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EP3247775B1 - Procédé et installation pour la transformation des déchets de matières plastiques en un combustible ayant les propriétés du diesel/du fioul - Google Patents

Procédé et installation pour la transformation des déchets de matières plastiques en un combustible ayant les propriétés du diesel/du fioul Download PDF

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Publication number
EP3247775B1
EP3247775B1 EP15707270.3A EP15707270A EP3247775B1 EP 3247775 B1 EP3247775 B1 EP 3247775B1 EP 15707270 A EP15707270 A EP 15707270A EP 3247775 B1 EP3247775 B1 EP 3247775B1
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EP
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Prior art keywords
heating device
cracking reactor
temperature
plastic materials
distillation column
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EP15707270.3A
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German (de)
English (en)
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EP3247775A1 (fr
Inventor
Gerold Weser
Teunis Christiaan VAN DER REE
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Bluealp Innovations BV
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Bluealp Innovations BV
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/40—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by indirect contact with preheated fluid other than hot combustion gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to a method and a plant for processing plastic waste, in particular plastic waste based on (i) polyolefins and / or (ii) organic liquids based on petroleum, converting such plastic waste into hydrocarbons with 1 carbon atom (methane). up to hydrocarbons with more than 22 carbon atoms.
  • Fractionated hydrocarbons are obtained from plastic waste and / or from oil-containing residues, the plastic waste and / or residues being sorted first and compressed using an entry system to exclude air.
  • the compacted mass is fed to a melting tank and heated therein, so that a separation into a first liquid phase, a first gas phase and a residue takes place, after which the first liquid phase and the first gas phase are transported into an evaporation tank, in which a second liquid phase with further heat input and a second gas phase arise, the second liquid phase being transferred to a post-heater and further heated there with further heat input, so that a third gas phase is formed, after which the second gas phase from the evaporation container and the third gas phase from the post-heater are fed to a cracking reactor, where further cracking of the long-chain hydrocarbons into short-chain hydrocarbons takes place and the resulting oil gas is then fed to a condenser in which the oil gas is condensed to liquid oil, the oil being the target product.
  • the gas phase present after the cracking zone of the reactor is, for example, fed to a distillation device which is operated in such a way that long-chain polymers condense and are fed back to the cracking zone of the reactor.
  • Relatively short-chain hydrocarbons (C1-C4) present in gaseous form after the distillation device and a cooler connected to it can be used as fuel for energy.
  • WO 2012/149590 A1 describes a process for the depolymerization of plastic material, in particular old or waste plastics, by means of heat input, the plastic material being melted and degassed into a plastic melt before it is fed to a depolymerization reactor, the plastic melt being added as a solvent from crude oil, so that the viscosity of the plastic melt solution supplied to the depolymerization reactor (3) is reduced compared to the viscosity of the plastic melt.
  • the withdrawn liquids can be cleaned in special adsorption and / or filter systems before being transferred to storage tanks and any interfering components (e.g. organic acids) that may have been removed can be removed.
  • interfering components e.g. organic acids
  • These acidic exhaust gases are preferably subjected to gas scrubbing with an alkali, such as sodium hydroxide solution, whereupon the scrubbing liquor, which contains practically no hydrocarbons, can be disposed of uncritically.
  • an alkali such as sodium hydroxide solution
  • the compression in the first stage (a2) is suitably carried out by means of a screw compressor and the second stage (a3) by means of an extruder, the compressor as well as the extruder should be heatable.
  • a preferred heating medium is thermal oil.
  • the supply of the plastic materials in a stage (a1) upstream of stage (a2) is suitably carried out via a system of at least two and preferably two buffer containers, which are preferably pressurized and / or flushed with nitrogen, and one of which is filled while the another is emptied, and both are connected to a weighing system, which allows a metered filling of the feeding system with plastic waste.
  • the recycle stream mentioned in (b5) above is obtained by pumping down plastic recyclables melted from the cracking reactor by means of a high-temperature pump, high-energy pitch and tar-like substances that do not convert into the gaseous state, and pumping excess carbon from the cracking of polymers and feeding them to a separator system .
  • This separator system is preferably a cyclone separator, optionally and preferably connected to a sedimentation tank (settling tank).
  • the gaseous hydrocarbons from the cracking reactor are preferably fed to the partial condenser via a packed column, so that the path for the separation of the hydrocarbons which have not yet been sufficiently cracked (usually more than 22 carbon atoms) becomes longer.
  • This has the positive effect that the partial condenser can be operated at a higher temperature without a substantial proportion of excessively long hydrocarbons being able to leave the cracking reactor, or that the temperature in the partial condenser does not have to be set so low that a substantial proportion of hydrocarbons also have 22 or fewer carbon atoms are returned to the cracking reactor and further cracked there, which would reduce the proportion of longer-chain hydrocarbons in the product diesel.
  • the gases / vapors emerging from the cracking reactor after the packed column and the condenser are fed to a distillation device with a reboiler and distillation column, which is at least partially designed as a packed column and with an intermediate plate.
  • the gases / vapors are broken down into a gaseous and a liquid fraction.
  • the liquid fraction is drawn off at the intermediate plate as product diesel and the gaseous fraction at the top of the distillation column.
  • the gaseous fraction is cooled so that low boilers (C5-C7 / C8) condense and can be drawn off as a liquid fraction.
  • the Uncondensed gases (C1-C4) are preferably used as fuel for heating the thermal oil.
  • the lengths of the hydrocarbons in the individual fractions can be controlled well, on the one hand by the temperature of the partial condenser, then by the length of the distillation column and the temperature in this and in the cooler.
  • the system can be operated continuously thanks to the entry of the recyclable plastics via two buffer systems.
  • Preferred first and second heating devices in the context of this invention are tubular heat exchangers which are flushed with thermal oil.
  • the temperature of the partial capacitor is adjustable, for example in a range from 150 ° C. to 350 ° C., for chain lengths of a maximum of 22 carbon atoms, preferably to 300 ° C.
  • the thermal fine separation of the gas emerging from the cracking reactor is preferably carried out by countercurrent distillation, in which part of the product diesel is returned to the distillation column above the removal point, in particular sprayed.
  • the temperature in this column can be varied or adjusted, e.g. in such a way that - depending on the setting - hydrocarbons with 8-9 to 20-22 carbon atoms are removed from the intermediate floor as product diesel.
  • the type of hydrocarbon mixture of the low boilers or the uncondensed gases can also be varied or determined via the temperature setting during cooling.
  • the product diesel and / or the low boilers are usually drawn off and stored for later use, while the uncondensed gases (C1-C4) are used directly as fuel for heating the thermal oil.
  • Any impurities present in the product diesel and / or the low boilers, in particular sulfur-containing compounds, halogen acids and organic acids can be removed by absorption and / or filtration.
  • a device for processing plastic-containing waste and organic liquids based on petroleum which is particularly suitable for carrying out the method described above, comprises a first heating device, a second heating device, a cracking reactor, and a return flow line leading from a lower region of the cracking reactor via a separator system into the feed of the molten plastic waste from the first heating device into the second heating device.
  • the first and the second heating device are each a tube heat exchanger which is flushed with thermal oil.
  • the first and / or the second heating device can also consist of a plurality of heating devices connected in series or in parallel, but as a whole they have the properties of the first and second heating devices.
  • the first and second heating devices and the cracking reactor have independently controllable heaters.
  • Preferred heating devices are heat exchangers which are designed as tubular heat exchangers, the tubes being filled with the melt and being washed around by thermal oil. This ensures the largest possible heat transfer area, which has the advantage that it is possible to work with a small temperature difference (usually max. 20 ° C) between the desired temperature in the melt and the temperature of the heat transfer medium, the thermal oil.
  • This cycle in particular the continuous pumping-out, brings about continuous mixing in the cracking reactor, which in many cases makes additional stirring unnecessary.
  • the separator system in addition to the cyclone separator, has a sedimentation tank which is arranged outside the recycle stream line but is connected to the cyclone separator, but can optionally be connected to the recycle stream line via the heater device bypass and is preferably connected .
  • the cracking reactor is equipped with a partial condenser which has a cooling / heating device which is designed such that a defined temperature can be set in the partial condenser.
  • a preferred cooling / heating device contains as a heat transfer medium a heat carrier which can be brought to a temperature by means of a temperature control unit which is required to set the temperature required within the partial condenser.
  • a preferred heat transfer medium is a thermal oil.
  • the partial capacitor in particular in combination with a packed column, has the effect that only - or at least predominantly - molecules of a defined chain length emerge from the cracking reactor.
  • a distillation device Downstream of the cracking reactor or the partial condenser is a distillation device which can be operated in such a way that long-chain molecules condense (product diesel) and from which short-chain molecules emerge as a gas phase.
  • This gas phase can be partially condensed in a cooler downstream of the distillation column (low boilers and uncondensed gases).
  • the distillation device comprises a reboiler and a distillation column, which preferably has an area designed as a packed column and also preferably an intermediate plate at which the liquid fraction, e.g. condensed product diesel, is withdrawn. Part of this liquid fraction, this product diesel, can be returned to the distillation column to optimize the temperature above the removal point, which serves for better separation of the hydrocarbon fractions.
  • a reboiler and a distillation column, which preferably has an area designed as a packed column and also preferably an intermediate plate at which the liquid fraction, e.g. condensed product diesel, is withdrawn.
  • the liquid fraction e.g. condensed product diesel
  • the cooler intended for further separation of the gas phase into low boilers and non-condensed gases has a heating / cooling device with which a defined temperature - and thus the composition of the hydrocarbon fractions - can be set in the cooler.
  • adsorption and / or filter units Downstream of the distillation column or the cooler, adsorption and / or filter units can be provided for adsorbing impurities from the light liquid and / or the product diesel.
  • These adsorption or filter units can comprise several adsorbers or filters, which alternate can be switched on or off for adsorbing or regenerating.
  • plastic waste Cleaned and pre-sorted polyolefin-rich waste, hereinafter also referred to as plastic waste, is stored in a bunker.
  • the pre-sorting can be carried out using standard methods.
  • the plastics e.g. PVC, PET recognized on the basis of their IR spectra or other characteristics and foreign substances e.g. removed by means of a selectively placeable air flow.
  • the plastic materials may still contain small amounts of contaminants, e.g. chlorine and / or sulfur containing compounds, rubber, metals, sand etc. which will be removed later in the process.
  • the plastics materials are preferably fed to the plant with the aid of the introduction system described below.
  • This system has the advantage that a permanent purging with inert gas (nitrogen) can be dispensed with when filling the melting zones and the cracking reactor, since the introduction system filled with at least partially melted plastic materials represents an airtight seal.
  • the system can also be filled with another delivery system.
  • This delivery system itself is divided into at least two zones that perform different tasks.
  • the plastic mixture to be processed is continuously fed to the introduction system from the buffer containers, which are alternately filled or emptied, first in a compressor, in which it is homogenized and essentially heated by friction. If necessary, the heating can be supported by additional heating, in particular via the outer wall of the compressor, which, e.g. with thermal oil, can be heated.
  • the material should be heated to a temperature of 120 to 150 ° C so that water vapor can be evaporated and extracted in this stage, especially by applying a slight vacuum.
  • the material is then conveyed into an extruder, preferably heated with thermal oil, and heated there to about 250-300 ° C. At these temperatures, sulfur-containing and chlorine-containing plastic parts are destroyed. HCl and H 2 S are drawn off from the extruder with a vacuum pump.
  • the acidic pollutants are preferably neutralized with sodium hydroxide solution as part of a gas wash and disposed of. At max.
  • the exhaust gas contains only small amounts of hydrocarbons at 300 ° C.
  • this technology also has the advantage that the heating devices (melting zones) and the cracking reactor are permanently flushed with inert gas (nitrogen) can be dispensed with, since the feed system or the extruder, which is already filled with partially melted plastic, is an airtight seal.
  • inert gas nitrogen
  • the extruder compresses and transports the plastic materials into a first heating device, a first tubular heat exchanger, in which the plastic materials flow through the tubes, which are washed with thermal oil as the heating medium.
  • the entire heating surface of the Tubes are chosen so large that the smallest possible temperature difference between the heating medium and plastic materials can be used. This minimizes the deposition of coke by cracking processes on the tube walls.
  • An additional advantage of tubular heat exchangers is that they are easy to clean. In order to melt the plastic materials completely, they are heated to approx. 380 ° C.
  • the output of the first heating device, the first heat exchanger is connected to a return flow line.
  • recycle stream which was passed out of the cracking reactor via a cyclone separator functioning as a slag discharge system, is mixed into the plastic melt from the first heating device.
  • the mixed stream flows into a second heating device, a second tubular heat exchanger, in which the plastic melt is heated to 400 ° C.
  • the molten plastic materials, together with the cracking gases already generated at this temperature enter the cracking reactor.
  • the plastic molecules become purely thermolytic at approx. 400 ° C, i.e. without the use of catalysts, broken down into an essentially gaseous hydrocarbon mixture (cracked).
  • the heat transfer in the cracking reactor is preferably not carried out or not only through the reactor wall (boiler principle).
  • the heat input preferably takes place over a large area with the smallest possible temperature difference, as a result of which baking and coke formation can be avoided or at least greatly reduced.
  • a suitable heating medium is a plurality of tubular heat exchangers or bundles of heating tubes which are arranged within the cracking reactor and which are filled with heat transfer medium, in particular heat transfer oil, or through which heat transfer medium flows.
  • the tube heat exchangers or heating pipes can easily be arranged within the cracking reactor in such a way that, even when they are present, a conventional, centrally located agitator can be dispensed with, i.e. that sufficient mixing of the melt is achieved solely due to the continuously pumped and recirculated recycle stream.
  • the heat transfer medium that is used to heat the plastic melt in the cracking reactor can be kept at a comparatively low temperature of preferably 405 ° C. to a maximum of 420 ° C.
  • a high temperature liquid pump At the bottom of the cracking reactor there is an outlet leading to a high temperature liquid pump.
  • This pump is able to pump fluids with a temperature of 400 ° C and is not affected by possible abrasive components in the plastic melt.
  • High-energy pitch-like and tar-like substances that do not change into the gaseous state, as well as the excess carbon that results from the cracking of polymers, are pumped through a separator system, in particular a cylindrical cyclone separator with a sedimentation container connected to it.
  • a separator system in particular a cylindrical cyclone separator with a sedimentation container connected to it.
  • the heavier parts flow downwards in the cyclone separator, preferably into a settling basin, since these still contain large amounts of molten plastic.
  • the flow rate in the settling tank is very low, so that an additional separation between high and low density parts, or solid particles and molten plastic can be achieved.
  • a phase obtained in the settling tank, which is rich in molten plastic, can be bypassed back into the recycle stream line, the separated phase of higher density, which comprises the solids, is removed and can be used as a high-energy fuel.
  • the gaseous hydrocarbon mixture formed in the cracking reactor flows from the cracking reactor into a partial condenser, and preferably first through a packed column and only then into a partial condenser.
  • This partial condenser is preferably actively heatable and / or coolable, in particular coolable and also preferably set such that hydrocarbons which do not correspond to the desired product character, e.g. diesel / heating oil character, condense and flow back into the cracking reactor, where they are cracked further until they are cracked are shorter than hydrocarbons with a maximum of 22 carbon atoms and can pass through the condenser.
  • the part boiling at lower temperatures (for example less than C20 or C22) is not retained by the condenser and is sent from it to a quench / distillation unit in which the low boilers and gases (C1-C7 / C8) are separated from the middle distillate (C8 / C9 - C20 / C22) is carried out.
  • This quench / distillation device comprises a reboiler (evaporator) and a distillation column.
  • the bottom temperature in this quench / distillation device is preferably controlled by an evaporator, a so-called reboiler, which can be heated up to 400 ° C. Hydrocarbons with more than 22 carbon atoms are accumulated in the reboiler and pumped back out of the reboiler into the cracking reactor.
  • the distillation column is at least partially designed as a packed column.
  • a tray is preferably also provided, in which at least a portion of the liquid hydrocarbons is collected.
  • These liquid hydrocarbons are drawn off and - preferably in a heat exchanger - cooled.
  • Part of the cooled liquid is returned as a recycling stream (reflux) for temperature control at the top of the distillation column, preferably after adding a radical inhibitor which acts as a stabilizer and prevents the formation of new paraffins in the product diesel.
  • the product diesel which is removed from the distillation step and preferably contains a radical inhibitor (as a result of the reflux mixed with such an inhibitor), is - as already mentioned above - preferably finally cooled in a further heat exchanger and, if appropriate, filtered and processed by means of an adsorption and / or filtering device.
  • an antioxidant is preferably added to prevent the degradation of the product diesel.
  • the steam that emerges from the top of the still includes the lower boiling components (gasoline hydrocarbons, e.g. C1 to C8).
  • This steam is cooled in an actively coolable condenser.
  • the condensate a low boiler (e.g. C5-C8), is drained into a storage container.
  • the part that is not condensed at room temperature, C1 to C4 or methane to butane is - optionally after cleaning, e.g. by means of adsorption / desorption processes - either placed in a storage container by means of a compressor, from which it can later be used in a burner for heating the heat transfer medium, or it is fed directly to such a burner.
  • the compressor 1 is preferably filled via two buffer systems (not shown) which are pressurized or flushed with nitrogen and which can be weighed in order to be able to precisely determine and regulate the quantity of plastic materials introduced. Thanks to the two buffer systems, the system can be operated continuously, since one buffer system is filled while the other buffer system is being emptied.
  • the plastic materials are homogenized, compressed and essentially heated by friction, if necessary supported by a thermal oil heater, preferably in the outer wall of the compressor, in particular a screw compressor. Heating in this compressor to 120-150 ° C allows the removal of most of the water it contains.
  • the water removal can be supported by applying a vacuum and is preferably supported by applying a vacuum.
  • the dried, compressed plastic materials are conveyed from the compressor 1 into an extruder 2, preferably heated with thermal oil, and further heated to approximately 250-300 ° C., so that at least some of the plastic materials are melted.
  • a vacuum pump sucks off the harmful gases, in particular the acidic gases HCl and H 2 S.
  • This entry system 1, 2 formed from compressor 1 and extruder 2, or this entry technique also has the advantage that when filling the melting zones and the cracking reactor to one permanent purging with inert gas (nitrogen) can be dispensed with, since the system filled with molten plastic is an airtight seal.
  • the at least partially melted plastic reaches a first heating device, a first tubular heat exchanger, 3 in which the plastic materials are heated to a temperature of 300 ° C. to 380 ° C., so that all plastic is melted.
  • This recycle stream is withdrawn from the cracking reactor 5 by means of the high-temperature pump 7 and conducted in the recycle stream line 10 via the cyclone separator 8 into the stream of plastic materials emerging from the heat exchanger 3.
  • the liquid phase formed from the molten plastic materials originating from heat exchanger 3 and the recycle stream, is melted further in a second heating device, a second heat exchanger, 4 at a temperature of 380 ° C. to 400 ° C., if necessary, whereby already a thermal one Can use cracking.
  • the molten plastic materials, together with vapors already containing hydrocarbons, are then fed to the cracking reactor 5, which can optionally be heated by means of a heat exchanger 6 and in which the molten hydrocarbons are broken down (cracked) at approx. 400 ° C.
  • the entire plastic melt which is located in the cracking reactor 5 and in the second heat exchanger 4, is continuously circulated by means of the high-temperature pump 7.
  • the gaseous hydrocarbons leaving the cracking reactor are fed to a filler column with a subsequent partial condenser 10 in which long-chain hydrocarbons (longer than e.g. C22) condense, returned to the cracking reactor 5 and cracked until they have a chain length of - depending on the setting - a maximum of C20 to Have C22.
  • long-chain hydrocarbons longer than e.g. C22
  • the gases which do not condense in the usually unheated packed column 12 or in the partial condenser 11 are fed to a distillation device 13, 14, 15, 16, in which they are broken down into a gaseous and a liquid fraction and from which the liquid fraction as middle distillate, the gaseous fraction as low boilers and uncondensed gases are withdrawn from the distillation device 13, 14, 15, 16.
  • the distillation device 13, 14, 15, 16 comprises a reboiler 13 and a distillation column 14.
  • the distillation column 14 preferably has an area designed as a packed column 15 and, if appropriate within this area containing the packed body or preferably above this area, an intermediate plate 16 on the liquid fraction (Product diesel) is collected and can be derived.
  • the product diesel derived from the distillation device 13, 14, 15, 16 is preferably cooled by means of a heat exchanger and part of this cooled product diesel can be returned to the distillation device via recycle stream line 17 in order to set optimal temperature conditions.
  • the return, the reflux usually takes place at the top of the distillation apparatus, but in any case above the intermediate base 16, the removal point of the product diesel.
  • a radical inhibitor which prevents the formation of long-chain paraffins etc. is preferably added to the product diesel serving as reflux. This addition is suitably carried out after the heat exchanger and after the reflux stream has branched off.
  • the removed liquids can be cleaned in adsorption and / or filter systems and any interfering components (e.g. organic acids) can be removed before the hydrocarbons are transferred to a storage tank.
  • any interfering components e.g. organic acids
  • At least one stabilizer Before storing the product diesel, it is preferred to add at least one stabilizer to it.
  • Free radical inhibitors as well as stabilizers and antioxidants are known to the person skilled in the art.
  • a suitable radical inhibitor is e.g. BHT (Butylhydroxitoluol)
  • suitable stabilizers are e.g. strongly basic amines
  • a suitable antioxidant is e.g. Phenyldiamine.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (20)

  1. Procédé d'obtention d'hydrocarbures à partir de déchets contenant du plastique et de liquides organiques à base de pétrole, appelés collectivement matières plastiques recyclables, de préférence à partir de matières plastiques recyclables riches en polyoléfine, par craquage purement thermolytique dans un réacteur de craquage (5), auquel un premier dispositif de chauffage (3) et un second dispositif de chauffage (4) sont connectés en amont, sans utilisation de catalyseurs, dans lequel
    (b1) les matières plastiques recyclables éventuellement et de préférence déjà partiellement fondues sont amenées dans un premier dispositif de chauffage (3) dans lequel elles sont fondues (encore davantage) à une température de 300 °C à 380 °C, (b2) les matières plastiques recyclables fondues ainsi que le flux de recyclage, qui a été pompé hors du réacteur de craquage (5), sont conduits à un second dispositif de chauffage (4), dans lequel ils sont en outre chauffés à des températures de 380 °C à 400 °C,
    (b3) les matières plastiques recyclables fondues ainsi que les vapeurs contenant des hydrocarbures déjà formées sont amenées du second dispositif de chauffage (4) au réacteur de craquage (5), dans lequel les matières plastiques recyclables fondues sont ensuite divisées (craquées) à environ 400 °C, les hydrocarbures gazeux étant amenés dans un condenseur partiel (11) dans lequel les hydrocarbures à longue chaîne se condensent et sont renvoyés vers le réacteur de craquage (5),
    (b4) les hydrocarbures à chaîne courte sortent du réacteur de craquage (5) et sont conduits dans une unité de distillation dans laquelle ils sont décomposés en une fraction gazeuse et une fraction liquide,
    (b5) les substances de type brai et goudron à haute énergie qui ne passent pas à l'état gazeux, ainsi que l'excès de carbone généré lors du craquage thermolytique des polymères sont pompés hors du réacteur de craquage (5) avec le flux de recyclage et séparés en flux de recyclage et résidus au moyen d'un système de séparateur (8, 9), le flux de recyclage étant mélangé, entre le premier dispositif de chauffage (3) et le second dispositif de chauffage (4), avec les matières plastiques recyclables fondues dans le dispositif de chauffage (3) et le résidu étant conduit à un récipient collecteur.
  2. Procédé selon la revendication 1, dans lequel les déchets plastiques sont amenés dans le premier dispositif de chauffage par l'intermédiaire d'un système d'entrée (1, 2) dans lequel
    (a2) dans une première étape, la vapeur d'eau est évacuée dans un compresseur mécanique (1) à 120 à 150 °C et une compression et un séchage sont effectués,
    (a3) dans une seconde étape, dans une extrudeuse (2), à 250 à 300 °C, les gaz acides, en particulier de HCl et H2S, sont au moins partiellement fondus et éliminés, au moyen du vide et, le cas échéant, lavés ultérieurement.
  3. Procédé selon la revendication 2, dans lequel la compression à la première étape (a2) a lieu au moyen d'un compresseur à vis.
  4. Procédé selon la revendication 2 ou 3, dans lequel (a1) les matières plastiques recyclables sont introduites dans le système d'entrée (1, 2) par l'intermédiaire d'un système d'au moins deux et de préférence deux conteneurs tampons éventuellement rincés avec du gaz inerte, en particulier de l'azote, au moins un et de préférence un conteneur tampon étant rempli tandis qu'au moins un autre et de préférence un autre conteneur tampon étant vidé dans le système d'entrée (1, 2), et tous (les deux) conteneurs tampons étant connectés à un système de pesage qui permet un remplissage dosé du système d'alimentation en déchets plastiques.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le flux de recyclage est obtenu en pompant du fond du réacteur de craquage (5) au moyen d'une pompe à haute température (7) des matières plastiques recyclables fondues, des substances de type brai et goudron à haute énergie mais qui ne passent pas à l'état gazeux et un excès de carbone généré lors du craquage des polymères et en les conduisant à un système de séparateur (8, 9), le système de séparateur (8, 9) comprenant un séparateur à cyclone (8) et un réservoir de sédimentation/décantation (9).
  6. Procédé selon l'une des revendications précédentes, dans lequel les hydrocarbures gazeux du réacteur de craquage (5) sont amenés au condenseur partiel (11) par l'intermédiaire d'une colonne garnie (12).
  7. Procédé selon l'une des revendications précédentes, dans lequel les gaz issus du réacteur de craquage (5) sont amenés, après le condenseur partiel (11), à un dispositif de distillation (13, 14, 15, 16) comprenant un rebouilleur (13) et une colonne de distillation (14), dans lequel la colonne de distillation (14) comporte une colonne garnie (15) et un fond intermédiaire (16), les gaz du réacteur de craquage (5) étant décomposés dans le dispositif de distillation (13, 14, 15, 16) en une fraction gazeuse et une fraction liquide, la fraction liquide étant retirée au niveau du fond intermédiaire (16) comme produit diesel et la fraction gazeuse étant retirée en haut de la colonne, les produits à bas point d'ébullition (par exemple en C5-C7) se condensant à partir de la fraction gazeuse retirée et étant séparés des gaz non condensés (par exemple en C1-C4).
  8. Procédé selon l'une des revendications précédentes, dans lequel l'installation fonctionne en continu.
  9. Procédé selon l'une des revendications précédentes, dans lequel le premier dispositif de chauffage (3) et le second dispositif de chauffage (4) sont chacun un échangeur de chaleur tubulaire baignant dans de l'huile thermique.
  10. Procédé selon l'une des revendications précédentes, dans lequel le condensateur partiel (11) est réglable à une température de 150 °C à 350 °C, de préférence à 300 °C, ce qui permet également de déterminer la longueur de chaîne des molécules pouvant traverser le condensateur partiel, la nature des mélanges d'hydrocarbures étant de préférence définie par l'intermédiaire du réglage de température dans le condenseur partiel dans lequel une partie de la fraction gazeuse est condensée.
  11. Procédé selon l'une des revendications précédentes, dans lequel la séparation thermique fine du gaz sortant du réacteur de craquage (5) traverse la colonne de distillation (14) au moyen d'une distillation à contre-courant de telle manière qu'une partie du produit diesel retiré au niveau du fond intermédiaire (16), de préférence après refroidissement et de préférence décalé avec un inhibiteur de radicaux, est renvoyé en haut de la colonne de distillation par l'intermédiaire d'une conduite de flux de recyclage (17), le type de mélanges d'hydrocarbures étant de préférence défini par le réglage de la température dans la colonne de distillation (14).
  12. Procédé selon l'une des revendications précédentes, dans lequel toutes les impuretés encore présentes dans le produit diesel et/ou dans le produit à bas point d'ébullition, notamment les composés soufrés, les acides halogènes et les acides organiques, sont éliminées par adsorption et/ou filtration.
  13. Procédé selon l'une des revendications précédentes, dans lequel des hydrocarbures à chaîne courte (par exemple en C1-C4) présents sous forme gazeuse après le condenseur sont utilisés à des fins énergétiques comme combustible éventuellement après compression et stockage intermédiaire.
  14. Procédé selon l'une des revendications précédentes, dans lequel les surfaces d'échange de chaleur pour le réglage de la température sont dimensionnées de sorte qu'il est possible de travailler avec un agent caloporteur à une température qui est au maximum de 20 °C au-dessus de la température souhaitée.
  15. Dispositif de traitement de déchets contenant du plastique et de liquides organiques à base de pétrole, appelés collectivement matières plastiques recyclables, comprenant un premier dispositif de chauffage (3), un second dispositif de chauffage (4), un réacteur de craquage (5) et une conduite de flux de recyclage (10), qui mène d'une zone inférieure du réacteur de craquage par l'intermédiaire d'un système de séparateur (8, 9) à l'alimentation des matières plastiques recyclables fondues du premier dispositif de chauffage (3) au second dispositif de chauffage (4), le réacteur de craquage (5) comportant un condenseur partiel (11) qui est doté d'un dispositif de refroidissement/chauffage conçu de sorte qu'une température définie peut être réglée dans le condenseur partiel (11), et le système de séparateur (8, 9) comprenant un séparateur à cyclone (8).
  16. Dispositif selon la revendication 15, dans lequel le premier dispositif de chauffage (3) et le second dispositif de chauffage (4) sont chacun un échangeur de chaleur tubulaire baignant dans de l'huile thermique, les dispositifs de chauffage (3, 4) et le réacteur de craquage (5) ayant des chauffages pouvant être réglés indépendamment les uns des autres, et/ou dans lequel les dispositifs de chauffage (3, 4) sont des échangeurs de chaleur qui sont conçus comme des échangeurs de chaleur tubulaires, les tubes étant remplis de matières plastiques recyclables fondues et baignés dans l'huile thermique.
  17. Dispositif selon l'une des revendications 15 ou 16, dans lequel le système de séparateur (8, 9), en plus du séparateur à cyclone (8), a un récipient de sédimentation/décantation (10) à l'extérieur de la conduite de flux de recyclage (10), mais qui est connecté au séparateur à cyclone (9), et qui est connecté à la conduite de flux de recyclage (10) par une dérivation côté dispositif de chauffage.
  18. Dispositif selon l'une des revendications 15 à 17, dans lequel le dispositif de refroidissement/chauffage comprend un fluide caloporteur qui peut être amené à une température nécessaire pour régler la température définie au moyen d'une unité de contrôle de la température, un fluide caloporteur préféré étant une huile thermique, de préférence une colonne garnie (12) étant disposée en amont du condenseur partiel (11) dans le réacteur de craquage (5).
  19. Dispositif selon l'une des revendications 15 à 18, dans lequel une unité de distillation (13, 14, 15, 16) comprenant un rebouilleur et une colonne de distillation (14) est disposée en aval du réacteur de craquage (5), la colonne de distillation (14) comportant un fond intermédiaire (16) de manière à ce que la fraction liquide puisse être retirée au niveau du fond intermédiaire et la fraction gazeuse en haut de la colonne, un refroidisseur destiné à refroidir la fraction liquide et/ou un condenseur destiné à condenser partiellement la fraction gazeuse étant de préférence disposés en aval de la colonne de distillation (14), le refroidisseur et/ou le condenseur comportant un dispositif de chauffage/refroidissement permettant de régler une température définie dans le refroidisseur et/ou dans le condenseur, la colonne de distillation (14) étant de préférence au moins partiellement conçue comme une colonne garnie (15) et la colonne de distillation (14) étant de préférence pourvue d'une conduite de flux de recyclage (17) de sorte qu'une partie de la fraction liquide retirée de la colonne de distillation (14) peut être renvoyée dans la colonne de distillation (14) au-dessus du fond intermédiaire (16), du point d'élimination.
  20. Dispositif selon l'une des revendications 15 à 20, comportant au moins une unité d'adsorption ou de filtrage pour adsorber les impuretés de la fraction liquide ou de la partie condensée de la fraction gazeuse, l'unité d'adsorption ou de filtrage comportant de préférence une pluralité d'adsorbeurs ou de filtres, qui peuvent être activés ou désactivés alternativement pour l'adsorption ou la régénération.
EP15707270.3A 2015-01-19 2015-01-19 Procédé et installation pour la transformation des déchets de matières plastiques en un combustible ayant les propriétés du diesel/du fioul Active EP3247775B1 (fr)

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ES2822597T3 (es) 2021-05-04
WO2016116114A8 (fr) 2017-03-16
EP3247775A1 (fr) 2017-11-29
US12448573B2 (en) 2025-10-21
PL3247775T3 (pl) 2020-12-14
US20230059944A1 (en) 2023-02-23
US20180010050A1 (en) 2018-01-11
WO2016116114A1 (fr) 2016-07-28

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