DE102005040490A1 - Apparatus and Process for a Biofuel Refinery: Direct thermochemical conversion of organic substances to liquid fuels - Google Patents

Abstract

The invention describes a process for the direct thermochemical conversion of organic substances into high-quality organic products which are present as low-viscosity liquids at room temperature and are flammable. The two-stage direct liquefaction process is characterized by very rapid heating of the raw materials with subsequent pressureless oiling or previous pressureless oiling, i.e. first a pressureless catalytic oiling with subsequent rapid heating of the raw materials and execution of the conversion reactions in the autocatalytic cycle of low-volatility product fractions in a sump-phase reactor with a selective productive reactor Dwell time control. As a result, unexpectedly good quality and yield of the products are achieved, necessary reaction temperatures and pressures are considerably reduced and the amount of additional catalysts to be used is greatly reduced. Surprisingly, additional catalysts can in some cases be completely dispensed with. Furthermore, with the two-stage liquefaction, the oxygen content and the sulfur content can be reduced more than in any other process. The lowering of the necessary overpressures relates in particular to applications in which the conversion reactions are carried out under a reducing or hydrogenating gas atmosphere. Furthermore, the number of substances which can be converted into liquid oils is increased to an unexpected extent. This mainly concerns the ...

Description

The The invention relates to a process for direct thermochemical conversion from organic substances to high quality organic products that present as low viscosity liquids at room temperature and flammable are.

organic Substances are here carbon-containing substances or substance mixtures, consisting of long-chain or crosslinked molecules. On the one hand, this can be renewable Raw materials such as biomass, energy crops or vegetable oil and animal fat and waste materials starting from hydrocarbons such as plastic waste, waste oils and Heavy oils, over lignocelluloses of vegetable origin, including their processed products like contaminated wood waste and corresponding household waste fractions up to protein-containing Problematic substances of animal origin such as animal and bone meal. Furthermore counting this sediment with increased organic components such as fine-grained Screening fractions of dredged material from harbor waters and sewage sludge.

Under high quality organic products are low viscosity liquids with high hydrocarbon content and high added value like z. B. petrochemical recyclables and engine fuels to understand. With regard to the target products, which are preferably pure hydrocarbons, d. H. consist only of the elements carbon and hydrogen, The organic components of the raw materials can be characterized according to their heteroatom content. Heteroatoms are other atoms in this context as carbon and hydrogen. Here come in particular oxygen and nitrogen but also halogens as well as sulfur, phosphorus etc. in question. For example, raw materials with a low content of heteroatoms are Old and heavy oils but also polyethylene and similar plastics. For example, high heteroatom content ingredients include biologicals Substances of plant and animal origin.

Separately of these organic raw material fractions are the inorganic constituents consider. These include Minerals or ash but also pure metals such. B. in electrical cable and car tire waste. The inorganic components of mentioned raw materials are very different according to content and composition. Old and heavy oils as well as pure plastic fractions but also pure biomass fractions usually contain very small amounts of ash. For bone meal and harbor silt against it can the inorganic content is more than 50% by weight.

The thermodynamically and chemically very demanding object of the invention It consists of both the inorganic side and the organic one Page to meet.

What As far as the inorganic side is concerned, it should follow the transformation process in an improved, freed from organic shares and reusable Form present. For example, in the case of heavy metals contaminated harbor silt The heavy metals are intended to be quantitatively in the inorganic fraction be bound so that the organic products are free of heavy metals. At the same time, however, the integration of heavy metals in the inorganic matrix done so that they are then no longer elutable. Then the mineral product fraction can easily be dumped either or used in construction, for example. In the conversion the organic raw material shares are important, at the same time on the one hand high molecular weight, d. H. long-chain, organic compounds selectively to crack, so shorten, that exactly the desired one Molecule chain length range comes out, the example of diesel oil with a boiling range preferably from 200 ° C to 380 ° C approximately between 11 and 21 C. Atoms, and on the other hand, the heteroatoms under possible to selectively remove low losses of carbon and hydrogen. Here you can Desired mineral parts develop catalytic effect. In addition, not only inorganic Toxins like heavy metals but also organic toxins such as B. prions of animal and bone meal completely from the organic products are eliminated and rendered harmless, and it allowed to no new toxins such. As dioxins are generated.

The described combined overall task has not been satisfactorily solved with previously existing methods, and it is surprising that such a method is possible according to the invention in the case of the multitude of conceivable raw materials. Existing thermal processes, so-called pyrolysis processes, on an industrial scale for the conversion of organic waste materials usually use high temperatures above 800 ° C. In this case, measured in terms of the above-mentioned target product, too small molecules are generated, so that a gas product is formed, which can be directly recycled or used as synthesis gas. The disadvantages are the high temperatures on the one hand with regard to the energy efficiency and on the other hand in the case of chlorine-containing raw materials because of the risk of the formation of dioxins. Moreover, the gases produced require expensive gas purification processes, and the gas products are not direct but only after additional and thus cost-increasing conversion processes can be used as petrochemical recyclables or as conventional motor fuels.

In developing low-temperature flash pyrolysis process in the temperature range approximately between 400 and 500 ° C, for example, the direct liquefaction be performed by wood in fluidized bed reactors lead to low-grade oil products, by no means the quality standards of conventional Motor fuels correspond. The products usually have high oxygen and water content and thus low calorific values, are corrosive and usually thermodynamically unstable.

alternative under development direct thermochemical processes for liquefaction of woody Biomass work with water as a reaction medium under very high levels To press to about 200 bar and at temperatures up to about 400 ° C. The disadvantages are here for one the very high process pressures that require expensive equipment, and again the extremely bad Product quality. The liquid product is more of a viscous tar as an oil and on top of that has comparatively high oxygen contents and accordingly low calorific values. The hydrogenation is known under pressure in stirred tanks or flow reactors to improve product quality in liquefaction of organic substances with hydrogen deficiency such. As coals or from organic substances with elevated Oxygen content such. Wood. These methods are characterized by Uneconomically high costs due to very high operating pressures of over 100 bar, high consumption of expensive hydrogen, high residence times the substances to be reacted in the reactor, considerable catalyst use and unsatisfactory product yield.

Also in direct liquefaction Organic substances are pressures up to 100 bar and temperatures of 450 ° C necessary. The single-stage Hydrogenating pressure conversion is used to liquefy biomass at 400-450 ° C and 20-80 bar hydrogen pressure for the production of liquid fuels. It comes because of the high temperature to strong coking because the coke crystallization temperature is 420 ° C. In this technique it comes to elevated Deposits in the pipes, so the longer life and high Maintenance costs are the result. The procedure works after shock heating of the Raw materials in combination with heavy oil circulation with an integrated Sump phase reactor. This works only under difficult technical reactor technology. The reactor must have both distillation functions as well as Strippfunktionen meet around gas flows selectively record. Furthermore it is both in the hydrogenating pressure conversion as also in the case of catalytic octopuses to single-stage liquefaction solid biomass. Mass and energy balance: In this process can from 100% wood an oil yield of 31% oil however, the energy yield is 73%. Either the high oxygen and the high sulfur content is in these Procedure unsatisfactory.

Furthermore there is the catalytic pressure-free oiling (catalytic Kaken). Catalytic liquefaction of biomass at 350-400 ° C under atmospheric pressure for the production of hydrocarbon-rich liquid fuels. This Procedure was originally developed from used oils and from oil skippers To win fuels. The procedure always works with addition of catalysts. The temperatures can also be between 280 ° C to 350 ° C. A disadvantage of this method is the high catalyst content of about 1% of the raw material quantity as well as the high deposition products. The Dwell time is about 3 minutes, so that no very large throughputs are possible. Furthermore is the yield of organic substances unsatisfactory. mass and energy balance: In this process, from 100% wood, an oil yield of 50% oil however, the energy yield is 70%. Either the high oxygen as well as the high sulfur content is in both Procedure unsatisfactory.

The Invention solves the problems described surprisingly, by optimizing the conversion reactions in two phases. Depending on the application and raw material can only be in the first stage catalytic pressure-free Kraken be preceded and in the second stage the hydrostatic pressure conversion or vice versa. The System can be switched automatically.

version1:

In The first phase is after shock heating of the raw materials in the autocatalytic Circulatory semi-volatiles Product in a sump phase reactor under pressure with selective Product-oriented residence time control can be performed. In the second phase, the raw material is in a pressureless rotary reactor processed. In this process, the reasons may be based on the raw material, that e.g. the raw materials are under pressure before being converted to get prepared.

Version 2:

Becomes e.g. switched the hydrostatic pressure conversion to the second stage, thus, e.g. the oxygen content and the sulfur content continue be lowered, the oil yield and the energy yield can be significantly increased.

This completely novel bundle was made renatural measures leads to completely unexpected results. At the same time, surprisingly good quality and yield of the products are achieved, necessary reaction temperatures and pressures are lowered, and the amount of additional catalysts to be used is greatly reduced. In some cases, it is even possible to completely dispense with additional catalysts. These extremely positive and unpredictable results put the direct thermochemical liquefaction of organic raw materials in the economically very attractive range. Moreover, the number of substances that can be converted into low-viscosity oils is being expanded to a previously unimaginable extent. This mainly concerns the residues, the sorted waste and the biological residues and problem substances. For the process according to the invention of central importance is the shock heating with subsequent pressureless oiling. It is achieved by heating the raw materials to reaction temperature in a few seconds or fractions of a second. This rapid heating according to the invention can be realized for example by direct introduction of sufficiently comminuted raw material into the intensively mixed bottom phase of the reactor. Preferably, the raw materials are preheated immediately prior to this rapid heating initially to a temperature just below the respective lowest cracking temperature of their components. Although it has now been found that the shock-heating treatment with subsequent pressureless oiling is a necessary prerequisite for the astonishing successes of the process according to the invention, surprisingly it leads to the best positive results only if it is used in combination with the circulation of low-volatility product phase.

Surprisingly but, conversely, the return is also low-volatility Product in the reactor not alone but only in conjunction with the shock warming with following unpressurized oiling or first with pressureless oiling and with following shock warming most successful, because only then were completely unexpected autocatalytic Found effects of this product phase, causing amazing reductions the cracking temperatures and the consumption of additional cracking catalysts were achieved. In many cases such as B. in wood and other lignocellulosic raw materials and waste as well as at Hafenschlick was even found that cracking catalysts are completely dispensable. Lying raw materials with a shortage Hydrogen and / or an elevated Heteroatomanteil before, a reducing gas stream is finely divided through the liquid Conducted reaction medium. As the reducing gas portion is preferably Hydrogen and / or carbon monoxide used. Combined with the combination according to the invention from shock heating with following unpressurized oiling and reaction in the semi-volatile Product cycle were surprisingly here, too, in the hydrogenation reactions, amazing improvements and savings over found conventional hydrogenation processes. So the necessary overpressures could considerably be reduced, usually to values far below 80 bar. moreover The demand for hydrogenation catalysts was surprisingly low. And also in terms of hydrogenation, even surprisingly good results found completely without hydrogenation catalysts, often just at the substances, which also rely on additional cracking catalysts can be waived.

In addition to the improvements made solely by the combination of shock heating with non-pressurized oiling and circulation low volatility Product opposite already known, a further, economically very important improvement surprisingly thereby that achieves shock heating with pressureless oiling and heavy oil circulation guide according to the invention connects with swamp phase reaction and selectively product-oriented residence time control. It was found that the product yield was decisive increase, the oxygen and sulfur levels drop significantly and the energy balance increases accordingly.

This application of the swamp phase reaction in combination with selectively product-oriented residence time control is in no way obvious in the compound according to the invention with the necessary shock heating of the raw materials in the autocatalytic cycle, since under normal technical criteria it must be assumed that such a compound is not possible at all. In fact, product selective residence time control means that cracking products are immediately and selectively removed from the reaction zone when their molecules have just reached the desired chain length. If they were removed too soon, the chains would be too long, and it would produce a viscous heavy oil. On the other hand, if they remained too long in the reaction zone, too short molecules would be formed on the one hand, primarily in the gas region, and on the other hand, the molecules would have an opportunity for undesirable crosslinking reactions, resulting in increased tar and coke production. The technically obvious solution would be to adjust the average flow residence time of the liquid reaction medium over the reactor volume and volume flow and to adapt it to the respective raw material. However, this obvious and technically common measure for residence time control is not sufficient in the inventive method because, firstly, the recirculated low-volatility product stream requires different residence than the raw materials, because secondly, the considered here Raw materials usually already themselves from many different chemical components, all of which require different residence times, exist and because, thirdly, both the shock heating and the unfolding of the autocatalytic effect of the circulation stream require intensive mixing of the substances in the reaction space. However, an intensive mixing is usually in complete contradiction to a targeted residence time control, because it produces extremely broad residence time distributions in the mixture, which leave the individual residence time of a particular component in the entire width completely to chance and thus escape the targeted control.

The Invention solves the problem of selective product-oriented retention control surprisingly in that either the first or the second reactor with a integrated phase separation is equipped and in addition with novel Distillation or stripping properties or combinations thereof is equipped. And the second reactor works after the first Phase separation followed by Nachverölung. A distillation function according to the invention receives the first reactor, when at the same time as evaporator at boiling temperature the reaction mixture works, with volatile, that is vaporizable components the liquid Reaction mixture are removed by switching to the vapor phase. A stripping function according to the invention is achieved when a carrier gas flow through the liquid Is passed the reaction mixture, the volatile components from the Reaction mixture receives selectively. Both measures can be combined when the reactor is operating at boiling temperature while at the same time carrying a carrier gas stream through the liquid Is passed reaction mixture. Such additional functions are for reactors especially in processes that are in the overpressure area work, technically not obvious, because the separation effects such functions usually decrease with increasing pressure. To make matters worse, that one additional Distillation function can only work if the desired reaction temperature coincides with the mixture boiling temperature. The boiling point, however, is known to be due to the Operating pressure determined here by the possibly necessary hydrogenating Effect of the gas atmosphere in the reactor within narrow limits. For example, the boiling point increase would be included Hydrocarbons in the range of fuel oil or diesel fraction in the Magnitude of about 200 Kelvin, when the pressure was increased from 1 bar to 20 bar, or about 300 Kelvin at pressure increase from 1 bar to 50 bar. In both cases one would be the cheap one Temperature range of a maximum of about 500 ° C with high probability exceed. Many known hydrocarbons are even above pressures of about 20 bar boiling states basically at all not possible anymore and always when the respective hydrocarbon or the Hydrocarbon mixture already thermodynamically supercritical has become. Despite these technically obvious objections, the additional functions lead in the context of the completely novel process procedure according to the invention too surprising good results. they hang in particular of the sometimes unusual thermodynamic Phase equilibrium behavior of the material systems at elevated pressures and Temperatures off.

In 1 Fig. 10 is a block flow diagram for an embodiment of the invention, which will be explained in detail as follows. Solid raw materials are first crushed, possibly freed of interfering impurities and possibly dehydrated. In comparison with known conversion processes, the process according to the invention requires only a surprisingly small amount of raw material processing, such as comminution, drying and removal of foreign matter. Only with low energy expenditure mechanically removable water fractions and pure metal fractions, such as those incurred for example in electrical cable and car tire waste, are previously to isolate. Minerals can participate in the conversion process and are sometimes even cracking catalysts such. B. in bone meal desired. The crushing is only to be carried out so far that the raw material can be promoted in an overpressure apparatus and for the organic components sufficiently fast heating times in the shock heating are possible. Solid raw materials can be conveyed via screw machines in pressure chambers, for example. If, in the case of high free water contents, a large part of this is to be removed mechanically before heating, then such screw machines can then fulfill a dual function if they are equipped as a Seiherschneckenpressen. In such a case, they serve both the promotion of the raw material and the squeezing of the water.

The promotion of liquid raw materials such as heavy oils and their suspensions, if mineral catalysts are to be added, can be done for example via pump systems. The heat energy requirement of subsequent process steps, these include in particular the heating of the reactor, the evaporator of the distillation column, the dryer for discharged mineral content and the steam gasification Ausschleusten organic residue, can be covered for example via the exhaust gases of a gas burner. The gas burner is preferably completely self-sufficient in energy supplied via the by-produced in the process reaction gas. This will only start the system Foreign energy needed. In addition, after the first reactor, a gas expansion plant is switched with the degraded on one side of the high pressure of the reactor and on the other hand, the energy is converted into electricity.

Around to minimize the heating time before the cracking reaction region preferably a preheating interposed. This can simultaneously improve the Energy balance through heat recovery from the process streams serve or be heated by the exhaust gases of the gas burner. preheated be the raw material stream and optionally supplied solid catalysts and chemicals. The final temperature of the preheating should preferably be short below that temperature, in the cracking reactions kick off. Depending on the raw material, this range may be on the order of magnitude between 200 ° C and 330 ° C lie. Hemicelluloses, for example, found in wood, very temperature sensitive and are at the bottom, while cellulose and in even stronger Dimensions stable Hydrocarbons are assigned to the upper range. Possibly. needed solid Catalysts and chemicals are preferably in powder form, for example via screw conveyors or Add lock systems. As cracking catalysts are, for example Zeolite-based solid catalysts are suitable. Will be hydrating worked, come with sulfur-free raw materials metallic catalysts such as nickel and platinum as support in question. In the case of Use of halogenated raw materials such. As chlorine-containing waste oils or PVC waste, alkaline Solid chemicals such as calcium hydroxide added be the chlorine before the onset of cracking reactions than Bind salt and thus remove it from the reaction zone. Herein lies an important advantage of the cracking process according to the invention in the Swamp phase opposite conventional cracking processes in the vapor phase, this possibility does not have. The preheated Stream is fed to the heated bottom phase in the cracking reactor. There finds according to the invention an intensive mixing instead, and there may also shock the invention to cracking reaction temperature be performed. Fast warming and reaction preferably take place in one apparatus, the reactor, instead of. In contrast, conventional heating methods are unsuitable for example about an upstream separate heat exchanger section or introducing it into a preheated to reaction temperature Gas-vapor phase. The required good mixing in the reactor can both by stirring systems as well as by turbulent flow conditions of introduced material flows be achieved. The shear forces on the heated reactor walls have to be so tall that there are no deposits due to esterification or coking form.

in the Reactor are the inventively required Temperatures, preferably between 290 ° C and 410 ° C, and pressures set. The latter judge according to the thermodynamic phase equilibrium behavior and the possibly necessary partial pressures on reducing or hydrogenating gas components in the reaction mixture. The invention in the circulation leading to low volatility liquid Product components, referred to as so-called heavy-oil fractions from the process be returned to the reactor 1 and 2, fall in the multi-stage phase separation 1, 2, and 3 of the subsequent solid treatment as a liquid phase, during drying as a vapor phase and finally during the distillation of the main organic product stream as bottoms fraction. These Fractions are subjected to further cracking reactions in the reactor and simultaneously unfold the surprising found catalytic effect, which saves additional catalysts, necessary reaction times for shorten the raw materials, required temperatures and pressures lowers and favorable reaction paths supported. Because the heavy oil fractions belong to the reaction products, Can this so far there not suspected effect as autocatalytic describe. As further reaction products arise as so-called product oil, the target fraction low molecular weight liquid fuels and reaction water and reaction gas.

A gas stream required according to the invention in the reactor is passed finely distributed through the liquid reaction medium. The gas stream can take over the stripping function and / or hydrogenation function according to the invention. For the former function, a portion of the reaction gas is preferably used in the recirculation, while for the latter function preferably hydrogen is suitable. However, it is also possible to use carbon monoxide or mixtures of hydrogen and carbon monoxide, for example. Possibly. required hydrogen can be generated completely self-sufficient from the by-products of the process. This means that no hydrogen has to be purchased from the outside. This fact is of particular importance for the economy of the process. The production of hydrogen can be carried out in two stages via a steam gasification of the solid coke-like and semi-volatile tarry reaction residues in the first stage and a downstream carbon monoxide conversion in the second stage. The hydrogen serves on the one hand to stabilize the cracking products by radical saturation and on the other hand to increase the hydrogen content in the product oil. This improves the calorific value, burning properties and storage stability of the product oil. For the hydrogen to develop its hydrogenating effect, an increased operating pressure is necessary. The necessary overpressure is, inter alia, a function of the elemental composition of the crude substance. Is the raw material, the target chemical already very similar, ie low in heteroatoms, as z. B. in used and heavy oils and hydrocarbon-based plastic waste is the case, it can be completely dispensed with inventive process control overpressure and hydrogen atmosphere. In part, even negative pressure operation is advantageous here. At elevated oxygen levels, such as. B. in wood with about 43 wt.% Oxygen in the dry matter, was surprisingly found in inventive process control that even without additional hydrogenation hydrogen partial pressures of less than 80 bar are usually sufficient. The reaction mixture according to the invention usually consists of the three phases gas-vapor phase, liquid phase and solid phase. The gas-vapor phase contains on the one hand the reaction gas, which is formed as a by-product of the cracking reactions, and on the other hand, the absorbed vapors, which are inventively substantially vaporized product oil hydrocarbons. Due to raw material, water vapor components can also be present. For this purpose, if necessary, further gas components such. B. hydrogen come as a hydrogenating gas. The liquid phase is essentially formed by low-volatility oil fractions, while the solid phase is composed of ash or mineral fractions of the raw material, optionally added solid catalysts and chemicals and solid reaction residues. Such solid reaction residues may, for. As charring residues, which form in part as by-products, be. This three-phase mixture is fed to the phase separation 1 after the reaction. Here, the liquid phase is separated together with the suspended solid phase of the gas-vapor phase. This can happen, for example, in centrifugal separators such as cyclones. This phase separation preferably runs under the same pressure as the first reactor. The separated in phase separation 1 suspension is expanded via a gas expansion plant when the reactor is operated under pressure, and undergoes a three-stage separation process via phase separation 2, phase separation 3 and drying to separate and recover the low-volatile oil phase, as described back to the reactor 1 and 2 is directed. The phase separation 2 separates the coarse-grained solids content together with fine-grained particles adhering thereto, for example, according to the sedimentation principle or also according to the centrifugal force principle. The remaining low-volatile oil phase is passed back to the reactor together with the remaining fines. In the phase separation 3, the coarse enriched suspension is mechanically z. B. via screw presses of further adhering oil phase, which is also returned to the reactors, freed. Finally, during drying, the solids-containing stream is freed from volatile oil fractions. These can also be added to the internal reflux to the reactors after a new condensation. The organic substance still remaining in the solids stream consists essentially of solid char residue and tarry residues. These organic fractions can be converted into synthesis gas consisting of carbon monoxide and hydrogen in the subsequent steam gasification. The thus freed from organic fractions mineral solids are discharged and optionally fed to a workup or regeneration. The synthesis gas can either be fed directly to the reactor as reducing gas or completely converted into hydrogen and carbon dioxide in a downstream carbon monoxide conversion. In the latter case, the hydrogen in the gas separation 2 is freed from carbon dioxide using, for example, a membrane separation process and optionally fed to the reactors as the hydrogenating gas component. If more hydrogen is produced than required by the process, the excess can be profitably marketed or converted, for example via a fuel cell process, into electricity for plant operation. In the case of steam gasification and carbon monoxide conversion, the reaction water formed as a by-product in the cracking reactions of oxygen-containing raw materials is utilized, so that as a rule an effluent-free process is realized. Excess water would be purified by the steam gasification simultaneously, so that any remaining small amount of waste water is the same clean, that is free of organic components, is obtained. If not enough water of reaction is available, add some fresh water. The respective proportions are different due to the raw material and depend on the ratio of the reaction water formed to the solid or low-volatility reaction residue.

The isolated in the above-described phase separation 1 gas-vapor phase is supplied in the case of elevated gas fractions after the reactor 2 of the condensation 1. This condensation, realized by cooling, serves to separate the gas fractions from the condensable oil and water fractions before the latter are fed to the distillative separation. The condensation 1 is preferably operated at the same pressure as the reactor 1. In overpressure operation, this has the advantages that the required admission pressure is available for the optionally subsequent gas separation 1, that less compression energy is consumed for the optionally subsequent hydrogen recirculation into the reactor and that in subsequent expansion valves, the undesirable occurrence of multiphase flows, which could lead there to significant malfunction, is avoided. The gas separation 1 can be realized in accordance with gas separation 2, for example, as a membrane separation process. Of the optionally separated from the reaction gas hydrogen content is fed back to the reactor. The separated reaction gas is expanded in the event of an overpressure process by a second gas expansion plant and can then be supplied to the burner for the above-described thermal energy supply of the entire process. Even before expansion, a portion of the reaction gas, if it requires the above-described stripping function of the reactor, can be returned to the reactor.

The condensed oil in condensation 1 and water phase is over as well an expansion turbine / engine can be relaxed if the reaction under overpressure running, and subsequently fed to the distillation. In this possibly performed Some relax in the oil under overpressure dissolved gas components released, which separated after the distillation in the condensation 2 and also fed to the burner can be. The distillation is preferably carried out as a Mehrstufenrektifikation, at the oil shares decomposed into boiling fractions. The high-boiling bottoms fraction The distillation is described as a low volatile oil content, as described above. according to the invention back to the reactor 1 and 2 led. After cooling condensation in condensation 2 becomes the liquid phase in phase separation 4 mechanically by settling in a conventional floating oil phase above, the desired product oil, and one usually separated below floating water phase. The product oil is used in Product tank collected while the water phase of the above-described steam gasification and / or Carbon monoxide conversion can be supplied.

To step Raw material causes no water content, eliminating the phase separation 4. This but mainly concerns raw materials without oxygen content, in which usually no hydrogenating gas is needed, so that then usually also no water requirement by steam gasification and / or carbon monoxide conversion arises. additional to the preceding description of the invention are in the following special raw material-specific aspects and examples are explained in more detail. When using protein-containing Raw materials such as animal and bone meal are of particular importance that possibly Existing toxins such as prions through the described transformation process Completely destroyed become. This is due to the reaction temperatures of 350 ° C on each Case ensured. Contamination of the environment with released Prions, which can occur in combustion processes, for example, is excluded here because of the air-free encapsulation of the process. The nitrogen content of the protein molecules becomes in the reducing atmosphere the method according to the invention essentially converted into ammonia and excreted over the aqueous phase. From the water phase, the ammonia content by a simple additional Rectification isolated and marketed.

at Chlorine-containing raw materials is to guarantee that no dioxins can arise. In the case of the method according to the invention This will be through the relevant low reaction temperatures of below 400 ° C ensured. Examples for heavy metal contaminated Sediments with elevated organic matter are sewage sludge and From the unloaded sand freed fine grain fractions of dredging sludge Rivers. At the same time, the conversion process in the reactor should ensure that that the heavy metals are removed from the organic product and be so firmly integrated in the inorganic matrix, that the eluates are virtually free of heavy metals. When using harbor silt from the port of Hamburg with 367-410 ppm Pb, 17-19 ppm Cd, 2100-2233 ppm Zn and 370-377 ppm Cu and with 25-26 % organic content in the dry matter were in inventive treatment of this raw material without additional Catalysts with 100 bar hydrogen pressure at 450 ° C following Results found. A proportion of 25-30% of the organic substance was converted into a high-quality low-viscosity oil, while 99.99% of Pb, 99.99% of Cd, 99.8% of Zn and 99.98% of Cu remained in the inorganic residue. Both the produced oil phase as well as the water phase were practically free of heavy metals. Surprisingly changed the bonding forms of the heavy metals in the inorganic matrix completely under the reaction conditions of the invention used without the known glazing, which requires much higher temperatures, such that all the heavy metals mentioned in tighter bond forms changed so that on the one hand practically no Pb and Cu and on the other hand, less than 1% of Cd and less than 5% of Zn still in an exchangeable, ie elutable, cation form. For comparison, in the raw material used before the conversion process of the invention still about 1 of Pb and Cu, about 14% of Cd and almost 30% of Zn in the elutable form.

When applying the invention to wood as a model raw material for lignocellulose raw and waste materials, the following results were found without additional catalysts with 80 bar hydrogen pressure followed by pressureless oiling at a temperature of 350 ° C. High-quality low-viscosity product oil was obtained in a yield of about 37% by weight, based on the amount of wood dry substance used. This oil had an oxygen content of about 4-5 wt%, a calorific value of about 42 MJ / kg and a boiling range of 180 ° C to 370 ° C. For this purpose, about 4 wt.% Water were in the reactor material, based on the wood pulp used, reacted, wherein the yield of both reaction gas and water of reaction in each case about 30 wt.% Was. The generated reaction gas with a calorific value of about 8.5 MJ per kg of gas is sufficient to cover the total process heat requirement of about 2.5 MJ per kg of wood. Measured by the calorific value of the wood used of about 18 MJ / kg, this results in an overall energy efficiency of about 86% for this liquefaction process according to the invention.

1

• solid raw material liquid raw material
• O + A + W + M O + W
• crushing
• Metal separation M
• predehydration W
• K preheating
• fast
• warming SE + F
• reaction
• G + H2 phase separation1 SÖ + R + A + K phase separation2
• Öld + WD + G + H2 SE + R + A + K
• Condensation1 phase separation3
• to burner G + H2 oil + W + G SE + R + A + K
• G Gas separation1 Drying
• H2 R + A + K
• Distillation SÖ
• Öld + WD + G W W. D. Gasification A + K
• G condensation2 CO + H2
• Phase separation4 W CO conversion
• product oil CO2 + N2
• H2 gas separation2 CO2

Designations in 1

• O = organic content of the raw material
• A = inorganic content of the raw material
• M = metal content of the raw material
• W = water content of the raw material, water of reaction and fresh water
• K = solid catalysts and chemicals
• SÖ = liquid Heavy oil fraction
• F = fine-grained Solids
• G = reaction gas
• H2 = hydrogen
• R = solid and tarry reaction residue
• öld = Oil vapor
• WD = water vapor
• oil = liquid oil fraction
• CO = carbon monoxide
• CO2 = carbon dioxide
• Phase separation1 = separation of gas / vapor phase and solids-containing liquid phase
• Phase separation2 = separation of coarse-grained solid with liquid phase fractions and liquid phase with fine grained Solids
• Phase separation3 = separation of liquid phase and solid phase with adherent residual liquid phase
• Phase separation4 = separation of water phase and oil phase
• Condensation1 = separation of gas phase and condensable liquid phase
• Condensation2 = separation of gas phase and condensable liquid phase
• Gas separation1 = separation of reaction gas and hydrogen
• Gas separation2 = separation of carbon dioxide and hydrogen
• W.-D. gasification = steam gasification
• CO conversion = carbon monoxide conversion

Claims (25)

Process for the direct thermochemical conversion of high molecular weight organic substances into high-quality low-molecular-weight organic products, which are present as low-viscosity liquids at room temperature and are flammable, characterized in that after very rapid heating of the raw material, the conversion reactions in the liquid phase with subsequent or previous pressureless oiling preferably in the temperature range be carried out between 290 ° C and 410 ° C taking advantage of autocatalytic effects in the cycle of low-volatility product fractions with selective product-oriented residence time control. Method according to claim 1, characterized in that that the conversion reactions are carried out in two reactor units, which preferably fulfill the following functions simultaneously: Intensive Mixing and very rapid heating with subsequent depressurization oiling the introduced substances or vice versa, that is first oiled without pressure and subsequently heated up quickly and mixed. Execution of cracking reactions as well Distillation and / or stripping function to remove volatile oil product components from the liquid Reaction mixture. Method according to claim 1 or 2, characterized that the thermal energy needs of the process via combustion of the reaction gas is covered. Method according to one of claims 1 to 3, characterized that the thermal and electrical energy needs of the process also about the Expansion plant are covered. The more generated energy can be fed to the grid. Method according to one of claims 1 to 4, characterized in that the product oil and or the product gas and or the hydrogen as Fuel used for combustion in a fuel cell for the production of thermal and electrical energy. Method according to one of claims 1 to 5, characterized that the conversion reactions are carried out in reducing overpressure atmosphere. Method according to one of claims 1 to 6, characterized that the conversion reactions are preferably under an atmosphere associated with Hydrogen and / or carbon monoxide is enriched, at pressures up 80 bar performed become. Method according to one of claims 1 to 7, characterized that the hydrogen used by steam gasification or by steam gasification with downstream carbon monoxide conversion with the help of process-related by-products of the transformation reactions is produced. Method according to one of claims 1 to 8, characterized in that accordingly 1 the product oil-containing material stream discharged after the conversion reaction is passed through the process stages phase separation 1, condensation 1, distillation, condensation 2 and phase separation 4 to the product oil. Method according to one of claims 1 to 9, characterized in that accordingly 1 the solids-containing material stream discharged after the conversion reaction is passed through the process stages phase separation 1, phase separation 2, phase separation 3 and drying to an enriched solids fraction, while the respectively separated heavy oil portions are completely or partially recirculated to the conversion reaction unit. Method according to one of claims 1 to 10, characterized that the enriched solids fraction alone or together with supplied Reaction water by subsequent steam gasification of the organic components is released. Method according to one of claims 1 to 11, characterized in that cracking catalysts are used in the conversion reaction unit. Method according to one of claims 1 to 12, characterized that in the conversion reaction unit alkaline chemicals for Halogen bond can be used. Method according to one of claims 1 to 13, characterized in that hydrogenation catalysts are used in the conversion reaction unit become. Method according to one of claims 1 to 14, characterized that as a raw contaminated or not contaminated wood or corresponding wood waste is used. Method according to one of claims 1 to 15, characterized that biomass and / or energy crops are used as the raw material. Method according to one of claims 1 to 16, characterized that as raw material vegetable oils and / or animal fats are used. Method according to one of claims 1 to 17, characterized that as raw material waste oil, heavy oil, bitumen and / or tar. Method according to one of claims 1 to 18, characterized that as a raw material halogen-containing or non-halogenated plastic waste is used. Method according to one of claims 1 to 19, characterized that electrical cable waste is used as raw material. Method according to one of claims 1 to 20, characterized that as a raw material tire waste is used. Method according to one of claims 1 to 21, characterized that as a commodity household waste is used. Method according to one of claims 1 to 22, characterized that as a raw material sewage sludge is used. Method according to one of claims 1 to 23, characterized that fine grain fractions of dredger sludge are used as raw material. Method according to one of claims 1 to 24, characterized that animal and / or bone meal are used as raw material.