JP7411429B2 - Method for evaluating suitability of waste treatment and method for insolubilizing waste - Google Patents
Method for evaluating suitability of waste treatment and method for insolubilizing waste Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims description 100
- 238000000034 method Methods 0.000 title claims description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 46
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 239000011669 selenium Substances 0.000 claims description 17
- 229960002089 ferrous chloride Drugs 0.000 claims description 16
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 4
- 229940065287 selenium compound Drugs 0.000 claims description 2
- 150000003343 selenium compounds Chemical class 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 50
- 239000000292 calcium oxide Substances 0.000 description 25
- 235000012255 calcium oxide Nutrition 0.000 description 25
- 239000002956 ash Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 238000010828 elution Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002440 industrial waste Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Description
本発明は、廃棄物の不溶化処理方法に関する。 The present invention relates to a method for insolubilizing waste.
廃棄物から、有害物質の溶出を抑制する処理方法として、不溶化材を混合する方法が知られている。
例えば、特許文献１には、Ｓｅ含有灰に第一塩鉄を添加、混練することにより、該Ｓｅ含有灰からのＳｅの溶出を防止するＳｅ含有灰の処理方法において、該Ｓｅ含有灰にアルカリを添加して該Ｓｅ含有灰をｐＨ１１以上とした後、ｐＨ１１以上を維持した状態で第一鉄塩の添加、混練を行うことを特徴とするＳｅ含有灰の処理方法が記載されている。
また、特許文献２には、重金属類を含む焼却灰、酸化マグネシウム含有物質、鉄化合物、及び水を含むことを特徴とする固化不溶化体が記載されている。該固化不溶化体は、重金属類を含む焼却灰を含むにもかかわらず、重金属類の溶出量が低く、土工資材として使用しても、土壌が重金属類によって汚染されるおそれがないものである。
A method of mixing an insolubilizing material is known as a treatment method for suppressing the elution of harmful substances from waste.
For example, Patent Document 1 describes a method for treating Se-containing ash that prevents the elution of Se from the Se-containing ash by adding and kneading ferrous chloride to the Se-containing ash. A method for treating Se-containing ash is described, which comprises adding ferrous salt to make the pH of the Se-containing ash at least 11, and then adding and kneading the ferrous salt while maintaining the pH at 11 or higher.
Further, Patent Document 2 describes a solidified insolubilized body characterized by containing incineration ash containing heavy metals, a substance containing magnesium oxide, an iron compound, and water. Although the solidified insolubilized material contains incineration ash containing heavy metals, the amount of heavy metals eluted is low, and even if it is used as an earthwork material, there is no risk of contaminating the soil with heavy metals.
廃棄物には、様々な種類があり、廃棄物の種類やその成分組成によっては、不溶化処理の効果に違いが生じる場合がある。
本発明の目的は、廃棄物に含まれている重金属類を不溶化することができる方法を提供することである。
There are various types of waste, and the effect of insolubilization treatment may vary depending on the type of waste and its component composition.
An object of the present invention is to provide a method capable of insolubilizing heavy metals contained in waste.
本発明者は、上記課題を解決するために鋭意検討した結果、重金属類を含む廃棄物と、塩化第一鉄を主成分として含む重金属類不溶化材を混合して、廃棄物に含まれている重金属類を不溶化する方法であって、廃棄物に含まれている、ＳＯ３とＣａＯの質量比、及び、ＳＯ３とＡｌ２Ｏ３の質量比が特定の数値範囲内である方法によれば、上記目的を達成できることを見出し、本発明を完成した。
すなわち、本発明は、以下の［１］～［５］を提供するものである。
［１］ 重金属類を含む廃棄物と、塩化第一鉄を主成分として含む重金属類不溶化材を混合して、上記廃棄物に含まれている重金属類を不溶化する方法であって、上記廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０４～０．５０であり、かつ、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０６～１１．５であることを特徴とする廃棄物の不溶化処理方法。
［２］ 上記廃棄物が、該廃棄物の生成前の材料を６００～１，３００℃で加熱したことによって生成されたものである前記［１］に記載の廃棄物の不溶化処理方法。
［３］ 上記廃棄物に含まれる重金属類が、セレンまたはセレン化合物である前記［１］または［２］に記載の廃棄物の不溶化処理方法。
［４］ 上記重金属類不溶化材が、２０℃の条件下で、上記重金属類不溶化材と蒸留水を、質量比（塩化第一鉄／蒸留水）が１／１０となる量で混合し攪拌した後、３時間経過した際のｐＨが２．０～３．０であるものである前記［１］～［３］のいずれかに記載の廃棄物の不溶化処理方法。
［５］ 上記廃棄物の元素組成を測定して、上記廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）、及び、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）を測定する測定工程と、上記廃棄物が、上記廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０４～０．５０であり、かつ、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０６～１１．５の範囲内であるという条件を満たしているかを調べて、上記廃棄物が上記条件を満たしている場合に、上記廃棄物を、上記重金属類不溶化材との混合による不溶化処理の対象物とし、上記廃棄物が上記条件を満たしていない場合に、上記廃棄物を、上記廃棄物単独では、上記重金属類不溶化材との混合による不溶化処理の対象物とはしないと判定する判定工程を含む、廃棄物の処理の適否の評価方法。
As a result of intensive studies to solve the above problems, the inventor of the present invention mixed waste containing heavy metals with a heavy metal insolubilizing material containing ferrous chloride as a main component, and solved the problem. According to a method of insolubilizing heavy metals, the mass ratio of SO 3 to CaO and the mass ratio of SO 3 to Al 2 O 3 contained in waste are within a specific numerical range. , has discovered that the above object can be achieved, and has completed the present invention.
That is, the present invention provides the following [1] to [5].
[1] A method for insolubilizing heavy metals contained in the waste by mixing waste containing heavy metals and a heavy metal insolubilizing material containing ferrous chloride as a main component, the method comprising: The mass ratio of SO 3 and CaO ( SO 3 /CaO) contained in ) is 0.06 to 11.5.
[2] The method for insolubilizing waste according to [1] above, wherein the waste is produced by heating the material before the waste is produced at 600 to 1,300°C.
[3] The method for insolubilizing waste according to [1] or [2] above, wherein the heavy metals contained in the waste are selenium or a selenium compound.
[4] The heavy metal insolubilizing material was prepared by mixing the heavy metal insolubilizing material and distilled water at 20°C in an amount such that the mass ratio (ferrous chloride/distilled water) was 1/10 and stirring the mixture. The method for insolubilizing waste according to any one of [1] to [3] above, wherein the pH after 3 hours has passed since then is 2.0 to 3.0.
[5] Measure the elemental composition of the waste and determine the mass ratio of SO 3 to CaO (SO 3 /CaO) and the mass ratio of SO 3 to Al 2 O 3 ( a measurement step of measuring SO 3 /Al 2 O 3 ), and the waste has a mass ratio of SO 3 to CaO (SO 3 /CaO) of 0.04-0.50. and the mass ratio of SO 3 and Al 2 O 3 (SO 3 /Al 2 O 3 ) is within the range of 0.06 to 11.5. If the above conditions are met, the above waste is subjected to insolubilization treatment by mixing with the above heavy metal insolubilizing material, and if the above waste does not meet the above conditions, the above waste is A method for evaluating the suitability of waste treatment, including a determination step of determining that waste alone is not a target for insolubilization treatment by mixing with the heavy metal insolubilization material.
本発明の方法によれば、廃棄物に含まれている重金属類を不溶化することができる。 According to the method of the present invention, heavy metals contained in waste can be insolubilized.
本発明の廃棄物の不溶化処理方法は、重金属類を含む廃棄物と、塩化第一鉄を主成分として含む重金属類不溶化材を混合して、廃棄物に含まれている重金属類を不溶化する方法であって、廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０４～０．５０であり、かつ、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０６～１１．５である方法である。
不溶化処理の対象となる重金属類としては、例えば、土壌汚染対策法（平成１５年）に規定されている第二種特定有害物質が挙げられ、具体的には、カドミウム及びその化合物、シアン化合物、六価クロム化合物、水銀及びその化合物、セレン及びその化合物、鉛及びその化合物、ひ素及びその化合物、ふっ素及びその化合物、および、ほう素及びその化合物が挙げられる。
重金属類の中でも、不溶化処理が難しく、比較的に問題となりやすい金属元素であるにもかかわらず、不溶化することができる観点から、セレン及びその化合物が好適である。
これらは、廃棄物中に、１種含まれていてもよく、２種以上含まれていてもよい。
The waste insolubilization treatment method of the present invention is a method for insolubilizing heavy metals contained in waste by mixing waste containing heavy metals with a heavy metal insolubilizing material containing ferrous chloride as a main component. The mass ratio of SO 3 to CaO (SO 3 /CaO) contained in the waste is 0.04 to 0.50, and the mass ratio of SO 3 to Al 2 O 3 (SO 3 /CaO) is 0.04 to 0.50. 3 /Al 2 O 3 ) is 0.06 to 11.5.
Examples of heavy metals that are subject to insolubilization treatment include Class II specified hazardous substances stipulated in the Soil Contamination Countermeasures Act (2003), specifically cadmium and its compounds, cyanide compounds, Examples include hexavalent chromium compounds, mercury and its compounds, selenium and its compounds, lead and its compounds, arsenic and its compounds, fluorine and its compounds, and boron and its compounds.
Among heavy metals, selenium and its compounds are preferred from the viewpoint of being able to be insolubilized, although they are metal elements that are difficult to insolubilize and are relatively likely to cause problems.
One type or two or more types of these may be contained in the waste.
本明細書中、廃棄物とは、産業廃棄物または一般廃棄物をいう。
産業廃棄物とは、事業活動に伴って生じた廃棄物をいう。
産業廃棄物の例としては、生コンスラッジ、各種汚泥（例えば、下水汚泥、浄水汚泥、製鉄汚泥等）、建築廃材、コンクリート廃材、各種焼却灰（例えば、石炭灰、鶏糞灰、家畜糞灰、バイオマス灰、汚泥焼却灰）、鋳物砂、ロックウール、廃ガラス、高炉２次灰、各種副産物、未利用資源（使用されずに残存した材料等）等が挙げられる。
一般廃棄物とは、産業廃棄物以外の廃棄物をいう。
一般廃棄物の例としては、下水汚泥乾粉、都市ごみ焼却灰、貝殻等が挙げられる。
中でも、重金属類をより不溶化することができる観点から、廃棄物の生成前の材料（例えば、廃棄物が石炭灰であれば、石炭）を６００～１，３００℃（好ましくは６２０～１２５０℃、より好ましくは６５０～１，１００℃、特に好ましくは６５０～１，０００℃）で加熱したことによって生成された廃棄物が好適である。
In this specification, waste refers to industrial waste or general waste.
Industrial waste refers to waste generated from business activities.
Examples of industrial waste include raw concrete sludge, various types of sludge (e.g., sewage sludge, purified water sludge, steel manufacturing sludge, etc.), construction waste, concrete waste, and various types of incineration ash (e.g., coal ash, chicken manure ash, livestock manure ash, biomass). Examples include ash, sludge incineration ash), foundry sand, rock wool, waste glass, secondary blast furnace ash, various by-products, unused resources (unused materials, etc.).
General waste refers to waste other than industrial waste.
Examples of general waste include dried sewage sludge, municipal waste incineration ash, and shells.
Among them, from the viewpoint of making heavy metals more insolubilized, the material before waste generation (for example, coal if the waste is coal ash) is heated at 600 to 1,300°C (preferably 620 to 1,250°C, Waste produced by heating at a temperature of more preferably 650 to 1,100°C, particularly preferably 650 to 1,000°C) is suitable.
廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）は、０．０４～０．５０、好ましくは０．０５～０．４８、より好ましくは０．１０～０．４６、さらに好ましくは０．１１～０．４５、特に好ましくは０．１２～０．４２である。上記質量比が０．０４未満であると、廃棄物からの重金属類の溶出量が大きくなる。上記質量比が０．５０を超えると、廃棄物の溶解性や反応性が高くなるため、重金属類の溶出量の低減が困難となる。
廃棄物に含まれている、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）は、０．０６～１１．５、好ましくは０．１０～１１．３、さらに好ましくは０．１２～１１．２、特に好ましくは０．１５～１１．０である。上記質量比が０．０６未満であると、廃棄物からの重金属類の溶出量が大きくなる。上記質量比が１１．５を超えると、廃棄物の溶解性や反応性が高くなるため、重金属類の溶出量の低減が困難となる。
The mass ratio of SO 3 to CaO (SO 3 /CaO) contained in the waste is 0.04 to 0.50, preferably 0.05 to 0.48, more preferably 0.10 to 0. 46, more preferably 0.11 to 0.45, particularly preferably 0.12 to 0.42. When the mass ratio is less than 0.04, the amount of heavy metals eluted from the waste becomes large. If the mass ratio exceeds 0.50, the solubility and reactivity of the waste will increase, making it difficult to reduce the amount of heavy metals eluted.
The mass ratio of SO 3 and Al 2 O 3 (SO 3 /Al 2 O 3 ) contained in the waste is 0.06 to 11.5, preferably 0.10 to 11.3, more preferably 0.12 to 11.2, particularly preferably 0.15 to 11.0. When the mass ratio is less than 0.06, the amount of heavy metals eluted from the waste becomes large. If the mass ratio exceeds 11.5, the solubility and reactivity of the waste will increase, making it difficult to reduce the amount of heavy metals eluted.
塩化第一鉄を主成分として含む重金属類不溶化材（以下、「重金属類不溶化材」ともいう。）とは、塩化第一鉄を、無水物換算で、好ましくは９０質量％以上、より好ましくは９５質量％以上、特に好ましくは９８質量％以上含むものである。
重金属類不溶化材は、２０℃の条件下で、重金属類不溶化材と蒸留水を、質量比（重金属類不溶化材／蒸留水）が１／１０となる量で混合し攪拌した後、３時間経過した際のｐＨが２．０～３．０（好ましくは２．１～２．９、より好ましくは２．２～２．８）であるものが好ましい。上記ｐＨが２．０未満の重金属類不溶化材は入手が困難である。また、不溶化処理にあたり、使用する設備に制約や制限が生じる場合がある。上記ｐＨが３．０以下であれば、廃棄物からの重金属類の溶出量がより小さくなる。
また、重金属類不溶化材に含まれる塩化第一鉄は、無水物であっても水和物（例えば、塩化第一鉄２水和物、塩化第一鉄４水和物）であってもよい。
A heavy metal insolubilizing material containing ferrous chloride as a main component (hereinafter also referred to as "heavy metal insolubilizing material") refers to a heavy metal insolubilizing material containing ferrous chloride, preferably 90% by mass or more, more preferably 90% by mass or more in terms of anhydride. It contains 95% by mass or more, particularly preferably 98% by mass or more.
The heavy metal insolubilizing material is prepared by mixing the heavy metal insolubilizing material and distilled water at a temperature of 20°C in an amount such that the mass ratio (heavy metal insolubilizing material/distilled water) is 1/10, and stirring the mixture for 3 hours. It is preferable that the pH at the time of heating is 2.0 to 3.0 (preferably 2.1 to 2.9, more preferably 2.2 to 2.8). It is difficult to obtain a heavy metal insolubilizer having a pH of less than 2.0. Further, in the insolubilization treatment, there may be restrictions or restrictions on the equipment used. If the pH is 3.0 or less, the amount of heavy metals eluted from the waste will be smaller.
Further, the ferrous chloride contained in the heavy metal insolubilizing material may be anhydrous or hydrated (for example, ferrous chloride dihydrate, ferrous chloride tetrahydrate). .
また、塩化第一鉄を主成分として含む重金属類不溶化材は、廃棄物からの重金属類の溶出量がより小さくなる観点から粉粒状物であることが好ましい。
ここで、本明細書中、「粉粒状」とは、粉状の材料（０．１ｍｍ未満の粒度を有するもの；粉体）の集合体、粒状の材料（０．１ｍｍ以上の粒度を有するもの；粒体）の集合体、または、粉状の材料および粒状の材料を含む集合体の形態を有することを意味する。また、「粉粒状物」とは、粉体の集合体、粒体の集合体、または、粉体および粒体を含む集合体を意味する。さらに、「粒度」とは、粉体または粒体における最大寸法（例えば、断面がだ円である粒体においては、長軸の寸法をいう。）
Further, the heavy metal insolubilizing material containing ferrous chloride as a main component is preferably in the form of powder or granules from the viewpoint of reducing the amount of heavy metals eluted from waste.
Here, in this specification, "powder-like" refers to an aggregate of powder-like materials (having a particle size of less than 0.1 mm; powder), and granular materials (having a particle size of 0.1 mm or more). It means having the form of an aggregate of particles) or an aggregate containing powdery material and granular material. Moreover, "powder-like material" means an aggregate of powder, an aggregate of granules, or an aggregate containing powder and granules. Furthermore, "particle size" refers to the maximum dimension of powder or granules (for example, in the case of granules with an elliptical cross section, it refers to the dimension of the major axis).
重金属類を含む廃棄物１００質量部に対する、重金属類不溶化材の量（無水物換算）は、好ましくは０．１～２０質量部、より好ましくは０．５～１５質量部、さらに好ましくは、１～１２質量部、特に好ましくは２～１０質量部である。該量が０．１質量部以上であれば、重金属類の溶出をより抑制することができる。該量が２０質量部以下であれば、重金属類不溶化材にかかるコストの過度の上昇を防ぐことができる。 The amount of the heavy metal insolubilizing agent (in terms of anhydride) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 100 parts by mass of waste containing heavy metals. ~12 parts by weight, particularly preferably 2 to 10 parts by weight. If the amount is 0.1 parts by mass or more, the elution of heavy metals can be further suppressed. If the amount is 20 parts by mass or less, an excessive increase in the cost of the heavy metal insolubilizer can be prevented.
上述した廃棄物と塩化第一鉄を主成分として含む重金属類不溶化材を混合することによって、該廃棄物からの重金属類の溶出を抑制することができる。
本発明において、上述した廃棄物と重金属類不溶化材を混合する際に、重金属類の溶出をより抑制する観点から、軽焼マグネシア、軽焼マグネシアの部分水和物、軽焼ドロマイト、又は、軽焼ドロマイトの部分水和物を含む酸化マグネシウム含有物質、並びに、塩化第二鉄、硫酸第一鉄、硫酸第二鉄、ポリ硫酸第二鉄等の鉄化合物等の他の不溶化材（重金属類を不溶化しうるもの）を、さらに混合してもよい。
また、材料にかかるコストを低減する観点から、上述した他の不溶化材を使用せずに、重金属類不溶化材を単独で使用してもよい。
By mixing the above-mentioned waste with a heavy metal insolubilizer containing ferrous chloride as a main component, it is possible to suppress the elution of heavy metals from the waste.
In the present invention, from the viewpoint of further suppressing the elution of heavy metals when mixing the above-mentioned waste with the heavy metal insolubilizer, light burnt magnesia, a partial hydrate of light burnt magnesia, light burnt dolomite, or light burnt dolomite is used. Magnesium oxide-containing substances, including partially hydrated calcined dolomite, and other insolubilizing materials (heavy metals (which can be insolubilized) may be further mixed.
Moreover, from the viewpoint of reducing the cost of materials, the heavy metal insolubilizing agent may be used alone without using the other insolubilizing agents mentioned above.
また、不溶化処理後の廃棄物のｐＨを中性領域（例えば、５．８～８．６）とし、該廃棄物を、土工資材等としての再利用する際に、その用途に制限が生じないようにしたり、不溶化処理後の廃棄物を造粒する（粒度を大きくする）観点から、アルカリ性材料をさらに混合してもよい。
アルカリ性材料の例としては、各種セメント、消石灰、生石灰、石灰石粉末、高炉スラグ微粉末等が挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
In addition, the pH of the waste after insolubilization treatment is in the neutral range (for example, 5.8 to 8.6), so that there are no restrictions on the use when reusing the waste as earthwork materials etc. Alternatively, from the viewpoint of granulating (increasing particle size) the waste after insolubilization treatment, an alkaline material may be further mixed.
Examples of alkaline materials include various cements, slaked lime, quicklime, limestone powder, blast furnace slag powder, and the like. These may be used alone or in combination of two or more.
上述した廃棄物の不溶化処理方法を行う前に、後述する測定工程と判定工程を含む廃棄物の処理の適否の評価方法を行ってもよい。該評価方法を予め行うことで、重金属類を含む廃棄物の効率的な不溶化処理を行うことができる。
［測定工程］
本工程は、重金属類を含む廃棄物の元素組成を測定して、上記廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）、及び、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）を測定する工程である。
［判定工程］
本工程は、上記廃棄物が、上記廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０４～０．５０であり、かつ、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０６～１１．５の範囲内であるという条件を満たしているかを調べて、上記廃棄物が上記条件を満たしている場合に、上記廃棄物を、上述した重金属類不溶化材との混合による不溶化処理の対象物とし、上記廃棄物が上記条件を満たしていない場合に、上記廃棄物を、上記廃棄物単独では、上記重金属類不溶化材との混合による不溶化処理の対象物とはしないと判定する工程である。
本工程において、上記廃棄物を、上記廃棄物単独では、上記重金属類不溶化材との混合による不溶化処理の対象物とはしないとした場合、上記廃棄物に、他の種類の廃棄物等を添加し混合することで、混合後の廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０４～０．５０となり、かつ、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０６～１１．５の範囲内となるように調整したり、塩化第一鉄を主成分として含む重金属類不溶化材と、他の不溶化材（例えば、酸化マグネシウム含有物質）を組み合わせたうえで、不溶化処理を行ってもよい。
Before performing the waste insolubilization treatment method described above, a method for evaluating the suitability of waste treatment including a measurement step and a determination step, which will be described later, may be performed. By performing this evaluation method in advance, wastes containing heavy metals can be efficiently insolubilized.
[Measurement process]
In this step, the elemental composition of waste containing heavy metals is measured, and the mass ratio of SO 3 and CaO (SO 3 /CaO) and SO 3 and Al 2 O 3 contained in the waste are determined. This is a step of measuring the mass ratio (SO 3 /Al 2 O 3 ).
[Judgment process]
In this step, the waste has a mass ratio of SO 3 and CaO (SO 3 /CaO) of 0.04 to 0.50, and SO 3 and Al 2 O It is checked whether the mass ratio of 3 (SO 3 /Al 2 O 3 ) is within the range of 0.06 to 11.5, and if the waste satisfies the above condition, the above If the waste is to be insolubilized by mixing it with the above-mentioned heavy metal insolubilizing material, and if the waste does not meet the above conditions, the waste alone cannot be treated with the heavy metal insolubilizing material. This is the process of determining that the substance is not to be subjected to insolubilization treatment by mixing with.
In this process, if the above waste alone is not subject to insolubilization treatment by mixing with the above heavy metal insolubilizing material, other types of waste, etc. are added to the above waste. By mixing, the mass ratio of SO 3 and CaO (SO 3 /CaO) contained in the mixed waste becomes 0.04 to 0.50, and the mass ratio of SO 3 and Al 2 O 3 The mass ratio (SO 3 /Al 2 O 3 ) may be adjusted to be within the range of 0.06 to 11.5, or a heavy metal insolubilizing material containing ferrous chloride as a main component and other insolubilizing materials ( For example, insolubilization treatment may be performed after combining magnesium oxide-containing substances).
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
［使用材料］
（１）廃棄物１～１２：廃棄物生成前の材料を８００～１，０００℃で加熱してなる、セレン及びその化合物を含む廃棄物（焼却灰）、各廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）、及び、環境省告示第１８号に準拠して測定した不溶化処理前の廃棄物からのセレン及びその化合物の溶出量（表１中、「セレンの溶出量」と示す。）を表１に示す。
（２）不溶化材１～２：塩化第一鉄を９８質量％以上含む粉粒状物、また、２０℃の条件下で、不溶化材と蒸留水を、質量比（不溶化材／蒸留水）が１／１０となる質量で混合し攪拌して検液を得た後、３時間経過した際の検液のｐＨを、「ＪＩＳ Ｋ ０１０２：２０１３（工場排水試験方法）」１２．１ガラス電極法に準拠して測定した結果を表１に示す。
EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
[Materials used]
(1) Wastes 1 to 12: Wastes containing selenium and its compounds (incineration ash) obtained by heating materials before waste generation at 800 to 1,000°C, contained in each waste, Mass ratio of SO 3 and CaO (SO 3 /CaO), mass ratio of SO 3 and Al 2 O 3 (SO 3 /Al 2 O 3 ), and insolubilization treatment measured in accordance with Ministry of the Environment Notification No. 18 Table 1 shows the amounts of selenium and its compounds eluted from the previous waste (indicated as "selenium elution amount" in Table 1).
(2) Insolubilizing material 1 to 2: Powder containing 98% by mass or more of ferrous chloride, and the mass ratio (insolubilizing material/distilled water) of the insolubilizing material and distilled water at 20°C is 1. /10 by mixing and stirring to obtain a test solution, and after 3 hours, the pH of the test solution was determined according to "JIS K 0102:2013 (factory wastewater test method)" 12.1 glass electrode method. Table 1 shows the results measured in accordance with the above.
［実施例１～７、比較例１～５］
表１に示す種類の廃棄物及び不溶化材を、廃棄物１００質量部に対して、不溶化材が５
質量部となる量（無水物換算）で、同時にホバート社製の縦型ミキサに投入した後、３分間混合して、不溶化処理を行った。
不溶化処理後の廃棄物からのセレン及びその化合物の溶出量を、環境省告示第１８号に準拠して測定した。結果を表１に示す。
[Examples 1 to 7, Comparative Examples 1 to 5]
The types of waste and insolubilizing material shown in Table 1 are added to 100 parts by mass of waste, and 5 parts of the insolubilizing material is
Parts by mass (in terms of anhydride) were simultaneously charged into a vertical mixer manufactured by Hobart, and mixed for 3 minutes to perform an insolubilization treatment.
The amount of selenium and its compounds eluted from the waste after the insolubilization treatment was measured in accordance with Ministry of the Environment Notification No. 18. The results are shown in Table 1.
表１から、実施例１～７（廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０５～０．４０であり、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．１７～１０．９であるもの）では、不溶化処理後の廃棄物からのセレン及びその化合物の溶出量は、環境省告示第１８号で規定されたセレン及びその化合物の溶出基準値（０．０１ｍｇ／リットル以下）を満たしていることがわかる。
一方、比較例１～５（廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０１～０．０７であり、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０１～０．０４であるもの）では、不溶化処理後の廃棄物からのセレンの溶出量は、環境省告示第１８号で規定されたセレン及びその化合物の溶出基準値（０．０１ｍｇ／リットル以下）を満たしていないことがわかる。
From Table 1, it can be seen that in Examples 1 to 7 (the mass ratio of SO 3 and CaO (SO 3 /CaO) contained in the waste was 0.05 to 0.40, and the mass ratio of SO 3 and Al 2 O 3 When the mass ratio (SO 3 /Al 2 O 3 ) is 0.17 to 10.9), the amount of selenium and its compounds eluted from waste after insolubilization treatment is specified in Ministry of the Environment Notification No. 18. It can be seen that the elution standard values for selenium and its compounds (0.01 mg/liter or less) were met.
On the other hand, Comparative Examples 1 to 5 (the mass ratio of SO 3 to CaO (SO 3 /CaO) contained in the waste is 0.01 to 0.07, and the mass ratio of SO 3 to Al 2 O 3 is (SO 3 /Al 2 O 3 ) is 0.01 to 0.04), the amount of selenium eluted from the waste after insolubilization treatment is the It can be seen that the elution standard value (0.01 mg/liter or less) of the compound is not met.
Claims (4)
上記廃棄物が、上記廃棄物に含まれている、ＳＯ３とＣａＯの質量比（ＳＯ３／ＣａＯ）が０．０４～０．５０であり、かつ、ＳＯ３とＡｌ２Ｏ３の質量比（ＳＯ３／Ａｌ２Ｏ３）が０．０６～１１．５の範囲内であるという条件を満たしているかを調べて、上記廃棄物が上記条件を満たしている場合に、上記廃棄物を、塩化第一鉄を主成分として含む重金属類不溶化材との混合による不溶化処理の対象物とし、上記廃棄物が上記条件を満たしていない場合に、上記廃棄物を、上記廃棄物単独では、上記重金属類不溶化材との混合による不溶化処理の対象物とはしないと判定する判定工程を含み、
上記廃棄物が、該廃棄物の生成前の材料を６００～１，３００℃で加熱したことによって生成されたものである、廃棄物の処理の適否の評価方法。 The elemental composition of waste containing heavy metals is measured to determine the mass ratio of SO 3 to CaO (SO 3 /CaO) and the mass ratio of SO 3 to Al 2 O 3 ( a measurement step of measuring SO 3 /Al 2 O 3 );
The waste has a mass ratio of SO 3 and CaO (SO 3 /CaO) of 0.04 to 0.50, and a mass ratio of SO 3 and Al 2 O 3 contained in the waste. It is checked whether the condition that (SO 3 /Al 2 O 3 ) is within the range of 0.06 to 11.5 is satisfied, and if the waste satisfies the above condition, the waste is If the waste is subject to insolubilization treatment by mixing it with a heavy metal insolubilizer containing ferrous chloride as a main component , and the waste does not meet the above conditions, the waste alone does not contain the heavy metals. including a determination step of determining that it is not a target for insolubilization treatment by mixing with a similar insolubilizing material,
A method for evaluating the suitability of waste treatment, wherein the waste is generated by heating a material before the waste is generated at 600 to 1,300°C .
上記判定工程において不溶化処理の対象物と判定した上記廃棄物と、上記重金属類不溶化材を混合して、上記廃棄物に含まれている重金属類を不溶化する廃棄物の不溶化処理方法。 After evaluating the suitability of waste treatment by the method for evaluating suitability of waste treatment according to claim 1,
A method for insolubilizing waste, which comprises mixing the waste determined as a target for insolubilization treatment in the determination step with the heavy metal insolubilizing material to insolubilize heavy metals contained in the waste.
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