NO854663L - PROCEDURE FOR THE PREPARATION OF CARBON-CONTAINED WASTE AND BIOMASS. - 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

The invention relates to a method for preparation

of carbonaceous waste and biomass by hydrogenating these at elevated temperature and a hydrogen pressure of at least 1 bar.

It is known to the public and the professional world that the worldwide waste is an increasing burden on the environment.

Since decades until today, waste is stored in depots, e.g. in abandoned pits, quarry pits and in other places. For a long time, the chemical structure of the waste and its long-term effects on the soil and groundwater have not been taken into account.

In recent times, certain waste has been stored in so-called special landfills. Hereby, efforts are being made to seal the landfills above ground water

and soil. Over a longer period of time, however, there is also a danger to the surroundings to be feared.

The professional world has therefore for some time been intensely striving to develop resp. processing of waste, firstly to protect the environment, and secondly to extract useful products from the waste. Thus is mentioned in "The Oil and Gas Journal", Dec. 25, 1978 page 80 a pilot plant, in which, by means of pyrolysis, plastics could be converted into gas and oil.

In "Hydrocarbon Processing" April 1979, page 183, incinerators are mentioned especially for special waste.

The biochemical degradation of plastics was also under-

applied (see e.g. European Chemical News", September 1979,

page 28). In "Chemical Engineering", 13 August 1979, page 41, a method is described according to which hazardous waste is embedded in hardening material, e.g. cement.

An overview of the most important methods is given in "Chemical and Engineering News" October 1, 1979, page 34.

Here, the gasification of biomass, namely wood waste and the like to carbon monoxide and hydrogen, is discussed in particular. On page 36, left-hand column of this publication, an experimental program for converting crushed wood suspended in water with hydrogen in the presence of Raney nickel as a catalyst is also mentioned.

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

Fluidized bed combustion and waste are discussed in "Chemiche Indu-strie". XXXII, April 1980, page 248. Conversion of the waste and biomass is heated with water and alkalis, discussed in "Chemistry International", 1880, No. 4, page 20.

Numerous other publications have also become known.

In recent times, above all the combustion in the most modern plants was further developed and large plants were created that work according to this method. Although dedusting and flue-gas washing are integrated in such facilities, the conversion of the waste into (and water) is an inevitable consequential problem.

Especially with regard to the enrichment of the atmosphere, C02 production is undesirable. Furthermore, harmful substances are also avoided by careful cleaning, thus e.g. heavy metals, SO2, NO^ and others in small amounts in the atmosphere.

In the meantime, pyrolysis is also being operated on a technical scale (see for example "Vereinigte Wirtschaftsdienste GmbH", 4 October 1985 page 9). However, pyrolysis has the disadvantage of predominantly forming gaseous products and a heavily soiled coke residue.

The problem of waste and biomass processing is therefore, as before, not satisfactorily solved.

A surprising, compared to the state of the art, significantly more favorable solution to this problem, especially with a view to the production of very large quantities of valuable products, is disclosed in the present invention which

relates to a method for processing carbonaceous waste and biomass, the method being characterized in that the carbonaceous waste and/or biomass is reacted with hydrogen and/or hydrogen-containing gases, and/or hydrogen-transferring compounds, in a temperature range of 75-600°C with a pressure of 1-600 bar, preferably of 2-500 bar,

and a residence time of from 1 minute to 8 hours, preferably from 15 minutes to 6 hours.

The method according to the invention makes it possible to process waste from which organic components such as glass, metals, stone materials and the like have been removed, without further sorting into valuable hydrocarbons, i.e. into C1-C4~hydrocarbon gases into hydrocarbons boiling in the petrol range, and into medium and heavy oils which can used as diesel oil and for heating purposes. According to the invention, unsorted materials are also processable, especially so that carbon-containing waste of synthetic origin such as, for example, plastics, resp. plastic mixtures, rubber, tires, textile waste, from which the vegetable part or the biomass part is at least roughly separated and then subjected to a separate hydrogenating treatment possibly together with industrial waste, such as e.g. lacquer and paint residues, and organic chemicals, industrial production waste, organic, synthetic shredder waste from the car industry, clear sludge or with used oils and the like. In this way, partly other waste such as paper, food residues, agricultural and forestry waste, wood, plants and the like can be separated as best as possible, however also

to some extent remain in the synthetic part.

Household rubbish can therefore, for example, be processed in such a way that at least plastics, rubber-textile residues or the like are roughly separated, and subjected separately to the hydrogenating treatment, e.g. together with used tires and/or plastic, and/or chemical waste from industry, and/or used oils and the like. Even in synthetic single components, under the conditions according to the invention, valuable liquid products are very easily processable.

Method according to the invention is also very well suited for the joint hydrogenating treatment of said waste or waste mixtures with carbon, carbon components, such as carbon oil residue, carbon oil, pyrolysis oils, petroleum, petroleum residues, other petroleum components, oil shale, oil shale components, oil sand, bitumen and the like, resp. mixtures of these materials.

The separation of the above-mentioned inorganic materials from the carbonaceous materials can be carried out according to the state of the art. These inorganic materials can be landfilled if they are not further processed. Crushing and separation of waste materials and biomass can also be carried out in

keep to the state of the art. If apparatus conditions do not oppose them, the method according to the invention can also be carried out in the presence of inorganic materials.

Constituents in waste that cannot be converted into hydrocarbons, such as e.g. sulphur, nitrogen, oxygen and halogens in the form of their compounds, appear at the hydrogenation reactor output as hydrogen compounds in gaseous form, i.e. as H2S, NH^, HC1, H20, and others.

It is the state of the art to separate these compounds by gas washing and possibly add them to further processing. Also the formation of dangerous substances formed by combustion

like for example. of NO X , S0 2~ . or of dioxins is avoided according to the present method. Likewise, highly combustible plastics such as polyvinyl chloride can be processed without risk.

The hydrogenation of the carbonaceous waste can through

is carried out without a catalyst with very good results. Partially even better results with regard to turnover and selectivity of fractions and specific boiling ranges can be obtained in the presence of catalysts such as, for example, in the presence of Fe, Mo,

Ni, CO, W, and other hydrogenation-active metals and/or their compounds, as these can consist of some, or at least two of these components and the metals and/or their compounds can be used on carriers, e.g. on aluminum oxide, silicon dioxide, aluminum silicates, zeolites and other carriers known to those skilled in the art, or carrier mixtures or without carriers. Certain zeolites as such are also suitable.

Further suitable catalysts can be so-called disposable catalysts, such as coke, Winkler gasification dust, dust and ash resulting from the hydrogenating gas treatment of carbon to methane (HKV dust), but also iron oxide-containing mixtures such as red mud, Bayer pulp, lux pulp , dust from the iron industry and others, since these materials can also be doped with hydration-active metals, and/or metal compounds, especially with heavy metal salts, such as e.g. iron salts or salts of chromium, zinc, molybdenum, tungsten, manganese, nickel, cobalt, further also with alkali, alkaline earth, and others, as well as with mixtures of these compounds. The catalyst can be at least partially pre-treated sulphiding.

The hydrogenating treatment can take place within wide pressure and temperature limits, namely at 75-600°C and 1-600

bar.

The hydrogenating treatment with and without catalysts of mixtures of synthetic waste such as plastic, and plastic mixtures, rubber, tires, textile waste, industrial waste and the like as well as their mixtures, since it can be worked in the presence of expelling oils, and can be worked in mixtures with carbon, carbon components, petroleum, petroleum residues and other petroleum constituents, oil shale, oil shale constituents, oil sands and its constituents, bitumen and similar materials, takes place at pressures of 30-500 bar, preferably at 50-450 bar. The temperature is at 200-600°C, preferably at 200-540°C, the residence time is at 1 minute to 8 hours, preferably at 15 minutes to 6 hours.

Different hydrogen qualities can be used as hydrogenation gas, including methyl mixtures, e.g. CO, C02, H.>S, methane, ethane, water vapor and the like. Very suitable are hydrogen qualities such as those produced by gasification reactions of carbonaceous materials with water vapour. Such materials can be residues from the processing of mineral oil or from coal, wood, peat and residues from coal processing, for example hydrogenation. Biomasses or those separated from household waste are also vegetable parts.

Pure r^ qualities, such as electrolytic hydrogen, are of course also very suitable. Thus, according to the invention, for example, household waste can first be separated into vegetable and synthetic part, and then the vegetable part is added to produce hydrogen for a gasification, while the synthetic part is subjected to the hydrogenating treatment.

The vegetable part can also be added to a pre-fermentation or other formation. The used products, usually strongly freed of inorganic materials, possibly dried, crushed or melted or mixed with expeller oil or other additives, are brought as such or mixed with catalysts to reaction temperature and treated in the reaction zone with hydrogenation gas.

In cases where, at an elevated temperature, there is already a pumpable slurry in the mixing container, the product used can be pumped into hydrogenation. To produce the pumpable porridge, a so-called expelling oil that appears in the process and can originate from various sources in the plant can be added. However, the expelling oil can also

be a foreign oil not originating from the plant.

Finally, water or steam can also be added. The addition of, for example, petroleum components, bitumen or carbon components can also result in a pumpable slurry.

However, the used product can also be transported using transport conveyors, including transport devices corresponding to the state of the art into the hydrogenation reactor.

The reaction zone can consist of one or more reactors connected one behind the other or in parallel. Downstream behind the reactor or reactors, there is usually at least one heat separator as is known from sump-phase hydrogenation in which a separation takes place at hot-separation temperature into gaseous components that are removed and in the heat separator sump.

The gaseous parts are cooled, as liquid hydrocarbons are produced which are further processed according to the state of the art, such as for example by further hydrogenating cleavage steps, resp. refining step of distillative separation. In part, however, these can also be traced back to

ning of the product used. Non-condensed gases are freed by means of gas washing for I^S, NH^, HC1, possibly also CO and C02.

The hydrogen in the gas formed can be returned as hydrogenation gas to the hydrogenation reactor or reactors.

A processing of the lower hydrocarbons contained in the gaseous products, e.g. steam reforming is also possible, as extra hydrogen is also produced. The products from the gas phase and the heat separator, especially the products that are liquid under normal conditions, can, as already mentioned above, be fed to a refining step which usually works hydrogenatingly. In addition, small amounts of heteroatom-containing compounds present can thereby be completely hydrogenated so that the products are then practically sulphur-, nitrogen- and halogen-free. Higher-boiling fractions can at least be fed to a cracker, especially a hydrocracker. From the processing, in cases of need, certain quantities can also be fed back evenly into the waste hydrogenation resp. before the waste hydrogenation.

The heat separator sump can be prepared in different ways,

e.g. by vacuum distillation, as the sump of the vacuum distillation can be supplied with gasification to H and CO. In this case, the gases formed by gasification are preferably integrated into the above-mentioned washings and gas processing. However, the vacuum distillation residues can also be coked and deasphalted, or further processed according to other methods according to the state of the art. The residues and ashes formed contain the metallic contaminants that can be deposited according to the state of the art, but they can also be added to a recovery of the metals in the metallurgical industry or possibly used as catalysts in the waste hydrogenation. The heat separator sump or -residuu can, however, also be subjected to an overcritical extraction, such as e.g.

with propane, butane or higher-boiling hydrocarbons, which can be taken from the process itself. Hereby, the extractant can at least partially already be introduced into the hydrogenation reactor itself in order to achieve the desired degree of extraction. The heat separator sump can also be used as stripping oil, as well as vacuum distillation residue, especially after deasphalting.

In fig. 1 shows, for example, the method according to the invention with exemplary follow-up steps.

In fig. 2 shows an example of the method according to the invention with a pre-connected solvent treatment.

In fig. 3 shows a combination of a used oil refinery with a method according to the invention.

In fig. 4 shows the dependence of the yields in the individual fractions in dependence on the temperature.

Fig. 1 will be explained in detail in the following.

The waste materials are crushed in the mixing equipment (1) as, if necessary, in connection with (1) or before (1) an additional grinding of the used goods can take place* In addition, a liquid (rubbing) oil can be added, which is taken out from the produced liquid products, or a foreign oil (2a) is added to the container (1). Catalyst (3) can also be added to the container (1). During the supply of hydrogen (4) resp. hydrogen-containing gas, the used material is hydrogenated in the reactor (5).

Instead of the reactor (5), several reactors can also be used. From (5) the hydrogenated product comes to the heat separator (6). Here, a separation takes place into gaseous product (7) at the heat separation temperature, which enters the separator (9) over the heat exchanger (8). In (9), liquid products are removed after cooling, while above the top, gaseous products are avoided.

The liquid products are processed in the usual way, e.g. by distillation or possibly hydrogenating cleavage of the heavier oil part, resp. by refining.

The gases are freed in (10) for admixtures of H2S, NH3. HC1, CO2 and the like. Hydrogen is cycled and returns before resp. in the hydrogenation reactor. Gaseous hydrocarbons can also be separated, and some or all of the hydrocarbons are converted by steam reforming (11)

to H2 and CO.

The liquid product is removed from the heat separator sump and supplied, for example, to a vacuum distillation (12). Here, additional oil (13) is produced which can also be used as stripping oil.

The vacuum distillation sump can, for example, be coked in (14). The products removed from coking over the top (15) also go to the plant's gas and liquid product processing.

The formed coke (16), which also contains ash constituents including metals, can be gasified (17), or, corresponding to the state of the art, can be deposited or partially used as a catalyst depending on the composition.

Alternatively, the vacuum distillation sump can be directly gasified

in (17). The formed gases (18) go to the plant's gas processing, but the formed ash (19) resp. the soot is deposited or can be burned or can be added to further processing, e.g. the metallurgical industry or can partially be used as catalysts depending on the composition.

Alternatively, the vacuum separator contents can be extracted with a supercritical gas. Propane, butane, naphtha mixtures or also hydrocarbon mixtures with a higher boiling point are suitable for this. The extract is further processed in the usual way. The remaining residue can be further processed as the heat separator sump, resp. - residue. The extracting agent can, especially in the case of several hydrogenation reactors connected one after the other, already be introduced at least partially into the reactor itself.

In the case of the product used with a relatively high content of heteroatoms such as sulphur, nitrogen or halogen, the liquid product from the separator (9) can first of all be subjected to a refining (20), usually a hydrogenating refining. The refined product enters a distillation (21), however, the distillates can also be subjected to a refinement. The sump of the distillation can in a cracking step

(22) is split into lower boiling products (23).

The one in fig. The processing shown in 1 is an example, and the hydrating processing according to the invention is not limited to waste, as the state of the art for products from hydrogenation reactors includes a majority of variants.

In the hydrogenating treatment of waste can also be used

oil or residues from used oil processing are used as shown in fig. 3.

Used oil can, for example, be used from a storage tank (1)

in a physical and/or chemical separation resp. treatment plant to remove solids, water and the like. Products pre-purified in this way can be used above (3) in the hydrogenation reactor (4) or in the refining (7).

Gaseous or liquid products from the heat separator

(5) of the hydrogenation can be added above (6) to the used oil refining (7). The sump from the distillation (8) of the refined used oil can be used above (9) in (4).

Waste to be hydrogenated is taken from storage (10) and arrives

primarily in a crushing and mixing container (11) from the used product above (12) comes to (4). For example, extra heavy mineral or carbon-derived oils can be added above (13). The heat separator sump or -residue, for example above (14) can be used in a gasification (15).

According to the invention, a solvent treatment with suitable solvents, especially a hydrogen-transferring solvent, can also be preceded by a hydrogenating treatment, then either the total mixture consisting of dissolved and undissolved can be fed to the hydrogenation reactor or a separation into dissolved and undissolved takes place behind the dissolving apparatus, and the solution or un- dissolved is supplied to the hydrogenation reactor or reactors. In the case of subsequent distillation, the solvent can be recycled in the usual way. Separated undissolved solids can also be added to a gasification or coking process.

Also in this process variant according to the invention, the product used can be hydrogenated in a mixture with carbon, and/or carbon components and/or petroleum residues and/or petroleum and the like.

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

Suitable solvents are e.g. tetralin, anthracene oil, isopropanol, cresol-containing oils, decalin, naphthalene, tetrahydrofuran, dioxane, however, also for example hydrocarbons, carbon or also from the plant itself, and oil and oxygen-containing hydrocarbons and oils. Finally, water or steam can also be added.

The use according to the invention of solvents is explained in more detail, for example, in fig. 2.

In container (1) at least partially dissolve resp. be suspended

the crushed goods at an elevated temperature. In facility (2), a separation can take place from undissolved, which for further processing, for example, leads to coking

(3) or a gasification (4). The solution or suspension is now hydrogenated in the hydrogenation reactor or reactors (5). Hydrogen-transferring solvents are preferably used, such as e.g. tetralin, decalin, anthracene oil, creosote oil or also higher-boiling oils and the like, so that the hydrogenation can also be carried out at low hydrogen pressures up to in the region of 1 bar hydrogen pressure.

Residence time and hydrogen pressure are coordinated with each other during the hydrogenation according to the invention. The hydrogenation product can be worked up in the usual way, e.g. by distillation (6) .

1 a further example is worked in the presence of anthracene oil, as the waste material to be hydrogenated possibly in a mixture with carbon and/or mineral materials is primarily dissolved with the addition of strong acids, e.g. of hydrogen fluoride and/or p-toluenesulfonic acid at approx. 370 -

420°C and then optionally after separation of undissolved materials hydrogenated while adding salts such as SbCl,-, SbF^, and the like, as well as HF, resp. HC1, which is capable of the formation of stronger complex acids at 75-220°C, preferably at 150-200°C and 1-5 bar hydrogen, preferably 1-2 bar hydrogen. In a subsequent hydrogenation step, unsaturated products can be converted into saturated ones.

Also, for example, under the condition for SRC (Solvent Refined Coal) carbon hydrogenation, waste can possibly be converted

in a mixture with biomass and possibly in a mixture with carbon and mineral materials, such as, for example, petroleum residues with high yields of distillable oils. Suitable conditions in the dissolution step are 380-480°C. In the hydrogenation step, work is usually done at 350-450°C and a pressure of 110-250 bar, preferably 120-220 bar, as the usual hydrogenation catalysts can be used.

The inventor's investigations have shown that methods developed for the hydrogenating carbon and petroleum residue processing are also applicable for the hydrogenating decomposition of carbon-containing completely different material-containing waste mixtures, especially synthetic parts of the waste, possibly in a mixture with carbon and mineral materials, although it also in simple or modified form.

However, non-limiting examples of such methods are the H-Oil method (HRI Inc. and Texaco Development Corp.). can with the procedure (Partec Lava-

lin Inc./Petro Canada), the LC-Fining method (Lummus Crest. Inc.), the Veba Kombikrack method (VEBA), VEBA

LO Krack method (VEBA) and RCD Unibon method (UOP Process Division Research Corp./UOP Co.), Resid-fining method (Exxon Research and Engineering Co.), Unicrack and Unicrack/HDS method, (Uinion Oil of California), the HC Unibon method (UOP Process Division

and UOP Inc.), the Isocracking process (Chevron Research Co.), the Heavy Oil Cracking process (Phillips Petroleum), the Dynacracking process (Hydrocarbon Research Inc.), the Linde-Hydroconverter process, and others.

In the cases in which these procedures apply

regarding immobilized catalyst methods, at least dissolved waste such as e.g. in carbon oil and petroleum oil resp. their components are hydrogenated according to the invention.

According to the invention, waste mixtures can also be processed and hydrogenated so that mixtures of vegetable and synthetic waste, optionally with the addition of biomass, are reacted in different steps under conditions where, on the one hand, essentially the hydrolytic and hydrogenating reaction of a vegetable or the paper part and the biomass part, and on the other hand the hydrogenating conversion of the synthetic organic waste. Both steps can also be carried out in the presence of a hydrogen donor solvent.

Thus, a hydrogenating treatment can take place in the first step, possibly in the presence of a hydrogenic catalyst, and

a pressure from 1 bar to 150 bar, preferably 25-60 bar,

preferably working in the presence of water and other protic solvents such as alcohols.

Subsequently, the oil formed mainly from the vegetable part can be separated from solvent extraction, after which the hydrogenating split part in the 2nd step can also be split hydrogenatingly under the conditions already mentioned.

The step-by-step processing can also take place so that the vegetable part or paper part or biomass can be decomposed hydrolytically in the first step, for example in the presence of alkalis or acids, as this reaction can possibly take place in the presence of CO, and is preferably reacted in the presence of water and/or other protic solvents such as alcohols and in the 2nd step it is reacted synthetic or predominantly synthetic part hydrogenating.

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

In these cases too, work can be done both with and without catalysts. If necessary, it can be dried before the 2nd step.

The "steps" are here to be understood as meaning that a specific step, such as the above-mentioned 1st step for hydrolytic degradation of the vegetable part, can itself again consist of several parallel or alternately connected steps.

Further examples follow, as good results were obtained even under test conditions of 5-500 bar pressure, 200-600°C and residence times from 1 minute to 8 hours not specified in Tables 1-7: The tests summarized in Table 1 were carried out in auto- piano at 450°C and 100 bar (cold) with synthesis gas hydrogen. A cracked vacuum distillate was used as stripping oil in a ratio of 3:7 to waste, the residence time was 4 hours. The work was done without a catalyst.

Using polystyrene increases the amount of aromatics. In the case of the plastic waste mixtures used, the aromatic part accounted for approx. 25% by weight.

Analogous results are obtained at elevated hydrogen pressure as it

shorter residence times can be set.

Table 2 summarizes the results of the hydrogenation treatment of the synthetic part formed in a waste separation plant, with a part of 15% by weight of chlorine-containing polymer, depending on the hydrogenation duration at 450°C. The pressure was at 200 bar (cold). As a mixing component, a used maxin oil in relation to waste of 1:2.3 was used for the last test. The work was done without a catalyst.

Table 2 shows that at constant temperature the yield of hydrocarbons with a boiling point <18 0°C increases from 24% by weight (2 hours) to 65% by weight (6 hours), while the part of the high-boiling fraction decreases in the boiling range > 390°C of 21% by weight to 1% by weight. If the fraction with a boiling range of 180-390°C is used as "own oil" in a mixture with the waste feed, then the own oil is also converted roughly quantitatively to lower-boiling hydrocarbons.

In the case of subsequent hydrogenating refining, the halogen content in the product fractions can be eliminated approximately quantitatively (< 1 ppm). The overall hydrocarbon product can also be refined hydrogenatingly as such.

For example, a hydrocarbon fraction boiling between 180 and 390°C boiling from synthetic waste with a content of 2400 ppm chlorine was subjected to hydrogenating refining at 50 bar hydrogen pressure and 270°C. In the product formed, chlorine was no longer detectable.

In fig. 4 shows the dependence of the yield of the individual fractions in dependence on the temperature with a residence time of 2 hours.

Essentially similar results are obtained when synthetic waste is used without the addition of a stripping oil, and when petroleum residual oil is used together with the waste.

Here, too, the waste is converted roughly quantitatively, as a hydrogenation of petroleum residue takes place at the same time. Mixtures with lignite and hard coal are also hydrogenatingly cleavable with very good results. This also applies in the presence of other mineral oils.

Tables 3 and 4 show results obtained by 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 matter as well as a mixture of synthetic waste with 20 to 60% by weight of waste paper . The work was carried out at 450°C, a pressure of 200 bar and a residence time of 4 hours without a catalyst.

A vacuum distillate from a carbon hydrogenation was used in a ratio of waste to vacuum still of 3:1. In addition to the specified products, water not specified in the table was formed.

Table 5 shows turnover and yield depending on the catalyst.

The work was carried out at 450°C, 200 bar pressure and a residence time of 4 hours. As admixture component, a used one was used

spindle oil in a ratio of spindle oil to waste of 1:2.

The synthetic organic part of a waste separation plant was used as waste. The conditions were chosen to be able to be compared with the previous tables. However, similar results were also obtained by varying the condition.

The table shows that with hydrogenation catalysts such as Ni/Mo/aluminosilicate, very high conversions can also be achieved, as a high proportion of fractions with a boiling range below 390°C are obtained at the same time. With the help of iron and nickel catalysts, a particularly high proportion of compounds with a boiling range of 180-390°C can be produced, while with catalysts such as furnace coke and FeS04, a high proportion of compounds with a boiling range of <180°C can be produced.

In case of variation in temperature, pressure and residence time, they allow

given selectivities likewise vary.

In continuous experiments, with a residence time of 2 hours at 450°C and a pressure of 200 bar, 2 kg/h of synthetic organic waste was converted into a petroleum residual oil in a ratio of 30:70, as the work was carried out without a catalyst with Ni/Mo/aluminium silicate and more blast furnace coke/FeSO^. Thereby, as table 6 shows, the results obtained in tables 2 and 5 could also be considerably improved. The experiments were carried out over resp. 700 hours.

The corresponding result was obtained in a used machine oil as an additive instead of petroleum residual oil. Even better results were obtained in an addition of 25% by weight of petroleum residual oil and 75% by weight of native oil (180-390°C) as Table 7 shows.

Since hydrogen is becoming increasingly important and is already produced in numerous companies today, whether it is by synthesis gas production by electrolysis or photoelectrolysis and can also be transported via pipes over large distances,

large-scale facilities according to the invention can be set up in numerous selected locations, above all in the presence of hubs, which can supply entire regions with waste while avoiding landfills, especially also special landfills and while avoiding waste incineration which, as mentioned above, causes additional unsolved problems.

Unlike waste incinerators which entail a

high C02 load and pyrolysis plant in which large quantities of gas are produced, valuable liquid products are produced with the help of the invention so that the recycling of the consumer products is ensured in an excellent way.

While, as the state of the art mentions in the professional world, the work has gone in a considerably different direction, and despite the urgent need, until now, was not able to satisfactorily remove waste, the present invention shows a surprisingly excellent solution.

Claims (17)

1. Process for processing carbonaceous waste and biomass, characterized in that the carbonaceous waste and/or biomasses are reacted with hydrogen and/or with hydrogen-containing gas, and/or hydrogen-transferring compounds (hydrogen-donor-solvent) in a temperature range of 75- 600°C, at a pressure of 1-600 bar, a preferred pressure of 2-500 bar and a residence time of from 1 minute to 8 hours, preferably 15 minutes to 6 hours. 2. Method according to claim 1, characterized in that hydrogenating mixtures of waste of synthetic origin and/or of vegetable origin, possibly containing waste paper, and/or biomass are treated. 3. Method according to claim 1, characterized in that mixtures of carbon-containing waste of synthetic or predominantly of synthetic origin at a temperature of 200-600°C, preferably a temperature of 200-540°C, and a pressure of 30-500 bar, preferably 50-450 bar, and a residence time of 1 minute to 8 hours, preferably 5 minutes to 6 hours. 4. Process according to claim 1, characterized in that a hydrogen donor solvent is used and reacted hydrogenatingly at a temperature of 75-500°C, preferably 80-480°C and a pressure of 1-300 bar, and a residence time of 1 minute to 8 hours, preferably 15 minutes to 6 hours. 5. Method according to notch 1, characterized in that in a first step it is reacted with or without a hydrogen donor solvent in the presence of a protic solvent, in particular water at a pressure of 1-150 bar and a temperature of 75-500°C, and in a second step at a temperature of 200-600°C, preferably 200-540°C and a pressure of 30-500 bar, preferably 50-480 bar. 6. Method according to claims 1-5, characterized in that an essentially hydrolytic step is connected before the hydrogenating treatment. 7. Method according to claims 1-6, characterized in that the waste and/or biomasses to be hydrogenated are converted into mixtures of petroleum and/or petroleum constituents, especially petroleum residue, and/or carbon, and/or carbon constituents, and/or oil shale, and/or oil shale components, and/or oil sand extract, and/or bitumen, and/or asphalt or asphaltenes. 8. Method according to claims 1-7, characterized in that work is carried out without a catalyst. 9. Method according to claims 1-8, characterized in that it is hydrogenated in the presence of so-called disposable catalysts. 10. Method according to claims 1-9, characterized in that the catalyst used is dust and ashes from carbon processing which are optionally doped with hydrogenation-active metals and/or their compounds. 11. Method according to claims 1-10, characterized in that the catalyst is worked in the presence of blast furnace coke and/or Winkler dust, e.g. HTW dust (high temperature Winkler dust) and ashes, and/or HKV dust (high temperature carbon gasification), which may be doped with hydrogenation-active metals and/or their compounds. 12. Method according to claims 1-11, characterized in that work is carried out in the presence of iron-containing catalysts which are optionally doped with further hydrogenation-active metals and/or their compounds. 13. Method according to claims 1-12, characterized in that work is carried out in the presence of Ni and/or molybdenum and/or tungsten and/or cobalt-containing catalysts, possibly on supports. 14. Method according to claims 1-13, characterized in that work is done with extraction oils. 15. Method according to claims 1-14, characterized in that the products from the hydrogenating reaction are at least partially subjected to a hydrogenating refining. 16. Method according to claims 1-15, characterized in that the carbon-containing waste and/or biomass to be hydrogenated is at least partially dissolved and then hydrogenated. 17. Method according to claims 1-16, characterized in that the reaction is hydrogenating in the presence of native oil.