ITVE20120013A1 - PROCEDURE FOR RECOVERY OF HUMIC SUBSTANCES FROM PERCOLATE COMING FROM LANDFILL OF SOLID URBAN OR ASSIMILABLE WASTE AND HUMAN SUBSTANCE OBTAINED BY PROCEEDINGS. - Google Patents
PROCEDURE FOR RECOVERY OF HUMIC SUBSTANCES FROM PERCOLATE COMING FROM LANDFILL OF SOLID URBAN OR ASSIMILABLE WASTE AND HUMAN SUBSTANCE OBTAINED BY PROCEEDINGS. Download PDFInfo
- Publication number
- ITVE20120013A1 ITVE20120013A1 IT000013A ITVE20120013A ITVE20120013A1 IT VE20120013 A1 ITVE20120013 A1 IT VE20120013A1 IT 000013 A IT000013 A IT 000013A IT VE20120013 A ITVE20120013 A IT VE20120013A IT VE20120013 A1 ITVE20120013 A1 IT VE20120013A1
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- IT
- Italy
- Prior art keywords
- leachate
- humic substances
- process according
- solution
- substances
- Prior art date
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- 239000000126 substance Substances 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 39
- 239000007787 solid Substances 0.000 title claims description 17
- 238000011084 recovery Methods 0.000 title claims description 8
- 239000002699 waste material Substances 0.000 title description 6
- 241000282414 Homo sapiens Species 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- 230000008569 process Effects 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- -1 alkyl phthalates Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000010813 municipal solid waste Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 159000000011 group IA salts Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 230000005070 ripening Effects 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 4
- 239000007791 liquid phase Substances 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- 150000003871 sulfonates Chemical class 0.000 claims 1
- 239000000523 sample Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000004021 humic acid Substances 0.000 description 14
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 14
- 239000002689 soil Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000002509 fulvic acid Substances 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 239000001175 calcium sulphate Substances 0.000 description 8
- 235000011132 calcium sulphate Nutrition 0.000 description 8
- 239000000149 chemical water pollutant Substances 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 description 1
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- FMWLUWPQPKEARP-UHFFFAOYSA-N bromodichloromethane Chemical compound ClC(Cl)Br FMWLUWPQPKEARP-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
- 239000012468 concentrated sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- IXORZMNAPKEEDV-UHFFFAOYSA-N gibberellic acid GA3 Natural products OC(=O)C1C2(C3)CC(=C)C3(O)CCC2C2(C=CC3O)C1C3(C)C(=O)O2 IXORZMNAPKEEDV-UHFFFAOYSA-N 0.000 description 1
- 239000003448 gibberellin Substances 0.000 description 1
- IXORZMNAPKEEDV-OBDJNFEBSA-N gibberellin A3 Chemical compound C([C@@]1(O)C(=C)C[C@@]2(C1)[C@H]1C(O)=O)C[C@H]2[C@]2(C=C[C@@H]3O)[C@H]1[C@]3(C)C(=O)O2 IXORZMNAPKEEDV-OBDJNFEBSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000003819 low-pressure liquid chromatography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000021749 root development Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B1/00—Dumping solid waste
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
- C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Fertilizers (AREA)
- Processing Of Solid Wastes (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Compounds Of Unknown Constitution (AREA)
Description
"Procedimento di recupero di sostanze umiche da percolato proveniente da discarica di rifiuti solidi urbani o assimilabili e sostanza umica ottenuta con il procedimento" "Process of recovery of humic substances from leachate coming from landfill of urban solid waste or similar and humic substance obtained with the process"
La presente invenzione concerne un procedimento di recupero di sostanze umiche da percolato proveniente da discarica di rifiuti solidi urbani o assimilabili ed una sostanza umica ottenuta con il procedimento. The present invention relates to a process for the recovery of humic substances from leachate coming from landfills of urban solid or similar waste and a humic substance obtained with the process.
Le sostanze umiche (HS) sono sostanze organiche complesse di struttura variabile ed ancora non ben completamente definita (struttura sovramolecolare, macromolecolare), costituita da catene ramificate di gruppi prevalentemente, ma non esclusivamente, aromatici, mono- e policiclici, anche eterociclici, con gruppi funzionali prevalentemente carbossilici, fenolici, ed idrossilici, ma anche eterici, esterici, amminici, ecc.. Humic substances (HS) are complex organic substances with a variable structure and still not fully defined (supramolecular, macromolecular structure), consisting of branched chains of groups mainly, but not exclusively, aromatic, mono- and polycyclic, even heterocyclic, with functional mainly carboxylic, phenolic, and hydroxyl, but also etheric, esteric, amino, etc.
Queste sostanze sono classificate in funzione della “solubilità †(più precisamente della capacità di formare “sol†colloidali) in acqua a diversi pH (pH 0-7 acido; pH 7 neutro; pH 7-14 basico) come di seguito indicato: These substances are classified according to the â € œsolubilityâ € (more precisely the ability to form colloidal â € œsolâ €) in water at different pH (acid pH 0-7; neutral pH 7; basic pH 7-14) as follows indicated:
†acidi Umici (HA) insolubili a pH acido e solubili a pH basico ⠀ Humic acids (HA) insoluble at acidic pH and soluble at basic pH
†acidi fulvici (FA) solubili a pH acido e basico ⠀ fulvic acids (FA) soluble at acidic and basic pH
†umine insolubili a pH acido e basico ⠀ Insoluble humins at acidic and basic pH
Queste caratteristiche di solubilità consentono di estrarre le sostanze umiche dai minerali carboniosi come la Leonardite, la lignite, la torba ed anche, proposte recenti, dal compost prodotto da trasformazione e stabilizzazione di rifiuti organici quali la frazione organica dei rifiuti solidi urbani (R.S.U.) in impianti controllati. These solubility characteristics allow the extraction of humic substances from carbonaceous minerals such as Leonardite, lignite, peat and also, recently proposed, from the compost produced by the transformation and stabilization of organic waste such as the organic fraction of municipal solid waste (R.S.U.) in controlled plants.
La Leonardite, che si forma nella lenta decomposizione delle sostanze organiche (in particolare la lignina) à ̈ la fase ancora ossidata, superficiale, più recente, della trasformazione geochimica delle sostanze organiche vegetali in torba e lignite. Essa à ̈ particolarmente ricca di HS, che sono estratte in soluzione acquosa basica con idrossido di potassio (pH 9-12). Queste soluzioni, che possono contenere sali inorganici solubili in acqua basica in quantità variabili, secondo le zone di origine, sono normalmente commercializzate, con varie concentrazioni in HS, in particolare quali ammendanti in agricoltura. Infatti le HS modificano le caratteristiche dei terreni e migliorano la crescita e la salute delle più svariate colture agricole sia per trattamento sul terreno, sia per applicazioni fogliari. Leonardite, which is formed in the slow decomposition of organic substances (in particular lignin), is the most recent, still oxidized, superficial phase of the geochemical transformation of vegetable organic substances into peat and lignite. It is particularly rich in HS, which are extracted in a basic aqueous solution with potassium hydroxide (pH 9-12). These solutions, which may contain inorganic salts soluble in basic water in variable quantities, according to the areas of origin, are normally marketed, with various concentrations in HS, in particular as soil improvers in agriculture. In fact, HS modify the characteristics of the soils and improve the growth and health of the most varied agricultural crops both for treatment on the ground and for foliar applications.
In particolare le HS migliorano: In particular the HS improve:
†la capacità di ritenzione idrica del suolo; ⠀ the water retention capacity of the soil;
†la struttura e la fertilità del suolo; grazie all’effetto chelante dei gruppi funzionali presenti nelle HS à ̈ evitato il dilavamento dei nutrienti e dei microelementi (ferro, calcio, fosforo etc.) ed aumentata la loro disponibilità nel tempo a vantaggio della crescita e della salute delle piante. â € the structure and fertility of the soil; thanks to the chelating effect of the functional groups present in the HS, the leaching of nutrients and microelements (iron, calcium, phosphorus etc.) is avoided and their availability increased over time to the benefit of plant growth and health.
Le HS sono praticamente non biodegradabili: esse sono costituite da macromolecole di medio (FA) ed alto peso molecolare (HA) con parti idrofobiche e gruppi funzionali idrofilici in parte acidi ed esibiscono, nelle forme salificate con metalli alcalini, proprietà tensioattive che ne consentono l’impiego anche come tensioattivi nel lavaggio di terreni e suoli per la loro decontaminazione da idrocarburi e/o metalli pesanti utilizzando anche le loro proprietà chelanti su vari metalli pesanti. HS are practically non-biodegradable: they are made up of medium (FA) and high molecular weight (HA) macromolecules with hydrophobic parts and hydrophilic functional groups that are partly acidic and exhibit, in the salified forms with alkali metals, surfactant properties that allow their € ™ also used as surfactants in the washing of soils and soils for their decontamination from hydrocarbons and / or heavy metals using also their chelating properties on various heavy metals.
Sostanze simili alle HS, ma non di origine naturale, sono state ottenute per ossidazione controllata del carbone e proposte come ammendanti agricoli o per l’inertizzazione di ceneri industriali ricche di metalli pesanti. Substances similar to HS, but not of natural origin, have been obtained by controlled oxidation of coal and proposed as agricultural amendments or for the inertization of industrial ashes rich in heavy metals.
E’ noto che il percolato da discariche di R.S.U. può contenere, in funzione della qualità dei rifiuti conferiti e del grado di maturazione della discarica, della piovosità , quantità (0,05-5% in peso) di HS oggi ritenute interessanti ai fini industriali e commerciali; tuttavia il loro recupero diretto dal percolato con le metodologie note non consente di ottenere a costi competitivi un prodotto esente dai vari contaminanti presenti nel percolato, con particolare riguardo ai composti azotati ed ammoniacali, e pertanto poco idoneo ad essere impiegato similmente alle HS ottenute per le vie descritte in precedenza. It is known that the leachate from landfills of R.S.U. it may contain, depending on the quality of the waste disposed of and the degree of maturation of the landfill, the rainfall, quantity (0.05-5% by weight) of HS today considered interesting for industrial and commercial purposes; however, their direct recovery from the leachate with the known methods does not allow to obtain at competitive costs a product free from the various contaminants present in the leachate, with particular regard to nitrogen and ammonia compounds, and therefore not very suitable to be used similarly to the HS obtained for ways described above.
Lo scopo della presente invenzione e quello di realizzare un procedimento che consenta di ottenere dal percolato di discarica di R.S.U. e rifiuti assimilabili HS di qualità commerciabile, realizzando il minor consumo di reagenti (acidi, additivi) ed utilizzando tecnologie semplici, integrabili ed utilizzabili, anche quelle esistenti, con bassi costi di investimento e gestione. The object of the present invention is to provide a process which allows to obtain from the landfill leachate of R.S.U. and comparable HS waste of marketable quality, achieving the lowest consumption of reagents (acids, additives) and using simple, integrable and usable technologies, even existing ones, with low investment and management costs.
Per raggiungere tale scopo à ̈ necessario considerare quanto di seguito esposto. To achieve this purpose it is necessary to consider the following.
La concentrazione di HS nel percolato si modifica con il tempo (l’età ) di attività della discarica di R.S.U.; considerando le fasi di degradazione biologica che si susseguono sulla componente organica del rifiuto una volta messo a dimora in discarica, si hanno notoriamente: The concentration of HS in the leachate changes with the time (age) of activity of the R.S.U landfill; considering the phases of biological degradation that follow one another on the organic component of the waste once it is placed in landfill, there are notoriously:
- una prima breve fase di biodegradazione aerobica, principalmente dovuta all’ossigeno interstiziale, durante la quale vi à ̈ scarsa produzione di percolato, né di HS; - a first short phase of aerobic biodegradation, mainly due to interstitial oxygen, during which there is little production of leachate, nor of HS;
- una seconda prolungata fase di degradazione anaerobica a sua volta divisa nelle seguenti fasi successive: - a second prolonged phase of anaerobic degradation in turn divided into the following successive phases:
a) fase acidogenica, in cui si formano per fermentazione acidi grassi volatili ed anidride carbonica, con conseguente diminuzione del pH. Si forma una grande quantità di percolato con pH acido (5-6) con BOD5elevato, elevata concentrazione di sali, mobilizzazione di metalli pesanti ma scarsa presenza di HS; a) acidogenic phase, in which volatile fatty acids and carbon dioxide are formed by fermentation, with a consequent decrease in pH. A large quantity of leachate with acid pH (5-6) is formed with high BOD5, high concentration of salts, mobilization of heavy metals but low presence of HS;
b) fase acetogenica, in cui si formano per fermentazione acidi volatili a catena corta, poi ulteriormente degradati per mezzo dei batteri acetogenici ad acido acetico, a sua volta substrato dei batteri metanigeni. Si ha produzione di metano, diminuzione di idrogeno e anidride carbonica e aumento del pH. Il percolato presenta una minore concentrazione di metalli e di BOD5rispetto alla fase precedente ed un aumento della concentrazione di HS e di ammoniaca; b) acetogenic phase, in which short-chain volatile acids are formed by fermentation, which are then further degraded by acetogenic bacteria to acetic acid, which in turn is a substrate for methanogenic bacteria. There is the production of methane, a decrease in hydrogen and carbon dioxide and an increase in pH. The leachate has a lower concentration of metals and BOD5 compared to the previous phase and an increase in the concentration of HS and ammonia;
c) fase metanigena, in cui si forma metano in grande quantità per prevalenza di batteri metanigeni idrogenofilici e soprattutto acetofilici (responsabili della produzione del 70% di metano). Questa fase caratterizza la “maturità †della discarica: il percolato presenta pH neutro-alcalino (7-10); basse concentrazioni di acidi volatili e di solidi disciolti (basso BOD5), bassa mobilità di metalli pesanti (ad esempio Fe, Zn), elevata concentrazione di ammoniaca, massima concentrazione di HS. c) methanogenic phase, in which methane is formed in large quantities due to the prevalence of hydrogenophilic and above all acetophilic methanogenic bacteria (responsible for the production of 70% of methane). This phase characterizes the â € œmaturity â € of the landfill: the leachate has a neutral-alkaline pH (7-10); low concentrations of volatile acids and dissolved solids (low BOD5), low mobility of heavy metals (eg Fe, Zn), high concentration of ammonia, maximum concentration of HS.
Il percolato di discarica “matura†à ̈ infatti riconoscibile visivamente dal colore bruno scuro tipico delle HS (HA colore bruno-nero; FA colore giallobruno). Studi condotti sulla natura chimica e strutturale delle HS ricavate dal percolato di diverse discariche di R.S.U. mediante analisi chimico-fisiche (spettroscopia UV, FTIR, NMR, etc) hanno evidenziato che queste sono simili, ma non uguali, a quelle ottenute dall’estrazione da Leonardite, torba, lignite, compost. The â € œmatureâ € landfill leachate is in fact visually recognizable by the dark brown color typical of HS (HA brown-black color; FA yellow-brown color). Studies conducted on the chemical and structural nature of HS obtained from the leachate of different landfills of R.S.U. by means of chemical-physical analyzes (UV spectroscopy, FTIR, NMR, etc) they have shown that these are similar, but not the same, to those obtained from extraction from Leonardite, peat, lignite, compost.
Nel trattamento di depurazione dei percolati di discarica, le HS sono prevalentemente rimosse assieme agli idrossidi ed ai carbonati basici dei metalli pesanti per precipitazione/ chiariflocculazione con sali di alluminio e di ferro, idrossido di calcio, flocculanti organici etc., cui possono seguire tecnologie con membrane (ultrafiltrazione, osmosi inversa) che risultano però facilmente intasabili dalle HS. I fanghi prodotti dalla depurazione dei percolati sono di solito riciclati in discarica o smaltiti altrimenti, non essendo economicamente conveniente recuperare le HS con una sufficiente qualità commerciale. In the purification treatment of landfill leachate, HS are mainly removed together with the hydroxides and basic carbonates of heavy metals by precipitation / clariflocculation with aluminum and iron salts, calcium hydroxide, organic flocculants etc., which can be followed by technologies with membranes (ultrafiltration, reverse osmosis) which are however easily clogged by HS. The sludge produced by the purification of leachate is usually recycled in landfills or otherwise disposed of, as it is not economically convenient to recover the HS with sufficient commercial quality.
Il percolato “maturo†à ̈ già una soluzione basica di HS ed à ̈ normalmente classificato, secondo la normativa italiana ed europea, come “rifiuto da percolato, speciale non pericoloso†(codice CER 190703). Inizialmente à ̈ anche prevista una eventuale filtrazione al fine di garantire gli eventuali “solidi sospesi†a livelli bassi, inferiori a 500 mg/Litro, essendo noto che taluni microinquinanti organici pericolosi, quali per esempio le policlorodibenzodiossine ed i policlorodibenzofurani, se presenti, sono praticamente adsorbiti nel particolato insolubile ( solidi sospesi). The â € œmatureâ € leachate is already a basic solution of HS and is normally classified, according to the Italian and European legislation, as â € œwaste from leachate, special not dangerousâ € (CER code 190703). Initially, a possible filtration is also envisaged in order to guarantee any â € œsuspended solidsâ € at low levels, lower than 500 mg / liter, as it is known that some dangerous organic micro-pollutants, such as for example polychlorinated dibenzodioxins and polychlorinated dibenzofurans, if present, they are practically adsorbed in the insoluble particulate matter (suspended solids).
Scopo dell’invenzione à ̈ quello di recuperare le HS da tale soluzione e purificarle dalle contaminazioni eventualmente presenti che non le rendono adatte a ciascun specifico impiego. The purpose of the invention is to recover the HS from this solution and purify it from any contamination that may not make it suitable for each specific use.
Nella presente invenzione si à ̈ trovato che, se invece di trattare il percolato maturo a pH 7-10 con acido inorganico, ad esempio acido solforico, fino alla completa precipitazione delle HS a pH 2-2.5, si esegue la stessa operazione sul percolato dopo averlo concentrato da dieci a venti volte per evaporazione, ad esempio sottovuoto, à ̈ sufficiente utilizzare una quantità di acido inorganico pari a circa un quarto di quella che si sarebbe impiegata trattando la stessa quantità di percolato non concentrato. Tale riduzione di circa quattro volte del consumo specifico di acido si ottiene grazie alla significativa diminuzione della alcalinità del percolato durante il procedimento di concentrazione, a causa della decomposizione termica dei bicarbonati ed in particolare del bicarbonato ammonico, tipicamente presente in elevata concentrazione nel percolato maturo, in ammoniaca ed anidride carbonica, allontanati poi dal percolato per evaporazione. In the present invention it has been found that, if instead of treating the mature leachate at pH 7-10 with inorganic acid, for example sulfuric acid, until the complete precipitation of the HS at pH 2-2.5, the same operation is carried out on the leachate after having concentrated it from ten to twenty times by evaporation, for example under vacuum, it is sufficient to use a quantity of inorganic acid equal to about a quarter of that which would have been used by treating the same quantity of unconcentrated leachate. This reduction of about four times of the specific acid consumption is obtained thanks to the significant decrease in the alkalinity of the leachate during the concentration process, due to the thermal decomposition of bicarbonates and in particular of ammonium bicarbonate, typically present in high concentration in mature leachate, in ammonia and carbon dioxide, then removed from the leachate by evaporation.
Altro vantaggio di operare la precipitazione acida delle HS sul percolato concentrato per evaporazione, ad esempio sotto vuoto, à ̈ la pressoché totale assenza nel percolato concentrato, e conseguentemente nelle HS precipitate da questo, di eventuali contaminanti volatili, sia organici (acidi carbossilici, idrocarburi, altre sostanze organiche alifatiche/aromatiche, anche alogenate, anche azotate) che inorganici (in primis ammoniaca); questo facilita la successiva fase di purificazione delle HS al fine di ottenere HS di qualità commerciale. Another advantage of operating the acid precipitation of the HS on the concentrated leachate by evaporation, for example under vacuum, is the almost total absence in the concentrated leachate, and consequently in the HS precipitated by it, of any volatile contaminants, both organic (carboxylic acids, hydrocarbons, other aliphatic / aromatic organic substances, including halogenated, also nitrogenous) and inorganic (primarily ammonia); this facilitates the subsequent purification phase of the HS in order to obtain HS of commercial quality.
Altro vantaggio à ̈ che la fase di precipitazione delle HS con acido può essere eseguita a caldo, 50-100°C, alla temperatura di scarico del percolato concentrato dall’evaporatore, senza aggiuntivi costi energetici, migliorando la morfologia del precipitato e l’efficienza delle successive fasi di separazione solido-liquido e purificazione per lavaggio con acqua, anche acidificata con acido inorganico a pH: <7 aventi lo scopo di ridurre le impurezze quali i sali inorganici ed i composti organici solubili in acqua. Another advantage is that the HS precipitation phase with acid can be performed hot, 50-100 ° C, at the discharge temperature of the concentrated leachate from the evaporator, without additional energy costs, improving the morphology of the precipitate and the ™ efficiency of the subsequent solid-liquid separation and purification phases by washing with water, also acidified with inorganic acid at pH: <7 with the aim of reducing impurities such as inorganic salts and water-soluble organic compounds.
Altro vantaggio di operare sul percolato concentrato à ̈ che nella fase di evaporazione esso subisce un trattamento termico con temperature di 50-130°C per un tempo medio di residenza elevato (2-7 ore) con conseguente riduzione della carica batterica iniziale, che viene ulteriormente ridotta anche nella successiva fase di acidificazione a pH 2, ottenendo un prodotto praticamente esente da batteri pericolosi, ad esempio Escherichia coli e salmonelle. Another advantage of operating on concentrated leachate is that in the evaporation phase it undergoes a heat treatment with temperatures of 50-130 ° C for a high average residence time (2-7 hours) with consequent reduction of the initial bacterial load, which is further reduced also in the subsequent acidification phase at pH 2, obtaining a product practically free from dangerous bacteria, for example Escherichia coli and salmonella.
Infine la presente invenzione, oltre alle vantaggiose implicazioni economiche (le HS sono un prodotto di pregio che, oltre agli attuali impieghi sopra citati, potrà trovare in futuro ulteriori proficue applicazioni) ha anche una elevata valenza ambientale, poiché, da un rifiuto, recupera sostanze altamente eco-compatibili, particolarmente utili per il recupero e risanamento dei terreni aridi e/o fortemente dilavabili, favorendo la conversione di anidride carbonica in biomassa vegetale da destinare a scopi alimentari o alla costituzione di fonti di energia rinnovabili con conseguente riduzione dell’immissione di questo gas-serra in atmosfera. Finally, the present invention, in addition to the advantageous economic implications (the HS are a valuable product that, in addition to the current uses mentioned above, may find further profitable applications in the future) also has a high environmental value, since, from a waste, it recovers highly eco-compatible substances, particularly useful for the recovery and rehabilitation of arid and / or highly washable soils, favoring the conversion of carbon dioxide into vegetable biomass to be used for food purposes or for the constitution of renewable energy sources with consequent reduction of release of this greenhouse gas into the atmosphere.
Tale scopo à ̈ raggiunto secondo l’invenzione con un procedimento di recupero di sostanze umiche da percolato proveniente da discarica di rifiuti solidi urbani o assimilabili come descritto nella rivendicazione 1. This object is achieved according to the invention with a process of recovery of humic substances from leachate coming from landfill of urban solid waste or similar as described in claim 1.
La presente invenzione viene qui di seguito ulteriormente chiarita in una sua preferita forma di pratica realizzazione con riferimento all’allegato schema a blocchi e ad alcuni esempi riportati a scopi esemplificativi e non limitativi The present invention is further clarified hereinafter in a preferred embodiment thereof with reference to the attached block diagram and to some examples given for illustrative and non-limiting purposes.
Come si vede dallo schema a blocchi il procedimento secondo l’invenzione prevede che il percolato proveniente da una discarica di R.S.U. o assimilabili in fase di “maturazione†, se contiene dei solidi sospesi venga inizialmente filtrato con idonei filtri quali per esempio filtri a sabbia, micro filtri, decantatori, centrifughe fino ad ottenere una concentrazione di “solidi sospesi†inferiore a 500 mg/litro (determinati col metodo IRSA-CNR 2090) allo scopo di rimuovere eventuali sostanze organiche contaminanti quali per esempio le policlorodibenzodiossine ed i policlorodibenzofurani che, se presenti, sono notoriamente adsorbite nel particolato solido sospeso. As can be seen from the block diagram, the process according to the invention provides that the leachate coming from a landfill of R.S.U. or similar in the `` ripening '' phase, if it contains suspended solids it is initially filtered with suitable filters such as sand filters, micro filters, decanters, centrifuges until a concentration of `` suspended solids '' is obtained below 500 mg / liter (determined with the IRSA-CNR 2090 method) in order to remove any contaminating organic substances such as for example polychlorinated dibenzodioxins and polychlorinated dibenzofurans which, if present, are notoriously adsorbed in the suspended solid particulate.
Il particolare percolato presenta pH neutro o basico (pH 7-10), di colore bruno, contiene una quantità di sostanze organiche maggiore del 0.1 % in peso, determinate come differenza fra il residuo secco a 105°C (R105) ed il residuo secco a 600°C (R600), determinati secondo il metodo IRSA Q64(2) 84 met.02 ed in particolare di Carbonio Umico maggiore dello 0,05% in peso, determinato col metodo DM 23-01-91 S.O.G.U, n. 29/91. The particular leachate has neutral or basic pH (pH 7-10), brown in color, contains a quantity of organic substances greater than 0.1% by weight, determined as the difference between the dry residue at 105 ° C (R105) and the dry residue at 600 ° C (R600), determined according to the IRSA Q64 (2) 84 met.02 method and in particular of Humic Carbon greater than 0.05% by weight, determined with the method DM 23-01-91 S.O.G.U, n. 29/91.
Il percolato viene quindi sottoposto ad una fase di evaporazione, anche sotto vuoto ed in continuo, ad una pressione di 5-200 KPa, temperatura di 50-130°C, meglio in continuo in multiplo effetto, per un tempo medio di residenza di 2-7 ore, fino ad ottenere un residuo liquido con volume ridotto pari a 1/5 – 1/20 del volume iniziale del percolato, con pH 8-11 basico. The leachate is then subjected to an evaporation phase, also under vacuum and in continuous, at a pressure of 5-200 KPa, temperature of 50-130 ° C, preferably in continuous multiple effect, for an average residence time of 2 -7 hours, until obtaining a liquid residue with a reduced volume equal to 1/5 - 1/20 of the initial volume of the leachate, with a basic pH of 8-11.
Il percolato concentrato contiene tutte le sostanze umiche HS in soluzione, in particolare HA solubili in ambiente basico, FA e sali inorganici, in particolare cloruri, solfati, fosfati, silicati alcalini (Sali di Na, K) e alcalinoterrosi (Sali di Ca, Mg). The concentrated leachate contains all the humic substances HS in solution, in particular HA soluble in basic environment, FA and inorganic salts, in particular chlorides, sulphates, phosphates, alkaline silicates (Salts of Na, K) and alkaline earth (Salts of Ca, Mg ).
L’acqua di condensa della fase di evaporazione-concentrazione contiene tutte le sostanze contaminanti volatili presenti nel percolato di partenza, quali ammoniaca, sostanze organiche volatili, idrocarburi, sostanze organiche alogenate. Tali sostanze vengono eliminate dall’acqua di condensa in una successiva fase di strippaggio/assorbimento che permette inoltre di recuperare una soluzione di solfato ammonico riutilizzabile nell’industria. L’acqua di condensa così purificata può essere utilizzata nella fase di lavaggio acido delle HS grezze o scaricata in pubblica fognatura, acque superficiali, suoli, previo eventuale ulteriore trattamento di depurazione con processi noti, ad esempio ossidazione, adsorbimento su carbone attivo, ultrafiltrazione, osmosi inversa, etc., per raggiungere i limiti di contaminazione consentiti allo scarico. The condensation water of the evaporation-concentration phase contains all the volatile contaminants present in the starting leachate, such as ammonia, volatile organic substances, hydrocarbons, halogenated organic substances. These substances are eliminated from the condensation water in a subsequent stripping / absorption phase which also allows the recovery of an ammonium sulphate solution that can be reused in industry. The condensed water thus purified can be used in the acid washing phase of the raw HS or discharged into the public sewer, surface water, soil, after any further purification treatment with known processes, for example oxidation, adsorption on activated carbon, ultrafiltration, reverse osmosis, etc., to reach the contamination limits allowed at the exhaust.
Il percolato concentrato viene sottoposto ad una fase di acidificazione con aggiunta di una soluzione acquosa di acido inorganico per esempio acido solforico concentrato al 37,5 %p., acido cloridrico al 37,5 %p., acido fosforico al 75%p., a temperatura compresa tra temperatura quella ambiente e quella di ebollizione del percolato concentrato, sotto agitazione, in precipitatore discontinuo o continuo, ad esempio a tre stadi, con dosaggio in continuo di acido in linea, in controllo di pH, e sotto agitazione, ad esempio a ricircolo con miscelatori statici, sino a completa precipitazione di un solido fioccoso di HS a pH 1-3, preferibilmente 2,0 stabile (costante); la quantità di acido necessaria varia con il tipo di percolato ed il tipo di acido: per esempio per un percolato maturo può essere, per acido solforico al 37,5%p., pari a circa il 10% in volume del volume di percolato concentrato. The concentrated leachate is subjected to an acidification step with the addition of an aqueous solution of inorganic acid, for example concentrated sulfuric acid at 37.5% w., Hydrochloric acid at 37.5% w., Phosphoric acid at 75% w., at a temperature between room temperature and the boiling point of the concentrated leachate, under stirring, in a discontinuous or continuous precipitator, for example with three stages, with continuous dosage of acid in line, in pH control, and under stirring, for example by recirculation with static mixers, until complete precipitation of a flaky solid of HS at pH 1-3, preferably 2.0 stable (constant); the quantity of acid required varies with the type of leachate and the type of acid: for example for a mature leachate it can be, for sulfuric acid at 37.5% w., equal to about 10% by volume of the volume of concentrated leachate .
La precipitazione delle HS inizia a pH 4,5-4,0 con possibile formazione di schiume che possono essere ridotte e controllate con aggiunte di piccole quantità di antischiuma, per esempio del tipo siliconici; il sistema di acidificazione e precipitazione à ̈ provvisto di mezzi di agitazione, sfiato e trattamento di vapori ed incondensabili quali per esempio anidride carbonica, acido solfidrico ed eventuali sostanze di acidi deboli inorganici ed organici volatili alle condizioni di pH e temperatura suddette; pertanto anche questa fase contribuisce alla purificazione delle HS da sostanze che ridurrebbero la loro qualità , per esempio solfuri pericolosi e di odore sgradevole. The precipitation of the HS begins at pH 4.5-4.0 with the possible formation of foams that can be reduced and controlled with the addition of small quantities of antifoam, for example of the silicone type; the acidification and precipitation system is equipped with means for stirring, venting and treatment of vapors and non-condensable substances such as carbon dioxide, hydrogen sulphide and any substances of weak inorganic and volatile organic acids at the aforementioned pH and temperature conditions; therefore also this phase contributes to the purification of HS from substances that would reduce their quality, for example dangerous sulphides and unpleasant odors.
Le HS vengono quindi sottoposte ad una fase di separazione solido / liquido ottenuta con una o più di note tecnologie quali la filtrazione, anche sotto vuoto, centrifugazione, decantazione, flottazione etc. Per migliorare l’efficienza di queste operazioni può essere opportuno aggiungere piccole quantità , generalmente inferiori a 1,0% in vol. di agenti flocculanti polimerici quali per esempio poliacrilati, polielettroliti cationici a base poliacrilammide, additivi che comunque non influenzano la qualità del prodotto finale. The HS are then subjected to a solid / liquid separation phase obtained with one or more of known technologies such as filtration, even under vacuum, centrifugation, decantation, flotation etc. To improve the efficiency of these operations it may be advisable to add small quantities, generally less than 1.0% by vol. of polymeric flocculating agents such as for example polyacrylates, cationic polyelectrolytes based on polyacrylamide, additives which in any case do not affect the quality of the final product.
Al termine di queste fasi si ottiene: At the end of these phases we obtain:
†una soluzione di sali inorganici, acida a pH 1-3 preferibilmente 2,0, in quantità di 20-90 % in vol. della sospensione precedentemente ottenuta per acidificazione, contenente una parte degli acidi fulvici (FA) (colorazione gialla) ed altre sostanze organiche non volatili idrosolubili presenti nel percolato di partenza; tale soluzione viene inviata ad una sezione di neutralizzazione a pH superiore a 4 e successivamente a smaltimento o a una fase di concentrazione e cristallizzazione per la separazione per precipitazione, in particolare dei sali dei metalli alcalini e pesanti, principalmente cloruri e solfati, mentre le acque di condensa, sono recuperate e riciclate alla sezione successiva di lavaggio o inviate a scarico previo eventuale trattamento, ⠀ a solution of inorganic salts, acidic at pH 1-3, preferably 2.0, in a quantity of 20-90% by vol. of the suspension previously obtained by acidification, containing a part of the fulvic acids (FA) (yellow color) and other water-soluble non-volatile organic substances present in the starting leachate; this solution is sent to a neutralization section at pH higher than 4 and subsequently to disposal or to a phase of concentration and crystallization for the separation by precipitation, in particular of the salts of the alkali and heavy metals, mainly chlorides and sulphates, while the condensate, are recovered and recycled to the next washing section or sent to drain after any treatment,
†una sospensione concentrata di HS grezze acida, pH 1-3, preferibilmente 2,0, in quantità di 80-10 % in vol. della sospensione di HS grezze precedentemente ottenuta per acidificazione del percolato concentrato, con residuo secco a 105 °C di 10-80% in peso di HS grezze, costituite in maggior parte da HA, in misura minore da FA. Le HS grezze vengono successivamente disciolte come umati alcalini solubili per aggiunta di una soluzione acquosa di idrossido alcalino, preferibilmente di potassio, fino a pH 5,0-10,0 preferibilmente pH 7,0; risulterà una soluzione acquosa di HS grezze che, eventualmente diluita, potrà essere utilizzata come ammendante in agricoltura dopo verifica qualitativa e quantitativa del rispetto dei limiti analitici previsti dalle normative vigenti per i prodotti di simile origine quali i fanghi da depuratori di acque reflue municipali ed i “compost†da frazione organica di R.S.U.. â € a concentrated suspension of acid crude HS, pH 1-3, preferably 2.0, in an amount of 80-10% by vol. of the suspension of crude HS previously obtained by acidification of the concentrated leachate, with a dry residue at 105 ° C of 10-80% by weight of crude HS, consisting mostly of HA, to a lesser extent of FA. The crude HS are subsequently dissolved as soluble alkaline humates by adding an aqueous solution of alkaline hydroxide, preferably potassium, up to pH 5.0-10.0, preferably pH 7.0; it will result in an aqueous solution of raw HS which, possibly diluted, can be used as a soil improver in agriculture after qualitative and quantitative verification of compliance with the analytical limits provided for by the regulations in force for products of similar origin such as sludge from municipal wastewater purifiers and â € œcompostâ € from organic fraction of R.S.U ..
Se ritenuto necessario, prima di essere disciolte con soluzione acquosa di idrossido alcalino, le HS grezze vengono purificate con lavaggi con acqua, anche derivante dalla purificazione delle condense prodotte nei processi di evaporazione del presente procedimento (Fig. 1), anche acidificata a pH <7, con acido inorganico, per esempio acido solforico e/o acido cloridrico e/o acido fosforico, il tutto con tecnologie note con lavaggi a cicli od in continuo. If deemed necessary, before being dissolved with an aqueous solution of alkaline hydroxide, the raw HS are purified by washing with water, also deriving from the purification of the condensates produced in the evaporation processes of this procedure (Fig. 1), also acidified to pH < 7, with inorganic acid, for example sulfuric acid and / or hydrochloric acid and / or phosphoric acid, all with known technologies with cycle or continuous washing.
Si ottiene una sospensione di HS purificate con residuo secco a 105 °C di 10-80 % in peso, preferibilmente 40%, a pH 5-7, e con bassa salinità espressa con residuo secco a 600°C, inferiore al 15 % in peso, preferibilmente 5 %p. A purified HS suspension is obtained with 10-80% by weight dry residue at 105 ° C, preferably 40%, at pH 5-7, and with low salinity expressed with dry residue at 600 ° C, lower than 15% in weight, preferably 5% w.
Se ritenuto necessario, la soluzione acquosa di HS grezze o purificate solubilizzate come umati alcalini, può essere ulteriormente purificata mediante trattamenti noti con prodotti solidi adsorbenti quali carboni attivi, caolini, argille, etc. al fine di rimuovere gli eventuali microinquinanti organici quali per esempio gli alchilftalati, in particolare 2etil-esilftalato, nonil- e ottil-fenoli, bisfenolo A. If deemed necessary, the aqueous solution of raw or purified HS solubilized as alkaline humates, can be further purified by known treatments with adsorbing solid products such as activated carbon, kaolins, clays, etc. in order to remove any organic micropollutants such as alkyl phthalates, in particular 2ethyl-hexyl phthalate, nonyl- and octyl-phenols, bisphenol A.
La soluzione acquosa di HS grezze o purificate come sopra descritto, oltre che essere utilizzata, previa eventuale diluizione, come ammendante dei terreni per coltivazioni in agricoltura nel rispetto dei limiti qualitativi quantitativi previsti dalle normative, può essere variamente trasformata nelle seguenti forme simili a quelle esistenti sul mercato delle HS: The aqueous solution of raw or purified HS as described above, as well as being used, after any dilution, as a soil improver for agricultural crops in compliance with the quantitative qualitative limits established by the regulations, can be variously transformed into the following forms similar to the existing ones on the HS market:
- prodotto in polvere o granulato, umidità 10-30% p., ottenuto per essiccamento per esempio in vasche di lagunaggio ed esposizione all’aria, forni riscaldati con termoresistenze o a microonde, raggi infrarossi etc., - prodotto in soluzione di umati di ferro (II) che si ottiene per aggiunta di solfato ferroso alla soluzione basica, - product in powder or granulate, humidity 10-30% w., obtained by drying for example in lagoon tanks and exposure to air, ovens heated with thermoresistances or microwaves, infrared rays etc., - product in solution of humates of iron (II) which is obtained by adding ferrous sulphate to the basic solution,
- prodotto in sospensione o essiccato di umato di calcio o magnesio che si ottiene per aggiunta di CaO, Ca(OH)2, o MgO o Mg(OH)2fino a pH > 7, con precipitazione di umati di calcio o di magnesio insolubili a pH basico. - suspension or dried product of calcium or magnesium humate obtained by adding CaO, Ca (OH) 2, or MgO or Mg (OH) 2 up to pH> 7, with precipitation of insoluble calcium or magnesium humates to basic pH.
I seguenti esempi illustrano la presente invenzione senza limitarne il trovato. The following examples illustrate the present invention without limiting its invention.
Esempio 1) Example 1)
A 100 ml di percolato t.q. (Camp.1p) proveniente da una discarica “matura†di R.S.U.,(A) filtrato, con solidi sospesi inferiori a 500 mg/L, di colore bruno scuro, avente le caratteristiche riportate in Tab.1, sono state aggiunte, a temperatura ambiente, sotto continua agitazione, quantità (ml) successive, incrementali, di una soluzione acquosa di acido solforico al 37,45 %p., densità 1,28 g/ml, misurando il pH con pH-metro dotato di elettrodo a vetro tarato e registrando i valori a pH costante, per ogni aggiunta di acido. A 100 ml of leachate t.q. (Sample 1p) from a `` mature '' landfill of R.S.U., (A) filtered, with suspended solids lower than 500 mg / L, dark brown in color, having the characteristics shown in Table 1, have been added to room temperature, under continuous stirring, successive, incremental quantities (ml) of an aqueous solution of sulfuric acid at 37.45% w., density 1.28 g / ml, measuring the pH with a pH-meter equipped with a glass electrode calibrated and recording the values at constant pH, for each addition of acid.
Inizialmente si osserva effervescenza con produzione di schiume che sono ridotte e controllabili con aggiunta di antischiuma siliconico ( 0.2 ml di soluzione al 10% di Dinapan 16WD). A pH: 4 circa si osserva l’inizio di formazione di un precipitato fioccoso di colore bruno, mentre il colore della soluzione schiarisce verso il giallo, finisce l’effervescenza e la formazione di schiume, si continua l’aggiunta di acido solforico. Initially, effervescence is observed with the production of foams that are reduced and controllable with the addition of silicone defoamer (0.2 ml of 10% solution of Dinapan 16WD). At pH: about 4 we observe the beginning of the formation of a brownish flaky precipitate, while the color of the solution lightens towards yellow, the effervescence and the formation of foams ends, the addition of acid continues sulfuric.
A pH: 2, si à ̈ interrotto l’aggiunta di acido solforico ed una aliquota di sospensione à ̈ stata posta su una provetta e centrifugata a 3200 rpm per 10 minuti e separato il surnatante, soluzione limpida, a questo à ̈ stato aggiunto acido solforico, non à ̈ stato osservato ulteriore formazione di precipitato, pertanto la precipitazione à ̈ ritenuta praticamente completa. Tutto il prodotto ottenuto viene centrifugato in idonea apparecchiatura da laboratorio a 3200 rpm per 10 minuti ed il surnatante limpido viene separato dal precipitato, sospensione di fondo, costituito da Sostanze Umiche (HS) grezze umide, gr.10, ( Camp.HS1) con le caratteristiche chimiche riportate in Tab.2. At pH: 2, the addition of sulfuric acid was stopped and an aliquot of suspension was placed on a test tube and centrifuged at 3200 rpm for 10 minutes and the supernatant, clear solution separated, to this was added sulfuric acid, no further precipitate formation was observed, therefore the precipitation is considered to be practically complete. All the product obtained is centrifuged in suitable laboratory equipment at 3200 rpm for 10 minutes and the clear supernatant is separated from the precipitate, bottom suspension, consisting of humid raw humid substances (HS), gr. 10, (Camp.HS1) with the chemical characteristics shown in Tab.2.
Per il suddetto campione (1p) sono riportate in Tab.3 le quantità , espresse in volume ed in peso, di acido solforico al 37,45 %p. aggiunto ed i valori di pH ottenuti dopo ogni aggiunta; a pH 2,2 sono stati impiegati 1,97 gr.di acido solforico puro (20,1 mgmoli) per 100 ml di percolato t.q. For the aforementioned sample (1p) the quantities, expressed in volume and weight, of sulfuric acid at 37.45% wt are reported in Table 3. added and the pH values obtained after each addition; at pH 2.2 1.97 g of pure sulfuric acid (20.1 mg moles) were used per 100 ml of leachate t.q.
2000 ml del suddetto percolato (Camp.1p) sono stati concentrati per evaporazione in apparecchiatura da laboratorio, Rotavapor, alla temperatura di 70 °C, sottovuoto alla pressione di 46 KPa per circa tre ore fino ad una riduzione di volume di 11 volte ottenendo 182 ml di percolato concentrato (Camp.1pc, caratteristiche in Tab.1) di colore bruno scuro e 1818 ml di condense acquose. Dopo raffreddamento a temperatura ambiente, a 100 ml di percolato concentrato, Camp.1pc ( corrispondenti a 1100 ml di percolato t.q.), si aggiungono quantità di acido solforico e si misura il pH fino a completa precipitazione di HS, secondo le stesse modalità ed osservazioni del Camp.1p, precedentemente descritto, dopo centrifugazione si sono ottenuti 41,8 gr. di precipitato umido di HS grezze (Camp.HS1c) con caratteristiche riportate in Tab.2. 2000 ml of the aforementioned leachate (Camp.1p) were concentrated by evaporation in laboratory equipment, Rotavapor, at a temperature of 70 ° C, under vacuum at a pressure of 46 KPa for about three hours until a volume reduction of 11 times obtaining 182 ml of concentrated leachate (Sample 1pc, characteristics in Table 1) of dark brown color and 1818 ml of aqueous condensates. After cooling at room temperature, to 100 ml of concentrated leachate, Camp.1pc (corresponding to 1100 ml of leachate t.q.), quantities of sulfuric acid are added and the pH is measured until complete precipitation of HS, according to the same procedures and observations of the previously described Sample 1p, after centrifugation 41.8 g. of raw HS wet precipitate (Camp.HS1c) with characteristics shown in Tab.2.
In Tab. 3 sono riportati i volumi (ml) ed il peso ( gr.) di acido solforico impiegati vs. pH per: Tab. 3 shows the volumes (ml) and the weight (gr.) Of sulfuric acid used vs. pH for:
1) Camp. 1p per 100 ml di percolato t.q.; 1) Camp. 1p per 100 ml of leachate t.q .;
2) Camp. 1pc per 100 ml di percolato concentrato 11 volte(corrispondente a 1100 ml di percolato t.q.); 2) Camp. 1pc per 100 ml of 11 times concentrated leachate (corresponding to 1100 ml of leachate t.q.);
3) Camp. 1pc normalizzato a 100 ml di percolato t.q. (corrispondente a 9,09 ml di percolato concentrato); 3) Camp. 1pc normalized to 100 ml of leachate t.q. (corresponding to 9.09 ml of concentrated leachate);
Il confronto mostra che sono stati impiegati 5,71gr. (5,82 mgmoli) di acido solforico per 100 ml di percolato concentrato (1pc) che per calcolo corrispondono a 0,519 gr. (5,29 mgmoli) di acido solforico per 100 ml di percolato t.q. prima della concentrazione; mentre per il campione non concentrato (Camp.1p) à ̈ stato necessario una quantità molto più elevata 1,97 gr. (20,1 mgmoli) di acido solforico per 100 ml di percolato t.q. (Camp.1p) con un aumento di tale consumo di ca. 3,7 volte. The comparison shows that 5.71gr was used. (5.82 mgmoles) of sulfuric acid per 100 ml of concentrated leachate (1pc) which by calculation correspond to 0.519 gr. (5.29 mgmoles) of sulfuric acid per 100 ml of leachate t.q. before the merger; while for the non-concentrated sample (Camp.1p) a much higher quantity was needed 1.97 gr. (20.1 mgmoles) of sulfuric acid per 100 ml of leachate t.q. (Camp.1p) with an increase in this consumption of approx. 3.7 times.
In tab 2 si osservano le differenze fra le caratteristiche chimiche dei due campioni, in particolare il prodotto da concentrato (Camp.HS1c) evidenzia un residuo secco a 105°C più elevato, 23,50 %, buon livello di carbonio umico e fulvico, bassi livelli di metalli pesanti, un elevato livello di sali alcalini solubili (sodio, potassio) eventualmente riducibili con successivi lavaggi. Tab 2 shows the differences between the chemical characteristics of the two samples, in particular the concentrated product (Camp.HS1c) shows a higher dry residue at 105 ° C, 23.50%, a good level of humic and fulvic carbon, low levels of heavy metals, a high level of soluble alkaline salts (sodium, potassium) possibly reducible with subsequent washing.
Questo esempio evidenzia la novità dell’invenzione che consiste nell’effettuare l’innovativa precipitazione acida sul percolato concentrato ottenuto per evaporazione termica, ottenendo un’importante riduzione della quantità di acido necessaria con conseguente vantaggio economico. This example highlights the novelty of the invention which consists in carrying out the innovative acid precipitation on the concentrated leachate obtained by thermal evaporation, obtaining an important reduction in the quantity of acid required with consequent economic advantage.
Riguardo la possibile contaminazione da composti organici pericolosi del percolato t.q. (Camp.1p) e del relativo concentrato (Camp.1pc) in tali campioni sono stati ricercati, con metodi analitici normati di adeguata sensibilità e specificità , anche: Regarding the possible contamination of the leachate t.q. by dangerous organic compounds. (Camp.1p) and the relative concentrate (Camp.1pc) in these samples were also searched, with standardized analytical methods of adequate sensitivity and specificity, also:
†policlorobifenili (PCB); ⠀ polychlorinated biphenyls (PCBs);
†idrocarburi policiclici aromatici (IPA) (naftalene, benzo(e)pirene, acenaftilene, acenaftene, fluorene, fenantrene, pirene, benzo(a)antracene, crisene, benzo(b)fluorantene, benzo(k)fluorantene, benzo(a)pirene, indeno(123cd)pirene, dibenzo(ah)antracene, benzo(ghi)perilene, dibenzo(al)pirene, dibenzo(ae)pirene, dibenzo(ai)pirene, dibenzo(ah)pirene); ⠀ polycyclic aromatic hydrocarbons (PAHs) (naphthalene, benzo (e) pyrene, acenaphthylene, acenaphthene, fluorene, phenanthrene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) ) pyrene, indene (123cd) pyrene, dibenzo (ah) anthracene, benzo (ghe) perylene, dibenzo (al) pyrene, dibenzo (ae) pyrene, dibenzo (ai) pyrene, dibenzo (ah) pyrene);
†composti alifatici alogenati cancerogeni (bromoformio, 1,2-dibromometano, clorodibromometano, bromodiclorometano); ⠀ Carcinogenic halogenated aliphatic compounds (bromoform, 1,2-dibromomethane, chlorodibromomethane, bromodichloromethane);
†composti alifatici clorurati non cancerogeni (1,1-dicloroetano, 1,2-dicloroetilene, 1,1,1-tricloroetano, 1,2-dicloropropano, 1,1,2-tricloroetano, 1,2,3-tricloropropano, 1,1,2,2-tetracloroetano); ⠀ non-carcinogenic chlorinated aliphatic compounds (1,1-dichloroethane, 1,2-dichloroethylene, 1,1,1-trichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,2,3-trichloropropane, 1,1,2,2-tetrachloroethane);
†composti alifatici clorurati cancerogeni (clorometano, diclorometano, cloroformio, cloruro di vinile, 1,2-dicloroetano, 1,1-dicloroetilene, tricloroetilene, tetracloroetilene); ⠀ carcinogenic chlorinated aliphatic compounds (chloromethane, dichloromethane, chloroform, vinyl chloride, 1,2-dichloroethane, 1,1-dichloroethylene, trichlorethylene, tetrachlorethylene);
†composti aromatici clorurati (clorobenzene, 1,2-diclorobenzene, 1,4-diclorobenzene, 1,2,4-triclorobenzene); ⠀ chlorinated aromatic compounds (chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene);
†solventi organici aromatici (benzene, toluene, etilbenzene, stirene, xileni, isopropilbenzene). ⠀ aromatic organic solvents (benzene, toluene, ethylbenzene, styrene, xylenes, isopropylbenzene).
I risultati relativi per tutti i suddetti composti organici sono stati di contenuti inferiori ai limiti di rilevabilità dei metodi analitici di 1 mg/Kg. Sono risultati inferiori ai rispettivi limiti di quantificazione analitica anche: The relative results for all the aforesaid organic compounds were of contents below the detection limits of the analytical methods of 1 mg / kg. The following were also below the respective analytical quantification limits:
†idrocarburi totali (< 10 mg/Kg); ⠀ total hydrocarbons (<10 mg / kg);
†idrocarburi C<12 (< 5 mg/Kg); ⠀ C <12 hydrocarbons (<5 mg / Kg);
†idrocarburi C>12 (< 5 mg/Kg). ⠀ C> 12 hydrocarbons (<5 mg / Kg).
Pertanto, anche dopo concentrazione di 11 volte il percolato di discarica “matura†(A) non ha mostrato contaminazione dai suddetti composti organici pericolosi con i limiti di quantificazione analitica specificati. Therefore, even after a concentration of 11 times the â € œmatureâ € (A) landfill leachate did not show contamination by the aforementioned hazardous organic compounds with the specified analytical quantification limits.
Esempio 2) Example 2)
2000 ml di percolato di discarica “matura†(A) come da esempio 1), sono stati concentrati in laboratorio con le modalità , temperatura e pressione come da esempio 1), ottenendo 166 ml di percolato concentrato 12,5 volte (Camp.2pc). 2000 ml of â € œmatureâ € (A) landfill leachate as in example 1), were concentrated in the laboratory with the methods, temperature and pressure as in example 1), obtaining 166 ml of concentrated leachate 12.5 times (Camp. 2pc).
Su una aliquota di 100 ml del suddetto percolato concentrato si sono aggiunte, sotto agitazione a temperatura ambiente (20 °C), quantità successive di acido fosforico al 75 %p (d:1,5) misurando il pH in continuo, come nel precedente esempio, le quantità in volume ed in peso (ml e gr) vs. pH sono riportate in tab.4. per i 100 ml di percolato concentrato e per la quantità di 8 ml di concentrato corrispondente a 100 ml di percolato t.q. non concentrato. On a 100 ml aliquot of the aforementioned concentrated leachate, successive quantities of phosphoric acid at 75% w (d: 1.5) were added under stirring at room temperature (20 ° C), measuring the pH continuously, as in the previous for example, the quantities in volume and weight (ml and gr) vs. pH are shown in table 4. for 100 ml of concentrated leachate and for the quantity of 8 ml of concentrate corresponding to 100 ml of leachate t.q. not concentrated.
Si osserva che la precipitazione di HS inizia, similmente all’esempio 1), a pH 4.4 e finisce a pH 2,3; acido fosforico impiegato à ̈ 143 mgmoli per 100 ml di percolato concentrato e di 11,48 mgmoli per 100 ml di percolato t.q. It is observed that the precipitation of HS begins, similarly to example 1), at pH 4.4 and ends at pH 2.3; phosphoric acid used is 143 mgmoles per 100 ml of concentrated leachate and 11.48 mgmoles per 100 ml of leachate t.q.
Per migliorare la filtrabilità del precipitato à ̈ stato aggiunto a quest’ultimo una soluzione di flocculante, Idrapol C180 (80 mg/100ml), dopo agitazione, si à ̈ filtrato su filtro di carta (fascia nera) sottovuoto ( 0,8 KPa di pressione residua), si sono ottenute HS umide per 31,7 % p/p del percolato concentrato, con residuo secco a 105°C (R105): 26%p. To improve the filterability of the precipitate, a flocculant solution, Idrapol C180 (80 mg / 100ml), was added to the precipitate, after shaking, it was filtered on a paper filter (black band) under vacuum (0.8 KPa residual pressure), wet HS were obtained for 31.7% w / w of the concentrated leachate, with dry residue at 105 ° C (R105): 26% w.
L’impiego dell’acido fosforico consente di ottenere HS contenenti fosfati che normalmente sono impiegati come concimi in agricoltura, consentendo anche una valorizzazione delle materie prime impiegate nella presente invenzione. The use of phosphoric acid allows to obtain HS containing phosphates which are normally used as fertilizers in agriculture, also allowing an enhancement of the raw materials used in the present invention.
Esempio 3) Example 3)
E’ stato utilizzato un percolato concentrato industriale ottenuto per evaporazione termica, sottovuoto, presso un impianto operante in una discarica “matura†(B) avente le seguenti caratteristiche: A concentrated industrial leachate obtained by thermal evaporation, under vacuum, was used at a plant operating in a â € œmatureâ € (B) landfill with the following characteristics:
pH: 9,6 pH: 9.6
residuo secco 105°C (R105) : 14,4 %p. dry residue 105 ° C (R105): 14.4% w.
residuo secco 600°C (R600) : 10,0 %p. dry residue 600 ° C (R600): 10.0% w.
sostanze organiche (R105-R600): 4,37 %p. organic substances (R105-R600): 4.37% w.
cloruri ( Cl): 3,9 %p. chlorides (Cl): 3.9% w.
solfati (SO4): 0,4 %p. sulphates (SO4): 0.4% w.
200ml del suddetto percolato (Camp.3pc) sono stati riscaldati a 65°C, allo scopo di simulare la possibile precipitazione per acidificazione alla temperatura di uscita dal concentratore, quindi mantenendo riscaldato il campione sono state aggiunte quantità progressive, con le stesse modalità riportate nell’esempio 1), di acido solforico al 37,45%p, misurando il pH in continuo, a fine precipitazione, pH: 2,2 sono stati necessari 22 ml di acido solforico (pari all’ 11% in volume del percolato concentrato). 200ml of the aforementioned leachate (Camp.3pc) were heated to 65 ° C, in order to simulate the possible precipitation by acidification at the outlet temperature from the concentrator, therefore, keeping the sample heated, progressive quantities were added, with the same modalities reported in € ™ example 1), of sulfuric acid at 37.45% wt, measuring the pH continuously, at the end of precipitation, pH: 2.2 22 ml of sulfuric acid were needed (equal to 11% by volume of the leachate concentrated).
Nella Tab. 5 sono riportate le quantità , espresse in volume ed in peso, di acido solforico al 37,45 %p. aggiunto a 100ml di percolato concentrato (Camp.3pc) ed i valori di pH ottenuti dopo ogni aggiunta; in totale sono state necessari 53,8 mgmoli/100ml di percolato concentrato, valore molto simile a quello riscontrato nell’esempio 1) di 58,2 mgmoli/100 ml di un diverso percolato concentrato. Table 5 shows the quantities, expressed in volume and weight, of sulfuric acid at 37.45% wt. added to 100ml of concentrated leachate (Camp.3pc) and the pH values obtained after each addition; a total of 53.8 mgmol / 100ml of concentrated leachate was required, a value very similar to that found in example 1) of 58.2 mgmol / 100ml of a different concentrated leachate.
Dalla sospensione ottenuta si sono separate per centrifugazione, come da esempio 1), le HS umide, grezze, (7,1 %p di Camp.3pc ) con residuo secco 105 °C : 28,9 %p; residuo secco 600°C: 17,1 %p; (R105-R600) : 10,8 %p; From the suspension obtained, the wet, raw HS (7.1% wt of Camp.3pc) with a dry residue 105 ° C: 28.9% wt were separated by centrifugation, as in example 1); dry residue 600 ° C: 17.1% wt; (R105-R600): 10.8% w;
Il surnatante, soluzione limpida di colore giallo-bruno, Ã ̈ il 92,9%p con R105: 14,67%p e R600: 12,5%p; (R105-R600): 2,17%p. The supernatant, a clear yellow-brown solution, is 92.9% w with R105: 14.67% w and R600: 12.5% w; (R105-R600): 2.17% wt.
Allo scopo di verificare l’efficienza di purificazione dai sali solubili mediante lavaggi con acqua, al precipitato, separato per centrifugazione, di HS à ̈ stata aggiunta una pari quantità (rapporto 1/1 in peso) di acqua acidificata a pH:1 con acido solforico; dopo normale miscelazione per agitazione, si centrifuga separando il surnatante costituito da una soluzione limpida gialla, dal precipitato lavato di HS; su entrambe le frazioni sono stati determinati: R105; R600; cloruri, solfati; i lavaggi per sequenze successive sono stati quattro. In order to verify the purification efficiency of soluble salts by washing with water, an equal quantity (ratio 1/1 by weight) of acidified water to pH: 1 was added to the precipitate, separated by centrifugation, sulfuric acid; after normal mixing by stirring, it is centrifuged separating the supernatant consisting of a clear yellow solution from the washed precipitate of HS; on both fractions the following were determined: R105; R600; chlorides, sulfates; there were four washes for subsequent sequences.
In Tab.6 sono riportati i risultati analitici, nella quale si osserva: nel surnatante le quantità estratte si riducono di circa il 50%p per ogni lavaggio in accordo col rapporto 1/1 p di lavaggio; dopo il 4° lavaggio si nota che i valori delle determinazioni effettuate sono ridotti a circa il 10% dei valori iniziali, indici di una soddisfacente capacità di estrazione dei sali solubili; In Tab.6 the analytical results are reported, in which it is observed: in the supernatant the extracted quantities are reduced by about 50% w for each wash in accordance with the 1/1 w washing ratio; after the 4th washing it is noted that the values of the determinations carried out are reduced to about 10% of the initial values, indices of a satisfactory ability to extract the soluble salts;
nelle HS precipitate si nota che al 4° lavaggio R105 si à ̈ ridotto del 10,7%p; R600 si à ̈ ridotto del 10,4%p, mentre le sostanze organiche, (R105-R600) sono 11,5%p, praticamente invariate. Questi risultati dimostrano la possibilità di purificare le HS dai Sali solubili con lavaggi con acqua, meglio acidificata. In un sistema di tecnologie integrate, à ̈ possibile utilizzare l’acqua che proviene dalle condense della fase di concentrazione termica, anche sottovuoto, come indicato nello schema di processo di Fig.1. in the precipitated HS it is noted that at the 4th washing R105 was reduced by 10.7% wt; R600 has been reduced by 10.4% p, while the organic substances (R105-R600) are 11.5% p, practically unchanged. These results demonstrate the possibility of purifying HS from soluble salts by washing with water, better acidified. In a system of integrated technologies, it is possible to use the water that comes from the condensates of the thermal concentration phase, even under vacuum, as indicated in the process diagram of Fig.1.
Esempio 4) Example 4)
A 25 kg di percolato concentrato industriale (Camp.4pc), proveniente dall’impianto operante presso la stessa discarica (B) dell’esempio 3) ma di diverso periodo, con le seguenti caratteristiche: 25 kg of concentrated industrial leachate (Camp 4pc), coming from the plant operating at the same landfill (B) of example 3) but of different periods, with the following characteristics:
pH: 9,6 pH: 9.6
densità : 1,1 g/ml density: 1.1 g / ml
Residuo secco 105°C (R105): 13.8 %p Dry residue 105 ° C (R105): 13.8% wt
Residuo secco 600°C (R600): 10. 5%p Dry residue 600 ° C (R600): 10. 5% w
sostanze organiche (R105-R600): 3,3%p organic substances (R105-R600): 3.3% w
calcio (Ca): 0,22 %p calcium (Ca): 0.22% w
sodio (Na): 3.0 %p sodium (Na): 3.0% w
magnesio (Mg) 0.1 %p magnesium (Mg) 0.1% w
sono stati aggiunti, sotto agitazione, 20ml di soluzione di antischiuma siliconico impiegato in esempio 1), e, lentamente controllando l’effervescenza e le relative schiume, alla temperatura ambiente di 20°C, 2,7 litri di acido solforico al 37,45 %p fino a pH: 2,1; si à ̈ ottenuto un precipitato fioccoso, bruno-scuro, al quale viene aggiunto 25 gr. di flocculante Idrapol C180;. il prodotto viene mantenuto sotto agitazione per 1 ora e successivamente filtrato per gravità su tela in polipropilene non tessuto, tipo Polyfelt TS20(4.01), separando il precipitato ed ottenendo 2,5 Kg di HS umide grezze. 20ml of silicone defoamer solution used in example 1) were added under stirring and, slowly checking the effervescence and the relative foams, at an ambient temperature of 20 ° C, 2.7 liters of sulfuric acid at 37, 45% wt up to pH: 2.1; a flaky, dark brown precipitate was obtained, to which 25 gr. of Idrapol C180 flocculant; the product is kept under stirring for 1 hour and subsequently filtered by gravity on a non-woven polypropylene cloth, type Polyfelt TS20 (4.01), separating the precipitate and obtaining 2.5 kg of raw wet HS.
Si preleva una frazione di 10gr. di HS umide grezze e si procede a lavaggi con acqua acidificata a pH:1 con acido solforico in rapporto 1/1 v/v di HS umide/acqua con successiva centrifugazione e separazione del precipitato; in totale sono stati eseguiti a step successivi quattro lavaggi per la purificazione dai Sali solubili in acqua. Si ottiene un campione di HS purificate (Camp.HS4). I risultati dell’analisi del Camp.HS4, espressi in %p sul residuo secco a 105°C, e le metodologie utilizzate sono riportati in tab.7. Si osserva in particolare l’elevato residuo secco a 600°C (17.3%p) ed elevati contenuti in calcio (Ca) (9.5%p) e solfato (SO4) (30.5 %p), fra loro in rapporto molare (0.7:1) tale da far ipotizzare la presenza della maggior parte di ione solfato (SO4) come solfato di calcio (CaSO4). A fraction of 10gr is taken. of raw wet HS and washings are carried out with acidified water at pH: 1 with sulfuric acid in the ratio 1/1 v / v of wet HS / water with subsequent centrifugation and separation of the precipitate; in total, four washes were carried out in successive steps for the purification of the water-soluble salts. A purified HS sample is obtained (Camp.HS4). The results of the analysis of Camp.HS4, expressed in% w on the dry residue at 105 ° C, and the methods used are shown in table 7. In particular, the high dry residue at 600 ° C (17.3% w) and high contents of calcium (Ca) (9.5% w) and sulphate (SO4) (30.5% w), in molar ratio (0.7 : 1) such as to suggest the presence of most of the sulphate ion (SO4) as calcium sulphate (CaSO4).
La composizione del Camp.HS4, parzialmente riprodotta sotto, evidenzia poi un ridotto contenuto di cloruro (Cl), di sodio (Na) e potassio (K): solfati (SO4): 30.5 %s/s The composition of the HS4 sample, partially reproduced below, then shows a reduced content of chloride (Cl), sodium (Na) and potassium (K): sulphates (SO4): 30.5% s / s
cloruri (Cl): 0.37 %s/s chlorides (Cl): 0.37% s / s
calcio(Ca): 9,5 %s/s calcium (Ca): 9.5% s / s
silice (SiO2): 5.9 %s/s silica (SiO2): 5.9% s / s
sodio (Na): 0.22 %s/s sodium (Na): 0.22% s / s
potassio (K): 0.08 %s/s potassium (K): 0.08% s / s
Si osserva pertanto che con le HS precipitano, per acidificazione con acido solforico, i solfati dei metalli alcalino terrosi, in particolare il solfato di calcio, e la silice colloidale. Tali composti sono insolubili nell’acqua acidificata a pH:1 con acido solforico utilizzata per i lavaggi, mentre i Sali dei metalli alcalini, in particolare cloruri (Cl) di sodio (Na) e potassio (K) sono presenti in concentrazione complessivamente inferiore all’1%. It is therefore observed that with HS, the sulphates of alkaline earth metals, in particular calcium sulphate, and colloidal silica precipitate by acidification with sulfuric acid. These compounds are insoluble in acidified water at pH: 1 with sulfuric acid used for washing, while the alkali metal salts, in particular sodium (Na) and potassium (K) chlorides (Cl), are present in a lower overall concentration. at 1%.
Si osserva che solfato di calcio (CaSO4) e silice colloidale (SiO2) sono anche usati come ammendanti, correttori di pH dei terreni in agricoltura (solfato di calcio), e pertanto da percolati ricchi di calcio si possono ottenere con la stessa tecnologia miscele di prodotti che possono svolgere più funzioni utili in agricoltura. It is noted that calcium sulphate (CaSO4) and colloidal silica (SiO2) are also used as soil improvers, pH correctors in agricultural soils (calcium sulphate), and therefore from calcium-rich leachate it is possible to obtain mixtures of products that can perform multiple functions useful in agriculture.
Una piccola aliquota del campione HS4, à ̈ stata essicata in stufa, in aria, a 105°C fino a peso costante, per due ore, circa 0.6 gr. sono stati miscelati con circa 200 mg di bromuro di potassio (KBr) e prodotta una pastiglia per compressione; su questa à ̈ stato eseguito uno spettro in FT-IR, riportato in Fig.2 (spettro N.1) a confronto con gli spettri di pastiglie in KBr, prodotte con la stessa preparativa, di un campione di HS commerciale estratto da leonardite (COM2) (spettro N.2) e di uno standard di solfato di calcio (spettro N.3). Il confronto tra gli spettri evidenzia nello spettro N.1 la contemporanea presenza delle bande di assorbimento caratteristiche di HS commerciale (COM2) e di quelle del solfato di calcio, confermando la presenza di quest’ultimo nel Camp.HS4. A small aliquot of the HS4 sample was dried in an oven, in air, at 105 ° C until constant weight, for two hours, about 0.6 gr. they were mixed with about 200 mg of potassium bromide (KBr) and produced a tablet by compression; an FT-IR spectrum was performed on this, shown in Fig. 2 (spectrum N.1) in comparison with the spectra of KBr tablets, produced with the same preparation, of a sample of commercial HS extracted from leonardite ( COM2) (spectrum No.2) and a calcium sulphate standard (spectrum No.3). The comparison between the spectra highlights in the spectrum N.1 the simultaneous presence of the absorption bands characteristic of commercial HS (COM2) and those of calcium sulphate, confirming the presence of the latter in Camp.HS4.
Riguardo la possibile contaminazione da composti organici non volatili pericolosi, Si osserva in Tab. 7-1 che anche nel percolato da discarica (B)e nelle HS purificate la maggior parte di quelli ricercati non sono presenti a concentrazioni superiori al limite di quantificazione delle tecniche analitiche utilizzate e quelli rilevati lo sono a concentrazioni inferiori ai limiti normativi vigenti in Italia e nell’Unione Europea relative all’uso come ammendante in agricoltura dei fanghi di depurazione, con particolare riguardo ai microinquinanti quali le policlorodibenzodiossine/furani (PCDD/PCDF), 2etilesilftalato, idrocarburi policiclici aromatici (IPA), policlorobifenili (PCB) . Regarding the possible contamination by dangerous non-volatile organic compounds, it is observed in Tab. 7-1 that even in landfill leachate (B) and in purified HS, most of those sought are not present at concentrations higher than the quantification limit of the techniques. analytical methods used and those detected are at concentrations lower than the regulatory limits in force in Italy and in the European Union relating to the use of sewage sludge as a soil improver in agriculture, with particular regard to micropollutants such as polychlorinated dibenzodioxins / furans (PCDD / PCDF ), 2ethylhexyl phthalate, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs).
Riguardo infine la contaminazione biologica nel percolato da discarica (B), nel percolato concentrato ottenuto da questa per evaporazione e nelle HU purificate HS4, le concentrazioni di coliformi totali riscontrati passano da 18000 UFC/100mL nel percolato ad <1 UFC/100mL sia nel percolato concentrato che nelle HU purificate HS4. Ciò dimostra come il processo di concentrazione del percolato per evaporazione termica sottovuoto condotta a Finally, regarding the biological contamination in the landfill leachate (B), in the concentrated leachate obtained from this by evaporation and in the purified HS4 HU, the concentrations of total coliforms found go from 18000 UFC / 100mL in the leachate to <1 UFC / 100mL and in the leachate concentrated than in HS4 purified HU. This demonstrates how the process of concentrating leachate by vacuum thermal evaporation conducted a
Dr. Ing. PAOLO PIOVESANA temperatura elevata sia efficace nella sterilizzazione del percolato concentrato. Una ulteriore garanzia di sterilizzazione delle HU precipitate à ̈ il trattamento acido fino a pH 2 del percolato concentrato. Dr. Ing. PAOLO PIOVESANA high temperature is effective in the sterilization of concentrated leachate. A further guarantee of sterilization of the precipitated HU is the acid treatment up to pH 2 of the concentrated leachate.
Le salmonelle invece non sono state rilevate né nel percolato da discarica (B), né nel percolato concentrato, né nel campione di HU purificate HS4. Salmonella, on the other hand, were not detected in the landfill leachate (B), nor in the concentrated leachate, nor in the HS4 purified HU sample.
Esempio 5) Example 5)
A 200 ml di percolato concentrato industriale proveniente dalla medesima discarica ( B) degli esempi 3-4) ma di diverso periodo (Camp.5pc) con le seguenti caratteristiche: A 200 ml of concentrated industrial leachate coming from the same landfill (B) as examples 3-4) but of a different period (Camp 5pc) with the following characteristics:
pH: 10 pH: 10
residuo secco 105°C (R105) : 15,4 %p. dry residue 105 ° C (R105): 15.4% w.
residuo secco 600°C (R600) : 11,1 %p. dry residue 600 ° C (R600): 11.1% w.
sostanze organiche (R105-R600): 4,3 %p. organic substances (R105-R600): 4.3% w.
cloruri (Cl): 4.2 %p. chlorides (Cl): 4.2% w.
solfati (SO4): 0,6 %p. sulphates (SO4): 0.6% w.
Si aggiunge, sotto agitazione, con le modalità descritte nei precedenti esempi, 1ml di antischiuma (Dinapan16WD al 10%p) e progressive quantità di acido cloridrico al 37,45%p (densità : 1,186 g/ml) misurando il pH in continuo fino a completa precipitazione delle HS a pH: 2,0. 1ml of antifoam (Dinapan16WD at 10% w) and progressive quantities of hydrochloric acid at 37.45% w (density: 1.186 g / ml) are added, under stirring, with the methods described in the previous examples, measuring the pH continuously up to after complete precipitation of the HS at pH: 2.0.
In Tab. 8 e Fig. 3 sono riportati i volumi e pesi (ml e gr.) di acido cloridrico vs. pH. In Tab. 8 and Fig. 3 the volumes and weights (ml and gr.) Of hydrochloric acid vs. pH.
A pH: 4,3 si osserva l’inizio della precipitazione, come nei precedenti esempi, di un solido fioccoso, bruno-scuro, che si completa a pH:2,0. Sono stati utilizzati in totale 15,6 ml di soluzione di acido cloridrico al 37,45%p (d:1,186 gr/ml), 6,85 gr. di acido puro, corrispondenti a 3,42 gr. di acido per 100 ml di percolato concentrato (Camp.5pc) equivalenti a 95 mgmoli di acido (HCl). At pH: 4.3 we observe the beginning of the precipitation, as in the previous examples, of a dark brown flaky solid, which is completed at pH: 2.0. A total of 15.6 ml of 37.45% w hydrochloric acid solution (d: 1.186 g / ml), 6.85 g were used. of pure acid, corresponding to 3.42 gr. of acid per 100 ml of concentrated leachate (Camp.5pc) equivalent to 95 mgmoles of acid (HCl).
Dopo l’aggiunta del flocculante e successiva centrifugazione, come nei precedenti esempi, si à ̈ separato un solido di HS umide grezze (Camp.HS5g) di 20,0 gr. pari al 10%p di (5pc) con residuo secco a 105°C del 25%p. After the addition of the flocculant and subsequent centrifugation, as in the previous examples, a solid of raw wet HS (Camp.HS5g) of 20.0 g was separated. equal to 10% wt of (5pc) with a dry residue at 105 ° C of 25% w.
Dopo essiccamento a 105°C fino a peso costante, un’aliquota di HS5g à ̈ stata sottoposta a quattro lavaggi successivi con acqua acidificata a pH: circa 1 con acido cloridrico con le modalità descritte nell’esempio 4. Si à ̈ recuperato un solido di HS umide purificate (Camp.HS5) con residuo secco a 105°C del 36%p. Una volta essiccato a 105°C il campione HS5 ha un peso pari al 26% del peso di HS5g essiccato a 105°C da cui à ̈ stato ottenuto. After drying at 105 ° C to constant weight, an aliquot of HS5g was subjected to four successive washes with acidified water to pH: about 1 with hydrochloric acid with the methods described in example 4. It was recovered a solid of purified humid HS (Camp.HS5) with a dry residue at 105 ° C of 36% w. Once dried at 105 ° C, the HS5 sample has a weight equal to 26% of the weight of HS5g dried at 105 ° C from which it was obtained.
In Tab. 9, sono riportate le caratteristiche dei campioni HS5g ed HS5. Da Tab. 9 si osserva che impiegando l’acido cloridrico per la precipitazione di HS si riduce drasticamente la presenza di solfato di calcio e di eventuali altri composti inorganici insolubili nelle HS purificate. Il campione HS5 presenta infatti un residuo secco a 600°C del 3.7% (pari al 10% del residuo secco a 105°C) mentre il campione HS4, ricco in solfato di calcio, presenta un residuo secco a 600°C del 17.3% (pari al 48% del residuo secco a 105°C) . Tab. 9 shows the characteristics of the HS5g and HS5 samples. From Tab. 9 it can be observed that by using hydrochloric acid for the precipitation of HS, the presence of calcium sulphate and any other insoluble inorganic compounds in the purified HS is drastically reduced. The HS5 sample has in fact a dry residue at 600 ° C of 3.7% (equal to 10% of the dry residue at 105 ° C) while the HS4 sample, rich in calcium sulphate, has a dry residue at 600 ° C of 17.3% (equal to 48% of the dry residue at 105 ° C).
Inoltre come mostrato negli esempi 1), 2) 3) anche in questo esempio à ̈ dimostrato che l’inizio della precipitazione avviene per pH inferiori a 5 e si completa per pH inferiori a pH: 2,5 per tipi di percolati diversi ed acidi inorganici diversi. Furthermore, as shown in examples 1), 2) 3) also in this example it is shown that the beginning of precipitation occurs for pH lower than 5 and is completed for pH lower than pH: 2.5 for different types of leachate and different inorganic acids.
Piccole quote dei campioni HS5g ed HS5, essiccate in stufa, in aria, a 105°C fino a peso costante, per due ore, sono stati miscelati con bromuro di potassio e pastigliate, su queste sono stati eseguiti gli spettri in FT-IR, similmente a quanto fatto per HS4 in esempio 4. In Fig.4 sono riportati lo spettro di HS5g (spettro N.1), di HS5 (spettro N.2) a confronto con lo spettro un campione di HS commerciale estratto da leonardite (COM2) (spettro N.3). Gli spettri di HS5g ed HS5 sono fra loro molto simili, evidenziando l’assenza di variazioni significative in seguito al processo di lavaggio. Entrambi presentano una buona sovrapponibilità con quello del prodotto commerciale. Small portions of HS5g and HS5 samples, dried in an oven, in air, at 105 ° C to constant weight, for two hours, were mixed with potassium bromide and tableted, on these spectra were performed in FT-IR, similarly to what was done for HS4 in example 4. Fig.4 shows the spectrum of HS5g (spectrum N.1), of HS5 (spectrum N.2) compared with the spectrum a sample of commercial HS extracted from leonardite (COM2 ) (spectrum # 3). The spectra of HS5g and HS5 are very similar to each other, highlighting the absence of significant variations following the washing process. Both have a good overlap with that of the commercial product.
In Fig. 5 sono riportati gli spettri N.1 e N.2 di Fig.4 assieme allo spettro N.4, ottenuto con analoghe modalità , dallo standard di HS denominato “Humic Acid†CAS 1415-93-6, sinonimi: NHA; pgs10; humic; enersol; agro-lig; humicacids; ulmicacids; Humic acid; Humifulvate; humification; Formula molecolare (minima) C9H9NO6; peso molecolare minimo: 227.17; materie prime: Lignite, idrossido di potassio, acido nitrico, idrossido di sodio. Gli spettri dei campioni HS5g ed HS5 mostrano buona sovrapponibilità anche con lo spettro del suddetto materiale di riferimento In Fig. 5 the spectra N.1 and N.2 of Fig.4 are shown together with the spectra N.4, obtained with similar modalities, from the HS standard called â € œHumic Acidâ € CAS 1415-93-6, synonyms: NHA; pgs10; humic; enersol; agro-lig; humicacids; ulmicacids; Humic acid; Humifulvate; humification; Molecular formula (minimum) C9H9NO6; minimum molecular weight: 227.17; raw materials: Lignite, potassium hydroxide, nitric acid, sodium hydroxide. The spectra of the HS5g and HS5 samples show good overlap even with the spectrum of the aforementioned reference material
Esempio 6) Example 6)
20,0 Kg. di percolato t.q. di una discarica matura italiana (C) (Camp.6p) à ̈ stato concentrato in laboratorio di 18 volte, ottenendo 1,10 Kg. di percolato concentrato (Camp.6pc) con le modalità operative riportate nei precedenti esempi e con le caratteristiche riportate in Tab.10, nella quale per il concentrato (6pc) si rileva in particolare la netta riduzione dell’azoto ammoniacale e dei solfuri. 20,0 Kg. Of leachate t.q. of an Italian mature landfill (C) (Camp.6p) was concentrated in the laboratory 18 times, obtaining 1.10 Kg. of concentrated leachate (Camp.6pc) with the operating methods reported in the previous examples and with the characteristics reported in Tab.10, in which for the concentrate (6pc) the net reduction of ammonia nitrogen and sulphides is noted in particular.
Al percolato concentrato (6pc) à ̈ stato aggiunto acido solforico al 37,45%p fino a pH: 2,0, con le stesse modalità riportate nell’esempio 4) ottenendo un precipitato fioccoso, bruno-scuro che separato, per centrifugazione, dal surnatante (soluzione limpida di acque madri), costituisce il campione di HS umide, grezze, non purificate con lavaggi con acqua; a questo campione di sospensione di HS à ̈ stato aggiunto idrossido di potassio (KOH) fino a neutralità (pH:7.0 ) ottenendo una soluzione acquosa di umati di potassio solubili (Camp.HS6). Le caratteristiche del suddetto campione a confronto di un prodotto commerciale (COM1) di soluzione di umati di potassio e di un ulteriore prodotto commerciale di HS in polvere (COM2) estratti da minerale Leonardite sono riportate in Tab.11. To the concentrated leachate (6pc) was added sulfuric acid at 37.45% wt up to pH: 2.0, with the same procedures reported in example 4) obtaining a flaky, dark-brown precipitate that separated, by centrifugation , from the supernatant (clear solution of mother liquors), constitutes the sample of wet, raw HS, not purified by washing with water; potassium hydroxide (KOH) was added to this sample of HS suspension until neutrality (pH: 7.0) obtaining an aqueous solution of soluble potassium humates (Camp.HS6). The characteristics of the aforesaid sample compared to a commercial product (COM1) of potassium humate solution and a further commercial product of HS in powder (COM2) extracted from Leonardite mineral are reported in Tab. 11.
Si osserva in particolare che il campione (HS6) in soluzione contiene una quantità di carbonio umico simile al campione commerciale in soluzione (COM1), le quantità di Sali inorganici solubili (residuo a 600°C) sono simili e costituiti da Sali alcalini (potassio, sodio) di cloruri, solfati, in particolare il campione in polvere (COM2) evidenzia elevate quantità di fosforo, i metalli pesanti sono bassi e praticamente simili fra i tre campioni ed entro i limiti delle Normative per le applicazioni in agricoltura,i due campioni commerciali ottenuti per estrazione da Leonardite mostrano più elevate quantità di ferro, che tuttavia à ̈ utilizzato come ammendante in agricoltura. In particular, it is observed that the sample (HS6) in solution contains a quantity of humic carbon similar to the commercial sample in solution (COM1), the quantities of soluble inorganic salts (residue at 600 ° C) are similar and made up of alkaline salts (potassium , sodium) of chlorides, sulphates, in particular the powder sample (COM2) shows high quantities of phosphorus, the heavy metals are low and practically similar between the three samples and within the limits of the Regulations for applications in agriculture, the two samples commercial products obtained by extraction from Leonardite show higher quantities of iron, which however is used as a soil conditioner in agriculture.
Pertanto si à ̈ dimostrato che con le HS ottenute per precipitazione acida da percolato concentrato à ̈ possibile preparare prodotti di composizione simile a quella dei vari e diversi prodotti commerciali impiegati in agricoltura. Therefore it has been shown that with HS obtained by acid precipitation from concentrated leachate it is possible to prepare products with a composition similar to that of the various and different commercial products used in agriculture.
Esempio 7) Example 7)
I campioni dell’esempio precedente 6), (HS6) e (COM1), come soluzioni di HS, sono stati analizzati dal Laboratorio di Analisi Chimico-Agraria del Dipartimento di Biotecnologie Agrarie dell’Università di Padova (Italia) per determinare la loro attività biostimolante secondo i metodi indicati in: The samples of the previous example 6), (HS6) and (COM1), as solutions of HS, were analyzed by the Chemical-Agricultural Analysis Laboratory of the Department of Agricultural Biotechnology of the University of Padua (Italy) to determine the their biostimulating activity according to the methods indicated in:
†Fertilias Agrorum 1(1): 47-53 –Serenella Nardi, Andrea Ertani, Giuseppe Concheri, Diego Pizzeghiello – “Metodi di determinazione dell’attività biostimolante†⠀ Fertilias Agrorum 1 (1): 47-53 â € “Serenella Nardi, Andrea Ertani, Giuseppe Concheri, Diego Pizzeghiello - â € œMethods for determining the biostimulating activityâ €
In Tab. 12 sono riportate le caratteristiche delle HS quali: densità , carbonio organico totale (TOC), carbonio Estraibile Totale(TEC), acidi Umici (HA), acidi Fulvici(HF);Grado di umificazione HD=(HA+HF)/TEC; Tasso di umificazione HR=(HA+HF)/TOC, indice di umificazione HI=[ TEC-(HA+HF)] / (HA+HF). Tab. 12 shows the characteristics of the HS such as: density, total organic carbon (TOC), total extractable carbon (TEC), humic acids (HA), fulvic acids (HF); Humification degree HD = (HA + HF) / TEC; Humification rate HR = (HA + HF) / TOC, humification index HI = [TEC- (HA + HF)] / (HA + HF).
I due campioni mostrano valori simili, entrambi con umificazione(HD, hR, hI) soddisfacente, tipici di prodotti “maturi†. The two samples show similar values, both with satisfactory humification (HD, hR, hI), typical of â € œmatureâ € products.
La distribuzione dei pesi molecolari, tab.13, determinati mediante permeazione in gel (LPLC), simile fra i due campioni, con il Camp.HS6 che mostra un maggior quantitativo di 1^ e 3^ frazione, generalmente correlate con il grado di maturazione e attività biologica delle HS. Anche l’attività biostimolante determinata con il biosaggio †AUDUS†, tab14, nel quale i due campioni sono stati trattati con quantità crescenti di acido 3indoleacetico e acido gibberellico(GA3) per determinare l’inibizione dello sviluppo radicale su crescione e la stimolazione dell’allungamento dell’ipocotile su radicchio biondo di Trieste, ottenendo la massima attività auxinica per il Camp.HS6, mentre entrambi i campioni non hanno manifestato alcuna attività gibberellinica. The molecular weight distribution, table 13, determined by gel permeation (LPLC), similar between the two samples, with the HS6 sample showing a greater quantity of 1st and 3rd fraction, generally correlated with the degree of ripeness and biological activity of HS. Also the biostimulating activity determined with the bioassay ⠀ AUDUS⠀, tab14, in which the two samples were treated with increasing quantities of 3indoleacetic acid and gibberellic acid (GA3) to determine the inhibition of root development on watercress and stimulation of hypocotyl elongation on blond radicchio from Trieste, obtaining the maximum auxin activity for Camp.HS6, while both samples did not show any gibberellin activity.
Infine sono riportate in Tab.15 le valutazioni dell’attività biostimolante su plantule di mais di 14gg.; Finally, the evaluations of the biostimulating activity on corn seedlings of 14 days are reported in Tab.15;
la prova, che consiste in un allevamento idroponico di plantule di mais per 12gg con sostituzione giornaliera della soluzione nutritiva ci segue un periodo di 48 ore nel quale le plantule sono poste a contatto con due concentrazioni (1,0 ml e 0,5 ml per litro) dei due campioni di estratti umici, ha evidenziato che il Camp.HS6 un migliore e buon accrescimento del peso fresco della plantula. the test, which consists of a hydroponic breeding of maize seedlings for 12 days with daily replacement of the nutrient solution, follows a period of 48 hours in which the seedlings are placed in contact with two concentrations (1.0 ml and 0.5 ml for liter) of the two samples of humic extracts, showed that Camp HS6 a better and good growth of the fresh weight of the seedling.
Pertanto l’esempio dimostra che le sostanze umiche HS anche grezze, come ottenute col procedimento della presente invenzione, anche senza lavaggi per ridurre i Sali solubili (purificazione) evidenziano buone caratteristiche per l’applicazione quali ammendanti in agricoltura. Therefore, the example shows that HS humic substances, even raw, as obtained with the process of the present invention, even without washing to reduce soluble salts (purification), show good characteristics for application as soil improvers in agriculture.
La presente invenzione à ̈ stata illustrata e descritta in una sua preferita forma di pratica realizzazione ed in alcuni esempi ma si intende che altre varianti realizzative potranno ad essa in pratica apportarsi senza peraltro uscire dall’ambito di protezione del presente brevetto per invenzione industriale. The present invention has been illustrated and described in a preferred embodiment thereof and in some examples but it is understood that other embodiments may be applied to it in practice without however departing from the scope of protection of the present patent for industrial invention.
Claims (12)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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IT000013A ITVE20120013A1 (en) | 2012-04-10 | 2012-04-10 | PROCEDURE FOR RECOVERY OF HUMIC SUBSTANCES FROM PERCOLATE COMING FROM LANDFILL OF SOLID URBAN OR ASSIMILABLE WASTE AND HUMAN SUBSTANCE OBTAINED BY PROCEEDINGS. |
CN201380019216.6A CN104245164B (en) | 2012-04-10 | 2013-03-22 | The method reclaiming humus from the transudate deriving from urban solid garbage field etc. |
PCT/EP2013/056081 WO2013152943A1 (en) | 2012-04-10 | 2013-03-22 | Process for recovering humic substances from percolate originating from urban solid refuse dumps or the like, and humic substance obtained by the process |
ROA201400754A RO130328B1 (en) | 2012-04-10 | 2013-03-22 | Process for recovering humic substances from percolate originating from urban solid refuse dumps or the like and humic substances obtained by said process |
HK15100464.0A HK1200024A1 (en) | 2012-04-10 | 2015-01-15 | Process for recovering humic substances from percolate originating from urban solid refuse dumps or the like, and humic substance obtained by the process |
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IT000013A ITVE20120013A1 (en) | 2012-04-10 | 2012-04-10 | PROCEDURE FOR RECOVERY OF HUMIC SUBSTANCES FROM PERCOLATE COMING FROM LANDFILL OF SOLID URBAN OR ASSIMILABLE WASTE AND HUMAN SUBSTANCE OBTAINED BY PROCEEDINGS. |
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HK (1) | HK1200024A1 (en) |
IT (1) | ITVE20120013A1 (en) |
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WO (1) | WO2013152943A1 (en) |
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CN105152387A (en) * | 2014-06-09 | 2015-12-16 | 三菱丽阳株式会社 | Processing method and device for waste water containing humic matter |
JP6743352B2 (en) * | 2014-06-09 | 2020-08-19 | 三菱ケミカル株式会社 | Humin-containing wastewater treatment method and humin-containing wastewater treatment device |
JP6861478B2 (en) * | 2015-08-17 | 2021-04-21 | 三菱ケミカルアクア・ソリューションズ株式会社 | Treatment method and treatment equipment for humic acid-containing wastewater |
WO2020152707A1 (en) * | 2019-01-21 | 2020-07-30 | Dr Prasad Vanita | Heavy metal removal from industrial effluents by combination of aerobic and anaerobic treatment |
JP2022529935A (en) * | 2019-04-15 | 2022-06-27 | ストラ エンソ オーユーイー | A method for recovering a solvent, a method for isolating humus, and a composition comprising a solvent or humus. |
CN111661979B (en) * | 2020-06-08 | 2022-05-13 | 厦门嘉戎技术股份有限公司 | Leachate recycling method and device |
LU501059B1 (en) | 2021-12-21 | 2023-06-21 | Luxembourg Inst Science & Tech List | Method for the production of a humic and fulvic acid based biostimulant and fertiliser |
CN114291931A (en) * | 2021-12-31 | 2022-04-08 | 东江环保股份有限公司 | Resource treatment method for landfill leachate |
Citations (2)
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JPS58112086A (en) * | 1981-12-25 | 1983-07-04 | Hitachi Plant Eng & Constr Co Ltd | Purification of waste water contg. biologically difficulty-decomposable substance |
US4459149A (en) * | 1982-09-24 | 1984-07-10 | Moran Edward F | Process for treating humus materials |
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ES2100123B1 (en) * | 1995-04-26 | 1998-01-01 | Depuracion Y Reciclaje S L | NEW PROCEDURE FOR THE PURIFICATION OF SPILLS WITH HIGH CONTENT OF ORGANIC MATTER. |
CN100404444C (en) * | 2006-09-01 | 2008-07-23 | 清华大学 | Method for decreasing sewage sludge from town and changing it to resources |
CN100448917C (en) * | 2006-09-27 | 2009-01-07 | 清华大学 | Method of extracting humic acids from rubbish percolation liquid membrane process concentrated liquid |
CN100519451C (en) * | 2007-03-05 | 2009-07-29 | 清华大学 | Method of resource protection, decrement treatment of town sewage and sludge |
CN101701025B (en) * | 2009-10-30 | 2013-03-20 | 华南理工大学 | Method for extracting humus acid from concentrated waste percolate and treating waste water |
CN102211794B (en) * | 2010-04-07 | 2013-01-23 | 中国科学院工程热物理研究所 | Landfill gas burning bubble bed and method for treating leachate by evaporating |
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2012
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58112086A (en) * | 1981-12-25 | 1983-07-04 | Hitachi Plant Eng & Constr Co Ltd | Purification of waste water contg. biologically difficulty-decomposable substance |
US4459149A (en) * | 1982-09-24 | 1984-07-10 | Moran Edward F | Process for treating humus materials |
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HK1200024A1 (en) | 2015-07-31 |
CN104245164A (en) | 2014-12-24 |
WO2013152943A1 (en) | 2013-10-17 |
RO130328B1 (en) | 2019-07-30 |
CN104245164B (en) | 2016-11-16 |
RO130328A2 (en) | 2015-06-30 |
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