JP4481360B1 - Insolubilizing material - Google Patents
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- JP4481360B1 JP4481360B1 JP2009232042A JP2009232042A JP4481360B1 JP 4481360 B1 JP4481360 B1 JP 4481360B1 JP 2009232042 A JP2009232042 A JP 2009232042A JP 2009232042 A JP2009232042 A JP 2009232042A JP 4481360 B1 JP4481360 B1 JP 4481360B1
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- 239000000463 material Substances 0.000 title claims abstract description 100
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 169
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 84
- 239000002351 wastewater Substances 0.000 claims abstract description 34
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 20
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 20
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 17
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 230000000887 hydrating effect Effects 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- 235000010755 mineral Nutrition 0.000 claims abstract description 8
- 239000011707 mineral Substances 0.000 claims abstract description 8
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 23
- 239000010440 gypsum Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 47
- 238000010828 elution Methods 0.000 abstract description 37
- 238000011109 contamination Methods 0.000 abstract description 6
- 239000002956 ash Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 229910052785 arsenic Inorganic materials 0.000 description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000010298 pulverizing process Methods 0.000 description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- 235000014380 magnesium carbonate Nutrition 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000010304 firing Methods 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000007922 dissolution test Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- -1 etc. Inorganic materials 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000287828 Gallus gallus Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Processing Of Solid Wastes (AREA)
- Water Treatment By Sorption (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
【課題】汚染濃度の高い土壌や、排水に対して、少ない添加量で、重金属類等の溶出を十分に抑制することができる不溶化材を提供する。
【解決手段】炭酸マグネシウム及び／又は水酸化マグネシウムを主成分とする鉱物を５５０〜１，４００℃で焼成して得た軽焼マグネシアの一部を水和してなる軽焼マグネシア部分水和物であって、該軽焼マグネシア部分水和物中、酸化マグネシウムの含有率が５０〜９６．５質量％、水酸化マグネシウムの含有率が３．５〜５０質量％であり、カルシウムの含有率が酸化物換算で５．０質量％以下である軽焼マグネシア部分水和物を含む不溶化材。
【選択図】なしThe present invention provides an insolubilizing material capable of sufficiently suppressing elution of heavy metals and the like with a small amount of addition to soil or wastewater with high contamination concentration.
A light-burned magnesia partial hydrate obtained by hydrating a part of light-burned magnesia obtained by baking a mineral mainly composed of magnesium carbonate and / or magnesium hydroxide at 550 to 1,400 ° C. In the light-burned magnesia partial hydrate, the magnesium oxide content is 50 to 96.5% by mass, the magnesium hydroxide content is 3.5 to 50% by mass, and the calcium content is An insolubilized material containing light-burned magnesia partial hydrate which is 5.0% by mass or less in terms of oxide.
[Selection figure] None
Description
本発明は、重金属類等を含む汚染土壌等から当該重金属等が溶出するのを抑制したり、あるいは、重金属類等を含む排水中の当該重金属等を不溶化することのできる不溶化材に関する。 The present invention relates to an insolubilizing material capable of suppressing the elution of the heavy metal or the like from contaminated soil containing the heavy metal or the like, or insolubilizing the heavy metal or the like in waste water containing the heavy metal or the like.
近年、工場、事業所、産業廃棄物処理場の跡地などにおいて、土壌が鉛、６価クロム、ヒ素等の重金属類やフッ素等（以下、重金属類等ともいう。）で汚染されていることが、しばしば報告されている。このように土壌が重金属類等で汚染されると、その汚染が地下水にまで広がり、人体や穀物にまで影響を及ぼすという安全衛生上の問題がある。また、当該土壌の汚染濃度が環境基準値を超える場合には、跡地をそのまま利用できなくなり、土地を有効利用することができないという問題もある。そのため、重金属類等を不溶化して、汚染の拡大を防止することが望まれている。
また、重金属類等を含む排水を処理する場合、重金属類等を不溶化することができれば、固液分離によって、重金属類等の含有率が減少した液分を容易に得ることができ、排水処理を効率的に行なうことができる。
In recent years, soil has been contaminated with heavy metals such as lead, hexavalent chromium, and arsenic, fluorine, etc. (hereinafter also referred to as heavy metals) at sites of factories, offices, and industrial waste disposal sites. Often reported. Thus, when soil is contaminated with heavy metals or the like, there is a safety and health problem that the contamination spreads to the ground water and affects the human body and grains. Further, when the soil contamination concentration exceeds the environmental standard value, there is a problem that the site cannot be used as it is and the land cannot be used effectively. Therefore, it is desired to insolubilize heavy metals and the like to prevent the spread of contamination.
In addition, when treating wastewater containing heavy metals, etc., if the heavy metals can be insolubilized, liquid components with a reduced content of heavy metals can be easily obtained by solid-liquid separation, and wastewater treatment can be performed. It can be done efficiently.
このような事情下において、重金属類等を不溶化するための技術が種々提案されている。
例えば、酸化マグネシウムを含む重金属溶出抑制固化材が提案されている（特許文献１）。
また、ＭｇＯおよび／またはＭｇＯ含有材からなることを特徴とする有害物質汚染土壌用固化不溶化剤が提案されている（特許文献２）。
また、７００〜１，０００℃で焼成され、粉末度４，０００ｃｍ２／ｇ以上に調整した酸化マグネシウムを、汚染土壌等に添加・混合することにより、該汚染土壌等を固化して、汚染物質の不溶化を行う汚染土壌等の固化・不溶化方法が提案されている（特許文献３）。
また、固化可能なバインダー中に物質を取り込む方法であって、当該方法が、スラリーとして、又は次のスラリーの形成のために、物質をバインダーと混合する工程を含み、該バインダーが苛性酸化マグネシウム源を含んでおり、及びスラリーに、バインダーの固化を促進する固化剤を加える工程を含む方法が提案されている（特許文献４）。
さらに、波長１．５４０５Åにおける粉末Ｘ線回折スペクトルが、２θ＝４２.８°±０.３°にピークの頂点を有し、該ピークのベースラインを基準とした半値幅が０．３２〜１.５°であることを特徴とする潜晶質マグネシアが提案されている（特許文献５）。
Under such circumstances, various techniques for insolubilizing heavy metals and the like have been proposed.
For example, a heavy metal elution suppression solidifying material containing magnesium oxide has been proposed (Patent Document 1).
Further, a solidifying and insolubilizing agent for toxic substance-contaminated soil characterized by comprising MgO and / or a MgO-containing material has been proposed (Patent Document 2).
In addition, by adding and mixing magnesium oxide baked at 700 to 1,000 ° C. and adjusted to a fineness of 4,000 cm 2 / g or more to the contaminated soil, the contaminated soil is solidified and contaminated. There has been proposed a method for solidifying and insolubilizing contaminated soil and the like (Patent Document 3).
A method of incorporating a material into a solidifiable binder, the method comprising mixing the material with a binder as a slurry or for the formation of a subsequent slurry, wherein the binder is a source of caustic magnesium oxide. And a method including a step of adding a solidifying agent that promotes solidification of the binder to the slurry has been proposed (Patent Document 4).
Further, the powder X-ray diffraction spectrum at a wavelength of 1.5405 mm has a peak apex at 2θ = 42.8 ° ± 0.3 °, and the half-value width based on the baseline of the peak is 0.32-1. Latent crystalline magnesia characterized by an angle of 0.5 ° has been proposed (Patent Document 5).
酸化マグネシウム（軽焼マグネシア等）を不溶化材として用いる特許文献１〜５の技術によると、汚染濃度の低い土壌に対しては、重金属類等の溶出を抑制することができる。しかし、汚染濃度の高い土壌に対しては、未だその効果（重金属類等の溶出抑制効果）は不十分であり、重金属類等の溶出量を所定の値（例えば、環境基準値）以下にするためには、不溶化材の使用量が増加し、高コストになるという問題がある。さらにこの場合、不溶化材の添加後のボリュームが大きくなり、副次的な対策が必要になるなどの問題がある。
一方、重金属類等を含む排水の処理技術の分野においても、少ない添加量で重金属類等を十分に不溶化することのできる不溶化材が望まれている。
そこで、本発明は、汚染濃度の高い土壌や、排水に対して、少ない添加量で、重金属類等の溶出を十分に抑制することができる不溶化材を提供することを目的とする。
According to the techniques of Patent Documents 1 to 5 using magnesium oxide (lightly burned magnesia or the like) as an insolubilizing material, elution of heavy metals and the like can be suppressed for soil having a low contamination concentration. However, the effect (elution suppression effect of heavy metals, etc.) is still insufficient for highly contaminated soil, and the elution amount of heavy metals, etc. is set to a predetermined value (for example, environmental standard value) or less. Therefore, there is a problem that the amount of the insolubilizing material used is increased and the cost is increased. Further, in this case, there is a problem that the volume after the addition of the insolubilizing material is increased, and secondary measures are required.
On the other hand, in the field of wastewater treatment technology including heavy metals and the like, an insolubilizing material that can sufficiently insolubilize heavy metals and the like with a small addition amount is desired.
Then, an object of this invention is to provide the insolubilization material which can fully suppress elution of heavy metals etc. with little addition amount with respect to soil with high pollution density | concentration, or waste_water | drain.
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、軽焼マグネシアの一部を水和してなる軽焼マグネシア部分水和物を含む不溶化材によれば、本発明の上記目的を達成しうることを見出し、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］ 炭酸マグネシウム及び／又は水酸化マグネシウムを主成分とする鉱物を５５０〜１，４００℃で焼成して得た軽焼マグネシアの一部を水和してなる軽焼マグネシア部分水和物であって、該軽焼マグネシア部分水和物中、酸化マグネシウムの含有率が５０〜９６．５質量％、水酸化マグネシウムの含有率が３．５〜５０質量％であり、カルシウムの含有率が酸化物換算で５．０質量％以下である軽焼マグネシア部分水和物を含むこと（ただし、炭酸カルシウムを８５質量％以上の含有率で含む粉末を、前記軽焼マグネシア部分水和物１００質量部に対して２０〜７０質量部加えた場合を除く。）を特徴とする不溶化材。
［２］ ブレーン比表面積が２，５００〜２０，０００ｃｍ２／ｇであり、かつ、粒度分布に関するロジン・ラムラーの式：Ｒ＝１００ｅｘｐ（−ｂＤp n）（式中、Ｒは積算残分値（％）であり、ふるい残分を表し、Ｄpは粒径（μｍ）であり、ふるいの目の寸法を表し、ｂ、ｎは定数である。）におけるｎ値が０．８０〜１．４５である上記［１］に記載の不溶化材。
［３］ 上記不溶化材は、粒状または粉状の固体物に添加するためのものである上記［１］又は［２］に記載の不溶化材。
［４］ 上記軽焼マグネシア部分水和物１００質量部に対して、石膏を５０質量部以下の配合量で含む上記［３］に記載の不溶化材。
［５］ 上記不溶化材は、排水に添加するためのものである上記［１］又は［２］に記載の不溶化材。
As a result of intensive studies to solve the above-mentioned problems, the inventor has obtained the above object of the present invention according to an insolubilized material containing a light-burned magnesia partial hydrate obtained by hydrating a part of light-burned magnesia. The present invention has been completed by finding out what can be achieved.
That is, the present invention provides the following [1] to [5].
[1] A light-burned magnesia partial hydrate obtained by hydrating a part of light-burned magnesia obtained by baking a mineral mainly composed of magnesium carbonate and / or magnesium hydroxide at 550 to 1,400 ° C. In the light-burned magnesia partial hydrate, the magnesium oxide content is 50 to 96.5% by mass, the magnesium hydroxide content is 3.5 to 50% by mass, and the calcium content is oxidized. Containing lightly burned magnesia partial hydrate which is 5.0% by mass or less in terms of product ( however, powder containing calcium carbonate at a content of 85% by mass or more, 100 parts by mass of the lightly burned magnesia partial hydrate) The insolubilizing material is characterized in that 20 to 70 parts by mass are added to the above.
[2] Blaine specific surface area of 2,500~20,000cm 2 / g, and wherein the Rosin-Rammler about the particle size distribution: R = 100exp (-bD p n ) ( wherein, R accumulated residue value (%), Representing the remainder of the sieve, D p is the particle size (μm), representing the size of the sieve eye, and b and n are constants). 45. The insolubilizing material according to the above [1], which is 45.
[3] The insolubilizing material according to [1] or [2], wherein the insolubilizing material is for addition to a granular or powdery solid.
[4] The insolubilized material according to [3], wherein gypsum is contained in an amount of 50 parts by mass or less with respect to 100 parts by mass of the lightly burned magnesia partial hydrate.
[5] The insolubilizing material according to [1] or [2], wherein the insolubilizing material is for addition to waste water.
本発明の不溶化材によると、汚染濃度の高い土壌や、焼却灰等の重金属含有ダスト等に対しても、少ない添加量で、重金属類等の溶出を十分に抑制することができる。
また、本発明の不溶化材によると、重金属類等を含む排水に対して、少ない添加量で、重金属類等を十分に不溶化することができる。この場合、排水を固液分離することによって、重金属類等の含有率が減少した液分を容易に得ることができ、排水処理を効率的に行なうことができる。
According to the insolubilizing material of the present invention, elution of heavy metals and the like can be sufficiently suppressed with a small amount of addition even to soil with high contamination concentration, heavy metal-containing dust such as incinerated ash, and the like.
Moreover, according to the insolubilizing material of the present invention, heavy metals can be sufficiently insolubilized with a small addition amount with respect to waste water containing heavy metals. In this case, by separating the drainage into solid and liquid, it is possible to easily obtain a liquid component having a reduced content of heavy metals and the like, and to efficiently perform the drainage treatment.
本発明の不溶化材は、（Ａ）軽焼マグネシア部分水和物、を必須成分として含み、さらに必要に応じて他の任意成分を含む。
［（Ａ）軽焼マグネシア部分水和物］
本発明の不溶化材に用いる（Ａ）軽焼マグネシア部分水和物は、炭酸マグネシウム及び／又は水酸化マグネシウムを主成分とする鉱物を５５０〜１，４００℃で焼成して得た軽焼マグネシアの一部を水和してなるものである。
なお、本発明において、軽焼マグネシア部分水和物は、通常、粉末のものが用いられる。
炭酸マグネシウムを主成分とする鉱物の例としては、マグネサイト、ドロマイト等が挙げられる。この場合、鉱物中の炭酸マグネシウムの含有率は、好ましくは８０質量％以上、より好ましくは８５質量％以上、特に好ましくは９０質量％以上である。
水酸化マグネシウムを主成分とする鉱物の例としては、ブルーサイト等が挙げられる。この場合、鉱物中の水酸化マグネシウムの含有率は、好ましくは８０質量％以上、より好ましくは８５質量％以上、特に好ましくは９０質量％以上である。
軽焼マグネシアは、酸化マグネシウムを主成分として含む。本発明で用いる、軽焼マグネシアを部分的に水和してなる軽焼マグネシア部分水和物は、水和により得られた水酸化マグネシウムと、酸化マグネシウムとを後述の特定の割合で含む。このような軽焼マグネシア部分水和物を用いることにより、土壌等の固体物中もしくは排水中における重金属類等の溶出に対する高い抑制効果を得ることができる。
焼成する際の温度は、５５０〜１，４００℃、好ましくは６５０〜１，４００℃、より好ましくは７５０〜１，０００℃、さらに好ましくは８６０〜９５０℃、特に好ましくは８７０〜９２０℃である。該温度が５５０℃未満であると、軽焼マグネシアが生成し難く、一方、１，４００℃を超えると、重金属類等の不溶化の効果が低下する。
The insolubilizing material of the present invention includes (A) light-burned magnesia partial hydrate as an essential component, and further includes other optional components as necessary.
[(A) Lightly burned magnesia partial hydrate]
The light-burned magnesia partial hydrate used for the insolubilizing material of the present invention is a light-burned magnesia obtained by baking a mineral mainly composed of magnesium carbonate and / or magnesium hydroxide at 550 to 1,400 ° C. A part is hydrated.
In the present invention, powdered magnesia partial hydrate is usually used.
Examples of minerals mainly composed of magnesium carbonate include magnesite and dolomite. In this case, the content of magnesium carbonate in the mineral is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more.
Examples of minerals mainly composed of magnesium hydroxide include brucite. In this case, the content of magnesium hydroxide in the mineral is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more.
Light-burned magnesia contains magnesium oxide as a main component. The light-burned magnesia partial hydrate obtained by partially hydrating light-burned magnesia used in the present invention contains magnesium hydroxide obtained by hydration and magnesium oxide in a specific ratio described later. By using such light-burned magnesia partial hydrate, it is possible to obtain a high inhibitory effect on elution of heavy metals or the like in solid matter such as soil or waste water.
The temperature at the time of baking is 550 to 1,400 ° C, preferably 650 to 1,400 ° C, more preferably 750 to 1,000 ° C, still more preferably 860 to 950 ° C, and particularly preferably 870 to 920 ° C. . When the temperature is less than 550 ° C., light-burned magnesia is difficult to be generated. On the other hand, when the temperature exceeds 1,400 ° C., the effect of insolubilizing heavy metals and the like is reduced.
（Ａ）軽焼マグネシア部分水和物中、酸化マグネシウムの含有率は５０〜９６．５質量％、好ましくは６０〜９５質量％、より好ましくは７０〜９４質量％、特に好ましくは７５〜９３質量％である。
（Ａ）軽焼マグネシア部分水和物中、水酸化マグネシウムの含有率は３．５〜５０質量％、好ましくは４〜４０質量％、より好ましくは５〜３０質量％、特に好ましくは６〜２０質量％である。
酸化マグネシウムの含有率が５０質量％未満、あるいは水酸化マグネシウムの含有率が５０質量％を超えると、重金属類等の不溶化の効果が低下する。一方、酸化マグネシウムの含有率が９６．５質量％を超えるか、あるいは、水酸化マグネシウムの含有率が３．５質量％未満であると、特に重金属類等による汚染の高い土壌等において、重金属類等の溶出を抑制する効果が低下する。
(A) In the lightly burned magnesia partial hydrate, the content of magnesium oxide is 50 to 96.5% by mass, preferably 60 to 95% by mass, more preferably 70 to 94% by mass, and particularly preferably 75 to 93% by mass. %.
(A) In the light-burned magnesia partial hydrate, the content of magnesium hydroxide is 3.5 to 50% by mass, preferably 4 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 6 to 20%. % By mass.
When the content of magnesium oxide is less than 50% by mass or the content of magnesium hydroxide exceeds 50% by mass, the effect of insolubilization of heavy metals and the like decreases. On the other hand, when the content of magnesium oxide exceeds 96.5% by mass or the content of magnesium hydroxide is less than 3.5% by mass, particularly in soils highly contaminated with heavy metals, etc., heavy metals The effect which suppresses elution etc. falls.
本発明において、得られる軽焼マグネシア部分水和物に含まれる酸化カルシウム及び／又は水酸化カルシウムの合計の含有率は、軽焼マグネシア部分水和物（１００質量％）中、酸化物換算で、５．０質量％以下、好ましくは４．０質量％以下、より好ましくは３．０質量％以下、特に好ましくは２．０質量％以下である。該含有率が５．０質量％を超えると、特に重金属類等による汚染の高い土壌等において、重金属類等の溶出を抑制する効果が低下する。
なお、軽焼マグネシア部分水和物は、上記成分（ＭｇＯ、Ｍｇ（ＯＨ）2、ＣａＯ、Ｃａ（ＯＨ）2）以外の他の成分（具体的には、ＳｉＯ2、Ｆｅ2Ｏ3等の不純物）を含むことができる。他の成分の含有率は、好ましくは４．０質量％以下、より好ましくは３．０質量％以下、特に好ましくは２．５質量％以下である。該含有率が４．０質量％を超えると、重金属類等の溶出を抑制する効果が低下することがある。
In the present invention, the total content of calcium oxide and / or calcium hydroxide contained in the obtained light calcined magnesia partial hydrate is in terms of oxide in the light calcined magnesia partial hydrate (100% by mass). It is 5.0 mass% or less, preferably 4.0 mass% or less, more preferably 3.0 mass% or less, and particularly preferably 2.0 mass% or less. When the content exceeds 5.0% by mass, the effect of suppressing elution of heavy metals and the like is reduced particularly in soils and the like highly contaminated with heavy metals and the like.
The light-burned magnesia partial hydrate is composed of other components (specifically, SiO 2 , Fe 2 O 3, etc.) other than the above components (MgO, Mg (OH) 2 , CaO, Ca (OH) 2 ). Impurities). The content of other components is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, and particularly preferably 2.5% by mass or less. When this content rate exceeds 4.0 mass%, the effect which suppresses elution of heavy metals etc. may fall.
軽焼マグネシアを水和する方法としては、得られる軽焼マグネシア部分水和物中の各成分（酸化マグネシウム、水酸化マグネシウム、及びカルシウム）の含有率が上記特定の範囲内となればよく、特に限定されないが、例えば、下記（１）又は（２）の方法が挙げられる。
（１）軽焼マグネシアに水を添加して混合する方法
（２）軽焼マグネシアを相対湿度８０％以上の環境下に、１週間以上保持する方法
なお、水和反応の前に、軽焼マグネシアを粉砕することが好ましい。
As a method for hydrating light-burned magnesia, it is sufficient that the content of each component (magnesium oxide, magnesium hydroxide, and calcium) in the obtained light-burned magnesia partial hydrate is within the above specific range. Although not limited, the following (1) or (2) method is mentioned, for example.
(1) Method of adding water to light-burned magnesia and mixing (2) Method of holding light-burned magnesia in an environment with a relative humidity of 80% or more for one week or more Note that, before the hydration reaction, light-burned magnesia Is preferably pulverized.
本発明の不溶化材を構成する軽焼マグネシアのブレーン比表面積は、好ましくは２，５００〜２０，０００ｃｍ２／ｇ、より好ましくは４，５００〜１５，０００ｃｍ２／ｇ、より好ましくは４，８００〜１０，０００ｃｍ２／ｇ、さらに好ましくは５，２００〜８，０００ｃｍ２／ｇ、特に好ましくは５，５００〜６，５００ｃｍ２／ｇである。該値を上記数値範囲内に調整することにより、重金属類等の溶出を抑制する効果を高めることができ、特に、重金属類等の溶出量の大きい土壌等に対しても少量で溶出を抑制することができる。また、ブレーン比表面積が８，０００ｃｍ２／ｇ以下であると、ブレーン比表面積が８，０００ｃｍ２／ｇを超える場合に困難なスラリーでの添加も可能となる。 The Blaine specific surface area of the lightly burned magnesia constituting the insolubilized material of the present invention is preferably 2,500 to 20,000 cm 2 / g, more preferably 4,500 to 15,000 cm 2 / g, more preferably 4,800. It is -10,000 cm < 2 > / g, More preferably, it is 5,200-8,000 cm < 2 > / g, Most preferably, it is 5,500-6,500 cm < 2 > / g. By adjusting the value within the above numerical range, the effect of suppressing elution of heavy metals and the like can be enhanced, and in particular, elution can be suppressed in a small amount even for soils and the like where elution of heavy metals and the like is large. be able to. Moreover, when the Blaine specific surface area is 8,000 cm 2 / g or less, addition in a difficult slurry becomes possible when the Blaine specific surface area exceeds 8,000 cm 2 / g.
［（Ｂ）石膏］
本発明の不溶化材は、土壌、焼却灰等の粒状または粉状の固体物に添加するためのものである場合、石膏を含むことができる。
石膏を適量含むことによって、粒状または粉状の固体物の固化強度を増大させることができる。なお、固化強度は、一軸圧縮強度を測定することによって評価することができる。
石膏の例としては、無水石膏、二水石膏、半水石膏が挙げられる。
石膏の配合量は、軽焼マグネシア部分水和物１００質量部に対して、無水物換算で、好ましくは５０質量部以下、より好ましくは３〜３５質量部、さらに好ましくは８〜３０質量部、特に好ましくは１２〜２５質量部である。
石膏の配合量が５０質量部を超えると、固化強度が低下するばかりか、重金属類等の溶出を抑制する効果が低下する。
本発明の不溶化材を構成する石膏のブレーン比表面積は、好ましくは３，０００〜８，０００ｃｍ２／ｇ、より好ましくは３，５００〜６，５００ｃｍ２／ｇ、さらに好ましくは４，０００〜６，０００ｃｍ２／ｇ、特に好ましくは４，５００〜５，５００ｃｍ２／ｇである。該値を上記数値範囲内に調整することにより、重金属類等の溶出を抑制する効果を高めることができ、特に、重金属類等の溶出量の大きい土壌等に対しても少量で溶出を抑制することができる。
なお、石膏が上記ブレーン比表面積を既に有する場合は、粉砕を行わず、そのまま用いることができる。
[(B) Gypsum]
The insolubilizing material of the present invention can contain gypsum when it is added to a granular or powdery solid such as soil or incinerated ash.
By including an appropriate amount of gypsum, the solidification strength of a granular or powdery solid can be increased. The solidification strength can be evaluated by measuring uniaxial compressive strength.
Examples of gypsum include anhydrous gypsum, dihydrate gypsum, and hemihydrate gypsum.
The blending amount of gypsum is preferably 50 parts by mass or less, more preferably 3 to 35 parts by mass, still more preferably 8 to 30 parts by mass, in terms of anhydride, with respect to 100 parts by mass of light-burned magnesia partial hydrate. Especially preferably, it is 12-25 mass parts.
When the amount of gypsum exceeds 50 parts by mass, not only the solidification strength is lowered, but also the effect of suppressing elution of heavy metals and the like is lowered.
The brane specific surface area of the gypsum constituting the insolubilizing material of the present invention is preferably 3,000 to 8,000 cm 2 / g, more preferably 3,500 to 6,500 cm 2 / g, still more preferably 4,000 to 6 , 000cm 2 / g, particularly preferably 4,500~5,500cm 2 / g. By adjusting the value within the above numerical range, the effect of suppressing elution of heavy metals and the like can be enhanced, and in particular, elution can be suppressed in a small amount even for soils and the like where elution of heavy metals and the like is large. be able to.
In addition, when gypsum already has the said Blaine specific surface area, it can use as it is, without grind | pulverizing.
本発明の不溶化材は、ブレーン比表面積が２，５００〜２０，０００ｃｍ２／ｇであり、かつ、粒度分布に関するロジン・ラムラーの式：Ｒ＝１００ｅｘｐ（−ｂＤp n）（式中、Ｒは積算残分値（％）であり、ふるい残分を表し、Ｄpは粒径（μｍ）であり、ふるいの目の寸法を表し、ｂ、ｎは定数である。）におけるｎ値が０．８０〜１．４５となる粒度構成を有することが好ましい。不溶化材の粒度構成を上記のように調整することにより、重金属類等の溶出を抑制する効果を高めることができ、特に、重金属類等の溶出量の大きい土壌等に対しても少量で溶出を抑制することができる。
不溶化材のブレーン比表面積は、より好ましくは４，８００〜１０，０００ｃｍ２／ｇ、さらに好ましくは５，２００〜８，０００ｃｍ２／ｇ、特に好ましくは５，５００〜６，５００ｃｍ２／ｇである。
ロジン・ラムラーの式におけるｎ値は、より好ましくは０．９０〜１．３０、特に好ましくは０．９５〜１．２０である。
なお、ロジン・ラムラーの式におけるｎ値は、例えば、日機装社製９３２０−Ｘ１０（粒度分布測定装置）を用いて測定することができる。測定に際しては、１００ｍｌビーカー内に収容した分散媒エタノール２０ｍｌに対して試料０．０５ｇを加えるものとし、アズワン社製の超音波洗浄機（ＶＳ−１００・周波数５０ｋＨｚ）を用いて１分間超音波分散後に測定を行う。測定は、試料の屈折率が１．７２の条件で行うものとする。
Insolubilized material of the present invention is the Blaine specific surface area of 2,500~20,000cm 2 / g, and wherein the Rosin-Rammler about the particle size distribution: R = 100exp (-bD p n ) ( wherein, R The integrated residual value (%) represents the sieve residue, D p is the particle size (μm), the size of the sieve eye, and b and n are constants). It is preferable to have a particle size configuration of 80 to 1.45. By adjusting the particle size composition of the insolubilizing material as described above, it is possible to enhance the effect of suppressing the elution of heavy metals and the like. Can be suppressed.
The brane specific surface area of the insolubilized material is more preferably 4,800 to 10,000 cm 2 / g, still more preferably 5,200 to 8,000 cm 2 / g, and particularly preferably 5,500 to 6,500 cm 2 / g. is there.
The n value in the Rosin-Rammler formula is more preferably 0.90 to 1.30, particularly preferably 0.95 to 1.20.
The n value in the Rosin-Rammler equation can be measured using, for example, 9320-X10 (particle size distribution measuring device) manufactured by Nikkiso Co., Ltd. In the measurement, 0.05 g of a sample is added to 20 ml of a dispersion medium ethanol contained in a 100 ml beaker, and ultrasonic dispersion is performed for 1 minute using an ultrasonic cleaning machine (VS-100, frequency 50 kHz) manufactured by ASONE. Measurement will be performed later. The measurement is performed under the condition that the refractive index of the sample is 1.72.
本発明の不溶化材は、軽焼マグネシア部分水和物のみからなる場合、例えば、下記（ａ）の方法により得られる。
（ａ）軽焼マグネシアを粉砕して所定の粒度を有する粉砕物を得る工程と、該粉砕物を水和させて、軽焼マグネシア部分水和物からなる粉末を得る工程と、を含む方法
本発明の不溶化材は、軽焼マグネシア部分水和物及び石膏からなる場合、例えば、下記（ｂ）〜（ｄ）のいずれかの方法により得られる。
（ｂ）軽焼マグネシアと石膏とを混合して混合物を得る工程と、前記混合物を粉砕して所定の粒度を有する混合物の粉砕物を得る工程と、前記混合物の粉砕物を水和させて、軽焼マグネシア部分水和物からなる粉末と石膏の粉末とからなる混合物を得る工程と、を含む方法
（ｃ）軽焼マグネシアを粉砕して、所定の粒度を有する軽焼マグネシア粉砕物を得る工程と、石膏を粉砕して、所定の粒度を有する石膏の粉砕物を得る工程と、前記軽焼マグネシア粉砕物と前記石膏の粉砕物とを混合して混合物を得る工程と、前記混合物を水和させて、軽焼マグネシア部分水和物からなる粉末と石膏の粉末とからなる混合物を得る工程と、を含む方法
（ｄ）軽焼マグネシアを粉砕して、所定の粒度を有する軽焼マグネシア粉砕物を得る工程と、前記軽焼マグネシア粉砕物を水和させて、軽焼マグネシア部分水和物からなる粉末を得る工程と、石膏を粉砕して、所定の粒度を有する石膏の粉末を得る工程と、前記軽焼マグネシア部分水和物からなる粉末と前記石膏の粉末とを混合して、これらの混合物を得る工程と、を含む方法
これら（ｂ）〜（ｄ）の方法の中で、重金属類等の溶出を抑制する効果、及び作業性の観点から、（ｂ）又は（ｃ）の方法が好ましく、（ｂ）の方法が、より好ましい。
The insolubilizing material of the present invention can be obtained, for example, by the following method (a) when it consists only of light-burned magnesia partial hydrate.
(A) A method comprising a step of pulverizing light-burned magnesia to obtain a pulverized product having a predetermined particle size, and a step of hydrating the pulverized product to obtain a powder comprising light-burned magnesia partial hydrate. When the insolubilizing material of the invention is composed of light-burned magnesia partial hydrate and gypsum, it is obtained, for example, by any of the following methods (b) to (d).
(B) mixing lightly-burned magnesia and gypsum to obtain a mixture, pulverizing the mixture to obtain a pulverized mixture having a predetermined particle size, and hydrating the pulverized mixture. A process comprising: obtaining a mixture comprising a powder comprising light-burned magnesia partial hydrate and gypsum powder; and (c) pulverizing the light-burned magnesia to obtain a light-burned magnesia pulverized product having a predetermined particle size. Pulverizing gypsum to obtain a gypsum pulverized product having a predetermined particle size, mixing the light-burned magnesia pulverized product and the gypsum pulverized product to obtain a mixture, and hydrating the mixture And (d) pulverizing the light-burned magnesia to obtain a mixture of the powder comprising the light-burned magnesia partial hydrate and the gypsum powder. And the light baking A step of obtaining a powder comprising light-burned magnesia partial hydrate by hydrating a pulverized gnesia, a step of obtaining gypsum powder having a predetermined particle size by pulverizing gypsum, and the light-burning magnesia partial hydration A method comprising: mixing a powder comprising a product and the gypsum powder to obtain a mixture thereof. In these methods (b) to (d), an effect of suppressing elution of heavy metals and the like, And from the viewpoint of workability, the method (b) or (c) is preferable, and the method (b) is more preferable.
上記の各方法において、粉砕前の軽焼マグネシアは、粒径が１μｍ〜５０ｍｍであることが好ましい。また、粉砕前の石膏は、粒径が１μｍ〜１００ｍｍであることが好ましく、２μｍ〜５０ｍｍであることがより好ましい。このような粒径を有する粉砕前の軽焼マグネシア及び石膏を用いることにより、本発明の不溶化材の粒度を容易に調整することができる。 In each of the above methods, the light-burned magnesia before pulverization preferably has a particle size of 1 μm to 50 mm. The gypsum before pulverization preferably has a particle size of 1 μm to 100 mm, and more preferably 2 μm to 50 mm. By using light-burned magnesia and gypsum before pulverization having such a particle size, the particle size of the insolubilized material of the present invention can be easily adjusted.
本発明の不溶化材の添加量は、粒状または粉状の固体物（例えば、土壌、焼却灰等）に対する添加材として用いる場合、添加対象物の性状や施工条件、重金属類等の溶出量や添加対象物の要求性能等にもよるが、一般的には、粒状または粉状の固体物１ｍ３あたり５０〜４００ｋｇが好ましく、１００〜３５０ｋｇがより好ましい。該量が５０ｋｇ未満では、排水中の重金属類等の溶出の抑制効果が不十分となる。該量が４００ｋｇを超えると、排水中の重金属類等の溶出の抑制効果の向上が頭打ちとなり、また、処理後の体積が増大するとともに、処理コストも増大する。
この場合、不溶化材の添加方法としては、不溶化材を粉体のまま添加・混合するドライ添加、あるいは、水を加えてスラリーとして添加・混合するスラリー添加を採用することができる。スラリー添加の場合の水／不溶化材の質量比は、０．５〜１．５が好ましく、０．８〜１．２がより好ましい。
本発明の不溶化材は、土壌に対して特に好適に用いられるが、土壌以外のもの、例えば、下水汚泥焼却灰、鶏糞焼却灰、製紙スラッジ焼却灰、石炭焼却灰等の焼却灰、焼却炉の排ガス中からバグフィルター、電気集塵機等のダスト捕集手段によって捕集した焼却飛灰等のダスト類や、重金属類等に汚染されたトンネルズリ、コンクリートガラ、スラグ類等の粒状の固体物にも用いることができる。
The addition amount of the insolubilizing material of the present invention, when used as an additive to a granular or powdered solid material (for example, soil, incineration ash, etc.), the properties of the addition object, construction conditions, the elution amount and addition of heavy metals, etc. Although it depends on the required performance of the object, generally 50 to 400 kg is preferable, more preferably 100 to 350 kg, per 1 m 3 of a granular or powdery solid. When the amount is less than 50 kg, the effect of suppressing the elution of heavy metals in the wastewater is insufficient. When the amount exceeds 400 kg, the improvement in the elution suppression effect of heavy metals in the wastewater reaches its peak, and the volume after treatment increases and the processing cost also increases.
In this case, as the method for adding the insolubilizing material, dry addition in which the insolubilizing material is added and mixed in powder form, or slurry addition in which water is added and mixed as a slurry can be employed. 0.5-1.5 are preferable and, as for the mass ratio of the water / insolubilized material in the case of slurry addition, 0.8-1.2 are more preferable.
The insolubilizing material of the present invention is particularly preferably used for soil, but other than soil, for example, sewage sludge incineration ash, chicken manure incineration ash, papermaking sludge incineration ash, incineration ash such as coal incineration ash, incinerator For dust such as incinerated fly ash collected by dust collecting means such as bag filters and electric dust collectors from exhaust gas, and for particulate solids such as tunnel sludge, concrete glass and slag contaminated by heavy metals Can be used.
本発明の不溶化材の添加量は、排水に対する添加材として用いる場合、添加対象物の性状や施工条件、重金属類等の溶出量や添加対象物の要求性能等にもよるが、一般的には、排水１００質量部に対して、好ましくは０．１〜１０質量部、より好ましくは０．３〜４質量部、特に好ましくは０．５〜２質量部である。
該量が０．１質量部未満では、排水中の重金属類等の溶出の抑制効果が不十分となる。該量が１０質量部を超えると、排水中の重金属類等の溶出の抑制効果の向上が頭打ちとなり、また、処理コストが増大する。
The amount of the insolubilizing material of the present invention, when used as an additive to waste water, depends on the properties of the object to be added and the construction conditions, the amount of elution of heavy metals, the required performance of the object to be added, etc. The amount is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 4 parts by mass, and particularly preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the waste water.
If the amount is less than 0.1 parts by mass, the effect of suppressing elution of heavy metals in the waste water is insufficient. When the amount exceeds 10 parts by mass, the improvement effect of the elution of heavy metals in the wastewater reaches its peak, and the processing cost increases.
以下、実施例に基いて本発明を説明する。
［不溶化材の調製］
以下の不溶化材Ａ〜Ｎを調製した。
（１）不溶化材Ａ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度１００％の保管室にて１０日間保管したもの
（２）不溶化材Ｂ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度１００％の保管室にて２０日間保管したもの
（３）不溶化材Ｃ：「不溶化材Ａ」１００質量部に対してブレーン比表面積５，５００ｃｍ2／ｇの天然無水石膏を１８質量部添加し、混合したもの
（４）不溶化材Ｄ：「不溶化材Ｂ」１００質量部に対してブレーン比表面積５，５００ｃｍ2／ｇの天然無水石膏を１８質量部添加し、混合したもの
（５）不溶化材Ｅ：「不溶化材Ａ」１００質量部に対してブレーン比表面積５，５００ｃｍ2／ｇの天然無水石膏を３質量部添加し、混合したもの
（６）不溶化材Ｆ：「不溶化材Ａ」１００質量部に対してブレーン比表面積５，５００ｃｍ2／ｇの天然無水石膏を５０質量部添加し、混合したもの
（７）不溶化材Ｇ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、エア・ジェット式ふるい装置で粒度調整した後、相対湿度１００％の保管室にて１０日間保管したもの
（８）不溶化材Ｈ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、エア・ジェット式ふるい装置で粒度調整した後、相対湿度１００％の保管室にて１０日間保管したもの
（９）不溶化材Ｉ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度６０％の保管室にて２０日間保管したもの
（１０）不溶化材Ｊ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度１００％の保管室にて５０日間保管したもの
（１１）不溶化材Ｋ：カルシウムの含有率の高いマグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度１００％の保管室にて１０日間保管したもの
（１２）不溶化材Ｌ：マグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物１００質量部に対し、試薬（関東化学社製；特級）である水酸化マグネシウム１１．５質量部を添加し混合したもの
（１３）不溶化材Ｍ：カルシウムの含有率の高いマグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度１００％の保管室にて２０日間保管したもの
（１４）不溶化材Ｎ：カルシウムの含有率の高いマグネサイトを８９０℃で焼成してなる軽焼マグネシアを粉砕して得られた粉砕物を、相対湿度１００％の保管室にて１０日間保管したもの
Hereinafter, the present invention will be described based on examples.
[Preparation of insolubilized material]
The following insolubilized materials A to N were prepared.
(1) Insolubilized material A: a pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite at 890 ° C. and stored for 10 days in a storage room with a relative humidity of 100%. (2) Insolubilized material B: A pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite at 890 ° C. for 20 days in a storage room with a relative humidity of 100%. (3) Insolubilizing material C: “Insolubilizing material A ”18 parts by mass of natural anhydrous gypsum having a specific surface area of 5,500 cm 2 / g to 100 parts by mass of Brene and mixed (4) Insolubilized material D: Blaine to 100 parts by mass of“ insolubilized material B ” 18 parts by mass of natural anhydrite with a specific surface area of 5,500 cm 2 / g was added and mixed. (5) Insolubilized material E: Blaine specific surface area of 5,500 cm 2 / g with respect to 100 parts by mass of “insolubilized material A” 3 masses of natural anhydrous gypsum Added, mixed ones (6) insoluble material F: that "insoluble material A" natural anhydrite of Blaine specific surface area of 5,500cm 2 / g were added 50 parts by weight per 100 parts by weight, were mixed (7) Insolubilizing material G: After pulverized light magnesia obtained by firing magnesite at 890 ° C., the particle size was adjusted with an air jet type sieve device, and then 10 in a storage room with a relative humidity of 100%. (8) Insolubilized material H: pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite at 890 ° C., and adjusting the particle size with an air jet sieving apparatus, and then relative humidity 100 (9) Insolubilized material I: A pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite at 890 ° C. in a storage room having a relative humidity of 60%. For 20 days (10) Insolubilized material J: A pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite at 890 ° C. and stored in a storage room with a relative humidity of 100% for 50 days (11) Insolubilized material K: a pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite with a high calcium content at 890 ° C., and storing it in a storage room with a relative humidity of 100% for 10 days (12 ) Insolubilizing material L: Magnesium hydroxide 11.5 which is a reagent (manufactured by Kanto Chemical Co., Ltd .; special grade) with respect to 100 parts by mass of a pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite at 890 ° C. (13) Insolubilized material M: pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite with a high calcium content at 890 ° C., having a relative humidity of 100% Storage room (14) Insolubilized material N: A pulverized product obtained by pulverizing light-burned magnesia obtained by firing magnesite with a high calcium content at 890 ° C., stored at a relative humidity of 100% Stored in the room for 10 days
［汚染土壌等の準備］
以下の汚染土壌、焼却灰、及び排水を準備した。
（１）ヒ素汚染土壌
湿潤密度１．６７ｇ／ｃｍ3、含水比５１．５％のシルト土２０００ｇに対し、ヒ酸水素ナトリウム・７水和物０．０４ｇを添加して混合し、ヒ素汚染土壌を得た。
（２）フッ素汚染土壌
湿潤密度１．５３ｇ／ｃｍ3、含水比７６．３％の粘性土２０００ｇに対し、フッ化カリウム０．０６ｇを添加して混合し、フッ素汚染土壌を得た。
（３）鉛汚染土壌
湿潤密度１．７１ｇ／ｃｍ3、含水比１０．５％の砂質土２０００ｇに対し、硝酸鉛（II）０．５０ｇを添加して混合し、鉛汚染土壌を得た。
（４）焼却灰
一般家庭ごみの焼却炉から焼却灰（都市ごみ焼却灰）を回収した。
（５）ヒ素汚染排水
水１００質量部に対して、０．００４３質量部のヒ酸水素ナトリウム（関東化学社製；特級）を添加して、ヒ素汚染排水を得た。
（６）フッ素汚染排水
水１００質量部に対して、０．００５８質量部のフッ化カリウム（関東化学社製；特級）を添加して、フッ素汚染排水を得た。
（７）鉛汚染排水
水１００質量部に対して、０．００３２質量部の硝酸鉛（II）（関東化学社製；特級）を添加して、鉛汚染排水を得た。
[Preparation of contaminated soil, etc.]
The following contaminated soil, incineration ash, and drainage were prepared.
(1) Arsenic-contaminated soil To arsenic-contaminated soil, 0.04 g of sodium hydrogen arsenate 7-hydrate is added to and mixed with 2000 g of silt soil with a wet density of 1.67 g / cm 3 and a water content of 51.5%. Got.
(2) Fluorine-contaminated soil 0.06 g of potassium fluoride was added to and mixed with 2000 g of viscous soil having a wet density of 1.53 g / cm 3 and a water content ratio of 76.3% to obtain fluorine-contaminated soil.
(3) Lead-contaminated soil 0.50 g of lead (II) nitrate was added to and mixed with 2000 g of sandy soil with a wet density of 1.71 g / cm 3 and a water content ratio of 10.5% to obtain lead-contaminated soil. .
(4) Incineration ash Incineration ash (city waste incineration ash) was recovered from incinerators for general household waste.
(5) Arsenic-contaminated wastewater 0.0043 parts by mass of sodium hydrogen arsenate (manufactured by Kanto Chemical Co., Inc .; special grade) was added to 100 parts by mass of water to obtain arsenic-contaminated wastewater.
(6) Fluorine-contaminated wastewater 0.0058 parts by mass of potassium fluoride (manufactured by Kanto Chemical Co., Inc .; special grade) was added to 100 parts by mass of water to obtain fluorine-contaminated wastewater.
(7) Lead-contaminated wastewater 0.0032 parts by mass of lead nitrate (II) (manufactured by Kanto Chemical Co., Ltd .; special grade) was added to 100 parts by mass of water to obtain lead-contaminated wastewater.
［試験方法］
（１）不溶化材の成分組成
Ｘ線回折、熱重量分析および化学分析値から算出した。
（２）ブレーン比表面積
「ＪＩＳ Ｒ ５２０１」に準じて測定した。
（３）ロジン・ラムラー式のｎ値
１００ミリリットル容量のビーカー中に、エタノール（分散媒）２０ミリリットル、不溶化材０．０５ｇを添加し、アズワン社製の超音波洗浄機（ＶＳ−１００・周波数５０ｋＨｚ）を用いて１分間超音波分散した。その後、日機装社製９３２０−Ｘ１０（粒度分布測定装置）を用いて、ロジン・ラムラー式のｎ値を求めた。なお、試料の屈折率は１．７２の条件で行うものとする。
（４）一軸圧縮強度
汚染土壌に対し、不溶化材を添加し、材齢７日の改良土壌を得た。この改良土壌の一軸圧縮強度を、ＪＩＳ Ａ １２１６に準じて測定した。
[Test method]
(1) Component composition of insolubilized material Calculated from X-ray diffraction, thermogravimetric analysis, and chemical analysis values.
(2) Blaine specific surface area Measured according to "JIS R 5201".
(3) Rosin-Rammler n value In a 100 ml capacity beaker, 20 ml of ethanol (dispersion medium) and 0.05 g of insolubilizing material were added, and an ultrasonic cleaning machine (VS-100, frequency 50 kHz manufactured by AS ONE Co., Ltd. ) For 1 minute. Then, n value of the rosin-ramler type | formula was calculated | required using Nikkiso Co., Ltd. 9320-X10 (particle size distribution measuring apparatus). Note that the refractive index of the sample is assumed to be 1.72.
(4) Uniaxial compressive strength An insolubilizing material was added to the contaminated soil to obtain improved soil on the age of 7 days. The uniaxial compressive strength of the improved soil was measured according to JIS A 1216.
（５）溶出試験１（ヒ素）
（ａ）土壌
ヒ素汚染土壌（含水比：７０％）に対し、不溶化材を添加し、材齢７日の改良土壌からのヒ素の溶出量を環境省告示４６号法に準拠して測定した。なお、ヒ素の環境基準値は０．０１ｍｇ／リットルである。
（ｂ）焼却灰
焼却灰に対し、不溶化材を添加し、材齢７日の改良焼却灰からのヒ素の溶出量を環境省告示４６号法に準拠して測定した。
（ｃ）排水
ヒ素汚染排水に対し、不溶化材を添加し、２００回／分で４時間振とうした後の排水からのヒ素の溶出量を測定した。この際、不溶化材の添加後のｐＨも測定した。
(5) Dissolution test 1 (arsenic)
(A) Soil An insolubilizing material was added to arsenic-contaminated soil (water content ratio: 70%), and the amount of arsenic eluted from the improved soil at 7 days of age was measured according to the Ministry of the Environment Notification No. 46. The environmental standard value for arsenic is 0.01 mg / liter.
(B) Incineration ash An insolubilizing material was added to the incineration ash, and the amount of arsenic eluted from the improved incineration ash on the age of 7 days was measured according to the Ministry of the Environment Notification No. 46.
(C) Wastewater An insolubilizing material was added to the arsenic-contaminated wastewater, and the amount of arsenic eluted from the wastewater after shaking at 200 times / minute for 4 hours was measured. At this time, the pH after addition of the insolubilizing material was also measured.
（６）溶出試験２（フッ素）
（ａ）土壌
フッ素汚染土壌（含水比：７５％）に対し、不溶化材を添加し、材齢７日の改良土壌からのフッ素の溶出量を環境省告示４６号法に準拠して測定した。なお、フッ素の環境基準値は０．８ｍｇ／リットルである。
（ｂ）焼却灰
焼却灰に対し、不溶化材を添加し、材齢７日の改良焼却灰からのフッ素の溶出量を環境省告示４６号法に準拠して測定した。
（ｃ）排水
フッ素汚染排水に対し、不溶化材を添加し、２００回／分で４時間振とうした後の排水からのヒ素の溶出量を測定した。この際、不溶化材の添加後のｐＨも測定した。
(6) Dissolution test 2 (fluorine)
(A) Soil Fluorine-contaminated soil (water content: 75%) was added with an insolubilizing material, and the amount of fluorine eluted from the improved soil at the age of 7 days was measured according to the Ministry of the Environment Notification No. 46 method. The environmental standard value of fluorine is 0.8 mg / liter.
(B) Incineration ash An insolubilizing material was added to the incineration ash, and the amount of fluorine eluted from the improved incineration ash on the age of 7 days was measured according to the Ministry of the Environment Notification No. 46.
(C) Wastewater An insolubilizing material was added to the fluorine-contaminated wastewater, and the amount of arsenic eluted from the wastewater after shaking for 4 hours at 200 times / minute was measured. At this time, the pH after addition of the insolubilizing material was also measured.
（７）溶出試験３（鉛）
（ａ）土壌
鉛汚染土壌（含水比：７０％）に対し、不溶化材を添加し、材齢７日の改良土壌からの鉛の溶出量を環境省告示４６号法に準拠して測定した。なお、鉛の環境基準値は０．０１ｍｇ／リットルである。
（ｂ）排水
鉛汚染排水に対し、不溶化材を添加し、２００回／分で４時間振とうした後の排水からのヒ素の溶出量を測定した。この際、不溶化材の添加後のｐＨも測定した。
(7) Dissolution test 3 (lead)
(A) Soil An insolubilizing material was added to lead-contaminated soil (water content ratio: 70%), and the amount of lead eluted from the improved soil on the age of 7 days was measured according to the Ministry of the Environment Notification No. 46 method. The environmental standard value for lead is 0.01 mg / liter.
(B) Wastewater The insolubilizing material was added to the lead-contaminated wastewater, and the amount of arsenic eluted from the wastewater after shaking for 4 hours at 200 times / minute was measured. At this time, the pH after addition of the insolubilizing material was also measured.
（８）溶出試験４（６価クロム）
焼却灰に対し、不溶化材を添加し、材齢７日の改良焼却灰からの６価クロムの溶出量を環境省告示４６号法に準拠して測定した。なお、６価クロムの環境基準値は０．０５ｍｇ／リットルである。
(8) Dissolution test 4 (hexavalent chromium)
An insolubilizing material was added to the incinerated ash, and the elution amount of hexavalent chromium from the improved incinerated ash on the age of 7 days was measured according to the Ministry of the Environment Notification No. 46 method. The environmental standard value for hexavalent chromium is 0.05 mg / liter.
［実施例１〜８、比較例１〜５］
表１に示すように、汚染土壌に各種の不溶化材を添加した場合（実施例１〜８、比較例１〜４）及び不溶化材を添加しない場合（比較例５）のヒ素等の溶出量及び一軸圧縮強度（表１中、「一軸強度」と略す。）を測定した。結果を表１に示す。
なお、表１中、「添加量（ｋｇ／ｍ3）」は、不溶化材の添加前の汚染土壌１ｍ3に対する不溶化材の添加量（ｋｇ）を表す。
[Examples 1-8, Comparative Examples 1-5]
As shown in Table 1, when various insolubilizing materials were added to the contaminated soil (Examples 1 to 8, Comparative Examples 1 to 4) and when no insolubilizing materials were added (Comparative Example 5), Uniaxial compressive strength (abbreviated as “uniaxial strength” in Table 1) was measured. The results are shown in Table 1.
In Table 1, “addition amount (kg / m 3 )” represents the addition amount (kg) of the insolubilizing material to 1 m 3 of the contaminated soil before the addition of the insolubilizing material.
表１から、本発明に該当する不溶化材を用いた場合（実施例１〜８）、少ない添加量で汚染土壌からのヒ素等の溶出量を低く抑えうること、及び、一軸圧縮強度も良好な値であることがわかる。一方、比較例１、２では、水酸化マグネシウムの含有率が本発明で規定する数値範囲から外れているため、実施例１〜８に比べて、同一添加量でのヒ素、フッ素、鉛の溶出量が大きい。比較例３では、カルシウムの含有率（酸化物換算）が本発明で規定する数値範囲を超えているため、実施例１〜８に比べて、同一添加量でのヒ素、フッ素、鉛の溶出量が大きい。比較例４では、軽焼マグネシア部分水和物ではなく、軽焼マグネシアと試薬である水酸化マグネシウムの混合物を用いているため、実施例１〜８に比べて、同一添加量でのヒ素、フッ素、鉛の溶出量が大きい。比較例５では、不溶化材を用いていないため、ヒ素、フッ素、鉛の溶出量が非常に大きい。 From Table 1, when the insolubilizing material corresponding to the present invention is used (Examples 1 to 8), it is possible to suppress the elution amount of arsenic and the like from the contaminated soil with a small addition amount, and the uniaxial compressive strength is also good. It turns out that it is a value. On the other hand, in Comparative Examples 1 and 2, since the content of magnesium hydroxide is out of the numerical range defined in the present invention, the elution of arsenic, fluorine and lead in the same addition amount as compared with Examples 1 to 8 The amount is large. In Comparative Example 3, since the calcium content (in oxide equivalent) exceeds the numerical range defined in the present invention, the amount of arsenic, fluorine, and lead eluted with the same addition amount compared to Examples 1-8 Is big. In Comparative Example 4, since a mixture of light-burned magnesia and magnesium hydroxide, which is a reagent, is used instead of light-burned magnesia partial hydrate, arsenic and fluorine at the same addition amount as compared with Examples 1-8 The amount of lead elution is large. In Comparative Example 5, since no insolubilizing material is used, the amount of elution of arsenic, fluorine, and lead is very large.
［実施例９〜１０、比較例６〜９］
表２に示すように、焼却灰に各種の不溶化材を添加した場合（実施例９〜１０、比較例６〜８）及び不溶化材を添加しない場合（比較例９）のヒ素等の溶出量を測定した。結果を表２に示す。
なお、表２中、「添加量（ｋｇ／ｍ3）」は、不溶化材の添加前の焼却灰１ｍ3に対する不溶化材の添加量（ｋｇ）を表す。
[Examples 9 to 10, Comparative Examples 6 to 9]
As shown in Table 2, when various insolubilizing materials were added to incinerated ash (Examples 9 to 10, Comparative Examples 6 to 8) and when no insolubilizing materials were added (Comparative Example 9) It was measured. The results are shown in Table 2.
In Table 2, “addition amount (kg / m 3 )” represents the addition amount (kg) of the insolubilizing material relative to 1 m 3 of incinerated ash before the addition of the insolubilizing material.
表２から、本発明に該当する不溶化材を用いた場合（実施例９〜１０）、少ない添加量で焼却灰からのヒ素等の溶出量を低く抑えうることがわかる。一方、比較例６、７では、水酸化マグネシウムの含有率が本発明で規定する数値範囲から外れているため、実施例９〜１０と同程度にヒ素、フッ素、６価クロムの各溶出量を低く抑えるためには、不溶化材の添加量を実施例９〜１０よりも大きくしなければならないことがわかる。比較例８では、カルシウムの含有率（酸化物換算）が本発明で規定する数値範囲を超えているため、実施例９〜１０と同程度にヒ素、フッ素、６価クロムの各溶出量を低く抑えるためには、不溶化材の添加量を実施例９〜１０よりも大きくしなければならないことがわかる。比較例９では、不溶化材を用いていないため、ヒ素、フッ素、６価クロムの溶出量が非常に大きい。 Table 2 shows that when the insolubilizing material corresponding to the present invention is used (Examples 9 to 10), the amount of arsenic and the like eluted from the incinerated ash can be kept low with a small addition amount. On the other hand, in Comparative Examples 6 and 7, since the magnesium hydroxide content is out of the numerical range defined in the present invention, each elution amount of arsenic, fluorine, and hexavalent chromium is the same as in Examples 9 to 10. In order to keep it low, it turns out that the addition amount of the insolubilizing material must be made larger than Examples 9-10. In Comparative Example 8, since the calcium content (in oxide conversion) exceeds the numerical range defined in the present invention, the elution amounts of arsenic, fluorine, and hexavalent chromium are as low as in Examples 9-10. In order to suppress, it turns out that the addition amount of an insolubilizing material must be larger than Examples 9-10. In Comparative Example 9, since no insolubilizing material was used, the amount of elution of arsenic, fluorine, and hexavalent chromium was very large.
［実施例１１〜１４、比較例１０〜１５］
表３に示すように、汚染排水に各種の不溶化材を添加した場合（実施例１１〜１４、比較例１０〜１４）及び不溶化材を添加しない場合（比較例１５）のヒ素等の溶出量を測定した。結果を表３に示す。
なお、表３中、「排水に対する添加量（質量％）」は、不溶化材の添加前の排水１００質量％に対する不溶化材の添加量（質量％）を表す。
[Examples 11-14, Comparative Examples 10-15]
As shown in Table 3, when various insolubilizing materials were added to the contaminated waste water (Examples 11 to 14, Comparative Examples 10 to 14) and when no insolubilizing materials were added (Comparative Example 15) It was measured. The results are shown in Table 3.
In Table 3, “addition amount to waste water (mass%)” represents the addition amount (mass%) of the insolubilizing material relative to 100 mass% of the waste water before the addition of the insolubilizing material.
表３から、本発明に該当する不溶化材を用いた場合（実施例１１〜１４）、少ない添加量で汚染排水からのヒ素等の溶出量を排水基準以下に低く抑えうることがわかる。一方、比較例１０、１１では、水酸化マグネシウムの含有率が本発明で規定する数値範囲から外れているため、実施例１１〜１４に比べて、同一添加量でのヒ素、フッ素、鉛の溶出量のバランスが悪い。比較例１２、１３では、カルシウムの含有率（酸化物換算）が本発明で規定する数値範囲を超えているため、実施例１１〜１４に比べて、同一添加量でのヒ素、フッ素、鉛の溶出量が大きい。比較例１４では、軽焼マグネシア部分水和物ではなく、軽焼マグネシアと試薬である水酸化マグネシウムの混合物を用いているため、実施例１１〜１４に比べて、同一添加量でのヒ素、フッ素、鉛の溶出量が大きい。比較例１５では、不溶化材を用いていないため、ヒ素、フッ素、鉛の溶出量が非常に大きい。 It can be seen from Table 3 that when the insolubilizing material corresponding to the present invention is used (Examples 11 to 14), the amount of arsenic and the like eluted from the contaminated wastewater can be kept low below the wastewater standard with a small addition amount. On the other hand, in Comparative Examples 10 and 11, the magnesium hydroxide content is out of the numerical range defined in the present invention, so that arsenic, fluorine, and lead are eluted at the same added amount as compared with Examples 11-14. The balance of quantity is bad. In Comparative Examples 12 and 13, since the calcium content (in oxide conversion) exceeds the numerical range defined in the present invention, arsenic, fluorine, and lead in the same addition amount compared to Examples 11-14. Large amount of elution. In Comparative Example 14, not a light-burned magnesia partial hydrate but a mixture of light-burned magnesia and magnesium hydroxide, which is a reagent, is used. The amount of lead elution is large. In Comparative Example 15, since an insolubilizing material is not used, the amount of arsenic, fluorine, and lead eluted is very large.
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