CN101707889A - Method and apparatus for crystallizing polymer particles - Google Patents

Method and apparatus for crystallizing polymer particles Download PDF

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Publication number
CN101707889A
CN101707889A CN200780052944.1A CN200780052944A CN101707889A CN 101707889 A CN101707889 A CN 101707889A CN 200780052944 A CN200780052944 A CN 200780052944A CN 101707889 A CN101707889 A CN 101707889A
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polymer
liquid
temperature
cooling liquid
solid polymer
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CN101707889B (en
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J·F·麦吉
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Honeywell UOP LLC
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UOP LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/165—Crystallizing granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0041—Crystalline

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The present invention is a process and apparatus for conserving loss of heat while forming and crystallizing polymer particles in a liquid. The cooling liquid quenches the polymer during particle molding to facilitate shaping. The cooling liquid cools the polymer particles not below a temperature that allows adequate crystallization to occur. Cooling liquid is quickly switched with a warming liquid, so the temperature of the polymer is in the crystallization range and the heat of crystallization self-heats the polymer to a higher temperature.

Description

The method and apparatus that is used for crystallizing polymer particles
Background of invention
The present invention relates to form and crystallization low-molecular weight polymer particle.More particularly, the present invention relates to be used for to extrude, cut and at the method and apparatus of liquid medium crystallizing polymer particles.
Fluoropolymer resin is molded as multiple useful product.Useful fluoropolymer resin comprises aromatic polyester, and PET (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly-naphthalenedicarboxylic acid propylene diester (PTN), poly terephthalic acid cyclohexyl (PCT) and PEN (PEN) are the examples.In the preparation of container for drink, film, fiber, packing material and cotton tyre cord, use mylar, particularly PET, terephthalic acid (TPA) and than the copolymer and the PBT of the M-phthalic acid of small scale.
Mylar prepares in melt phase polymerization (MPP) technology, has lower molecular weight, is not enough to be used for commercial the application.Must improve the molecular weight of MPP product.Therefore, this MPP product is made particle and through solid state condensation (SSP) under inert gas purge or vacuum, to remove this product simultaneously and improve its molecular weight by this solid polymer particle being remained under the temperature between gamma transition and the melting temperature.
Typically will under pressure, extrude and cut into granule from the molten polyester resin of MPP.US 4,436, and 782 disclose the machinery that is used to form PET fusion spherolite and makes this spherolite chilling in water.GB 1,143, and 182 have instructed die face polymer cutting machine, and its die face is immersed in the water so that in a single day spherolite just forms chilling immediately.WO 00/23497 A1 discloses this molten polymer has been extruded bunchy, and should restraint in cooling liquid chilling and this bundle is cut into polymer beads.
According to US 4,064,112,, can reduce and even eliminate in solid state condensation (SSP) process because viscosity causes the tendency of particle aggregation if before this solid-state polymerization, comprise heat treated crystallisation step.US 5,540, and disclosed method has been made and has been suitable as the low molecular weight polyester particle that having of SSP raw material is higher than 15% degree of crystallinity in 868.US 5,290, and 913 disclose in the liquid bath of stirring the crystalline PET particle and have been heated to crystallization temperature.US5,532,335 and WO 00/23497A1 instructed crystalline polyester in surpassing 100 ℃ liquid.US 6,740,733B2, US 6,297,315 B1 and US 6,461, among the 575B1 disclosed method in will granulating used colder water separate with the PTT spherolite and make the crystallization in being no more than 100 ℃ the water of heat of this spherolite.WO 00/23497A1 discloses in forming process or has cooled off PET afterwards and make the PET spherolite be higher than 100 ℃ of crystallizations then.
Method among the WO 2004/033174A1 defines polymer to be granulated or immediately particle is imported to temperature and is higher than in 100 ℃ the liquid bath.After crystallization, this particle-liquid mixture is cooled to about 60 ℃, mix with coolant liquid and reduce pressure, then particle is separated from liquid.
US 6,749, and 821 have shown in typical SSP method, and polymer beads is transported in the SSP reactor assembly, enter the fluid bed pre-crystallizer of operation with the heating that realizes certain degree of crystallinity by hopper.Then this polymer beads is transported in first crystallizer, randomly enters second crystallizer then.Described crystallizer heats this polymer beads under mechanical agitation, so that it reaches the required reaction temperature and the crystallization degree of the SSP reactor that is applicable to subsequently.If there is not crystallization to arrive enough degree, polyester polymers bears the heat release of crystallization.In the SSP reactor, continue the problem that this crystallization process causes heat release and particle aggregation or sintering, cause the uneven and efflux of solids interruption of distribution of gas.The inlet of high SSP reactor is above the ground level, and makes this particle must rise to this inlet to enter SSP technology.In industrial practice, this is normally undertaken by the pneumatic conveying that slowly moves.
The fusing point T of polymer mPreferably the conduct of measuring by differential scanning calorimetric (DSC) records in the maximum that adds for the first time the fusion endothermic curve of pining for. glass transition temperature (T g) be flex point with the relevant step transition of the gamma transition on the DSC curve of 10 ℃/min heating.The average bulk temperature of polymer beads (average bulk temperature) is the mean temperature of most of this particle or in the temperature-averaging value of each position of this particle.Term " is measured or actual maximum crystalline rate temperature (T c) " be measuring definition well known in the prior art.T gAnd T mMensuration be described among the ASTM D-3419-99 " Standard Test Method forTransition Temperatures of Polymers by Differential Scanning Calorimetry ".
Can be by the maximum crystalline rate temperature of several method measuring (T c).A kind of this method is by the initial growth speed of polarized light microscopic examination from the spherulitic crystal structure of amorphous melt thin slice, carries out photographic measurement, and draws this speed with respect to the figure that applies temperature.This and additive method is described in J.M.Schultz, and " Polymer Crystallization:TheDevelopment of Crystalline Order in Thermoplastic Polymers " is among the 2001Oxford U.Press 127-139.
Can find the T of wide range of polymers in the literature cValue.According to US5,540,868, also can use formula (1) by calculating the mean value estimation T of gamma transition and melt temperature c: T c=(T g+ T m)/2 (1)
For the object of the invention, this T cValue is the reasonable approximation of the maximum crystalline rate temperature of reality.US 6,451, and 966B 1 has provided the approximate T for some available polyester gAnd T mValue, T in following table cCalculated value adds wherein. T g, T cAnd T mValue can have some variations with for example form, thermal history, molecular weight, humidity level and the primary crystallization degree along with polymer.For example, have 10～20 typically have 250 ℃ T than the PET of low polymerization degree m, 60 ℃ T gT with 155 ℃ cUS 5,744, and 578 have instructed in liquid than glass transition temperature (T g) high 20 ℃ to than melt temperature (T m) crystallization PEN under the temperature in low 10 ℃ the scope.
The objective of the invention is the new melt polymerization composition granule that forms of chilling in cooling liquid so that solidify the outside of this polymer beads and still keep the average bulk temperature of polymer beads in its scope with suitable speed crystallization simultaneously.
Another object of the present invention is to replace the aforementioned cooling liquid (cooling liquid) that comprises this solid polymer particle with the geothermal liquid (warming liquid) that adds of the temperature with the aforementioned average bulk temperature that is equal to or higher than this polymer.
Another object of the present invention is that the solid polymer particle in liquid upwards is transported in the SSP reactor assembly.
Another object of the present invention is the solid polymer crystallization that makes when being sent to the polymer in the liquid in the SSP reactor assembly in the liquid.
Summary of the invention
The present invention is the method and apparatus that is used for saving heat loss in liquid formation and crystallizing polymer particles. we found by temperature of regulating cooling liquid and the duration of cooling off in appropriate device, the average bulk temperature of this polymer beads can be reduced to be enough to extrude with cutting operation in effectively form the solid spherolite, but the average bulk temperature of this particle still is retained in the temperature range that rapid crystallization takes place.
With adding after geothermal liquid replaces cooling liquid, the temperature of this polymer is in this crystallization range, and the exothermic nature of this crystallization further is heated to higher temperature with this particle, and this has quickened the speed of crystallization.
In embodiments, the temperature that adds geothermal liquid is lower than the average bulk temperature of this polymer never, makes this add geothermal liquid and cools off this polymer never.The invention provides less owing to hot melt being cooled down fully and being heated the heat-energy losses of the hot melt that crystallization temperature causes then.In addition, in embodiments, most of crystallization occurs in this particle is sent to used adding in the geothermal liquid among the SSP, has reduced the essential process time.In addition, eliminated the needs of thermoplasticity fragment pneumatic conveying in the SSP, this has been avoided because the friction of hot fragment and the risk of the gathering that efflorescence causes.
Description of drawings
Accompanying drawing is a schematic diagram of the present invention.
The specific embodiment
If polymer must cool off after making required form, the present invention can be used for molten polymer is made particle so.The preferably crystallizable thermoplastic polymer of polymer of the present invention.Polyester polymers is specially adapted to the present invention, preferred pet polymer.The copolymer of PET and polyester also is suitable for.
Present invention is described with reference to the accompanying drawings.The present invention includes the granulation of cooling liquid service and chilling system 2, by the crystalline portion 4 and the SSP reactor assembly 6 that add the geothermal liquid service.This granulation and chilling system 2 comprise the device for molding 10 that receives fluoropolymer resin from pipeline 12.Resin in this pipeline 12 or fusionization, perhaps this device for molding 10 is heated and is higher than melt temperature so that this polymer becomes molten state.That can use several method makes particle with this molten polymer arbitrarily.Yet importantly this polymer beads will spend the short time in this quench liquid, and make to be formed into from particle and enter the time minimization that adds between the geothermal liquid.Yet GB 1,143, and the cooling before 182 die face polymer cutting machine is preferred for making and heats minimizes.In embodiments, the fluoropolymer resin of this fusion is entered pressurizing chamber 14, and extrude, skim over the surface of orifice plate with rotary knife cutter by orifice plate 16.The polymer of extruding enters cooling chamber 18 by the hole, and cuts into polymer beads, simultaneously chilling in the pressurized cooling fluid body that is transported to by pipeline 20 by inlet in this chamber 18.This cooling liquid solidifies the outside of this polymer beads, preferably makes its inside still be molten state simultaneously.Polymer beads in the cooling liquid preferably directly is sent to the screen cloth trap 22 from this cooling chamber 18.In this screen cloth trap 22, slanted screen net 24 has hole dimension to be passed through to allow maximum sized polymer beads, and will melt by pipeline 26 greater than this maximum sized particle is superseded again.Although not shown, this pipeline 26 can be transported to the polymer beads of eliminating in the lock hopper with continued operation pressure valve, to avoid the system pressure loss.Preferably directly enter cooling liquid removal device 28 by the cooling liquid of this slanted screen net 24 and the mixture of polymer beads.This cooling liquid removal device 28 can comprise ancon section sieve, dehydration cone, removes the centrifuge or the hydrocyclone of polymer beads fast from a large amount of cooling liquids.In embodiments, this cooling liquid removal device 28 is disc set centrifuges of being made by Alfa-LavalAB.Alternative centrifuge is by Dorr-Oliver Eimco, Ltd makes. and the centrifuge of this cooling liquid removal device 28 rotates at a high speed with the polymer solids during portion is removed to the cooling liquid in the pipeline 30 and is removed to pipeline 32 from it separately. and higher separative efficiency will cause heat reservation higher in the polymer beads in this cooling liquid removal device 28. and centrifuge can be realized 90% efficient in the separating of liquid and solid, and the efficient of staticizer only can have the cooling liquid of solid polymer particle to be used for promoting particle to flow out this centrifuge at pipeline 32 residue for 60%.. the target of the cooling liquid in the pipeline 20 is to help polymer to form particle, and this will need lower temperature the average bulk temperature of this polymer not to be reduced to the minimum crystallization temperature (T of this polymer with the cured granulate outside Cmin) under.The T of polymer CminBe spherulite growth rate less than 10% temperature of the maximum growth rate of this polymer.By under the polarized light effect, align the direct optical detection of the polymer samples of crystallization with hot platform microscope known in the art, measure the spherulite growth rate of little meter per second of considering with growth in thickness.Definition like this, the T of PET CminBe 120 ℃, compare T cLow 45 ℃.120 ℃ T CminUsually can be applied to all polyester in the context of the invention.Therefore, should operate chilled liquid temperature and polymer beads, make the average bulk temperature of this polymer will be not less than this T in cooling chamber 18 combination of the holdup time to the cooling liquid between this cooling liquid removal device 28 CminThe temperature of molten polymer before chilling will be higher than 260 ℃, preferably at least 270 ℃.For PET, the temperature of cooling liquid typically will be no more than 100 ℃.Yet, under the elevated pressures that is fit to, can use higher temperature to avoid liquid boiling.Cooling liquid can be selected from any compatible material, preferably has compatibility with this mylar and introduces those of least degrading.This cooling liquid is water preferably, can comprise additive, and ethylene glycol for example is to improve boiling point.Yet, also can add other liquid, for example ethylene glycol or relevant dihydroxylic alcohols are used for for example promoting crystallization.The temperature of polymer with cooling liquid as the formula (2) to the relation of its amount of cooling water of carrying out: (T Fusion-T q) * (mC The p resin)=Q Cooling(2) wherein, T qBe that m is the mass velocity of resin, C in the average bulk temperature of resin particle being removed afterwards and be immersed in this resin particle before adding in the geothermal liquid from cooling liquid The p resinBe the mean heat capacity of resin, Q CoolingBe the heat loss in granulation and quench step process, T FusionIt is the temperature of in pipeline 12, leaving this fusion phase technology and entering the molten polymer in this device for molding 10.In embodiments, desirable is to guarantee T qBe not reduced to T CminUnder (is 120 ℃ for PET).In embodiments, integrated each other so that polymer minimizes and easier keep-uping pressure cool time with device for molding 10, screen cloth trap 22 and cooling liquid removal device 28 integral body of this granulation and chilling part.Also be expected under the situation that this device for molding 10 and cooling liquid removal device 28 is integrated, this screen cloth trap 22 can omit.The pipeline that connects each parts is also expected, but the longer pipe road will improve the cooling degree, and this is unacceptable.
To be sent to cooling liquid storage tank 40 at the cooling liquid in the pipeline 30 that leaves cooling liquid removal device 28.Remove cooling liquid by pump 50 in pipeline 42 from cooling liquid storage tank 40, be discharged in the pipeline 52, pipeline 52 is transported in the filter 44, removes too small polymer beads, is used for further handling in pipeline 46 again.In one embodiment, this filter can be the backwash type.On pipeline 46, can use the lock hopper (not shown), the pressure that can not reduce system in order to allow to remove degranulation.Pipeline 48 is transported to cooling liquid in the optional cooler 54, pipeline 20 with this cooling liquid from wherein be recycled to device for molding 10.Can comprise that cooler 54 is to remain on chilled liquid temperature in the optimum Cutting temperature range of operating that is used to granulate.
This crystalline portion 4 is from pipeline or pipeline 38, and its conveying adds geothermal liquid to be carried at the polymer that leaves this cooling liquid removal device 28 in the pipeline 32.This pipeline 38 preferably will add geothermal liquid and be transported to cooling liquid removal device 28 places or its downstream.This temperature that adds geothermal liquid is higher than cooling liquid.Yet in embodiments, this adds geothermal liquid and cooling liquid is communicated with fluid, and under identical system pressure, replaces this cooling liquid fast with adding geothermal liquid when leaving this cooling liquid removal device at cooling liquid.Like this, realized the purpose of minimal thermal losses.The polymer that leaves this cooling liquid removal device 28 will still be in the Optimal Temperature scope that crystallization takes place, and it is more than or equal to T CminThe outside of polymer beads should be solid-state, and the inside of this particle is molten state, therefore promotes to continue crystallization.The polymer of this positive crystallization will discharge crystallization heat, and it will be used for from heating this polymer beads.In order to utilize this crystallization heat, importantly the temperature of introducing in the pipeline 38 that adds geothermal liquid is remained on be not less than this polymer with add the maximum on average temperature of bulk temperature that reaches when geothermal liquid contact.This average bulk temperature that adds the positive crystalline polymer in the geothermal liquid is with T wExpression.In embodiments, T wWith at least greater than the T that is 120 ℃ for PET Cmin, be 150 ℃～180 ℃ for PET preferably, it is at T cIn ± 15 ℃ of scopes, the temperature range that this expression is fit to, it comprises the temperature that reaches maximum crystalline rate.Higher temperature also can be fit to.Formula (3) has shown T wWith T qRelation: T w〉=T q+ m (Δ X f) (H c) (3) T wherein wBe the average bulk temperature of polymer in crystallisation step, Δ X fBe the degree of crystallinity mark that in crystallisation step, will reach and granulating and quench step crystallinity of polymer mark poor afterwards H cBe crystallization heat, it typically is 120J/g for PET.T wPreferably in the maximum rate scope of primary crystallization (primarycrystallization), for the PET polyester, it should be 150 ℃～180 ℃, but can be the same with the temperature of further downstream high, but is lower than the softening temperature of PET.The softening range of typical PET copolymer is considered to be in that it begins to experience the temperature of irreversible plastic deformation under the mechanical strain, typically by deformation temperature (DTUL) Instrument measuring under thermomechanical analyzer or the load.For the main melting peak temperature of being measured by DSC is 250 ℃ typical commercial resins, and softening range will be 230 ℃～250 ℃.In this temperature range, the molecular motion height must make that crystalline rate significantly is lower than at T cThe time.
Pipeline 32 can be sent to the polymer beads and the mixtures of liquids of heating in the optional holding vessel 34, can give the sufficient holdup time therein so that this polymer beads can crystallization arrive required degree.The required crystallinity level of this polymer is defined as minimum degree of crystallinity percentage with regard to further solid state (solid stating), and its enough height makes can not further release heat in the solid state reactor.The accurate level of different resins can be different.Percent crvstallinity is estimated by the density of particle by its buoyancy in the gradient column density according to ASTM D1505-98 " Standard Test Method For TheDensity Of Plastics by Density-Gradient Technique " typically, suppose that 0% degree of crystallinity (complete unbodied resin) has the density of 1.322g/cc, 100% degree of crystallinity has the density of 1.455g/cc. and for the representative value of the resin degree of crystallinity that is applicable to the PET copolymer in the SSP in downstream is the inlet that mixture that 15～35%. pipelines 36 will add geothermal liquid and polymer beads is transported to lifter 60, this lifter adds geothermal liquid and polymer beads with this and upwards is transported to height near SSP reactor assembly top, give this polymer beads time enough with crystallization simultaneously. this carries liquid lifter 60 with plug flow operation, and in embodiments, if have minimum and be 1 minute holdup time. use holding vessel 34, then to expect the shorter holdup time. pipeline 62 is transported to the outlet of effluent from lifter 60 hydrocyclone 64 (for example disengaging type hydrocyclone), to add geothermal liquid therein is the polymer beads crude separation of 15～35% degree of crystallinity with having reached based on density measurement. this adds geothermal liquid and removes from this disengaging type hydrocyclone 64 with major part by pipeline 66, and be transported in the wet tank 68 of heating. replenish pressure fluid by the pressure-control valve of regulating by pressure control PC 109 to the wet tank 68 of heating that is used for whole system and will keep system pressure to be higher than the flashing pressure that this adds geothermal liquid, so that being added geothermal liquid, this remains on liquid phase. because this adds geothermal liquid will have 120 ℃～230 ℃ for PET temperature, if so this to add geothermal liquid be water, consider the overvoltage of 35kPa (5psig), gauge pressure will be 131kPa (19.1psig)～2731kPa (136psig). for example, when adding geothermal liquid is water and when remaining on 180 ℃, this system's gauge pressure will be 935.9kPa (136psig). for having the more high boiling geothermal liquid that adds, can use lower pressure. polymer beads and the remaining geothermal liquid that adds are removed from this hydrocyclone 64, and transfer in the flash chamber 72 by inlet valve 70. in this flash chamber 72, pressure is discharged so that the geothermal liquid that adds under the high temperature flashes away as steam from polymer beads as gas. this steam that flashes off that adds geothermal liquid is got rid of from flash chamber 72 in pipeline 74. and this flash vapors that adds geothermal liquid can be discharged into the atmosphere, or in another is provided with, being condensed into liquid and being pumped in the circulation total amount that adds geothermal liquid. this set is not shown in the drawings. and this flash chamber 72 can comprise two lock hoppers, to enter by the inlet valve of opening 70 from the effluent of hydrocyclone 64 by it, close outlet valve 76. simultaneously after a collection of wet polymer particle enters inlet valve 70, close inlet valve 70 and open outlet valve 76, pressure is reduced fast and make and add geothermal liquid and in pipeline 74, flash away. for successive flash vaporization from polymer beads adds geothermal liquid, having the optional container (not shown) of being regulated with the inlet that keeps upstream pressure and keep apart with the downstream lower pressure by ball valve and pinched valve can make the wet polymer particle from hydrocyclone 64 enter in the lower pressure vessel. and this lower pressure vessel can comprise the dehydration screen cloth, from wherein this being added the geothermal liquid venting and flashing away, and be transported in the pipeline 74, it randomly is transported in the wet tank 68 of heating, yet what proposed in describing as described above is such., in embodiment according to accompanying drawing, the polymer effluent from flash chamber 72 in pipeline 78 is a crystal habit, and the ready SSP that is used for handles.
In SSP reactor assembly 6, in the embodiment of accompanying drawing, described reactor assembly starts from vibrated fluidized bed 80 with this crystalline state polymer particle transport.Hair-dryer 82 is blown into hot inert gas in this fluid bed 80, enters distributor pipeline 84.This hot inert gas bubbling forms ebullated bed by this polymer beads, is used for further dry this polymer beads and carries out further crystallization.Inert gas leaves fluid bed 80 by pipeline 86, and this dry polymeric particle transport is by pipeline 88 and enter crystallizer 90 simultaneously.In crystallizer 90, this polymer beads heated and by blade rotor to its mechanical agitation, so that this polymer beads moves to the port of export from arrival end.The temperature that enters the polymer beads of this SSP reactor assembly 6 is 180 ℃～200 ℃, is preferably 190 ℃, and it is the preferred inlet temperature that enters the polymer beads of SSP reactor 94.Yet other temperature also can be fit to.Suction line 92 is transported to polymer beads the SSP reactor 94 from crystallizer 90, and this SSP reactor 94 is sinking SSP reactor preferably, but batch (-type) SSP reactor also can be fit to.In some cases, crystallizer that needs are other.Yet, under some conditions, the flow chart of accompanying drawing can be operated needing to avoid fluid bed 80, hair-dryer 82 and crystallizer 90, and before polymer beads is entering this hydrocyclone 64 in case in lifter 60, reached sufficient crystallization, just will be delivered directly in the SSP reactor 94 from the polymer beads of the flash distillation of flash chamber 72.Polymer beads moves downward in SSP reactor 94, with hot inert gas (it is nitrogen preferably) stream adverse current, its molecular weight is upgraded to the extent of polymerization of polymer beads.Inert gas can enter by pipeline 96, and the polymer beads after the upgrading leaves this SSP reactor 94 by effluent pipeline 98.Pressure-control valve 109 that can be by entering pipeline 100 adds geothermal liquid and adds in the wet tank 68 of heating replenishing, and adds the geothermal liquid loss to replenish.Add geothermal liquid and leave this wet tank 68 of heating, and be pumped into by pump 108 and enter filter 104 in the pipeline 110 by pipeline 102.Add from this in filter 104 and filter out any polymer beads the geothermal liquid, to remove too small particle, this particle leaves being further processed by pipeline 106.Can on pipeline 106, use the lock hopper (not shown) can remove the pressure that degranulation does not reduce this system simultaneously.Pipeline 111 will add geothermal liquid and be transported in the balance heater (trim heater) 112, and become the geothermal liquid that adds in the pipeline 38, be introduced in the polymer beads that leaves cooling liquid removal device 28 in crystalline portion 4.
Operate flow process of the present invention so that minimize the time of contact between new cured polymer particle and the cooling liquid.This new cured polymer particle and cooling liquid are sent to cooling liquid removal device 28 fast from device for molding 10, with this cooling liquid of quick separation and polymer beads, and with adding alternative this cooling liquid of geothermal liquid.Minimize cooling the outside of polymer beads is solidified to form particle, simultaneously because the average bulk temperature of this particle still is in the best crystallization range, so crystallization is still continued in the inside of molten state.Cooling liquid and the quick replacing that adds between the geothermal liquid can make crystallization proceed, simultaneously this particle is sent in the SSP reactor, in embodiments, by pressure-control valve 109 this system pressure is remained on and to prevent to add the pressure that geothermal liquid enters gas phase, reach required degree until the transmission and the crystallization of polymer beads.
The present invention is favourable, because this polymer beads is to be cured under the technological temperature far below softening temperature (being 250 ℃ for PET), therefore this molded polymer has good shape. and polymer beads is crystallization in liquid, can absorb the crystallization heat of emitting in the liquid at an easy rate therein, this is than the molded and crystal system of the inlet of .SSP reactor assembly 6 far above this technology of being more convenient for managing of the exotherm in the control dry gas attitude environment of the risk that has fusing or particle-particle aggregation and particle-pipeline caking. and liquid lifter 60 is convenient to the transmission fully fast from crystal region to the SSP conversion zone, to avoid contingent thermal degradation in polymer beads. at high temperature (for PET, usually above 270 ℃) molding process of operation and typically too much heat loss does not take place being higher than between the SSP technology of 190 ℃ of operations for PET. in addition, following shortcoming has been avoided in the transmission in the liquid lifter: polymer beads must be cooled to be lower than glass transition temperature (is 70 ℃ for PET) with the viscosity avoiding being caused by insufficient crystallization and this polymer beads must be heated to the SSP reaction temperature more then in transport process.

Claims (10)

1. be used to prepare the method for polymer beads, comprise:
Molten polymer is formed the molten polymer form;
With cooling liquid this molten polymer of chilling under pressure, to obtain the solid polymer that average bulk temperature is equal to or greater than minimum crystallization temperature;
From a large amount of these cooling liquids, remove this solid polymer;
Under pressure, this solid polymer added to and have the adding in the geothermal liquid of the temperature that is higher than this cooling liquid;
Add at this and to make this solid polymer crystallization in geothermal liquid; With
Add from this and to remove this solid polymer geothermal liquid.
2. the process of claim 1 wherein that this polymer is a polyester.
3. the method for claim 2, wherein this polymer is PET.
4. claim 1,2 or 3 method, wherein this adds geothermal liquid and is under the pressure that is enough to prevent to vaporize in the crystallisation step process.
5. claim 1,2 or 3 method, wherein this adds geothermal liquid and this cooling liquid fluid is communicated with.
6. claim 1,2 or 3 method, this that wherein will have a solid polymer add geothermal liquid through decompression so that the flash distillation from this solid polymer of this liquid is come out.
7. claim 1,2 or 3 method, the temperature that wherein this is added geothermal liquid remains on the average bulk temperature more than or equal to this solid polymer.
8. claim 1,2 or 3 method, wherein this quench step is made the solid polymer of the temperature with the softening temperature that is lower than this polymer.
9. be used to prepare the equipment of the polymer beads of solid crystal, comprise:
Device for molding (10) is used for forming molten polymer in chilling chamber (18), and this chilling chamber has and is used at the described molten polymer of cooling liquid chilling to obtain the cooling liquid inlet of solid polymer;
Cooling liquid removal device (28) is communicated with described chilling chamber fluid, is used for removing a large amount of described cooling liquids from described solid polymer;
Pipeline (36) is used for solid polymer is sent to lifter (60) from described cooling liquid removal device adding geothermal liquid; With
Described lifter (60) is used for described solid polymer and adds the top that geothermal liquid rises to SSP reactor assembly (6).
10. the equipment of claim 9 further comprises pipeline (38), is used at described cooling liquid removal device place or will adds geothermal liquid in its downstream introducing described solid polymer.
CN200780052944.1A 2007-05-11 2007-05-11 For the method and apparatus of crystallizing polymer particles Expired - Fee Related CN101707889B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2007/068789 WO2008140522A1 (en) 2007-05-11 2007-05-11 Method and apparatus for crystallizing polymer particles

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CN108602961A (en) * 2016-06-21 2018-09-28 环球油品公司 Method and apparatus for the molecular weight for crystallizing and improving polymer particle
CN115819869A (en) * 2017-08-06 2023-03-21 阿里尔科学创新有限公司 Composition, polymer article comprising the composition and replica
JP7461751B2 (en) 2020-02-07 2024-04-04 株式会社日本製鋼所 Cooling water circulation equipment and pellet manufacturing equipment

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US7956101B2 (en) 2005-01-24 2011-06-07 Biotech Products, Llc Anaerobically compostable polymeric compositions, articles and landfill biodegradation
US11298853B2 (en) 2016-06-21 2022-04-12 Uop Llc Processes and apparatuses for conditioning polymer particles for an SSP reactor

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US5532335A (en) * 1995-04-26 1996-07-02 Hosokawa Bepex Corporation Method for thermally processing polyester pellets
DE10007726A1 (en) * 2000-02-19 2001-08-23 Mitsubishi Polyester Film Gmbh Transparent, sealable, UV-stabilized and flame-retardant polyester film, process for its production and its use
US6740733B2 (en) * 2001-11-30 2004-05-25 Shell Oil Company Process and apparatus for crystallization of polytrimethylene terephthalate (PTT)
US7157032B2 (en) * 2003-11-21 2007-01-02 Gala Industries, Inc. Method and apparatus for making crystalline PET pellets

Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN108602961A (en) * 2016-06-21 2018-09-28 环球油品公司 Method and apparatus for the molecular weight for crystallizing and improving polymer particle
CN115819869A (en) * 2017-08-06 2023-03-21 阿里尔科学创新有限公司 Composition, polymer article comprising the composition and replica
JP7461751B2 (en) 2020-02-07 2024-04-04 株式会社日本製鋼所 Cooling water circulation equipment and pellet manufacturing equipment

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