Method and plant for recycling carbon-containing composite materials having a carbon-containing matrix material and fibre-, filament- or wire-reinforcement

Abstract

The invention relates to a method for recycling carbon-containing composite materials having a carbon-containing matrix material and fibre-, filament- or wire-reinforcement, in particular glass-fibre- or carbon-fibre-reinforced plastics materials, GFRP / CFRP, wherein the method comprises the following steps: at least extensive separation of the reinforcement from the carbon-containing matrix material; gasifying and / or pyrolysing the carbon-containing matrix material in order to produce synthesis gases containing hydrogen and carbon monoxide or a fluid mixture containing hydrocarbons; and processing the products of the gasifying and / or the pyrolysing to form at least one, preferably liquid, fuel; wherein separating the reinforcement from the carbon-containing matrix material comprises coarse comminution of the composite material by cutting and / or crushing, fine comminution of the coarsely comminuted composite material by pressing and / or squeezing in order to release the comminuted reinforcement from the comminuted composite material, and separating the released comminuted reinforcement from the comminuted matrix material.

Description

[0001] Process and plant for recycling carbon-containing composite materials with carbon-containing matrix material and fiber, thread or wire reinforcement

[0002] The invention relates to a method for recycling carbon-containing composite materials with a carbon-containing matrix material and fiber, thread, or wire reinforcement, in particular glass fiber or carbon fiber reinforced plastics (GFRP / CFRP), and to a plant for recycling carbon-containing composite materials with a carbon-containing matrix material and fiber, thread, or wire reinforcement, in particular glass fiber or carbon fiber reinforced plastics (GFRP / CFRP), in particular for carrying out the method. In particular, the invention relates to a plant and a method for materially recycling waste from polymeric materials, in particular composites with polymeric components.

[0003] Composite materials with, for example, a fiber, thread, or wire reinforcement and a polymer matrix material surrounding them are currently difficult or even impossible to recycle on an industrial scale.

[0004] Car tires, for example, are recycled to a high degree, but are mainly thermally recycled, particularly through co-incineration in cement production plants.

[0005] Thermosetting composites such as glass fiber or carbon fiber reinforced plastics (GRP / CFRP) pose an even greater problem, since the separation of reinforcing fibers and matrix material has not yet been possible on a large scale.

[0006] The incineration of GRP and CFRP is also highly problematic. The glass component of GRP melts and drips downwards, forming glass layers that lead to system malfunctions. When CFRP is incinerated, however, unburned carbon fibers enter the exhaust air purification system and can cause short circuits in the electrostatic cleaning stage. Finally, landfilling is very limited. In the EU, for example, only inert material may be landfilled in large quantities. However, GRP and CFRP have a very high calorific value, comparable to that of hard coal.

[0007] This situation represents both an ecological and an operational and economic problem and affects a wide range of products manufactured in large quantities, such as blades and nacelle housings of wind turbines, boats and ships, shower trays and bathtubs, pipes, shafts and tanks, components of automobiles and aircraft, and electrical engineering.

[0008] Furthermore, as part of the politically driven restructuring of the fuel industry in Europe, defined in EU Directive 2018 / 2001 and implemented through national regulations, the demand for fluid fuels produced from non-fossil sources, particularly waste, will grow significantly in the coming years. However, available technologies for producing fluid fuels from plastics require a low proportion of inert materials. Since the fiber content is typically more than 50%, at least in high-quality GRP components, GRP is currently unavailable for this recycling pathway.

[0009] The present invention is therefore based on the object of enabling the recycling of carbon-containing composite materials with carbon-containing matrix material and fiber, thread or wire reinforcement.

[0010] According to the invention, this object is achieved by a process for recycling carbon-containing composite materials with carbon-containing matrix material and fiber, thread or wire reinforcement, in particular glass fiber or carbon fiber reinforced plastics, GRP / CFRP, wherein the process comprises the steps of: at least largely separating the reinforcement from the carbon-containing matrix material,

[0011] - gasifying and / or pyrolyzing the carbonaceous matrix material to produce a mixture containing hydrogen and carbon monoxide and

[0012] Processing the products of gasification and / or pyrolysis into at least one, preferably fluid, fuel, wherein the separation of the reinforcement from the carbon-containing matrix material comprises coarse comminution of the composite material by cutting and / or breaking, fine comminution of the coarsely comminuted composite material by pressing and / or squeezing to release the comminuted reinforcement from the comminuted composite material, and separating the released comminuted reinforcement from the comminuted matrix material.

[0013] In the first part of the plant, the proportion of reinforcement of fiber, thread or wire reinforced carbon-containing composites is reduced and in the third part of the plant, the matrix material freed from the reinforcement is converted into a, preferably fluid, fuel

[0014] Furthermore, this object is achieved by a plant or plant unit for recycling carbon-containing composite materials with carbon-containing matrix material and fiber thread or wire reinforcement, in particular glass fiber or carbon fiber reinforced plastics, GRP / CFRP, in particular for carrying out a method according to one of claims 1 to 19, wherein the plant or plant unit comprises: a first plant part for at least largely separating the reinforcement from the carbon-containing matrix material,

[0015] - a second plant section for gasifying and / or pyrolyzing the carbon-containing matrix material to produce a synthesis gas containing hydrogen and carbon monoxide or a hydrocarbon-containing fluid mixture and

[0016] - a third plant part for processing the products of gasification and / or pyrolysis into at least one, preferably fluid, fuel, wherein the first plant part contains at least one cutting or breaking coarse comminution device for coarse comminution of the composite material, at least one pressing and / or squeezing fine comminution device for fine comminution of the coarsely comminuted composite material to release the comminuted reinforcement from the comminuted composite material and a separation device for separating the released comminuted reinforcement from the comminuted matrix material.

[0017] Furthermore, the object is achieved by a system or system unit according to claim 40 and a method according to claim 41. Particular embodiments thereof result from any combination of claim 40 with one or more of claims 21 to 39 and from any combination of claim 41 with one or more of claims 2 to 19.

[0018] The method may provide for the composite material to be reduced to a length and / or width and / or thickness in the range of approximately 50 mm to approximately 150 mm during coarse comminution.

[0019] Advantageously, during fine comminution, the composite material is crushed to a length and / or width and / or thickness in the range of approximately 1 mm to approximately 5 mm.

[0020] Preferably, the fine comminution is carried out using at least one hammer mill and / or at least one grinder. This enables particularly efficient and / or cost-effective comminution.

[0021] Advantageously, frictional heat generated during fine shredding is dissipated.

[0022] According to a particular embodiment, the separation is carried out by means of at least one sieve and / or at least one air classifier.

[0023] Advantageously, after separation, the matrix material contains approximately 5 to approximately 15 wt.% fibers from the reinforcement.

[0024] In a particular embodiment of the invention, the particle size of the matrix material is reduced after sieving, e.g. by grinding or beating, to max. 1500 μm, preferably max. 500 pm.

[0025] Advantageously, gasification is carried out at a process temperature in the range of preferably approximately 950°C to approximately 1,400°C for entrained flow gasifiers and up to approximately 1,150°C for fixed bed gasifiers.

[0026] In particular, it can be provided that the gasification is carried out at a process pressure in the range of preferably approximately 5 bar to approximately 20 bar.

[0027] According to a particular embodiment, the gasification comprises a fixed bed and / or a fluidized bed or an entrained flow gasification, preferably with a sump of liquid glass.

[0028] According to a further particular embodiment of the present invention, the carbon monoxide produced by gasification is converted into a mixture of hydrogen and carbon dioxide, preferably by steam reforming and / or water gas shift.

[0029] In particular, it can be provided that hydrogen is separated from the mixture and is thus available as fuel.

[0030] It may also be provided that the carbon dioxide separated from the mixture is liquefied or compressed in order to facilitate its transport.

[0031] In a further particular embodiment of the invention, methanol can be synthesized from the carbon monoxide and hydrogen produced by gasification using the exothermic reaction CO + 2 H2<-> CH3OH.

[0032] In addition, the invention also includes embodiments in which the hydrogen is synthesized to ammonia, preferably with atmospheric nitrogen.

[0033] The gasification process requires the addition of significant amounts of oxygen, on the order of 50% by weight of the material to be gasified.

[0034] As an alternative to purchasing, oxygen can be conveniently extracted from the air, in particular by means of low-temperature rectification, pressure swing adsorption or membrane technology.

[0035] Furthermore, the reactant oxygen can also be partially replaced by carbon dioxide and / or water or water vapor.

[0036] According to a further particular embodiment, hydrogen and oxygen are produced by electrolysis and the oxygen produced is used as a reactant in gasification.

[0037] Ideally, at least 50% of the oxygen required for gasification is provided by electrolysis or extracted from the air.

[0038] According to the state of the art, the carbon dioxide produced can be released into the atmosphere.

[0039] In contrast, capturing and storing carbon dioxide, or replacing it with carbon dioxide produced from natural gas, is more environmentally friendly. This can include devices for removing undesirable trace substances from the carbon dioxide, as well as devices for compressing or liquefying the carbon dioxide.

[0040] In a further particular embodiment, carbon released during the splitting of the carbon dioxide can be synthesized into a fluid fuel or precursors thereto, the main components of which are carbon and hydrogen.

[0041] According to a further particular embodiment, the carbon dioxide separated from the mixture is separated, preferably by means of oscillating electromagnetic fields, preferably wherein the frequency of the electromagnetic fields is approximately 2000 to approximately 3000 MHz, or electrostatic fields, preferably wherein the voltage of the electrostatic fields is approximately 20,000 V to approximately 50,000 V.

[0042] In the first plant section AT1, the coarse comminution device can be designed to comminute composite materials to a length and / or width and / or thickness in the range of approximately 50 mm to approximately 150 mm.

[0043] Advantageously, the fine comminution device is designed to comminute composite materials to a length and / or width and / or thickness in the range of approximately 1 mm to approximately 5 mm.

[0044] The fine comminution device expediently comprises at least one hammer mill and / or at least one grinding mechanism, preferably with surfaces moving against one another, which at least in sections form an annular gap tapering in the direction of material flow.

[0045] The fine comminution device expediently has at least one cooling device for dissipating frictional heat.

[0046] Likewise advantageously, the separation device comprises at least one sieve and / or at least one air classifier.

[0047] Advantageously, the separation device is designed so that after separation, the matrix material contains approximately 5 to approximately 15 wt.% fibers from the reinforcement.

[0048] Advantageously, the second plant section AT2 comprises a gasification device, in particular, whose process temperature is approximately 950°C to approximately 1400°C in the case of entrained-flow gasification or approximately 1150°C in the case of fixed-bed gasification and / or whose process pressure is approximately 5 bar to approximately 15 bar. Advantageously, the gasification device is designed as a fixed-bed, entrained-flow, or fluidized-bed gasification device, preferably with a sump of liquid glass.

[0049] Advantageously, the third plant section AT3 contains a steam reforming and / or water gas shift device for converting the carbon monoxide produced in the gasification device into a mixture of hydrogen and carbon dioxide or a methanol synthesis device for synthesizing methanol from hydrogen and the carbon monoxide or carbon dioxide produced in the gasification device.

[0050] In particular, it can be provided that the third part of the plant has a separation device for separating carbon dioxide from the mixture of hydrogen and carbon dioxide produced in the third part of the plant.

[0051] It can also be provided that the third part of the plant has a compression or liquefaction device to increase the density of the separated carbon dioxide.

[0052] Advantageously, the third part of the plant comprises an ammonia synthesis device for synthesizing ammonia from the hydrogen, preferably with atmospheric nitrogen.

[0053] Advantageously, the plant further comprises a further plant part which has an electrolysis device for producing hydrogen and oxygen by means of electrolysis, which is connected to the gasification device for supplying the oxygen produced for gasification.

[0054] It can also be provided that the plant or plant unit further comprises a further plant part which has an atmospheric oxygen extraction device for extracting oxygen from the air, in particular by means of low-temperature rectification, pressure swing adsorption or membrane technology.

[0055] According to a further particular embodiment, the third plant part AT3 has a separation device for separating the carbon dioxide separated from the mixture, preferably by means of oscillating electromagnetic fields, preferably wherein the frequency of the electromagnetic fields is approximately 2000 to approximately 3000 MHz, or electrostatic fields, preferably wherein the voltage of the electrostatic fields is approximately 20,000 V to approximately 50,000 V.

[0056] In particular, it can be provided that the third part of the plant has a fuel or precursor synthesis device for the synthesis of fluid fuel or precursors thereto, the main components of which are carbon and hydrogen, from the carbon released during the separation of the carbon dioxide.

[0057] Advantageously, the plant or plant unit is designed such that at least 50% of the oxygen required by the gasification device is provided by the electrolysis device or the atmospheric oxygen recovery device.

[0058] Advantageously, the function of at least one of the system components is integrated into another of the system components.

[0059] Finally, it may be provided that the system components are not installed in close proximity, but separately from one another, even at different locations.

[0060] The present invention is based on the surprising finding that, as a result of extensive process development, the special type of separation makes stable and process-reliable gasification possible for the first time.

[0061] At least in one particular embodiment, particularly efficient and / or cost-effective shredding is made possible.

[0062] In addition, at least in one particular embodiment, a robust and process-reliable combination of machines for separating the reinforcement from the carbon-containing matrix material is provided.

[0063] Furthermore, at least in one particular embodiment, the carbon dioxide produced is separated into hydrocarbons and oxygen, wherein the oxygen covers the entire gasification requirement and the hydrocarbons can be used as fuels or for the production of fuels.

[0064] Further features and advantages of the invention will become apparent from the claims and the following description of specific embodiments with reference to the schematic drawings.

[0065] Figure 1 is a vertical sectional view of a grinder of a plant according to a particular embodiment of the present invention;

[0066] Figure 2 schematically shows components of a first plant section of a plant according to a particular embodiment of the present invention; Figure 3 schematically shows a plant with a gasification device according to a further particular embodiment of the present invention; and

[0067] Figure 4 shows schematically a plant with a pyrolysis device according to another particular embodiment of the present invention; and

[0068] Figure 5 schematically shows a plant with a gasification device according to another particular embodiment of the present invention.

[0069] In a plant or plant unit according to a particular embodiment of the present invention, carbon-containing composite materials, in this example fiber composite materials, of components are largely separated into fibers or threads and powder and granular matrix material in a first plant part.

[0070] For this purpose, the components to be recycled are first manually disassembled to a size that is smaller than the receiving opening of a coarse shredding device belonging to the first part of the system. In an advantageous embodiment of the invention, the receiving opening has a width of approximately 2 m to approximately 2.5 m and a height of approximately 1 m to approximately 2 m.

[0071] Manual disassembly is preferably carried out using saws, especially circular saws, waterjet cutters, and hydraulic tongs. The advantage of waterjet cutters over saws is that they avoid dust and produce significantly less noise. This also allows for the removal of metal components, such as frames, flanges, etc., so that they cannot damage or excessively wear a downstream shredding device, which is also part of the first part of the system.

[0072] In the coarse shredding device, the components are then cut or crushed to a size that can be accommodated by the subsequent fine shredding device. This size is preferably between approximately 50 mm and approximately 150 mm. Below approximately 50 mm, the power consumption of the shredding device can become excessive, and above approximately 150 mm, the power consumption of the downstream fine shredding device can become excessive.

[0073] The coarse shredding device can comprise several coarse shredding devices or machines. These can be designed, for example, as single- or twin-shaft machines and are preferably equipped with overload protection with reversing operation to prevent damage to the coarse shredding devices or machines. Alternatively or additionally, the use of a coarse shredding device or machine whose products are as uniform in size as possible is preferred.

[0074] The coarse grinding device can comprise several coarse grinding devices or machines of different designs. For example, crushers and / or shredders and / or hammer mills and / or cross-flow shredders can be combined.

[0075] In the fine shredding device, the shredded, still fiber-reinforced components are at least largely separated into reinforcement and matrix material. To achieve this, the material is not cut or broken, but rather pressed or crushed, which loosens and breaks down the bond between the reinforcement and the matrix material.

[0076] The fine grinding device can also comprise several fine grinding devices or machines of identical different designs, in particular hammer mills and grinding mills.

[0077] Hammer mills and grinding mills are suitable devices for fine grinding. In hammer mills, the size of the matrix material remaining after the grinding process can be adjusted, for example, by adjusting the distance between the hammers and the screen basket and the screen basket's hole size.

[0078] Grinding mechanisms that preferably have a tapered gap, at least in sections, are particularly suitable, whereby the elements of the grinding mechanism forming the gap can move against each other in order to increasingly grind the still fiber-reinforced components in this tapered gap. Advantageously, the gap is formed from, for example, two truncated cones. This construction preferably has smooth gap walls, at least in the last region, whereby grinding only takes place between the fiber-reinforced composite material elements in order to achieve the separation of the fibers, threads, or wires from the carbon-containing matrix material, whereby the fiber, thread, or wire length is largely retained. The basic shape of such a grinding mechanism is shown in EP000002288452B1 as an example, but does not limit the teaching of the invention.

[0079] In such a grinder, either the inner or outer truncated cone can serve as the stator, and the other as the rotor. The axes of the truncated cones can be identical, but can also be offset parallel to each other and / or at an angle to each other.

[0080] Advantageously, the surfaces of the truncated cones where the grinding takes place are made of a particularly tough and abrasion-resistant material, preferably with a hardness of at least HBW 500. In a preferred embodiment, the surfaces of the truncated cones where the grinding takes place are designed to be replaceable.

[0081] The surfaces of the truncated cones on which the grinding takes place can be smooth or at least partially structured.

[0082] The axes of the truncated cones preferably have an angle of between 30° and 90° relative to the horizontal, whereby the angle between the inner side of the outer truncated cone at its lowest position relative to the horizontal is preferably greater than 0° in order to support the material flow.

[0083] An advantageous embodiment of the grinders includes devices for dissipating the heat generated during grinding. In the simplest embodiment, these comprise cooling fins, which are preferably arranged on the movable part of the grinder in such a way as to achieve the greatest possible forced convection. Especially on the stationary part, forced convection can also be achieved with a fan.

[0084] Heat can also be dissipated using cooling water, for example. For stationary elements, this can be achieved by using pipe coils attached to the wall or cooling water channels running within the wall. Especially for moving parts, it can be advantageous to spray cooling water into or onto the element. If the grinder is not installed in a frost-protected area, the cooling water should preferably be treated with an antifreeze additive.

[0085] In this example, the product of the grinder is a mixture of glass fibers and powdered or granular matrix material.

[0086] Figure 1 shows a grinding mill 100 of a first plant part AT1 (see, for example, Figure 2) of a plant for recycling carbon-containing composite materials with carbon-containing matrix material and fiber, thread or wire reinforcement according to a particular embodiment of the present invention.

[0087] The grinder 100 comprises a frame 106, a stator 101 which is conical in its lower region and mounted in the frame 106, and a rotor 102 which is also conical in its lower region, wherein the truncated cones of the stator and the rotor form a downwardly tapered annular gap S. The rotor 102 is driven by a motor, e.g., a geared motor 103, via a shaft, e.g., a hollow shaft 104, which is mounted in the geared motor 103 and a bearing, e.g., a thrust bearing 105. The lumen of the hollow shaft 104 is blocked at a point 104.1 in this example and has two openings 104.2 and 104.3 in this example. This allows the rotor to be cooled by admitting, for example, water as cooling water into the upper opening 104.2 of the hollow shaft 104.

[0088] In this example, the rotor 102 has several inspection openings 102.1 and can include devices such as baffles or spray nozzles for distributing the cooling water and thus improving heat transfer. The pre-shredded composite materials are fed to the grinder 100 via a feed opening 101.1. In the tapered conical annular gap S between the stator 101 and the rotor 102, the composite materials are ground and exit the grinder 100 via a discharge opening 101.2.

[0089] Further embodiments of the fine comminution device according to the invention include, for example, ball or hammer mills.

[0090] In this example, the glass fibers can be separated from the matrix material in a separation device connected to the mill. Complete separation is not required; a reduction in the glass fiber content from, for example, the original 50-60% to, for example, 5-15% is generally sufficient for trouble-free reuse of the material in the second section of a plant according to a particular embodiment of the present invention.

[0091] A preferred separation method is sieving. The prerequisite for sieving is that the majority of the fibers are longer than the diameter of the powdered or granular matrix material. Preferably, at least 90% by weight of the fibers have a length that is greater than the diameter of 90% by weight of the matrix material.

[0092] Since the density of glass is more than twice that of the polymer matrix material, a high degree of separation at high throughput can be achieved, for example, with air classifiers.

[0093] A separation device can, for example, also consist of a combination of different screening systems and air classifiers.

[0094] Figure 2 schematically shows components of a first plant section AT1 of a plant 200 according to a particular embodiment of the present invention. The first plant section, in which the reinforcement content of the fiber-, thread-, or wire-reinforced carbon-containing composite materials is reduced, comprises a coarse comminution device 1, a fine comminution device 2, and a separation device 3. Components made of composite materials 11, whose dimensions may, for example, amount to several meters, are broken or crushed in the coarse comminution device 1. Depending on the downstream equipment, the components can preferably be crushed to a size of approximately 50 mm to approximately 800 mm. In this exemplary embodiment, the coarse comminution device 1 comprises only one coarse comminution device or machine.

[0095] In this example, the fine comminution device 2 comprises a hammer mill 2-1 and a grinder 2-2. In the hammer mill 2-1, the bond between the glass fibers 16 and the matrix material 15 is loosened. The two fractions are then separated in the grinder 2-2.

[0096] In this example, the separation device 3 comprises an air classifier 3-1, in which part of the matrix material 15 is separated, and a sieve or a sieving device 3-2, in which the remaining material is largely completely separated into matrix material 15 and glass fibers 16.

[0097] The connections between the fine comminution device 2 and the separation device 3 are preferably designed to be closed to prevent dust from spreading. This also applies to the connection of the screening device 3-2 to any storage devices for, in this example, the glass fibers and the powdered matrix material.

[0098] The first part of the system preferably comprises air extraction and filter systems and / or explosion protection and fire extinguishing equipment and / or is preferably installed spatially separated from other parts of the system, e.g. in a separate hall.

[0099] Preferably, a pelletizing device is (also) provided in order to reduce the risk of dust explosions of the powdered matrix material and / or to simplify its transport and further processing.

[0100] In a third part of the plant (not shown in Figure 2), fluid fuels are produced from the products of the first part of the plant.

[0101] Preferably, a second plant part (not shown in Figure 2), which is connected downstream of the first plant part and upstream of the third plant part, has a pyrolysis device for producing predominantly liquid hydrocarbons or a gasification device for producing a synthesis gas with the main components hydrogen and carbon monoxide.

[0102] The gasification device can, for example, be designed for continuous and / or batch operation.

[0103] In a batch operation design, quasi-continuous operation can be achieved by having several gas generation units in the plant, which allow for staggered operation and material changes.

[0104] Continuous devices for synthesis gas production are advantageous because they facilitate the process control of downstream devices. Examples such as those described in EP2639289A1 have proven successful.

[0105] The gasification temperature is advantageously between approximately 1000°C and approximately 1100°C, since the greatest hydrogen production takes place in this range.

[0106] The gasification pressure is preferably between approximately 5 bar and approximately 20 bar. While hydrogen production would be somewhat higher at ambient pressure, larger gas volumes would have to be processed and compressed in the subsequent process steps, which would reduce the overall efficiency.

[0107] In principle, both fluidized-bed and fixed-bed gasification can be used. Fixed-bed gasification enables a more stable process, especially with fluctuating quality and variable size of the input materials. Furthermore, fixed-bed gasification allows for the confinement of the vast majority of by-products in a vitrified and thus extremely inert slag.

[0108] In this example, a fixed-bed gasification system with a liquid glass slurry as the fixed bed is particularly advantageous. In this case, the remaining glass fiber content in the products of the first plant section is actually advantageous because it replaces the glass additive otherwise required to maintain the glass slurry.

[0109] Plasma gasification can also be considered. This has the advantage that, due to the high process temperatures of over 3000°C, the synthesis gas contains hardly any higher molecular weight components. The disadvantages are the lower hydrogen concentration in the synthesis gas and the very high power consumption.

[0110] A combination of a gasification device with process temperatures up to 1500°C and a downstream plasma gasification process with temperatures above 2000°C also offers advantages. This increases hydrogen production and reduces electricity consumption compared to pure plasma gasification.

[0111] In a third plant section, according to a special embodiment, the hydrocarbon-containing mixture from the pyrolysis device is synthesized into the desired end products. Preferably, methanol (CO + H2 -> CH3OH) is produced from the carbon monoxide contained in the synthesis gas, or further hydrogen and carbon dioxide (CO + H2O -> CO2 + H2) are produced by steam reformation (water gas shift reaction).

[0112] The second and / or third plant section advantageously includes devices for cooling and / or purifying the gases of undesirable or toxic components. Depending on the contamination of the synthesis gas, an air filter and / or water scrubber, for example, may be sufficient. In the case of contamination with sulfur, chlorine, etc., it may be necessary to use chemical or absorption / adsorption filtration systems.

[0113] In the third part of the plant, a produced gas mixture can be separated, if necessary, and the resulting fluid fuel can be released. The separation of a hydrogen-carbon dioxide mixture can, in principle, be achieved using all available technologies, such as membrane, absorption, and adsorption systems. If the gas mixture is present at elevated pressures, membrane separation systems are particularly suitable, because the main effort in this case is to compress the gas mixture to approximately 10 bar, and this can be significantly reduced.

[0114] In the simplest case, the hydrogen can be released, for example, via a compressor station that feeds the produced hydrogen into a pipeline. However, this system component can also contain components for storing the fuel and, if necessary, for liquefying it.

[0115] The third part of the plant can also have an ammonia synthesis device in which produced hydrogen is converted into ammonia with atmospheric nitrogen (e.g. using a Haber-Bosch process) in order to convert it into a fuel that is easier to transport and store.

[0116] The plant can also have a section in which waste heat from other plant components can be collected and made available as process heat. At appropriate temperatures, electricity can also be generated, for example, using a generator coupled to a steam turbine. The state of the art in gasification plants is to release the produced carbon dioxide into the atmosphere. According to a particular embodiment of the present invention, however, the carbon dioxide is processed for further uses. This can include components by means of which the produced carbon dioxide can be compressed or liquefied and thus made available as a replacement for fossil-based carbon dioxide.

[0117] Furthermore, the plant can be provided with one or more components to produce oxygen to supply the gasification plant. An electrolyzer is advantageously used in this case, as the resulting hydrogen further increases the plant's total hydrogen production:

[0118] For example, the gasification of 22,000 liters of plastic requires approximately 11,500 liters of oxygen. This produces 3,000 tons of hydrogen. If these 11,500 tons of oxygen are extracted through electrolysis, an additional 1,275 tons of hydrogen are produced.

[0119] According to a particular embodiment, at least one atmospheric oxygen extraction device for extracting oxygen from the atmosphere, such as low-temperature rectification, pressure swing adsorption or membrane technology, can also be provided.

[0120] It is particularly advantageous to produce the oxygen to supply the gasification device from the carbon dioxide produced.

[0121] A preferred embodiment of the plant includes devices for separating the carbon dioxide into carbon and oxygen and for synthesizing the carbon into hydrocarbons, which can be further processed, for example, in a refinery into commercially available fuels and raw materials for the chemical industry.

[0122] The separation devices for separating the carbon dioxide preferably have elements for generating oscillating electromagnetic or electrostatic fields, which assist the separation of the CO double formations.

[0123] The preferred frequency of electromagnetic fields is approximately 200 to approximately 3000 MHz. The preferred voltage for electrostatic fields is approximately 20,000 to approximately 50,000 V.

[0124] The carbon dioxide production in a state-of-the-art gasification device is approximately twice the mass of the carbonaceous materials to be gasified. The oxygen content in the carbon dioxide is 16 forty-fourths of its mass, i.e., 32 forty-fourths of the mass of the carbonaceous materials to be gasified, and thus significantly more than the oxygen demand of the gasification device, thus meeting the objective of covering the entire oxygen demand of the gasification.

[0125] Figure 3 schematically illustrates a system 300 with a gasification device 4 according to a further particular embodiment of the present invention. For the sake of clarity, the illustration of, for example, pumps / compressors, throttle devices, heat exchangers,

[0126] Conveyor systems, buffer storage, etc. are dispensed with.

[0127] In a first plant section AT1, previously manually disassembled composite materials 11, comminuted by a coarse comminution device 1, as described above with reference to Figure(s) 1 and / or 2, are fed via a fine comminution device 2, as described above with reference to Figure(s) 1 and / or 2, and a separation device 3, as described above with reference to Figure(s) 1 and / or 2, to a gasification device (gasifier) ​​4 in a second plant section AT2. Glass fibers 16 are separated in the separation device 3. A synthesis gas produced in the gasification device 4 with a supplied reactant 17 is fed to a steam reforming device (steam reformer) 5, and slag 13 is removed. The reactant 17 can, in particular, comprise oxygen, carbon dioxide, and / or water (steam).In the steam reformer 5, the CO portion of the synthesis gas produced in the gasification device 4 is synthesized into H2 and CO2 using steam generated in a steam generator 6. In a purification system 7, the synthesis gas can be purified and, if necessary, cooled. In a separation device 8, the H2 / CO2 mixture is separated, i.e., hydrogen 12 is obtained. In a separation device 9 in a third plant section AT3, the remaining CO2 is separated into oxygen and carbon, and hydrocarbons are synthesized. The hydrocarbons can be used as fuel or as a precursor, and in this example, oxygen is metered into the gasifier 4.

[0128] Figure 4 schematically illustrates a system 400 with a pyrolysis device 40 according to another specific embodiment of the present invention. For the sake of clarity, pumps / compressors, throttling devices, heat exchangers, conveyors, buffer storage, cooling and cleaning devices, etc., have been omitted.

[0129] In a first plant section AT1, composite materials 11 comminuted and previously manually disassembled by a coarse comminution device 1, as described above with reference to Figure(s) 1 and / or 2 and / or 3, are fed via a fine comminution device 2, as described above with reference to Figure(s) 1 and / or 2 and / or 3, and a separation device 3, as described above with reference to Figure(s) 1 and / or 2 and / or 3, to the pyrolysis device (pyrolysis reactor) 40 in a second plant section AT2. Glass fibers 16 are separated in a separation device 3.

[0130] In the pyrolysis device 40, liquid hydrocarbons 14a and gaseous hydrocarbons 14b are produced.

[0131] Figure 5 illustrates a further particular embodiment of a system 500 according to the invention. In a first system section AT1, previously manually disassembled composite materials 11 are fed to a coarse comminution device 1, in which the matrix material is removed from the glass fiber fabric by beating, whereby the glass fiber fabric remains largely intact.

[0132] The dissolved matrix material is then comminuted in a fine comminution device 2 to a particle size of, for example, no more than 1.5 mm, preferably, for example, 0.5 mm. In a second plant section AT2, this powdered matrix material is fed to an entrained-flow gasifier, in which synthesis gas containing hydrogen and carbon monoxide is produced.

[0133] A synthesis gas produced in a gasification device 4 with a supplied reactant 17 is fed to a steam reforming device (steam reformer) 5, and slag 13 is removed. The reactant 17 can, in particular, comprise oxygen, carbon dioxide, and / or water (steam). In the steam reformer 5, the CO portion of the synthesis gas produced in the gasification device 4 is synthesized into H2 and CO2 with the aid of steam produced in a steam generator 6. In a purification system 7, the synthesis gas can be purified and, if necessary, cooled. In a separation device 8, the H2 / CO2 mixture is separated, i.e., hydrogen 12 is obtained. In a separation device 9 in a third plant section AT3, the remaining CO2 is separated into oxygen and carbon, and hydrocarbons are synthesized. The hydrocarbons can be used as fuel or as a precursor, and in this example oxygen is added to the carburetor 4.

[0134] The system components described above can be installed in close proximity, but also separately, even at different locations.

[0135] The features of the invention disclosed in the above description, in the drawings and in the claims may be essential both individually and in any combination for the realization of the invention in its various embodiments.

[0136] List of reference symbols

[0137] 1 coarse shredding device

[0138] 2 Fine grinding device

[0139] 2-1 Hammer Mill

[0140] 2-2 grinder

[0141] 3 Separation device

[0142] 3-1 Wind sifter

[0143] 3-2 Screening device

[0144] 4 Gasification device

[0145] 5 steam reformers

[0146] 6 steam generators

[0147] 7 Cleaning system

[0148] 8 Separator

[0149] 9 ripping device

[0150] 11 Composite material

[0151] 12 Hydrogen

[0152] 13 Slag 14a Liquid hydrocarbons

[0153] 14b gaseous hydrocarbons

[0154] 15 Matrix material

[0155] 16 glass fibers

[0156] 17 Reactant

[0157] 40 Pyrolysis device 100 Grinder

[0158] 101 Stator

[0159] 101.1 Feed opening

[0160] 101.2 Discharge opening

[0161] 102 Rotor

[0162] 102.1 Inspection openings

[0163] 103 Geared motor

[0164] 104 Hollow shaft

[0165] 104.1 Position

[0166] 104.2 Opening 104.3 Opening 105 Thrust bearing 106 Frame

[0167] 200 plant 300 plant 400 plant 500 plant AT1first plant section AT2second plant section AT3third plant section

[0168] S annular gap

Claims

Claims 1. A method for recycling carbon-containing composite materials (11) with carbon-containing matrix material (15) and fiber, thread or wire reinforcement, in particular glass fiber (16) or carbon fiber reinforced plastics, GFRP / CFRP, wherein the method comprises the steps of: at least extensive separation of the reinforcement from the carbon-containing matrix material (15), Gasification and / or pyrolysis of the carbon-containing matrix material (15) to produce synthesis gas containing hydrogen and carbon monoxide or a fluid mixture containing hydrocarbons and Processing the products of gasification and / or pyrolysis into at least one, preferably fluid, fuel (14), wherein the separation of the reinforcement from the carbon-containing matrix material (15) comprises coarse comminution of the composite material (11) by cutting and / or breaking, fine comminution of the coarsely comminuted composite material (11) by pressing and / or squeezing to release the comminuted reinforcement from the comminuted composite material (11), and separating the released comminuted reinforcement from the comminuted matrix material (15).

2. Method according to claim 1, wherein during coarse comminution the composite material (11) is reduced to a length and / or width and / or thickness in the range of approximately 50 mm to approximately 150 mm.

3. Method according to claim 1 or 2, wherein, during fine comminution, the composite material (11) is comminuted to a length and / or width and / or thickness in the range of approximately 1 mm to approximately 5 mm.

4. Method according to one of the preceding claims, wherein the fine comminution is carried out by means of at least one hammer mill (2-1) and / or at least one grinding mill (2-2; 100).

5. Method according to one of the preceding claims, wherein frictional heat generated during fine comminution is dissipated. A method according to any one of the preceding claims, wherein the separation is carried out using at least one sieve (3-2) and / or at least one air classifier (3-1). A method according to any one of the preceding claims, wherein after separation the matrix material (15) contains approximately 5 to approximately 15 wt% fibers from the reinforcement. A method according to any one of the preceding claims, wherein the gasification is carried out at a process temperature preferably in the range of approximately 950°C to approximately 1400°C for entrained-flow gasifiers, and up to approximately 1150°C for fixed-bed gasifiers. A method according to any one of the preceding claims, wherein the gasification is carried out at a process pressure preferably in the range of approximately 5 bar to approximately 20 bar. A method according to any one of the preceding claims, wherein the gasification comprises fixed-bed and / or entrained-flow or fluidized-bed gasification, preferably with a sump of liquid glass.A method according to any one of the preceding claims, wherein the carbon monoxide produced by gasification is converted, preferably by steam reforming and / or water-gas shift, into a mixture of hydrogen and carbon dioxide. A method according to claim 11, wherein hydrogen is separated from the mixture. A method according to claim 12, wherein the carbon dioxide separated from the mixture is liquefied or compressed. A method according to any one of claims 11 to 13, wherein the hydrogen is synthesized to ammonia, preferably with atmospheric nitrogen. A method according to any one of the preceding claims, wherein hydrogen and oxygen are produced by electrolysis and the oxygen produced is used as a reactant in gasification. A method according to any one of claims 1 to 14, wherein oxygen is obtained from the air, in particular by low-temperature rectification, pressure swing adsorption, or membrane technology. - A method according to claim 15 or 16, wherein at least 50% of the oxygen required for gasification is provided by electrolysis or obtained from the air. A method according to any one of claims 12 to 17, wherein the carbon dioxide separated from the mixture is preferably separated by means of oscillating electromagnetic fields, preferably wherein the frequency of the electromagnetic fields is approximately 2000 to approximately 3000 MHz, or electrostatic fields, preferably wherein the voltage of the electrostatic fields is approximately 20,000 V to approximately 50,000 V. A method according to claim 18, wherein carbon released during the separation of the carbon dioxide is synthesized into a fluid fuel (14) or precursors thereto, the main components of which are carbon and hydrogen.Plant or plant unit (200; 300; 400) for recycling carbon-containing composite materials (11) with carbon-containing matrix material (15) and fiber thread or wire reinforcement, in particular glass fiber (16) or carbon fiber reinforced plastics, GFRP / CFRP, in particular for carrying out a process according to one of the preceding claims, wherein the plant or plant unitThe plant unit (200; 300; 400) comprises: a first plant section AT1 for at least extensively separating the reinforcement from the carbon-containing matrix material (15), a second plant section AT2 for gasifying and / or pyrolyzing the carbon-containing matrix material (15) to produce synthesis gas containing hydrogen and carbon monoxide or a fluid mixture containing hydrocarbons, and a third plant section AT3 for processing the products of gasification or pyrolysis into at least one, preferably fluid, fuel (14), wherein the first plant section AT1 comprises at least a cutting or crushing coarse comminution device (1) for coarsely comminuting the composite material (11), at least one pressing or squeezing fine comminution device (2) for finely comminuting the coarsely comminutioned composite material (11) to separate the comminutioned reinforcement from the comminutioned composite material (11), and a separation device. (3) for separating the extracted, crushed reinforcement from the crushed matrix material (15). Plant or plant unit (200; 300; 400) according to claim 20, wherein the coarse crushing device (1) is configured to crush composite materials (11) to a length and / or width and / or thickness in the range of approximately 50 mm to approximately 150 mm. Plant or plant unit (200; 300; 400) according to claim 20 or 21, wherein the fine crushing device (2) is configured to crush composite materials (11) to a length and / or width and / or thickness in the range of approximately 1 mm to approximately 5 mm. Plant or plant unit (200; 300; 400) according to any one of claims 20 to 22, wherein the fine comminution device (2) comprises at least one hammer mill (2-1) and / or at least one grinding mill (2-2; 100), preferably with surfaces moving relative to each other which form at least sectionally an annular gap S tapering in the direction of material flow. Plant or plant unit (200; 300; 400) according to one of claims 20 to 23, wherein the fine grinding device (2) has at least one cooling device for dissipating frictional heat. Plant or plant unit (200; 300; 400) according to one of claims 20 to 24, wherein the separation device (3) comprises at least one sieve (3-2) and / or at least one air classifier (3-1). Plant or plant unit (200; 300; 400) according to any one of claims 20 to 25, wherein the separation device (3) is designed such that, after separation, the matrix material (15) contains approximately 5 to approximately 15 wt% fibers from the reinforcement. Plant or plant unit (300) according to any one of claims 20 to 26, wherein the second plant part AT2 comprises a gasification device (4), in particular wherein its process temperature is approximately 950°C to approximately 1400°C in the case of a fluidized bed gasifier, and up to approximately 1150°C in the case of fixed-bed gasifiers, and / or its process pressure is approximately 5 bar to approximately 20 bar. Plant or plant unit (300) according to any one of claims 20 to 27, wherein the gasification device (4) is a fixed-bed or fluidized bed gasifier. A fluidized bed gasification device, preferably designed with a sump of liquid glass. - A plant or plant unit (300) according to claim 27 or 28, wherein the third plant part AT3 comprises a steam reforming (5) and / or water-gas shift device for converting the carbon monoxide produced in the gasification device (4) into a mixture of hydrogen and carbon dioxide, or a methanol synthesis device for synthesizing methanol from hydrogen and the carbon monoxide or carbon dioxide produced in the gasification device (4). - A plant or plant unit (300) according to claim 29, wherein the third plant part AT3 comprises a separation device (8) for separating carbon dioxide from the mixture of hydrogen and carbon dioxide produced in the third plant part AT3.Plant or plant unit (300) according to claim 30, wherein the third plant part AT3 comprises a compression or liquefaction device for increasing the density of the separated carbon dioxide. Plant or plant unit (300) according to any one of claims 29 to 31, wherein it comprises an ammonia synthesis device for synthesizing ammonia from the hydrogen, preferably with atmospheric nitrogen. Plant or plant unit (300) according to any one of claims 27 to 32, further comprising a further plant part comprising an electrolysis device for producing hydrogen and oxygen by electrolysis, which is connected to the gasification device (4) for supplying the produced oxygen for gasification.A system or system unit (300) according to any one of claims 27 to 32, further comprising a further system part comprising an air oxygen recovery device for obtaining oxygen from the air, in particular by means of low-temperature rectification, pressure swing adsorption or membrane technology. A system or system unit (300) according to claim 33 or 34, wherein it is designed such that at least 50% of the oxygen required by the gasification device (4) is provided by the electrolysis device or the air oxygen recovery device. A plant or plant unit (300) according to any one of claims 30 to 35, wherein the third plant part AT3 comprises a separation device (9) for separating the carbon dioxide separated from the mixture, preferably by means of oscillating electromagnetic fields, preferably wherein the frequency of the electromagnetic fields is approximately 2000 to approximately 3000 MHz, or electrostatic fields, preferably wherein the voltage of the electrostatic fields is approximately 20,000 V to approximately 50,000 V. A plant or plant unit (300) according to claim 36, wherein the third plant part AT3 comprises a fuel or precursor synthesis device for synthesizing fluid fuel (14a) or precursors thereto, the main components of which are carbon and hydrogen, from the carbon released during the separation of the carbon dioxide.Plant or plant unit (200; 300; 400) according to any one of claims 20 to 37, wherein the function of at least one of the plant parts is integrated into another of the plant parts. Plant or plant unit (200; 300; 400) according to any one of claims 20 to 38, wherein the plant parts are not installed in close proximity but separately from one another, even at different locations. Plant or plant unit (500) for recycling carbon-containing composite materials (11) with carbon-containing matrix material (15) and fiber. Thread or wire reinforcement, in particular fiberglass (16)- or carbon fiber reinforced plastics, GFRP / CFRP, in particular for carrying out a process according to one of claims 1 to 19 and 41, wherein the plant or plant unit (500) comprises: a first plant part AT1 for at least extensively separating the reinforcement from the carbon-containing matrix material (15), a second plant part AT2 for gasifying and / or pyrolyzing the carbon-containing matrix material (15) to produce a synthesis gas containing hydrogen and carbon monoxide, or a fluid mixture containing hydrocarbons, and a third plant part AT3 for processing the products of gasification or pyrolysis into at least one, preferably fluid, fuel (14), wherein the first plant component AT1 comprises at least a coarse crushing device designed to remove the matrix material by impact from fabric made of glass fiber reinforced plastic, and a fine crushing device designed to reduce the removed matrix material, preferably to a particle size of max. 1.5 mm, particularly preferably 0.5 mm, and wherein the second plant component AT2 comprises a entrained flow carburetor, preferably wherein the entrained flow carburetor is operated or can be operated at temperatures in the range of 1200°C to 1450°C. Method for recycling carbon-containing composite materials (11) with carbon-containing matrix material (15) and fiber, thread or wire reinforcement, in particular glass fiber (16) or carbon fiber reinforced plastics, GFRP / CFRP, wherein the method comprises the steps: at least extensive separation of the reinforcement from the carbon-containing matrix material (15), Gasification and / or pyrolysis of the carbon-containing matrix material (15) to produce synthesis gas containing hydrogen and carbon monoxide or a fluid mixture containing hydrocarbons and Processing the products of gasification and / or pyrolysis into at least one, preferably fluid, fuel (14), wherein the separation of the reinforcement from the carbon-containing matrix material (15) comprises coarse comminution of the composite material (11) by beating the matrix material out of the glass fiber fabric, and fine comminution of the dissolved matrix material, preferably to a particle size of max. 1.5 mm, particularly preferably 0.5 mm, and the finely comminuted matrix material is subjected to entrained flow gasification, preferably at temperatures in the range of 1200°C to 1450°C.

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