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EP1027109A1 - Procede de deshalogenation reductrice de substances halogeno-organiques - Google Patents

Procede de deshalogenation reductrice de substances halogeno-organiques

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Publication number
EP1027109A1
EP1027109A1 EP98954202A EP98954202A EP1027109A1 EP 1027109 A1 EP1027109 A1 EP 1027109A1 EP 98954202 A EP98954202 A EP 98954202A EP 98954202 A EP98954202 A EP 98954202A EP 1027109 A1 EP1027109 A1 EP 1027109A1
Authority
EP
European Patent Office
Prior art keywords
substances
reducing agent
mill
mixture
solid
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.)
Granted
Application number
EP98954202A
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German (de)
English (en)
Other versions
EP1027109B1 (fr
Inventor
Volker Birke
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Individual
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Individual
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Application filed by Individual filed Critical Individual
Publication of EP1027109A1 publication Critical patent/EP1027109A1/fr
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Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • 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 invention relates to a process for the reductive dehalogenation of organohalogen substances in solid and liquid substance mixtures, in which the substance or the substance mixture with the addition of elemental alkali metal, alkaline earth metal, aluminum or iron as reducing agent and at least one reagent with at least slightly activated hydrogen as what - source of hydrogen is treated. It is particularly suitable for the detoxification of organically contaminated soils and other materials with a complex composition, but also for decontamination and, if necessary, recycling of liquid or predominantly liquid halogen-organically contaminated substances.
  • Toxic polyhalogenated organic pollutants have so far not been detoxified under economically and ecologically advantageous and future-oriented conditions with any of the remediation technologies known today. These substances are often present as impurities, moreover in large quantities, in soils, river or marine sediments, sewage sludges, filter dust, building materials, seepage oils, waste oils etc., i.e. associated with an indefinable number of foreign and accompanying substances with different properties.
  • the detoxification and remediation of such complex, heterogeneous, solid, solid-liquid or liquid materials and contaminated sites poses particularly extensive problems.
  • Halogen-containing organics containing 10 solids are often difficult for reagents to reach due to the high transport inhibitions in solid-solid reactions.
  • polyhalogenated organic substances which are contaminants in the environment such. B. in soils, river or sea food
  • Seepage oils i.e. solid or solid-liquid, without exception very heterogeneous materials, can be found in large quantities due to the complex condition of these matrices and the resulting diverse transport inhibitions
  • the method should have a process sequence that is as easy to handle as possible and should work relatively quickly.
  • the invention is applicable to organohalogen compounds which are contained in solid or liquid foreign substances or mixtures of foreign substances, but which can also be present as solid or liquid pure substances or in mixtures thereof.
  • these substances or mixtures of substances are treated in a single process step, i.e. all components, including at least one reducing agent and one hydrogen source, are intimately mixed under mild reaction conditions.
  • the method comprises grinding the reactants while entering a more or less large amount of mechanical energy.
  • a fine distribution into very small particles and thereby an intensive mixing of all components of the mixture is brought about, so that intensive contact is established on average over time with the reagents used and these are brought to the desired reaction.
  • the reactivity of the solid components is increased by the fine distribution due to surface-physical effects.
  • the process according to the invention has the advantage that under mild reaction conditions, i.e. is generally feasible at room temperature and under normal pressure and is technically far less complex. It can therefore also be designed for small mobile systems. Another advantage is that recycling or re-use of the materials to be decontaminated is possible, which would in principle be destroyed by incineration.
  • the process basically works at low temperatures, preferably at room temperature under normal pressure. However, it is possible that the intensive introduction of mechanical energy and / or the heat of reaction liberated during dehalogenation causes heating in the course of the process.
  • the metallic reducing agent is advantageously used at least in a slight excess.
  • the required amount of reducing agent can be determined in preliminary tests on samples of the specific decontamination object.
  • Base metals are generally used as reducing agents, specifically alkali metals, alkaline earth metals, aluminum and iron. Sodium and potassium are preferred among the alkali metals, magnesium and calcium among the alkaline earths. However, other base metals can be used using the principles of this invention, it should be understood that the formation of toxic products should be avoided.
  • alcohols, ethers, polyethers, amines or hydroxides such as. Calcium hydroxide, or metal or non-metal hydrides such as e.g. Calcium hydride, sodium hydride, sodium boranate, lithium alanate, trialkylsilanes, polyalkylhydrosiloxanes, used individually or in combination.
  • low molecular weight aliphatic alcohols can be used, for example.
  • Low molecular weight alcohols are, for example, aliphatic alcohols with 1 to 7 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, sec- and tert-butanol, pentanol, hexanol, heptanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol , 2-
  • ethers for example, simple symmetrical or asymmetrical aliphatic ethers, cyclic ethers or polyethers can be used.
  • examples include diethyl ether, propylene ether, isopropyl ether, n-butyl ether and dimeric or trimeric polyethers, coronands, cryptands, spherands, ether amines such as e.g. 2-methoxyethylamine etc.
  • aliphatic amines and lower primary or secondary aliphatic amines are preferred.
  • suitable amines are: primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines,
  • certain amides can also be considered.
  • 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidone (diethyl propylene urea, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea) can be used , DMEU), l-methyl-2-pyrrolidone (NMP), l-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutyramide.
  • a separate addition of a hydrogen source can be dispensed with if it is known that a substance suitable as a hydrogen source is already present in sufficient quantity in the mixture to be treated.
  • the mechanical preparation according to the invention can consist of grinding in a mechanical mill, for example a ball mill, a hammer mill or a vibratory mill. Additional grinding aids can be used for this grinding. Materials that can reduce the surface energy and / or the plastic deformation of solids when exposed to mechanical energy are generally used as grinding aids.
  • Surface-active substances in various states or preparation forms such as quaternary ammonium compounds, which can not only be used in pure substance, but also immobilized on inert, surface-active carriers, such as layered silicates, clays (so-called "organophilic bentonites") and also substituted Alkylimidazolines and sulfosuccinamides, fatty acids, fatty acid esters and amides, primary, secondary and tertiary alkyl and fatty amines with one or more amine groups, alicyclic amines, such as, for example, cyclohexylamine, polyhydrogen nitrogen heterocycles, such as, for example, piperidine (hexahydropyridine) mono-, di- or trialka nolamines, simple glycols, polyalkylene glycols, such as, for example, polyethylene and polypropylene glycols, and their mono- or diethers, organosilicon compounds, in particular silicones, special inorganic
  • reaction accelerators capable of partially or completely dissolving base metals, in particular alkali and alkaline earth metals, and / or dissociating them in metal cations and anions and / or promoting the formation of solvated electrons and / or organometallic ones can be used as reaction accelerators
  • the grinding aid (s) and / or reaction accelerator can be added to the substance or mixture of substances in a subsequent step, i.e. separately after the addition of the reactants, and mechanically incorporated.
  • the metallic reducing agent can be added directly to the batch in pure form. This is particularly useful for alkaline earth metals, which are less reactive in air than the alkali metals, e.g. with magnesium chips.
  • the metallic reducing agent can be dispersed or suspended in a preparation, for example dispersed in a non-oxidizing liquid or the liquid hydrogen source.
  • Dispersions of the selected metal in white oil, paraffin or in ethers are advantageously to be used, and also polyethers such as diglyme, triglyme, tetraglyme, polyethylene glycol and polyethylene glycol derivatives, etherified di- and polyglymas.
  • the metallic reducing agent can be mixed with or applied to a solid carrier.
  • a mixture of alkali metal, in particular sodium, with calcium silicate or calcium oxide has proven to be an advantageous preparation. It has been found that ball milling is also suitable for increasing the reactivity of the metals in an isolated working step by mechanical fine distribution, in particular for fine distribution of alkali metals on surface-active solid inert carriers.
  • the new method offers the advantage that it is carried out at room temperature and the procedure is simpler and faster by using the alkali metal and the like Simply fill the carrier material together into a grinding vessel or the mill and grind it to a homogeneous, finely powdery dispersion within a few minutes.
  • the process can also be designed in two stages, e.g. finely divided metal pre-produced by ball milling in a first step is only milled in a second step with the addition of reaction accelerators and possibly further additives.
  • alkali metal dispersions obtained by conventional means, i.e. to incorporate or mix in dispersions in inert fluids as well as on inert solid carriers, with reaction accelerators and possibly other additives in an organohalogenous solid and thereby effect the dehalogenation.
  • the method can also be used to complement other methods, e.g. of washing processes, can be used or combined with these.
  • a previous treatment of contaminated soils with calcium oxide (quicklime or quicklime), which is also known in other treatment processes and among other things. used to dry the mixture may be useful in some cases.
  • the process can be carried out batchwise, batchwise or continuously.
  • all the reactants ie at least the substance to be treated or the mixture / batch, the metallic reducing agent and the hydrogen donor, are first placed in a device which enables mechanical processing, such as a mill or a (dynamic) mixer.
  • a mill for example a ball mill, a hammer mill or an oscillating mill, is used, whereas in the case of liquid systems a mixer can suffice.
  • friction, screw or roller mixers are suitable as mixers.
  • processing can take place in only one step, the reactants being able to be added sequentially or gradually.
  • a continuous process could be carried out, for example, in a screw mill or a screw mixer.
  • the model floor had been artificially contaminated by adding a mixture of 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide which had been ground in for five minutes.
  • the GC-ECD analysis (internal standard: decachlorobiphenyl) of a model soil sample after this treatment shows a 99.7% degradation of the PCB. Furthermore, the presence or formation of other halogenated substances can be excluded on the basis of the GC findings »
  • ESM 234" In an eccentric vibratory mill "ESM 234" (data see example 1), 3.8 kg quartz sand (bulk density 1.27 g / ml) are mixed with 200 g calcium oxide for drying for ten minutes by grinding. A mixture of 5 g of chlorophen A30 and 150 g of calcium oxide / calcium hydroxide, 18.2 g of n-butylamine and 51.1 g of tetraethylene glycol dimethyl ether (tetraglyme) is mixed in, likewise by grinding, for two minutes. Finally, 102 g of magnesium shavings are ground in for two hours.
  • the GC-ECD analysis (internal standard: decachlorobiphenyl) shows a 99.7% degradation of the PCB. The presence or formation of other halogenated substances can be excluded. If Mg powder is used instead of Mg chips, there is practically no dehalogenation.
  • a PCB-contaminated, cohesive soil is treated that has previously been subjected to a washing process with water and surfactants.
  • a residual contamination of approx. 250 ppm PCB could no longer be removed from the suspended fraction of this process, which was precipitated with the aid of flocculants based on polyamide.
  • ESM 234" eccentric vibratory mill “ESM 234" (data see example 1) 3 kg of this PCB-contaminated soil fraction, residual moisture after thermal predrying approx. 2%, are mixed with 200 g calcium oxide for drying for 30 minutes by grinding. Mix in, likewise by grinding, 150 g of n-propylamine for one minute and wait for another 5 minutes. Finally, 200 g of sodium are ground in the form of cylindrical pieces (each 1 to 2 cm long and thick) for 45 minutes.
  • the GC-ECD analysis (internal standard: decachlorobiphenyl) shows a 98.5% degradation of the PCB.
  • the presence or formation of other halogenated substances can be excluded.
  • ESM 234" In an eccentric vibratory mill "ESM 234" (data see example 1), 3 kg of the PCB-contaminated soil fraction used in Example 4 from a washing process, residual moisture after thermal predrying approx. 2%, with 200 g calcium oxide for the purpose Drying mixed for 30 minutes by grinding. You mix likewise by "grinding, 100 g of tetraglyme for one minute. Finally, 200 g of sodium (cylindrical pieces, 1 to 2 cm long and thick) are ground in for 90 minutes, and the contents of the mill are then left overnight without further measures.
  • GC-ECD analysis (internal standard: decachlorobiphenyl) shows a 90% degradation of the PCB after 90 minutes, and more than 99.9% after standing overnight. The presence or formation of other halogenated substances can be excluded.
  • Preparation of a 52% i ⁇ en sodium-calcium oxide dispersion One way to dryly distribute sodium on calcium oxide consists in small pieces of sodium with calcium oxide in a centrifugal ball mill for 5 to 15 minutes, as in surface-active materials described (see above), to be ground. In this way, 5% of the alkali metal can be homogeneously distributed on the support.
  • Useful sodium-calcium oxide dispersions are obtained if the alkali metal is first allowed to act on calcium oxide in the presence of toluene under reflux conditions and then the batch is mixed with a high-speed stirrer or dispersant, for example Ultra-Turrax from "Janke &Kunkel" mixed at high speed.
  • the method can be used very flexibly: for example, it can also be used to prepare a 25% potassium
  • Calcium oxide dispersion which externally resembles the sodium dispersion. A dark gray, completely homogeneous powder is obtained. However, it is pyrophoric in air and therefore cannot be used for the dechlorination of polychloroaromatics in solid or solid-liquid matrices. Such a potassium-calcium oxide dispersion would, however, have interesting applications for organic-chemical implementations on the laboratory scale with suitable protective gas and security technology.
  • a centrifugal ball mill S 1 (see Example 5), 15 g of sea sand (pA), 0.5 g of calcium oxide-calcium hydroxide mixture are produced by partially quenching 56 g of CaO with 14 g of H 2 O. Grind 5 g of triglyme, 0.11 g of Chlophen A30, 0.3544 g of methanol and 0.51 g of magnesium powder after covering the mixture with argon in an open grinding bowl for 5 hours at high speed.
  • the GC-MS analysis shows a complete degradation of the PCB (main degradation product: biphenyl, besides little phenylcyclohexane). The presence or formation of other halogenated substances can be excluded.
  • Chlophene-contaminated sea sand (model) / Mg / n-propylamine In a centrifugal ball mill S 1 (see, example 5), 15 g of sea sand (pA), 1 g of calcium oxide-calcium hydroxide mixture, 0.25 ml of n-propylamine, 0 , 1 g of Chlophen A30, and 0.76 g of magnesium shavings for 1 hour at high speed.
  • the mechanical processing can be done by stirring in a reactor or in a suitable mixer.
  • a centrifugal ball mill S 1 (see Example 5), 7.5 g of sea sand (p.A.) and 2.0 g of magnesium shavings are ground under argon for five minutes. Then add 0.1 g of Chlophen A30. 7.5 g sea sand (pA) and 0.5 g 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) - pyrimidone (dimethylpropyleneurea, DMPU) are added, rinsed with argon and ground at high speed for 30 minutes. The GC analysis shows a complete degradation of the PCB (main degradation product: biphenyl). The experiment can be carried out with other special amides instead of DMPU, e.g. 1, 3-Dimethyl-2-imidazolidinone (N-N-dimethylethylene urea, DMEU) or 1-methyl-2-pyrrolidone (NMP), in a very similar configuration with the same result.
  • DMPU main degradation product: biphenyl
  • Figures 1 to 6 show the results of some exemplary gas chromatographic analyzes before and after the treatment. The analyzes show that it is possible to effectively treat even complex mixtures in a short time (see Fig. 3 to 6)
  • Pollutants found in relatively pure form such as highly concentrated PCB oils or insecticidal HCH isomers which e.g. in the order of magnitude of several 10,000 tons were deposited in open pits in the Bitterfeld area (purity content up to 95%), detoxifying particularly effectively.
  • the method according to the invention offers itself as an alternative to existing methods (Degussa sodium, NaPEG, KPEG, KPEG-PLUS), since it has a simpler and more secure design and can be implemented with simple means under mild conditions. This offers the possibility of weighing contaminated oils to a large extent. to be recycled instead of having to burn them. Especially have transformer oils
  • the organic pollutants can be completely eliminated under ecologically and economically favorable conditions at room temperature and in a short time, especially when they occur in different mixtures.
  • the pollutants are broken down directly in the matrix in which they are distributed by simply structured reagents. This can be, for example, materials that occur in large quantities elsewhere as residues and can thus be usefully recycled.
  • Detoxified materials such as Building materials or waste oils can be sent to useful recycling measures or recycled.
  • the new method thus avoids the disadvantages of the processes practiced on a larger scale in the remediation of contaminated sites, such as high-temperature combustion.
  • Areas of application for the method according to the invention are in particular:
  • PCB-contaminated building materials and building equipment (wall coatings, fine plaster, elastic expansion and window joint compounds in buildings of different types);
  • Adsorbents for cleaning exhaust gases, waste water flows such as activated carbon, clays, etc.

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  • Business, Economics & Management (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Management (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé de déshalogénation réductrice de substances halogéno-organiques qui peut être mis en oeuvre avec des mélanges de matières solides ou liquides. Si l'on procède à une adaptation correspondante des paramètres du procédé, des liquides ainsi que de la terre contaminés par des substances halogéno-organiques peuvent être traités mécaniquement, et ainsi déshalogénés de façon réductrice, par apport d'énergie mécanique et ajout de métal alcalin élémentaire, de métal alcalinoterreux, d'aluminium ou de fer comme agent de réduction, ainsi que d'au moins un réactif avec au moins de l'hydrogène légèrement activé comme source d'hydrogène.
EP98954202A 1997-09-25 1998-09-19 Procede de deshalogenation reductrice de substances halogeno-organiques Revoked EP1027109B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19742297 1997-09-25
DE19742297A DE19742297C2 (de) 1997-09-25 1997-09-25 Verfahren zur reduktiven Dehalogenierung von halogenorganischen Stoffen
PCT/DE1998/002787 WO1999015239A1 (fr) 1997-09-25 1998-09-19 Procede de deshalogenation reductrice de substances halogeno-organiques

Publications (2)

Publication Number Publication Date
EP1027109A1 true EP1027109A1 (fr) 2000-08-16
EP1027109B1 EP1027109B1 (fr) 2002-10-23

Family

ID=7843573

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98954202A Revoked EP1027109B1 (fr) 1997-09-25 1998-09-19 Procede de deshalogenation reductrice de substances halogeno-organiques

Country Status (11)

Country Link
US (1) US6382537B1 (fr)
EP (1) EP1027109B1 (fr)
JP (1) JP2001517641A (fr)
AT (1) ATE226466T1 (fr)
AU (1) AU758391B2 (fr)
CA (1) CA2304802A1 (fr)
DE (2) DE19742297C2 (fr)
DK (1) DK1027109T3 (fr)
ES (1) ES2186237T3 (fr)
PT (1) PT1027109E (fr)
WO (1) WO1999015239A1 (fr)

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DE19903986A1 (de) * 1999-02-02 2000-08-10 Friedrich Boelsing Verfahren zur reduktiven Dehalogenierung von Halogenkohlenwasserstoffen
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JP2002187858A (ja) * 2000-12-18 2002-07-05 Nippon Soda Co Ltd 難分解性ハロゲン化合物の分解方法
DE10112720A1 (de) * 2001-03-14 2002-10-02 Kaercher Gmbh & Co Alfred Basische, nicht-wässrige Dekontaminationsflüssigkeit
JP4697837B2 (ja) * 2001-08-03 2011-06-08 ミヨシ油脂株式会社 固体状廃棄物の処理方法
US20050056598A1 (en) * 2003-06-06 2005-03-17 Chowdhury Ajit K. Method for treating recalcitrant organic compounds
JPWO2009087994A1 (ja) * 2008-01-07 2011-05-26 財団法人名古屋産業科学研究所 芳香族ハロゲン化物の脱ハロゲン化方法
KR101899291B1 (ko) * 2010-08-18 2018-09-14 시오노 케미컬 가부시키가이샤 수소 또는 중수소의 제조 방법
WO2013121997A1 (fr) * 2012-02-17 2013-08-22 シオノケミカル株式会社 Procédé de fabrication d'hydrogène ou de deutérium, procédé de fabrication d'un composé organique hydrogéné ou deutéré, procédé pour hydrogéner ou deutérer un composé organique, procédé pour déshalogéner un composé organique ayant un halogène et bille destinée à être utilisée dans une réaction mécano-chimique
US11548802B2 (en) 2016-05-05 2023-01-10 Remediation Products, Inc. Composition with a time release material for removing halogenated hydrocarbons from contaminated environments
US10479711B2 (en) 2016-05-05 2019-11-19 Remediation Products, Inc. Composition with a time release material for removing halogenated hydrocarbons from contaminated environments
CN106881343A (zh) * 2016-11-29 2017-06-23 清华大学 一种土壤中卤代持久性有机污染物的机械化学分解的方法
DE102018000418A1 (de) 2018-01-20 2019-07-25 Bürkle Consulting Gmbh Mechanochemisches Verfahren zur Herstellung von von persistenten organischen Schadstoffen und anderen Organohalogenverbindungen freien Wertprodukten aus Abfällen von Kunststoffen und Kunststofflaminaten
DE102019006084A1 (de) 2019-02-12 2020-08-13 Elke Münch Mechanochemisches Verfahren

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Also Published As

Publication number Publication date
US6382537B1 (en) 2002-05-07
JP2001517641A (ja) 2001-10-09
WO1999015239A1 (fr) 1999-04-01
DE59806075D1 (de) 2002-11-28
EP1027109B1 (fr) 2002-10-23
AU1143299A (en) 1999-04-12
DK1027109T3 (da) 2003-03-10
ATE226466T1 (de) 2002-11-15
ES2186237T3 (es) 2003-05-01
DE19742297C2 (de) 2000-06-29
PT1027109E (pt) 2003-03-31
DE19742297A1 (de) 1999-04-01
CA2304802A1 (fr) 1999-04-01
AU758391B2 (en) 2003-03-20

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