CN111672876B - Method for performing hydrothermal harmless treatment on waste incineration fly ash - Google Patents
Method for performing hydrothermal harmless treatment on waste incineration fly ash Download PDFInfo
- Publication number
- CN111672876B CN111672876B CN202010553992.6A CN202010553992A CN111672876B CN 111672876 B CN111672876 B CN 111672876B CN 202010553992 A CN202010553992 A CN 202010553992A CN 111672876 B CN111672876 B CN 111672876B
- Authority
- CN
- China
- Prior art keywords
- fly ash
- hydrothermal
- heavy metals
- waste
- hydroxyapatite
- 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.)
- Active
Links
- 239000010881 fly ash Substances 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000004056 waste incineration Methods 0.000 title claims abstract description 35
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 84
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 65
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 62
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 26
- 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 claims abstract description 25
- 230000005291 magnetic effect Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000002918 waste heat Substances 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000005294 ferromagnetic effect Effects 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- 210000003278 egg shell Anatomy 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 210000001124 body fluid Anatomy 0.000 claims description 2
- 239000010839 body fluid Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 30
- 230000001988 toxicity Effects 0.000 abstract description 30
- 230000006641 stabilisation Effects 0.000 abstract description 24
- 238000011105 stabilization Methods 0.000 abstract description 24
- 238000002386 leaching Methods 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 238000001784 detoxification Methods 0.000 abstract description 7
- 239000002920 hazardous waste Substances 0.000 abstract description 7
- 239000010791 domestic waste Substances 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 description 32
- 230000008569 process Effects 0.000 description 28
- 239000011575 calcium Substances 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 239000010813 municipal solid waste Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000008399 tap water Substances 0.000 description 9
- 235000020679 tap water Nutrition 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 7
- 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 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 229910052586 apatite Inorganic materials 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000002910 solid waste Substances 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229960001714 calcium phosphate Drugs 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
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
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for performing hydrothermal harmless treatment on waste incineration fly ash, which comprises the following steps: (1) adding hydroxyapatite precursor liquid into the fly ash, and then carrying out a first-step normal-pressure hydrothermal reaction at 40-50 ℃ to stabilize heavy metals in the fly ash; (2) and (2) adding magnetic hydroxyapatite powder and hydrogen peroxide into the mixture obtained by the reaction in the step (1), and then carrying out a second-step microwave high-pressure hydrothermal reaction at 120-150 ℃ to further stabilize heavy metals in the fly ash and degrade polycyclic aromatic hydrocarbons. The invention can efficiently and synchronously realize the stabilization of heavy metals in the waste incineration fly ash and the degradation and detoxification of polycyclic aromatic hydrocarbons, not only the leaching toxicity of the heavy metals is lower than the identification standard of hazardous wastes and can be reduced to meet the pollution control standard of domestic waste landfill, but also the heavy metals are really stabilized in the fly ash and are not transferred to hydrothermal waste liquid in large scale, and the toxicity equivalent degradation rate of 16 polycyclic aromatic hydrocarbons reaches more than 95.06 percent and secondary pollution is prevented.
Description
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, and particularly relates to a method for performing hydrothermal harmless treatment on waste incineration fly ash.
Background
The waste incineration treatment technology has the characteristics of short treatment period, good reduction effect, small occupied area and the like, and can utilize the generated heat to generate power and supply heat for recycling, so the waste incineration treatment technology becomes a waste treatment technology commonly applied in all countries around the world. According to the latest statistics, as for 2018, 331 seats of garbage incineration plants are built in China, the number of the garbage incineration plants is 45.1% of the harmless quantity of the garbage (Chinese statistics yearbook 2019), the harmless rate of incineration treatment is increased by 4.9% compared with the harmless rate of the garbage incineration treatment in the last year, and the trend of rapid development of the garbage incineration treatment scale in China is seen. In the secondary pollution prevention and control process of waste incineration, the incineration flue gas contains ash content which is entrained along with the rising of gas in a combustion chamber, namely Fly ash (Fly ash), and the Fly ash can be efficiently collected by a flue gas pollution purification system, the mass of the Fly ash content accounts for about 2-5% of the mass of primary waste, and the annual production capacity is about 203-509 ten thousand tons. The fly ash is rich in a large amount of heavy metals (such as about 2088-65850 mg/kg of Zn and about 783-12113 mg/kg of Pb in the fly ash from the incineration of Chinese garbage), refractory toxic and harmful organic matters (such as Polycyclic Aromatic Hydrocarbons (PAHs) which are three-cause substances), and the like, and is listed in the national hazardous waste record (number HW 18). Therefore, in order to prevent secondary pollution of fly ash and to achieve actual waste disposal without harm, it is necessary to dispose fly ash without harm before final disposal.
At present, the main treatment technologies for the waste incineration fly ash are as follows: curing techniques, heat treatment techniques, chemical stabilization techniques, and the like. The cement solidification technology is one of the most common fly ash solidification technologies, has low treatment cost and good stabilization effect on heavy metals in fly ash, but has the problems that the treated solidified body has large volume-increasing ratio, the solidified body is easy to be eroded by acid media, the heavy metals are leached again, and the degradation-resistant organic pollutants such as polycyclic aromatic hydrocarbon and the like are not decomposed. The heat treatment technologies such as melting/vitrification have the advantages of high volume reduction rate, capability of decomposing organic pollutants and the like, but high-temperature treatment consumes a large amount of energy, partial heavy metals (Pb, Zn, Cd and the like) are volatile at high temperature, flue gas needs to be treated, the treatment cost is too high, and the heat treatment technologies are not widely applied to engineering at present. The chemical agent stabilizing technology is a treatment technology for converting heavy metal ions in the fly ash into water-insoluble high-molecular complex or inorganic mineral substances by using a chemical agent and converting toxic substances in the fly ash into low-toxicity and low-mobility substances, and has the advantages of little or no capacity increase, low treatment cost compared with a high-temperature treatment technology and the like. Commonly used chemical stabilizing agents include: inorganic and organic chelating agents (such as dithioamino chelating agents, glycine, EDTA, gluconic acid, citrate, and the like), sulfide precipitating agents (soluble inorganic sulfur precipitating agents, insoluble inorganic sulfur precipitating agents, organic sulfur precipitating agents), carbonate precipitating agents, silicate precipitating agents, and phosphate precipitating agents, but none of these chemical stabilizing agents has decomposition or detoxification effects on persistent organic pollutants.
As the phosphate has better stabilization effect on heavy metals, except for the common phosphates such as dipotassium hydrogen phosphate, calcium dihydrogen phosphate and the like which are adopted to stabilize heavy metals in fly ash, the reference is made to apatite (such as fluorapatite Ca)5(PO4)2F2Hydroxyapatite Ca5(PO4)2(OH)2) The technology for repairing and fixing the soil polluted by heavy metal, Zhangan and the like, adopts natural apatite minerals (Hydroxyapatite, called HAP for short as a main component) as stabilizing agents, soaks and washes out slime, dries and grinds the slime, mixes the slime with fly ash, and then maintains the mixture for 24 hours at room temperature. Research finds that the smaller the particle size of the apatite depends on the mechanism of adsorption and precipitation of the apatite, the better stabilization effect on fly ash from incineration is better, so that the apatite needs to be sufficiently ground and sieved by a 200-mesh sieve to achieve a better stabilization effect, and additives such as sodium sulfide and the like are often needed to obtain a better stabilization effect on fly ash with high heavy metal content (such as Cd and the like) (Zhangan and the like, research on medicament stabilization technology of fly ash from incineration fly ash apatite, environmental science 2006,27(1): 189:192). As hydroxyapatite is one of main components of bones and teeth of human and animals, Mu and other people of Kyushu university in Japan stabilize heavy metals in the fly ash from domestic garbage incineration by utilizing natural fishbone powder (organic tissues such as fish meat are removed by boiling in water, and are ground after being dried or burned, and the main component is hydroxyapatite after being measured), but a leaching experiment after the stabilization for 72 hours at normal temperature shows that the mass ratio of the fishbone powder to the fly ash is up to 1: at 1, the maximum stabilization efficiency of Pb is only 59.31%, and the method has still not been very effective compared with other stabilization techniques (Mu et al, stabilization of waste natural)Journal of Cleaner production.2018,172: 3111-; mu et al, flame of ignition of water generating heating metal stabilization in a biological water absorption (MSWI) flash. journal of Cleaner production.2018,189: 398-. Chinese patent with application publication No. CN 106316307A provides a composite passivating agent for fly ash generated by burning household garbage (the mass percentage is 65-85% of slag, 8-20% of clinker, 2-8% of alkaline activator and 3-10% of hydroxyapatite). when the composite passivating agent is used, the hydroxyapatite is dissolved in hydrochloric acid, and then the fly ash, the alkaline activator, the slag and the clinker are added, and the test block is cured after compaction molding. The method is mainly based on substances (hydrated gel) generated by hydration of minerals such as slag, clinker and the like and phosphate radical generated by dissolving hydroxyapatite in acid to generate good stabilizing effect on heavy metal anion groups and amphoteric heavy metal cations in the fly ash. In conclusion, the solidification stabilization technology based on the hydroxyapatite adsorption or exchange mechanism has a certain effect on heavy metals, but still can not realize the decomposition and detoxification of the refractory, toxic and harmful organic pollutants in the fly ash.
The Hydrothermal method (Hydrothermal technology) heats a system using an aqueous solution as a reaction medium, and usually utilizes an external heat source to heat and pressurize a specially-made closed reaction container (high-pressure reaction kettle) except for a medium-low temperature (lower than 100 ℃) Hydrothermal technology under normal pressure, so that the reaction medium water in the container is in a high-temperature and high-pressure state. Wherein, the temperature is 100-374 ℃, the water is in a subcritical state when the pressure is kept at 5-22.5 MPa, the mass transfer resistance among reactants is reduced, the intermolecular hydrogen bond action is weakened, the solubility of organic matters is increased rapidly, and the solubility of inorganic matters is also reduced greatly in a hydrothermal system under the subcritical condition, so that the reaction time is shortened greatly, and the reaction efficiency is improved. Chinese patent No. ZL201610264481.6 discloses a method for inducing hydrothermal stabilization of heavy metals in waste incineration fly ash by adding seed crystals, wherein fly ash and the like are added as exogenous aluminum conditioner and tobermorite seed crystals are used for inducing fly ash to synthesize aluminosilicate zeolite products to stabilize heavy metals under alkaline hydrothermal condition. Chinese patent publication No. CN107265470A discloses a method for synthesizing tobermorite-stabilized fly ash heavy metal under alkaline hydrothermal conditions by using incinerator slag as a silicon-aluminum conditioner. The method for stabilizing the fly ash heavy metal by the alkaline hydrothermal method based on silicon-aluminum regulation not only needs a large amount of strong base as an excitant for dissolving silicon-aluminum, but also cannot realize detoxification of Polycyclic Aromatic Hydrocarbons (PAHs). Aiming at polycyclic aromatic hydrocarbon in fly ash, a Master academic paper (Zhang jin Lu. subcritical hydrothermal control technical research of heavy metal and organic pollutant in waste incineration fly ash, Chinese Master academic paper, 2018) adopts 200 ℃ hydrothermal for 48 hours on the waste incineration fly ash, the toxicity equivalent of PAHs is reduced by about 40-67%, and hydrogen peroxide (H) with the mass fraction of 30% is added2O2) The toxicity equivalent of the PAHs is reduced by 93 percent. Chinese patent ZL201910315109.7 discloses a method for degrading polycyclic aromatic hydrocarbon in fly ash from waste incineration by catalyzing subcritical water oxidation, wherein after the fly ash is subjected to water washing treatment, the toxicity equivalent degradation rate of the polycyclic aromatic hydrocarbon in the fly ash is up to more than 96.5% by a two-step hydrothermal oxidation process for 18 hours in total. Although the invention has obvious detoxification effect on polycyclic aromatic hydrocarbon, oxidant (H) is used in each step2O2) Or a composite oxidant (H)2O2And O2) The method causes large consumption of the oxidant, high difficulty in accurate control of the oxidation process, complicated processes such as water washing pretreatment and oxidation, and the like, and still does not solve the problem of harmlessness of heavy metals. Chinese patent application publication No. CN 108721824 a discloses a hydrothermal treatment method for synchronously stabilizing heavy metals and degrading polycyclic aromatic hydrocarbons by adding an exogenous silicon-aluminum conditioner, tobermorite seed crystals and hydrogen peroxide in a proper proportion into fly ash. After the treatment by the method, the leaching concentration of heavy metals in the fly ash is reduced below a standard value for identifying hazardous wastes (GB5085.3-2007), and the content and toxicity equivalent of 16 PAHs in the fly ash are respectively reduced by 64.4-80.4% and 72.0-94.4%. Although the method realizes the harmlessness of heavy metals and polycyclic aromatic hydrocarbons to a certain extent, the method has extremely high requirements on the precise regulation and control of the silicon-aluminum element ratio in the fly ash reaction system based on the stabilization mechanism of inducing the target tobermorite to generate the heavy metals at 150-200 ℃, and the treatment effect needs to be realizedFurther improves (for example, the heavy metal leaching toxicity of the stabilized fly ash still does not reach the entry standard of a refuse landfill (GB16889-2008), and the toxicity equivalent degradation rate of the polycyclic aromatic hydrocarbon does not exceed 95%). Therefore, the field of fly ash treatment by a hydrothermal method still has urgent needs in the aspects of easy technological operation, high-efficiency realization of synchronous harmless treatment of polycyclic aromatic hydrocarbon and heavy metal in fly ash and the like.
Disclosure of Invention
In view of the above, the present invention provides a method for performing hydrothermal harmless treatment on waste incineration fly ash, which can efficiently and synchronously realize stabilization of heavy metals in the waste incineration fly ash and detoxification of polycyclic aromatic hydrocarbon degradation.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for performing hydrothermal harmless treatment on waste incineration fly ash, which comprises the following steps:
(1) adding hydroxyapatite precursor liquid into the fly ash, and then carrying out a first-step normal-pressure hydrothermal reaction at 40-50 ℃ to stabilize heavy metals in the fly ash;
(2) and (2) adding magnetic hydroxyapatite powder and hydrogen peroxide into the mixture obtained by the reaction in the step (1), and then carrying out a second-step microwave high-pressure hydrothermal reaction at 120-150 ℃ to further stabilize heavy metals in the fly ash and degrade polycyclic aromatic hydrocarbons.
As a preferred technical scheme, the preparation method of the hydroxyapatite precursor fluid comprises the following steps: adding phosphoric acid and water into the calcium carbonate substance, reacting to obtain a calcium phosphate salt solution, and then adding a calcium hydroxide solution to obtain a hydroxyapatite precursor solution.
As a preferred technical scheme, the calcium carbonate substance is egg shells with inner membranes removed.
Preferably, in the step (1), the solid-to-liquid ratio of the fly ash to the body fluid before hydroxyapatite is 1: 3-1: 5g/mL, and water is added before hydrothermal reaction to keep the solid-to-liquid ratio of the fly ash to the total liquid amount in the system at 1:10 g/mL.
As a preferred technical scheme, the preparation method of the magnetic hydroxyapatite powder comprises the following steps: mixing trisodium citrate and FeCl3·6H2Adding O and urea into water, then adding polyacrylic acid solution, then adding hydroxyapatite precursor solution, then carrying out high-pressure hydrothermal reaction at 160-180 ℃, carrying out solid-liquid separation after the reaction, drying, and grinding to obtain magnetic hydroxyapatite powder.
Preferably, in the step (2), the mass ratio of the magnetic hydroxyapatite powder to the fly ash is 1: 15-1: 20, and the H content in the hydrogen peroxide is 1: 15-1: 202O2The ratio of the fly ash to the fly ash is 0.003-0.005 mol/g.
In the step (1), the time of the first step of the normal-pressure hydrothermal reaction is 10-12 hours; in the step (2), the time of the microwave high-pressure hydrothermal reaction in the second step is 0.5-1 hour.
As a preferable technical scheme, in the step (2), the mixture obtained by the microwave high-pressure hydrothermal reaction in the second step is cooled to room temperature, then solid-liquid separation is performed to obtain a fly ash hydrothermal reactant and waste liquid, the fly ash hydrothermal reactant is dried, and then the magnetic hydroxyapatite powder is recovered by ferromagnetic separation.
As a preferable technical scheme, in the step (2), after the microwave high-pressure hydrothermal reaction, waste heat is recovered when the temperature is reduced to room temperature for drying the fly ash hydrothermal reactant.
In the step (1), the particle size of the fly ash is preferably 200 μm or less; in the step (2), the particle size of the magnetic hydroxyapatite powder is less than 100 μm.
The basic theoretical basis of the invention is as follows:
the invention adopts a two-step hydrothermal process, realizes the adsorption and substitution combined stabilization of heavy metals based on the Hydroxyapatite (HAP) hydrothermal synthesis process in the two-step hydrothermal process, the adsorption stabilization of magnetic hydroxyapatite powder (MHAP) and aluminosilicate mineral based on the catalytic hydrothermal oxidation process, and the catalytic subcritical hydrothermal oxidative degradation of polycyclic aromatic hydrocarbons.
1. In the first step of hydrothermal treatment, HAP precursor liquid prepared by using calcium carbonate as a calcium source is added into fly ash, and three types of substances can be formed in the fly ash hydrothermal product under the medium-temperature normal-pressure hydrothermal condition: (1) hydrothermally synthesized hydroxyl radicalApatite (HAP), the hexagonal columnar crystal has a special structure similar to an ion exchange column, has strong adsorption capacity, ion exchange capacity and thermal stability, and all ions or groups of the crystal can be replaced to keep the HAP crystal structure unchanged; based on the properties that HAP is soluble in strong acid and insoluble in alkali, HAP can be synthesized and stably exist in a strong alkaline (pH is more than 12) environment like a fly ash hydrothermal process, and fully and uniformly contacts various ions such as heavy metal in a fly ash hydrothermal system in the synthesis process so as to efficiently stabilize the heavy metal through surface adsorption/complexation; (2) precipitation of hydroxyapatite salts of heavy metals, e.g. lead hydroxyapatite (Pb)10(PO4)6(OH)2) Cadmium hydroxyapatite (Ca)8Cd2(PO4)6(OH)2) The substances are HAP which makes heavy metal replace 10 Ca in HAP completely or partially by ion exchange2+(4 Ca (I) and 6 Ca (II) positions), the HAP substituted by heavy metal still maintains the HAP crystal structure and still has strong stability and adsorption capacity; (3) phosphates of heavy metals, e.g. lead (Pb) phosphate3(PO4)2) Zinc phosphate (Zn)3(PO4)2) The heavy metal phosphate with stable properties has an immobilization effect on heavy metals. Based on the effects of the three substances, the high-efficiency stability of the heavy metal is realized, and the secondary pollution that the heavy metal is lost due to the migration of the heavy metal to hydrothermal waste liquid in the hydrothermal process is prevented.
2. In the second step of hydrothermal reaction, hydrogen peroxide (H) is added2O2) As an oxidant, MHAP is used as a catalyst, and the high-efficiency hydrothermal catalytic oxidative decomposition of the polycyclic aromatic hydrocarbon and the secondary stabilization of heavy metals at a low subcritical water reaction temperature (120-150 ℃) under the assistance of microwaves can be realized. The method mainly comprises the following mechanisms: (1) h2O2Oxidative degradation of organic substances by generation of hydroxyl radicals, but if H2O2When added too much, will react with hydroxyl radical and inhibit H2O2Is decomposed to result in H2O2The utilization rate is reduced, which not only causes the waste of the oxidant and the increase of the process cost, but also causes the toxicity of the polycyclic aromatic hydrocarbonThe equivalent degradation rate is difficult to exceed 95%. MHAP is used as a catalyst, the proportion of an oxidant, the catalyst and fly ash is reasonably regulated, the utilization efficiency of the oxidant is improved on the premise of improving the degradation rate of organic matters, the cost is reduced, and the reaction time is greatly shortened by adopting a microwave-assisted subcritical hydrothermal process. (2) In the traditional hydrothermal catalytic oxidation process, ferrous ions (ferrous salt) are used as a homogeneous catalyst, the suitable pH range is 2-5, but the fly ash is strong in alkalinity (the pH is about 11-13), and the ferrous ions or ferric ions react with hydroxide in a system to generate hydroxide precipitates or complexes of iron in other forms, so that the catalytic capability is reduced and the reaction is hindered. Based on the special spatial structure of HAP, the catalyst carrier can enhance the dispersity of catalytic active components and obtain the potential of higher catalytic activity and thermal stability2O2Polycyclic aromatic hydrocarbon is degraded by reaction, and the catalytic effect is better than that of Fe3O4The iso-iron oxide heterogeneous catalyst is better, can avoid secondary pollution caused by metal ions in the Fe system homogeneous catalyst flowing out of hydrothermal liquid in the hydrothermal process, and can realize the recycling of the magnetic catalyst. (3) When the MHAP is used as a catalyst, the MHAP also has the effects of ion exchange, surface complexation, adsorption and dissolution coprecipitation (PO formed by micro-dissolution of the MHAP) in the microwave-assisted hydrothermal process4 3-、HPO4 2-、H2PO4 -The plasma reacts with the heavy metal to generate a stable heavy metal phosphate precipitate) stabilizes the heavy metal, and secondary stabilization of the heavy metal in the second hydrothermal process is achieved. (4) Due to efficient microwave-assisted hydrothermal synthesis, tobermorite (Ca) can be hydrothermally synthesized by using Ca, Si and Al elements in fly ash, HAP precursor liquid in the first step and Ca element partially dissolved in MHAP in the second step at a lower subcritical temperature (120-150 ℃)5Si6(OH)2O16·4H2O), Callitse (Ca)3Al2(SiO4)(OH)8) Isoaluminosilicate minerals and zeolites such as A-type zeolite, based on these materialsThe large specific surface area and porosity, and the strong exchange and adsorption capacity realize the stabilization of heavy metal in the hydrothermal synthesis process. Under the traditional hydrothermal process, the substances can be efficiently synthesized only by high-temperature hydrothermal at 150-200 ℃, and under the assistance of microwaves, the aluminosilicate minerals and the zeolite are efficiently synthesized by hydrothermal synthesis, so that the secondary stabilization of the heavy metal is realized, the process energy consumption is saved, and the process cost is reduced.
The invention has the beneficial effects that: the invention can efficiently and synchronously realize the stabilization of heavy metals in the waste incineration fly ash and the degradation and detoxification of polycyclic aromatic hydrocarbons, not only the leaching toxicity of the heavy metals is lower than the identification standard of hazardous wastes, but also can be reduced to meet the pollution control standard of domestic waste landfill (especially the Pb leaching concentration which is the most difficult to reach the standard can stably reach the standard and is lower than 0.25mg/L), the heavy metals are really stabilized in the fly ash and are not transferred to hydrothermal waste liquid in a large scale, and the toxicity equivalent degradation rate of 16 polycyclic aromatic hydrocarbons reaches more than 95.06 percent, thereby solving the problems that the leaching toxicity of the fly ash heavy metal in the original synchronous harmless technology is difficult to reach the pollution control standard of domestic garbage landfill and the toxicity equivalent degradation rate of the polycyclic aromatic hydrocarbon is difficult to break through and improve at 94.4 percent, reducing the reaction energy consumption and the time, realizing the recycling of the catalyst and preventing the secondary pollution of heavy metal migration in the hydrothermal process.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is phase analysis (XRD) of MHAP and phase change analysis (XRD) of hydrothermal product of waste incineration fly ash after hydrothermal innocent treatment.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1:
as shown in figure 1, the method for performing hydrothermal harmless treatment on waste incineration fly ash comprises the following steps:
A. the collected waste incineration fly ash is subjected to grinding pretreatment, so that the collected waste incineration fly ash is uniform and has the particle size of less than 200 mu m.
B. Adding 10g egg shell (calcium carbonate) with inner membrane removed, adding 7mL industrial phosphoric acid and 93mL tap water, ultrasonic reacting at room temperature for 30 min, standing until no CO is present2Generating bubbles to obtain about 100mL of calcium phosphate stock solution, then dropwise adding 100mL of 0.1mol/L calcium hydroxide at 10mL/min in the stirring process, adding NaOH to maintain the pH at about 12-13, and then stirring for 1 hour to obtain 200mL of hydroxyapatite precursor solution (HAP precursor solution).
C. Adding HAP precursor liquid into fly ash in a vibration or stirring type heater, wherein the solid-to-liquid ratio of the fly ash to the HAP precursor liquid is 1:3g/mL, then adding tap water to keep the solid-to-liquid ratio of the fly ash to the total liquid amount in the system at 1:10(g/mL), uniformly mixing, and then carrying out normal pressure hydrothermal reaction for 10 hours at 40 ℃.
D. 10.8g of trisodium citrate and 4.32g of FeCl3·6H2Adding O and 2.8g of urea into 96.5mL of tap water, adding 3.5mL of PAA dispersing agent in the stirring process, wherein the PAA dispersing agent is an aqueous solution containing 0.5% of polyacrylic acid to obtain 100mL of mixed solution, dropwise adding 300mL of HAP precursor liquid into the mixed solution, transferring the mixed solution into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, carrying out vacuum drying on a solid-phase product after solid-liquid separation for 24 hours, and carrying out grinding treatment to prepare magnetic hydroxyapatite powder (MHAP) with the particle size of less than 100 microns.
E. Transferring the mixture of fly ash and HAP precursor liquid after normal pressure hydrothermal reaction to a microwave high pressure hydrothermal reaction kettle, adding magnetic hydroxyapatite powder (MHAP) and hydrogen peroxide, wherein the particle size of the MHAP is less than 100 mu m, the mass ratio of the MHAP to the fly ash is 1:20, and H in the hydrogen peroxide2O2The ratio of the fly ash to the fly ash is 0.003mol/g, the concentration of hydrogen peroxide is 0.5mol/L, then the microwave high-pressure hydrothermal reaction is carried out for 45 minutes at 120 ℃, the temperature is reduced to room temperature, and the waste heat is recovered.
F. And performing solid-liquid separation on the mixture after the microwave high-pressure hydrothermal reaction to obtain a fly ash hydrothermal reactant and waste liquid, drying the fly ash hydrothermal reactant by utilizing recovered waste heat, recovering MHAP through ferromagnetic separation, and storing in a finished product bin. The waste liquid enters a waste water treatment system.
G. The recycled MHAP powder is ground to be less than 100 mu m, stored and used for the hydrothermal treatment of the next batch of fly ash.
Phase analysis (XRD) of the prepared MHAP is shown in figure 2, phase change analysis (XRD) of the hydrothermal product of the waste incineration fly ash treated by the hydrothermal harmless process is shown in figure 2, and hydroxyapatite (Ca) is formed in the hydrothermal product of the fly ash after the treatment by the process of the embodiment10(PO4)6(OH)2) And lead hydroxyapatite (Pb)10(PO4)6(OH)2) Cadmium hydroxyapatite (Ca)8Cd2(PO4)6(OH)2) Precipitation of hydroxyapatite salt of the same heavy metal with the formation of lead phosphate (Pb)3(PO4)2) Zinc phosphate (Zn)3(PO4)2) Phosphates of equal heavy metals, in addition to tobermorite (Ca)5Si6(OH)2O16·4H2O), Callitse (Ca)3Al2(SiO4)(OH)8) And aluminosilicate minerals and zeolite such as A-type zeolite.
The leaching toxicity of various heavy metals before and after the fly ash treatment and the content of the heavy metals in the hydrothermal waste liquid are shown in table 1, the content change of polycyclic aromatic hydrocarbon is shown in table 2, after the fly ash is treated by the process of the embodiment, the leaching concentration of various heavy metals such as Pb, Zn, Cu, Cr, Cd and the like in the incineration fly ash of the household garbage is lower than the specified value of hazardous waste identification standard-leaching toxicity identification (GB5085.3-2007) (by adopting a sulfuric acid-nitric acid method for leaching toxicity of solid waste (HJ/T299-2007)), and is also lower than the specified value of pollution control standard for landfill (GB16889-2008) (by adopting an acetic acid buffer solution method for leaching toxicity of solid waste (HJ/T300-2007)), the content of various heavy metals in the hydrothermal waste liquid is extremely low (by adopting inductively coupled plasma mass spectrometry), the heavy metals are fixed in the fly ash and are not transferred to the waste liquid in a large scale to cause the transfer and secondary pollution of the heavy metals, the total content of 16 polycyclic aromatic hydrocarbons is reduced to 568.96 mu g/kg, the toxicity equivalent is reduced to 2.15TEQ mu g/kg, and the contents are respectively reduced by 80.36 percent and 95.06 percent.
Example 2:
as shown in figure 1, the method for performing hydrothermal harmless treatment on waste incineration fly ash comprises the following steps:
A. the collected waste incineration fly ash is subjected to grinding pretreatment, so that the collected waste incineration fly ash is uniform and has the particle size of less than 200 mu m.
B. Adding 10g of calcium carbonate into an ultrasonic reactor, adding 7mL of industrial phosphoric acid and 93mL of tap water, carrying out ultrasonic reaction for 30 minutes at normal temperature, and standing until no CO exists after ultrasonic reaction2Generating bubbles to obtain about 100mL of calcium phosphate stock solution, then dropwise adding 100mL of 0.1mol/L calcium hydroxide at 10mL/min in the stirring process, adding NaOH to maintain the pH at about 12-13, and then stirring for 1 hour to obtain 200mL of hydroxyapatite precursor solution (HAP precursor solution).
C. Adding HAP precursor liquid into fly ash in a vibration or stirring type heater, wherein the solid-to-liquid ratio of the fly ash to the HAP precursor liquid is 1:4g/mL, then adding tap water to keep the solid-to-liquid ratio of the fly ash to the total liquid amount in the system at 1:10(g/mL), uniformly mixing, and then carrying out normal pressure hydrothermal reaction at 45 ℃ for 11 hours.
D. 10.8g of trisodium citrate and 4.32g of FeCl3·6H2Adding O and 2.8g of urea into 96.5mL of tap water, adding 3.5mL of PAA dispersing agent in the stirring process, wherein the PAA dispersing agent is an aqueous solution containing 0.5% of polyacrylic acid to obtain 100mL of mixed solution, dropwise adding 300mL of HAP precursor liquid into the mixed solution, transferring the mixed solution into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, carrying out vacuum drying on a solid-phase product after solid-liquid separation for 24 hours, and carrying out grinding treatment to prepare magnetic hydroxyapatite powder (MHAP) with the particle size of less than 100 microns.
E. Transferring the mixture of fly ash and HAP precursor liquid after normal pressure hydrothermal reaction to a microwave high pressure hydrothermal reaction kettle, adding magnetic hydroxyapatite powder (MHAP) and hydrogen peroxide, wherein the particle size of the MHAP is less than 100 mu m, the mass ratio of the MHAP to the fly ash is 1:18, and H in the hydrogen peroxide2O2The ratio of fly ash to fly ash is 0.004mol/g and 0.5mol/L hydrogen peroxide, then carrying out microwave high-pressure hydrothermal reaction at 140 ℃ for 45 minutes, cooling to room temperature, and recovering waste heat.
F. And performing solid-liquid separation on the mixture after the microwave high-pressure hydrothermal reaction to obtain a fly ash hydrothermal reactant and waste liquid, drying the fly ash hydrothermal reactant by utilizing recovered waste heat, recovering MHAP through ferromagnetic separation, and storing in a finished product bin. The waste liquid enters a waste water treatment system.
G. The recycled MHAP powder is ground to be less than 100 mu m, stored and used for the hydrothermal treatment of the next batch of fly ash.
Phase analysis (XRD) of the prepared MHAP is shown in figure 2, phase change analysis (XRD) of the hydrothermal product of the waste incineration fly ash treated by the hydrothermal harmless process is shown in figure 2, and hydroxyapatite (Ca) is formed in the hydrothermal product of the fly ash after the treatment by the process of the embodiment10(PO4)6(OH)2) And lead hydroxyapatite (Pb)10(PO4)6(OH)2) And cadmium hydroxyapatite (Ca)8Cd2(PO4)6(OH)2) Precipitation of hydroxyapatite salt of the same heavy metal with the formation of lead phosphate (Pb)3(PO4)2) Zinc phosphate (Zn)3(PO4)2) Phosphates of equal heavy metals, in addition to tobermorite (Ca)5Si6(OH)2O16·4H2O), Callitse (Ca)3Al2(SiO4)(OH)8) And aluminosilicate minerals and zeolite such as A-type zeolite.
The leaching toxicity of various heavy metals before and after the fly ash treatment and the content of the heavy metals in the hydrothermal waste liquid are shown in table 1, the content change of polycyclic aromatic hydrocarbon is shown in table 2, after the fly ash is treated by the process of the embodiment, the leaching concentration of various heavy metals such as Pb, Zn, Cu, Cr, Cd and the like in the incineration fly ash of the household garbage is lower than the specified value of hazardous waste identification standard-leaching toxicity identification (GB5085.3-2007) (by adopting a sulfuric acid-nitric acid method for leaching toxicity of solid waste (HJ/T299-2007)), and is also lower than the specified value of pollution control standard for landfill (GB16889-2008) (by adopting an acetic acid buffer solution method for leaching toxicity of solid waste (HJ/T300-2007)), the content of various heavy metals in the hydrothermal waste liquid is extremely low (by adopting inductively coupled plasma mass spectrometry), the heavy metals are fixed in the fly ash and are not transferred to the waste liquid in a large scale to cause the transfer and secondary pollution of the heavy metals, the total content of 16 polycyclic aromatic hydrocarbons is reduced to 410.64 mu g/kg, the toxicity equivalent is reduced to 1.63 TEQ mu g/kg, and the contents are respectively reduced by 85.83 percent and 96.26 percent.
Example 3:
as shown in figure 1, the method for performing hydrothermal harmless treatment on waste incineration fly ash comprises the following steps:
A. the collected waste incineration fly ash is subjected to grinding pretreatment, so that the collected waste incineration fly ash is uniform and has the particle size of less than 200 mu m.
B. Adding 10g egg shell (calcium carbonate) with inner membrane removed, adding 7mL industrial phosphoric acid and 93mL tap water, ultrasonic reacting at room temperature for 30 min, standing until no CO is present2Generating bubbles to obtain about 100mL of calcium phosphate stock solution, then dropwise adding 100mL of 0.1mol/L calcium hydroxide at 10mL/min in the stirring process, adding NaOH to maintain the pH at about 12-13, and then stirring for 1 hour to obtain 200mL of hydroxyapatite precursor solution (HAP precursor solution).
C. Adding HAP precursor liquid into fly ash in a vibration or stirring type heater, wherein the solid-to-liquid ratio of the fly ash to the HAP precursor liquid is 1:5g/mL, then adding tap water to keep the solid-to-liquid ratio of the fly ash to the total liquid amount in the system at 1:10(g/mL), uniformly mixing, and then carrying out normal pressure hydrothermal reaction at 40 ℃ for 12 hours.
D. 10.8g of trisodium citrate and 4.32g of FeCl3·6H2Adding O and 2.8g of urea into 96.5mL of tap water, adding 3.5mL of PAA dispersing agent in the stirring process, wherein the PAA dispersing agent is an aqueous solution containing 0.5% of polyacrylic acid to obtain 100mL of mixed solution, dropwise adding 300mL of HAP precursor liquid into the mixed solution, transferring the mixed solution into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, carrying out vacuum drying on a solid-phase product after solid-liquid separation for 24 hours, and carrying out grinding treatment to prepare magnetic hydroxyapatite powder (MHAP) with the particle size of less than 100 microns.
E. Transferring the mixture of fly ash and HAP precursor liquid after normal pressure hydrothermal reaction to a microwave high pressure hydrothermal reaction kettle, adding magnetic hydroxyapatite powder (MHAP) and hydrogen peroxide, wherein the particle size of the MHAP is less than 100 mu m, the mass ratio of the MHAP to the fly ash is 1:15, and H in the hydrogen peroxide2O2The ratio of the fly ash to the fly ash is 0.005mol/g, the concentration of hydrogen peroxide is 0.5mol/L, then the microwave high-pressure hydrothermal reaction is carried out for 45 minutes at 150 ℃, the temperature is reduced to the room temperature, and the waste heat is recovered.
F. And performing solid-liquid separation on the mixture after the microwave high-pressure hydrothermal reaction to obtain a fly ash hydrothermal reactant and waste liquid, drying the fly ash hydrothermal reactant by utilizing recovered waste heat, recovering MHAP through ferromagnetic separation, and storing in a finished product bin. The waste liquid enters a waste water treatment system.
G. The recycled MHAP powder is ground to be less than 100 mu m, stored and used for the hydrothermal treatment of the next batch of fly ash.
Phase analysis (XRD) of the prepared MHAP is shown in figure 2, phase change analysis (XRD) of the hydrothermal product of the waste incineration fly ash treated by the hydrothermal harmless process is shown in figure 2, and hydroxyapatite (Ca) is formed in the hydrothermal product of the fly ash after the treatment by the process of the embodiment10(PO4)6(OH)2) And lead hydroxyapatite (Pb)10(PO4)6(OH)2) Cadmium hydroxyapatite (Ca)8Cd2(PO4)6(OH)2) Precipitation of hydroxyapatite salt of the same heavy metal with the formation of lead phosphate (Pb)3(PO4)2) Zinc phosphate (Zn)3(PO4)2) Phosphates of equal heavy metals, in addition to tobermorite (Ca)5Si6(OH)2O16·4H2O), Callitse (Ca)3Al2(SiO4)(OH)8) And aluminosilicate minerals and zeolite such as A-type zeolite.
The leaching toxicity of various heavy metals before and after the fly ash treatment and the content of the heavy metals in the hydrothermal waste liquid are shown in table 1, the content change of polycyclic aromatic hydrocarbon is shown in table 2, after the fly ash is treated by the process of the embodiment, the leaching concentration of various heavy metals such as Pb, Zn, Cu, Cr, Cd and the like in the incineration fly ash of the household garbage is lower than the specified value of hazardous waste identification standard-leaching toxicity identification (GB5085.3-2007) (by adopting a sulfuric acid-nitric acid method for leaching toxicity of solid waste (HJ/T299-2007)), and is also lower than the specified value of pollution control standard for landfill (GB16889-2008) (by adopting an acetic acid buffer solution method for leaching toxicity of solid waste (HJ/T300-2007)), the content of various heavy metals in the hydrothermal waste liquid is extremely low (by adopting inductively coupled plasma mass spectrometry), the heavy metals are fixed in the fly ash and are not transferred to the waste liquid in a large scale to cause the transfer and secondary pollution of the heavy metals, the total content of 16 polycyclic aromatic hydrocarbons is reduced to 436.55 mu g/kg, the toxicity equivalent is reduced to 1.14 TEQ mu g/kg, and the contents are respectively reduced by 84.93 percent and 97.40 percent.
TABLE 1 Leaching toxicity (mg/L) of various heavy metals before and after fly ash treatment and their content (mg/L) in hydrothermal waste liquor
TABLE 2 fly ash treatment front and back 16 polycyclic aromatic content distribution (ug/kg) and toxicity equivalent (TEQ ug/kg)
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (5)
1. The method for performing hydrothermal harmless treatment on waste incineration fly ash is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a hydroxyapatite precursor liquid into fly ash, and then carrying out a first-step normal-pressure hydrothermal reaction at 40-50 ℃ to stabilize heavy metals in the fly ash, wherein the preparation method of the hydroxyapatite precursor liquid comprises the following steps: adding phosphoric acid and water into calcium carbonate substances, reacting to obtain a calcium phosphate salt solution, and then adding a calcium hydroxide solution to obtain hydroxyapatite precursor fluid, wherein the calcium carbonate substances are eggshells with inner membranes removed;
in the step (1), the solid-to-liquid ratio of the fly ash to the body fluid before hydroxyapatite is 1: 3-1: 5g/mL, and water is added before hydrothermal reaction to keep the solid-to-liquid ratio of the fly ash to the total liquid amount in the system at 1:10 g/mL;
(2) adding magnetic hydroxyapatite powder and hydrogen peroxide into the mixture obtained by the reaction in the step (1), and then carrying out a second-step microwave high-pressure hydrothermal reaction at 120-150 ℃ to further stabilize heavy metals in the fly ash and degrade polycyclic aromatic hydrocarbons; the preparation method of the magnetic hydroxyapatite powder comprises the following steps: mixing trisodium citrate and FeCl3·6H2Adding O and urea into water, then adding a polyacrylic acid solution, then adding a hydroxyapatite precursor solution, then carrying out high-pressure hydrothermal reaction at 160-180 ℃, carrying out solid-liquid separation after the reaction, drying, and grinding to obtain magnetic hydroxyapatite powder;
in the step (2), the mass ratio of the magnetic hydroxyapatite powder to the fly ash is 1: 15-1: 20, and H in hydrogen peroxide2O2The ratio of the fly ash to the fly ash is 0.003-0.005 mol/g.
2. The method for the hydrothermal innocent treatment of waste incineration fly ash according to claim 1, characterized in that: in the step (1), the time of the first-step normal-pressure hydrothermal reaction is 10-12 hours; in the step (2), the time of the microwave high-pressure hydrothermal reaction in the second step is 0.5-1 hour.
3. The method for the hydrothermal innocent treatment of waste incineration fly ash according to claim 1, characterized in that: in the step (2), the mixture obtained by the microwave high-pressure hydrothermal reaction in the second step is cooled to room temperature, then solid-liquid separation is carried out to obtain a fly ash hydrothermal reactant and waste liquid, the fly ash hydrothermal reactant is dried, and then the magnetic hydroxyapatite powder is recovered through ferromagnetic separation.
4. The method for the hydrothermal innocent treatment of waste incineration fly ash according to claim 3, characterized in that: in the step (2), after the microwave high-pressure hydrothermal reaction in the second step, the waste heat is recovered when the temperature is reduced to room temperature, and the waste heat is used for drying the fly ash hydrothermal reactant.
5. The method for the hydrothermal innocent treatment of waste incineration fly ash according to claim 1, characterized in that: in the step (1), the particle size of the fly ash is below 200 mu m; in the step (2), the particle size of the magnetic hydroxyapatite powder is less than 100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010553992.6A CN111672876B (en) | 2020-06-17 | 2020-06-17 | Method for performing hydrothermal harmless treatment on waste incineration fly ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010553992.6A CN111672876B (en) | 2020-06-17 | 2020-06-17 | Method for performing hydrothermal harmless treatment on waste incineration fly ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111672876A CN111672876A (en) | 2020-09-18 |
| CN111672876B true CN111672876B (en) | 2021-11-02 |
Family
ID=72455315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010553992.6A Active CN111672876B (en) | 2020-06-17 | 2020-06-17 | Method for performing hydrothermal harmless treatment on waste incineration fly ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111672876B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112893416B (en) * | 2021-02-05 | 2022-07-19 | 南京理工大学 | Recycling method of fly ash and fly ash hydrothermal treatment fluid |
| CN113350737A (en) * | 2021-06-08 | 2021-09-07 | 江苏乐尔环境科技股份有限公司 | Fly ash chelating agent capable of effectively inhibiting selenium leaching and preparation method thereof |
| CN113458127B (en) * | 2021-08-12 | 2022-07-05 | 杭州灰弘环保科技有限公司 | Cooperative disposal method for household garbage incineration fly ash and pyrite tailing |
| CN114212964B (en) * | 2021-12-13 | 2024-03-15 | 重庆德润环境有限公司 | River and lake dredging sediment recycling method |
| CN114425549B (en) * | 2021-12-16 | 2023-10-13 | 中南大学 | Method for microwave hydrothermal detoxification and synchronous synthesis of tobermorite by using waste incineration fly ash |
| CN114985413B (en) * | 2022-05-30 | 2023-03-21 | 常熟理工学院 | Improvement method for realizing harmless treatment of waste incineration fly ash based on magnesium phosphate cement |
| CN117358732B (en) * | 2023-10-26 | 2024-06-25 | 北京科技大学 | Fly ash resource product and treatment method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513138A (en) * | 2011-11-11 | 2012-06-27 | 深圳职业技术学院 | Multi-phase light-assisted Fenton catalyst and preparation method thereof |
| CN104741067A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method of carbonate hydroxylapatite-carbon aerosol composite material |
| CN109940029A (en) * | 2019-04-18 | 2019-06-28 | 重庆大学 | The method for being catalyzed polycyclic aromatic hydrocarbon in subcritical water oxidation degradation incineration of refuse flyash |
-
2020
- 2020-06-17 CN CN202010553992.6A patent/CN111672876B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513138A (en) * | 2011-11-11 | 2012-06-27 | 深圳职业技术学院 | Multi-phase light-assisted Fenton catalyst and preparation method thereof |
| CN104741067A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method of carbonate hydroxylapatite-carbon aerosol composite material |
| CN109940029A (en) * | 2019-04-18 | 2019-06-28 | 重庆大学 | The method for being catalyzed polycyclic aromatic hydrocarbon in subcritical water oxidation degradation incineration of refuse flyash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111672876A (en) | 2020-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111672876B (en) | Method for performing hydrothermal harmless treatment on waste incineration fly ash | |
| Jiang et al. | Disposal technology and new progress for dioxins and heavy metals in fly ash from municipal solid waste incineration: A critical review | |
| Chen et al. | Early solidification/stabilization mechanism of heavy metals (Pb, Cr and Zn) in Shell coal gasification fly ash based geopolymer | |
| CN103664126A (en) | Sludge curing treatment agent and method for treating sludge by use of curing treatment agent | |
| CN101941755B (en) | Modified coal ash, preparation method thereof and method thereof for treating humic acid | |
| CN101690934B (en) | Method for stabilizing fly ash from refuse incineration by combination of complementary type medicaments | |
| CN114425549B (en) | Method for microwave hydrothermal detoxification and synchronous synthesis of tobermorite by using waste incineration fly ash | |
| CN108421805A (en) | A kind of electrolytic manganese residues solidification and stabilization processing method | |
| CN111848130A (en) | Modified ceramsite capable of efficiently removing phosphorus and preparation method thereof | |
| CN101585522B (en) | Method for recovering phosphorus from urban mud anaerobic digestion solution | |
| Ji et al. | A review of metallurgical slag for efficient wastewater treatment: Pretreatment, performance and mechanism | |
| CN111960765B (en) | Evaporation residue curing process based on garbage leachate full-quantization treatment | |
| CN112374711A (en) | Sludge curing agent based on industrial waste residues and application method thereof | |
| Fan et al. | Subcritical hydrothermal treatment of municipal solid waste incineration fly ash: A review | |
| Liu et al. | Controlling role of CaClOH in the process of dechlorination for municipal solid incineration fly ash utilization | |
| Liang et al. | The resource utilization and environmental assessment of MSWI fly ash with solidification and stabilization: A review | |
| Xu et al. | Heavy metal stabilization in MSWI fly ash using an additive-assisted microwave hydrothermal method | |
| JP5976437B2 (en) | Earthwork materials | |
| JP2004050158A (en) | Heavy metal immobilizing material and method for treating contaminated soil | |
| CN101560008B (en) | Method for treating low-concentration phosphorus-containing wastewater | |
| Yang et al. | Immobilization of chromium in real tannery sludge via heat treatment with coal fly ash | |
| CN115138668A (en) | Fly ash treatment method | |
| CN114988826A (en) | Heavy metal combined contaminated soil solidification stabilization repair material and preparation method and use method thereof | |
| KR101766861B1 (en) | A Complex Adsorbent To Treat Ethyanolamine And Preparation Method Of The Same | |
| CN111558361A (en) | Industrial wastewater remediation material and application thereof, and treatment method of industrial wastewater containing cobalt-nickel divalent metal cations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240425 Address after: 401120 3-1 and 3-2, unit 7, building 15, Chongqing advertising industrial park, No. 18, Food City Avenue, baoshenghu street, Yubei District, Chongqing Patentee after: Chongqing vertical and horizontal Engineering Design Co.,Ltd. Country or region after: China Address before: 400044 No. 174 Sha Jie street, Shapingba District, Chongqing Patentee before: Chongqing University Country or region before: China |