EP1910499A2

EP1910499A2 - Mehtod and device for thermochemically converting organic substances into a high-quality organic product

Info

Publication number: EP1910499A2
Application number: EP06754555A
Authority: EP
Inventors: Yaver Demir
Original assignee: Demir Yaver
Current assignee: Demir Yaver
Priority date: 2005-07-25
Filing date: 2006-06-24
Publication date: 2008-04-16
Also published as: WO2007012368A2; DE102005040490A1; WO2007012368A3

Abstract

The invention relates to a method for thermochemically directly converting educts containing high-molecular weight organic components into low-molecular weight products containing flammable liquid at room temperature organic products. The inventive method consists in heating and hydrogenating the educts for carrying out a liquid phase thermal conversion reaction in such a way that a reaction three-phase mixture is obtained. The first phase, separated from the liquid phase, comprises a component catalysing the conversion reaction and is returned at least partially to the liquid phase and the second phase comprises a certain proportion of low-molecular weight and liquid at room temperature organic products which are devoid of or poor in heteroatoms. Said invention also relates to carrying out the inventive method in a device, which is provided with two heated and pressurised reactors (RI, RII) and comprises a phase-separation unit for separating reaction phases. Said reactors (RI, RII) are fluidly connected in such a way that the separated phase containing catalysing components is returned to the reactor (RI) by means of a recycling device. The highly-volatile component-containing phase is transferable from the first (RI) to second (RII) reactor.

Description

METHOD FOR THE THERMOCHEMICAL CONVERSION OF ORGANIC SUBSTANCES IN HIGH-QUALITY ORGANIC ISCHE PRODUCTS

description

The invention relates to a method and a device for thermochemical conversion of educts which contain high molecular weight organic components into low molecular weight products which comprise organic, liquid at room temperature, flammable products.

In times of high energy consumption and at the same time constantly increasing energy costs, the requirement to reintroduce waste materials, especially so-called high-value waste or recyclable materials, into the energy chain by converting them into an easily usable energy source increases.

The following methods are already known, which have meanwhile found their way into the common teaching literature:

Experiencing pyrolylyvs Pyrolysis processes are known which are used on an industrial scale for the conversion of oganic waste materials; the case NECESSARY temperatures are usually higher than 800 ⁰ C. The pyrolysis products are very small molecules, which are in gaseous form and are therefore reused directly, for example as synthesis gases. Disadvantages are the high temperatures on the one hand in terms of energy expenditure and on the other hand because of the risk of dioxin formation, if the waste reacted chlorine are. Moreover, the gases produced require extensive Gasremigungsprozessc, and the gaseous Pyiolyseproduktc are not directly but only after additional and thus the Cost-increasing conversion processes can be used as petrochemical recyclables or as conventional engine fuel Under Development low temperature Flashpyrolyseverfahren in the temperature range between about 400 ⁰ C and 500 ⁰ C which are performed, for example for the direct liquefaction of wood in fluidized bed reactors, lead to inferior oil products which do not meet the quality expecta- conventional motor fuels. As a rule, these products have high oxygen and water contents and therefore low calorific values, are corrosive and as a rule thermodynamically unstable.

(Direct) thermochemical process: alternative to the pyrolytic

There are (direct) thermochemical processes for the liquefaction of woody biomass, which work with water as the reaction medium under very high pressures up to over 200 bar and at temperatures up to about 400 ° C and require expensive equipment. The products of these methods have also not met the quality requirements of conventional motor fuels to date, as it is more of a viscous tar than an oil with high oxygen contents and correspondingly low calorific value.

Hydrogenating pressure conversion: Also known is the hydrogenation under pressure in stirred tanks or flow reactors to improve the product quality in the liquefaction of organic materials with hydrogen deficiency such. As coals, or of organic substances with increased oxygen content such. Wood. Disadvantageous prove in these methods, the high cost, which arise because of very high operating pressures of over 100 bar, high consumption of expensive hydrogen, high residence times of the substances to be reacted in the reactor, considerable catalyst use and unsatisfactory product yield.

Single-stage hydrostatic pressure conversion: This process is used to produce liquid fuels and fuels from biomass. Also in the direct liquefaction of organic substances by single-stage hydrogenating Pressure conversion is pressures up to 100 bar or 20-80 bar hydrogen pressure and temperatures of 450 ° C necessary. It comes because of the high temperatures to strong coking because the Kokskristallbildungstemperatur is 420 ° C. This process leads to increased deposits in the pipes, resulting in longer service lives and high maintenance costs. The process works after shock heating of the raw materials in combination with heavy oil circulation with an integrated bottom phase reactor, which makes difficult technical demands on the reactor: It has to fulfill both distillation functions and strip functions in order to selectively absorb gas streams. The mass and energy balance in this process is 100% wood as starting material with an oil yield of about 31% oil, but the energy yield is 73%. Both the high oxygen content and the high sulfur content in the product are unsatisfactory in these processes.

In addition, there is the catalytic pressure-free oiling (catalytic cracking). Catalytic liquefaction of biomass at 350 ° C to 400 ⁰ C under atmospheric pressure is used for producing kohlenwasserstoffrei- chen liquid fuels and fuels. This process was originally developed to extract fuels from waste oils and oil shale. The process always works with the addition of catalysts. The temperatures can also be between 280 ° C to 350 ° C. A disadvantage of this process is that a comparatively high proportion of catalyst of about 1% of the raw material quantity is required and that a high proportion of precipitation products is formed. The residence time in the reactor is about 3 minutes, so that no very large throughputs are possible. In addition, the yield of organic substances is unsatisfactory. Mass and energy balance: In this process, oil yield of 50% oil can be achieved from 100% wood, but the energy yield is 70%. Both the high oxygen content and the high sulfur content are unsatisfactory in both processes. Special methods and devices are also known from the following patent applications or patents:

DE 103 16 969 A1 discloses a process for the catalytic treatment of residues in the tube bundle reactor for the conversion of hydrocarbon-containing residues, wherein an oil for use in diesel engines is produced using special ion-exchanging catalysts in the oil-catalyst suspension cycle.

DE 100 49 377 C2 sets out a process in which the residues are decomposed in a circulating in evaporator and reactor recycled carrier oil using sodium aluminum silicate as a catalyst inter alia in diesel oil.

DE 199 41 497 A1 also describes a process for the catalytic oiling of hydrocarbon-containing residues, which is characterized by the mixing of the residues with catalysts of aluminum silicate in a distillation vessel and by the use of a combustion vessel with honeycomb catalyst, wherein the polluted catalysts together after removal be placed in a Schwelbehälter with residues.

EP 1 538 191 A1 describes the production of diesel oil from hydrocarbon-containing residues using doped aluminum silicates as catalysts, in which the energy input through pumps and counter-rotating agitators takes place in an oil circuit with solids separation and product distillation, and the surfaces are continuously fed by the agitators getting cleaned. Finally, EP 1 101 812 B1 discloses a process for the conversion of chlorine-containing plastic waste into oil, which, however, is carried out using supercritical water.

Based on this prior art, the present invention has the object, a new method and a new device for direct thermochemical conversion (or: conversion) of higher molecular weight organic starting materials in low molecular weight organic liquid at room temperature, preferably free or poor in heteroatoms to achieve a good energy balance or high conversion efficiency and to minimize or eliminate waste.

This object is achieved by a method with the features of claim 1 and by a device having the features of claim 29.

Preferred embodiments and further developments of the method and the device of the invention will become apparent from the dependent claims and the following description including the figures.

The process according to claim 1 for the thermochemical conversion of educts (or: starting substances, raw materials) containing higher molecular weight organic components into low molecular weight products comprising organic, combustible products comprises at least two stages. In a first stage, at least the following steps are performed:

Heating at least one educt to carry out a thermal conversion reaction in a sump, whereby a reaction mixture with at least two phases is formed,

Separating at least a first phase and a second phase from the reaction mixture, the second phase at least one contains low molecular weight organic and liquid at room temperature, flammable product,

In a second stage, at least the following steps are carried out: heating at least a portion of the first phase of the reaction mixture from the first stage to perform a thermal

Conversion reaction, in turn, a reaction mixture is formed with at least two phases and

Separating a phase from the reaction mixture formed in the second stage, which phase contains at least one low molecular weight organic combustible product.

In an advantageous variant, the second stage likewise comprises a bottom reaction and, moreover, depending on the starting material, may comprise a reaction taking place thermodynamically under high pressure or a catalytic reaction taking place in particular at low pressures, for example about atmospheric pressure.

In a preferred embodiment, the first phase of the reaction mixture formed in the first stage and / or a second phase of the reaction mixture formed in the second stage is a substantially solid phase and is preferably fed to a pyrolysis reaction in the second stage.

The phase (s) containing at least one low molecular weight organic, combustible product are preferably separated from the reaction mixture in the gas phase or vapor phase, and then a separation of substances, in particular by distillation, is preferably carried out.

In a particularly advantageous embodiment, the first phase is at least partially returned to the sump of the first stage and / or the first phase of the reaction mixture formed in the first stage and / or a second phase of a reaction mixture formed in the second stage, preferably in a sump, is a substantially liquid phase and is separated into a less viscous subphase and a more viscous subphase, and in which the thinner partial phase of the reaction of the respective stage is recycled.

When a catalytic reaction is carried out in the second stage, it is now preferable to seed the viscous subphase of the second phase of the second stage reaction mixture with catalyst (s) and then return it to the second stage catalytic reaction. The thicker phase portion of the first phase of the first stage reaction mixture of the reaction is preferably fed to the second stage for further decomposition or cracking.

The first stage and / or the second stage preferably comprises a hydrogenation reaction of the reaction mixture.

In particular, a process for (direct) thermochemical conversion of educts comprising higher molecular weight organic components in low molecular weight organic liquid at room temperature products, in a first step, heating the reactants to reaction temperature for performing an at least partial cracking reaction in a bottom phase under hydrogenating Conditions. After completion of the reaction, a separation of the individual phases of the three-phase reaction mixture takes place, wherein this phase separation is designed such that the implementation of a first stage causes a product-oriented residence time control of the individual phases, respectively components. Particularly advantageous is the at least partial recycling of the low-volatility product fraction into the bottom phase, since their catalytic properties substantially contribute to obtaining the desired product yield and purity. Transfer of the volatile Product fractions after a first phase separation into a next reaction stage, which can be carried out in a second reactor, and repressurizing cracking and hydrolysis reactions in the presence of a catalyzing bottoms, provides a further advantageous increase in the yield of the desired product and, moreover, improves its purity because its heteroatom content can be lowered.

Depending on the educt composition and field of application, the process can be adapted and optimized in the two step sequences, for example with regard to the pressurization of the reaction vessels.

It is advantageous that the system allows the switching or flexible handling of the sequences of steps, which contributes to an economic reaction leadership; both in terms of the energy to be used and the reactants, as well as in terms of time. Thus, for example, first a catalytic pressure-free cracking or cleaning can be performed, which can be followed by a hydrostatic pressure conversion, if the educts make sense. Alternatively, it can be cracked under pressure and hydrogenated without pressure. Finally, it is also possible to follow the cracking under pressure, possibly resulting Kokskomponenten a pyrolysis step: So these hard cokes are converted into product oil. Depending on the educt composition and the desired product distribution, it is also conceivable that both cracking and hydrogenation are either carried out both under pressure or both under pressure.

The bottoms produced in the process, which contain catalytic components, are always returned to the first catalyzed stage and thus support the process in an advantageous manner. The person skilled in the art, who knows the properties of the starting products, can thus by choosing the named alternatives, combined with the selective handling of the paste Pressure and temperature, favorably determine the quality of the product and improve the energy balance.

In one embodiment, in the first step after Schokkerwärmung the educts under autocatalytic circulation of the heavy-volatile product fraction in the bottom phase reactor under pressure cracking with selective product-oriented residence time control is performed and in the second step sequence, the raw material is processed in a non-pressurized rotary reactor. The reasons for choosing this procedure can be determined by the educt composition.

It is also advantageous that by-products are formed in the process itself, which again flow into the process: Thus, a nonvolatile product fraction with catalytic properties can be obtained which, once formed, is always recycled to the process and thus reduces or eliminates the purchase of catalyst. The said circulation leads advantageously to very good quality and yield of the products while reducing the reaction temperatures and pressures. Finally, a considerable number of substances by means of the inventive method in low-viscosity, combustible oils, ie energy carriers, convertible: even residues, sorted garbage, biological residues and problematic substances come into question for the implementation of the invention, thus an ecological and economic problem to be solved could.

The inventive device according to claim 29 is suitable for carrying out the method according to the invention. It essentially comprises two heatable reactors with at least one inlet and one outlet device each for charging with educt and for removing product and intermediate product. It is advantageous if at least one of the reactors is a pressure reactor, so that, for example, the hydrogenation can be carried out under pressure. For The first reactor with product is connected to a delivery system. Then, a first phase separator is arranged on or in the first reactor, so that the reaction mixture can be separated into its volatile and nonvolatile constituents. The volatile constituents, which ultimately contain the target product, namely low-viscosity, combustible oil, are transferred from the first reactor to the second reactor for further refining; Advantageously, both reactors are in direct fluid communication with each other. In order for a second separated reaction phase, which contains essentially sparingly volatile components, to also be processed further, it is subjected to further phase separation steps in phase separators, which are also connected to the first reactor. Thus, advantageously, a heavy oil fraction, optionally with fine-grained solid fractions, separated over several steps and recycled back into the first reactor, where it unfolds their advantageous catalyzing effect.

Various embodiments of the device according to the invention are equipped with different phase separation, gas separation, condensation or distillation or heating devices which are known to the person skilled in the art and which are matched to the product-dependent requirements.

The following explanations first define the terms used in the description and the claims.

Raw materials or educts: In principle, the process of the present invention for direct thermochemical conversion into low-viscosity and combustible at room temperature liquids, the following organic substances or organic substances containing mixtures or "starting materials" subjected: Carbonaceous substances or mixtures consisting of long-chain or crosslinked Molecules like Renewable resources, such as biomass, energy crops or vegetable oil and animal fat, or waste starting from hydrocarbons such as plastic waste, used and heavy oils, on celluloses of plant origin including their processing products such as contaminated wood waste and corresponding household waste fractions. Also suitable are organic protein-containing waste materials, which also include animal waste. Further suitable substances to be converted are sediments with increased organic content, such as fine-grained sieve fractions of dredged material from harbor waters and sewage sludge as starting materials.

Thermochemical transformation: This essentially means two terms, namely classic cracking, ie the conversion of long-chain into shorter-chain molecules, and cleaning. Cleaning is particularly in question when dirty oil is to be converted into a higher quality product. The oil is then substantially distilled off and the residue or sump further worked up.

High-quality organic products: In the following, "low-grade organic products" are the following low-viscosity substances or liquids with a high proportion of hydrocarbons and high added value, such as petrochemical heteroatom-poor or -free recyclables and motor fuels, just to name a few examples ,

Target products: The target products are especially pure high-quality organic products, namely essentially pure hydrocarbons, which thus consist only of the elements carbon and hydrogen and contain no heteroatoms.

Heteroatoms: Hydrocarbons that are not pure may contain heteroatoms. These include atoms in the hydrocarbon which are not carbon or hydrogen. At least one carbon or hydrogen is replaced in the hydrocarbon by a heteroatom such as nitrogen, oxygen, sulfur, phosphorus or metal. Raw materials with a low content of heteroatoms are for example used and heavy oils but also polyethylene and similar plastics. For example, high heteroatom content ingredients include biological substances of plant and animal origin. Accordingly, raw materials can also be characterized by their heteroatom content.

Inorganic constituents of the educts: In addition to the abovementioned organic substances, inorganic constituents are to be taken into consideration, which are among others. a. Minerals or ash but also pure metals include z. B. are included in electrical cable and car tire waste. The inorganic proportions of said wastes or starting materials vary in content and composition. Old and heavy oils and pure plastic fractions, but also pure biomass fractions usually contain very low levels of ash. By contrast, in the case of bone meal and port silt, the inorganic content may be more than 50% by weight.

Product oil: The main reaction products produced by reacting the products according to the process of the invention are so-called product oils, which are the target fraction of low molecular weight liquid fuels.

Pressurized: This refers to work in the pressure range up to 10 ^"1 bar: Supercritical: When the liquid phase and gas phase due to the pressure and pressure

Temperature conditions are no longer distinguishable, there is a supercritical fluid or a supercritical state, in the present process in the range of 20 to 80 bar.

Selective Product-Oriented Residence Time Control: In the present context, a selective product-oriented residence time control means the use of an integrated phase separation in one of the reactors used, wherein the phase separation comprises a distillation or stripping function or a combination of both, so that the residence time of the heavy and the volatile components in the reactor can be specifically controlled. Thus, the cracking products are immediately and selectively removed from the reaction zone when their molecules have just reached the desired chain length. Thus, the non-volatile product stream circulated in the circuit has a different residence time in the reactor than the raw materials, because these raw materials usually already consist of various chemical components which require component-specific, different residence times in order to convert into product.

Preferably, the method according to the invention can be carried out according to three alternatives:

Alternative 1: Here, in a first phase, after heating the raw materials in the autocatalytic circuit of low-volatility product, cracking with selective product-oriented residence time control is carried out under pressure in a bottom phase reactor. In the second phase, the raw material is transferred to a second reactor, which here is a non-pressurized rotary reactor. The process steps hydrogenating or oiling are carried out here without pressurization; So there is a pressureless oiling. The necessity of using two reactors with a first, pressurized and a second, which is operated without pressure, may be due to the properties of the raw material to be reacted.

Alternative 2: Procedure as in alternative 1, but with reverse handling of the pressures in the reactors. This advantageous alternative 2 can further reduce the oxygen content and the sulfur content in the product oil, whereby the oil yield and the energy yield are considerably increased. Alternative 3: With regard to the first phase, it is advantageously carried out in the same way as the first alternative, that is to say that after severe heating of the raw materials in the autocatalytic cycle of the low-volatility product, cracking under pressure in a bottom-phase reactor; the residence time in the reactor is selective and product oriented. In the second phase, the resulting so-called "hard" cokes are now subjected to a pyrolytic step, so that takes place at temperatures of up to 1400 ⁰ C, a transfer to the product oil.

This completely new bundle of procedural measures leads to advantageous 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 thermo-chemical liquefaction of organic raw materials in the economically very attractive range. In addition, the number of substances that can be converted into low-viscosity oils is being expanded to an unprecedented degree. This mainly concerns the residues, the sorted waste and the biological residues and problem substances.

The shock heating with subsequent pressureless oiling is achieved by heating the raw materials in a few seconds or fractions of seconds to reaction temperature. This rapid heating according to the invention can be realized for example by directly introducing sufficiently comminuted raw material into the intensively mixed bottom phase of the reactor. Preferably, immediately before this rapid heating, the raw materials are first preheated to a temperature just below the respective lowest cracking temperature of their components. For best results, a shock-heating treatment with subsequent depressurisation results when used in combination with the recirculation of the low volatility product phase produced in the reactor. Conversely, the return of low-volatility product in the reactor or in the reactors only in conjunction with the shock heating, combined with subsequent pressureless oiling or first with pressureless oiling and subsequent shock heating most successful, because then the catalytic effects of this product phase can be affected. These catalytic or autocatalytic effects, as the catalyst is generated during the reaction, can now cause reductions in the required cracking temperatures and in the consumption of additional cracking catalysts.

The trial with wood and other lignocellulosic raw and waste materials and harbor silt has shown that additional cracking catalysts are completely dispensable. If there are raw materials with a lack of hydrogen and / or an increased proportion of heteroatoms, a reducing gas stream is passed finely distributed through the liquid reaction mixture. Hydrogen and / or carbon monoxide is preferably used as the reducing gas component. In conjunction with the combination of shock heating according to the invention and subsequent pressureless oiling with recycling of low-volatility components into the product cycle, the hydrogenation reactions can also be optimized: Thus, required overpressures can be considerably reduced, generally to values far below 80 bar. The demand for hydrogenation catalysts also surprisingly decreases. And even with regard to the hydrogenation even surprisingly good results were found completely without hydrogenation catalysts, often just in those substances in which can be dispensed with additional cracking catalysts. In addition to the improvements that are already achieved by the combination of shock heating with pressureless oiling and circulation heavy product over known methods, a further, economically very important improvement is surprisingly achieved by shock heating with pressureless oiling and heavy oil circuit guidance in accordance with the invention combines with swamp phase reaction and selectively product-oriented residence time control. It was found that this can significantly increase the product yield, the oxygen and sulfur content drops significantly and the energy balance increases accordingly.

This application of the sump phase reaction in combination with selectively product-oriented residence time control is by no means obvious, especially 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. Selective product-oriented residence time control means that cracking products are immediately and specifically removed from the reaction zone when their molecules have just reached the desired chain length. Too long chains of molecules are formed if they are taken out of the reactor too early, ie if the residence time is too short, producing a viscous heavy oil. Too late removal from the reactor, ie too long a residence time lead to the formation of short or small molecules, especially in the gas sector, and also could run off unwanted side or cross-linking reactions, resulting in increased tar and coke production.

The known from the prior art solution of the stated undesirable product formation is the adjustment of the average flow residence time of the liquid reaction medium over reactor volume and

Volumetric flow and the adaptation of the flow residence time to the respective raw material. This obvious and technically usual measure for Residence time control does not meet the requirements of the process according to the invention because the circulating low-volatility product stream requires different residence times than the raw materials, which usually already consist of many different chemical components whose implementation requires different residence times, and because both the shock heating and the unfolding of the autocatalytic action of the circulation stream requires intensive mixing of the substances in the reaction space. In the conventional methods, however, intensive mixing contradicts targeted residence time control because it produces extremely broad residence time distributions in the mixture, which does not allow a particular component to have an individual residence time.

In the method and device according to the invention, the aspect of the selective product-oriented residence time control is achieved by either at least the first or the second reactor being equipped with an integrated phase separation or phase separation device and having novel distillation or stripping properties or combinations thereof. When the phase separator is connected to the first reactor or drains through simple handling of the reactor, the second reactor operates after the first phase separation or phase separation stage followed by re-oiling.

The first reactor obtains the distillation function according to the invention when it is simultaneously operated as an evaporator at the boiling point of the reaction mixture. This volatile or vaporizable components are removed from the liquid reaction mixture by going into the vapor phase. A stripping function according to the invention is achieved when a carrier gas stream is passed through the liquid reaction mixture which selectively absorbs volatile components from the reaction mixture. Both measures can be combined if the Reactor operates at boiling temperature, while a carrier gas stream is passed through the liquid reaction mixture.

Such additional functions are technically not obvious for reactors, especially in processes that work in the overpressure range, because the separation effects of such functions usually decrease with increasing pressure. To make matters worse, that an additional distillation function can only work if the desired reaction temperature matches the mixture boiling temperature. The boiling temperature, however, is known to be determined by the operating pressure, which is specified by the possibly necessary hydrogenating effect of the gas atmosphere in the reactor within narrow limits. The boiling point increase in hydrocarbons, for example, is in the range of fuel oil or diesel fraction at about 200 ⁰ C, if the pressure is increased from 1 bar to 20 bar, or at about 300 ⁰ C with pressure increase from 1 bar to 50 bar. In both cases, the favorable temperature range of a maximum of about 500 ^° C. would be exceeded with a high probability. In many known hydrocarbons even at pressures above about 20 bar boiling conditions are no longer possible if the respective hydrocarbon or the hydrocarbon mixture has already become thermodynamically supercritical.

Although these physico-chemical conditions exist, the distillation and stripping function can be used to improve the process in the process of the invention. They depend in particular on the sometimes unusual thermodynamic phase equilibrium behavior of the material systems at elevated pressures and temperatures.

The subject of claim 35 is a device (or: a reactor) for the thermochemical conversion of educts (or: raw materials, raw materials), the higher molecular weight organic components um- in low molecular weight products comprising organic liquid at room temperature flammable products, in particular organic fuels. This device is particularly suitable as a reactor for the process according to the invention and in particular for the Verölung or liquefaction of biomass such as wood or for the production of biodiesel suitable and / or is preferably operated under pressure, but can also be operated without pressure. This device according to the invention comprises at least one reaction space (reaction chamber, reactor interior) for carrying out an at least partial decomposition or cracking reaction of at least one educt, at least one inlet for introducing or introducing the educt (s) into the reaction space and at least one outlet for discharging or discharging the low molecular weight products from the reaction space.

It is now provided in a first variant at least one arranged within the reaction chamber crushing device (or: separation device, cutting or Zerspanvorrichtung) for mechanically comminuting (or: separating or cutting or machining) of the educts (s) or raw materials (s). As a result, a raw material that has been compressed or caked together before entry into the reactor can also be processed efficiently for the reaction as a result of high delivery pressures, which are necessary for a correspondingly high process pressure in the reaction space.

In a variant alternative to or in combination with the first variant conceivable second variant within the reaction space at least one mixing and / or shearing device, which preferably has one or more mixing and / or shear blades, for mixing and / or homogenizing the educts or (S) and / or a reaction and / or phase mixture provided in the reaction space. In a variant alternative to or in combination with the first and / or second variant providable third variant at least one, preferably rotatable or rotating scraping elements having scraper for scrapping or cleaning surfaces of a wall of the reaction space is provided.

The comminuting device, mixing and / or shearing device and / or scraper device can be arranged as rotating elements on a common or also different, at least partially extending through the reaction space rotating shafts. The mixing and / or shearing device can at least partially have common elements or be designed as a structural unit.

The invention will be explained below with reference to embodiments further ter. Reference is also made to the drawings. Each shows in a schematic representation:

1 shows a block flow diagram of a performance example of the method according to the invention,

2 shows an embodiment of a horizontal reactor in a simplified representation without the mechanical components within the reactor space,

3 shows an embodiment of a horizontal reactor with illustrated mechanical conveying and comminution devices in the reactor chamber, FIG. 4 shows a partial section through the reactor according to FIG. 3 with more visible comminution device, FIG. 5 shows a partial section through the reactor according to FIG. 3 with more visible mixing device,

6 shows an exemplary embodiment of a vertical reactor, and FIG. 7 shows a schematic circuit diagram of a device according to the invention. Corresponding parts and sizes are provided in the Figures 1 to 7 with the same reference numerals.

The block flow diagram in FIG. 1, which shows the method sequence according to the invention for one exemplary embodiment, first of all shows that a step of comminution takes place for solid raw materials which contain organic fractions O, inorganic fractions A and metal fractions M.

Disturbing metals are separated in a next metal separation step; they are collected as metal shares of the raw material M.

If other interfering foreign substances are present, they should also be removed. In the present case, the raw materials are moisture-containing, therefore, a step of pre-dewatering, wherein the discharged water W is also collected. 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, must be separated beforehand.

These above-described steps of comminution, drying and foreign matter separation are subject to the general term of raw material preparation, which here requires an advantageously low expenditure, since the main part of the educts can be used in its original state. The comminution is only to be carried out so far that the raw material in a first reactor I, which may be an overpressure apparatus, can be promoted and that for the organic components sufficiently fast heating times in the shock heating are possible. Minerals, such as. B. contained in bone meal, can participate in the conversion process and are sometimes even desirable as cracking catalysts. Solid raw materials can be conveyed to the reactor I, for example via screw machines. If, in the case of high free water contents, a large part of the water W is to be removed mechanically before heating, then such screw machines can then be used Double function when equipped as a screen screw presses. In such a case, they serve both the promotion of the raw material and the squeezing of the water W.

The supply of any required solid catalysts and chemicals is not shown in the diagram of FIG 1, these are preferably added in powder form, for example via screw conveyors or lock systems directly into the first reactor RI. As cracking catalysts, for example, zeolite-based solid catalysts are suitable, whereas, in contrast, in the hydrogenation step described below, e.g. B. in sulfur-free raw materials metallic catalysts such as nickel and platinum come as support in question. In the case of the use of halogen-containing raw materials such. As chlorine-containing waste oils or PVC waste, alkaline solid chemicals such as calcium hydroxide can be added, which bind the chlorine before the onset of cracking reactions as a salt and thus remove from the reaction zone. This is an important advantage of the cracking process according to the invention in the sump phase over conventional cracking processes in the vapor phase, in which this possibility does not exist.

For example, for pre-processing solids can be crushed and fed via dosing on a drying belt a drying tunnel and dried there by continuous supply of hot air. Moisture measurement is automatic and controls the drying process. The pre-treated material is stored upstream in silos. From there, the pre-treated material can be transported via rotary valves to a twin extruder screw press to be finely ground and compacted. It creates pressure and heat, the material is mixed with catalyst material if necessary, and it can be introduced into the reactor RI. The twin extruder screw press counteracts the reactor pressure and thus excludes a setback. The loading of reactor RI with liquid raw materials such as heavy oils and their suspensions, when mineral catalysts are to be added, however, can be done, for example, via pump systems.

Before the reactor RI is now charged with the abovementioned solid raw materials and / or liquid raw materials, respectively educts, as well as with other chemicals or reactants, a step of preheating the reactants and chemicals, thereby minimizing the heating time before the cracking reaction. In principle, however, it is also conceivable to carry out the method in other embodiments without the preheating.

In essence, the preheating can serve to improve the energy balance through heat recovery from the process streams. The heat energy supply can also be done by the exhaust gases of the gas burner. The raw material stream and optionally supplied solid catalysts and chemicals are preheated. The final temperature of the preheating should preferably be just below the temperature at which the cracking reactions begin. Depending on the raw material, this range may be on the order of 200 ° C to 330 ° C. For example, hemicelluloses found in wood, for example, are very sensitive to temperature and are in the lower part of the required cracking temperature, cellulose and, to a greater extent, stable hydrocarbons are assigned to the upper area.

The heat required for the preheating and the heat energy requirement of subsequent process steps, these include, in particular, the heating of the reactor RI, the evaporator of the distillation column, the dryer for discharged mineral components and the water vapor gasification discharged organic residue can, for example on the Exhaust gases of a gas burner are covered. The gas burner is preferably supplied with complete energy independence via the reaction gas G which is produced as a by-product in the process. As a result, foreign energy is needed only to start the system.

Now, the preheated stream of heated sump phase in the cracking reactor RI is supplied. There intensive mixing takes place, and there also the shock heating can be carried out at cracking reaction temperature according to the invention. Rapid heating and reaction preferably take place in a reaction vessel or reactor RI, RII. The abovementioned shock-heating is advantageous for carrying out the method compared to the use of conventional heating methods, as they are for. B. a pre-circuit of separate heat exchanger sections o- represents the introduction of the reactants in a preheated to reaction temperature gas-vapor phase.

For optimum conversion of the starting materials into the products or intermediates, good mixing in the reactor RI ₃ RII is required. This can be achieved both by stirring systems and by turbulent flow states of the introduced material streams. The shear forces on the heated reactor walls must be so great that no deposits form there due to esterification or coking.

In the reactor RI, the cracking and hydrogenation steps take place after the required temperatures and pressures have been set. The temperatures are preferably set between 290 ⁰ C and 410 ⁰ C, the pressures depend on the thermodynamic phase equilibrium behavior, which is known in the art, and also known possibly necessary partial pressures of reducing or hydrogenating gas components in the reaction mixture. The reactor RI is followed by an expansion plant, with the one hand, the high pressure of the reactor RI degraded and on the other hand, the energy is converted via a turbine into electricity.

After the reaction comprising the steps of cracking and hydrogenation has elapsed, in the next process step a first phase separation stage PI of the three-phase mixture present in the reactor RI is carried out.

The liquid phase is essentially formed by low volatility Ölfraktio- SO. In this case, the nonvolatile liquid product components are produced. These are the so-called heavy oil fractions SO, which at this stage of the process are first recycled to the reactor RI, which are thus advantageously recycled, because they can thus be subjected to further cracking reactions in the reactor RI and thus the yield increased in product. At the same time they advantageously develop a catalytic effect, which eliminates the need for additional catalysts. The required reaction times for the cracking and / or hydrogenation reactions of the raw materials are shortened by the catalysis, favorable reaction paths are supported and the required temperatures and pressures for carrying out the reaction are thus reduced in the process according to the invention compared with the processes of the prior art.

These heavy oil fractions SO occur in the multistage phase separation comprising the phase separation stages PI, PII and Pill. After the phase separation stage PI, a second phase separation stage PII and a phase separation stage Pill of the mixture of liquid heavy fraction SO, a solid and tarry reaction residue R, inorganic portion of the raw material A, respectively Educts, and solid catalysts K. The phase separation stages PII and Pill falls the heavy oil fraction SO as a liquid phase. Furthermore, the heavy oil fractions fall SO when drying as a vapor phase and finally in the distillation of the main organic product stream as bottom fraction. Since the heavy oil fractions are among the reaction products, the above catalytic benefit effect will be referred to herein as autocatalytic.

The solid phase of the three-phase mixture is composed of Aschebzw. Minerals A shares of the raw material, optionally added solid catalysts K and chemicals and solid reaction residues R. Such solid reaction residues R can, for. B. charring residues, which form in part as by-products.

In the phase separation stage PI following reactor RI, the liquid phase is separated from the gas-vapor phase together with the suspended solid phase. This can happen, for example, in centrifugal separators such as cyclones. This phase separation stage PI is preferably carried out under the same pressure as prevails in the first reactor RI. The separated in phase separation stage PI suspension is expanded by a gas expansion plant when the reactor RI, as shown in FIG 1, operated under pressure and undergoes a three-stage separation process on the phase separation stage PII, phase separation stage Pill and drying to separate and recover the low volatile oil phase, which, as described, is recycled to the reactors RI and RII.

The phase separation stage PII 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 SO is led together with the remaining fine fraction back to the reactor RI.

In the phase separation stage Pill the coarse enriched suspension is mechanically, z. B. via screw presses, from further low-volatile oil phase SO, which is returned to the reactors RI and RII, freed.

Finally, the drying step frees the solids-containing stream of vaporizable oil fractions. These can also be recycled to the internal reflux into the reactors RI, RII after a renewed condensation KII.

The organic substance still remaining in the solids stream consists essentially of solid char residue and tarry residues R, optionally of inorganic raw material fractions A or solid catalyst K and chemicals. The organic components R can be converted in the subsequent steam gasification WDV in synthesis gas, consisting of carbon monoxide CO and hydrogen H ₂ . The thus liberated from organic fractions mineral solids A, K are discharged and optionally fed to a workup or regeneration.

The synthesis gas CO + H ₂ can either be fed directly to the reactors RI, RII as reducing gas or converted completely into hydrogen H ₂ and carbon dioxide CO ₂ in a downstream carbon monoxide conversion CO conversion. In the latter case, the hydrogen H ₂ in the gas separation GII is freed from carbon dioxide CO ₂ using, for example, a membrane separation process and optionally fed to the reactors RI, RII as the hydrogenating gas component. If more hydrogen produces H ₂ than needed by the process, the excess can be profitably marketed or converted, for example via a fuel cell process, into electrical power for plant operation.

In the case of steam gasification and carbon monoxide conversion, the raw materials used in the cracking reactions of oxygen-containing raw materials are used as secondary product reaction water used, so that essentially a wastewater-free process is realized. Any resulting excess water is purified by the steam gasification WDV simultaneously, so that any resulting excess small wastewater quantity W is equal to pure, 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.

Back to the step of the first phase separation stage PI of the reaction mixture from the reactor RI: As further reaction products in the reactor RI, the target fraction containing the product of the process: an oil as oil vapor Ö1D, which is a low molecular weight liquid fuel. Furthermore, water of reaction is formed as water vapor WD and reaction gas G and hydrogen H ₂ . These components are combined in the third phase, the gas-vapor phase of the three-phase mixture. For product refining this phase or fraction, respectively, is now transferred to a second reactor RII, and again subjected to the steps of cracking and hydrogenation.

The gas-vapor phase of the three-phase mixture is supplied in the case of elevated gas fractions after the reactor RII the condensation in the first condensation KI. This condensation step KI realized by cooling is used to separate the gas fractions reaction gas G and hydrogen H ₂ from the condensable oil and water fractions Ö1D + W, before the latter are fed to the distillative separation. The condensation step KI is preferably operated at the same pressure as the reactor RII. In the case of overpressure operation, this has the advantages that the required admission pressure is available for the optionally subsequent gas separation GI, that for the optionally following hydrogen recycled in the reactor RII less compression energy is used and that in subsequent expansion valves, the undesirable occurrence of multiphase flows, which could lead there to significant malfunction, is avoided.

The gas separation GI can be realized as the gas separation GII, for example as a membrane separation process. The optionally separated from the reaction gas G hydrogen content H ₂ is fed back to the reactor RI, RII. In the case of an overpressure process, the separated reaction gas G is expanded by a second gas expansion plant, which is not illustrated in FIG. 1, and subsequently supplied to the burner for the above-described thermal energy supply of the entire process.

The phase separations or phase separators described above may comprise the step of stripping with gas. Therefore, prior to expansion in said expansion device, part of the reaction gas G, if required by the above-described stripping function of the reactor RI, RII, can be recycled to the reactor RI, RII.

The expansion plant could also be connected in other embodiments with a turbine for generating electrical energy,

Therefore, if according to the invention in the reactor RI and reactor RII a gas stream G + H ₂ needed for stripping, this is first in reactor RI, then in reactor RII, when both reactors are operated simultaneously, passed finely divided through the liquid reaction mixture. The gas stream G + H ₂ can generally assume the said phase separation phase separation function as set forth above and / or the hydrogenation function. For the stripping function, a proportion of the reaction gas in the recirculation is preferably used, while the hydrogenation is preferred. example, by hydrogen H ₂ occurs. However, it is also possible for example to use carbon monoxide or mixtures of hydrogen H ₂ and carbon monoxide CO. Possibly. required hydrogen can be generated completely self-sufficient from the by-products of the process. This means that advantageously no hydrogen H ₂ must be purchased from the outside. This fact is of particular importance for the economy of the process.

The production of hydrogen H ₂ can take place in two stages via a water vapor gasification WDV of the solid coke-like and low-volatility tar-like reaction residues R in the first stage and a downstream carbon monoxide conversion in the second stage. The hydrogen H ₂ 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 H _{2 to} develop its hydrogenating effect, an increased operating pressure is necessary. The necessary overpressure is, among other things, a function of the elemental composition of the raw material. 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 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 G, which is formed as a by-product of the cracking reactions in the reactors I and II, and on the other hand the received vapors, which are inventively substantially vaporized product oil hydrocarbons. Due to the raw material, water vapor components WD can also be present. For this purpose, if necessary, further gas components such. B. hydrogen H ₂ come as a hydrogenation gas.

As also shown in FIG. 1, the oil and water phase oil + W + G condensed in the condensation step KI can also be expanded via an expansion turbine or an engine if the reaction in reactor RII is under overpressure, followed by subsequent distillation. During this relaxation, if necessary, certain gas components dissolved in the oil under excess pressure are released which, after distillation, can be separated off in a second condensation step KII and likewise fed to the burner. The distillation is preferably carried out as a Mehrstufenrektifikation in which the oil fractions are decomposed into boiling fractions. According to the invention, the high-boiling bottoms fraction of the distillation is passed back into reactor RI, RII as low-volatile oil fraction SO, as described above.

After cooling condensation in the condensation step KII, the liquid phase in phase separation stage PIV is mechanically separated by settling in an oil phase, the desired product oil, and a water phase so that the heavier water phase can be drained first before the product oil is collected in the product tank. The water phase W can be supplied to the above-described water vapor gasification WDV and / or carbon monoxide conversion.

If there are no water components as a result of the raw material, the phase separation stage PIV is eliminated. This applies above all to raw materials without oxygen Part, which usually also no hydrogenating gas is needed, so that then usually no water requirement by steam gasification and / or carbon monoxide conversion is formed.

It should be noted that in principle in the presently disclosed process of either or both reactors I, II can be operated without pressure or even under reduced pressure, the pressurization of both reactors, depending on the reactant, the expert in terms of its cracking and Hydrabigenschaften knows, proves useful. Accordingly, then the interposition of an expansion plant is mandatory.

It is further to be considered that the process according to the invention can generally also be carried out in more than two reactors, the material streams exemplified in FIG. 1, in particular the recycling of the heavy oil fraction, then have to be fed by the person skilled in the art according to the indicated process steps.

Finally, special process-specific aspects must be taken into account when carrying out the process, which will be explained by means of examples:

When using proteinaceous raw materials such as animal and bone meal, it is of particular importance that any possible toxins such as prions are completely destroyed by the described conversion process. This should be ensured by the reaction temperatures of 350 ⁰ C. An electrolytic decomposition as a pretreatment of the bone meal may prove to be advantageous to release mineral components as a catalyst material. A likelihood of contamination of the environment with released prions, which can occur, for example, in combustion processes, is significantly reduced here because of the air-free encapsulation of the process. The nitrogen content of Protein molecules are essentially converted into ammonia in the reducing atmosphere of the process according to the invention and eliminated via the aqueous phase. From the water phase, the ammonia fraction can be isolated and marketed by simple additional rectification.

In the case of chlorine-containing raw materials, it may be assumed that no dioxins are formed, since the process according to the invention operates at reaction temperatures of below 400 ° C., whereby it is no longer necessary to start from dioxin production.

When using heavy oil as starting material, instead of cracking in the first phase, a distillative purification step occurs because the main constituent of the waste oil is the diesel fraction. Coking residues are in the second phase z. B. worked up by a pyrolysis step.

Examples of heavy metal-contaminated sediments with an increased organic content are sewage sludge and fine-grained fractions of dredger sludges from river courses freed from the unloaded sand. At the same time, the conversion process in the reactor should ensure that the heavy metals are removed from the organic product and firmly bound in the inorganic matrix in such a way 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 carrying out the inventive method with Found this starting material without additional catalysts with 100 bar hydrogen pressure at 450 ⁰ C, the following results: 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 the Zn and 99.98% of the Cu remained in the inorganic residue. Both the oil phase produced and the water phase were virtually heavy tallfrei. Surprisingly, the bonding forms of the heavy metals in the inorganic matrix under the reaction conditions used according to the invention completely changed without the known glazing, which requires much higher temperatures, such that all of the above heavy metals changed in tighter bonding forms, so that on the one hand practically no Pb and Cu and On the other hand, less than 1% of the Cd and less than 5% of the Zn were still in a replaceable, ie elutable, cation form. For comparison, about 1% of the Pb and Cu, about 14% of the Cd and almost 30% of the Zn were present in the elutable form in the raw material used before the conversion process according to the invention.

Implementation of the method according to the invention with the raw material wood as a model raw material for lignocellulosic raw materials and waste materials gave the following values: In the model experiment, the raw material wood without additional catalysts at 80 bar hydrogen pressure followed by pressureless oiling at a temperature of 350 ⁰ C was subjected to the conversion, with high quality low-viscosity product oil in a yield of about 37 wt.%, Based on wood pulp used, was obtained. 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 ⁰ C to 370 ⁰ C. For this purpose in the reactor about 4 wt.% Hydrogen, based on wood pulp used, used, 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. Based on 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. Thus, by means of the process and apparatus for carrying out the process described above, the thermodynamically and chemically very demanding task of thermochemical conversion of high molecular weight organic E- products with optimization of the energy balance in low molecular weight organic, liquid at room temperature products free of or poor At heteroatoms are handled taking into account the inorganic as well as the organic requirements.

As requirements for inorganic chemistry, reference is made, for example, to the implementation of harbor sludge, an organic substance as defined above, but containing inorganic components. These inorganic components are substantially in an improved and freed from organic components form after they have been subjected to the inventive method. In harbor silt, which is loaded with heavy metals, the heavy metals can be bound quantitatively in the inorganic fraction, so that the organic products are free of heavy metals. At the same time, however, the heavy metals are incorporated into the inorganic matrix in such a way that they can no longer be eluted, so that the mineral product fraction can advantageously either be landfilled or used, for example, in the construction industry, thus resulting in an ecological relief of the environment after the highly toxic one Hazardous potential port silt material was subjected to the method according to the invention.

By the present method, it is also possible in the conversion of the organic starting materials such. B. animal and bone meal on the one hand high-molecular, ie long-chain organic compounds selectively to crack, so shorten so that exactly the desired molecular chain length range comes out, for example, in diesel oil with a boiling range preferably from 200 ⁰ C to 380 ⁰ C. On the other hand, the heteroatoms can be selectively removed with as little loss of carbon and hydrogen as possible. In this case, mineral components can develop the desired catalytic effect. Advantageously, it is possible by means of the presented method according to the invention in addition to the inorganic toxins such as heavy metals and organic toxins such. B. prions from animal and bone meal to eliminate partially or completely from the organic starting materials or render harmless and at the same time prudent reaction, the emergence of new toxins such. As to prevent dioxins.

Thus, with the method according to the invention is an ecologically and economically significant process for raw material recycling.

FIGS. 2 to 5 show exemplary embodiments of a horizontal reactor 2, and FIG. 6 shows an exemplary embodiment of a vertical reactor 2 which comprises a reaction chamber 3 surrounded pressure-tight by a wall 32, which in turn is subdivided into a phase separation zone 31 and a conveying zone 30. The reactor 2 is usually designed for pressures of-1 bar to + 80 bar, each based on atmospheric pressure.

The wall 32 of the reaction space 3 is predominantly spherical in the phase separation zone 31 according to FIGS. 2 to 5 and approximately cylindrical in accordance with FIG. 6 and substantially cylindrical or tubular in the region of the conveying zone 30. The design of the reaction space 3 and its wall 32 is not limited to these special forms. The conveying zone 30 opens into the phase separation zone 31. In turn, two inlets 4 and 5 for introducing raw material (or educt (s)) RS into the conveying zone 30 open into the conveying zone 30. The two inlets 4 and 5 face each other slightly off-center to a central axis A of the conveying zone 30. The raw material RS is conveyed through a feed pressure, which is greater than the process pressure prevailing in the reactor chamber 3, from a conveying device (not shown), in particular an extruder screw press, through the inlets 4 and 5 into the conveying zone 30. The entire delivery zone 30 and a part of the phase separation zone 31 is filled with a sump (or a sump phase mixture) S, which consists of various phases and substances and in particular the raw material RS and the resulting thermal and / or catalytic decomposition or Cracking formed reaction products in solid, liquid and gaseous phase as phase mixture comprises.

A conveying device 12 arranged in the conveying zone 30 and also extending into the phase separation zone 31 in FIG. 3 comprises a screw conveyor which is fastened to a rotary shaft 21 driven by a rotary drive 41 and the sump S or the phase mixture with the raw material RS in the conveying direction FR transported to the phase separation zone 31.

In an upper sump-free region above the level of the sump S of the phase separation zone 31 is not filled with sump S and can thus escape a vapor phase or gaseous substances from the sump S to o- ben and through an above or at the top of the separation zone 31 in the wall 32 provided outlet 6 are removed above an outlet valve means 10 for reducing pressure (pressure reducing valve) and further processed as a useful substance for the low molecular weight, in particular usable as fuel components.

In the upper part of the separation zone 31, an overpressure protection device 1 1 is additionally provided, which usually comprises a pressure relief valve. At least one and preferably several outlets 7 are provided in the wall 32 in the lower region of the separation zone 11, through which a part S 'of the sump phase S is returned to the conveying zone 30 via a return line 9, preferably assisted by a conveyor 8, preferably in FIG The feed means 8 in the return lines 9 are preferably oil or gas operated pumps, such as screw pumps, for example, with a discharge pressure of 1 bar (differential pressure) can work. In the return lines 9 and heaters 18 are also arranged, which can be operated in particular heat recovery from process heat or gas-fired by the resulting during the process fuel gas or oil-fired from emerging during the process oil or with heat from other processes, such as a combined heat and power plant etc.

The direction of gravity (gravitational force, gravitational force) G is indicated by an arrow and points in FIGS 2 to 6 down. In the case of the horizontal reactor 2 according to FIGS. 2 to 5, the delivery zone 30 and the phase separation zone 31 are horizontal or perpendicular to

Gravity G arranged side by side and in the vertical reactor 2 according to FIG 6 vertically or in parallel to the gravitational force G over each other, wherein the phase separation zone 31 is above the conveying zone 30. The conveying direction FR extends horizontally or orthogonally to the gravitational force G in the case of the horizontal reactor 2 according to FIGS. 2 to 5 and vertically in the vertical reactor 2 according to FIGS. 2 to 5 and opposite to the direction of the gravitational force G. Otherwise, the two reactor types horizontal reactor and vertical reactor have a similar structure.

If a raw material is at least predominantly in solid form, it is advantageous, the raw material prior to introduction into the reactor as possible in comminuted form in the form of particles such as powder or granules to obtain the largest possible surface area for the decomposition reaction or cracking. For example, when using wood or wood-like raw material, preferably a wood flour or wood powder having particle sizes of typically 0.5 mm is provided, as known, for example, from wood pellet production.

In the case of decomposition reactions or high pressure under pressure in the reactor 2, the pressures may be up to 80 bar. Here, however, due to the correspondingly high delivery pressure required thereby, the wood particles are compressed and caked together even before they enter the conveying zone, so that the wood raw material RS is not in the desired shape of individual particles but as a caked mass with an undesirably high density and compactness from the inlets 4 and 5 enters the conveying zone 30.

According to the invention, a shredding device 20 is now arranged in the region of the inlets 4 and 5 which, in the illustrated embodiment (FIGS. 3 and 4 and 5), consists of a plurality of saw blades or saw elements 40 which are arranged parallel to each other and rotatable about the axis A, respectively are facing with the turning portions of their outer periphery the inlets 4 and 5. The compressed mass of the raw material RS is now crushed back into small particles as soon as it enters the conveying zone 30 due to the large number of small saw teeth of the sawing elements 40 (see FIG. 4), preferably again a particle size in the order of magnitude of 0.5 mm is sought.

The sawing elements 40 of the comminution device 20 are preferably provided axially in the direction of the axis of rotation A with openings or in the form of open support structures, for example as in the case of a wheel with hub and spokes, in order to minimize the amount To provide flow resistance against the flowing in the conveying direction FR medium of the sump S. At the periphery a plurality of cutting teeth are distributed, preferably evenly distributed, arranged to each other. In addition to a sawing device with saw teeth, a milling device with milling teeth or another cutting device for mechanical comminution of the incoming raw material RS can also be provided.

The sawing elements 40 of the comminuting device 20 are preferably fastened to the rotary shaft 21, which also rotates the conveying screw of the conveying device 12 about the axis of rotation A, and thus also rotate at the same rotational speed as the conveying screw. However, it may also be provided a separate drive for the shredding device 20.

Furthermore, the reactor 2 at the bottom of the phase separation zone 31, a further outlet 17, which is designed in particular as a pipe socket, for discharging there due to gravity G settling heavy components of the reaction mixture or sump S. The accumulating on the outlet 17 heavy Components or outlet products are subjected to a further treatment not shown in FIG. In particular, these heavier components of the sump S can be fed via the outlet 17 to a phase separation, wherein the outlet products at the outlet 17, for example, from a separator, are separated into solid and liquid components and then preferably the liquid components again in lower viscosity components on the one hand and thicker or higher-viscosity components, on the other hand. The solid constituents can then be further decomposed in a pyrolysis plant, not shown in FIGS. 1 to 5, and converted into lower molecular weight useful products. The thinner-fluid constituents, since they contain the low molecular weight products, can be recycled to the reaction space 3. The higher viscosity or thicker components of the outlet products at the outlet 17, however, in a second stage in a second reactor subjected to a further decomposition reaction, in particular by unpressurized catalytic decomposition or cracking reaction.

Such an outlet 17 is usually also provided in the other embodiments according to FIG 2 and 4 to 5, but not shown there.

Furthermore, a mixing and / or shearing device 23 is rotatably arranged on a rotary shaft 22 and arranged according to FIG 3 at the transition region to the conveying zone 30 in the phase separation zone 31 and comprises in the illustrated embodiment shown in FIG 5 four offset by 90 ° to each other arranged mixing and / or Shearing blades 29, which are designed in the manner of rotor blades and have relatively sharp shearing edges in order to achieve a shearing or possibly even cutting action for the passing medium with the raw material RS and the reaction products and other components of the sump S.

In FIG. 3, the mixing and / or shear blades 29 are curved and follow the course of the wall 32 of the reactor 2, and are arranged relatively close to the wall 32 in order to additionally achieve a cleaning action for the wall 32. FIG. 6 also shows the parts of the mixing and / or shear blades 29 of the wall 32 of the reactor 2 pointing radially to the axis A and further parts of the mixing and / or shear blades 29 running axially to the axis A extending to the shaft bearing 24. where they are attached. The mixing and / or shear blades in FIG. 6 thus have a Z-shaped basic shape in an axial section. Also, the wings 29 in FIG. 3 may be configured as in FIG. 6.

Finally, in the phase separation zone 31 of the reaction space 3, at least one scraper device with three scraper elements 25, 26 and 27 rotatably mounted on the shaft 22 is provided for scrapping Residues on the inner surface of the wall 32 in the phase separation zone 31, in particular at and around the outlets 6, 7 and 17.

This scraping or cleaning action can also be achieved by combination or structural integration with the mixing and / or shearing means 23, for example by further drawing the wings 29 around the wall 32, e.g. 6 also run along the lateral and vertical wall regions of the wall 32 in the Phasentrennzo- ne 31, and then preferably at a second end also inside again connected to the shaft 22 and thus have a bow shape. Likewise, a scraping device for the wall can also be provided in the conveying zone 30.

Preferably, the mixing and / or shearing device 23 and its mixing vanes 29 (and the scraping elements 25, 26 and 27) rotate in the opposite direction of rotation to the conveying screw of the conveying device 12. This achieves a greater mixing and shearing effect. For this purpose, the two rotary shafts 21 and 22 are connected to one another in a shaft bearing 24 so as to be freely rotatable about the same axis of rotation A and are driven apart from one another by the associated drives 41 and 42. As an alternative to two separate rotary shafts, in all embodiments, a single continuous rotary shaft can also be provided, so that all rotating components in the reactor 2 are driven by the same drive and at the same rotational speed. In the case of a common rotary shaft, mixing device 23 and conveying device 12 rotate in the same direction of rotation and generally at the same rotational speed. The training with two separate shafts 21 and 22 also has the advantage that not only different directions of rotation, but also different rotational speeds for the mechanical components 23, 25, 26 and 27 in the phase separation zone 31 on the one hand and the conveyor 12 and the comminuting device 20 in the On the other hand, conveying zone 30 can be adjusted. Especially if a part of the conveyor is also arranged in the phase separation zone 31, the same direction of rotation is preferred.

The drives 41 and 42 may be provided as direct drives for the associated shafts 21 to 22 or may also include gears or other translation means between motors and shafts. As motors electric motors or hydraulic motors or oil or gas-powered internal combustion engines can be provided.

The entire reactor 2 is preferably designed explosion-proof.

7 shows a circuit diagram of a device according to the invention with a first reactor 50, a second reactor 60 and a pyrolysis reactor 70. The raw material RS is fed to the first reactor 50 at an inlet 51 and thermally decomposed there. The usable decomposition product exits as a vapor phase Dl at an upstream outlet 52 of the first reactor 50 and may be further separated, for example by distillation, to remove the fuel, e.g. Diesel or kerosene, and possibly other useful products. At an outlet 53 of the first reactor 50, an outlet product Al exits and is withdrawn continuously or in individual batches and fed to a separator 80 which separates the outlet product Al into a substantially solid outlet product portion Al S and a substantially liquid outlet product portion AlL.

The liquid outlet product fraction AlL is separated in a subsequent phase separator 81 into a low-viscosity or low-viscosity outlet product fraction AlLI and a more viscous or high-viscosity outlet product fraction A1L2. The less viscous Auslassproduktanteil AlLl contains low molecular weight reaction products and is therefore returned directly to an input 54 of the first reactor 50. The higher viscous, more viscous outlet product A1L2, on the other hand, contains higher molecular components and is therefore supplied to an input 61 of the second reactor for further and more efficient decomposition in the second reactor 60. In this case, the decomposition reaction in the second reactor 60 can be adapted specifically to the viscous outlet product portions A1L2 which are formed during the decomposition process in the first reactor 50. For example, in the case of wood as a raw material RS which is difficult to decompose, thermochemical decomposition under high pressure can take place in the first reactor 50, while in the second reactor 60 a catalytic decomposition or cracking reaction takes place in the second reactor 60 to crack the relatively high molecular weight fractions in the Auslassproduktanteil A1L2 can be performed.

Also on the second reactor 60, the useful products are discharged at an outlet 62 arranged at the top as the vapor phase D2 and, as a rule, further separated from one another by distillation. The second reactor 60 also has, preferably at the bottom, an outlet 63 at which outlet products A2 are withdrawn continuously or at regular intervals and fed to a separator 82 which separates the outlet products A2 into solid outlet product portions A2S and liquid outlet product portions A2L. The liquid outlet product portions A2L are again separated from a phase separator 83 into low-viscosity outlet product portions A2L1 and thick-liquid outlet product portions A2L2.

The low-viscosity outlet product portions A2L1 are returned directly to the inlet 61 of the second reactor 60 again. The viscous Auslassproduktanteile A2L2 containing higher molecular weight, not uncracked shares are fed to increase the efficiency of the process of a seed 84, in which at least one catalyst K is added in particular in a mixing and / or stirring or spinning process. The seeded viscous outlet product portion A2L2 + K is now returned to the inlet 61 of the second reactor 60. The solids fractions Al S and A2S of the outlet products A1 and A2 are in each case directly supplied by the separators 80 and 82 to an inlet 71 of the pyrolysis reactor 70 and are pyrolytically decomposed there. The resulting gaseous decomposition products are led via an outlet 72 of the pyrolysis reactor 70 as vapor phase D3 and further separated or recycled. Outlet products A3, such as tar, which are present at an outlet 73 of the pyrolysis reactor 70, can also be used as useful products.

Thus, according to FIG. 7 and the above description according to the invention, a process and system is produced in which the generation of unusable waste is avoided and the raw material RS used can be converted practically completely to produce useful substances.

LIST OF REFERENCE NUMBERS

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

SO = liquid heavy oil fraction

F = fine-grained solids G = reaction gas

H ₂ = hydrogen

R = solid and tarry reaction residue

Ö1D = oil vapor

WD = water vapor oil = liquid oil fraction

CO = carbon monoxide

CO ₂ = carbon dioxide

RI, RII = reactor I, II

PI = phase separation stage I of gas / vapor phase and solids-containing liquid phase

PII = phase separation stage II of coarse-grained solid with liquid phase fractions and liquid phase with fine-grained solid fraction

Pill = phase separation stage III of liquid phase and solid phase with residual liquid phase adhering PIV = phase separation stage IV of water phase and oil phase

KI, KII = condensation steps I, II: separation of gas phase and condensable liquid phase

GI = gas separation I of reaction gas and hydrogen

GII = gas separation II of carbon dioxide and hydrogen WDV = water vapor gasification

CO conversion = carbon monoxide conversion 2 reactor

3 reaction space

4, 5 inlet

6 outlet

7 outlet

8 conveyor

9 return line

10 exhaust valve device

11 Overpressure protection device

12 conveyor

17 outlet

18 heating

20 crusher

21, 22 rotary shaft

23 mixing and / or shearing device

24 shaft bearings

25, 26, 27 scrapbooks

29 wings

30 conveying zone

31 phase separation zone

32 wall

40 saw blades

41, 42 drive

50 reactor

51 inlet

52, 53 outlet

54 inlet

60 reactor

61 inlet

62, 63 outlet

70 pyrolysis reactor

71 inlet

80 separator

81, 83 phase separator 84 vaccine device

RS commodity

Rl raw material of wood

D vapor phase

Dl, D2, D3 vapor phase

Al, A2 outlet product

AlS, A2S solid outlet product fraction

AlL, A2L liquid outlet product fraction AlLl low-viscosity outlet product fraction

A1L2, A2L2 higher viscous viscous outlet product fraction

A2L2 + K vaccinated viscous outlet product fraction

AS swamp phase

S 'recirculated bottom phase FR conveying direction

K catalyst

Claims

claims

1. A process for the thermochemical conversion of educts containing higher molecular weight organic components, into low molecular weight products comprising organic, combustible products, a) in at least two stages, wherein b) a first stage comprises the following steps: bl) heating at least b) separating at least one first phase and one second phase from the reaction mixture, wherein the second phase comprises at least one low molecular weight organic liquid and one liquid at room temperature, b) separating a starting material into a thermoprecipitation reaction in a sump; c) a second stage comprises the steps of: c1) heating at least a portion of the first phase of the reaction mixture from the first stage to effect a thermal conversion reaction, again forming a reaction mixture having at least two phases and c2) separating a phase from the in the second stage resulting reaction mixture, which phase contains at least one low molecular weight organic, combustible product.

2. The method of claim 1, wherein the first phase of the reaction mixture formed in the first stage and / or a second phase of the reaction mixture formed in the second stage is a substantially solid phase and is preferably fed to a pyrolysis reaction in the second stage.

3. The method of claim 1 or claim 2, wherein the phase (s) comprising at least one low molecular weight organic combustible product contains, is separated in the gas phase or vapor phase from the reaction mixture or are and then preferably a material separation, in particular by distillation, is performed.

4. The method according to any one of the preceding claims, wherein the first phase is at least partially recycled to the sump of the first stage and / or in which the first phase of the resulting in the first stage reaction mixture and / or a second phase of a in the second stage, preferably formed in a sump, the reaction mixture is a substantially liquid phase and is separated into a thinner partial phase and a thicker partial phase and in which the thinner partial phase of the reaction of the respective stage is recycled.

5. The method of claim 4, wherein in the second stage, a catalytic reaction is carried out and the viscous part phase of the second phase of the resulting in the second stage reaction mixture with catalyst (s) is seeded and then the catalytic reaction of the second see Stage is returned.

A process according to claim 4 or claim 5, wherein the thicker phase of the first phase of the first stage reaction mixture is fed to the second stage reaction.

A process according to any one of the preceding claims, wherein the first stage and / or the second stage comprises a hydrogenation reaction of the reaction mixture.

8. A process for the thermochemical reaction of educts containing higher molecular weight organic components in low molecular weight products, the organic, preferably at room temperature liquid, combustible products, in particular process according to one of the preceding claims, wherein the reaction of the educts comprises at least a first stage comprising the steps of: a first heating to carry out a thermal conversion reaction in a first bottom phase, wherein a reaction mixture with three phases is formed,

- Carrying out a first hydrogenation reaction of the reaction mixture, - Performing a first at least one stage phase separation of the three phases, wherein a first phase is separated from the reaction mixture containing at least one conversion reaction catalyzing component in which the first phase at least partially recycled to the first bottom phase is separated, and a second phase is separated from the reaction mixture, which contains at least a proportion of low molecular weight organic and liquid at room temperature products which are free or poor at heteroatoms.

9. The method of claim 8, wherein the reaction of the educts comprises at least a second stage comprising the steps of: a second heating for carrying out a thermal conversion reaction in a second bottom phase, wherein a reaction mixture with three phases is formed,

Carrying out a hydrogenation reaction of the reaction mixture,

Carrying out a second at least one-stage phase separation of the three phases, a second first phase being separated from the reaction mixture which contains at least one component catalyzing the conversion reaction, characterized in that the second first phase at least partially into the second and / or first Is returned to the sump phase, and a second second phase is separated from the reaction mixture containing at least a proportion of low molecular weight organic and liquid at room temperature products which are free or poor in heteroatoms.

10. The method according to any one of the preceding claims, wherein the thermal conversion reaction in

- A temperature from a temperature range of 200 ° C to 450 ⁰ C, preferably from 290 ° C to 410 ° C, and at - a pressure in the range of 10 ^"1 bar to 80 bar, preferably from 10 ^{" 1} bar - 16 bar, more preferably from 1 bar to 16 bar, wherein: either the first stage when pressurized from the range of 10 ^"1 to 3 bar, and the second stage when pressurized from the

Range of more than 1 bar up to 80 bar, preferably from about 1 bar up to 16 bar, is performed, or vice versa.

A process according to any one of the preceding claims, wherein the thermal conversion reaction is cracking or distillative cleaning.

12. The method according to any one of the preceding claims, wherein the second stage a pyrolysis step at a temperature up to

1400 ⁰ C includes.

13. The method according to any one of the preceding, in which a pressurization with the introduction of a reducing component is performed.

14. The method according to any one of the preceding claims, wherein the first stage in a first reactor (RI) and the second stage in a second reactor (RII) is carried out, wherein preferably the reactors (RI, RII) are connected in series.

15. The method of claim 14, wherein the first separated phase from the first stage is at least partially transferred to the second reactor (RII).

16. The method according to any one of the preceding claims, wherein when exposed to pressure from the range of 10 ^"1 to 1 bar, a residence time for reacting the reaction mixture for 5 to 30 seconds in the reactor (I, II) and / or at an admission with pressure from the range of more than 1 bar up to 80 bar, preferably of more than 1 bar up to 16 bar, a residence time for reacting the reaction mixture in the reactor (I, II) is up to 3 minutes.

17. The method according to any one of the preceding claims, wherein the residence time is controlled product-oriented and / or in which during the period of residence of at least one of the steps stripping of volatile components or distilling takes place.

18. The process according to claim 17, wherein at least one gas is passed through the reaction mixture in the reactor (RI, RII) to effect stripping and / or at which the reactor (RI ₅ RII) as evaporator at a boiling temperature of the reaction mixture is operated so that the distillation takes place.

19. The method according to any one of the preceding claims, wherein the reaction mixtures, in particular in the reactors (RI, RII) and / or subjected during the reaction, a mechanical and / or caused by turbulent flow conditions mixing.

20. The process as claimed in one of the preceding claims, in which the educt (s) are subjected to a pretreatment before the first stage is carried out, wherein the pretreatment of the edducts comprises at least one of the steps:

- crushing, - separating metal (M),

Separating water (W), drying,

- and preheating includes.

A process according to any one of the preceding claims wherein the second stage is followed by condensation with at least one condensation step (KI, KII) condensing condensable products and releasing a reaction gas (G) and hydrogen (H ₂ ).

22. The method according to any one of the preceding claims, wherein the pressure in the range of about 1 bar to 80 bar, preferably from about 1 bar to 16 bar, is produced by means of or in a gas comprising hydrogen (H ₂ ), wherein the hydrogen is preferably at least partially derived from the process, and / or carbon monoxide (CO), which is introduced into the reactors (RI ₅ RII).

23. The method according to any one of the preceding claims, wherein the phase separated in a first phase separation step (PI) of the first phase separation, which contains at least a proportion of low molecular weight organic and liquid at room temperature products which are free or poor in heteroatoms, a Schrittab- followed by condensation (KI), distillation, condensation (KII) and phase separation of a fourth phase separation step (PIV).

24. A process according to any one of the preceding claims, wherein the separated phase comprising the low volatility product fraction is subjected to a step sequence with a phase separation of a second phase separation stage (PII) and a third phase separation stage (Pill) in this sequence, one enriched one Solid fraction is formed, which is subjected to drying, and wherein a resulting heavy oil fraction (SO) in at least one stage or a reactor (RI, RII) is returned.

25. The method according to any one of the preceding claims, wherein for carrying out at least one of the steps of heating, the

Preheating and drying energy is required, this energy being provided by combustion of the reaction gas (G) and / or electrical energy required to carry it out, this electric energy passing through the pressurized reactor (RI ₅ RII), which is connected to an expansion plant, via which a turbine is operated to generate electricity, is fed to the process.

26. The method according to any one of the preceding claims, comprising the step of supplying at least one of the substances

Cracking catalysts,

- Hydrogenation catalysts

- Alkaline chemicals, preferably calcium hydroxide, in at least one of the reactors (RI, RII) comprises.

27. The method according to any one of the preceding claims, wherein the or the reactant (s) at least one of the following raw materials - contaminated or uncontaminated wood,

- wood waste,

- biomass and / or energy crops,

Vegetable oils and / or animal fats, waste oil, heavy oil, bitumen and / or tar,

- halogenated or non-halogenated waste plastic,

- electrical cable waste,

- car tire waste,

- domestic waste, - sludge, in particular sewage sludge and dredging sludge, silt, in particular harbor sludge,

- include animal and / or bone meal.

28. Use of a low molecular weight, organic, liquid at room temperature, flammable product, the product gas (G) and / or hydrogen (H ₂ ) as fuel for combustion in a fuel cell for generating thermal and electrical energy, characterized in that the low molecular weight, organic, liquid at room temperature, flammable product has been produced by a process according to claims 1 to 27.

29. Device, in particular for carrying out a method according to one of claims 1 to 27, for the thermochemical conversion of educts comprising higher molecular weight organic components in low molecular weight products which comprise organic, preferably liquid at room temperature, flammable products, wherein the Device comprises:

at least two heatable reactors (RI, RII) with at least one inlet each and an outlet for charging and discharging, wherein at least one of the reactors (RI, RII) can be pressurized, at least one conveying system for conveying starting material into the reactor (RI),

at least one phase separation device for the separation of reaction phases, in which a first phase separation device is arranged on the first reactor (I), and the reactors (RI, RII) are in fluid communication with each other, so that a first separated reaction phase, the difficultly volatile components contains, from the first reactor (RI) in a second phase separation device for the separation of catalyzing

Component containing heavy oil fractions is transferable, wherein the second phase separator is equipped with a device for recycling the heavy oil fractions in the reactor (RI), and wherein a second separated reaction phase containing volatile components, from the first reactor (RI) in the second Reactor (RII) is convertible.

30. The apparatus of claim 29, wherein the second reactor (RII) at least one condensation device (KI, KII) is connected downstream.

31. The apparatus of claim 29 or 30, wherein the first phase separation means is in fluid communication with a second, third and fourth phase separation means, wherein the first phase separation means preferably comprises a still, a stripper or a rectification column, the second phase separation means and / or the third phase separator is a solid separator, preferably a centrifugal separator such as a cyclone, or a sedimentation apparatus, and wherein the fourth phase separator is a liquid-liquid separator.

32. Device according to one of claims 29 to 31, wherein at least one of the pressurizable reactors (RI, RII) is equipped with at least one pressure regulator, preferably a compressor or an expansion plant, wherein preferably the

Pressure regulation, in particular expansion plant, in connection with a turbine for the production of electric power.

33. Device according to one of claims 29 to 32, wherein the reactor (RI _J RII) is a stirred tank or rotary reactor with at least one device for temperature adjustment and for pressure control.

34. Device according to one of claims 29 to 33, wherein the reactor (RI ₅ RII) is in direct or indirect connection to a gas burning device, so that in the at least one phase separation separated combustible gas of the gas burning device are supplied to obtain burning energy can.

35. An apparatus for the thermochemical conversion of educts comprising higher molecular weight organic components, in low molecular weight products comprising organic liquid at room temperature, flammable products, in particular organic fuels, in particular apparatus or as a reactor for a device according to any one of claims 29 to 34 and or for carrying out a method according to one of claims 1 to 27, comprising: a) at least one reaction space for carrying out an at least partial thermal decomposition reaction or cracking reaction of at least one educt, b) at least one inlet for introducing the educt (s) into the reaction chamber, c) at least one outlet for discharging the low-molecular-weight products from the reaction space d) at least one comminution device arranged inside the reaction space for mechanically comminuting the educt (s)

at least one mixing and / or shearing device arranged within the reaction space, which preferably has at least one mixing and / or shear blade, for mixing and / or homogenizing the educt (s) and / or a reaction mixture and / or phase mixture in the reaction space and / or at least one, preferably rotatable or rotating scraping elements having scraper for scraping or cleaning surfaces of a wall of the reaction space.

36. Apparatus according to claim 35, wherein at least one comminution device is arranged in the region of the inlet for the educts.

37. Apparatus according to claim 35 or claim 36, wherein the shredding device comprises at least one cutting device or milling device or sawing device.

38. The apparatus of claim 37, wherein the cutting device or milling device or sawing at least one and preferably a plurality of juxtaposed about a common axis of rotation rotatable or rotating cutting, sawing or milling element (s) whose or its peripheral sides with cutting, Sawing or milling teeth is or are provided and are preferably in sections facing the at least one inlet during rotation.

39. Device according to one of the preceding claims with at least one in the reaction chamber, preferably in a conveying zone of the reaction chamber, arranged conveying device, in particular a screw conveyor, for conveying the educts (s) and / or of the resulting reaction products or (s) and optionally further substances in the reaction space from the at least one inlet into a phase separation zone of the reaction space, wherein preferably the at least one outlet for discharging the low molecular weight products from the reaction space at the

Phase separation zone is provided.

40. Apparatus according to claim 39, wherein a common axis of rotation and preferably also a common and / or driven by a common drive or driven rotary shaft for the

Conveying device, in particular screw conveyor, and the shredding device is or are provided.

41. Apparatus according to claim 39 or claim 40, wherein at least one mixing and / or shearing device in the conveying direction of

Conveyor is arranged after or downstream of the at least one inlet for the educts and / or in the phase separation zone or at a transition region between the conveying zone and phase separation zone.

42. Device according to one of the preceding claims with at least one further, preferably provided in the phase separation zone, outlet of the reaction space, wherein preferably the outlet for a present in the reaction space swamp or reaction ons and / or phase mixture or for discharging heavy and / or solid components and / or residues is provided and / or arranged below.

43. Apparatus according to claim 42, having at least one return line connected to the outlet for returning the bottoms and / or reaction and / or phase mixture into the delivery zone, preferably to at least one inlet upstream of the one or more

Inlet or inlet for the educt (s), wherein preferably in the return line at least one heating device and / or at least one conveyor for heating or conveying the bottom and / or reaction and / or phase mixture is provided.

44. Apparatus according to claim 42, wherein at least one outlet is connected to a phase separation device, which in turn is preferably connected to an inlet of a further reaction space or reactor.

45. Device according to one of the preceding claims, wherein the scraper for scrapping or cleaning surfaces of the wall of the reaction space in the phase separation zone and preferably in the region around the at least one or each outlet in the reaction space or the phase separation zone is formed.

46. Device according to one of the preceding claims, wherein a common axis of rotation and preferably also a common and / or by a common drive driven or driven rotary shaft for the scraper or scraper elements and at least one mixing and / or shearing or mixing and / or or shear wing is or are provided.

47. Apparatus according to claim 40 and claim 46, wherein the two rotary shafts are rotatably mounted coaxially relative to one another relative to each other and / or a common axis of rotation for the conveyor and the shredding device is or are provided for the scraper or the scraping elements and for the at least one mixing and / or shearing device.