JP4020511B2 - Waste incineration residue treatment method - Google Patents
Waste incineration residue treatment method Download PDFInfo
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- JP4020511B2 JP4020511B2 JP27307198A JP27307198A JP4020511B2 JP 4020511 B2 JP4020511 B2 JP 4020511B2 JP 27307198 A JP27307198 A JP 27307198A JP 27307198 A JP27307198 A JP 27307198A JP 4020511 B2 JP4020511 B2 JP 4020511B2
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- molten slag
- incineration
- zirconium
- lead
- melting
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- 238000000034 method Methods 0.000 title claims description 20
- 238000004056 waste incineration Methods 0.000 title description 4
- 239000002893 slag Substances 0.000 claims description 40
- 239000002699 waste material Substances 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 description 22
- 230000008018 melting Effects 0.000 description 22
- 238000010828 elution Methods 0.000 description 14
- 229910001385 heavy metal Inorganic materials 0.000 description 13
- 230000007613 environmental effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000002956 ash Substances 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 zirconium alkoxide Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Gasification And Melting Of Waste (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、廃棄物を焼却する際に発生する焼却灰及び飛灰などの焼却残渣の溶融方法に関するものであり、さらに詳しくは、発生した溶融スラグから有害重金属類がほとんど溶出しない廃棄物の焼却残渣の溶融方法に関するものである。
【０００２】
【従来の技術】
わが国において廃棄物の処理は、埋立処分場の確保が困難であるという事情から、焼却処理が一般的に採用され、廃棄物を焼却により減容させた後に埋立処分が行われている。また、地球規模での環境問題への取り組みの高まりから、リサイクル方法の一つとして、廃棄物を燃焼し、発生したエネルギーを回収するサーマルリサイクルが行われるようになってきている。
廃棄物を焼却処理することにより、廃棄物中の可燃物はガス化し、不燃物すなわち灰分は残渣として排出される。これらの残渣中には、有害な重金属類やダイオキシン類が含まれているため、残渣をそのまま埋立処分すると、有害物質が溶出するという問題がある。そこで、これらの問題点を解決し、さらに、残渣を減量化する方法として、残渣を溶融固化処理して溶融スラグとする方法が提案されている。さらに、発生した溶融スラグを路盤材、コンクリート用骨材、埋め戻し材、コンクリート二次製品等に再利用することが提案されており、すでに路盤材などに利用し始めている地域もある。
【０００３】
【発明が解決しようとする課題】
しかしながら、溶融固化処理によりダイオキシン類は分解するものの、重金属類はそのまま溶融スラグに含まれているため、できた溶融スラグを用いた２次製品から有害物質が溶出してくる可能性があり、溶融スラグから有害物質の溶出を完全に抑制する必要がある。さらに、平成１０年４月には、溶融スラグの再利用に関する指針値が自治体に対し通達され、鉛を含む有害物質の溶出が規制され始めた。
【０００４】
廃棄物の焼却残渣を高温溶融固化する際に添加する溶融助剤としては、特開昭６１−２３８３８７号公報や特開平４−３２１５３９号公報には、塩基度やナトリウム含有量を調整することにより溶融スラグの溶流点を低下し、溶融固化に必要なエネルギーを低減させることができることや、特公昭６１−１５９３４号公報や特開平８−８９９２３号公報には、ケイ素源や金属が、スラグ層やメタル層から特定元素を減少させることができることなどが提案されているが、これらの溶融助剤はいずれも、溶融スラグからの有害物質の溶出を抑制することを目的とするものではなかった。
本発明は、発生する溶融スラグから重金属類がほとんど溶出しない廃棄物の焼却残渣の処理方法を提供することを目的とするものである。
【０００５】
【課題を解決するための手段】
本発明者は、このような課題を解決するために鋭意検討の結果、ジルコニウム含有物を廃棄物の焼却残渣に添加して高温溶融固化後、磁性成分を除去することにより、発生した溶融スラグから重金属類がほとんど溶出しないということを見いだし、本発明に到達した。
【０００６】
すなわち、本発明は廃棄物の焼却残渣にジルコニウム含有物を添加して溶融固化処理することで廃棄物の焼却残渣に含まれる鉛をメタル中に移行させた後、処理物から磁性成分を除去することにより溶融スラグから鉛を取り除くことを特徴とする焼却残渣の処理方法を要旨とするものである。
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明における廃棄物の焼却残渣とは、一般廃棄物、産業廃棄物、下水汚泥などを焼却して生じる焼却灰及び排ガスから集塵機などで収集した飛灰など、焼却工程で生じるガス以外の成分すべてである。また、ガス化溶融炉や直接溶融炉のように、焼却工程における焼却残渣を一旦取り出さないで溶融固化する場合にも適用することが可能である。
【０００８】
本発明においては、まず、ジルコニウム含有物を廃棄物の焼却残渣に添加する。添加するジルコニウム化合物としては、特に限定されるものではなく、ジルコニウム、酸化ジルコニウム、炭化ジルコニウム、オキシ塩化ジルコニウム、ジルコニウムアルコキシド、窒化ジルコニウム、けい酸ジルコニウム、塩化ジルコニウム、水素化ジルコニウム、硝酸ジルコニウム、ほう化ジルコニウムなどがあげられる。また、ジルコニウム含有物の添加量としては、酸化物換算で全重量の０.５〜１０％、好ましくは１〜５％である。ジルコニウム含有物の添加量が上記の範囲以下では、重金属類の溶出防止効果が少なくなり、また、範囲以上であっても添加量が増加するのみで著しい効果は得られないため好ましくない。
【０００９】
次に、ジルコニウム含有物を添加した廃棄物の焼却残渣を溶融処理後、水砕又は空冷して固化する。焼却残渣の溶融方法としては、重油、灯油、ガス、コークスなどの補助燃料を用いて溶融する方法、アーク式、プラズマ式、電気抵抗式、低周波誘導式などのような電気を熱源とした溶融方法及び熱分解溶融やコークスベット方式のような直接溶融方法などがあげられる。また、溶融温度としては、焼却残渣が溶融する温度であれば特に限定されるものではないが、１１００〜１５００℃程度で溶融することが好ましく、溶融時間としては、溶融方法に応じて適宜選択することが好ましく、通常１０分〜１０時間溶融すればよい。
【００１０】
次に、このような方法によって調製した処理物には、溶融スラグとメタルが含まれているので、磁性成分を除去することによってメタルを除去する。磁性成分の分離は、必要に応じて処理物を破砕してから行ってもよい。磁性成分の除去方法としては、永久磁石、電磁石をクロスベルト式、回転ドラム式などの磁選機を用いて行うことができる。
本発明においては、ジルコニウムの存在下で焼却残渣を溶融固化処理する際に溶融スラグ中から重金属類、特に鉛がメタル中へ移行するため、溶融スラグ中の重金属類の含有濃度が低下するものと考えられる。
【００１１】
図１は、様々な条件により調製した溶融スラグ中の鉛の含有量と、「土壌の汚染に係る環境基準について」（平成３年環境庁告示第４６号）に定める方法により測定した溶融スラグからの鉛の溶出濃度との関係を示す図である。この図から、溶融スラグ中の鉛の含有量と溶融スラグからの鉛の溶出量には、おおよそ正の相関があることがわかる。このため、本発明においては、発生する溶融スラグ中の重金属の含有濃度が低下しているので、溶融スラグから重金属類がほとんど溶出しない。そして、「土壌の汚染に係る環境基準について」（平成３年環境庁告示第４６号）に定める方法により溶出試験を行った場合の溶融スラグからの各重金属類の溶出濃度を以下の表１に示す値以下にすることができる。
【００１２】
【表１】
このように、本発明の方法によって発生する溶融スラグからは重金属類、特に溶融スラグからの溶出の可能性の高い鉛の溶出が防止されているため、様々な用途への再利用が可能である。
【００１４】
【実施例】
次に、本発明を実施例により具体的に説明する。
実施例１
表２に示す組成を有するストーカ式焼却場から発生した焼却灰と飛灰を混合した焼却残渣（ＰｂＯを焼却残渣に対し０.３重量％添加し、Ｐｂ含有量を増加してある。）２５０ｇに対し、酸化ジルコニウム２.５ｇを添加、混合した。
小型電気炉にるつぼを入れ、昇温して１３５０℃に保持し、調製した焼却残渣を投入して、３０分間溶融し、溶融処理物を水１０リットルに注ぎ入れ、水砕スラグとした。この水砕スラグを１０５℃で２４時間乾燥した後、粉砕し、永久磁石を用いて磁性成分を除去した。
【００１５】
【表２】
この溶融スラグ中（磁性成分を除去した水砕スラグ）の鉛の含有量をＩＣＰ（高周波誘導結合プラズマ）発光分析法で測定した結果、溶融スラグ中には０.０７ｍｇ／ｇの鉛しか含有されていなかった。また、この溶融スラグからの鉛の溶出量を環境庁告示４６号法に基づいて測定した結果、鉛の溶出は検出限界以下（＜０.００５ｍｇ／ｌ）であった。
【００１７】
比較例１
酸化ジルコニウムを添加しないで行った以外は、実施例１と同様にして、溶融スラグを調製し、この溶融スラグの鉛の含有量及び溶融スラグからの鉛の溶出量を実施例１と同様にして測定した結果、溶融スラグ中には１.５ｍｇ／ｇの鉛が含有されており、溶出液には０.０２５ｍｇ／ｌの鉛の溶出が認められた。
【００１８】
【発明の効果】
本発明によれば、焼却残渣を溶融固化処理して発生する溶融スラグから重金属類がほとんど溶出しないため、発生する溶融スラグの再利用が容易となる。
【図面の簡単な説明】
【図１】溶融スラグ中の鉛の含有量と、溶融スラグからの鉛の溶出濃度との関係を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for melting incineration residues such as incineration ash and fly ash generated when incinerating waste, and more specifically, incineration of waste from which almost no harmful heavy metals are eluted from the generated molten slag. The present invention relates to a residue melting method.
[0002]
[Prior art]
In Japan, incineration treatment is generally adopted for the disposal of waste because it is difficult to secure a landfill site, and landfill disposal is performed after the volume of waste is reduced by incineration. In addition, with increasing efforts to deal with environmental problems on a global scale, thermal recycling has been performed as one of the recycling methods to burn waste and recover the generated energy.
By incinerating the waste, combustibles in the waste are gasified, and incombustibles, that is, ash, are discharged as residues. Since these residues contain harmful heavy metals and dioxins, there is a problem in that harmful substances are eluted when the residue is disposed as landfill. Thus, as a method for solving these problems and further reducing the amount of the residue, a method of melting and solidifying the residue to obtain a molten slag has been proposed. Furthermore, it has been proposed to reuse the generated molten slag for roadbed materials, concrete aggregates, backfill materials, concrete secondary products, etc., and some areas have already begun to be used for roadbed materials.
[0003]
[Problems to be solved by the invention]
However, although dioxins are decomposed by melting and solidifying treatment, heavy metals are contained in the molten slag as they are, so there is a possibility that harmful substances may be eluted from the secondary product using the molten slag. It is necessary to completely suppress the elution of harmful substances from the slag. Furthermore, in April 1998, a guideline value regarding the reuse of molten slag was notified to local governments, and the elution of harmful substances including lead began to be regulated.
[0004]
As a melting aid to be added when waste incineration residue is melted at high temperature, Japanese Patent Application Laid-Open No. 61-238387 and Japanese Patent Application Laid-Open No. 4-321539 can adjust the basicity and sodium content. The melting point of the molten slag can be lowered and the energy required for melting and solidification can be reduced. In Japanese Patent Publication No. 61-15934 and Japanese Patent Laid-Open No. 8-89923, a silicon source or a metal is added to the slag layer. Although it has been proposed that specific elements can be reduced from metal layers and metal layers, none of these melting aids was intended to suppress the elution of harmful substances from molten slag.
An object of this invention is to provide the processing method of the incineration residue of the waste material from which heavy metals are hardly eluted from the molten slag to generate | occur | produce.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve such problems, the present inventor has added zirconium-containing materials to the incineration residue of waste, and after high-temperature melting and solidification, the magnetic components are removed from the generated molten slag. The inventors have found that heavy metals hardly elute and have reached the present invention.
[0006]
That is, the present invention removes the magnetic component from the treated product by transferring the lead contained in the incinerated residue of the waste into the metal by adding a zirconium-containing material to the incinerated residue of the waste and subjecting it to solidification treatment. The main point is a method for treating incineration residues, characterized in that lead is removed from molten slag .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
Incineration residue of waste in the present invention refers to all components other than gas generated in the incineration process, such as incineration ash generated by incineration of general waste, industrial waste, sewage sludge, etc. and fly ash collected from exhaust gas with a dust collector, etc. It is. Further, the present invention can also be applied to the case where the incineration residue in the incineration process is melted and solidified without being taken out once, such as a gasification melting furnace or a direct melting furnace.
[0008]
In the present invention, first, the zirconium-containing material is added to the waste incineration residue. The zirconium compound to be added is not particularly limited. Zirconium, zirconium oxide, zirconium carbide, zirconium oxychloride, zirconium alkoxide, zirconium nitride, zirconium silicate, zirconium chloride, zirconium hydride, zirconium nitrate, zirconium boride Etc. The amount of the zirconium-containing material added is 0.5 to 10%, preferably 1 to 5% of the total weight in terms of oxide. If the addition amount of the zirconium-containing material is not more than the above range, the effect of preventing the elution of heavy metals is reduced.
[0009]
Next, the waste incineration residue to which the zirconium-containing material is added is melted and then solidified by water granulation or air cooling. Incineration residue melting methods include melting using auxiliary fuels such as heavy oil, kerosene, gas, coke, etc., melting using electricity as a heat source such as arc type, plasma type, electric resistance type, low frequency induction type, etc. And direct melting methods such as pyrolysis melting and coke bed method. In addition, the melting temperature is not particularly limited as long as the incineration residue is melted. However, the melting temperature is preferably about 1100 to 1500 ° C., and the melting time is appropriately selected according to the melting method. It is preferable that melting is usually performed for 10 minutes to 10 hours.
[0010]
Next, since the processed product prepared by such a method contains molten slag and metal, the metal is removed by removing the magnetic component. Separation of the magnetic component may be performed after crushing the processed product as necessary. As a method for removing the magnetic component, permanent magnets and electromagnets can be used using a magnetic separator such as a cross belt type or a rotating drum type.
In the present invention, when the incineration residue is melted and solidified in the presence of zirconium, heavy metals, particularly lead migrates into the metal from the molten slag, so that the concentration of heavy metals in the molten slag decreases. Conceivable.
[0011]
Figure 1 shows the content of lead in molten slag prepared under various conditions and the molten slag measured by the method specified in "Environmental standards for soil contamination" (Environmental Agency Notification No. 46 of 1991). It is a figure which shows the relationship with the elution density | concentration of lead. From this figure, it can be seen that there is a roughly positive correlation between the lead content in the molten slag and the lead elution amount from the molten slag. For this reason, in this invention, since the content concentration of the heavy metal in the molten slag to generate | occur | produce is falling, heavy metals are hardly eluted from molten slag. Table 1 below shows the elution concentration of each heavy metal from molten slag when the elution test was conducted according to the method specified in “Environmental Standards Concerning Soil Contamination” (Environmental Agency Notification No. 46, 1991). It can be less than or equal to the value shown.
[0012]
[Table 1]
In this way, the molten slag generated by the method of the present invention prevents the elution of heavy metals, particularly lead, which has a high possibility of elution from the molten slag, and can be reused for various purposes. .
[0014]
【Example】
Next, the present invention will be specifically described with reference to examples.
Example 1
250 g of incineration residue mixed with incineration ash and fly ash generated from a stoker-type incineration plant having the composition shown in Table 2 (PbO was added in an amount of 0.3% by weight to the incineration residue to increase the Pb content) 250 g On the other hand, 2.5 g of zirconium oxide was added and mixed.
A crucible was placed in a small electric furnace, heated to 1350 ° C., the prepared incineration residue was charged, melted for 30 minutes, and the melted product was poured into 10 liters of water to obtain granulated slag. The granulated slag was dried at 105 ° C. for 24 hours, then pulverized, and the magnetic component was removed using a permanent magnet.
[0015]
[Table 2]
As a result of measuring the lead content in the molten slag (granulated slag from which magnetic components had been removed) by ICP (high frequency inductively coupled plasma) emission spectrometry, the molten slag contained only 0.07 mg / g of lead. It wasn't. Moreover, as a result of measuring the elution amount of lead from the molten slag based on the Environmental Agency Notification No. 46 method, the elution of lead was below the detection limit (<0.005 mg / l).
[0017]
Comparative Example 1
A molten slag was prepared in the same manner as in Example 1 except that zirconium oxide was not added. The lead content of this molten slag and the amount of lead eluted from the molten slag were the same as in Example 1. As a result of measurement, 1.5 mg / g of lead was contained in the molten slag, and elution of 0.025 mg / l of lead was observed in the eluate.
[0018]
【The invention's effect】
According to the present invention, since heavy metals hardly elute from the molten slag generated by melting and solidifying the incineration residue, the generated molten slag can be easily reused.
[Brief description of the drawings]
FIG. 1 is a diagram showing the relationship between the content of lead in molten slag and the elution concentration of lead from molten slag.
Claims (1)
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| JP27307198A JP4020511B2 (en) | 1998-09-28 | 1998-09-28 | Waste incineration residue treatment method |
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| JP27307198A JP4020511B2 (en) | 1998-09-28 | 1998-09-28 | Waste incineration residue treatment method |
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| CN115261080B (en) * | 2022-09-01 | 2023-10-20 | 西安热工研究院有限公司 | A three-stage solid waste municipal solid waste gasifier and its use method |
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