MXPA00002924A - Method for reductive dehalogenation of halogen-organic substances - Google Patents

Abstract

The invention relates to a method for reductive dehalogenation of halogen-organic substances which can be used in solid or liquid mixtures of substances. When the parameters of the inventive method are correspondingly adapted, liquids and halogen-organic contaminated soils can be mechanically treated and consequently reductively dehalogenated by applying mechanical energy and adding elementary alkali metal, earth-alkaline metal, aluminum or iron as a reducing agent and at least one reactant with slightly activated hydrogen as a hydrogen source.

Description

METHOD FOR SHALOGENAR, BY REDUCTION, HALOGENIC ORGANIC SUBSTANCES FIELD OF THE INVENTION This invention relates to a process for dehalogenating, by reduction, halogenated organic substances mixed with other substances, in the solid or liquid form. During this process the substance or mixture of substances is treated by adding elemental alkali metal, alkaline earth elements, aluminum or iron, as the reducing agent, and at least one reagent with slightly activated hydrogen, to provide the source, of hydrogen. This process is especially convenient not only for the oxidation of soils contaminated with organic halogenated compounds and other materials with complex compounds, but also for de-amination and if the recycling of liquid or predominantly liquid substances that have been contaminated is required. by organic hal halted compounds.

REF .: a3157 BACKGROUND OF THE INVENTION Until now, it has not been possible to detoxify or eliminate toxic organic compounds by halogenated, with any of the commonly available cleaning techniques or technologies, in ways that are economically or ecologically advantageous, or that have a potential in the future. . These substances are present, frequently, as they contaminate and in large quantities in the earth, in the sediment of riverbeds or on the seabed, in muddy deposits, in the dust particles collected in the filters, in building materials , in infiltrated oil, in used oil, etc., which means that they have been in contact with, and that they are accompanied by, an indeterminate number of foreign substances with a great variety of different characteristics. The decontamination and cleaning of this complex combination of heterogeneous materials, solids, solid solids or liquids, and old dumps, implies particularly difficult problems.

It is true that there are a number of thermal processes and other processes with high energy consumption, to destroy dangerous hydrocarbons, of those named above, and also for those that in particular are dispersed through materials of a complex composition. Included in this, among others, is high temperature incineration and incineration in molten glass baths or salt baths. However, each of these processes has some specific disadvantages, such that there is a need to develop alternative technologies. For example, high temperature incineration is not only extremely expensive but also creates new problems. In polychlorinated compounds can cause the formation of PCDD (dioxin s) / PCDF (dibenzofurans) that must be removed later using various processes involved, the combustion gas and dust particles collected in the filters, and then must be discarded. The method commonly used to "discard" these highly toxic dust particles is often to empty them into the known hazardous waste dumps. Of the biological methods for decomposing toxic organic compounds into complex matrices, each also presents its own specific disadvantages that restrict the ability to make general use of oneself. Processes based on the use of alkali metals have found some acceptance. In these processes, pulverized metal suspensions or dispersions of the metal are used in different liquid media, such as, for example, white oil; However, the range of its applications is mainly restricted to a few specific problems, that is to say, the poisoning of relatively pure liquid pollutants or mixtures of pollutants or contaminated liquids that are practically homogeneous and do not contain water. such as transformer oil or used motor oil, containing PCBs.

The additional processes, in which other non-noble metals are used, alone, with a low power of reduction, such as for example aluminum, zinc or iron, are not suitable for the intoxication of certain groups of important materials, for example of polychlorinated aromatic compounds, because the latter can not be completely dechlorinated with these metals. Not all the chlorine atoms of a polychlorinated molecule are removed in this form and therefore disinfection is not achieved, it is only achieved in the presence of toxic catalysts or promoters, for example, triphenylphosphine, nickel or compounds of nickel that for toxicological reasons also cause serious problems. The use of toxic substances for the dehalogenation of halogenated organic substances present in the earth, in sediments, etc., only means exchanging the type of existing contamination by another type, and therefore does not offer a solution to the problem. Known processes that are used for liquids or liquid mixtures can not be easily transferred to solids. It is often difficult for the reactants to reach the halogenated organic substances that are contained in the solids, due to the high level of resistance to transport, in the reactions, between solids. Polihalogenated organic substances are present in the environment as pollutants, for example, in the soil, in the sediment of riverbeds or on the seabed, in sludge deposits, in dust particles collected in filters, in materials of construction or in the infiltrated oil, in this way without exception in solid or solid-liquid heterogeneous materials. These organic substances can be found in large quantities and due to the complex forms and conditions in which these matrices can be found and as a result of the different ways in which they can offer resistance in transportation, they are particularly difficult to obtain and can only be partially reacted or they may not react at all.

DESCRIPTION OF THE INVENTION In this way, the problem that represents the basis of this invention consists in creating a process for shaking, by reduction, halogenated organic substances, in such a way that it is possible to dehalogen, using a universally applicable process, several heterogeneous solids and liquid mixtures of substances, in particular also mixtures of a complex composition and contaminated areas of the earth, in which all the substances present are not known. This process should neutralize as many pollutants as possible and should not produce harmful new byproducts. In addition, the process should be able to be carried out in as simple a manner as possible and emerge relatively quickly. To solve this problem in accordance with the invention, the idea is to use a process like the one described at the beginning, and then subject the halogenated organic material or the mixture of substances, to a mechanically activated milling, where all the substances present they are treated together in a single step and dehalogenated, by reduction, in a more or less complete form. The invention can be applied to halogenated organic compounds that are contained in foreign substances or in mixtures of foreign substances, in the solid or liquid form, and also to halogenated solid or liquid organic substances, whether they are present in their pure form or mixed with other halogenated organic substances. When the basic process is used, these substances or mixtures of substances are treated only in a single step, in which all the components are mixed together intensively, together with at least one reducing agent and a source of hydrogen, and where The reaction takes place under moderate operating conditions. The process involves grinding the components involved in the reaction, with a greater or lesser amount of mechanical energy. This has the effect of at least pulverizing the components of the mixture, to form very small particles, thus producing an intensive mixing of all the components, such that in an average time a very intense contact is established between the reagents used and the halogenated organic substances, and the latter can be caused to react in the desired manner. In addition, the reactive capacity of the solid components increases during the spraying process, due to the physical effects on their surfaces. Moreover, with the application of a sufficient amount of energy, the reactive capacity can be greatly increased. This treatment, mechanically activated, for solids or solids, seems to be particularly convenient for completely or almost completely decomposing the polyacrylated compounds, with the help of hydrogen donors. Due to the increase in the reactive capacity of the solids, as a consequence of the special mechanical activation, even the substances scattered through complex solid materials or solids solids can be converted chemically and efficiently. Consequently, the organic pollutants that are present in solid matrices such as soil, sediment, etc., can be specifically reached and destroyed through the use of decomposing reactions that are aided by mechanical activation. In comparison with high temperature incineration and other high energy consuming processes, the process described in this invention has the advantage that when the reaction is carried out it only requires that moderate operating conditions are provided, i.e., generally It can be done at room temperature and under normal pressure, which is technically much less complicated. Therefore it can be fixed or prepared as a mobile unit. An additional advantage consists of the fact that if necessary, it is possible to recycle or make additional use of the material to be decontaminated, thus avoiding destroying it, which would inevitably happen if it were incinerated. In principle, the process works at low temperatures, preferably room temperature and under normal pressure. However, it is also possible that an increase in temperature occurs due to the intensive application of mechanical energy and / or due to the heat provided by the reaction that occurs during the course of the shalogenation process. It is advantageous to use at least a slightly excessive amount of the metallic reducing agent. The required amount of the reducing agent can be determined during previous experimental tests performed on the material to be decontaminated. In general, the idea is to use non-noble metals as reducing agents, and in particular alkali metals, alkaline earth metals, aluminum and iron. Sodium and potassium are preferred among the alkali metals, and magnesium and calcium are among the alkaline earth metals. However, when the principles of this invention are used other non-noble metals may be employed although care must be taken to avoid the formation of toxic products. The reductive elimination of halogens of halogenated organic substances, with the help of non-noble metals, in particular with alkali metals, has been known in principle for a long time and its mechanics has been well analyzed. However, so far only very few people have recognized that some of these reactions can also be used to remove toxic organic materials from our environment. In accordance with this invention, reduction with metal is also aided by the application of mechanical energy and the addition of at least one hydrogen donor. The surprising thing is that the polychlorinated aromatic compounds, in liquid, solid or solid materials, can also be completely dechlorinated, by reduction, with magnesium, in a reaction carried out in a single container and at room temperature. Among other things, magnesium chips of the type that have been used on a large scale for decades in laboratories and in industry were used for the production of Grignard reagents. There is a widely held view that Grignard reactions can be carried out only in a practical way in special solutions, highly purified, highly flammable, which toxicologically are of concern, such as, for example, diethyl ether or tetrahydrofuran, and besides being strictly excluded all the humidity, an inert gas and special catalysts need to be used. In contrast to this, it was observed for example that, only in a state of pure liquid, the dissolution of the metal and methanol in a solid matrix, using a ball mill and adding a little methanol, ethanol, or primary amines of low molecular weight, the reactions of Grignard and Zerewitinof f, which were associated with each other, were successfully carried out in a solid sand matrix. As a hydrogen source with at least slightly activated hydrogen, it is preferable to use alcohols, ethers, polyethers, amines or hydroxides, such as for example calcium hydroxide, metal hydrides or non-metal hydrides, such as for example calcium hydride, sodium hydride, sodium boronate, lithium alanate, trialk 1 if 1 year, po 1 ia 1 qui lhi drogeno si 1 oxano, individually or in combination. From the group of alcohols, for example, low molecular weight aliphatic alcohols can be used. Aliphatic alcohols of low molecular weight, for example of an amount of 1 to 7 carbon atoms, are understood to mean alcohols such as methanol, ethanol, propanol, isopropanol, butanol, secondary and tertiary butanol, pentanol, hexanol, heptanol, cyclopropanol , cyclobutylol, cyclic open 1, cyclohexane 1, cycloheptanol, 2-methylcyclopropanol, cyclopropylmethanol, polyalkylene glycols, simple etherified polyalkylene glycols, aminoalcohols, polyols, such as, for example, ethylene glycol, glycerin, pentaerythritol and others. From the group of ethers, for example, symmetric or asymmetric, simple aliphatic ethers, cyclic ethers or polyethers can be used. Examples include diethyl ether, propyl ether, isopropyl ether, butyl n-ether as well as dimeric or trimeric polyethers, coronands, cryptands, dialkens, etheramines, such as, for example, 2-methyl and i amine, etc. From the group of amines it is preferred to use aliphatic amines and among these the primary or secondary aliphatic amines of low molecular weight. Examples of suitable amines are: aliphatic and alicyclic, primary, secondary or tertiary monoamines or polyamines, methylamine, ethylamine, 1-propylamine and 2-propylamine, 1-butylamine and 2-butylamine, ethylenediamine, trihexamethylenediamine, tetrahexamethylenediamine, pentahexamethylenediamine, dimethylamine, diethylamine, di-n-propylamine, cyclopentel, amine and cyclohexylamine, nitrogen heterocycles and perhydroxy heterocycles, for example piperidine, 1 - (2-amino eti 1) -pip az ine, l- (2-aminoe ti 1) -pyrrolidine and 1 - (2-amino eti 1) -piperidine, 4 - (2-ami no eti 1) -mo-pho 1 -na. In addition, liquid ammonia is also suitable for the same purpose. As an alternative to amines, certain amides can be considered. For example, the following can be used: 1,3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidone (dime ti lpr opi 1 enur ea, DMPU), 1, 3-dime ti 1 - 2-imidazole idinone (N, N-dime thi 1 eti 1 enure, DMEU), l-methyl-2-pyrrolidone (NMP), l-ethyl-2-pyrrolidone, N, N-di eti 1 ace t ami Da, N, N-diethylpropionamide, N, N-diethylisobutyramide. The separate addition of a hydrogen source can be omitted if it is known that a substance that is suitable as a source of hydrogen is already present in a sufficient amount in the mixture to be treated. The mechanical processing as described in this invention may consist of milling in a mechanical mill, for example in a ball mill, a hammer mill or a vibratory mill. Grinding supplements can also be used during this grinding. In general, grinding supplements are materials that can reduce the amount of energy on surfaces and / or reduce the degree to which the shape of solids deforms when mechanical energy is applied. Included herein are, for example: active substances on the surface that are in various states, forms or preparations, such as for example quaternary ammonium compounds that not only have to be applied in their pure form but also immobilized on surface active inert carriers, such as silicate, clay layers (so-called "organophilic bentonites") as well as substituted alkylamino imidazoles and sulphosuccinates, fatty acids, fatty acid esters and fatty acid amides , primary, secondary and tertiary alkylamines and fatty amines with one or more amine groups, alicyclic amines, such as, for example, cyclohexylamine, heterocyclic or hydrogenated heterocycles, such as, for example, piperidine (hexahi dropi r idine) amine s, di to 1 cano 1 amines otria 1 c ano 1 amine s, simple glycols, polyalkylene glycols, such as for example poly ethylene glycol and polypropylene glycol, and their monoethers or diethers, organic silicon compounds, particularly silicones, specific inorganic salts which are suitable for this purpose, such as for example aluminum chloride. The course of the reaction that has already been mechanically activated can be further intensified or accelerated by the additional application of reaction accelerators. The substances which can be used as reaction accelerators are those which have the ability to partially or completely dissolve non-noble metals, in particular alkali and alkaline earth metals and / or promote their dissociation in metal cations and metal anions and / or to promote formation solvated electrons and / or solvate and / or stabilize metallic organic compounds, such as for example organic compounds of alkali metal or alkaline earth metal, such as for example liquid ammonia, aliphatic and alicyclic monoamines or polyamines, primary, secondary or tertiary, heterocycles po 1 ihi drogenates, aliphatic and cyclic monoethers, pruners, coronands, cryptands, diallodes, etheramines, such as for example 2-methoxymethylamine, amides such as, for example, 1.3 dime ti 1 - 3, 4, 5, 6 - tet rahi dr o- 2 (1 H) -pyrimidone (dime ti lpropi 1 enurea, DMPU), 1,3-dimet i 1-2 - imidazole idinone (N, N-dimet i le ti lenur ea, DMEU), 1 -me ti 1 - 2 -pi r ro 1 i dona (NMP), l-ethyl-2-pyrrolidone, N, N-diet i 1 ace tamide, N, N-di eti lpropionamide, N , N-di eti 1 is obut ir ami da.

The grinding supplements and / or reaction accelerators can be added to the substance or mixture of substances in a later step, that is to say separately after the reagents have been added and can then be mechanically manipulated in the mixture. . On the other hand, the metallic reducing agent can be added directly to the mixture in a pure form. In particular this would seem to be the case to be carried out with the alkaline earth compounds that are less reactive when exposed to air, of the alkali metals, such as for example the magnesium chips. Alternatively, the metal reducing agent may be present in a preparation, either finely dispersed or suspended, for example, finely dispersed in a non-oxidizing liquid or in the liquid source of hydrogen. It is advantageous to use dispersions of the selected metal in white oil, paraffin or ethers, including polyethers such as diglymes, triglyphs, tetraglimides, polyethylene glycol and polyethylene glycol derivatives, diglymes and etherified polyglyphs. In addition, the metallic reducing agent can be mixed with or bound to a solid carrier. A favorable preparation has been shown to be, for example, a mixture of alkali metal, particularly sodium, with calcium silicate or calcium oxide. It was found that the use of only one ball mill was also adequate to increase the reactivity of the metals in an isolated step of the process, mechanically pulverizing them. It was particularly suitable for spraying alkali metals onto inert, solid, surface active carriers. Compared with conventional processing methods, in which the molten alkali metal is placed on inert, solid carrier substances, by stirring them in a special machine at elevated temperatures, the new method has the advantage that it works at room temperature and that the process It is simpler and faster. This is because the alkaline material and the carrier material are simply placed in a grinding mill or container and within a few minutes are milled to form a homogeneous dispersion consisting of fine powder. If desired, the process can be carried out in two steps, whereby, for example, pulverized metal is produced in the first step using a ball mill and then milled again in a second step with the reaction accelerators or , as required, additional supplementary substances are added. In addition it is also possible to grind or mix in the alkali metal dispersions which have been produced using conventional methods, ie both dispersions in inert fluids and on inert solid carriers, reaction accelerators and if necessary other supplementary substances in a solid which contains halogenated organic substances and in this way carry out the dehalogenation. The process can also be used to complement other processes, for example, washing processes, or it can be combined with those processes. The anticipated preparation of the contaminated soil, with calcium oxide (lime or quicklime) that is also known from other treatment processes and that between fillers stuff serves to dry the mixture, can make good sense in certain cases. The process may be carried out discontinuously, batchwise or continuously. When the batch method is used, the first step is to place all the components involved in the reaction, ie at least the substance to be treated or the mixture, the metal reducing agent and the hydrogen donor, in a machine that will treat mechanically, such as a mill or a mixer (dynamic) When solid media are decontaminated, it is more usual to use a mill, for example, a ball mill, a hammer mill or a vibratory mill, whereas with liquid systems an mixer. As mixers are convenient, for example, friction mixers, screw type mixers or roller mixers. An advantage of this invention is that the processing can be completed in a single step in which the components of the reaction can be added one after the other or gradually. The continuous method could, for example, be carried out in a screw type mill or in a screw type mixer. In the next section the process will be explained in more detail, with the help of some examples.

Example 1 Test soil contaminated with clofen / Na-Ca / n-b-tilamine silicate Using an eccentric vibratory mill, model No. "ESM 234", from the company Siebtechnik located in the town of Mülheim and der Ruhr, which is 80% full with steel balls (each with a diameter of 20 mm), 3.8 kg of quartz sand (bulk weight of 1.27 g / ml) are mixed with 180 g of calcium oxide for the purpose of drying, and ground for 10 minutes. 10.2 g of n-butylamine are also added and ground for 1 minute. Finally, 156.7 g of a 26% sodium and calcium silicate dispersion are added and the contaminated test soil is milled for up to 30 minutes. The test soil was artificially contaminated by adding a mixture of 5 g of clofen A30 and 150 g of calcium oxide 1 / calcium hydroxide which was ground for 5 minutes. The analysis by GC-ECD (internal standard: decachlorobi feni lo) of a test soil sample, after this treatment, showed a 99.7% reduction of PCBs. In addition, based on the results by GC, the presence or formation of other halogenated organic substances can be ruled out.

Production of calcium silicate dispersion at 25% sodium: A ball mill, centrifugal, Sl was used, from the company Retsch located in the village of Haan, which had a 500 ml stainless steel grinding vessel with 3 stainless steel balls (each with a diameter of 20 mm. ) and a stainless steel lid with a rubber sealing ring. To this is placed 150 g of active calcium silicate on the surface (for example, the company "Cape-Boards Siborit" GmbH located in the town of Lüneburg, or xonolit, the company "Eternit" located in the town of Kapelle OP den Bor in Belgium mixed with 50 g of pieces of sodium and an atmosphere of argon and this was ground for a time of 5 to 15 minutes at maximum revolutions (approximately 500 min "1). dark gray color, homogeneous, highly reactive Other particularly favorable carrier substances have proved to be clays without water, for example the tixogel or the tixosorb from the Südchemie company located in the town of Moosburg.

Example 2 Test soil contaminated with clofen / Mg / tetragimes / n-bu ti lamina In a vibratory, eccentric mill "ESM 234" (for details see example 1), 3.8 kg of quartz sand (bulk weight of 1.27 g / ml) are mixed with 200 g of calcium oxide for the purpose of drying and grind for up to 10 minutes. Then, also by grinding for a period of two minutes, a mixture of 5 g of clofen A30 and 150 g of calcium oxide 1 / calcium hydroxide, 18.2 g of n-butylamine is added and 51.1 g of water are added. dimethyl ether of tet rae ti lengl i co 1 (tetr agí imas). Finally, 102 g of magnesium chips are ground for two hours. The analysis by GC-ECD (internal standard: of cac 1 or ob i f i) shows a reduction of 99.7% of PCBs. The presence or formation of other halogenated organic subtances can be ruled out. If Mg powder is used for this, instead of Mg chips, then there is practically no gene shaping.

Example 3 Pre-treated soil, contaminated with PCB / Na / n propylamine The object to be treated is a section of cohesive earth that has been contaminated with PCB and that has been subjected to a process of washing with water and surfactant before treatment. From the suspended-fraction of this process that was precipitated with the help of flocculants based on polyamides, there was some residual contamination by PCB of approximately 250 ppm that could not be eliminated. In an eccentric vibratory mill "ESM 234" (for details see example 1), 3 kg of this fraction of earth that had been contaminated with PCB and which, after thermal pre-drying had a residual moisture level of about 2%, was mix with 200 g of calcium oxide for the purpose of drying and grinding for 30 minutes. Also 150 g of n-propylamine are mixed by grinding for 1 minute, and then left to stand for 5 minutes. Finally, 200 g of sodium are milled in the form of cylindrical pieces (each with a length and thickness of 1 to 2 cm) for 45 minutes. The analysis by GC-ECD (internal standard: 1 orobi f eni lo decays) shows a reduction of 98.5; c of PCBs. The presence or formation of the halogenated organic substances can be ruled out. As high amounts of polyamides were mixed, a larger amount of sodium had to be added, which would have been required for the complete dechlorination only of the PCBs Example 4 Pretreated earth, contaminated with PCB / Na / tetraglimas 3 kg of a soil fraction that had been contaminated with PCB, as used in example 3, is passed through a washing process and then thermally dried before it had a residual moisture level of approximately 2. %. It is placed in an eccentric vibratory mill "ESM 234" (for details see example 1) and mixed with 200 g of calcium oxide for the purpose of drying, then ground for up to 30 minutes. 100 g of tetraglimas are mixed, it is also ground together with the same, during 1 minute. Finally, 200 g of sodium (cylindrical pieces, 1 to 2 cm in length and thickness) are ground in the same for 90 minutes and then the mill content is allowed to stand overnight without taking any additional measurements. The analysis by GC-ECD (internal standard: decay lorobi feni lo) shows that PCBs have been decomposed in 92% after 90 minutes and after being allowed to stand overnight they have decomposed by more than 99.9%. The presence or formation of other halogenated organic substances can be ruled out.

Example 5 Sea sand contaminated with clofen / Na-CaO / ECOH-triglybs In a centrifugal ball mill Sl, of the Retsch company located in the town of Haan, with a 50 ml stainless steel grinding bowl with 3 stainless steel balls (each with 10 mm diameter) and a stainless steel lid with a rubber sealing ring, they are placed: 0.05 g of clofen A30, 10 g of sea sand (analytical grade), 0.25 g of triglyphs and 0.32 g of ethanol (= 19.1 equivalents per total chlorine) and ground during one minute at maximum revolutions of approximately 500 min. "1) After one minute of grinding, the grinding vessel is removed from the mill, opened and rinsed with argon under an upward funnel (5.0, from the company Linde). Then a dispersion of sodium and calcium oxide (52% of Na) is added quickly, in an argon shower, the addition of the argon gas is continued for a short period and finally the lid of the grinding container is put back on. grinding is carried out for 1 hour at maximum speed The analysis by GC-MS shows that the PCBs have completely decomposed (the main product left after this process was the chlo-hexane fuel). The presence or formation of other halogenated organic substances can be ruled out.

Production of a dispersion of 52% of sodium and calcium oxide: A possible way to distribute the sodium in the calcium oxide, in dry form, is to grind the small pieces of sodium with calcium oxide in a centrifugal ball mill, for a time of 5 to 15 minutes, as described for the active materials on the surface (see above). In this form, up to 5% alkali metal can be homogeneously distributed in the carrier. To obtain useful sodium and calcium oxide dispersions, the alkali metal should first be allowed to work on the calcium oxide, in the presence of toluene, under conditions that allow reflux and then mix the result of this process at high speed a high-speed agitator or in a dispersion machine, for example the ultraturrax of the company "Janke &Kunkel". After distilling off the toluene, there remains a dark gray solid constituted by a fine powder which, when observed, appears to be completely homogeneous. By using this method, different, continuously variable concentrations of the alkali metal can be created in the dispersion. Apart from the sodium and calcium oxide system, the method can be applied very flexibly: for example, it can be used to prepare a dispersion of calcium oxide and potassium at 25% that resembles the sodium dispersion. The result is a homogeneous powder completely dark gray. However, it is pyrophoric when exposed to air and therefore can not easily be used for the dechlorination of polychloroaromatic compounds in solid or solid-liquid matrices. For organic and chemical conversions on a laboratory scale, with adequate inert gas and safety techniques, however the possibilities of applying that dispersion of calcium and potassium oxide would be interesting.

Example 6 Clofen, contaminated sea sand (test sample) / Mg / MeOH g of sea sand (analytical grade), 0.5 g of calcium oxide / calcium hydroxide mixture that had been produced by partially dissolving 56 g of CaO with 14 g of H20, 0.5 g of triglyphs, 0.11 g of clofen A30, 0.3544 g of methanol and 0.51 g of magnesium powder are placed in a centrifugal ball mill Sl (see example 5) and milled for 5 hours at maximum revolutions after the mixture had been covered with an atmosphere of argon in the open grinding vessel. The analysis by GC-MS showed that the PCBs had been completely decomposed (the main product left after this process was biphenyl, together with a small amount of f eni 1 c i c loxane). The presence or formation of other halogenated organic substances can be ruled out.

Example 7 Sea sand contaminated with clofen (test sample) / Mg / n-propylamin g of sea sand (analytical grade), 1 g of lime oxide / calcium hydroxide mixture, 0.25 ml of n-propylamine, 0.1 g of clofen A30 and 0.76 g of magnesium chips were placed in a centrifugal ball mill S 1 (see example 5) and ground for 1 hour at maximum revolutions. The analysis by GC-MS showed that the PCBs had completely decomposed (the main product left through this process was biphenyl, together with 1-f eni 1 c i c 1 oxano, and a little of f eni 1 ci clohexane). The presence or formation of other halogenated organic substances can be ruled out.

EXAMPLE 8 Dehalogenation of polychloroaromatic compounds in solution, by the addition of small amounts of short chain aliphatic amines.

Surprisingly it was found that polychloroaromatic compounds and similar to 1,3,5-TCB could be dechlorinated much better with sodium in the presence of even small portions of n-butylamine, than with other systems that had been analyzed.

Table 1- The dechlorination of 1, 3, 5-trichlorobenzene in dodecylbenzole (3 ml of each) a) using in each case about 2 equivalentsa) of sodium b > and adding several polyethers (5 ml of each) at room temperature after 2 hours.

Equivalents 1.99 2.05 2.11 2.02 2.05 of Na Additives diglimas triglimas PEGDM TEGMe) 500d) nre? (Cl ") c) 3.7 59.0 58.9 69.6 44.1 [% mol] a) equivalents or total organic chlorine b) Na in the form of a hard paraffin dispersion of Na at 45% c) The percentage ratio of chlorine released (determined by mer cy) to the total organic chlorine d) mixture of polyethylene glycol and dimethyl ether, or an average molar mass of 500e of monomethyl ether of tri et i 1 engl i co 1.

Table 2 Dechlorination of 1, 3, 5- trichlorobenzene in dodecylben 1 (3 ml of each), in each case with approximately 2 equi va 1 ent es) of sodium b) in the presence of several aliphatic amines under varying conditions at temperature ambient. equivalents 2.03 2.07 1.97 Na amine Et3N Et2NH n-BuNH2 Amine quantity 2 / 3.5 2 / 4.6 1 / 2.4 [ml] / equivalent31 nre? (Cl ") c) [mol%] 2.3 31.4 94.2 to equivalents or total organic chlorine b Na in the form of a hard paraffin dispersion of 45% Na Table 3 Dechlorination of 1, 3, 5-tricylobenzene in dodecybin zo 1 (3 ml of each) in each case with approximately 2 equivalents of sodium in mixtures of but i 1 amine / di, the reduction of the content of amine after two hours at room temperature. equivalents of Na 2.04 2.04 2.01 2.02 n-BuNH2 [ml] / equivalent 2 / 4.88 0.4 / 0.98 0.2 / 0.49 0.05 / 0.12 diglyme [ml] 0.5 4 4 4 nrei.Cl ") [mol%] 95.5 91.7 91.3 91.4 The mechanical processing can be done by stirring in a reactor or in a suitable mixer.

Example 9 Sea sand contaminated with clofen (test sample) / Mg / DMPU 7. 5 g of sea sand (analytical grade) and 2.0 g of magnesium chips mixed with argon are ground for 15 minutes in a centrifugal ball mill Sl (see example 5). Then 0.1 g of clofen A is added, 7.5 g of sea sand (analytical grade) and 0.5 g of 1,3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidone (dime ti lpr opi 1 enur ea, DMPU), rinse with argon and grind at maximum revolutions for 30 minutes. GC analysis showed that PCBs had completely decomposed (the main product left after this process was biphenyl). The experiment can also be carried out with other special amides instead of the DMPU, such as, for example, 1,3-dime ti 1-2-imide zo 1 i dinone (NN-dime ti lenur ea, DMEU) or 1 - me ti 1 - 2 -pir ro 1 idona (NMP), with a very similar development and with the same result.

Example 10 Dehalogenation in pure liquids 7. 0 g of decane in which 0.8 g of clone A30 were dissolved and still contained 2 g of n-propylamine, are ground with 9.4 g of magnesium chips for 30 minutes at maximum revolutions in a centrifugal ball mill Sl (see example 6). After that the analysis by GC-FID showed that the PCBs had decomposed almost completely (the main product left after this process was biphenyl, together with only insignificant amounts of 3 gold monoclonal if in i o di c 1 o robi feni 1 os). The untreated samples and the samples that had been treated using the process described in this invention were all examined by gas chromatography. Diagrams 1 to 6 show the results of some exemplary gas chromatographic analyzes, in each case before and after treatment. The analyzes prove that it is possible to treat even complex mixtures, effectively, in a short time (see diagrams 3 to 6). With the aid of the process described in this invention, the polychlorinated organic contaminants are successfully eliminated completely. This happens even when they are distributed together with an abundance of foreign substances and accompanied by other substances in complex solid or semi-solid materials, and in some cases very tightly bound to them by adsorption. This process makes it possible to selectively remove contaminants within a few minutes with complete reductive dechlorination at room temperature. Of course, contaminants that are found in a relatively pure form, such as for example highly concentrated PCB oils or HCH isomers that were ineffective with insecticides and that, for example, were emptied into open pits in the Bitterfeld area located in the former East Germany (with a degree of purity of up to 95%) of the order of several times 10,000 tons, can be intoxicated especially effectively. In the case of transformer oils, the process described in this invention can be used as an alternative to existing processes (Degus s a odi o, NaPEG-, KPEG-, KPEG-PLUS), since the central idea of This is simpler and safer, and can be carried out with simple methods and devices under moderate operating conditions. This gives rise to the possibility of recycling contaminated oils on a large scale instead of having to be incinerated. Transformer oils, in particular, have a great value as materials and therefore a high recycling value which, however, are completely lost when they are incinerated. The organic contaminants can be completely removed under conditions that are ecologically and economically favorable at room temperature and in a short time, in particular even when several meclas are present. The pollutants are decomposed simply by reagents structured directly in the matrix in which they are distributed. At the same time, the materials in question, for example, can be ones that accumulate elsewhere in considerable quantities as leftover materials and that through this process can now be used again to a significant degree. Only a few nontoxic or less toxic and biologically degradable products are formed. This greatly improved compatibility with the environment is a result of the complete conversion of the reducing agent and all the organically bonded halogens to non-hazardous inorganic halides. At the same time, the halogen-free primary bodies, of the halogenated po 1 compounds, are formed. Oxidized materials, such as, for example, construction materials or used oil, can receive significant uses or can be recycled. In most cases there is no need for complicated and costly treatment processes, which are subsequently carried out, such as, for example, the removal and elimination of excess reagents or toxic products that overlap the decomposition process. As a consequence, with this new process, the disadvantages of processes that are commonly used widely when cleaning contaminated sites, such as, for example, high temperature incineration, are avoided. The areas where the process described in this invention can be applied, are in particular: Lands and sediments contaminated with halogenated organic compounds; Building materials and flanges and accessories in buildings that have been contaminated with PCBs (wall paint, thin plasters, stretchy elastic filling material, used to fill empty spaces, for example around windows, in buildings of various types ); Mud contaminated with PCB; The intoxication of dust particles contaminated with organic halogenated compounds, which have been collected in filters, for example from the steel industry or from plants for the incineration of garbage; The disposal of surplus products from the chemical industry, for example from the production of lindane (HCH isomers in the order of several times 10,000 tons in the area of Bitterfeld in the former East Germany); Red mud containing dioxins; The de-amination of transformer oils and mooil contaminated with PCB; The decontamination of material contaminated with organic halogenated compounds, collected in filters, for example, adsorbents used to clean smoke emissions, waste water streams, such as for example activated carbon, clays, etc.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (12)

1. A process for reducing shalogenac ion of halogenated organic substances, in solid and liquid mixtures of materials, in which the substance or mixtures of substances are treated by adding elemental alkali metal, alkaline earth elements, aluminum or iron, as a reducing agent, and minus a reagent with slightly activated hydrogen as a source of hydrogen. The process is characterized by the fact that the halogenated organic substance, or mixture of substances, is dehalogenated in a practical way and completely, in a step in which all the substances together are subjected to a mechanically activated milling.

2. The process according to the description of claim 1, characterized in that it is preferred to use Na, K, Mg, Ca or Al as the reducing agent.

3. The process according to the description of claims 1 or 2, characterized in that alcohols, ethers, polyethers, amines, hydroxides or hydrides are used as the source of hydrogen, either individually or in combination.

4. The process according to the description of claim 3, characterized in that at least one aliphatic amine, preferably a primary or secondary aliphatic amine is used as an amine.

5. The process according to the description of claims 1 to 4, characterized in that grinding supplements and / or reaction accelerators are also used.

6. The process according to the description of claim 5, characterized in that these grinding supplements are used and can reduce or prevent the possibility of deforming a shape and / or that an agglomeration of solids forms when energy is applied mechanical, such as, for example, certain active substances on the surface.

7. The process according to the description of claim 5, characterized in that reaction accelerators are used, which can dissolve at least partially non-noble metals and / or promote their dissociation in metal cations and metal anions and / or solvate and / or stabilizing the formation of solvated electrons and / or organic metal compounds.

8. The process according to the description of any of claims 5 to 7, characterized in that the grinding supplement (s) and / or the reaction accelerators are added to the substance. or mixture of substances in a step (which is either before or after the main process) and then mechanically worked or ground.

The process according to the description of one of claims 1 to 8, characterized in that the metal reducing agent is present in a preparation, for example, dispersed in a non-oxidizing liquid or in the liquid source of hydrogen or in an inert solid carrier.

10. The process according to the description of claim 9, characterized in that the reducing agent is present in the form of a suspension in paraffin, a dispersion in ether or a dispersion in polyether.

11. The process according to the description of any of claims 1 to 10, characterized in that the mixture of substance is prepared or dried with calcium oxide and / or with other supplementary substances, in a step that It takes place before the main process.

12. The process according to the description according to any of claims 1 to 11, characterized in that the mechanical processing is carried out in a mill, for example in a ball mill, in a mill of hammers or in a vibratory mill, or in a mixer that can transfer mechanical energy in sufficient quantities, preferably a dynamic mixer, such as for example a friction mixer, a screw type mixer or a roller mixer. METHOD OF DEHALOGENING, BY REDUCTION, HALOGENIC ORGANIC SUBSTANCES SUMMARY OF THE INVENTION The invention relates to a method for dehalogenating, by reduction, halogenated organic substances, which can be used in solid or liquid mixtures of substances. When the parameters of the inventive method are adapted accordingly, soils contaminated with organic halogenated compounds and with liquids, can be treated mechanically and consequently can be dehalogenated by reduction, by applying mechanical energy and by adding a metal or an elemental alkali metal, a metal alkaline earth metal, aluminum or iron, as a reducing agent, and at least one reagent with slightly activated hydrogen, as a source of hydrogen.