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EP4450592A1 - Procédé d'obtention d'une cire à partir d'un résidu de pyrolyse - Google Patents

Procédé d'obtention d'une cire à partir d'un résidu de pyrolyse Download PDF

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Publication number
EP4450592A1
EP4450592A1 EP23168522.3A EP23168522A EP4450592A1 EP 4450592 A1 EP4450592 A1 EP 4450592A1 EP 23168522 A EP23168522 A EP 23168522A EP 4450592 A1 EP4450592 A1 EP 4450592A1
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EP
European Patent Office
Prior art keywords
wax
solvent
pyrolysis residue
mixture
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP23168522.3A
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German (de)
English (en)
Inventor
Matthias MASTALIR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OMV Downstream GmbH
Original Assignee
OMV Downstream GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by OMV Downstream GmbH filed Critical OMV Downstream GmbH
Priority to EP23168522.3A priority Critical patent/EP4450592A1/fr
Priority to CN202480025442.3A priority patent/CN121002149A/zh
Priority to PCT/EP2024/060468 priority patent/WO2024218178A1/fr
Publication of EP4450592A1 publication Critical patent/EP4450592A1/fr
Priority to MX2025010796A priority patent/MX2025010796A/es
Withdrawn legal-status Critical Current

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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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • 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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • 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
    • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
    • C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents

Definitions

  • the invention relates to a process for obtaining a wax from a pyrolysis residue.
  • the separation of the wax serves primarily to purify the starting product.
  • the separated wax can have a relatively low purity.
  • One object of the invention is to provide such a process.
  • the invention is based on the finding that a Pyrolysis residue, particularly a pyrolysis residue obtained by plastic pyrolysis, is a valuable source of wax.
  • a Pyrolysis residue particularly a pyrolysis residue obtained by plastic pyrolysis
  • the wax can dissolve largely or even completely in the solvent and can subsequently be separated from the pyrolysis residue with a high degree of purity.
  • the wax obtained can represent a sustainable alternative to wax obtained directly from petroleum.
  • the pyrolysis residue can be obtained by pyrolyzing a plastic, in particular a waste plastic.
  • the pyrolysis can take place in a pyrolysis reactor, preferably at a temperature of 300 to 500 °C, in particular 350 to 450 °C. This makes it possible to achieve a good balance between economic viability and process efficiency.
  • the pyrolysis may be thermal pyrolysis (i.e. thermal cracking without the addition of a catalyst) and/or catalytic pyrolysis (i.e. catalytic cracking).
  • Thermal pyrolysis is preferred to avoid any contamination of the wax and/or the solid due to catalyst components.
  • Pyrolysis can be carried out largely in the absence of oxygen, particularly in an inert atmosphere, for example under nitrogen. A lack of oxygen or the absence of oxygen can prevent complete combustion and a polymer contained in the plastic can be split or depolymerized.
  • the pyrolysis residue is therefore obtained by pyrolyzing a plastic and separating at least one fraction, preferably a gaseous fraction, from the pyrolyzed plastic.
  • the separated fraction preferably has a lower boiling temperature (or a lower boiling range) than the pyrolysis residue.
  • the pyrolysis residue has a boiling temperature (or a lower end of a boiling range) of at least 100 °C, preferably at least 150 °C, more preferably at least 200 °C, more preferably at least 240 °C, more preferably at least 270 °C, more preferably at least 300 °C.
  • the pyrolysis residue preferably has a boiling temperature (or a lower end of a boiling range) in the range from 100 °C to 700 °C, preferably from 150 °C to 600 °C, more preferably from 200 °C to 500 °C, more preferably from 240 °C to 460 °C, more preferably from 270 °C to 430 °C, more preferably from 300 °C to 400 °C. It has been found that fractions with such a boiling temperature can have particularly high wax contents and are therefore particularly well suited for the process according to the invention.
  • the pyrolysis residue is a spindle oil, preferably with a boiling temperature (or a lower end of a boiling range) in the range from 300 °C to 400 °C.
  • the wax content of the pyrolysis residue can be, for example, approximately 50% by weight.
  • the boiling temperature (or boiling range) can preferably be determined using the ASTM D7500-15:2019 standard. Alternatively, the ASTM D2887-22:2022 standard can be used.
  • the plastic preferably comprises a polyolefin and/or a polystyrene (PS), whereby the polyolefin can comprise a polyethylene (PE) and/or a polypropylene (PP).
  • PS polystyrene
  • the plastic preferably comprises the polyolefin and/or the polystyrene in an amount of at least 65% by weight, more preferably at least 70% by weight, in particular at least 90% by weight, based on the total weight of the plastic. This makes it possible to obtain a pyrolysis residue which comprises a significant proportion of an aliphatic hydrocarbon (or a mixture of several aliphatic hydrocarbons), i.e. a significant proportion of the wax.
  • the plastic comprises at least 20% by weight of the polyolefin, more preferably at least 50% by weight, even more preferably at least 70% by weight, in particular at least 90% by weight, based on the total weight of the plastic.
  • the amount of wax obtained using the process according to the invention can be increased, which can improve the economic efficiency of the process.
  • the plastic therefore has a PE content of at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, more preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight.
  • the plastic may comprise another polymer from the group consisting of thermoplastics, thermosets and/or elastomers, in particular an acrylonitrile-butadiene-styrene copolymer (ABS), a polyvinyl chloride (PVC), a polyamide (PA) and/or a polyester.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • PVC polyvinyl chloride
  • PA polyamide
  • the plastic Before pyrolysis, the plastic can be plasticized, for example in a mixer, in particular in an extruder.
  • the plastic is preferably heated to a temperature of at least 120 °C in order to plasticize it, more preferably to a temperature of 200 to 500 °C, even more preferably 400 to 470 °C.
  • the subsequent pyrolysis can then be carried out more energy efficiently and in a shorter time.
  • the plastic can also be degassed in the extruder in order to produce a uniform mass without gas inclusions, so that a homogeneous pyrolysis product can be obtained by the subsequent pyrolysis.
  • a diluent can be added to the plastic, in particular the plasticized plastic, to reduce the viscosity.
  • the diluent is preferably added to the plastic in an amount of at least 5% by weight, more preferably at least 9% by weight, based on the total weight of the plastic.
  • the ratio of plastic to diluent is preferably at least 1:4, preferably at least 1:9.
  • the risk of overheating of plastic in wall areas of the pyrolysis reactor can be reduced, since its heating is usually carried out by a heating device.
  • the risk of coking of the plastic during pyrolysis can also be reduced by reducing the viscosity.
  • its viscosity can preferably be reduced by at least 30%, more preferably by at least 50%, particularly preferably by at least 80%, based on the viscosity of the plastic without diluent under the same measuring conditions, in particular at a temperature in the range of 180 to 240 °C. This can improve the pumpability of the plastic, which can facilitate its processing.
  • the plastic When the diluent is added, the plastic preferably has a temperature of at least 120 °C, more preferably a temperature of 150 to 300 °C, in particular of 200 to 300 °C.
  • the diluent can be heated to a temperature of preferably at least 120 °C, more preferably at least 150 °C, in particular to a temperature of 200 to 300 °C before being added to the plastic.
  • the diluent can be mixed into the plastic more quickly and efficiently. The subsequent pyrolysis can also be carried out more energy-efficiently and more quickly.
  • the diluent can be added to the plastic using a adding device.
  • the adding device can have a metering device, such as a metering pump.
  • the plastic in particular the plasticized plastic, can be fed to a mixer, e.g. a static mixer, and mixed there with the diluent.
  • the diluent can be added directly in the extruder.
  • the adding device can be arranged, for example, in the compression zone or mixing zone of the extruder.
  • the diluent may comprise a hydrocarbon selected from an alkane, a cycloalkane and/or an aromatic.
  • a diluent can be converted into a gaseous and/or liquid product, which can be at least partially separated from the pyrolysis residue. and can be further utilized.
  • the diluent can comprise a fraction obtained from crude oil, preferably a heavy oil.
  • the heavy oil can be an oil obtained from crude oil in a petroleum refinery, e.g. a residual oil from a pyrolysis plant.
  • the diluent preferably comprises at least part of a liquid fraction of the pyrolysis residue. This can be separated, for example, in a hydrocyclone.
  • the diluent preferably has a boiling point (or a lower end of a boiling range) of at least 300 °C, in particular at least 350 °C. This makes it possible to avoid the diluent evaporating immediately after a mixture of plastic and diluent is introduced into the pyrolysis reactor, but rather evaporation, splitting and/or depolymerization of the diluent can only take place as the mixture spends longer in the pyrolysis reactor and the mixture is heated up as a result. This makes it possible to obtain a homogeneous pyrolysis product.
  • the pyrolysis residue provided in step (a) of the process can comprise a liquid fraction in addition to the wax and the solid.
  • the proportion of the liquid fraction is preferably a maximum of 95% by weight, more preferably 30 to 95% by weight, in particular 50 to 70% by weight, based on the total weight of the pyrolysis residue.
  • the speed at which at least part of the wax dissolves in the solvent can increase, or a smaller amount of solvent can be added to the pyrolysis residue in order to at least partially dissolve the wax in the solvent. This can also make it easier to separate at least part of the wax from the low-solids mixture.
  • the use of solvent can also be reduced as a result. The process can thus be made more efficient.
  • the pyrolysis residue provided in step (a) of the process can be obtained by pyrolyzing the plastic in a pyrolysis reactor and then increasing a solid concentration of the pyrolysis residue.
  • the proportion of the liquid fraction of the resulting pyrolysis residue can be reduced to preferably a maximum of 95% by weight, more preferably 30 to 95 wt.%, in particular 50 to 70 wt.%, based on the total weight of the pyrolysis residue.
  • a hydrocyclone can be used, which can be connected downstream of the pyrolysis reactor.
  • a gaseous fraction can be separated from the pyrolysis residue after pyrolysis and before step (a) of the process.
  • the gaseous fraction can be separated by evaporation, for example in a hydrocyclone, which can be connected downstream of the pyrolysis reactor.
  • the separation of the gaseous fraction from the pyrolysis residue and the increase in the solid concentration of the pyrolysis residue can be carried out, for example, with one separation device or with several separation devices connected in series.
  • both the separation of the gaseous fraction from the pyrolysis residue and the increase in the solid concentration of the pyrolysis residue are carried out in just one process step by means of a hydrocyclone, which can be connected downstream of the pyrolysis reactor.
  • a hydrocyclone is used in the WO 2023/036751 A1 described.
  • a vortex flow can be generated in the hydrocyclone, whereby the gaseous fraction can be separated from the pyrolysis residue and discharged via an outlet arranged in the upper region of the hydrocyclone (e.g. on its ceiling).
  • the pyrolysis residue can then be discharged due to gravity in the direction of a bottom of the hydrocyclone, whereby a tangential speed of a developing vortex flow can continuously increase.
  • the pyrolysis residue in particular at least a part of the pyrolysis residue that at least partially comprises the wax and the solid, can be discharged via an outlet arranged in the bottom of the hydrocyclone, while at least part of the liquid fraction of the pyrolysis residue can reach an inner container arranged in the hydrocyclone and can be discharged from there via an outlet, e.g. for further use as a diluent.
  • the one above the one in the floor of the The pyrolysis residue discharged from the outlet arranged in the hydrocyclone can then be provided according to step (a) of the process.
  • the hydrocyclone is preferably operated at a temperature in the range of 300 to 450 °C, more preferably from 320 to 420 °C, particularly preferably from 360 to 400 °C.
  • the pyrolysis residue can be cooled before the addition of the solvent, either before step (a) of the process, or between steps (a) and (b).
  • the cooling can be carried out by means of a cooling unit.
  • the pyrolysis residue is preferably cooled to a temperature of not more than 220 °C, more preferably not more than 200 °C, particularly preferably not more than 180 °C.
  • the cooling of the pyrolysis residue can be necessary in particular if the pyrolysis residue is obtained by immediately preceding processing of a plastic (by pyrolyzing and optionally subsequently separating a gaseous fraction from the pyrolysis residue and/or increasing the solids concentration of the pyrolysis residue).
  • the pyrolysis residue is preferably cooled to a temperature of not less than 30 °C, more preferably not less than 80 °C, even more preferably not less than 100 °C, particularly preferably not less than 120 °C. Further cooling below the stated temperature can impair the solubility of the wax in the solvent.
  • the solvent can be added to the pyrolysis residue by means of an introduction device.
  • the introduction device can have a metering device, such as a metering pump.
  • the pyrolysis residue can be fed to a container to which the introduction device can be connected.
  • the container can be heatable so that the wax can be dissolved in the solvent at a certain temperature.
  • the mixing in step (b) of the process preferably takes place at at least 50 °C (ie at 50 °C or above), more preferably at at least 80 °C (ie at 80 °C or above).
  • a fraction of the wax having a melting point above room temperature i.e. above 20 to 25 °C.
  • Mixing in step (b) is preferably carried out at a temperature in the range from 50 to 200 °C, more preferably from 100 to 200 °C, even more preferably from 80 to 200 °C, particularly preferably from 80 to 120 °C.
  • This not only allows the wax to be dissolved in the solvent to a large extent or in its entirety, but it can also be ensured that the solvent does not evaporate due to excessively high temperatures.
  • the wax can dissolve particularly well in the solvent at a temperature of 100 to 120 °C, while a temperature of 120 to 140 °C can be optimal in terms of process technology.
  • step (b) of the process is preferably carried out at a pressure in the range from 1 to 25 bar, in particular from 5 to 16 bar. This can further improve the process control and achieve rapid dissolution of the wax in the solvent.
  • the solvent preferably has a boiling temperature (or boiling range) in the range of 20 to 250 °C, more preferably 50 to 150 °C, even more preferably 35 to 130 °C.
  • the lower the boiling temperature of the solvent the lower the temperature at which the wax can be brought into a liquid state.
  • the boiling temperature (or boiling range) of the solvent can be determined using ASTM D5399-09:2017 or ASTM D2887-22:2022.
  • the solvent preferably comprises an aliphatic hydrocarbon or a mixture of two or more aliphatic hydrocarbons.
  • An impurity that dissolves in the solvent can then remain dissolved while the wax is already crystallizing. Thus, the wax can be separated in a high purity and the impurity can remain in the mixture.
  • the impurity can contain an organic impurity that includes nitrogen, oxygen, sulfur, silicon, chlorine, bromine and/or iodine, for example a heteropolymer (e.g. a polyamide, a polyethylene terephthalate, a polyvinyl chloride and/or an acrylonitrile-butadiene-styrene copolymer) and/or an additive (e.g. an ageing inhibitor, a plasticizer, a color pigment and/or a flame retardant).
  • a heteropolymer e.g. a polyamide, a polyethylene terephthalate, a polyvinyl chloride and/or an acrylonitrile-but
  • the solvent preferably comprises at least 10% by weight, preferably at least 20% by weight, more preferably at least 50% by weight, of the aliphatic hydrocarbon or a mixture of two or more aliphatic hydrocarbons, based on the total weight of the solvent.
  • proportion of aliphatic hydrocarbon increases, not only can the ability of the solvent to dissolve the wax improve, but the solubility of the solid in the solvent can also be reduced.
  • the proportion of an aromatic in the solvent is high, however, the solid, in particular an asphaltene or a tar, can dissolve well in the solvent, which can make the subsequent separation of the wax more difficult or can contaminate the separated wax.
  • the proportion of a cycloalkane in the solvent is high, the wax can dissolve well, but the yield can be comparatively low.
  • the aliphatic hydrocarbon is preferably selected from the group of aliphatic hydrocarbons with up to 15 carbon atoms per molecule, in particular from 4 to 12 carbon atoms per molecule. This enables the process to be carried out efficiently and enables good separation of the wax from the low-solids mixture.
  • the aliphatic hydrocarbon is preferably selected from n-pentane, n-hexane, n-heptane, n-octane, an isomer thereof, or a mixture of the foregoing (ie from a mixture comprising n-pentane, n-hexane, n-heptane, n-octane, an isomer of these alkanes, and/or several isomers of these alkanes). Since the boiling temperature of these aliphatic hydrocarbons is in the range of 35 to 130 °C, the process can be carried out efficiently and economically.
  • step (b) of the process can then preferably take place at 120 °C or below, more preferably at 100 °C or below, in order to avoid evaporation of the solvent. Furthermore, due to the low molecular weight of these solvents, the wax can not only dissolve well in them, but can also have a good tendency to crystallize during subsequent cooling in step (c) of the process.
  • the solvent preferably comprises at least 10% by weight of an alcohol, more preferably at least 20% by weight, based on the total weight of the solvent. This allows a polar impurity to be dissolved in the solvent and thereby separated from the wax, which crystallizes when the mixture cools. This can further increase the purity of the wax obtained.
  • the solvent preferably comprises 10 to 30% by weight of the alcohol, more preferably 10 to 20% by weight of the alcohol, based on the total weight of the solvent. Particularly preferably, the solvent comprises at least 50% by weight of the aliphatic hydrocarbon and 10 to 30% by weight of the alcohol. This allows both the non-polar wax and a polar impurity to be well dissolved in the solvent and well separated from one another during the subsequent cooling of the mixture. Overall, a wax with a high level of purity can then be obtained.
  • the alcohol can preferably be selected from methanol, ethanol, propanol or a mixture thereof.
  • Propanol is particularly preferred because it can reduce adhesions between wax crystals. This can enable easier separation of the wax from the solvent in step (d) of the process. Furthermore, solvent remaining in the wax after washing can subsequently be easily separated from the wax during drying of the wax.
  • the ratio of pyrolysis residue to solvent in the mixture obtained in step (b) of the process may depend on the melting temperature of the wax. The higher the melting temperature of the wax, the more solvent may be required to dissolve the wax. It is preferred if the ratio of pyrolysis residue to solvent is in the range from 5:1 to 1:5, preferably from 2:1 to 3:1, in particular 1:1. The wax can then dissolve largely or even completely in the solvent.
  • the pyrolysis residue contains a solid
  • this can be at least partially separated from the mixture before step (c).
  • the separation of the solid can comprise filtration, adsorption and/or centrifugation.
  • the solid is separated by adsorption.
  • An adsorbent can be added to the pyrolysis residue, which can include activated carbon and/or bleaching earth. This allows the solid to be separated efficiently and as completely as possible from the mixture.
  • the solid can comprise an inorganic salt, a ceramic raw material, an asphaltene, a tar and/or a coke.
  • the solid can comprise talcum, an iron oxide (e.g. iron(III) oxide), aluminum oxide, titanium dioxide, magnesium oxide and/or calcium carbonate.
  • the pyrolysis residue provided is obtained by pyrolyzing a plastic
  • the solid can comprise an additive contained in the plastic.
  • the additive can comprise a filler, a color pigment and/or an additive. A person skilled in the art knows which additives are used depending on the respective plastic and field of application.
  • the solid can be dried after it has been separated from the mixture, for example in an oven. This makes the solid free-flowing and thus easier to process.
  • the solid is preferably dried at a temperature in the range from 50 to 250 °C, more preferably from 100 to 200 °C, even more preferably from 130 to 160 °C.
  • the drying time is preferably up to 120 minutes, in particular from 5 to 60 minutes.
  • One or more components can be separated from the solid, particularly from the dried solid, e.g. by means of filtration and/or centrifugation. Separated components can then be reused, e.g. as an additive for a plastic.
  • Solvent separated during drying of the solid can be reused in step (b) of the process.
  • the solvent Before being returned to the process, the solvent can be purified, preferably by evaporation, in particular by rotary evaporation.
  • step (c) of the process the mixture is cooled to crystallize at least a portion of the wax dissolved in the solvent.
  • the mixture is preferably heated at a rate of not more than 25 °C/min, more preferably not more than 15 °C/min, more preferably a maximum of 10 °C/min, more preferably a maximum of 5 °C/min, more preferably a maximum of 2 °C/min. Cooling is preferably carried out at a rate in the range of 0.05 to 25 °C/min, more preferably from 0.1 to 15 °C/min, more preferably from 0.2 to 10 °C/min, more preferably from 0.4 to 5 °C/min, more preferably from 0.5 to 2 °C/min.
  • Wax crystals can form well at a slow cooling rate in this range, which can enable better mechanical separation. It has also been shown that slow cooling can lead to a clean product. Faster cooling, on the other hand, can lead to increased formation of microcrystals, which are more difficult to separate mechanically and which can also carry more impurities.
  • step (c) of the process takes place over a period of at least 5 minutes, more preferably at least 10 minutes, more preferably at least 30 minutes, more preferably at least 60 minutes.
  • the cooling takes place over a period of 5 to 240 minutes, more preferably from 10 to 180 minutes, more preferably from 30 to 150 minutes, more preferably from 60 to 120 minutes.
  • the wax crystals which form in this process can have a flaky shape which is characteristic of these process parameters.
  • the mixture is preferably cooled to 10 °C or below, more preferably to 0 °C or below, even more preferably to -10 °C or below.
  • the wax can in principle crystallize when cooled at a slow cooling rate, in particular a maximum of 5 °C/min, from e.g. 100 to just 50 °C, a relatively large amount of solvent can be trapped in the wax crystals, which can reduce the purity of the wax, especially since the solvent can also contain a contaminant dissolved in it, which can then also be trapped in the wax crystals.
  • a lower temperature e.g. to 10 °C or below
  • the inclusion of solvent can be reduced or completely prevented, so that the purity of the wax obtained can be significantly increased.
  • step (d) of the process at least a portion of the crystallized wax can be separated from the mixture.
  • the Separation can comprise filtration and/or centrifugation.
  • the temperature during separation is preferably 80°C or below, more preferably 30°C or below.
  • the temperature is preferably in the range from -10 to 80°C, in particular from 0 to 30°C. This can prevent the wax from dissolving again in the solvent.
  • separation can preferably take place at a pressure of up to 10 bar, more preferably at 5 to 10 bar. This can improve the process efficiency.
  • solvent contained in the mixture can be at least partially separated from the mixture.
  • the separation can be carried out by evaporation or distillation. Separated solvent can be reused in step (b) of the process.
  • the solvent Before being returned to the process, the solvent can be additionally purified, preferably by evaporation, in particular by rotary evaporation.
  • the wax separated in step (d) of the process may have a boiling temperature (or a lower end of a boiling range) of preferably at least 270 °C, more preferably at least 300 °C, even more preferably a boiling temperature (or a boiling range) in the range from 340 to 700 °C.
  • the boiling temperature (or boiling range) of the wax can be determined by means of the standard ASTM D7500-15:2019 (preferably for a wax with a boiling temperature or a boiling range of 100 to 850 °C, in particular from 100 to 735 °C) or by means of the standard ASTM D2887-22:2022 (preferably for a wax with a boiling temperature or a boiling range of 55 to 538 °C).
  • the separated wax preferably has at least 15 carbon atoms per molecule, more preferably at least 20, in particular at least 40.
  • the wax has 20 to 80 carbon atoms per molecule, in particular 20 to 65.
  • Such waxes are well suited for further use.
  • the separated wax can be fed to a processing plant of a refinery, in particular a Fluid Catalytic Cracking (FCC) plant, a Thermal Gasoil Unit (TGU plant), a hydrogenation plant and/or a coker.
  • FCC Fluid Catalytic Cracking
  • TGU plant Thermal Gasoil Unit
  • the separated wax can be used in other technical areas, for example as a lubricant and/or additive.
  • the separated wax can be processed before further use. For example, the wax can be cleaned and/or separated into different carbon fractions.
  • the separated wax preferably has a proportion of one (or more) carbon fractions of at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, in particular at least 85% by weight, based on the total weight of the separated wax.
  • This proportion provides information about the purity of the separated wax, with a high proportion of the carbon fraction corresponding to a high purity of the separated wax.
  • the proportion of the carbon fraction can be determined by means of a gravimetric analysis, wherein the gravimetric analysis can comprise a determination of the masses of the pyrolysis residue, the added solvent and the separated wax.
  • the separated wax can be washed after step (d) of the process.
  • the wax can be washed one to three times. This can further increase the purity of the separated wax.
  • the temperature of the wax is preferably 80°C or below, more preferably 30°C or below, even more preferably in the range of -10 to 80°C, especially 0 to 30°C. This can prevent the wax from dissolving again in the solvent.
  • a similar or the same temperature can be selected as when separating the wax in step (d) of the process.
  • the wax is washed with an alcohol.
  • the alcohol used for washing is preferably selected from methanol, ethanol, propanol or a mixture thereof. This not only allows any remaining polar contamination to be washed out well, but any solvent remaining in the wax after washing can then be easily separated from the wax during drying.
  • the method may comprise a further step (e): drying the separated wax.
  • Fig. 1 shows a flow diagram of a pyrolysis process in which wax is extracted from a pyrolysis residue.
  • a plastic comprising at least 50% by weight of a polyolefin is fed to an extruder 1 in which the plastic is plasticized and degassed.
  • the plasticized plastic has a temperature of at least 120 °C and is then added to a static mixer 2.
  • a diluent 3 can be added to the plasticized plastic in order to reduce its viscosity.
  • a part of a liquid fraction 4 separated from a pyrolysis residue can be mixed with the plasticized plastic in order to reduce its viscosity.
  • the resulting mixture is then fed to a pyrolysis reactor 5, in which the plastic is pyrolyzed at a temperature of 350 to 450 °C.
  • a pyrolysis product 6 comprising a gaseous fraction and a pyrolysis residue, the pyrolysis residue comprising a liquid fraction, a wax and a solid.
  • the pyrolysis product 6 is fed to a hydrocyclone 7 downstream of the pyrolysis reactor 5.
  • the gaseous fraction is at least partially separated in the hydrocyclone 7.
  • the separated part of the gaseous fraction 8 can then be further separated into a light oil (e.g. with a boiling range of 35 to 225 °C) and a heavy oil (e.g.
  • the liquid fraction is at least partially separated in the hydrocyclone 7.
  • the separated part of the liquid fraction 4 can be discharged via an outlet 9 of the hydrocyclone 7 and reused in the process for reducing the viscosity of the plastic, as previously described.
  • At least part of the pyrolysis residue, which at least partially comprises the wax and the solid, is discharged via an outlet 10 arranged in the bottom of the hydrocyclone 7.
  • the pyrolysis residue discharged via the outlet 10 is fed to a first cooling unit 11 for cooling to a temperature in the range from 80 to 240 °C.
  • a solvent 13 comprising at least 20% by weight of an aliphatic hydrocarbon is then added to the pyrolysis residue in a container 12 by means of an introduction device 14 in order to obtain a mixture in which the wax is at least partially dissolved in the solvent 13.
  • the aliphatic hydrocarbon is selected from the group of aliphatic hydrocarbons having 4 to 12 carbon atoms per molecule.
  • the resulting mixture has a ratio of pyrolysis residue to solvent in the range from 2:1 to 3:1.
  • the container 12 is heated so that dissolving can take place at a temperature in the range from 80 to 200 °C.
  • a separation device 15 the solid is at least partially separated from the mixture by means of adsorption on activated carbon.
  • the separated solid 16 is then dried in an oven 17 at a temperature in the range of 100 to 200 °C.
  • individual components can be separated from the solid and reused (not shown).
  • Solvent 13 separated during drying is reused in step (b) of the process by being returned to the container 12 via the introduction device 14. Before being returned, the solvent 13 can be purified, e.g. by evaporation (not shown).
  • the mixture is prepared according to Fig.
  • the separated wax 21 is washed in a washer 22, wherein an alcohol is used for washing.
  • the washed, separated wax 21 is then fed to a dryer 23 to dry the wax crystals.
  • the wax 24 obtained can then be used for further purposes (not shown).
  • Solvent 13 separated during drying of the separated wax 21 is also returned to the container 12 via the introduction device 14. Before being returned, the solvent 13 can be purified, e.g. by evaporation (not shown).

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
EP23168522.3A 2023-04-18 2023-04-18 Procédé d'obtention d'une cire à partir d'un résidu de pyrolyse Withdrawn EP4450592A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP23168522.3A EP4450592A1 (fr) 2023-04-18 2023-04-18 Procédé d'obtention d'une cire à partir d'un résidu de pyrolyse
CN202480025442.3A CN121002149A (zh) 2023-04-18 2024-04-18 用于从热解残余物中提取蜡的方法
PCT/EP2024/060468 WO2024218178A1 (fr) 2023-04-18 2024-04-18 Procédé d'extraction d'une cire à partir d'un résidu de pyrolyse
MX2025010796A MX2025010796A (es) 2023-04-18 2025-09-12 Metodo para la extraccion de cera de un residuo de pirolisis

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EP23168522.3A EP4450592A1 (fr) 2023-04-18 2023-04-18 Procédé d'obtention d'une cire à partir d'un résidu de pyrolyse

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614065A (en) * 1950-03-30 1952-10-14 Standard Oil Co Propane dewaxing chilling procedure
US3720599A (en) * 1971-05-03 1973-03-13 Exxon Research Engineering Co Continuous dewaxing of oils by in situ refrigeration
US5006222A (en) * 1990-05-23 1991-04-09 Texaco Inc. Solvent dewaxing of lubricating oils
US20020096451A1 (en) 2001-01-19 2002-07-25 Ackerson Michael D. Solvent extraction refining of petroleum products
WO2017168165A1 (fr) * 2016-03-31 2017-10-05 Trifol Resources Limited Procédé de préparation d'une huile de base lubrifiante comprenant la décomposition thermique sélective d'un polymère de polyoléfine plastique
WO2021115982A1 (fr) 2019-12-10 2021-06-17 Shell Internationale Research Maatschappij B.V. Récupération d'hydrocarbures aliphatiques
WO2023036751A1 (fr) 2021-09-07 2023-03-16 OMV Downstream GmbH Appareil et procédé de séparation de composants d'un flux d'hydrocarbures multiphasique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614065A (en) * 1950-03-30 1952-10-14 Standard Oil Co Propane dewaxing chilling procedure
US3720599A (en) * 1971-05-03 1973-03-13 Exxon Research Engineering Co Continuous dewaxing of oils by in situ refrigeration
US5006222A (en) * 1990-05-23 1991-04-09 Texaco Inc. Solvent dewaxing of lubricating oils
US20020096451A1 (en) 2001-01-19 2002-07-25 Ackerson Michael D. Solvent extraction refining of petroleum products
WO2017168165A1 (fr) * 2016-03-31 2017-10-05 Trifol Resources Limited Procédé de préparation d'une huile de base lubrifiante comprenant la décomposition thermique sélective d'un polymère de polyoléfine plastique
WO2021115982A1 (fr) 2019-12-10 2021-06-17 Shell Internationale Research Maatschappij B.V. Récupération d'hydrocarbures aliphatiques
WO2023036751A1 (fr) 2021-09-07 2023-03-16 OMV Downstream GmbH Appareil et procédé de séparation de composants d'un flux d'hydrocarbures multiphasique

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WO2024218178A1 (fr) 2024-10-24
CN121002149A (zh) 2025-11-21

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