DE4235785A1 - Continuous polymerisation of olefinic monomers - uses a tubular reactor contg. a special temp.-controlled section followed by an adiabatic section discharging into a vacuum degassing chamber - Google Patents

Continuous polymerisation of olefinic monomers - uses a tubular reactor contg. a special temp.-controlled section followed by an adiabatic section discharging into a vacuum degassing chamber

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Publication number
DE4235785A1
DE4235785A1 DE19924235785 DE4235785A DE4235785A1 DE 4235785 A1 DE4235785 A1 DE 4235785A1 DE 19924235785 DE19924235785 DE 19924235785 DE 4235785 A DE4235785 A DE 4235785A DE 4235785 A1 DE4235785 A1 DE 4235785A1
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section
tubular reactor
polymerisation
continuous
reactor
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DE19924235785
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German (de)
Inventor
Joachim Prof Dr Breme
Reiner Prof Dr Thiele
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BASF SE
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BASF SE
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    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow

Abstract

A system for the continuous polymerisation of olefinically unsatd. cpds. (I) consists of a tubular reactor which discharges into an apparatus in which unreacted monomers and any oligomers produced are removed immediately after polymerisation, by evaporation under reduced pressure. On the inlet side, at least one reactor section is designed as a heat exchanger with baffles, to give a specific heat exchange surface of at least 80 m2 per m3 free reactor vol., so that the temp. difference between heat exchange medium and reaction mixt. at any point in this section can be limited to not more than 30 K. On the outlet side there is a section which is capable of largely adiabatic operation, ending in a perforated plate which is connected to a vacuum chamber. Also claimed is a process for the continuous radical polymerisation of (I) using a tubular reactor as described above, which can be operated with virtually no back-mixing. USE/ADVANTAGE - Provides a pure (unstirred) tubular reactor system which enables the continuous bulk or soln. (co)polymerisation of (I) (e.g. acrylic esters, vinyl cpds. etc.) under conditions of optimum temp. control and minimal back-mixing, to give homogeneous prods. (no "fish eyes" etc.) with high space-time yields.

Description

Die Herstellung von Formmassen durch (radikalisch gestartete) Polymerisation von olefinisch ungesättigten Verbindungen wie Acrylestern und Vinylverbindungen und deren Copolymerisation vor allem mit vorgebildeten kautschukelastischen Polymeren wird in vielen Fällen als Massen- oder Lösungspolymerisation, vorzugs­ weise fortlaufend (kontinuierlich) betrieben.The production of molding compounds by (radically started) Polymerization of olefinically unsaturated compounds such as Acrylic esters and vinyl compounds and their copolymerization everything with pre-formed rubber-elastic polymers is in many cases as bulk or solution polymerization, preferred operated continuously.

Dabei sind die wesentlichen verfahrenstechnisch zu beachtenden Umstände die hohe Wärmetönung bei gleichzeitig stark zunehmender Viskosität des Reaktionsgemisches und die Tatsache, daß sich zwei miteinander gekoppelte, jeweils stark temperaturabhängige chemi­ sche Reaktionen abspielen, nämlich die Zerfallsreaktion des Star­ ters und die Polymerisation selbst. Schließlich ist zu beachten, daß die zeitlich abnehmende Startermenge, die zunehmende Visko­ sität und die abnehmende Monomerkonzentration, vor allem im kon­ tinuierlichen, rückvermischungsfreien Prozeß zur unvollständigen Umsetzung führen, auch wenn eine lange Verweilzeit angeboten wird.The essential procedural aspects must be observed Circumstances the high heat tone at the same time increasing strongly Viscosity of the reaction mixture and the fact that there are two coupled, strongly temperature-dependent chemi play reactions, namely the decay of the star ters and the polymerization itself. Finally, it should be noted that the decreasing amount of starters, the increasing viscosity and the decreasing monomer concentration, especially in the con continuous, back-mixing-free process for incomplete Implementation even if a long dwell is offered becomes.

Dies alles führt zu einem Zusammentreffen widersprüchlicher ver­ fahrenstechnischer Forderungen: Einerseits ist man bestrebt, die Umsetzung so schnell wie möglich, also bei möglichst hoher Tempe­ ratur zu betreiben, um die vorhandenen Reaktionsräume so gut wie möglich zu nutzen (hohe Raum-Zeit-Ausbeute). Andererseits soll die Umsetzung unter keinen Umständen außer Kontrolle geraten können, was leicht möglich ist, weil durch die stark temperatur­ abhängige Radikalbildung (Zerfallsreaktion) schon bei geringer Temperatursteigerung die Zahl der wachsenden Polymerketten zunimmt und damit die Wärmeentwicklung ansteigt. Dieses, zuerst von van t′Hoff untersuchte Phänomen wird als sogenannte Wärme­ explosion bezeichnet.All of this leads to a meeting of contradictory ver driving requirements: On the one hand, one strives to achieve the Implementation as quickly as possible, i.e. at the highest possible temperature to operate the existing reaction spaces as good as possible to use (high space-time yield). On the other hand, should the implementation will never get out of control can, which is easily possible because of the high temperature dependent radical formation (decay reaction) even at low Temperature increase the number of growing polymer chains increases and thus the heat development increases. This, first The phenomenon examined by van t′Hoff is called heat called explosion.

Schließlich soll an keiner Stelle eines Reaktionsraumes lokale Überhitzung möglich sein, auch wenn deren Abbau großräumig gesi­ chert scheint, weil dies zu inhomogenen Produkten führt (sog. Stippenbildung; "Fischaugen"), die unter Umständen dann pigmen­ tiert oder gefüllt werden müssen und sich nicht mehr als transpa­ rente Massen einsetzen lassen.After all, there should be no local reaction area at any point Overheating may be possible, even if they are broken down over a large area chert seems because this leads to inhomogeneous products (so-called Speck formation; "Fisheye"), which then pigmen under certain circumstances must be filled or filled and no longer as transparent allow pension masses to be used.

Bisher wird die kontinuierliche (Massen-)polymerisation z. B. von Styrol oder Acrylestern daher meist in aufwendigen sogenannten Turmreaktoren betrieben, die gerührt werden und weder einfach aufgebaut sind noch rückvermischungsfrei betrieben werden können, obwohl man durch spezielle Einbauten und Rührwerksausbildung ver­ sucht, möglichst nur radiale, aber keine axiale Rührwirkung aus­ zuüben.So far, the continuous (mass) polymerization z. B. from Styrene or acrylic esters are therefore usually in complex so-called Tower reactors operated, which are stirred and neither easy  can still be operated without backmixing, although one ver through special installations and agitator training seeks, if possible, only radial, but no axial stirring action to practice.

Es ist eine Aufgabe der Erfindung, für ein Verfahren zur kontinu­ ierlichen Polymerisation von olefinisch ungesättigten Verbin­ dungen eine Vorrichtung in Form eines im wesentlichen rückvermi­ schungsfrei betreibbaren Rohrreaktors anzugeben, der - an seinem austragsseitigen Ende - in einen Apparat mündet zur unmittelbar an die Polymerisation anschließenden Entfernung von nicht umge­ setzten Monomeren und gebildeten Oligomeren durch Verdampfung unter vermindertem Druck.It is an object of the invention for a method for continuous Polymerization of olefinically unsaturated verbin a device in the form of a substantially backmeas to specify a pipe reactor that can be operated without the use of - at its discharge end - opens into an apparatus for immediate after the polymerization removal of not vice versa set monomers and oligomers formed by evaporation under reduced pressure.

Erfindungsgemäß wird diese Aufgabe gelöst durch ein Verfahren der vorstehenden Art und eine hierzu dienliche Vorrichtung in Form eines im wesentlichen rückvermischungsfrei betreibbaren Rohrreak­ tors, der mindestens einen eintrittsseitigen Abschnitt aufweist, der als Einbauten aufweisender Wärmetauscher ausgebildet ist, wobei die spezifische Wärmeaustauschfläche in diesem Abschnitt, mindestens 80 m2 je m2 freiem Reaktorvolumen beträgt, so daß die Temperaturdifferenz zwischen Wärmetauschmedium und Reaktionsge­ misch an jeder Stelle dieses Abschnitts auf höchstens 30 K begrenzt werden kann, und einen austragsseitigen Abschnitt, der im wesentlichen adiabatisch betrieben werden kann und durch eine Lochplatte abgeschlossen ist, die mit einer evakuierbaren Kammer (Entgasungs- oder Vakuumkammer oder -zone) zusammenwirkt.According to the invention this object is achieved by a method of the above type and a device useful for this purpose in the form of an essentially backmix-free operable pipe reactor which has at least one inlet-side section which is designed as internals having heat exchangers, the specific heat exchange surface in this section, at least 80 m 2 per m 2 of free reactor volume, so that the temperature difference between the heat exchange medium and the reaction mixture can be limited to a maximum of 30 K at any point in this section, and a discharge-side section which can be operated essentially adiabatically and is closed off by a perforated plate which interacts with an evacuable chamber (degassing or vacuum chamber or zone).

Wesentliches Merkmal der Erfindung ist somit eine als reiner Rohrreaktor (also ohne mechanisches Rührwerk) ausgebildete Poly­ merisationsstrecke, die im vorderen, eintrittsseitigen Abschnitt als Wärmetauscher ausgebildet ist, wobei die dem Wärmetausch dienenden Einbauten vorzugsweise auch der Behinderung der Rück­ vermischung dienen.An essential feature of the invention is thus a pure one Tube reactor (i.e. without mechanical agitator) trained poly merisation route, in the front, entry-side section is designed as a heat exchanger, the heat exchange serving internals preferably also the hindrance of the back serve mixing.

Geeignete Einbauelemente sind z. T. handelsüblich oder sie können vom Apparatebau leicht verwirklicht werden; insbesondere sind achsparallele Rohrbündel oder Platten geeignet, die eine im Verhältnis zum Reaktordurchmesser ausreichende Länge (z. B. 5-fach oder mehr) aufweisen. Sie können natürlich in mehrere hinterein­ anderliegende Einzelelemente bzw.-gruppen unterteilt sein und bei Bedarf getrennt temperiert werden. Abgesehen von der Phase der Inbetriebnahme sollte nirgends Wärmezufuhr von außen nötig sein, weswegen in einzelnen Abschnitten die Strömungsrichtung von Produkt (Reaktionsgemisch) und Kühlmittel (Wärmetauschmedium) unterschiedlich (Gleich- und Gegenstrom) sein kann.Suitable installation elements are e.g. T. commercially available or they can be easily realized by apparatus engineering; are in particular axially parallel tube bundles or plates suitable, the one in Sufficient length in relation to the reactor diameter (e.g. 5 times or more). You can, of course, put in several other individual elements or groups can be divided and at Temperature can be controlled separately. Apart from the phase of Commissioning should nowhere be necessary to supply heat from outside, which is why the flow direction of Product (reaction mixture) and coolant (heat exchange medium) can be different (co-current and counter-current).

BeispieleExamples

Zu Versuchszwecken wurde ein Rohrreaktor aufgebaut, der für Mas­ sepolymerisation (z. B. für PS, SAN, HIPS, ABS) geeignet ist und einer Gesamtlänge LR von 150 m aufweist. Der Reaktor weist einen Rohrdurchmesser von . . . auf und ist mit Einbauten in Form von . . . ausgerüstet, die eine Pfropfenströmung ermöglichen. Der Rohr­ reaktor hat eine spezifische Kühlfläche vonFor experimental purposes, a tubular reactor was constructed which is suitable for bulk polymerization (e.g. for PS, SAN, HIPS, ABS) and has a total length L R of 150 m. The reactor has a tube diameter of. . . on and is with internals in the form of. . . equipped that allow a plug flow. The tubular reactor has a specific cooling surface of

Die ersten 120 m des Reaktors (hier bezeichnet als temperierte Rohrstrecke) können durch Gleichstromkühlung durchgehend oder abschnittweise versorgt werden, wobei ein erster Abschnitt von 20 m zum Aufheizen dient. Im Abstand von jeweils 10 m befinden sich in der Rohrstrecke Temperaturmeßfühler und Probenahmestutzen.The first 120 m of the reactor (here referred to as tempered Pipe section) can be continuously or by direct current cooling in sections, a first section of 20 m is used for heating. At a distance of 10 m each in the pipe section temperature sensor and sampling nozzle.

Die effektive axiale Strömungsgeschwindigkeit Weff, ax beträgt bei den nachstehend erläuterten Beispielen 4 cm/s, was einer auf den leeren Rohrquerschnitt bezogenen Strömungsgeschwindigkeit von 2 cm/s entspricht.The effective axial flow velocity W eff , ax is 4 cm / s in the examples explained below, which corresponds to a flow velocity of 2 cm / s based on the empty pipe cross section.

Die letzten 30 m des Rohrreaktors werden im wesentlichen adiabat betrieben; es ist lediglich am äußersten Ende ein Kühlaggregat zum Einstellen der gewünschten Austrittstemperatur vorgesehen.The last 30 m of the tubular reactor are essentially adiabatic operated; it is only a cooling unit at the extreme end provided to set the desired outlet temperature.

Das austrittsseitige Ende des Rohrreaktors bildet eine Loch­ platte, aus deren Bohrungen die Polymerlösung in Form von Fäden in eine Vakuumkammer eintritt, in der sie entgast wird. Eine Zahnradpumpe fördert die Polymerschmelze aus dem Sumpf der Vakuumkammer zur Dachbearbeitung (z. B. Einmischen von Hilfs- und Füllstoffen sowie Pigmenten, sodann Granulierung. The outlet end of the tubular reactor forms a hole plate, from whose holes the polymer solution in the form of threads enters a vacuum chamber in which it is degassed. A Gear pump conveys the polymer melt out of the sump Vacuum chamber for roof processing (e.g. mixing in auxiliary and Fillers and pigments, then granulation.  

Beispiel 1example 1

Zulaufgemisch:
98 Gew.-% Styrol
 2 Gew.-% EthylbenzolFeed mixture:
98% by weight styrene
2% by weight of ethylbenzene

Axiale Profile der temperierten Rohrstrecke (vgl. Fig. 1)Axial profiles of the tempered pipe section (see Fig. 1)

Die Temperatur am Ende des adiabatisch betriebenen Teils der
Rohrstrecke betrug 234°C. Das entgaste Endprodukt hatte einen Polymerisationsgrad von Pw = 1810, die Uneinheitlichkeit U war 1. The temperature at the end of the adiabatically operated part of the
Pipe length was 234 ° C. The degassed end product had a degree of polymerization of P w = 1810, the inconsistency U was 1.

Beispiel 2Example 2

Zulaufgemisch:
84 Gew.-% eines Gemisches von Styrol und Acrylnitril im Masseverhältnis
2,5 : 1
16 Gew.-% EthylbenzolFeed mixture:
84% by weight of a mixture of styrene and acrylonitrile in the mass ratio
2.5: 1
16% by weight of ethylbenzene

Die Austrittstemperatur der adiabatisch betriebenen Rohrstrecke betrug 223°C. Das entgaste Endprodukt hatte folgende Parameter:
w = 1500; U = 1,4.The outlet temperature of the adiabatically operated pipe section was 223 ° C. The degassed end product had the following parameters:
w = 1500; U = 1.4.

Beispiel 3Example 3

Bei diesem Ausführungsbeispiel (schlagzäh modifiziertes SAN; ABS) wurde die Phaseninversion durch eine Düse (Verengung) erzeugt, die an der axialen Position Z = 80 in angebracht war.In this embodiment (impact modified SAN; ABS) the phase inversion was generated by a nozzle (constriction), the at the axial position Z = 80 in was attached.

Zulaufgemisch:
84 Gew.-% eines Gemisches von Styrol und Acrylnitril im Masseverhältnis 2,5 : 1
 8 Gew.-% cis-Polybutadien
 2 Gew.-% Paraffin
 6 Gew.-% Ethylbenzol
 0,1 Gew.-% DitertiärbutylperoxidFeed mixture:
84% by weight of a mixture of styrene and acrylonitrile in a mass ratio of 2.5: 1
8% by weight of cis-polybutadiene
2% by weight paraffin
6% by weight of ethylbenzene
0.1% by weight of ditertiary butyl peroxide

Reaktionsführung und Produktcharakterisierung (vgl. Fig. 3).Reaction management and product characterization (see. Fig. 3).

Durch segmentweise Temperierung wurde zwischen 60 m und 120 m eine Temperatur von T = 140-145°C eingehalten. Der Gesamtpolymer­ massenbruch Yp·ges betrug bei z = 120 m: 0,53; der massenmittlere Polymerisationsgrad w der Polymerphase betrug an dieser Stelle 2300.A temperature of T = 140-145 ° C was maintained between 60 m and 120 m by segmental tempering. The total polymer weight fraction Y p · ges was at z = 120 m: 0.53; the mass-average degree of polymerization w of the polymer phase was 2300 at this point.

Die Temperatur am Ende des adiabatisch betriebenen Teils der Rohrstrecke betrug 228°C. Das entgaste Endprodukt hatte folgende Parameter: w = 2020; U = 1,3.The temperature at the end of the adiabatically operated part of the pipe section was 228 ° C. The degassed end product had the following parameters: w = 2020; U = 1.3.

Die Schlagzähigkeit war um 20% höher als die von Produkten mit vergleichbarem Kautschukgehalt, die nach einem Emulsionspolymeri­ sationsverfahren hergestellt wurden, wobei das Endprodukt einen Kautschukgehalt von 10,4% aufwies.The impact strength was 20% higher than that of products with comparable rubber content after an emulsion polymer were produced, the end product being a Rubber content of 10.4% had.

Das erhaltene Produkt war opak.The product obtained was opaque.

Claims (2)

1. Vorrichtung zur kontinuierlichen Polymerisation von ole­ finisch ungesättigten Verbindungen in Form eines Rohr­ reaktors, der - an seinem austragsseitigen Ende - in einen Apparat mündet zur unmittelbar an die Polymerisation an­ schließenden Entfernung von nicht umgesetzten Monomeren und gebildeten Oligomeren durch Verdampfung unter vermindertem Druck, dadurch gekennzeichnet, daß mindestens ein eintritts­ seitiger Abschnitt vorgesehen ist, der als Einbauten auf­ weisender Wärmetauscher ausgebildet ist, wobei die spezi­ fische Wärmeaustauschfläche in diesem Abschnitt mindestens 80 m2 je m3 freiem Reaktorvolumen beträgt, so daß die Temperatur­ differenz zwischen Wärmetauschmedium und Reaktionsgemisch an jeder Stelle dieses Abschnitts auf höchstens 30 K begrenzt werden kann, und ein austragsseitiger Abschnitt, der im wesentlichen adiabatisch betrieben werden kann und durch eine Lochplatte abgeschlossen ist, die mit einer evakuierbaren Kammer zusammenwirkt.1. Device for the continuous polymerization of olefinically unsaturated compounds in the form of a tubular reactor which - at its discharge end - opens into an apparatus for the subsequent removal of unreacted monomers and oligomers formed by evaporation under reduced pressure, thereby immediately following the polymerization characterized in that at least one inlet-side section is provided, which is designed as internals on pointing heat exchangers, the speci fische heat exchange surface in this section is at least 80 m 2 per m 3 free reactor volume, so that the temperature difference between the heat exchange medium and the reaction mixture at each The location of this section can be limited to a maximum of 30 K, and a discharge-side section which can be operated essentially adiabatically and is closed off by a perforated plate which interacts with an evacuable chamber. 2. Verfahren zur kontinuierlichen radikalischen Polymerisation olefinisch ungesättigter Verbindungen in einem im wesent­ lichen rückvermischungsfrei betreibbaren Rohrreaktors, d.g., daß man als Rohrreaktor eine Vorrichtung nach Anspruch 1 verwendet.2. Process for continuous radical polymerization essentially olefinically unsaturated compounds pipe mixer that can be operated without backmixing, i.e. that as a tubular reactor, a device according to claim 1 used.
DE19924235785 1992-10-23 1992-10-23 Continuous polymerisation of olefinic monomers - uses a tubular reactor contg. a special temp.-controlled section followed by an adiabatic section discharging into a vacuum degassing chamber Withdrawn DE4235785A1 (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5637646A (en) * 1995-12-14 1997-06-10 Minnesota Mining And Manufacturing Company Bulk radical polymerization using a batch reactor
US6815525B2 (en) 2000-12-07 2004-11-09 Eastamn Chemical Company Component introduction into manufacturing process through recirculation
US7649109B2 (en) 2006-12-07 2010-01-19 Eastman Chemical Company Polyester production system employing recirculation of hot alcohol to esterification zone
US7718759B2 (en) 2000-12-07 2010-05-18 Eastman Chemical Company Polyester process using a pipe reactor
US7829653B2 (en) 2007-07-12 2010-11-09 Eastman Chemical Company Horizontal trayed reactor
US7842777B2 (en) 2007-07-12 2010-11-30 Eastman Chemical Company Sloped tubular reactor with divided flow
US7847053B2 (en) 2007-07-12 2010-12-07 Eastman Chemical Company Multi-level tubular reactor with oppositely extending segments
US7858730B2 (en) 2007-07-12 2010-12-28 Eastman Chemical Company Multi-level tubular reactor with dual headers
US7863477B2 (en) 2007-03-08 2011-01-04 Eastman Chemical Company Polyester production system employing hot paste to esterification zone
US7868130B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Multi-level tubular reactor with vertically spaced segments
US7868129B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Sloped tubular reactor with spaced sequential trays
US7872089B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Multi-level tubular reactor with internal tray
US7872090B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753768A (en) * 1995-12-14 1998-05-19 Minnesota Mining And Manufacturing Company Bulk radical polymerization using a batch reactor
US5986011A (en) * 1995-12-14 1999-11-16 Minnesota Mining And Manufacturing Company Bulk radical polymerization using a batch reactor
US5637646A (en) * 1995-12-14 1997-06-10 Minnesota Mining And Manufacturing Company Bulk radical polymerization using a batch reactor
US7842778B2 (en) 2000-12-07 2010-11-30 Eastman Chemical Company Polyester process using a pipe reactor
US6815525B2 (en) 2000-12-07 2004-11-09 Eastamn Chemical Company Component introduction into manufacturing process through recirculation
US7718759B2 (en) 2000-12-07 2010-05-18 Eastman Chemical Company Polyester process using a pipe reactor
US8114954B2 (en) 2000-12-07 2012-02-14 Grupo Petrotemex, S.A. De C.V. Polyester process using a pipe reactor
US7649109B2 (en) 2006-12-07 2010-01-19 Eastman Chemical Company Polyester production system employing recirculation of hot alcohol to esterification zone
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel
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