DD249036B5 - Process for the treatment of carbon-containing wastes - Google Patents

Abstract

1. Process for the hydrogenative reprocessing of carbon containing waste materials, with the exclusion of a process for hydrocracking of waste tires in the presence of a catalyst of an iron compound and an auxiliary catalyst of metal compounds of the group Cr, Mo, W, Se and Te, based on a synergistic catalyst action with sulfur, by treatment of the waste materials with hydrogen und/or hydrogen transferring solvents (hydrogen donor solvents), characterized in that mixtures of carbon containing waste materials of synthetic respectively predominantly synthetic origin are reacted with hydrogen and/or hydrogen containing gases at a temperature of 200-600 degrees C, preferably at a temperature of 200-540 degrees C, at a pressure of 30-500 bar, preferably of 50-450 bar and a residence time of 1 minute to 8 hours, preferably of 15 minutes to 6 hours and in the case of reaction with a hydrogen-donor-solvent at a temperature of 75-500 degrees C, preferably of 80-480 degrees C and a pressure of 1-300 bar.

Description

Field of application of the invention

The present invention relates to a process for the treatment of waste and biomass containing carbon by hydrogenating it at elevated temperature and a hydrogen pressure of at least 1 bar.

Characteristic of the known technical solutions

It is well known in the public and in the art that the world's waste is an increasing burden on the environment.

For decades, waste in landfills, z. B. stored in abandoned gravel pits, mine mines and other places. For a long time, the chemical structure of the waste and its long-term impact on soil and groundwater were ignored.

More recently, certain waste has been stored in so-called special landfills. Here it is endeavored to seal the landfill against groundwater and soil. In the long term, however, dangers for the environment are to be feared.

For some time now, experts have been working hard to recycle or process the waste, for once to protect the environment and to extract usable products from the waste.

Thus, in "The Oil and Gas Journal", Dec. 25, 1978, p. 80, a pilot plant is described in which plastics can be converted into gases and oils by pyrolysis.

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

The biochemical degradation of plastics has also been investigated (see, for example, "European Chemical News", Sept. 10, 1979, p. 28). "Chemical Engineering", August 13, 1979, p the hazardous waste in hardening materials, eg. As cement, are poured.

An overview of the most important processes is presented in "Chemical and Engineering News", Oct. 1, 1979, page 34. Here, in particular, the gasification of biomass, namely wood waste and the like to carbon monoxide and hydrogen is described.

On page 36, left column of this document is also an experimental program for the implementation of crushed wood suspended in water, with hydrogen in the presence of Raney nickel, described as a catalyst.

In "Europa Chemie", 25, 1979, p.417, a process is described, after plasticized unsorted plastic waste and pressed.

Fluidized bed incineration of wastes 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.

In addition, numerous other publications have become known.

Most recently, incineration in state-of-the-art plants has been further developed and large-scale plants built using this process have been built. Although dedusting and flue gas scrubbing are integrated into such plants, the conversion of waste into CO2 (and water) is an inevitable accompanying problem.

Especially with regard to the enrichment of CO2 in the atmosphere, CO ₂ production is undesirable. Furthermore, pollutants escape even with careful cleaning, such as heavy metals, SO ₂ , NO _x, etc., in small amounts in the atmosphere.

Pyrolysis is now also being operated on an industrial scale (see for example "Vereinigte Wirtschaftsdienste GmbH",

4 Oct. 1985, p. 9). However, pyrolysis has the disadvantages of predominantly forming gaseous products and heavily contaminated coke residue.

The problem of waste and biomass processing is therefore still not satisfactorily solved.

Object of the invention

The aim of the invention is to provide an improved and universally applicable method for waste disposal or treatment, with which the disadvantages of known methods are avoided.

Explanation of the essence of the invention

The invention has for its object to find a new process for the processing of carbon-containing waste and biomass.

A surprising solution to the problem of waste disposal, which is considerably more favorable than the prior art, especially with regard to obtaining very high levels of valuable products, is disclosed in the present invention, which relates to a process for the treatment of waste and biomass containing carbon, characterized in that the carbon-containing wastes and / or biomass are reacted with hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring compounds in a temperature range of 75-600 ⁰ C, at a pressure of 1-600bar, preferably 2- 500 bar and a residence time of 1 minute to 8 hours, preferably from 15 minutes to 6 hours.

The process according to the invention makes it possible to process wastes from which inorganic constituents, such as glass, metals, stone materials and the like, without further sorting into valuable hydrocarbons, ie to C 1 -C ₄ -hydrocarbons, to hydrocarbons boiling in the gasoline range and to medium-boiling hydrocarbons. and heavy oils that can be used as diesel oil and for heating purposes. According to the invention, presorted materials are also processable, in particular in such a way that carbonaceous wastes of synthetic origin, such as plastics or plastic mixtures, rubber, tires, textile waste are at least roughly separated from the vegetable portion or biomass portion and then subjected to a separate hydroentation treatment , if necessary.

together with industrial waste, such. As paint and paint residues and organic chemicals, industrial production waste, organic-synthetic shredder waste the car industry, sewage sludge or with waste oils u. The like. Partly other waste such as paper, food waste, agricultural and forestry waste, wood, plants and the like, are largely separated, but also remain in the synthetic proportion to some extent.

Domestic waste can accordingly be worked up, for example, in such a way that the plastics, rubber, textile rest e and the like at least roughly separated and separately subjected to the hydrogenation treatment or z. B. together with scrap tires and / or plastic and / or chemical waste from industry and / or waste oils u. Likewise, the synthetic individual components are very easy to process under the conditions of the invention to valuable liquid products.

The inventive method is also very well suited for the joint hydrogenating treatment of said wastes or waste mixture with coal, coal constituents such as coal oil residues, coal oils, pyrolysis oils, petroleum, petroleum residues, other petroleum components, oil shale, oil shale components, oil sands, bitumen u. similar or the mixtures of these materials. The separation of the above-mentioned inorganic materials from the carbonaceous materials can be carried out according to the prior art. These inorganic materials can, if they are not reprocessed, be deposited. The comminution and separation of waste materials and biomass can also be carried out according to the prior art. Insofar as apparatus conditions do not conflict with this, the process according to the invention can also be carried out in the presence of inorganic materials.

Ingredients in the waste, which are not convertible into hydrocarbons, such. For example, sulfur, nitrogen, oxygen and halogen in the form of their compounds fall on the hydrogenation as gaseous hydrogen compounds, ie as H ₂ S, NH ₃ , HCl, H ₂ O and others

It is state of the art to separate these compounds by gas scrubbing and, if necessary, to feed them to a further processing.

The formation of dangerous substances resulting from the combustion, such. As of NO x, SO ₂ or dioxins is avoided according to the present method. Likewise, hard-to-burn plastics ₍ such as polyvinyl chloride can be worked up without risk.

The hydrogenation of the carbonaceous waste can be carried out without catalysts with very good results.

Partially even better results in terms of conversion and selectivity of fractions of certain boiling ranges can be obtained in the presence of catalysts, such as in the presence of Fe, Mo, Ni, Co, W and other hydrogenation-active metals and / or their compounds, these being single or at least two of these components can exist and the metals and / or their compounds can be used on carriers, for. Example, on alumina, silica, aluminum silicates, zeolites and other carriers known in the art or carrier mixtures or carriers. Certain zeolites as such are also suitable.

Other suitable catalysts may be so-called. Disposable catalysts, such as Herdofenkoks, Winklervergasungsstäube, dusts and ashes incurred in the hydrogenating gasification of coal to methane (HCV dusts), but also iron oxides containing mixtures such as red mud, Bayermasse, Luxmasse , Dusts from the iron industry and others, which materials may also be doped with hydrogenation-active metals and / or metal compounds, in particular with heavy metal salts, such as. As iron salts or salts of chromium, zinc, molybdenum, tungsten, manganese, nickel, cobalt, also with alkali, alkaline earth, u.a. as well as with mixtures of these compounds. The catalysts can be at least z. Part be pretreated sulfiding.

The hydrogenation treatment can take place in wide pressure and temperature limits, namely 75-600 ⁰ C and 1-600 bar.

Hydrogenating treatment with and without catalysts of mixtures of synthetic wastes such as plastics, mixed plastics, rubber, tires, textile waste, industrial waste and the like, and mixtures thereof, which may be carried out in the presence of drift oils and in mixtures with coal, coal constituents, petroleum, petroleum residues, other petroleum components, oil shale, oil shale components, oil sands and their components, bitumen and similar materials, can be carried out at a pressure of 30-500 bar, preferably from 50-450 bar instead. The temperature is 200-600 ⁰ C, preferably at 200-540 ° С ^ іе residence time at 1 min to 8 hours, preferably 15 minutes to 6 hours.

Different hydrogen qualities can be used as the hydrogenation gas: also with admixtures ₍ such as, for example, CO, CO ₂ , H ₂ S, methane, ethane, water vapor, inter alia

Highly suitable are hydrogen qualities, such as those produced in gasification reactions of carbonaceous materials with water vapor. Such materials may be residues from the processing of mineral oils or from coal, wood, peat or residues from coal processing, for example hydrogenation. Also suitable are biomasses or the vegetable parts separated from domestic waste.

Of course, very good qualities are also suitable, such as, for example, electrolysis hydrogen. For example, according to the invention, for example, household waste can firstly be separated into vegetable and synthetic components, and then the vegetable component for hydrogen production can be fed to a gasification, while the synthetic component is subjected to the hydrogenating treatment.

The vegetable portion can also be fed to a fermentation or other formation.

The generally freed from inorganic materials, optionally dried, crushed or molten or blended with Anreiböl or other additives feedstock is mixed as such or with catalyst, brought to reaction temperature and treated in the reaction zone with hydrogenating gas.

In cases where at elevated temperature already in the mixing container a pumpable slurry is produced, the feedstock

be pumped into the hydrogenation. To produce the pumpable slurry may be a so-called. Anreiböl, which is obtained in the process and can come from different sources in the system, are added. However, dripping oil can also be a foreign oil not originating from the plant.

Finally, water or steam can be added. Also, by adding, for example, petroleum components, bitumen or coal components, a pumpable slurry can be produced.

However, the feedstock can also, for example, by means of screw conveyors u.a. The prior art conveying devices are conveyed into the hydrogenation reactor.

The reaction zone can consist of one or more reactors connected in series or in parallel.

Downstream of the reactor (s), there may generally be at least one hot separator known in the sump phase dehydrogenation in which separation at the hot separator temperature takes place into gaseous constituents which are withdrawn and into the hot separator sump.

The gaseous components are cooled, resulting in liquid hydrocarbons, which are further processed according to the prior art, such as by further hydrogenating cleavage stages or refining stages and distillative separation. However, some of these can also be recycled for grinding the feedstock. The non-condensed gases are freed by gas scrubbing of H ₂ S, NH ₃ , HCl, if appropriate also CO and CO ₂ .

The hydrogen in the resulting gas can be recycled as hydrogenation gas to the (the) hydrogenation reactor (s). A processing of the lower hydrocarbons contained in the gaseous products, for example by steam reforming is also possible, with additional hydrogen being recovered.

The products from the gas phase of the hot separator, in particular the products which are liquid under normal conditions can, as already mentioned above, be supplied to a refining stage which generally works by hydrogenation. In this case, even small amounts of heteroatom-containing compounds can be worked up completely hydrogenating, so that then the products are practically sulfur, nitrogen and halogen-free. Higher-boiling fractions can be fed to at least one cracking plant, in particular a hydrocracking plant. If necessary, certain components can also be recycled from the processing back into the waste hydrogenation or before the waste hydrogenation.

Heißabscheidersumpf can be worked up in various ways, for. B. by vacuum distillation, wherein the bottom of the vacuum distillation of a gasification to H ₂ and CO can be supplied. The resulting gases in the gasification are advantageously integrated in this case in the gas scrubbing and gas processing described above. However, the vacuum distillation residue may also be coked or deasphalted or further processed by other methods of the prior art. The resulting residues and ashes contain the metallic impurities that may be deposited according to the state of the art, but they can also be recycled to metals in the metallurgical industry, or optionally used as catalysts in waste hydrogenation.

However, the Heißabscheidullumpf or residue can also be subjected to a supercritical extraction, such as. As with propane, butane or higher boiling hydrocarbons, which can be removed from the process itself. Here, the extractant may at least partially already be introduced into the hydrogenation reactors themselves in order to achieve the desired degree of extraction. Heißabscheidersumpf can also be used as Anreiböl, as well as the vacuum distillation residue, especially after deasphalting.

embodiment

The invention is explained in more detail below with reference to some examples

 In the attached drawing show:

1 shows by way of example the method according to the invention with exemplary subsequent steps;

2 shows an example of the process according to the invention with an upstream solvent treatment;

3: the combination of a waste oil refining with the method according to the invention;

4 shows the dependence of the yields on the individual fractions as a function of the temperature.

Fig. 1 will be explained in detail below:

The waste material passes into the mixing apparatus 1 after crushing, wherein if necessary, can take place after the mixing apparatus 1 or before the mixing apparatus 1, an additional grinding of the feedstock. In addition, a mash (-reib) oil 2 is taken from the recovered liquid products or a foreign oil 2 a of the mixing apparatus 1 are supplied. Furthermore, catalyst 3 can be added to the mixing apparatus 1. By supplying hydrogen 4 or hydrogen-containing gas, the feed is hydrogenated in reactor 5.

Instead of reactor 5, several reactors can be used. From the reactor 5, the hydrogenated product enters the hot separator 6. Here, a separation takes place in at Heißabscheidertemperatur gaseous products 7, which pass through heat exchanger 8 in the separator 9. In the separator 9, the products which are cooled after cooling are withdrawn, while the gaseous products escape overhead.

The liquid products are worked up in the usual way, such as. B. by distillation or optionally hydrogenating cleavage of the heavier oil content or by refining.

The gases are freed in the gas separator 10 by admixtures of H ₂ S, NH ₃ , HCl, CO ₂ and others. Hydrogen is recirculated and passes back into or into the hydrogenation reactor 5. Gaseous hydrocarbons may also be separated and some or all of the hydrocarbons may be converted to H ₂ and CO by treatment in the steam reforming 11.

From the Heißabscheidersumpf the liquid product is withdrawn and fed, for example, a vacuum distillation 12.

There are further oils 13 won, which can also be used as Anreiböl.

The bottom of the vacuum distillation 12 can be coked, for example, in FIG. The products 15 removed from the coking 14 also pass into the gas and liquid product processing of the plant. The resulting coke 16, which also contains the ash constituents including metals, may enter a gasification 17 or may be disposed of in accordance with the prior art or may be used in part as a catalyst, depending on the composition.

Alternatively, the vacuum distillation bottoms may be gasified directly into 17. The resulting gases 18 reach the gas processing of the plant, while the resulting ash 19 or the soot can be dumped or burned or further processing, for. B. the metallurgical industry can be supplied or partially used as catalysts, depending on the composition.

As a further alternative, the Heißabscheiderinhalt can be extracted with a supercritical gas. Propane, butane, naphtha cuts, for example, but also hydrocarbon cuts with a higher boiling point are suitable for this purpose. The extract is processed in the usual way. The remaining residue can be further processed as the Heißabscheidersumpf or residue. The extractant may already be at least partially introduced into the reactors themselves, in particular in the case of several hydrogenation reactors connected in series.

In the case of feedstocks having a relatively high content of heteroatoms such as sulfur, nitrogen or halogens, the liquid product from separator 9 may first be subjected to refining 20, generally hydrogenation refining. The refined product passes into a distillation 21, but also the distillates can be subjected to refining. The bottom of the distillation 21 can be split in a cracking step 22 to lower boiling products 23.

The processing shown by Fig. 1 is exemplary and does not limit the hydroprocessing of waste according to the present invention, since the prior art for products of hydrogenation reactors comprises a plurality of variants.

Waste oils or residues from waste oil processing can also be used in the hydrogenating treatment of waste, as shown by way of example in FIG.

Waste oil can be used, for example, from a storage tank 1 in a physical and / or chemical separation or cleaning system 2 to separate solids, water and the like. The thus prepurified product can be used via line 3 in the hydrogenation reactor 4 or in the refining 7. Gaseous or liquid products from the hot separator 5 of the hydrogenation can be added via line 6 of waste oil refining 7. The bottoms from the distillation 8 of the refined waste oil can also be used in the hydrogenation reactor 4 via line 9.

Waste to be hydrogenated are removed from storage tank 10 and first pass into a crushing and mixing vessel 11, is transferred from the feedstock via line 12 into the hydrogenation reactor 4. Via line 13, for example, in addition heavy mineral or kohlestämmige oils can be added. Heißabscheidersumpf or residue can be used for example via line 14 in a gasification 15.

According to the invention, a solvent treatment with suitable solvents, in particular hydrogen-transferring solvents, can also be preceded by the hydrogenating treatment, then either the entire mixture consisting of dissolved and unresolved can be fed to the hydrogenation reactor 4 or a separation into dissolved and insoluble material takes place behind the dissolving apparatus and solution or undissolved are fed to the hydrogenation reactor (s) 4. Downstream distillation usually allows the solvent to be recycled.

The separated, undissolved solid can also be fed to gasification or coking.

Also in this process variant of the invention, the feedstock in admixture with coal and / or coal components and / or petroleum residues and / or petroleum u. a., Are hydrogenated.

Also for this processing of waste according to the invention numerous apparatus variants are possible, as they correspond to the prior art.

Suitable solvents are, for. As tetralin, anthracene, isopropanol, cresol-containing oils, decalin, naphthalene, tetrahydrofuran, dioxane, but also, for example, petroleum-derived, kohlestämmige or from the plant itself derived hydrocarbons and oils and oxygen entidenting hydrocarbons and oils. Finally, water or steam can be added.

The use of solvents according to the invention is explained in more detail by way of example in FIG. 2:

In extinguishing container 1, the comminuted material is at least partially dissolved or suspended at elevated temperature. In the separation device 2, a separation of insoluble can take place, which arrives for further processing, for example, in a coking 3 or gasification 4.

The solution or suspension is then hydrogenated in the hydrogenation reactor (s) 5. Preferably, hydrogen-carrying solvents such. As tetralin, decalin, anthracene oil, creosote oil or higher boiling oils u. a. used, so that the hydrogenation can be carried out even at low hydrogen pressures up to the range of 1 bar hydrogen pressure.

Residence time and hydrogen pressure are matched to one another in the case of the hydrogenations according to the invention. The hydrogenation product can be worked up in a conventional manner, for. B. by distillation. 6

In a further example, working in the presence of anthracene oil, wherein the waste material to be hydrogenated, optionally in admixture with carbon and / or mineral materials, first with the addition of strong acids, eg. B. of hydrogen fluoride and / or p-toluenesulfonic acid at about 370-420 ⁰ C and then optionally after separation of undissolved materials with the addition of salts such as SbCI ₅ , SbF ₅ , etc., and HF or HCI, the formation of more complex Acids are capable of hydrogenating at 75 to 220 ⁰ C, preferably at 150-200 ⁰ C and 1-5 bar hydrogen, preferably 1-2 bar hydrogen. In a subsequent hydrogenation step, unsaturated products can be converted to saturated.

Also, for example, under conditions of SRC (Solvent Refined Coal) coal hydrogenation waste can optionally be implemented in admixture with biomass and optionally in admixture with carbon and mineral materials, such as petroleum residues with high yields of distillable oils. Suitable conditions in the dissolution stage are 380-480 ⁰ C. In the hydrogenation stage is generally carried out at 350-450 ⁰ C and a pressure of 110-250 bar, preferably from 120 to 220 bar, wherein the usual hydrogenation catalysts can be used.

Applicant's investigations have shown that the process developed for hydro-carbon and petroleum residue processing is also applicable to the hydrodynamic fission of waste mixtures containing carbon, very different materials, in particular the synthetic part of waste, in admixture with coal and mineral materials are, albeit in detail if necessary, in a modified form.

Examples, but not limiting, of such methods are: the H-OiI method, the Canmet method, the LC-Fining method, the Veba combi-crack method (VEBA), the VEBA LO cracking method (VEBA), the RCD Unibon method , the Residfining method, the Unicracking and Unicracking / HDS method, the HC Unibon method, the Isocracking method, the Heavy Oil Cracking method, the Dynacracking method, the Linde Hydroconverter method and others

In cases where these processes are fixed bed catalyst processes, at least dissolved waste such as e.g. B. in coal oil and petroleum or their components, are hydrogenated according to the invention.

According to the invention, waste mixtures can also be hydrogenated in such a way that mixtures of vegetable and synthetic waste, optionally with the addition of biomass, are reacted in different stages under conditions in which essentially the hydrolytic and hydrogenating conversion of vegetable or paper fraction and biomass Share and on the other hand, the hydrogenating reaction of the synthetic organic waste takes place. Both stages can also be carried out in the presence of a hydrogen donor solvent.

Thus, in the 1st stage, a hydrogenating treatment may optionally be carried out in the presence of hydrogenation catalysts and a pressure of 1 bar to 150 bar, preferably 25-60 bar, preferably in the presence of water and other protic solvents such as alcohols.

Subsequently, the oils obtained predominantly from the vegetable fraction can be separated off by solvent extraction, after which the nonhydrogenated split fraction in the second stage can likewise be split in a hydrogenating manner under conditions already described.

The stepwise processing can also be carried out in such a way that vegetable parts or paper components or biomass have been cleaved hydrolytically in the first stage, for example in the presence of alkalis or acids, this reaction may optionally take place in the presence of CO, and preferably in the presence of water and / or other protic solvents such as alcohols and in the second stage of the synthetic or predominantly synthetic fraction is hydrogenated.

Alternatively, the waste and / or biomass can be separated into a vegetable portion and a synthetic portion and processed separately under the conditions described.

Also in these cases can be worked both with and without catalysts. If necessary. can be dried before the 2nd stage.

"Steps" in the present invention are to be understood as meaning that a particular stage, such as the one mentioned above

1st stage for the hydrolytic degradation of the vegetable portion, itself again consist of several parallel or successive stages connected.

Further examples follow, whereby even in the experimental conditions not indicated in Tables 1-7 of 50-500 bar pressure, 200-600 ⁰ C and residence times of 1 min. until 8 hours good results were obtained:

The experiments summarized in Table 1 were carried out in autoclaves at 45O ⁰ C and 100 bar (cold) with synthesis gas. As a dripping oil, a cracking vacuum distillate was used in relation to the waste of 3: 7. The residence time was 4 hours. It was worked without catalyst.

Table 1

sales CO-CO ₂ hydrocarbons Siedepkt. <390 ⁰ C% by weight Siedepkt. > 390 ⁰ C% by weight feedstock 99.5 0.5-3 C ₁ -C ₄ KW's% by weight 42-93 0.5 to 56.5 Plastic waste ¹ 99.3 2 1-6 82 14 Green bin ² 98 19 2 52 19 Foam ³ 97 1-6 10 35-52 7-54 carpet 99.7 0.5 10-35 93 5.5 Mixture v. Polyethylene Polypropylene, polystyrene 98.5 3 1 58 35 Mixture of tires polyethylene, Plexiglas 4

1 mixture of polyethylene, polypropylene, polyacrylates, rubber, tires, polystyrene

2 synthetic organic waste components including PVC from a daily sample of a waste separation plant

3 polyurethane / polystyrene

Polystyrene increases the proportion of aromatics. In the plastic waste mixtures used, the proportion of aromatics was about 25% by weight.

Analogous results are obtained at elevated hydrogen pressure, whereby shorter residence times can be set. Table 2 shows the results of the hydrotreating obtained in a refuse separation plant synthetic component with a proportion of 15wt .-% of chlorine-containing polymers are summarized in dependence upon the hydrogenation at 450 ⁰ C. The pressure was 200 bar (cold). As addition component, except for the last attempt, a used machine oil was used in relation to the drop of 1: 2.3. It was worked without catalyst.

Table 2

Sales in (%) KWs with Spt. <390 ° C Hydrocarbons / boiling ranges <180 ° C% by weight 180-390 ⁰ C% by weight > 390 ⁰ C% by weight Reaction time Stdn. 59 C ₁ -C ₄ KWs% by weight 24 34 41 2 81 1 34 45 19 4 86 2 47 18 14 4 ¹⁾ 89.5 21 47 14 10.5 ₄ 2> 97 28.5 56 20 3 6 99 21 65 11 1 ₆ 3. 23

After 2 hours, the mixture was cooled, relieved of pressure and re-pressed 200 bar H ₂ .

2 With bitumen addition in the ratio waste to bitumen 2: 1.

3 With "Eigenör" (180-390 ° C)

Table 2 shows that at constant temperature, the yield of hydrocarbons with boiling point <180 ° C increases from 4% by weight (2 hours) to 65% by weight (6 hours) while the proportion of high boiling fraction with boiling range> 39O ⁰ C decreases from 21% by weight to 1% by weight. If the fraction boiling range 180-390 ⁰ C is used as "own oil" in admixture with a waste feed, then the own oil is converted almost quantitatively into low-boiling hydrocarbons.

Subsequent hydrogenating refining allows the halogen content in the product fractions to be eliminated almost quantitatively (<1 ppm). The entire hydrocarbon product may also be hydrogenated as such.

By way of example, a hydrocarbon fraction obtained from synthetic green litter waste and boiling between 180 and 390 ° C. and containing 2,400 ppm of chlorine was subjected to hydrogenating refining at 50 bar hydrogen pressure and 270 ^° C. In the product obtained, chlorine was no longer detectable ,

FIG. 4 shows the dependence of the yield on the individual fractions as a function of the temperature at a residence time of 2 hours.

Substantially similar results are obtained when synthetic waste is used without the addition of a drift oil and when petroleum residual oils are used along with the waste.

Again, the waste is almost quantitatively implemented, at the same time there is a hydrogenating splitting of the petroleum residue.

Mixtures with lignite and hard coal are also hydrolytically fissile with very good results. This also applies in the presence of other mineral oils.

Tables 3 and 4 show results obtained in the hydrogenation of a mixture of synthetic waste components, including PVC, from a daily sample of a waste separation plant containing 10-50% by weight of vegetable portion and a mixture of synthetic waste with 20-60% by weight. % Waste paper. It was at 450 ⁰ C a pressure of 200 bar and a residence time of 4h. worked without catalysts.

A vacuum distillate from a coal hydrogenation in the ratio of waste to VD of 3: 1 was used.

In addition to the indicated products, unrecognized water was formed in the tables.

Table 3

Feedstock Synthetic content to vegetable. Share (wet) from green tub sales COVCO ₂ % by weight C ₁ -C ₄ KWs% by weight Sdpkt. <390 ° C% by weight Sdpkt. > 390 ° C% by weight 9: 1 99.5 3 3 79 15 8: 2 99.6 4 5 74 17 1: 1 99.6 7 10 63 20 2: 8 vegetab. Proportion dried 78 5 16 50 29 Table 4 Feedstock Synthetic fraction to waste paper content (moist) from green tub sales CO / CO ₂ % by weight C ₁ -C ₄ KWs% by weight Sdpkt. <390 ° C% by weight Sdpkt. > 390 ° C% by weight 80:20 99.5 5 5 65 25 66:34 99.5 7 11 49 33 40:60 99.5 13 9 41 37

Table 5 shows conversion and yield as a function of catalysts.

It was carried out at 450 ⁰ C, 200 bar pressure and 4 hours residence time. As Zumischkomponente a used spindle oil was used in the ratio spindle oil to waste of 1: 2.

The waste used was the synthetic organic fraction of a waste separation plant. The conditions were chosen to compare with the previous tables. However, similar results are obtained even under variation of conditions.

Table 5

Sales at KWs with Sdpkt. <390 ⁰ C C ₁ -C ₄ KWs% by weight boiling ranges 180-390 ⁰ C% by weight > 390 ⁰ C% by weight catalyst 81.4 2 <180 ° C% by weight 45 15 - 88 1 38 46 12 Ni / Mo / Al ₂ O ₃ 98 14 41 26 2 Ni / Mo / aluminum silicate 92 11 58 43 8th Fe (I) acetylacetonate 92 9 38 50 8th Ni (II) acetate 90 6 33 31 10 Hearth furnace coke +5 wt.% FeS (Xi 53

The table shows that by hydrogenation catalysts such as Ni / Mo / aluminum silicate also very high conversions can be achieved, at the same time a high proportion of fractions having a boiling range below 390 ⁰ C is obtained. By iron and nickel catalysts can in particular a high proportion of compounds of boiling range 180-390 ⁰ C win, while can be with catalysts such Herdofenkoksund FeSO _{4 win} a high proportion of compounds of boiling range <180 ⁰ C. By varying the temperature, pressure and residence time, the specified selectivities can also be varied. In continuous experiments, with a residence time of 2 hours at 450 ⁰ C and a pressure of 200 bar 2 kg / h of synthetic organic waste in a petroleum residue oil in the ratio 30:70 reacted, with no catalyst, with Ni / Mo / aluminum silicate and with Herdofenkoks / FeS0 _{4 was} worked. Here, as Table 6 shows, the results obtained in Tables 2 and 5 could be significantly improved. The experiments were run over 700 hours each.

Table 6

Sales at KWs with Sdpkt. <390 ° C boiling ranges C ₁ -C ₄ KWs% by weight <180 ° C% by weight 180-390 ° C% by weight > 390 ° C% by weight catalyst 88 1.5 39.5 47 12 - 99 10 65 24 1 Ni / Mo / AI. silicate 93 4 58 31 7 I ^- hearth furnace coke 1 + 5 wt.% FeSO ₄

A similar result was obtained with a used machine oil additive in place of petroleum residual oil. Slightly better results were obtained with an addition of 25% by weight petroleum residual oil and 75% by weight self-oil (180-390 ° C.) as shown in Table 7.

Table 7

Sales at KWs with Sdpkt. <390 ° C boiling ranges Ci-C ₄ KWs% by weight <180 ° C% by weight 180-390 ° C% by weight > 390 ⁰ C% by weight catalyst 89 2 38 49 11 - 99 7 68 24 1 Ni / Mo / AI. silicate 95 3 62 30 5 Stove coke + 5% by weight FeSO ₄

Since hydrogen is becoming increasingly important and is already being produced in numerous companies, be it by synthesis gas production, by electrolysis or photoelectrolytes and also by pipelines can be transported over long distances, can in many selected locations, especially in the vicinity of population centers according to the present invention large-scale plants which can dispose of entire regions of waste, avoiding landfills, especially special landfills and avoiding waste incineration, which, as described above, creates additional unresolved problems.

In contrast to waste incineration plants which involve a high CO ₂ load and pyrolysis plants in which large quantities of gases are produced, valuable liquid products are produced in the present invention, so that recycling of consumer products is ensured in an outstanding manner.

While, as described in the prior art, the experts have endeavored in a complicated other direction and despite an urgent need for a satisfactory disposal of waste was previously unable, the present invention is suddenly shown an excellent solution.

Claims (10)

claims: 1. A process for the processing of carbon-containing waste, characterized in that plastics or plastic mixtures, optionally in admixture with rubber, tires, textiles, industrial waste and the like with molecular hydrogen and / or with molecular hydrogen-containing gases at a temperature of 200 600 ⁰ C, preferably at a temperature of 200-540 ⁰ C, at a pressure of 30-500 bar, preferably from 50-450 bar and a residence time of 1 minute to 8 hours, preferably from 15 minutes to 6 hours are reacted to Ci ^ ^ Hydrocarbons, hydrocarbons boiling in the gasoline range and medium and heavy oils. 2. The method according to claim 1, characterized in that the waste to be hydrogenated mixed with petroleum and / or petroleum components, in particular petroleum residues and / or coal and / or coal components and / or oil shale and / or oil shale components and / or oil sands and / or bitumen and / or asphalt and asphaltenes. 3. Process according to claims 1 and 2, characterized in that one works without a catalyst. 4. Process according to claims 1 and 2, characterized in that is hydrogenated in the presence of so-called disposable catalysts. 5. Process according to claims 1, 2 and 4, characterized in that dusts and ashes from coal processing, which are optionally doped with hydrogenation-active metals and / or compounds thereof, are used as catalysts. 6. Process according to claims 1, 2, 4 and 5, characterized in that in the presence of hearth furnace coke and / or Winkler dusts, z. As HTW dust (high-temperature Winkler dust) and ash and / or HKV dust (high-temperature coal gasification), which are optionally doped with hydrogenation-active metals and / or compounds thereof, is working. 7. Process according to claims 1, 2, 4, 5 and 6, characterized in that in the presence of iron-containing catalysts, which are optionally doped with further hydrogenation-active metals and / or compounds thereof, is worked. 8. Process according to claims 1, 2, 4, 5, 6 and 7, characterized in that in the presence of nickel and / or molybdenum and / or tungsten and / or cobalt-containing catalysts, if appropriate, working on carriers. 9. Process according to claims 1 to 8, characterized in that working with Anreibölen. 10.A method according to claims 1 to 9, characterized in that in the presence of Self-oil is hydrogenated.
11.Verfahren according to claim 1, characterized in that the VEBA Kombicrack method is used.
12. The method according to claims 1 and 11, characterized in that the VEBA Kombicrack method is used in a modified form. 13.Verfahren according to claim 1, characterized in that the VEBA LO cracking process is used.
14. The method according to claims 1 and 13, characterized in that the VEBA LO cracking process is used in a modified form. For this 4 pages drawings