EP4345147A1 - Procédé continu de récupération de ressources secondaires à partir de déchets contenant des composés organiques par huilage - Google Patents

Procédé continu de récupération de ressources secondaires à partir de déchets contenant des composés organiques par huilage Download PDF

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Publication number
EP4345147A1
EP4345147A1 EP23000125.7A EP23000125A EP4345147A1 EP 4345147 A1 EP4345147 A1 EP 4345147A1 EP 23000125 A EP23000125 A EP 23000125A EP 4345147 A1 EP4345147 A1 EP 4345147A1
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EP
European Patent Office
Prior art keywords
reactor
continuous process
process according
oil
part reactor
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.)
Pending
Application number
EP23000125.7A
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German (de)
English (en)
Inventor
Stephan ASCHAUER
Gerhard Olbert
Ralf BURGSTAHLER
Olivier Inhoff
Ulrich Grote
Luzius Veith
Louis Weber
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.)
Carboliq GmbH
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Carboliq GmbH
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Filing date
Publication date
Application filed by Carboliq GmbH filed Critical Carboliq GmbH
Publication of EP4345147A1 publication Critical patent/EP4345147A1/fr
Pending 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
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation

Definitions

  • the invention relates to a process for the recovery of secondary resources from waste containing organic compounds.
  • oiling process also known as catalytic pressureless oiling (KDV) or thermocatalytic low-temperature conversion (NTK)
  • KDV catalytic pressureless oiling
  • NTK thermocatalytic low-temperature conversion
  • the processed residual waste is fed into the lower area of the reactor using a screw below the liquid level. This ensures that the material supplied mixes with the oil supplied and a suspension is created, which is sucked in at the lower end of the reactor via the turbines or pumps and injected back into the upper part of the reactor via external lines and connected nozzles.
  • the intensive mixing breaks up the polymers and evaporates as soon as the chain length is sufficiently short.
  • the vapors are drawn off at the top of the reactor using a slight negative pressure and condensed using a spray cooler to obtain the product oil. However, this does not have a constant quality and the ability of the system to operate continuously could not be demonstrated.
  • the object of the invention was to provide an oil conversion process for the extraction of secondary resources from waste containing organic compounds as starting material, which can be operated continuously and which ensures a uniform quality of the product oil with regard to the maximum permissible oxygen and nitrogen content as well as the minimum calorific value, provided that the starting material used contains organic compounds in a mass fraction of at least 60%.
  • the oxygen content in the product oil should not exceed a mass fraction of 4% and the nitrogen content a mass fraction of 1.2%, and the minimum calorific value of the same should be 41 MJ/kg.
  • the invention is based on known oiling processes for processing waste containing organic compounds, in particular the so-called “Dieselwest” process, which was presented in the above-mentioned final report of the Federal Environment Agency "Evaluation of new developments in alternative thermal waste treatment plants with a focus on oiling processes" by M. Pohl and P. Quicker (Texte 77/2018, project number 82615, UBA-FB 002679).
  • Any waste can be used as starting material, provided it contains organic compounds in a mass proportion of at least 60%.
  • Starting materials with organic compounds in a mass fraction of at least 80%, more preferably at least 90%, are preferred, in particular starting materials containing artificial organic compounds in a mass fraction between 60 and 80% and natural organic compounds in a mass fraction between 0 and 30%.
  • Long-chain organic compounds are usually understood to be polymers that are made up of several hundred to 4000 similar molecular units, the monomers.
  • the artificial polymers in this case are in particular mixtures of low-density polyethylene, high-density polyethylene, polypropylene, polystyrene, polyisobutene, polyethylene terephthalate, polyamide 6, polyamide 6.6 and/or plastic waste based on isocyanates, which, due to their material properties and the associated production, are formed from around 2000 to 4000 of the respective monomer units.
  • the starting material can contain municipal waste, in particular non-sortable plastic parts thereof, in particular sorting fractions which are separated due to their dimensions and/or film residues and/or black sorting residues which cannot be detected by near-infrared spectroscopy, and/or commercial waste, in particular production waste, preferably waste from the recycling of passenger cars, in particular lightweight car shredder material.
  • the waste used as starting material often contains, in addition to organic compounds, inert substances, fillers, metals and/or residual moisture, in particular inert substances and/or fillers in a mass proportion of 0 to 10%, preferably less than 1%, metals in a mass proportion of 0 to 1%, preferably less than 1%, and residual moisture in a mass fraction of 0 to 10%, preferably less than 1%.
  • the starting material (A) can additionally contain, as inert materials, silicon dioxide in the form of quartz sand or building materials and/or aluminum oxide and/or calcium hydroxide and/or hollow glass and/or ceramic spheres, glass and/or carbon fibers and/or rubber particles as fillers also contain metallic materials, in particular magnetic and non-magnetic metal composite materials and/or aluminum-coated materials.
  • the above inert and/or fillers are added to the waste used as starting material in order to adjust various properties, such as strength and extensibility.
  • the starting material Before being fed into the reactor, the starting material is processed in several stages in advance in a known manner, in particular as in the "Dieselwest” process described above, i.e. crushed, sieved to a grain size of a maximum of 2 mm, ferrous and non-ferrous metals are separated, additives in the form of synthetic or natural zeolites as catalysts and quicklime as a neutralizer are added and the starting material is finally dried to a water content of less than 2%.
  • the oiling process is carried out in a two-part reactor with a first, lower and a second, upper area, which is preferably directly connected to the first, lower area.
  • the first, lower and/or the second, upper area each taper at the bottom to allow the fluid to drain off during cleaning work and downtimes.
  • the opening connecting the two regions preferably has a diameter of at least 1/5 of the diameter of the second, upper region, preferably of at least 1/3 of the diameter of the second, upper region.
  • both reactor regions can be integrated into a common reactor shell.
  • the first, lower region of the two-part reactor can have a height to diameter ratio of 3:1 to 1:3, preferably 1.5:1, and can in particular be designed as a standing or lying cylinder.
  • the reactor contents are fed from the lower end via one or more external pipelines using one, two or more pumps or turbines with a ratio of directional to non-directional pulse power in the range of 1/6 to 1/2 the first, lower area of the two-part reactor.
  • a starting oil is placed in the first, lower area up to a height of at least half of the total height of the same, preferably up to a height of at least 2/3 of the total height of the same.
  • the starting oil is advantageously a mixture of product oil and a mineral oil with a boiling point greater than 280 ° C, preferably in a mass ratio of 10% mineral oil to 90% product oil to 90% mineral oil to 10% product oil, in particular 50% Mineral oil to 50% product oil is used.
  • the start-up oil is first heated by pumping over one, two or more pumps to an operating temperature in the range of 280 to 420 ° C, whereupon the previously prepared starting material is continuously fed into the first, lower region of the two-part reactor below the liquid level, preferably above one or more snails.
  • the pre-processed starting material can also be fed via one or more extruders.
  • the reactor contents are continuously transferred from the lower end of the first, lower region of the two-part reactor into the second, upper region of the two-part reactor via the one or more external pipelines by means of one, two or more pumps and/or turbines Ratio of directional to non-directional pulse power pumped in the range of 1/6 to 1/2.
  • Preferred pumps are liquid ring vacuum pumps, impeller pumps with a recessed impeller, rotary piston pumps and screw spindle pumps.
  • the directed pulse power is determined by the delivery pressure (pressure loss) and the volume flow in relation to the pump power applied.
  • the undirected pulse power is also referred to by experts as dissipated power.
  • the advantage of this energy input is the homogeneous heating of the fluid from the inside to the outside; there are no hot walls as with external heating methods via the wall.
  • the second significant advantage of the direct dissipative energy input is the high mixing and stress on the starting material.
  • the required heat of fusion is provided by the surrounding fluid.
  • the high mixing performance of the pumps causes the introduced solid particles to be crushed and torn apart in the pumped flow.
  • the catalyst particles are also mixed and crushed with the introduced and melted solid particles.
  • the high shear forces and cavitation caused by peripheral speeds of around 15 to 20 m/s and the sudden evaporation and condensation on the pumping elements cause the original long-chain organic compounds to crack from the introduced solid particles in the liquid phase.
  • the high shear rates also mean that the active centers of the catalysts are continuously renewed. As a result, For example, low-density polyethylene waste with originally typically 2000 to 4000 monomer units is cracked to an average of 3 to 16 monomer units.
  • the process is carried out in such a way that the ratio of the feed residence time of the starting material to the pumped residence time of the reactor contents is in the range from 250 to 1 to 5000 to 1, i.e. H.
  • the pumping of the reactor contents takes place much faster than the supply of the starting material. This is crucial in order to achieve the high shear rates required for the depolymerization processes explained above.
  • the feed residence time is defined by the ratio of total reactor volume to the feed volume flow of the feed materials.
  • the pumping residence time is defined by the ratio of the total liquid reactor volume to the total pump volume flow.
  • the total liquid reactor volume as well as the total pump volume flow are determined by mass flow meters (mass flow meters), for example standard Coriolis mass flow meters.
  • the pumping residence time is divided into the pumping residence time in the first, lower region of the two-part reactor and the pumping residence time in the second, upper region of the two-part reactor.
  • Ratios of the feed residence time of the starting material to the circulation residence time of the reactor contents in the range from 250 to 1 to 5000 to 1 are preferred.
  • the process is preferably operated in such a way that the pumping residence time of the reactor contents is in the range from 15 to 55 seconds, more preferably in the range from 25 to 40 seconds. Accordingly, the feed residence times of the starting material are preferably in the range from about 2 hours to about 75 hours.
  • the liquid pumped flow is slightly overheated as it flows through due to the undirected energy input through the pumps and is expanded into the second, upper region of the two-part reactor by a small pressure difference.
  • the liquid jet bursts and spreads over the existing wall surface in the second, upper area of the two-part reactor, and the low boilers can escape more easily.
  • the surface load B is understood to be the throughput of the pumped volume flow based on the area, in this case the area of the inner walls in the second, upper region of the two-part reactor.
  • the inner walls of the two-part reactor in the second, upper region thereof are partially or completely heated and/or wetted with product oil. This supports the evaporation of more volatile hydrocarbons.
  • the vapors are continuously removed from the second, upper area of the two-part reactor and condensed in a known manner, in particular in a spray cooler, to obtain the product oil.
  • a multi-stage spray cooler is particularly advantageous.
  • the residue from the first, lower section of the two-part reactor is advantageously discharged and allowed to settle as needed or at regular intervals and the supernatant oil mixture is returned to the first, lower section of the two-part reactor.
  • the reactor contents or a partial stream of the reactor contents are advantageously pumped back tangentially into the upper third of the second, upper region of the two-part reactor.
  • a high distribution on the surface of the second, upper region of the two-part reactor and thus good outgassing of the products produced can be achieved.
  • only a first partial flow of 20 to 80% of the reactor contents is pumped from the lower end of the first, lower region of the two-part reactor into the second, upper region of the two-part reactor and a second partial flow of 80 to 20%, preferably 60 up to 70% of the reactor contents from the lower end of the first, lower area of the two-part reactor into the first, pumped back to the lower area of the two-part reactor.
  • This driving style results in better mixing and better distribution of the input starting material between the pumps.
  • the second, upper region of the two-part reactor can be used as a single-stage or multi-stage separation column by providing a separable flange over which one or more horizontal perforated plates can be inserted.
  • Perforated plates with an opening ratio of 20 to 40% are advantageously used.
  • a central pipe via a separable flange can be used to supply the pumped flow. This can prevent unwanted foaming.
  • the continuous process according to the invention makes it possible, in particular, for the oxygen content in the product oil to be lower by 40 to 90%, in particular by 80%, compared to the starting material, and for the nitrogen content in the product oil to be lower by 50 to 80%, in particular by 70%, compared to the starting material.
  • the continuous process according to the invention makes it possible in particular to obtain a product oil having a calorific value between 41 and 46 megajoules per kilogram, preferably of about 45 megajoules per kilogram.
  • the formation of polycyclic aromatic hydrocarbons is minimized, in particular in the product oil, and the sum of the polycyclic aromatic hydrocarbons is between 100 and a maximum of 1000 ppm, preferably a maximum of 600 ppm.
  • Figure 1 a schematic representation of a preferred reactor for carrying out the process according to the invention and the Figures 2A and 2B Cross-sectional representations through two preferred embodiments of reactors for carrying out the process according to the invention.
  • Figure 1 shows a two-part reactor R with a first, lower area I and a second, upper area II.
  • the starting material A is continuously fed via a conveyor screw into the first, lower section I of the two-part reactor R below the liquid level therein.
  • the reactor contents RI are pumped from the first, lower region I of the reactor R into the second, upper region II of the reactor R via an external pipeline 1 using a pump 2.
  • Product vapor is withdrawn from the upper end of the second, upper region II of the reactor R and quenched with a partial stream of cold product oil, obtaining the product oil P, which is withdrawn.
  • Table 1 Source material Product oil Calorific value in megajoules per kilogram 39.1 44.9 Moisture in percent by weight 2 0.25 Inert substances in percent by weight 3 0.1 (bulk) density in kilograms per cubic meter 38 822 C (measured value) in percent by weight 77.10 83.3 H (measured value) in percent by weight 12.90 13.2 N (measured value) in percent by weight 1.72 1.11 O (measured value) in percent by weight 7.0 1.7 Plastic in percent by weight 86.1 Biomass in percent by weight 13.9 Metals in percent by weight 0.0
  • the material data shows a significant reduction in the nitrogen and especially the oxygen content in the product oil as well as a significant increase in the calorific value.
  • the material data show a significant reduction in the nitrogen and especially the oxygen content in the product oil as well as a significant increase in the calorific value.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
EP23000125.7A 2022-09-27 2023-09-20 Procédé continu de récupération de ressources secondaires à partir de déchets contenant des composés organiques par huilage Pending EP4345147A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102022003576.6A DE102022003576A1 (de) 2022-09-27 2022-09-27 Kontinuierliches Verfahren zur Sekundärressourcengewinnung aus organische Verbindungen enthaltenden Abfällen durch Verölung

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EP4345147A1 true EP4345147A1 (fr) 2024-04-03

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EP23000125.7A Pending EP4345147A1 (fr) 2022-09-27 2023-09-20 Procédé continu de récupération de ressources secondaires à partir de déchets contenant des composés organiques par huilage

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DE (1) DE102022003576A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106399A2 (fr) * 2009-03-14 2010-09-23 Bl Laboratories Sp. Z O.O. Appareil pour réaliser la thermolyse de déchets plastiques et procédé de thermolyse en continu
WO2010116211A1 (fr) * 2009-04-08 2010-10-14 Bl Laboratories Sp.Z.O.O. Appareil pour la thermolyse de déchets de matières plastiques et procédé pour la thermolyse de déchets de matières plastiques

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018189267A1 (fr) 2017-04-11 2018-10-18 Innoil Ag Cuve à réaction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106399A2 (fr) * 2009-03-14 2010-09-23 Bl Laboratories Sp. Z O.O. Appareil pour réaliser la thermolyse de déchets plastiques et procédé de thermolyse en continu
WO2010116211A1 (fr) * 2009-04-08 2010-10-14 Bl Laboratories Sp.Z.O.O. Appareil pour la thermolyse de déchets de matières plastiques et procédé pour la thermolyse de déchets de matières plastiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Verölung", WIKIPEDIA, 25 January 2022 (2022-01-25)

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