EP0588998B1 - Olefin production process - Google Patents

Olefin production process Download PDF

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EP0588998B1
EP0588998B1 EP93905182A EP93905182A EP0588998B1 EP 0588998 B1 EP0588998 B1 EP 0588998B1 EP 93905182 A EP93905182 A EP 93905182A EP 93905182 A EP93905182 A EP 93905182A EP 0588998 B1 EP0588998 B1 EP 0588998B1
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process according
stage
viscosity
adjusted
thermal
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French (fr)
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EP0588998A1 (en
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Hartmut Hammer
Hermann HÖVER
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RWE Entsorgung AG
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RWE Entsorgung AG
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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
    • C10G1/02—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. and thermal treatment of the product from the first treatment stage at a temperature from 700 to 1100 ° C.
  • 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.
  • About 60% by weight of liquid hydrocarbons, about 30% by weight of gaseous hydrocarbons and about 10% by weight of carbon-like residue can be obtained in a temperature range up to about 500 ° C.
  • Approx. 50% of the liquid product is unsaturated hydrocarbons.
  • Ethylene and propylene are only 4.5 and 7.6% by weight in the gaseous product.
  • 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 by thermal cracking at a temperature of 380 ° C to 650 ° C a residence time of 2 minutes to 1500 minutes is set and the product is heated to 700 to 1100 ° C. during a residence time of 0.02 to 10 seconds.
  • the applicant has now for the first time succeeded in proving that the thermal cracking of the waste according to the invention while setting a desired viscosity in a temperature range from 380 to 650 ° C, preferably from 400 to 600 ° C and particularly preferably from 450 to 550 ° C and thermal Cracking the pretreated Materials at 700 to 1100 ° C, ethylene in yields of about 30% or even further improved yields, and C 3 -C 4 olefins can be obtained.
  • the temperature range of the entire thermal treatment lies in the melting range from plastic waste to the cracking range, the latter as it is known from the thermal cracking of residual petroleum oils and high-boiling petroleum fractions, for example by so-called visbreaking or more severe cracking processes.
  • the temperature to be used in the thermal cracking stage for adjusting the viscosity is preferably chosen so that the plastic waste is liquefied and thermally cracked and thereby evaporable, and can be conveyed as liquid by means of pumps or extruders or other conveying devices, for example, into the second thermal cracking stage, where Evaporation and thermal cleavage to olefins occurs.
  • the dwell time is 2 to 1500 minutes. However, evaporation can take place in the cracking stage to adjust the viscosity.
  • An important aspect when adjusting the temperature and residence time in the thermal cracking stage to adjust the viscosity is maximizing the ethylene or propylene yield in the treatment stage at 700-1100 ° C, i.e. the procedure in the first-mentioned thermal cracking stage is adjusted so that optimum olefin yields are obtained in the cracking 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.
  • the thermal cracking stage has proven to be advantageous to precede the thermal cracking stage with a further thermal cracking stage in order to set the desired viscosity, 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.
  • the upstream thermal cracking stage is carried out in such a way that chlorine present in the feed product is largely or completely removed as HCl.
  • the removal of the hydrogen chloride can be facilitated by introducing an inert gas stream.
  • the HCl elimination of bases such as alkali and alkaline earth bases can be improved or completed.
  • Both the cracking stage for adjusting the viscosity and the upstream thermal cracking stage are preferably operated under inert gas, such as, for example, under nitrogen, hydrogen, water vapor, CO 2, etc. It is also possible to apply vacuum or pressure. Bases can also be used in the cracking stage to adjust the viscosity to facilitate the elimination of HCl.
  • the temperature range and the residence time in the cracking stage at 700-1100 ° C. essentially correspond to those set in the production of ethylene from other feed materials, as already mentioned above.
  • the apparatus or systems used can also correspond to those 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 thermal cracking stage for olefin production 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 it is preferred to adjust the viscosity so that the feed product evaporates or evaporates in the thermal cracking stage operated at 700 to 1100 ° C. and is split into olefins as steam.
  • the material with the adjusted viscosity can also be used liquid in the thermal cracking 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 else linear polybutadiene, among others
  • halogen-containing feedstocks in particular polyvinyl chloride
  • the chlorine is completely or almost completely or at least predominantly removed as hydrogen chloride, and bases can also be added.
  • the cracking stage products can be worked up at 700 ° -1100 ° C. in an analogous manner to that known from ethylene production.
  • the cleavage can take place by using the feed product in directly fired apparatus, e.g. Pipe coils in a mixture of 0.1 to 2 parts by weight of steam per part by weight of feed product are reacted with residence times of 0.02 to 10 seconds or 0.1 to 2 seconds.
  • steam hydrogen or a mixture of water vapor and hydrogen can be used.
  • the splitting of the product from the cracking stage to adjust the viscosity or from the upstream thermal cracking stage can, however, also take place autothermally in the fluidized bed, a material forming the fluidized bed, such as coke, sand and others, coming into contact with the preferably initially liquid feed product to be split can be located and part of the feed product is converted into water and CO 2 to maintain the gap temperature.
  • the feed product can also be converted to ethylene, for example, in analogy to Union Carbide's Advanced Cracking Reactor Process, the Dow process or other crude oil cracking processes.
  • (1) represents a store for plastic waste, eg from household waste.
  • the waste Via (2) the waste is conveyed into the upstream thermal cracking 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 by thermal cracking. Steam is supplied via (7). Bases can also be used in (6). From (6) the material flows into the one working at 700 to 1100 ° C Splitting plant (8).
  • the cleavage product flows via (10) through quench cooler (11) into the separation system (12), in which the cleavage 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

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Olefinen aus Kunststoffabfällen durch Einstellung einer gewünschten Viskosität durch thermische Vorbehandlung der Kunststoffabfälle in einem Temperaturbereich von 380 - 680°C und 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. and thermal treatment of the product from the first treatment stage at a temperature from 700 to 1100 ° C.

Die Entsorgung von Kunststoffabfällen, insbesondere von verschmutzten Kunststoffabfallgemischen, unter Erzeugung von Wertstoffen ist nach wie vor ein technisch ungelöstes Problem.The disposal of plastic waste, in particular of contaminated plastic waste mixtures, with the production of valuable materials is still a technically unsolved problem.

Die seit kurzem an Probestandorten in der Bundesrepublik Deutschland eingeführte 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) that has recently been introduced at trial locations in the Federal Republic of Germany leads to a packaging waste volume 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 Kunststoffabfälle in Abwesenheit von Sauerstoff zu als Wertstoffe weitgehend unbrauchbaren Produkten führt, gibt es zur Zeit nur sehr wenige Verfahren, die es ermöglichen, aus den Kunststoffabfällen 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. heating the plastic waste in the absence of oxygen leads to products which are largely unusable as valuable materials, there are currently very few processes which make it possible to generate 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 3442506 C2 und EP 0236701 B1 offenbarte Hydrierung von Kunststoffabfallgemischen unter hohem Wasserstoffdruck und bei hoher Temperatur, wobei in Abhängigkeit von den Einsatzmaterialien bis zu 90 Gew.-% an gesättigten Kohlenwasserstoffen gewonnen werden können, die im Benzin- und Mittelölbereich sieden.One such method is that described in several patents, e.g. Hydrogenation of plastic waste mixtures under high hydrogen pressure and at high temperature disclosed in DE 3442506 C2 and EP 0236701 B1, with up to 90% by weight of saturated hydrocarbons boiling in the gasoline and medium oil range being able to be obtained depending on the starting materials.

Ein weiteres Verfahren zur Aufarbeitung von Verbundfolien, insbesondere von Papier-/ Polyethylen-/Aluminiumfolien, die als Getränkeverpackungen dienen, zu reinem Zellstoff, Aluminium und Polyethylen ist in DE 4028999 C2 offenbart.A further process for processing composite films, in particular paper / polyethylene / aluminum films, which serve as beverage packaging, into pure cellulose, aluminum and polyethylene is disclosed in DE 4028999 C2.

Durch diese Verfahren, wenn sie zur technischen Reife entwickelt sind, läßt sich zumindest ein Teil des Kunststoffverpackungsabfalls sinnvoll wiederverwerten.With these processes, when they are developed to technical maturity, at least part of the plastic packaging waste can be meaningfully recycled.

Ein Verfahren, durch das in einer thermischen und einer katalytischen Stufe Polyethylen, Polypropylen und Polystyrol bzw. Gemsiche derselben in ungesättigte und gesättigte Kohlenwasserstoffe gespalten werden, ist in Japan Chemical Week, 31. Mai 1990, Seite 6 und 7 beschrieben. In einem Temperaturbereich bis ca. 500°C lassen sich ca. 60 Gew.-% flüssige Kohlenwasserstoffe, 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. About 60% by weight of liquid hydrocarbons, about 30% by weight of gaseous hydrocarbons and about 10% by weight of carbon-like residue can be obtained in a temperature range up to about 500 ° C. Approx. 50% of the liquid product is unsaturated hydrocarbons. Ethylene and propylene are only 4.5 and 7.6% by weight in the gaseous product.

Trotz der zitierten Ergebnisse bestand nach wie vor die Aufgabe, die Olefinausbeuten, insbesondere die Ethylenausbeute bei der thermischen Spaltung von Kunststoffen bzw. Kunststoffabfällen weiter zu verbessern.Despite the results cited, there was still the task of further improving the olefin yields, in particular the ethylene yield during the thermal splitting of plastics or plastics waste.

Der Anmelderin ist es nunmehr gelungen, das Recycling von Kunststoffabfällen durch ein Verfahren weiter zu verbessern, das dadurch gekennzeichnet ist, daß Kunststoffabfälle durch Erhitzen geschmolzen werden, eine gewünschte Viskosität der Kunststoffschmelze durch thermisches Cracken bei einer Temperatur von 380°C bis 650°C mit einer Verweilzeit von 2 Min. bis 1500 Min. eingestellt wird und das Produkt während einer Verweilzeit von 0,02 bis 10 Sek. auf 700 bis 1100°C erhitzt wird.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 by thermal cracking at a temperature of 380 ° C to 650 ° C a residence time of 2 minutes to 1500 minutes is set and the product is heated to 700 to 1100 ° C. during a residence 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.

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 Vakuumgasöl in befriedigenden Ausbeuten zu Ethylen und Propylen 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 Kunststoffabfällen direkt durch thermische Behandlung nach thermischer Vorbehandlung Ethylen und Propylen zu gewinnen und damit ein echtes Recycling herbeizuführen.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 are also converted to ethylene and propylene in satisfactory yields 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 task of obtaining ethylene and propylene from plastic waste directly by thermal treatment after thermal pretreatment and thus to bring about real recycling .

Der Anmelderin ist nunmehr erstmalig der Nachweis gelungen, daß durch das erfindungsgemäße thermische Cracken der Abfälle unter Einstellung einer gewünschten Viskosität in einem Temperaturbereich von 380 bis 650°C, bevorzugt von 400 bis 600°C und besonders bevorzugt von 450 bis 550°C und thermisches Cracken des vorbehandelten Materials bei 700 bis 1100°C, Ethylen in Ausbeuten von ca. 30 % oder noch weiter verbesserten Ausbeuten, sowie C3-C4-Olefine gewonnen werden können. Der Temperaturbereich der gesamten thermischen Behandlung liegt im Schmelzbereich von Kunststoffabfällen bis zum Crackbereich, wobei letzterer wie er von dem thermischen Cracken von Erdölrückstandsölen und hoch siedenden Erdölfraktionen, beispielsweise durch sogenanntes Visbreaking oder auch schärfere Crackverfahren, bekannt ist.The applicant has now for the first time succeeded in proving that the thermal cracking of the waste according to the invention while setting a desired viscosity in a temperature range from 380 to 650 ° C, preferably from 400 to 600 ° C and particularly preferably from 450 to 550 ° C and thermal Cracking the pretreated Materials at 700 to 1100 ° C, ethylene in yields of about 30% or even further improved yields, and C 3 -C 4 olefins can be obtained. The temperature range of the entire thermal treatment lies in the melting range from plastic waste to the cracking range, the latter as it is known from the thermal cracking of residual petroleum oils and high-boiling petroleum fractions, for example by so-called visbreaking or more severe cracking processes.

Die anzuwendende Temperatur in der thermischen Crackstufe zur Einstellung der Viskosität wird vorzugsweise so gewählt, daß der Kunststoffabfall verflüssigt wird und thermisch gecrackt wird und hierdurch verdampfbar wird, sowie als Flüssigkeit durch beispielsweise Pumpen oder Extruder oder andere Fördervorrichtungen in die zweite thermische Crackstufe 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 Crackstufe zur Einstellung der Viskosität erfolgen.The temperature to be used in the thermal cracking stage for adjusting the viscosity is preferably chosen so that the plastic waste is liquefied and thermally cracked and thereby evaporable, and can be conveyed as liquid by means of pumps or extruders or other conveying devices, for example, into the second thermal cracking stage, where Evaporation and thermal cleavage to olefins occurs. The dwell time is 2 to 1500 minutes. However, evaporation can take place in the cracking stage to adjust the viscosity.

Es ist hierbei ein mildes oder auch schärferes Cracken durchzuführen. Dies kann in üblichen Crackapparaten durchgeführt werden, aber auch in Rührbehältern, Extrudern u.a. Apparaten.Mild or sharper cracking must be carried out. This can be done in conventional crackers, but also in stirred tanks, extruders, etc. Apparatus.

Ein wichtiger Gesichtspunkt bei der Einstellung von Temperatur- und Verweilzeit in der thermischen Crackstufe zur Einstellung der Viskosität ist die Maximierung der Ethylen- oder auch Propylen-Ausbeute in der Behandlungsstufe bei 700 - 1100°C, d.h. die Verfahrungsführung in der zuerst genannten thermischen Crackstufe wird so eingestellt, daß in der Crackstufe 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 Verdampfbarkeit des verflüssigten Materials zu unterstützen.An important aspect when adjusting the temperature and residence time in the thermal cracking stage to adjust the viscosity is maximizing the ethylene or propylene yield in the treatment stage at 700-1100 ° C, i.e. the procedure in the first-mentioned thermal cracking stage is adjusted so that optimum olefin yields are obtained in the cracking 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.

Es hat sich als vorteilhaft erwiesen, der thermischen Crackstufe zur Einstellung der gewünschten Viskosität eine weitere thermische Crackstufe vorzuschalten, in der bereits ein Aufschmelzen erfolgt und bei der eine Temperatur von 200 bis 480°C, bevorzugt von 250 bis 430°C, eingestellt wird. Die Verweilzeit liegt bei 2 bis 1500 Minuten. Ferner wird die vorgeschaltete thermische Crackstufe so durchgeführt, daß im Einsatzprodukt vorhandenes Chlor als HCl 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.It has proven to be advantageous to precede the thermal cracking stage with a further thermal cracking stage in order to set the desired viscosity, 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 cracking stage is carried out in such a way that chlorine present in the feed product is largely or completely removed as HCl. The removal of the hydrogen chloride can be facilitated by introducing an inert gas stream. Furthermore, the HCl elimination of bases such as alkali and alkaline earth bases can be improved or completed.

Hierbei, und dies gilt auch für die Crackstufe zur Einstellung der Viskosität in der auch die Halogenabspaltung vervollständigt werden kann, sind im allgemeinen 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 cracking stage for adjusting the viscosity, in which the halogen splitting 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 Crackstufe zur Einstellung der Viskosität als auch die vorgeschaltete thermische Crackstufe werden bevorzugt unter Inertgas betrieben, wie z.B. unter Stickstoff, Wasserstoff, Wasserdampf, CO2 u.a. Auch das Anlegen von Vakuum oder Druck ist möglich. Auch in der Crackstufe zur Einstellung der Viskosität können Basen zur Erleichterung der HCI-Abspaltung eingesetzt werden.Both the cracking stage for adjusting the viscosity and the upstream thermal cracking stage are preferably operated under inert gas, such as, for example, under nitrogen, hydrogen, water vapor, CO 2, etc. It is also possible to apply vacuum or pressure. Bases can also be used in the cracking stage to adjust the viscosity to facilitate the elimination of HCl.

Der Temperaturbereich und die Verweilzeit in der Crackstufe bei 700 - 1100°C entsprechen im wesentlichen denjenigen, wie sie bei der Ethylengewinnung aus anderen Einsatzmaterialien, wie sie oben bereits genannt wurden, eingestellt werden. Auch die verwendeten Apparate bzw. Anlagen können denjenigen konventioneller Ethylenanlagen entsprechen.The temperature range and the residence time in the cracking stage at 700-1100 ° C. essentially correspond to those set in the production of ethylene from other feed materials, as already mentioned above. The apparatus or systems used can also correspond to those 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.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.

Ein bevorzugtes Verhältnis ist 1 Gew.-Teil zu 0,3 bis 1,3 Gew.-Teilen. Die Temperatur in der thermischen Crackstufe zur Olefinerzeugung 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 sec., bevorzugt bei 0,1 bis 2 sec.A preferred ratio is 1 part by weight to 0.3 to 1.3 parts by weight. The temperature in the thermal cracking stage for olefin production 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 Crackstufe verdampft und als Dampf zu Olefinen gespalten wird. Grundsätzlich kann das Material mit eingestellter Viskosität jedoch auch flüssig in die thermische Crackstufe bei 700 - 1100°C eingesetzt werden.It is preferred to adjust the viscosity so that the feed product evaporates or evaporates in the thermal cracking stage operated at 700 to 1100 ° C. and is split into olefins as steam. In principle, however, the material with the adjusted viscosity can also be used liquid in the thermal cracking stage at 700 - 1100 ° C.

Besonders geeignete Einsatzprodukte in das erfindungsgemäße Verfahren sind Kunststoffabfälle bzw. beliebige Gemische aus der Gruppe Polyethylen, Polypropylen, 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 else linear polybutadiene, among others

In der der Crackstufe zur Einstellung der Viskosität vorgeschalteten thermischen Crackstufe wird bei Vorliegen von halogenhaltigen Einsatzmaterialen, insbesondere von Polyvinylchlorid im Einsatzprodukt das Chlor vollständig bis nahezu vollständig bzw. zumindest überwiegend als Chlorwasserstoff entfernt, wobei zusätzlich Basen zugesetzt werden können.In the thermal cracking stage upstream of the cracking stage to adjust the viscosity, if halogen-containing feedstocks, in particular polyvinyl chloride, are present in the feedstock, the chlorine is completely or almost completely or at least predominantly removed as hydrogen chloride, and bases can also be added.

Die Aufarbeitung der Produkte der Crackstufe 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 eingesetzt werden.The cracking stage products can be worked up at 700 ° -1100 ° C. in an analogous manner to that known from ethylene production. For example, the cleavage can take place by using the feed product in directly fired apparatus, e.g. Pipe coils in a mixture of 0.1 to 2 parts by weight of steam per part by weight of feed product are reacted 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 Crackstufe zur Einstellung der Viskosität oder aus der vorgeschalteten thermischen Crackstufe kann jedoch auch autotherm 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 CO2 umgewandelt wird. Das Einsatzprodukt kann auch beispielsweise 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 cracking stage to adjust the viscosity or from the upstream thermal cracking stage can, however, also take place autothermally in the fluidized bed, a material forming the fluidized bed, such as coke, sand and others, coming into contact with the preferably initially liquid feed product to be split can be located and part of the feed product is converted into water and CO 2 to maintain the gap temperature. The feed product can also be converted to ethylene, for example, in analogy to Union Carbide's Advanced Cracking Reactor Process, the Dow process or other crude oil cracking processes.

Erfindungsgemäß wesentlich ist jedoch nicht der aus der Ethylenerzeugung bekannte Spaltprozeß, sondern die Kombination des thermischen Crackens der Kunststoffabfälle in ein Produkt mit der gewünschten Viskosität und die Anwendung 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 the production of ethylene, but rather the combination of the thermal cracking of the plastic waste into a product with the desired viscosity and the application of the cracking temperature from 700 to 1100 ° C. to the thermal cracking of the product to olefins with a residence 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 vorgeschaltete thermische Crackstufe (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 durch thermisches Cracken. 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 Spaltprodukt 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) represents a store for plastic waste, eg from household waste. Via (2) the waste is conveyed into the upstream thermal cracking 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 by thermal cracking. Steam is supplied via (7). Bases can also be used in (6). From (6) the material flows into the one working at 700 to 1100 ° C Splitting plant (8). The cleavage product flows via (10) through quench cooler (11) into the separation system (12), in which the cleavage 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 (14)

  1. Process for the production of olefins, characterized in that plastic waste is liquified by melting and that by thermal cracking of the melt at a temperature of 380 to 650 °C and at a residence time of 2 minutes to 1.500 minutes a desired viscosity of the melt is adjusted and that the product of desired viscosity is heated up to 700 to 1.100 °C at a residence time of 0,02 to 10 seconds.
  2. Process according to claim 1, characterized in that the desired viscosity is adjusted at a temperature of 400 to 600 °C, preferably of 450 to 550 °C.
  3. Process according to at least one of claims 1 and 2, characterized in that such a viscosity is adjusted that the material is vaporizable and can be cracked in the state of vapor in a thermal cracking stage at 700 to 1.100 °C.
  4. Process according to at least one of claims 1 to 3, characterized in that a thermal precracking stage ist installed in front of the stage for adjusting the viscosity, within which the feed material is heated up to 200 to 480 °C, preferably 250 to 430 °C at a residence time of 2 to 1.500 minutes.
  5. Process according to claim 4, characterized in that in case of feeding at least in part polyvinylchlorid into the precracking stage, the chlorine content is at least predominantly, preferably completely up to almost completely removed.
  6. Process according to at least one of claims 4 and 5, characterized in that a base is additionally fed into the precracking stage.
  7. Process according to claim 1, characterized in that the melt of adjusted viscosity is treated in the subsequent cracking stage at a temperature of 750 to 900 °C, preferably of 780 to 860 °C.
  8. Process according to claim 1, characterized in that the residence time at the temperature of 700 to 1.100 °C is adjusted to 0,1 to 2 seconds.
  9. Process according to claim 1, characterized in that the plastic melt of adjusted viscocity is cracked at 700 to 1.000 °C in the presence of water vapor.
  10. Process according to claims 1 and 3, characterized in that the vaporization of the plastic melt of adjusted viscosity is supported by addition of water vapor.
  11. Process according to claim 9, characterized in that one uses a ratio of added water vapor to plastic melt with adjusted viscosity of 0,1 to 2 weight-% to 1 weight-%, preferably of 0,3 to 1,3 weight-% to 1 weight-%.
  12. Process according to at least one of claims 1 to 11, characterized that one uses as a plastic waste feed at least one plastic of the group polyethylene, polypropene, polystyrene, polybutene, polyisobutene, linear polybutadiene.
  13. Process according to claim 1, characterized in that the thermal cracking stage for adjusting the viscosity, is operated under inert gas.
  14. Process according to claim 4, characterized in that the precracking stage, installed in front of the cracking stage for adjusting the viscocity is operated under inert gas.
EP93905182A 1992-03-13 1993-03-12 Olefin production process Expired - Lifetime EP0588998B1 (en)

Applications Claiming Priority (3)

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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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WO1993018112A1 (en) 1993-09-16
US5639937A (en) 1997-06-17
DE59305526D1 (en) 1997-04-03
EP0588998A1 (en) 1994-03-30
DE4207976A1 (en) 1993-09-16
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JPH06507647A (en) 1994-09-01
CA2108968A1 (en) 1993-09-14
ES2102018T3 (en) 1997-07-16

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