WO2011006812A1 - Catalytic composition for treatment of soil and sediment - Google Patents
Catalytic composition for treatment of soil and sediment Download PDFInfo
- Publication number
- WO2011006812A1 WO2011006812A1 PCT/EP2010/059725 EP2010059725W WO2011006812A1 WO 2011006812 A1 WO2011006812 A1 WO 2011006812A1 EP 2010059725 W EP2010059725 W EP 2010059725W WO 2011006812 A1 WO2011006812 A1 WO 2011006812A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- remediation composition
- soil
- metal
- zerovalent
- remediation
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000013049 sediment Substances 0.000 title claims abstract description 38
- 239000002689 soil Substances 0.000 title claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000011282 treatment Methods 0.000 title description 11
- 239000000356 contaminant Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 9
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 9
- 238000005067 remediation Methods 0.000 claims description 48
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 5
- 229940116333 ethyl lactate Drugs 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000006065 biodegradation reaction Methods 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 238000006911 enzymatic reaction Methods 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 241000863430 Shewanella Species 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002082 metal nanoparticle Substances 0.000 claims 3
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 12
- 230000002829 reductive effect Effects 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 9
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 238000005202 decontamination Methods 0.000 description 9
- 230000003588 decontaminative effect Effects 0.000 description 9
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000039 congener Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- -1 nitrogen-containing organic compounds Chemical class 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 238000006042 reductive dechlorination reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002503 metabolic effect Effects 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003256 environmental substance Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- IUTPYMGCWINGEY-UHFFFAOYSA-N 2,3',4,4',5-Pentachlorobiphenyl Chemical compound C1=C(Cl)C(Cl)=CC=C1C1=CC(Cl)=C(Cl)C=C1Cl IUTPYMGCWINGEY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 244000005706 microflora Species 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
Definitions
- the present invention provides for a remediation composition for injection into environmental substances such as groundwater, soil material or underwater sediment. More particularly the invention relates to such remediation composition comprising a mixture in a solvent of biologically degradable monomers, oligomers and polymers of hydroxycarbolylic acid which are combined with catalytic hydrogenation zero valent metallic nanoparticles for treatment of recalcitrant environmental contaminants contained in sediments and soils such as PCB, metals and volatiles organochlorines .
- the present invention also relates to a process for the treatment of contaminated soils and sediments with such remediation composition as well as a process to prepare such remediation composition.
- halosubstituted organic molecules particularly polychlorinated biphenyl molecules, or with certain metals
- treatment with known remediation composition does not result in decontamination of these substances under ambient environmental conditions even in the course of a few months, depending on the nature and concentration level of the contaminants. It is also known in the art that such type of treatment needs to excavate the soil or sediment to treat it ex-situ by heating and stirring. These treatments are not generally operated under ambient environmental conditions and in-situ.
- the composition's mode of action is a microbiologically driven physico- chemical catalytic degradation of halosubstituted organic molecules .
- compositions and formulations for environmental remediation purposes often in the form of slow-release substrates that release organic acids slowly over time, as for example in US Patent 6,420,594 which describes a composition that releases hydroxy acid slowly over time, and Wood and Huang (2006) which describe bioremediation of chlorinated solvent using a hydrogen release compound.
- the preferred use of the compositions described in the prior art is for bioremediation purposes, wherein they provide a time-release source of lactic acid to support growth and reductive activity of microbes present in a system or medium, such as an aquifer, bioreactor, soil, industrial process, wastestream, body of water, river or well.
- the microbes use the reducing equivalents, such as short-chain organic acid or molecular hydrogen, originating from the depolymerized composition, as a source of energy to drive the metabolic conversion of compounds which are capable of being reduced, such as nitrogen-containing organic compounds, oxygen-containing organic compounds, polyaromatic hydrocarbons, and halogen-containing organic compounds. All of these examples are aimed at stimulating a (micro-) biological action as an end-point in the reaction chain.
- biological degradation may result in very long removal processes for the contaminants or even in certain cases biological degradation may not be observed, due to limited mass transfer, limited biological activity, limited bio-availability of the contaminants, toxicity of the environment, non-ideal physicochemical parameters for the conversion (such as redox potential, pH, temperature, ... ) and so on .
- catalytic zero valent iron particles for chemical degradation of environmental contaminants in soil, but such particles need to be protected from unwanted physicochemical processes during the conversion of reactants by contacting these particles by a polymer or by polymers.
- a hydrophilic binder can be coated onto the surface of fine iron particles to protect the surface from oxidation, and other processes. In all of these processes, it is the purpose of the polymer to protect the catalyst but not take part in the catalytic reaction.
- zero valent iron is a catalyst for dehalogenation organic haloginated molecules at elevated temperatures of 300 0 C (Varnasi et al, 2007).
- An object of the present invention is to provide a remediation composition to remedy these drawbacks in order to improve remediation of soils and contaminants.
- Another object of the invention is to provide a remediation composition for the in situ decontamination of soil and sediments contaminated with halogenated organic molecules.
- Another object of the present invention is to provide a remediation composition containing only one catalytic metal and in the absence of iron particles.
- Still another object of the present invention is to use as mode of action of the remediation composition, a microbiologically-driven physic-chemical catalytic degradation of halosubstituted organic molecules.
- Still another object of the present invention is a process using such remediation composition to achieve a complete decontamination of soils and sediments in reasonable times.
- a further object is also a process to prepare such remediation composition.
- remediation composition a product consisting of a mixture of biodegradable, viscous, semi-polar polymers, oligomers and monomers of carboxylic acid dissolved in a biodegradable solvent containing a limited amount of a well-dispersed solid metallic hydrogenation catalyst selected from the group comprising metals of Group VIb or Group VIIIb, and more particularly platinum or palladium where the catalytic particles are either nano- or micron- sized, halogenated organic molecules, and especially PCB' s can be dechlorinated to hydrocarbon that can be further biodegraded by soil's or sediment's microflora.
- the mode of action of this remediation composition is by a combined action of microbiological metabolic conversion of the biodegradable polymers, oligomers, monomers and solvent and chemical catalytic conversion of halogenated molecules on the metallic catalyst without the need of the presence of iron as a source of electrons or hydrogen.
- the redox potential in the soil or sediment where such a product is injected or mixed is reduced to negative values by the presence of biodegradable components, enhancing the reductive dehalogenation driven by the catalyst.
- electrons are released, which are combined with the halogenated organic molecules in order to be reduced on the catalyst surface.
- the biodegradable polymer is then metabolized by indigenous bacteria to produce hydrogen and to create ideal redox conditions for reductive dechlorination.
- the remediation composition is injected in low concentrations in-situ under the form of a liquid, pumpable composition, in order to bring about complete decontamination under ambient environmental conditions (redox potential, temperature, pH and other environmental parameters) .
- remediation composition of the invention is a mixture consisting of:
- polyester of hydrocarboxylic acid is preferentially lactic acid
- biodegradable solvent is preferentially an ester of said hydrocarboxylic acid, and particularly ethylactate when polyester of lactic acid is selected
- the biodegradable solvent is generally used in a concentration in the range of in between 2 % and 50 % (w/w) , and preferably in a range between 7 and 15% (w/w)
- This solvent has two functions: i) to extract the contaminating compounds (PCBs and other) from the soil or sediment matrix and liberate these contaminants for catalytic degradation, and ii) to serve as a source of hydrogen through biodegradation .
- biodegradable solvent may be used alone, it may also be used in conjunction with a surfactant, to allow penetration of the solvent into the core of the contaminated aggregates.
- remediation composition was a performant reductive catalyst for polychlorinated biphenyls and other recalcitrant environmental contaminants when mixed into water-submerged or non-submerged sediment of a lake or when mixed into soil samples or sediment samples in the presence or absence of air.
- the remediation composition of the invention it was unexpectedly found that the chlorinated molecules are completely dechlorinated to hydrocarbons that can be further degraded biocatalytically .
- the catalytic remediation composition (polymer mixture and nanoparticles) of the invention has a viscous character and can be transported by pumping action or gravity. The catalytic remediation composition is heavier than water and will remain mixed into the sediment when a water column is present above it.
- hydrophobic contaminants such as polychlorinated biphenyls, which are strongly adsorbed to organic material inside of the sediment matrix, can be desorbed and made available for reductive dechlorination inside of the product matrix.
- the present invention also comprises a process for the catalytic dehydrohalogenation of PCB and other contaminants in soils and sediments which comprises the steps of:
- a remediation agent under the form of a slurry comprising a biodegradable polymer dissoved in a solvent and a powder of zerovalent Pd or Pt nanoparticles dispersed therein ;
- the present invention also comprise a process to prepare the remediation catalytic composition which comprises the steps of preparing the powder of zerovalent Pd or Pt nano particles is obtained by :
- the remediation composition is mixed and injected at ambient temperature into a contaminated soil or sediment, the polymer is partially hydrolyzed into monomers and monomers are oxidized into end-products by enzymatic (biocatalytic) action from the autochtonous microbial population present inside the sediment or soil matrix.
- the hydrogen thus generated through the enzymatic reaction then reacts with the contaminant, such as a polychlorinated biphenyl molecule, through a reductive halosubstitution or other reductive reaction mechanism catalyzed at ambient temperatures by the hydrogenation catalyst, constituted by the nanoparticles of metal selected from Group VIb or VIIIb, generally Pd, Ni, Pt, Rh, and particularly Pd or Pt, dispersed in small quantities inside of the catalytic composition.
- the hydrogenation catalyst constituted by the nanoparticles of metal selected from Group VIb or VIIIb, generally Pd, Ni, Pt, Rh, and particularly Pd or Pt, dispersed in small quantities inside of the catalytic composition.
- the powder of zero valent nanoparticles of Pd or Pt may be prepared by a method described in "De Windt et al . 2005". It has been found that a continuous significant decrease of PCB concentrations over time inside of sediments treated with this remediation composition reaching a reduction between 69% and 98% after 53 days. Hence, the Applicant has unexpectedly found that the composition lowers the redox potential of the surrounding environments to values below 0 mV, and typically to values between -100 mV and -400 mV.
- An advantage of the process of the present invention is there is no need for external hydrogen source for the decontamination, since the hydrogen is formed out of the product itself by biocatalysis .
- the catalyst is preferably a heterogeneous catalyst, which is in separate phase than the contaminants (i.e. a solid phase catalyst and contaminants in a gaseous or liquid phase) .
- This catalyst is a usual hydrogenation catalyst that catalyzes reactions at low to medium range temperatures (0-60 0 C), such as metals of Group VIb or VIIIb and particularly Pt or Pd; while bimetallic or trimetallic alloys of precious metals may be used, but with well known drawback of non-homogeneous distribution in the remediation composition.
- the contaminants to be degraded combined with molecular hydrogen can be reduced at ambient temperature at the surface of the hydrogenation catalyst through a reductive reaction, for example a hydrodechlorination reaction.
- the low to medium temperature range allows the system to perform its function of decontamination under ambient environmental temperature ranges.
- the catalyst is present as a component of the described composition, in a concentration between 10 and 10,000 mg/kg mixture (dry weight) .
- This composition is mixed into the contaminated sediment or soil in a concentration of about 10 to 10,000 ⁇ g of catalyst/kg sediment or soil (dry weight) .
- PCB congeners are more resistent towards Pd- catalyzed hydrodechlorination, as is evidenced by the results for PCB 118 removal.
- the mixture of oligomers and polymers of hydro carboxylic acid can be produced through usual condensation reactions at industrial scale; according to the present invention, it is preferred to use a polylactic acid polymer in admixture with its oligomer and monomer; it is common knowledge that polylactic acid is a well-known component in food and feed market applications .
- the Invention furthermore brings the following advantages to the field of environmental remediation: (1) limited need for excavation or dredging of substances, since the composition is injected in situ; (2) limited need for transport of substances, for the same reason; (3) limited need for landfilling of contaminated substances, since a technology is proposed to decontaminate these substances to below threshold levels suggested by national environmental authorities; (4) limited energy consumption for the decontamination, since no heating or transportation is required; (5) limited risk since end- concentrations of contaminants after treatment by the method described in this invention are low, and since the reaction products are biodegradable and environmentally benign molecules
- a remediation composition was produced by mixing at temperature of 60 0 C, 980 kg of polylactic acid of degry of polymerization about 5 units, obtained by polycondensation of lactic acid at 97% with 158 kg of ethyl-lactate 98.5% as biodegrable solvent and 120 kg of lactic acid at 97%.
- the temperature was decreased at 25°C before the drumming.
- the catalytic palladium nanoparticles were produced by a protocol described in "De Windt et al . , 2005".
- the palladium nanoparticles were examined by X-Ray Diffraction analysis and Scanning and Transmission Electron Microscopy, and found to exist out of individual, non-agglomerated metallic PdO nanoparticles with a size between 1 and 50 nm, on average 10 nm.
- This palladium suspension was then further processed by spray-drying and atomized into a powder.
- Spray drying was done with a Niro Production Minor atomizer with an inlet temperature of 180 0 C and an outlet temperature of 60 0 C. After the atomization process, a palladium containing powder was obtained.
- the powder was mixed and homogenized into the remediation composition by mixing in a heated mixing tank with anchor agitator.
- An equivalent of 250 mg/kg of palladium was mixed into the remediation composition liquid to result in the final dispersion .
- the product was heated to maximum 30 0 C in order to limit viscosity and to allow good dispersion of the nanopowder into the liquid.
- Example 2 Pilot-scale testing with in situ PCB degradation by injection of catalytically active remediation composition into sediment
- Table 1 results are shown for the in situ application of the catalytic remediation composition of this invention, in PCB contaminated sediment.
- the catalytic remediation composition as prepared in Example 1 was applied in a concentration of 3 g/kg sediment dry weight in the top 15 cm of contaminated sediment by mechanical mixing .
- zone S8 and zone S9 Three sediment zones were treated: zone S8 and zone S9, two zones which served as independent replicates, and zone C which served as a control zone where only the polymeric compound comprising polylactic acid and ethyl lactate as prepared in Example 1 was injected without the presence of the catalytic particles.
- PCB congeners was observed, although some of lower chlorinated PCBs may have been dechlorinated by the increased microbiological activity in the sediment due to addition of carbon source.
- Table 1 Results of treatment with 5 g/kg of the remediation composition in Zone Marnage area, from 10
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Abstract
Object of this invention is a catalyst and a process for the hydrodehalogenation of halogenated and polyhalogenated aromatic and aliphatic hydrocarbons or for reductive conversion of recalcitrant environmental contaminants in soil and sediments comprising a polymeric phase constituted of a mixture of biodegradable polymer, oligomer and monomers dissolved in a biodegradable solvent and a catalytic component constituted of zerovalent metal.
Description
Catalytic composition for treatment of soil and sediment
Domain of the invention
The present invention provides for a remediation composition for injection into environmental substances such as groundwater, soil material or underwater sediment. More particularly the invention relates to such remediation composition comprising a mixture in a solvent of biologically degradable monomers, oligomers and polymers of hydroxycarbolylic acid which are combined with catalytic hydrogenation zero valent metallic nanoparticles for treatment of recalcitrant environmental contaminants contained in sediments and soils such as PCB, metals and volatiles organochlorines .
The present invention also relates to a process for the treatment of contaminated soils and sediments with such remediation composition as well as a process to prepare such remediation composition.
Prior art
When environmental substances are contaminated with low or high concentrations of halosubstituted organic molecules, particularly polychlorinated biphenyl molecules, or with certain metals, treatment with known remediation composition does not result in decontamination of these substances under ambient environmental conditions even in the course of a few months, depending on the nature and concentration level of the contaminants. It is also known in the art that such type of treatment needs to excavate the soil or sediment to treat it ex-situ by heating and stirring. These treatments are not generally operated under ambient environmental conditions and in-situ. The composition's mode of action is a microbiologically driven physico-
chemical catalytic degradation of halosubstituted organic molecules .
It has already been described in the prior art biodegradable compositions and formulations for environmental remediation purposes, often in the form of slow-release substrates that release organic acids slowly over time, as for example in US Patent 6,420,594 which describes a composition that releases hydroxy acid slowly over time, and Wood and Huang (2006) which describe bioremediation of chlorinated solvent using a hydrogen release compound. The preferred use of the compositions described in the prior art is for bioremediation purposes, wherein they provide a time-release source of lactic acid to support growth and reductive activity of microbes present in a system or medium, such as an aquifer, bioreactor, soil, industrial process, wastestream, body of water, river or well. The microbes use the reducing equivalents, such as short-chain organic acid or molecular hydrogen, originating from the depolymerized composition, as a source of energy to drive the metabolic conversion of compounds which are capable of being reduced, such as nitrogen-containing organic compounds, oxygen-containing organic compounds, polyaromatic hydrocarbons, and halogen-containing organic compounds. All of these examples are aimed at stimulating a (micro-) biological action as an end-point in the reaction chain. Although various studies have reported efficient degradation of pollutants by microorganisms due to metabolic pathways and degradative genes responsible for enzyme production, biosorption, co-metabolism, bioaccumulation, and biotransformation (Ju, 1997 and Davis, 2002), it is however of common knowledge that
biological degradation is not always possible. Limitations exist in the case of toxic components that are very persistent to biological degradation. For example, it is well known from the art that only a very limited number of polychlorinated biphenyl congeners are susceptible for (micro-) biological degradation. There is a wide variety of the rate, extent and specificity towards flanked and unflanked meta, para and ortho microbial dechlorinations (reviewed by Wiegel and Wu, 2000) .
Furthermore, it is also of common knowledge that biological degradation may result in very long removal processes for the contaminants or even in certain cases biological degradation may not be observed, due to limited mass transfer, limited biological activity, limited bio-availability of the contaminants, toxicity of the environment, non-ideal physicochemical parameters for the conversion (such as redox potential, pH, temperature, ... ) and so on .
It is also known from the art to use, catalytic zero valent iron particles for chemical degradation of environmental contaminants in soil, but such particles need to be protected from unwanted physicochemical processes during the conversion of reactants by contacting these particles by a polymer or by polymers. For that purpose, we noted that it is described in EP 1,151,807 that a hydrophilic binder can be coated onto the surface of fine iron particles to protect the surface from oxidation, and other processes. In all of these processes, it is the purpose of the polymer to protect the catalyst but not take part in the catalytic reaction.
While it is generally also known that zero valent iron is a catalyst for dehalogenation organic haloginated molecules at elevated temperatures of 3000C (Varnasi et al, 2007). Chuang et al . (1995) observed that reductive dechlorination of PCBs using Fe0 as reductant was only happening at 400 0C, whereas there was no dechlorination at room temperature. It is sometimes described that rapid reductive dechlorination can be achieved while using bimetallic materials, such as palladized FeO (Pd/Fe) as a reductant (Korte et al . , 1997). But of course, bimetallic catalyst are needed that is known as not being an easy way to solve the decontamination problem, since it involves incomplete decontamination of the soil and sediments associated to the well known difficulty of homogeneously distribution of the Pd/Fe catalyst. On top of that, it is also well known that the redox potential cannot be controlled by the Pd/Fe catalyst.
It is therefore a need to have a remediation composition which enable to remedy the drawbacks of the prior art, hereabove mentioned.
An object of the present invention is to provide a remediation composition to remedy these drawbacks in order to improve remediation of soils and contaminants. Another object of the invention is to provide a remediation composition for the in situ decontamination of soil and sediments contaminated with halogenated organic molecules.
Another object of the present invention is to provide a remediation composition containing only one catalytic metal and in the absence of iron particles.
Still another object of the present invention is to use as mode of action of the remediation composition, a
microbiologically-driven physic-chemical catalytic degradation of halosubstituted organic molecules.
Still another object of the present invention is a process using such remediation composition to achieve a complete decontamination of soils and sediments in reasonable times.
A further object is also a process to prepare such remediation composition.
Summary of the invention
The Applicant has now unexpectedly found that by using as remediation composition a product consisting of a mixture of biodegradable, viscous, semi-polar polymers, oligomers and monomers of carboxylic acid dissolved in a biodegradable solvent containing a limited amount of a well-dispersed solid metallic hydrogenation catalyst selected from the group comprising metals of Group VIb or Group VIIIb, and more particularly platinum or palladium where the catalytic particles are either nano- or micron- sized, halogenated organic molecules, and especially PCB' s can be dechlorinated to hydrocarbon that can be further biodegraded by soil's or sediment's microflora. The mode of action of this remediation composition is by a combined action of microbiological metabolic conversion of the biodegradable polymers, oligomers, monomers and solvent and chemical catalytic conversion of halogenated molecules on the metallic catalyst without the need of the presence of iron as a source of electrons or hydrogen. The redox potential in the soil or sediment where such a product is injected or mixed is reduced to negative values by the presence of biodegradable components, enhancing the reductive dehalogenation driven by the catalyst. Furthermore, during metabolic
conversions of the biodegradable part of the remediation composition, electrons are released, which are combined with the halogenated organic molecules in order to be reduced on the catalyst surface. Hence, the biodegradable polymer is then metabolized by indigenous bacteria to produce hydrogen and to create ideal redox conditions for reductive dechlorination.
According to the present invention the remediation composition is injected in low concentrations in-situ under the form of a liquid, pumpable composition, in order to bring about complete decontamination under ambient environmental conditions (redox potential, temperature, pH and other environmental parameters) .
Description of the invention
More specifically, the remediation composition of the invention is a mixture consisting of:
(i) a polyester of hydrocarboxylic acid, which may also contain oligomers and monomers of said polyester
(ii) a biodegradable solvent; said polyester of hydrocarboxylic acid is preferentially lactic acid, while the biodegradable solvent is preferentially an ester of said hydrocarboxylic acid, and particularly ethylactate when polyester of lactic acid is selected,
(iii) nanoparticles of a metal of Group VIb or VIIIb, particularly palladium, as hydrogenation catalyst which are then easily dispersed in the mixture of polyester and solvent
The biodegradable solvent is generally used in a concentration in the range of in between 2 % and 50 %
(w/w) , and preferably in a range between 7 and 15% (w/w) This solvent has two functions: i) to extract the contaminating compounds (PCBs and other) from the soil or sediment matrix and liberate these contaminants for catalytic degradation, and ii) to serve as a source of hydrogen through biodegradation .
To illustrate this second function, hydrogen release, we use the example of ethyl lactate:
While the biodegradable solvent may be used alone, it may also be used in conjunction with a surfactant, to allow penetration of the solvent into the core of the contaminated aggregates.
The Applicant have surprisingly found that such remediation composition was a performant reductive catalyst for polychlorinated biphenyls and other recalcitrant environmental contaminants when mixed into water-submerged or non-submerged sediment of a lake or when mixed into soil samples or sediment samples in the presence or absence of air. With the remediation composition of the invention it was unexpectedly found that the chlorinated molecules are completely dechlorinated to hydrocarbons that can be further degraded biocatalytically .
The catalytic remediation composition (polymer mixture and nanoparticles) of the invention has a viscous character and can be transported by pumping action or gravity. The catalytic remediation composition is heavier than water and will remain mixed into the sediment when a water column is present above it. Due to the presence of a semi-polar ester of lactic acid with an alcohol such as ethyl lactate in the product, hydrophobic contaminants such as polychlorinated biphenyls, which are strongly adsorbed to organic material inside of the sediment matrix, can be desorbed and made available for reductive dechlorination inside of the product matrix.
The present invention also comprises a process for the catalytic dehydrohalogenation of PCB and other contaminants in soils and sediments which comprises the steps of:
Preparing a remediation agent under the form of a slurry comprising a biodegradable polymer dissoved in a solvent and a powder of zerovalent Pd or Pt nanoparticles dispersed therein ;
Injecting or pumping the remediation agent into the soil and sediments
Achieving the biodegradation of the biodegradable polymer present in the slurry of remediation agent so that hydrogen is generated through enzymatic reaction while simultaneously zerovalent Pd or Pt nano particles are dispersed in soil and sediment to be treated
Achieving dehydrohalogenation at temperature comprised between 0° and 600C
Recovering the treated soil substantially freed from contaminants.
The present invention also comprise a process to prepare the remediation catalytic composition which comprises the steps of preparing the powder of zerovalent Pd or Pt nano particles is obtained by :
Fermenting of Shewanella in the presence of a
C-source and salt of Pd or Pt
Achieving reduction of the Pd or Pt salt in the presence of an electron donor at ambiant temperature by incubation
Recovering the cells containing the zerovalent Pd or Pt nano particles
Processing the so-recovered cells into a powderAccording to an embodiment of the process of the present invention, the remediation composition is mixed and injected at ambient temperature into a contaminated soil or sediment, the polymer is partially hydrolyzed into monomers and monomers are oxidized into end-products by enzymatic (biocatalytic) action from the autochtonous microbial population present inside the sediment or soil matrix. The hydrogen thus generated through the enzymatic reaction, then reacts with the contaminant, such as a polychlorinated biphenyl molecule, through a reductive halosubstitution or other reductive reaction mechanism catalyzed at ambient temperatures by the hydrogenation catalyst, constituted by the nanoparticles of metal selected from Group VIb or VIIIb, generally Pd, Ni, Pt,
Rh, and particularly Pd or Pt, dispersed in small quantities inside of the catalytic composition. By small quantities, it is understood quantities comprised between
(10 mg/kg mixture) and (10000 mg/kg mixture) . The powder of zero valent nanoparticles of Pd or Pt may be prepared by a method described in "De Windt et al . 2005". It has been found that a continuous significant decrease of PCB concentrations over time inside of sediments treated with this remediation composition reaching a reduction between 69% and 98% after 53 days. Hence, the Applicant has unexpectedly found that the composition lowers the redox potential of the surrounding environments to values below 0 mV, and typically to values between -100 mV and -400 mV. An advantage of the process of the present invention is there is no need for external hydrogen source for the decontamination, since the hydrogen is formed out of the product itself by biocatalysis .
The catalyst is preferably a heterogeneous catalyst, which is in separate phase than the contaminants (i.e. a solid phase catalyst and contaminants in a gaseous or liquid phase) . This catalyst is a usual hydrogenation catalyst that catalyzes reactions at low to medium range temperatures (0-600C), such as metals of Group VIb or VIIIb and particularly Pt or Pd; while bimetallic or trimetallic alloys of precious metals may be used, but with well known drawback of non-homogeneous distribution in the remediation composition. According to the process of the invention, the contaminants to be degraded combined with molecular hydrogen can be reduced at ambient temperature at the surface of the hydrogenation catalyst through a reductive reaction, for example a hydrodechlorination reaction. The low to medium
temperature range allows the system to perform its function of decontamination under ambient environmental temperature ranges. The catalyst is present as a component of the described composition, in a concentration between 10 and 10,000 mg/kg mixture (dry weight) . This composition is mixed into the contaminated sediment or soil in a concentration of about 10 to 10,000 μg of catalyst/kg sediment or soil (dry weight) .
Some PCB congeners are more resistent towards Pd- catalyzed hydrodechlorination, as is evidenced by the results for PCB 118 removal.
Further, the mixture of oligomers and polymers of hydro carboxylic acid can be produced through usual condensation reactions at industrial scale; according to the present invention, it is preferred to use a polylactic acid polymer in admixture with its oligomer and monomer; it is common knowledge that polylactic acid is a well-known component in food and feed market applications .
The Invention furthermore brings the following advantages to the field of environmental remediation: (1) limited need for excavation or dredging of substances, since the composition is injected in situ; (2) limited need for transport of substances, for the same reason; (3) limited need for landfilling of contaminated substances, since a technology is proposed to decontaminate these substances to below threshold levels suggested by national environmental authorities; (4) limited energy consumption for the decontamination, since no heating or transportation is required; (5) limited risk since end- concentrations of contaminants after treatment by the method described in this invention are low, and since the
reaction products are biodegradable and environmentally benign molecules
Detailed Description of the Preferred Embodiments
Example 1: Production of the remediation composition
A remediation composition was produced by mixing at temperature of 600C, 980 kg of polylactic acid of degry of polymerization about 5 units, obtained by polycondensation of lactic acid at 97% with 158 kg of ethyl-lactate 98.5% as biodegrable solvent and 120 kg of lactic acid at 97%. The temperature was decreased at 25°C before the drumming. The catalytic palladium nanoparticles were produced by a protocol described in "De Windt et al . , 2005". The palladium nanoparticles were examined by X-Ray Diffraction analysis and Scanning and Transmission Electron Microscopy, and found to exist out of individual, non-agglomerated metallic PdO nanoparticles with a size between 1 and 50 nm, on average 10 nm.
This palladium suspension was then further processed by spray-drying and atomized into a powder. Spray drying was done with a Niro Production Minor atomizer with an inlet temperature of 180 0C and an outlet temperature of 60 0C. After the atomization process, a palladium containing powder was obtained.
The powder was mixed and homogenized into the remediation composition by mixing in a heated mixing tank with anchor agitator. An equivalent of 250 mg/kg of palladium was
mixed into the remediation composition liquid to result in the final dispersion . The product was heated to maximum 300C in order to limit viscosity and to allow good dispersion of the nanopowder into the liquid.
Example 2: Pilot-scale testing with in situ PCB degradation by injection of catalytically active remediation composition into sediment In Table 1, results are shown for the in situ application of the catalytic remediation composition of this invention, in PCB contaminated sediment. The catalytic remediation composition as prepared in Example 1 was applied in a concentration of 3 g/kg sediment dry weight in the top 15 cm of contaminated sediment by mechanical mixing .
Three sediment zones were treated: zone S8 and zone S9, two zones which served as independent replicates, and zone C which served as a control zone where only the polymeric compound comprising polylactic acid and ethyl lactate as prepared in Example 1 was injected without the presence of the catalytic particles.
The results in Table 1 show a continuous significant decrease of indicator PCB concentrations inside of the treated sediments S8 and S9 over time. Fifty three days after the initial application, between 69% and 98% of the indicator PCB congeners had been removed from the sediment, resulting in residual concentrations as low as 36μg/kg. In the control zone, no significant reduction of
PCB congeners was observed, although some of lower chlorinated PCBs may have been dechlorinated by the
increased microbiological activity in the sediment due to addition of carbon source.
In all of the zones, the redox potential dropped to values below -100 mV, and even a value of -400 mV was observed. These results indicate the redox-lowering characteristic of the micture of biodegradable polymers, oligomers, monomers and solvent.
Table 1: Results of treatment with 5 g/kg of the remediation composition in Zone Marnage area, from 10
September until 13 november (S8 and S9) and from treatment with the mixture in Zone Control (C) area, from
11 September until 8 november (C) . Concentrations of the sum of 7 indicator PCBs are expressed in function of time (days) after treatment, in μg PCB/kg sediment dry weight.
Cone (dw) 7
Ballschmitter
Day (μg/kg)
Zone S8 0 1600
13 1148,7
33 679
53 36
Zone S9 0 440
13 226,4
33 147
53 137
Zone C 0 269,0
10 210, 0
23 273,8
48 202,0
Claims
1. Remediation composition, having catalytic dehydrohalogenation properties, for contaminated soil and sediments, which comprises a mixture of slurry of a biodegradable polymer dissolved in a biodegradable solvent and a powder of zerovalent nano particles of metal having catalytic hydrogenation properties, dispersed therein.
2. Remediation composition according to claim 1 wherein the biodegradable polymer is a polyester of hydrocarboxylic acid and preferably lactic acid.
3. Remediation composition according to claims 1 or 2 wherein the biodegradable solvent is selected from ester of lactic acid, and preferably ethyllactate .
4. Remediation composition according claims 1 to 3 wherein the metal is selected among metals of Group VI to VIII.
5. Remediation composition according to claim 4, wherein the metal is preferably selected from Pd, Ni, Pt and
Rh.
6. Remediation composition according to claims 1 to 5, wherein the zerovalent nano particles of metal have a size comprised between lnm and 500 nm.
7. Process for the catalytic dehydrohalogenation of PCB and other contaminants in soil and sediments which comprises the steps of :
Preparing a remediation composition under the form of a slurry, as described in any one of claims 1 to 6 ;
Injecting or pumping said remediation composition into the soil and sediments Achieving the biodegradation of the biodegradable polymer present in the slurry of remediation composition so that hydrogen is generated through enzymatic reaction while simultaneously zerovalent metal nano particles are dispersed in soil and sediment to be treated
Achieving dehydrohalogenation at temperature comprised between 0° and 600C
- Recovering the treated soil substantially freed from contaminants.
8. Process according to claim 7, wherein the powder of zerovalent metal nano particles, as described in any one of claims 1 to 6 is obtained by :
Fermenting of Shewanella in the presence of a C-source and salt of metal having catalytic hydrogenation properties ;
Achieving reduction of said metal salt in the presence of an electron donor at ambiant temperature by incubation ;
Recovering the cells containing the zerovalent metal nano particles
Processing the so-recovered cells into a powder
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EP10729883A EP2454032A1 (en) | 2009-07-15 | 2010-07-07 | Catalytic composition for treatment of soil and sediment |
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EP09165547.2 | 2009-07-15 |
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Cited By (1)
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CN105170624A (en) * | 2015-10-14 | 2015-12-23 | 国家电网公司 | Method for remediating polychlorinated biphenyl polluted soil through combination of chemical elution and plants |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6214202B1 (en) * | 2000-06-19 | 2001-04-10 | The Regents Of The University Of California | Situ treatment of contaminated groundwater |
EP1151807A1 (en) | 1999-07-29 | 2001-11-07 | Hazama Corporation | Soil purification agent and method for purifying soil |
US6420594B1 (en) | 1997-11-12 | 2002-07-16 | Regenesis Bioremediation Products | Polylactate release compounds and methods of using same |
US20040133059A1 (en) * | 2003-01-06 | 2004-07-08 | Michael Scalzi | Method for accelerated dechlorination of matter |
-
2010
- 2010-07-07 WO PCT/EP2010/059725 patent/WO2011006812A1/en active Application Filing
- 2010-07-07 EP EP10729883A patent/EP2454032A1/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6420594B1 (en) | 1997-11-12 | 2002-07-16 | Regenesis Bioremediation Products | Polylactate release compounds and methods of using same |
EP1151807A1 (en) | 1999-07-29 | 2001-11-07 | Hazama Corporation | Soil purification agent and method for purifying soil |
US6214202B1 (en) * | 2000-06-19 | 2001-04-10 | The Regents Of The University Of California | Situ treatment of contaminated groundwater |
US20040133059A1 (en) * | 2003-01-06 | 2004-07-08 | Michael Scalzi | Method for accelerated dechlorination of matter |
Non-Patent Citations (1)
Title |
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WOOD, RYAN C. ET AL: "Modeling chlorinated solvent bioremediation using hydrogen release compound (HRC)", BIOREMEDIATION JOURNAL , 10(3), 129-141 CODEN: BIJOFP; ISSN: 1088-9868, 2006, XP009124946 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105170624A (en) * | 2015-10-14 | 2015-12-23 | 国家电网公司 | Method for remediating polychlorinated biphenyl polluted soil through combination of chemical elution and plants |
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