EP1027109B1 - Procede de deshalogenation reductrice de substances halogeno-organiques - Google Patents

Procede de deshalogenation reductrice de substances halogeno-organiques Download PDF

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EP1027109B1
EP1027109B1 EP98954202A EP98954202A EP1027109B1 EP 1027109 B1 EP1027109 B1 EP 1027109B1 EP 98954202 A EP98954202 A EP 98954202A EP 98954202 A EP98954202 A EP 98954202A EP 1027109 B1 EP1027109 B1 EP 1027109B1
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process according
substances
grinding
reducing agent
mixture
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EP1027109A1 (fr
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Volker Birke
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    • 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 method for reductive dehalogenation of halogenated organic substances in solid and liquid Mixtures of substances in which the substance or mixture of substances under Addition of elemental alkali metal, alkaline earth metal, aluminum or iron as a reducing agent and at least one Reagent with at least slightly activated hydrogen as a hydrogen source is treated. It is particularly useful for detoxification of organically contaminated soils and others complex materials, but also for decontamination and optionally recycling liquid or predominantly liquid halogen organically contaminated substances.
  • Toxic polyhalogenated organic pollutants can be So far under economically and ecologically equally advantageous and forward-looking terms with none of the nowadays known detoxification technologies. Frequently are these substances as impurities, also in large quantities, in soils, river or marine sediments, sewage sludge, filter dust, Building materials, seepage oils, waste oils etc. before, 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.
  • Halogenated organics contained in solids can be due to the high Transport inhibitions common in solid-solid reactions difficult to be reached by reagents.
  • polyhalogenated organic matter in the environment can be polyhalogenated organic matter in the environment as impurities z. B. in soils, river or marine sediments, Sewage sludge, filter dust, building materials or Seepage oils, therefore solid or liquid, without exception very much heterogeneous materials can be found in large quantities, due to the complex state forms of these matrices and the resulting diverse transport inhibitions in particular difficult to attack and therefore only incomplete or not at all Bring reaction.
  • the problem underlying the invention is therefore a process for the reductive dehalogenation of organic halogen Design fabrics so that it is possible to create different ones heterogeneous solid and liquid mixtures, in particular also complex mixtures and contaminated soils with partially unknown other ingredients in one to dehalogenate universal processes as far as possible, whereby no new harmful by-products should arise.
  • the method should be as easy to use as possible Own process flow and work relatively quickly.
  • the invention is applicable to organohalogen compounds which in solid or liquid foreign substances or foreign substance mixtures are included, but also as solid or liquid pure substances or can be present in mixtures of these. These substances or mixtures of substances, as far as the basic process is concerned, in dealt with in a single process step, i.e. it will all components including mild reaction conditions at least one reducing agent and one hydrogen source, intimate mixed.
  • the process includes grinding the reactants under Entry of a more or less large amount of mechanical Energy.
  • a fine distribution in very small particles and therefore an intensive mixing of all Components of the mixture causes so that between the used reagents and the organohalogen in time Intensive contact is established and this means be brought to the desired reaction.
  • the reactivity of the solid components through the fine distribution increased due to surface physical effects.
  • the method according to the invention has the Advantage that under mild reaction conditions, i.e. in general at room temperature and under normal pressure, feasible and is technically far less complex. It is therefore also can be designed for small mobile systems. Another advantage is there in the fact that there may be recycling or reuse of the materials to be decontaminated is possible with a Combustion would be destroyed in principle.
  • the process basically works at low temperatures, preferably at room temperature under normal pressure. there it is possible, however, that due to the intensive mechanical input Energy and / or that released during dehalogenation Heat of reaction in the course of the process a warming entry.
  • the metallic reducing agent is advantageously at least in little excess used.
  • the required amount of reducing agent can be carried out in preliminary tests on samples of the specific decontamination object be determined.
  • Common metals are reducing agents, namely in particular alkali metals, alkaline earth metals, aluminum and Iron provided.
  • alkali metals are sodium and potassium preferred, among the alkaline earths magnesium and calcium.
  • other base metals can also be used, taking into account is that the formation of toxic products should be avoided.
  • a hydrogen source with at least slightly activated hydrogen are preferably alcohols, ethers, polyethers, amines or hydroxides, such as.
  • As calcium hydroxide, or metal or Non-metal hydrides such as Calcium hydride, sodium hydride, sodium boranate, Lithium alanate, trialkylsilanes, polyalkylhydrogensiloxanes, used individually or in combination.
  • low molecular weight aliphatic alcohols can be used.
  • 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-methylcyclopropanol, Cyclopropylmethanol, polyalkylene glycols, simply etherified polyalkylene glycols, amino alcohols, polyols, such as. Ethylene glycol, glycerin, pentaerythritol, etc.
  • Simple symmetrical groups can be selected from the ether group or asymmetric aliphatic ethers, cyclic ethers or polyether can be used. Examples include diethyl ether, Propyl ether, isopropyl ether, n-butyl ether and dimers or trimeric polyethers, coronands, cryptands, spherands, Ether amines, e.g. 2-methoxyethylamine etc.
  • aliphatic amines from the group of amines are aliphatic amines and below lower primary or secondary aliphatic amines are preferred.
  • suitable amines are: primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines, Methylamine, ethylamine, 1- and 2-propylamine, 1- and 2-butylamine, Ethylenediamine, tri-, tetra-, penta-, hexamethylenediamine, dimethylamine, Diethylamine, di-n-propylamine, cyclopentylamine and cyclohexylamine, Nitrogen heterocycles and perhydro nitrogen heterocycles, e.g.
  • Piperidine 1- (2-aminoethyl) piperazine, 1- (2-aminoethyl) pyrrolidine and 1- (2-aminoethyl) piperidine, 4- (2-aminoethyl) morpholine. It is also suitable for the same purpose liquid ammonia.
  • 1,3 dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidone can be used (Dimethylpropylene, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea, DMEU), 1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutyramide.
  • the mechanical preparation according to the invention can be carried out in one Ground in a mechanical mill, for example a ball mill, hammer mill or vibrating mill. Additional grinding aids can be used for this grinding become. Substances are generally used as grinding aids the surface energy and / or the plastic deformation of Can reduce solids when exposed to mechanical energy. These include, for example: Surface-active substances in various forms of condition or preparation, e.g.
  • quaternary ammonium compounds that are not only in pure substance can be used, but also immobilized on inert, surface-active carriers, such as layered silicates, clays (so-called “organophilic bentonites”) 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.
  • surface-active carriers such as layered silicates, clays (so-called “organophilic bentonites") 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,
  • Piperidine mono-, di- or trialkanolamines, simple glycols, polyalkylene glycols, e.g. polyethylene and polypropylene glycols, and their mono- or diether, Organosilicon compounds, especially silicones, special for inorganic salts suitable for the purpose, e.g. Aluminum chloride.
  • reaction accelerators be reinforced or accelerated.
  • a reaction accelerator can be used fabrics that are able to base Metals, especially alkali and alkaline earth metals, partially or completely dissolve and / or dissociate them in metal cations and anions and / or the formation of solvated To transport electrons and / or organometallic compounds, such as. alkali or alkaline earth metal organic compounds, to solvate and / or stabilize, e.g.
  • liquid Ammonia primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines, polyhydrogen nitrogen heterocycles, aliphatic and cyclic monoethers, podands, coronands, Cryptands, spherands, ether amines, e.g.
  • 2-methoxyethylamine Amides such as -pyrimidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) (Dimethyl propylene urea, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea, DMEU), 1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N / N-diethylisobutyramide.
  • the grinding aid (s) and / or reaction accelerator can Substance or mixture of substances in a subsequent step, i.e. separately after adding the reactants, added and mechanically be incorporated.
  • the metallic reducing agent can on the one hand be mixed can be added directly in pure form. This is particularly useful alkaline earth metals, less in the air are more reactive than the alkali metals, e.g. with magnesium chips.
  • the metallic reducing agent can be in a preparation are dispersed or suspended, for example dispersed in a non-oxidizing liquid or the liquid hydrogen source.
  • Dispersions are advantageous to use from the selected metal in white oil, paraffin or in Ethers, including polyethers such as diglyme, triglyme, tetraglyme, polyethylene glycol and polyethylene glycol derivatives, etherified diund Polyglymen.
  • the metallic reducing agent can be mixed with a solid Carrier mixed or applied to this.
  • advantageous preparation has e.g. a mixture of alkali metal, especially sodium, with calcium silicate or Calcium oxide proven.
  • the method can thus also be designed in two stages , e.g. by ball milling in a first step pre-produced finely divided metal only in a second Step with the addition of reaction accelerators and if necessary other additives are ground. It is also possible also alkali metal dispersions obtained by conventional means, i.e. both dispersions in inert fluids as well on inert solid supports, with reaction accelerators and If necessary, other additives in an organohalogenous Solid grinding or mixing and thereby dehalogenation to effect.
  • the method can also be used to complement other methods, e.g. of washing processes, used or combined with these become.
  • the process can be carried out batchwise, batchwise or continuously be performed.
  • first of all Reaction partner i.e. at least the substance to be treated or the mixture / mixture, the metallic reducing agent and the Hydrogen donor, placed in a device that is mechanical Machining enables, like a mill or a (dynamic) Mixer.
  • a device that is mechanical Machining enables, like a mill or a (dynamic) Mixer.
  • a mill e.g. a ball mill, a hammer mill or a vibratory mill can be used while at a mixer can be sufficient for liquid systems.
  • a mixer For example, friction, screw or roller mixers are suitable.
  • the model floor was artificial by adding a mixture of 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide, the five Minutes, were contaminated.
  • ESM 234 In an eccentric vibratory mill "ESM 234" (data see example 1) 3.8 kg quartz sand (bulk density 1.27 g / ml) with 200g calcium oxide mixed by grinding for drying for ten minutes. A mixture is mixed, likewise by grinding from 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide, 18.2 g n-butylamine and 51.1 g tetraethylene glycol dimethyl ether (Tetraglyme) for two minutes. Finally, 102 g of magnesium shavings ground in for two hours.
  • the GC-ECD analysis confirms a 99.7% reduction in PCB.
  • the presence or education other halogenated substances can be excluded.
  • Pretreated PCB contaminated soil / Na / n-propylamine Treated is a PCB-contaminated, cohesive soil that previously was subjected to a washing process with water and surfactants. From the suspended fraction of this process, which is carried out with the help of Flocculants based on polyamide was precipitated do not remove residual contamination of approx. 250 ppm PCB.
  • ESM 234" eccentric vibratory mill "ESM 234" (for data see Example 1). 3 kg of this PCB-contaminated soil fraction, residual moisture after thermal predrying approx. 2%, with 200 g calcium oxide mixed by grinding for drying for 30 minutes. you mixes, likewise by grinding, 150 g of n-propylamine Minute and waits 5 minutes. Finally, 200 g Sodium in the form of cylindrical pieces (each 1 to 2 cm long and thick) ground in for 45 minutes.
  • the GC-ECD analysis confirms a 98.5% reduction in PCB.
  • the presence or education other halogenated substances can be excluded.
  • the GC-ECD analysis confirms 92% degradation of the PCB after 90 minutes after standing over 99.9% overnight. The presence or The formation of other halogenated substances can be excluded.
  • argon 5.0, Linde
  • the GC-MS analysis shows that the PCB has been completely degraded (Main degradation product phenylcyclohexane). The presence or education other halogenated substances can be excluded.
  • Preparation of a 52% Sodium Calcium Oxide Dispersion One way to dryly distribute sodium onto calcium oxide is to grind small pieces of sodium with calcium oxide in a centrifugal ball mill for 5 to 15 minutes, as described for surface-active materials (see above). 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 mixture is mixed at high speed with a high-speed stirrer or dispersant, for example Ultra-Turrax from "Janke &Kunkel" mixed.
  • the method can be used very flexibly: for example, it can also be used to prepare a 25% potassium calcium oxide dispersion that looks like 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 (p.A.), 1 g calcium oxide-calcium hydroxide mixture, 0.25 ml n-propylamine, 0.1 g Chlophen A30, and 0.76 g magnesium shavings grind for 1 hour at maximum speed.
  • polychloroaromatics such as 1,3,5-TCB can be dechlorinated much better with sodium in the presence of even small amounts of n-butylamine than in other systems investigated.
  • the mechanical processing can be done by stirring in a reactor or done in a suitable mixer.
  • the process according to the invention offers itself as an alternative to existing processes (Degussa sodium, NaPEG, KPEG, KPEG-PLUS), since it has a simpler and safer design and can be implemented with simple means under mild conditions. This offers the possibility of recycling contaminated oils to a large extent instead of having to burn them. Especially have transformer oils a high material and thus reuse value, which would, however, be completely written off if incinerated.
  • the organic pollutants can be classified under ecological and economically favorable conditions at room temperature and in a short time Time, especially when it is in different Mixtures occur, completely eliminate them.
  • the pollutants are directly in the matrix in which they are distributed are degraded by simply structured reagents.
  • these can be materials that elsewhere in large quantities as residues, and thereby lead to a meaningful utilization to let.
  • Detoxified materials such as Building materials or waste oils can be fed into useful recycling measures or recycled become.
  • the new process consequently eliminates the disadvantages of today practiced on a larger scale during the remediation of contaminated sites Processes such as high temperature combustion avoided.

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Claims (12)

  1. Procédé pour déhalogéner par réduction les substances halogéno-organiques dans des mélanges de substances solides et liquides, dans lequel on traite la substance ou le mélange de substances avec de l'hydrogène au moins légèrement activé en tant que source d'hydrogène sous apport de métal alcalin, métal alcalino-terreux, aluminium ou fer élémentaire comme agent réducteur et d'au moins un réactif,
    caractérisé en ce que la substance halogéno-organique ou le mélange de substances est déhalogéné pratiquement en totalité par réduction en une seule étape sous activation mécanique dans un broyage englobant toutes les substances
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise de préférence Na, K, Mg, Ca ou Al comme agent réducteur.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que comme source d'hydrogène on utilise des alcools, éthers, polyéthers, amines, hydroxydes ou hybrides, isolément ou en combinaison.
  4. Procédé selon la revendication 3, caractérisé en ce que comme amine on utilise au moins une amine aliphatique, de préférence une amine aliphatique primaire ou secondaire.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on utilise en outre des moyens d'aide au broyage et/ou des accélérateurs de réaction.
  6. Procédé selon la revendication 5, caractérisé en ce que comme moyen d'aide au broyage on utilise des substances capables d'empêcher ou diminuer une éventuelle déformation plastique et/ou agglomération de substances solides sous l'action d'une énergie mécanique, comme par exemple des agents tensio-actifs.
  7. Procédé selon la revendication 5, caractérisé en ce qu'on utilise des accélérateurs de réaction qui dissolvent au moins partiellement les métaux communs et/ou favorisent leur dissociation en cations métalliques et anions métalliques et/ou la formation d'électrons solvatés et/ou solvatisent et/ou stabilisent les composés organométalliques.
  8. Procédé selon l'une des revendications 5 à 7, caractérisé en ce que le(s) moyen(s) d'aide au broyage et/ou l(es) accélérateur(s) de réaction sont, dans une étape précédente ou suivante, ajoutés à la substance ou au mélange de substances et incorporés et en particulier broyés mécaniquement.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que l'agent réducteur métallique se trouve dans une préparation, par exemple dispersé dans un fluide non oxydant ou dans la source d'hydrogène fluide ou sur un porteur solide inerte.
  10. Procédé selon la revendication 9, caractérisé en ce que l'agent réducteur se trouve sous forme d'une suspension de paraffine, d'une dispersion d'éther ou d'une dispersion de polyéther.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que le mélange de substances est préparé, en particulier séché, dans une étape de procédé précédente avec de l'oxyde de calcium et/ou d'autres substances d'agrégation.
  12. Procédé selon l'un des revendications 1 à 11, caractérisé en ce que la préparation mécanique est réalisée dans un broyeur, par exemple un broyeur à boules, un broyeur à marteaux ou un broyeur vibrant, ou dans un mélangeur, de préférence dynamique, transmettant suffisamment d'énergie mécanique, comme par exemple un mélangeur à friction, à vis ou à cylindres.
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

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

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EP98954202A Revoked EP1027109B1 (fr) 1997-09-25 1998-09-19 Procede de deshalogenation reductrice de substances halogeno-organiques

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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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ITMI922961A1 (it) * 1992-12-24 1994-06-24 Sea Marconi Technologies Sas Procedimento per la dealogenazione chimica di composti organici alogenati.
WO1995018652A1 (fr) 1994-01-04 1995-07-13 Neos Technology Inc. Procede de production de dispersions de sodium et de mise en reaction d'organohalogenures

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AU758391B2 (en) 2003-03-20
WO1999015239A1 (fr) 1999-04-01
CA2304802A1 (fr) 1999-04-01
DK1027109T3 (da) 2003-03-10
DE19742297C2 (de) 2000-06-29
JP2001517641A (ja) 2001-10-09
ATE226466T1 (de) 2002-11-15
ES2186237T3 (es) 2003-05-01
AU1143299A (en) 1999-04-12
EP1027109A1 (fr) 2000-08-16
PT1027109E (pt) 2003-03-31
US6382537B1 (en) 2002-05-07
DE59806075D1 (de) 2002-11-28
DE19742297A1 (de) 1999-04-01

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