EP0588998A1 - Olefin production process. - Google Patents

Olefin production process.

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Publication number
EP0588998A1
EP0588998A1 EP93905182A EP93905182A EP0588998A1 EP 0588998 A1 EP0588998 A1 EP 0588998A1 EP 93905182 A EP93905182 A EP 93905182A EP 93905182 A EP93905182 A EP 93905182A EP 0588998 A1 EP0588998 A1 EP 0588998A1
Authority
EP
European Patent Office
Prior art keywords
viscosity
thermal
stage
gekenn
plastic
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.)
Granted
Application number
EP93905182A
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German (de)
French (fr)
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EP0588998B1 (en
Inventor
Hartmut Hammer
Hermann Hoever
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RWE Entsorgung AG
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RWE Entsorgung AG
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Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a process for the production of olefins from plastic waste by setting a desired viscosity by thermal pretreatment of the plastic waste in a temperature range from 380 to 680 ° C., thermal treatment of the product from the first treatment stage at a temperature of 700.degree. 1100 ° C.
  • a further method for processing composite films, in particular paper / polyethylene / aluminum films, which serve as beverage packaging, into pure cellulose, aluminum and polyethylene is disclosed in P 4028999.
  • the applicant has now succeeded in further improving the recycling of plastic waste by a process which is characterized in that plastic waste is melted by heating, a desired viscosity of the plastic melt is set by thermal cracking, and the product during heated to 700 to 1100 ° C for a residence time of 0.02 to 10 seconds.
  • the method according to the invention is shown in the figure by way of example and in a greatly simplified manner.
  • the applicant has now for the first time succeeded in proving that the thermal pretreatment of the waste according to the invention while setting a desired viscosity in a temperature range from 380 to 600 ° C., preferably from 400 to 600 ° C. and particularly preferably from 450 to 550 ° C. and more thermally Treatment of the pretreated material at 700 to 1100 ° C ethylene in yields of about 30% or even further improved yields, and C 3 -C 4 -01efins can be obtained.
  • the temperature range of the entire thermal pretreatment lies in the melting range from plastic waste to the cracking range, the latter as is known from the thermal cracking of residual petroleum oils and high-boiling petroleum fractions, for example by so-called visbreaking or also more severe cracking processes.
  • the temperature to be used in the treatment stage for adjusting the viscosity is preferably selected so that the plastic waste is liquefied and thermally cracked and thereby evaporable, and can be conveyed as a liquid into the second treatment stage, for example by pumps or extruders or other conveying devices, where Evaporation and thermal cleavage to olefins occurs.
  • the dwell time is 2 to 1500 minutes. However, the evaporation can already take place in the stage for adjusting the viscosity.
  • An important aspect when setting the temperature and residence time in the treatment stage for adjusting the viscosity is the maximization of the ethylene or also propylene yield in the treatment stage at 700-1100 ° C., ie the procedure in the first
  • the treatment stage mentioned is adjusted so that optimum olefin yields are obtained in the treatment stage at 700-1000 ° C.
  • the dwell time is 2 to 1500 minutes. Furthermore, the upstream thermal treatment stage is carried out in such a way that chlorine present in the feed product is largely or completely removed as HC1. The removal of the hydrogen chloride can be facilitated by introducing an inert gas stream. Furthermore, the HCl elimination from bases such as. B. Alkali and alkaline earth bases can be improved or completed.
  • Both the stage for adjusting the viscosity and the upstream thermal stage are preferably operated under inert gas, such as. B. under nitrogen, hydrogen, water vapor, C0 2, etc.
  • inert gas such as. B. under nitrogen, hydrogen, water vapor, C0 2, etc.
  • the application of vacuum or pressure is also possible.
  • Bases can also be used in the viscosity adjustment step to facilitate or release HCl.
  • the temperature range and the dwell time in the treatment stage at 700-1100 ° C. essentially correspond to those which are set when ethylene is obtained from other feed materials, as have already been mentioned above.
  • the apparatus or systems used can also correspond to that of conventional ethylene systems.
  • the quantitative ratio of plastic waste to added water vapor or hydrogen is usually 1 part by weight to 0.1 to 2 parts by weight. A preferred ratio is 1 part by weight to 0.3 to 1.3 parts by weight.
  • the temperature in the subsequent treatment stage is 700 to 1100 ° C, preferably 750 to 900 ° C and particularly preferably 780 to 860 ° C.
  • the residence time is 0.02 to 10 seconds, preferably 0.1 to 2 seconds.
  • the viscosity so that the feed product evaporates or evaporates in the thermal treatment stage operated at 700 to 1100 ° C. and is split into olefins as steam.
  • the material with the viscosity set can also be used liquid in the thermal treatment stage at 700-1100 ° C.
  • Particularly suitable products used in the process according to the invention are plastic waste or any mixtures from the group consisting of polyethylene, polypropylene, polystyrene, polybutane, polyvinyl chloride or linear polybutadiene and the like. a.
  • halogen-containing feed materials in particular polyvinyl chloride
  • the chlorine is completely or almost completely or at least predominantly removed as hydrogen chloride, bases additionally being able to be added.
  • the processing of the products of the treatment stage at 700 - 1100 ° C can be carried out in an analogous manner, as is known from ethylene production. So the cleavage can take place in that the feed product in directly fired apparatus such.
  • the splitting of the product from the treatment step to adjust the viscosity or from the pretreatment step can, however, also take place autothermally in the fluidized bed.
  • B. coke, sand, etc. can be in contact with the to be split preferably initially liquid feed product and Maintaining the gap temperature converts part of the feed to water and C0.
  • the feed product can also be converted into ethylene, for example, in analogy to Union Carbide's Advanced Cracking Reactor Process, by the Dow process or by other crude oil cracking processes.
  • (1) provides a warehouse for plastic waste, e.g. B. from household waste. Via (2) the waste is conveyed to the thermal pretreatment stage (3), to which bases can be added via (4). HCl can be removed via (5).
  • the liquid product which is essentially halogen-free, flows into device (6) for setting the desired viscosity. Steam is supplied via (7). Bases can also be used in (6).
  • the material flows from (6) into the splitting plant (8) working at 700 to 1100 ° C.
  • the fission product flows through (10) through quench coolers (11) into the separation system (12), in which the fission products are separated into olefins and liquid products under normal conditions.
  • the separation technology including the technology of the olefin mixture into individual olefins, is known to the person skilled in the art and need not be described in more detail.

Abstract

PCT No. PCT/DE93/00226 Sec. 371 Date Jan. 12, 1994 Sec. 102(e) Date Jan. 12, 1994 PCT Filed Mar. 12, 1993 PCT Pub. No. WO93/18112 PCT Pub. Date Sep. 16, 1993The instant invention relates to a process for the production of olefins from plastic waste, which comprises adjustment of a desired viscosity by thermal pretreatment of plastic waste in a temperature range of 350 DEG to 550 DEG C. and thermal treatment of the product obtained by the thermal pretreatment in a temperature range of 700 DEG to 1100 DEG C.

Description

Verfahren zur Herstellung von OlefinenProcess for the production of olefins
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Olefinen aus Kunststoffabfallen durch Einstellung einer gewünschten Visko¬ sität durch thermische Vorbehandlung der Kunststoffabfalle in einem Tempe¬ raturbereich von 380 - 680 °C, thermische Behandlung des Produkts aus der ersten Behandlungsstufe bei einer Temperatur von 700 - 1100 °C.The present invention relates to a process for the production of olefins from plastic waste by setting a desired viscosity by thermal pretreatment of the plastic waste in a temperature range from 380 to 680 ° C., thermal treatment of the product from the first treatment stage at a temperature of 700.degree. 1100 ° C.
Die Entsorgung von Kunststoffabfällen, insbesondere von verschmutzten Kunststoffabfallgemisehen, unter Erzeugung von Wertstoffen ist nach wie vor ein technisch ungelöstes Problem.The disposal of plastic waste, especially contaminated plastic waste mix, with the production of valuable materials is still a technically unsolved problem.
Die seit kurzem an Probestandorten in der Bundesrepublik Deutschland einge¬ führte getrennte Sammlung von Kunststoffverpackungen in Haushalten und Gewerbe (Duales System) führt bei Einführung in der gesamten Bundesrepublik zu einer Verpackungsabfallmenge von mehr als 1 Mio. t/a.The separate collection of plastic packaging in households and businesses (dual system), which has recently been introduced at trial locations in the Federal Republic of Germany, leads to a packaging waste quantity of more than 1 million t / a when introduced throughout the Federal Republic.
Da die Verbrennung als "Thermisches Recycling" in der Öffentlichkeit auf starken Widerstand stößt und die Pyrolyse, d. h. das Erhitzen der Kunst¬ stoffabfälle in Abwesenheit von Sauerstoff zu als Wertstoffe weitgehend unbrauchbaren Produkten führt, gibt es zur Zeit nur sehr wenige Verfahren, die es ermöglichen, aus den Kunststoffabfallen nützliche Wertstoffe zu erzeugen, die unter Einsparung von Erdöl wiederverwendet werden können. Zudem befinden sich diese Verfahren erst im Versuchsstadium.Since combustion as "thermal recycling" is met with strong resistance from the public and pyrolysis, i.e. H. the heating of the plastic waste in the absence of oxygen leads to products which are largely unusable as valuable materials, at the moment there are very few processes which make it possible to produce useful valuable materials from the plastic waste which can be reused while saving petroleum. In addition, these processes are only in the experimental stage.
Ein solches Verfahren ist die in mehreren Patenten, wie z. B. in DE-PS 3442506 und EP 0236701 offenbarte Hydrierung von Kunststoffabfallge isehen unter hohem Wasserstoffdruck und bei hoher Temperatur, wobei in Abhängig¬ keit von den Einsatzmaterialien bis zu 90 Gew.-% an gesättigten Kohlenwas¬ serstoffen gewonnen werden können, die im Benzin- und Mittelölbereich sieden.One such method is that described in several patents, e.g. B. disclosed in DE-PS 3442506 and EP 0236701 hydrogenation of plastic waste under high hydrogen pressure and at high temperature, depending on the starting materials up to 90% by weight of saturated hydrocarbons which can be obtained in gasoline - and medium oil boil.
Ein weiteres Verfahren zur Aufarbeitung von Verbundfolien, insbesondere von Papier-/Polyethylen-/Aluminiumfolien, die als Getränkeverpackungen dienen, zu reinem Zellstoff, Aluminium und Polyethylen ist in P 4028999 offenbart. Durch diese Verfahren, wenn sie zur technischen Reife entwickelt sind, läßt sich zumindest ein Teil des Kunststoffverpackungsabfalls sinnvoll wieder¬ verwerten.A further method for processing composite films, in particular paper / polyethylene / aluminum films, which serve as beverage packaging, into pure cellulose, aluminum and polyethylene is disclosed in P 4028999. By means of these processes, when they are developed to technical maturity, at least part of the plastic packaging waste can be usefully recycled.
Ein Verfahren, durch das in einer thermischen und einer katalytischen Stufe Polyethylen, Polypropylen und Polystyrol bzw. Gemische derselben in unge¬ sättigte und gesättigte Kohlenwasserstoffe gespalten werden, ist in Japan Chemical Week, 31. Mai 1990, Seite 6 und 7 beschrieben. In einem Tempera¬ turbereich bis ca. 500 °C lassen sich ca. 60 Gew.-% flüssige Kohlenwasser¬ stoffe, ca. 30 Gew.-% gasförmige Kohlenwasserstoffe und ca. 10 Gew.-% kohlenstoffartiger Rückstand erhalten. Ca. 50 % des flüssigen Produkts sind ungesättigte Kohlenwasserstoffe. Ethylen und Propylen fallen im gasförmigen Produkt nur mit 4,5 bzw. 7,6 Gew.-% an.A process by which polyethylene, polypropylene and polystyrene or mixtures thereof are split into unsaturated and saturated hydrocarbons in a thermal and a catalytic stage is described in Japan Chemical Week, May 31, 1990, pages 6 and 7. In a temperature range up to approx. 500 ° C., approx. 60 wt.% Liquid hydrocarbons, approx. 30 wt.% Gaseous hydrocarbons and approx. 10 wt.% Carbon-like residue can be obtained. Approximately 50% of the liquid product is unsaturated hydrocarbons. Ethylene and propylene are only 4.5 and 7.6% by weight in the gaseous product.
Der Anmelderin ist es nunmehr gelungen, das Recycling von Kunststoffabf l¬ len durch ein Verfahren weiter zu verbessern, das dadurch gekennzeichnet ist, daß Kunststoffabf lle durch Erhitzen geschmolzen werden, eine ge¬ wünschte Viskosität der Kunststoffschmelze durch thermisches Cracken eingestellt wird und das Produkt während einer Verweilzeit von 0,02 bis 10 Sek. auf 700 bis 1100 °C erhitzt.The applicant has now succeeded in further improving the recycling of plastic waste by a process which is characterized in that plastic waste is melted by heating, a desired viscosity of the plastic melt is set by thermal cracking, and the product during heated to 700 to 1100 ° C for a residence time of 0.02 to 10 seconds.
In der Figur ist das erfingungsgemäße Verfahren beispielhaft und stark vereinfacht dargestellt.The method according to the invention is shown in the figure by way of example and in a greatly simplified manner.
Obgleich die thermische Spaltung von sogenanntem Naphtha, eines bei ca. 100 bis 170 °C siedenden Erdölschnitts, das zur Zeit wichtigste Verfahren zur Erzeugung von Ethylen und Propylen ist und obgleich bekannt ist, daß auch Mittelöl und Vakuu gasöl in befriedigenden Ausbeuten zu Ethylen und Propy¬ len umgesetzt werden können und obgleich bekannt ist, auch durch thermische Behandlung von rohem Erdöl Ethylen und Propylen zu erzeugen, hat der Fachmann bisher keine Lösung der Aufgabenstellung gefunden, aus Kunststoff- abfallen direkt durch thermische Behandlung nach thermischer Vorbehandlung Ethylen und Propylen zu gewinnen und damit ein echtes Recycling herbei¬ zuführen. Der Anmelderin ist nunmehr erstmalig der Nachweis gelungen, daß durch die erfindungsgemäße thermische Vorbehandlung der Abfälle unter Einstellung einer gewünschten Viskosität in einem Temperaturbereich von 380 bis 600 °C, bevorzugt von 400 bis 600 °C und besonders bevorzugt von 450 bis 550 °C und thermischer Behandlung des vorbehandelten Materials bei 700 bis 1100 °C Ethylen in Ausbeuten von ca. 30 % oder noch weiter verbesserten Ausbeuten, sowie C3-C4-01efine gewonnen werden können.Although the thermal cracking of so-called naphtha, a petroleum cut boiling at approx. 100 to 170 ° C, which is currently the most important process for the production of ethylene and propylene and although it is known that medium oil and vacuum gas oil in satisfactory yields to ethylene and propy ¬ len can be implemented and although it is known to also produce ethylene and propylene by thermal treatment of crude petroleum, the person skilled in the art has so far not found a solution to the problem of obtaining ethylene and propylene from plastic waste directly by thermal treatment after thermal pretreatment and to bring about real recycling. The applicant has now for the first time succeeded in proving that the thermal pretreatment of the waste according to the invention while setting a desired viscosity in a temperature range from 380 to 600 ° C., preferably from 400 to 600 ° C. and particularly preferably from 450 to 550 ° C. and more thermally Treatment of the pretreated material at 700 to 1100 ° C ethylene in yields of about 30% or even further improved yields, and C 3 -C 4 -01efins can be obtained.
Der Temperaturbereich der gesamten thermischen Vorbehandlung liegt im Schmelzbereich von Kunststoffabfallen bis zum Crackbereich, wobei letzterer wie er von dem thermischen Cracken von Erdölrückstandsölen und hoch sieden¬ den Erdölfraktionen, beispielsweise durch sogenanntes Visbreaking oder auch schärfere Crackverfahren, bekannt ist.The temperature range of the entire thermal pretreatment lies in the melting range from plastic waste to the cracking range, the latter as is known from the thermal cracking of residual petroleum oils and high-boiling petroleum fractions, for example by so-called visbreaking or also more severe cracking processes.
Die anzuwendende Temperatur in der Behandlungsstufe zur Einstellung der Viskosität wird vorzugsweise so gewählt, daß der Kunststoffabfall verflüs¬ sigt wird und thermisch gecraekt wird und hierdurch verdampfbar wird, sowie als Flüssigkeit durch beispielsweise Pumpen oder Extruder oder andere Fördervorrichtungen in die zweite Behandlungsstufe förderbar ist, wo Verdampfung und thermische Spaltung zu Olefinen eintritt. Die Verweilzeit liegt bei 2 bis 1500 Minuten. Die Verdampfung kann jedoch bereits in der Stufe zur Einstellung der Viskosität erfolgen.The temperature to be used in the treatment stage for adjusting the viscosity is preferably selected so that the plastic waste is liquefied and thermally cracked and thereby evaporable, and can be conveyed as a liquid into the second treatment stage, for example by pumps or extruders or other conveying devices, where Evaporation and thermal cleavage to olefins occurs. The dwell time is 2 to 1500 minutes. However, the evaporation can already take place in the stage for adjusting the viscosity.
Es ist hierbei ein mildes oder auch schärferes Cracken durchzuführen. Dies kann in üblichen Crackapparaten durchgeführt werden, aber auch in Rührbe¬ hältern, Extrudern u. a. Apparaten.Mild or sharper cracking must be carried out. This can be carried out in conventional crackers, but also in stirred tanks, extruders and the like. a. Apparatus.
Ein wichtiger Gesichtspunkt bei der Einstellung von Temperatur- und Ver¬ weilzeit in der Behandlungsstufe zur Einstellung der Viskosität ist die Maxi ierung der Ethylen- oder auch Propylen-Ausbeute in der Behandlungsstu¬ fe bei 700 - 1100° C, d. h. die Verfahrensführung in der zuerst genannten Behandlungsstufe wird so eingestellt, daß in der Behandlungsstufe bei 700 - 1000° C optimale Olefinausbeuten erhalten werden. Es ist von Vorteil, in die Stufe der Viskositätseinstellung bereits Wasserdampf einzuleiten. Dieser kann auch dazu dienen, die Verda pfbarkeit des verflüssigten Materi¬ als zu unterstützen. Es hat sich als vorteilhaft erwiesen, der thermischen Behandlungsstufe zur Einstellung der gewünschten Viskosität eine thermische Behandlung vorzu¬ schalten, in der bereits ein Aufschmelzen erfolgt und bei der eine Tempera¬ tur von 200 bis 480 °C, bevorzugt von 250 bis 430 °C, eingestellt wird. Die Verweilzeit liegt bei 2 bis 1500 Minuten. Ferner wird die vorgeschalte¬ te thermische Behandlungsstufe so durchgeführt, daß im Einsatzprodukt vorhandenes Chlor als HC1 überwiegend bis vollständig entfernt wird.- Die Entfernung des Chlorwasserstoffs kann hierbei durch Einleiten eines Inertgasstroms erleichtert werden. Ferner kann die HCl-Abspaltung von Basen wie z. B. Alkali- und Erdalkalibasen verbessert bzw. vervollständigt werden.An important aspect when setting the temperature and residence time in the treatment stage for adjusting the viscosity is the maximization of the ethylene or also propylene yield in the treatment stage at 700-1100 ° C., ie the procedure in the first The treatment stage mentioned is adjusted so that optimum olefin yields are obtained in the treatment stage at 700-1000 ° C. It is advantageous to introduce water vapor into the viscosity setting stage. This can also serve to support the vaporizability of the liquefied material. It has proven to be advantageous to precede the thermal treatment stage to set the desired viscosity with a thermal treatment in which melting is already taking place and at which a temperature of 200 to 480 ° C., preferably 250 to 430 ° C., is set. The dwell time is 2 to 1500 minutes. Furthermore, the upstream thermal treatment stage is carried out in such a way that chlorine present in the feed product is largely or completely removed as HC1. The removal of the hydrogen chloride can be facilitated by introducing an inert gas stream. Furthermore, the HCl elimination from bases such as. B. Alkali and alkaline earth bases can be improved or completed.
Hierbei, und dies gilt auch für die Stufe zur Einstellung der Viskosität in der auch die Halogenabspaltung vervollständigt werden kann, sind im allge¬ meinen kurze Verweilzeiten dann möglich, wenn bei hohen Temperaturen gearbeitet wird, während lange Verweilzeiten bei tiefen Temperaturen erforderlich sein können.Here, and this also applies to the stage for adjusting the viscosity, in which the halogen elimination can also be completed, short residence times are generally possible when working at high temperatures, while long residence times at low temperatures may be necessary.
Sowohl die Stufe zur Einstellung der Viskosität als auch die vorgeschaltete thermische Stufe werden bevorzugt unter Inertgas betrieben, wie z. B. unter Stickstoff, Wasserstoff, Wasserdampf, C02 u. a. Auch das Anlegen von Vakuum oder Druck ist möglich. Auch in der Stufe zur Einstellung der Viskosität können Basen zur Erleichterung oder HCl-Abspaltung eingesetzt werden.Both the stage for adjusting the viscosity and the upstream thermal stage are preferably operated under inert gas, such as. B. under nitrogen, hydrogen, water vapor, C0 2, etc. The application of vacuum or pressure is also possible. Bases can also be used in the viscosity adjustment step to facilitate or release HCl.
Der Temperaturbereich und die Verweilzeit in der Behandlungsstufe bei 700 - 1100° C entsprechen im wesentlichen denjenigen, wie sie bei der Ethylenge- winnung aus anderen Einsatzmaterialien, wie sie oben bereits genannt wurden, eingestellt werden. Auch die verwendeten Apparate bzw. Anlagen können demjenigen konventioneller Ethylenanlagen entsprechen.The temperature range and the dwell time in the treatment stage at 700-1100 ° C. essentially correspond to those which are set when ethylene is obtained from other feed materials, as have already been mentioned above. The apparatus or systems used can also correspond to that of conventional ethylene systems.
Es ist bevorzugt, diese Behandlungsstufe bei 700 bis 1100 °C in Gegenwart von zugeführtem Wasserdampf durchzuführen. Anstelle von Dampf kann jedoch auch Wasserstoff zugesetzt werden bzw. es können Gemische von Wasserdampf und Wasserstoff eingesetzt werden.It is preferred to carry out this treatment step at 700 to 1100 ° C in the presence of supplied steam. Instead of steam, however, hydrogen can also be added, or mixtures of water vapor and hydrogen can be used.
Das Mengenverhältnis von Kunststoffabfall zu zugesetztem Wasserdampf bzw. Wasserstoff liegt üblicherweise bei 1 Gew.-Teil zu 0,1 bis 2 Gew.-Teilen. Ein bevorzugtes Verhältnis ist 1 Gew.-Teil zu 0,3 bis 1,3 Gew.-Teilen. Die Temperatur in der nachgeschalteten Behandlungsstufe liegt bei 700 bis 1100 °C, bevorzugt bei 750 bis 900 °C und besonders bevorzugt bei 780 bis 860 °C. Die Verweilzeit liegt bei 0,02 bis 10 Sek., bevorzugt bei 0,1 bis 2 Sek.The quantitative ratio of plastic waste to added water vapor or hydrogen is usually 1 part by weight to 0.1 to 2 parts by weight. A preferred ratio is 1 part by weight to 0.3 to 1.3 parts by weight. The temperature in the subsequent treatment stage is 700 to 1100 ° C, preferably 750 to 900 ° C and particularly preferably 780 to 860 ° C. The residence time is 0.02 to 10 seconds, preferably 0.1 to 2 seconds.
Es ist bevorzugt, die Viskosität so einzustellen, daß das Einsatzprodukt verdampft bzw. in der bei 700 bis 1100 °C betriebenen thermischen Behand¬ lungsstufe verdampft und als Dampf zu Olefinen gespalten wird. Grundsätz¬ lich kann das Material mit eingestellter Viskosität jedoch auch flüssig in die thermische Behandlungsstufe bei 700 - 1100° C eingesetzt werden.It is preferred to adjust the viscosity so that the feed product evaporates or evaporates in the thermal treatment stage operated at 700 to 1100 ° C. and is split into olefins as steam. In principle, however, the material with the viscosity set can also be used liquid in the thermal treatment stage at 700-1100 ° C.
Besonders geeignete Einsatzprodukte in das erfindungsgemäße Verfahren sind Kunststoffabfalle bzw. beliebige Gemische aus der Gruppe Polyethylen, Po¬ lypropylen, Polystyrol, Polybutane, Polyvinylchlorid oder auch lineares Polybutadien u. a.Particularly suitable products used in the process according to the invention are plastic waste or any mixtures from the group consisting of polyethylene, polypropylene, polystyrene, polybutane, polyvinyl chloride or linear polybutadiene and the like. a.
In der Stufe zur Einstellung der Viskosität vorgeschalteten thermischen Vorbehandlungsstufe, wird bei Vorliegen von halogenhaltigen Einsatzmateria¬ lien, insbesondere von Polyvinylchlorid im Einsatzprodukt das Chlor voll¬ ständig bis nahezu vollständig bzw. zumindest überwiegend als Chlorwasser¬ stoff entfernt, wobei zusätzlich Basen zugesetzt werden können.In the stage for adjusting the viscosity upstream of the thermal pretreatment stage, if halogen-containing feed materials, in particular polyvinyl chloride, are present in the feed product, the chlorine is completely or almost completely or at least predominantly removed as hydrogen chloride, bases additionally being able to be added.
Die Aufarbeitung der Produkte der Behandlungsstufe bei 700 - 1100° C kann in analoger Weise erfolgen, wie sie aus der Ethylenerzeugung bekannt ist. So kann die Spaltung dadurch erfolgen, daß das Einsatzprodukt in direkt befeuerten Apparaten, wie z. B. Rohrschlangen im Gemisch von 0,1 bis 2 Gew.-Teilen Dampf pro Gewichtsteil Einsatzprodukt bei Verweilzeiten von 0,02 bis 10 Sek. bzw. 0,1 bis 2 Sek. umgesetzt wird. Anstelle von Dampf kann Wasserstoff oder ein Gemisch von Wasserdampf und Wasserstoff einge¬ setzt werden.The processing of the products of the treatment stage at 700 - 1100 ° C can be carried out in an analogous manner, as is known from ethylene production. So the cleavage can take place in that the feed product in directly fired apparatus such. B. coils in a mixture of 0.1 to 2 parts by weight of steam per part by weight of the starting product with residence times of 0.02 to 10 seconds or 0.1 to 2 seconds. Instead of steam, hydrogen or a mixture of water vapor and hydrogen can be used.
Die Spaltung des Produkts aus der Behandlungsstufe zur Einstellung der Viskosität oder aus der Vorbehandlungsstufe kann jedoch auch autother in der Wirbelschicht erfolgen, wobei sich ein die Wirbelschicht bildendes Material, wie z. B. Koks, Sand u. a. in Kontakt mit dem zu spaltenden vorzugsweise zunächst flüssigen Einsatzprodukt befinden kann und zur Aufrechterhaltung der Spalttemperatur ein Teil des Einsatzprodukts in Wasser und C0 umgewandelt wird. Das Einsatzprodukt kann auch beispielswei¬ se in Analogie zum Advanced Cracking Reactor Process der Union Carbide, nach dem Dow-Verfahren oder nach anderen Rohölspaltverfahren zu Ethylen umgesetzt werden.The splitting of the product from the treatment step to adjust the viscosity or from the pretreatment step can, however, also take place autothermally in the fluidized bed. B. coke, sand, etc. can be in contact with the to be split preferably initially liquid feed product and Maintaining the gap temperature converts part of the feed to water and C0. The feed product can also be converted into ethylene, for example, in analogy to Union Carbide's Advanced Cracking Reactor Process, by the Dow process or by other crude oil cracking processes.
Erfindungsgemäß wesentlich ist jedoch nicht der aus der Ethylenerzeugung bekannte Spaltprozeß, sondern die Kombination der Umwandlung der Kunst¬ stoffabfälle in ein Produkt mit der gewünschten Viskosität und- die Anwen¬ dung der Spalttemperatur von 700 bis 1100 °C auf die thermische Spaltung des Produkts zu Olefinen bei einer Verweilzeit von 0,02 bis 10 Sek.According to the invention, however, it is not the cracking process known from ethylene production that is essential, but rather the combination of converting the plastic waste into a product with the desired viscosity and applying the cracking temperature of 700 to 1100 ° C. to the thermal cracking of the product to olefins with a dwell time of 0.02 to 10 seconds
In der Figur ist das erfindungsgemäße Verfahren beispielhaft und stark vereinfacht dargestellt. In the figure, the method according to the invention is shown by way of example and in a highly simplified manner.
(1) stellt ein Lager für Kunststoffabfälle, z. B. aus Hausmüll dar. Über (2) wird der Abfall in die thermische Vorbehandlungsstufe (3) gefördert, zu der über (4) Basen zugesetzt werden können. Über (5) kann HCl entfernt werden. Das flüssige Produkt, das im wesentlichen halogenfrei ist, fließt in Vorrichtung (6) zur Einstellung der gewünschten Viskosität. Über (7) wird Wasserdampf zugeführt. Auch in (6) können Basen eingesetzt werden. Von (6) fließt das Material in die bei 700 bis 1100 °C arbeitende Spaltanlage (8). Das Spaltpro¬ dukt fließt über (10) durch Quenchkühler (11) in die Trennanlage (12), in der die Spaltprodukte in Olefine und bei Normalbedingungen flüssige Produkte aufgetrennt werden. Die Trenntechnologie einschließlich der Technologie des Olefingemisches in einzelne Olefine ist dem Fachmann bekannt und braucht nicht näher dargestellt zu werden. (1) provides a warehouse for plastic waste, e.g. B. from household waste. Via (2) the waste is conveyed to the thermal pretreatment stage (3), to which bases can be added via (4). HCl can be removed via (5). The liquid product, which is essentially halogen-free, flows into device (6) for setting the desired viscosity. Steam is supplied via (7). Bases can also be used in (6). The material flows from (6) into the splitting plant (8) working at 700 to 1100 ° C. The fission product flows through (10) through quench coolers (11) into the separation system (12), in which the fission products are separated into olefins and liquid products under normal conditions. The separation technology, including the technology of the olefin mixture into individual olefins, is known to the person skilled in the art and need not be described in more detail.

Claims

Patentansprüche ^ Claims ^
1. Verfahren zur Herstellung von Olefinen, dadurch gekennzeichnet, daß man Kunststoffabfalle durch Erhitzen schmilzt und durch thermisches Cracken eine gewünschte Viskosität der Kunststoffschmelze einstellt und das Produkt während einer Verweilzeit von 0,02 bis 10 Sek. auf 700 bis 1100 °C erhitzt.1. A process for the preparation of olefins, characterized in that plastic waste is melted by heating and a desired viscosity of the plastic melt is set by thermal cracking and the product is heated to 700 to 1100 ° C for a residence time of 0.02 to 10 seconds.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die ge¬ wünschte Viskosität bei einer Temperatur von 380 bis 650 °C, bevorzugt von 400 bis 600 °C und besonders bevorzugt von 450 bis 550 °C ein¬ stellt.2. The method according to claim 1, characterized in that one sets the desired viscosity at a temperature of 380 to 650 ° C, preferably from 400 to 600 ° C and particularly preferably from 450 to 550 ° C.
3. Verfahren nach wenigstens einem der Ansprüche 1 und 2, dadurch gekenn¬ zeichnet, daß man die gewünschte Viskosität bei einer Verweilzeit von 2 Min. bis 1500 Min. einstellt.3. The method according to at least one of claims 1 and 2, characterized gekenn¬ characterized in that the desired viscosity is set with a residence time of 2 minutes to 1500 minutes.
4. Verfahren nach wenigstens einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß man eine solche Viskosität einstellt, daß das Material verdampfbar ist und als Dampf in einer thermischen Behandlungsstufe von 700 bis 1100 °C gespalten wird.4. The method according to at least one of claims 1 to 3, characterized gekenn¬ characterized in that such a viscosity is set that the material is evaporable and is split as steam in a thermal treatment stage of 700 to 1100 ° C.
5. Verfahren nach wenigstens einem der Ansprüche 1 bis 4, dadurch gekenn¬ zeichnet, daß man der Stufe zur Einstellung der gewünschten Viskosität eine thermische Vorbehandlungsstufe vorschaltet, in der man das Einsatzmaterial 2 bis 1500 Min. auf 200 bis 480 °C, bevorzugt auf 250 bis 430 °C, erhitzt.5. The method according to at least one of claims 1 to 4, characterized gekenn¬ characterized in that the stage for setting the desired viscosity is preceded by a thermal pretreatment stage, in which the feed 2 to 1500 min. To 200 to 480 ° C, preferably at 250 to 430 ° C, heated.
6. Verfahren nach wenigstens einem der Ansprüche 1 bis 5, dadurch gekenn¬ zeichnet, daß man bei wenigstens teilweisem Einsatz von Polyvinylchlo¬ rid den Chloranteil in der thermischen Vorbehandlungsstufe zumindest überwiegend, vorzugsweise vollständig bis nahezu vollständig, ent¬ fernt.6. The method according to at least one of claims 1 to 5, characterized gekenn¬ characterized in that with at least partial use of polyvinylchloride the chlorine in the thermal pretreatment stage at least predominantly, preferably completely to almost completely, removed.
7. Verfahren nach wenigstens einem der Ansprüche 1 bis 6, dadurch gekenn¬ zeichnet, daß man in die thermische Vorbehandlungsstufe zusätzlich eine Base einsetzt. 7. The method according to at least one of claims 1 to 6, characterized gekenn¬ characterized in that an additional base is used in the thermal pretreatment stage.
8. Verfahren nach wenistens einem der Ansprüche 1 bis 7, dadurch gekenn¬ zeichnet, daß man die Kunststoffschmelze mit eingestellter Viskosität in der folgenden thermischen Behandlungsstufe bei 750 bis 900 °C, bevorzugt bei 780 bis 860 °C thermisch behandelt.8. The method according to at least one of claims 1 to 7, characterized gekenn¬ characterized in that the plastic melt with adjusted viscosity in the following thermal treatment step at 750 to 900 ° C, preferably at 780 to 860 ° C thermally treated.
9. Verfahren nach wenigstens einem der Ansprüche 1 bis 8, dadurch gekenn¬ zeichnet, daß man die Verweilzeit im Temperaturbereich von 700 bis 1100 °C auf 0,1 bis 2 Sek. einstellt.9. The method according to at least one of claims 1 to 8, characterized gekenn¬ characterized in that the residence time in the temperature range from 700 to 1100 ° C to 0.1 to 2 seconds.
10. Verfahren nach wenigstens einem der Ansprüche 1 bis 9, dadurch gekenn¬ zeichnet, daß man die Kunststoffschmelze mit eingestellter Viskosität in Gegenwart von zugesetztem Wasserdampf bei 700 bis 1000 °C thermisch behandelt.10. The method according to at least one of claims 1 to 9, characterized gekenn¬ characterized in that the plastic melt with adjusted viscosity in the presence of added steam at 700 to 1000 ° C thermally.
11. Verfahren nach wenigstens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß man den Wasserdampf zur Unterstützung der Verdamp¬ fung der Kunststoffschmelze mit eingestellter Viskosität benutzt.11. The method according to at least one of claims 1 to 10, characterized in that the water vapor is used to support the evaporation of the plastic melt with the viscosity set.
12. Verfahren nach wenigstens einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß man ein Verhältnis von zugesetztem Wasserdampf zu Kunststoffschmelze mit eingestellter Viskosität von 0,1 bis 2 Gew.-Tlen. zu 1 Gew.-Tl., bevorzugt von 0,3 bis 1,3 Gew.-Tlen. zu 1 Gew.-Tl. , einsetzt.12. The method according to at least one of claims 1 to 11, characterized in that a ratio of added water vapor to plastic melt with a set viscosity of 0.1 to 2 parts by weight. to 1 part by weight, preferably from 0.3 to 1.3 parts by weight. to 1 part by weight , starts.
13. Verfahren nach wenigstens einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß man Kunststoffabfall einsetzt, der wenigstens einen Kunststoff aus der Gruppe Polyethylen, Polypropylen, Polystyrol, Polyvinylchlorid, Polybutene, Polyisobutene, lineares Polybutadien, enthält.13. The method according to at least one of claims 1 to 12, characterized in that plastic waste is used which contains at least one plastic from the group polyethylene, polypropylene, polystyrene, polyvinyl chloride, polybutenes, polyisobutenes, linear polybutadiene.
14. Verfahren nach wenigstens einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß man die Vorbehandlungsstufe zur Einstellung der Viskosität unter Inertgas betreibt.14. The method according to at least one of claims 1 to 13, characterized in that one operates the pretreatment stage for adjusting the viscosity under inert gas.
15. Verfahren nach wenigstens einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß man die der Vorbehandlungsstufe zur Einstellung der Viskosität vorgeschaltete thermische Behandlung unter Inertgas durchführt. 15. The method according to at least one of claims 1 to 14, characterized in that the pretreatment stage for adjustment thermal treatment upstream of the viscosity is carried out under inert gas.
EP93905182A 1992-03-13 1993-03-12 Olefin production process Expired - Lifetime EP0588998B1 (en)

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DE4207976 1992-03-13
DE4207976A DE4207976C2 (en) 1992-03-13 1992-03-13 Process for the production of olefins by thermal treatment of plastic waste
PCT/DE1993/000226 WO1993018112A1 (en) 1992-03-13 1993-03-12 Olefin production process

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DE4207976A1 (en) 1993-09-16
DE4207976C2 (en) 2001-03-15
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