CN1146169A - Process for treatment of contaminated land - Google Patents
Process for treatment of contaminated land Download PDFInfo
- Publication number
- CN1146169A CN1146169A CN95192575A CN95192575A CN1146169A CN 1146169 A CN1146169 A CN 1146169A CN 95192575 A CN95192575 A CN 95192575A CN 95192575 A CN95192575 A CN 95192575A CN 1146169 A CN1146169 A CN 1146169A
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- China
- Prior art keywords
- soil
- metal
- sulfate
- sulfide
- sulfuric acid
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 23
- 239000002689 soil Substances 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 59
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 22
- 244000005700 microbiome Species 0.000 claims description 17
- 239000003344 environmental pollutant Substances 0.000 claims description 13
- 231100000719 pollutant Toxicity 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000002306 biochemical method Methods 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 125000004122 cyclic group Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000001131 transforming effect Effects 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 3
- 230000003851 biochemical process Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000000035 biogenic effect Effects 0.000 description 6
- 230000004992 fission Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000015097 nutrients Nutrition 0.000 description 6
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- 230000036983 biotransformation Effects 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 241000605716 Desulfovibrio Species 0.000 description 3
- 241000605118 Thiobacillus Species 0.000 description 3
- 229910052768 actinide Inorganic materials 0.000 description 3
- 150000001255 actinides Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000186541 Desulfotomaculum Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 241000228347 Monascus <ascomycete fungus> Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005255 beta decay Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000009277 landfarming Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005258 radioactive decay Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007616 round robin method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- 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
- C02F11/004—Sludge detoxification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/10—Apparatus specially adapted for treating harmful chemical agents; Details thereof
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Microbiology (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Molecular Biology (AREA)
- Water Supply & Treatment (AREA)
- General Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Biomedical Technology (AREA)
- Toxicology (AREA)
- Mycology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
A process for the treatment of metal species contaminated land or soil which includes the steps of treating the land or soil to convert the metal species into metal sulphate and thereafter treating the land or soil to convert the metal sulphate contained therein by a biochemical process into insoluble metal sulphide.
Description
The present invention relates to a kind of processing method of contaminated land, particularly relate to a kind of biochemical method, in order to fixedly soil or pollutant in soil, especially heavy metal contaminants.
Worldwide, because industry, Waste disposal and other movable result, a large amount of soils is polluted by organic and inorganic compound.The example of these pollutants comprises: poisonous heavy metal comprises mercury, cadmium, barium and lead, radionuclide such as actinides and fission product, and organic pollution such as Polychlorinated biphenyls (PCBs), dioxin (dioxins), coal tar and trichloro-ethylene.These pollutant serious threat underground water, and serious threat drinking water supply therefrom, and restriction or hinder re-using of soil in many cases.In addition, because legislation of the modern times of the U.S. and the result that European Economic Community's scope is interior and other local cardinal principles are similarly made laws, if the waste maker is for their not action responsibly of refuse, they will bear the legal liabilities that increase day by day and be that regeneration is paid a price with purification.Therefore, the technology for energy contaminated solution soil problem has growing needs.
So far, some technology have been developed with the improvement contaminated ground.Example comprises: soil stabilization, electromigration, vitrifying, volatilization, burning, soil washing, pump and treatment system, land farming, mud is biological modification etc. mutually.Many these known technologies have a series of limitation, comprising:
A) be not suitable for handling the soil of metallic pollution, for example under bio-pump and treatment system situation;
B) produce the secondary refuse be difficult to manage with disposal and/or large volume, for example soil stabilization and
Under the burning situation;
C) be not suitable for handling on the spot the soil, for example many soil washings and systems stabilisation require returning on the spot
Excavate soil before filling out and carry out preliminary treatment;
D) be not suitable for handling the variation of different regions, for example the efficient of removing metal with electrokinetic technique is subjected to
Have the restriction of deposited salt or secondary mineral, the efficient of soil stabilization technology is had
The restriction of machine thing;
E) expensive, technology such as landfill, burning, vitrifying and electrokinetics for example.
The object of the present invention is to provide the minimize method of processing contaminated land of degree of above-mentioned shortcoming.
According to the present invention, a kind of method of handling metal species contaminated land or soil is provided, this method comprises handles the soil or soil is the step of metal sulfate to transform metal species, and handles metal sulfate that soil or soil will wherein be comprised is converted into insoluble metal sulfide with biochemical method step afterwards.Other slaine that is included in soil or the soil is reduced similarly.
Metal species is converted into metal sulfate, can be realized by the method that soil or soil contact with sulfuric acid solution or solution of metal sulfates.Use another kind of method, soil or soil can cause the sulphur-containing substance source to generate sulfuric acid with for example following biochemical method in soil or in external bioreactor to carry out biology and leach.The sulfuric acid of Sheng Chenging can make the dissolving of metal species pollutant thus.
Can have a series of metal kinds in soil or soil, these metal species can be converted into various metal sulfates together.Used this term of " metal species " (" metal species ") of this literary composition comprises metal, alloy, slaine, metalloid and metallic compound and complex.
For this reason, the present invention has advantageously provided metal (particularly heavy metal) method of mineralising on the spot in contaminated land with insoluble sulfide that makes.This method and the existing biochemical method in organic pollutant degradation and processing metallic pollution soil that makes are suitable, for example in applicant common unsettled GB9414426.8 and the circulation means to save the situation described in the GB9414425.0 (proposing the theme of two common unsettled PCT applications therewith same date).This method is specially adapted to:
1, the metal that has insoluble sulfate, and be not suitable for therefrom leaching or sulfuric acid with biological
Washing to be to remove these metals, for example lead and barium.
2, metallic pollution seriously occurs in below ground, and is not suitable for therefrom non-ly just being located in
The reason technology for example derives from the pollution of underground storage tank.
3, conduct is as GB9414426.8 and the described circulating biological of the GB9414425.0 side of remedying
" locked in " operation in the method after biological on the spot the leaching.This can prevent surplus after the remediation
Surplus metal enters underground water.
4, pollute and to appear at the anoxybiotic area, maybe can keep anoxybiotic thereby can not leach processing
The area.
5, processing procedure enters minimizing the metal concentration of underground water aquifer to reach acceptable limit
Degree.
6, processing procedure will make pollutant move to more the depths in the soil and danger is subtracted
Little.
The present invention includes the step of converting of sulfate, promote naturally-occurring or add SRB at Polluted area to sulfide so that water-based metal sulfate directly or the effect by hydrogen sulfide be converted into insoluble metal sulfide.This microorganism transformed be can carry out and Desulfovibrio (Desulfovibrio), desulfurization monascus (Desulfomonas) and Desulfotomaculum (Desulfotomaeulum) comprised.The simple organic compound of these microbiological oxidations such as lactate and ethanol, and sulphate reducing is a sulfide simultaneously, to obtain the essential energy of they growths.Yet the carbon element source of more complicated also is employed sometimes, for example the compound of phenol or the organic substance in soil.
Because SRB (SRB) is for their growth needs anoxybiotic environment, promptly oxidation-reduction potential＜-100nV, and existence naturally in the soil environment of anoxybiotic is so they are ideally suited in being applied in the sulfate step of converting.In addition, owing to avoided the necessity of oxygen supply, so overcome a major defect of many existing processes of bioremediation on the spot.
Except that the organic electronq donor of needs, also need to add of the growth and activity of one or more nourishing additive agents to promote them to SRB, this additive comprises following one or more: sulfate, phosphate, ammonium and have magnesium sulfate or calcium chloride, determine by particular scene.The available existing method of one or more of these components is injected Polluted area.
Metal for fear of any nutrient or dissolving escapes into underground water source, and this method also can comprise the leachate recovery system.In this way, leachate can be drawn out of, collects and separate from soil.Insoluble sulfide can be stayed in the soil, because they bring near the dangerous little of pollution of waterhead.
The metal species pollutant can be included in the surface of soil particulate matter or be combined in the inside of this particulate matter in the soil of handling according to the inventive method.
The metal of described metal species pollutant can comprise:
I) actinides or their radioactive decay product or its compound;
Ii) fission product;
Iii) heavy metal or its compound.
Actinides is the element of atomic number in 89 to 104 scopes.
The used term " fission product " of this literary composition when being meant as fuel fission direct product (or usually said " fission fragment ") and the element that forms and the product that forms through β decay or interior transition by these direct products.Element in fission product is included in the periodic table from selenium to the cerium scope comprises that element for example
56Ba,
40Zr and
52Te,
55Cs and
58Ce.
The on-radiation heavy metal land pollution thing of handling with the inventive method includes noxious metals such as nickel, lead, cadmium, barium and mercury, and these metals are usually near use contains the factory of chemicals of these elements and found in as clay contaminated thing or the precipitum at water in the Waste disposal place.
The metal species pollutant that is fixed in the methods of the invention can comprise the mixture of radioactive and inactive metal species pollutant.
In using the method according to this invention, can be injected in the soil handled or the soil or mix mutually with it with the conversion of realization to metal sulfate but the aqueous solution and bio-transformation are the suitable mixture in the sulphur-containing substance source of sulfuric acid.Other component such as rich nitrogen or rich phosphorus substance and air can randomly add.Bio-transformation to sulfate can be realized in a known way by the microorganism medium that are present in the soil.These microorganism medium can exist or be added in the soil naturally.Described sulphur-containing substance can comprise other reduction form of elemental sulfur or sulphur, preferably injects in water-bearing media.
But as the another kind system of selection, the sulfuric acid in each above-mentioned example can be in the bioreactor that separates chemically or biochemistry ground produce, and after producing, be added in soil or the soil material.
The generation of metal sulfate also can cause by adding other slaine, and sodium sulphate for example is to react with contaminant metals.
When the bio-transformation that produces sulfate ion is when carrying out in processed soil, this bio-transformation can be caused that by the known action of abiogenous sulfur-oxidizing microorganisms these sulfur-oxidizing microorganisms comprise: Thiobacillus ferooxidans (thiobacillus ferrooxidant) and Thiobacillus thiooxidans (Thiobacillus thioxidans).The reduction form of these microorganisms by sulphur is oxidized to metal sulfate and sulfuric acid or is that ferric ion obtains their necessary energy of growing by the oxidation ferrous ion.Remove above-mentioned acidleach out, metal disengages also and can take place by following one or more mechanisms:
A) the direct chemical etch of metal sulfide;
B) electrochemical process (galvanic cell transforms (Galvanic conversion)), this process results from and is immersed in
Suitable electrolyte, as sulfuric acid, in two kinds of different metal kinds between contact; Or
C) oxidation of ferric sulfate.
Be used in soil forming the acid of metal sulfate, can be by the sulfur-oxidizing microorganisms of existence naturally, Thiobacilli (thiobacilli) for example, association (consortinm) growth and produce.If soil lacks suitable microorganism, then these microorganisms can be used as the conglomeration body that obtains and are added into from similar soil environment.
In a special case of the present invention, sulfate is to the conversion on the spot (reduction) of sulfide, can carry out according to the round-robin method of handling contaminated land, as the applicant 9414426.8 or 9414425.0 described in.In both situations, metal species in contaminated land is leached by biology with sulphate form, described sulfate is reduced to sulfide in the bioreactor that separates, and hydrogen sulfide and solvable sulfide are separated from insoluble sulfide and are converted into the sulphur-containing substance form that can re-use and re-uses so that leach in the step at biology.The reduction on the spot of sulfate can promptly be carried out at the end of cyclic process in that easy dissolution of metals is carried out after biological the leaching with metal sulfate (or other soluble salt) form.The soil that biological leaching was handled can add the suitable microorganism of artificial cultivation to be handled, and generates the needed SRBs of sulfide (SRB) on the spot to provide.This microorganism can with this method circulation time in bioreactor, use identical.In fact, the described microorganism that is applied to the soil can be to provide more used in the bioreactor that generates sulfide in cycle period.
Now embodiment of the present invention are described by example and method with reference to the accompanying drawings, wherein:
Fig. 1 is with the sectional schematic diagram that embodies used in zone, soil that method of the present invention handles on the spot and the method.
As shown in Figure 1, handle with the circularly purifying process at first in soil zone, afterwards through mineralising step on the spot to finish recovery.Zone, described soil comprises covers soil horizon 1 and the underground reservoir 3 of waterline below 2.Soil horizon 1 comprises metallic pollution district 4, and this contaminated area is owing to be arranged on the migration of the pollutant of the waste hold up tank 5 of layer in 1 ground and cause.Zone 4 expands within the underground reservoir 3.Monitor well 6 stretches out downwards by zone 4 to measure the pollution level in zone 4.The degree of depth of Polluted area 4 and area size adopt suitable known analytical technology in advance after measured.The horizon is represented with numeral 18.
But in suitable liquid-carrier such as gassy water, put on the substrate of sky storagetank 5 from the nutrient of nutrient source 22 and acid carrier band.This operation is finished by sprinkler 7.This liquid also can be used through the injection well 8 of proper arrangement with by seepage channel 9, so that infiltrate in the material of contaminated area and quicken the acidifying of soil.Elemental sulfur also can add and be mixed into the shallow-layer contaminated area, as the substrate of storagetank 5, with the aforesaid bioleaching process on the spot of further promotion.
In order in the scope of Polluted area 4, to form and keep the condition of aerobic, connect a series of ventilation shafts 10 (one of them has been shown) with air blast 21 and be blown into air, or exhaust by layer 1 Polluted area 4 or blow in the underground water that air enters water-bearing layer 3 or both all have it.In addition, the adding speed of nutrient can change, to avoid causing anoxia condition in the scope of Polluted area 4.Supply is marked by reference number 20 with the layer 1 of nutrient and acid and the pinniform area or the zone in water-bearing layer 3.This pinniform area comprises the Polluted area 4 in layer 1 and the water-bearing layer 3.
This processing process causes that in zone 4 acidleach of metal goes out in the above described manner.Sustainable a few weeks longer of this process or more than the several months does not have pollution metal substantially until reaching in the soil of Polluted area 4, measure constantly with suitable analytical method around here.
The product that metal leaches processing procedure is collected within the part in water-bearing layer 3, this part is on the x direction or naturally-occurring or manually cause, simultaneously with suitable pump (not shown) by a series of recovery wells 11 (one of them has been shown), this product is received and is recycled on the ground of layer 1.The horizontal plane 2 in water-bearing layer 3 can add into water by seepage channel 24 to be regulated, to quicken the current of x direction.
The solution of collecting then is delivered to one of following selection:
(a) surge tank 12, and for inflation before being applied to Polluted area again and adding proper nutrition element, this is the method main route at operation initial stage;
(b) the biogenic sediment reactor 13;
(c) gas-liquid contactor 14, with elution from the hydrogen sulfide in the waste gas of biogenic sediment process.
Solution enters reactor 13 and upwards flows through reactor 13 from the bottom.When so carrying out, be present in the reactor 13 sulfate also pathogenic microorganism in the above described manner the sulfate that flows into is converted into sulfide.
The waste gas that biogenic sediment produced between the stage of reaction in reactor 13 is by the gas-liquid contactor 14 that communicates with reactor 13.Contactor 14 can make hydrogen sulfide reclaim.Leaving the air communication of contactor 14 crosses secondary scrubbing plant 19 and is disposed in the atmosphere.
The mud that contains the biogenic sediment reaction of insoluble sulfide is collected in the bottom of reactor 13, and is delivered to the separating treatment process by pipeline 15, and for example biological metal that strengthens is fixed, or dehydration and collect and be transported to other place to carry out metal recovery.The solution of slurry dewatering gained maybe can return bioleaching process to reuse.Or can further handle and discharge.
Be drawn out of and join from the outflow liquid that contains dissolved sulfide of biogenic sediment process with sulfide solution from gas/liquid contactor 14.Sulfide solution after the junction is carried by gas/liquid contactor 16 with pump afterwards and is entered sulfide oxidation reactor 17.Contactor 16 guarantees that the alkali lye that can be flowed into by the sour any stink damp that discharges dissolves again in reactor 17.
In oxidation reactor 17, the solution that contains sulfide closely mixes with suitable microorganism and is oxidized to sulfate with aforementioned manner.Be delivered to surge tank or bioreactor 12 after the acid solution that produces, can further add elemental sulfurs and the microorganisms that brought by reactor 17 be oxidized to sulfuric acid with it by sulphur source 23 if desired at this, add to again in the contaminated material of soil horizon 1 (by well 8 and passage 9 and sprinkler 7) with aforementioned manner afterwards.
As known from the above, this processing procedure of removing metal circulates, metal pollutant in the part 3 of soil horizon 1 is in the different cycle periods of removing metal process, little by little contained the biological leaching liquor etch that produces sulfuric acid and come out, and be recovered with the insoluble sulphided form that in biogenic sediment reactor 13, forms.Part sulphur reclaims by the oxidation of sulfide in oxidation reactor 17, and goes out in the process to reuse in the acidleach of soil metal pollutant.
After this procedure division circulation, used microorganism is transferred with aqueous solution form in bioreactor 13, is added in the soil 1 by well 8, passage 9 and sprinkler 7.Also do not leached in part cycle period of this process and to remove and still be retained in metal in the soil 1 by biology, can little by little be converted into insoluble sulfide therefrom and be fixed in the soil, eliminate therefrom owing to continuously slow etch surpasses any problem that causes after a period of time.Can often replenish and add microorganism, water and other is suitable for quickening the nutrient of known reduction step.The soil pattern composition can be analyzed by reasonable time at interval, is that insoluble sulfide process is finished until suitable bio-transformation on the spot.
Claims (6)
1, a kind of method of handling metal species contaminated land or soil, comprising being the processing soil of metal sulfate or the step of soil, and be that this metal sulfate that conversion wherein contains is the processing soil of insoluble metal sulfide or the step of soil after this with biochemical method for transforming metal species.
2, the process of claim 1 wherein that described metal sulfate transforms and finish that soil or soil contact with the sulfuric acid elutriant in this process by leaching process.
3, the process of claim 1 wherein that the leaching of soil or geobiont generates sulfuric acid by sulphur-containing substance source in the soil with biochemical method and cause that so the sulfuric acid that generates can make the metal pollutant dissolving.
4, the method for claim 3, wherein said biological leaching is to implement as the part of circulating treatment procedure, be reduced to hydrogen sulfide and metal sulfide in the bioreactor that the biological sulfate that leaches is separating in this cyclic process, and the sulphur source that this hydrogen sulfide is separated from insoluble sulfide and oxidized formation can be reused.
5, the method for claim 4, wherein soil or soil are handled so that the on the spot conversion of sulfate to sulfide to be provided after the biology of circulating treatment procedure leaches.
6, the method for claim 5, wherein basic identical in described bioreactor, being applied to provide the microorganism of reduction to be added in soil or the soil to promote the reduction on the spot of the sulfate in soil or the soil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9402976A GB9402976D0 (en) | 1994-02-16 | 1994-02-16 | Process for the treatment of contaminated land |
| GB9402976.6 | 1994-02-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1146169A true CN1146169A (en) | 1997-03-26 |
Family
ID=10750458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95192575A Pending CN1146169A (en) | 1994-02-16 | 1995-02-13 | Process for treatment of contaminated land |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0745006A1 (en) |
| JP (1) | JPH09508573A (en) |
| CN (1) | CN1146169A (en) |
| AU (1) | AU1587495A (en) |
| CA (1) | CA2183584A1 (en) |
| CZ (1) | CZ241796A3 (en) |
| GB (1) | GB9402976D0 (en) |
| WO (1) | WO1995022418A1 (en) |
| ZA (1) | ZA951284B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949805A (en) * | 2010-09-15 | 2011-01-19 | 上海岩土工程勘察设计研究院有限公司 | Method for testing physical and mechanical properties of acid contaminated soil |
| CN102534210A (en) * | 2012-01-17 | 2012-07-04 | 江西理工大学 | Metal ore heap leaching, anaerobic enrichment transformation and biological leaching extraction process |
| CN102825063A (en) * | 2012-09-14 | 2012-12-19 | 武汉大学 | Regeneration method and circulating restoration device for organic contaminated soil restoration eluate |
| CN103418608A (en) * | 2013-07-16 | 2013-12-04 | 中国科学院过程工程研究所 | Method for jointly repairing heavy metal contaminated soil at mining areas through microorganism-chemical method |
| CN110026431A (en) * | 2019-05-20 | 2019-07-19 | 成都科泰技术有限公司 | A method of utilizing microorganism nano material in-situ cadmium pollution soil repair |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5562588A (en) * | 1994-12-30 | 1996-10-08 | Maxus Energy Corporation | Process for the in situ bioremediation of Cr(VI)-bearing solids |
| GB9605334D0 (en) * | 1996-03-13 | 1996-05-15 | British Nuclear Fuels Plc | Biodecontamination reactor |
| KR100945477B1 (en) * | 2009-12-08 | 2010-03-05 | 한라건설주식회사 | Combined process with bioleaching and electrokinetics for remediation of heavy metal contaminated soil |
| FI125550B (en) * | 2013-11-22 | 2015-11-30 | Teknologian Tutkimuskeskus Vtt Oy | Procedure for the recovery of rare earth metals from waste sulphates |
| JP6325835B2 (en) * | 2014-02-07 | 2018-05-16 | 株式会社熊谷組 | Groundwater resource recovery system |
| CN104056852B (en) * | 2014-06-20 | 2016-04-06 | 四川大学 | The chemistry of compound heavy-metal contaminated soil and microbial association restorative procedure and application |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2651673C2 (en) * | 1976-11-12 | 1980-02-21 | Battelle-Institut E.V., 6000 Frankfurt | Process for the separation of heavy metals from sewage sludge |
| US4108722A (en) * | 1976-12-10 | 1978-08-22 | Atlantic Richfield Company | Method for the restoration of an underground reservoir |
| DE3300402A1 (en) * | 1983-01-07 | 1984-10-11 | Hoechst Ag, 6230 Frankfurt | Process for removing hydrogen sulphide from gases or liquids, and microorganism for carrying out the process |
| US4789478A (en) * | 1986-10-14 | 1988-12-06 | Revis Nathaniel W | Conversion of inorganic ions to metal sulfides by microorganisms |
| JP2604598B2 (en) * | 1987-09-07 | 1997-04-30 | 大樹 中山 | How to remove heavy metals from sludge |
| GB9000236D0 (en) * | 1990-01-05 | 1990-03-07 | Shell Int Research | Waste treatment |
| DE4117515C2 (en) * | 1991-05-24 | 1995-03-16 | Noell Gmbh | Process for the combined decontamination of fine grain soils contaminated with heavy metals and organic pollutants |
| US5263795A (en) * | 1991-06-07 | 1993-11-23 | Corey John C | In-situ remediation system for groundwater and soils |
-
1994
- 1994-02-16 GB GB9402976A patent/GB9402976D0/en active Pending
-
1995
- 1995-02-13 JP JP7520834A patent/JPH09508573A/en active Pending
- 1995-02-13 WO PCT/GB1995/000286 patent/WO1995022418A1/en not_active Application Discontinuation
- 1995-02-13 CA CA002183584A patent/CA2183584A1/en not_active Abandoned
- 1995-02-13 CZ CZ962417A patent/CZ241796A3/en unknown
- 1995-02-13 CN CN95192575A patent/CN1146169A/en active Pending
- 1995-02-13 EP EP95907785A patent/EP0745006A1/en not_active Withdrawn
- 1995-02-13 AU AU15874/95A patent/AU1587495A/en not_active Abandoned
- 1995-02-16 ZA ZA951284A patent/ZA951284B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949805A (en) * | 2010-09-15 | 2011-01-19 | 上海岩土工程勘察设计研究院有限公司 | Method for testing physical and mechanical properties of acid contaminated soil |
| CN102534210A (en) * | 2012-01-17 | 2012-07-04 | 江西理工大学 | Metal ore heap leaching, anaerobic enrichment transformation and biological leaching extraction process |
| CN102825063A (en) * | 2012-09-14 | 2012-12-19 | 武汉大学 | Regeneration method and circulating restoration device for organic contaminated soil restoration eluate |
| CN103418608A (en) * | 2013-07-16 | 2013-12-04 | 中国科学院过程工程研究所 | Method for jointly repairing heavy metal contaminated soil at mining areas through microorganism-chemical method |
| CN103418608B (en) * | 2013-07-16 | 2015-09-30 | 中国科学院过程工程研究所 | A kind of method of microbial-chemical method combine d bioremediation heavy metal polluted soil in mine field |
| CN110026431A (en) * | 2019-05-20 | 2019-07-19 | 成都科泰技术有限公司 | A method of utilizing microorganism nano material in-situ cadmium pollution soil repair |
| CN110026431B (en) * | 2019-05-20 | 2020-12-22 | 成都科泰技术有限公司 | Method for in-situ remediation of cadmium-polluted soil by using microbial nano-material |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ241796A3 (en) | 1996-12-11 |
| JPH09508573A (en) | 1997-09-02 |
| AU1587495A (en) | 1995-09-04 |
| ZA951284B (en) | 1995-10-23 |
| MX9603460A (en) | 1997-12-31 |
| WO1995022418A1 (en) | 1995-08-24 |
| GB9402976D0 (en) | 1994-04-06 |
| CA2183584A1 (en) | 1995-08-24 |
| EP0745006A1 (en) | 1996-12-04 |
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