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WO2001083038A1 - Detoxification de composes halogenes dans un milieu contamine - Google Patents

Detoxification de composes halogenes dans un milieu contamine Download PDF

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Publication number
WO2001083038A1
WO2001083038A1 PCT/NZ2001/000069 NZ0100069W WO0183038A1 WO 2001083038 A1 WO2001083038 A1 WO 2001083038A1 NZ 0100069 W NZ0100069 W NZ 0100069W WO 0183038 A1 WO0183038 A1 WO 0183038A1
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WO
WIPO (PCT)
Prior art keywords
urea
milling
ball mill
slag
soil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NZ2001/000069
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English (en)
Inventor
Bryan Geoffrey Black
Bianca Kuipers
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ENVIRONMENTAL DECONTAMINATION Ltd
Original Assignee
ENVIRONMENTAL DECONTAMINATION Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from NZ50434100A external-priority patent/NZ504341A/xx
Priority claimed from NZ51052201A external-priority patent/NZ510522A/xx
Application filed by ENVIRONMENTAL DECONTAMINATION Ltd filed Critical ENVIRONMENTAL DECONTAMINATION Ltd
Priority to AU60817/01A priority Critical patent/AU6081701A/en
Publication of WO2001083038A1 publication Critical patent/WO2001083038A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • 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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the present invention relates to the detoxification of halogenated organic compounds and particularly, but not solely, those in contaminated media.
  • the invention also consists in related plant systems and methods as well as the decontaminated products or media.
  • Organo-halogen compounds are recognised as a problem in the environment. Many methods have been proposed whereby the levels of such troublesome organo-halogen compounds may be reduced.
  • PCT/AU93/00660 indicates that suitable reagents may include oxidising agents such as iron oxide, manganese dioxide and oxygen. Alternatively it is suggest that the reagent may be a reducing agent such as aluminium metal, iron metal and zinc metal. Other suitable reagents mentioned include sodium hydroxide, graphite, red mud, lime or quicklime, water, carbon dioxide, calcium oxide, copper oxide, aluminium oxide and magnesium oxide.
  • PCT/DE98/02787 (WO 99/15239) of V. Birke discloses a method for reductive dehalogenation of halo-organic substances in a manner similar to that mentioned previously but with a mixture of reagents.
  • One is selected from elementary alkali metal, elementary alkaline earth metal, elementary aluminium and elementary iron and the other from compounds having an activated hydrogen as a hydrogen source.
  • Preferred sources of hydrogen mentioned include alcohols, ethers, poly ethers, amines or hydroxides (eg; calcium hydroxide), metal hydrides or non-metal hydrides (eg; calcium hydride), sodium hydride, sodium boronate, lithium alanate, trialkylsilane, polyalkylhydrogensiloxane or combinations thereof.
  • Specific amines mentioned include primary, secondary or tertiary aliphatic and alicyclic monamines or polyamines, methylamine, ethylamine, 1- and 2-propylamine, 1- and 2-butylamine, ethylene diamine, hi-, terra-, penta-, hexamethylene diamine, dimethylamine, diethylamine, di-n-propylamine, cyclopentyl- and cyclohexylamine, nitrogen heterocycles and perhydro nitrogen heterocycles, for example piperidine, l-(2-aminoethyl)-piperazine, l-(2-armnoethyl)-pyrrolidine and 1-2(2- aminoethyl)-piperidine, 4-(2-aminoethyl)-morpholine and liquid ammonia.
  • PCT/DE98/02787 indicates as a possible alternative to the amines certain amides can be considered.
  • certain amides can be considered.
  • 1,3 dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidon (dimethylpropylene urea, DMPU), 1,3- dimethyl-2-imidazolidinon (N,N-dimethylethylene urea, DMEU), l-methyl-2-pyrrolidon (NMP), l-ethyl-2-pyrrolidon, N,N-diethylacetamide, N,N-diethylpropionamide, N,N- diethylisobutyramide.
  • NMP l-methyl-2-pyrrolidon
  • PCT/DE98/02787 Specific examples given in PCT/DE98/02787 relate to PCB ' s, chlophen and 1 ,3 ,5-TCB only. No example is given of any dehalogenation of the persistent organo-halogen compounds dichlorodiphenyl trichloroethane (DDT or DDE), and Dieldrin. Indeed our own experimentation utilising procedures such as disclosed in PCT/DE98/02787 has failed to show an acceptable reduction in the levels of, for example, DDT, DDE and/or Dieldrin in contaminated soils where, as suggested, an elementary metal (eg; magnesium) is utilised in conjunction with, for example, calcium oxide or an amine such as butylamine.
  • an elementary metal eg; magnesium
  • the present invention consists in a method of reducing the levels of an organo-halogen compound which involves the milling (single, simultaneous or sequential) of the compound (eg; when in a contaminated media) in the presence of one or more of:
  • the present invention consists in a method of reducing the level of at least one organo-halogen compound in and/or on a matrix which comprises or involves milling the matrix with the at least one organo-halogen compound in a ball mill with one or more of a) urea, b) an iron sand, c) steel makers slag, and/or d) a suitable acid.
  • urea is used and preferably with an iron sand or steel makers slag.
  • the energising of the ball mill is such that a temperature of at least about 70 °C is generated in the ball mill mix.
  • said ball mill is of a kind with ferrous balls and/or a ferrous ball confinement chamber.
  • ferrous is meant iron or steel or some alloy which includes iron.
  • said organo-halogen compound is an impurity or contaminant in and/or a matrix.
  • said matrix is soil, clay or the like.
  • said organo-halogen compound is typified by, for example, DDT (or the related DDE, DDD), dieldrin, PCBs, etc.
  • said ball mill has balls of less than 30 mm diameter.
  • the balls of the ball mill are of about 20 mm diameter.
  • the ball mill is operated with sufficient energy so as to raise the mill mix temperature to at least 70 °C but to maintain the mill mix temperature below temperatures which will lead to excessive vaporisation of the organo-halogen compound being handled.
  • the operating temperature of the ball mill is in the range of from 70 to 140 °C (most preferably 70 to 110°C), [ie; the upper threshold being substantially below the vaporisation point of DDT in most of its forms which is at about 146 °C].
  • the ball mill is operated to a temperature range of from about 70 to 140° C (most preferably 70 ° to 110°C) which again is well below the vaporisation temperature which in respect of dieldrin in about 150 °C. in some forms of the present invention where a ball mill of sufficient energy is utilised urea may be used alone or in conjunction with a suitable acid.
  • a suitable iron sand or steel makers slag may be used alone or in conjunction with a suitable acid or urea.
  • both (I) a suitable iron sand and/or steel makers slag and (II) urea is utilised (optionally with (Hi) acetic acid or vinegar) and preferably also the ball mill is one with ferrous balls and/or a ferrous ball confinement chamber.
  • the present invention consists in a method of reducing the DDT and/or dieldrin content of a contaminated matrix which comprises subjecting particles of such contaminated matrix to ball milling in the presence of urea at sufficient energy as to impart to the reaction mix a temperature of at least 70°C but below 146°C.
  • the reaction mix with such contaminated particles comprises urea - 5 to 15% (preferably about 10% by weight) iron sand - 0 to 15% (preferably 5 to 10% by weight) acetic acid - 0 to 5% (preferably about 2% by weight).
  • white vinegar (as a source of acetic acid) about 1% by w/w.
  • the percentages take advantage of the iron values and titanium values of steel makers slag as is readily available in New Zealand to provide in conjunction with readily available urea and white vinegar an economic expendables input for such a ball milling procedure.
  • said contaminated particles are those of soil and/or clay and/or crushed rock in a substantially dry form.
  • the balls of said ball mill are less than 30mm in diameter and preferably are about 20mm or less.
  • the ball mill is one with ferrous balls and/or a ferrous ball confinement chamber.
  • the present invention consists in a method of decreasing the organo-halogen compound contamination of a media which involves a use of a method as aforesaid sufficient to reduce the level to one that is desired.
  • the present invention consists in a method of decontaminating an organo-halogen contaminated media (eg; soil) which comprises or includes milling the media (optionally in the presence of a suitable acid) with one or both of
  • an organo-halogen contaminated media eg; soil
  • milling the media optionally in the presence of a suitable acid
  • iron sand or any other metal values source eg; steel makers slag
  • said milling is followed by a subsequent milling of the output of the first milling and such second milling is with the addition of one or both of i) urea, and ii) iron sand or any other metal values source (eg; steel makers slag).
  • the initial milling is in the presence of acetic acid and/or iron sand.
  • Urea may be present irrespective of whether or not acetic acid and/or iron sand is present.
  • the subsequent or a subsequent milling step involves the output of an earlier milling procedure and the addition of urea and/or iron sand.
  • said milling is in a ball mill and preferably said ball mill includes balls with an elementary iron content.
  • said elevated temperature is above 70 °C.
  • the elevated temperature is within a range as previously set forth.
  • the milling can be performed in a closed environment thereby to restrict (eg; by pressurisation, for example, in a pressure vessel) the loss of freed ammonia from the milling procedure.
  • the present invention consists in a method of media decontamination which involves a procedure substantially as herein described with reference to any of the accompanying drawings and/or using any of the methods herein described.
  • the present invention consists in a method of decontaminating a media (eg; soil and/or clay) which involves the performance of methods in accordance with the present invention at or adjacent the site of contamination utilising a ball mill positioned for the purpose.
  • a media eg; soil and/or clay
  • said ball mill is apparatus as described in our patent application filed simultaneously herewith.
  • the present invention consists in a method of soil or clay decontamination which comprises or includes subjecting at least the lower particulate sized fraction of the soil or clay to ball milling so as to perform a process as previously described.
  • said soil or clay has had larger particles removed therefrom or crushed.
  • a larger particle size fraction is separated from a finer particle fraction with the larger particle size fraction being subjected to optional exterior washing prior and/or to optional crushing and/or optional re-inclusion thereof with the finer particle size fraction before or after (preferably after) the subjection of the finer particle size fraction to the ball milling.
  • the smaller particle size fraction includes sizes generally less than 10 mm.
  • the ball milling is for such duration as will reduce the less than 10 mm particle sizes to about 0.4 microns.
  • the present invention consists in a method of decontaminating earth (whether one or more of top soil, clay, rock or the like) which comprises subjecting in a reasonably or substantially dry form the more contaminated smaller particulate fraction of he earth to a ball milling procedure which has the effect of reducing the DDT and/or dieldrin contamination thereof, such ball milling being for such duration at a temperature of at least 70 °C but below the boiling point of any part of the DDT and any dieldrin.
  • any one or more of the reactants previously described for inclusion in a reaction mix in such a ball mill is included.
  • suitable is such as will enable the desired outcome, namely, a reduction in the level of the organo-halogen compound in its original form.
  • a suitable acid is acetic acid (whether as white vinegar or otherwise) which (substantially as hereinafter described with reference to the examples) may be used in a first stage with, for example, urea and/or iron sand.
  • said "metal source” is a metal complex, ie; of several metals and/or at least one metal in one or more oxidation states (eg; a titanoferromagnitite), whether zero and/or otherwise.
  • iron sand includes any appropriate iron sand for the procedure. All such iron sands are preferably titanoferromagnetite sands. One such sand is that of, for example, BHP New Zealand Steel Limited having a content substantially as set out in Table 1 (being an analytical report of two samples).
  • DDT may also include the related DDD (ie DDT minus CI) and/or the reatled DDE (ie DDT minus HC1)
  • the Fe values are present in other than the zero oxidation state.
  • Reference hereto to "steel makers slag” includes any suitable slag with iron or titanium values but preferably is a slag with both iron and titanium values such as that of BHP New Zealand Steel Limited.
  • the slag such as that set out in Table 2 is preferably post-crushing, and magnestic extraction of any zero oxidation state values initially present prior to oxidation thereof.
  • Table 2 is an example of BHP New Zealand Steel Gap 10 slag.
  • the Fe values are present as oxides or other than zero oxidation state values.
  • Elevated temperature(s) is to temperature(s) below that at which the organo-halogen evaporates.
  • elevated temperature(s) is to temperature(s) below that at which the organo-halogen evaporates.
  • the organo-halogen preferably in the range 70 °C to 140°C.
  • the present invention consists in a method of decontaminating a media which involves a process in accordance with the present invention as previously defined and one or more of the procedures hereinafter described with or without reference to any of the accompanying drawings.
  • the present invention consists in a method of decontaminating soil contaminated with an organo-halogen compound (for example, DDT, DDE, DDD, Dieldrin, PCBs, dioxins, halogenated furans and lindane) which involves the step of
  • an organo-halogen compound for example, DDT, DDE, DDD, Dieldrin, PCBs, dioxins, halogenated furans and lindane
  • said material after the ball mill(s) is subjected to a process which tends to ensure a better agglomeration property thereof.
  • Such process involves the addition of a suitable polymer or other material (eg; urea itself or lime).
  • a suitable polymer or other material eg. urea itself or lime.
  • the reactants are (I) iron sand and/or steel makers slag and (II) urea with optionally (III) a suitable acid as well (preferably acetic acid), preferably the staging being substantially as herein described.
  • reaction conditions in each ball mill is such that the mechanical agitation is at a temperature of 70 °C or above.
  • the system or plant is such as will perform a procedure substantially as hereinafter described with reference to Figure 1 and/or Figure 2.
  • the invention consists in degrading a persistent/toxic organo- halogen into safer form(s) which includes, at elevated temperatures (eg; as in, say, a ball mill above, say, 70 °C), vigorously mixing the organo-halogen with (in any order if sequential, or simultaneously) reagents:
  • (C) if (I) is steel makers slag, a suitable amide and/or urea, and (III) optionally an acid (eg; acetic acid).
  • an acid eg; acetic acid
  • the present invention also consists in reaction products or detoxification media and/or soil resulting from a process or procedure of the present invention.
  • Figure 1 is a simplistic two stage milling procedure in accordance with the present invention capable of reducing the level of, for example, DDT (and/or the related DDE and
  • DDD DDD
  • Dieldrin in soils although not restricted to such organo-halogens as such process is applicable with different effectiveness to others such as PCBs, dioxins, halogenated furans and lindane, and
  • Figure 2 is one preferred plant/flow diagram
  • Figure 3 is a preferred flow diagram in accordance with the present invention showing by same reference numerals as used in Figure 2 some of the components in common between the slightly different processes of Figures 2 and 3
  • Figure 4 is a flow diagram showing how preferably two larger particle streams are utilised and preferably each is crashed to the extent necessary to ensure proper stabilisation of the small particle sizes provided as the decontaminated outflow from the dehalogenation plant, the fines (where the bulk of halo-organic contamination lies in soil and/or clays) preferably alone being dehalogenated
  • Figure 5 is a simplified side elevation view of a preferred transportable unit capable of being utilised to initiate a treatment site in conjunction preferably with other transportable componentry.
  • Stage I Ball Milling of the soil (wet or dry) [with/without acetic acid (or any other suitable acid)] with urea preferably and/or iron sand (or any other metal source).
  • Stage II Ball Milling of the Stage 1 output with additional urea (optionally with iron sand and/or optionally with acetic acid (or other suitable acid).
  • Temperature for the step involving urea can vary the number of batches process can instead be continuous or in batches can vary the order of reagent addition (eg; adding urea before or after iron sand or steel makers slag addition). can consider pretreatment of lime (calcium oxide or calcium sulphate) to dry (at least in part) soil mixture.
  • Preferred Starting Point Preferred Starting Point:
  • Soil (or any other solid or liquid form) contaminated with any halo-organic substance. Our tests to date have been performed on soil contaminated with DDT, DDE and Dieldrin.
  • Figure 1 shows several preferred variants.
  • the flow diagram is as shown in Figure 2.
  • That contaminated soil is preferably then passed through a rotary screen 2 with larger materials, eg; stones, being passed to a washer 3 and then being stockpiled at 4.
  • Material eg; soil or clay
  • a primary separation eg; using a screen 2
  • the fine material stream is preferably further streamed in a dry trommel 5 to provide a second larger particle stream.
  • the second finer particle stream is optionally dried at 9 prior to entry into a hopper 11.
  • the first larger particle stream from screen 2 is washed at 3 and stockpiled at 4. Thereafter as required it may be reduced in particle size in a "crusher" 20.
  • the second larger particle stream in vibrating screen 6 removes clay and fines go to dryer 9 optionally via a drier
  • the dry materials of small particle size (preferably 0 to 5 mm in particle size) is passed into an optional dryer 9 and thereafter enters into an auger 10 via a hopper 11. It is possible therefore for the material from 9 to be passed directly only into the first ball mill 12 and thereafter have other reagent or reagents from either or both hoppers 13 and 14 fed via the worm feed 10 to premix with the out feed from either the first ball mill 12 or the second ball mill 15.
  • a third ball mill 16 is provided to which, if desired, a recycle feed from the output can be provided.
  • ball mills While reference is made to ball mills, one or more of them may be substituted with other milling form of apparatus. Also the same ball mill can be used in a staged version of the overall process.
  • Means to feed a polymer or even urea and/or lime 17 is preferably provided such that the output from the ball mill 16 can be agglomerated at 18 and then stockpiled at 19 with an option of some recycle back into ball mill or reactor 3.
  • the output otherwise from the stockpiles 19 can go to site reconstruction, ie; for example, back to the site of the soil elimination 1.
  • FIG. 3 shows an alternative procedure to that of Figure 1.
  • the excavation at 1 visually recognises clay layers and treats them to drying in a solar drying room 8 whereupon they are fed as stream 28 along with a fines stream 27 from the jaw crasher 20 into the reactor 21, they are preferably pre-blended for that purpose with the fines output of the rotary dryer 9.
  • the unit designated generally as 21 is preferably as described in the specifications filed simultaneously herewith but preferably utilises a Palla 65U ball mill of KHD Humboldt Wedag AG of Germany having ball sizes below 30 mm in diameter (preferably from 15 to 25 mm diameter) (eg; 20 mm in diameter which are of steel or iron within the iron reactant reactor cylinders).
  • the ball mill is supported on a mobile chassis 36 with upstanding pedestals 27 on which the vibrating mass of inlet 25, cylinder 25, cylinder 23 and out take 24 can vibrate violently under the rotation of the drive shaft 32 driven eccentric or eccentrics.
  • the ball mill is straddled by banks of the pedestals 27 and the synthetic or natural rubber pads 38 allow the degree of movement required.
  • the unit 36 with a static mass sufficient to counter weight the vibrating masses of the ball mill assembly is driven by an engine 30 (preferably a GM Detroitt Diesel 8N71 producing 600 BHP and a maximum torque of 3500 ⁇ M) such that via a torque converter or more preferably an overcentre clutch (twin disc) 31 the shaft 32 can be rotated from rest.
  • an engine 30 preferably a GM Detroitt Diesel 8N71 producing 600 BHP and a maximum torque of 3500 ⁇ M
  • a torque converter or more preferably an overcentre clutch (twin disc) 31 the shaft 32 can be rotated from rest.
  • a brake 33 is provided to allow braking of the ball mill when the clutch is engaged.
  • the engine 30 has a minimum power output of 400 BHP with no upper limit.
  • the engine is a diesel capable of producing 600 BHP and greater than 3396 ⁇ M.
  • GC-ECD analysis showed a 99% reduction in DDT levels, and a 99.1% reduction in dieldrin levels. No other halo-organic substances were detected.
  • Example 2 Soil (7 kg) contaminated with DDT (390 mg/kg dry weight) and dieldrin (71.4 mg/kg dry weight) was mixed with vinegar (630 g) and cast iron filings (1.40 kg). The soil was undried and had a moisture content of 9.3% prior to the addition of vinegar. This mixture was placed in a vibratory ball mill and milled for 30 minutes. The mill was then discharged, and urea (1.05 kg) and iron sand (700 g) were mixed into the soil. The mill was reloaded, and the mixture was ground for a further 30 minutes. The mill was discharged again, an additional batch of urea (1.05 kg) and cast iron (700 g) was mixed into the soil, and the mixture was milled for a further 30 minutes. The mill temperature was above 90°C for the entire process.
  • GC-ECD analysis showed a 98.4% reduction in DDT levels, and a 99.7% reduction in dieldrin levels. No other halo-organic substances were detected.
  • GC-ECD analysis showed a 97.9% reduction in DDT levels, and a 99.0% reduction in dieldrin levels. No other halo-organic substances were detected.
  • This mixture was placed in a vibratory ball mill and milled for 30 minutes. The mill was then discharged, and urea (350 g) and iron sand (350 g) were mixed into the soil. The mill was reloaded, and the mixture was ground for 15 minutes. The mill was then discharged again, and an additional batch of urea (350 g) and iron sand (350 g) was mixed into the soil. This mixture was milled for 15 minutes. The mill temperature was above 70 °C for the entire process. .
  • GC-ECD analysis showed a 96.9% reduction in DDT levels, and a 98% reduction in dieldrin levels. No other halo-organic substances were detected.
  • Example 5 Soil (7 kg) contaminated with DDT (390 mg kg dry weight) and dieldrin (71.4 mg/kg dry weight) was mixed with iron sand (1.40 kg) and urea (700g). The soil was oven-dried at 60 ° C prior to use. This mixture was fed through an open vibratory ball mill. The residence time in the mill was 6 minutes. Additional urea (350 g) and iron sand (700 g) was mixed into the soil, and the mixture was fed through an open mill. The mill took 9 minutes to discharge. A final batch of urea (350 g) and iron sand (700 g) was mixed into the soil, and the soil was once again fed through an open vibratory bore mill. The time taken for total mill discharge was 14 minutes. This mixture was milled for 15 minutes. The mill temperature was above 70 °C for the entire process.
  • GC-ECD analysis showed a 95.1% reduction in DDT levels, and a 90.9% reduction in dieldrin levels. No other halo-organic substances were detected.
  • Soil (6.62 kg, oven-dried and pre-milled) contaminated with DDT (720 mg/kg dry weight) and dieldrin (64 mg/kg dry weight) was mixed with iron sand (1.24 kg) and urea (1.24 kg). This mixture was placed in a vibratory ball mill and milled for 30 minutes. The top of the mill was then opened, and urea (662 g) was poured in on top of the soil. The mixture was then milled for a further 30 minutes.
  • GC-ECD analysis showed a >99% reduction in DDT levels, and a >97% reduction in dieldrin levels. No other halo-organic substances were detected.
  • sample (II) was taken at the beginning of the discharge
  • sample (IN) was taken at the end of the discharge.
  • sample (IN) a further 5% of urea was added to sample (IN), and it was milled for a further 30 minutes (sample (N)).
  • sample (VI) a further 5% portion of urea was added to sample (N), and it was milled for a further 60 minutes (sample (VI)).
  • Example (A) Sydney clay (3 kg) (as used in Example 10) had iron sand (10%) and acetic acid (3%) added to it. The mixture was run through ball mill, and samples were taken after 40 min (Sample (A)).
  • Mapua soil with a mean contamination content in a less than 5 mm screened fraction of 71.9 mg/kg of dry weight Dieldrin and of 412 mg/kg of dry weight total of DDT isomers was then subjected to a milling procedure.
  • Contaminated soil as excavated was spread out on a tarpaulin and mixed well. Soil was then sieved through a 5mm sieve. The ⁇ 5mm fraction was collected and dried overnight in an oven kept at 50 °C prior to use in the milling trials. The > 5mm fraction was used in soil washing trials. Approximately 43% of stockpile was ⁇ 5mm, and approximately 57% was > 5mm.
  • MCD Mechanochemical Dehalogenation Process
  • Soil (4kg of the oven-dried ⁇ 5mm fraction) was mixed with iron sand (200g, 5%) and acetic acid (2%). This mixture was introduced into the ball mill and milled for 30 minutes. The mill was the discharged, and a soil sample (150g) was taken. The milled soil was then mixed well with urea (400g, 10%) and iron sand (200g, 5%). This mixture was milled for a further 30 minutes. The mill was then discharged, and tlie soil was re-introduced into the mill (no extra reagent addition), and milled for another 30 minutes. A sample (150g) was taken for analysis.
  • dieldrin In respect of dieldrin, the same can be said, where initial concentrations have varied from 80 mg/kg to 70 mg/kg. First stage results generally are down to the region of 10 mg/kg.
  • Run l 5kg of material identical to the control sample was extracted from the mixer
  • the material was mixed with 10% of the SR3 slag, 5% of unfiltered white vinegar
  • the mill was operated for 20 minutes.
  • the Run 1 sample was extracted.
  • the material was mixed with 10% of Gap 10 slag (ie, screened to particle size less than 10 mm), unfiltered white vinegar (10% concentrate) and 5% urea.
  • the mixed product was sampled to provide the spiked sample.
  • Material will be excavated from agreed contamination zones, to designated depths by a tracked excavator, having a wide bucket, with a sharp cutting edge.
  • Product > 5mm is washed in a wet trommel, where the extracted sediment is rotary dried and joins the ⁇ 5mm particle sizing.
  • the > 5mm washed product is crushed to client preference, sizing and also replaced on site as base fill and/or be part of the end product homogenized mix.
  • Clay Identifying specific clay seams, during excavation is important. Physical clay seam separation during excavation for separate drying reduces processing costs. Pre-drying would be of a passive type, in a dedicated fully enclosed shed, constructed on site, similar to a commercial vegetable growers hothouse. An air extraction/dust collection system will be installed.

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Abstract

L'invention concerne un procédé permettant de réduire le niveau d'au moins un composé organo-halogéné dans et/ou sur une matrice. Le procédé consiste à broyer la matrice associée à au moins un composé organo-halogéné dans un broyeur à boulets, conjointement à (I) de l'urée, (II) un sable de fer, (III) des scories d'acier et/ou (IV) un acide adéquat.
PCT/NZ2001/000069 2000-05-03 2001-05-02 Detoxification de composes halogenes dans un milieu contamine Ceased WO2001083038A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU60817/01A AU6081701A (en) 2000-05-03 2001-05-02 Detoxification of halogenated compounds in contaminated media

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
NZ504341 2000-05-03
NZ50434100A NZ504341A (en) 2000-05-03 2000-05-03 Decontaminating a media such as soil of organo halogen compounds such as DDT
NZ510521 2001-03-12
NZ51052201A NZ510522A (en) 2001-03-12 2001-03-12 Decontaminating a media such as soil of organo halogen compounds such as DDT
NZ510522 2001-03-12
NZ51052101 2001-03-12
NZ510752 2001-03-23
NZ51075201 2001-03-23
NZ51082401 2001-03-28
NZ510824 2001-03-28

Publications (1)

Publication Number Publication Date
WO2001083038A1 true WO2001083038A1 (fr) 2001-11-08

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Family Applications (2)

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PCT/NZ2001/000069 Ceased WO2001083038A1 (fr) 2000-05-03 2001-05-02 Detoxification de composes halogenes dans un milieu contamine
PCT/NZ2001/000068 Ceased WO2001083127A1 (fr) 2000-05-03 2001-05-02 Installation et procedures de decontamination

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/NZ2001/000068 Ceased WO2001083127A1 (fr) 2000-05-03 2001-05-02 Installation et procedures de decontamination

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AU (2) AU6081601A (fr)
WO (2) WO2001083038A1 (fr)

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WO2007105972A1 (fr) 2006-03-15 2007-09-20 Mcd Technology Limited APPAREIL de fraisage
EP2727662A1 (fr) * 2012-10-26 2014-05-07 Biodermol Ambiente S.r.l. Méthode pour abaisser le degré de contamination de DDT, DDE, DDD et/ou de leurs isomères dans les sols
CN106807735A (zh) * 2017-01-24 2017-06-09 中石化炼化工程（集团）股份有限公司 一种污染土壤修复系统和污染土壤修复的方法
WO2020206528A1 (fr) 2019-04-10 2020-10-15 Queen's University At Kingston Procédé d'assainissement des sols contaminés par le polyfluorocarbone
CN112730651A (zh) * 2020-12-15 2021-04-30 湖南微谱检测技术有限公司 一种二噁英样品快速前处理方法
CN114054472A (zh) * 2021-10-22 2022-02-18 中石化宁波工程有限公司 一种降解含卤有机污染物的方法
CN115261631A (zh) * 2022-08-10 2022-11-01 贵州大学 一种电解金属锰阳极渣回收处理方法

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CN102824719B (zh) * 2012-09-03 2015-01-21 清华大学 一种基于机械力化学处理全氟和多氟化合物固体废物的方法
CN111168171B (zh) * 2020-03-16 2021-04-09 沈阳飞机工业（集团）有限公司 超塑成形/扩散连接零件化铣方法

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WO2007105972A1 (fr) 2006-03-15 2007-09-20 Mcd Technology Limited APPAREIL de fraisage
CN101410185B (zh) * 2006-03-15 2010-06-16 Mcd技术有限公司 研磨设备以及使用该研磨设备修复化学污染基体的方法
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EP2727662A1 (fr) * 2012-10-26 2014-05-07 Biodermol Ambiente S.r.l. Méthode pour abaisser le degré de contamination de DDT, DDE, DDD et/ou de leurs isomères dans les sols
CN106807735A (zh) * 2017-01-24 2017-06-09 中石化炼化工程（集团）股份有限公司 一种污染土壤修复系统和污染土壤修复的方法
WO2020206528A1 (fr) 2019-04-10 2020-10-15 Queen's University At Kingston Procédé d'assainissement des sols contaminés par le polyfluorocarbone
CN112730651A (zh) * 2020-12-15 2021-04-30 湖南微谱检测技术有限公司 一种二噁英样品快速前处理方法
CN114054472A (zh) * 2021-10-22 2022-02-18 中石化宁波工程有限公司 一种降解含卤有机污染物的方法
CN114054472B (zh) * 2021-10-22 2023-09-19 中石化宁波工程有限公司 一种降解含卤有机污染物的方法
CN115261631A (zh) * 2022-08-10 2022-11-01 贵州大学 一种电解金属锰阳极渣回收处理方法

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