EP0236701B1 - Process for the recovery of carbon-containing wastes - Google Patents

Abstract

1. A process for treating carbon-bearing organic wastes of synthetic or predominantly synthetic origin, with hydrogen and/or hydrogen-bearing gases and/or hydrogen-transferring solvents, possibly in the presence of a catalyst or catalysts, characterised in that : a) the treatment is carried out at a temperature of from 200 to 600 degrees C, preferably from 200 to 540 degrees C and particularity preferably from 300 to 540 degrees C, under a pressure of from 30 to 500 bars, preferably from 50 to 450 bars and particularity preferably from 50 to 350 bars and for a residence time of from 1 minute to 8 hours, preferably 10 minutes to 6 hours and particular preferably from 15 minutes to 4 hours, and b) the carbon-bearing organic wastes of synthetic or predominantly synthetic origin are at least partially subjected to a preliminary treatment in hydrogen and/or hydrogen-bearing gases and/or hydrogen-transferring solvents, at a temperature of from 75 to 600 degrees C, preferably from 75 to 540 degrees C and particular preferably from 120 to 500 degrees C, under a pressure of from 1 to 600 bars, preferably from 1 to 500 bars and particular preferably from 1 to 350 bars, and for a residence time of from 1 minute to 6 hours, preferably from 1 minute to 4 hours, and/or are at least in part subjected to a preliminary treatment in an inert atmosphere at a temperature of from 75 to 600 degrees C, preferably from 75 to 500 degrees C, particulary preferably from 120 to 475 degrees C, under a pressure of from 1 to 600 bars, preferably from 1 to 500 bars and particular preferably from 1 to 350 bars, and for a residence time of from 1 minute to 6 hours, preferably from 1 minute to 4 hours.

Description

The invention relates to a process for the reprocessing of carbon-containing waste by thermal pretreatment of the same in the presence or absence of hydrogen and subsequent hydrogenation of the pretreated material at elevated temperature and at least 200 bar hydrogen pressure.

It is well known to the public that waste accumulating worldwide is an increasing environmental problem.

Waste has been used in landfills for decades, e.g. stored in abandoned gravel pits, mine pits and elsewhere. For a long time, the chemical structure of the waste and its long-term effects on soil and groundwater have not been taken into account. More recently, certain types of waste have been dumped in so-called special landfills. Here, efforts are made to seal the landfill from groundwater and soil.

For some time now, experts have made intensive efforts to process and process the waste, firstly to protect the environment and secondly to obtain usable products from the waste.

In "The Oil and Gas Journal", Des. 25, 1978, p. 80, describes a pilot plant in which plastics can be converted into gases and oils by pyrolysis.

In "Hydrocarbon Processing", April 1979, p. 183, an incineration plant is described, in particular for special waste.

The biochemical degradation of plastics has also been investigated (see e.g. "European Chemical News", Sept. 10, 1979, p. 28). In Chemical Engineering, August 13, 1979, p. 41, a method is described according to which hazardous wastes are deposited in hardening materials, e.g. Cement to be poured.

An overview of the most important processes is given in "Chemical and Engineering News", Oct. 01, 1979, p. 34. In particular, the gasification of biomass, namely wood waste and the like to carbon monoxide and hydrogen, is described here. On page 36, left column of this document, a test program for converting shredded wood into water is also described, using hydrogen in the presence of Raney nickel as a catalyst.

In Europa Chemie ", 25, 1979, p. 417, a method is described according to which unsorted plastic waste is plasticized and pressed.

The fluidized bed combustion of waste is described in "Chemische Industrie", XXXII, April 1980, p. 248. The conversion of waste and biomass by heating with water and alkalis is described in "Chemistry International", 1980, no. 4, p. 20.

Numerous other publications have also become known.

In recent times, combustion in modern facilities in particular has been further developed and large-scale plants have been built that use this process. Although dedusting and flue gas scrubbing are integrated in such systems, pollutants escape into the atmosphere in small proportions even with careful cleaning, such as heavy metals, SO ₂ , NO _x and others.

Pyrolysis is now also being operated on a technical scale (see, for example, "Vereinigte Wirschaftsdienste GmbH", October 4, 1985, p. 9). However, pyrolysis has the disadvantages of the predominant formation of gaseous products and a heavily contaminated coke residue in a relatively large amount and the formation of effluent containing hydrochloric acid from waste containing nitrogen (Rubbish and Waste, 6 (1980) p. 189, right column). The problem of waste and biomass processing is therefore still not satisfactorily solved according to this prior art.

A surprising, much cheaper solution to this problem compared to the prior art, in particular with regard to the high yields of valuable liquid products, is disclosed by the same applicant in German patent DE-PS 3442506 and in European subsequent application EP-A-0 182 309.

This invention relates to hydrogenation treatment with or without catalyst, synthetic waste materials such as e.g. Plastics or Kungstoffgemischen, rubber, waste tires, textile waste, chemical industrial waste, waste oils, waste oils and other or mixtures of these materials, the hydrogenating treatment at pressures from 30 to 500 bar, preferably from 50 to 450 bar and particularly preferably from 50 to 350 bar is carried out and at temperatures from 200 to 600 ° C, preferably from 200 to 540 ° C and particularly preferably from 300 to 540 ° C and residence times from 1 minute to 8 hours, preferably from 10 minutes to 6 hours and particularly preferably from 15 Minutes to 4 hours.

Rubbing oils can be added to the waste feed products as well as coal, coal components, crude oil, crude oil components and crude oil residues, shale oils and shale oil components, oil sand extracts and their components, bitumen, asphalt, asphaltenes and similar materials.

The feed product or the feed mixture can also be treated with solvents and the extract can then be used in the hydrogenating treatment.

After separating inorganic components such as glass, metals, stone materials and others, the process allows the synthetic waste materials to be converted into valuable hydrocarbons without further separation. These are gaseous C, -C ₄ hydrocarbons, liquid hydrocarbons in the naphtha boiling range as well as middle distillates and heavy oils, which are used as heating oils or diesel power fabric can be used. The pre-sorting of waste materials is preferably carried out in such a way that carbon-containing organic waste of synthetic origin such as plastics and mixtures of plastics, rubber, waste tires, textile waste or mixtures of these materials and further organic synthetic waste are at least roughly separated from vegetable waste and / or biomass are then subjected to a hydrogenating treatment or the same in a mixture with organic industrial waste of synthetic origin such as paint and paint residues, organic chemicals, waste from industrial plants, organic synthetic shredder waste from the automotive industry, sewage sludge, waste oils or other industrial organic waste of synthetic origin from the hydrogenation be subjected.

Other waste materials such as paper, food scraps, agricultural and forestry waste, plant residues and others can be roughly separated or remain to some extent in the synthetic portion.

Household waste can be processed, for example, by roughly separating plastics, rubber, textiles and other synthetic materials and separately subjecting them to a hydrogenation treatment, or mixed with waste tires and / or industrial chemicals and / or plastic waste and / or waste oils and others be subjected to this hydrating treatment.

Werwer is also very well suited for the hydrating treatment of the waste or waste mixtures mentioned in combination with coal, coal components such as residual oils from coal, coal oils, pyrolysis oils, crude oil, residual oils from crude oil, other crude oil components, oil shale and oil shale components, oil sand extracts, asphalt and Bitumen and similar materials as well as with mixtures of the materials mentioned.

The separation of the above-mentioned inorganic materials from the carbon-containing waste can be carried out according to the prior art. These inorganic materials can be stored in landfills provided they are not recycled and reprocessed. The crushing and shredding and separation of waste materials can also be carried out according to the prior art. If this is not contradicted by equipment, the process can also be carried out in the presence of inorganic materials.

Waste components that cannot be converted to hydrocarbons, such as sulfur, nitrogen, oxygen and halogens in the form of their compounds, are converted into their gaseous hydrogen compounds, namely H ₂ S, NH ₃ , HCl, H ₂ 0 and others. These compounds can be separated by gas washing and further work-up according to the prior art.

Another advantage of the process is that the formation of hazardous compounds that occur during waste incineration, namely NO _X , SO. or dioxins is avoided. Furthermore, plastics, such as polyvinyl chloride, which are problematic in combustion, can be processed without risk to the environment.

The hydrogenation of carbon-containing waste materials can, according to this disclosure, be carried out with very good results in the absence of catalysts. However, improved results, particularly with regard to the selective formation of certain hydrocarbon fractions, can be obtained in the presence of catalysts, e.g. in the presence of metals and their compounds which are catalytically active in hydrogenation reactions, e.g. Fe, Cr, Zn, Mo, W, Mn, NI, Pd, Co, Pt, furthermore alkali and alkaline earths such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and other metals and / or their compounds , wherein these catalysts can consist of a single active component or a mixture of at least 2 of the components mentioned, and wherein these metals or their compounds can be applied to catalyst supports, such as on aluminum oxide, silicon oxide, aluminum silicate, zeolites and other supports which are known from the prior art, as well as on mixtures of these supports or also without a support. Certain zeolites and other carriers are also active as catalysts in the disclosed process without doping.

Other suitable catalysts are so-called disposable catalysts such as hearth furnace coke, gasification dusts and ashes such as, for example, high-temperature Winkler dust and ashes, dusts and ashes which are obtained in the hydrogenating gasification of coal, in which methane is formed (HKV dust), and materials that contain iron oxides such as red mud, Bayer mass, Lux mass, dusts from the steel industry and others. These materials can be used as such as catalysts or doped with metals and / or metal compounds which are active in hydrogenations, in particular with heavy metals and / or their compounds such as Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt , Pd, also alkali and alkaline earth metals or their compounds such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and mixtures of these metals and / or their compounds.

The catalysts can optionally be sulfided before or during the process.

All catalysts can be used as individual components or in a mixture of at least two of the components.

The hydrating treatment can be carried out within wide limits of temperature and pressure, depending on the waste material used, namely from 200-600 ° C. and 30-500 bar, with residence times of 1 minute to 8 hours.

The hydrogenation gas can be of different quality, for example it can contain certain amounts of CO, CO ₂ , H ₂ S, methane, ethane, steam and others in addition to hydrogen.

Suitable hydrogen qualities are, for example, those obtained when gasifying carbon-containing materials.

Such materials can be residues from mineral oil processing or other oils or hydrocarbons from mineral oil origin, or coal such as lignite, but also hard coal, wood, peat or residues from coal processing such as coal hydrogenation. Suitable gasification materials are also biomass and the vegetable portion of household waste. Of course, pure hydrogen qualities, such as those obtained electrolytically: are also very suitable.

Household waste can accordingly be processed in such a way that a separation into a vegetal and a synthetic part takes place and then the vegetable part is gasified to provide hydrogen in the hydrogenation process, while the synthetic part is treated with hydrogen.

According to this method, treatment with suitable solvents is also possible, in particular with hydrogen-transferring solvents, this treatment being carried out before the actual hydrogenation. Subsequently, dissolved and undissolved material can be separated from one another and subjected separately to a hydrogenation, or dissolved and undissolved material can be reacted together in a reactor in a hydrogenating manner. The solvent can be separated off and recycled by subsequent distillation. Alternatively, the undissolved material can be subjected to gasification or coking.

In this variant, too, the waste material used can be mixed with coal and coal components, crude oil and crude oil components and other similar materials, as already explained above.

Suitable hydrogen-transferring solvents are, for example, tetralin, anthracene oil, isopropanol, oils containing cresols, decalin, naphthalene, tetrahydrofuran, dioxane and other hydrocarbons from crude oil and coal or hydrocarbons which originate from the process itself, and also oxygen-containing hydrocarbons and oils. Finally, water and steam can also be added, the latter also being able to be added to the alternative hydrogenating treatments already explained above.

On the other hand, the waste material can first be separated into a vegetable, biomass or cellulose portion and a synthetic portion, both portions being further processed separately, and the vegetable, biomass or cellulose portion being essentially hydrolytically split, for example in the presence of bases or acids, this conversion preferably being carried out in the presence of protic solvents, in particular water and alcohols, and / or in the presence of carbon monoxide and / or hydrogen and, on the other hand, the essentially proportion of the hydrogenating treatment described above.

• a, Die Behandlung bei einer Temperatur von 200-600°C durchgeführt wird, vorzugsweise von 200-540°C, besonders bevorzugt von 300-540°C, bei einem Druck von 30-500 bar, vorzugsweise von 50-450 bar, besonders bevorzugt von 50-350 bar und einer Verweilzeit von 1 Minute bis 8 Stunden, vorzugsweise von 10 Minuten bis 6 Stunden und besonders bevorzugt von 15 Minuten bis 4 Stunden,
• b, das Kohelnstoff enthaltende organische Abfallmaterial synthetischen bzw. überwiegend synthetischen Ursprungs zumindest teilweise einer Vorbehandlung unter Wasserstoff und/oder Wasserstoff enthaltenden Gasen und/oder Wasserstoff übertragende Lösungsmittel unterworfen wird, bei einer Temperatur von 75―600°C, vorzugsweise von 75-540°C und besonders bevorzugt von 120-500°C, einem Druck von 1 bis 600 bar, vorzugsweise von 1 bis 500 bar und besonders bevorzugt von 1-350 bar und einer Verweilzeit von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden und/oder zumindestens teilweise einer Vorbehandlung unter (enem) Inertgas unterworfen wird, bei einer Temperatur von 75-600°C, vorzugsweise von 75-500°C, besonders bevorzugt von 120-475°C, einem Druck von 1-600 bar, vorzugsweise von 1-500 bar und besonders bevorzugt von 1-350 bar und einer Verweilzeit von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden.

An improvement of this method disclosed in DE-PS 3442506 or the European subsequent application EP-A-0 182 309 is in the present invention, which deals with the treatment of carbon-containing organic wastes of synthetic or predominantly synthetic origin with hydrogen and / or hydrogen-containing gases and / or relates to hydrogen-transferring solvents, optionally in the presence of a catalyst (s), characterized in that

• a, The treatment is carried out at a temperature of 200-600 ° C, preferably 200-540 ° C, particularly preferably 300-540 ° C, at a pressure of 30-500 bar, preferably 50-450 bar, particularly preferably from 50-350 bar and a residence time from 1 minute to 8 hours, preferably from 10 minutes to 6 hours and particularly preferably from 15 minutes to 4 hours,
• b, the carbon-containing organic waste material of synthetic or predominantly synthetic origin is at least partially subjected to a pretreatment under hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents, at a temperature of 75-600 ° C, preferably of 75-540 ° C and particularly preferably from 120-500 ° C, a pressure of 1 to 600 bar, preferably from 1 to 500 bar and particularly preferably from 1-350 bar and a residence time of 1 minute to 6 hours, preferably 1 minute to 4 hours and / or at least partially subjected to a pretreatment under (en) inert gas, at a temperature of 75-600 ° C, preferably 75-500 ° C, particularly preferably 120-475 ° C, a pressure of 1-600 bar, preferably from 1-500 bar and particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours.

The investigations of the applicant have shown that the pretreatment of wastes according to the invention, which are subsequently subjected to hydrogenation, can convert these wastes into products which, as a result of the viscosities obtained, can be handled much more easily in the subsequent steps compared to such materials. that only melt or dissolve during a short treatment period. For example, the products according to the invention can be pumped without problems or conveyed with screw conveyors and, depending on the conditions used, can be converted into liquid hydrocarbons in the subsequent hydrogenation much more easily.

The pretreatment according to the invention can be carried out in the presence of hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents, and also in Inert atmosphere or in solvents which are not considered. Hydrogen carriers work. The process can also be carried out with or without catalysts.

The splitting pretreatment is carried out according to the invention in mixing devices in a general sense, in particular in extruders and mixing / kneading devices, since these generally convey into a downstream apparatus without pulsation. For this purpose, extruders can be used, for example, with single or multiple screw conveyance or, for example, those as used for conveyance or, for example, those as described in DE-OS 30 01 318 or DE-OS 29 49 537, the latter in which the screw conveyor ( n) protrudes (s) behind the actual conveying section into an enlarged reaction space, so that additional mixing takes place through the screw (s). However, numerous other mixing devices such as, for example, kneading disc screw presses, kneaders, hollow screw heat exchangers, screw kneaders, kneading extruders, stirring apparatuses, continuous mixers, kneaders, grinding devices or mills such as bead, hammer or vibrating mills are suitable for the pretreatment according to the invention. In the case of kneaders, stirred tanks, mills and the like, a feed extruder can optionally be connected downstream, which brings about a pressure increase up to the pressure of the hydrogenation reactor.

Apparatuses which are very suitable according to the invention are, in particular, those which simultaneously mix and knead. The desired plasticization, dispersion, homogenization, degassing and degradation reaction takes place in a particularly suitable manner, which leads to the desired viscosities. It is known that the reaction rate can also be increased by improving the mixing.

The devices mentioned can optionally also be adapted to certain feedstocks, for example containing gas feeds, feed devices at different points on the pretreatment section, drying, heating and cooling sections, addition devices for liquid feed products and the like. Furthermore, several of the devices mentioned can be connected in series or in parallel so that a total of a feed mixture of the desired properties is present at the entrance of the hydrogenation reactor (s) downstream, in particular with regard to the degree of degradation and viscosity.

Depending on the waste products and biomass to be used, there are, for example, coarse mills, cutting devices, separating devices for inorganic materials, melting devices for inorganic materials, melting devices, devices for metal separation and the like, before the devices mentioned, if necessary, freeze comminution can also be used. As a result, products with the desired physical states can already be used in the mixing device used for the pretreatment according to the invention. If the pretreatment according to the invention is carried out in conjunction with hydrogen, hydrogen-containing gases or hydrogen-transferring solvents, the devices mentioned are preferably selected from the point of view that a sufficient amount of hydrogen required for the reaction reaches the feedstock to be converted. Suitable for this purpose are, for example, stirring devices, mixing / kneading devices, extruders or the devices disclosed in DE-OS 30 01 318 and DE-OS 29 43 537 or other of the devices mentioned can be used, if appropriate with appropriate feeds for hydrogen. Alternatively, hydrogen can also be supplied upstream of the mixing device.

According to the invention, the hydrogenating treatment is carried out in the pretreatment device at a temperature of 75-600 ° C, preferably 75-540 ° C, particularly preferably 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar , particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours, the desired amount of hydrogen being able to be supplied in one or more stages, depending on the mixing device. The thermal pretreatment is carried out in the mixing device at 75-600 ° C, preferably from 75-540 ° C, particularly preferably at 120-475 ° C, a pressure of 1-600 bar, preferably of 1-500 bar, particularly preferably of 1-350 bar and a residence time of 1 minute to 6 hours, preferably 1 minute to 4 hours.

In principle, the pretreatment according to the invention, in particular in the case of thermal pretreatment, can also be carried out under a pressure lower than 1 bar.

In the case of thermal pretreatment, inert gas can be introduced in one or more stages, depending on the mixing device used. Inert gases can be, for example, nitrogen, carbon dioxide, steam, carbon monoxide, methane and other low-boiling hydrocarbons, as well as mixtures of these gases. Hydrogen can also be present in small quantities. Small amounts of oxygen or air may also be permitted.

According to the invention, mixing devices for hydrogenating or thermal pretreatment can be combined in parallel connection or in series connection. The gases mentioned can also be added before the actual pretreatment.

A hydrogen-transferring solvent or a mixture of such solvents can also be used as such or in combination with additional hydrogen or inert gas. In this case too, the hydrogenating pretreatment is carried out at a temperature of 75-600 ° C, preferably at 75-540 ° C and particularly preferably at 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar and particularly preferably from 1-350 bar and a residence time of 1 minute to 6 hours, preferably from 1 minute to 4 hours.

According to the invention, the conversion in the mixing device can also be carried out in the presence of protic solvents, in particular in the presence of water or methanol and / or at least one component from the group: ethanol, C ₃ -C ₄ alcohols and higher alcohols.

Protic solvents, depending on the type of waste used, at least partially lead to hydrolysis. If the reaction is carried out in the pretreatment mixing device, temperatures of 75-600 ° C are used, preferably 75-540 ° C and particularly preferably 120-500 ° C, pressures of 1-600 bar, preferably 1-500 bar, particularly preferably from 1-350 bar and residence times from 1 minute to 6 hours, preferably from 1 minute to 4 hours. The hydrolysis can also be carried out in the presence of hydrogen, hydrogen-containing gases or hydrogen-transferring solvents with or without a catalyst or with or without CO. Typical hydrolysis catalysts, such as acids or bases including organic amines, can be used. The catalysts mentioned on pages 6 and 7 can also be included.

Furthermore, the pretreatment according to the invention can be carried out in the presence of solvents which do not have a hydrogen transfer effect, such as of aromatics such as benzene, toluene or the xylenes. Non-aromatic solvents can also be used, such as saturated or substantially saturated aliphatic hydrocarbons in boiling ranges between, for example, 30 and more than 500 ° C. The high-boiling fractions can, for example, be residual oils, as already mentioned above.

According to the invention, the hydrating cleavage in the pre-treatment device can be set to the desired extent, up to a breakdown as described in the hydrating treatment of waste according to DE-PS 34 42 506 or in the European subsequent application EP-A-182,309. In such a case, a downstream hydrogenation reactor can be dispensed with.

According to the invention, the hydrogenating pretreatment can be carried out with or without the catalysts which are disclosed on pages 6 and 7. Catalysts can be introduced into the pretreatment device or added before it.

According to the invention, the waste from organic synthetic materials can be converted into liquid hydrocarbons which boil essentially in the naphtha or gasoline range or middle distillate range. Examples of such waste are disclosed on pages 3 and 4.

However, the convertible wastes of the present invention are not limited to those specified there.

A particular advantage of the method according to the invention results from the fact that the conditions in the pretreatment device can be set so that a product is obtained which can be handled without problems in subsequent steps, e.g. can be pumped or conveyed via screw conveyors, whereby the conditions can be adapted to the type of waste used, which, as already mentioned above, plastic materials, paint residues, paint compositions, industrial chemicals such as those that have to be deposited in special landfills according to the prior art, shredder waste from the automotive industry, used lubricating oils, elastomers, textile materials but also to a certain extent paper, cardboard and other cellulose-containing materials such as wood waste, sawdust or vegetables from household waste.

As an alternative to conveying by pumps or screw conveyors, the pretreated product can also be conveyed directly from the pretreatment device into the hydrogenation reactor, for example by means of an extruder.

The method according to the invention therefore also allows only a little pre-sorted waste to be implemented. However, for reasons of equipment, it is desirable to separate inorganic materials such as stones, metals, glass and others before the pretreatment, at least rough materials.

According to the invention, it is preferred, at least predominantly, to separate materials containing vegetable and cellulose from the organic waste of synthetic origin, although a complete separation of the materials containing vegetable and cellulose is not necessary according to the invention.

These materials, e.g. Vegetables can be processed separately, for example by fermentation.

An important advantage of the present invention results from the fact that the hydrogenating or thermal pretreatment according to the invention, in combination with the subsequent hydrogenation of the pretreated waste, means that even very inhomogeneous waste mixtures can be used as the feed product, these being converted into valuable liquid hydrocarbons in high yields. The heteroatoms such as oxygen, sulfur, nitrogen or halogens, which are contained in many waste materials, are converted according to the invention into their hydrogen derivatives, which can be worked up further according to the prior art without any problems.

This is particularly important in the case of waste containing chlorine, bromine or fluorine.

The bitter problem of waste disposal, particularly in the case of toxic and halogenated waste, is therefore solved by the present invention without any risk to the environment. Such halogenated wastes are, for example, polychlorobiphenylenes, polyvinyl chloride, fluorine-containing polymers or halogens-containing solvents.

A particularly advantageous effect of the thermal or hydrogenating pretreatment is the result that, depending on the temperature, residence time and pressure, a large amount of halogens, essentially as hydrogen halides, is eliminated in the pretreatment. For example, about 90% of the halogen is already removed from waste containing polyvinyl chloride at 250 ° C., a residence time of 30 minutes and a hydrogen or nitrogen pressure of 10 bar or less as hydrogen chloride.

Halogen elimination can also be promoted by increasing the temperature and increasing the residence time. Halogen elimination can also be promoted by catalysts such as those mentioned on pages 6 and 7. Such catalysts which are used according to the prior art for the elimination of hydrogen halide, such as Friedel-Crafts catalysts and / or organic amines and / or other basic compounds, can also be used according to the invention. As a result, hydrogen halides can be split off even under mild conditions.

According to the invention, materials can also be added to the waste used, or added to the pretreatment device or the hydrogenation reactor, such as crude oil, crude components and products derived from crude oil, asphalts, bitumen, mineral tars, coal, coal components, products from coal, lignite, Peat, pyrolysis oils such as those obtained from coking processes or pyrolysis processes, oil sands, oil sand products, residual oils from crude oil processing, from cracking plants, vacuum residues, shale oils and shale oil products and similar materials.

Depending on the type of waste used, a hydrolysis stage can precede the thermal or hydrogenating pretreatment. In this case, the hydrolysis reaction is preferably carried out in a mixing device as described above, in the presence of protic solvents, in particular in the presence of water and / or methanol and / or at least one component from the group: ethanol, C ₃ -C ₄ alcohols and higher alcohols , at a pressure of 1-150 bar, preferably of 1-120 bar and a temperature of 50-300 ° C and preferably of 75-250 ° C. Lower pressures are preferred if the gases that are formed during the hydrolysis are to be removed from the hydrolysis device.

Under certain conditions, the hydrolysis stage can alternatively be switched between the pretreatment and the actual hydrogenation. In this case, the hydrolysis conditions are preferably adapted to the temperature and the pressure in the pretreatment stage or hydrogenation stage or both.

In this way, for example, vegetables and biomass can be hydrolytically split and separated from waste of synthetic organic origin. The hydrolysis reaction can be accelerated by adding acids or bases in accordance with the prior art. The hydrolytic reaction can also be carried out in the presence of hydrogen, hydrogen-containing gases, hydrogen-transferring solvents, catalysts as exemplified on pages 6 and 7 or solvents which are not suitable for mass transfer, or in the presence of inert gases.

So-called grating oils are also added according to the invention in the pretreatment device or before or after this. The grinding oils can originate from the process itself or can be of foreign origin.

According to the invention, metals or metal compounds which are present in the wastes can advantageously be worked up, since they occur in residues or ashes in a relatively high concentration after the hydrogenation. These residues or ashes can be worked up, for example, to obtain the pure metals.

The process according to the invention is explained in more detail in the following examples:

example 1

A mixture of essentially organic-synthetic waste from a technical waste sorting plant, without waste containing polyvinyl chloride and other chlorine, is mixed with a used lubricating oil in a ratio of waste to oil of 1: 3 and for 2 hours under a hydrogen pressure of 10 bar and temperatures of 250 ° C, 300 ° C and 350 ° C in a stirred reactor.

Pumpable products are obtained with the viscosities shown in Table 1.

Example 2

Example 1 was repeated, but under a nitrogen pressure of 10 bar. In the case of the temperature of 300 ° C, an additional nitrogen pressure of 2 bar was used. The results are shown in Table 2.

Example 3

A mixture of essentially synthetic waste from an industrial waste sorting plant which contained 10% by weight of polyvinyl chloride was mixed with a used lubricating oil in a waste to oil ratio of 1: 3, as described in Example 1 and at temperatures of 250 ° C., 300 ° C and 350 ° C treated for two hours at a pressure of 10 bar nitrogen or hydrogen.

Pumpable products with the viscosities shown in Table 3 were obtained.

Example 4

A mixture of 90% by weight of essentially organic waste of synthetic origin, which was obtained from a technical waste sorting plant, and 10% by weight of waste paper, mixed with a mineral residual oil in the ratio of waste to oil of 1: 3, was 20 minutes at 20 bar Hydrogen treated in a twin-screw mixer / kneader at 150 ° C, 250 ° C and 350 ° C, in the presence of a catalyst consisting of oven coke treated with 5% by weight iron sulfate.

Pumpable products were included with the viscosities shown in Table 4.

Example 5

A mixture of mineral residual oils and a waste mixture consisting of 10% by weight of old tires, 70% by weight of essentially synthetic-organic waste from a technical waste separation system and 20% by weight of polyvinyl chloride was mixed and kneaded at 350 ° C. for 20 minutes and 450 ° C treated with a hydrogen or nitrogen pressure of 200 bar. The ratio of waste to oil was 1: 3. FeS0 ₄ treated with NaOH was used as catalyst.

Pumpable products with the viscosities shown in Table 5 were obtained.

Example 6

Waste that consisted mainly of organic synthetic material and a technical Waste sorting plant was obtained, with 15 wt.% Polyvinyl chloride, was treated in a mixer / kneader at 200 bar hydrogen and temperatures of 350 ° C and 470 ° C for 30 minutes. At the temperature of 350 ° C, an experiment was carried out with and without a catalyst. A nickel / molybdenum catalyst was used as the catalyst. No rubbing oil was used. The viscosities obtained are shown in Table 6.

Example 7

• 60 Gew.% Polyethylen und Polypropylen
• 10 Gew.% Polyvinylchlorid
• 15 Gew.% Polycarbonate und
• 15 Gew.% Polyamide wurde gemischt mit Krackvakuumdestillat im Verhältnis Abfall zu Öl von 1:3 und unter 10 bar Stickstoff jeweils 1 Stunde bzw. 2 Stunden in einer Knetvorrichtung bei Tempeaturen von 200°C und 250°C behandelt.

Waste, from a technical waste disposal system, which essentially consisted of the following hard plastics:

• 60% by weight of polyethylene and polypropylene
• 10% by weight of polyvinyl chloride
• 15% by weight of polycarbonates and
• 15% by weight of polyamides were mixed with cracking vacuum distillate in the ratio of waste to oil of 1: 3 and under 10 bar of nitrogen in each case for 1 hour or 2 hours in a kneader at temperatures of 200 ° C. and 250 ° C.

The viscosities of the products are shown in Table 7.

Example 8

Waste which consisted essentially of organic synthetic material from a technical waste separation plant and which contained 5% by weight of perfluorinated polyethylene (Teflon) and 20% by weight of textile waste made of 50% wool and 50% polyacrylonitrile was treated as described in Example 6. The viscosities obtained are shown in Table 8.

The examples show that the feedstock is broken down both under nitrogen and under hydrogen in the mixing devices, products being obtained which are easy to handle in the subsequent steps and can be easily transported, for example by pumps or screw conveyors. This also applies to waste that consists of very different materials.

The examples further show that at higher temperatures, e.g. almost quantitative oil yields with a boiling range <500 ° C can be obtained at 475 ° C. Furthermore, the results in Tables 3, 5, 6, 7 and 8 show that the pretreatment according to the invention leads to an extensive elimination of chlorine, fluorine and nitrogen. This also applies to treatments under relatively mild conditions, such as 250 ° C and 10 bar or less nitrogen or hydrogen pressure, depending on the starting mixtures.

The results according to the invention are of great importance for waste hydrogenation on an industrial scale, since the downstream hydrogenation reactors and other parts of the plant which are exposed to high pressures can be made from less valuable materials.

Furthermore, the surprising, unpredictable result was obtained that in the treatment of waste materials containing chlorinated constituents, both under inert gases and under hydrogen, there is an increased degradation of the feed waste material compared to feed materials which do not contain these chlorinated components.

The process according to the invention is therefore of particular importance for waste feed materials which contain chlorinated constituents.

The examples also show that, under suitable conditions and conditions, increased degradation takes place under nitrogen compared to hydrogen.

Depending on the feed mixture, a decrease in viscosity can initially occur, followed by an increase in the same with increasing temperature and finally a decrease in viscosity at an even higher temperature.

Since the conditions of the pretreatment can be varied over a wide range of temperature, pressure and residence times, the conditions for the subsequent hydrogenation can also be varied over a wide range, the two treatments complementing one another.

If e.g. the pretreatment according to the invention is carried out at a relatively high temperature and residence time or corresponding pressure, in particular at a relatively high hydrogen pressure, the subsequent hydrogenation can, depending on the product used, be carried out under relatively mild conditions. This applies in particular if the pretreatment has already led to extensive dismantling.

Conversely, relatively mild conditions in the pretreatment can be compensated for by more severe conditions in the hydrogenation stage.

Both stages therefore complement one another in accordance with the invention and can be adapted excellently to the operational waste material as required.

Claims (12)

1. A process for treating carbon-bearing organic wastes of synthetic or predominantly synthetic origin, with hydrogen and/or hydrogen-bearing gases and/or hydrogen-transferring solvents, possibly in the presence of a catalyst or catalysts, characterised in that:

a) the treatment is carried out at a temperature of from 200 to 600°C, preferably from 200 to 540°C and particularly preferably from 300 to 540°C, under a pressure of from 30 to 500 bars, preferably from 50 to 450 bars and particularly preferably from 50 to 350 bars and for a residence time of from 1 minute to 8 hours, preferably 10 minutes to 6 hours and particularly preferably from 15 minutes to 4 hours, and

b) the carbon-bearing organic wastes of synthetic or predominantly synthetic origin are at least partially subjected to a preliminary treatment in hydrogen and/or hydrogen-bearing gases and/or hydrogen-transferring solvents, at a temperature of from 75 to 600°C, preferably from 75 to 540°C and particularly preferably from 120 to 500°C, under a pressure of from 1 to 600 bars, preferably from 1 to 500 bars and particularly preferably from 1 to 350 bars, and for a residence time of from 1 minute to 6 hours, preferably from 1 minute to 4 hours, and/or are at least in part subjected to a preliminary treatment in an inert atmosphere at a temperature of from 75 to 600°C, preferably from 75 to 500°C, particulalry preferably from 120 to 475°C, under a pressure of from 1 to 600 bars, preferably from 1 to 500 bars and particularly preferably from 1 to 350 bars, and for a residence time of from 1 minute to 6 hours, preferably from 1 minute to 4 hours.

2. A process according to claim 1 characterised by using combinations of preliminary treatment mixing apparatuses which operate on the one hand in the presence of hydrogen or hydrogen-bearing gases and/or hydrogen-transferring solvents and on the other hand under an inert atmosphere and/or solvents and/or pasting oils which do not transfer hydrogen.

3. A process according to claims 1 and 2 characterised in that the waste materials used, in accordance with step a) and/or step b) of claim 1, include vegetable wastes and/or cellulose-containing wastes.

4. A process according to claims 1 to 3 characterised in that the waste charge product is treated in the preliminary treatment mixing apparatus in the presence of one or more protic solvents, preferably in the presence of water and/or methanol and/or at least one component from the group consisting or C2-C4 alcohols, at a temperature of from 75 to 600°C, preferably from 75 to 540°C and particularly preferably from 120 to 500°C, under a pressure of from 1 to 600 bars, preferably from 1 to 500 bars and particularly preferably from 1 to 350 bars, and for a residence time of from 1 minute to 6 hours, preferably from 1 minute to 4 hours, or that the waste charge product is treated in an apparatus in the presence of one or more protic solvents, which is disposed upstream of the preliminary treatment mixing apparatus, preferably in the presence of water and/or methanol and/or at least one component from the group consisting of C₂-C₄ alcohols, at a temperature of from 50 to 300°C, preferably from 75 to 250°C, under a pressure of from 1 to 150 bars, preferably from 1 to 120 bars, and for a residence time of from 1 minute to 6 hours, preferably from 1 minute to 4 hours.

5. A process according to claims 1 to 4 characterised in that the preliminary treatment is carried out in a single or multiple screw extruder, in a mixing/kneading apparatus or stirrer apparatus.

6. A process according to claims 1 to 5 characterised in that steps a) and/or b) of claim 1 are carried out with a charge mixture which contains at least one component from the following groups: crude oil, crude oil components and products of crude oil, coal including brown coal, coal components and products from coal, oil shale, oil shale components and products from oil shale, oil sand, oil sand components and products from oil sand, pyrolysis oils and products from pyrolysis oils, bitumen, bitumen components and products from bitumen, asphalt and asphaltenes, asphalt and asphaltene components and products from asphalt and asphaltenes, pasting oils from the hydration of wastes and/or thermal treatment of wastes or from other sources, tar, tar components, products from tar, biomaterial, including vegetables, biomaterial components and products from biomaterial, domestic refuse, domestic refuse components and products from domestic refuse, and peat, peat components and products from peat.

7. A process according to claims 1 to 6, characterised in that a catalyst which includes at least one component from the following group is used in step a) and/or step b) of claim 1: Fe, Cr, Pt, Pd, Zn, Mo, W, Mn, Ni, Co, V, alkali metals, alkaline earth metals and compounds of those metals, those metals and compounds thereof on catalyst supports such as aluminium oxide, silicon dioxide, aluminum silicates, zeolites and mixed supports, hearth furnace coke with or without doping with metals and compounds thereof, dusts and ashes with or without doping with metals and compounds thereof, high-temperature Winkler dust with or without doping with metals and compounds thereof, coal gasification dusts and ashes with or without doping with metals and compounds thereof, dusts from the steel industry with or without doping with metals and compounds thereof, red mud, Bayer mass and Lux mass.

8. A process according to claims 1 to 6 characterised in that a catalyst which includes at least one component from the following group is used in steps a) and/or b) of claim 1: Fe, Cr, Mo, W, Mn, Ni, Co, V, Pt, Pd and compounds thereof with or without a support.

9. A process according to claims 1 to 6, characterised in that operation is effected in steps a) and/or b) of claim 1 in the absence of a catalyst or catalysts.

10. A process according to claims 1 to 9 characterised in that waste charge materials which include chlorinated materials are used in steps a) and/or b) of claim 1.

11. A process according to claims 1 to 10 characterised in that the preliminary treatment is carried out in an inert gas atmosphere.

12. A process according to claims 1 to 11 characterised in that nitrogen and/or steam or C0₂ is used as the inert gas.