WO2012145930A1 - 一种颗粒物中所含持久性有机污染物的处理方法 - Google Patents
一种颗粒物中所含持久性有机污染物的处理方法 Download PDFInfo
- Publication number
- WO2012145930A1 WO2012145930A1 PCT/CN2011/073562 CN2011073562W WO2012145930A1 WO 2012145930 A1 WO2012145930 A1 WO 2012145930A1 CN 2011073562 W CN2011073562 W CN 2011073562W WO 2012145930 A1 WO2012145930 A1 WO 2012145930A1
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- WO
- WIPO (PCT)
- Prior art keywords
- organic pollutant
- persistent organic
- water
- treating
- particulate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 80
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 23
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 144
- 239000010881 fly ash Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 47
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 34
- 239000013618 particulate matter Substances 0.000 claims description 28
- 239000003993 organochlorine pesticide Substances 0.000 claims description 24
- 229910001385 heavy metal Inorganic materials 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000002689 soil Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 9
- 239000000356 contaminant Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- -1 polychlorinated Benzene PCBs Chemical class 0.000 claims description 5
- 150000004677 hydrates Chemical class 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000004566 building material Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 150000002013 dioxins Chemical class 0.000 description 48
- 231100000331 toxic Toxicity 0.000 description 34
- 230000002588 toxic effect Effects 0.000 description 34
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 21
- 231100000770 Toxic Equivalency Factor Toxicity 0.000 description 17
- 231100000419 toxicity Toxicity 0.000 description 15
- 230000001988 toxicity Effects 0.000 description 15
- 238000002386 leaching Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 238000004056 waste incineration Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 7
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 7
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 7
- 229960002809 lindane Drugs 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000010813 municipal solid waste Substances 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 230000000185 dioxinlike effect Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006042 reductive dechlorination reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009284 supercritical water oxidation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 description 1
- 150000004826 dibenzofurans Chemical class 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
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000010583 slow cooling Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
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- 239000004071 soot Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
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- 235000020679 tap water Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NYVOYAFUSJONHU-UHFFFAOYSA-K trisodium;1,3,5-triazine-2,4,6-trithiolate Chemical compound [Na+].[Na+].[Na+].[S-]C1=NC([S-])=NC([S-])=N1 NYVOYAFUSJONHU-UHFFFAOYSA-K 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/24—Organic substances containing heavy metals
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S588/00—Hazardous or toxic waste destruction or containment
- Y10S588/901—Compositions
Definitions
- the invention belongs to the technical field of harmless treatment of dangerous solid wastes, and particularly relates to a method for treating persistent organic pollutants such as dioxins, organochlorine pesticides and polychlorinated biphenyls contained in particulate matter by hydrothermal reaction.
- persistent organic pollutants such as dioxins, organochlorine pesticides and polychlorinated biphenyls contained in particulate matter by hydrothermal reaction.
- PCBs PCBs.
- POPs Persistent organic pollutants referred to as POPs It is a class of compounds that may cause serious harm to the environment and human health. Their characteristics are: toxicity, refractory, fluidity, bioaccumulation and bioaccumulation. Even at very low exposure levels, POPs It is harmful to humans and animals, and POPs pollution has become a global environmental problem.
- Incineration is an important treatment method for garbage disposal.
- the fly ash incineration of garbage (including domestic garbage, industrial garbage and medical waste) generally contains a relatively high concentration of heavy metals and a certain concentration of dioxins, along with the domestic municipal solid waste incineration technology. Widely used, the amount of fly ash produced by incinerators is increasing.
- Dioxin (dioxin) is a kind of colorless, odorless and highly toxic fat-soluble substances. They are two kinds of organic compounds with many similar structures and similar properties.
- PCDDs polychlorinated dibenzo--- Dioxins
- PCDFs polychlorinated dibenzofurans
- POPs persistent organic pollutants
- organochlorine pesticides mainly include hexachlorocyclohexane (HCH) and DDT. (DDT) and hexachlorobenzene (HCB), etc., all made from benzene as raw material chlorinated, they are all POPs POPs
- HSH hexachlorocyclohexane
- DDT DDT
- HAB hexachlorobenzene
- POPs hexachlorobenzene
- the residual organochlorine pesticides in the soil will be transferred to the water body, pollute the drinking water, and even transfer to the replanted crops. Similar to the above pollutants, there are also PCBs.
- PCBs polychlorinated biphenyls
- PCBs also known as chlorinated biphenyls
- PCBs are formed by two benzene rings. The carbon atoms on the benzene ring are replaced by 1 to 10 chlorine atoms.
- the World Health Organization has defined the toxic equivalent factors of these 12 coplanar PCBs, similar to dioxins, so it is also known as dioxins. PCBs. Because of its stable chemical properties, good thermal conductivity and good insulation, it has been widely used as an insulating oil for capacitors, transformers, and other electrical equipment. It has been produced in many countries in China and the world in the 20th century. It has been banned since the beginning of the year, but it is estimated that it is present in the world's oceans, soils, and the total amount of PCBs in the world, ranging from 250,000 to 300,000 tons. The scope of pollution is wide.
- High temperature method includes a melt solidification method and a sintering method.
- the dioxins can be destroyed and prevented from being resynthesized, but the energy consumption is high, and the secondary soot and the flue gas need to be treated, and the treatment cost is difficult to promote. Implementation.
- a more effective method for treating POPs is supercritical water oxidation.
- Chinese invention patent ZL200510075433.4 discloses a supercritical water oxidation method which is very effective for treating waste solutions containing toxic organic substances. Under supercritical conditions (T c ⁇ 373.95 ° C, P c ⁇ 220.64 bar), organic matter, oxygen and water form a single homogeneous phase, so that the oxidation reaction proceeds rapidly, thus effectively destroying such as PCDD/Fs The organic matter; however, when the technology is suitable for engineering design and operation, the cost of the reactor and the maintenance cost are high.
- Supercritical water has enhanced solubility in organic matter, but its ability to dissolve inorganic substances is not high.
- Inorganic particles such as pharmaceuticals cannot function well in supercritical liquids unless very well dispersed, such as in fly ash.
- the dioxin-like contaminants in the granules can be oxidized under supercritical conditions, but the salts in the fly ash are likely to precipitate and foul on the walls, making the maintenance of the reactor difficult.
- researchers have considered the use of subcritical ( Subcritical ) Even high temperature hydrothermal environment decomposes dioxin.
- a hydrothermal treatment method for waste incineration fly ash is disclosed, which specifically includes the use of hydrothermal reaction to treat dioxins in waste incineration fly ash, adding terpenoids to promote decomposition of dioxin and wall anti-corrosion technology; The decomposition of dioxins under subcritical conditions, but not only to prevent pre-decomposition of antimony, but also to the cooling rate.
- particulate matter such as porous particles in activated carbon in incineration fly ash
- the adsorbed dioxins, PCBs have no chance to react with zero-valent iron.
- the object of the present invention is to provide a convenient and efficient method for eliminating persistent organic pollutants such as dioxins, organochlorine pesticides or the like in particulate matter under hydrothermal conditions. Methods for PCBs contamination.
- the object of the present invention is achieved by the following method.
- the method for treating persistent organic pollutants contained in the particles of the present invention is to subject the persistent organic pollutants in the particles to hydrothermal conditions in the presence of Fe 2+ and Fe 3+ . reaction.
- the persistent organic pollutants described in the present invention mainly refer to dioxins, organochlorine pesticides or PCBs contaminants.
- the POPs in the particles are reacted in a sub-critical or sub-critical sub-hydrothermal environment to be eliminated.
- Fe 2+ and Fe 3+ added to the reaction system react to form fresh, active iron oxides (Fe x O y ) and ferrites (Fe 3 O 4 insoluble). It has a strong catalytic effect on the decomposition of dioxins, organochlorine pesticides and PCBs; since they come from liquid Fe 2+ and Fe 3+ , they can fully contact with dioxin, organochlorine pesticides and PCBs. Therefore, good results can be achieved, and dioxin, organochlorine pesticides and PCBs can be eliminated to the utmost extent.
- the method of the invention is under subcritical or subcritical conditions (temperature below 373.95 °C, pressure below 220.64bar) is carried out to minimize the elimination of POPs and to achieve a decomposition rate of over 70%.
- the particulate matter forms a slurry mixture with water, and Fe 2+ salt and Fe 3+ salt, and the reaction is carried out at a temperature of 180 to 300 ° C under subcritical or subcritical conditions.
- Conditions below subcritical or subcritical are those in which the saturation pressure and temperature are below a critical value.
- the method of the present invention can eliminate the effects of these organic contaminants regardless of the temperature. When the temperature selection is too high, the project implementation is difficult; when the temperature is too low, the reaction is slow, the reaction time to achieve the same effect is relatively long, and the economy is not good. Therefore, it is preferably carried out at a temperature of 180 to 300 °C. reaction.
- the molar ratio of the Fe 2+ to the Fe 3+ is 1:4 to 3:1, more preferably 1:3 to 1.5:1.
- ORP oxidation-reduction potential
- the slurry mixture formed by the particulate matter and water has a higher oxidation-reduction potential (ORP) in the slurry mixture (positive and positive value Large), that is, the stronger the oxidizing property; when the molar ratio of Fe 2+ and Fe 3+ tends to 1:4, the lower the oxidation-reduction potential (ORP) of the slurry mixture (negative and negative) That is, the more the reducing property of the slurry mixture is.
- the Fe 2+ and the The total amount of Fe 3+ is from 1 wt% to 8 wt% of the particulate matter.
- the particulate matter may be first mixed with Fe 2+ salt and Fe 3+ salt and then mixed with water; or the particulate matter may be mixed with water before adding Fe 2+ salt.
- the pollutants in the particles can be sufficiently contacted with Fe 2+ and Fe 3+ to facilitate the decomposition reaction.
- the addition of water is to form an environment in which hydrothermal reaction can be carried out.
- the amount of water to be added one skilled in the art can make a reasonable selection according to the needs of the hydrothermal reaction.
- the weight ratio of the particulate matter to the water is 1:1 ⁇ 1:5, more preferably 1:1.5 ⁇ 1:3.5.
- the donor of the ferrous ion Fe 2+ and the iron ion Fe 3+ is also not particularly limited, and a compound of Fe 2+ and Fe 3+ , a salt or a hydrate thereof, and Fe may be provided. Both 2+ and Fe 3+ solutions can be used.
- the Fe 2+ salt is selected from one or more of ferrous sulfate, ferrous chloride, ferrous nitrate and hydrates thereof; the Fe 3+ salt is selected from the group consisting of iron sulfate, iron chloride, and nitric acid. One or more of iron and their hydrates.
- the donors of Fe 2+ and Fe 3+ are not limited to the iron salts listed above, and other solutions containing iron ions, such as iron-containing pickling waste liquid (mainly containing Fe 2+ ) formed by cleaning iron products with acid, may also be used. For the treatment of dioxins.
- the slurry mixture in order to avoid rapid large-scale evaporation of moisture, it is preferred that the slurry mixture is reacted under closed reaction conditions or under controlled pressure conditions, and at the completion of the reaction, no less than 5 wt% remains in the reactor.
- Water In the specific implementation, the water content in the reaction mixture is determined mainly by controlled venting (steam), controlling the reaction temperature to a suitable temperature difference that does not exceed the saturation temperature of the water at the corresponding pressure.
- the slurry mixture is reacted for 20 to 200 minutes.
- the decomposition rate of the persistent organic pollutants contained in the particles is more than 70%.
- the toxic equivalent of dioxin is reduced by more than 70%, and the decomposition rate of organochlorine pesticides and toxic PCBs is 70%. the above.
- the process of the invention can be carried out in a reactor suitable for carrying out a hydrothermal reaction, preferably in a high temperature closed reactor or in a pressure controlled reactor.
- the method further comprises the steps of:
- the reacted mixture may be directly preserved by liquid retention, the water may be naturally evaporated, or the reaction mixture may be liquid-solidified by suction filtration, pressure filtration or centrifugation. After separation, the obtained filter cake is cured until the water content meets the requirements, and then the building materials are used or directly landfilled.
- the method of the present invention can also combine the heavy metal stabilization technology in the prior art, stabilize the heavy metal contaminants therein by using a common heavy metal stabilizer, and further adjust the leaching of heavy metals.
- a common heavy metal stabilizer such as Zhang Qing, Chen Dezhen, etc., cement solidification experiment after waste incineration fly ash pretreatment, Nonferrous Metallurgy Design and Research, 2007, 28(2 ⁇ 3): 113 ⁇ 116+130; Zhou Bin, Hu Yuyan, et al. Comparison and research on chemical stabilization technology of waste incineration fly ash under the new standard, Journal of Environmental Science, 2009 , 29 ( 11 ): 2372 ⁇ 2377 ; Zhang Haijun, Yu Ying et al.
- a heavy metal stabilizer to stabilize heavy metals
- a raw material for raw materials to fire cement such as Zhang Xinhui, Shi Huisheng, a new process technology for developing waste incineration fly ash, cement technology, 2007, (3): 31-35
- a building material after sintering T. Mangialardi, Sintering of MSW fly ash for reuse As a concrete aggregate , Journal of Hazardous materials. 200l, B87:225-239
- the persistent organic pollutants are dioxins PCDD/Fs, organochlorine pesticides or polychlorinated biphenyls PCBs, as well as structure and properties PCDD/Fs-like substances, such as Cl, are replaced by fluorine (F); organochlorine pesticides include hexachlorocyclohexane (HCH), DDT (DDT), and hexachlorobenzene (HCB).
- the particulate matter may be from incineration fly ash from garbage (living, medical, industrial) incinerators, or may contain PCDD/Fs , organochlorine pesticides, PCBs contaminated soil, sediments, sediments, soils that need to be reclaimed in landfills that are no longer used, or contaminated river sediments and bay sediments.
- the hydrothermal condition refers to a condition in which the particulate matter is mixed with water to form a slurry, and the temperature of the reaction system and the saturation pressure of water are directly related.
- the Fe 2+ and Fe 3+ refer to iron ions having a valence state of divalent and trivalent.
- the slurry mixture refers to a liquid-solid mixture of particulate matter, divalent, ferric ion and water.
- the treatment or elimination of the POPs refers to the dechlorination of dioxins, organochlorine pesticides and PCBs into non-toxic, easily decomposable substances, such as 17 toxic dioxins dechlorinated into non-toxic, easily decomposable substances, and other dioxins turned into relatively structurally unstable substances; and organochlorine pesticides and 12 toxic PCBs
- the chlorine atom on the benzene ring is removed.
- the water may be industrial soft water, natural river water, other fresh water, tap water sterilized without chlorine gas.
- the Fe 2+ and Fe 3+ compounds used are cheap, safe, and widely available, and even Fe 2+ and Fe 3+ from waste liquid can be used;
- the liquid ferrous ions and ferric ions before the reaction are in a dissolved state, and are sufficiently dispersed on the surface of the particles to achieve the most complete contact; the reaction is carried out on the entire surface of the particles without being adsorbed and the like. The impact of this is that zero-valent iron cannot be achieved.
- the method of the present invention is simpler in operation and more effective in adding the catalyst from the outside or in the reaction process, and the reaction product adheres to the contaminated particulate matter, and has good leaching for other possible pollution such as heavy metals.
- the prevention and treatment effect does not require separation.
- the invention provides a simple and economical decomposition method of dioxin-like toxic organic substances, organochlorine pesticides and PCBs in the particulate matter, and has good implementation effects.
- the toxic dioxin concentration refers to the total concentration of 17 toxic dioxins
- total PCDD/Fs Concentration refers to the concentration of 210 dioxins
- the equivalent toxicity equivalent (TEQ) concentration is the equivalent toxicity equivalent of the concentration of toxic dioxins multiplied by the corresponding toxicity equivalent factor.
- the leaching of heavy metals in the treated material is in accordance with the environmental protection industry standard of the People's Republic of China HJ/T 300-2007' Solid Waste Leaching Toxicity Leaching Method Acetate Buffer Solution Method' Perform leaching test.
- the iron salts used are all commercially available except that the use of the ferric acid-containing waste liquid is specifically described.
- the concentration of toxic dioxins was 11463.3 ng/kg and the total PCDD/Fs was 47540 ng/kg.
- the dioxin-like organic pollutants contained in the incineration fly ash with a toxic equivalent concentration of 628.8 ng-TEQ/kg are treated and destroyed.
- the incineration fly ash and water are mixed at a weight ratio of 1:2, and then FeSO 4 and Fe 2 (SO 4 ) 3 are added , and the molar ratio of Fe 2+ /Fe 3+ is 1:2, and Fe 2+ and Fe are added.
- the total weight of 3+ is 5wt% of the weight of the incineration fly ash.
- the sample of the slurry mixture after the reaction was dried at 80 ° C for dioxin detection, and the results were as follows: the concentration of toxic dioxin was 436.5ng/kg, the equivalent toxicity concentration was 53.9ng-TEQ/kg, the total PCDD/Fs concentration was 3056ng/kg, and the total degradation rate of dioxins was 90%. the above.
- Example 2 The same incineration fly ash as in Example 1 was treated with only a saturated FeSO 4 solution and a saturated Fe 2 (SO 4 ) 3 solution, respectively, and the weights of Fe 2+ and Fe 3+ were respectively 5 wt% of the incineration fly ash.
- Example 1 When only saturated Fe 2 (SO 4 ) 3 was added, the equivalent toxic equivalent concentration of incineration fly ash after treatment was 300 ng-TEQ/kg, which was 457% higher than that of Example 1, and the concentration of toxic dioxins was 2316 ng/kg. Example 1 is 431% higher.
- Example 2 The same incineration fly ash as in Example 1 was subjected to stabilization of heavy metals at normal temperature (pharmaceutical treatment and wastewater separation) After that, the concentration of toxic dioxins was 11594.5 ng/kg, the concentration of isotoxic equivalents was 558 ng-TEQ/kg, and the concentration of total PCDD/Fs was 48019 ng/kg.
- the method of the invention is used to destroy dioxins.
- the incineration fly ash and water are mixed at a weight ratio of 1:1.5, and then a saturated FeSO 4 solution and saturated Fe 2 (SO 4 ) 3 are added, and the molar ratio of Fe 2+ /Fe 3+ is 1:1, and finally Fe
- the total weight of 2+ and Fe 3+ is 3wt% of the weight of the fly ash, and the mixture is sufficiently contacted by stirring to form a slurry mixture, which is then sent to the high temperature reactor, and the reaction temperature in the high temperature reactor is set to 290 ° C, after 60 minutes of reaction. ,cool down.
- the sample of the slurry mixture after the reaction was dried at 80 ° C to carry out dioxin detection, and the results were as follows: the concentration of toxic dioxin was 820ng/kg, the equivalent toxicity concentration is 85ng-TEQ/kg, the total PCDD/Fs concentration is 18999ng/kg, and the toxic equivalent degradation rate of dioxins is 84.8%. .
- Example 2 The same incineration fly ash as in Example 2; when the dioxin therein is destroyed by the method of the present invention, the incineration fly ash and water are mixed at a weight ratio of 1:1.5, and then an aqueous FeSO 4 solution and Fe 2 (SO 4 ) are added. 3 , the aqueous solution is added in a molar ratio of Fe 2+ /Fe 3+ of 1:1, and finally the total weight of Fe 2+ and Fe 3+ is 1 wt% of the weight of the fly ash.
- the reaction temperature in the subcritical hydrothermal reactor was set to 300 ° C, and after 20 min of reaction, it was cooled.
- the sample of the slurry mixture after the reaction was dried at 80 ° C to carry out dioxin detection, and the results were as follows: the concentration of toxic dioxin was 713ng/kg, the equivalent toxicity concentration was 80.1ng-TEQ/kg, the total PCDD/Fs concentration was 9891ng/kg, and the toxic equivalent degradation rate of dioxins was 85.6%. .
- the incineration fly ash and water are mixed at a weight ratio of 1:1.8, and then a FeSO 4 solution and a saturated Fe 2 (SO 4 ) 3 solution are added, according to Fe 2+ /Fe.
- the molar ratio of 3+ is 2.5:1, and the total weight of Fe 2+ and Fe 3+ is 8 wt% of the weight of the fly ash.
- the formed slurry mixture is sent to the hydrothermal reactor, and the reaction temperature in the hydrothermal reactor is set at 290 ° C for 75 min. After cooling.
- the sample of the slurry mixture after the reaction was dried at 80 ° C for dioxin detection.
- the results were as follows: the concentration of toxic dioxin was 656 ng/kg, and the concentration of the toxic equivalent was 71ng-TEQ/kg, the total PCDD/Fs concentration was 2189ng/kg, and the toxic equivalent degradation rate of dioxins was 98%.
- the incineration fly ash of an incineration plant has a dioxin content of 422 ng I-TEQ/kg, which contains 17
- the total concentration of toxic dioxins is 4963 ng/kg.
- the incineration fly ash and water are mixed at a weight ratio of 1:1.8, and then the Fe(NO 3 ) 2 solution and the Fe 2 (NO 3 ) 3 solution are added, according to Fe 2+ /
- the molar ratio of Fe 3+ was 1:2, and the total weight of Fe 2+ and Fe 3+ was 7 wt% of the weight of fly ash.
- the formed slurry mixture was sent to the reactor, and the reaction temperature in the reactor was 240 ° C, and the reaction was carried out for 72 min. After that, the slurry mixture after the reaction is cooled, and a small sample is dried and leached according to the standard HJ/T 300 method, and the leaching of the heavy metal Pb reaches 1.15 mg/L, so after the slurry mixture is cooled, it is added. 1wt% disodium hydrogen phosphate stabilizes heavy metals.
- the treated sample is dried at 80 ° C for dioxin detection while following the standard HJ/T 300
- the method is performed by leaching test.
- the results were as follows: the concentration of toxic dioxin was 1600 ng/kg, the concentration of isotoxic equivalent was 100 ng-TEQ/kg, and the degradation rate of toxic equivalent concentration of dioxins was 76.3%. . Pb leaching 241ug/L.
- the soil in a certain area was contaminated by PCBs, and the concentration of tested PCBs reached 11 mg/kg.
- the organic contaminant is treated by the method of the invention, the soil and water are mixed at a weight ratio of 1:3.5, and then a saturated FeSO 4 solution and a saturated Fe 2 (NO 3 ) 3 solution are added, according to the molar ratio of Fe 2+ /Fe 3+ The ratio is 1:2.5.
- the total weight of Fe 2+ and Fe 3+ is 6wt% of the weight of fly ash.
- a small amount of lime is added to adjust the pH to 8 ⁇ 9.6.
- the formed slurry mixture is sent to the hydrothermal reactor, and the reaction temperature in the hydrothermal reactor is set to 300 ° C, and the reaction is 200 min. After that, the slurry mixture of the soil-water after the reaction is cooled.
- PCBs The concentration was 72 ug/kg, the total PCDD/Fs concentration was not detected, and the decomposition rate of PCBs was 99.3%.
- the soil in a certain area was contaminated after long-term use of pesticides.
- the total DDT content was 57.6 ug/kg; the total HCH content was 50.6 ug / kg, and the total HCB content was 12.2 ug/kg.
- the soil and water are mixed at a weight ratio of 1:5, and a saturated FeCl 2 solution and a saturated Fe 2 (SO 4 ) 3 solution are added according to a molar ratio of Fe 2+ /Fe 3+ .
- the total weight of Fe 2+ and Fe 3+ is 8 wt% of the weight of the incineration fly ash, and a little lime is added to bring the pH of the system between 6 and 7.5.
- the formed slurry mixture is sent to a high temperature reactor, and the reaction temperature in the high temperature reactor is set to 180 ° C, and the reaction pressure is 10 bar. After 200 min, the slurry mixture of the soil-water after the reaction was cooled.
- the sample of the reacted mixture was dried at 40 ° C to measure total DDT, total HCH and total HCB.
- the results are as follows: The DDT content is 16.2 ug/kg; the total HCH content is 14.6 ug/kg, the total HCB concentration is 3.6 ug/kg, and the total decomposition rate of organochlorine pesticides is 71.4%.
- fly ash In an industrial waste incineration plant, its flue gas purification system uses a semi-dry method + filter bag to collect dust, and the daily output of fly ash is 1 ton. It has been tested that its ash content in fly ash is as high as 6500 ng I-TEQ/kg, containing toxic dioxins at a concentration of 24,630 ng/kg.
- the pickling waste liquid of the steel cable factory near the incineration plant is cleaned with dilute sulfuric acid and contains Fe 2+ 13g/L, which is mixed with the incineration fly ash to make fly ash.
- the weight ratio of water is 1:2, and then the Fe 2 (SO 4 ) 3 solid is added, and the molar ratio of Fe 2+ /Fe 3+ is 1:2, and the total weight of Fe 2+ and Fe 3+ is fly. 7.8 wt% of ash weight.
- the formed slurry mixture is sent to a hydrothermal reactor, and the reaction temperature in the hydrothermal reactor is 300 ° C, and the reaction is 65 min. After that, the slurry mixture after the reaction is cooled, and a small sample is dried and leached according to the standard HJ/T 300 method, and the leaching of the heavy metal Pb reaches 2.1 mg/L, so after the slurry mixture is cooled, it is added. 1.5wt% of commercially available heavy metal stabilizer TMT-18, stable heavy metals.
- the treated sample is dried at 80 ° C for dioxin detection while following the standard HJ/T 300
- the method is performed by leaching test.
- the results were as follows: the concentration of toxic dioxins was 246.4 ng/kg, the concentration of isotoxic equivalents was 99 ng-TEQ/kg, and the total decomposition rate of 17 toxic dioxins was 99%.
- the toxic equivalent degradation rate of dioxins was 98.5%.
- the treated incineration fly ash meets the requirements of sanitary landfill.
- the fly ash of the industrial waste incineration plant in Example 8 was subjected to a subcritical hydrothermal reaction at 300 ° C and the weight of the zero-valent iron powder was 7.2 wt% of the weight of the fly ash. During the process, the temperature was found to be 300 ° C. There is a continuous increase, and it is necessary to continuously remove the gas. After 1.5 hours of reaction, it is divided into 1) flashing and quenching, and then need to bag to collect dust to prevent dust; and 2) slow cooling in the water-cooled jacket of the reactor.
- the FeSO 4 .7H 2 O/Fe 2 (SO 4 ) 3 solid is mixed with the incineration fly ash, and water is added to: 1) Fe 2+ /Fe 3+
- the molar ratio is 1:2, 2) the ratio of ash:water is 1:3, 3) the total weight of Fe 2+ and Fe 3+ is 7.2 wt% of the weight of fly ash.
- the formed slurry mixture is sent to a subcritical hydrothermal reactor, the temperature in the reactor is 300 ° C, and the pressure is basically stable during the reaction. After 65min, the slurry mixture after the reaction is also cooled in two ways. 1) flashing and cooling rapidly, and then bagging is required to collect dust to prevent dust; 2 In the water-cooled jacket of the reactor, the water is cooled; after cooling, drying, the test found: 1) After the treatment of the rapidly cooled fly ash, the concentration of 17 toxic dioxin is 249.8 ng / kg, and the equivalent toxicity concentration is 130ng-TEQ/kg, the total decomposition rate of 17 toxic dioxins was 98.98%; the equivalent toxicity degradation rate of dioxin was 98%.
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Description
本发明属于危险固体废弃物无害化处理技术领域，具体涉及一种利用水热反应处理颗粒物中所含持久性有机污染物如二恶英类物质、有机氯农药和多氯联苯
PCBs 的方法。
持久性有机污染物简称 POPs
，是可能对环境和人体健康造成严重危害的一类化合物。它们的特性主要有：毒性、难降解性、流动性、生物累积性和生物富集性。即使在很低的暴露程度时， POPs
对人体和动物都是有害的， POPs 污染已经成为全球性环境问题。
焚烧是垃圾处置的重要处理手段，垃圾（包括生活垃圾、工业垃圾和医疗垃圾）焚烧的飞灰一般都含有较高浓度的重金属和一定浓度的二恶英，随着国内城市固体垃圾焚烧技术的广泛应用，焚烧炉产生的飞灰量日益增加。二恶英
(dioxin) 是一类无色无味、毒性严重的脂溶性物质，它们是结构和性质都很相似的包含众多同类物的两大类有机化合物，化学名称分别叫多氯二苯并 - 对 -
二恶英 (PCDDs) 和多氯二苯并呋喃 (PCDFs) ，总称 PCDD/Fs ，它们共有 210 个同族异构体，是持久性有机污染物 POPs
中的重要种类，在焚烧飞灰、被污染的土壤中存在，常温下难以分解。
另外，在我国有机氯农药的污染日益严重，有机氯农药 (OCPs) ，主要包括六六六 (HCH) 、滴滴涕
(DDT) 和六氯苯 (HCB) 等，均由苯为原料氯代制成，它们均属于持久性有机污染物 POPs
的范畴，使用以后，土壤中残留的有机氯农药会转移到水体中，污染饮用水 , 甚至转移到再种植的作物中。与上述污染物类似的还有多氯联苯
(polychlorinated biphenyls,PCBs) ，又称氯化联苯，由两个苯环联结而成，苯环上的碳原子被 1~10 个氯原子取代，共有 209
种同族异构体，其中 12 种共平面 PCBs 具有毒性。世界卫生组织规定了这 12 种共平面 PCBs 的毒性当量因子，同二恶英类似，因此又称为类二恶英
PCBs 。由于它化学性质稳定、热传导性好、绝缘性好，曾大量用于电容器、变压器、等电力设备作为绝缘油，我国以及世界上很多国家都生产过，于 20 世纪 70
年代起被禁止，但是由于不易分解，据估计存在于全世界海洋、土壤、大气中的 PCB 总量达到 25 ～ 30 万吨以上 , 污染的范围很广。
现有的持久性有机污染物的处置方法主要有高温法、超临界流体萃取 (SCFE) 、超临界水氧化 (SCWO)
法、利用紫外光降解的方法、生物降解法、零价铁还原脱氯技术、中低温热处理法、以及催化还原法等，这些方法均存在一定的缺陷或局限性。例如高温法包括熔融固化法和烧结法，条件控制良好时可以销毁二恶英并防止其再合成，但是能耗很高，且需要对二次烟尘和烟气进行处理，处理成本较高难以推广实施。
比较有效的处理持久性有机污染物的方法是超临界水氧化法，如中国发明专利 ZL200510075433.4
公开了一种超临界水氧化法，对于处理含毒性有机物的废物溶液非常有效。在超临界反应条件下 (T c ≥373.95℃, P
c ≥220.64bar), 有机物、氧和水形成了单一的均相，以使氧化反应迅速地进行，从而有效地销毁如 PCDD/Fs 之类的有机物 ;
然而当该技术适合工程设计和操作的要求时，反应器的成本和维护费用昂贵。
超临界水对有机物的溶解能力加强，但是对无机物的溶解能力不高，无机物颗粒如药剂在超临界液体中不能被很好地起作用，除非得到非常良好的分散，例如含在飞灰颗粒中的二恶英类污染物可在超临界条件下被氧化，但是飞灰中的盐却被可能析出而在壁面结垢，给反应器的维护造成困难。为了利用水在高温下具有溶解和破坏有机物的能力但是又避免特别高要求的反应或者设备条件，研究人员考虑利用亚临界（
subcritical
）甚至是高温水热环境分解二恶英类物质。水的温度越高，其离子活度积越大，对有机物的氧化或者破坏能力越强，因此高温水热环境或者亚临界环境对有毒的有机物如二恶英的分解氧化能力不如超临界，加强高温水热或者亚临界条件环境下，有机污染物的分解或者氧化效率是非常有必要的。中国专利申请
200710040771.3
公布了一种垃圾焚烧飞灰的水热处理方法，具体包括利用水热反应处理垃圾焚烧飞灰中的二恶英时，加入肼类物质促进二恶英的分解与壁面防腐蚀技术；该技术促进了在亚临界条件下二恶英的分解，但是实施时不仅要防止肼的预分解，也对冷却速度有要求。
此外，受到大家关注的还有零价铁还原脱氯技术，它既有在常温下进行的 (
陈少瑾，梁贺升，零价铁还原脱氯污染土壤中 PCBs 的实验研究生态环境学报 2009 ， 18(1) ： 193-196) ，也有在水热条件下进行的（ YAK
H K ， WENCLAWIAK B W ， CHENG I F ， et a1 ． Reductive dechlorination of
polychlorinated biphenyls by zero valent iron in subcritical water ，
Environmental Science and Technology ， 1999 ， 33: 1307-1310 ； Nikolay Kluyev,
Andrei Cheleptchikov et al., Reductive dechlorination of polychlorinated
dibenzo-p-dioxins by zerovalent iron in subcritical water, Chemosphere 2002,46:
1293-1296 ），但是固态的零价铁 Fe0 在水 / 颗粒物的混合物中与颗粒物以及溶出的 PCDD/Fs 、 PCB
等并不能良好的接触，因此效率的提高受到影响；而且由于 Fe 0
在亚临界水中易于生成氢，使反应容器有增压的危险、带来运行中的安全隐患。此外，零价铁还原脱氯技术对氯取代程度小的 PCBs
以及二恶英类物质很难实现脱氯，对氯取代程度较高的 PCBs
和二恶英类物质才有一定的还原脱氯作用，脱氯反应是在零价铁颗粒表面进行的，当颗粒物（如焚烧飞灰中的活性炭那样的多孔颗粒物）对 PCBs
、二恶英有很强的吸附作用时，被吸附的二恶英、 PCBs 则没有机会与零价铁反应。
为了更经济、安全高效地处理固体颗粒物中的有机污染物，本领域的技术人员致力于开发一种处理固体颗粒物中所含的二恶英类有机污染物、有机氯农药、 PCBs
的方法。
本发明的目的是提供一种便捷、高效地在水热条件下消除颗粒物中持久性有机污染物如二恶英、有机氯农药或者
PCBs 污染物的方法。
本发明的目的是通过如下方法实现的。
具体的，本发明的颗粒物中所含持久性有机污染物的处理方法，是在 Fe 2+ 和
Fe 3+
存在的条件下，使所述颗粒物中的持久性有机污染物在水热条件下进行反应。在本发明中所述的持久性有机污染物主要是指二恶英类、有机氯农药或者 PCBs
污染物。所述颗粒物中的持久性有机污染物在亚临界或亚临界以下的水热环境下反应，得以消除。
在水热条件下 , 加入反应体系的 Fe 2+ 和 Fe 3+
反应生成了新鲜的、富有活性的的铁氧化物 (Fe x O y ) 和铁氧体 (Fe 3
O 4 不溶态 ) ，它们对二恶英类污染物、有机氯农药和 PCBs 的分解有强烈的催化作用；由于它们来自液态的 Fe
2+ 和 Fe 3+ ，可以与含有二恶英、有机氯农药和 PCBs
的颗粒物充分接触，因而能达到很好的效果，使二恶英、有机氯农药和 PCBs 得以最大程度的消除。
本发明的方法在亚临界或亚临界以下的条件下 ( 温度低于 373.95 ℃ 、压力低于
220.64bar) 进行，使持久性有机污染物得以最大程度的消除，可使它们的分解率达到 70% 以上。
本发明的方法中，所述颗粒物与水、以及 Fe 2+ 盐和 Fe
3+ 盐形成浆状混合物，在亚临界或亚临界以下的条件下，优选在 180~300℃
的温度下进行反应。亚临界或亚临界以下的条件是指饱和压力与温度低于临界数值的条件。实际上，在 Fe 2+ 和
Fe3+
同时存在和水热条件下，不管温度如何选择，本发明的方法都可以起到消除这些有机污染物的效果。当温度选择过高时，工程实施困难较大；温度过低时，反应较慢，达到相同效果的反应时间会相对较长，经济性不好，因此，优选在
180~300℃ 的温度下进行反应。
在本发明的方法中，优选所述 Fe 2+ 和所述 Fe 3+
的摩尔比为 1:4~3:1 ，更优选为 1:3 ~1.5:1 。当所述 Fe 2+ 和 Fe 3+ 的摩尔比趋于
3:1 时，所述颗粒物与水形成的浆状混合物，在浆状混合物氧化还原电位 (ORP) 越高 ( 为正且正值越大 ) ，也就是氧化性越强；当所述 Fe
2+ 和 Fe 3+ 的摩尔比趋于 1:4 时，浆状混合物氧化还原电位 (ORP) 越低 ( 为负且负值越大 )
，也就是所述浆状混合物还原性越强。
在本发明的方法中， Fe 2+ 和 Fe 3+
的总用量越多，污染物分解的效果越好，但考虑到经济性、*** pH 的调整的因素，优选所述 Fe 2+ 和所述 Fe
3+ 的总量为所述颗粒物的 1wt% ~ 8wt% 。
在本发明的方法的具体实施时，可先将所述颗粒物与 Fe 2+ 盐和 Fe
3+ 盐混合后再与水混合；或者先将所述颗粒物与水混合后，再加入 Fe 2+ 盐和 Fe 3+
盐的混合物搅拌或者 Fe 2+ 的溶液和 Fe 3+ 的溶液搅拌，形成浆状混合物，然后加热升温在 180~300℃
下反应，使二恶英、有机氯农药、 PCBs 进行反应。这样，可使颗粒物中的污染物能充分接触 Fe 2+ 和 Fe
3+ ，以利于进行分解反应。
在本发明的方法中，水的加入是为了形成可进行水热反应的环境，对于水的加入量，本领域人员可以根据水热反应的需要进行合理的选择。优选所述颗粒物与所述水的重量比为
1:1~1:5 ，更优选 1:1.5~1:3.5. 。
在本发明的方法中，对于亚铁离子 Fe 2+ 和铁离子 Fe
3+ 的供体也没有特别的限制，可以提供 Fe 2+ 和 Fe 3+ 的化合物、盐或其水合物、及含有
Fe 2+ 和 Fe 3+ 的溶液都可以使用。优选所述 Fe 2+
盐选自硫酸亚铁、氯化亚铁、硝酸亚铁和它们的水合物中的一种或多种；所述 Fe 3+
盐选自硫酸铁、氯化铁、硝酸铁和它们的水合物中的一种或多种。 Fe 2+ 和 Fe 3+
的供体并不限于上述列出的铁盐，其他含有铁离子的溶液，如用酸清洗铁制品形成的含铁酸洗废液（主要含 Fe 2+
）也可用于处理二恶英。
在本发明的方法中，为避免水分的快速大量蒸发，优选所述浆状混合物在密闭的反应条件下或者在控压条件下反应，在反应完毕时，反应器内应残留不少于 5wt%
的水。在具体实施时，主要是通过受控制的放气（汽），控制反应温度不超过对应压力下水的饱和温度的合适的温度差，来确定反应混合物中的水含量。
在本发明的方法中，优选所述浆状混合物反应 20~200min
，使所述颗粒物中所含的持久性有机污染物的分解率达到 70% 以上。如二恶英的等毒性当量降低达到 70% 以上，有机氯农药、有毒 PCBs 的分解率达到 70%
以上。
本发明的方法可以在适合进行水热反应的反应器中进行，优选在高温密闭反应器中或者在可控压的反应器中进行。
在本发明的方法的优选实施方案中，还包括以下步骤：
将所述反应后的混合物冷却；然后可将所述反应后的混合物保留液体直接养护、使水份自然蒸发，或通过抽滤、压滤或者离心的方式将所述反应后的混合物进行液固分离，所得滤饼养护至含水率满足要求后进行建材化利用或进行直接填埋处理。
当所述颗粒物中还含有重金属污染物时，本发明的方法也可以结合现有技术中的重金属稳定技术，采用常用的重金属稳定剂稳定其中的重金属污染物，进一步调节重金属的浸出情况。如张清，陈德珍等，垃圾焚烧飞灰预处理后水泥固化实验研究，
有色冶金设计与研究 ， 2007, 28(2~3) ： 113~116+130 ；周斌，胡雨燕等，新标准下垃圾焚烧飞灰化学稳定技术的比选和研究，环境科学学报，
2009 ， 29 （ 11 ）： 2372~2377 ；张海军，于颖等，采用巯基捕收剂稳定化处理垃圾焚烧飞灰中的重金属，环境科学， 2007, 28(8):
1899~1904 ；中国发明专利申请 200910197214.1 ,' 一种互补型药剂配合稳定垃圾焚烧飞灰的方法 ' 等公开的技术。
优选地，将所述反应后的颗粒物 -
水混合物冷却后，与重金属稳定剂混合，以稳定重金属；或者作为生料的原料烧制水泥（如张新辉，施惠生，开发垃圾焚烧飞灰的新型工艺技术，水泥技术，
2007,(3):31-35 ）或烧结后做为建材（ T. Mangialardi ， Sintering of MSW fly ash for reuse
as a concrete aggregate ， Journal of Hazardous materials. 200l, B87:225-239
）。
本发明的一个具体实施方案，包含以下步骤：
（ 1 ）将含有二恶英 PCDD/Fs 、有机氯农药和 PCBs
的颗粒物（如焚烧飞灰、被污染土壤、沉积物、底泥等）与二价亚铁盐及三价铁盐混合后再加水混合，或者所述颗粒物与水混合后再分别加入含有二价铁离子 Fe
2+ 的溶液和含有三价铁离子 Fe 3+ 的溶液，或者将所述颗粒物直接与二价铁离子 (Fe 2+ )
的水溶液和三价铁离子 (Fe 3+ ) 的水溶液混合，最终使颗粒物与水的重量比例在 1:1~ 1:5 ；同时控制 Fe
2+ 和 Fe 3+ 的摩尔比在 1: 4 ~ 3:1 之间， (Fe 2+ 和 Fe
3+ ) 的总用量占所述颗粒物的 1.0wt% ~ 8wt% 。
（ 2 ）将上述混合物送入高温反应器内，将所述反应器内的混合物加热到 180~300℃
，让其处于密闭的反应条件下或者控压的反应条件下反应 20~200min ；
（ 3 ）反应结束后，将反应物冷却后排出；
（ 4 ）根据需要可以进一步调节其中含有的其他重金属的浸出情况。
在本发明的方法中，各用语的含义如下：
所述持久性有机污染物为二恶英 PCDD/Fs 、有机氯农药或多氯联苯 PCBs ，以及结构和性质与
PCDD/Fs 相似的物质，例如其中的 Cl 被氟 (F) 所代替；有机氯农药包括六六六 (HCH) 、滴滴涕 (DDT) 和六氯苯 (HCB) 等。
所述颗粒物可以来自垃圾 ( 生活、医疗、工业 ) 焚烧炉的焚烧飞灰，也可以是含有 PCDD/Fs
、有机氯农药、 PCBs 污染的土壤、沉积物、底泥，不再使用的垃圾填埋场需要修复的土壤，或被污染的河道底泥和海湾沉积物等。
所述水热条件是指所述颗粒物与水混合成浆状、反应***的温度和水的饱和压力直接相关联的条件。
所述 Fe 2+ 和 Fe 3+
是指化合价态为二价和三价的铁离子。
所述浆状混合物是指颗粒物、二价、三价铁离子与水形成的液固混合物。
所述持久性有机污染物的处理或消除是指二恶英、有机氯农药和 PCBs 脱氯转变成无毒、易分解的物质，例如
17 种有毒性二恶英化合物脱氯变成无毒、易分解的物质，以及其它的二恶英类物质转变为结构相对不稳定的物质；以及有机氯农药和 12 种有毒 PCBs
脱去其苯环上的氯原子。
所述的水可以是工业用软水，自然界河水、其它淡水、未经氯气消毒的自来水。
本发明的方法的有益效果如下：
1）
本发明的方法中，使用的Fe2+和Fe3+的化合物便宜、安全，来源广泛，甚至可以使用来自废液中的Fe2+和Fe3+；
2） 本发明的方法中，在反应过程中不需加入其它处理助剂，便于反应器的安全运行和维护；
3）
本发明的方法中，反应前液态二价铁离子和三价铁离子是溶解态的，在颗粒的表面充分分散，达到最充分的接触；使反应在颗粒物的整个表面进行，不受吸附等因素的影响，这是零价铁不能实现的。
4）
本发明的方法与任何自原料中或者反应过程中从外部加入催化剂相比，操作更简单，效果更优化，且反应产物附着在被污染的颗粒物上，对其它可能的污染如重金属的浸出有良好的防治作用，不需要分离。
5）
本发明提供了一种简便、经济的颗粒物中二恶英类毒性有机物、有机氯农药和PCBs的分解方法，并有很好的实施效果。
下面通过具体实施例来详细说明本发明的实施方案和效果。
在本发明的具体实施例中，有毒二恶英浓度是指 17 种有毒的二恶英异构体的总浓度，总 PCDD/Fs
浓度是指 210 种二恶英异构体浓度，等毒性当量（ TEQ ）浓度是指有毒二恶英的浓度乘以对应的毒性当量因子后相加转换而成的等毒性当量。
一般标准检测法 ( 如美国环保局的 EPA 1613 的方法和日本工业用的 JIS K0311 方法 )
采用高分辨率的色谱 - 质谱联检法，即 HRGC/HRMS 法，通常检测报告只给出 17
种有毒二恶英异构体浓度和转化后的等毒性当量浓度，但该检测方法也可检测出 210 种异构体的总浓度。本发明的方法中， 210
种异构体的总浓度也是使用该检测方法测出的。
对于有机氯农药和对于 PCBs 来说主要指其质量浓度 , 检测采用美国 EPA METHOD 508.1
，即配电子捕获检测器 ECD 的气相色谱方法。
在本发明的具体实施例中，处理后颗粒物重金属的浸出按照中华人民共和国环境保护行业标准 HJ/T
300-2007' 固体废物浸出毒性浸出方法醋酸缓冲溶液法 ' 进行浸出检验。
在本发明的具体实施例中，除特别说明使用含铁酸洗废液外，所用的铁盐均为市售产品。
实施例 1
对含有有毒二恶英浓度为 11463.3ng/kg 、总 PCDD/Fs 的浓度为 47540ng/kg
、等毒性当量浓度为 628.8ng-TEQ/kg 的焚烧飞灰中所含的二恶英类有机污染物进行处理，使之销毁。
将焚烧飞灰和水按重量比 1:2 混合，再加入 FeSO4 和
Fe2(SO4)3, 按照 Fe2+/Fe3+
的摩尔比为 1:2, 并使 Fe2+ 和 Fe3+ 的总重量为焚烧飞灰重量的 5wt%
，在混合器中混合搅拌形成浆状混合物后，送入水热反应器，设置高温反应器内的反应温度为 290 ℃ 、压力为 74.42bar ，反应 1h 后，冷却。
将反应后的浆状混合物样品在 80 ℃ 下烘干，进行二恶英检测，结果如下：有毒二恶英浓度是
436.5ng/kg , 等毒性当量浓度为 53.9ng-TEQ/kg, 总 PCDD/Fs 的浓度为 3056ng/kg ，二恶英的总降解率均在 90%
以上。
对比例 1
分别仅加入饱和 FeSO4 溶液和饱和
Fe2(SO4)3 溶液处理与实施例 1 相同的焚烧飞灰，且使
Fe2+ 和 Fe3+ 的重量分别为焚烧飞灰的 5wt% 。
仅加入 FeSO4 时，处理后焚烧飞灰的等毒性当量浓度为
143ng-TEQ/kg, 比实施例 1 高出 167% ；有毒二恶英总浓度是 1434ng/kg, 比实施例 1 高出 229% 。
仅加入饱和 Fe2(SO4)3 时 ,
处理后焚烧飞灰的等毒性当量浓度为 300ng-TEQ/kg, 比实施例 1 高出 457% ；有毒二恶英浓度是 2316ng/kg, 比实施例 1 高出
431% 。
实施例 2
与实施例 1 相同的焚烧飞灰， 经过常温下重金属的稳定化处理 ( 药剂处理和废水分离 )
后，所含有毒二恶英浓度为 11594.5ng/kg, 等毒性当量浓度降为 558ng-TEQ/kg, 总 PCDD/Fs 浓度为 48019ng/kg
，使用本发明的方法来销毁二恶英。
将该焚烧飞灰和水按重量比 1:1.5 混合，再加入饱和 FeSO4 溶液和饱和
Fe2(SO4)3, 按照 Fe2+/Fe3+
的摩尔比为 1:1 加入 , 最后 Fe2+ 和 Fe3+ 的总重量为飞灰重量的 3wt%
，搅拌使之充分接触，形成浆状混合物后，送入高温反应器，设置高温反应器内的反应温度为 290℃ ，反应 60min 后，冷却。
将反应后的浆状混合物样品在 80℃ 下烘干，进行二恶英检测，结果如下：有毒二恶英浓度是
820ng/kg, 等毒性当量浓度为 85ng-TEQ/kg, 总 PCDD/Fs 的浓度为 18999ng/kg ，二恶英的等毒性当量降解率为 84.8%
。
实施例 3
与实施例 2 相同的焚烧飞灰；利用本发明的方法来销毁其中的二恶英时，将焚烧飞灰和水按重量比 1:1.5
混合，再加入 FeSO4 水溶液和 Fe2(SO4)3, 水溶液，按照
Fe2+/Fe3+ 的摩尔比为 1:1 加入 , 最后 Fe2+ 和
Fe3+ 的总重量为飞灰重量的 1wt% 。设置亚临界水热反应器内的反应温度为 300℃ ，反应 20min 后，冷却。
将反应后的浆状混合物样品在 80℃ 下烘干，进行二恶英检测，结果如下：有毒二恶英浓度是
713ng/kg, 等毒性当量浓度为 80.1ng-TEQ/kg, 总 PCDD/Fs 的浓度为 9891ng/kg ，二恶英的等毒性当量降解率为 85.6%
。
实施例 4
某焚烧厂的焚烧飞灰，其中二恶英含量为 3900ng I-TEQ/kg, 有毒二恶英浓度为
13555ng/kg 。
利用本发明的方法来销毁其中的二恶英时，将焚烧飞灰和水按重量比 1:1.8 混合，再加入
FeSO4 溶液和饱和 Fe2(SO4)3 溶液，按照
Fe2+/Fe3+ 的摩尔比为 2.5:1 加入 , 最后 Fe2+ 和
Fe3+ 的总重量为飞灰重量的 8wt% 。
将形成的浆状混合物送入水热反应器，设置水热反应器内的反应温度为 290℃ ，反应 75min
后，冷却。将反应后的浆状混合物样品在 80℃ 下烘干，进行二恶英检测，结果如下：有毒二恶英浓度是 656ng/kg, 等毒性当量浓度为
71ng-TEQ/kg, 总 PCDD/Fs 的浓度为 2189ng/kg ，二恶英的等毒性当量降解率为 98% 。
实施例 5
某焚烧厂的焚烧飞灰，其二恶英含量为 422ng I-TEQ/kg, 所含 17
种有毒的二恶英异构体的总浓度为 4963ng/kg 。
利用本发明的方法来销毁二恶英时，将焚烧飞灰和水按重量比 1:1.8 混合，再加入
Fe(NO3)2 溶液和 Fe2(NO3)3
溶液 , 按照 Fe2+/Fe3+ 的摩尔比为 1:2 加入 , Fe2+ 和
Fe3+ 的总重量为飞灰重量的 7wt% 。
将形成的浆状混合物送入反应器，反应器内的反应温度为 240℃ ，反应 72min
后，将反应后的浆状混合物冷却，取少许样品干燥后按照标准 HJ/T 300 方法浸滤，重金属 Pb 的浸出达到 1.15mg/L ，因此在浆状混合物冷却后再加入
1wt% 的磷酸氢二钠，稳定重金属。
将处理后的样品在 80℃ 下烘干，进行二恶英检测，同时按照标准 HJ/T 300
的方法进行浸出检验。结果如下：有毒二恶英浓度是 1600ng/kg, 等毒性当量浓度为 100ng-TEQ/kg, 二恶英的等毒性当量浓度降解率为 76.3%
。 Pb 的浸出 241ug/L 。
实施例 6
某地土壤被 PCBs 污染 , 经检测 PCBs 浓度达 11mg/kg
。利用本发明的方法来处理有机污染物时，土壤和水按重量比 1:3.5 混合，再加入饱和 FeSO4 溶液和饱和
Fe2(NO3)3 溶液 , 按照
Fe2+/Fe3+ 的摩尔比为 1 : 2.5 加入 , 最后
Fe2+和Fe3+ 的总重量为飞灰重量的 6wt% ，加入少量的石灰使 pH 调节到 8~9.6 。
将形成的浆状混合物送入水热反应器，设置水热反应器内的反应温度为 300℃ ，反应 200min
后，将反应后的土壤 --- 水的浆状混合物冷却。
将反应后混合物样品在 40℃ 下烘干，检测 PCBs 及总 PCDD/Fs ，结果如下： PCBs
的浓度是 72ug/kg, 总 PCDD/Fs 的浓度没有检出， PCBs 的分解率为 99.3% 。
实施例 7
某地土壤长期使用农药后被污染， 总 DDT 含量 57.6ug/kg; 总 HCH 的含量 50.6
ug /kg, 总 HCB 的含量为 12.2ug/kg 。利用本发明的方法来处理污染土壤时，土壤和水按重量比 1: 5 混合，再加入饱和
FeCl2 溶液和饱和 Fe2(SO4)3 溶液 , 按照
Fe2+/Fe3+ 的摩尔比为 1 : 3.5 加入 , 最后 Fe2+ 和
Fe3+ 的总重量为焚烧飞灰重量的 8wt%, 加入少许石灰使***的 pH 在 6~7.5 之间。
将形成的浆状混合物送入高温反应器，设置高温反应器内的反应温度为 180℃ ，反应压力 10bar,
200min 后，将反应后的土壤 --- 水的浆状混合物冷却。
将反应后混合物样品在 40℃ 下烘干，检测 总 DDT ，总 HCH 和总 HCB, 结果如下： 总
DDT 含量 是 16.2ug/kg ； 总 HCH 的含量 14.6ug/kg, 总 HCB 的浓度 3.6ug/ kg ，有机氯农药的总分解率为
71.4% 。
实施例 8
某工业垃圾焚烧厂，其烟气净化***采用半干法 + 滤袋收尘，日产飞灰 1 吨。经检测其飞灰中二恶英含量高达
6500 ng I-TEQ/kg, 所含有毒二恶英浓度为 24630ng/kg 。
利用本发明的方法来处理二恶英时，该焚烧厂附近的钢缆厂用稀硫酸清洗钢缆的酸洗废液含
Fe2+ 13g/L, 用来与焚烧飞灰混合，使飞灰：水的重量比为 1:2 ，再加入
Fe2(SO4)3 固体 , 按照
Fe2+/Fe3+ 的摩尔比为 1:2 加入 , Fe2+ 和
Fe3+ 的总重量为飞灰重量的 7.8wt% 。
将形成的浆状混合物送入水热反应器，水热反应器内的反应温度为 300℃ ，反应 65min
后，将反应后的浆状混合物冷却，取少许样品干燥后按照标准 HJ/T 300 方法浸滤，重金属 Pb 的浸出达到 2.1mg/L ，因此在浆状混合物冷却后再加入
1.5wt% 的市售重金属稳定剂 TMT-18 ，稳定重金属。
将处理后的样品在 80℃ 下烘干，进行二恶英检测，同时按照标准 HJ/T 300
的方法进行浸出检验。结果如下：有毒二恶英浓度是 246.4ng/kg, 等毒性当量浓度为 99ng-TEQ/kg,17 种有毒二恶英的总分解率为 99%
；二恶英的等毒性当量降解率为 98.5% 。 Pb 的浸出 191ug/L 。处理后的焚烧飞灰符合卫生填埋的要求。
实施例 9
实施例 8 中的工业垃圾焚烧厂的飞灰，利用 300 ℃ 的亚临界水热反应并加入零价铁粉重量为飞灰重量的
7.2wt% ，在实施该过程中发现温度在 300 ℃ 下压力有持续升高现象，需要不断排除气体，反应 1.5h 后，分为 1 ）闪蒸急冷，
后面需要布袋收尘防止逸尘；和 2 ）在反应器的水冷夹套中通水缓慢冷却两种冷却方式进行冷却，冷却至 40 ℃ 算完毕，干燥，测试发现： 1
）处理以后急冷的飞灰， 17 种有毒二恶英浓度是 3364ng/kg, 等毒性当量浓度为 909ng-TEQ/kg, 17 种有毒二恶英的总分解率为
86.3% ；二恶英的等毒性当量降解率为 86% 。 2 ）处理以后缓慢冷却的飞灰， 17 种有毒二恶英浓度是 3104ng/kg, 等毒性当量浓度为
1107ng-TEQ/kg, 17 种有毒二恶英的总分解率为 87.4% ；二恶英的等毒性当量降解率为 83% 。采用本发明的方法来处理二恶英时，将
FeSO4.7H2O/Fe2(SO 4) 3
固体与焚烧飞灰混合，再加入水，使 :1) Fe2+/Fe3+ 的摩尔比为 1:2, 2) 灰：水的比例为 1:3
， 3) Fe2+ 和 Fe3+ 的总重量为飞灰重量的 7.2wt% 。
将形成的浆状混合物送入亚临界水热反应器，反应器内的温度为 300 ℃ ，反应过程中压力基本平稳，反应
65min 后，将反应后的浆状混合物也采用两种方式 冷却， 1 ）闪蒸快速冷却，后面需要布袋收尘防止逸尘； 2
）在反应器的水冷夹套中通水冷却；冷却完毕，干燥，测试发现： 1 ）处理以后急冷的飞灰， 17 种有毒二恶英浓度是 249.8ng/kg, 等毒性当量浓度为
130ng-TEQ/kg, 17 种有毒二恶英的总分解率为 98.98% ；二恶英的等毒性当量降解率为 98% 。 2 ）处理以后缓慢冷却的飞灰， 17
种有毒二恶英浓度是 249ng/kg, 等毒性当量浓度为 107ng-TEQ/kg, 17 种有毒二恶英的总分解率为 99% ；二恶英的等毒性当量降解率为
98.35% 。
上述实施例表明：使用本发明的方法可以对焚烧飞灰中的二恶英进行销毁并将其等毒性当量浓度降低到
100ng-TEQ/kg 或以下；同时对土壤中 PCBs 的污染有非常良好的分解效果。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (12)
- 一种颗粒物中所含持久性有机污染物的处理方法，其特征在于：在Fe2+和Fe3+存在的条件下，使所述颗粒物中的所述持久性有机污染物在水热条件下进行反应。
- 如权利要求1所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：所述Fe2+和所述Fe3+的摩尔比为1:4 ~3:1，优选为1:3 ~1.5:1；所述Fe2+和所述Fe3+的总量为所述颗粒物的1wt% ~ 8wt%。
- 如权利要求2所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：所述颗粒物与水、Fe2+盐和Fe3+盐形成浆状混合物，在180~300℃的温度下进行反应。
- 如权利要求3所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：将所述颗粒物与水混合后，再加入所述Fe2+盐和所述Fe3+盐的混合物，或者所述Fe2+的溶液和所述Fe3+的溶液，形成所述浆状混合物，使所述持久性有机污染物进行分解反应。
- 如权利要求3所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：所述颗粒物与所述水的重量比为1 : 1~1 : 5，优选为1:1.5~1: 3.5。
- 如权利要求3所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：将所述颗粒物与所述Fe2+盐和所述Fe3+盐混合，再加入水形成所述浆状混合物，使所述颗粒物与所述水的重量比为1 : 1~1 : 5。
- 如权利要求3-6之一所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：所述Fe2+盐选自硫酸亚铁、氯化亚铁、硝酸亚铁和它们的水合物中的一种或多种；所述Fe3+盐选自硫酸铁、氯化铁、硝酸铁和它们的水合物中的一种或多种。
- 如权利要求1-6之一所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：所述浆状混合物在密闭或者控压的反应条件下反应，反应完毕时，残留不少于5wt%的水。
- 如权利要求8所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于：所述浆状混合物反应20~200min，使所述持久性有机污染物的分解率达到70%以上。
- 如权利要求1-6之一所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于，还包括以下步骤：将所述反应后的混合物冷却；然后可将所述反应后的混合物保留液体直接养护、水分自然蒸发，或通过抽滤、压滤或者离心的方式将所述反应后的混合物进行液固分离，所得滤饼养护至含水率满足要求后进行建材化利用或进行直接填埋处理。
- 如权利要求10所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于，当所述颗粒物中含有重金属污染物时，将所述反应后的混合物冷却后，与重金属稳定剂混合，以稳定重金属。
- 如权利要求1-6之一所述的颗粒物中所含持久性有机污染物的处理方法，其特征在于，所述持久性有机污染物为二恶英PCDD/Fs、有机氯农药或多氯联苯PCBs，所述颗粒物为焚烧炉产生的焚烧飞灰、被有机氯农药污染的土壤和沉积物、被PCBs污染的土壤、不再使用的垃圾填埋场需要修复的土壤、或被所述持久性有机污染物污染的河道底泥和海湾沉积物。
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| US20140051902A1 (en) | 2014-02-20 |
| CN103596704A (zh) | 2014-02-19 |
| CN103596704B (zh) | 2016-04-20 |
| US9029623B2 (en) | 2015-05-12 |
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