EP1079916A1 - Gaseous phase fluidized-bed reactor - Google Patents

Gaseous phase fluidized-bed reactor

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Publication number
EP1079916A1
EP1079916A1 EP99922161A EP99922161A EP1079916A1 EP 1079916 A1 EP1079916 A1 EP 1079916A1 EP 99922161 A EP99922161 A EP 99922161A EP 99922161 A EP99922161 A EP 99922161A EP 1079916 A1 EP1079916 A1 EP 1079916A1
Authority
EP
European Patent Office
Prior art keywords
gas
fluidized bed
reactor
phase fluidized
bed reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99922161A
Other languages
German (de)
French (fr)
Inventor
Rainer Karer
Kaspar Evertz
Wolfgang Micklitz
Hans-Jacob Feindt
Philipp Rosendorfer
Peter KÖLLE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Basell Polyolefine GmbH
Elenac 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
Priority claimed from DE1998121955 external-priority patent/DE19821955A1/en
Priority claimed from DE1999104811 external-priority patent/DE19904811A1/en
Application filed by Basell Polyolefine GmbH, Elenac GmbH filed Critical Basell Polyolefine GmbH
Publication of EP1079916A1 publication Critical patent/EP1079916A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/44—Fluidisation grids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours

Definitions

  • the present invention relates to a gas phase fluidized bed reactor for the polymerization of ethylenically unsaturated monomers.
  • a reactor chamber (1) in the form of a vertical tube, if desired a calming zone (2) adjoining the upper part of the reactor chamber, a circulating gas line (3), a circulating gas compressor (4) and a cooling device (5), characterized in that in the area of the transfer of the reaction gas from the circulating gas line into the reactor space and in the lower part of the reactor space itself there is either no gas distributor plate at all or only a gas distributor plate whose total area of the gas passage openings is more than 20% of the total area of this gas distributor plate.
  • the schematic structure of the reactor is shown in Figure 1.
  • the invention relates to processes for the polymerization of ethylene or copolymerization of ethylene with C 3 - to Cs-Ct olefins and for the production of EPDM, which are carried out in such a reactor.
  • Gas phase polymerization processes are among the preferred processes for the polymerization of ethylenically unsaturated monomers, in particular for the polymerization of ethylene, if desired in the presence of further unsaturated monomers. Polymerization processes in fluidized beds are particularly economical.
  • Gas phase fluidized bed reactors for carrying out such processes have long been known.
  • the reactors common today have many common structural features: Among other things, they consist of a reactor space in the form of a vertical tube, which usually has an enlarged diameter in the upper part. In this calming zone there is a smaller gas flow due to the larger pipe diameter, which leads to a limitation of the discharge of the fluidized bed consisting of small polymer.
  • these reactors contain a circulating gas line, in which cooling units for removing the heat of polymerization, a compressor and, if desired, further elements such as a cyclone for removing fine polymer particles are attached.
  • a reactor floor in the usual form today i.e. a close-meshed network or a metal plate with narrow bores of different geometries, has some disadvantages: Both on the inflow side of the floor and on the top of the floor, polymer deposits caused by dust can occur again and again. shaped polymer and catalyst particles, which are entrained by the gas flow into the circulating gas line. This danger is particularly prevalent in the so-called condensed mode mode, i.e. when liquid monomers are present in the cycle gas. In addition to these deposits, which can lead to an increase in pressure and ultimately to a termination of the polymerization, the pressure loss in normal operation also causes additional energy costs, since the compressor has to compensate for this pressure loss by higher output.
  • the object of the present invention was therefore to provide a gas phase fluidized bed reactor which no longer has these disadvantages.
  • the gas phase fluidized bed reactor according to the invention is suitable in principle for the polymerization of various ethylenically unsaturated monomers.
  • ethylenically unsaturated monomers examples include ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene and also higher ⁇ -olefins; dienes such as butadiene and cyclopentadiene and cycloolefins such as cyclopentene and cyclohexene are also suitable.
  • the ethylenically unsaturated monomers can be polymerized alone or as a mixture.
  • the reactor according to the invention is particularly suitable for the homopolymerization of ethylene, for the production of ethylene-hexene and ethylene-butene copolymers and for the production of EPDM.
  • a preferred embodiment of the gas phase fluidized bed reactor according to the invention is characterized in that there is no gas distributor floor itself in the area of the transfer of the reaction gas from the circulating gas line into the reactor space and in the lower part of the reactor space itself.
  • a reactor in which in the area of the reaction gas transfer from the circulating gas line into the reactor space or in the lower part of the reaction space itself a gas distributor plate, the total area of the gas passage openings of which is more than 50%, particularly preferably more than 90%, of the total surface area of this gas distributor plate , is available.
  • flow transducers should be installed, particularly in the case of large reactor dimensions, when the circulating gas is transferred from the circulating gas line to the reaction space in order to convert the flow pulse of the incoming gas.
  • This can be done by various gas deflecting devices such as baffles, deflectors, impact plates or the like, as are known to the person skilled in the art.
  • gas phase fluidized bed reactors in which flow baffles are arranged in the area of the reaction gas transfer from the circulating gas line into the reactor space for converting the flow impulse of the incoming gas, which are arranged in such a way that a largely homogeneous introduction of the gas flow into the fluidized bed is achieved.
  • sheet metal is of course not intended to describe the material of the device, but only its shape and function; the kind of
  • Another preferred device for gas distribution when entering the reaction space of the reactor according to the invention consists in that in the area of the reaction gas transfer from the circulating gas line into the reactor space for converting the flow impulse of the entering gas, a coarse-meshed network is attached, on which balls are fixed in such number, size and distribution that a largely homogeneous introduction of the gas flow into the fluidized bed is achieved.
  • the net should be so coarse-meshed that there is practically no pressure loss;
  • the task of this network is to keep the balls, which act as deflectors or deflectors for the gas flow, in the desired position.
  • the balls can be evenly distributed over the network. In the case of a large reactor diameter in particular, however, it can make sense to that is, directly above the gas influence in the middle of the reactor section, to arrange a larger number of such balls than in the edge area.
  • the gas phase fluidized bed reactors according to the invention show their advantageous properties, especially on an industrial scale.
  • Reactors are preferred in which the inner diameter of the reaction space (1) is more than 0.5 m, particularly preferably more than 1 m.
  • Reactors with internal diameters between 2 and 8 m are particularly advantageous.
  • the reactor according to the invention can be provided with various devices for gas / solid separation.
  • a calming zone (2) adjoins the upper part of the reactor space (1).
  • Another embodiment of the gas phase fluidized bed reactor according to the invention is characterized in that a cyclone for separating polymer and catalyst particles from the circulating gas is attached between the reactor space (1) and the aggregates of the circulating gas line. If desired, this cyclone can also be combined with a calming zone (2).
  • this calming zone is dispensed with, so that the circulating gas line or, in addition, a device for separating polymer and catalyst particles from the circulating gas, for example a cyclone, is connected directly to the reactor space.
  • a device for separating polymer and catalyst particles from the circulating gas for example a cyclone
  • the reactors according to the invention have no reactor base which can prevent the polymer particles from flowing back into the circulating gas line when the compressor is switched off, it may be expedient to take measures to prevent this backfeeding.
  • a flap or a slide in the area of the mouth of the circulating gas line can be attached to the reaction space. B. can also be closed when filling the reactor before the start of the polymerization, but when starting the compressor is opened.
  • a preferred embodiment of the invention provides that the closable flap or the slide is provided with uniformly distributed holes, which preferably have a diameter between 1 and 7 mm. With the help of this flap, the bulk material can be whirled up when the flap is initially closed.
  • the gas phase fluidized bed reactor described here is particularly suitable for carrying out processes for the polymerization of ethylene or for the copolymerization of ethylene with C 3 - to Cs-.alpha.-olefins, as mentioned at the outset.
  • a process for the production of EPDM is preferred, which is characterized in that the copolymerization is carried out in a reactor according to the invention.
  • an advantageous embodiment of the process according to the invention consists in feeding a mixture containing gaseous and liquid monomers into the reactor space.
  • the polymerization process according to the invention is carried out in such a way that the polymerization takes place essentially in the reactor space (1) and only small amounts of particles circulate with the circulating gas. This can be achieved by the above-mentioned devices for gas-solid separation. Often, however, such devices can largely be described if the polymerization is carried out only just below the softening temperature of the polymers.
  • a copolymerization was carried out in this reactor under the following conditions:
  • the polymerization was carried out continuously for 60 hours. After the polymerization, the reactor was opened, there were kei ⁇ nerlei chunks or coverings visible.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a gaseous phase fluidized-bed reactor for the polymerization of ethylenically unsaturated monomers. Said reactor comprises a reactor chamber (1) in the shape of a vertical tube, and preferably an equalizing zone (2) which connects to the upper part of the reactor chamber. The reactor also comprises a circulating gas line (3), a circulating gas compressor (4), and a cooling device (5). Either generally no gas distributor base or only one gas distributor base whose entire surface area of the gas inlet openings is greater than 20 % of the entire surface area of said gas distributor base is situated in the vicinity of the overflow of the reaction gas from the circulating gas line into the reaction chamber and in the lower part of the reactor chamber itself

Description

GasphasenwirbelschichtreaktorGas phase fluidized bed reactor
Beschreibungdescription
Die vorliegende Erfindung betrifft einen Gasphasenwirbel - schichtreaktor zur Polymerisation ethylenisch ungesättigter Mono- irierer. umfassend einen Reaktorraum (1) in Form eines vertikalen Rohres, gewünschtenfalls eine an den oberen Teil des Reaktorrau- mes anschließende Beruhigungszone (2) , eine Kreisgasleitung (3) , einen Kreisgaskompressor (4) und eine Kühleinrichtung (5) , dadurch gekennzeichnet, daß im Bereich des .Übertritts des Reaktionsgases von der Kreisgasleitung in den Reaktorraum und im unteren Teil des Reaktorraumes selbst entweder überhaupt kein Gas- verteilerboden oder nur ein Gasverteilerboden, dessen Gesamtfläche der Gasdurchlaßöffungen mehr als 20 % der Gesamtfläche dieses Gasverteilerbodens beträgt, vorhanden ist. Den schematischen Aufbau des Reaktors zeigt Abbildung 1. Weiterhin betrifft die Erfindung Verfahren zur Polymerisation von Ethylen oder Copolymerisation von Ethylen mit C3- bis Cs-Ct-Olefinen sowie zur Herstellung von EPDM, welche in einem solchen Reaktor durchgeführt werden.The present invention relates to a gas phase fluidized bed reactor for the polymerization of ethylenically unsaturated monomers. comprising a reactor chamber (1) in the form of a vertical tube, if desired a calming zone (2) adjoining the upper part of the reactor chamber, a circulating gas line (3), a circulating gas compressor (4) and a cooling device (5), characterized in that in the area of the transfer of the reaction gas from the circulating gas line into the reactor space and in the lower part of the reactor space itself there is either no gas distributor plate at all or only a gas distributor plate whose total area of the gas passage openings is more than 20% of the total area of this gas distributor plate. The schematic structure of the reactor is shown in Figure 1. Furthermore, the invention relates to processes for the polymerization of ethylene or copolymerization of ethylene with C 3 - to Cs-Ct olefins and for the production of EPDM, which are carried out in such a reactor.
Gasphasenpolymerisationsverfahren gehören heute zu den bevorzug - ten Verfahren zur Polymerisation ethylenisch ungesättigter Mono- merer, insbesondere zur Polymerisation von Ethylen, gewünschten- falls in Gegenwart weiterer ungesättigter Monomerer . Dabei gelten Polymerisationsverfahren in Wirbelschichten als besonders wirtschaftlich.Gas phase polymerization processes are among the preferred processes for the polymerization of ethylenically unsaturated monomers, in particular for the polymerization of ethylene, if desired in the presence of further unsaturated monomers. Polymerization processes in fluidized beds are particularly economical.
Gasphasenwirbelschichtreaktoren zur Durchführung solcher Verfahren sind seit langem bekannt. Die heute üblichen Reaktoren weisen dabei viele gemeinsame Strukturmerkmale auf: Sie bestehen unter anderem aus einem Reaktorraum in Form eines vertikalen Rohres, welches im oberen Teil meist eine Erweiterung des Durchmessers aufweist. In dieser Beruhigungszone herrscht infolge des größeren Rohrdurchmessers ein geringerer Gasstrom, der zu einer Begrenzung des Austrags des aus kleinteiligem Polymerisat bestehenden Wirbelbetts führt. Weiterhin enthalten diese Reaktoren eine Kreisgasleitung, in welcher Kühlaggregate zur Abführung der Polymerisationswärme, ein Kompressor und gewünschtenfalls weitere Elemente wie beispielsweise ein Zyklon zur Entfernung von Polyme- risat-Feinstaub angebracht sind. Beispiele solcher Gasphasen- wirbelschichtreaktoren wurden beispielsweise in EP-A-0 202 076, EP-A-0 549 252 und EP-A-0 697 421 beschrieben. Alle bekannten Gasphasenwirbelschichtreaktoren besitzen im unteren Teil des Reaktionsraumes einen Reaktorboden, der den Reak- tonsraum von der Kreisgasleitung und dem Gasverteilungsraum räumlich abschließt. Aufgabe dieses Reaktorbodens ist es zum einen, ein Zurückfließen der Polymerisatpartikel in das Kreisgasrohr beim Ausschalten des Kompressors zu verhindern. Andererseits ist die allgemeine technische Lehre, daß der Druckverlust, der an diesem Reaktorboden infolge der relativ engen Eintrittsöffnung auftritt, eine gleichmäßige Gasverteilung im Reaktionsraum ge- währleistet. Diese Lehrmeinung wird z. B. in US-A-3 298 792 und EP-A-0 697 421 vertreten.Gas phase fluidized bed reactors for carrying out such processes have long been known. The reactors common today have many common structural features: Among other things, they consist of a reactor space in the form of a vertical tube, which usually has an enlarged diameter in the upper part. In this calming zone there is a smaller gas flow due to the larger pipe diameter, which leads to a limitation of the discharge of the fluidized bed consisting of small polymer. Furthermore, these reactors contain a circulating gas line, in which cooling units for removing the heat of polymerization, a compressor and, if desired, further elements such as a cyclone for removing fine polymer particles are attached. Examples of such gas phase fluidized bed reactors have been described, for example, in EP-A-0 202 076, EP-A-0 549 252 and EP-A-0 697 421. All known gas phase fluidized bed reactors have a reactor bottom in the lower part of the reaction space, which spatially closes off the reaction space from the circulating gas line and the gas distribution space. The purpose of this reactor bottom is, on the one hand, to prevent the polymer particles from flowing back into the circulating gas tube when the compressor is switched off. On the other hand, the general technical teaching is that the pressure loss which occurs on this reactor floor as a result of the relatively narrow inlet opening ensures an even gas distribution in the reaction space. This doctrine is such. B. represented in US-A-3 298 792 and EP-A-0 697 421.
Ein Reaktorboden in der heute üblichen Form, also ein engmaschiges Netz oder eine Metallplatte mit engen Bohrungen unterschied- licher Geometrie weist jedoch einige Nachteile auf: Sowohl an der Anströmseite des Bodens als auch an der Bodenoberseite kann es immer wieder zu Polymerisatablagerungen, verursacht durch staub - förmige Polymerisat- und Katalysatorpartikel, die von der Gas - Strömung in die Kreisgasleitung mitgerissen werden, kommen. Diese Gefahr besteht besonders bei sogenannter Condensed-Mode-Fahr - weise, d.h., wenn im Kreisgas flüssige Monomere vorhanden sind. Neben diesen Ablagerungen, die zu Druckanstieg und letztenendes zu einem Abbruch der Polymerisation führen können, verursacht aber auch der Druckverlust im Normalbetrieb zusätzliche Energie- kosten, da der Kompressor diesen Druckverlust durch höhere Leistung kompensieren muß.A reactor floor in the usual form today, i.e. a close-meshed network or a metal plate with narrow bores of different geometries, has some disadvantages: Both on the inflow side of the floor and on the top of the floor, polymer deposits caused by dust can occur again and again. shaped polymer and catalyst particles, which are entrained by the gas flow into the circulating gas line. This danger is particularly prevalent in the so-called condensed mode mode, i.e. when liquid monomers are present in the cycle gas. In addition to these deposits, which can lead to an increase in pressure and ultimately to a termination of the polymerization, the pressure loss in normal operation also causes additional energy costs, since the compressor has to compensate for this pressure loss by higher output.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, einen Gasphasenwirbelschichtreaktor bereitzustellen, der diese Nach- teile nicht mehr aufweist.The object of the present invention was therefore to provide a gas phase fluidized bed reactor which no longer has these disadvantages.
Demgemäß wurde der eingangs beschriebene Gasphasenwirbelschichtreaktor sowie Verfahren zur (Co- ) olymerisation in einem solchen Reaktor gefunden.We have found that this object is achieved by the gas-phase fluidized-bed reactor described at the outset and processes for (co) polymerization in such a reactor.
Der erfindungsgemäße Gasphasenwirbelschichtreaktor ist prinzipell zur Polymerisation verschiedener ethylenisch ungesättigter Mono- merer geeignet. Zu nennen sind beispielsweise Ethylen, Propylen, 1-Buten, Isobuten, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen und auch höhere α-Olefine; weiterhin kommen z.B. auch Diene wie Butadien und Cyclopentadien und Cycloolefine wie Cyclopenten und Cyclo- hexen in Betracht. Die ethylenisch ungesättigen Monomere können allein oder in Mischung polymerisiert werden. Besonders geeignet ist der erfindungsgemäße Reaktor zur Homopolymerisation von Ethylen, zur Herstellung von Ethylen-Hexen- und Ethylen-Buten- Copolymeren sowie zur Herstellung von EPDM. Eine bevorzugte Ausführungsform des erfindungsgemäßen Gasphasen- wirbelschichtreaktors ist dadurch gekennzeichnet, daß im Bereich des Übertritts des Reaktionsgases von der Kreisgasleitung in den Reaktorraum und im unteren Teil des Reaktorraumes selbst kein Gasverteilerboden vorhanden ist.The gas phase fluidized bed reactor according to the invention is suitable in principle for the polymerization of various ethylenically unsaturated monomers. Examples include ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene and also higher α-olefins; dienes such as butadiene and cyclopentadiene and cycloolefins such as cyclopentene and cyclohexene are also suitable. The ethylenically unsaturated monomers can be polymerized alone or as a mixture. The reactor according to the invention is particularly suitable for the homopolymerization of ethylene, for the production of ethylene-hexene and ethylene-butene copolymers and for the production of EPDM. A preferred embodiment of the gas phase fluidized bed reactor according to the invention is characterized in that there is no gas distributor floor itself in the area of the transfer of the reaction gas from the circulating gas line into the reactor space and in the lower part of the reactor space itself.
Weiterhin bevorzugt ist ein Reaktor, bei welchem im Bereich des Übertritts des Reaktionsgases von der Kreisgasleitung in den Reaktorraum oder im unteren Teil des Reaktionsraumes selbst ein Gasverteilerboden, dessen Gesamtfläche der Gasdurchlaßöffungen mehr als 50 %, besonders bevorzugt mehr als 90 % der Gesamtfläche dieses Gasverteilerbodens beträgt, vorhanden ist.Also preferred is a reactor in which in the area of the reaction gas transfer from the circulating gas line into the reactor space or in the lower part of the reaction space itself a gas distributor plate, the total area of the gas passage openings of which is more than 50%, particularly preferably more than 90%, of the total surface area of this gas distributor plate , is available.
Für den Fall, daß ganz auf einen Reaktorboden verzichtet wird, aber auch für die anderen Bodenkonstruktionen mit sehr geringem Druckverlust sollten besonders bei großen Reaktordimensionen beim Übergang des Kreisgases aus der Kreisgasleitung in den Reaktions- raum zur Umformung des Strömungsimpulses des eintretenden Gases Strömungsumformer angebracht sein. Dies kann durch verschiedene Gasumlenkvorrichtungen wie Leitbleche, Deflektoren, Aufprallbleche oder ähnliches erfolgen, wie sie dem Fachmann geläufig sind.In the event that a reactor base is completely dispensed with, but also for the other base constructions with very little pressure loss, flow transducers should be installed, particularly in the case of large reactor dimensions, when the circulating gas is transferred from the circulating gas line to the reaction space in order to convert the flow pulse of the incoming gas. This can be done by various gas deflecting devices such as baffles, deflectors, impact plates or the like, as are known to the person skilled in the art.
Bevorzugt sind Gasphasenwirbelschichtreaktoren, bei denen im Bereich des Übertritts des Reaktionsgases von der Kreisgasleitung in den Reaktorraum zur Umformung des Strömungsimpulses des eintretenden Gases Strömungsleitbleche angebracht sind, die so angeordnet sind, daß eine weitgehend homogene Einleitung der Gas - Strömung in die Wirbelschicht erzielt wird. Der Begriff "Blech" soll hier natürlich nicht das Material der Vorrichtung beschrei- ben, sondern lediglich deren Form und Funktion; die Art desPreferred are gas phase fluidized bed reactors in which flow baffles are arranged in the area of the reaction gas transfer from the circulating gas line into the reactor space for converting the flow impulse of the incoming gas, which are arranged in such a way that a largely homogeneous introduction of the gas flow into the fluidized bed is achieved. The term “sheet metal” is of course not intended to describe the material of the device, but only its shape and function; the kind of
Materials ist dabei unerheblich, es muß lediglich mit den Polymerisationsbedingungen kompatibel sein.Material is irrelevant, it only has to be compatible with the polymerization conditions.
Eine weitere bevorzugte Vorrichtung zur Gasverteilung beim Ein- tritt in den Reaktionsraum des erfindungsgemäßen Reaktors besteht darin, daß im Bereich des Übertritts des Reaktionsgases von der Kreisgasleitung in den Reaktorraum zur Umformung des Strömungs- impulses des eintretenden Gases ein grobmaschiges Netz angebracht ist, auf welchem Kugeln in solcher Zahl, Größe und Verteilung fixiert sind, daß eine weitgehend homogene Einleitung der Gas- strömung in die Wirbelschicht erzielt wird. Das Netz sollte dabei so grobmaschig sein, daß es praktisch keinen Druckverlust bewirkt; Aufgabe dieses Netzes ist es, die Kugeln, die als Ablenkeinrichtungen oder Deflektoren für den Gasstrom fungieren, in der gewünschten Position zu halten. Die Kugeln können gleichmäßig über das Netz verteilt sein. Besonders bei großem Reaktordurchmesser kann es jedoch sinnvoll sein, im Bereich der Reaktorachse, also direkt über dem Gaseinfluß in der Mitte des Reaktorschnittes, eine größere Zahl solcher Kugeln anzuordnen als im Randbereich.Another preferred device for gas distribution when entering the reaction space of the reactor according to the invention consists in that in the area of the reaction gas transfer from the circulating gas line into the reactor space for converting the flow impulse of the entering gas, a coarse-meshed network is attached, on which balls are fixed in such number, size and distribution that a largely homogeneous introduction of the gas flow into the fluidized bed is achieved. The net should be so coarse-meshed that there is practically no pressure loss; The task of this network is to keep the balls, which act as deflectors or deflectors for the gas flow, in the desired position. The balls can be evenly distributed over the network. In the case of a large reactor diameter in particular, however, it can make sense to that is, directly above the gas influence in the middle of the reactor section, to arrange a larger number of such balls than in the edge area.
Natürlich können statt der Kugeln auch andere geometrische Körper verwendet werden, Kugeln sind jedoch bevorzugt, da sie eine besonders gleichmäßige und verwirblungsarme Gasverteilung bewirken.Of course, other geometrical bodies can also be used instead of the spheres, but spheres are preferred because they produce a particularly uniform and low-swirl gas distribution.
Die erfindungsgemäßen Gasphasenwirbelschichtreaktoren zeigen ihre vorteilhaften Eigenschaften besonders im industriellen Maßstab. Dabei sind Reaktoren bevorzugt, bei denen der Innendurchmesser des Reaktionsraumes (1) mehr als 0,5 m, besonders bevorzugt mehr als 1 m beträgt. Besonders vorteilhaft sind Reaktoren mit Innendurchmessern zwischen 2 und 8 m.The gas phase fluidized bed reactors according to the invention show their advantageous properties, especially on an industrial scale. Reactors are preferred in which the inner diameter of the reaction space (1) is more than 0.5 m, particularly preferably more than 1 m. Reactors with internal diameters between 2 and 8 m are particularly advantageous.
Um zu verhindern, daß größere Mengen Feststoff in das Kreisgas - System gelangen, kann der erfindungsgemäße Reaktor mit verschiedenen Vorrichtungen zur Gas/Feststofftrennung versehen sein. In einer Ausführungsform des erfindungsgemäßen Reaktors schließt, wie eingangs erwähnt, an den oberen Teil des Reaktorraums (1) eine Beruhigungszone (2) an. Eine weitere Ausführungsform des erfindungsgemäßen Gasphasenwirbelschichtreaktors ist dadurch gekennzeichnet, daß zwischen dem Reaktorraum (1) und den Aggregaten der Kreisgasleitung ein Zyklon zur Abtrennung von Polymerisat - und Katalysatorpartikeln aus dem Kreisgas angebracht ist. Dieser Zyklon kann gewünschtenfalls auch mit einer Beruhigungszone (2) kombiniert werden. In einer weitern Ausführungsform wird auf diese Beruhigungszone verzichtet, so daß sich direkt an den Reaktorraum die Kreisgasleitung bzw. zusätzlich eine Einrichtung zur Abtrennung von Polymerisat- und Katalysatorpartikeln aus dem Kreisgas, also beispielsweise ein Zyklon, anschließt. Auch für den Fall, daß der Reaktor weder eine Beruhigungszone noch eine andere Einrichtung zur Trennung von Kreisgas und Feststoff aufweist, soll der Begriff "Reaktorraum" so verstanden werden, daß in diesem Teil des Reaktors im Wesentlichen die Polymerisation stattfindet und nur geringfügig Teile des Polymerisats mit dem Kreisgas zirkuliert werden.In order to prevent larger amounts of solid from getting into the circulating gas system, the reactor according to the invention can be provided with various devices for gas / solid separation. In one embodiment of the reactor according to the invention, as mentioned at the beginning, a calming zone (2) adjoins the upper part of the reactor space (1). Another embodiment of the gas phase fluidized bed reactor according to the invention is characterized in that a cyclone for separating polymer and catalyst particles from the circulating gas is attached between the reactor space (1) and the aggregates of the circulating gas line. If desired, this cyclone can also be combined with a calming zone (2). In a further embodiment, this calming zone is dispensed with, so that the circulating gas line or, in addition, a device for separating polymer and catalyst particles from the circulating gas, for example a cyclone, is connected directly to the reactor space. In the event that the reactor neither has a settling zone nor any other device for separating circulating gas and solid, the term "reactor space" should be understood to mean that essentially the polymerization takes place in this part of the reactor and only minor parts of the polymer be circulated with the cycle gas.
Da die erfindungsgemäßen Reaktoren keinen Reaktorboden besitzen, der ein Zurückfließen vom Polymerisatteilchen in die Kreisgasleitung bei ausgeschaltetem Kompressor verhindern kann, kann es zweckmäßig sein, Maßnahmen zur Verhinderung dieses ZurückfHeßens zu ergreifen. So kann beispielsweise eine Klappe oder ein Schieber im Bereich der Mündung der Kreisgasleitung in den Reaktions- räum angebracht werden, die bei ausgeschaltetem Kompressor und z. B. auch beim Befüllen des Reaktors vor dem Beginn der Polymerisation geschlossen sein kann, beim Starten des Kompressors jedoch geöffnet wird. Eine bevorzugte Ausführungsform der Erfindung sieht vor, daß die verschließbare Klappe oder der Schieber mit gleichmäßig verteilten Löchern versehen ist, die vorzugsweise einen Durchmesser zwischen 1 und 7 mm aufweisen. Mit Hilfe dieser Klappe ist ein Aufwirbeln des Schüttgutes bei zunächst geschlossener Klappe möglich.Since the reactors according to the invention have no reactor base which can prevent the polymer particles from flowing back into the circulating gas line when the compressor is switched off, it may be expedient to take measures to prevent this backfeeding. For example, a flap or a slide in the area of the mouth of the circulating gas line can be attached to the reaction space. B. can also be closed when filling the reactor before the start of the polymerization, but when starting the compressor is opened. A preferred embodiment of the invention provides that the closable flap or the slide is provided with uniformly distributed holes, which preferably have a diameter between 1 and 7 mm. With the help of this flap, the bulk material can be whirled up when the flap is initially closed.
Erfindungsgemäß eignet sich der hier beschriebenen Gasphasenwirbelschichtreaktor besonders zur Durchführung von Verfahren zur Polymerisation von Ethylen oder zur Copolymerisation von Ethylen mit C3- bis Cs-α-Olefinen, wie sie Eingangs genannt sind. Weiterhin ist ein Verfahren zur Herstellung von EPDM bevorzugt, welches dadurch gekennzeichnet ist, daß die Copolymerisation in einem erfindungsgemäßen Reaktor durchgeführt wird.According to the invention, the gas phase fluidized bed reactor described here is particularly suitable for carrying out processes for the polymerization of ethylene or for the copolymerization of ethylene with C 3 - to Cs-.alpha.-olefins, as mentioned at the outset. Furthermore, a process for the production of EPDM is preferred, which is characterized in that the copolymerization is carried out in a reactor according to the invention.
Da die Gefahr von Polymerisatablagerungen im Bereich des Reaktor - bodens nicht oder nur sehr eingeschränkt besteht, kann auf viele aufwendige Vorsichtsmaßnahmen, wie sie bei der Verwendung herkömmlicher Gasverteilungsböden häufig ergriffen werden, verzich- tet werden. So ist beispielsweise der Einbau eines Zyklons zur Feinstaubabtrennung am Reaktionsraumausgang im allgemeinen überflüssig. Auch kann problemlos flüssiges Monomer zudosiert werden, und zwar in größerer Menge, als sonst bei kondensierter Fahrweise üblich ist. Eine Durchführung des erfindungsgemäßen Verfahrens in Gegenwart kondensierter Monomerer ist daher besonders vorteilhaft.Since there is no or only a very limited risk of polymer deposits in the area of the reactor floor, many complex precautionary measures, such as are often taken when using conventional gas distribution floors, can be dispensed with. For example, the installation of a cyclone to separate fine dust at the reaction chamber exit is generally superfluous. Liquid monomer can also be metered in without any problems, and in greater quantities than is otherwise customary in the case of condensed operation. Carrying out the process according to the invention in the presence of condensed monomers is therefore particularly advantageous.
Demgemäß besteht eine vorteilhafte Ausführungsform des erfindungsgemäßen Verfahrens darin, daß man ein Gemisch enthal- tend gasförmige und flüssige Monomere in den Reaktorraum einspeist.Accordingly, an advantageous embodiment of the process according to the invention consists in feeding a mixture containing gaseous and liquid monomers into the reactor space.
Das erfindungsgemäße Polymerisationsverfahren wird in einer Weise durchgeführt, daß die Polymerisation im Wesentlichen im Reaktor- räum (1) erfolgt und nur geringe Partikelmengen mit dem Kreisgas zirkulieren. Dies kann durch die oben genannten Einrichtungen zur Gas-Feststofftrennung erreicht werden. Oft kann auf solche Einrichtungen jedoch weitgehend erzichtet werden, wenn man die Polymerisation nur knapp unterhalb der Erweichungstemperatur der Polymeren durchführt.The polymerization process according to the invention is carried out in such a way that the polymerization takes place essentially in the reactor space (1) and only small amounts of particles circulate with the circulating gas. This can be achieved by the above-mentioned devices for gas-solid separation. Often, however, such devices can largely be described if the polymerization is carried out only just below the softening temperature of the polymers.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist daher dadurch gekennzeichnet, daß man zur Herstellung eines (Co) Polymerisats einer vorgewählten Dichte d die (Co) Polymeri- sation bei einer Temperatur durchführt, welche in einem Bereich liegt, der von einer oberen Umhüllenden der Gleichung (I) TH = 171 + ( I )A preferred embodiment of the process according to the invention is therefore characterized in that, in order to produce a (co) polymer of a preselected density d, the (co) polymerization is carried out at a temperature which lies in a range which is from an upper envelope of the equation ( I) T H = 171 + (I)
0 , 84 - d '0, 84 - d '
und einen unteren Umhüllenden der Gleichung (II)and a lower envelope of equation (II)
7,3d'7.3d '
TN = 173 + (II) 0,837-d'T N = 173 + (II) 0.837-d '
begrenzt wird, worin die Variablen die folgende Bedeutung haben:is limited, in which the variables have the following meaning:
TH höchste Reaktionstemperatur in °CT H highest reaction temperature in ° C
TN niedrigste Reaktionstemperatur in °CT N lowest reaction temperature in ° C
d' Zahlenwert der Dichte (d) des herzustellenden (Co) Polymeri - sats .d 'numerical value of the density (d) of the (co) polymer to be produced.
Durch diese Hochtemperaturfahrweise fällt nur ein geringer Fein¬ staubanteil an, so daß eine Feststoffabtrennung meist überflüssig ist.Through this high-temperature mode, only a small fine falls to dust ¬ share, so that a solids separation is usually unnecessary.
Beispielexample
In einem Wirbelschichtreaktor gemäß Abb. 1 mit einem Reaktions- rauminnendurchmesser von 0,5 m und einer Reaktionsraumhöhe von 3 m wurde im Eingangsbereich des Reaktionsraumes ein Strömungsum¬ former angebracht. Ein Gasverteilerboden war nicht vorhanden.In a fluidized bed reactor according to Fig. 1, with a reaction space inside diameter of 0.5 m and a reaction room height of 3 m, a Strömungsum ¬ former mounted in the entrance area of the reaction space. There was no gas distributor floor.
In diesem Reaktor wurde eine Copolymerisation unter folgenden Bedingungen durchgeführt:A copolymerization was carried out in this reactor under the following conditions:
Gaszusammensetzung: 50 % Ethylen 45 % StickstoffGas composition: 50% ethylene 45% nitrogen
5 % 1-Buten Kreisgasgeschwindigkeit: 35 m/s Temperatur: 115°C5% 1-butene circulating gas velocity: 35 m / s temperature: 115 ° C
Druck: 20 barPressure: 20 bar
Die Polymerisation wurde kontinuierlich über 60 h durchgeführt. Nach der Polymerisation wurde der Reaktor geöffnet, es waren kei¬ nerlei Brocken oder Beläge sichtbar. The polymerization was carried out continuously for 60 hours. After the polymerization, the reactor was opened, there were kei ¬ nerlei chunks or coverings visible.

Claims

Patentansprüche claims
1. Gasphasenwirbelschichtreaktor zur Polymerisation ethylenisch ungesättigter Monomerer, umfassend einen Reaktorraum (1) in1. Gas phase fluidized bed reactor for the polymerization of ethylenically unsaturated monomers, comprising a reactor space (1) in
Form eines vertikalen Rohres, eine Kreisgasleitung (3), einen Kreisgaskompressor (4) und eine Kühleinrichtung (5) , dadurch gekennzeichnet, daß im Bereich des Übertritts des Reaktions- gases von der Kreisgasleitung in den Reaktorraum und im un- teren Teil des Reaktorraumes selbst entweder überhaupt kein Gasverteilerboden oder nur ein Gasverteilerboden, dessen Gesamtfläche der Gasdurchlaßöffnungen mehr als 20 % der Gesamtfläche dieses Gasverteilerbodens beträgt, vorhanden ist.Form of a vertical tube, a circulating gas line (3), a circulating gas compressor (4) and a cooling device (5), characterized in that in the area of the transfer of the reaction gas from the circulating gas line into the reactor space and in the lower part of the reactor space itself either no gas distributor plate at all or only a gas distributor plate, the total area of the gas passage openings of which is more than 20% of the total surface of this gas distributor plate.
2. Gasphasenwirbelschichtreaktor nach Anspruch 1, dadurch gekennzeichnet, daß im Bereich des Übertritts des Reaktionsga- ses von der Kreisgasleitung in den Reaktorraum und im unteren Teil des Reaktorraumes selbst kein Gasverteilerboden vorhan- den ist.2. Gas phase fluidized bed reactor according to claim 1, characterized in that in the area of the transfer of the reaction gas from the circulating gas line into the reactor space and in the lower part of the reactor space itself there is no gas distributor base.
3. Gasphasenwirbelschichtreaktor nach Anspruch 1, dadurch gekennzeichnet, daß im Bereich des Übertritts des Reaktionsga- ses von der Kreisgasleitung in den Reaktorraum oder im un- teren Teil des Reaktorraumes selbst ein Gasverteilerboden, dessen Gesamtfläche der Gasdurchlaßöffnungen mehr als 90 % der Gesamtfläche dieses Gasverteilerbodens beträgt, vorhanden ist.3. Gas phase fluidized bed reactor according to claim 1, characterized in that in the area of the transfer of the reaction gas from the circulating gas line into the reactor space or in the lower part of the reactor space itself a gas distributor plate, the total area of the gas passage openings of which is more than 90% of the total area of this gas distributor plate , is available.
4. Gasphasenwirbelschichtreaktor nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß im Bereich des Übertritts des Reaktionsgases von der Kreisgasleitung in den Reaktorraum zur Umformung des Strömungsimpulses des eintretenden Gases Strömungsumformer angebracht sind, die so angeordnet sind, daß eine weitgehend homogene Einleitung der GasStrömung in die Wirbelschicht erzielt wird.4. Gas phase fluidized bed reactor according to claims 1 to 3, characterized in that in the area of the transfer of the reaction gas from the circulating gas line into the reactor space for converting the flow pulse of the incoming gas flow transducers are attached, which are arranged so that a largely homogeneous introduction of the gas flow in the fluidized bed is achieved.
Zeichn. Sign.
5. Gasphasenwirbelschichtreaktor nach 'den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß im Bereich des Übertritts des Reaktionsgases von der Kreisleitung in den Reaktorraum zur Umformung des Strömungsimpulses des eintretenden Gases ein 5 grobmaschiges Netz angebracht ist, auf welchem Kugeln in solcher Zahl, Größe und Verteilung fixiert sind, daß eine weitgehend homogene Einleitung der Gasströmung in die Wirbelschicht erzielt wird.5. gas phase fluidized bed reactor according to ' claims 1 to 3, characterized in that in the area of the transfer of the reaction gas from the circuit into the reactor space for converting the flow pulse of the incoming gas a 5 coarse mesh is attached, on which balls in such number, size and Distribution are fixed so that a largely homogeneous introduction of the gas flow into the fluidized bed is achieved.
10 6. Gasphasenwirbelschichtreaktor nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß der Innendurchmesser des Reaktor - raumes (1) mehr als 0,5 m beträgt.10 6. Gas phase fluidized bed reactor according to claims 1 to 5, characterized in that the inner diameter of the reactor space (1) is more than 0.5 m.
7. Gasphasenwirbelschichtreaktor nach den Ansprüchen 1 bis 6, 15 dadurch gekennzeichnet, daß zur Verhinderung des Eindringens vom Polymerisatpartikeln in die Kreisgasleitung bei abgeschaltetem Kompressor im Bereich des Übergangs von der Kreisleitung in den unteren Teil des Reaktorraumes eine verschließbare Klappe angebracht ist. 207. Gas phase fluidized bed reactor according to claims 1 to 6, 15 characterized in that a lockable flap is attached to prevent the penetration of polymer particles into the circulating gas line when the compressor is switched off in the region of the transition from the circular line to the lower part of the reactor space. 20th
8. Gasphasenwirbelschichtreaktor nach Anspruch 7, dadurch gekennzeichnet, daß die verschließbare Klappe mit gleichmäßig verteilten Löchern mit einem Durchmesser zwischen 1 und 7 mm versehen ist.8. gas phase fluidized bed reactor according to claim 7, characterized in that the closable flap is provided with uniformly distributed holes with a diameter between 1 and 7 mm.
2525
9. Gasphasenwirbelschichtreaktor nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß an dem oberen Teil des Reaktor - raumes (1) eine Beruhigungszone (2) anschließt.9. Gas phase fluidized bed reactor according to claims 1 to 8, characterized in that a calming zone (2) adjoins the upper part of the reactor space (1).
30 10. Gasphasenwirbelschichtreaktor nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß zwischen dem Reaktorraum (1) und den Aggregaten der Kreisgasleitung ein Zyklon zur Abtrennung von Polymerisat- und Katalysatorpartikeln aus dem Kreisgas angebracht ist.30 10. Gas phase fluidized bed reactor according to claims 1 to 9, characterized in that a cyclone for separating polymer and catalyst particles from the circulating gas is attached between the reactor space (1) and the aggregates of the cycle gas line.
3535
11. Verfahren zur Polymerisation von Ethylen oder zur Copolymerisation von Ethylen mit C3 - bis Cs-α-Olefinen, dadurch gekennzeichnet, daß die (Co- ) Polymerisation in einem Gasphasenwirbelschichtreaktor gemäß den Ansprüchen 1 bis 10 durchgeführt11. A process for the polymerization of ethylene or for the copolymerization of ethylene with C 3 - to Cs-α-olefins, characterized in that the (co) polymerization is carried out in a gas phase fluidized bed reactor according to claims 1 to 10
40 wird.Turns 40.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Polymerisation in Gegenwart kondensierter Monomerer und/oder kondensierter Kohlenwasserstoffe durchgeführt wird.12. The method according to claim 11, characterized in that the polymerization is carried out in the presence of condensed monomers and / or condensed hydrocarbons.
45 45
13. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß man ein Gemisch enthaltend gasförmige und flüssige Monomere in den Reaktorraum einspeist.13. The method according to claim 11, characterized in that a mixture containing gaseous and liquid monomers is fed into the reactor space.
14. Verfahren nach den Ansprüchen 11 bis 13, dadurch gekennzeichnet, daß man zur Herstellung eines (Co) Polymerisats einer vorgewählten Dichte d die (Co) Polymerisation bei einer Temperatur durchführt, welche in einem Bereich liegt, der von einer oberen Umhüllenden der Gleichung (I)14. The method according to claims 11 to 13, characterized in that to produce a (co) polymer of a preselected density d, the (co) polymerization is carried out at a temperature which lies in a range which is from an upper envelope of the equation ( I)
6d'6d '
171 + (I!171 + (I!
0,84-d'0.84-d '
und einen unteren Umhüllenden der Gleichung (II)and a lower envelope of equation (II)
7,3d'7.3d '
TN = 173 + :n)T N = 173 +: n)
0,837-d'0.837-d '
begrenzt wird, worin die Variablen die folgende Bedeutung haben:is limited, in which the variables have the following meaning:
TH höchste Reaktionstemperatur in °CT H highest reaction temperature in ° C
TN niedrigste Reaktions emperatur in °CT N lowest reaction temperature in ° C
d' Zahlenwert der Dichte (d) des herzustellenden (Co) Polymerisats .d 'numerical value of the density (d) of the (co) polymer to be prepared.
15. Verfahren zur Herstellung von EPDM, dadurch gekennzeichnet, daß die Copolymerisation in einem Reaktor gemäß den Ansprüchen 1 bis 10 durchgeführt wird. 15. A process for the preparation of EPDM, characterized in that the copolymerization is carried out in a reactor according to claims 1 to 10.
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DE1999104811 DE19904811A1 (en) 1999-02-05 1999-02-05 Gas phase fluidized bed reactor for polymerizing ethylenically unsaturated monomers
DE19904811 1999-02-05
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CN1301192A (en) 2001-06-27
US8034884B2 (en) 2011-10-11
CN1191114C (en) 2005-03-02
KR100632907B1 (en) 2006-10-16
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US7601303B1 (en) 2009-10-13
JP2002515516A (en) 2002-05-28

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