WO2017222956A1 - Method and apparatus for crystallizing and increasing molecular weight of polymer particles - Google Patents

Method and apparatus for crystallizing and increasing molecular weight of polymer particles Download PDF

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Publication number
WO2017222956A1
WO2017222956A1 PCT/US2017/038076 US2017038076W WO2017222956A1 WO 2017222956 A1 WO2017222956 A1 WO 2017222956A1 US 2017038076 W US2017038076 W US 2017038076W WO 2017222956 A1 WO2017222956 A1 WO 2017222956A1
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Prior art keywords
particles
pet
pet particles
solid
cooling liquid
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Ceased
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PCT/US2017/038076
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French (fr)
Inventor
Jan DE REN
Stephan Dietmer WILHELMI
Roel Julia Julien BAUTERS
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Honeywell UOP LLC
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UOP LLC
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Application filed by UOP LLC filed Critical UOP LLC
Priority to RU2018129882A priority Critical patent/RU2685299C1/en
Priority to RU2018129882K priority patent/RU2748939C1/en
Priority to CN201780011294.XA priority patent/CN108602961B/en
Publication of WO2017222956A1 publication Critical patent/WO2017222956A1/en
Priority to US16/206,992 priority patent/US10940613B2/en
Anticipated expiration legal-status Critical
Priority to US17/130,947 priority patent/US11298853B2/en
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G63/80Solid-state polycondensation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/16Auxiliary treatment of granules
    • 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
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • C08G63/183Terephthalic acids
    • 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
    • C08G63/88Post-polymerisation treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26DRYING
    • F26BDRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00Drying solid materials or objects by processes not involving the application of heat
    • F26B5/08Drying solid materials or objects by processes not involving the application of heat by centrifugal treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/16Auxiliary treatment of granules
    • B29B2009/165Crystallizing granules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003PET, i.e. poylethylene terephthalate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to forming and crystallizing low molecular weight polymer particles. More particularly, this invention relates to a method and apparatus for extruding, cutting and crystallizing polymer particles with a molecular weight increasing process afterwards.
  • Polymer resins are molded into a variety of useful products.
  • Useful polymer resins include aromatic polyesters of which polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polytrimethylene naphthalate (PTN), polycyclohexyl terephthalate (PCT) and polyethylene naphthalate (PEN) are examples.
  • Polyester resins particularly PET, copolymers of terephthalic acid with lower proportions of isophthalic acid and PBT are used in the production of beverage containers, films, fibers, packages and tire cord.
  • Polyester resin is conventionally produced in a melt phase polymerization (MPP) process with relatively low molecular weight inadequate for commercial uses.
  • MPP melt phase polymerization
  • the molecular weight of MPP product must be upgraded. Consequently, the MPP product is formed into particles and subjected to solid state poly condensation (SSP) to increase its molecular weight by maintaining the solid polymer particles at temperatures between the glass transition and the melting point temperatures while removing the reaction products under an inert gas sweep or vacuum.
  • SSP solid state poly condensation
  • Molten polyester resin from the MPP is typically extruded under pressure and cut into small particles.
  • US 4,436,782 discloses a machine for forming molten pellets of PET and quenching the pellets in water.
  • UK 1, 143,182 teaches a die-face polymer cutter with the die face submerged in water to immediately quench pellets upon forming.
  • WO 00/23497 discloses extruding the molten polymer into strands, quenching the strands in cooling liquid and cutting the strands into polymer particles.
  • the granulate-liquid mixture is cooled down to around 60°C, admixed with a cooler liquid, and depressurized after which the granulate is separated from liquid.
  • the present invention is a process and apparatus for a SSP process that does not require re-heating the PET pellets after they are cut and crystallized in the UWC section.
  • a first embodiment of the invention is a process for making PET particles comprising a PET melt having a temperature of 230°C to 310°C; cutting the molten PET particles into pellets while quenching with a cooling liquid; drying the solid PET particles; passing the solid PET particles to a crystallization bin wherein crystallization of the particles takes place, resulting in a temperature increase and crystallization of the PET particles which forms from core to surface; and contacting the solid PET particles with hot inert gas.
  • FIG. 1 is a schematic view of the present invention.
  • the present invention can be used for forming molten polymer into particles if the polymer must be cooled after it is formed into a desired shape.
  • the polymer of the present invention is preferably a crystallizable thermoplastic polymer. Polyester polymer is particularly suitable for the present invention and PET polymer is preferred. Copolymers of PET and other polyesters are also suitable.
  • Description of the present invention will be made with respect to FIG 1.
  • the present invention comprises a particulation and quench system 1 serviced by cooling liquid, a crystallization and transportation section 2 serviced by an inert gas or air and an SSP reactor system 3 serviced by a hot inert gas.
  • the particulation and quench system 1 comprises a molding device 12 that receives polymer resin from a line 11.
  • the resin in the line 11 is either already molten or the molding device 12 heats it above the melting temperature to put the polymer into the molten state.
  • Any of several ways can be used to form the molten polymer into particles. However, it is important that the polymer particles spend relatively little time in the quench liquid and the time between particles forming and entry into the warming liquid be minimized.
  • the die-face polymer cutter of GB 1, 143,182 is preferred for minimizing cooling before warming.
  • the molten polymer resin enters a pressurized chamber and is extruded though an orifice plate whose face is swept by a rotating cutter.
  • the extruded polymer enters a cooling chamber 14 through the orifices and is cut into polymer particles while quenched under pressurized cooling liquid delivered through an inlet into the chamber 14 by a line 17.
  • the cooling liquid entering in line 17 is water.
  • the cooling liquid solidifies the exterior of the polymer particles while preferably leaving the interior molten.
  • the polymer particles in the cooling liquid will be transported from the cooling chamber 14 directly to a cooling liquid removal device 16.
  • the cooling liquid removal device may include an elbow-shaped profile screen, a dewatering cone, a centrifuge or a hydrocyclone which quickly removes polymer particles from a substantial amount of the cooling liquid.
  • the centrifuge of the cooling liquid removal device revolves at high speed to separate the cooling liquid removed from the top thereof in a line and the polymer solids removed in a line. Higher efficiency of the separation in the cooling liquid removal device will result in higher conservation of heat in the polymer particles. Centrifuges may achieve 90% efficiency in separating liquid from solids whereas static devices may only be 60% efficient.
  • the objective of the cooling liquid in the line 15 will be to facilitate forming of the polymer into solid particles which requires a lower temperature to solidify the particle exterior while not reducing the average bulk temperature of the polymer below the desired temperature for molecular weight increasing reactions for the polymer.
  • the combination of the cooling liquid temperature and the residence time of the polymer particles in the cooling liquid between the cooling chamber 14 through the cooling liquid removal device 16 should operate such that the average bulk temperature of the polymer will not go below this temperature.
  • the temperature of the molten polymer before quenching will be above 260°C and preferably at least 270°C.
  • the temperature of the cooling liquid will typically be no more than 100°C for PET. However, higher temperatures may be used at suitably higher pressures to avoid liquid boiling.
  • Cooling liquid may be selected from any compatible material, preferably those which have compatibility with the polyester resin and introduce minimal degradation.
  • the cooling liquid is preferably water and may include additives such as ethylene glycol to raise the boiling point. However, other liquids such as related glycols may be added.
  • the relationship of the temperature of a polymer to the amount of cooling to which it is subjected by the cooling liquid is shown in Formula (2):
  • Tq is the average bulk temperature of the resin particle after it is removed from the cooling liquid
  • m is the mass flow rate of the resin
  • Cp resm is the average heat capacity of resin
  • T mo i ten is the temperature of molten polymer leaving the melt phase process in the line 11 and entering the molding device 12.
  • the molding device 12, cooling chamber 14, cooling liquid removal device 16 and the screen catcher 18 (which is optional, thereby being indicated in dashed lines in FIG. 1) of the particulation and quench section are integrally united to each other to minimize polymer cooling time and more easily maintain pressure. It is also contemplated the screen catcher may be omitted in which case the liquid removal device 16 and the crystallization bin 20 would be integrally united. Conduits connecting the units are also contemplated, but relatively long conduits will increase the degree of cooling which is undesirable.
  • the crystallization section 2 begins with a conduit or line 19 that delivers the particles to a crystallization bin 20 in which sufficient residence time may be given to allow the polymer particles to crystallize to the desired level.
  • the desired level of crystallinity for the polymer with respect to further solid stating is defined as that minimum percent crystallinity which is high enough so that further exothermic heat release in the solid stating reactor is not likely. The exact level may differ between resins.
  • the percent crystallinity is typically estimated from the density of the granule by its buoyancy in a gradient density column according to ASTM D 1505-98 "Standard Test Method for the Density of Plastics by Density-Gradient Technique", assuming 0% crystallinity (completely amorphous resin) to have a density of 1.332 g/cc and 100% crystallinity to have density of 1.455 g/cc.
  • a typical value for resin crystallinity suitable for PET copolymer in a downstream SSP is 30 % to 50 %.
  • a line 21 delivers the polymer particles to the inlet of a riser 24 which transports the polymer particles up to an elevation near the top of an SSP reactor system while giving the polymer particles sufficient time to crystallize.
  • the transport riser 24 operates in plug-flow, using a gas supplied via line 23, and, in an embodiment, with a minimum of a one-minute residence time. Shorter residence times are contemplated.
  • the gas from line 23 is preferably hot and inert, such as nitrogen, to reduce cooling and undesirable side-reactions. Other gasses are contemplated.
  • a line 25 delivers the effluent from an outlet of the riser 24 directly to the SSP reactor. At this point the polymer particles have achieved a crystallization roughly between 30 and 50% based on density measurement.
  • the crystalline polymer particles are delivered to the SSP reactor 30 in system 3.
  • the polymer particles entering the SSP reactor system 3 are at a temperature of 190°C to 220°C and preferably 210°C which is the preferred inlet temperature of polymer particles entering an SSP reactor 30.
  • the SSP reactor 30 is preferably a downwardly flowing SSP reactor, but a batch SSP reactor may be suitable.
  • Polymer particles move downwardly in the SSP reactor 30 counter-currently to the flow of hot inert gas, which is preferably nitrogen, to upgrade the molecular weight to the degree of polymerization of the polymer particles.
  • Inert gas may enter through a line 39 while upgraded polymer particles exit the SSP reactor 30 through a line 31.
  • a lock hopper (not shown) may be used to enable removal of the particles without depressurizing the system.
  • a cooling device 32 may be applied to cool the particles, using a cooling medium supplied by a line 35. The particles exit this device through an effluent line 33.
  • the flow scheme of FIG. 1 may operate to obviate the need for cooling device 32 and deliver the upgraded polymer particles from the SSP reactor 30 directly to effluent line 33.
  • a line 37 brings the inert gas to a gas purification and recycle system 38, preferably including a nitrogen purification unit (NPU) as described in patent EP 0660746B2, which has an effluent in line 39 that is brought back to the SSP reactor 30.
  • NPU nitrogen purification unit
  • the inert gas can be supplied from the same purification system 38 to the transporting riser 24 via line 23 (not shown).
  • the flow scheme of the present invention operates to minimize or eliminate the heating of the polymer particles, thus minimizing the added crystallization layer that is formed when the polymer particles are re-heated.
  • the present invention is advantageous because by obviating the extra crystalline layer, diffusion of by-products and reduced molecular weight increasing reactions are strongly mitigated.
  • Table 1 demonstrates the benefits of the process claimed in this invention.
  • the SSP process claimed results in significant quality and flexible improvement in SSP operation, which also results in significant OPEX savings as demonstrated in Table 1.
  • the formation of a crystalline layer at the outside of the PET pellet is prevented. Therefore, the AA diffusion is not inhibited as compared to the UWC SSP concept where reheating results in a higher allowable AA content in the SSP feed.
  • the final crystallinity of the PET pellets will be significantly lower than compared to other SSP concepts, resulting in energy savings for preform producers.
  • Lower crystallinity results in heating energy savings for producing preforms, since the lower the crystallinity requires less heat to deform the structure, due to less rigid initial morphology.
  • Resin clogging behavior is further reduced by having a higher initial driving force (higher PET pellet resin temperature of 30° to 60°C, compared to the existing under water cutting process) which results in more homogenous crystallization behavior and consequently mitigates downstream exothermic re-crystallization, which could result in clogging.
  • a reactivity similar to the conventional gravity flow SSP processing is expected, since as already mentioned, the crystalline layer formation in avoided in the claimed SSP process.
  • high temperature under water cutting and avoidance of reheating results in superior, homogenous properties of the PET pellets compared to other SSP concepts.
  • the high temperature cutting is a driving force that ensures homogeneous crystallization, and the obviation of reheating results in a single crystallization regime (from inside to outside).
  • a first embodiment of the invention is a process for making PET particles comprising a PET melt having a temperature of 230°C to 310°C; cutting the molten PET into particles while quenching with a cooling liquid; drying the solid PET particles; passing the solid PET particles to a crystallization bin wherein crystallization of the particles takes place, resulting in a temperature increase; and contacting the solid PET particles with hot inert gas or air.
  • a second embodiment of the invention is a process for making PET particles as in claim 1, further comprising transporting the solid PET particles upwardly to the top of a SSP reactor with hot inert gas.
  • a third embodiment of the invention is a process for making PET particles as in claim 1, wherein the cooling liquid has a temperature from 60°C to 140°C.
  • a fourth embodiment of the invention is a process for making PET particles as in claim 1, wherein the cooling liquid has a contact time of 0.01 seconds to 5 seconds to obtain solid PET particles.
  • a fifth embodiment of the invention is a process for making PET particles as in claim 1, wherein drying the solid PET particles comprises a physical separation using a centrifugal dryer.
  • a sixth embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein the solid PET particles include a temperature of 190°C to 220°C.
  • a seventh embodiment of the invention is a process for making PET particles as in claim 1, wherein a temperature increase ranging from 5°C to 10°C due to the exothermic
  • An eighth embodiment of the invention is a process for making PET particles as in claim 1, wherein passing the solid PET particles to a crystallization bin includes an outlet temperature of 190°C to 220°C.
  • a ninth embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein crystallization is caused by the residual heat from the PET melt.
  • An embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein the PET particles include a crystallinity of 30% to 50%.
  • An embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein PET particle crystallization forms from core to surface.
  • An embodiment of the invention is a process for making PET particles comprising a PET melt having a temperature of 230°C to 310°C; cutting the molten PET particles while quenching with a cooling liquid at a temperature that is from 60°C to 140°C having a contact time of 0.01 seconds to 5 seconds to obtain solid PET particles; drying the solid PET particles wherein the drying is a physical separation using a centrifugal dryer; passing the solid PET particles to a crystallization bin wherein the crystallization of the particles takes place, resulting in a temperature increase ranging from 5°C to 10°C due to the exothermic crystallization wherein the solid PET particles include a temperature of 190°C to 225°C and wherein the PET particles having a crystallinity of 30% to 50% wherein the crystallization is caused by the residual heat from the PET melt which results in a crystallization from a core to a surface of the PET particles; contacting the solid PET particles with hot inert gas; and transporting the solid PET particles upwardly
  • An embodiment of the invention is a process for making PET particles as in claim 12, further comprising a process to purify and recycle the inert gas exiting the SSP reactor.
  • An embodiment of the invention is a process for marking PET particles as in claim 12 or 13, wherein the inert gas has a temperature of 80°C to 220°C.
  • An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the residence time in the SSP reactor is 12 hours to 40 hours.
  • An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the temperature of SSP reactor is 190°C to 230°C.
  • An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the gas to solid ratio in the SSP reactor is 0.2 to 1.5.
  • An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the crystallinity at the outlet of the reactor is 38 to 60.
  • An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the temperature of the solid PET particles at the outlet of the reactor are 160°C to 220°C.
  • An embodiment of the invention is a process for making PET particles as in claim 13, wherein the process contains a nitrogen purification unit (PU) as described in patent EP066746B2 comprising of Adding an oxygen containing gas to the inert gas; Circulating the gas stream on a catalytic bed containing Pt or mixtures of Pt and Pd supported on an inert porous support at temperatures of 250°C to 600°C, characterized in that the quantity of oxygen used is stoichiometric with respect to the inorganic impurities or in such an excess that the gas at the outlet of the oxidation reactor contains up to 50 ppm of oxygen; Recycling the gas stream to the SSP reactor after a drying treatment to remove the water formed in the oxidation reactor.
  • PU nitrogen purification unit
  • An embodiment of the invention is a process for making PET particles as in claim 12, 13 or 20, wherein the inert gas is nitrogen or includes nitrogen.
  • An embodiment of the invention is a process for making PET particles as in claim 20 or 21, wherein air is used as an oxygen containing gas.
  • An embodiment of the invention is an apparatus for producing solid crystallized polymer particles comprising a molding device for forming molten polymer in a quenching chamber with a cooling liquid inlet for quenching the molten polymer in a cooling liquid to obtain solid polymer; a cooling liquid removal device in fluid communication with the quenching chamber for removing a substantial amount of the cooling liquid from the solid polymer; a crystallization bin; a pneumatic inert gas conveying system; and a SSP reactor with a countercurrent flow of inert gas.
  • An embodiment of the invention is an apparatus for producing solid crystallized polymer particles as in claim 23, further comprising a cooling device at the outlet of the SSP reactor.
  • An embodiment of the invention is an apparatus for producing solid crystallized polymer particles as in claim 23 or 24, further comprising an inert gas cleaning section, for example a nitrogen purification unit (NPU), as described in patent EP 0660746B2.
  • NPU nitrogen purification unit

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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Abstract

The present subject matter claims a process and apparatus for forming, crystallizing and increasing the molecular weight of polymer particles which does not require re-heating the polyethylene terephthalate (PET) pellets after they are cut and crystallized in the under water cutting (UWC) section. In the existing solid state polycondensation (SSP) technologies where an UWC is used, high crystallinity of the PET pellets can occur, by cooling and re-heating the PET pellets, which results in reduced removal efficiency of by-products, such as acetaldehyde (AA) and furthermore also a reduction of the reaction rates of molecular weight increasing reactions.

Description

METHOD AND APPARATUS FOR CRYSTALLIZING AND INCREASING
MOLECULAR WEIGHT OF POLYMER PARTICLES
PRIORITY CLAIM OF EARLIER NATIONAL APPLICATION
[0001] This application claims priority to U.S. Application No. 62/352,761 filed June 21, 2016, the contents of which cited application are hereby incorporated by reference in its entirety.
BACKGROUND
[0002] The present invention relates to forming and crystallizing low molecular weight polymer particles. More particularly, this invention relates to a method and apparatus for extruding, cutting and crystallizing polymer particles with a molecular weight increasing process afterwards.
[0003] Polymer resins are molded into a variety of useful products. Useful polymer resins include aromatic polyesters of which polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polytrimethylene naphthalate (PTN), polycyclohexyl terephthalate (PCT) and polyethylene naphthalate (PEN) are examples.
Polyester resins, particularly PET, copolymers of terephthalic acid with lower proportions of isophthalic acid and PBT are used in the production of beverage containers, films, fibers, packages and tire cord.
[0004] Polyester resin is conventionally produced in a melt phase polymerization (MPP) process with relatively low molecular weight inadequate for commercial uses. The molecular weight of MPP product must be upgraded. Consequently, the MPP product is formed into particles and subjected to solid state poly condensation (SSP) to increase its molecular weight by maintaining the solid polymer particles at temperatures between the glass transition and the melting point temperatures while removing the reaction products under an inert gas sweep or vacuum.
[0005] Molten polyester resin from the MPP is typically extruded under pressure and cut into small particles. US 4,436,782 discloses a machine for forming molten pellets of PET and quenching the pellets in water. UK 1, 143,182 teaches a die-face polymer cutter with the die face submerged in water to immediately quench pellets upon forming. WO 00/23497 discloses extruding the molten polymer into strands, quenching the strands in cooling liquid and cutting the strands into polymer particles.
[0006] According to US 4,064,112, the tendency of the particles to agglomerate due to stickiness during solid state poly condensation (SSP) can be reduced and even eliminated if the solid state polymerization is preceded by a crystallization step which comprises thermal treatment. A process described in US 5,540,868 forms low molecular weight polyester particles with a degree of crystallinity greater than 15% suitable for use as an SSP feedstock. US 5,290,913 discloses crystallizing PET particles in an agitated liquid bath and heating to crystallization temperature. US 5,532,335 and WO 00/23497 teach crystallizing polyesters in liquid over 100°C. Processes disclosed in US 6,740,733 B2, US 6,297,315 Bl and US 6,461,575 Bl separate relatively cool water used in pelletizing from PTT pellets and crystallize the pellets in relatively warm water at no more than 100°C. WO 00/23497 discloses cooling PET during or after forming and then crystallizing PET pellets at above 100°C.
[0007] The process in WO 2004/033174 entails granulating polymer in a liquid bath or immediately conducting granulate into a liquid bath with a temperature above 100°C.
Following crystallization, the granulate-liquid mixture is cooled down to around 60°C, admixed with a cooler liquid, and depressurized after which the granulate is separated from liquid.
[0008] US 6,749,821 shows that in a typical SSP process, polymer particles are delivered to an SSP reactor system through a hopper to a heated, fluidized bed pre-crystallizer operating to achieve a degree of crystallinity. The polymer particles are then fed into a first crystallizer and then optionally into a second crystallizer. The crystallizers heat the polymer particles under mechanical agitation to bring them to the desired reaction temperature and degree of crystallinity suitable for the ensuing SSP reactor. Polyester polymers undergo exothermic heat of crystallization if not crystallized to a sufficient degree. The continuance of the crystallization process in the SSP reactor leads to problems of heat release and
agglomerization or sintering of the particles, causing maldistribution of gases and solids flow interruptions. The inlet of the tall SSP reactor is high above the ground, so the particles will have to be lifted to the inlet to enter the SSP process. In industrial practice, this is usually by slow motion pneumatic conveying. [0009] In the existing SSP technologies where an under water cutter (UWC) is used, the following problems are frequently observed: high crystallinity of the PET pellets which results in reduced removal efficiency of acetaldehyde (AA) and furthermore also a reduction of the reaction rates of molecular weight increasing reactions. The aforementioned problems are assumed to be caused by re-heating of the PET pellets, thereby creating an extra crystalline layer at the surface of the resin which blocks the removal of AA and reduces the reaction rates by reducing the diffusion of byproducts such as ethylene glycol (EG), water (H2O) and AA. Next to the crystalline layer formation, the overall crystallinity of the PET pellet is significantly increased by re-heating. Therefore, there is a need to create a SSP process that does not require re-heating the PET pellets after they are cut and crystallized in the UWC section.
SUMMARY
[0010] The present invention is a process and apparatus for a SSP process that does not require re-heating the PET pellets after they are cut and crystallized in the UWC section.
[0011] A first embodiment of the invention is a process for making PET particles comprising a PET melt having a temperature of 230°C to 310°C; cutting the molten PET particles into pellets while quenching with a cooling liquid; drying the solid PET particles; passing the solid PET particles to a crystallization bin wherein crystallization of the particles takes place, resulting in a temperature increase and crystallization of the PET particles which forms from core to surface; and contacting the solid PET particles with hot inert gas.
BRIEF DESCRIPTION OF THE DRAWING
[0012] FIG. 1 is a schematic view of the present invention.
DETAILED DESCRIPTION
[0013] The present invention can be used for forming molten polymer into particles if the polymer must be cooled after it is formed into a desired shape. The polymer of the present invention is preferably a crystallizable thermoplastic polymer. Polyester polymer is particularly suitable for the present invention and PET polymer is preferred. Copolymers of PET and other polyesters are also suitable. [0014] Description of the present invention will be made with respect to FIG 1. The present invention comprises a particulation and quench system 1 serviced by cooling liquid, a crystallization and transportation section 2 serviced by an inert gas or air and an SSP reactor system 3 serviced by a hot inert gas. The particulation and quench system 1 comprises a molding device 12 that receives polymer resin from a line 11. The resin in the line 11 is either already molten or the molding device 12 heats it above the melting temperature to put the polymer into the molten state. Any of several ways can be used to form the molten polymer into particles. However, it is important that the polymer particles spend relatively little time in the quench liquid and the time between particles forming and entry into the warming liquid be minimized. However, the die-face polymer cutter of GB 1, 143,182 is preferred for minimizing cooling before warming.
[0015] In an embodiment, the molten polymer resin enters a pressurized chamber and is extruded though an orifice plate whose face is swept by a rotating cutter. The extruded polymer enters a cooling chamber 14 through the orifices and is cut into polymer particles while quenched under pressurized cooling liquid delivered through an inlet into the chamber 14 by a line 17. In the example shown in FIG. 1, the cooling liquid entering in line 17 is water. The cooling liquid solidifies the exterior of the polymer particles while preferably leaving the interior molten. The polymer particles in the cooling liquid will be transported from the cooling chamber 14 directly to a cooling liquid removal device 16. The cooling liquid removal device may include an elbow-shaped profile screen, a dewatering cone, a centrifuge or a hydrocyclone which quickly removes polymer particles from a substantial amount of the cooling liquid. The centrifuge of the cooling liquid removal device revolves at high speed to separate the cooling liquid removed from the top thereof in a line and the polymer solids removed in a line. Higher efficiency of the separation in the cooling liquid removal device will result in higher conservation of heat in the polymer particles. Centrifuges may achieve 90% efficiency in separating liquid from solids whereas static devices may only be 60% efficient.
[0016] The objective of the cooling liquid in the line 15 will be to facilitate forming of the polymer into solid particles which requires a lower temperature to solidify the particle exterior while not reducing the average bulk temperature of the polymer below the desired temperature for molecular weight increasing reactions for the polymer. Hence, the combination of the cooling liquid temperature and the residence time of the polymer particles in the cooling liquid between the cooling chamber 14 through the cooling liquid removal device 16 should operate such that the average bulk temperature of the polymer will not go below this temperature. The temperature of the molten polymer before quenching will be above 260°C and preferably at least 270°C. The temperature of the cooling liquid will typically be no more than 100°C for PET. However, higher temperatures may be used at suitably higher pressures to avoid liquid boiling. Cooling liquid may be selected from any compatible material, preferably those which have compatibility with the polyester resin and introduce minimal degradation.
[0017] The cooling liquid is preferably water and may include additives such as ethylene glycol to raise the boiling point. However, other liquids such as related glycols may be added. The relationship of the temperature of a polymer to the amount of cooling to which it is subjected by the cooling liquid is shown in Formula (2):
(Tmolten'Tq )*(mCpresin)= Qcooling (2) wherein, Tq is the average bulk temperature of the resin particle after it is removed from the cooling liquid, m is the mass flow rate of the resin, Cpresm is the average heat capacity of resin, QCOoling 1S tne neatst during the particulation and quenching step and Tmoiten is the temperature of molten polymer leaving the melt phase process in the line 11 and entering the molding device 12. In an embodiment, it is desirable to ensure that Tq remains above the temperature at which molecular weight increasing reactions take place at a considerable rate, which is 190°C for PET. In an embodiment, the molding device 12, cooling chamber 14, cooling liquid removal device 16 and the screen catcher 18 (which is optional, thereby being indicated in dashed lines in FIG. 1) of the particulation and quench section are integrally united to each other to minimize polymer cooling time and more easily maintain pressure. It is also contemplated the screen catcher may be omitted in which case the liquid removal device 16 and the crystallization bin 20 would be integrally united. Conduits connecting the units are also contemplated, but relatively long conduits will increase the degree of cooling which is undesirable.
[0018] The crystallization section 2 begins with a conduit or line 19 that delivers the particles to a crystallization bin 20 in which sufficient residence time may be given to allow the polymer particles to crystallize to the desired level. The desired level of crystallinity for the polymer with respect to further solid stating is defined as that minimum percent crystallinity which is high enough so that further exothermic heat release in the solid stating reactor is not likely. The exact level may differ between resins. The percent crystallinity is typically estimated from the density of the granule by its buoyancy in a gradient density column according to ASTM D 1505-98 "Standard Test Method for the Density of Plastics by Density-Gradient Technique", assuming 0% crystallinity (completely amorphous resin) to have a density of 1.332 g/cc and 100% crystallinity to have density of 1.455 g/cc. A typical value for resin crystallinity suitable for PET copolymer in a downstream SSP is 30 % to 50 %. A line 21 delivers the polymer particles to the inlet of a riser 24 which transports the polymer particles up to an elevation near the top of an SSP reactor system while giving the polymer particles sufficient time to crystallize. The transport riser 24 operates in plug-flow, using a gas supplied via line 23, and, in an embodiment, with a minimum of a one-minute residence time. Shorter residence times are contemplated. The gas from line 23 is preferably hot and inert, such as nitrogen, to reduce cooling and undesirable side-reactions. Other gasses are contemplated. A line 25 delivers the effluent from an outlet of the riser 24 directly to the SSP reactor. At this point the polymer particles have achieved a crystallization roughly between 30 and 50% based on density measurement.
[0019] The crystalline polymer particles are delivered to the SSP reactor 30 in system 3. The polymer particles entering the SSP reactor system 3 are at a temperature of 190°C to 220°C and preferably 210°C which is the preferred inlet temperature of polymer particles entering an SSP reactor 30. However, other temperatures may be suitable. The SSP reactor 30 is preferably a downwardly flowing SSP reactor, but a batch SSP reactor may be suitable. Polymer particles move downwardly in the SSP reactor 30 counter-currently to the flow of hot inert gas, which is preferably nitrogen, to upgrade the molecular weight to the degree of polymerization of the polymer particles. Inert gas may enter through a line 39 while upgraded polymer particles exit the SSP reactor 30 through a line 31. A lock hopper (not shown) may be used to enable removal of the particles without depressurizing the system. A cooling device 32 may be applied to cool the particles, using a cooling medium supplied by a line 35. The particles exit this device through an effluent line 33. However, in some conditions, the flow scheme of FIG. 1 may operate to obviate the need for cooling device 32 and deliver the upgraded polymer particles from the SSP reactor 30 directly to effluent line 33. A line 37 brings the inert gas to a gas purification and recycle system 38, preferably including a nitrogen purification unit (NPU) as described in patent EP 0660746B2, which has an effluent in line 39 that is brought back to the SSP reactor 30. In some conditions, in which the gas used in the transporting riser 24 is inert, the inert gas can be supplied from the same purification system 38 to the transporting riser 24 via line 23 (not shown).
[0020] The flow scheme of the present invention operates to minimize or eliminate the heating of the polymer particles, thus minimizing the added crystallization layer that is formed when the polymer particles are re-heated. The present invention is advantageous because by obviating the extra crystalline layer, diffusion of by-products and reduced molecular weight increasing reactions are strongly mitigated.
EXAMPLES
[0021] The following examples listed in table 1 are intended to further illustrate the subject embodiments. These illustrations of different embodiments are not meant to limit the claims to the particular details of these examples.
TABLE 1
PET Resin Conventional UWC Indirect UWC Direct SSP Product Properties SSP (existing) SSP (existing) (patent application
IV SSP in // out 0,55-0,64 dL/g // 0,78- 0,60-0,64 dL/g // 0,78-0,86 0,55-0,75 dL/g // 0,78-0,86
0,86 dL/g dL/g dL/g
AA in CP melt Max. 100 ppm Max. 50-70 ppm Max. 70 ppm
AA SSP RX in Max. 20 ppm Max. 15 ppm Max. 20 ppm
AA SSP RX out < 1 ppm < 1 ppm < 1 ppm
Crystallinity SSP in (after 0-10 % 38-42 % 38-42 % cutting)
Crystallinity SSP RX in 40-45 % 42-45 % 38-42 %
Crystallinity SSP RX out 50-55 % 55-65 % 38-60 %
Resin Clogging behavior Limitation 210-215 °C Limitation 210-215 °C Limitation 225 °C during SSP
Reactivity @ 205 °C 0,0145 dL/g*h 0,0120 - 0,0140 dL/g*h 0,0145 dL/g*h
(due to layer creation) (no layer creation)
Crystalline layer appearing? No Yes No
Heat for polycondensation From Outside From Inside & Outside From Inside reactions
Electrical Energy 60 kWh/ton 42 kWh/ton 29 kWh/ton (fluidized bed Consumption cooler)
(600 MTD) 13kwh/ton (static cooler)
Heat Energy Consumption 63 kWh/ton 20 kWh/ton 8 kWh/ton (600 MTD)
[0022] Table 1 demonstrates the benefits of the process claimed in this invention. The SSP process claimed results in significant quality and flexible improvement in SSP operation, which also results in significant OPEX savings as demonstrated in Table 1. By avoiding the polyester resin reheating steps, the formation of a crystalline layer at the outside of the PET pellet is prevented. Therefore, the AA diffusion is not inhibited as compared to the UWC SSP concept where reheating results in a higher allowable AA content in the SSP feed.
Furthermore, also by avoiding the formation of the crystalline layer, the final crystallinity of the PET pellets will be significantly lower than compared to other SSP concepts, resulting in energy savings for preform producers. Lower crystallinity results in heating energy savings for producing preforms, since the lower the crystallinity requires less heat to deform the structure, due to less rigid initial morphology.
[0023] Resin clogging behavior is further reduced by having a higher initial driving force (higher PET pellet resin temperature of 30° to 60°C, compared to the existing under water cutting process) which results in more homogenous crystallization behavior and consequently mitigates downstream exothermic re-crystallization, which could result in clogging. A reactivity similar to the conventional gravity flow SSP processing is expected, since as already mentioned, the crystalline layer formation in avoided in the claimed SSP process. Also, high temperature under water cutting and avoidance of reheating results in superior, homogenous properties of the PET pellets compared to other SSP concepts. The high temperature cutting is a driving force that ensures homogeneous crystallization, and the obviation of reheating results in a single crystallization regime (from inside to outside).
[0024] Further, as shown in Table 1, by eliminating the requirement for reheating, two pieces of standard process pre-conditioning equipment can be eliminated compared to the conventional gravity flow SSP processing. For example, it may be possible to eliminate equipment which was traditionally used to pre-condition the PET pellets to allow proper polycondensation in the countercurrent SSP reactor. The elimination of this equipment results in more than 50 % electrical consumption savings and almost 90% heat energy savings both compared to the original SSP gravity flow process. Compared to the UWC indirect SSP process, electrical energy savings are more than 40%, and the savings in heat energy are more than 50%. In addition to the OPEX being advantageous, elimination of the two pieces of preconditioning equipment also results in increased flexibility, by allowing direct connection to high IV CP concepts. As illustrated in Table 1, a SSP feed ranging from 0.55 dL/g to 0.75 dL/g can be processed, whereas in previous concepts, this range was not feasible.
[0025] It should be noted that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the spirit and scope of the present subject matter and without diminishing its attendant advantages.
SPECIFIC EMBODIMENTS
[0026] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
[0027] A first embodiment of the invention is a process for making PET particles comprising a PET melt having a temperature of 230°C to 310°C; cutting the molten PET into particles while quenching with a cooling liquid; drying the solid PET particles; passing the solid PET particles to a crystallization bin wherein crystallization of the particles takes place, resulting in a temperature increase; and contacting the solid PET particles with hot inert gas or air.
[0028] A second embodiment of the invention is a process for making PET particles as in claim 1, further comprising transporting the solid PET particles upwardly to the top of a SSP reactor with hot inert gas. A third embodiment of the invention is a process for making PET particles as in claim 1, wherein the cooling liquid has a temperature from 60°C to 140°C. A fourth embodiment of the invention is a process for making PET particles as in claim 1, wherein the cooling liquid has a contact time of 0.01 seconds to 5 seconds to obtain solid PET particles. A fifth embodiment of the invention is a process for making PET particles as in claim 1, wherein drying the solid PET particles comprises a physical separation using a centrifugal dryer.
[0029] A sixth embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein the solid PET particles include a temperature of 190°C to 220°C. A seventh embodiment of the invention is a process for making PET particles as in claim 1, wherein a temperature increase ranging from 5°C to 10°C due to the exothermic
crystallization takes place in the crystallization bin. An eighth embodiment of the invention is a process for making PET particles as in claim 1, wherein passing the solid PET particles to a crystallization bin includes an outlet temperature of 190°C to 220°C. A ninth embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein crystallization is caused by the residual heat from the PET melt.
[0030] An embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein the PET particles include a crystallinity of 30% to 50%. An embodiment of the invention is a process for making PET particles as in claim 1 or 2, wherein PET particle crystallization forms from core to surface.
[0031] An embodiment of the invention is a process for making PET particles comprising a PET melt having a temperature of 230°C to 310°C; cutting the molten PET particles while quenching with a cooling liquid at a temperature that is from 60°C to 140°C having a contact time of 0.01 seconds to 5 seconds to obtain solid PET particles; drying the solid PET particles wherein the drying is a physical separation using a centrifugal dryer; passing the solid PET particles to a crystallization bin wherein the crystallization of the particles takes place, resulting in a temperature increase ranging from 5°C to 10°C due to the exothermic crystallization wherein the solid PET particles include a temperature of 190°C to 225°C and wherein the PET particles having a crystallinity of 30% to 50% wherein the crystallization is caused by the residual heat from the PET melt which results in a crystallization from a core to a surface of the PET particles; contacting the solid PET particles with hot inert gas; and transporting the solid PET particles upwardly to the top of an SSP reactor with hot inert gas.
[0032] An embodiment of the invention is a process for making PET particles as in claim 12, further comprising a process to purify and recycle the inert gas exiting the SSP reactor. An embodiment of the invention is a process for marking PET particles as in claim 12 or 13, wherein the inert gas has a temperature of 80°C to 220°C. An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the residence time in the SSP reactor is 12 hours to 40 hours. An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the temperature of SSP reactor is 190°C to 230°C.
[0033] An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the gas to solid ratio in the SSP reactor is 0.2 to 1.5. An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the crystallinity at the outlet of the reactor is 38 to 60. An embodiment of the invention is a process for making PET particles as in claim 12 or 13, wherein the temperature of the solid PET particles at the outlet of the reactor are 160°C to 220°C.
[0034] An embodiment of the invention is a process for making PET particles as in claim 13, wherein the process contains a nitrogen purification unit ( PU) as described in patent EP066746B2 comprising of Adding an oxygen containing gas to the inert gas; Circulating the gas stream on a catalytic bed containing Pt or mixtures of Pt and Pd supported on an inert porous support at temperatures of 250°C to 600°C, characterized in that the quantity of oxygen used is stoichiometric with respect to the inorganic impurities or in such an excess that the gas at the outlet of the oxidation reactor contains up to 50 ppm of oxygen; Recycling the gas stream to the SSP reactor after a drying treatment to remove the water formed in the oxidation reactor. An embodiment of the invention is a process for making PET particles as in claim 12, 13 or 20, wherein the inert gas is nitrogen or includes nitrogen. An embodiment of the invention is a process for making PET particles as in claim 20 or 21, wherein air is used as an oxygen containing gas.
[0035] An embodiment of the invention is an apparatus for producing solid crystallized polymer particles comprising a molding device for forming molten polymer in a quenching chamber with a cooling liquid inlet for quenching the molten polymer in a cooling liquid to obtain solid polymer; a cooling liquid removal device in fluid communication with the quenching chamber for removing a substantial amount of the cooling liquid from the solid polymer; a crystallization bin; a pneumatic inert gas conveying system; and a SSP reactor with a countercurrent flow of inert gas.
[0036] An embodiment of the invention is an apparatus for producing solid crystallized polymer particles as in claim 23, further comprising a cooling device at the outlet of the SSP reactor. An embodiment of the invention is an apparatus for producing solid crystallized polymer particles as in claim 23 or 24, further comprising an inert gas cleaning section, for example a nitrogen purification unit (NPU), as described in patent EP 0660746B2.
[0037] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent
arrangements included within the scope of the appended claims.
[0038] In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.

Claims

CLAIMS:
1. A process for making PET particles comprising:
a PET melt having a temperature of 230°C to 310°C;
cutting the molten PET particles into pellets while quenching with a cooling liquid resulting in sold PET particles;
drying the solid PET particles;
passing the solid PET particles to a crystallization bin wherein crystallization of the particles takes place, resulting in a temperature increase; and
contacting the solid PET particles with hot inert gas or air.
2. The process for making PET particles as in claim 1, further comprising
transporting the solid PET particles upwardly to the top of a SSP reactor with hot inert gas.
3. The process for making PET particles as in claim 1, wherein the cooling liquid has a temperature from 60°C to 140°C.
4. The process for making PET particles as in claim 1, wherein the cooling liquid has a contact time of 0.01 seconds to 5 seconds to obtain solid PET particles.
5. The process for making PET particles as in claim 1, wherein drying the solid PET particles comprises a physical separation using a centrifugal dryer.
6. The process for making PET particles as in claim 1 or 2, wherein the solid PET particles include a temperature of 190°C to 215°C.
7. The process for making PET particles as in claim 1, wherein a temperature increase ranging from 5°C to 10°C due to the exothermic crystallization takes place in the crystallization bin.
8. The process for making PET particles as in claim 1, wherein passing the solid PET particles to a crystallization bin includes an outlet temperature of 190°C to 225°C.
9. The process for making PET particles as in claim 1 or 2, wherein crystallization is caused by the residual heat from the PET melt.
10. An apparatus for producing solid crystallized polymer particles comprising:
a molding device for forming molten polymer in a quenching chamber with a cooling liquid inlet for quenching said molten polymer in a cooling liquid to obtain solid polymer;
a cooling liquid removal device in fluid communication with said quenching chamber for removing a substantial amount of said cooling liquid from said solid polymer; a screen catcher;
a crystallization bin;
a pneumatic inert gas conveying system; and
an SSP reactor vessel with a countercurrent flow of inert gas.
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