EP1861195A1 - Modulare vorrichtung zur kontinuierlichen entgasung und herstellung polymerer vorkondensate, mit reaktionstechnisch hohem verhältnis produktoberfläche zu volumen, bei schonender behandlung der reaktionsproduktmasse - Google Patents

Modulare vorrichtung zur kontinuierlichen entgasung und herstellung polymerer vorkondensate, mit reaktionstechnisch hohem verhältnis produktoberfläche zu volumen, bei schonender behandlung der reaktionsproduktmasse

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Publication number
EP1861195A1
EP1861195A1 EP06723801A EP06723801A EP1861195A1 EP 1861195 A1 EP1861195 A1 EP 1861195A1 EP 06723801 A EP06723801 A EP 06723801A EP 06723801 A EP06723801 A EP 06723801A EP 1861195 A1 EP1861195 A1 EP 1861195A1
Authority
EP
European Patent Office
Prior art keywords
product
reactor
modules
reaction
reaction product
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Withdrawn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
EP06723801A
Other languages
German (de)
English (en)
French (fr)
Inventor
Andreas Hilpert
Stephan Biller
Clifford SCHÄFERSKÜPPER
Michael Streng
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.)
Epc Industrial Engineering GmbH
Original Assignee
Epc Industrial Engineering GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Epc Industrial Engineering GmbH filed Critical Epc Industrial Engineering GmbH
Publication of EP1861195A1 publication Critical patent/EP1861195A1/de
Withdrawn legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J14/00Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/2415Tubular reactors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/245Stationary reactors without moving elements inside placed in series
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/247Suited for forming thin films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02Feed or outlet devices therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/12Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
    • B01J8/125Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow with multiple sections one above the other separated by distribution aids, e.g. reaction and regeneration sections
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/785Preparation processes characterised by the apparatus used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00018Construction aspects
    • B01J2219/0002Plants assembled from modules joined together
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00018Construction aspects
    • B01J2219/00024Revamping, retrofitting or modernisation of existing plants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094Jackets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00121Controlling the temperature by direct heating or cooling
    • B01J2219/00123Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00168Controlling or regulating processes controlling the viscosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00245Avoiding undesirable reactions or side-effects
    • B01J2219/00247Fouling of the reactor or the process equipment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00245Avoiding undesirable reactions or side-effects
    • B01J2219/00252Formation of deposits other than coke
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18Details relating to the spatial orientation of the reactor
    • B01J2219/185Details relating to the spatial orientation of the reactor vertical
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/245Plate-type reactors
    • B01J2219/2461Heat exchange aspects
    • B01J2219/2462Heat exchange aspects the reactants being in indirect heat exchange with a non reacting heat exchange medium

Definitions

  • the invention relates to a reactor (modular apparatus) for the continuous degassing of reaction products of a carboxylic acid or dicarboxylic acids with a polyhydric alcohol, which can be used for the production of precondensates (or prepolymers) and in which a reaction-technically higher ratio of product surface to product volume is to be achieved, which is proportional to the generation of the intrinsic viscosity (IV) of the product of 0.2 - 0.35 dl / g, and which allows a thermally and mechanically gentle treatment of this reaction product mass, according to the features in the preamble of the main claim.
  • a reactor module for the continuous degassing of reaction products of a carboxylic acid or dicarboxylic acids with a polyhydric alcohol, which can be used for the production of precondensates (or prepolymers) and in which a reaction-technically higher ratio of product surface to product volume is to be achieved, which is proportional to the generation of the intrinsic viscosity (IV) of
  • DE 10155419 A1 discloses a "process for the continuous production of high molecular weight polyester and apparatus for carrying out the process.”
  • the reaction and the production of surfaces takes place by means of a falling film evaporator.
  • Horizontal reactors are equipped with a complex agitator for surface generation.
  • the mechanical loads on the shaft seals during operation result in leaks over time which can lead to an entry of atmospheric oxygen into the reaction space that is detrimental to the product.
  • the invention has for its object to provide a device with which a reaction-technically optimal ratio of product surface to product volume is achieved, which ensures a high degassing of the product. Furthermore, the process should be feasible without the use of an agitator, which means that the reactor can be operated maintenance-free.
  • the reactor should be modular so that the greatest possible standardization of the reactor can be achieved. The modular design and the simple design allow a production-technically efficient effort and a cost-effective design. Due to the modular design, the assembly can be carried out on site for large reactors whose transport dimensions exceed the given conditions. Likewise, an expansion of capacity to be achieved without reinstalling by the installed reactor is increased by using additional modules.
  • the device or the reactor consists of at least 3 basic modules (Ia, Ib and Ie, see sketch, Fig. 1). These basic modules are only represented once in the reactor and fulfill the function of the product entry (Ib), the product sump with product discharge (Ie) and the vapor collection and the vapor discharge (Ia). Based on the product volume, a high specific product surface is generated.
  • the expansion modules (Ic and Id) serve to generate additional surface.
  • the extension modules are used if a higher system throughput is to be achieved while maintaining the same reactor diameter. By installing the extension modules, the necessary reaction surface is generated.
  • the basic module (Ib) is followed by the expansion module (Ic).
  • the expansion module (Ic) is then followed by the expansion module (Id). If more expansion modules are required, there will always be an alternating sequence of expansion modules Ic and Ib until the necessary number of expansion modules has been reached.
  • the floors of the modules Ib, Ic and Id are formed in a defined arched shape. Emerging openings for the nozzles of the inlets, overflows and drains are designed and placed in such a way that fluidic dead spaces are avoided.
  • the overflow tube (6, 12, 13) on the floors of the modules Ib, Ic and Id are dimensioned so that the product after flowing over from the product surface into the overflow pipe on the inner wall forms a defined, fully formed film. As a result, more product surface is generated and improved by the vapor stream in the core space of the overflow pipe mass transfer.
  • the trays of the modules Ib, Ic and Id are designed in a smaller diameter d than the reactor shell with the diameter D. It arises in this way Peripheral edge area outside the bottom circumference, which serves as a flow channel for the vapor.
  • the edge areas are dimensioned so that a sufficiently high vapor velocity is achieved, which leads to a self-cleaning of the reactor with respect to product adherence to the reactor walls, or resulting adhesions is cleaned by entrainment.
  • the shelves of modules Ib, Ic, Id and the reactor shell with the outlet for the vapor outlet and product outlet are equipped with heaters, which, if necessary, can be regulated separately.
  • the heating contributes the required process energy.
  • the wall heating prevents product buildup in the event of an occurrence and, in combination with the high vapor velocity, purifies it.
  • the incoming fresh precursor (1) from the upstream reaction stage in the module Ib is pre-distributed by a distributor device (16) transversely to the direction of entry.
  • This distributor device (16) is equipped with heating depending on the type of product entering.
  • the distributor device (16) is used for the reliable sub-level feed and thus the start of the reaction in the module Ib and for preventing premature strong transgression of the precursor into the vapor space.
  • the exiting end product from the bottom module Ie is fluidly influenced by a displacement device (17) such that the finished product melt does not acquire a preferential core exit flow and thus there is still a sufficient mass transfer from the outer module diameter to the central exit point.
  • Outer jacket of the reactor is supplied. About this outer jacket of the heat transfer steam to the inside doppelmantelausmake floors (9) are supplied. The condensate which is formed during the heat transfer process will flow off in the case of the module 1b via the double jacket of the product inlet line (1), in the case of the modules Ic and Id this is done by a guided from the inside to the outside
  • Condensate return line (21) The heating of the displacer device (17) provided in the bottom Ie as well as the associated heating coil (19) takes place via the steam inlet lines (20). The heat transfer condensate flows through the connection to the
  • the reactor is modular. This allows a standardized and effective production. If required, it is also possible to increase the plant capacity of installed reactors by using the modules Ic and Id. This opens up economically highly efficient effects.
  • the reactor is characterized by a simple design and construction with minimized production costs.
  • the reactor is designed without stirrers. potential
  • Fig. 1 shows the reactor in the overall view.
  • the prepolycondensation reactor described by way of example is made from 5 individual modules Ia to Ie. Each module is heated by thermal oil both in the wall and in the bottom areas to the temperature required for the reaction. Homogeneous heating of the entire reactor prevents buildup of material that can occur at relatively cold spots.
  • the modules 1 are: 1. the product sump Ie, in which the surface and residence time is generated, with the product sequence 2, from which the product is discharged into the subsequent process stage,
  • the product inlet bottom (4) which adjoins below the vapor space Ia, the product enters the submirror or underfloor centrally via a heated product line (5) and distributed with the aid of the distributor device (16) on the product inlet bottom (4).
  • the product inlet bottom (4) is provided on a defined circumference with overflows (6) over which the product on the following floor (7) runs.
  • the overflows (6) are designed to efficiently direct the product and avoid dead spaces (non-flow areas).
  • this soil has a bottom discharge (8), which also directs the product to the subsequent soil (7).
  • the product inlet bottom (4) like all other trays, has a smaller diameter than the reactor casing (10).
  • the following two trays (7 and 11) are constructed in principle similar to the product inlet bottom (4). In contrast to the product entry bottom, however, these only have overflows (12 and 13) for the product on the next floor or in the reactor sump. These floors also have a low point discharge (14 and 15).
  • the product is also conducted on the following trays so that in each case from the outer areas to the centrally arranged overflow (12) in the bottom (7) and then back to the overflows (13) on the defined circle of the soil (11) (analog product ingress floor 4) is performed.
  • the vapors are also guided through the free edge area (9) into the vapor chamber in the following trays (7 and 11). Also in these soils, the area of the free edge area (9) is dimensioned so that the vapors have such a high velocity that no material can settle on the reactor shell (10) and any deposits are cleaned (entrained). This ensures the self-cleaning effect.
  • the product is withdrawn centrally via nozzle (2) and fed to the next production stage.
  • the product sump in the module Ie is designed with a heated displacer device (17) for optimized flow cross distribution, whose incoming and outgoing heat carrier lines serve to hold, but by means of which solidified (frozen) residual material in the product sump can be melted in the event of a malfunction.
  • the product sump in Ie is sized so that it can take in case of a standstill or a malfunction, the entire product volume located in the reactor without overflow into the module arranged above it.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP06723801A 2005-03-22 2006-03-22 Modulare vorrichtung zur kontinuierlichen entgasung und herstellung polymerer vorkondensate, mit reaktionstechnisch hohem verhältnis produktoberfläche zu volumen, bei schonender behandlung der reaktionsproduktmasse Withdrawn EP1861195A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005013764A DE102005013764B3 (de) 2005-03-22 2005-03-22 Modulare Vorrichtung zur kontinuierlichen Entgasung und Herstellung polymerer Vorkondensate, mit reaktionstechnisch hohem Verhältnis Produktoberfläche zu Volumen, bei schonender Behandlung der Reaktionsproduktmasse
PCT/EP2006/002832 WO2006100105A1 (de) 2005-03-22 2006-03-22 Modulare vorrichtung zur kontinuierlichen entgasung und herstellung polymerer vorkondensate, mit reaktions technisch hohem verhältnis produktoberfläche zu volumen, bei schonender behandlung der reaktionsproduktmasse

Publications (1)

Publication Number Publication Date
EP1861195A1 true EP1861195A1 (de) 2007-12-05

Family

ID=36584155

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06723801A Withdrawn EP1861195A1 (de) 2005-03-22 2006-03-22 Modulare vorrichtung zur kontinuierlichen entgasung und herstellung polymerer vorkondensate, mit reaktionstechnisch hohem verhältnis produktoberfläche zu volumen, bei schonender behandlung der reaktionsproduktmasse

Country Status (6)

Country Link
US (1) US8124018B2 (zh)
EP (1) EP1861195A1 (zh)
CN (1) CN101146602B (zh)
DE (1) DE102005013764B3 (zh)
EA (1) EA012362B1 (zh)
WO (1) WO2006100105A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150051367A1 (en) * 2011-06-10 2015-02-19 Clive Alexander Hamilton Variable pressure drop up flow-pre-polymerizer (ufpp) systems and methods
US20130196053A1 (en) * 2012-01-10 2013-08-01 State of Oregon acting by and through the State Board of Higher Education on behalf of Oregon Stat Flow cell design for uniform residence time fluid flow
CN103361264B (zh) * 2012-03-30 2014-12-31 北京愿景宏能源环保科技发展有限公司 一种可调整容积的发酵罐及其控制装置和方法

Family Cites Families (11)

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Publication number Priority date Publication date Assignee Title
US2727882A (en) * 1952-10-14 1955-12-20 Du Pont Process and apparatus for the continuous polymerization of bis-2-hydroxyethyl terephthalate
BE564025A (zh) * 1957-01-17
FR1357905A (fr) * 1962-05-11 1964-04-10 Hoechst Ag Appareil de réaction pour la préparation de polyphtalates d'éthylène
NL292245A (zh) * 1962-05-11
US3359074A (en) * 1963-06-11 1967-12-19 Monsanto Co Polycondensation apparatus
US3651125A (en) * 1968-08-12 1972-03-21 Eastman Kodak Co Continuous method for formation of a liquid monomer for a condensation polymer
US3620283A (en) * 1969-02-04 1971-11-16 Artisan Ind Falling film evaporator stripper
US4158092A (en) * 1974-07-25 1979-06-12 Hoechst Aktiengesellschaft Process for the manufacture of vinyl chloride polymer dispersions with a low monomer content
DE2504258A1 (de) * 1975-02-01 1976-08-05 Dynamit Nobel Ag Verfahren und apparatur zur herstellung von oligomeren alkylenterephthalaten
US5310955A (en) * 1991-01-18 1994-05-10 The Dow Chemical Company Vertical continuous reactor and process for liquid epoxy resin
DE10155419B4 (de) * 2001-11-12 2005-06-16 Inventa-Fischer Gmbh & Co. Kg Verfahren zur kontinuierlichen Herstellung von hochmolekularem Polyester sowie Vorrichtung zur Durchführung des Verfahrens

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006100105A1 *

Also Published As

Publication number Publication date
EA200701842A1 (ru) 2008-12-30
EA012362B1 (ru) 2009-10-30
US20090047186A1 (en) 2009-02-19
US8124018B2 (en) 2012-02-28
WO2006100105A1 (de) 2006-09-28
CN101146602B (zh) 2011-03-09
CN101146602A (zh) 2008-03-19
DE102005013764B3 (de) 2006-10-12

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