WO2009053234A1 - Procédé et dispositif pour obtenir du gazole ou du fioul à partir de résidus contenant des hydrocarbures - Google Patents

Procédé et dispositif pour obtenir du gazole ou du fioul à partir de résidus contenant des hydrocarbures Download PDF

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Publication number
WO2009053234A1
WO2009053234A1 PCT/EP2008/063351 EP2008063351W WO2009053234A1 WO 2009053234 A1 WO2009053234 A1 WO 2009053234A1 EP 2008063351 W EP2008063351 W EP 2008063351W WO 2009053234 A1 WO2009053234 A1 WO 2009053234A1
Authority
WO
WIPO (PCT)
Prior art keywords
residues
hydrocarbon
evaporator
rectification
raw material
Prior art date
Application number
PCT/EP2008/063351
Other languages
German (de)
English (en)
Inventor
Esther Stölzer
Dawlet Hannoudi
Ullrich Fiedler
Original Assignee
Hii 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 Hii Gmbh filed Critical Hii Gmbh
Publication of WO2009053234A1 publication Critical patent/WO2009053234A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • 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
    • C10G9/06—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by pressure distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for the production of diesel or fuel oil from hydrocarbonaceous residues and a device for this purpose.
  • Catalytic processes for the conversion of hydrocarbon-containing residues for the production of diesel are known from the prior art, which are usually carried out at temperatures of 300 to 400 0 C.
  • WO 2006/092306 A1 describes a process for the depolymerization of hydrocarbon-containing residues to diesel, wherein on the one hand a heated reactor in which the catalytic cracking of the raw material takes place is used and on the other hand the raw material is preheated and injected under pressure into the reactor.
  • stepwise heating of the raw material causes carbon to be deposited on walls of the apparatus used to perform the processes, for example by local overheating. This disturbs the heat transfer in the mixture and jeopardizes the safety of the process.
  • the use of depolymerization catalysts is also expensive and requires further equipment to regenerate or exchange the catalyst. Continuous process control is therefore only possible with increased expenditure on equipment.
  • This object is achieved in that the raw material is vaporized abruptly in a suitable evaporation device.
  • the raw material is not slowly heated, which would lead to the disadvantages described above, but within a very short time to a temperature in the range of about 150 0 C to about 450 0 C, preferably about 250 0 C to about 400 0 C heated, whereby the thermal decomposition of the hydrocarbon chains contained in the raw material occurs immediately.
  • the process of the invention does not require a catalyst to crack the carbon water chains.
  • the sudden evaporation of the raw material can be carried out, for example, in a thin-film evaporator and / or in a screw conveyor system which is operated or heated, for example, by a circulating fluidized-bed furnace.
  • waste material Used as hydrocarbon-containing residues (raw material) for carrying out the process are, for example, waste, heavy and bilge oils, refinery residues and plastics or else oil-laden sands.
  • waste, residual and waste materials come into consideration, such as plastics, oils, fats, natural and synthetic rubbers.
  • Mixtures of all the aforementioned substances are also suitable as raw material for the process of the present invention. Particularly suitable are mixtures of waste oil and plastics.
  • the actual splitting of the raw material may be preceded by at least one desulfurization and / or dechlorination stage.
  • desulfurization and / or dechlorination of the raw material can be accomplished.
  • waste oil can be preheated to about 120 0 C before it is fed to the cleavage stage with higher temperatures.
  • plastics and plastic granules it may be advantageous to subject them to a drying step.
  • the cleavage of the raw material can be carried out in a thin-film evaporator or in a screw conveyor system which is operated or heated, for example, by a circulating fluidized-bed furnace.
  • Liquid raw materials such as waste, heavy and bilge oils, refinery residues and molten plastics are preferred using a Split thin film evaporator.
  • the raw material contained in oil-laden sands is preferably cleaved using said screw conveyor system.
  • Thin-film evaporation is the thermal separation of substances from a mechanically generated, thin and highly turbulent liquid film.
  • the liquid comes after entering the thin film evaporator with a rotor into contact: It is evenly distributed by a distribution ring on the circumference, detected by first, underlying rotor blades and as a film (eg 0.5 to 3.5 mm film thickness) to a distributed heated wall. Before each rotor blade, the liquid forms a bow wave. This is absorbed by the rotor blade and passes in the gap between the rotor and wall in a highly turbulent zone, in which it comes in the radial direction to intense heat and mass transfer. The high turbulence ensures high heat transfer rates even with viscous liquids. Due to the intensive product mixing in the bow wave, temperature-sensitive products are also protected against overheating and the formation of deposits on the heating surface is counteracted.
  • the introduction of the raw materials is carried out depending on the selected material flow on granulator or injector, each under the usual procedural pressure.
  • the input liquid raw materials are suddenly vaporized.
  • the generated hydrocarbon vapors rise into a rectifier and can subsequently be treated in an optional stage with superheated steam to saturate free valencies.
  • heated fine-grained granules such as sand or quartz sand
  • the raw materials are se introduced by means of a gear pump directly into the granules or applied to the granules and cleaved immediately after the entry in or order on the heated granules.
  • the residues eg coke, metals and salts
  • the heating of the screw conveyor system succeeds, for example, with a circulating fluidized bed combustion coupled thereto.
  • a circulating fluidized bed combustion with combustion chamber, cyclone and fluidized bed lock can be used.
  • the granules are heated in the circulation through cyclone and lock to the necessary temperature.
  • the system is operated with a gas burner to a temperature of max. 1400 0 C driven;
  • part of the required energy is supplied by coke burnup.
  • the fluidized bed combustion with a temperature of about 450 0 C to about 1400 0 C are operated.
  • the resulting exhaust air is cleaned and fed, for example, an exhaust chimney.
  • the fluidized bed therefore has on the one hand the task of heating the granules to the temperature necessary for the conversion and, on the other hand, of facilitating the regeneration of the granules contaminated during the conversion with residues.
  • the process of circulating fluidized bed combustion is characterized by uniform temperature control and high mass and heat transfer during operation of the plant.
  • the screw conveyor system (mixing screw) and / or the distillation column described below can be operated under reduced pressure.
  • rectification which serves for the separation of low boilers and cleavage gases
  • a distillation column with evaporator and condenser can be used.
  • distillation and rectification By distillation and rectification is meant the physical separation of mixtures.
  • the rectification or rectification apparatus vapor or liquid fed inlet mixtures are decomposed into their components or separated into partial mixtures.
  • a rectification is carried out, for example, in column apparatuses with various internals and rectification plates, random packings and / or packings.
  • column apparatuses with various internals and rectification plates, random packings and / or packings.
  • the hydrocarbons obtained for binding of the free valences with superheated steam can, for example, at temperatures greater than about 1000 0 C, are treated under pressure. This ensures that a clean and shelf-stable product is produced.
  • the products obtained according to the invention can be used to generate electricity in corresponding power plants, as heating oil or as fuel for diesel engines.
  • the method according to the invention can comprise the following steps:
  • the cleavage of the raw material according to step C) of the process can be carried out by means of a thin-film evaporator or in a screw conveyor system operated by a circulating fluidized bed furnace. It is essential that no catalyst is used for cleavage.
  • a device according to the invention may comprise the following devices:
  • At least one waste heat boiler and / or at least one turbine and / or at least one superheater may be included in the device.
  • the superheater is present only if the pyrolysis reactor is designed as a screw conveyor system.
  • the rectification device is downstream of the pyrolysis reactor.
  • conduits to interconnect the various facilities such as conduits to interconnect the various facilities, pipes such as exhaust pipes, measuring and control equipment, stairs, stages, venting and ventilation ducts.
  • FIG. 1 shows the flowchart of a first method according to the invention
  • FIG. 2 shows the flow chart of a second method according to the invention
  • FIG. 3 shows a device according to the invention with fluidized bed
  • FIG. 4 shows a device according to the invention with a thin film evaporator in a vertical embodiment
  • FIG. 5 shows a device according to the invention with a thin film evaporator in a horizontal configuration.
  • the process shown in Fig. 1 comprises a desulfurization step and a dechlorination step which reduce the sulfur and chlorine contents of the raw materials (plastics and waste oils) stored in respective storage facilities.
  • the treated plastics are dried;
  • the oils treated in this way are preheated to approx. 120 ° C.
  • the dried plastics and preheated waste oils are mixed and fed to a thin-film evaporator together with further dried plastic and / or preheated waste oil.
  • the product mixture produced in the thin-film evaporator is treated with superheated steam, then rectified in a distillation column and finally cooled.
  • Diesel or heating oil which comply with the DIN standard 51 601 and the Euro standard EN 590 for diesel and extra fuel oil.
  • the process shown in Fig. 2 comprises a desulfurization step and a dechlorination step, which reduce the sulfur and chlorine contents of the raw materials (plastics and anthers) stored in appropriate stores.
  • the treated plastics are dried;
  • the treated waste oils are preheated to approx. 120 ° C.
  • the dried plastic and preheated waste oil are mixed, and together with a soft terem dried plastic and / or pre-heated used oil a pyrolysis reactor (auger system) supplied to the at about 150 0 C to about 450 0 C, preferably about 250 0 C to about 400 0 C. is operated.
  • the granulate for the screw conveyor system is heated and cleaned with a fluidized bed furnace.
  • the granules Before the granules enter the pyrolysis reactor, the granules are cooled to the desired temperature.
  • the product mixture produced in the pyrolysis reactor is treated with superheated steam, then rectified in a distillation column and finally cooled.
  • Diesel or heating oil which comply with the DIN Norm 51 601 and the Euro Norm EN 590 for diesel and extra-light fuel oil, are obtained.
  • FIG. 3 shows a fluidized-bed installation according to the invention, for example for carrying out the method outlined in FIG. 2.
  • a circulating fluidized bed 10 which is connected to a screw conveyor 11 a.
  • the sand used is recirculated.
  • a burner 15 ensures the heating of the sand.
  • the screw conveyor system 11 a is continuously supplied via a pipe 31 waste oil.
  • the products obtained by sudden evaporation of the waste oil in the screw conveyor 11 a products are fed to a column 12, in which they are rectified.
  • the desired products are condensed, then cooled and fed via the pipe 30 to a storage tank.
  • the system further comprises an activated carbon filter 16 for cleaning the exhaust air from the fluidized bed.
  • the exhaust air is supplied to the activated carbon filter 16 via an exhaust pipe 20.
  • the exiting the activated carbon filter 16 exhaust air is supplied via the pipe 21 an exhaust chimney.
  • Fig. 4 shows a system according to the invention with upright thin-film evaporator 11 b.
  • the temperature required for the evaporation is generated by a burner 15. Via a buffer tank 18, fuel can be supplied to the burner 15, which consists of volatile, combustible constituents of the vaporized plastic and the distillate produced (corresponding supply lines are not shown).
  • the thin-film evaporator 11 b is supplied by means of fluid bed dryer 17 dried plastic.
  • a plastic conveyor belt 32 delivers the plastic to the dryer.
  • the products obtained by sudden evaporation of the plastic in the thin film evaporator 11 b are fed to a column 12, in which they are rectified.
  • the desired products are condensed, then cooled and fed via the tube 30 to a storage tank. Shown is a column with two outlets, where up to seven outlets are possible.
  • the system further comprises an activated carbon filter 16 for cleaning the exhaust air produced in the process.
  • Fig. 5 shows a system according to the invention with horizontal thin-film evaporator 11c.
  • the temperature required for the evaporation is generated by a burner 15.
  • the thin-film evaporator 11 c desulfurized by means of desulfurization 41 and supplied preheated by preheater 19 waste oil.
  • Shown in this context are ds pipe 40, which connects the preheater 19 with the desulfurizer 41 and pipe 31 from the waste oil tank in the preheater 19.
  • the products obtained by sudden evaporation of waste oil in the thin film evaporator 11 c products are fed to a column 12 in which they rectified become.
  • the desired products are condensed, then cooled and fed via the pipe 30 to a storage tank.
  • the system further comprises an activated carbon filter 16 for cleaning the exhaust air produced in the process.
  • the high molecular weight material having a solid consistency at room temperature was first pre-heated to 120 0 C, and thus converted into a pumpable state. In this state, the material was metered in portions under atmospheric pressure in a thin-film evaporator whose wall was heated to a temperature of about 400 0 C. On the hot wall of the high molecular weight hydrocarbon was distributed by a fast-running agitator to about 2 to 3 mm thick layer, which immediately began a sudden evaporation.
  • the resulting hydrocarbon vapors were then condensed and then fed to a multistage distillation column equipped with a bottom vaporizer and a top condenser.
  • the obtained middle distillate oil was then treated at a pressure of up to 2 atmospheres with superheated steam, the inlet temperature was maintained 1000-1100 0 C. This resulted in storable products.

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

Abstract

La présente invention concerne un procédé pour obtenir du gazole ou du fioul à partir de résidus contenant des hydrocarbures qui est caractérisé en ce que les résidus contenant des hydrocarbures sont brusquement évaporés dans une installation d'évaporation chauffée sans catalyseur. Un dispositif pour réaliser le procédé comprend un réacteur de pyrolyse sous la forme d'un système d'hélice transporteuse ou d'un évaporateur à couche mince ainsi qu'une installation de rectification.
PCT/EP2008/063351 2007-10-26 2008-10-06 Procédé et dispositif pour obtenir du gazole ou du fioul à partir de résidus contenant des hydrocarbures WO2009053234A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007051373.0 2007-10-26
DE102007051373A DE102007051373B4 (de) 2007-10-26 2007-10-26 Verfahren und Vorrichtung zur Gewinnung von Diesel oder Heizöl aus kohlenwasserstoffhaltigen Rückständen

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WO2009053234A1 true WO2009053234A1 (fr) 2009-04-30

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PCT/EP2008/063351 WO2009053234A1 (fr) 2007-10-26 2008-10-06 Procédé et dispositif pour obtenir du gazole ou du fioul à partir de résidus contenant des hydrocarbures

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DE (1) DE102007051373B4 (fr)
WO (1) WO2009053234A1 (fr)

Cited By (1)

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US10093860B2 (en) 2013-02-20 2018-10-09 Recycling Technologies Ltd Process and apparatus for treating waste comprising mixed plastic waste

Families Citing this family (4)

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DE102017108852B4 (de) * 2017-04-25 2019-11-07 Innovative Environmental Technologie FZE Vorrichtung zur thermischen Aufarbeitung von schadstoffhaltigen organischen Abfällen zur Herstellung von Gas, Öl und Aktivkoks
DE102019110186A1 (de) * 2019-04-17 2020-11-12 Pruvia Gmbh Plastik-zu-Öl-Werk, entsprechender Cracking-Reaktor und damit verbundene Verfahren zum Umwandeln von Plastikabfall in petrochemische Produkte
WO2022056212A1 (fr) 2020-09-14 2022-03-17 Ecolab Usa Inc. Additifs d'écoulement à froid pour charge de départ synthétique dérivée de matière plastique
EP4416248A1 (fr) 2021-10-14 2024-08-21 Ecolab Usa Inc. Agents antisalissure pour matières premières synthétiques dérivées du plastique

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DE19852007A1 (de) * 1998-11-11 2000-05-18 Mineraloel Raffinerie Dollberg Verfahren zur Wiederaufarbeitung von Altölen, die mit dem Verfahren erhältlichen Grundöle und deren Verwendung
DE19950062A1 (de) * 1999-10-16 2001-04-26 Siempelkamp Guss Und Anlagente Verfahren und Anlage zur Aufbereitung von flüssigen und/oder festen organischen Abfallstoffen
WO2003057800A1 (fr) * 2002-01-10 2003-07-17 Aston University Reacteur de thermolyse ablatif

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DE3545954A1 (de) * 1985-12-23 1987-07-02 Bbc Brown Boveri & Cie Verfahren zum pyrolytischen aufarbeiten von ausgangsmaterial
DE3721475C1 (de) * 1987-06-30 1989-03-23 Asea Brown Boveri Anlage zur Pyrolyse von Abfallmaterial
DE3721476C1 (de) * 1987-06-30 1988-12-22 Asea Brown Boveri Verfahren zum Regeln der Wirbelschichthoehe in einem Pyrolysereaktor sowie Anordnung zur Durchfuehrung des Verfahrens
DE3728871C1 (de) * 1987-08-29 1989-01-19 Asea Brown Boveri Verfahren zum pyrolytischen Verwerten von Destillationsrueckstand und Anwendung des Verfahrens
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Publication number Priority date Publication date Assignee Title
DE19852007A1 (de) * 1998-11-11 2000-05-18 Mineraloel Raffinerie Dollberg Verfahren zur Wiederaufarbeitung von Altölen, die mit dem Verfahren erhältlichen Grundöle und deren Verwendung
DE19950062A1 (de) * 1999-10-16 2001-04-26 Siempelkamp Guss Und Anlagente Verfahren und Anlage zur Aufbereitung von flüssigen und/oder festen organischen Abfallstoffen
WO2003057800A1 (fr) * 2002-01-10 2003-07-17 Aston University Reacteur de thermolyse ablatif

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10093860B2 (en) 2013-02-20 2018-10-09 Recycling Technologies Ltd Process and apparatus for treating waste comprising mixed plastic waste
US10717934B2 (en) 2013-02-20 2020-07-21 Recycling Technologies Ltd. Apparatus for treating waste comprising mixed plastic waste
US10760003B2 (en) 2013-02-20 2020-09-01 Recycling Technologies Ltd Process and apparatus for treating waste comprising mixed plastic waste

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DE102007051373A1 (de) 2009-04-30
DE102007051373B4 (de) 2010-11-11

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