処理剤としては、本発明例で
は、上記硫化物処理剤Ｒの代表例としてＲＨＦを使用し
た。また、比較例ではＮａ2 Ｓを使用した。添加量は、
それぞれ、飛灰１００ｇに対して３０％水溶液を３重量
％混合した。そして、調整剤として、本発明例では、酸
化鉄からなる電炉ダストおよび塩化鉄（ＦｅＣｌ3 ）、
比較例では、ＰＡＣ（ポリ塩化アルミ）およびＨＣｌを
使用した。添加量は、それぞれ、硫化物処理剤に対する
添加倍量を×０．５、×１．０、×１．５とした。処理
後のＳｂ溶出量およびＰｂ溶出量を、表１に示す。[Example] Fly ash generated in a municipal waste incinerator, pH = 1
2.26, Sb elution amount = 84.2 ppb, Pb elution amount =
The experiment was conducted using 7.7 ppm as a sample. The fly ash was kneaded by adding a sulfide treating agent, water and an iron compound modifier in this order. As the sulfide treating agent, RHF was used as a representative example of the sulfide treating agent R in the present invention. In addition, Na 2 S was used in the comparative example. The amount of addition
3% by weight of a 30% aqueous solution was mixed with 100 g of fly ash. And, as an adjusting agent, in the present invention example, electric furnace dust made of iron oxide and iron chloride (FeCl 3 ),
In the comparative example, PAC (polyaluminum chloride) and HCl were used. The addition amount was set to x0.5, x1.0, and x1.5, respectively, with respect to the addition amount with respect to the sulfide treating agent. Table 1 shows the amounts of Sb and Pb eluted after the treatment.
【００１４】本発明例と比較例の結果を比較すると、Ｓ
ｂの溶出値にはそれぞれ効果がある程度出てはいるが、
本発明による鉄化合物の処理結果（Ｎｏ．１〜６）は安
定した数値を示している。比較例（Ｎｏ．７〜２２）
は、大きな数値を示しているものがあるため、本発明法
の有効性が判明した。また、Ｓｂを処理する目的であっ
ても、Ｐｂも同時に処理できなくてはならず、Ｐｂの溶
出値（環境基準値０．３mg／リッター）が高いと意味が
ないことになる。硫化物処理剤としてＮａ2 Ｓを使用し
た比較例は、Ｓｂは処理できてもＰｂは処理できていな
いのに対し、ＲＨＦを使用した本発明例は、Ｓｂ、Ｐｂ
ともに少ない数値を示しており、本発明法が有効である
ことが判明した。本発明例では、Ｓｂ溶出量が１．４ｐ
ｐｂ以下に抑えられ、かつ、Ｐｂ溶出量が０．３ｐｐｍ
以下に抑えられた。なお、一般的に、Ｐｂ溶出量が抑え
られれば、Ｓｂを除く他の重金属の溶出量も抑えられる
ことが判明している。Comparing the results of the present invention example and the comparative example, S
Although there are some effects on the elution value of b,
The treatment results (Nos. 1 to 6) of the iron compound according to the present invention show stable numerical values. Comparative examples (No. 7-22)
Indicates that the method of the present invention is effective. Further, even for the purpose of treating Sb, it is necessary to treat Pb at the same time, and it is meaningless if the elution value of Pb (environmental standard value 0.3 mg / liter) is high. In the comparative example using Na 2 S as the sulfide treating agent, Sb can be treated but Pb cannot be treated, whereas in the example of the present invention using RHF, Sb, Pb
Both of them show small numerical values, which proves that the method of the present invention is effective. In the present invention example, the Sb elution amount was 1.4 p
It is kept below pb and the amount of Pb elution is 0.3 ppm
It was suppressed below. It has been found that, generally, if the elution amount of Pb is suppressed, the elution amounts of other heavy metals other than Sb can also be suppressed.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【発明の効果】本発明法により、各種廃棄物中に含まれ
るＳｂを難溶性の固体化合物に転化し安定化処理するこ
とができる。そして、本発明法により使用される鉄化合
物も、産業廃棄物であって、鉄鋼製造工程で発生する電
炉ダスト、スケール粉、酸洗スラジ等の廃棄物が有効利
用され、同時に処理されることとなる。According to the method of the present invention, Sb contained in various wastes can be converted into a sparingly soluble solid compound for stabilization treatment. Then, the iron compound used by the method of the present invention is also an industrial waste, and the wastes such as electric furnace dust, scale powder, and pickling sludge generated in the steel manufacturing process are effectively used, and are treated at the same time. Become.
【図１】本発明法によるゴミ焼却飛灰の処理工程例を示
す説明図である。FIG. 1 is an explanatory view showing an example of a treatment process of refuse incineration fly ash according to the method of the present invention.
１…ゴミ収集ピット ２…焼却炉 ３…温水ボイラー ４…排ガス処理装置 ５…アルカリ剤タンク ６…灰冷却装置 ７…集塵装置 ８…煙突 ９…混合機 １０…希釈タンク １１…硫化物処理剤タンク １２…ダストタンク １３…灰排出コンベア １４…灰ピット 1 ... Garbage collection pit 2 ... Incinerator 3 ... Hot water boiler 4 ... Exhaust gas treatment device 5 ... Alkaline agent tank 6 ... Ash cooling device 7 ... Dust collector 8 ... Chimney 9 ... Mixer 10 ... Dilution tank 11 ... Sulfide treatment agent Tank 12 ... Dust tank 13 ... Ash discharge conveyor 14 ... Ash pit
Claims (1)
と水を添加する処理法において、硫黄イオンを遊離する
薬剤にカルボン酸基を含む有機高分子を配合してなる硫
化物処理剤を添加した後の工程で、鉄化合物を添加する
ことにより前記廃棄物中のアンチモンを難溶性の固体化
合物に転化することを特徴とする含Ｓｂ廃棄物の安定化
処理方法。1. A treatment method in which a sulfide treating agent and water are added to a waste containing a heavy metal, and a sulfide treating agent prepared by blending a sulfur ion-releasing agent with an organic polymer containing a carboxylic acid group. A method for stabilizing treatment of Sb-containing waste, which comprises converting an antimony in the waste into a hardly soluble solid compound by adding an iron compound in a step after the addition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34252395A JP3696676B2 (en) | 1995-12-28 | 1995-12-28 | Method for stabilizing Sb-containing waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34252395A JP3696676B2 (en) | 1995-12-28 | 1995-12-28 | Method for stabilizing Sb-containing waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09174015A true JPH09174015A (en) | 1997-07-08 |
| JP3696676B2 JP3696676B2 (en) | 2005-09-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34252395A Expired - Lifetime JP3696676B2 (en) | 1995-12-28 | 1995-12-28 | Method for stabilizing Sb-containing waste |
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| Country | Link |
|---|---|
| JP (1) | JP3696676B2 (en) |
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1995
- 1995-12-28 JP JP34252395A patent/JP3696676B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP3696676B2 (en) | 2005-09-21 |
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