JP2005262204A - Dust treatment method - Google Patents

Dust treatment method Download PDF

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JP2005262204A
JP2005262204A JP2005025880A JP2005025880A JP2005262204A JP 2005262204 A JP2005262204 A JP 2005262204A JP 2005025880 A JP2005025880 A JP 2005025880A JP 2005025880 A JP2005025880 A JP 2005025880A JP 2005262204 A JP2005262204 A JP 2005262204A
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dust
slurry
solid
raw material
heavy metal
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JP5028740B2 (en
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Masaharu Ishiwatari
正治 石渡
Yasunari Tenkai
泰成 天海
Hideki Muramatsu
英樹 村松
Haruki Miura
春樹 三浦
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Mitsubishi Materials Corp
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    • 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
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Abstract

<P>PROBLEM TO BE SOLVED: To efficiently reduce the concentration of heavy metals in a liquid after solid-liquid separation with respect to dust containing only a small amount of a calcium component. <P>SOLUTION: The subject dust treatment method includes a process 12 for adding a lime powder 11 to heavy metal-containing dust 10 with a calcium content of 4 wt.% or below so that the calcium content of the dust becomes 5 wt.% or below, a process 14 for mixing the dust mixed with the lime powder and water 13 to prepare a slurry with a pH of 12 or above, a process 17 for blowing carbon dioxide gas 16 in the slurry to lower the pH of the slurry to sediment heavy metals in a hydroxide or carbonate form, a process 18 for allowing the slurry in which the carbon dioxide is blown to stand to further sediment heavy metals dissolved and left in water by the coprecipitation effect with a calcium salt, and a process 19 for subjecting the stationary substance to solid-liquid separation. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、セメントキルンから塩素、アルカリ等をバイパスさせて得られたキルンダスト、或いは焼却炉、溶融炉、ガス化溶融炉等から得られた飛灰、溶融飛灰、ダスト等の中で、Ｃａ分が少量しか含まれていないダスト処理方法に関する。更に詳しくは重金属、塩素、アルカリ等を含有する飛灰、ダストからの有価金属、含有塩化物、肥料原料、化学原料、製錬原料、セメント原料等の再資源化のためのダスト処理方法に関するものである。更に本発明は、ダスト等からの肥料原料又は化学原料の製造方法並びに製錬原料又はセメント原料の製造方法に関するものである。   The present invention relates to kiln dust obtained by bypassing chlorine, alkali, etc. from a cement kiln, or fly ash, molten fly ash, dust, etc. obtained from an incinerator, melting furnace, gasification melting furnace, etc. The present invention relates to a dust processing method containing only a small amount. More specifically, it relates to a dust treatment method for recycling heavy metals, chlorine, alkali and other fly ash, valuable metals from dust, contained chlorides, fertilizer raw materials, chemical raw materials, smelting raw materials, cement raw materials, etc. It is. Furthermore, this invention relates to the manufacturing method of the fertilizer raw material or chemical raw material from dust etc., and the manufacturing method of a smelting raw material or a cement raw material.

従来、この種のダスト処理方法として、キルン熱処理ガスのダストに水に代表されるｐＨ調整剤を添加することにより、このダスト中の第１障害物質の沈殿に最適なｐＨの１次スラリーに調製する工程と、この１次スラリー中で沈殿した第１障害物質を除去する工程と、この１次スラリーにキルン排ガスに代表されるｐＨ調整剤を添加し、第２障害物質の沈殿に最適なｐＨの２次スラリーにする工程とを備えたキルンダストの処理システムが開示されている（例えば、特許文献１参照。）。   Conventionally, as a dust treatment method of this type, a pH-adjusting agent represented by water is added to the dust of the kiln heat treatment gas to prepare a primary slurry having a pH optimum for precipitation of the first obstacle substance in the dust. And a step of removing the first obstacle substance precipitated in the primary slurry, and a pH adjusting agent represented by kiln exhaust gas is added to the primary slurry, so that a pH optimum for the precipitation of the second obstacle substance is obtained. The kiln dust processing system including the process of making the secondary slurry is disclosed (for example, see Patent Document 1).

また別のダスト処理方法として、可溶性重金属塩とＮａＣｌ、ＫＣｌ、Ｎａ2ＳＯ4、Ｋ2ＳＯ4等のアルカリ金属塩を含む微粉状廃棄物または微粉状にした廃棄物を水に浸漬し、この廃棄物中に含まれる可溶性重金属塩及びアルカリ金属塩を水に溶解するとともに、ＮａＯＨ、Ｃａ(ＯＨ)2等のアルカリを添加し、このアルカリによって可溶性重金属塩を不溶性の重金属水酸化物とし、次いでこれをろ過し、ろ液中に上記アルカリ金属塩を移行せしめることにより、このアルカリ金属塩を分離したろ過残渣を作成し、このろ過残渣を高温焼結または高温溶融処理する微粉状廃棄物の処理方法が開示されている（例えば、特許文献２参照。）。
特許第２７６４５０８号公報（請求項１、［００１１］、図１） 特公昭６３−５８６３８号公報（特許請求の範囲、図１） As another dust treatment method, a pulverized waste or a pulverized waste containing a soluble heavy metal salt and an alkali metal salt such as NaCl, KCl, Na 2 SO 4 or K 2 SO 4 is immersed in water. The soluble heavy metal salt and alkali metal salt contained in the waste are dissolved in water, and an alkali such as NaOH and Ca (OH) 2 is added to convert the soluble heavy metal salt into an insoluble heavy metal hydroxide by this alkali. By filtering this and transferring the alkali metal salt into the filtrate, a filtration residue is prepared by separating the alkali metal salt, and the filtration residue is subjected to high-temperature sintering or high-temperature melting treatment. A method is disclosed (for example, refer to Patent Document 2).
Japanese Patent No. 2764508 (Claim 1, [0011], FIG. 1) Japanese Patent Publication No. 63-58638 (Claims, FIG. 1)

一般に、この種のダストは組成変動が大きく、中にはＣａＯが少量しか含まれていないものもある。このようなダストを水に浸漬しても、得られたスラリーのｐＨは十分に高くない。１次スラリーのｐＨが高いことを前提条件とする特許文献１の処理方法はカルシウム金属塩が少量しか含まれていないダストには適しない。また特許文献１の処理方法では、ｐＨ調整を二段階で行いかつ第１障害物質を除去する必要があり、工程が煩雑になるとともに、水酸化物の最小溶解度までしか重金属を除去できず、結果としてろ液中の重金属濃度を低減することが困難である。   In general, this type of dust has a large composition variation, and some of them contain only a small amount of CaO. Even if such dust is immersed in water, the pH of the obtained slurry is not sufficiently high. The treatment method of Patent Document 1 on the precondition that the pH of the primary slurry is high is not suitable for dust containing a small amount of calcium metal salt. Moreover, in the processing method of patent document 1, it is necessary to perform pH adjustment in two steps and to remove the first obstacle substance, the process becomes complicated, and heavy metal can be removed only up to the minimum solubility of hydroxide. It is difficult to reduce the heavy metal concentration in the filtrate.

一方、特許文献２の処理方法では、ダストを水に浸漬して得られたスラリーにＮａＯＨ、Ｃａ(ＯＨ)2等のアルカリを添加することによって可溶性重金属塩を不溶性の重金属水酸化物としているけれども、重金属水酸化物はその種類毎に溶解度が異なるため、上記アルカリによって水酸化物を生成させる処理では、複数の重金属を低濃度まで除去し難く、結果としてろ液中の重金属濃度を低減することができない。
本発明の目的は、カルシウム分が少量しか含まれていないダストに対して、固液分離した後の液中の重金属濃度を効率的に低減することができるダストの処理方法を提供することにある。 On the other hand, in the treatment method of Patent Document 2, soluble heavy metal salt is made into insoluble heavy metal hydroxide by adding alkali such as NaOH, Ca (OH) 2 to slurry obtained by immersing dust in water. Since the solubility of heavy metal hydroxides varies depending on the type, it is difficult to remove a plurality of heavy metals to a low concentration in the above-described treatment of generating hydroxides with alkali, and as a result, the concentration of heavy metals in the filtrate is reduced. I can't.
An object of the present invention is to provide a dust processing method capable of efficiently reducing heavy metal concentration in a liquid after solid-liquid separation with respect to dust containing only a small amount of calcium. .

請求項１に係る発明は、図１の実線で示すように、カルシウム含有量が４重量％以下の重金属を含むダスト１０にこのダストのカルシウム含有量が５重量％以上になるように石灰粉１１を添加混合する工程１２と、この石灰粉を混合したダストと水１３とを混合してｐＨ１２以上のスラリーを調製する工程１４と、このスラリーに炭酸ガス１６を吹き込みこのスラリーのｐＨを低下させて上記重金属を水酸化物又は炭酸塩の形態で沈殿させる工程１７と、この炭酸ガスを吹き込んだスラリーを静置してカルシウム塩との共沈効果により水に溶解して残留している重金属を更に沈澱させる工程１８と、この静置物を固液分離する工程１９とを含むダストの処理方法である。   In the invention according to claim 1, as shown by the solid line in FIG. 1, the dust 10 containing heavy metal having a calcium content of 4% by weight or less is added to the lime powder 11 so that the calcium content of the dust is 5% by weight or more. The step 12 for adding and mixing the dust, the step 14 for preparing the slurry having a pH of 12 or more by mixing the dust mixed with the lime powder and the water 13, and blowing the carbon dioxide gas 16 into the slurry to lower the pH of the slurry. The step 17 for precipitating the heavy metal in the form of hydroxide or carbonate and the slurry in which the carbon dioxide gas is blown are allowed to stand still to dissolve the heavy metal remaining in the water due to the coprecipitation effect with the calcium salt. This is a dust processing method including a step 18 for precipitation and a step 19 for solid-liquid separation of the stationary object.

請求項２に係る発明は、請求項１に係る発明であって、石灰粉の添加量を、ダスト１０の一部を採取してこのダストのカルシウム含有量を分析した後、この分析値と目標となるカルシウム含有量との差から決定する処理方法である。   The invention according to claim 2 is the invention according to claim 1, wherein after adding a part of the dust 10 and analyzing the calcium content of the dust, the analysis value and the target are added. It is a processing method determined from the difference with the calcium content.

請求項３に係る発明は、請求項１又は２に係る発明であって、石灰粉が石灰石、生石灰又は消石灰の少なくとも１種からなる粉体である。
請求項４に係る発明は、請求項１ないし３いずれか１項に係る発明であって、固液分離により得られたろ液２１を蒸発・晶析する工程２２と、この蒸発・晶析により得られた固形物２３から肥料原料又は化学原料を生成する工程とを更に含む処理方法である。
請求項５に係る発明は、請求項１ないし３いずれか１項に係る発明であって、固液分離により得られた残渣２４から製錬原料又はセメント原料を生成する工程を更に含む処理方法である。 The invention according to claim 3 is the invention according to claim 1 or 2, wherein the lime powder is a powder composed of at least one of limestone, quicklime and slaked lime.
The invention according to claim 4 is the invention according to any one of claims 1 to 3, wherein a step 22 for evaporating and crystallizing the filtrate 21 obtained by solid-liquid separation is obtained by this evaporation and crystallization. And a step of generating a fertilizer raw material or a chemical raw material from the obtained solid material 23.
The invention according to claim 5 is the processing method according to any one of claims 1 to 3, further comprising a step of generating a smelting raw material or a cement raw material from the residue 24 obtained by solid-liquid separation. is there.

請求項６に係る発明は、図１の実線で示すように、カルシウム含有量が４重量％以下の重金属を含むダスト１０にこのダストのカルシウム含有量が５重量％以上になるように石灰粉１１を添加混合する工程１２と、この石灰粉を混合したダストと水１３とを混合してｐＨ１２以上のスラリーを調製する工程１４と、このスラリーに炭酸ガス１６を吹き込みこのスラリーのｐＨを低下させて上記重金属を水酸化物又は炭酸塩の形態で沈殿させる工程１７と、この炭酸ガスを吹き込んだスラリーを静置してカルシウム塩との共沈効果により水に溶解して残留している重金属を更に沈澱させる工程１８と、この静置物を固液分離する工程１９と、固液分離により得られたろ液２１を蒸発・晶析する工程２２と、蒸発・晶析により得られた固形物２３から肥料原料又は化学原料を生成する工程とを含む肥料原料又は化学原料の製造方法である。   In the invention according to claim 6, as shown by the solid line in FIG. 1, lime powder 11 is added so that the dust 10 containing heavy metal having a calcium content of 4 wt% or less has a calcium content of 5 wt% or more. The step 12 for adding and mixing the dust, the step 14 for preparing the slurry having a pH of 12 or more by mixing the dust mixed with the lime powder and the water 13, and blowing the carbon dioxide gas 16 into the slurry to lower the pH of the slurry. The step 17 for precipitating the heavy metal in the form of hydroxide or carbonate, and the slurry into which the carbon dioxide gas is blown are allowed to stand still to dissolve the heavy metal remaining in the water due to the coprecipitation effect with the calcium salt. Step 18 for precipitation, Step 19 for solid-liquid separation of this stationary product, Step 22 for evaporation / crystallization of the filtrate 21 obtained by solid-liquid separation, and Solid matter 23 obtained by evaporation / crystallization A method for producing a fertilizer material or chemical raw materials and a step of generating Luo fertilizers or chemical feedstock.

請求項７に係る発明は、図１の実線で示すように、カルシウム含有量が４重量％以下の重金属を含むダスト１０にこのダストのカルシウム含有量が５重量％以上になるように石灰粉１１を添加混合する工程１２と、この石灰粉を混合したダストと水１３とを混合してｐＨ１２以上のスラリーを調製する工程１４と、このスラリーに炭酸ガス１６を吹き込みこのスラリーのｐＨを低下させて上記重金属を水酸化物又は炭酸塩の形態で沈殿させる工程１７と、この炭酸ガスを吹き込んだスラリーを静置してカルシウム塩との共沈効果により水に溶解して残留している重金属を更に沈澱させる工程１８と、この静置物を固液分離する工程１９と、固液分離により得られた残渣２４から製錬原料又はセメント原料を生成する工程とを含む製錬原料又はセメント原料の製造方法である。   In the invention according to claim 7, as shown by the solid line in FIG. 1, lime powder 11 is added so that the dust 10 containing heavy metals having a calcium content of 4 wt% or less has a calcium content of 5 wt% or more. The step 12 for adding and mixing the dust, the step 14 for preparing the slurry having a pH of 12 or more by mixing the dust mixed with the lime powder and the water 13, and blowing the carbon dioxide gas 16 into the slurry to lower the pH of the slurry. The step 17 for precipitating the heavy metal in the form of hydroxide or carbonate and the slurry in which the carbon dioxide gas is blown are allowed to stand still to dissolve the heavy metal remaining in the water due to the coprecipitation effect with the calcium salt. A smelting raw material comprising a step 18 of precipitating, a step 19 of solid-liquid separation of the stationary product, and a step of generating a smelting raw material or a cement raw material from the residue 24 obtained by the solid-liquid separation It is a method of manufacturing the instrument raw materials.

本発明の処理方法では、次の効果を奏する。
(1) スラリー化する際に予め石灰粉を水と混合して石灰乳にし、この石灰乳とダストを水に加える場合には石灰乳を調製する装置を必要とするけれども、本発明にはこの石灰乳の調製装置を必要としない。
(2) 石灰粉とダストを水に一緒に加える場合には石灰粉が水により塊状になり易く、この石灰塊を砕いて溶解させるまで長時間要するけれども、本発明ではスラリー化する前に石灰粉をダストに混合するため、石灰が粉末状でダストと混合され、スラリー化したときに、石灰粉が塊状になり難く、石灰がより容易かつ短時間で水と反応する。
(3) ダストのカルシウム含有量に応じて石灰粉の添加量を決めるため、スラリーのｐＨ値は安定し、このスラリーに炭酸ガスを吹き込んで所望のｐＨ値に調整することにより、ダストに含まれていた重金属を水酸化物又は炭酸塩の形態で沈殿させることができる。
(4) 炭酸ガスを吹き込んだスラリーを静置することにより、水に溶解して残留していた重金属がカルシウム塩の沈殿に伴われて一緒に沈殿し、この結果、特許文献１及び２の処理方法と比較して、液中の重金属濃度をより効率的にかつより一層低減することができる。
(5) 特許文献１の処理方法では、ダストをスラリー化し、ｐＨ調整を行った際に発生する沈澱物質（第１障害物質）を除去していたものが、本発明では除去しないため、固液分離回数が減少し、工程を簡素化できる。
(6) 固液分離した液を蒸発・晶析することにより得られた固形物には、カリウム及び塩素等のハロゲン類が多量に含まれるので、これらを肥料の原料、又は化学原料に利用することができる。
(7) 固液分離により得られた残渣は若干重金属を含むものの大部分がカルシウム化合物、シリカから構成されているので、この残渣は製錬原料又はセメント原料に利用することができる。 The processing method of the present invention has the following effects.
(1) When slurrying, lime powder is mixed with water in advance to make lime milk, and when adding this lime milk and dust to water, an apparatus for preparing lime milk is required. Does not require lime milk preparation equipment.
(2) When lime powder and dust are added to water together, the lime powder tends to agglomerate with water, and it takes a long time to break up and dissolve this lime lump. Therefore, when lime is mixed with dust in a powder form and slurried, the lime powder is less likely to be agglomerated, and lime reacts with water more easily and in a short time.
(3) Since the amount of lime powder added depends on the calcium content of the dust, the pH value of the slurry is stable, and carbon dioxide is blown into this slurry to adjust it to the desired pH value, so that it is contained in the dust. The heavy metals that have been deposited can be precipitated in the form of hydroxides or carbonates.
(4) By leaving the slurry into which carbon dioxide gas has been blown, the heavy metal remaining in the water is precipitated together with the precipitation of the calcium salt. As a result, the treatments of Patent Documents 1 and 2 are performed. Compared with the method, the heavy metal concentration in the liquid can be more efficiently and further reduced.
(5) In the treatment method of Patent Document 1, the dust that has been slurried and the precipitated substance (first obstacle substance) that is generated when the pH is adjusted is removed. The number of separations is reduced and the process can be simplified.
(6) The solids obtained by evaporating and crystallizing the solid-liquid separated liquid contain a large amount of halogens such as potassium and chlorine, so these are used as fertilizer raw materials or chemical raw materials. be able to.
(7) Although the residue obtained by solid-liquid separation contains a little heavy metal, most of it is composed of a calcium compound and silica, so this residue can be used as a smelting raw material or a cement raw material.

本発明の実施の形態を実線で示された図１に基づいて説明する。
本発明処理方法の対象となるダストは、カルシウム含有量（ＣａＯ）が４重量％以下の重金属を含むダスト１０である。カルシウム含有量が４重量％以下のダストは、水と混合してスラリーにしたときに、スラリーのｐＨが５〜１０になる。このダストを例示すれば、セメントキルンから塩素、アルカリ等をバイパスさせて得られたキルンダスト、或いは焼却炉、溶融炉、ガス化溶融炉等から得られた飛灰、溶融飛灰、ダスト等、或いは都市ごみ、廃水処理工程からでるスラッジ等を焼却処理した際に排出されるダストである。ダストに含まれる重金属には、Ｃｄ、Ｐｂ、Ｚｎ、Ｃｕ等が例示される。 An embodiment of the present invention will be described with reference to FIG. 1 indicated by a solid line.
The dust targeted for the treatment method of the present invention is the dust 10 containing heavy metal having a calcium content (CaO) of 4% by weight or less. Dust having a calcium content of 4% by weight or less has a slurry pH of 5 to 10 when mixed with water to form a slurry. To illustrate this dust, kiln dust obtained by bypassing chlorine, alkali, etc. from cement kiln, fly ash obtained from incinerator, melting furnace, gasification melting furnace, etc., molten fly ash, dust, etc. It is dust discharged when incineration of municipal waste and sludge from wastewater treatment process. Examples of heavy metals contained in the dust include Cd, Pb, Zn, and Cu.

石灰粉の添加量は、ダスト１０の一部を採取してこのダストのカルシウム含有量を蛍光Ｘ線分析法等により分析する工程１０ａを経て、この分析値と目標となるカルシウム含有量との差から決定される（工程１０ｂ）。即ち、この石灰粉の添加量は、ダストのカルシウム含有量によって変動するが、次のスラリー化したときのｐＨ値を１２以上にするために、ダスト１００重量％に対して５重量％以上、好ましくは１０〜１５重量％の範囲から決められる。下限値未満ではスラリーのｐＨ値が１２未満になり、また上限値を越えて添加してもｐＨ値はそれ程上昇しないためである。   The amount of lime powder added is the difference between this analytical value and the target calcium content after the process 10a in which a part of the dust 10 is collected and the calcium content of the dust is analyzed by fluorescent X-ray analysis or the like. (Step 10b). That is, the amount of lime powder added varies depending on the calcium content of the dust, but in order to make the pH value when the next slurry is 12 or more, preferably 5% by weight or more with respect to 100% by weight of dust. Is determined from the range of 10 to 15% by weight. This is because if the pH is less than the lower limit, the pH value of the slurry is less than 12, and even if the slurry is added exceeding the upper limit, the pH value does not increase so much.

ダストへのカルシウム添加量の決定工程１０ｂに基づいて、石灰粉１１をダスト１０に添加され、均一に混合される（工程１２）。なお、ダスト１０のカルシウム含有量が既知である場合には、工程１０ａ及び工程１０ｂは省略される。ここで、石灰粉は石灰石（ＣａＣＯ3）、生石灰（ＣａＯ）又は消石灰（Ｃａ(ＯＨ)2）の少なくとも１種からなる粉体である。この中で化学的に安定で、水に溶けやすい消石灰が好ましい。石灰粉は市販されている平均粒径が１０〜５００μｍのものであれば、ダストと均一に混合でき、かつ水に容易に反応する。 Based on the determination step 10b of the amount of calcium added to the dust, the lime powder 11 is added to the dust 10 and mixed uniformly (step 12). In addition, when the calcium content of the dust 10 is known, the steps 10a and 10b are omitted. Here, the lime powder is a powder composed of at least one of limestone (CaCO 3 ), quick lime (CaO), and slaked lime (Ca (OH) 2 ). Of these, slaked lime that is chemically stable and easily soluble in water is preferred. As long as the lime powder has a commercially available average particle size of 10 to 500 μm, it can be uniformly mixed with dust and easily reacts with water.

次いで石灰粉を混合したダストと水１３とを混合してスラリーを調製する（工程１４）。具体的には重量比でダストの２〜２０倍量、好ましくは３〜１０倍量の水と混合する。前述した石灰粉の所定量の添加によりスラリーのｐＨは１２以上になる。スラリーのｐＨが１２以上になると、ダストに含まれる重金属のうち、Ｃｄ、Ｃｕ等はそのほとんどが水酸化物になる。この水酸化物は水に対する溶解度が非常に小さく沈殿する。ダストに含まれる重金属のうち、Ｐｂ、Ｚｎ等については、ｐＨ１２以上では水に対する溶解度が高くなり、一部がアルカリ水溶液に溶解している。   Next, dust mixed with lime powder and water 13 are mixed to prepare a slurry (step 14). Specifically, it is mixed with 2 to 20 times, preferably 3 to 10 times, the amount of dust by weight. By adding a predetermined amount of lime powder as described above, the pH of the slurry becomes 12 or more. When the pH of the slurry is 12 or more, most of the heavy metals contained in the dust are hydroxides such as Cd and Cu. This hydroxide precipitates with very low solubility in water. Among heavy metals contained in dust, Pb, Zn, and the like have high solubility in water at pH 12 or higher, and some are dissolved in an alkaline aqueous solution.

次にこのスラリーに炭酸ガス１６を吹き込み、スラリーのｐＨをスラリー調製時のｐＨ値より低下させる。好ましくはｐＨを１２未満、更に好ましくは１０〜１１．５の範囲に低下させる（工程１７）。この炭酸ガスは、キルン、焼却炉、溶融炉等の炭酸ガスを含む排ガスでもよい。炭酸ガスの吹き込みの際に、水に不溶性の重金属水酸化物は、分散していても、或いは沈降して沈澱物であってもよい。特許文献１に記載されているようにこの不溶性の重金属水酸化物を除去する必要はない。この炭酸ガスの吹き込みとスラリーのｐＨを低下させることにより、溶解していたＰｂ、Ｚｎ等は、水に対する溶解度が低下するため、水酸化物になるとともに、炭酸塩を生成する。また僅かに溶存するＣｄ等も炭酸塩になる。この水に不溶性の重金属の水酸化物、炭酸塩は時間の経過とともに沈殿する。   Next, carbon dioxide gas 16 is blown into this slurry, and the pH of the slurry is lowered from the pH value at the time of slurry preparation. Preferably, the pH is lowered to less than 12, more preferably 10 to 11.5 (step 17). The carbon dioxide gas may be exhaust gas containing carbon dioxide gas such as kiln, incinerator, melting furnace or the like. When carbon dioxide gas is blown in, the heavy metal hydroxide that is insoluble in water may be dispersed or may be precipitated and precipitated. As described in Patent Document 1, it is not necessary to remove this insoluble heavy metal hydroxide. By blowing this carbon dioxide gas and lowering the pH of the slurry, the dissolved Pb, Zn, etc. are reduced in water solubility, and thus become hydroxides and produce carbonates. In addition, slightly dissolved Cd and the like also become carbonate. This water-insoluble heavy metal hydroxide and carbonate precipitates over time.

続いて上記スラリーを静置する（工程１８）。静置は３０分以上、好ましくは１〜１２時間行う。除去効率を考慮すれば１時間以上静置すれば十分であるが、装置、操業上の観点から上記範囲内から静置時間が決められる。上記上限値を越えて静置しても除去効率はそれ程向上しない。この静置により、水に溶解して残留していた重金属がカルシウム塩の沈殿に伴われて一緒に沈殿する。この共沈効果により水に溶解している重金属の濃度がより一層低減する。   Subsequently, the slurry is allowed to stand (step 18). The standing is performed for 30 minutes or more, preferably 1 to 12 hours. Considering the removal efficiency, it is sufficient to stand for 1 hour or more, but the standing time is determined from the above range from the viewpoint of the apparatus and operation. The removal efficiency does not improve so much even if the product is left standing above the upper limit. By this standing, the heavy metal remaining in the water is precipitated together with the precipitation of the calcium salt. This coprecipitation effect further reduces the concentration of heavy metals dissolved in water.

更に続いて液と沈殿物を含む静置物を遠心分離、フィルタプレス等により固液分離する（工程１９）。ろ液２１を加熱することによりその水分を蒸発させ、液に溶解していた物を晶析させる（工程２２）。得られた固形物２３にはカリウム、ナトリウム等のアルカリ金属と、塩素、臭素等のハロゲン類が多量に含まれるので、この固形物により肥料の原料や化学原料が製造される。一方固液分離により得られた残渣２４には若干重金属を含むものの大部分がカルシウム化合物、シリカから構成されているので、この残渣により製錬原料又はセメント原料が製造される。   Subsequently, the stationary product containing the liquid and the precipitate is subjected to solid-liquid separation by centrifugation, filter press or the like (step 19). The filtrate 21 is heated to evaporate the water and crystallize the substance dissolved in the liquid (step 22). Since the obtained solid 23 contains a large amount of alkali metals such as potassium and sodium and halogens such as chlorine and bromine, a fertilizer raw material and a chemical raw material are produced from the solid. On the other hand, since the residue 24 obtained by solid-liquid separation contains a little heavy metal, most of it is composed of a calcium compound and silica, so that a smelting raw material or a cement raw material is produced from this residue.

次に本発明の実施例を説明する。
＜実施例１＞
表１に示すセメントキルンダストを用意した。このダストはそのままダストの５倍量の水を加えてスラリー化すると、スラリーのｐＨが５．０になるものであった。この用意したセメントキルンダストに１．９重量％のＣａ(ＯＨ)2を添加し均一に混合した。このダストとＣａ(ＯＨ)2の混合物を重量比で５倍量の水にてスラリー化した。図１の破線に示すように、このスラリーの一部を抜き取りろ過した後、ｐＨ１２．０のろ液１を得た。
その後、このスラリーに１０％ＣＯ2−空気混合ガスを吹き込んでスラリーのｐＨを１０．５に調整した。ｐＨを調整した後、１０％ＣＯ2−空気混合ガスを吹き込みを止め、図１の破線に示すように、スラリーの一部を抜き取りろ過した後、ろ液２を得た。ｐＨ調整したスラリーを１時間静置した後、静置物をフィルタプレスにより固液分離した。図１の破線に示すように、このときのろ液の一部を抜き取りろ液３とした。 Next, examples of the present invention will be described.
<Example 1>
Cement kiln dust shown in Table 1 was prepared. When this dust was made into a slurry by adding 5 times the amount of water as it was, the pH of the slurry was 5.0. To this prepared cement kiln dust, 1.9 wt% Ca (OH) 2 was added and mixed uniformly. This dust and Ca (OH) 2 mixture was slurried with 5 times the weight of water. As shown by the broken line in FIG. 1, a part of this slurry was extracted and filtered, and then a filtrate 1 having a pH of 12.0 was obtained.
Thereafter, a 10% CO 2 -air mixed gas was blown into the slurry to adjust the pH of the slurry to 10.5. After adjusting the pH, blowing of 10% CO 2 -air mixed gas was stopped, and a portion of the slurry was extracted and filtered as shown by the broken line in FIG. After the pH-adjusted slurry was allowed to stand for 1 hour, the stationary product was subjected to solid-liquid separation using a filter press. As shown by the broken line in FIG. 1, a part of the filtrate at this time was extracted and designated as filtrate 3.

Figure 2005262204
Figure 2005262204

＜実施例２＞
表１に示すセメントキルンダストに３．３重量％のＣａ(ＯＨ)2を添加し均一に混合した。このダストとＣａ(ＯＨ)2の混合物を重量比で５倍量の水にてスラリー化した。図１の破線に示すように、このスラリーの一部を抜き取りろ過した後、ｐＨ１２．０のろ液１を得た。それ以外は実施例１と同様にダストを処理した。
＜実施例３＞
表１に示すセメントキルンダストに８．４重量％のＣａ(ＯＨ)2を添加し均一に混合した。このダストとＣａ(ＯＨ)2の混合物を重量比で５倍量の水にてスラリー化した。図１の破線に示すように、このスラリーの一部を抜き取りろ過した後、ｐＨ１２．１のろ液１を得た。それ以外は実施例１と同様にダストを処理した。 <Example 2>
To the cement kiln dust shown in Table 1, 3.3 wt% Ca (OH) 2 was added and mixed uniformly. This dust and Ca (OH) 2 mixture was slurried with 5 times the weight of water. As shown by the broken line in FIG. 1, a part of this slurry was extracted and filtered, and then a filtrate 1 having a pH of 12.0 was obtained. Otherwise, dust was treated in the same manner as in Example 1.
<Example 3>
8.4 wt% Ca (OH) 2 was added to the cement kiln dust shown in Table 1 and mixed uniformly. This dust and Ca (OH) 2 mixture was slurried with 5 times the weight of water. As shown by the broken line in FIG. 1, a part of this slurry was extracted and filtered, and then a filtrate 1 having a pH of 12.1 was obtained. Otherwise, dust was treated in the same manner as in Example 1.

＜実施例４＞
表１に示すセメントキルンダストに１０重量％のＣａ(ＯＨ)2を添加し均一に混合した。このダストとＣａ(ＯＨ)2の混合物を重量比で５倍量の水にてスラリー化した。図１の破線に示すように、このスラリーの一部を抜き取りろ過した後、ｐＨ１２．１のろ液１を得た。それ以外は実施例１と同様にダストを処理した。
＜実施例５＞
表１に示すセメントキルンダストに１２．５重量％のＣａ(ＯＨ)2を添加し均一に混合した。このダストとＣａ(ＯＨ)2の混合物を重量比で５倍量の水にてスラリー化した。図１の破線に示すように、このスラリーの一部を抜き取りろ過した後、ｐＨ１２．１のろ液１を得た。それ以外は実施例１と同様にダストを処理した。 <Example 4>
10% by weight of Ca (OH) 2 was added to the cement kiln dust shown in Table 1 and mixed uniformly. This dust and Ca (OH) 2 mixture was slurried with 5 times the weight of water. As shown by the broken line in FIG. 1, a part of this slurry was extracted and filtered, and then a filtrate 1 having a pH of 12.1 was obtained. Otherwise, dust was treated in the same manner as in Example 1.
<Example 5>
12.5 wt% Ca (OH) 2 was added to the cement kiln dust shown in Table 1 and mixed uniformly. This dust and Ca (OH) 2 mixture was slurried with 5 times the weight of water. As shown by the broken line in FIG. 1, a part of this slurry was extracted and filtered, and then a filtrate 1 having a pH of 12.1 was obtained. Otherwise, dust was treated in the same manner as in Example 1.

＜ろ液の分析と評価＞
実施例１〜５で得られたろ液１、ろ液２及びろ液３の各重金属成分についてＩＣＰ発光分光分析法により化学分析を行った。重金属であるＰｂとＣｄとＺｎの合計値を表２に示す。 <Analysis and evaluation of filtrate>
Each heavy metal component of the filtrate 1, filtrate 2 and filtrate 3 obtained in Examples 1 to 5 was subjected to chemical analysis by ICP emission spectroscopy. Table 2 shows the total values of Pb, Cd, and Zn, which are heavy metals.

Figure 2005262204
Figure 2005262204

表２からＣａ(ＯＨ)2添加量を増加させることにより、ろ液１〜３すべてにおいて、Ｐｂ、Ｃｄ、Ｚｎが効率的に除去されることが判った。またろ液１とろ液２の各分析値により、水酸化物による重金属の除去とＣＯ2吹き込みによる重金属の除去とを比較すると、後者の方が効果的であった。更にろ液２とろ液３の各分析値の比較から、水酸化物や炭酸塩の形態で重金属を除去した後において、静置工程のカルシウム塩による共沈効果で重金属が更に除去されることが判った。 From Table 2, it was found that Pb, Cd and Zn were efficiently removed in all the filtrates 1 to 3 by increasing the amount of Ca (OH) 2 added. Moreover, when the removal of heavy metal by hydroxide and the removal of heavy metal by CO 2 blowing were compared based on the analysis values of filtrate 1 and filtrate 2, the latter was more effective. Furthermore, from the comparison of the analytical values of the filtrate 2 and the filtrate 3, after removing heavy metals in the form of hydroxide or carbonate, the heavy metals may be further removed by the coprecipitation effect of the calcium salt in the standing step. understood.

＜固液分離後のろ液・残渣の処理＞
実施例１〜５において、固液分離した後の各ろ液を加熱してろ液に溶解していた物を晶析し、得られた各固形物を分析したところ、すべての固形物にはＫ等のアルカリ金属と、Ｃｌ等のハロゲン類が多量に含まれており、肥料又は化学原料として利用可能であった。また固液分離により得られた各残渣を分析したところ、すべての残渣が若干重金属を含むもののその大部分がＣａ化合物、ＳｉＯ2から構成されていた。従って、これらの残渣は製錬工程でのフラックス又はセメント原料への利用が可能であった。 <Treatment of filtrate and residue after solid-liquid separation>
In Examples 1 to 5, each filtrate after solid-liquid separation was heated to crystallize what was dissolved in the filtrate, and each solid obtained was analyzed. A large amount of alkali metals such as Cl and halogens such as Cl were contained, and they could be used as fertilizers or chemical raw materials. Moreover, when each residue obtained by solid-liquid separation was analyzed, although all the residues contained some heavy metals, most of them were composed of a Ca compound and SiO 2 . Therefore, these residues could be used as a flux or cement raw material in the smelting process.

本発明は、キルンダスト、或いは焼却炉、溶融炉、ガス化溶融炉等から得られた飛灰、溶融飛灰、ダスト等の中で、Ｃａ分が少量しか含まれていないダスト処理に利用できる。また上記キルンダスト等から、肥料原料、化学原料、製錬原料、セメント原料等を製造できる。   INDUSTRIAL APPLICABILITY The present invention can be used for dust treatment in which only a small amount of Ca is contained in kiln dust, fly ash obtained from an incinerator, melting furnace, gasification melting furnace or the like, molten fly ash, dust, and the like. Further, fertilizer raw materials, chemical raw materials, smelting raw materials, cement raw materials and the like can be produced from the kiln dust and the like.

本発明のダスト処理工程を示す図。The figure which shows the dust treatment process of this invention.

符号の説明Explanation of symbols

１０ ダスト
１１ 石灰粉
１２ ダストと石灰粉の混合工程
１３ 水
１４ スラリーの調製工程
１６ 炭酸ガス
１７ 重金属の沈殿工程
１８ 静置による残留重金属のカルシウム塩との共沈工程
１９ 固液分離工程
２１ ろ液
２２ 蒸発・晶析工程
２３ 固形物
２４ 残渣
DESCRIPTION OF SYMBOLS 10 Dust 11 Lime powder 12 Mixing process of dust and lime powder 13 Water 14 Slurry preparation process 16 Carbon dioxide 17 Precipitation process of heavy metal 18 Co-precipitation process with residual heavy metal calcium salt by standing 19 Solid-liquid separation process 21 Filtrate 22 Evaporation and crystallization process 23 Solid matter 24 Residue

Claims (7)

カルシウム含有量が４重量％以下の重金属を含むダスト(10)に前記ダストのカルシウム含有量が５重量％以上になるように石灰粉(11)を添加混合する工程(12)と、前記石灰粉を混合したダストと水(13)とを混合してｐＨ１２以上のスラリーを調製する工程(14)と、前記スラリーに炭酸ガス(16)を吹き込み前記スラリーのｐＨを低下させて前記重金属を水酸化物又は炭酸塩の形態で沈殿させる工程(17)と、前記炭酸ガスを吹き込んだスラリーを静置してカルシウム塩との共沈効果により水に溶解して残留している重金属を更に沈澱させる工程(18)と、前記静置物を固液分離する工程(19)とを含むダストの処理方法。   Adding (12) lime powder (11) to dust (10) containing heavy metal having a calcium content of 4% by weight or less so that the calcium content of the dust is 5% by weight or more; and A step (14) of preparing a slurry having a pH of 12 or more by mixing dust mixed with water and water (13), and blowing the carbon dioxide gas (16) into the slurry to lower the pH of the slurry to hydroxylate the heavy metal. A step of precipitating in the form of a product or carbonate (17), and a step of allowing the slurry into which the carbon dioxide gas has been blown to stand to dissolve in water by a coprecipitation effect with calcium salt to further precipitate the remaining heavy metal (18) A dust processing method comprising: a solid-liquid separation of the stationary object (19). 石灰粉の添加量を、ダスト(10)の一部を採取してこのダストのカルシウム含有量を分析した後、この分析値と目標となるカルシウム含有量との差から決定する請求項１記載の処理方法。   The amount of lime powder added is determined from the difference between the analytical value and the target calcium content after sampling a portion of the dust (10) and analyzing the calcium content of the dust. Processing method. 石灰粉が石灰石、生石灰又は消石灰の少なくとも１種からなる粉体である請求項１又は２記載の処理方法。   The processing method according to claim 1 or 2, wherein the lime powder is a powder composed of at least one of limestone, quicklime and slaked lime. 固液分離により得られたろ液(21)を蒸発・晶析する工程(22)と、前記蒸発・晶析により得られた固形物(23)から肥料原料又は化学原料を生成する工程とを更に含む請求項１ないし３いずれか１項に記載の処理方法。   A step (22) of evaporating and crystallizing the filtrate (21) obtained by solid-liquid separation, and a step of generating a fertilizer raw material or a chemical raw material from the solid matter (23) obtained by the evaporation and crystallization. The processing method of any one of Claim 1 thru | or 3 containing. 固液分離により得られた残渣(24)から製錬原料又はセメント原料を生成する工程を更に含む請求項１ないし３いずれか１項に記載の処理方法。   The processing method according to any one of claims 1 to 3, further comprising a step of producing a smelting raw material or a cement raw material from the residue (24) obtained by solid-liquid separation. カルシウム含有量が４重量％以下の重金属を含むダスト(10)に前記ダストのカルシウム含有量が５重量％以上になるように石灰粉(11)を添加混合する工程(12)と、前記石灰粉を混合したダストと水(13)とを混合してｐＨ１２以上のスラリーを調製する工程(14)と、前記スラリーに炭酸ガス(16)を吹き込み前記スラリーのｐＨを低下させて前記重金属を水酸化物又は炭酸塩の形態で沈殿させる工程(17)と、前記炭酸ガスを吹き込んだスラリーを静置してカルシウム塩との共沈効果により水に溶解して残留している重金属を更に沈澱させる工程(18)と、前記静置物を固液分離する工程(19)と、固液分離により得られたろ液(21)を蒸発・晶析する工程(22)と、前記蒸発・晶析により得られた固形物(23)から肥料原料又は化学原料を生成する工程とを含む肥料原料又は化学原料の製造方法。   Adding (12) lime powder (11) to dust (10) containing heavy metal having a calcium content of 4% by weight or less so that the calcium content of the dust is 5% by weight or more; and A step (14) of preparing a slurry having a pH of 12 or more by mixing the dust mixed with water (13), and blowing the carbon dioxide gas (16) into the slurry to lower the pH of the slurry to hydroxylate the heavy metal. A step of precipitating in the form of a product or carbonate (17), and a step of allowing the slurry into which the carbon dioxide gas has been blown to stand to dissolve in water by a coprecipitation effect with calcium salt to further precipitate the remaining heavy metal (18), a step (19) of solid-liquid separation of the stationary product, a step (22) of evaporation / crystallization of the filtrate (21) obtained by solid-liquid separation, and the evaporation / crystallization. A fertilizer raw material or a step of generating a fertilizer raw material or a chemical raw material from the solid (23) Manufacturing method of academic raw materials. カルシウム含有量が４重量％以下の重金属を含むダスト(10)に前記ダストのカルシウム含有量が５重量％以上になるように石灰粉(11)を添加混合する工程(12)と、前記石灰粉を混合したダストと水(13)とを混合してｐＨ１２以上のスラリーを調製する工程(14)と、前記スラリーに炭酸ガス(16)を吹き込み前記スラリーのｐＨを低下させて前記重金属を水酸化物又は炭酸塩の形態で沈殿させる工程(17)と、前記炭酸ガスを吹き込んだスラリーを静置してカルシウム塩との共沈効果により水に溶解して残留している重金属を更に沈澱させる工程(18)と、前記静置物を固液分離する工程(19)と、固液分離により得られた残渣(24)から製錬原料又はセメント原料を生成する工程とを含む製錬原料又はセメント原料の製造方法。   Adding (12) lime powder (11) to dust (10) containing heavy metal having a calcium content of 4% by weight or less so that the calcium content of the dust is 5% by weight or more; and A step (14) of preparing a slurry having a pH of 12 or more by mixing the dust mixed with water (13), and blowing the carbon dioxide gas (16) into the slurry to lower the pH of the slurry to hydroxylate the heavy metal. A step of precipitating in the form of a product or carbonate (17), and a step of allowing the slurry into which the carbon dioxide gas has been blown to stand to dissolve in water by a coprecipitation effect with calcium salt to further precipitate the remaining heavy metal (18), a smelting raw material or cement raw material comprising a step (19) of solid-liquid separation of the stationary product, and a step of generating a smelting raw material or cement raw material from the residue (24) obtained by solid-liquid separation Manufacturing method.
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CN103130254A (en) * 2013-03-18 2013-06-05 中国铝业股份有限公司 Method for producing aluminum oxide by using alkaline method

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