EP1678236A1 - Reacteur a colonne et son utilisation pour produire en continu du polyester a poids moleculaire eleve - Google Patents

Reacteur a colonne et son utilisation pour produire en continu du polyester a poids moleculaire eleve

Info

Publication number
EP1678236A1
EP1678236A1 EP04791054A EP04791054A EP1678236A1 EP 1678236 A1 EP1678236 A1 EP 1678236A1 EP 04791054 A EP04791054 A EP 04791054A EP 04791054 A EP04791054 A EP 04791054A EP 1678236 A1 EP1678236 A1 EP 1678236A1
Authority
EP
European Patent Office
Prior art keywords
tower reactor
reactor according
reaction
heat exchanger
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Withdrawn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
EP04791054A
Other languages
German (de)
English (en)
Inventor
Eike Schulz Van Endert
Christian Atlas
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.)
Uhde Inventa Fischer GmbH
Original Assignee
Uhde Inventa Fischer 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 Uhde Inventa Fischer GmbH filed Critical Uhde Inventa Fischer GmbH
Publication of EP1678236A1 publication Critical patent/EP1678236A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/785—Preparation processes characterised by the apparatus used
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • 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
    • 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
    • B01J19/247—Suited for forming thin films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • 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
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger 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
    • 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
    • B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/0011—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
    • 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
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • 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
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • 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
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment

Definitions

  • the invention relates to a tower reactor and its use for the production of high molecular weight polyesters such as Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene terephthalate (PEN), polytrimethylene terephthalate (PTT) and / or polyesters of other dicarboxylic acids and diols including their copolymers. It is a single-stage tower reactor.
  • PET Polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polynaphthalene terephthalate
  • PTT polytrimethylene terephthalate
  • polyesters of other dicarboxylic acids and diols including their copolymers. It is a single-stage tower reactor.
  • polyesters Processes for the continuous production of polyesters are known from the prior art, in which multi-stage reactor systems are used which consist of three to five different reaction vessels connected to one another. In these processes, the polyester is formed in several reaction stages, which are usually designed as stirred tanks, which are spatially separated from one another. running: esterification, transesterification, precondensation, polycondensation and polyesterification.
  • the reaction conditions for the esterification are at temperatures between 200 and 280 ° C and pressures between 0 and 4 bar, while the conditions for the transesterification are usually at atmospheric pressures and at temperatures between 150 and 240 ° C, depending on the starting substances of the diols. Low temperatures and low pressures are desirable for the processes in order to avoid undesired side reactions.
  • DE 35 44 551 A1 discloses a process for the continuous production of high molecular weight polybutylene terephthalate, in which the process is carried out under atmospheric pressure.
  • DE 101 55 419 discloses a process for producing high molecular weight polyester and an apparatus for carrying out this process, the individual reaction zones being integrated in a single reactor vessel.
  • a tower reactor for the continuous production of high molecular weight polyester which has reaction zones for the simultaneous esterification and / or transesterification and precondensation.
  • the individual reaction zones are combined in a tower reactor and can be connected to at least one reactor for polycondensation in the solid and / or liquid phase.
  • the tower reactor is constructed as follows: In the upper third, the tower reactor is designed in the form of a hydrocyclone with an attached heat exchanger and has a feed for the paste, the slurry and / or the liquid raw material mixture.
  • the area of the tower reactor below the hydrocyclone is designed in the form of a downdraft cascade. This cascade is connected via a suitable inlet pipe to the lower part of the tower reactor, which is designed in the form of a single- or multi-stage falling film zone with pre-relaxation.
  • This construction method has various advantages. In this way, the product flow from the entire tower reactor can be ensured by gravimetric flow without the use of a pump. Long external pressure lines for the transport of the monomer into the reactor are also superfluous. Further advantages relate to the fact that there is no heating of the upper reactor cover, which leads to corresponding cost savings, and that the reaction vapor can be partially used to heat the reaction product in the hydrocyclone. There is also a uniform pressure drop across the entire reactor in the pressure reactor. This means that the wall material thickness can be reduced.
  • the hydrocyclone preferably has a vapor connector and is connected to a heat exchanger in the upper part of the tower reactor. This makes it possible to lead the product in a natural or forced cycle through the heat exchanger into the hydrocyclone.
  • the heat exchanger has a separate gas fireplace which leads to an upper part of the cyclone.
  • the cascade preferably has at least two, particularly preferably four, reaction cups.
  • a stirring unit can be integrated in at least one cascade area to support the input of diol or additives.
  • the additive can also be added to a product drain pipe of the penultimate cup via an injection lance, which ensures an optimal distribution of the same in the product mass.
  • the pressure line is preferably designed as a double jacket line, which continues inside the first head cup as a heating coil.
  • the pressure line can be equipped with a volume feed pump and static mixing elements or a mixing pump.
  • the hydrocyclone preferably has a gas inlet in its conical area.
  • one of the head cups in the vapor area also has an inert gas inlet.
  • the reaction gases and / or foreign gases are preferably passed from reaction zone to reaction zone in cocurrent by means of submerged feeds the reaction liquid passed, creating a pressure drop between the cups.
  • the reaction mass is fed centrally to the next cup by means of a likewise submerged tube.
  • the pre-relaxation zone to the falling film zone also has the form of a hydrocyclone, which supports the flash effect and ensures adequate separation of the liquid / gas phases and generates a further pressure gradation.
  • the product is fed from the pre-expansion zone to the falling film zone by suitably designing the process from it in the concentric outer area of the falling film zones and the product is evenly distributed over alleys in the tube field.
  • the falling film zone has at least one tube field.
  • An inlet cylinder is assigned to each pipe in the pipe field, which ensures uniform wetting of the inside of the pipe, which is equipped with overlapping, non-axial slots on the circumference, a constant fill level is generated above the pipe rows due to the loss of slot pressure, and a maximum overflow with jagged Krone has, the slots being designed in such a way that differences in viscosity only cause negligible changes in the fill level, but a proportional change from fill level to liquid throughput.
  • the length of the falling film tubes is dimensioned such that total wetting takes place.
  • the diameter of the falling film tubes is preferably larger than the largest reaction vapor bubble that occurs selected.
  • the reaction vapors are carried out in cocurrent with the product flowing downwards.
  • the falling film tube field can preferably also be used for heat transfer.
  • the entire tower reactor is preferably equipped with a jacket for heating with organic heating media in vapor form.
  • the tower reactor preferably has a plate bottom valve designed as a feed with a special plate.
  • the feed of the raw mixture is arranged centrally in the spherical bottom below the heat exchanger. This has the advantage that the plate of the bottom valve creates a baffle plate effect, which enables a uniform turbulent distribution of the raw mixture with the reaction mixture.
  • the tower reactor preferably has static mixing elements to improve the mixing of the raw mixture into the reaction mixture.
  • the mixing of the raw mixture into the reaction mixture is improved by the complete or partial filling of the heat exchanger tubes. The result of this is that the reaction can be accelerated due to the higher mass exchange and the reaction product is spared due to the improved heat exchange (lower wall temperature).
  • the raw mixture entering the lower part of the external heat exchanger is subjected to intensive mixing into the liquid reaction mixture.
  • the ratio of the circulating reaction mixture to the raw mixture entered is in the range from 100: 1 to 300: 1, so that satisfactory mixing is ensured by the dilution if a 100% mixture is assumed.
  • a three-dimensional statistical mixing element is particularly preferably used, which generates a large number of diagonal cross-flows with simultaneous axial flow before the reaction mixture enters the heat exchanger. Problems such as streaking of the raw mixture in the reaction mixture can thus be ruled out, so that an inhomogeneous reaction in the heat exchanger which would disturb the natural circulation can be hindered. Sedimentation of a raw material component, which can lead to process disturbances over time, can also be avoided in this way.
  • the use of a three-dimensional static mixing element has proven to be particularly advantageous. With this, a radial distribution of reaction mixture and raw mixture with simultaneous axial upward movement can take place, ie there is intensive mixing of the components and thus a uniform reaction.
  • the three-dimensional static mixing element consists of cross-shaped, perforated sheet metal sections, the inclination of which is adjusted in such a way that the impact pressure loss is only a few mmWWS / m.
  • the ratio of the axial height to the heat exchanger diameter is preferably between 0.2: 1 to 0.5: 1. This ratio is important in order to disturb the natural circulation as little as possible.
  • Another variant of the mixing is realized by folded layer packs, as are often used in distillation columns. Good results can also be achieved with this, particularly with regard to the crosswise and diagonal flow, the axial leakage flow and the low pressure loss.
  • the individual heat exchanger areas preferably have a different pipe division.
  • the vapor spaces have adhesion-reducing coatings.
  • adhesion-reducing organochemicals and inorganic chemistries can be used as coatings in the thin-film process (up to 10 ⁇ m) at a high application temperature of up to 350 ° C. With this surface treatment, the susceptibility to contamination of the polymeric reaction masses can be reduced.
  • all heat exchange surfaces in the individual zones are equipped for liquid heat carriers for process-relevant temperature and heat quantity distribution.
  • the reactor according to the invention can be used to carry out a process for the continuous production of high molecular weight polyesters, based on the esterification of dicarboxylic acids and / or transesterification of dicarboxylic acid esters with diols in the presence of catalysts with simultaneous formation of a prepolymer and its polycondensation to give high molecular weight polyesters.
  • the following steps characterize the procedure:
  • a paste and / or a slurry of the dicarboxylic acids and the diol is produced, a molar ratio of diol to dicarboxylic acid being maintained from 0.8 to 1.8.
  • the temperature is kept between 20 and 90 ° C and the pressure between 0.1 and 1 bar.
  • a dicarboxylic acid ester can be melted and mixed with the diol in a molar ratio of diol to dicarboxylic acid ester of 1.2 to 1.8 at a temperature of 145 to 165 ° C.
  • reaction product water from the esterification or methanol from the transesterification, the by-products and excess diol from reaction steps bl) and b3) to b5) are removed and the diol is returned to the individual process stages after purification.
  • the prepolymer obtained from b4) is continuously processed into the polymer in a conventional polycondensation apparatus at temperatures between 240 and 290 ° C. and pressures between 0.0002 to 0.003 bar.
  • c2 As an alternative to cl), it is also possible to freeze the pre-polymer, process it into pellets and subject it to post-condensation in the solid phase at temperatures between 160 and 230 ° C under inert gas.
  • the new process enables parallel, uninterrupted transesterification / esterification and precondensation of dicarboxylic acids and their esters with diols in a single tower reactor. This enables the mechanical and procedural integration of several process stages for polyester synthesis for the first time.
  • the gaseous by-products formed in stage b1) and the excess diol are preferably separated off by means of a hydrocyclone in the "statu nascendi".
  • the rapid removal of lower-boiling reaction gases is of great importance with regard to minimizing the formation of by-products by cars
  • the content of by-products in the reaction mass is determined on the basis of the partial pressures of these products by the reaction pressure and the existing static product heights: the higher the total pressure, the higher the by-product formation.
  • thermosiphon circulation is decisive for a short dwell time of the by-products in the reaction mass with increasing static product height and because immediate effective degassing in the hydrocyclone and in the heat exchanger is ensured.
  • step bl When carrying out an esterification, a temperature between 200 and 270 ° C. and a pressure between 0.3 and 3 bar are preferred in step bl) respected. If, on the other hand, a transesterification is carried out, step b1) is carried out at a temperature between 170 and 200 ° C. and at a pressure between 0.3 and 1 bar.
  • step b2) when an esterification is carried out, the pressure is preferably kept between 2 and 6 bar, the residence time between 1 and 5 min and the temperature is preferably kept between 220 and 280 ° C. and particularly preferably between 230 and 250 ° C. If, on the other hand, a transesterification is carried out, the pressure in stage b2) is preferably in the range between 2 and 5 bar, the residence time between 1 and 4 min and the temperature in the range between 200 and 240 ° C., particularly preferably between 210 to Kept at 230 ° C.
  • step b3) the reaction product continuously fed from step b2) is passed over a falling flow cascade, with a 20 to
  • a dry inert gas and / or superheated process gas is preferably fed into at least the first shell under the reaction mass surfaces. This will separate the by-products by "dragging", i.e. Saturation of gases, supported. At the same time, the internal mixing of the reaction mass is promoted.
  • the dwell time in the individual shells is moves in a range between 5 and 15 min.
  • the product is supplied centrally in the shells.
  • the product runs on the outer edge of the
  • Shells distributed evenly over the outer wall, which is used for accelerated degassing, and is then brought together again centrally.
  • Step b4) is designed as a falling film zone with pretensioning and is preferably carried out at a temperature between 245 and 270 ° C. and a residence time between 4 and 30 minutes and a pressure between 0.01 and 0.05 bar. This creates a precondensate with 10 to 40 repetition units with a conversion of 99.8%.
  • the reaction product After leaving one or more falling film zone (s), the reaction product is preferably brought together by a heated cone, a gas-liquid separation being carried out in its central region by means of a spoiler.
  • the diol 1, butanediol, ethanediol or propanediol is preferably used.
  • the process is also suitable for cyclohexane dimethanol.
  • Terephthalic acid is preferably used as the dicarboxylic acid.
  • dimethyl terephthalate (DMT) is preferably used as the dicarboxylic acid ester.
  • DMT dimethyl terephthalate
  • the known tin, antimony, germanium, manganese, calcium and / or titanium metals etc. are preferably used as catalysts, in particular as their organic compounds.
  • the catalysts can also be accommodated in a porous carrier substance in order to develop a targeted effect.
  • FIG. 1 shows a first variant of a tower reactor according to the invention
  • Fig. 6 shows an embodiment of the process of the second film reaction zone
  • Fig. 7 shows an embodiment of the tube sheets in the form of a spherical cap.
  • Fig. 1 shows the schematic structure of a tower reactor.
  • a slurry of the dicarboxylic acid with the diol or the molten dicarboxylic acid ester and the diol are injected into the reaction mass under pressure in the lower region of a heat exchanger 5 attached to the tower reactor, and by suitable design of the injection nozzle 3 it mixes optimally with the one in the lower part -
  • the reaction product comes.
  • a catalyst that is used for some polyester is partial, be fed.
  • the heat exchanger ensures that the mixture is heated to the reaction boiling point.
  • the boiling reaction mixture passes through a short connecting line which tangentially opens into a hydrocyclone 2 for further reaction.
  • the majority of these gases are passed from the heat exchanger into the gas space of the cyclone via a separate line, a steam chimney 6.
  • cyclization of butanediol creates the undesirable tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the formation is enhanced by the presence of water, which is formed, for example, during the esterification.
  • a preheated, unsaturated entraining gas or superheated process vapors can advantageously be introduced in the lower region of the cyclone, thereby accelerating the removal of, in particular water, methanol, acetaldehyde or tetrahydrofuran from the reaction mass.
  • the reactor has a pressure line for the product, into which the diol is intimately mixed with the reaction mass via static mixing elements.
  • a pressure of up to 10 bar can be set using a pressure control valve.
  • the mixing and the pressure can also be Target mixing pump are generated.
  • reaction time is set in that part of the pressure line is arranged in the form of a heating coil in the uppermost reaction cup of the tower reactor.
  • the double jacket ensures that the reaction mass, cooled by expansion, is brought back to the reaction temperature.
  • the relaxed reaction mass is then passed through a downflow cascade 7, which consists of at least 2, preferably 4 to 5, reaction shells equipped with heating coils, into which the product flows centrally and submerged below the surface.
  • the reaction gas is passed through the reaction mass separately from the respective overlying shell by means of likewise submerged tubes. This results in a differential pressure, which preferably has the effect of lowering the pressure from shell to shell from top to bottom.
  • each bowl into a conically shaped collector, the drain of which is located at the lowest point of the cone.
  • the collector also contains the immersion tubes that feed the reaction gas into the next bowl.
  • the dishes are preferably laid out for a residence time of 5 to 10 minutes in order to achieve the desired reaction progress.
  • each bowl is equipped with heating coils.
  • reaction gas is conducted in cocurrent with the product flow, the gas bubbling through the reaction mass and ensuring optimum mixing on the one hand, and on the other hand not reaching its saturation limit due to the pressure drop with simultaneous temperature increase and thus remaining receptive for newly forming reaction gas (drag effect).
  • Drag effect Another important effect of the downflow cascade described is that the initially present low-boiling short-chain oligomers of the product with the reaction gas are returned to the reaction mass and continue to participate in the reaction there. Bubble formation also promotes the speed of the reaction by introducing the gas into the reaction mass, by additional surface formation and by contact with the gaseous diol.
  • an obliquely positioned stirrer 10 can be arranged in the last bowl, which supports the mixing of the vapor bubbles.
  • reaction mass is then brought through a suitable feeder for renewed expansion in a hydrocyclone-like arrangement which, like the previous shells, is equipped with heating coils for temperature adjustment.
  • the gas / liquid Separation takes place on the surface, with suitable baffles ensuring that the reaction mass runs evenly over the jagged outer edge of the shell, unaffected by the reaction gas bubbles that form.
  • the reaction mass running on the periphery is collected on a tube plate - also on its periphery - and is distributed with the help of so-called. "Alleys" evenly on the floor.
  • the tube sheet is part of a straight tube bundle 9, which also serves for film formation on the inner tube surfaces and for heat exchange.
  • An inlet cylinder 11 (cf. FIG. 5) is assigned to each tube in the bundle. This is designed with a series of non-axial, overlapping slots with a particularly balanced geometry on its periphery. The geometry is set so that
  • the upper edge of the inlet cylinder 11 serves as an emergency overflow and is equipped with a serrated crown.
  • the tube diameter is selected so that it is larger than the largest possible reaction gas bubble.
  • the reaction steam is co-current with the descending product film.
  • the ratio of pipe length to pipe diameter should be between 10 and 25 and the surface of the falling film pipes must be adapted to the wettability of the product.
  • the product emerges as a film and / or strands on the underside of the falling film tubes, is brought together by conical collector plates which let the gas flow through, and is fed to a second falling film reaction zone on the periphery. This is basically the same as the first zone, but takes into account the increased viscosities by taking appropriate measures on the inlet cylinders 11, distributing the pipes and length of the module.
  • a device for bringing the melt together which contains a central tube in the center for carrying out the reaction gases and the product.
  • the product running off on the device, preferably on the wall, is separated from the gas stream by a spoiler device 12 (cf. FIG. 6), which is deflected and removed in the gas space of the integrated prepolymer collector.
  • the collected prepolymer is discharged from the collector after a calming and post-reaction time of 5 to 15 minutes on the reactor floor and can now be subjected to further treatment, e.g. granulation with subsequent solid phase post-condensation or melt phase post-condensation.
  • the possibility is provided to return a partial stream of the prepolymer into the lower falling film module and to mix it with the preliminary product from the upper falling film module, so that the reaction time can be advantageously extended in a simple manner.
  • the outer shell of the reactor is equipped with a heating jacket, which is preferably provided for heating as an active insulation, with a synthetic heat transfer vapor.
  • the temperature profile required for the reaction is generated zone by zone with the aid of the inner heating surfaces, essentially using a liquid heat transfer oil.
  • the reaction gases from the different zones are discharged through conventional devices such as condensers, columns and vacuum systems, the diol with small amounts of oligomer essentially being returned to the process.
  • FIG. 2 shows a further variant of the tower reactor, which has the essential elements as in FIG. 1.
  • Fig. 3 shows an embodiment of the reaction cup with foam brakes and vapor-liquid separation.
  • the reaction cup shown here has a foam brake 13 and an adjustable, serrated overflow 14.
  • the liquid is led through the reaction gases and can run off via the central liquid drain (dip tube) 15, which serves to generate the differential pressure.
  • the reaction cup has a closable drainage opening 16, which consists of a bore hole with a conical extension, into which a conical closure with an additional temperature-resistant sealing element is inserted. leads is.
  • the actuation takes place from the outside with the aid of a double vacuum-sealed rod 17.
  • the reaction cups have heating tubes 18.
  • the AH ratio / ⁇ is preferably between 2 and 10
  • the flow velocity W is between 1 and 5 m / s and Wl between 0.05 and 0.3 m / s.
  • the tine angle of the overflow can be between 45 and 90 ° C and the tine height between 5 and 20 mm.
  • the gap / hole geometry is determined using a suitable differential equation, whereby a minimum level, which is necessary for optimal distribution, is maintained.
  • FIG. 6 shows an embodiment of the sequence of the second film reaction zone in the form of a spoiler 21.
  • the product from this zone already has a melt viscosity that has film and fiber-forming properties.
  • the exit of such a melt from a tube can then already take the form of an elastic hose.
  • a gas passes through, in this case the reaction gas, there is a risk that this film tube will be torn open and that flat parts of it will enter the downstream condensation and vacuum systems with the gas stream. This would lead to unpleasant malfunctions and losses.
  • this problem was solved by bundling the polymer stream, which then only flows through the tube in strands, with the simultaneous release of gas passage areas with the aid of the spoiler 21.
  • Fig. 7 shows a variant of the tube sheets in the form of a spherical cap.
  • the tube sheets can be designed in the form of a spherical cap, by means of which a targeted height difference in the liquid level is generated. This eliminates the distribution non-uniformity caused by the mass difference and pressure loss of the mass on the floor and ensures that all pipes are evenly loaded on the floor.
  • ⁇ H corresponds to the natural decrease in level in the flow from the outside, ie from the reactor wall 22, to the inside. example
  • a paste of the reactants PTA and diol or the liquid carboxyester and diol at a temperature of 150 ° C. with molar ratios between 0.8 and 1.8 are injected into a first chamber with the temperature of 20-90 ° C.
  • Existing monomer / prepolymer reaction mass is intensively mixed in the heat exchanger with product recirculated from the hydrocyclone and at least one catalyst.
  • reaction mass is further degassed in a connected hydrocyclone at pressures between 500 and 3000 hPa.
  • any inert medium or one of the purified gaseous by-products (superheated) can be used as the carrier gas.
  • the product is passed through at least two or a plurality of steam-stirred integrated trays with a residence time of between 5 and 15 minutes, the temperature increasing continuously in steps of 1 to 20 ° C. and the pressure increasing continuously by 5 to 50 hPa per tray. le is reduced.
  • the vapors generated by continuing the reaction are in an unsaturated gaseous state and are introduced below the liquid surface of the following bowl, while the product flows into the following container in a liquid-tight manner.
  • the vapors promote the removal of the reaction side products by intensive mixing with the primary product.
  • dried inert gas or process gas can be admitted into the first shell in order to further improve the progress of the reaction by saturating steam and gas.
  • the available reaction progress is between 10 and 40% for the simultaneous reactions between carboxyl and hydroxyl groups as well as ester end groups.
  • the product is transferred to another flash tank, in which the pressure is 1/5 to 1/50 lower than in the last steam-stirred tank and the reaction temperature is raised by 2 to 20 ° C.
  • the resulting polyesters have a chain length of 5-20, preferably between 10 and 15 Repeat units with sales of more than 99.5%.
  • the product remains in the system for between 2 and 10 minutes.
  • the polymer is transferred to a polycondensation reactor, in which a PG of 80-150 is achieved.
  • a suitable reactor is described for example in US 5,779,986 and EP 0 719 582.
  • the product pumped off after 2 to 10 minutes can be processed into granules, which can then be further heat-treated in the solid state in order to obtain a polymer with a PG of 90-200.
  • Both polymers manufactured according to items 1-11 as well as items 1-10 and item 12 are excellently suitable for fiber-forming processes, as a resin for bottle applications, especially for "still water", and for film-forming and technical plastic applications. Among other things, they stand out due to an improved yellowness level by up to 2.5 points according to CIELAB (b * value) and an improved whiteness level (L * value) by up to 5 points.
  • the device according to the invention therefore represents a new concept which is advanced in its features.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un réacteur à colonne, ainsi que son utilisation pour produire du polyester à poids moléculaire élevé, par exemple du polyéthylène téréphtalate (PET), du polybutylène téréphtalate (PBT), du polynaphtalène téréphtalate (PEN), du polytriméthylène téréphtalate (PTT) et/ou des polyesters d'autres acides dicarboxyliques et diols, copolymères compris. Le réacteur à colonne selon l'invention est un réacteur à colonne à un étage.
EP04791054A 2003-10-31 2004-10-29 Reacteur a colonne et son utilisation pour produire en continu du polyester a poids moleculaire eleve Withdrawn EP1678236A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10351085A DE10351085A1 (de) 2003-10-31 2003-10-31 Turmreaktor sowie dessen Verwendung zur kontinuierlichen Herstellung von hochmolekularem Polyester
PCT/EP2004/012297 WO2005042615A1 (fr) 2003-10-31 2004-10-29 Reacteur a colonne et son utilisation pour produire en continu du polyester a poids moleculaire eleve

Publications (1)

Publication Number Publication Date
EP1678236A1 true EP1678236A1 (fr) 2006-07-12

Family

ID=34530015

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04791054A Withdrawn EP1678236A1 (fr) 2003-10-31 2004-10-29 Reacteur a colonne et son utilisation pour produire en continu du polyester a poids moleculaire eleve

Country Status (7)

Country Link
US (1) US7608225B2 (fr)
EP (1) EP1678236A1 (fr)
KR (1) KR100948229B1 (fr)
CN (1) CN100491439C (fr)
DE (1) DE10351085A1 (fr)
RU (1) RU2275236C2 (fr)
WO (1) WO2005042615A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013120989A2 (fr) 2012-02-17 2013-08-22 Uhde Inventa-Fischer Gmbh Procédé de préparation d'un polyester ou copolyester hétéroaromatique de poids moléculaire élevé

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10351085A1 (de) 2003-10-31 2005-06-16 Inventa-Fischer Gmbh & Co. Kg Turmreaktor sowie dessen Verwendung zur kontinuierlichen Herstellung von hochmolekularem Polyester
US7943036B2 (en) 2009-07-21 2011-05-17 Chevron U.S.A. Inc. Systems and methods for producing a crude product
US7872090B2 (en) * 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
KR20110007186A (ko) 2008-04-15 2011-01-21 바스프 에스이 생분해성 폴리에스테르의 연속 제조 방법
KR101543489B1 (ko) 2008-04-15 2015-08-10 바스프 에스이 생분해성 폴리에스테르의 연속 제조 방법
US7931797B2 (en) * 2009-07-21 2011-04-26 Chevron U.S.A. Inc. Systems and methods for producing a crude product
US8236169B2 (en) * 2009-07-21 2012-08-07 Chevron U.S.A. Inc Systems and methods for producing a crude product
US9068132B2 (en) 2009-07-21 2015-06-30 Chevron U.S.A. Inc. Hydroprocessing catalysts and methods for making thereof
US8759242B2 (en) 2009-07-21 2014-06-24 Chevron U.S.A. Inc. Hydroprocessing catalysts and methods for making thereof
US8927448B2 (en) 2009-07-21 2015-01-06 Chevron U.S.A. Inc. Hydroprocessing catalysts and methods for making thereof
CN102549072B (zh) 2009-10-15 2014-10-29 巴斯夫欧洲公司 连续生产聚酯混合物的方法
US8802587B2 (en) 2010-12-30 2014-08-12 Chevron U.S.A. Inc. Hydroprocessing catalysts and methods for making thereof
BR112013031805A2 (pt) * 2011-06-10 2017-01-24 Invista Tech Sarl sistemas e métodos de pré-polimerizador de fluxo ascendente com pressão variável
CN102585191B (zh) * 2012-01-13 2014-10-22 华东理工大学 塔式反应器及其连续生产聚酯多元醇的应用
EP2660270B1 (fr) 2012-04-30 2023-10-25 HDC POLYALL Co., Ltd. Procédé de séparation de substances volatiles à base de mélanges de matières ainsi que dispositif de fabrication de sulfures de polyarylènes
CN102775589B (zh) * 2012-08-17 2014-06-25 江苏长乐纤维科技有限公司 一种聚酯工艺塔系统
DE102012111445A1 (de) * 2012-11-26 2014-05-28 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Reaktor zum Herstellen oder Behandeln einer Polymerschmelze
EP2969179A2 (fr) * 2013-03-15 2016-01-20 Invista Technologies S.A R.L. Appareil d'estérification de thermosiphon
WO2014210276A1 (fr) * 2013-06-28 2014-12-31 Uop Llc Dispositif de mélange de fluides et de distribution et procédé pour des réacteurs à lits multiples
WO2015199798A2 (fr) 2014-04-22 2015-12-30 Plastipak Packaging, Inc. Pastille et précurseur contenant de la matière recyclée
WO2016045020A1 (fr) * 2014-09-24 2016-03-31 中国纺织科学研究院 Système de mise en œuvre de réaction d'échange, système de production de polyester modifié comprenant celui-ci, procédé de production de polyester modifié et produit de type fibre de polyester modifié
CN104277212B (zh) * 2014-09-28 2015-09-30 浙江古纤道新材料股份有限公司 四釜聚合装置及其工艺
US10344119B2 (en) * 2015-01-30 2019-07-09 Sabic Global Technologies B.V. Continuous process for making polybutylene terephthalate using purified terephthalic acid and 1,4-butane diol
WO2018093823A1 (fr) 2016-11-15 2018-05-24 Sabic Global Technologies B.V. Procédés de formation de compositions polymères réticulées dynamiques à l'aide d'allongeurs de chaînes fonctionnels dans un processus continu
ES2876266T3 (es) 2017-05-31 2021-11-12 Basf Se Poliéster alifático-aromático con elevado Indice de Grado de Blancura
KR20200085337A (ko) 2017-11-20 2020-07-14 바스프 에스이 지방족 폴리에스테르의 정제 방법
WO2019096918A1 (fr) 2017-11-20 2019-05-23 Basf Se Procédé continu de production d'un polyester aliphatique
WO2020234294A1 (fr) * 2019-05-22 2020-11-26 Basf Se Procédé continu de production d'un polyester aliphatique-aromatique
KR20220012897A (ko) * 2019-05-22 2022-02-04 바스프 에스이 지방족-방향족 폴리에스테르의 정제 방법
CN110548467B (zh) * 2019-08-13 2020-09-15 绍兴大兴锅炉容器有限公司 一种基于特种橡胶绿色化生产的反应釜
CN113583227B (zh) * 2021-07-15 2023-07-28 江苏志成新材料科技有限公司 一种全连续可降解聚酯的生产系统

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US531955A (en) * 1895-01-01 Burglar-alarm
US2761889A (en) * 1952-09-17 1956-09-04 Exxon Research Engineering Co Suspension-type polymerization process
DE2504258A1 (de) * 1975-02-01 1976-08-05 Dynamit Nobel Ag Verfahren und apparatur zur herstellung von oligomeren alkylenterephthalaten
DE3544551C2 (de) 1985-12-17 2002-02-28 Zimmer Ag Verfahren zur kontinuierlichen Herstellung von hochmolekularem Polybutylenterephthalat
US5310955A (en) * 1991-01-18 1994-05-10 The Dow Chemical Company Vertical continuous reactor and process for liquid epoxy resin
US5469914A (en) * 1993-06-14 1995-11-28 Tranter, Inc. All-welded plate heat exchanger
DE59505196D1 (de) * 1994-12-30 1999-04-08 Fischer Karl Ind Gmbh Reaktorvorrichtung für fliessfähige und höherviskose Medien
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
DE10351085A1 (de) 2003-10-31 2005-06-16 Inventa-Fischer Gmbh & Co. Kg Turmreaktor sowie dessen Verwendung zur kontinuierlichen Herstellung von hochmolekularem Polyester

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005042615A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013120989A2 (fr) 2012-02-17 2013-08-22 Uhde Inventa-Fischer Gmbh Procédé de préparation d'un polyester ou copolyester hétéroaromatique de poids moléculaire élevé
DE102012003417A1 (de) 2012-02-17 2013-08-22 Uhde Inventa-Fischer Gmbh Verfahren zur Herstellung eines hochmolekularen, heteroaromatischen Polyesters oder Copolyesters

Also Published As

Publication number Publication date
CN1867607A (zh) 2006-11-22
RU2004110060A (ru) 2005-10-10
US20070116615A1 (en) 2007-05-24
KR20060094532A (ko) 2006-08-29
WO2005042615A1 (fr) 2005-05-12
DE10351085A1 (de) 2005-06-16
KR100948229B1 (ko) 2010-03-18
US7608225B2 (en) 2009-10-27
CN100491439C (zh) 2009-05-27
RU2275236C2 (ru) 2006-04-27

Similar Documents

Publication Publication Date Title
EP1448658B1 (fr) Procede de production continue de polyester macromoleculaire et dispositif pour mettre en oeuvre celui-ci
EP1678236A1 (fr) Reacteur a colonne et son utilisation pour produire en continu du polyester a poids moleculaire eleve
DE102006025942B4 (de) Verfahren zur kontinuierlichen Herstellung von hochmolekularen Polyestern durch Veresterung von Dicarbonsäuren und/oder Umesterung von Dicarbonsäuren mit Diolen und/oder deren Mischungen sowie Vorrichtung hierzu
DE60006005T3 (de) Kontinuierliches verfahren zur herstellung von poly(trimethylenterephthalat)
JP2005519141A5 (fr)
EP0000918A2 (fr) Procédé pour la préparation de polyesters linéaires de haut poids moléculaire
DE1958777C3 (de) Verfahren zur kontinuierlichen Herstellung von Polyestern
DE2504258A1 (de) Verfahren und apparatur zur herstellung von oligomeren alkylenterephthalaten
WO2013092554A1 (fr) Procédé de polycondensation en phase solide
WO2002087723A1 (fr) Reacteur pour reactions gaz/liquide ou gaz/liquide/solide
DE2557580A1 (de) Verfahren und vorrichtung zur herstellung von polykondensaten
DE2014818A1 (de) Verfahren und Vorrichtung zur kon tinuierlichen Herstellung von Polyester kunststoffen
WO2007085433A1 (fr) Procede d’esterification d’acide terephtalique avec du butanediol, procede de fabrication de polybutylene terephtalate et dispositif associe
US7300999B2 (en) Method of making polyesters
WO2006060930A1 (fr) Procede et dispositif pour produire un granulat et/ ou des pieces moulees en polyester a faible teneur en acetaldehyde
DE1520284A1 (de) Kontinuierliches Verfahren zur Herstellung von Polyaethylenterephthalat mit faserbildenden Eigenschaften
DE2738093B1 (de) Verfahren und Vorrichtung zur Herstellung von linearen hochmolekularen Polyestern
MXPA06003983A (en) Tower reactor and use thereof for the continuous production of high molecular weight polyesters

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060315

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UHDE INVENTA-FISCHER GMBH

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: ATLAS, CHRISTIAN

Inventor name: SCHULZ VAN ENDERT, EIKE

17Q First examination report despatched

Effective date: 20140603

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20180501