JP2020132746A - Fluorine insolubilization agent, its manufacturing method, processed gypsum, fluorine-containing contaminated soil and processing method of contaminated water - Google Patents
Fluorine insolubilization agent, its manufacturing method, processed gypsum, fluorine-containing contaminated soil and processing method of contaminated water Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 239000011737 fluorine Substances 0.000 title claims abstract description 176
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 176
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002689 soil Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000010440 gypsum Substances 0.000 title claims description 21
- 229910052602 gypsum Inorganic materials 0.000 title claims description 21
- 239000003795 chemical substances by application Substances 0.000 title abstract description 6
- 238000003672 processing method Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000003929 acidic solution Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 22
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 17
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims abstract description 17
- 235000019700 dicalcium phosphate Nutrition 0.000 claims abstract description 17
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 17
- -1 calcium hydrogen dihydrate Chemical class 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 23
- 238000007654 immersion Methods 0.000 claims description 22
- 239000007790 solid phase Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 abstract description 84
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 24
- 239000000843 powder Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000007598 dipping method Methods 0.000 abstract description 6
- 238000009434 installation Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012890 simulated body fluid Substances 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride 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
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium phosphate dihydrate Substances O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本発明は、石膏中、汚染水中又は汚染土壌中のフッ化物イオンを安定な鉱物であるフッ素アパタイト(ＦＡｐ）として不溶化し、長期的な安定性を担保するフッ素不溶化剤、その製造方法、処理石膏、フッ素含有汚染土壌及び汚染水の処理方法に関するものである。 The present invention is a fluorine insolubilizer that insolubilizes fluoride ions in gypsum, contaminated water, or contaminated soil as a stable mineral, fluorine apatite (FAp), and ensures long-term stability, a method for producing the same, and treated gypsum. It relates to a method for treating fluorine-containing contaminated soil and contaminated water.
フッ素は、先端技術産業の分野で広く使用されており、それに伴って排水や土壌のフッ素汚染が深刻な問題となっている。このフッ素汚染土壌は、我が国の汚染土壌では２番目にサイト数が多いものとなっている。このため、排水中又は土壌中のフッ素（フッ化物イオン）を安定なフッ素アパタイト(ＦＡｐ）として不溶化する技術が多数、提案されている。 Fluorine is widely used in the field of advanced technology industry, and along with this, wastewater and soil pollution with fluorine have become serious problems. This fluorine-contaminated soil has the second largest number of sites in Japan's contaminated soil. For this reason, many techniques have been proposed for insolubilizing fluorine (fluoride ion) in wastewater or soil as stable fluorine apatite (FAp).
従来、このようなフッ素不溶化剤としては、各種アルミニウム化合物やカルシウム化合物の他に、リン酸ナトリウム（Ｎａ３ＰＯ４）、リン酸水素二ナトリウム（Ｎａ２ＨＰＯ４）、リン酸二水素ナトリウム（ＮａＨ２ＰＯ４）、リン酸水素カルシウム二水和物（ＣａＨＰＯ４・２Ｈ２Ｏ）、水酸アパタイト（Ｃａ５（ＰＯ４）３ＯＨ）等、各種のリン酸化合物が知られている。 Conventionally, as such a fluorine insolubilizer, in addition to various aluminum compounds and calcium compounds, sodium phosphate (Na3PO4), disodium hydrogen phosphate (Na2HPO4), sodium dihydrogen phosphate (NaH2PO4), calcium hydrogen phosphate Various phosphoric acid compounds such as dihydrate (CaHPO4.2H2O) and hydroxyapatite (Ca5 (PO4) 3OH) are known.
この中、リン酸水素カルシウム二水和物（以下、単に「ＤＣＰＤ」との言う。）は、直接フッ化物イオンと反応するのではなく、反応初期に粒子表面に数十ｎｍのリン酸カルシウム系前駆体を生成し、それがトリガーとなってＦＡｐを生成することが見いだされている（非特許文献１）。この前駆体相の生成には数時間の誘導時間（遅れ時間）を必要とし、さらにこの前駆体相生成は、例えばＭｇイオン、Ｃｄイオン、フッ化物イオンなどの共存イオンによって容易に妨害される（非特許文献２等）という問題がある。 Among these, calcium hydrogen phosphate dihydrate (hereinafter, simply referred to as "DCPD") does not directly react with fluoride ions, but is a calcium phosphate-based precursor having a particle surface of several tens of nm at the initial stage of the reaction. It has been found that FAp is generated by generating FAp (Non-Patent Document 1). The formation of this precursor phase requires an induction time (delay time) of several hours, and the formation of this precursor phase is easily hindered by coexisting ions such as Mg ion, Cd ion, and fluoride ion (). There is a problem of non-patent document 2 etc.).
ＤＣＰＤとフッ化物イオンとの反応に見られる遅れ時間を改善する技術として、例えば、国際公開番号ＷＯ２０１０/０４１３３０号（特許文献１）には、ＤＣＰＤを水あるいは温水処理により前駆体相を表面に誘起する方法が開示されている。また、特開２０１１−２５６３５６号公報（特許文献２）には、ＤＣＰＤと水酸アパタイト（ＨＡｐ）の混合物であるフッ素不溶化剤が開示されている。また、非特許文献３には、ＤＣＰＤを人の体液と同じイオン濃度を有する擬似体液に浸漬して、ＨＡｐを粒子表面に析出させる方法が開示されている。 As a technique for improving the delay time observed in the reaction between DCPD and fluoride ions, for example, in International Publication No. WO2010 / 041330 (Patent Document 1), DCPD induces a precursor phase on the surface by water or hot water treatment. The method of doing so is disclosed. Further, Japanese Patent Application Laid-Open No. 2011-256356 (Patent Document 2) discloses a fluorine insolubilizer which is a mixture of DCPD and hydroxyapatite (HAp). Further, Non-Patent Document 3 discloses a method of immersing DCPD in a simulated body fluid having the same ion concentration as a human body fluid to precipitate HAp on the particle surface.
しかしながら、これら従来の方法は、未だＤＣＰＤとフッ化物イオンとの反応に見られる遅れ時間を改善するには不十分であるか、あるいはＤＣＰＤの活性化が不十分であり、フッ素汚染土壌中のフッ素の不溶化という点では、満足がいくものではなかった。また、疑似体液を用いる方法は、疑似体液の調製や保管が難しいという問題がある。また、ＤＣＰＤとＨＡｐの混合物であるフッ素不溶化剤の場合、実際には、ＤＣＰＤは合成したものを使用しており、限られた用途にしか適用できなかった。このため、例えば、汚染土壌の処理現場において、市販のＤＣＰＤを簡単に処理して得られるフッ素不溶化剤が求められていた。 However, these conventional methods are still insufficient to improve the delay time seen in the reaction of DCPD with fluoride ions, or the activation of DCPD is insufficient and fluorine in fluorine-contaminated soil. In terms of insolubilization of fluorine, it was not satisfactory. Further, the method using the simulated body fluid has a problem that it is difficult to prepare and store the simulated body fluid. Further, in the case of the fluorine insolubilizer which is a mixture of DCPD and HAp, the DCPD is actually a synthetic one, and it can be applied only to a limited use. Therefore, for example, at a treatment site for contaminated soil, there has been a demand for a fluorine insolubilizer obtained by easily treating a commercially available DCPD.
従って、本発明の目的は、ＤＣＰＤとフッ化物イオンとの反応に見られる遅れ時間を改善し、ＤＣＰＤの高い活性化を有するフッ素不溶化剤、より単純な組成の溶液を使用して施工現場で調製可能なフッ素不溶化剤の製造方法、処理石膏及びフッ素含有汚染土壌又は汚染水の処理方法を提供することにある。 Therefore, an object of the present invention is to improve the delay time observed in the reaction between DCPD and fluoride ions, and to prepare at the construction site using a fluorine insolubilizer having high activation of DCPD, a solution having a simpler composition. It is an object of the present invention to provide a method for producing a possible fluorine insolubilizer, a method for treating treated gypsum and a method for treating fluorine-containing contaminated soil or contaminated water.
かかる実情において、本発明者等は、フッ素不溶化剤の製造方法について、鋭意検討を行った結果、ＤＣＰＤの表面に前駆体を形成する溶液である弱酸性溶液において、疑似体液のＣａ２＋イオンとＨＰＯ４ ２−イオンに着目し、更にこれらのイオンに、不溶化の対象物であるフッ化物イオンを併存させるという逆転の発想に基づき作成された溶液を使用し、ＤＣＰＤの表面にフッ素アパタイトを予め積極的に形成してフッ素不溶化剤を得たところ、ＤＣＰＤとフッ化物イオンとの反応に見られる遅れ時間を大きく改善でき、ＤＣＰＤが高い活性化を示すことを見出し、本発明を完成するに至った。 In such a situation, the present inventors diligently studied a method for producing a fluorine insolubilizer, and as a result, in a weakly acidic solution which is a solution for forming a precursor on the surface of DCPD, Ca 2+ ions and HPO of the pseudo-form solution 4 2- Focusing on ions, using a solution created based on the reverse idea of coexisting fluoride ions, which are the objects of insolubilization, with these ions, positively apply fluorine apatite to the surface of DCPD in advance. When a fluorine insolubilizer was obtained, it was found that the delay time observed in the reaction between DCPD and fluoride ions could be greatly improved, and that DCPD showed high activation, and the present invention was completed.
すなわち、本発明は、リン酸水素カルシウム二水和物の表面に、フッ素アパタイトが付着してなることを特徴とするフッ素不溶化剤を提供するものである。 That is, the present invention provides a fluorine insolubilizer characterized in that fluorine apatite adheres to the surface of calcium hydrogen phosphate dihydrate.
また、本発明は、Ｃａ２＋イオン２．０〜５．０ｍｍｏｌ/ｌ、ＨＰＯ４ ２−イオン０．５〜２．０ｍｍｏｌ/ｌ及びＦ−イオン１．０〜３．０ｍｍｏｌ/ｌを含有する弱酸性溶液に、リン酸水素カルシウム二水和物を浸漬させ、リン酸水素カルシウム二水和物の表面に、フッ素アパタイトを沈着させる第１工程を有すること特徴とするフッ素不溶化剤の製造方法を提供するものである。 Further, the present invention, Ca 2+ ions 2.0~5.0mmol / l, HPO 4 2- ions 0.5~2.0mmol / l and F - weak containing ion 1.0~3.0mmol / l Provided is a method for producing a fluorine insolubilizer, which comprises a first step of immersing calcium hydrogen phosphate dihydrate in an acidic solution and depositing fluorine apatite on the surface of the calcium hydrogen phosphate dihydrate. It is something to do.
また、本発明は、前記不溶化剤が添加された石膏であり、フッ素の溶出を低減したことを特徴とする処理石膏を提供するものである。 The present invention also provides a gypsum to which the insolubilizing agent has been added, which is characterized by reducing elution of fluorine.
また、本発明は、前記フッ素不溶化剤を、フッ化物イオンで汚染された土壌に添加することを特徴とする汚染土壌の処理方法を提供するものである。 The present invention also provides a method for treating contaminated soil, which comprises adding the fluorine insolubilizer to soil contaminated with fluoride ions.
また、本発明は、前記フッ素不溶化剤を、フッ化物イオンで汚染された汚染水に添加することを特徴とする汚染水の処理方法を提供するものである。 The present invention also provides a method for treating contaminated water, which comprises adding the fluorine insolubilizer to contaminated water contaminated with fluoride ions.
本発明によれば、ＤＣＰＤとフッ化物イオンとの反応に見られる遅れ時間を改善し、ＤＣＰＤの高い活性化を有するフッ素不溶化剤を提供できる。また、本発明によれば、より単純な組成の溶液を使用して施工現場で調製可能なフッ素不溶化剤の製造方法を提供できる。また、本発明によれば、フッ素不溶化剤を直接または水に混合したものを、汚染土壌や汚染水に添加するという簡単な工程の実施のみで汚染土壌や汚染水中のフッ化物イオンを効率よく不溶化できる。 According to the present invention, it is possible to provide a fluorine insolubilizer having a high activation of DCPD by improving the delay time observed in the reaction between DCPD and fluoride ions. Further, according to the present invention, it is possible to provide a method for producing a fluorine insolubilizer that can be prepared at a construction site using a solution having a simpler composition. Further, according to the present invention, fluoride ions in contaminated soil and contaminated water are efficiently insolubilized only by carrying out a simple step of adding a fluorine insolubilizer directly or mixed with water to contaminated soil or contaminated water. it can.
（フッ素不溶化剤）
本発明のフッ素不溶化剤は、ＤＣＰＤの表面に、フッ素アパタイト（以下、単に「ＦＡｐ」とも言う。）が付着してなるものであり、例えば、このＦＡｐは、ＤＣＰＤ粉末の表面を被覆しているものが挙げられる。ＤＣＰＤは、Ｘ線分析及び示差熱分析で特定することができる。ＤＣＰＤは、汚染土壌や汚染水中の汚染物であるフッ化物イオンと反応し、最終的には、ＦＡｐに転換される。
(Fluorine insolubilizer)
The fluorine insolubilizer of the present invention is formed by adhering fluorine apatite (hereinafter, also simply referred to as "FAp") to the surface of DCPD. For example, this FAp covers the surface of DCPD powder. Things can be mentioned. DCPD can be identified by X-ray analysis and differential thermal analysis. DCPD reacts with fluoride ions, which are pollutants in contaminated soil and contaminated water, and is eventually converted to FAp.
本発明のフッ素不溶化剤において、ＦＡｐは、針状体の集合物であり、この針状体は、最大長さ５μｍ、好ましくは最大長さ０．５μｍである。また、針状体のアスペクト比（長辺と短辺の比）としては、１：１００〜１：５０である。ＦＡｐは、Ｘ線分析及び示差熱分析で特定でき、その針状形状及び長さ寸法は、電子顕微鏡で特定できる。 In the fluorine insolubilizer of the present invention, FAp is an aggregate of needle-shaped bodies, and the needle-shaped bodies have a maximum length of 5 μm, preferably a maximum length of 0.5 μm. The aspect ratio (ratio of long side to short side) of the needle-shaped body is 1: 100 to 1:50. FAp can be identified by X-ray analysis and differential thermal analysis, and its needle-like shape and length dimension can be identified by an electron microscope.
本発明のフッ素不溶化剤において、ＦＡｐの含有量は、フッ素不溶化剤中、０．１質量％以上、好ましくは１．０〜３０．０質量％以上、更に好ましくは５．０〜４０．０質量％である。フッ素不溶化剤中、ＦＡｐの含有量は、上記数値範囲内において、多い方が汚染物であるフッ化物イオンとＤＣＰＤとの反応に見られる遅れ時間の改善効果が高い。図１のフッ素不溶化剤は、フッ素不溶化剤中、ＦＡｐの含有量が１０．０質量％のものであり、図２のフッ素不溶化剤は、フッ素不溶化剤中、ＦＡｐの含有量が１８．０質量％のものである。 In the fluorine insolubilizer of the present invention, the FAp content in the fluorine insolubilizer is 0.1% by mass or more, preferably 1.0 to 30.0% by mass or more, and more preferably 5.0 to 40.0% by mass. %. Within the above numerical range, the higher the FAp content in the fluorine insolubilizer, the higher the effect of improving the delay time observed in the reaction between the contaminant fluoride ion and DCPD. The fluorine insolubilizer of FIG. 1 has a FAp content of 10.0% by mass in the fluorine insolubilizer, and the fluorine insolubilizer of FIG. 2 has a FAp content of 18.0 mass in the fluorine insolubilizer. %belongs to.
本発明のフッ素不溶化剤は、汚染物であるフッ素を含んだ石膏、汚染水あるいは汚染土壌に対し、直接または水に混合して添加することで、フッ化物イオンとＤＣＰＤとの反応における遅れ時間を短縮して、汚染物のフッ素を不溶化できる。 The fluorine insolubilizer of the present invention can be added directly or mixed with water to gypsum, contaminated water or contaminated soil containing fluorine, which is a pollutant, to reduce the delay time in the reaction between fluoride ions and DCPD. It can be shortened to insolubilize the contaminant fluorine.
（フッ素不溶化剤の製造方法）
本発明の第１の実施の形態におけるフッ素不溶化剤の製造方法は、Ｃａ２＋イオン２．０〜５．０ｍｍｏｌ/ｌ、好ましくは、２．５ｍｍｏｌ/ｌ、ＰＯ４ ２−イオン０．５〜２．０ｍｍｏｌ/ｌ、好ましくは、１．０ｍｍｏｌ/ｌ、及びＦ−イオン１．０〜３．０ｍｍｏｌ/ｌ、好ましくは１．２〜３．０ｍｍｏｌ/ｌを含有する弱酸性溶液に、ＤＣＰＤを浸漬させ、ＤＣＰＤの表面に、ＦＡｐを沈着させる第１工程を有する方法である。
(Manufacturing method of fluorine insolubilizer)
Method for producing a fluorine-insolubilizing agent in the first embodiment of the present invention, Ca 2+ ions 2.0~5.0mmol / l, preferably, 2.5mmol / l, PO 4 2- ions 0.5-2 Immerse DCPD in a weakly acidic solution containing 0.0 mmol / l, preferably 1.0 mmol / l, and F - ions 1.0-3.0 mmol / l, preferably 1.2-3.0 mmol / l. It is a method having a first step of depositing FAp on the surface of DCPD.
Ｃａ２＋イオンとしては、塩化カルシウム、硝酸カルシウム又は酢酸カルシウムが使用でき、ＰＯ４ ２−イオンとしては、リン酸ナトリウム、リン酸アンモニウム又はリン酸が使用でき、Ｆ−イオンとしては、フッ化ナトリウム、フッ化水素酸又はフッ化アンモニウムが使用できる。カルシウム化合物、リン酸化合物及びフッ化化合物の添加順序は特に制限されず、純水中に、一度に添加してもよく、別個に添加してもよい。この際、沈殿が生じないよう、ｐＨ調整しながら行う。弱酸性溶液には、上記イオンの他、例えばマグネシウムイオン、ナトリウムイオン、カリウムイオンなどが含まれていてもよい。 The Ca 2+ ion, calcium chloride, can be used calcium nitrate or calcium acetate, as a PO 4 2-ions, sodium phosphate, can be used ammonium phosphate or phosphoric acid, F - as the ion, sodium fluoride, Hydrofluoric acid or ammonium fluoride can be used. The order of addition of the calcium compound, the phosphoric acid compound and the fluorinated compound is not particularly limited, and the calcium compound, the phosphoric acid compound and the fluorinated compound may be added to pure water at once or separately. At this time, the pH is adjusted so that precipitation does not occur. In addition to the above ions, the weakly acidic solution may contain, for example, magnesium ions, sodium ions, potassium ions and the like.
弱酸性溶液のｐＨは、２．５〜６．５、好ましくは３．５〜６．５である。すなわち、ＤＣＰＤの表面に、ＦＡｐを沈着させた後の溶液のｐＨが６．１となるように、該弱酸性溶液のｐＨを調整すればよい。ｐＨがこの範囲であれば、溶液の沈殿は起こらず、溶解状態を保持することができる。弱酸性溶液のｐＨが小さ過ぎると、ＤＣＰＤが溶解して原料の損失が大きくなり、ｐＨが大き過ぎると、溶液中に白濁が生じて分化するため、いずれも好ましくない。 The pH of the weakly acidic solution is 2.5 to 6.5, preferably 3.5 to 6.5. That is, the pH of the weakly acidic solution may be adjusted so that the pH of the solution after depositing FAp on the surface of DCPD is 6.1. When the pH is in this range, precipitation of the solution does not occur and the dissolved state can be maintained. If the pH of the weakly acidic solution is too small, DCPD will dissolve and the loss of raw materials will be large, and if the pH is too large, cloudiness will occur in the solution and differentiation will occur, which is not preferable.
本発明のフッ素不溶化剤の製造方法において、ＤＣＰＤとしては、工業用、化粧品用、食品添加物用、医薬品用等の各種グレードの市販品が使用できる。また、ＤＣＰＤは、例えば、消石灰の水分散液とリン酸とを、ｐＨ４〜５に調整した水系媒体中で反応させることで製造する公知の方法で得たものを使用することができる。 In the method for producing a fluorine insolubilizer of the present invention, various grades of commercially available products such as those for industrial use, cosmetics, food additives, and pharmaceuticals can be used as DCPD. Further, as the DCPD, for example, one obtained by a known method produced by reacting an aqueous dispersion of slaked lime and phosphoric acid in an aqueous medium adjusted to pH 4 to 5 can be used.
次に、ＤＣＰＤを上記弱酸性溶液に浸漬する。ＤＣＰＤと弱酸性溶液の固液比（質量/体積）は、１/１００〜１/５、好ましくは１/５０〜１/１０である。固液比が小さ過ぎると、ＤＣＰＤが溶解して原料の損失が生じ、大き過ぎると弱酸性溶液に供給できるカルシウム、リン、フッ素量が少なる結果、ＦＡｐの生成量が少なくなり、いずれも好ましくない。 Next, the DCPD is immersed in the weakly acidic solution. The solid-liquid ratio (mass / volume) of DCPD to the weakly acidic solution is 1/100 to 1/5, preferably 1/50 to 1/10. If the solid-liquid ratio is too small, DCPD will dissolve and the raw material will be lost. Absent.
浸漬条件としては、弱酸性溶液とＤＣＰＤが十分、混合されれば、特に制限されず、例えば、１０〜３０℃、好ましくは室温下、撹拌又は振とう下、１日〜１０日間、好ましくは、１日〜７日間、混合処理する方法が挙げられる。 The immersion conditions are not particularly limited as long as the weakly acidic solution and DCPD are sufficiently mixed, and are not particularly limited. For example, 10 to 30 ° C., preferably at room temperature, under stirring or shaking, 1 day to 10 days, preferably. Examples thereof include a method of mixing treatment for 1 to 7 days.
上記浸漬により、ＤＣＰＤの表面に、ＦＡｐが沈着する。ＤＣＰＤの表面へのＦＡｐの沈着の終了は、液中のフッ素濃度の低下をイオン選択性電極や比色分析により判断する（以上が第１工程）。液中のフッ素濃度は、０．１ｍｍｏｌ/ｌまで低下すれば、第１工程終了と判断してよい。 By the above immersion, FAp is deposited on the surface of DCPD. The completion of FAp deposition on the surface of DCPD is determined by determining the decrease in fluorine concentration in the liquid by an ion-selective electrode or colorimetric analysis (the above is the first step). If the fluorine concentration in the liquid drops to 0.1 mmol / l, it may be determined that the first step is completed.
ＤＣＰＤの表面にＦＡｐの沈着が完了した固液相は、公知の固液分離により、固相を得る（第２工程）。特に、固液分離後、固相を脱水、乾燥して粉末の不溶化剤として得ることが好ましい。脱水方法としては、デカンテーション、濾過、遠心分離などの公知の方法を使用すればよい。乾燥した粉末のフッ素不溶化剤は、活性化に実質的に影響はなく、保管、運搬及び使用の際、都合がよい。 The solid-liquid phase in which FAp has been deposited on the surface of DCPD obtains a solid phase by known solid-liquid separation (second step). In particular, it is preferable to dehydrate and dry the solid phase after solid-liquid separation to obtain it as a powder insolubilizer. As the dehydration method, a known method such as decantation, filtration, or centrifugation may be used. The dried powder fluorine insolubilizer has substantially no effect on activation and is convenient for storage, transportation and use.
次に、本発明の第２の実施の形態におけるフッ素不溶化剤の製造方法について説明する。第２の実施の形態における製造方法において、第１の実施の形態における製造方法と同一構成要素については、その説明を省略し、異なる点について主に、説明する。すなわち、第２の実施の形態の製造方法において、第１の実施の形態の製造方法と異なる点は、第１の実施の形態における製造方法で得られた固相を再度、又は更に引き続き、直前で得られた固相を弱酸性溶液に浸漬する浸漬繰り返し工程を複数回行い、ＤＣＰＤの表面へのＦＡｐの沈着量を増やす点にある。 Next, a method for producing a fluorine insolubilizer according to the second embodiment of the present invention will be described. In the manufacturing method according to the second embodiment, the same components as the manufacturing method according to the first embodiment will be omitted, and the differences will be mainly described. That is, the difference between the production method of the second embodiment and the production method of the first embodiment is that the solid phase obtained by the production method of the first embodiment is again or continuously immediately before. The point is to increase the amount of FAp deposited on the surface of DCPD by performing the immersion repetition step of immersing the solid phase obtained in 1 in a weakly acidic solution a plurality of times.
すなわち、本発明の第２の実施の形態における製造方法は、Ｃａ２＋イオン２．０〜５．０ｍｍｏｌ/ｌ、ＨＰＯ４ ２−イオン０．５〜２．０ｍｍｏｌ/ｌ及びＦ−イオン１．０〜３．０ｍｍｏｌ/ｌを含有する弱酸性溶液に、該第２工程で得られた固相を浸漬させ、リン酸水素カルシウム二水和物の表面に、更にフッ素アパタイトを沈着させる浸漬繰り返し工程と、を有する方法（都合２回の浸漬方法）が挙げられ、更に、Ｃａ２＋イオン２．０〜５．０ｍｍｏｌ/ｌ、ＨＰＯ４ ２−イオン０．５〜２．０ｍｍｏｌ/ｌ及びＦ−イオン１．０〜３．０ｍｍｏｌ/ｌを含有する弱酸性溶液を使用した浸漬繰り返し工程を、更に複数回繰り返し行う方法（都合３回以上の浸漬方法）が挙げられる。合計の浸漬回数は、最大１０回、好ましくは最大５回、特に好ましくは最大３回である。合計の浸漬回数が、多過ぎても、ＦＡｐの沈着量はそれほど増えず、効率が悪くなり、また、すくな過ぎても、ＦＡｐの沈着量を増やすことができない。 That is, the manufacturing method in the second embodiment of the present invention, Ca 2+ ions 2.0~5.0mmol / l, HPO 4 2- ions 0.5~2.0mmol / l and F - ions 1.0 In a weakly acidic solution containing ~ 3.0 mmol / l, the solid phase obtained in the second step is immersed, and a fluorine apatite is further deposited on the surface of calcium hydrogen phosphate dihydrate. , it includes a method (method of dipping twice convenience) having a further, Ca 2+ ions 2.0~5.0mmol / l, HPO 4 2- ions 0.5~2.0mmol / l and F - ions 1 A method of repeating the dipping repetition step using a weakly acidic solution containing 0 to 3.0 mmol / l a plurality of times (conveniently, a dipping method of 3 times or more) can be mentioned. The total number of immersions is a maximum of 10, preferably a maximum of 5, and particularly preferably a maximum of 3. If the total number of immersions is too large, the amount of FAp deposited does not increase so much, which results in inefficiency, and if it is too small, the amount of FAp deposited cannot be increased.
すなわち、本発明の第２の実施の形態における製造方法において、再度及び複数回の浸漬処理を行う際、使用する弱酸性溶液は、常に当初濃度を有する、Ｃａ２＋イオン２．０〜５．０ｍｍｏｌ/ｌ、好ましくは、２．５ｍｍｏｌ/ｌ、ＰＯ４ ２−イオン０．５〜２．０ｍｍｏｌ/ｌ、好ましくは、１．０ｍｍｏｌ/ｌ、及びＦ−イオン１．０〜３．０ｍｍｏｌ/ｌ、好ましくは１．２〜３．０ｍｍｏｌ/ｌを含有する溶液である。一度、ＤＣＰＤを浸漬した使用済みの弱酸性溶液は、それぞれのイオン濃度が低減しており、使用できない。また、再度及び複数回の浸漬処理を行う際、浸漬される固相は、直前で浸漬処理された固相である。すなわち、例えば３回目の浸漬処理で使用する固相は、２回目の浸漬処理で得られた固相であり、４回目の浸漬処理で使用する固相は、３回目の浸漬処理で得られた固相である。第２の実施の形態例では、再度及び更に複数回の浸漬処理を行うことで、処理前のフッ素不溶化剤と比べて、処理後のフッ素不溶化剤は、ＦＡｐの沈着量が多くなる。 That is, in the production method according to the second embodiment of the present invention, the weakly acidic solution used when performing the immersion treatment again and a plurality of times always has an initial concentration of Ca 2+ ions 2.0 to 5.0 mmol. / l, preferably 2.5 mmol / l, PO 4 2- ion 0.5-2.0 mmol / l, preferably 1.0 mmol / l, and F - ion 1.0-3.0 mmol / l, A solution containing 1.2 to 3.0 mmol / l is preferable. The used weakly acidic solution in which DCPD is once immersed cannot be used because the respective ion concentrations are reduced. Further, when the immersion treatment is performed again and a plurality of times, the solid phase to be immersed is the solid phase to be immersed immediately before. That is, for example, the solid phase used in the third immersion treatment was the solid phase obtained in the second immersion treatment, and the solid phase used in the fourth immersion treatment was obtained in the third immersion treatment. It is a solid phase. In the second embodiment, by performing the dipping treatment again and a plurality of times, the fluorine insolubilizer after the treatment has a larger amount of FAp deposited than the fluorine insolubilizer before the treatment.
本発明の実施の形態におけるフッ素不溶化剤の製造方法において、ＤＣＰＤは、市販品を使用できること、使用する弱酸性溶液は簡単な組成であること、ＤＣＰＤの浸漬条件は、室温下でできる簡単な操作であることから、現場の施工場所において製造可能であり、フッ素不溶化剤の用途の拡大が図れる。 In the method for producing a fluorine insolubilizer according to the embodiment of the present invention, the DCPD can be a commercially available product, the weakly acidic solution used has a simple composition, and the immersion conditions of the DCPD are simple operations that can be performed at room temperature. Therefore, it can be manufactured at the construction site at the site, and the use of the fluorine insolubilizer can be expanded.
（処理石膏）
次に、本発明に係る含有フッ素の溶出を低減させた処理石膏について説明する。本発明において石膏は、フッ素を含有するものであれば、特に制限されず、二水塩、半水塩、無水塩が挙げられ、この内、半水塩が入手し易い点で好ましい。石膏の具体例としては、天然石膏、排煙脱硫処理によって副生する石膏、天然無水石膏、ふっ酸の製造過程で副産するふっ酸無水石膏等が挙げられる。
(Treatment plaster)
Next, the treated gypsum in which the elution of contained fluorine according to the present invention is reduced will be described. In the present invention, gypsum is not particularly limited as long as it contains fluorine, and examples thereof include dihydrate, hemihydrate, and anhydrous salt, and among these, hemihydrate is preferable because hemihydrate is easily available. Specific examples of gypsum include natural gypsum, gypsum produced as a by-product by flue gas desulfurization treatment, natural anhydrous gypsum, and hydrous acid anhydrous gypsum produced as a by-product in the process of producing hydrofluoric acid.
本発明において、フッ素を含有する石膏に、本発明のフッ素不溶化剤を添加する方法としては、特に制限されず、両者を粉末状とし、単にそのまま混合すればよい。フッ素含有石膏に対するフッ素不溶化剤の添加量としては、フッ素含有石膏１００質量部に対して、フッ素不溶化剤０．５質量部以上、好ましくは０．５〜５質量部である。フッ素不溶化剤の添加量が少な過ぎると、石膏からのフッ素の溶出量を土壌環境基準値以下にするのが難しくなり、フッ素不溶化剤の添加量が多過ぎても、フッ素の溶出低減効果は大きく変わらない。本発明によれば、ＤＣＰＤと石膏中のフッ素（フッ化物イオン）との反応に見られる遅れ時間を改善できるため、石膏中のフッ素を固定化して、溶出フッ化物イオンを低減できる。本発明の処理石膏は、そのまま埋立処分することもできるが、石膏ボード、プラスター、土壌固化材等の原料として再使用することもできる。 In the present invention, the method for adding the fluorine insolubilizer of the present invention to gypsum containing fluorine is not particularly limited, and both may be powdered and simply mixed as they are. The amount of the fluorine insolubilizer added to the fluorine-containing gypsum is 0.5 parts by mass or more, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the fluorine-containing gypsum. If the amount of fluorine insolubilizer added is too small, it becomes difficult to keep the amount of fluorine eluted from gypsum below the soil environmental standard value, and even if the amount of fluorine insolubilizer added is too large, the effect of reducing the elution of fluorine is large. does not change. According to the present invention, since the delay time observed in the reaction between DCPD and fluorine (fluoride ion) in gypsum can be improved, fluorine in gypsum can be immobilized and eluted fluoride ions can be reduced. The treated gypsum of the present invention can be disposed of in landfill as it is, but it can also be reused as a raw material for gypsum board, plaster, soil solidifying material and the like.
（汚染土壌の処理方法）
次に、本発明に係る汚染土壌の処理方法について説明する。本発明は、フッ化物イオンで汚染された土壌に、本発明のフッ素不溶化剤を添加するものである。本発明において、フッ素汚染土壌に、フッ素不溶化剤を添加する方法としては、特に制限されず、単にそのまま混合する方法、両者の混合前、混合中又は混合後に必要に応じて適宜脱水又は加水して水分調整する方法などが挙げられる。水分調整の場合、混合後の水分が５〜２０質量％となるようにするのが好ましい。
(Treatment method for contaminated soil)
Next, a method for treating contaminated soil according to the present invention will be described. The present invention is to add the fluorine insolubilizer of the present invention to soil contaminated with fluoride ions. In the present invention, the method of adding the fluorine insolubilizer to the fluorine-contaminated soil is not particularly limited, and is simply a method of mixing as it is, or dehydrating or adding water as necessary before, during or after mixing the two. Examples include a method of adjusting the water content. In the case of water content adjustment, it is preferable that the water content after mixing is 5 to 20% by mass.
本発明において、フッ素汚染土壌に対するフッ素不溶化剤の添加量としては、フッ素汚染土壌の乾燥物１００質量部に対して、フッ素不溶化剤１質量部以上、好ましくは１〜２０質量部である。フッ素不溶化剤の添加量が少な過ぎると、フッ素汚染土壌からのフッ素の溶出量を土壌環境基準値以下にするのが難しくなり、フッ素不溶化剤の添加量が多過ぎても、フッ素の溶出低減効果は大きく変わらない。本発明によれば、ＤＣＰＤと汚染土壌中のフッ素（フッ化物イオン）との反応に見られる遅れ時間を改善できるため、汚染土壌中のフッ素を固定化して、溶出フッ化物イオンを低減できる。 In the present invention, the amount of the fluorine insolubilizer added to the fluorine-contaminated soil is 1 part by mass or more, preferably 1 to 20 parts by mass, based on 100 parts by mass of the dried product of the fluorine-contaminated soil. If the amount of fluorine insolubilizer added is too small, it becomes difficult to keep the amount of fluorine eluted from the soil contaminated with fluorine below the soil environmental standard value, and even if the amount of fluorine insolubilizer added is too large, the effect of reducing the elution of fluorine Does not change much. According to the present invention, the delay time observed in the reaction between DCPD and fluorine (fluoride ion) in the contaminated soil can be improved, so that the fluorine in the contaminated soil can be immobilized and the eluted fluoride ion can be reduced.
（汚染水の処理方法）
次に、本発明に係る汚染水の処理方法について説明する。本発明は、フッ化物イオンで汚染された汚染水に、本発明のフッ素不溶化剤を添加するものである。本発明において、フッ素汚染水に、フッ素不溶化剤を添加する方法としては、特に制限されず、単にそのまま混合する方法が挙げられる。
(Contaminated water treatment method)
Next, a method for treating contaminated water according to the present invention will be described. The present invention is to add the fluorine insolubilizer of the present invention to contaminated water contaminated with fluoride ions. In the present invention, the method of adding the fluorine insolubilizer to the fluorine-contaminated water is not particularly limited, and examples thereof include a method of simply mixing as it is.
本発明において、フッ素汚染水に対するフッ素不溶化剤の添加量としては、フッ素汚染濃度により変わるため、一概に決定できないものの、例えば、フッ素汚染水１００質量部に対して、フッ素不溶化剤０．１質量部以上、好ましくは１．０〜５．０質量部である。フッ素不溶化剤の添加量が少な過ぎると、フッ素汚染水からのフッ素の溶出量を基準値以下にするのが難しくなり、フッ素不溶化剤の添加量が多過ぎても、フッ素の溶出低減効果は大きく変わらない。本発明によれば、ＤＣＰＤと汚染水中のフッ素（フッ化物イオン）との反応に見られる遅れ時間を改善できるため、汚染水中のフッ素を固定化して、溶出フッ化物イオンを低減できる。 In the present invention, the amount of the fluorine insolubilizer added to the fluorine-contaminated water varies depending on the fluorine-contaminated concentration and cannot be unconditionally determined. As mentioned above, it is preferably 1.0 to 5.0 parts by mass. If the amount of the fluorine insolubilizer added is too small, it becomes difficult to reduce the amount of fluorine elution from the fluorine-contaminated water to the standard value or less, and even if the amount of the fluorine insolubilizer added is too large, the effect of reducing the elution of fluorine is large. does not change. According to the present invention, since the delay time observed in the reaction between DCPD and fluorine (fluoride ion) in the contaminated water can be improved, the fluorine in the contaminated water can be immobilized and the eluted fluoride ion can be reduced.
本発明において、処理石膏、汚染土壌及び汚染水に配合されたフッ素不溶化剤は、フッ素を短時間で充分にフッ素アパタイトとして不溶化することができる。すなわち、ＦＡｐが表面に付着したＤＣＰＤにおけるＤＣＰＤ部分は、そのままの形状を保持して、内部までＦＡｐに転化される。このため、ＤＣＰＤに付着していたＦＡｐを含めて、粉末全体が、ＦＡｐを形成することになる。 In the present invention, the fluorine insolubilizer blended in treated gypsum, contaminated soil and contaminated water can sufficiently insolubilize fluorine as fluorine apatite in a short time. That is, the DCPD portion of the DCPD to which the FAp is attached to the surface retains its original shape and is converted into the FAp to the inside. Therefore, the entire powder, including the FAp adhering to the DCPD, forms the FAp.
（実施例）
次に、実施例を挙げて本発明を更に具体的に説明する。
(Example)
Next, the present invention will be described in more detail with reference to examples.
＜フッ素不溶化剤Ａの調製＞
（ＤＣＰＤ粉末Ａ）
市販品である粉末状のリン酸水素カルシウム二水和物（ＤＣＰＤ粉末Ａ）（米山化学工業社製；特級試薬）を使用した。また、ＤＣＰＤ粉末Ａの電子顕微鏡（ＳＥＭ）写真を図８に、ＸＲＤの結果を図４の符号（４−１）に示した。
<Preparation of Fluorine Insolubilizer A>
(DCPD powder A)
A commercially available powdered calcium hydrogen phosphate dihydrate (DCPD powder A) (manufactured by Yoneyama Chemical Industry Co., Ltd .; a special grade reagent) was used. Further, an electron microscope (SEM) photograph of DCPD powder A is shown in FIG. 8, and the result of XRD is shown in reference numeral (4-1) in FIG.
（弱酸性溶液Ａの調製）
室温下、超純水に超純水１０００ｍｌ換算で、ＣａＣｌ２を０．２７８ｇ（Ｃａ２＋濃度２．５ｍｍｏｌ）、Ｋ２ＨＰＯ４・３Ｈ２Ｏを０．２２８ｇ（ＨＰＯ４ ２−濃度１．０ｍｍｏｌ）及びＮａＦを０．０６６ｇ（Ｆ−濃度１．５ｍｍｏｌ）添加し、更に塩酸を添加することでｐＨ４．６に調整された沈殿物のない弱酸性溶液Ａを得た。
(Preparation of weakly acidic solution A)
At room temperature, with ultrapure water 1000ml converted to ultrapure water, the CaCl 2 0.278g (Ca 2+ concentration 2.5mmol), K 2 HPO 4 · 3H 2 O and 0.228 g (HPO 4 2-density 1.0mmol ) And NaF (F − concentration 1.5 mmol) were added, and hydrochloric acid was further added to obtain a weakly acidic solution A having a pH adjusted to 4.6 without a precipitate.
（フッ素不溶化剤Ａの調製）
次に、室温下、容器に入れた弱酸性溶液ＡにＤＣＰＤ粉末Ａを投入し、浸漬した。この際、ＤＣＰＤ粉末Ａと弱酸性溶液Ａの固液比（質量/体積）は、ＤＣＰＤ粉末Ａ１ｇに対して、弱酸性溶液Ａを５０ｍｌ混合したものであり、１/５０であった。混合後、溶液をポリプロピレン製瓶に封入し、毎分８０回にて７日間、振とうさせて混合させた。
(Preparation of Fluorine Insolubilizer A)
Next, at room temperature, DCPD powder A was put into a weakly acidic solution A in a container and immersed. At this time, the solid-liquid ratio (mass / volume) of the DCPD powder A and the weakly acidic solution A was 1/50 of 1 g of the DCPD powder A mixed with 50 ml of the weakly acidic solution A. After mixing, the solution was sealed in a polypropylene bottle and shaken at 80 times per minute for 7 days to mix.
７日間の振とう後、得られた懸濁物を０．４５μｍのメンブレンフィルターにて濾過して固相を採取し、更に乾燥して、粉末状のフッ素不溶化剤Ａを得た。フッ素不溶化剤Ａを、粉末Ｘ線回折装置（ＸＲＤ）、粒子表面の形態及び構成相をＳＥＭを用いて調べた。 After shaking for 7 days, the obtained suspension was filtered through a 0.45 μm membrane filter to collect a solid phase, and further dried to obtain a powdery fluorine insolubilizer A. The fluorine insolubilizer A was examined using a powder X-ray diffractometer (XRD) and the morphology and constituent phases of the particle surface using a SEM.
上記の調製で得られたフッ素不溶化剤ＡのＳＥＭ写真を図１に、ＸＲＤの結果を図４の符号（２−１）に示した。この結果、フッ素不溶化剤Ａは、ＤＣＰＤの表面にＦＡｐが沈着していることを確認した。この時の弱酸性溶液ＡのｐＨは５．６であった。これは、ＤＣＰＤの一部が溶解してカルシウムイオンとリン酸イオンを溶出し、リン酸イオンの加水分解により溶液のｐＨが５．６程度まで上昇したものであり、これらカルシウムイオンとリン酸イオンは、溶液中のフッ化物イオンと反応して、ＤＣＰＤ粉末の表面上にＦＡｐを生成したものと思われる。また、ＤＣＰＤの表面に沈着したＦＡｐは、針状物が集合したものであった。また、フッ素不溶化剤Ａ中のＦＡｐの含有量を、ＩＣＰ（誘導結合プラズマ）分析により求めたところ、フッ素不溶化剤中、１０．０質量％であった。 The SEM photograph of the fluorine insolubilizer A obtained by the above preparation is shown in FIG. 1, and the result of XRD is shown in reference numeral (2-1) in FIG. As a result, it was confirmed that the fluorine insolubilizer A had FAp deposited on the surface of DCPD. The pH of the weakly acidic solution A at this time was 5.6. This is because a part of DCPD dissolves and elutes calcium ions and phosphate ions, and the pH of the solution rises to about 5.6 due to the hydrolysis of phosphate ions. These calcium ions and phosphate ions Is thought to have reacted with fluoride ions in the solution to form FAp on the surface of the DCPD powder. The FAp deposited on the surface of DCPD was an aggregate of needle-like substances. Moreover, when the content of FAp in the fluorine insolubilizer A was determined by ICP (inductively coupled plasma) analysis, it was 10.0% by mass in the fluorine insolubilizer.
＜フッ素含有汚染水の処理方法Ａ＞
（反応容器）
フッ素不溶化剤Ａと除去対象物であるフッ化物イオンとの反応を調べるために、撹拌用テフロン（登録商標）羽根を備えた反応容器を使用した。反応容器には、フッ化物イオン濃度を測定するフッ化物イオン選択性電極を設置した。
<Treatment method A for fluorine-containing contaminated water>
(Reaction vessel)
In order to investigate the reaction between the fluorine insolubilizer A and the fluoride ion to be removed, a reaction vessel equipped with a Teflon (registered trademark) blade for stirring was used. A fluoride ion selective electrode for measuring the fluoride ion concentration was installed in the reaction vessel.
（処理方法及び測定結果）
室温下、反応容器中に超純水を１０００ｍｌ入れ、所定量のフッ化ナトリウム試薬４４ｍｇを溶解させて、フッ化物イオン濃度２０ｍｇ/Ｌのフッ化物溶液（フッ素含有汚染水Ａ）を調製した。ここにフッ素不溶化剤Ａの粉末１．０ｇ（固液比１:１０００）を添加し、撹拌羽根の撹拌速度２００ｒｐｍ下、反応を開始させ、溶液中のフッ化物イオン濃度の変化を経時的にイオン選択性電極で測定した。その測定結果を図３に実施例１として示した。
(Processing method and measurement results)
At room temperature, 1000 ml of ultrapure water was placed in a reaction vessel, and a predetermined amount of 44 mg of sodium fluoride reagent was dissolved to prepare a fluoride solution (fluorine-containing contaminated water A) having a fluoride ion concentration of 20 mg / L. 1.0 g of a fluorine insolubilizer A powder (solid-liquid ratio 1: 1000) was added thereto, the reaction was started at a stirring speed of 200 rpm of the stirring blade, and the change in the fluoride ion concentration in the solution was ionized over time. Measured with a selective electrode. The measurement result is shown in FIG. 3 as Example 1.
また、処理時間２４０分後の懸濁液を０．４５μｍのメンブレンフィルターにて濾過して固相を採取し、乾燥させた構成相をＸＲＤ、粒子表面の形態及び構成相をＳＥＭを用いて調べた。ＳＥＭ写真を図５に、ＸＲＤの結果を図４の符号（２−２）に示した。その結果、処理済のフッ素不溶化剤は、全体がＦＡｐと確認できた。また、フッ素不溶化剤ＡのＤＣＰＤ部分は、その形状を保持したまま、ＦＡｐに転換されたものであった。 Further, the suspension after 240 minutes of treatment time was filtered through a 0.45 μm membrane filter to collect a solid phase, and the dried constituent phase was examined using XRD, and the morphology and constituent phase of the particle surface were examined using SEM. It was. The SEM photograph is shown in FIG. 5, and the XRD result is shown in reference numeral (2-2) in FIG. As a result, it was confirmed that the treated fluorine insolubilizer as a whole was FAp. Further, the DCPD portion of the fluorine insolubilizer A was converted to FAp while maintaining its shape.
＜フッ素不溶化剤Ｂの調製＞
固液比１/５０の振とう７日間に代えて、固液比１/１０の振とう１日間としたこと、及びＤＣＰＤ粉末Ａに代えて、粉末状のフッ素不溶化剤Ａを使用し、これを弱酸性溶液Ａに投入し、混合処理したこと以外は、実施例１と同様の方法で、フッ素不溶化剤Ａ-１を調製した。次いで、同様の振とう１日間とし、ＤＣＰＤ粉末Ａに代えて、粉末状のフッ素不溶化剤Ａ-１を使用し、これを弱酸性溶液Ａに投入し、浸漬した以外は、実施例１と同様の方法で、フッ素不溶化剤Ｂを調製した。すなわち、フッ素不溶化剤Ｂは、本発明の第２の実施の形態における製造方法に相当するものであり、２度の繰り返し浸漬、合計３度の浸漬処理を行ったものである。
<Preparation of fluorine insolubilizer B>
Instead of 7 days of shaking with a solid-liquid ratio of 1/50, 1 day of shaking with a solid-liquid ratio of 1/10 was used, and instead of DCPD powder A, a powdered fluorine insolubilizer A was used. Was put into a weakly acidic solution A and mixed, and the fluorine insolubilizer A-1 was prepared in the same manner as in Example 1. Next, the same shaking was performed for one day, and instead of DCPD powder A, powdered fluorine insolubilizer A-1 was used, which was put into a weakly acidic solution A and immersed in the same manner as in Example 1. Fluorine insolubilizer B was prepared by the method of. That is, the fluorine insolubilizer B corresponds to the production method according to the second embodiment of the present invention, and has been subjected to repeated immersion twice and a total of three immersion treatments.
実施例２で得られたフッ素不溶化剤ＢのＳＥＭ写真を図２に、ＸＲＤの結果を図４の符号（１−１）に示した。この結果、フッ素不溶化剤Ｂは、ＤＣＰＤの表面にＦＡｐが沈着していることを確認した。また、ＤＣＰＤの表面に沈着したＦＡｐは、針状物が集合したものであった。また、フッ素不溶化剤Ｂにおいて、ＩＣＰ分析の結果よりＦＡｐの含有量を求めたところ、フッ素不溶化剤中、１８．０質量％であった。また、Ｃａ/Ｐ比は、１．１０であった。 The SEM photograph of the fluorine insolubilizer B obtained in Example 2 is shown in FIG. 2, and the result of XRD is shown in reference numeral (1-1) in FIG. As a result, it was confirmed that the fluorine insolubilizer B had FAp deposited on the surface of DCPD. The FAp deposited on the surface of DCPD was an aggregate of needle-like substances. Further, when the FAp content of the fluorine insolubilizer B was determined from the result of ICP analysis, it was 18.0% by mass in the fluorine insolubilizer. The Ca / P ratio was 1.10.
＜フッ素含有汚染水の処理方法Ｂ＞
フッ素不溶化剤Ａに代えて、フッ素不溶化剤Ｂを使用した以外は、実施例１のフッ素含有汚染水の処理方法Ａと同様の方法で行った。その測定結果を図３に実施例２として示した。また、処理時間２４０分後の懸濁液を０．４５μｍのメンブレンフィルターにて濾過して固相を採取し、乾燥させた構成相をＸＲＤ、粒子表面の形態及び構成相をＳＥＭを用いて調べた。ＳＥＭ写真を図６に、ＸＲＤの結果を図４の符号（１−２）に示した。その結果、処理済のフッ素不溶化剤は、全体がＦＡｐと確認できた。また、フッ素不溶化剤ＡのＤＣＰＤ部分は、その形状を保持したまま、ＦＡｐに転換されたものであった。
<Treatment method B for fluorine-containing contaminated water>
The treatment was carried out in the same manner as in the treatment method A for the fluorine-containing contaminated water of Example 1 except that the fluorine insolubilizer B was used instead of the fluorine insolubilizer A. The measurement result is shown in FIG. 3 as Example 2. Further, the suspension after 240 minutes of treatment time was filtered through a 0.45 μm membrane filter to collect a solid phase, and the dried constituent phase was examined using XRD, and the morphology and constituent phase of the particle surface were examined using SEM. It was. The SEM photograph is shown in FIG. 6, and the XRD result is shown in reference numeral (1-2) in FIG. As a result, it was confirmed that the treated fluorine insolubilizer as a whole was FAp. Further, the DCPD portion of the fluorine insolubilizer A was converted to FAp while maintaining its shape.
（比較例１）
（弱酸性溶液Ｂの調製）
室温下、１０００ｍｌの水に、ＣａＣｌ２を０．２７８ｇ（Ｃａ２＋濃度２．５ｍｍｏｌ）及びＫ２ＨＰＯ４・３Ｈ２Ｏを０．２２８ｇ（ＨＰＯ４ ２−濃度１．０ｍｍｏｌ）添加してｐＨ４．６に調整した。これにより、沈殿物のない弱酸性溶液Ｂを得た。すなわち、弱酸性溶液Ｂは、実施例１の弱酸性溶液Ａにおいてフッ素化合物の添加を省略したものである。
(Comparative Example 1)
(Preparation of weakly acidic solution B)
At room temperature, the water of 1000 ml, the CaCl 2 0.278g (Ca 2+ concentration 2.5 mmol) and K 2 HPO 4 · 3H 2 O and 0.228 g (HPO 4 2-density 1.0 mmol) was added pH 4. Adjusted to 6. As a result, a weakly acidic solution B without a precipitate was obtained. That is, the weakly acidic solution B is the weakly acidic solution A of Example 1 in which the addition of the fluorine compound is omitted.
（フッ素不溶化剤Ｃの調製）
弱酸性溶液Ａに代えて、弱酸性溶液Ｂとした以外は、実施例１のフッ素不溶化剤Ａの調製と同様の方法で調製し、フッ素不溶化剤Ｃを得た。フッ素不溶化剤ＣのＳＥＭ写真を図７に、ＸＲＤの結果を図４の符号（３−１）に示した。この結果、フッ素不溶化剤Ｃは、ＤＣＰＤの表面にＦＡｐの沈着は当然、確認されないものであった。
(Preparation of Fluorine Insolubilizer C)
A fluorine insolubilizer C was obtained by preparing the fluorine insolubilizer A in the same manner as in Example 1 except that the weakly acidic solution A was replaced with the weakly acidic solution B. The SEM photograph of the fluorine insolubilizer C is shown in FIG. 7, and the result of XRD is shown in reference numeral (3-1) in FIG. As a result, the fluorine insolubilizer C was not confirmed to have FAp deposited on the surface of DCPD.
＜フッ素含有汚染水の処理方法Ｃ＞
フッ素不溶化剤Ａに代えて、フッ素不溶化剤Ｃを使用した以外は、実施例１のフッ素含有汚染水の処理方法と同様の方法で行った。その測定結果を図３に比較例１として示した。また、２４０時間処理後の固相の乾燥物のＸＲＤの結果を図４の符号（３−２）に示した。
<Treatment method C for fluorine-containing contaminated water>
The method was the same as the method for treating fluorine-containing contaminated water in Example 1 except that the fluorine insolubilizer C was used instead of the fluorine insolubilizer A. The measurement result is shown in FIG. 3 as Comparative Example 1. The XRD results of the solid-phase dried product after the treatment for 240 hours are shown by reference numerals (3-2) in FIG.
（比較例２）
＜フッ素含有汚染水の処理方法Ｄ＞
フッ素不溶化剤Ａに代えて、ＤＣＰＤ粉末Ａを使用した以外は、実施例１のフッ素含有汚染水の処理方法と同様の方法で行った。その測定結果を図３に比較例２として示した。汚染水の処理方法Ｄの２４０時間処理後の固相の乾燥物のＸＲＤの結果を図４の符号（４−２）に示した。
(Comparative Example 2)
<Treatment method D for fluorine-containing contaminated water>
The procedure was the same as the method for treating fluorine-containing contaminated water in Example 1 except that DCPD powder A was used instead of the fluorine insolubilizer A. The measurement result is shown in FIG. 3 as Comparative Example 2. The XRD results of the solid-phase dried product after the 240-hour treatment of the contaminated water treatment method D are shown by reference numerals (4-2) in FIG.
図３の結果から、ＦＡｐ付着ＤＣＰＤ粉体をフッ素不溶化剤とした実施例１では、ＤＣＰＤと汚染物質であるフッ化物イオンの反応遅れ時間が約半分に短縮できた。また、３度の繰り返し浸漬により、ＤＣＰＤ粉体に付着したＦＡｐの付着量を高めた実施例２では、遅れ時間が無視できる程度にまで短縮できた。また、ＤＣＰＤの浸漬に使用する弱酸性溶液のフッ化物イオンの添加を省略した比較例１では、未処理のＤＣＰＤ粉体を使用した比較例２と同等の結果であり、反応開始までの誘導時間（遅れ時間）に改善は見られなかった。 From the results shown in FIG. 3, in Example 1 in which the FAp-adhered DCPD powder was used as a fluorine insolubilizer, the reaction delay time between DCPD and fluoride ion, which is a pollutant, could be reduced to about half. Further, in Example 2 in which the amount of FAp adhering to the DCPD powder was increased by repeated immersion three times, the delay time could be shortened to a negligible level. Further, in Comparative Example 1 in which the addition of the fluoride ion of the weakly acidic solution used for dipping the DCPD was omitted, the result was the same as in Comparative Example 2 using the untreated DCPD powder, and the induction time until the reaction started. No improvement was seen in (delay time).
（フッ素不溶化剤の調製方法における固液比の影響‐１回浸漬処理）
実施例１の（フッ素不溶化剤Ａの調製）において、固液比１/１０、１/２０、１/３０、１/５０（実施例１）の４つの系の、振とう日数１日、３日、７日におけるフッ素不溶化剤についてＩＣＰ分析を行い、Ｃａ/Ｐ値、フッ素不溶化剤中のＦＡｐの質量％を測定した。その結果を表１に示す。
(Effect of solid-liquid ratio on the method of preparing fluorine insolubilizer-1 time immersion treatment)
In Example 1 (preparation of fluorine insolubilizer A), the four systems having a solid-liquid ratio of 1/10, 1/20, 1/30, and 1/50 (Example 1) were shaken for 1 day, 3 days. ICP analysis was performed on the fluorine insolubilizer on the 7th day, and the Ca / P value and the mass% of FAp in the fluorine insolubilizer were measured. The results are shown in Table 1.
（参考例２）
（フッ素不溶化剤の調製方法における固液比の影響‐繰り返し浸漬処理）
＜フッ素不溶化剤Ｂの調製＞の繰り返し浸漬３回に代えて、１回、２回、４回とした以外は、実施例２と同様に、フッ素不溶化剤Ｂの調製を行い、得られた固相乾燥物についてＩＣＰ分析を行い、Ｃａ/Ｐ値、フッ素不溶化剤中のＦＡｐの質量％を測定した。その結果を表２に示す。
(Reference example 2)
(Effect of solid-liquid ratio in the method of preparing fluorine insolubilizer-repeated immersion treatment)
<Preparation of Fluorine Insolubilizer B> The fluorine insolubilizer B was prepared in the same manner as in Example 2 except that the immersion was repeated once, twice, and four times instead of three times, and the obtained solid was obtained. ICP analysis was performed on the phase dried product, and the Ca / P value and the mass% of FAp in the fluorine insolubilizer were measured. The results are shown in Table 2.
表１から、１回浸漬処理の場合、振とう日数が増えるほど、また、固液比が小さいほど、ＦＡｐの沈着量は多くなることが判る。また、表２から、繰り返し処理の場合、繰り返し処理数が多いほどＦＡｐの沈着量は多くなることが判る。 From Table 1, it can be seen that in the case of the one-time immersion treatment, the amount of FAp deposited increases as the number of shaking days increases and the solid-liquid ratio decreases. Further, from Table 2, in the case of repeated treatment, it can be seen that the larger the number of repeated treatments, the larger the amount of FAp deposited.
本発明によれば、ＤＣＰＤと汚染物であるフッ化物イオンとの反応に見られる遅れ時間が改善でき、ＤＣＰＤの高い活性化が可能となった。また、より単純な組成の溶液を使用できるため、施工現場においてＤＣＰＤの処理が可能となる。従来、ＤＣＰＤとフッ化物イオンとの反応に見られる遅れ時間を改善する方法として、ＤＣＰＤの表面にリン酸カルシウムの前駆体を形成する方法が知られているが、本発明のように、ＤＣＰＤの表面に、原位置において固定化されるＦＡｐを、予め沈着させるという発想はこれまでになく、これによる活性効果も大きく、フッ素汚染処理に大きな貢献をもたらすものである。 According to the present invention, the delay time observed in the reaction between DCPD and the fluoride ion which is a contaminant can be improved, and high activation of DCPD becomes possible. In addition, since a solution having a simpler composition can be used, DCPD can be processed at the construction site. Conventionally, as a method for improving the delay time observed in the reaction between DCPD and fluoride ions, a method of forming a precursor of calcium phosphate on the surface of DCPD has been known, but as in the present invention, on the surface of DCPD. The idea of pre-depositing FAp immobilized in the in-situ position has never been seen before, and the activation effect of this is large, which greatly contributes to the treatment of fluorine contamination.
Claims (13)
Ｃａ２＋イオン２．０〜５．０ｍｍｏｌ/ｌ、ＨＰＯ４ ２−イオン０．５〜２．０ｍｍｏｌ/ｌ及びＦ−イオン１．０〜３．０ｍｍｏｌ/ｌを含有する弱酸性溶液に、該第２工程で得られた固相を浸漬させ、リン酸水素カルシウム二水和物の表面に、更にフッ素アパタイトを沈着させる浸漬繰り返し工程と、を有する請求項５〜８のいずれか１項に記載のフッ素不溶化剤の製造方法。 The second step of solid-liquid separation of the solid-liquid phase obtained in the first step to take out the calcium hydrogen phosphate dihydrate on which fluorine apatite, which is a solid phase, is deposited, and the second step.
In a weakly acidic solution containing Ca 2+ ion 2.0 to 5.0 mmol / l, HPO 4 2- ion 0.5 to 2.0 mmol / l and F - ion 1.0 to 3.0 mmol / l, the first solution. The method according to any one of claims 5 to 8, further comprising a repeating immersion step of immersing the solid phase obtained in the two steps and further depositing fluorine apatite on the surface of calcium hydrogen phosphate dihydrate. A method for producing a fluorine insolubilizer.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007216156A (en) * | 2006-02-17 | 2007-08-30 | Institute Of National Colleges Of Technology Japan | Treatment agent and treatment method of fluorine-contaminated soil |
| WO2010041330A1 (en) * | 2008-10-10 | 2010-04-15 | 独立行政法人国立高等専門学校機構 | Fluorine insolubilizing agent, gypsum with elution of fluorine contained therein being reduced, and method for treating soil contaminated with fluirine |
| JP2010221103A (en) * | 2009-03-23 | 2010-10-07 | Chiyoda Ute Co Ltd | Fluorine-containing wastewater treatment method |
| JP2010241665A (en) * | 2009-04-10 | 2010-10-28 | Chiyoda Ute Co Ltd | Method and apparatus for producing activated calcium hydrogen phosphate dihydrate |
| JP2011256356A (en) * | 2010-05-10 | 2011-12-22 | Institute Of National Colleges Of Technology Japan | Fluorine insolubilizer and method for producing the same |
| JP2017001909A (en) * | 2015-06-10 | 2017-01-05 | チヨダウーテ株式会社 | Fluorine insolubilization agent for steel slag |
-
2019
- 2019-02-19 JP JP2019027014A patent/JP7315160B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007216156A (en) * | 2006-02-17 | 2007-08-30 | Institute Of National Colleges Of Technology Japan | Treatment agent and treatment method of fluorine-contaminated soil |
| WO2010041330A1 (en) * | 2008-10-10 | 2010-04-15 | 独立行政法人国立高等専門学校機構 | Fluorine insolubilizing agent, gypsum with elution of fluorine contained therein being reduced, and method for treating soil contaminated with fluirine |
| JP2010221103A (en) * | 2009-03-23 | 2010-10-07 | Chiyoda Ute Co Ltd | Fluorine-containing wastewater treatment method |
| JP2010241665A (en) * | 2009-04-10 | 2010-10-28 | Chiyoda Ute Co Ltd | Method and apparatus for producing activated calcium hydrogen phosphate dihydrate |
| JP2011256356A (en) * | 2010-05-10 | 2011-12-22 | Institute Of National Colleges Of Technology Japan | Fluorine insolubilizer and method for producing the same |
| JP2017001909A (en) * | 2015-06-10 | 2017-01-05 | チヨダウーテ株式会社 | Fluorine insolubilization agent for steel slag |
Non-Patent Citations (2)
| Title |
|---|
| 蓬莱秀人: "半水石膏に含まれるフッ素の不溶化技術", 公益社団法人地盤工学会中国支部論文報告集, vol. 28, no. 1, JPN6022020090, 2010, JP, pages 31 - 38, ISSN: 0005038118 * |
| 袋布昌幹: "リン酸水素カルシウム二水和物（ＤＣＰＤ）と水溶液中低濃度フッ化物イオンとの反応", JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, vol. 113, no. 5, JPN6022020091, 2005, JP, pages 363 - 367, ISSN: 0005038117 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175623A (en) * | 2020-10-15 | 2021-01-05 | 森特士兴集团股份有限公司 | Stabilizer for repairing fluoride-contaminated soil and using method thereof |
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