CN107109185A - The insoluble method of harmful substance insolubilizing agent and harmful substance - Google Patents
The insoluble method of harmful substance insolubilizing agent and harmful substance Download PDFInfo
- Publication number
- CN107109185A CN107109185A CN201680003565.2A CN201680003565A CN107109185A CN 107109185 A CN107109185 A CN 107109185A CN 201680003565 A CN201680003565 A CN 201680003565A CN 107109185 A CN107109185 A CN 107109185A
- Authority
- CN
- China
- Prior art keywords
- harmful substance
- particle
- insolubilizing agent
- insoluble
- phosphate
- 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
- 239000000126 substance Substances 0.000 title claims abstract description 168
- 238000000034 method Methods 0.000 title claims description 49
- 239000002245 particle Substances 0.000 claims abstract description 139
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 99
- 239000011575 calcium Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 5
- 239000010459 dolomite Substances 0.000 claims description 58
- 229910000514 dolomite Inorganic materials 0.000 claims description 56
- 239000002893 slag Substances 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 229910052731 fluorine Inorganic materials 0.000 claims description 29
- 239000011737 fluorine Substances 0.000 claims description 29
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 239000002686 phosphate fertilizer Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000002956 ash Substances 0.000 description 47
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 26
- 238000012545 processing Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 21
- 239000010883 coal ash Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 17
- 238000007922 dissolution test Methods 0.000 description 16
- 239000002689 soil Substances 0.000 description 16
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 15
- 239000000395 magnesium oxide Substances 0.000 description 14
- 235000012245 magnesium oxide Nutrition 0.000 description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 12
- 229910000160 potassium phosphate Inorganic materials 0.000 description 11
- 235000011009 potassium phosphates Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 238000003672 processing method Methods 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 229910052586 apatite Inorganic materials 0.000 description 8
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 239000001095 magnesium carbonate Substances 0.000 description 8
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 8
- 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 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 240000006909 Tilia x europaea Species 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 235000014380 magnesium carbonate Nutrition 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000005261 decarburization Methods 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 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
- 230000033228 biological regulation Effects 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
- 239000003818 cinder Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 240000007313 Tilia cordata Species 0.000 description 1
- 240000001142 Tilia japonica Species 0.000 description 1
- 235000017860 Tilia japonica Nutrition 0.000 description 1
- 240000001085 Trapa natans Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FPWJLQXCGHQXLL-UHFFFAOYSA-N [P].OP(O)(O)=O Chemical compound [P].OP(O)(O)=O FPWJLQXCGHQXLL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- -1 cyanogen compound Chemical class 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 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
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 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 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
It is that particle diameter is below 2mm, makes the thawless harmful substance insolubilizing agent of harmful substance, it is included the present invention relates to harmful substance insolubilizing agent：Comprising calcium and magnesium and their at least any one mol ratio (P/Ca) for foring calcium component in the particle A of oxide, carbonate or hydroxide and particle B, above-mentioned particle A comprising phosphate cpd and the phosphorus composition of the phosphate cpd in above-mentioned particle B is 0.1~1.0.
Description
Technical field
The present invention relates to harmful substance insolubilizing agent and the insoluble method of harmful substance.
Background technology
As the slag produced in steel and iron manufacturing technique, workshop waste water, workshop old site, the underground water of contaminated soil, burn
The processing method of the harmful substance such as contained fluorine, heavy metal, have studied so far in ashing, coal ash, casting sand, waste gypsum etc.
Various methods.In such background, China (Japan) has formulated soil pollution countermeasure method for 15 years in Heisei, is used as heavy metal
Deng, by cadmium and its compound, lead and its compound, hexavalent chromium compound, arsenic and its compound, mercury and mercuric compounds, selenium and its
Compound, fluorine and its compound, boron and its compound and cyanogen compound special provision are second of special harmful substance.
In above-mentioned, the slag produced in steel and iron manufacturing technique contains the fluorine from fluorite with high concentration, in slag again
The dissolution of fluorine turns into problem sometimes during utilization.Now, when slag is reused in into roadbed material etc., 3 years environment of Heisei are used
Dissolution test method is carried out specified in No. 46 dissolution tests of Room bulletin (hereinafter also referred to " No. 46 dissolution tests ") or JIS
Whether stripping quantity meets the confirmation of Soil-environmental standard.So far, carried out under the situation when being recycled specified in JIS
The dissolution test of fluorine, but be possible to arrange the dissolution test in No. 46 dissolution tests under the -2.00mm of defined from now on, again
Required standard is to carry out more strict dissolution test.Therefore, also become desirable for carrying out for slag out of question in the past insoluble
Change disposal, to for preventing the insolubilizing agent of dissolution, the further research of insoluble method become necessary.
Among this, for example, proposed in patent document 1 makes phosphoric acid alkali (great soil group) metal salt of solid-like in an acidic solution
The fluorine insolubilizing agent of dissolving.In addition, proposing following soil-solidified-agent in patent document 2：For inorganic system's discarded object
Addition slightly solubility calcium compound (calcium hydroxide, dicalcium phosphate dihydrate, calcium phosphate) is simultaneously mixed, and then adds fluorine sorbing material
(monosulfate, entringite, apatite, magnesia, magnesium hydroxide), it is mixed, fluorine is turned into below 0.8mg/L.And then, specially
Following processing method is proposed in sharp document 3：For the steel slag (A) that Oil repellent is more than 0.15 mass %, addition tool
There is the steel slag (B) of mineral facies and Oil repellent containing phosphorus and calcium less than 0.15 mass %, generate fluorine-containing slightly solubility
Compound, is fixed in slag.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-189927 publications
Patent document 2：Japanese Unexamined Patent Publication 2012-214591 publications
Patent document 3：Japanese Unexamined Patent Publication 2009-40650 publications
The content of the invention
The invention problem to be solved
But, the fluorine insolubilizing agent of patent document 1 is added to due to making solid-like phosphoric acid alkali (great soil group) dissolving metal salts
In slag, therefore increase makes equipment, the process of dissolving metal salts.Further, since being the processing only with phosphorus, therefore make in large quantities
It is used as the phosphorus of valuable resource, processing cost rise.
For the soil-solidified-agent of patent document 2, relative to the parts by weight of discarded object 100, slightly solubility calcium compound is 1~
250 parts by weight, fluorine sorbing material is 0.1~10 parts by weight, substantial amounts of inorganic agent is added sometimes, processing cost is still raised.
For the processing method of patent document 3, it is more than 0.3 mass % (preferably 0.6 matter to exist using phosphorus content
Measure more than %) and No. 46 dissolution tests in the solubility of Ca of institute's dissolution limited as more than 100mg/L steel slag (B) etc.
System, processing becomes miscellaneous.
The present invention is completed in view of the foregoing, it is therefore intended that offer can efficiently make harmful substance not in a short time
The harmful substance insolubilizing agent and the insoluble method of harmful substance dissolved.
Means for solving the problems
The inventors discovered that can solve the problem that above-mentioned problem using following harmful substance insolubilizing agents, the present invention is completed.
The harmful substance insolubilizing agent has defined particle diameter, is included with specific ratio：Comprising in calcium and magnesium and they at least
Any one forms the particle of oxide, carbonate or hydroxide and the particle comprising phosphate cpd,
That is, the present invention is as described in following.
[1] harmful substance insolubilizing agent, is that particle diameter is below 2mm, makes the thawless harmful substance of harmful substance insoluble
Agent, it is included：Comprising calcium and magnesium and in them at least any one form the particle of oxide, carbonate or hydroxide
The phosphorus of calcium component in A and particle B, above-mentioned particle A comprising phosphate cpd and the phosphate cpd in above-mentioned particle B into
The mol ratio (P/Ca) divided is 0.1~1.0.
[2] the harmful substance insolubilizing agent described in [1], it includes at least any in iron containing compoundses and aluminum contained compound
Person.
[3] the harmful substance insolubilizing agent described in [1] or [2], wherein, above-mentioned particle A is dolomite or dolomite system
Compound.
[4] the harmful substance insolubilizing agent described in any one of [1]~[3], it includes aluminum contained compound, relative to upper
Particle A and above-mentioned particle B total 100 mass parts are stated, the content of above-mentioned aluminium compound is 10~350 mass parts.
[5] the harmful substance insolubilizing agent described in any one of [1]~[4], wherein, above-mentioned harmful substance be fluorine, boron,
In 6 valency chromium, selenium and arsenic at least any one.
[6] the harmful substance insolubilizing agent described in any one of [1]~[5], wherein, above-mentioned phosphate cpd is phosphoric acid
It is at least any in potassium dihydrogen, dipotassium hydrogen phosphate, tripotassium phosphate, tertiary sodium phosphate and their hydrate and phosphate fertilizer
Person.
[7] the harmful substance insolubilizing agent described in any one of [1]~[6], it makes the above-mentioned harmful substance in slag
It is insoluble.
[8] the insoluble method of harmful substance, be by comprising calcium and magnesium and in them at least any one form oxygen
The particle A of compound, carbonate or hydroxide and the particle B comprising phosphate cpd are mixed into having containing harmful substance
The insoluble method of harmful substance in the solids of evil material, with the phosphorus in the calcium component in above-mentioned particle A and above-mentioned particle B
Above-mentioned particle A and above-mentioned particle B are mixed into by the mode that the mol ratio (P/Ca) of the phosphorus composition of acid compound turns into 0.1~1.0
In the above-mentioned solids containing harmful substance.
[9] the insoluble method of the harmful substance described in [8], wherein, above-mentioned particle A, above-mentioned particle B and above-mentioned containing having
The order by merging of the solids of evil material is any one of following (1)~(3)：
(1) in the state of above-mentioned particle A and above-mentioned particle B are mixed with or by above-mentioned particle A and above-mentioned particle B
Simultaneously or serially it is mixed into the above-mentioned solids containing harmful substance respectively.
(2) after mixing above-mentioned particle A and the above-mentioned solids containing harmful substance, above-mentioned particle B is mixed.
(3) after mixing above-mentioned particle B and the above-mentioned solids containing harmful substance, above-mentioned particle A is mixed.
[10] the insoluble method of the harmful substance described in [9], wherein, above-mentioned order by merging is suitable described in above-mentioned (1)
Sequence, uses the harmful substance insolubilizing agent described in any one of [1]~[7] to carry out the mixing of above-mentioned (1).
[11] the insoluble method of the harmful substance described in any one of [8]~[10], wherein, it is above-mentioned to contain nuisance
The solids of matter is slag.
The effect of invention
In accordance with the invention it is possible to which providing can efficiently make the thawless harmful substance of harmful substance insoluble in a short time
The insoluble method of agent and harmful substance.
Embodiment
[1] harmful substance insolubilizing agent
The particle diameter that the harmful substance insolubilizing agent (hereinafter sometimes referred to simply as " insolubilizing agent ") of the present invention is below 2mm, bag
A containing particle and particle B, particle A comprising calcium and magnesium and in them at least any one form oxide, carbonate or hydrogen-oxygen
Compound, particle B includes phosphate cpd.Moreover, calcium component and the phosphorus composition of the phosphate cpd in particle B in particle A
Mol ratio (P/Ca) becomes 0.1~1.0.
Above-mentioned " below 2mm particle diameter " means to make particle diameter turn into below 2mm particle diameter using screening.If using screening
Obtained particle diameter becomes heterogeneity more than 2mm, the then admixture of the solids containing harmful substance such as insolubilizing agent and slag,
The insoluble of harmful substance becomes insufficient.The particle diameter is preferably 0.1~2mm, more preferably 0.1~1.5mm.
Further, screening is carried out using the testing screen (sieve) (sieve) of JIS-Z-8801 JIS standards.
Being taken as the harmful substance insolubilizing agent of the present invention makes its thawless harmful substance contain thing, can include liquid
Body thing and solids, as liquids, for the draining comprising harmful substance, (also referred to as " contain harmful substance as solids
Solids "), it is the slag, soil comprising harmful substance, burning ash, coal ash, casting sand, useless produced in steel and iron manufacturing technique
Gypsum etc..Contain thing, preferably solids as harmful substance, wherein more preferably slag.
Contain harmful substance contained in thing as harmful substance, the soil pollution pair that Heisei is implemented for 15 years can be exemplified
Contained cadmium, lead, 6 valency chromium, arsenic, mercury, selenium, fluorine, boron and cyanide in second of special harmful substance specified in plan method, and then
Antimony etc. can be illustrated, also the compound comprising them.Wherein, play high insoluble from the harmful substance insolubilizing agent of the present invention
It is preferably at least any of in fluorine, boron, 6 valency chromium, selenium and arsenic from the viewpoint of effect, more preferably fluorine and boron.The present invention
In, can a kind of list in draining, soil, burning ash, coal ash, slag, casting sand, waste gypsum of thing etc. is contained as harmful substance
Foregoing illustrative harmful substance solely is included, two or more can be also included.
As comprising calcium and magnesium and they at least any one form the particle of oxide, carbonate or hydroxide
A, can include dolomite and the dolomite based compound as derived from dolomite.As dolomite based compound, half can be included
Burn till dolomite, light dolomite, hydroxide dolomite etc..
Dolomite (Dolomite) is known as the calcium carbonate (CaCO of calcite (Calcite)3) with being referred to as magnesite
(Magnesite) magnesium carbonate (MgCO3), ideally 1：1 complex salt.From composition, it is positioned at calcite and water chestnut
The material of the centre of magnesium ore deposit.If heated dolomite under the conditions of comparatively gentle, occur decarburization acid reaction, obtain being claimed
For the mixture of the calcium oxide (CaO) and magnesia (MgO) of " light dolomite ".If the progress that added water in light dolomite is ripe
Change, then obtain as calcium hydroxide (Ca (OH)2) and magnesium hydroxide (Mg (OH)2) mixture hydroxide dolomite.Hydroxide
In dolomite, calcium carbonate, calcium oxide, magnesium carbonate, silica, oxidation can be contained in the range of the effect of the without prejudice to present invention
The other compositions such as aluminium, iron oxide.
Mass ratio [the Ca (OH) of contained calcium hydroxide and magnesium hydroxide in above-mentioned hydroxide dolomite2/Mg(OH)2Quality
Than] preferably 10/90~90/10, more preferably 20/80~85/15, further preferred 40/60~80/20.If the mass ratio is
Above-mentioned scope, then harmful substance it is insoluble when, fully play the characteristic of calcium component, both magnesium components.
As above-mentioned hydroxide dolomite, spy number and the hydroxide dolomite of No. 1 specified in preferably JIS R9001.
In addition, as the raw material of hydroxide dolomite, light dolomite can be used.It is used as light dolomite, preferably JIS
The light dolomite of special number and No. 1 specified in R9001.Light dolomite by with as the draining of object to be processed, soil,
Water contained by burning ash or coal ash etc. reacts and cures and be hydrated, and change turns to hydroxide dolomite, even if therefore omission preparation
The process of hydroxide dolomite and directly use light dolomite, can also play the effect of hydroxide dolomite.
In addition, so-called partly burn till dolomite, refer to partly burn till product using magnesia and calcium carbonate as the dolomite of principal component.
Partly burn till dolomite can be by being burnt till so that in dolomite composition at a temperature of 600~900 DEG C to dolomite
Most of decarburization acid of magnesium carbonate and magnesia is made, on the other hand, almost do not make calcium carbonate decarburization acid, make it residual as former state
Obtain with staying.
It is used as the content of the free magnesium partly burnt till in dolomite, preferably more than 8 mass %, more preferably 15 matter
Measure more than %, more preferably more than 20 mass %.
Wherein, the content of so-called free magnesium, refers to as the magnesium carbonate (MgCO in dolomite3) decarburization acid and generate
Magnesia (MgO) the amount that is calculated of amount (quality %).The calculating can be carried out according to following step.
First, using method specified in JIS R9011 " analysis method of lime ", to CaO, MgO and Ig.loss
(heat-flash decrement) is analyzed.Next, whether the amount of free calcium oxide according to obtained from by analysis reaches 1.5 matter
% is measured, following (i) or (ii) any one is selected.
(i) when the amount of free calcium oxide is more than 1.5 mass %：Directly make using by the value of MgO obtained from analysis
For the amount of free magnesium.
(ii) when the amount of free calcium oxide is less than 1.5 mass %：The amount of free magnesium passes through [by obtained from analysis
MgO- is used as MgCO3The MgO of presence] calculate.
It is used as MgCO3The MgO of presence amount is obtained according to following formula.
It is used as MgCO3The MgO (quality %) of presence={ Ig.loss- (CaO ÷ 56 × 44) } ÷ 44 × 40
Dolomite and dolomite based compound are because the magnesium component in its compound and calcium component are with the level of crystal particles
Coexist, therefore speculate the synergy for easily playing this 3 composition of particle B phosphate composition Yu magnesium component and calcium component, Neng Gou
The insoluble of harmful substance is carried out in shorter time.
In dolomite and dolomite based compound, more preferably hydroxide dolomite and light dolomite, further preferably
Hydroxide dolomite.
As the phosphate cpd used in particle B, as long as with the calcium in particle A (such as in hydroxide dolomite
Calcium) react and formed the phosphate cpd crystallized as phosphonium hydroxide lime stone, then can unrestrictedly it use, specifically,
Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, di(2-ethylhexyl)phosphate can be included
Phosphate fertilizer such as hydrogen ammonium, diammonium hydrogen phosphate, triammonium phosphate and their hydrate and superphosphate etc..Phosphoric acid chemical combination
Thing can a kind be used alone, two or more can be also applied in combination.Wherein, preferably phosphoric acid potassium dihydrogen, dipotassium hydrogen phosphate, tricresyl phosphate
It is at least any of in potassium, tertiary sodium phosphate and their hydrate and phosphate fertilizer, more preferably potassium dihydrogen phosphate and its
Hydrate.
For example, calcium hydroxide reacts with phosphate cpd, generation phosphoric acid apatite Ca5(PO4)3(OH).Utilize the phosphoric acid phosphorus
Lime stone, easily makes harmful substance insoluble.For example, in the case that harmful substance is fluorine, by anti-shown in following formula (1)
Should, not only make draining insoluble, and make the fluorine in the solids containing harmful substance as slag, soil insoluble.
Ca5(PO4)3(OH)+F-→Ca5(PO4)3F+OH- (1)
By above-mentioned formula (1), in stoichiometry, as mol ratio of the phosphorus composition relative to calcium component of phosphoric acid apatite,
As Ca：P=5：3 amount ([P/Ca] mol ratio：0.6) it is equivalent.
Wherein, hydroxide dolomite contains magnesium hydroxide while containing calcium hydroxide, and detailed mechanism is unclear,
But think because magnesium hydroxide makes any difference to the structure of phosphoric acid apatite, thus with simple calcium compound (it is above-mentioned that
The calcium hydroxide of sample) to compare, reaction speed is accelerated, can be insoluble by harmful substance in a short time.
Especially, the magnesium component in hydroxide dolomite has while the generation of phosphoric acid apatite is promoted, promotes phosphorus
The effect of the immobilization of fluoride caused by sour apatite.Think under the non-existent situation of magnesium component, due to phosphoric acid apatite
The surface of calcium hydroxide is covered, therefore the immobilization of fluoride is obstructed, and is existed by magnesium component, can be made calcium hydroxide and phosphorus
Sour apatite separation, constantly obtains the immobilized reactant of fluoride.
It is the phosphorus composition (P) of phosphate cpd relative in hydroxide dolomite on the addition of phosphate cpd
The mol ratio ([P/Ca] mol ratio) of calcium component (Ca) turns into 0.1~1.0 scope.If [P/Ca] mol ratio is less than 0.1,
For example the insoluble 0.8mg/L to environmental standard value of Funing tablet is become difficult below.If [P/Ca] mol ratio is more than 1.0,
Then the use quantitative change of phosphate cpd is more, causes the rising of cost.
In addition, for the addition of phosphate cpd, from the viewpoint for the high leaching retention effect for obtaining harmful substance
Set out, be preferably that [P/Ca] mol ratio turns into 0.1~0.7 scope.If [P/Ca] mol ratio is less than 0.7, nuisance
The leaching retention effect of matter is high, reduces the addition of the phosphate cpd of high price, while can carry out in a short time insoluble straight
Low concentration to environmental standard value.
From the viewpoint of more than, the addition of phosphate cpd is more preferably [P/Ca] mol ratio as 0.1~0.6
Scope, more preferably as 0.3~0.6 scope.
Particle A average grain diameter is preferably 5~30 μm, more preferably 10~20 μm.Particle B average grain diameter is preferably
0.1~2.0mm, more preferably 0.5~1.5mm and particle diameter is neat.Average grain diameter equivalent to the value determined by screening, or
Equivalent to the value described in goods catalogue etc. in the case of commercially available product.
The harmful substance insolubilizing agent of the present invention preferably comprise iron containing compoundses and aluminum contained compound at least any one.It is logical
Cross containing these compounds, even the hazardous solid thing of display strong basicity, can also be carried out insoluble.
As iron containing compoundses, frerrous chloride, iron chloride, ferrous sulfate, ferric sulfate and their hydration can be included
Thing, iron powder etc..Wherein, ferrous 1 hydrate of preferably sulfuric acid.Iron containing compoundses preferably in harmful substance insolubilizing agent containing 3~
30 mass %, further preferably 5~10 mass %.By the way that containing more than 3 mass %, the absorption of iron compound generation can be reduced
Effect or dissolution pH.In addition, by the way that containing below 30 mass %, the consolidation of material can be prevented.
As aluminum contained compound, aluminum sulfate, PAC (polyaluminium chloride), aluminum oxide etc. can be included.Wherein preferably sulfuric acid aluminium.
Aluminum contained compound contains 5~70 mass %, further preferably 20~60 mass % preferably in harmful substance insolubilizing agent.Pass through
Containing more than 5 mass %, it can be reacted with free calcium component and generate entringite, while reducing the pH of dissolution fluid.In addition, logical
Cross containing below 70 mass %, can prevent from exceedingly declining pH, prevent the consolidation of chemical reagent.
In addition, in the case of comprising aluminum contained compound, the aluminium of total 100 mass parts relative to particle A and particle B
The content of compound is preferably 10~350 mass parts, more preferably 10~110 mass parts, more preferably 30~70 mass
Part.By containing 10~350 mass parts, resulting in more good insoluble effect.In addition, especially, even in particle A
With P/Ca in particle B it is low in the case of (for example, 0.1~0.3), can also play more good insoluble effect.
It is preferred that iron containing compoundses and aluminum contained compound are also respectively particle shape.It is preferred that average grain diameter is all 10~50 μm, more
Preferably 15~30 μm.Average grain diameter is equivalent to the value determined using Laser particle-size distribution meter, or in the case of commercially available product
Equivalent to the value described in goods catalogue etc..
And then, harmful substance insolubilizing agent of the invention preferably comprises iron containing compoundses and aluminum contained compound.Especially, it is right
It is effective in the processing method of slag described later, flying ash.In the case of comprising iron containing compoundses and aluminum contained compound, iron content
Compound and the compounding ratio of aluminum contained compound, i.e. relative to the mass parts of aluminum contained compound 100 iron containing compoundses be preferably 5~
50 mass parts, more preferably 10~30 mass parts.
The present invention harmful substance insolubilizing agent in, without prejudice to the present invention effect in the range of can comprising other into
Point.As other compositions, it can illustrate for slurried water etc..
The harmful substance insolubilizing agent of the present invention is preferably applied to the insoluble method of harmful substance of the invention described later,
But beyond it, it can also apply to such as drainage processing method.
It is used as the insoluble side for the draining containing harmful substance for the harmful substance insolubilizing agent for having used the present invention
Method, preferably puts into the draining containing harmful substance and the method mixed by insolubilizing agent.And then, from more effective
Reduce from the viewpoint of the concentration of the harmful substance in draining on ground, it is preferred to use the method that multisection type is handled, such as it is as follows
Method：By the way that harmful substance insolubilizing agent is put into the draining containing harmful substance, it is isolated by filtration and removes sediment
Afterwards, again putting into harmful substance insolubilizing agent in filtrate reacts it, so that harmful substance is insoluble.
It is used as addition of the harmful substance insolubilizing agent in draining, it is necessary to which the concentration of narmful substance being directed in draining comes
Determine.If for example, harmful substance is fluorine, it is necessary to turned into using the Funing tablet in the draining after processing and be used as standard of drainage value
Below 8mg/L mode determines optimal addition.For the row that the Funing tablet in draining is high concentration as thousands of mg/L
Water, is handled by using multisection type, so as to cut down usage amount.
From the viewpoint of more than, as the amount for once adding harmful substance insolubilizing agent, relative to containing nuisance
The draining of matter, the preferably amount as 0.05~5 mass %.If the addition of harmful substance insolubilizing agent is 0.05 mass %
More than, then fully obtain draining in harmful substance dissolution inhibition.If the addition of harmful substance insolubilizing agent
For below 5 mass %, then the inhibition of the dissolution for the harmful substance being consistent with the addition of insolubilizing agent is obtained, can be suppressed
The increase of load, processing cost during stirring.From this viewpoint, relative to the draining containing harmful substance, harmful substance is not
The addition of solvation is more preferably 0.1~1.5 mass %, more preferably 0.1~1.0 mass %, particularly preferably 0.4
~0.8 mass %.
It is used as processing time, usually 10 minutes~24 hours, preferably 30 minutes~2 hours.
On the processing draining pH after the addition of harmful substance insolubilizing agent, on sufficient process performance is played, preferably
PH is 7~13, in the case of as coexisting substances comprising lead, zinc etc., and more preferably pH is 10~12.In addition, for example, harmful
Material be fluorine, without these coexisting substances, only fluorine is handled in the case of, in order to cut down pH regulation necessary to acid
Matter, can be handled under conditions of pH12~13 as the balance pH of the harmful substance insolubilizing agent of the present invention.
[2] the insoluble method of harmful substance
The insoluble method of the harmful substance of the present invention, is by least any one formation comprising calcium and magnesium and in them
The particle A of oxide, the carbonate or hydroxide and particle B comprising phosphate cpd is mixed into containing containing harmful substance
There is the method in the solids of harmful substance, with rubbing for the calcium component in particle A and the phosphorus composition of the phosphate cpd in particle B
Particle A and particle B are mixed into the solids containing harmful substance by you than (P/Ca) mode for turning into 0.1~1.0.Wherein,
Particle A and particle B details are as has been described.
Further, by already described iron containing compoundses and/or aluminum contained compound and use in the case of, can with particle A and/or
Particle B is mixed together or independently mixed.
By application by the harmful substance insolubilizing agent of the present invention for the consolidating containing harmful substance containing harmful substance
Body thing is put into the method mixed, mixed with water and method known to method that pulp-like is mixed etc. is made with powdered, energy
It is enough fully to make harmful substance insoluble.In the case where being put into powder, can put into particle A and particle B are pre-mixed and
Into material, also can by particle A and particle B respectively simultaneously put into, also respectively can gradually put into.Put into pulp-like
In the case of, insolubilizing agent is preferably 0.03~0.2 relative to the mass ratio [insolubilizing agent/water] of water.
As has been described, as the order by merging of particle A, particle B and the solids containing harmful substance, special limit is had no
It is fixed.For example, the particle A and/or particle B of a part can be mixed into the solids containing harmful substance, and then by one
Point or remaining particle B and/or particle A be mixed into the solids containing harmful substance gradually addition mixing；To be each total
Blanket mixing mixed with including etc., can be set according to the environment of the solids containing harmful substance, surrounding.Its
In, preferably following (1)~(3) any one.
(1) in the state of particle A and particle B are mixed with or by particle A and particle B difference simultaneously or serially
It is mixed into the solids containing harmful substance.
(2) after the solids mixing by particle A and containing harmful substance, stuff and other stuff B,
(3) after the solids mixing by particle B and containing harmful substance, stuff and other stuff A.
It is preferably the order described in (1), more preferably using already described harmful substance of the invention not as order by merging
Solvation carries out the mixing of (1).
Further, the harmful substance insolubilizing agent of the present invention is mainly made up of particle A and particle B, but as long as they are in mixing
Coexisted at the time of into the solids containing harmful substance, then equivalent to the harmful substance insolubilizing agent as the present invention
Use.
The processing method corresponding with the solids containing harmful substance species illustrated below, but the present invention do not limit
In these.
(slag, the processing method of flying ash)
Addition of the harmful substance insolubilizing agent in slag, flying ash is preferably 10~100kg/t- solids.Such as
The addition of fruit insolubilizing agent is that more than 10kg/t- solids then slag is sufficiently mixed with insolubilizing agent, is fully melted
The inhibition of the dissolution of harmful substance in slag.If the addition of insolubilizing agent is below 100kg/t- solids, obtain
The inhibition of the dissolution for the harmful substance being consistent with the addition of insolubilizing agent is obtained, the processing cost after processing can be suppressed
Increase.From this viewpoint, the addition of insolubilizing agent is more preferably 15~90kg/t- solids, more preferably 30~
75kg/t- solids.
Wherein, as slag, the steel slag produced in steel and iron manufacturing process as accessory substance can be included, because of stove
Species, the difference of cooling means, have blast furnace cinder (blast furnace Xu Leng slags, blast furnace water quenching slag), steel-smelting clinker (converter slag,
Electric furnace slag) as the different slag of character.Steel slag is with lime (CaO) and silica (SiO2) as principal component,
As other compositions, aluminum oxide (Al is contained in the case of blast furnace cinder2O3), magnesia (MgO) and a small amount of sulphur (S), in refining
Contain iron oxide (FeO), magnesia (MgO) in the case of steel slag.In the case of steel-smelting clinker, metallic element (such as iron
Deng) be incorporated into the form of the oxide in slag, but because refining time is short, lime content is high, therefore the lime of auxiliary material
A part is remained using undissolved original state as free lime (Free-CaO).The present invention can be applied for any slag.
Further, the Free-CaO in slag can be obtained as described below.First, slag is crushed to below 200 mesh,
Ethylene glycol is added in the crushed material, is extracted at 80 DEG C or so and obtains extract solution.Then, the extract solution is divided using ICP
Analysis, by subtracting Ca (OH) by the assay value2Part, so as to obtain Free-CaO.
In slag as described above, flying ash, particularly if CaO is more, then the rising due to pH or fluorine are insoluble
When CaF2Generation etc., easily occurs Funing tablet and is not reduced to unfavorable situation as purpose concentration.Even in such feelings
Under condition, the insoluble processing of harmful substance also can efficiently be carried out using the insolubilizing agent of the present invention in a short time.That is, for
CaO is more than 30 mass % slag, flying ash, can more preferably be used.
Further, CaO can be according to the EDTA titrations according to JIS R 9011 " test method of lime " or Japanese lime
The quantitative approach of 11. available limes is measured and obtained specified in association criterion test method (2006).
[agent, soil treatment method]
The insoluble method for the soil containing harmful substance in the present invention is preferably through by above-mentioned insolubilizing agent
Mixed with soil, so as to by the thawless method of harmful substance in soil.
Addition of the harmful substance insolubilizing agent in soil is preferably 50~300kg/m3.If the addition of insolubilizing agent
Measure as 50kg/m3More than, then soil is sufficiently mixed with insolubilizing agent when constructing, and can fully obtain the harmful substance in soil
Dissolution inhibition.If the addition of insolubilizing agent is 300kg/m3Hereinafter, then the addition with insolubilizing agent is obtained
The inhibition of the dissolution for the harmful substance being consistent, can suppress the increase or the increasing of processing cost of the soil volume after processing
Greatly.From this viewpoint, the addition of insolubilizing agent is preferably 50~150kg/m3, more preferably 50~100kg/m3。
On the processing soil after addition insolubilizing agent, from the viewpoint of the pollution to underground water or the exposure to people,
It is preferred that pH is 6~8, more preferably pH is 7~8.
[burning ash processing method/Treatment of Coal Ash method]
As the insoluble method of harmful substance contained in the burning ash or coal ash in the present invention, preferably through will be upper
State insolubilizing agent to mix with burning ash or coal ash, make the thawless method of harmful substance contained in burning ash or coal ash.
The addition of the harmful substance insolubilizing agent in burning ash or coal ash, relative to burning ash or coal ash, preferably 1
~50 mass %.If the addition of insolubilizing agent is more than 1 mass %, in construction, burning ash and insolubilizing agent be fully
Mixing, can fully obtain the inhibition of the dissolution of harmful substance in burning ash or coal ash.If the addition of insolubilizing agent
Measure as below 50 mass %, then obtain the inhibition of the dissolution for the harmful substance being consistent with the addition of insolubilizing agent, can
The increase or the increase of processing cost of the volume of burning ash or coal ash after suppression processing.From this viewpoint, insolubilizing agent
Addition is relative to burning ash or coal ash, more preferably preferably 3~30 mass %, 5~20 mass %.
As burning ash or coal ash, for example, it can include the paper mill sludge burning ash from papermaking workshop, by wooden biology
Burning ash (cigarette ash, the flying dust produced in the biomass system burning ash that is produced when matter fuel is with boiler combustion, urban waste incinerator
With main ash), coal thermal power generation when the combustion ash such as the coal ash, downflow sludge burning ash, the various industrial wastes that produce etc., but as long as
It is the burning ash or coal ash for including harmful substance, then is not limited to these.
After the mixture for having obtained mixing insolubilizing agent with burning ash or coal ash, from the dissolution suppression for improving harmful substance
From the viewpoint of effect processed, it can also add water and the mixture is conserved.To maintenance process, there is no particular restriction, can be with
Simply insolubilizing agent and the mixture of burning ash or coal ash are merely placed, can also be when lenitively the mixture be mixed
Carry out.During as maintenance, preferably 1~30 day, more preferably 3~10 days.If more than 1 day, then obtain and be sufficiently harmful into
The leaching retention effect and intensity divided show effect, within 30 days, then it can be seen that the leaching retention effect of harmful components
Improvement.
Burning ash or coal ash are handled by using the harmful substance insoluble method of the present invention, will can be met
Effectively utilized according to the burning ash or coal ash of Environmental Agency's bulletin environmental standard value of No. 46 in roadbed material etc..
(other contain the processing method of the solids of harmful substance)
Contain the solids of harmful substance for other, the already described " place of the solids containing harmful substance can be referred to
Reason method ", as needed with reference to known processing method, carries out the insoluble of harmful substance.
Contain the solids of harmful substance as other, casting sand, waste gypsum etc. can be included, but be not limited to this
A bit.
As previously discussed, the insoluble method of harmful substance of the invention is only simply by insolubilizing agent with containing nuisance
The solids mixing of matter, therefore efficiency is all high in time, in operation.
Embodiment
Next, the present invention is specifically described by embodiment, but the present invention is not limited to these embodiments.
(embodiment 1~4 and comparative example 1~4)
Hydroxide dolomite (particle A), potassium phosphate (particle B), magnesia are coordinated as shown in following Tables 1 and 2s,
To have made the harmful substance of embodiment 1~4 and comparative example 1~4 by way of screening and as defined particle size range not
Solvation.
It should illustrate, hydroxide dolomite, potassium phosphate, magnesia have used material as shown below.In addition, embodiment and
The particle diameter of comparative example is adjusted using the testing screen (sieve) of JIS-Z-8801 JIS standards.
Hydroxide dolomite (particle A)：Yoshizawa Lime Industry manufacture JIS R9001 No. 1 standard is adapted to
Product
Potassium phosphate (particle B)：Potassium dihydrogen phosphate is manufactured with Guang Chun medicines Co., Ltd.
Magnesia：Superfine magnesia is manufactured with Guang Chun medicines Co., Ltd.
Each example with insolubilizing agent slag A match ratio as shown in table 1, be sufficiently mixed, melted in bag
Slag A (steel-smelting clinker) insoluble processing, has carried out the dissolution test of the fluorine based on Heisei Environmental Agency's bulletin in 3 years the 46th.Will
As a result it is shown in table 1 below and table 2.
It should illustrate, comparative example 1 does not carry out insoluble processing.The pH of dissolution test is divided using HORIBA pH meters
Analysis, for F concentration, is obtained according to JISK0102, using absorption photometry.In addition, slag A has used slag as shown below.
Slag A：CaO；20~40 mass %, SiO2；10~20 mass %, Al2O3；10~20 mass %, FeO；10~
15 mass %
[table 1]
Table 1
The unit of use level is mass parts
[table 2]
Table 2
The unit of use level is mass parts
So far, fluorine it is insoluble in used magnesia.But, steel-smelting clinker turns into highly basic due to dissolution pH
Property, therefore as shown in comparative example 2, insoluble effect is not obtained.On the other hand, it is white for the hydroxide of embodiment 1~4
For the mixture of marble particle and potassium phosphate particle, the insoluble effect of fluorine is obtained, P/Ca is bigger, and insoluble sexuality is higher.
In addition, as shown in comparative example 3, comparative example 4, it is known that if simply potassium phosphate, although obtain insoluble effect, but fail
Standard value (below 0.8mg/L) is realized, by being combined with hydroxide dolomite, high insoluble effect is resulted in.
(embodiment 5~9)
Hydroxide dolomite, potassium phosphate, magnesia, ferrous sulfate, aluminum sulfate are coordinated as described in Table 3, with
The harmful substance insolubilizing agent of embodiment 5~9 has been made by way of sieving and turning into defined particle size range.
It should illustrate, hydroxide dolomite, potassium phosphate have used the " thing used in embodiment 1~4 and comparative example 1~4 "
Matter.Ferrous sulfate, aluminum sulfate have used material as shown below.
Ferrous sulfate：Sakai Chemical Industry Co., Ltd. manufactures the hydrate of ferrous sulfate 1
Aluminum sulfate：Taimei Kagaku Kogyo Kabushiki Kaisha manufactures aluminum sulfate
The amount of the insolubilizing agent of each example and flying ash A match ratio are fully mixed in bag like that as shown in table 3
Close, carry out flying ash A insoluble processing, carried out the dissolution test of the fluorine based on Heisei Environmental Agency's bulletin in 3 years the 46th.
Show the result in Table 3 below.
It should illustrate, comparative example 5 does not carry out insoluble processing.Dissolution test and " embodiment 1~3 and comparative example 1,2 "
Equally.In addition, flying ash A has used flying ash as shown below.
Flying ash A：Ig.loss；3~10 mass %, CaO；35~50 mass %, SiO2；15~30 mass %, most
Big particle diameter；Less than 250 μm
It should illustrate, the insolubilizing agent comprising " particle A and particle B and ferrous sulfate and aluminum sulfate " of embodiment 5,6
Particle diameter after screening is below 1.5mm, the sieve of the insolubilizing agent comprising " particle A and particle B and aluminum sulfate " of embodiment 7~9
Particle diameter after point is below 1.5mm.
[table 3]
Table 3
The unit of use level is mass parts
In the flying ash A of display strong basicity containing pump-down process etc. in contained calcium hydroxide, it is believed that it hinders fluorine
It is insoluble.By adding acid ferrous sulfate or aluminum sulfate, so that pH when reducing insoluble, while by adding sulfuric acid
Aluminium, can expect to react and have the generation of the entringite of insoluble effect with calcium source.By being constituted by particle A and particle B
Insolubilizing agent in both or any one are added as embodiment 5~9 so that pH is reduced, Funing tablet is also reduced, obtained not
Dissolve effect.
(embodiment 10~19 and comparative example 6,7)
Hydroxide dolomite, potassium phosphate, aluminum sulfate are coordinated as described in Table 4, to turn into regulation by screening
Particle size range mode, made the harmful substance insolubilizing agent of embodiment 10~19.
It should illustrate, hydroxide dolomite, potassium phosphate have used the " thing used in embodiment 1~4 and comparative example 1~4 "
Matter.Aluminum sulfate has used the " material used in embodiment 5~9 ".
The amount of the insolubilizing agent of each example and burning ash B match ratio are sufficiently mixed in bag like that as shown in table 4,
Burning ash B insoluble processing is carried out, the dissolution test of the fluorine based on Heisei Environmental Agency's bulletin in 3 years the 46th has been carried out.Will knot
Fruit is shown in table 4 below.
It should illustrate, comparative example 6 does not carry out insoluble processing.Comparative example 7 is not use particle A and particle B, only make
With the example of aluminum sulfate.Dissolution test with " embodiment 1~4 and comparative example 1~4 " are same.In addition, burning ash B used with
Lower shown burning ash.
Burning ash B：SiO2；45~60 mass %, Al2O3；20~35 mass %, maximum particle diameter；Less than 250 μm
It should illustrate, after the screening of the insolubilizing agent comprising " particle A and particle B and aluminum sulfate " of embodiment 10~19
Particle diameter is below 1.5mm.
[table 4]
Table 4-1
The unit of use level is mass parts
[table 5]
Table 4-2
The unit of use level is mass parts
(embodiment 20~23 and comparative example 8)
Hydroxide dolomite, potassium phosphate, aluminum sulfate are coordinated as described in Table 5, to turn into regulation by screening
Particle size range mode, made the harmful substance insolubilizing agent of embodiment 20~23.
It should illustrate, hydroxide dolomite, potassium phosphate have used the " thing used in embodiment 1~4 and comparative example 1~4 "
Matter.Aluminum sulfate has used the " material used in embodiment 5~9 ".
The amount of the insolubilizing agent of each example and burning ash C match ratio are sufficiently mixed in bag like that as shown in table 5,
Burning ash C insoluble processing is carried out, the dissolution test of the fluorine based on Heisei Environmental Agency's bulletin in 3 years the 46th has been carried out.Will knot
Fruit is shown in table 5 below.
It should illustrate, comparative example 8 does not carry out insoluble processing.Dissolution test and " embodiment 1~4 and comparative example 1~4 "
Equally.In addition, burning ash C has used burning ash as shown below.
Burning ash C：CaO；30~50 mass %, SiO2；30~50 mass %, maximum particle diameter；Less than 250 μm
It should illustrate, after the screening of the insolubilizing agent comprising " particle A and particle B and aluminum sulfate " of embodiment 20~23
Particle diameter is below 1.5mm.
[table 6]
Table 5
The unit of use level is mass parts.
Claims (11)
1. harmful substance insolubilizing agent, it is that particle diameter is below 2mm, makes the thawless harmful substance insolubilizing agent of harmful substance,
It is included：
Comprising calcium and magnesium and in them at least any one form oxide, carbonate or hydroxide particle A and
Particle B comprising phosphate cpd,
The mol ratio of calcium component in the particle A and the phosphorus composition of the phosphate cpd in the particle B is P/Ca for 0.1~
1.0。
2. harmful substance insolubilizing agent according to claim 1 is comprising in iron containing compoundses and aluminum contained compound
At least any one.
3. harmful substance insolubilizing agent according to claim 1 or 2, wherein, the particle A is dolomite or dolomite system
Compound.
4. according to harmful substance insolubilizing agent according to any one of claims 1 to 3 comprising aluminum contained compound, relatively
In the particle A and particle B total 100 mass parts, the content of the aluminum contained compound is 10~350 mass parts.
5. according to harmful substance insolubilizing agent according to any one of claims 1 to 4, wherein, the harmful substance be fluorine,
In boron, 6 valency chromium, selenium and arsenic at least any one.
6. according to harmful substance insolubilizing agent according to any one of claims 1 to 5, wherein, the phosphate cpd is phosphorus
At least appointing in acid dihydride potassium, dipotassium hydrogen phosphate, tripotassium phosphate, tertiary sodium phosphate and their hydrate and phosphate fertilizer
One.
7. according to harmful substance insolubilizing agent according to any one of claims 1 to 6, wherein, the harmful substance is insoluble
Agent makes the harmful substance in slag insoluble.
8. the insoluble method of harmful substance, its be by comprising calcium and magnesium and in them at least any one form oxidation
The particle A of thing, carbonate or hydroxide and the particle B comprising phosphate cpd be mixed into containing harmful substance containing harmful
The insoluble method of harmful substance in the solids of material,
Mol ratio with the calcium component in the particle A and the phosphorus composition of the phosphate cpd in the particle B is that P/Ca turns into
The particle A and the particle B are mixed into the solids containing harmful substance by 0.1~1.0 mode.
9. the insoluble method of harmful substance according to claim 8, wherein, the particle A, the particle B and described
The order by merging of solids containing harmful substance for it is following 1)~3) any one：
1) it is same respectively in the state of the particle A is mixed with the particle B or by the particle A and the particle B
When or be successively mixed into the above-mentioned solids containing harmful substance,
2) after mixing the particle A and the solids containing harmful substance, the particle B is mixed,
3) after mixing the particle B and the solids containing harmful substance, the particle A is mixed.
10. the insoluble method of harmful substance according to claim 9, wherein, the order by merging for it is described 1) in institute
The order stated, the harmful substance insolubilizing agent any one of usage right requirement 1~7, carries out the mixing 1).
11. the insoluble method of the harmful substance according to any one of claim 8~10, wherein, it is described containing harmful
The solids of material is slag.
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| JP2015069081 | 2015-03-30 | ||
| PCT/JP2016/060041 WO2016158914A1 (en) | 2015-03-30 | 2016-03-29 | Toxic substance insolubilizer and method for toxic substance insolubilization |
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| WO2019004024A1 (en) * | 2017-06-29 | 2019-01-03 | 宇部興産株式会社 | Insolubilizing material and production method therefor |
| JP6485513B1 (en) * | 2017-09-22 | 2019-03-20 | 住友大阪セメント株式会社 | Heavy metal pollution control material and heavy metal pollution control method using the pollution control material |
| JP7440859B2 (en) | 2019-01-29 | 2024-02-29 | 国立大学法人九州大学 | How to treat boron-containing water |
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| JP2014184437A (en) * | 2001-11-30 | 2014-10-02 | Matsuda Giken Kogyo Kk | Solidification insolubilization agent for contaminated soil |
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| JPWO2016158914A1 (en) | 2017-09-07 |
| KR20170126003A (en) | 2017-11-15 |
| WO2016158914A1 (en) | 2016-10-06 |
| KR101909853B1 (en) | 2018-12-18 |
| JP6271081B2 (en) | 2018-01-31 |
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