JP3965769B2 - Fly ash treatment method - Google Patents
Fly ash treatment method Download PDFInfo
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- JP3965769B2 JP3965769B2 JP10922198A JP10922198A JP3965769B2 JP 3965769 B2 JP3965769 B2 JP 3965769B2 JP 10922198 A JP10922198 A JP 10922198A JP 10922198 A JP10922198 A JP 10922198A JP 3965769 B2 JP3965769 B2 JP 3965769B2
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- Prior art keywords
- fly ash
- leaching
- sulfuric acid
- residue
- calcium
- Prior art date
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- Expired - Fee Related
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- 239000010881 fly ash Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 62
- 238000002386 leaching Methods 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 239000011575 calcium Substances 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004568 cement Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- 150000002013 dioxins Chemical class 0.000 claims description 12
- 238000006298 dechlorination reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000001784 detoxification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Processing Of Solid Wastes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、焼却炉から排出される飛灰の再資源化処理方法に関する。より詳しくは、飛灰を脱塩素処理およびダイオキシン類の分解無害化処理を施した後に、セメント焼成用キルンに投入して、セメント原料として、再資源化する飛灰の処理方法に関する。
【０００２】
【従来技術】
都市ゴミ等を焼却処分する際に発生する飛灰はセメントによる固化処理等の中間処理を施した後に処分場に埋め立てられている。また最近は飛灰の再資源化を図るために飛灰を溶融処理してコンクリート用の骨材等を製造することが検討されている。しかし、埋立処分については、十分な埋立処分場を確保することが次第に困難な状況になっており、また、溶融固化後の再利用にも有害物質の溶出等の問題点がある。
【０００３】
一方、飛灰の主成分はシリカやアルミナ等であるので、これをセメント原料として再利用する試みがなされている。しかし、飛灰中には約１０wt％程度の塩素が含まれており、セメント原料とするには塩素濃度を０.１wt％以下まで低減させる必要がある。そこで、飛灰を水浸出して脱塩素処理することが検討されているが、水浸出では飛灰中の塩素濃度をセメント原料として利用できる程度にまで下げることは困難であった。
【０００４】
【発明の解決課題】
本発明は、飛灰をセメント原料に利用できる程度にまで、塩素含有濃度を下げる脱塩素処理方法を提供することを目的とする。更に、飛灰中に含まれるダイオキシン等の分解無害化処理を行なうことによって、飛灰をセメント原料として再資源化することを目的とするものである。
【０００５】
【課題の解決手段】
本発明者等は、飛灰を硫酸浸出することにより、浸出残渣中の塩素濃度を０.０５wt％程度まで低減できることを見出した。しかし、単なる硫酸浸出では、飛灰中のカルシウムと硫酸が反応して石膏を生じ、これが浸出残渣に残るので硫黄分の多い残渣となり、このままではセメント原料として適さない。そこで、本発明では、飛灰を予め塩酸浸出することにより、飛灰中のカルシウム分を液中に浸出除去しておき、硫酸浸出時の石膏の生成を少量にとどめて残渣中の硫黄分の含有量を許容範囲内とし、セメント原料として利用可能なものとした。
また、飛灰中にはダイオキシン類が含まれているため、飛灰の脱塩素処理の後に処理残渣を加熱処理してダイオキシン類の分解無害化を行なうことにより、飛灰をセメント原料として利用し易くした。
【０００６】
すなわち、本発明は、（１）飛灰をｐＨ１〜４の液性下で塩酸浸出して塩素分とカルシウム分を溶出させ、これを固液分離した浸出残渣を、更にｐＨ１〜４の液性下で硫酸浸出して脱塩素処理を行なうことによって、硫酸浸出残渣中のカルシウム分を１/４〜１/１８に低減することを特徴とする飛灰の処理方法に関するものである。
【０００７】
本発明の処理方法は、好ましくは、（２）硫酸浸出残渣の塩素量が０ . ０９〜０ . ０５ wt ％、カルシウム量が２ . ９〜０ . ７ wt ％である上記 ( １ ) に記載する飛灰の処理方法、（３）塩酸浸出の前、あるいは硫酸浸出の後に、飛灰ないし浸出残渣を６００〜１０００℃に加熱してダイオキシン類を分解除去し、硫酸浸出後の残渣をセメン卜原料として用いる上記(１)または上記(２)に記載する飛灰の処理方法である。
【０００８】
【発明の実施形態】
以下に本発明を具体的に説明する。図１に本発明の処理方法の工程図を示す。図示するように、本発明の処理方法は、飛灰を塩酸浸出して塩素分とカルシウム分を溶出させた後に固液分離し、次いで浸出残渣を硫酸浸出して脱塩素処理を行ない、更に必要に応じて、この浸出残渣を６００〜１０００℃に加熱してダイオキシン類を分解除去した後に、セメント焼成用キルンに投入してセメン卜原料として用いる処理方法である。
【０００９】
( Ｉ ) 塩酸浸出工程
先に述べたように、飛灰を硫酸浸出すれば浸出残渣中の塩素濃度を低減できるが、硫酸浸出の際に飛灰中のカルシウムと硫酸が反応して石膏を生じ、これが浸出残渣中に固形分として残る。そこで、本発明の処理方法では、硫酸浸出に先立ち塩酸浸出を行う。塩酸浸出により、飛灰中の塩素分とカルシウム分を液中に浸出させて浸出残渣から除去し、カルシウム分を低減することにより、次工程の硫酸浸出において石膏の生成を抑制する。塩酸浸出液の塩酸濃度はｐＨ値１〜４が適当であり、ｐＨ値２〜３が好ましい。ｐＨ値４を上回るとカルシウムの浸出率が低く、ｐＨ値１未満では浸出残渣の濾過性が悪くなる。
【００１０】
(II)硫酸浸出工程
塩酸浸出に引き続き硫酸浸出を行う。硫酸浸出によって飛灰中の塩素量が低減する。具体的には、実施例の表１に示すように塩素量が０ . ０９〜０ . ０５ wt ％に低減し、また、カルシウム分も実施例の表１に示すように２ . ９〜０ . ７ wt ％に低減する。硫酸浸出液の硫酸濃度はｐＨ値１〜４が適当であり、ｐＨ値２〜４が好ましい。ｐＨ値４を上回ると塩素の浸出率が低く、ｐＨ値１未満では浸出残渣の濾過性が悪くなる。
【００１１】
(III) 加熱分解処理
飛灰中のダイオキシン類を分解無害化するために、塩酸浸出前あるいは硫酸浸出後に、飛灰ないし浸出残渣を６００〜１０００℃で加熱処理する。加熱温度が６００℃より低いとダイオキシン類の分解が不十分になる。ダイオキシン類の分解率は１０００℃で９９.９９％以上であるので、加熱温度の上限は１０００℃が適当である。
【００１２】
【実施例】
本発明を実施例によって以下に具体的に示す。なお、これらは例示であり、本発明の範囲を限定するものではない。
【００１３】
実施例１
一般ゴミの焼却飛灰（Cl:10.6wt％,Ca:12.7wt％,S:1.3wt％）１００gを各々異なったｐＨ値(pH:4,2,1)の塩酸浸出液１０００mlを用いて浸出した後に濾過し、引き続き、この塩酸浸出残渣をｐＨ値２の硫酸浸出液１０００mlを用いて浸出を行ない、濾過後、浸出残渣に含まれる塩素、カルシウムおよび硫黄の含有量を測定した。測定結果を表１に示した。表１に示すように、硫酸浸出残渣中のカルシウム分は１／４〜１／１８程度に大幅に減少しており、硫酸浸出残渣に含まれる石膏分も格段に少ない。
【００１４】
【表１】
実施例１の塩酸浸出処理および硫酸浸出処理を行った浸出残渣１５gを、温度６００℃、８００℃、１０００℃の各温度で２時間、加熱処理し、残渣中のダイオキシン類を分析した。この結果を表２に示した。表２に示すように、処理前の飛灰に含まれていたダイオキシン類は大部分が分解除去された。
【００１５】
【表２】
比較例
実施例１で用いたものと同じ飛灰１００gを各々異なったｐＨ値(4,2,1)の硫酸浸出液１０００mlを用いて浸出を行い、濾過後の浸出残渣中の塩素および硫黄の含有量を測定した。この分析結果を表３に示した。表３に示すように、本例の浸出残渣にはカルシウムと硫黄分が多量に含まれている。
【００１７】
【表３】
【発明の効果】
本発明の脱塩素処理およびダイオキシン類の分解無害化処理によれば、飛灰をセメント原料に適するものに処理することができるので、大量に発生する焼却飛灰を有効に再資源化することが可能になる。
【図面の簡単な説明】
【図１】 本発明の処理方法を示す工程図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for recycling fly ash discharged from an incinerator. More specifically, the present invention relates to a fly ash treatment method in which fly ash is subjected to dechlorination treatment and detoxification treatment of dioxins, and then input into a cement firing kiln to be recycled as a cement raw material.
[0002]
[Prior art]
Fly ash generated when municipal waste is incinerated is buried in a disposal site after intermediate treatment such as solidification with cement. Recently, in order to recycle fly ash, it has been studied to produce aggregates for concrete by melting fly ash. However, with regard to landfill disposal, it is becoming increasingly difficult to secure a sufficient landfill site, and there are problems such as elution of harmful substances in reuse after melting and solidification.
[0003]
On the other hand, since the main component of fly ash is silica, alumina, or the like, attempts have been made to reuse it as a cement raw material. However, about 10 wt% of chlorine is contained in the fly ash, and it is necessary to reduce the chlorine concentration to 0.1 wt% or less in order to use it as a cement raw material. Therefore, it has been studied to leach fly ash and dechlorinate it. However, it was difficult to reduce the chlorine concentration in the fly ash to such an extent that it can be used as a cement raw material.
[0004]
[Problem to be Solved by the Invention]
An object of this invention is to provide the dechlorination processing method which reduces a chlorine containing density | concentration to such an extent that fly ash can be utilized for a cement raw material. Furthermore, it aims at recycling | recycling fly ash as a cement raw material by performing the detoxification process of dioxin etc. which are contained in fly ash.
[0005]
[Means for solving problems]
The present inventors have found that the chlorine concentration in the leaching residue can be reduced to about 0.05 wt% by leaching the fly ash with sulfuric acid. However, in mere sulfuric acid leaching, calcium and sulfuric acid in fly ash react to form gypsum, which remains in the leaching residue, resulting in a residue with a high sulfur content, and as such is not suitable as a cement raw material. Therefore, in the present invention, the calcium content in the fly ash is leached and removed in the liquid by leaching the fly ash with hydrochloric acid in advance, and the generation of gypsum during the sulfuric acid leaching is limited to a small amount, so that the sulfur content in the residue is reduced. The content was within the allowable range, and could be used as a cement raw material.
In addition, since fly ash contains dioxins, the fly ash is used as a raw material for cement by heat-treating the treatment residue after dechlorination of the fly ash to detoxify the dioxins. Made it easier.
[0006]
That is, the present invention is (1) leaching fly ash under hydrochloric acid at pH 1 to 4 to elute hydrochloric acid and calcium, and leaching residue obtained by solid-liquid separation of the ash is further converted to liquid pH 1 to 4 The present invention relates to a fly ash treatment method characterized in that the calcium content in the sulfuric acid leaching residue is reduced to 1/4 to 1/18 by performing sulfuric acid leaching and dechlorination.
[0007]
Processing method of the present invention, preferably, according to (2) chlorine content of sulfuric acid leach residue is 0. 09~0. 05 wt%, calcium content is from 2.9 to 0.7 above (1) is wt% (3) Before leaching hydrochloric acid or after leaching with sulfuric acid, the fly ash or leaching residue is heated to 600-1000 ° C to decompose and remove dioxins, and the residue after leaching with sulfuric acid is treated with cement. The fly ash treatment method described in the above (1) or (2) used as a raw material.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be specifically described below. FIG. 1 shows a process diagram of the processing method of the present invention. As shown in the figure, in the treatment method of the present invention, the fly ash is leached with hydrochloric acid to elute the chlorine and calcium components and then separated into solid and liquid, and then the leaching residue is leached with sulfuric acid for dechlorination, and further required. Accordingly, the leaching residue is heated to 600 to 1000 ° C. to decompose and remove dioxins, and is then charged into a cement firing kiln and used as a raw material for cement.
[0009]
( I ) Hydrochloric acid leaching process As mentioned above, leaching sulfuric acid with sulfuric acid can reduce the chlorine concentration in the leaching residue, but the calcium and sulfuric acid in the fly ash react with each other during sulfuric acid leaching. Gypsum, which remains as a solid in the leach residue. Therefore, in the treatment method of the present invention, hydrochloric acid leaching is performed prior to sulfuric acid leaching. By hydrochloric acid leaching, the chlorine and calcium contents in the fly ash are leached into the liquid and removed from the leaching residue, and the calcium content is reduced, thereby suppressing the formation of gypsum in the sulfuric acid leaching in the next step. The hydrochloric acid concentration of the hydrochloric acid leaching solution is suitably a pH value of 1 to 4, preferably a pH value of 2 to 3. If the pH value exceeds 4, the leaching rate of calcium is low, and if the pH value is less than 1, the filterability of the leaching residue is deteriorated.
[0010]
(II) Sulfuric acid leaching process Sulfuric acid leaching is performed following hydrochloric acid leaching. The amount of chlorine in fly ash is reduced by sulfuric acid leaching. Specifically, the chlorine content as shown in Table 1 of Example is 0.09 to 0.05 decrease in wt%, also 2 to be calcium components shown in Table 1 of Example. 9-0. Reduce to 7 wt %. The sulfuric acid concentration of the sulfuric acid leachate is suitably pH value 1-4, and preferably pH value 2-4. When the pH value exceeds 4, the leaching rate of chlorine is low, and when the pH value is less than 1, the leaching residue has poor filterability.
[0011]
(III) Thermal decomposition treatment In order to decompose and detoxify the dioxins in the fly ash, the fly ash or leaching residue is heat-treated at 600 to 1000C before or after leaching with hydrochloric acid. When the heating temperature is lower than 600 ° C., decomposition of dioxins becomes insufficient. Since the decomposition rate of dioxins is 99.99% or more at 1000 ° C., the upper limit of the heating temperature is suitably 1000 ° C.
[0012]
【Example】
The present invention will be specifically described below with reference to examples. Note that these are examples and do not limit the scope of the present invention.
[0013]
Example 1
100g of incinerated fly ash (Cl: 10.6wt%, Ca: 12.7wt%, S: 1.3wt%) of general waste was leached using 1000ml of hydrochloric acid leachate with different pH values (pH: 4,2,1) Subsequently, this hydrochloric acid leaching residue was leached using 1000 ml of sulfuric acid leaching solution having a pH value of 2, and after filtration, the contents of chlorine, calcium and sulfur contained in the leaching residue were measured. The measurement results are shown in Table 1. As shown in Table 1, the calcium content in the sulfuric acid leaching residue is greatly reduced to about 1/4 to 1/18, and the gypsum content contained in the sulfuric acid leaching residue is remarkably small.
[0014]
[Table 1]
15 g of the leaching residue subjected to the hydrochloric acid leaching treatment and the sulfuric acid leaching treatment of Example 1 were heated at temperatures of 600 ° C., 800 ° C., and 1000 ° C. for 2 hours, and dioxins in the residue were analyzed. The results are shown in Table 2. As shown in Table 2, most of the dioxins contained in the fly ash before the treatment were decomposed and removed.
[0015]
[Table 2]
Comparative Example 100 g of the same fly ash as used in Example 1 was leached using 1000 ml of sulfuric acid leachate with different pH values (4,2,1), and chlorine in the leaching residue after filtration. And the sulfur content was measured. The analysis results are shown in Table 3. As shown in Table 3, the leaching residue of this example contains a large amount of calcium and sulfur.
[0017]
[Table 3]
【The invention's effect】
According to the dechlorination treatment and the detoxification treatment of dioxins of the present invention, fly ash can be processed into a material suitable for a cement raw material, so that incinerated fly ash generated in large quantities can be effectively recycled. It becomes possible.
[Brief description of the drawings]
FIG. 1 is a process diagram showing a treatment method of the present invention.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10922198A JP3965769B2 (en) | 1998-04-20 | 1998-04-20 | Fly ash treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10922198A JP3965769B2 (en) | 1998-04-20 | 1998-04-20 | Fly ash treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11300310A JPH11300310A (en) | 1999-11-02 |
| JP3965769B2 true JP3965769B2 (en) | 2007-08-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10922198A Expired - Fee Related JP3965769B2 (en) | 1998-04-20 | 1998-04-20 | Fly ash treatment method |
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| JP (1) | JP3965769B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5716892B2 (en) * | 2010-11-30 | 2015-05-13 | 三菱マテリアル株式会社 | Cleaning method of sludge |
| CN111018376A (en) * | 2019-11-20 | 2020-04-17 | 浙江工业大学 | Household garbage incineration fly ash washing dechlorinating device and tail water discharging method |
| JP7056791B1 (en) * | 2021-10-14 | 2022-04-19 | 住友大阪セメント株式会社 | Waste treatment equipment and waste treatment method |
| JP7056793B1 (en) * | 2021-10-14 | 2022-04-19 | 住友大阪セメント株式会社 | Waste treatment equipment and waste treatment method |
| JP7056792B1 (en) * | 2021-10-14 | 2022-04-19 | 住友大阪セメント株式会社 | Waste treatment equipment and waste treatment method |
-
1998
- 1998-04-20 JP JP10922198A patent/JP3965769B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| JPH11300310A (en) | 1999-11-02 |
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