JPWO2009001719A1 - Hazardous substance insolubilizer and method of insolubilizing hazardous substances - Google Patents
Hazardous substance insolubilizer and method of insolubilizing hazardous substances Download PDFInfo
- Publication number
- JPWO2009001719A1 JPWO2009001719A1 JP2009520494A JP2009520494A JPWO2009001719A1 JP WO2009001719 A1 JPWO2009001719 A1 JP WO2009001719A1 JP 2009520494 A JP2009520494 A JP 2009520494A JP 2009520494 A JP2009520494 A JP 2009520494A JP WO2009001719 A1 JPWO2009001719 A1 JP WO2009001719A1
- Authority
- JP
- Japan
- Prior art keywords
- substance
- insolubilizing agent
- ash
- insolubilizing
- soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000383 hazardous chemical Substances 0.000 title claims abstract description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 68
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000126 substance Substances 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 34
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 34
- 239000000292 calcium oxide Substances 0.000 claims abstract description 30
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 30
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 16
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000002956 ash Substances 0.000 claims description 28
- 239000010883 coal ash Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000003440 toxic substance Substances 0.000 claims description 11
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 9
- 229960002089 ferrous chloride Drugs 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 231100000167 toxic agent Toxicity 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000010424 alunite Substances 0.000 claims description 3
- 229910052934 alunite Inorganic materials 0.000 claims description 3
- FAYYUXPSKDFLEC-UHFFFAOYSA-L calcium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Ca+2].[O-]S([O-])(=O)=S FAYYUXPSKDFLEC-UHFFFAOYSA-L 0.000 claims description 3
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 3
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 3
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- IAZSTYDOYUHVAO-UHFFFAOYSA-K aluminum phosphoric acid trichloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].OP(O)(O)=O IAZSTYDOYUHVAO-UHFFFAOYSA-K 0.000 claims 1
- 231100001261 hazardous Toxicity 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 235000011147 magnesium chloride Nutrition 0.000 claims 1
- 238000010828 elution Methods 0.000 abstract description 49
- 239000002689 soil Substances 0.000 abstract description 46
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052796 boron Inorganic materials 0.000 abstract description 36
- 239000011737 fluorine Substances 0.000 abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 29
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 18
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 17
- 238000011109 contamination Methods 0.000 abstract description 17
- 229910052711 selenium Inorganic materials 0.000 abstract description 17
- 239000011669 selenium Substances 0.000 abstract description 17
- 229910052785 arsenic Inorganic materials 0.000 abstract description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 11
- 230000001629 suppression Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 description 15
- 230000007613 environmental effect Effects 0.000 description 14
- 238000004898 kneading Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- -1 iron ions Chemical class 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 150000002506 iron compounds Chemical class 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 235000014380 magnesium carbonate Nutrition 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical group [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052599 brucite Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010426 asphalt Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/24—Organic substances containing heavy metals
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/49—Inorganic substances containing halogen
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Toxicology (AREA)
- Soil Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
高濃度のホウ素、フッ素、セレン、六価クロム、ヒ素等を含む土壌、灰などの効率的かつ経済的な溶出抑制を可能とする有害物質の不溶化剤を提供する。軽焼マグネシアと、生石灰又は消石灰とを含有させた。酸性物質を含有し、軽焼マグネシアと生石灰又は消石灰、酸性物質との配合重量比を、１．０：（０．１〜１．０）：（０．０〜２．０）の範囲とすれば被処理物に加えて混練したときの被処理物のｐＨが１０．５以上１２．５以下となる。さらに、還元剤を含有させてもよい。土壌や灰等に含まれる高濃度のホウ素、フッ素の溶出抑制を確実に、経済的に行うことができる。また、セレン、ヒ素、六価クロム等を含む、複合汚染の溶出抑制を、効率よく一括処理することが可能である。本発明の有害物質不溶化剤を用いて無害化された土壌や焼却灰などは堅固に硬化するため、安全にリサイクル利用することができる。Provided is an insolubilizing agent for harmful substances that enables efficient and economical suppression of soil and ash containing high concentrations of boron, fluorine, selenium, hexavalent chromium, arsenic and the like. Lightly burned magnesia and quick lime or slaked lime were contained. It contains an acidic substance, and the weight ratio of light-burned magnesia and quicklime or slaked lime and acidic substance is within the range of 1.0: (0.1-1.0) :( 0.0-2.0). For example, the pH of the object to be processed when kneaded in addition to the object to be processed is 10.5 or more and 12.5 or less. Furthermore, you may contain a reducing agent. It is possible to reliably and economically suppress elution of high concentrations of boron and fluorine contained in soil and ash. Moreover, it is possible to efficiently and collectively process elution suppression of complex contamination including selenium, arsenic, hexavalent chromium and the like. The soil or incinerated ash that has been rendered harmless using the hazardous substance insolubilizing agent of the present invention hardens firmly and can be safely recycled.
Description
本発明は、土壌、石炭灰、焼却灰等に含まれる重金属等有害物質の不溶化剤組成に関する。 The present invention relates to a composition for insolubilizing harmful substances such as heavy metals contained in soil, coal ash, incineration ash, and the like.
我が国においては、土壌汚染が判明した土地の件数が平成８年度から飛躍的に増加し、現在、約３２万箇所の土地で土壌汚染が発生していると推定されている。また、海外における土壌汚染の状況は、米国で５０万箇所、ヨーロッパにおいてはフランスで７０万箇所、ドイツで３０万箇所と推定されている。さらに、アジア地域では近年の急速な工業化により、土壌汚染を含む環境面での様々な問題が複合的に発生しているといわれている。 In Japan, the number of land where soil contamination has been found has increased dramatically since FY 1996, and it is estimated that soil contamination has occurred in about 320,000 locations at present. In addition, the situation of soil contamination overseas is estimated at 500,000 locations in the United States, 700,000 locations in France in Europe, and 300,000 locations in Germany. Furthermore, in the Asian region, it is said that various environmental problems including soil contamination are occurring in combination with the rapid industrialization in recent years.
環境省発表の「平成１６年度土壌汚染対策法の実施状況及び土壌汚染調査・対策事例等にする調査結果」によると、平成１７年度末日までに都道府県等が把握した土壌汚染調査結果では、超過事例が１，９０６件となり、我が国の深刻な土壌汚染の現状が明らかになっている。このような背景の中、我が国では平成１５年に土壌汚染対策法が施行され、直接摂取によるリスク、地下水等の摂取によるリスクの回避に重点をおいた対策が示され、土壌汚染対策法の厳しい環境基準に対応できるような、抜本的な対策技術の確立が求められている。 According to the Ministry of the Environment's announcement, “Survey Results of 2004 Soil Contamination Countermeasures Law and Soil Contamination Survey / Measures, etc.”, the soil contamination survey results grasped by the prefectures by the end of the 2005 fiscal year exceeded The number of cases was 1,906, and the current state of serious soil contamination in Japan has been clarified. Against this background, the Soil Contamination Countermeasures Law was enforced in Japan in 2003, and measures focusing on avoiding risks from direct intake and groundwater intake were shown. There is a need to establish drastic countermeasure technologies that can meet environmental standards.
判明した土壌汚染原因の内訳は、重金属等超過事例が６１％、揮発性有機化合物（ＶＯＣ）超過事例が２５％、複合汚染超過事例が１４％となっており、重金属等が汚染原因となっている割合が非常に高い。また重金属等の汚染原因物質の順位は、鉛、ヒ素、フッ素、六価クロム、水銀、シアン、セレン、カドミウム、ホウ素、アルキル水銀の順になっている。環境基準の改定された平成1５年度以降は、フッ素の超過事例が顕著に増加している傾向が認められる。 The breakdown of the causes of soil contamination was 61% for excess cases of heavy metals, 25% for excess cases of volatile organic compounds (VOC), and 14% for excess cases of combined pollution. The ratio is very high. The order of pollutants such as heavy metals is in the order of lead, arsenic, fluorine, hexavalent chromium, mercury, cyan, selenium, cadmium, boron, and alkylmercury. Since FY 1995 when the environmental standards were revised, there has been a noticeable increase in the number of cases of excess fluorine.
一方、火力発電により発生する大量の石炭灰の安全で経済的な処理やリサイクル利用の促進も重要な課題となっている。近年の原油価格の高騰により、発電燃料は石油から石炭へと急速にシフトが進んできている。平成１４年度末に３，３７７万ｋＷであった石炭火力発電設備は、平成１９年度には３，９２２万ｋＷ、平成２４年度には４，３１５万ｋＷとなる計画となっており、これにより、国内の石炭灰発生量は、平成１４年度末の約９２０万トンが、平成１９年度末には約１，０００万トンに達するものと予測されている。 On the other hand, the safe and economical treatment of large quantities of coal ash generated by thermal power generation and the promotion of recycling are also important issues. Due to soaring crude oil prices in recent years, the power generation fuel is rapidly shifting from oil to coal. The coal-fired power generation facility, which was 33.77 million kW at the end of 2002, is planned to be 39.22 million kW in 2007 and 43.15 million kW in 2012. The amount of coal ash generated in Japan is projected to reach approximately 10 million tons at the end of 2007, from about 9.2 million tons at the end of 2002.
現在の石炭灰の処理の状況をみると、排出量の５５％が有効利用され、４５％が主に海域で埋め立て処分されているが、この埋め立て処分地の確保が非常に困難になってきている。また、石炭灰の具体的な有効利用の用途としては、セメント原料及び土木・建築分野での利用が９０％を占めている。 Looking at the current state of coal ash treatment, 55% of the emissions are effectively used, and 45% is mainly landfilled in the sea, but it is very difficult to secure this landfill site. Yes. In addition, as a concrete effective use of coal ash, 90% is used in cement raw materials and civil engineering / architecture fields.
我が国で排出されている石炭灰は基本的には重金属の溶出は少ないが、一部には土壌環境基準を超過するホウ素、フッ素、六価クロム、ヒ素などの溶出量を生ずるものが存在している。石炭灰は、路盤材、軽量裏込材など建設分野での応用範囲が広いため、安価で確実な有害物質の不溶化技術が確立されれば、さらに、そのリサイクル利用を推進することができると考えられる。 Coal ash discharged in Japan has little elution of heavy metals, but there are some that produce elution amounts of boron, fluorine, hexavalent chromium, arsenic, etc. that exceed soil environmental standards. Yes. Coal ash has a wide range of applications in the construction field such as roadbed materials and lightweight backing materials, so if low-cost and reliable technology for insolubilizing harmful substances is established, we can further promote the recycling of coal ash. It is done.
一般廃棄物、ごみ処理施設から排出される焼却灰などの処理残渣を合わせた埋め立て総量は、平成１３年度では９９０万トンとなっている。ごみの選別・破砕などによる再資源化の努力により、この埋め立て総量は年々減少しているが、一般廃棄物の最終処分場の残余年数は逼迫した状況にある。したがって、焼却灰の減容と焼却灰等に含まれる有害物質を無害化し、前記のように建設分野などでリサイクル利用を推進することで、処分量の低減を図ることが望まれる。 The total amount of landfill including processing waste such as general waste and incinerated ash discharged from waste disposal facilities is 9.9 million tons in FY2001. The total amount of landfill has been decreasing year by year due to efforts to recycle by sorting and crushing garbage, but the remaining years of the final landfill site for general waste are tight. Therefore, it is desirable to reduce the amount of disposal by reducing the volume of incinerated ash and detoxifying harmful substances contained in the incinerated ash, etc., and promoting recycling in the construction field as described above.
重金属等の有害物質で汚染された土壌や灰の一般的な無害処理対策として、置き換え法，土壌洗浄、遮蔽、不溶化処理などが挙げられる。置き換え法は汚染土を処理場に処分し、良質土と置き換える方法である。また、土壌洗浄は、汚染土を洗浄し、汚染物質と分離した後に現地に戻す方法であり、土壌より有害成分を完全に除去するため、安全で確実な方法であるが、比較的コストは高く、また、汚染土を処分するため廃棄物が発生する。また、遮蔽はシートパイル、地中壁を設置することで汚染領域を遮蔽し、汚染の拡散を防ぐ方法である。 Common harmless treatment measures for soil and ash contaminated with toxic substances such as heavy metals include replacement methods, soil cleaning, shielding, and insolubilization treatment. The replacement method is a method in which contaminated soil is disposed of at a treatment plant and replaced with high-quality soil. In addition, soil cleaning is a method that cleans contaminated soil, separates it from the pollutant, and returns it to the site. It is a safe and reliable method to completely remove harmful components from the soil, but the cost is relatively high. In addition, waste is generated to dispose of contaminated soil. Shielding is a method of shielding the contaminated area by installing sheet piles and underground walls to prevent the spread of the contamination.
不溶化処理は本発明のように、有害物質溶出抑制効果をもつ薬剤を汚染土、灰に混合し、再び現地に戻す方法で、経済的で廃棄物が発生しない利点がある。不溶化処理法は、置き換え法において、汚染土壌を処分場に処理するため、含有する有害物質の溶出量低減を行うために用いられる。これらの技術の中で、不溶化処理は経済性に優れるため、大量に発生する灰などの廃棄物の処理に適する。 As in the present invention, the insolubilization treatment is a method in which a chemical having an inhibitory effect on the elution of harmful substances is mixed with contaminated soil and ash, and returned to the site again, and has an advantage that it is economical and does not generate waste. The insolubilization method is used in the replacement method to reduce the amount of toxic substances contained in the disposal site in order to treat contaminated soil at a disposal site. Among these techniques, the insolubilization treatment is excellent in economic efficiency, and is suitable for the treatment of waste such as ash generated in large quantities.
現在の土壌環境基準第二種（重金属等）特定有害物質には、総水銀、カドミウム、鉛、六価クロム、ヒ素、全シアン、フッ素、ホウ素の９種が規定されている。これら中では、特にホウ素、フッ素、セレンの溶出抑制が困難であるといわれている。 Nine types of total mercury, cadmium, lead, hexavalent chromium, arsenic, total cyanide, fluorine, and boron are specified as specific hazardous substances of the current soil environment standard type 2 (heavy metals, etc.). Among these, it is said that it is particularly difficult to suppress elution of boron, fluorine and selenium.
ホウ素、フッ素の溶出抑制を行う既存技術としては、例えば、特許文献１に開示されたようにセメント・石灰などのカルシウム原料と、硫酸バンドを組み合わせてアルミン酸カルシウムを形成し溶出抑制を行う方法、鉄粉・ウスタイト（ＦｅＯ）、マグネタイト（Ｆｅ３Ｏ４）などの酸化鉄などの鉄化合物を用いる方法、さらには、リン酸とカルシウムなどのアルカリ物質を加えて撹拌し難溶化を図る方法などが挙げられる。As an existing technique for suppressing elution of boron and fluorine, for example, a method of suppressing elution by forming calcium aluminate by combining a calcium raw material such as cement and lime and a sulfate band as disclosed in Patent Document 1, Methods using iron compounds such as iron oxides such as iron powder, wustite (FeO), magnetite (Fe 3 O 4 ), and methods of adding alkaline substances such as phosphoric acid and calcium to stir hardly solubilize Can be mentioned.
また、特許文献４は、石炭灰の造粒に関する技術を開示している。ここでは重金属抑制剤として消石灰、腐食酸、及びキレート剤を用いているが、キレート剤の使用については、処理コストが高いという問題点が生ずる。特許文献５には、軽焼マグネシウムを主な組成として用いたシアン、リン、窒素、ヒ素の不溶化剤組成に関するものが開示されている。 Moreover, patent document 4 is disclosing the technique regarding granulation of coal ash. Here, slaked lime, corrosive acid, and a chelating agent are used as the heavy metal inhibitor, but the use of the chelating agent causes a problem of high processing costs. Patent Document 5 discloses an insolubilizer composition of cyan, phosphorus, nitrogen, and arsenic using light burned magnesium as a main composition.
また、セレンの溶出抑制を行う技術として、特許文献６には、セレンを含む土壌に、リン酸、２価の鉄イオンの水溶性塩及び生石灰を含有する吸湿剤を添加する方法が示されている。また、特許文献７には、２価鉄化合物もしくは３価鉄化合物とチオ硫酸化合物の溶液を添加して混練し、その後に加熱処理する方法が示されている。
前述のようにホウ素、フッ素、セレンの溶出抑制には様々な方法があるが、高濃度の汚染に対応することは難しい。また、複合汚染においては、汚染の原因物質に応じて処理方法を変更する必要があることから、複合汚染の場合には、すべての原因物質について厳しい環境基準に対応するように処理することは難しく、処理が煩雑、高コストになるという問題があった。 As described above, there are various methods for suppressing elution of boron, fluorine, and selenium, but it is difficult to cope with high concentration contamination. In complex pollution, it is necessary to change the treatment method according to the causative substance of the pollution, so in the case of complex pollution, it is difficult to treat all causative substances so as to comply with strict environmental standards. There is a problem that the processing is complicated and expensive.
また、キレート剤を用いる方法では、キレート剤が一般的に高価であることによるコスト上の問題があるほか、キレート剤が有機材料であることにより、環境中で劣化しやすいという問題があった。 In addition, the method using a chelating agent has a problem of cost due to the fact that the chelating agent is generally expensive, and also has a problem that it easily deteriorates in the environment because the chelating agent is an organic material.
本発明の解決しようとする課題は、高濃度のホウ素、フッ素を含む土壌、灰などの効率的かつ経済的な溶出抑制技術を提供することにある。さらには、ホウ素、フッ素に加えて、セレン、六価クロム、ヒ素等の陰イオン型の有害物質、及びこれらによる複合汚染を生じている土壌、灰の効果的な溶出抑制技術を提供することにある。このような陰イオン型の複数の有害物質を含む材料の典型的な例としては、例えば石炭灰などがある。また、本発明はこれらの溶出抑制技術を提供することにより、処理した土壌や灰のリサイクル利用の促進を図ることを目的とする。 The problem to be solved by the present invention is to provide an efficient and economical elution control technique for soil and ash containing high concentrations of boron and fluorine. Furthermore, in addition to boron and fluorine, to provide an effective leaching control technology for anion-type harmful substances such as selenium, hexavalent chromium and arsenic, and soil and ash that have caused complex contamination with these substances. is there. A typical example of such a material containing a plurality of anionic type harmful substances is, for example, coal ash. Another object of the present invention is to promote recycling of treated soil and ash by providing these elution suppression techniques.
本発明の有害物質の不溶化剤は、軽焼マグネシアと、生石灰又は消石灰とを含有することを特徴とする。 The hazardous substance insolubilizing agent of the present invention is characterized by containing light-burned magnesia and quicklime or slaked lime.
本発明の有害物質の不溶化剤は、さらに酸性物質を含有し、軽焼マグネシアと生石灰又は消石灰、酸性物質との配合重量比が、１．０：（０．１〜１．０）：（０．０〜２．０）の範囲にあることを特徴とする。 The harmful substance insolubilizing agent of the present invention further contains an acidic substance, and the blended weight ratio of light-burned magnesia and quicklime or slaked lime, acidic substance is 1.0: (0.1 to 1.0) :( 0 0.0-2.0).
本発明の有害物質の不溶化剤は、さらに被処理物に加えて混練したときの被処理物のｐＨが１０．５以上１２．５以下となることを特徴とする。 The harmful substance insolubilizing agent of the present invention is further characterized in that the pH of the object to be treated when kneaded in addition to the object to be treated is 10.5 or more and 12.5 or less.
本発明の有害物質の不溶化剤は、前記酸性物質が、硫酸、塩酸、硝酸、酢酸、石膏、硫酸マグネシウム、硫酸第１鉄、硫酸第２鉄、鉄明礬石、塩化第１鉄、塩化第２鉄、硫酸アルミニウム、塩化アルミウム、正リン酸、第一リン酸マグネシウム、第二リン酸マグネシウム、第三リン酸マグネシウム、ピロリン酸マグネシウム、メタリン酸マグネシウム、第一リン酸アルミニウム、第二リン酸アルミニウム、第三リン酸アルミニウム、メタリン酸アルミニウム、及び重過石から選ばれる少なくとも１種を含むことを特徴とする。 The harmful substance insolubilizing agent of the present invention is such that the acidic substance is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, gypsum, magnesium sulfate, ferrous sulfate, ferric sulfate, iron alunite, ferrous chloride, ferric chloride 2 Iron, aluminum sulfate, aluminum chloride, orthophosphoric acid, primary magnesium phosphate, secondary magnesium phosphate, tertiary magnesium phosphate, magnesium pyrophosphate, magnesium metaphosphate, primary aluminum phosphate, secondary aluminum phosphate, It contains at least one selected from tertiary aluminum phosphate, aluminum metaphosphate and bitumenite.
本発明の有害物質の不溶化剤は、さらに還元剤を含有することを特徴とする。 The harmful substance insolubilizing agent of the present invention further comprises a reducing agent.
本発明の有害物質の不溶化剤は、前記還元剤が金属鉄、硫酸第１鉄、塩化第１鉄、硫化ナトリウム、チオ硫酸ナトリウム、チオ硫酸カルシウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、金属アルミニウム、高炉スラグ粉末、粉末硫黄、石炭微粉末のいずれかであることを特徴とする。 The insolubilizing agent for harmful substances according to the present invention is such that the reducing agent is metallic iron, ferrous sulfate, ferrous chloride, sodium sulfide, sodium thiosulfate, calcium thiosulfate, sodium sulfite, sodium hydrogen sulfite, metallic aluminum, blast furnace slag. It is one of powder, powdered sulfur, and fine coal powder.
本発明の有害物質の不溶化剤は、さらに珪酸アルカリ金属塩を含有することを特徴とする。 The harmful substance insolubilizing agent of the present invention is characterized by further containing an alkali metal silicate.
本発明の有害物質の不溶化剤は、前記珪酸アルカリ金属塩が水ガラス、カリウム水ガラス、シリカゾル、リチウム水ガラス、粉末珪酸ソーダ、粉末珪酸カリウムのいずれかであることを特徴とする。 The insolubilizing agent for harmful substances of the present invention is characterized in that the alkali metal silicate is one of water glass, potassium water glass, silica sol, lithium water glass, powdered sodium silicate, and powdered potassium silicate.
本発明の有害物質の不溶化方法は、本発明の有害物質の不溶化剤を用い、石炭灰、焼却灰、又はガス化炉から排出される灰を不溶化することを特徴とする。 The toxic substance insolubilization method of the present invention is characterized by using the toxic substance insolubilizer of the present invention to insolubilize coal ash, incineration ash, or ash discharged from a gasification furnace.
本発明の有害物質の不溶化方法は、前記有害物質の不溶化剤の添加量が１０質量％以下であることを特徴とする。 The toxic substance insolubilization method of the present invention is characterized in that the addition amount of the toxic substance insolubilizer is 10% by mass or less.
本発明の有害物質不溶化剤によれば、土壌や灰等に含まれる高濃度のホウ素、フッ素の溶出抑制を確実に、経済的に行うことができる。また、本発明の有害物質の不溶化剤によれば、さらに、これに加えてセレン、ヒ素、六価クロム等を含む、複合汚染の溶出抑制を、効率よく一括処理することが可能である。本発明の有害物質不溶化剤を用いて無害化された土壌や焼却灰などは堅固に硬化するため、安全にリサイクル利用することができる。 According to the hazardous substance insolubilizing agent of the present invention, it is possible to reliably and economically suppress elution of high concentrations of boron and fluorine contained in soil and ash. In addition, according to the hazardous substance insolubilizing agent of the present invention, it is possible to efficiently and collectively treat elution suppression of complex contamination containing selenium, arsenic, hexavalent chromium and the like. The soil or incinerated ash that has been rendered harmless using the hazardous substance insolubilizing agent of the present invention hardens firmly and can be safely recycled.
以下、本発明の有害物質の不溶化剤について詳細に説明する。 Hereinafter, the hazardous substance insolubilizing agent of the present invention will be described in detail.
本発明の不溶化剤は、軽焼マグネシアと、生石灰又は消石灰とを含有するものである。本発明の不溶化剤は、特にホウ素、フッ素を不溶化するために用いることができる。 The insolubilizing agent of the present invention contains light-burned magnesia and quick lime or slaked lime. The insolubilizing agent of the present invention can be used particularly for insolubilizing boron and fluorine.
ここで、本発明に用いられる軽焼マグネシア（酸化マグネシウム）としては、天然鉱物であるマグネサイト（炭酸マグネシウム）を７００〜８００℃で焼成したもの、ブルーサイト（水酸化マグネシウム）を３００〜８００℃で焼成したものが好適である。なお、マグネサイト、ブルーサイトを１０００℃を超える高温で焼成したものは、反応活性が低いため好ましくない。 Here, as light-burned magnesia (magnesium oxide) used in the present invention, natural mineral magnesite (magnesium carbonate) is fired at 700 to 800 ° C., and brucite (magnesium hydroxide) is 300 to 800 ° C. What was baked with is suitable. In addition, what burned magnesite and brucite at a high temperature exceeding 1000 ° C. is not preferable because of low reaction activity.
また、本発明において使用する生石灰又は消石灰は、石灰石（炭酸カルシウム）を９００℃以上で焼成してつくられ、また、消石灰は生石灰を水と反応させてつくられる。生石灰、消石灰は最も安価なアルカリ剤であり、日本国内にも多く産出する。 The quick lime or slaked lime used in the present invention is made by baking limestone (calcium carbonate) at 900 ° C. or more, and the slaked lime is made by reacting quick lime with water. Quicklime and slaked lime are the cheapest alkaline agents, and many are produced in Japan.
ドロマイトは炭酸マグネシウム及び炭酸カルシウムを含有するものであり、この焼成物については、通常炭酸カルシウムを分解するために１０００℃以上で焼成が行われるため、酸化マグネシウム部分の活性が低下するため、本発明に用いることは好ましくない。 Dolomite contains magnesium carbonate and calcium carbonate, and the fired product is usually fired at 1000 ° C. or higher in order to decompose calcium carbonate, so that the activity of the magnesium oxide portion is reduced. It is not preferable to use it.
本発明の有害物質の不溶化剤を重金属等の有害物質で汚染された土壌、有害物質を含有するごみ、製紙スラッジ、下水汚泥、石炭等の飛灰及び燃え殻、高炉スラグ、ガス化炉のスラグ等の焼却灰などの被処理物に加え、加水して混練し、湿潤状態を保ったまま数日間養生を行うことで、本発明の有害物質の不溶化剤の組成中に含まれるマグネシウム、カルシウムは硫酸化合物、リン酸化合物等を生成し、あるいは空気との接触により炭酸化合物を形成し、堅固に硬化する。また、粉末珪酸ソーダなどの珪酸アルカリ金属塩を添加した場合には、さらに固化強度を増加させることができる。本発明の不溶化剤と水を添加し混練処理した土壌や灰のｐＨは概ね１０．５〜１２．５を示し、その後の養生により、硫酸化合物、リン酸化合物の生成と炭酸化にともない若干低下する傾向を示す。 Soil contaminated with toxic substances such as heavy metals, waste containing toxic substances, papermaking sludge, sewage sludge, coal fly ash and husk, blast furnace slag, gasifier slag, etc. In addition to the material to be treated such as incineration ash, water, knead, and curing for several days while maintaining a wet state, magnesium and calcium contained in the composition of the insoluble agent for harmful substances of the present invention is sulfate. A compound, a phosphoric acid compound, etc. are produced | generated, or a carbonic acid compound is formed by contact with air, and it hardens | cures firmly. Further, when an alkali metal silicate such as powdered sodium silicate is added, the solidification strength can be further increased. The pH of the soil and ash kneaded by adding the insolubilizing agent and water of the present invention is approximately 10.5 to 12.5, and is slightly lowered by the subsequent curing due to the formation and carbonation of sulfate compounds and phosphate compounds. Show a tendency to
本発明の有害物質不溶化剤は汚染土壌や灰を堅固に固め、処理した土壌や灰の飛散や解砕を防ぎ、透水性を低下させることにより、有害物の溶出、流出を防ぐ効果を発揮する。さらに、本発明の有害物質不溶化剤は以下に述べるように有害物質の溶出抑制機能を有する組成物を含有するため、優れた溶出低減効果をもつと考えられる。 The hazardous substance insolubilizing agent of the present invention solidifies contaminated soil and ash, prevents the treated soil and ash from scattering and crushing, and reduces water permeability, thereby preventing the leaching and outflow of harmful substances. . Furthermore, since the harmful substance insolubilizing agent of the present invention contains a composition having a function of suppressing the dissolution of harmful substances as described below, it is considered to have an excellent elution reduction effect.
ここで、軽焼マグネシアと、生石灰又は消石灰は、アルカリ域では水酸化物となり沈殿し、この共沈作用や化合物の形成によりホウ素、フッ素の溶出抑制効果が生じると考えられる。また、酸性化合物を添加した場合においては、例えば硫酸カルシウム（石膏）、リン酸カルシウムなどの難溶性化合物形成時の共沈作用によりホウ素、フッ素の溶出抑制効果が生じる。 Here, light-burned magnesia and quicklime or slaked lime are precipitated as hydroxides in the alkaline region, and this coprecipitation action and the formation of compounds are considered to produce a boron and fluorine elution suppression effect. In addition, when an acidic compound is added, for example, an elution suppression effect of boron and fluorine is produced by coprecipitation when forming a hardly soluble compound such as calcium sulfate (gypsum) or calcium phosphate.
ところで、ホウ素は、濃度やｐＨにより形態が変化することが知られている。ホウ素は、比較的濃度が低い場合は、アルカリ性の領域では次式のように解離が進み、ｐＨ１０〜１２の範囲ではほとんどが溶液中でイオン化しＢ（ＯＨ）４ −の形態で存在する。また、ｐＨ８〜９以下ではほとんど解離せずＨ３ＢＯ３の形態となる。By the way, it is known that the form of boron changes depending on the concentration and pH. When the concentration of boron is relatively low, dissociation proceeds as shown in the following formula in the alkaline region, and most of it is ionized in the solution in the range of pH 10 to 12 and exists in the form of B (OH) 4 − . Further, the H 3 BO 3 in the form hardly dissociated in pH8~9 below.
また、ホウ素は０．０２５Ｍ（およそ３００ｍｇ／Ｌ）以上の濃度、ｐＨ６〜１１の範囲で、Ｂ３Ｏ３（ＯＨ）４ −、Ｂ５Ｏ５（ＯＨ）４ −、Ｂ７Ｏ７（ＯＨ）４ −などのポリマー状の形態となる。Boron has a concentration of 0.025 M (approximately 300 mg / L) or more and a pH of 6 to 11, and B 3 O 3 (OH) 4 − , B 5 O 5 (OH) 4 − , B 7 O 7 (OH ) 4 - a polymeric form of such.
したがって、効率よくホウ素を固定するためにはｐＨを制御し、ホウ素を溶出抑制に都合の良いイオン化した状態に変化させることが重要である。 Therefore, in order to immobilize boron efficiently, it is important to control the pH and change the boron to an ionized state convenient for elution suppression.
本発明の有害物質の不溶化剤においては、軽焼マグネシアと、生石灰又は消石灰と、酸性物質を加えて混練時のｐＨを１０．５以上１２．５以下の範囲にコントロールすることで、ホウ素を効率よく固定することができる。これに対し、生石灰又は消石灰を加えずに軽焼マグネシアのみを添加した場合には、土壌や灰の硬化後のｐＨは概ね１０以下の条件となり、前述のホウ素固定のために望ましいｐＨ範囲とすることができない。また、生石灰又は消石灰のみでは、フッ素やホウ素の高い固定能力を得ることはできない。 In the hazardous substance insolubilizing agent of the present invention, light burned magnesia, quick lime or slaked lime, and an acidic substance are added to control the pH during kneading to a range of 10.5 or more and 12.5 or less, thereby improving the efficiency of boron. Can be fixed well. On the other hand, when only light calcined magnesia is added without adding quick lime or slaked lime, the pH after hardening of the soil and ash is approximately 10 or less, which is a desirable pH range for the above-described boron fixation. I can't. Moreover, high fixability of fluorine and boron cannot be obtained only by quick lime or slaked lime.
軽焼マグネシアと、例えば、水酸化ナトリウムなどのナトリウム化合物を添加すれば、同様にｐＨ制御を容易に行うことができるが、ナトリウム化合物は溶解度が高いため、環境中において長期的安定性に欠けると思われる。このため、不溶化剤の組成物としては溶解度の低いカルシウム原料を用いることが好ましい。 If lightly burned magnesia and, for example, a sodium compound such as sodium hydroxide are added, the pH can be controlled easily, but the sodium compound has a high solubility, and thus lacks long-term stability in the environment. Seem. For this reason, it is preferable to use a calcium raw material with low solubility as the composition of the insolubilizing agent.
フッ素の溶出抑制方法として、先ず石灰を添加する方法が挙げられるが、これに軽焼マグネシア、水酸化マグネシウムを加えることで溶出抑制効果はさらに大きくなる。また、これに硫酸イオン、リン酸イオンなどを与え、カルシウムの難溶性化合物形成に伴う共沈作用により不溶化効果を高めることができる。 As a method for suppressing the elution of fluorine, there can be mentioned a method of adding lime first, but the effect of suppressing elution is further increased by adding light-burned magnesia and magnesium hydroxide thereto. In addition, sulfate ions, phosphate ions, and the like can be given thereto, and the insolubilizing effect can be enhanced by coprecipitation accompanying the formation of a poorly soluble compound of calcium.
本発明の有害物質の不溶化剤は、さらに酸性物質を含有してもよい。この場合の軽焼マグネシアと生石灰又は消石灰、酸性物質との配合重量比は、１．０：（０．１〜１．０）：（０．０〜２．０）の範囲とし、この配合条件によってｐＨ制御の自由度が増し、本発明の有害物質の不溶化剤を用いて処理して固化した有害物質を含む土壌や灰の処理物のｐＨを１０．５以上、好ましくは１０．５〜１２．０の範囲に容易に制御することができる。さらに、酸性化合物の添加により、例えば、硫酸カルシウムやリン酸カルシウムなどの難溶性化合物形成に伴う共沈作用により、ホウ素及びフッ素の効率的吸着を行うことができる。 The harmful substance insolubilizing agent of the present invention may further contain an acidic substance. In this case, the blending weight ratio of light-burned magnesia and quicklime or slaked lime and acidic substance is in the range of 1.0: (0.1-1.0) :( 0.0-2.0), and this blending condition The degree of freedom of pH control is increased by the above, and the pH of the treated soil or ash containing the toxic substance treated with the toxic substance insolubilizer of the present invention and solidified is 10.5 or more, preferably 10.5-12. It can be easily controlled within the range of 0.0. Furthermore, by adding an acidic compound, for example, boron and fluorine can be efficiently adsorbed by coprecipitation accompanying the formation of a hardly soluble compound such as calcium sulfate or calcium phosphate.
ここで、酸性物質としては、硫酸、塩酸、硝酸、酢酸、石膏、硫酸マグネシウム、硫酸第１鉄、硫酸第２鉄、鉄明礬石、塩化第１鉄、塩化第２鉄、硫酸アルミニウム、塩化アルミウム、さらに、リン酸化合物として、正リン酸、第一リン酸マグネシウム、第二リン酸マグネシウム、第三リン酸マグネシウム、ピロリン酸マグネシウム、メタリン酸マグネシウム、第一リン酸アルミニウム、第二リン酸アルミニウム、第三リン酸アルミニウム、メタリン酸アルミニウム、及び重過石などを用いることができる。これらのうち１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。 Here, as the acidic substance, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, gypsum, magnesium sulfate, ferrous sulfate, ferric sulfate, iron alunite, ferrous chloride, ferric chloride, aluminum sulfate, aluminum chloride Furthermore, as a phosphoric acid compound, orthophosphoric acid, primary magnesium phosphate, secondary magnesium phosphate, tertiary magnesium phosphate, magnesium pyrophosphate, magnesium metaphosphate, primary aluminum phosphate, secondary aluminum phosphate, Tertiary aluminum phosphate, aluminum metaphosphate, bitumen, and the like can be used. Among these, only 1 type may be used and 2 or more types may be used in combination.
本発明の有害物質の不溶化剤は、さらに還元剤を含有してもよい。還元剤を含有することで、六価クロム、セレン、ヒ素等の有害物質の良好な溶出抑制効果が得られる。例えば、有害な六価クロムを無害な三価クロムに還元し、セレンを６価から４価、０価に還元することで、より固定しやすい形態へ変化させ、これらの有害物質の効率的な溶出抑制を行うことができる。 The hazardous substance insolubilizing agent of the present invention may further contain a reducing agent. By containing the reducing agent, a good elution suppression effect of harmful substances such as hexavalent chromium, selenium and arsenic can be obtained. For example, harmful hexavalent chromium is reduced to harmless trivalent chromium, and selenium is reduced from hexavalent to tetravalent to zero valent, so that the form is more easily fixed, and the efficiency of these harmful substances is improved. Elution suppression can be performed.
ここで、還元剤としては、金属鉄、硫酸第１鉄、塩化第１鉄、硫化ナトリウム、チオ硫酸ナトリウム、チオ硫酸カルシウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、金属アルミニウム、高炉スラグ粉末、粉末硫黄、石炭微粉末などが挙げられる。硫酸第１鉄、塩化第１鉄の２価鉄化合物は、本発明では、酸性物質としても用いることができる。硫酸第１鉄、塩化第１鉄などは前述のように酸性物質としても利用することができる。 Here, as the reducing agent, metallic iron, ferrous sulfate, ferrous chloride, sodium sulfide, sodium thiosulfate, calcium thiosulfate, sodium sulfite, sodium hydrogen sulfite, metallic aluminum, blast furnace slag powder, powdered sulfur, coal Examples include fine powder. In the present invention, divalent iron compounds of ferrous sulfate and ferrous chloride can also be used as acidic substances. Ferrous sulfate, ferrous chloride and the like can also be used as acidic substances as described above.
本発明の有害物質の不溶化剤は、さらに珪酸アルカリ金属塩を含有してもよい。珪酸アルカリ金属塩を含有することで、本発明の不溶化剤によって固化された処理材の強度発現を高めることができ、これにより不溶化効果が向上し、また、好適にリサイクル利用を促進することができる。 The hazardous substance insolubilizing agent of the present invention may further contain an alkali metal silicate. By containing an alkali metal silicate, the strength expression of the treatment material solidified by the insolubilizing agent of the present invention can be enhanced, thereby improving the insolubilizing effect and suitably promoting recycling. .
すなわち、珪酸アルカリ金属塩溶液は、Ｃａ、Ｍｇ、Ａｌ、Ｂａなどの多価金属イオンと反応して、不溶性の珪酸金属塩水和物や珪酸を同時に生成してゲル化する。例えば、珪酸アルカリ金属塩として珪酸ソーダ、多価金属イオンとしてＭｇを用いた場合、化１の反応によりゲル化する。なお、この反応においてＳｉＯ２も同時に生成する。この機構により、不溶化処理剤の強度特性は向上する。That is, the alkali metal silicate solution reacts with polyvalent metal ions such as Ca, Mg, Al, and Ba to simultaneously generate insoluble silicate metal salt hydrate and silicic acid and gel. For example, when sodium silicate is used as the alkali metal silicate salt and Mg is used as the polyvalent metal ion, gelation occurs by the reaction of Chemical Formula 1. In this reaction, SiO 2 is also generated at the same time. By this mechanism, the strength characteristics of the insolubilizing agent are improved.
ここで、珪酸アルカリ金属塩としては、特定のものに限定されるものではないが、例えば、水ガラス、カリウム水ガラス、シリカゾル、リチウム水ガラス、粉末珪酸ソーダ、粉末珪酸カリウムを用いることができる。特に、水ガラス、カリウム水ガラス、リチウム水ガラスを用いた場合は、その分散効果に基づく減水作用により、被処理物の強度特性を向上させる。 Here, the alkali metal silicate salt is not limited to a specific one. For example, water glass, potassium water glass, silica sol, lithium water glass, powdered sodium silicate, and powdered potassium silicate can be used. In particular, when water glass, potassium water glass, or lithium water glass is used, the strength characteristics of the object to be processed are improved by the water reducing action based on the dispersion effect.
本発明の有害物質の不溶化剤は、さらに遅延剤を含有してもよい。この遅延剤は、混練処理に必要な時間、混練後の運搬、埋め立てなどの処理に必要な時間を確保するために、固化反応を遅延させる目的で用いられる。遅延剤の添加量は、不溶化剤成分合計質量の１０質量部以下が好ましい。 The hazardous substance insolubilizing agent of the present invention may further contain a retarder. This retarder is used for the purpose of delaying the solidification reaction in order to secure the time necessary for the kneading treatment and the time necessary for the transportation after the kneading, landfilling and the like. The addition amount of the retarder is preferably 10 parts by mass or less of the total mass of the insolubilizer component.
ここで、遅延剤としては、特定のものに限定されるものではなく、例えば、オキシカルボン酸塩、スルフォン酸ソーダ、澱粉分解生成物、多糖類、有機酸、コンクリート混和剤、アルカリリン酸化合物、炭酸ナトリウム、炭酸水素ナトリウムを用いることができる。 Here, the retarder is not limited to a specific one, for example, oxycarboxylate, sodium sulfonate, starch decomposition product, polysaccharide, organic acid, concrete admixture, alkali phosphate compound, Sodium carbonate and sodium hydrogen carbonate can be used.
本発明の有害物質の不溶化剤によれば、以上の組成物を適宜組み合わせることで、土壌環境基準に規定する第２種有害物による複合汚染、特にホウ素、フッ素、セレン、ヒ素、六価クロムなどの陰イオン型有害物質による複合汚染を一括で処理することができる。一部の石炭灰にはホウ素、フッ素の溶出を伴うものがある。また、これに加えて、セレン、ヒ素、六価クロムの溶出を伴うものもあり、これらの溶出を一括で処理する方法として、本発明の不溶化剤組成物が最適である。本発明の有害物質不溶化剤は、これらの有害物質の優れた固定能力を有するため、灰の固形物分に対して10質量％以下の添加で、環境基準以下まで溶出抑制を行うことが可能である。 According to the harmful substance insolubilizing agent of the present invention, by combining the above compositions as appropriate, complex contamination by the second kind harmful substances specified in the soil environmental standards, particularly boron, fluorine, selenium, arsenic, hexavalent chromium, etc. It is possible to batch treat complex contamination with anionic harmful substances. Some coal ash is accompanied by elution of boron and fluorine. In addition to this, some of them involve elution of selenium, arsenic, and hexavalent chromium, and the insolubilizing agent composition of the present invention is optimal as a method for treating these elutions in a lump. Since the hazardous substance insolubilizing agent of the present invention has an excellent fixing ability of these harmful substances, it is possible to suppress elution to below the environmental standard by adding 10% by mass or less to the solid content of ash. is there.
なお、本発明の有害物質の不溶化剤を用いて、有害物質を確実に不溶化するためには、不溶化剤と被処理物を十分に混練することが望ましい。本不溶化剤は微細な無機粒子で構成されるため容易に攪拌・混練を行うことができるため、特殊な混練方法は必要としない。実際の処理には、ミキサーを用いた混練や、重機による攪拌混合処理などにより混練を行う方法が用いられる。例えばスタビライザー、ブルドーザ、バックホウ、自走式土壌改良機、高圧噴射法を用いた混練処理を行うことができ、さらに、ベルトコンベヤーと重力式混合装置の組み合わせや、回転打撃による撹拌方法など公知の混練方法を使用してもよい。 In order to reliably insolubilize harmful substances using the hazardous substance insolubilizer of the present invention, it is desirable to sufficiently knead the insolubilizer and the object to be treated. Since the insolubilizing agent is composed of fine inorganic particles and can be easily stirred and kneaded, no special kneading method is required. For the actual treatment, a method of kneading by a kneading using a mixer or a stirring and mixing treatment using a heavy machine is used. For example, kneading using a stabilizer, bulldozer, backhoe, self-propelled soil conditioner, high-pressure spray method can be performed, and further known kneading methods such as a combination of a belt conveyor and a gravitational mixing device, and a stirring method by rotary impact A method may be used.
本発明の有害物質不溶化剤は、汚染土壌や灰を堅固に固め、処理した土壌や灰の飛散や解砕を防ぎ、さらに透水性を低下させることにより、有害物の溶出、流出を防ぐ効果を発揮する。したがって、本発明の有害物質の不溶化剤を用いることによって、重金属を含有する石炭灰や焼却灰等と混合して、安全に埋め立て処理を行うことができ、さらに、例えば、粒状物に加工して道路路盤材料、裏込め材として安全にリサイクル利用を行うことができる。そして、本発明の有害物質の不溶化剤は、固化強度が従来の技術よりも大きいため、地盤強度を容易に確保することができ、また、長期の不溶化効果が期待できる。 The hazardous substance insolubilizing agent of the present invention has the effect of preventing the elution and outflow of harmful substances by solidifying the contaminated soil and ash, preventing the treated soil and ash from scattering and crushing, and further reducing the water permeability. Demonstrate. Therefore, by using the hazardous substance insolubilizing agent of the present invention, it can be mixed with coal ash or incinerated ash containing heavy metals, and can be safely landfilled. It can be safely recycled as roadbed material and backfill material. The harmful substance insolubilizing agent of the present invention has a solidification strength higher than that of the conventional technology, so that the ground strength can be easily secured and a long-term insolubilizing effect can be expected.
なお、本発明は上記の実施例に限定されるものでなく、本発明の要旨の範囲内において種々の変形実施が可能である。 In addition, this invention is not limited to said Example, A various deformation | transformation implementation is possible within the scope of the summary of this invention.
以下、具体例に基づき、さらに詳細に説明する。 Hereinafter, based on a specific example, it demonstrates in detail.
フッ化水素酸を用いて、フッ素含有量２００ｍｇ／ｋｇに調整した汚染土壌を模擬的に作成し、これを容器に入れて密閉し、乾燥を防ぎながら３日間養生した。 Using hydrofluoric acid, a contaminated soil adjusted to a fluorine content of 200 mg / kg was simulated, placed in a container, sealed, and cured for 3 days while preventing drying.
次に表１に示す組成物粉体を所定の割合（表中の質量％）で配合した組成物を、このフッ素含有土壌に添加し、これをモルタルミキサーにより３分混練後、セメント協会基準ＪＣＡＳ Ｌ−０１:２００３に基づきφ５０ｍｍ、Ｈ１００ｍｍの圧縮強度試験供試体を作成し、２０℃の恒温で１週間養生を行った。この供試体を用いて、圧縮強度試験を行った。さらに、圧縮強度試験を行った試験片を粉砕し、平成３年環境省告示第４６号に示す方法に従い溶出試験を実施した。この結果を表２に示す。 Next, a composition in which the composition powder shown in Table 1 is blended at a predetermined ratio (mass% in the table) is added to this fluorine-containing soil, and this is kneaded with a mortar mixer for 3 minutes, and then cement association standard JCAS. Based on L-01: 2003, a compression strength test specimen having a diameter of 50 mm and a height of H100 mm was prepared and cured at a constant temperature of 20 ° C. for 1 week. A compressive strength test was conducted using this specimen. Furthermore, the test piece which performed the compressive strength test was grind | pulverized, and the elution test was implemented according to the method shown in Ministry of the Environment notification No. 46 in 1991. The results are shown in Table 2.
表２に示すように、石灰を用いて溶出抑制を施した比較例のフッ素溶出量に比べ、本発明の軽焼マグネシア、生石灰を混合した実施例のフッ素溶出量は低減された。さらに、圧縮強度も２Ｎ／ｍｍ２以上となり、処理土壌の硬化強度は良好な値を示した。生石灰のみを添加した土壌の混練時のｐＨは１２．７、軽焼マグネシアと生石灰を併せて配合することで混練処理土壌のｐＨは上昇し１１．２を示している。As shown in Table 2, the fluorine elution amount of the example in which the light-burned magnesia and quick lime of the present invention were mixed was reduced as compared with the fluorine elution amount of the comparative example in which elution suppression was performed using lime. Furthermore, the compressive strength was 2 N / mm 2 or more, and the hardening strength of the treated soil showed a good value. The pH at the time of kneading of the soil to which only quicklime is added is 12.7, and the pH of the kneaded soil is increased to 11.2 by blending lightly burned magnesia and quicklime together.
ここでフッ化水素酸は関東化学製試薬、軽焼マグネシアは中国産軽焼マグネシア（ＭｇＯ：９２．４％、ＣａＯ：２．１％、Ｃｌ：２．０％、Ｆｅ２Ｏ３：０．６％、Ａｌ２Ｏ３：０．２％、３２５メッシュ通過９５％）、上田石灰製造(株)製（ＣａＯ：９４．８％、ＳｉＯ２：０．７％、Ａｌ２Ｏ３：０．３％、Ｆｅ２Ｏ３：０．１％、ＭｇＯ：０．９％、ｉｇ．ｌｏｓｓ：２．７％、−０．５ｍｍふるい通過９７％）を使用した。Here, hydrofluoric acid is a reagent manufactured by Kanto Chemical Co., and light-burned magnesia is Chinese light-burned magnesia (MgO: 92.4%, CaO: 2.1%, Cl: 2.0%, Fe 2 O 3 : 0. 6%, Al 2 O 3 : 0.2%, 325 mesh passing 95%), manufactured by Ueda Lime Manufacturing Co., Ltd. (CaO: 94.8%, SiO 2 : 0.7%, Al 2 O 3 : 0. 3%, Fe 2 O 3: 0.1%, MgO: 0.9%, ig.loss: 2.7%, - using 0.5mm sieve passing 97%).
表３に示す組成を有し、表４に示す量の有害物質を含有する石炭灰の溶出試験を行った。なお、この石炭灰は酸化カルシウム成分を比較的多く含むアルカリ灰で、ホウ素、六価クロムの溶出を伴うことが多いタイプの組成である。 An elution test for coal ash having the composition shown in Table 3 and containing harmful substances in the amounts shown in Table 4 was performed. The coal ash is an alkaline ash containing a relatively large amount of calcium oxide component and has a composition often accompanied by elution of boron and hexavalent chromium.
この原灰の溶出試験結果を表５に示すが、六価クロム、セレン、ホウ素が第１溶出量基準を超過している。中でもセレンは基準値の１０倍、ホウ素は１６倍の濃度となっている。 The results of the elution test for raw ash are shown in Table 5. Hexavalent chromium, selenium, and boron exceed the first elution amount standard. Among them, selenium has a concentration 10 times the reference value and boron has a concentration 16 times.
当該石炭灰に表６に示す所定の割合（表中の質量％）で配合した組成物を、所定の割合（表中の質量％）で添加し、これをモルタルミキサーにより３分混練後、セメント協会基準ＪＣＡＳ Ｌ−０１:２００３に基づきφ５０ｍｍ，Ｈ１００ｍｍの圧縮強度試験供試体を作成し、２０℃の恒温で４週間養生を行った。 A composition blended in the coal ash at a predetermined ratio (mass% in the table) shown in Table 6 was added at a predetermined ratio (mass% in the table), and this was kneaded for 3 minutes with a mortar mixer, and then cement. Based on the association standard JCAS L-01: 2003, a compression strength test specimen having a diameter of 50 mm and a height of 100 mm was prepared and cured at a constant temperature of 20 ° C. for 4 weeks.
この供試体を用いて、圧縮強度試験を行い、試験後の試験片を粉砕し、環境省告示第４６号に示す方法に従い溶出試験を実施した。 Using this specimen, a compressive strength test was conducted, the test piece after the test was pulverized, and an elution test was performed according to the method shown in Ministry of the Environment Notification No. 46.
表７に示すように本発明の有害物質抑制剤は大きな効果を発揮し、高含有のホウ素、セレン及び六価クロムを環境基準値以下に溶出抑制を行うことができた。 As shown in Table 7, the harmful substance inhibitor of the present invention exhibited a great effect, and was able to suppress elution of a high content of boron, selenium and hexavalent chromium below the environmental standard value.
比較例２にはホウ素、フッ素に対して同様に溶出抑制効果をもつといわれる軽焼マグネシアを用いた試験結果を示した。この比較例では混練処理時のｐＨは１０程度と本発明の抑制剤より低くなり、六価クロムの溶出量は基準値以下となるものの、セレン、ホウ素の溶出量は依然環境基準を超過した。軽焼マグネシアのみを添加した比較例２の混練時ｐＨは１０．０、軽焼マグネシアと生石灰を併せて配合した実施例３における混練時ｐＨは１２を示しており、これにより石炭灰に含まれるホウ素についても環境基準以下に不溶化することができた。 Comparative Example 2 shows the test results using light-burned magnesia, which is said to have the same elution suppressing effect on boron and fluorine. In this comparative example, the pH during the kneading treatment was about 10, which was lower than the inhibitor of the present invention, and the elution amount of hexavalent chromium was below the standard value, but the elution amount of selenium and boron still exceeded the environmental standard. The pH at the time of kneading in Comparative Example 2 to which only light-burned magnesia was added was 10.0, and the pH at the time of kneading in Example 3 in which light-burning magnesia and quicklime were blended together was 12, thereby being included in coal ash. Boron was also insolubilized below the environmental standard.
ここで軽焼マグネシアは中国産軽焼マグネシア（ＭｇＯ：９２．４％、ＣａＯ：２．１％、Ｃｌ：２．０％、Ｆｅ２Ｏ３：０．６％、Ａｌ２Ｏ３：０．２％、３２５メッシュ通過９５％）、生石灰は上田石灰製造株式会社製（ＣａＯ：９４．８％、ＳｉＯ２：０．７％、Ａｌ２Ｏ３：０．３％、Ｆｅ２Ｏ３：０．１％、ＭｇＯ：０．９％、ｉｇ．ｌｏｓｓ：２．７％、−０．５ｍｍふるい通過９７％）、硫酸第１鉄は株式会社テツゲン製 硫酸第一鉄七水和物（純度９３〜９９重量％）、水ガラス３号は富士化学株式会社製ＪＩＳ Ｋ１４０８を使用した。Here, light-burned magnesia is Chinese light-burned magnesia (MgO: 92.4%, CaO: 2.1%, Cl: 2.0%, Fe2O3: 0.6%, Al2O3: 0.2%, passing through 325 mesh) 95%), quick lime manufactured by Ueda Lime Manufacturing Co., Ltd. (CaO: 94.8%, SiO 2 : 0.7%, Al 2 O 3 : 0.3%, Fe 2 O 3 : 0.1%, MgO: 0.9%, ig.loss: 2.7%, -0.5 mm sieve passing 97%), ferrous sulfate ferrous sulfate heptahydrate (purity 93-99 wt%) manufactured by Tetsugen Co., Ltd. As water glass No. 3, JIS K1408 manufactured by Fuji Chemical Co., Ltd. was used.
表８に示す量の有害物質を含有する石炭灰の溶出試験を行った。表８右欄にこの石炭灰の環境省告示第４６号に示す方法による溶出試験結果を示す。この石炭灰はホウ素の含有量が非常に多く、その溶出量は環境基準値の４０倍となっている。また、六価クロム、フッ素の溶出量も環境基準値以上になっている。 The dissolution test of coal ash containing harmful substances in the amounts shown in Table 8 was conducted. The right column of Table 8 shows the results of the dissolution test of the coal ash by the method shown in Ministry of the Environment Notification No. 46. This coal ash has a very high boron content, and its elution amount is 40 times the environmental standard value. In addition, the elution amount of hexavalent chromium and fluorine is more than the environmental standard value.
当該石炭灰に表９に示す所定の割合（表中の質量％）で配合した組成物を、所定の割合（表中の質量％）で添加し、これをモルタルミキサーにより３分混練後、セメント協会基準ＪＣＡＳ Ｌ−０１:２００３に基づきφ５０ｍｍ、Ｈ１００ｍｍの圧縮強度試験供試体を作成し、２０℃の恒温で１週間養生を行った。 A composition blended in the coal ash at a predetermined ratio (mass% in the table) shown in Table 9 is added at a predetermined ratio (mass% in the table), and this is kneaded for 3 minutes with a mortar mixer, and then cement. Based on the association standard JCAS L-01: 2003, a compression strength test specimen of φ50 mm and H100 mm was prepared and cured at a constant temperature of 20 ° C. for 1 week.
この供試体を用いて、圧縮強度試験を行い、試験後の試験片を粉砕し、平成３年環境省告示第４６号に示す方法に従い溶出試験を実施した。各処理剤のｐＨは２ｍｍ以下の粉砕原料を用いて測定を行った。この結果を表１０に示す。 Using this specimen, a compressive strength test was conducted, the test piece after the test was pulverized, and an elution test was conducted according to the method shown in Notification No. 46 of the Ministry of the Environment in 1991. The pH of each treatment agent was measured using a pulverized raw material of 2 mm or less. The results are shown in Table 10.
表１０に示すように本発明の有害物質抑制剤は大きな効果を発揮し、高含有のホウ素を環境基準値以下に溶出抑制を行うことができた。また、環境基準を超過していた六価クロム、フッ素の溶出量も基準値以下となった。 As shown in Table 10, the harmful substance inhibitor of the present invention exerted a great effect and was able to suppress elution of a high content of boron to an environmental standard value or less. In addition, the elution amount of hexavalent chromium and fluorine that exceeded the environmental standard was below the standard value.
比較例３にはホウ素、フッ素に対して同様に溶出抑制効果をもつといわれる軽焼マグネシアを用いた試験結果を示した。軽焼マグネシアのみを添加した比較例３の混練時ｐＨは１０．３と本発明の不溶化剤より低くなり、軽焼マグネシアと生石灰を併せて配合した実施例４、５における混練時ｐＨはおよそ１２を示している。この比較例では、六価クロム、フッ素の溶出量は基準値以下となるもののホウ素溶出量は１６と基準値を満足することができなかった。また、フッ素の溶出量は本発明の組成物以上の結果となった。 Comparative Example 3 shows the test results using light-burned magnesia, which is said to have the same elution suppressing effect on boron and fluorine. The pH at the time of kneading in Comparative Example 3 to which only light-burned magnesia was added was 10.3, which is lower than that of the insolubilizer of the present invention, and the pH at the time of kneading in Examples 4 and 5 in which light-burning magnesia and quicklime were blended was about 12. Is shown. In this comparative example, the elution amount of hexavalent chromium and fluorine was below the reference value, but the boron elution amount was 16, which could not satisfy the reference value. Moreover, the amount of elution of fluorine was higher than that of the composition of the present invention.
ここで軽焼マグネシアは中国産軽焼マグネシア（ＭｇＯ：９２．４％、ＣａＯ：２．１％、Ｃｌ：２．０％、Ｆｅ２Ｏ３：０．６％、Ａｌ２Ｏ３：０．２％、３２５メッシュ通過９５％）、生石灰は上田石灰製造株式会社製（ＣａＯ：９４．８％、ＳｉＯ２：０．７％、Ａｌ２Ｏ３：０．３％、Ｆｅ２Ｏ３：０．１％、ＭｇＯ：０．９％、ｉｇ．ｌｏｓｓ：２．７％、−０．５ｍｍふるい通過９７％）、硫酸第１鉄は株式会社テツゲン製 硫酸第一鉄七水和物（純度９３〜９９重量％）、水ガラス３号は富士化学株式会社製ＪＩＳ Ｋ１４０８を使用した。Here, light-burned magnesia is Chinese light-burned magnesia (MgO: 92.4%, CaO: 2.1%, Cl: 2.0%, Fe2O3: 0.6%, Al2O3: 0.2%, passing through 325 mesh) 95%), quick lime manufactured by Ueda Lime Manufacturing Co., Ltd. (CaO: 94.8%, SiO 2 : 0.7%, Al 2 O 3 : 0.3%, Fe 2 O 3 : 0.1%, MgO: 0.9%, ig.loss: 2.7%, -0.5 mm sieve passing 97%), ferrous sulfate ferrous sulfate heptahydrate (purity 93-99 wt%) manufactured by Tetsugen Co., Ltd. As water glass No. 3, JIS K1408 manufactured by Fuji Chemical Co., Ltd. was used.
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| JP5068245B2 (en) * | 2008-12-04 | 2012-11-07 | 太平洋セメント株式会社 | Insolubilized material |
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