JP2010131517A - Insolubilizing agent - Google Patents
Insolubilizing agent Download PDFInfo
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- JP2010131517A JP2010131517A JP2008309435A JP2008309435A JP2010131517A JP 2010131517 A JP2010131517 A JP 2010131517A JP 2008309435 A JP2008309435 A JP 2008309435A JP 2008309435 A JP2008309435 A JP 2008309435A JP 2010131517 A JP2010131517 A JP 2010131517A
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- 239000000463 material Substances 0.000 claims abstract description 176
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 38
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 38
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 32
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 22
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 10
- 239000011707 mineral Substances 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 54
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims description 4
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 4
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 43
- 239000002689 soil Substances 0.000 abstract description 40
- 238000011109 contamination Methods 0.000 abstract description 7
- 230000000887 hydrating effect Effects 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000004580 weight loss Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 53
- 238000002156 mixing Methods 0.000 description 44
- 238000010828 elution Methods 0.000 description 43
- 235000014380 magnesium carbonate Nutrition 0.000 description 34
- 238000000034 method Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- 230000001629 suppression Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000036571 hydration Effects 0.000 description 9
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 9
- 229910052785 arsenic Inorganic materials 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000002198 insoluble material Substances 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 210000004556 brain Anatomy 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 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
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000000706 filtrate 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000003518 caustics Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
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 elution of heavy metals and the like from contaminated soil containing heavy metals and 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。
ここで、汚染土壌中の重金属類等を不溶化して、これら重金属類等が土壌から溶出するのを抑制・防止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）。
Here, various techniques for insolubilizing heavy metals and the like in contaminated soil and suppressing and preventing these heavy metals and the like from eluting from the soil 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。
そこで、本発明は、汚染濃度の高い土壌に対しても、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.
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 concentration.
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、炭酸マグネシウムを主成分とする鉱物（例えば、マグネサイト）を、炭酸マグネシウムの一部が残存するように焼成し、かつ焼成後に部分的に水和することによって得られる特定のマグネシウム系材料からなる粉末を含む不溶化材によれば、本発明の上記目的を達成することができることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventor calcinated a mineral (eg, magnesite) containing magnesium carbonate as a main component so that a part of the magnesium carbonate remains, and a part after the calcination. It has been found that the above-mentioned object of the present invention can be achieved by an insolubilizing material containing a powder made of a specific magnesium-based material obtained by hydration. The present invention has been completed.
すなわち、本発明は、以下の［１］〜［５］を提供するものである。
［１］ （Ａ）以下の条件（ａ）〜（ｃ）をすべて満たすマグネシウム系材料からなる粉末、を含むことを特徴とする不溶化材。
（ａ）炭酸マグネシウムを主成分とする鉱物を６５０〜１，０００℃で焼成して得た酸化マグネシウムと炭酸マグネシウムとを含む焼成物を、当該焼成物の一部が水酸化マグネシウムになるように水和したものであること
（ｂ）カルシウムの酸化物換算の含有量が３．０質量％以下であること
（ｃ）１，０００℃における強熱減量率が６〜３０質量％であること
［２］ （Ｂ）炭酸カルシウム、高炉スラグ、水酸化マグネシウム、第二リン酸カルシウム、硫酸カルシウム、及びゼオライトからなる群より選ばれる少なくとも１種からなる粉末、を含む上記［１］に記載の不溶化材。
［３］ ブレーン比表面積が４，５００〜７，０００ｃｍ２／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、篩残分を表し、Ｄｐは粒子径（μｍ）であり、篩の目の寸法を表し、ｂ、ｎは定数である。）におけるｎ値が０．９０〜１．２０である上記［１］又は［２］に記載の不溶化材。
［４］ 平均粒子径が２０〜４０μｍである上記［１］〜［３］のいずれか１つに記載の不溶化材。
［５］ （Ｃ）水溶性硫酸塩及び水溶性塩化物から選ばれた１種以上の添加物、を含む上記［１］〜［４］のいずれか１つに記載の不溶化材。
That is, the present invention provides the following [1] to [5].
[1] An insolubilizing material comprising (A) a powder made of a magnesium-based material that satisfies all of the following conditions (a) to (c).
(A) A fired product containing magnesium oxide and magnesium carbonate obtained by firing a mineral mainly composed of magnesium carbonate at 650 to 1,000 ° C. so that a part of the fired product becomes magnesium hydroxide. (B) The oxide equivalent content of calcium is 3.0% by mass or less (c) The ignition loss rate at 1,000 ° C. is 6 to 30% by mass [ 2] The insolubilizing material according to the above [1], comprising (B) at least one powder selected from the group consisting of calcium carbonate, blast furnace slag, magnesium hydroxide, dicalcium phosphate, calcium sulfate, and zeolite.
[3] Blaine specific surface area of 4,500~7,000cm 2 / g, and wherein the Rosin-Rammler about the particle size distribution: R = 100exp (-bD p n ) ( wherein, R accumulated residue value a (%) represents the sieve residue, D p is the particle diameter ([mu] m), represents the size of the sieve, b, n is the n value at a constant.) from 0.90 to 1. The insolubilizing material according to [1] or [2], which is 20.
[4] The insolubilizing material according to any one of [1] to [3], wherein the average particle size is 20 to 40 μm.
[5] The insolubilizing material according to any one of the above [1] to [4], comprising (C) one or more additives selected from water-soluble sulfates and water-soluble chlorides.
本発明の不溶化材によると、特定のマグネシウム系材料からなる粉末を含むことにより、汚染濃度の高い土壌等に対しても、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。 According to the insolubilizing material of the present invention, by including a powder made of a specific magnesium-based material, it is possible to sufficiently suppress the elution of heavy metals and the like with a small addition amount even for soil with a high contamination concentration. .
本発明の不溶化材は、（Ａ）特定のマグネシウム系材料からなる粉末、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（（Ｂ）成分、（Ｃ）成分等）を含む。
［（Ａ）成分］
本発明の不溶化材に用いる（Ａ）成分である特定のマグネシウム系材料からなる粉末は、以下の条件（ａ）〜（ｃ）をすべて満たすものである。
（ａ）炭酸マグネシウムを主成分とする鉱物を６５０〜１，０００℃で焼成して得た酸化マグネシウムと炭酸マグネシウムとを含む焼成物を、当該焼成物の一部が水酸化マグネシウムになるように水和したものであること
（ｂ） カルシウムの酸化物換算の含有量が３．０質量％以下であること
（ｃ） １，０００℃における強熱減量率が６〜３０質量％であること
以下、前記（ａ）〜（ｃ）の各条件について詳述する。
［（ａ）の条件］
本発明で用いるマグネシウム系材料は、炭酸マグネシウムを主成分とする鉱物を６５０〜１，０００℃で焼成して得た酸化マグネシウムと炭酸マグネシウムとを含む焼成物を、当該焼成物の一部が水酸化マグネシウムになるように水和したものである。
なお、本発明で用いるマグネシウム系材料は、酸化マグネシウムと炭酸マグネシウムとを含む焼成物の一部を水和したものであるから、酸化マグネシウム、炭酸マグネシウム、及び水酸化マグネシウムの３種のマグネシウム化合物を含むものである。
このようにして得られたマグネシウム系材料を用いることによって、土壌等に添加して混合した場合に、重金属類等の溶出に対して高い抑制効果を得ることができ、また、実用上十分な固化強度を発現することができる。例えば、個別に入手した酸化マグネシウム粉末、炭酸マグネシウム粉末、及び水酸化マグネシウム粉末を単に混合したものでは、本発明のような優れた効果を得ることができない。
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。
上記焼成は、炭酸マグネシウムを主成分とする鉱物の一部が酸化マグネシウムとなり、残部が炭酸マグネシウムのままで残存するように行われる。焼成する際の温度は、６５０〜１，０００℃、好ましくは７５０〜９００℃、より好ましくは８００〜９００℃である。該温度が６５０℃未満であると、酸化マグネシウムが生成し難くなる。該温度が１，０００℃を超えると、重金属類等の溶出抑制効果が低下する。
なお、焼成においては、その時間や温度によって、焼成物に含まれる酸化マグネシウムと炭酸マグネシウムの割合を適宜調整することができる。
焼成時間は、キルン等の焼成手段を用いる場合、本発明の効果が十分に得られるマグネシウム系材料を得る観点から、好ましくは３０〜２４０分間、より好ましくは６０〜２１０分間、特に好ましくは９０〜１８０分間である。なお、後述の実施例で用いるような実験用電気炉を用いる場合、均一に加熱することができるため、好ましい焼成時間は、キルンを用いる場合よりも短くてよく、例えば、３０〜９０分間である。
The insolubilizing material of the present invention contains (A) a powder made of a specific magnesium-based material as an essential component, and further contains other optional components ((B) component, (C) component, etc.) as necessary.
[(A) component]
The powder made of a specific magnesium-based material as the component (A) used for the insolubilizing material of the present invention satisfies all the following conditions (a) to (c).
(A) A fired product containing magnesium oxide and magnesium carbonate obtained by firing a mineral mainly composed of magnesium carbonate at 650 to 1,000 ° C. so that a part of the fired product becomes magnesium hydroxide. (B) The oxide equivalent content of calcium is 3.0% by mass or less (c) The ignition loss rate at 1,000 ° C. is 6-30% by mass. The conditions (a) to (c) will be described in detail.
[Conditions for (a)]
The magnesium-based material used in the present invention is a fired product containing magnesium oxide and magnesium carbonate obtained by firing a mineral mainly composed of magnesium carbonate at 650 to 1,000 ° C., and a part of the fired product is water. It is hydrated to become magnesium oxide.
In addition, since the magnesium-type material used by this invention hydrates a part of baking products containing magnesium oxide and magnesium carbonate, three types of magnesium compounds, magnesium oxide, magnesium carbonate, and magnesium hydroxide, are used. Is included.
By using the magnesium-based material thus obtained, when added to the soil or the like and mixed, it is possible to obtain a high inhibitory effect on elution of heavy metals and the like, and practically sufficient solidification Strength can be expressed. For example, a simple mixture of magnesium oxide powder, magnesium carbonate powder, and magnesium hydroxide powder that are obtained individually cannot achieve the excellent effects of the present invention.
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.
The calcination is performed so that a part of the mineral mainly composed of magnesium carbonate becomes magnesium oxide and the remainder remains as magnesium carbonate. The temperature at the time of baking is 650-1,000 degreeC, Preferably it is 750-900 degreeC, More preferably, it is 800-900 degreeC. When the temperature is lower than 650 ° C., magnesium oxide is hardly generated. When the temperature exceeds 1,000 ° C., the elution suppression effect of heavy metals and the like is reduced.
In firing, the ratio of magnesium oxide and magnesium carbonate contained in the fired product can be appropriately adjusted depending on the time and temperature.
The firing time is preferably from 30 to 240 minutes, more preferably from 60 to 210 minutes, particularly preferably from 90 to 240 minutes from the viewpoint of obtaining a magnesium-based material capable of sufficiently obtaining the effects of the present invention when a firing means such as a kiln is used. 180 minutes. In addition, since it can heat uniformly when using the electric furnace for experiment which is used by the below-mentioned Example, a preferable baking time may be shorter than the case where a kiln is used, for example, is 30 to 90 minutes. .
得られた焼成物を水和する方法としては、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）焼成物に水を添加して混合する方法
（２）焼成物を相対湿度８０％以上の環境下に、１週間以上保持する方法
なお、詳しくは後述するが、本発明の不溶化材が（Ｂ）成分を含む場合には、焼成物と（Ｂ）成分とを混合してから、上記水和反応を行ってもよい。また、水和反応の前に、焼成物（あるいは、焼成物と（Ｂ）成分との混合物）を粉砕することが好ましい。
Although it does not specifically limit as a method of hydrating the obtained baked material, For example, the method of following (1) or (2) is mentioned.
(1) Method of adding water to the fired product and mixing (2) Method of holding the fired product in an environment having a relative humidity of 80% or more for 1 week or more. Although details will be described later, the insolubilizing material of the present invention is When the component (B) is included, the hydration reaction may be performed after mixing the fired product and the component (B). Moreover, it is preferable to grind the fired product (or a mixture of the fired product and the component (B)) before the hydration reaction.
本発明で用いるマグネシウム系材料は、酸化マグネシウム、炭酸マグネシウム、及び水酸化マグネシウムの３種のマグネシウム化合物を含むものである。
酸化マグネシウムの含有率は、（Ａ）マグネシウム系材料の全量を１００質量％として、好ましくは３５〜９１．５質量％、より好ましくは４５〜８７質量％、特に好ましくは５５〜８５質量％である。
炭酸マグネシウムの含有率は、（Ａ）マグネシウム系材料の全量を１００質量％として、好ましくは５〜５５質量％、より好ましくは７〜５０質量％、特に好ましくは８〜３０質量％である。
水酸化マグネシウムの含有率は、（Ａ）マグネシウム系材料の全量を１００質量％として、好ましくは３．５〜３０質量％、より好ましくは５〜２０質量％、特に好ましくは７〜１５質量％である。
酸化マグネシウム、炭酸マグネシウム、及び水酸化マグネシウムの含有率を上記範囲内とすることにより、重金属類等の溶出に対して高い抑制効果を得ることができ、また、不溶化材の固結を防止することができて、優れた作業性を得ることができる。
The magnesium-based material used in the present invention contains three kinds of magnesium compounds: magnesium oxide, magnesium carbonate, and magnesium hydroxide.
The content of magnesium oxide is preferably 35 to 91.5% by mass, more preferably 45 to 87% by mass, and particularly preferably 55 to 85% by mass, with the total amount of the (A) magnesium-based material being 100% by mass. .
The content of magnesium carbonate is preferably 5 to 55% by mass, more preferably 7 to 50% by mass, and particularly preferably 8 to 30% by mass, with the total amount of (A) magnesium-based material being 100% by mass.
The content of magnesium hydroxide is preferably 3.5 to 30% by mass, more preferably 5 to 20% by mass, particularly preferably 7 to 15% by mass, with the total amount of (A) magnesium-based material being 100% by mass. is there.
By controlling the content of magnesium oxide, magnesium carbonate, and magnesium hydroxide within the above range, it is possible to obtain a high inhibitory effect on elution of heavy metals, etc., and to prevent consolidation of the insolubilized material. And excellent workability can be obtained.
［（ｂ）の条件］
本発明で用いるマグネシウム系材料は、カルシウムの酸化物換算の含有率が３．０質量％以下のものである。
なお、マグネシウム系材料に含まれているカルシウム成分としては、酸化カルシウム、水酸化カルシウム、炭酸カルシウム等が挙げられる。
上記のカルシウムの酸化物換算の含有率は、（Ａ）マグネシウム系材料の全量を１００質量％として、３．０質量％以下、好ましくは２．５質量％以下、より好ましくは２．０質量％以下、特に好ましくは１．５質量％以下である。該含有率が３．０質量％を超えると、特に重金属類等による汚染の程度が高い土壌において、重金属類等の溶出抑制効果が低下する。
［（ｃ）の条件］
本発明で用いるマグネシウム系材料は、１，０００℃における強熱減量率が６〜３０質量％のものである。
該強熱減量率は、６〜３０質量％、好ましくは６〜２４質量％、より好ましくは６〜１８質量％である。該強熱減量率が６質量％未満、または３０質量％を超えると、重金属類等の溶出抑制効果が低下し、特に、汚染濃度の高い土壌において重金属類等の溶出を十分に抑制することができない。
[Conditions for (b)]
The magnesium-based material used in the present invention has a calcium oxide content of 3.0% by mass or less.
Examples of the calcium component contained in the magnesium-based material include calcium oxide, calcium hydroxide, and calcium carbonate.
The content of calcium in terms of oxide is 3.0% by mass or less, preferably 2.5% by mass or less, more preferably 2.0% by mass, with the total amount of (A) magnesium-based material being 100% by mass. Hereinafter, it is particularly preferably 1.5% by mass or less. When this content rate exceeds 3.0 mass%, the elution inhibitory effect of heavy metals etc. will fall especially in the soil where the degree of contamination with heavy metals etc. is high.
[Conditions for (c)]
The magnesium-based material used in the present invention has an ignition loss rate at 1,000 ° C. of 6 to 30% by mass.
The ignition loss rate is 6 to 30% by mass, preferably 6 to 24% by mass, and more preferably 6 to 18% by mass. If the ignition loss ratio is less than 6% by mass or exceeds 30% by mass, the elution suppression effect of heavy metals and the like is reduced, and in particular, the elution of heavy metals and the like can be sufficiently suppressed in soil with a high contamination concentration. Can not.
［（Ｂ）成分］
本発明の不溶化材は、必要に応じて、（Ｂ）炭酸カルシウム、高炉スラグ、水酸化マグネシウム、第二リン酸カルシウム、硫酸カルシウム、及びゼオライトからなる群より選ばれる少なくとも１種からなる粉末、を含むことができる。
（Ｂ）成分を適量だけ配合することによって、重金属類等の溶出抑制効果をさらに向上させることができ、また、不溶化材の固結の防止効果を高めて、作業性をさらに向上させることができる。
上記炭酸カルシウムとしては、特に限定されないが、例えば、工業用炭酸カルシウム、試薬の炭酸カルシウム、石灰石粉末、炭酸カルシウムを主成分とする貝殻の粉砕物、サンゴの粉砕物等を使用することができる。中でも、コストの観点から、石灰石粉末が好ましく用いられる。
（Ｂ）成分は、本発明の不溶化材の製造過程において、（ｉ）平均粒径１〜２０ｍｍ（好ましくは２〜１０ｍｍ）、あるいは、（ｉｉ）ブレーン比表面積３，０００〜１２，０００ｃｍ２／ｇ（好ましくは４，０００〜１０，０００ｃｍ２／ｇ）となるように粒度を調整して用いることが好ましい。（ｉ）の場合には、水和前の（Ａ）成分と混合して、これら２種の材料を同時に粉砕した後に、水和に供することが好ましく、また、（ｉｉ）の場合には、粒度を調整済みの水和前の（Ａ）成分と混合した後に、水和に供することが好ましい。
（Ｂ）成分の配合量は、不溶化材の全量１００質量％中、好ましくは４０質量％以下、より好ましくは３０質量％以下、特に好ましくは２０質量％以下である。該配合量が４０質量％を超えると、それに伴って必須成分である（Ａ）マグネシウム系材料の割合が少なくなり、重金属類等の溶出抑制効果が低下する場合もあるため、好ましくない。
（Ｂ）成分の配合量は、（Ｂ）成分の効果を十分に得る観点から、不溶化材の全量１００質量％中、好ましくは１質量％以上、より好ましくは３質量％以上、特に好ましくは５質量％以上である。
[Component (B)]
The insolubilizing material of the present invention contains (B) a powder consisting of at least one selected from the group consisting of calcium carbonate, blast furnace slag, magnesium hydroxide, dicalcium phosphate, calcium sulfate, and zeolite, as necessary. Can do.
By blending an appropriate amount of the component (B), it is possible to further improve the elution suppression effect of heavy metals and the like, and to further improve the workability by enhancing the effect of preventing the insolubilizing material from solidifying. .
The calcium carbonate is not particularly limited, and for example, industrial calcium carbonate, reagent calcium carbonate, limestone powder, ground shells of calcium carbonate, coral grounds, and the like can be used. Among these, limestone powder is preferably used from the viewpoint of cost.
In the process of producing the insolubilized material of the present invention, the component (B) is (i) an average particle diameter of 1 to 20 mm (preferably 2 to 10 mm), or (ii) a Blaine specific surface area of 3,000 to 12,000 cm 2 / It is preferable to adjust the particle size to be g (preferably 4,000 to 10,000 cm 2 / g). In the case of (i), it is preferable to mix with the component (A) before hydration and pulverize these two materials at the same time, and then subject to hydration, and in the case of (ii), It is preferable that the particle size is mixed with the component (A) before hydration that has been adjusted and then subjected to hydration.
The blending amount of the component (B) is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less in the total amount of 100% by mass of the insolubilized material. If the blending amount exceeds 40% by mass, the proportion of the (A) magnesium-based material, which is an essential component, decreases accordingly, and the elution suppression effect of heavy metals and the like may be reduced, which is not preferable.
The blending amount of the component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% in the total amount of the insolubilized material from the viewpoint of sufficiently obtaining the effect of the component (B). It is at least mass%.
本発明の不溶化材中の（Ａ）成分と（Ｂ）成分との合計の粉末（ただし、（Ｂ）成分を含まない場合は、（Ａ）成分のみからなる粉末）は、ブレーン比表面積が４，５００〜７，０００ｃｍ２／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、篩残分を表し、Ｄpは粒径（μｍ）であり、篩の目の寸法を表し、ｂ、ｎは定数である。）におけるｎ値が０．９０〜１．２０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、重金属類等の溶出抑制効果を高めることができ、重金属類等の溶出量の大きい土壌に対しても少量で溶出を抑制することができる。
前記のブレーン比表面積は、より好ましくは５，０００〜６，５００ｃｍ２／ｇである。前記のロジン・ラムラーの式におけるｎ値は、より好ましくは０．９５〜１．１５である。
また、本発明の不溶化材中の（Ａ）成分と（Ｂ）成分との合計の粉末（ただし、（Ｂ）成分を含まない場合は、（Ａ）成分のみからなる粉末）は、平均粒径が２０〜４０μｍであることが好ましく、２５〜４０μｍであることがより好ましい。該平均粒径が上記範囲内であることにより、重金属類等の溶出抑制効果を高めることができ、重金属類等の溶出量の大きい土壌に対しても、少量の使用でその溶出を抑制することができる。
なお、ロジン・ラムラーの式におけるｎ値、及び、平均粒径は、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。
なお、本明細書において、「平均粒径」の語は、５０％質量累積粒径を意味する。
また、本発明の不溶化材中の（Ａ）成分と（Ｂ）成分との合計の粉末（ただし、（Ｂ）成分を含まない場合は、（Ａ）成分のみからなる粉末）は、上記と同様の方法で測定して得た粒度の頻度分布曲線において、２つのピークがあることが好ましい。ここで、第１ピークは１〜５μｍの範囲内に、第２ピークは２０〜５０μｍの範囲内にあることが好ましい。
The total powder of the component (A) and the component (B) in the insolubilized material of the present invention (however, when the component (B) is not included, the powder consisting of only the component (A)) has a specific surface area of 4 a 500~7,000cm 2 / g, and wherein the rosin-Rammler about the particle size distribution: R = 100exp (-bD p n ) ( wherein, R is accumulated residue value (%), Furuizan the minutes, D p is the particle size ([mu] m), represents the size of the sieve, b, n may have a particle size configuration n value in a constant.) is 0.90 to 1.20 Is preferred. By adjusting the particle size composition of the insolubilizing material as described above, the elution suppression effect of heavy metals and the like can be enhanced, and elution can be suppressed in a small amount even for soil with a large amount of elution of heavy metals and the like. .
The Blaine specific surface area is more preferably 5,000 to 6,500 cm 2 / g. The n value in the Rosin-Rammler equation is more preferably 0.95 to 1.15.
Further, the total powder of the component (A) and the component (B) in the insolubilized material of the present invention (however, when the component (B) is not included, the powder consisting of only the component (A)) has an average particle diameter. Is preferably 20 to 40 μm, more preferably 25 to 40 μm. When the average particle diameter is within the above range, the effect of suppressing the elution of heavy metals can be enhanced, and the elution can be suppressed with a small amount of use even for soil with a large amount of elution of heavy metals. Can do.
The n value and the average particle diameter 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.
In the present specification, the term “average particle size” means a 50% mass cumulative particle size.
Further, the total powder of the component (A) and the component (B) in the insolubilized material of the present invention (however, when the component (B) is not included, the powder consisting of only the component (A)) is the same as described above. It is preferable that there are two peaks in the frequency distribution curve of the particle size obtained by measuring by the above method. Here, the first peak is preferably in the range of 1 to 5 μm, and the second peak is preferably in the range of 20 to 50 μm.
［（Ｃ）成分］
本発明の不溶化材は、必要に応じて（Ｃ）水溶性硫酸塩及び水溶性塩化物から選ばれた１種以上の添加物、を含むことができる。該添加物を適量だけ配合することによって、重金属類等の溶出抑制効果をより向上させることができる。
水溶性硫酸塩としては、硫酸第一鉄（硫酸鉄(II)）、硫酸アルミニウム、硫酸アルミニウムカリウム、硫酸アルミニウムナトリウム等が挙げられる。水溶性塩化物としては、塩化第一鉄（塩化鉄(II)）、塩化第二鉄（塩化鉄(III)）等が挙げられる。これらは、１種単独で、あるいは２種以上を組み合わせて用いることができる。さらに、これらは、粉末の形態で用いてもよいし、水溶液の形態で用いてもよい。
（Ｃ）成分の配合量（ただし、水溶液として用いる場合は固形分換算の量である。また、水和物である場合は水和水を除く質量を基準とする。）は、配合量が多過ぎても重金属類等の溶出抑制効果は向上しないこと、及び、コストの観点から、不溶化材の全量１００質量％中、２５質量％以下であることが好ましく、２０質量％以下であることがより好ましい。
（Ｃ）成分の配合量（ただし、水溶液として用いる場合は固形分換算の量である。また、水和物である場合は水和水を除く質量を基準とする。）は、重金属類等の溶出抑制効果の向上の効果を十分に得るために、不溶化材全体１００質量％中、好ましくは３質量％以上である。
なお、（Ｃ）成分を粉末の形態で用いる場合、該粉末の粒径は、特に限定されないが、作業性等の観点から、１ｍｍ以下が好ましく、０．５ｍｍ以下がより好ましい。
[Component (C)]
The insolubilizing material of this invention can contain the 1 or more types of additive chosen from (C) water-soluble sulfate and water-soluble chloride as needed. By blending an appropriate amount of the additive, the effect of suppressing elution of heavy metals can be further improved.
Examples of the water-soluble sulfate include ferrous sulfate (iron (II) sulfate), aluminum sulfate, potassium aluminum sulfate, and sodium aluminum sulfate. Examples of water-soluble chlorides include ferrous chloride (iron (II) chloride) and ferric chloride (iron (III) chloride). These can be used singly or in combination of two or more. Furthermore, these may be used in the form of powder or in the form of an aqueous solution.
The blending amount of component (C) (however, when used as an aqueous solution, it is an amount in terms of solid content. In the case of a hydrate, the blending amount is based on the mass excluding hydration water). Even if it passes too much, it is preferable that it is 25 mass% or less in 100 mass% of the whole quantity of an insolubilization material from a viewpoint of the elution suppression effect of heavy metals etc. not being improved, and it is more preferable that it is 20 mass% or less. preferable.
The blending amount of the component (C) (however, when used as an aqueous solution, it is an amount in terms of solid content. In the case of a hydrate, the mass is based on the weight excluding hydration water.) In order to sufficiently obtain the effect of improving the elution suppression effect, the total insolubilized material is 100% by mass, preferably 3% by mass or more.
In addition, when (C) component is used with the form of a powder, the particle size of this powder is although it does not specifically limit, From viewpoints of workability | operativity etc., 1 mm or less is preferable and 0.5 mm or less is more preferable.
本発明の不溶化材が（Ａ）成分のみからなる場合には、上述の条件・方法に従って、炭酸マグネシウムを主成分とする鉱物を焼成し、必要に応じて粉砕し、焼成物（あるいは焼成物の粉砕物）を部分的に水和することにより、不溶化材を得ることができる。粉砕は、得られる焼成物の粉砕物のブレーン比表面積が好ましくは４，５００〜７，０００ｃｍ２／ｇ、より好ましくは５，０００〜６，５００ｃｍ２／ｇとなるように行われる。
不溶化材が（Ｂ）成分を含む場合には、例えば、下記（ａ）〜（ｃ）の方法により、不溶化材を得ることができる。
（ａ） 焼成物と（Ｂ）成分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、マグネシウム系材料（（Ａ）成分）と（Ｂ）成分とを含む不溶化材を得る工程と、を含む方法
（ｂ） 焼成物を粉砕して、所定の粒度を有する焼成物の粉砕物を得る工程と、（Ｂ）成分を粉砕して、所定の粒度を有する（Ｂ）成分の粉砕物を得る工程と、前記焼成物の粉砕物と（Ｂ）成分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、マグネシウム系材料と（Ｂ）成分とを含む不溶化材を得る工程と、を含む方法
（ｃ） 焼成物を粉砕して、所定の粒度を有する焼成物の粉砕物を得る工程と、前記焼成物の粉砕物を水和させて、マグネシウム系材料を得る工程と、（Ｂ）成分を粉砕して、所定の粒度を有する（Ｂ）成分の粉砕物を得る工程と、前記マグネシウム系材料と（Ｂ）成分の粉砕物とを混合して不溶化材を得る工程と、を含む方法
これらのうち、重金属類等の溶出抑制効果、及び作業性の観点から、好ましくは（ａ）又は（ｂ）の方法であり、より好ましくは（ａ）の方法である。
When the insolubilizing material of the present invention comprises only the component (A), the mineral containing magnesium carbonate as a main component is calcined according to the above-mentioned conditions and methods, pulverized as necessary, and the calcined product (or the calcined product) The insolubilized material can be obtained by partially hydrating the pulverized product. Milling, Blaine specific surface area of the pulverized calcined product obtained preferably 4,500~7,000cm 2 / g, more preferably performed such that the 5,000~6,500cm 2 / g.
When the insolubilizing material contains the component (B), for example, the insolubilizing material can be obtained by the following methods (a) to (c).
(A) a step of mixing the fired product and the component (B) to obtain a mixture, a step of pulverizing the mixture to obtain a pulverized product of a mixture having a predetermined particle size, and hydrating the pulverized product of the mixture A step of obtaining an insolubilized material containing a magnesium-based material (component (A)) and a component (B) (b) pulverizing the baked product to obtain a pulverized product of the baked product having a predetermined particle size. A step of mixing the step of obtaining, the step of obtaining the pulverized product of the component (B) having a predetermined particle size by pulverizing the component (B), and the pulverized product of the fired product and the pulverized product of the component (B) And a step of hydrating the mixture to obtain an insolubilizing material containing the magnesium-based material and the component (B) (c) calcination of the fired product and firing having a predetermined particle size A process for obtaining a pulverized product, and a magnesium-based material by hydrating the pulverized product of the fired product Obtaining the insolubilizing material by mixing the step of obtaining, the step of obtaining a pulverized product of component (B) having a predetermined particle size by pulverizing component (B), and the pulverized product of component (B) Among these, from the viewpoint of the elution suppression effect of heavy metals and the like and workability, the method (a) or (b) is preferred, and the method (a) is more preferred. .
上記（ａ）の方法では、粉砕前の焼成物は、粒径が１μｍ〜５０ｍｍであることが好ましい。また、粉砕前の（Ｂ）成分は、粒径が１μｍ〜５０ｍｍであることが好ましく、２μｍ〜２０ｍｍ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焼成物及び（Ｂ）成分を用いることにより、混合物の粉砕物、ひいては不溶化材の粒度構成を容易に調整することができる。
粒径が１μｍ〜５０ｍｍである焼成物と、粒径が１μｍ〜５０ｍｍである（Ｂ）成分とを同時に粉砕して、これら２種の材料の混合物からなる粉砕物のブレーン比表面積を４，５００〜７，０００ｃｍ２／ｇ（好ましくは５，０００〜６，５００ｃｍ２／ｇ）の範囲内に調整すると、１〜５μｍの範囲内の第１ピークと、２０〜５０μｍの範囲内の第２ピークとの２つのピークを有する、粒度の頻度分布曲線を形成する粉末を得ることができる。この場合、第２ピーク（頻度％）／第１ピーク（頻度％）の比は、好ましくは２〜４である。なお、後述の実施例８〜１０、１４〜１６は、これらの条件をすべて満たすものである。
また、上記（ａ）の方法では、焼成物と（Ｂ）成分を同時に粉砕するため、これらを個別に粉砕する上記（ｂ）又は（ｃ）の方法に比して、作業が簡易であるという利点を有する。
In the method (a), the fired product before pulverization preferably has a particle size of 1 μm to 50 mm. The component (B) before pulverization preferably has a particle size of 1 μm to 50 mm, more preferably 2 μm to 20 mm. By using the fired product before pulverization having such a particle size and the component (B), the pulverized product of the mixture, and thus the particle size constitution of the insolubilized material can be easily adjusted.
The fired product having a particle size of 1 μm to 50 mm and the component (B) having a particle size of 1 μm to 50 mm are pulverized at the same time, so that the pulverized product made of a mixture of these two materials has a Blaine specific surface area of 4,500. When ~7,000cm 2 / g (preferably 5,000~6,500cm 2 / g) is adjusted to the range of a first peak in the range of 1 to 5 [mu] m, the second peak in the range of 20~50μm The powder which forms the frequency distribution curve of a particle size which has two peaks with these can be obtained. In this case, the ratio of the second peak (frequency%) / first peak (frequency%) is preferably 2 to 4. In addition, Examples 8 to 10 and 14 to 16 described later satisfy all of these conditions.
Further, in the method (a), the fired product and the component (B) are pulverized at the same time, so that the work is simpler than the method (b) or (c) in which these are pulverized separately. Have advantages.
上記（ｂ）又は（ｃ）の方法においては、焼成物は、ブレーン比表面積が好ましくは４，５００〜７，０００ｃｍ２／ｇ、より好ましくは５，０００〜６，５００ｃｍ２／ｇとなるように粉砕される。また、（Ｂ）成分は、ブレーン比表面積が好ましくは３，０００〜７，０００ｃｍ２／ｇ、より好ましくは４，０００〜６，０００ｃｍ２／ｇとなるように粉砕される。このような比表面積を有する焼成物の粉砕物（あるいは、その部分水和物）と（Ｂ）成分の粉砕物とを混合することにより、上述の好ましい粒度構成を有する不溶化材を得ることができる。
なお、（Ｂ）成分が上記ブレーン比表面積をすでに有する場合は、粉砕を行わず、そのまま用いることができる。
In the above method (b) or (c), the calcined product, the Blaine specific surface area of preferably 4,500~7,000cm 2 / g, so that more preferably the 5,000~6,500cm 2 / g To be crushed. Also, (B) component, Blaine specific surface area of preferably 3,000~7,000cm 2 / g, more preferably ground to a 4,000~6,000cm 2 / g. By mixing the pulverized product (or a partially hydrated product thereof) having such a specific surface area and the pulverized product of the component (B), an insolubilized material having the above preferred particle size constitution can be obtained. .
In addition, when (B) component already has the said brain specific surface area, it can use as it is, without grind | pulverizing.
本発明の不溶化材の添加量は、対象土の性状や施工条件、重金属類等の溶出量や処理土の要求性能等にもよるが、一般的には、対象土１ｍ３あたり５０〜４００ｋｇが好ましく、１００〜３５０ｋｇがより好ましい。
不溶化材の添加方法としては、対象土に不溶化材を粉体のまま添加して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して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。
なお、（Ｃ）成分のみを水溶液で用いる場合、（Ａ）成分もしくは（Ａ）成分と（Ｂ）成分の混合物と、（Ｃ）成分とを別々に対象土に添加することもできる。
また、本発明の不溶化材は、土壌に対して好適に用いられるが、土壌以外のもの、例えば、灰類、ダスト類などにも用いることができる。この場合の添加量及び添加方法は、土壌に対して用いる場合と同じである。
Although the amount of the insolubilizing material of the present invention depends on the properties and construction conditions of the target soil, the amount of elution of heavy metals, the required performance of the treated soil, etc., in general, 50 to 400 kg per 1 m 3 of the target soil. Preferably, 100 to 350 kg is more preferable.
As a method for adding the insolubilizing material, dry addition in which the insolubilizing material is added to the target soil as powder and mixed, or slurry addition in which water is added and added 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.
In addition, when using only (C) component with aqueous solution, the mixture of (A) component or (A) component and (B) component, and (C) component can also be added separately to object soil.
Moreover, although the insolubilizing material of this invention is used suitably with respect to soil, it can be used also for things other than soil, for example, ash, dusts, etc. The addition amount and addition method in this case are the same as those used for soil.
以下、本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。
［不溶化材の製造］
（不溶化材Ａ）
マグネサイト（炭酸マグネシウムの含有率：９５質量％）を８５０℃で３０分間、実験用電気炉を用いて焼成して、酸化マグネシウム及び炭酸マグネシウムを含む焼成物を得た。次いで、得られた焼成物を粉砕し、ブレーン比表面積５，５００ｃｍ２／ｇの焼成物の粉砕物を得た。
得られた焼成物の粉砕物を相対湿度１００％の保管室にて１０日間保管することによりその一部を水和させ、マグネシウム系材料（（Ａ）成分）からなる不溶化材Ａを得た。
（不溶化材Ｂ）
焼成時間を２１分間に変更したこと以外は、不溶化材Ａと同様にして、不溶化材Ｂを得た。
（不溶化材Ｃ）
焼成時間を１６分間に変更したこと以外は、不溶化材Ａと同様にして、不溶化材Ｃを得た。
（不溶化材Ｄ）
水和の条件を、湿度１００％の保管室に２０日間に変更したこと以外は、不溶化材Ａと同様にして、不溶化材Ｄを得た。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Manufacture of insolubilized materials]
(Insolubilized material A)
Magnesite (magnesium carbonate content: 95% by mass) was fired at 850 ° C. for 30 minutes using an experimental electric furnace to obtain a fired product containing magnesium oxide and magnesium carbonate. Next, the obtained fired product was pulverized to obtain a pulverized product of the fired product having a Blaine specific surface area of 5,500 cm 2 / g.
The obtained pulverized product was stored in a storage room with a relative humidity of 100% for 10 days to hydrate a part thereof, thereby obtaining an insolubilized material A made of a magnesium-based material (component (A)).
(Insolubilized material B)
Insolubilized material B was obtained in the same manner as insolubilized material A, except that the firing time was changed to 21 minutes.
(Insolubilized material C)
Insolubilized material C was obtained in the same manner as insolubilized material A except that the firing time was changed to 16 minutes.
(Insolubilized material D)
Insolubilized material D was obtained in the same manner as insolubilized material A, except that the hydration conditions were changed to a storage room at 100% humidity for 20 days.
（不溶化材Ｅ）
マグネサイト（炭酸マグネシウムの含有率：９５質量％）を８５０℃で６０分間、実験用電気炉を用いて焼成して、酸化マグネシウムからなる焼成物を得た。次いで、得られた焼成物を粉砕し、ブレーン比表面積５，２００ｃｍ２／ｇの焼成物の粉砕物を得た。
得られた焼成物の粉砕物を湿度６０％の保管室にて２０日間保管することによりその一部を水和させ、酸化マグネシウムと水酸化マグネシウムとからなる不溶化材Ｅを得た。
（不溶化材Ｆ）
不溶化材Ｅ（酸化マグネシウムと水酸化マグネシウムとからなる不溶化材）に、炭酸マグネシウム及び水酸化マグネシウム（試薬特級）を添加することにより、不溶化材Ａと同一組成を有する不溶化材Ｆを得た。
（不溶化材Ｇ）
不溶化材Ｅ（酸化マグネシウムと水酸化マグネシウムとからなる不溶化材）に、炭酸マグネシウム及び水酸化マグネシウム（試薬特級）を添加することにより、不溶化材Ｂと同一組成を有する不溶化材Ｇを得た。
（不溶化材Ｈ）
不溶化材Ｅ（酸化マグネシウムと水酸化マグネシウムとからなる不溶化材）に、炭酸マグネシウム及び水酸化マグネシウム（試薬特級）を添加することにより、不溶化材Ｃと同一組成を有する不溶化材Ｈを得た。
（不溶化材Ｉ）
原料として、カルシウムの含有率の大きいマグネサイトを用いたこと以外は不溶化材Ａと同様にして、不溶化材Ｉを得た。
(Insolubilized material E)
Magnesite (magnesium carbonate content: 95% by mass) was fired at 850 ° C. for 60 minutes using an experimental electric furnace to obtain a fired product made of magnesium oxide. Subsequently, the fired product obtained was pulverized to obtain a pulverized product of the fired product having a Blaine specific surface area of 5,200 cm 2 / g.
The obtained pulverized product was stored in a storage room at a humidity of 60% for 20 days to hydrate a part thereof, thereby obtaining an insolubilized material E composed of magnesium oxide and magnesium hydroxide.
(Insolubilized material F)
An insolubilized material F having the same composition as the insolubilized material A was obtained by adding magnesium carbonate and magnesium hydroxide (special grade reagent) to the insolubilized material E (insolubilized material composed of magnesium oxide and magnesium hydroxide).
(Insolubilized material G)
An insolubilized material G having the same composition as the insolubilized material B was obtained by adding magnesium carbonate and magnesium hydroxide (special grade reagent) to the insolubilized material E (insolubilized material composed of magnesium oxide and magnesium hydroxide).
(Insolubilized material H)
Insoluble material H having the same composition as insolubilized material C was obtained by adding magnesium carbonate and magnesium hydroxide (special grade reagent) to insolubilized material E (insolubilized material consisting of magnesium oxide and magnesium hydroxide).
(Insolubilized material I)
Insolubilized material I was obtained in the same manner as insolubilized material A except that magnesite having a high calcium content was used as a raw material.
（不溶化材Ａ−１〜Ａ−７）
不溶化材Ａに対して、副材として、（Ｃ）成分のみ、または、（Ｃ）成分及び（Ｂ）成分を添加することにより、不溶化材Ａ−１〜Ａ−７を得た。
なお、下記の副材の配合割合は、得られた不溶化材Ａ−１〜Ａ−７中における各副材の割合である。また、下記の（Ｃ）成分の配合割合は、水和水を除く質量を基準とする。
具体的には、不溶化材Ａに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；５質量％、粒径：０．１〜０．３ｍｍ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ａ−１を得た。
不溶化材Ａに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；１０質量％、粒径：０．１〜０．３ｍｍ）、及び、（Ｂ）成分である二水石膏（配合割合；１０質量％、ブレーン比表面積：１０，０００ｃｍ2／ｇ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ａ−２を得た。
不溶化材Ａに対して、（Ｃ）成分である硫酸アルミニウム無水塩（配合割合；５質量％、粒径：３０〜６０μｍ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ａ−３を得た。
不溶化材Ａに対して、（Ｃ）成分である硫酸アルミニウム無水塩（配合割合；１０質量％、粒径：３０〜６０μｍ）、及び、（Ｂ）成分である第二リン酸カルシウム（配合割合；１０質量％、ブレーン比表面積：４，０００ｃｍ2／ｇ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ａ−４を得た。
不溶化材Ａに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；５質量％、粒径：０．１〜０．３ｍｍ）を添加し、ミルで均一に混合することにより、不溶化材Ａ−５を得た。
不溶化材Ａに対して、（Ｃ）成分である塩化第二鉄六水塩（配合割合；５質量％、特級試薬）を添加し、ミルで均一に混合することにより、不溶化材Ａ−６を得た。
不溶化材Ａに対して、（Ｃ）成分である塩化第一鉄四水塩（配合割合；５質量％、特級試薬）を添加し、ミルで均一に混合することにより、不溶化材Ａ−７を得た。
(Insolubilized materials A-1 to A-7)
Insoluble materials A-1 to A-7 were obtained by adding only the component (C) or the components (C) and (B) as sub-materials to the insolubilized material A.
In addition, the mixing | blending ratio of the following submaterial is a ratio of each submaterial in the obtained insolubilized materials A-1 to A-7. Moreover, the blending ratio of the following component (C) is based on the mass excluding hydration water.
Specifically, ferrous sulfate monohydrate (mixing ratio: 5 mass%, particle size: 0.1 to 0.3 mm) as component (C) is added to insolubilized material A, and the mixture is added to the hensil mixer. Insoluble material A-1 was obtained by mixing uniformly.
For insolubilized material A, ferrous sulfate monohydrate (mixing ratio; 10 mass%, particle size: 0.1 to 0.3 mm) as component (C) and dihydrate as component (B) Gypsum (mixing ratio: 10% by mass, Blaine specific surface area: 10,000 cm 2 / g) was added and uniformly mixed with a Hensyl mixer to obtain an insolubilized material A-2.
To the insolubilized material A, an anhydrous aluminum sulfate salt (component (C): 5 mass%, particle size: 30 to 60 μm) is added and mixed uniformly with a hensil mixer, thereby insolubilizing material A- 3 was obtained.
With respect to insolubilized material A, anhydrous aluminum sulfate (C) component (mixing ratio: 10 mass%, particle size: 30 to 60 μm) and dicalcium phosphate (B) component (mixing ratio: 10 mass) as component (C) %, Blaine specific surface area: 4,000 cm 2 / g) and uniformly mixed with a Hensyl mixer, to obtain insolubilized material A-4.
Add ferrous sulfate monohydrate (mixing ratio: 5 mass%, particle size: 0.1 to 0.3 mm), which is component (C), to insolubilized material A, and mix uniformly with a mill. As a result, an insolubilized material A-5 was obtained.
To the insolubilized material A, ferric chloride hexahydrate (mixing ratio: 5% by mass, special grade reagent) as component (C) is added and mixed uniformly by a mill to obtain insolubilized material A-6. Obtained.
By adding ferrous chloride tetrahydrate (mixing ratio; 5 mass%, special grade reagent) as component (C) to insolubilized material A, and mixing uniformly with a mill, insolubilized material A-7 Obtained.
（不溶化材Ｂ−１〜Ｂ−７）
不溶化材Ｂに対して、副材として、（Ｃ）成分のみ、または、（Ｃ）成分及び（Ｂ）成分を添加することにより、不溶化材Ｂ−１〜Ｂ−７を得た。
なお、下記の副材の配合割合は、得られた不溶化材Ｂ−１〜Ｂ−７中における各副材の割合である。
具体的には、不溶化材Ｂに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；１０質量％、粒径：０．１〜０．３ｍｍ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｂ−１を得た。
不溶化材Ｂに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；１０質量％、粒径：０．１〜０．３ｍｍ）、及び、（Ｂ）成分である炭酸カルシウム（配合割合；１０質量％、ブレーン比表面積：５，０００ｃｍ2／ｇ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｂ−２を得た。
不溶化材Ｂに対して、（Ｃ）成分である硫酸アルミニウム無水塩（配合割合；１０質量％、粒径：３０〜６０μｍ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｂ−３を得た。
不溶化材Ｂに対して、（Ｃ）成分である硫酸アルミニウム無水塩（配合割合；１０質量％、粒径：３０〜６０μｍ）、及び、（Ｂ）成分であるゼオライト（配合割合；１０質量％、ブレーン比表面積：５，０００ｃｍ2／ｇ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｂ−４を得た。
不溶化材Ｂに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；１０質量％、粒径：０．１〜０．３ｍｍ）を添加し、ミルで均一に混合することにより、不溶化材Ｂ−５を得た。
不溶化材Ｂに対して、（Ｃ）成分である塩化第二鉄六水塩（配合割合；１０質量％、特級試薬）を添加し、ミルで均一に混合することにより、不溶化材Ｂ−６を得た。
不溶化材Ｂに対して、（Ｃ）成分である塩化第一鉄四水塩（配合割合；１０質量％、特級試薬）を添加し、ミルで均一に混合することにより、不溶化材Ｂ−７を得た。
(Insolubilized materials B-1 to B-7)
Insoluble materials B-1 to B-7 were obtained by adding only the component (C) or the components (C) and (B) as sub-materials to the insolubilized material B.
In addition, the mixture ratio of the following submaterial is a ratio of each submaterial in the obtained insolubilized materials B-1 to B-7.
Specifically, ferrous sulfate monohydrate (mixing ratio: 10% by mass, particle size: 0.1 to 0.3 mm) as component (C) is added to insolubilized material B, and the mixture is added to the hensil mixer. The mixture was uniformly mixed to obtain an insolubilizing material B-1.
For insolubilized material B, ferrous sulfate monohydrate (C) component (mixing ratio: 10 mass%, particle size: 0.1 to 0.3 mm), and calcium carbonate as component (B) (Mixing ratio: 10% by mass, Blaine specific surface area: 5,000 cm 2 / g) was added and mixed uniformly with a Hensyl mixer to obtain insolubilized material B-2.
To the insolubilizing material B, anhydrous aluminum sulfate (C) component (mixing ratio: 10% by mass, particle size: 30 to 60 μm) is added and mixed uniformly with a Hensyl mixer, so that the insolubilizing material B- 3 was obtained.
With respect to insolubilized material B, anhydrous aluminum sulfate (C) component (mixing ratio: 10% by mass, particle size: 30 to 60 μm) and zeolite (B) component (mixing ratio: 10% by mass, (Blaine specific surface area: 5,000 cm 2 / g) was added and mixed uniformly with a Hensyl mixer to obtain an insolubilized material B-4.
Add ferrous sulfate monohydrate (mixing ratio: 10 mass%, particle size: 0.1 to 0.3 mm) as component (C) to insolubilized material B, and mix uniformly with a mill. As a result, an insolubilized material B-5 was obtained.
To the insolubilized material B, ferric chloride hexahydrate (C) component (mixing ratio: 10 mass%, special grade reagent) is added to the insolubilized material B, and mixed uniformly with a mill to obtain the insolubilized material B-6. Obtained.
To the insolubilized material B, ferrous chloride tetrahydrate (mixing ratio; 10% by mass, special grade reagent) as component (C) is added and mixed uniformly by a mill to obtain insolubilized material B-7. Obtained.
（不溶化材Ｃ−１〜Ｃ−７）
不溶化材Ｃに対して、副材として、（Ｃ）成分のみ、または、（Ｃ）成分及び（Ｂ）成分を添加することにより、不溶化材Ｃ−１〜Ｃ−７を得た。
なお、下記の副材の配合割合は、得られた不溶化材Ｃ−１〜Ｃ−７中における各副材の割合である。
具体的には、不溶化材Ｃに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；２０質量％、粒径：０．１〜０．３ｍｍ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｃ−１を得た。
不溶化材Ｃに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；１０質量％、粒径：０．１〜０．３ｍｍ）、及び、（Ｂ）成分である水酸化マグネシウム（配合割合；１０質量％、ブレーン比表面積：８，０００ｃｍ2／ｇ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｃ−２を得た。
不溶化材Ｃに対して、（Ｃ）成分である硫酸アルミニウム無水塩（配合割合；２０質量％、粒径：３０〜６０μｍ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｃ−３を得た。
不溶化材Ｃに対して、（Ｃ）成分である硫酸アルミニウム無水塩（配合割合；１０質量％、粒径：３０〜６０μｍ）、及び、（Ｂ）成分である高炉スラグ（配合割合；１０質量％、ブレーン比表面積：４，０００ｃｍ2／ｇ）を添加し、ヘンシルミキサにて均一に混合することにより、不溶化材Ｃ−４を得た。
不溶化材Ｃに対して、（Ｃ）成分である硫酸第一鉄一水塩（配合割合；２０質量％、粒径：０．１〜０．３ｍｍ）を添加し、ミルで均一に混合することにより、不溶化材Ｃ−５を得た。
不溶化材Ｃに対して、（Ｃ）成分である塩化第二鉄六水塩（配合割合；２０質量％、特級試薬）を添加し、ミルで均一に混合することにより、不溶化材Ｃ−６を得た。
不溶化材Ｃに対して、（Ｃ）成分である塩化第一鉄四水塩（配合割合；２０質量％、特級試薬）を添加し、ミルで均一に混合することにより、不溶化材Ｃ−７を得た。
(Insolubilized materials C-1 to C-7)
Insoluble materials C-1 to C-7 were obtained by adding only the component (C) or the components (C) and (B) to the insolubilized material C as sub-materials.
In addition, the mixture ratio of the following submaterial is a ratio of each submaterial in the obtained insolubilized materials C-1 to C-7.
Specifically, ferrous sulfate monohydrate (mixing ratio: 20% by mass, particle size: 0.1 to 0.3 mm) as component (C) is added to insolubilized material C, and the mixture is added to the hensil mixer. The mixture was uniformly mixed to obtain an insolubilizing material C-1.
For insolubilized material C, ferrous sulfate monohydrate (C) component (mixing ratio: 10% by mass, particle size: 0.1 to 0.3 mm) and (B) component hydroxylated Magnesium (mixing ratio: 10% by mass, Blaine specific surface area: 8,000 cm 2 / g) was added, and the mixture was uniformly mixed with a Hensyl mixer to obtain insolubilized material C-2.
To the insolubilized material C, an anhydrous aluminum sulfate salt (component (C): 20% by mass, particle size: 30 to 60 μm) is added and mixed uniformly with a Hensyl mixer, so that the insolubilized material C- 3 was obtained.
With respect to the insolubilized material C, anhydrous aluminum sulfate (C) component (mixing ratio: 10% by mass, particle size: 30 to 60 μm) and blast furnace slag (B) component (B) component (C) Brain specific surface area: 4,000 cm 2 / g) was added and mixed uniformly with a Hensyl mixer to obtain insolubilized material C-4.
Add ferrous sulfate monohydrate (mixing ratio; 20 mass%, particle size: 0.1 to 0.3 mm) as component (C) to insolubilized material C, and mix uniformly with a mill. Thus, insolubilized material C-5 was obtained.
To the insolubilized material C, ferric chloride hexahydrate (compounding ratio: 20% by mass, special grade reagent) which is component (C) is added and mixed uniformly with a mill to obtain insolubilized material C-6. Obtained.
To the insolubilized material C, ferrous chloride tetrahydrate (mixing ratio: 20% by mass, special grade reagent) which is component (C) is added and mixed uniformly by a mill to obtain insolubilized material C-7. Obtained.
［実施例１〜４、比較例１〜６］
不溶化材Ａ〜Ｉに対して、成分組成、ブレーン比表面積、ロジン・ラムラーの式のｎ値、平均粒径、強熱減量率を下記の方法により求めた。結果を表１に示す。
また、不溶化材Ａ〜Ｉを用いて（実施例１〜４、比較例１〜５）、あるいは、不溶化材を用いずに（比較例６）、下記の重金属類等の溶出試験１〜５を行った。結果を表２に示す。
（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。
（ブレーン比表面積）
「ＪＩＳ Ｒ ５２０１」に準じて測定した。
（ロジン・ラムラーの式のｎ値、平均粒径）
１００ｍｌビーカー中に、エタノール（分散媒）２０ｍｌ、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、平均粒径（５０％質量累積粒径）、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。
（強熱減量率）
「ＪＩＳ Ｒ ５２０２ ポルトランドセメントの化学分析方法 ８．強熱減量の定量方法」に準じて、強熱温度を１，０００℃として測定した。
[Examples 1 to 4, Comparative Examples 1 to 6]
With respect to the insolubilized materials A to I, the component composition, the Blaine specific surface area, the n value of the Rosin-Rammler formula, the average particle size, and the ignition loss rate were determined by the following methods. The results are shown in Table 1.
Further, using the insolubilizing materials A to I (Examples 1 to 4, Comparative Examples 1 to 5) or without using the insolubilizing material (Comparative Example 6), the following elution tests 1 to 5 for heavy metals and the like are performed. went. The results are shown in Table 2.
(Component composition)
Calculated from X-ray diffraction, thermogravimetric analysis and chemical analysis values.
(Brain specific surface area)
It measured according to "JISR5201".
(Rosin Ramler equation n value, average particle size)
In a 100 ml beaker, 20 ml of ethanol (dispersion medium) and 0.05 g of an insolubilizing material were added, and ultrasonically dispersed for 1 minute using an ultrasonic cleaner (VS-100, frequency 50 kHz) manufactured by ASONE. Then, using Nikkiso Co., Ltd. 9320-X10 (particle size distribution measuring apparatus), the average particle diameter (50% mass cumulative particle diameter) and the n value of the rosin-Rammler type were determined. Note that the refractive index of the sample is assumed to be 1.72.
(Ignition loss rate)
The ignition temperature was measured at 1,000 ° C. according to “JIS R 5202 Portland cement chemical analysis method 8. Determination method of ignition loss”.
（重金属類等の溶出試験１；ろ液を用いたヒ素の溶出試験）
亜ヒ酸ナトリウム（ＮａＡｓＯ2）を蒸留水に溶解し、ヒ素濃度が９．６ｍｇ／リットルの溶液を調製する。該溶液１００ｇに不溶化材１ｇを投入し、２００回／分の速度で６時間振とう後、０．４５μｍのメンブレンフィルターにて濾過し、ろ液のヒ素濃度を測定した。
（重金属類等の溶出試験２；汚染土壌を用いたヒ素の溶出試験）
ヒ素汚染土壌（含水率７０％）に対し、不溶化材を表２に示す量添加し、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。
（重金属類等の溶出試験３；汚染土壌を用いたフッ素の溶出試験）
フッ素汚染土壌（含水率７５％）に対し、不溶化材を表２に示す量添加し、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。
（重金属類等の溶出試験４；汚染土壌を用いた鉛の溶出試験）
鉛汚染土壌（含水率７０％）に対し、不溶化材を表２に示す量添加し、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。
（重金属類等の溶出試験５；汚染土壌を用いた６価クロムの溶出試験）
６価クロム汚染土壌（含水率８０％）に対し、不溶化材を表２に示す量添加し、材齢７日の改良土壌からの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。
(Elution test 1 for heavy metals, etc .; Arsenic elution test using filtrate)
Sodium arsenite (NaAsO 2 ) is dissolved in distilled water to prepare a solution having an arsenic concentration of 9.6 mg / liter. 1 g of insolubilizing material was added to 100 g of the solution, shaken at a rate of 200 times / minute for 6 hours, filtered through a 0.45 μm membrane filter, and the arsenic concentration of the filtrate was measured.
(Elution test for heavy metals 2; Arsenic elution test using contaminated soil)
The amount of insolubilized material shown in Table 2 was added to the arsenic-contaminated soil (water content 70%), and the amount of arsenic 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 for arsenic is 0.01 mg / liter.
(Elution test 3 for heavy metals; elution test for fluorine using contaminated soil)
The amount of insolubilized material shown in Table 2 was added to fluorine-contaminated soil (water content 75%), and the amount of fluorine 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 of fluorine is 0.8 mg / liter.
(Elution test for heavy metals 4; Lead elution test using contaminated soil)
The amount of insolubilized material shown in Table 2 was added to the lead-contaminated soil (water content 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.
(Elution test 5 for heavy metals, etc .; Elution test for hexavalent chromium using contaminated soil)
To the hexavalent chromium contaminated soil (water content 80%), the amount of insolubilized material is added as shown in Table 2, and the amount of hexavalent chromium eluted from the improved soil on the age of 7 days conforms to the Ministry of the Environment Notification No. 46. Measured. The environmental standard value for hexavalent chromium is 0.05 mg / liter.
［実施例５〜２５］
上記不溶化材Ａ−１〜Ａ−７、Ｂ−１〜Ｂ−７、Ｃ−１〜Ｃ−７を用いて、実施例１と同様にして、（Ａ）成分と（Ｂ）成分とからなる粉末の物性の測定、及び、重金属類等の溶出試験１〜５を行った。結果を表３及び表４に示す。
[Examples 5 to 25]
Using the insolubilizing materials A-1 to A-7, B-1 to B-7, and C-1 to C-7, the component (A) and the component (B) are formed in the same manner as in Example 1. Measurement of powder physical properties and elution tests 1 to 5 for heavy metals and the like were performed. The results are shown in Tables 3 and 4.
表２から、本発明の不溶化材によると、少ない添加量で、重金属類等（ヒ素、フッ素、鉛、６価クロム）の溶出抑制効果に優れることがわかる（実施例１〜４）。一方、焼成の際に、原料である炭酸マグネシウムを完全に酸化マグネシウムとし、そのため、炭酸マグネシウムを含まず、酸化マグネシウム及び水酸化マグネシウムのみからなるマグネシウム系材料を用いた比較例１では、実施例１〜４に比して、重金属類等の溶出抑制効果が低いことがわかる。また、酸化マグネシウム及び水酸化マグネシウムのみからなる不溶化材に対して、炭酸マグネシウム及び水酸化マグネシウムを後添加しても（比較例２〜４）、比較例１と同様に重金属類等の溶出抑制効果に劣ることがわかる。
また、（Ａ）成分中のカルシウムの含有量が本発明の範囲外である比較例５では、重金属類等の溶出抑制効果に劣ることがわかる。
表４から、（Ｃ）成分を添加すると、さらに重金属類等の溶出抑制効果に優れることがわかる（実施例５〜２５）。
From Table 2, it can be seen that the insolubilizing material of the present invention is excellent in the elution suppressing effect of heavy metals and the like (arsenic, fluorine, lead, hexavalent chromium) with a small addition amount (Examples 1 to 4). On the other hand, at the time of baking, the raw material magnesium carbonate is completely converted to magnesium oxide. Therefore, in Comparative Example 1 using a magnesium-based material which does not contain magnesium carbonate and consists only of magnesium oxide and magnesium hydroxide, Example 1 It can be seen that the elution suppression effect of heavy metals and the like is low as compared to ˜4. Moreover, even if magnesium carbonate and magnesium hydroxide are post-added to the insolubilized material consisting only of magnesium oxide and magnesium hydroxide (Comparative Examples 2 to 4), the elution suppression effect of heavy metals and the like as in Comparative Example 1 It turns out that it is inferior to.
Moreover, it turns out that it is inferior to the elution suppression effect of heavy metals etc. in the comparative example 5 whose content of calcium in (A) component is outside the range of this invention.
From Table 4, when (C) component is added, it turns out that it is further excellent in the elution suppression effect of heavy metals etc. (Examples 5-25).
Claims (5)
（ａ）炭酸マグネシウムを主成分とする鉱物を６５０〜１，０００℃で焼成して得た酸化マグネシウムと炭酸マグネシウムとを含む焼成物を、当該焼成物の一部が水酸化マグネシウムになるように水和したものであること
（ｂ）カルシウムの酸化物換算の含有量が３．０質量％以下であること
（ｃ）１，０００℃における強熱減量率が６〜３０質量％であること (A) An insolubilizing material comprising a powder made of a magnesium-based material that satisfies all of the following conditions (a) to (c).
(A) A fired product containing magnesium oxide and magnesium carbonate obtained by firing a mineral mainly composed of magnesium carbonate at 650 to 1,000 ° C. so that a part of the fired product becomes magnesium hydroxide. Being hydrated (b) Oxide content of calcium is 3.0% by mass or less (c) The ignition loss at 1,000 ° C. is 6-30% by mass
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| JP2011078895A (en) * | 2009-10-06 | 2011-04-21 | Taiheiyo Cement Corp | Material for suppressing spread of dioxins |
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