CN101438116A - Process for separating and drying thermoplastic particles under high pressure - Google Patents
Process for separating and drying thermoplastic particles under high pressure Download PDFInfo
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- CN101438116A CN101438116A CNA2005800381727A CN200580038172A CN101438116A CN 101438116 A CN101438116 A CN 101438116A CN A2005800381727 A CNA2005800381727 A CN A2005800381727A CN 200580038172 A CN200580038172 A CN 200580038172A CN 101438116 A CN101438116 A CN 101438116A
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- 238000000034 method Methods 0.000 title claims abstract description 123
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- 238000001035 drying Methods 0.000 title abstract description 31
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Abstract
A process for feeding a slurry of thermoplastic synthetic polymer particles such as polyethylene terephthalate homopolymers and copolymers in combination with a liquid such as water at a liquid temperature greater than the normal boiling point of the liquid, under a pressure greater than the vapor pressure of the liquid at the liquid temperature, into a separation zone such as a centrifugal dryer, and within the separation zone: a. separating the liquid from the particles, and b. drying the particles; while under a high pressure equal to or greater than the vapor pressure of the liquid. There is also provided a process for decoupling the dried particles from the separation zone to an atmosphere having a pressure less than the vapor pressure of the liquid while maintaining the vapor pressure of the particles prior to decoupling equal to or above the vapor pressure of the liquid at the liquid temperature.
Description
Quoting mutually of related application
The application requires the right of No. 60/606,729, the U.S. Provisional Application that proposed on September 2nd, 2004, incorporates this paper in full by reference into.
The technology of the present invention field
Fluid separation applications such as the slurry (slurry) that the present invention relates to be used for to contain polymer beads such as polyester granulate and water, and, simultaneously the pressure on this particle is maintained the above method and apparatus of this vapor pressure liquid with this particle drying.
Background technology of the present invention
Thermoplastic synthetic polymer's particle is supplied with converter with the hemihedral crystal type as polyester (or copolyesters) particle (pellet).Converter wishes to handle the particle of hemihedral crystal type, rather than unbodied particle because the particle of hemihedral crystal type can be under higher temperature dry and not agglomeration.Provide the general industrial method of crystalline particle to comprise, form polyester polymers through melt phase polymerization, make its inherent viscosity (It.V.) reach about 0.5, fused mass is extruded into line material (strand), make this line material quenching to below 0.70, the polymer strands of cooling is cut into solid amorphous pellet, usually store this particle then, make it to enter second phase-polymerization, i.e. solid-state polymerization, thereby further improve the It.V. of pellet, to be fit to final the application.With this pellet reheat to its more than Tg, make it crystallization under flow of warm nitrogen gas or thermal air current then, to prevent the adhesion in the solid state polymer reactor of this pellet, then, (or under vacuum) further heats this solid-state pellet to higher temperature under nitrogen purges, to continue to improve molecular weight or It.V. (being solid state).Therefore, in the solid state process or agglomeration in the drying steps before fused mass is extruded into bottle base, must make its crystallization for fear of pellet.
We find to make polyester polymers thermal crystalline under fluid, but not make the particle crystallization in thermal current, have a lot of benefits.Can obtain under the situation that the continuous process of polyester polymers (being referred to as " polymer beads ") crystallization in hot fluids such as hot water of fusion droplet or spherical form or solid grain or spherical form is being met the following conditions: the temperature of this fluid is enough high, can not only make polymer beads at brief stay time intercrystalline, and can make polymer beads be enough to prevent crystallization under the high temperature that particle sticks to each other in to the reinforced drier of extrusion apparatus.Make the particle crystallization and prevent that particle required temperature of adhesion in these driers is much higher than the boiling point of water under atmospheric pressure, is generally about 130 ℃ to 180 ℃.Can use other fluid that under higher temperature, seethes with excitement, but use these fluids, after fluid and particle separation, also need the additional step of washing granule, to remove any residual fluid of staying particle surface.Can use other fluid that is difficult for adhering to particle surface, but these fluids usually have lower boiling point, the same with the water of making peace, above-mentioned required temperature has also surpassed their boiling point.
Therefore, carry out crystallization process under pressure, be gasified totally to prevent liquid, thereby particle is maintained in the liquid phase, particle shifts easily and can crystallization under the temperature of liquid like this.Particle thermal crystalline in liquid will produce liquid/granulate mixture.In some position of this process, must be with particle and fluid separation applications.Separation should realize under the situation that does not significantly reduce crystal region pressure under the liquid.If reduce the pressure of crystallization circuit or Disengagement zone, can produce several shortcomings.One of them shortcoming is to make to keeping fluid to be in the liquid phase energy consumption increase of piezocrystallization circuit continuously.Another shortcoming is that unexpected decompression will make liquid flashes become gas phase, causes fluid loss or increase to make the steam equipment of condensation again.For water, because the heat of gasification height of water, decompression will make surface and surface following flash distillation or the gasification of water from particle, thereby reduce the temperature of particle fast.
Back one shortcoming may have no impact, but we find to make the temperature of separating the back particle to keep and separate before the temperature of particle near being very desirable.Between separation period in case reduce pressure on the particle, on the particle and/or intragranular water will gasify fast, thereby reduce the temperature of particle.
We find, at the pressure of maintenance system with particle and fluid separation applications, and under the situation that does not significantly reduce particle temperature the convection drying particle, all will be desirable.
The present invention's general introduction
The invention provides a kind of method, described method is included under the fluid temperature that is higher than described liquid standard boiling point and is equal to or higher than described liquid provides the pressurization that comprises thermoplastic synthetic polymer's particle and liquid under the pressure of the vapour pressure under this fluid temperature slurry, with the slurry feed of described pressurization to the Disengagement zone, with in this Disengagement zone, be equal to or higher than under the high pressure of this vapor pressure liquid:
A) separating liquid and particle and
B) dried particles.
The present invention also provides a kind of wherein particle to break away from the method for (decouple) from the Disengagement zone, and this method comprises that the pressure with particle is reduced to the low pressure that is lower than this vapor pressure liquid, keeps the high pressure that is higher than this vapor pressure liquid on the particle and made before decompression.
Described particle is preferably polyester polymer particles, preferably before disengaging is 0.5% weight or still less, described liquid is preferably water with particle drying to water capacity, and the pressure after the disengaging is reduced to below the 50psig ideally, most preferably is reduced to atmospheric pressure.
In another preferred embodiment, the temperature of liquid is higher than 130 ℃ in the slurry, and the temperature of particle is higher than 100 ℃ during disengaging.
In the inventive method, by first dried particles before disengaging, the heat energy of particle is retained in the particle substantially, this is because lessly stay on the particle or intragranular water gasifies because of particle reduces pressure when breaking away from particle and Disengagement zone.
The present invention also provides in order to carry out solid/liquid separation, and is dry under pressure, then the embodiment of the equipment of Tuo Liing.
Accompanying drawing is simply described
Fig. 1 is being equal to or higher than described liquid under the steam pressure of the vapour pressure under this temperature, makes the process chart of the separated from one another and dried particles of liquid and polymer beads.
The present invention describes in detail
With reference to following detailed description of the present invention, comprise accompanying drawing, and the reality that wherein provides Execute example, can more easily understand the present invention. Should be understood that and the invention is not restricted to described tool Body method and condition, concrete grammar and/or the treatment conditions of processing such plastic articles are certain Can change.
Also must be pointed out, unless context has other clear in this specification and the claims The regulation of Chu, otherwise when mentioning something, represent this material itself and an affiliated class thing thereof Matter maybe when mentioning a certain condition, then also comprises all in a certain scope under this condition Many conditions. For example, when mentioning at least a certain temperature or a certain pressure, comprise in this scope Any temperature and pressure, can keep constant value, but perhaps temporal evolution, as long as extremely Few in part-time, numerical value is in the described scope. Mention and contain a certain composition or a certain The composition of polymer means respectively except this composition or polymer of mentioning, also Comprise other composition or other polymer.
The scope of this paper can be expressed as by " pact " or " approximately " particular value and/or to " pact " Or " approximately " another particular value. When such scope was expressed, another embodiment comprised By a described particular value and/or to another expressed particular value. In addition, scope comprises All numerical value and subset thereof in this scope.
" comprise " or " containing " refers at least pointed compound, Constitution Elements, particle or side Method step etc. must be present in described composition, article or the method, but does not get rid of other change Even the existence of compound, material, particle, method step etc. is described other such chemical combination Thing, material, particle, method step etc. have the function identical with described object.
Should also be understood that and mention a step or the multistep method step is not precluded within the described step of combination Before or after also have other step, perhaps between clear those method steps of determining also Be interspersed with other method step.
Should also be understood that test method or method or the equivalent that composition was satisfied No matter whether be expressed in the claim, all needn't for whether identifying invention required for protection Can implement and in concrete industrial practice, implement. Test method and equivalent are easily Balancing method, in case of necessity, whether the invention that can be used to answer enforcement belongs to the model of claim Enclose this problem.
Through the described inherent viscosity of specification take dL/g as unit representation, by according to lower State computational methods, with consolidating that the phenol/tetrachloroethanes of 60/40 w/w records under 25 ℃ Viscosity calculations is arranged.
The invention provides a kind of method, described method is included under the fluid temperature that is higher than described liquid standard boiling point and is equal to or higher than described liquid provides the pressurization that comprises thermoplastic synthetic polymer's particle and liquid under the pressure of the vapour pressure under this fluid temperature slurry, when the slurry feed of described pressurization maintained the level that is equal to or higher than the vapour pressure of this liquid under this fluid temperature to the Disengagement zone with the pressure on the liquid:
A) separating liquid and particle and
B) dried particles.
In further embodiment, described particle experience breaks away from step, wherein the pressure on the dried particles is reduced to the level below the vapour pressure of the used liquid of this slurry.
The slurry of pressurization comprises the combination of thermoplastic synthetic polymer's particle and liquid, wherein puts on the vapour pressure that pressure on the liquid is higher than described liquid under fluid temperature.In this mode, prevent described liquid boiling.
Coating of particles can comprise particle, spheroid, pellet, discontinuous fibre or chopped strand, cylindrical, irregular shape, rhombus, star, thin slice shape or any other shape without limits.In the preferred embodiment, described particle is spherical substantially, is 1.5 or more hour in the particle average aspect ratio, can be obtained by molten polymer under the cutting liquid.The size of particle is also unrestricted, as long as this method can be carried out required separation, drying and decompression.Weigh with particle diameter maximum on the particle, the scope of the average grain diameter that is fit to is 0.1mm to 25mm, preferred 1mm to 4mm.
The state of polymer can be molten condition, semi-solid state or solid state in the slurry, and condition is that described polymer exists with grain shape in liquid.Therefore, the slurry in the inventive method is not limited to solid/liquid mixture, but also comprises melt granules/liquid mixture and semisolid/liquid mixture.But before particle and fluid separation applications, if with 20 ℃/minute heating rate polymer is carried out dsc analysis, can define the ebb fusing point and exist, then the temperature of liquid is preferably below the ebb fusing point of polymer; If there is not the ebb fusing point to exist, then the temperature of liquid is preferably below the fusing point of the peak of polymer.More preferably at the fluid temperature in any moment of particle crystallization, more preferably add the Disengagement zone liquid temperature and/or be higher than 100 ℃ in the temperature with liquid particle separation the solid/liquid separator liquid outlet, or at least 120 ℃, or at least 130 ℃, or at least 140 ℃, and it is the highest 190 ℃, or the highest 180 ℃.
The method for preparing particle slurry in liquid is unrestricted.A kind of this quadrat method be, force the polymer stream of fusion to pass through mould, when the polymerization logistics of fusion is forced to by mould, flow down at liquid, cut the polymerization logistics of fusion continuously at the mould place, and allow the polymer under cutting become entrained in the liquid stream, thereby produce the slurry of polymer beads and liquid.Perhaps, can only obtain the supply of original copolymer (virgin polymer) or PCR polymer beads, and they are mixed with liquid obtain slurry, this mixing can under atmospheric pressure mix, to the slurry pressurization, the particle entrainment that provides is implemented in the liquid stream of pressurization then.In another embodiment, can under pressure, force the thermoplastic synthetic polymer of fusion to enter in the liquid bath, form the line material, make this line material, thereby form the slurry of particle and liquid by cutting machine in the line or pelleter by mould.
Described thermoplastic synthetic polymer obtains and has thermoplastic any polymer by polymerization single polymerization monomer, and thermoplasticity makes this polymer can be transformed into particle, becomes useful articles then, maybe can heat the sheet material of shaping as fiber, mechanograph.When preferably not comprising fusion, described polymer obtains the liquid crystal polymer of regular texture.The preferred thermoplastic polymer is by the condensation monomer, or combines with addition reaction by condensation reaction, thus the condensation polymer that aggregates into, and polymer backbone is the graft polymers of condensation polymer.
The example of condensation polymer comprises polyester, polyamide, Merlon and copolymer thereof and graft polymers.The number-average molecular weight of wishing polymer is 1000 to 500,000, is generally 2000 to 50,000.
Polyester polymers contains ester and connects the multiple unit of basic weight.Polyester polymers can be polymer aliphatic series or partially aromatic.The preferred polyester polymer contains at least 60% mole terephthalic acid (TPA) alkylene ester repetitive or alkylene naphthalate repetitive, based on the total mole number calculating of polymer unit.Polyester polymers can be chosen such separation wantonly.
More preferably polyester polymers comprises:
(a) carboxyl acid component, described carboxyl acid component contains at least 80% mole, or at least 85% mole, or at least 90% mole, or at least 96% mole terephthalic acid residue, terephthaldehyde acid derivative residue, naphthalene-2,6-dioctyl phthalate residue, naphthalene-2,6-dicarboxylic acid derivatives residue or its mixture and
(b) hydroxy component, described hydroxy component contains at least 60% mole, or at least 90% mole, or at least 96% mole glycol residue or propane diols residue, more preferably glycol residue,
Percentage wherein calculates based on 100% moles of carboxylic acids component residue in the polyester polymers and 100% mole of hydroxy component residue.
All compound or derivatives thereofs of carboxy-containing acid group comprise " carboxyl acid component " in the product.The molar percentage of all compound or derivatives thereofs of carboxy-containing acid group amounts to 100 in the product." residue " of carboxy-containing acid group's compound or derivatives thereof is meant described compound and contains the part of staying after the compound generation condensation reaction of hydroxyl in oligomer and/or the polymer chain in the product.
The compound or derivatives thereof of multiple hydroxyl can become the part of polyester product.The compound or derivatives thereof that becomes all hydroxyls of described product part comprises hydroxy component.The molar percentage that becomes all hydroxy-containing compounds or derivatives thereofs of described product part amounts to 100.The residue that becomes hydroxy functional compound's or derivatives thereof of described product part is meant described compound and carboxy-containing acid group's compound or derivatives thereof condensation, and further with the polyester polymers chain polycondensation of different length after, still stay the part of the described compound in the described product.
The molar percentage of hydroxyl residue and carboxylic acid residues can be determined by proton N MR in the product.
The reaction of carboxyl acid component and hydroxy component is not subjected to the restriction of described molar percentage in the polyester polymers preparation process, because if need, can use excessive greatly hydroxy component, for example, can use approximately mostly to be most 200% mole hydroxy component with respect to the carboxyl acid component of using 100% mole.But the polyester polymers that reaction makes will contain the aromatic dicarboxylic acid residue and the glycol residue of described amount.
The derivative of terephthalic acid (TPA) and naphthalenedicarboxylic acid comprises terephthalic acid (TPA) two (C
1-C
4) Arrcostab and tea dioctyl phthalate two (C
1-C
4) Arrcostab, for example terephthalic acid (TPA) dimethyl esters and naphthalenedicarboxylic acid dimethyl esters.
Except terephthalic acid (TPA), terephthaldehyde acid derivative, naphthalene-2,6-dioctyl phthalate, naphthalene-2, the diacid component of 6-dicarboxylic acid derivatives or its mixture, the carboxyl acid component of polyester of the present invention can comprise the modifier carboxylic acid compound that one or more are other.These other modifier carboxylic acid compounds comprise monocarboxylic acid compound, dicarboxylic acid compound and have more multi-carboxy acid group's compound.Example comprises the aromatic dicarboxylic acid that preferably has 8 to 14 carbon atoms, preferably has an aliphatic dicarboxylic acid of 4 to 12 carbon atoms or preferably have the alicyclic dicarboxylic acid of 8 to 12 carbon atoms.As the modifier dicarboxylic acids of acidic components more specifically example be phthalic acid, M-phthalic acid, naphthalene-2,6-dioctyl phthalate, cyclohexane cyclohexanedimethanodibasic, cyclohexanediacetic, biphenyl-4,4 '-dioctyl phthalate, butanedioic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid etc., most preferably M-phthalic acid, naphthalene-2,6-dioctyl phthalate and cyclohexane cyclohexanedimethanodibasic.Should be understood that term " carboxylic acid " comprises the corresponding acid anhydrides of these acid, ester and acyl chlorides.Also can and have more multi-carboxy acid group's compound modified polyester with three carboxyl compounds.
Except containing the hydroxy component of ethylene glycol, the hydroxy component of described polyester can comprise other modifier list alcohol, glycol or have more polyhydric compound.The example of modifier hydroxy compounds comprises the alicyclic diol that preferably has 6 to 20 carbon atoms and/or preferably has the aliphatic diol of 3 to 20 carbon atoms.Such glycol example more specifically comprises diethylene glycol (DEG); Triethylene glycol; 1, the 4-cyclohexanedimethanol; 1, ammediol; 1, the 4-butanediol; 1, the 5-pentanediol; 1, the 6-hexylene glycol; 3-methyl pentanediol-(2,4); 2 hexylene glycol-(1,4); 2,2,4-TMPD-(1,3); 2,5-ethohexadiol-(1,3); 2,2-DEP-(1,3); Hexylene glycol-(1,3); 1,4-two (hydroxyl-oxethyl)-benzene; 2,2-two (4-hydroxy-cyclohexyl) propane; 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane; 2,2-two-(3-hydroxyl-oxethyl phenyl)-propane; With 2,2-two-(4-hydroxyl propoxyl group phenyl)-propane.
Polyester polymers can preferably contain just like M-phthalic acid, naphthalenedicarboxylic acid, cyclohexanedimethanol and diethylene glycol (DEG), as modifier.
The polyester granulate composition can comprise the blend of polyalkylene terephthalates and/or poly-alkylene naphthalate and other thermoplastic polymer (as Merlon (PC) and polyamide).Preferred described polymer blend should comprise most polyester polymers, the more preferably polyester polymers of at least 80% weight or at least 95% weight, the polyester polymers of 100% weight most preferably, percent by weight wherein are based on the weight (except filler, inorganic compound or particle, fiber, impact modifier or other may form the polymer of discontinuous phase) of all thermoplastic polymers and calculate.Also the preferred polyester polymer does not contain any filler, fiber or impact modifier, or other forms the polymer of discontinuous phase.
Polymer blend can be by the polymerization preparation that is enough to finish esterification and polycondensation known in the art.Polyester fusion phase production technology is included in esterification zone and makes dicarboxylic acids and the direct condensation of glycol, chooses wantonly in the presence of esterification catalyst and carries out, then in the prepolymer district with finish district, polycondensation in the presence of polycondensation catalyst; Perhaps carry out ester exchange, in the presence of transesterification catalyst, carry out usually in transesterification zone; The pre-polymerization merging is finished in the presence of polycondensation catalyst then, and above-mentioned two kinds of technologies can be chosen wantonly by known method by solid state separately.
Other method of producing condensation polymer and thermoplastic addition polymer is conventional method, and is described in John Wiley ﹠amp; The Kirk Othmer Encyclopedia of ChemicalTechnology of Sons.
The It.V. scope that the thermoplastic synthetic polymer is fit to is 0.55dl/g to 1.15dl/g.But an advantage of this technology is to avoid the solid state step.Solid state is generally used for increasing the molecular weight (and It.V) of solid granulates, increases 0.05It.V. unit at least usually, increases by 0.1 more generally to 0.5It.V. unit.Therefore, for fear of the solid state step, the It.V. that polymer obtains mutually in fusion is 0.7dL/g at least preferably, or 0.75dL/g at least, the highest about 1.2dL/g, or 1.15dL/g.Polymer can be measured by to deriving from the particle sampling in the pelleter that the melt phase compound is carried out pelletizing easily at the It.V. of fusion phase.
In a single day the thermoplastic synthetic polymer produces in melt phase polymerization, just is cured.Will be unrestricted by the method that the thermoplastic synthetic polymer that fusion phase technology obtains is solidified.For example, the thermoplastic synthetic polymer that can make the fusion that is obtained mutually by fusion is by mould, or only with its cutting, or makes it pass through to cut behind the mould polymer of fusion again.Available gear pump is as power, and the thermoplastic synthetic polymer who orders about fusion passes through mould.Except using gear pump, also the thermoplastic synthetic polymer of fusion can be added single screw rod or double screw extruder, and extrude by mould, choose wantonly under 190 ℃ or higher temperature and extrude in extruder nozzle.In case by mould, the thermoplastic synthetic polymer can be drawn as the line material, contacts with cooling fluid, and is cut into particle, perhaps polymer can be made into particle at the die head position, chooses wantonly under liquid and carries out.Optional filtering thermoplastic synthetic polymer fused mass is to remove the particle above designated size before cutting.Can use hot cut pellet method or the side's grain pelletizing method and the conventional equipment of any routine, the side's of including but not limited to grain pelletizing, the pelletizing of line material, line material (forced conveyance) pelletizing, pelleter, water ring pelleter, hot die face pelletizer, underwater pelletizer and centrifugal pelleter.The example of underwater pelletizer is suggested in No. 5059103,6592350,6332765,5611983,6551087,5059103,4728276,4728275,4500271,4300877,4251198,4123207,3753637 and 3749539, United States Patent (USP), more than all incorporate this paper by reference into.
The source of used polymer is unrestricted in the slurry.Above-mentioned fusion phase technology of serving as reasons the preparation original copolymer obtains the method for polymer.Perhaps, molten polymer can be obtained by the polymer of side crops or regeneration (＂ PCR ＂).Polymer historical unrestricted becoming polymer transition particle or polymer beads added before liquid makes slurry, and this polymer can experience any history and any state.
The method of the condensation product of fusion being introduced liquid is unrestricted.For example in one embodiment, will obtain by any source, no matter be the original copolymer or the molten polymer of PCR polymer by mould, or only cutting, or by cutting the polymer of fusion behind the mould again.In another embodiment; available single screw rod or double screw extruder melt extrude the thermoplastic synthetic polymer by mould; choose wantonly under 190 ℃ or higher temperature and extrude, and be cut into particle or be extruded into the line material or any other mold shape in extruder nozzle.In another optional embodiment; with gear pump the thermoplastic synthetic polymer of fusion being finished container (finisher vessel) mutually from fusion directly or indirectly pumps; force it to pass through mould, and be cut into particle or be moulded and be line material, sheet or other mold shape.
Concrete used liquid is unrestricted.Should avoid using and under all operations condition, cause It.V. to produce the fluid composition of undesirable high loss.The example that is fit to the liquid of use in the inventive method comprises: water; PAG is as diethylene glycol (DEG) and triethylene glycol; And ethanol.
In the embodiment, particle at high temperature contacts with liquid, makes the crystallization of polymer moieties ground.In the case, it is desirable to use liquid, thereby, particle is carried out best heat conduction with the shortest possible time of staying with high heat capacity.Liquid with low-vapor pressure also helps further reducing equipment cost, because can use the container of lower pressure grade.But it is important in liquid selective; sometimes be that primary Consideration is; the complexity of liquid and particle separation, liquid be by the complexity of particle volatilization, also has and handle, heat and make the liquid recirculation that separates to contact relevant cost with the particle that initiate preparation enters liquid.The thermal capacitance of water is 1cal/g/ ℃, is gratifying, water and particle separation and all be very easy to by particle volatilization.If desired, can make water and other reduce the mixture of the material (for example liquid or salt) of vapor pressure liquid.For example, water can mix with other glycol, and the amount of other glycol is no more than this glycol solubility in water under the operating condition in fluid zone.Preferred use water-soluble liquid is so that remaining liquid can be removed from particle by washing.
The residing stress level of slurry that particle and liquid form equals or exceeds the vapour pressure of this liquid.Pressure on the liquid surpasses the vapour pressure of this liquid, keeps liquid to guarantee this fluid.Therefore, contain the pipeline of slurry or container and may have 1 (1) atmospheric malleation of surpassing slurry.For example when aqueous medium at 100 ℃ or surpass when using under 100 ℃ the fluid temperature and this situation can occur.Selected concrete pressure for slurry will depend on the composition and the required temperature that is put on particle by liquid of liquid.But, in the embodiment, bottom line, the boiling point of liquid under 1 atmospheric pressure is lower than the temperature of this liquid that contacts with particle.The temperature of the liquid that contacts with particle is higher than the boiling point of this liquid under 1 atmospheric pressure conversely speaking.
Can produce pressure by the inert gas that adds supercharging, these gases such as nitrogen or air or other any suitable gas, perhaps the liquid pumping liquid district by volume more is to produce pressure.Perhaps can be used in combination the method for above-mentioned generation pressure.
The vapour pressure of liquid is usually with test method, and the steam of liquid institute applied pressure is determined when being in dynamic equilibrium by liquid and steam.But, in practice, liquid in the fluid zone and steam may not be put at any time or fluid in any position all be in poised state, this is because well known to a person skilled in the art by the system perturbation and caused the pressure variation, for example the pressure gap located such as pipeline, valve, weir (weir); Also, uneven heating changes because producing pressure.As a result, for preventing that the needed static pressure that puts on the liquid of liquid boiling may be less than prevent the static pressure that same liquid boiling is required in the closed system under the dynamic equilibrium.Therefore, although the static pressure of fluid zone reality may if liquid does not seethe with excitement, also just think that the pressure of fluid zone is equal to or greater than the vapour pressure of liquid a shade below in theory for surpassing the required pressure of dynamic vapour pressure of liquid.
The pressure that will contain the fluid zone of particle slurry is set at above the vapour pressure of liquid under this fluid temperature, and the pressure of described fluid zone is the function of the required time of staying together with flow velocity.With water is example, and the boiling point of water under the pressure of 52psia is 140 ℃, and the boiling point under the pressure of 69psia is 150 ℃, and the boiling point under the pressure of 115psia is 170 ℃, and the boiling point under the pressure of 145psia is 180 ℃.Therefore, can set high pressure, with the boiling point that improves water and the time of staying that reduces particle in the hot liquid.Think surpass 25psi, surpass 50psi or surpass 75psi surpass 100psi or surpass 150psi or surpass 200psi, the pressure of the highest about 300psi is to be fit to the great majority application.
This liquid can be static, so that make the shaped polymer of fusion be pulled by this liquid (when polymer is the line material) or have the required time of staying when making particle fall by this liquid, thereby produces required crystallization degree.Perhaps this liquid can flow, and particle is carried into required terminal point, if perhaps do not carry particle, can cause enough flowing or disturbance at least, sticks to each other to prevent particle.
Preferred this liquid flows, and flow velocity that is provided with and pattern of flow energy submergence particle.Concrete flow velocity will depend on the feed rate of liquid medium district capacity and particle.When liquid has surrounded whole particle, think that promptly particle is liquid-immersed by this.But, although some particles (not all particle) temporarily are in or are higher than this liquid surface (this situation may occur in bumpy weather) at any one time point, if but any moment during the particle crystallization, these a large amount of particles all are enclosed in this fluid, think that then particle is submerged.Preferably in the basic institute of particle crystallization was free, particle was submerged.
Wish that particle is preferably shorter for the time that obtains required crystallization degree and stop,, reduce equipment cost, and make It.V. minimization of loss (if this be concerned about) with restriction circulation timei.The time of staying is meant from particle and is added into (more than the Tg of polymer) beginning the hot liquid, until with fluid separation applications before thermoplastic synthetic polymer's temperature descend and rest on below thermoplastic synthetic polymer's the Tg in, perhaps leave in the liquid until this thermoplastic synthetic polymer, the time period that this thermoplastic synthetic polymer experienced is in the short time period.In the embodiment preferred, the length of following the time of staying of other operating condition is not in order significantly to increase or reduce thermoplastic synthetic polymer's It.V. (It.V. is relevant with the weight average molecular weight of polymer).Though method of the present invention allows to keep particle to contact the long enough time with hot liquid, to increase the It.V. of particle, but more preferably will be reduced to the crystallization that makes polymer the time of staying and reach the necessary time of required degree, as mentioned below, the polymer of high It.V. is crystallized out from fused mass, can avoid the solid state step fully.
The time of staying of particle in liquid is unrestricted.But, the advantage of the inventive method allows to foreshorten to 15 minutes or shorter the time of staying so that the degree of crystallinity of particle reaches 20% or higher, perhaps 25% or higher, 30% or higher, even, measure immediately after particle that is produced and the fluid separation applications up to 40% or higher.Use for majority, 25% to 45% degree of crystallinity is fit to.According to crystallization temperature, time of staying even may be as little to 0 second to 10 minutes.When temperature is 140 ℃ to 180 ℃, obtain 25% or higher, even 30% or the higher required crystallization time of degree of crystallinity be 5 seconds to about 8 minutes, perhaps shorter.
In the preferred embodiment, in fluid zone, there is not crystallization under the situation of the stirring that rotating machinery causes.The rotation oar that known level is full of liquid stirs the motion that container can provide necessity, to prevent particle agglomeration during crystallization.But in the present embodiment, also avoid agglomeration simultaneously by avoiding rotating machinery during the crystallization to stir, with minimizing fund and running cost.This can realize by several modes.With particle add non-level to the fluid zone that is full of or is full of liquid nearly, allow described particle by liquid to the sedimentation of the bottom of this container, simultaneously by flowing liquid upwards and/or by the density variation between control particle and the liquid, be particle and optionally provide the buoyancy and the necessary time of staying for the particle that produces.Perhaps, can move through pipeline to keep particle with the particle adding and by pipeline under liquid flow as fluid zone.It is desirable to, flow velocity and the pattern of flow of liquid by pipeline prevents or helps to prevent particle agglomeration or adhere to tube wall.
In the embodiment, make particle crystallization in pipeline, can avoid using expensive rated pressure crystallizing tank.Make particle in liquid, flow through the pipeline that draw ratio L/D is at least 15:1, can make particle crystallization in pipeline, wherein said particle in described pipeline in surpassing crystallization under the fluid temperature of thermoplastic synthetic polymer Tg.The difference of pipeline and generic container is that the length of pipeline and diameter draw ratio are preferably greater than 25:1, more preferably greater than 50:1 greater than 15:1.The length that draw ratio is at least the pipeline of 15:1 comprises a series of pipelines that link together by pipe union, elbow, U-shaped connector, union elbow etc.
In the pipe design, fluid temperature is suitably for about 90 ℃ or higher, and preferred 100 ℃ or higher, more preferably 130 ℃ or higher, most preferably 140 ℃ or higher.Also wish to be equal to or higher than the exert pressure pipeline of vapor pressure liquid.
Can design pipeline so that part or incomplete crystallization to be provided, or fully crystallization.The crystallization degree of giving particle in the pipeline preferably at least 20%, more preferably at least 30%, most preferably at least 40%.In the time of staying is 15 minutes or shorter, or 10 minutes or shorter, even 7 minutes or more in short-term, particle is crystallizable to 25% or higher.In the embodiment, at 10 minutes or shorter, or 5 minutes or shorter, or in 3 minutes or shorter time, particle crystallizes to 30% or higher degree of crystallinity in pipeline; Perhaps at 10 minutes or shorter, or 5 minutes or shorter, or in 3 minutes or shorter time, particle crystallizes to 40% or higher degree of crystallinity in pipeline.
Pipeline does not preferably have interior arrangement, as machinery rotation oar, does not more preferably have blender, overflow plate or constrictor in the line, and wishes that liquid flow and particle flow are in same direction.Pipeline can be full of the slurry of liquid and particle.Perhaps, pipeline can be full of steam, liquid and particle.Pipeline can be a horizontal direction; Can be oblique under, make gravity help particle flow; Can make progress by contrary gravity, high-pressure fluid upwards flows and produces the disturbance of height; Perhaps can be these combination of features.Polymer, liquid and the optional steam or the air-flow that will comprise fusion and/or crystallization by the fluid of pipeline.
Stir even without rotating machinery, make particle flow through pipeline continuously, also can avoid sticking to each other or particle and pipeline adhesion between serious pipeline endoparticle.Should regulate the viscosity of liquid, to reduce the particle agglomeration in the pipeline.Though have agglomeration that be dispersed in or a spot of in the pipeline, the frequency of particle agglomeration or quantity do not hinder dehydration equipment, particle or the particle got rid of by such equipment disperse.
1ft/s or higher flow rate of liquid are suitable for producing continuous grain flow in pipeline, reduce the trend that particle rolls and sticks to each other along duct wall in large quantities simultaneously.The time of staying, duct length can be 30ft to 9600ft when being 30 seconds to 20 minutes, and diameter can be 1 inch to 14 inches, and flow rate of liquid can be 1ft/s to 8ft/s.Other duct length and diameter are also applicable, and best pipe design will depend on for example following various factors of balance: pipeline is based on other cost of its length, diameter, constituent material and pressure stage; The energy that pumping liquid is required; Be used at the temperature required heat energy of crystallization down; Polymer IV loss; With the required time of staying.
In case particle has crystallized to required degree, with the particle of particle or generation from fluid separation applications.Why particle can be like this from fluid separation applications, be because under 100 ℃ to 180 ℃ temperature, in case particle crystallization, has enough intensity and hardness, and be under enough blowdown presssures, to avoid between separation period or the after separating phenomenon that occurs that excessive separation equipment stops up or particle sticks to each other.Perhaps, before separation, can allow particle be cooled to the temperature that is lower than its adhesion point, or be cooled to the following temperature of Tg of the polymer that forms particle, make liquid easier with separating of polymer.Before separation, allow polymer cooling form particle, can reduce polymer and separation equipment adhesion or with the risk of other polymer beads adhesion.
The method of above-mentioned formation particle and crystallization only is the several non-limiting examples that form the method for particle slurry under the pressure of described vapor pressure liquid being equal to or higher than in liquid.No matter select what technology, in the stage (for simplicity, being called " Disengagement zone ") with particle and fluid separation applications and dried particles, particle is under the vapour pressure that is equal to or higher than described vapor pressure liquid.Therefore, method of the present invention is under the fluid temperature that is higher than described liquid standard boiling point and be equal to or higher than described liquid provides the pressurization that comprises thermoplastic synthetic polymer's particle and liquid under the pressure of the vapour pressure under this fluid temperature slurry, the slurry of described pressurization is added the Disengagement zone, with in this Disengagement zone, be equal to or higher than under the high pressure of this vapor pressure liquid:
A) separating liquid and particle and
B) dried particles.
In the inventive method, the pressure on the particle reduce to the vapour pressure of separated liquid below horizontal before, will be in particle and fluid separation applications and dry under the vapour pressure that is equal to or higher than described vapor pressure liquid.Dry run is to reduce on the particle or residual wet branch in the particle.The amount of liquid that only reduces in the particle slurry is not a drying steps.In the inventive method, when particle is not immersed in the liquid and be not present in liquid bath or the liquid cell or in the intergranular liquid continuous phase time, particle is dried, on the particle or intragranular water capacity reduce.
In the preferred embodiment, under high pressure extremely to a certain degree with particle drying, making the water capacity that breaks away from preceding particle is 5% weight or lower, or 3% weight or lower, or 2% weight or lower, or 1% weight or lower, or 0.65% weight or lower, or 0.5% weight or lower, or 0.4% weight or lower.The water capacity of particle is not directly to measure before breaking away from, because particle is under the high pressure.But water capacity can be associated with the temperature differential before and after breaking away from.The water capacity of particle is calculated by following test method: be determined at front, abscission zone or upstream, perhaps be used to make particle break away from the front of valve of separation equipment or upstream particle temperature and be right after the abscission zone after the temperature of particle.Decrease of temperature was directly indicated on the particle or intragranular maximum water capacity when particle broke away from.The temperature of particle can be measured by conventional methods before and after breaking away from, and is included in the gas/particle mixture and inserts temp probe.It is relevant with the water capacity that breaks away from preceding particle that temperature descends, and can be illustrated by following equation:
f
max＝C
pΔT/ΔH
vap
Wherein:
f
Max=the liquid fraction of maximum possible in the particle before breaking away from
C
p=the thermal capacitance of polymer under the temperature before breaking away from
Δ H
Vap=the heat of gasification of liquid under the temperature before breaking away from
Δ T=temperature descends: the temperature of particle deducts the temperature that breaks away from the back particle before breaking away from
The water capacity that breaks away from the back particle does not have indicative function to the water capacity of particle before breaking away from, because when breaking away from, the wet branch from the particle flash distillation, causes evaporative cooling.Therefore, in this preferred embodiment, purpose is not only and will be under atmospheric pressure made dried granules (for example water capacity is lower than 1%), and the water capacity of particle is enough low before will guaranteeing to break away from, so that the evaporative cooling of particle when breaking away from minimizes, thus the grain flow that produces not only heat but also do.
Keep the vapour pressure that pressure is equal to or higher than liquid in the Disengagement zone.Allow pressure drop to below the vapor pressure liquid between separation period, need the energy of a great deal of that the slurry that enters the Disengagement zone is pressurizeed again.Keep the pressure on the particle between separation period and do not keep the pressure on the particle between dry period, will cause on the particle or interior residual flash distillation in wet minute or the evaporation of particle.Allow residual liquid by particle evaporation or flash distillation, cause the liquid loss, or need the steam again condensation of equipment flash distillation.Therefore, the separation of particle and drying are all carried out under pressure.
The method of particle and fluid separation applications is unrestricted.Suitable method comprises use centrifugal force, for example uses whizzer; Slurry is added sieve cage (screened cage), perhaps make slurry on the porous barrier through or pass the porous barrier, make liquid flow through this barrier, and particle can not flow through this barrier; Or by using impact that liquid is broken away from from polymer surfaces.
The method of dried particles is also unrestricted.Suitable method comprises uses centrifugal force to particle; Use impact that liquid is broken away from from polymer surfaces; Make air-flow or the dry gas stream particle surface of flowing through; Or from particle, extrude by the branch that will wet.
The Disengagement zone comprises the operation of separation and dried particles.The drying of liquid and particle separation and particle can occur in the discontinuous step, is actually simultaneous, or in a continuous process, separates and develop into drying process gradually.Can be under high pressure and high temperature that any container of liquid and particle separation and dried particles is all applicable.Perhaps, a series of containers of carrying out function separately respectively can link to each other for fluid.If desired, fluid links to each other and can link to each other with second the independent container or the container series of another function of common execution (drying) with a series of containers of function of common execution (as separating) each other.Separate and the preparation of dried particles unrestricted with design, be to carry out under the pressure of used vapor pressure liquid in being higher than slurry as long as separate with drying.
Can make a non-limiting example of the container of particle and fluid separation applications and dry gained particle is centrifugal dryer.The example of centrifugal dryer can be referring to United States Patent (USP) 3,458, No. 045; DE 1953741 A1; DE4330078A1; USP 4,218, and 323; USP 5,611, and 150; DE2819443A1; USP 4,565, and 015; With USP 5,265,347; Each full patent texts is all incorporated this paper by reference into.In a kind of typical centrifugal dryer, rotor rotates in the space of fixing cylindrical screen.But, if wish further to reduce residual moisture content on the particle, also applicable and preferred other design.Other such container for example comprises various centrifuges, and as horizontal revolving drum or screen cloth rotating cylinder sedimentation-type centrifuge, rotor and basket rotate therein; Vertical basket centrifuge, basket rotates therein; And pusher centrifuge; Perhaps liquid is discharged and use air knife drying (air-flow method) again; Perhaps liquid is discharged again with belt extruding (extrusion).Preferred centrifugal dryer and centrifuge.
In a preferred embodiment of the present invention, the slurry that comprises the pressurization of synthetic particle of thermoplasticity and liquid is added in the centrifugal dryer, in centrifugal dryer, be equal to or higher than under the high pressure of vapor pressure liquid, make liquid and particle separation and make particle drying, wherein, preferably use centrifugal force at least separating and during drying, particle being used centrifugal force and/or impact.Centrifugal force and/or impact can separate and dry part during use, or liquid and particle separation and particle in centrifugal dryer, be dried whole during use.If desired, other mechanism that further specifies below available promotes dry.
In another embodiment of the present invention, the temperature of separated and dried granules is near the temperature of liquid in the slurry that enters the Disengagement zone in the Disengagement zone.In this optional embodiments, we have found that, can advantageously provide the dry heat grain flow that gives off, to reduce the energy requirement that reheats particle in the ensuing processing operation.Comparatively speaking, if during drying allow the temperature of particle significantly descend, reheating particle in ensuing operation just needs more energy.Therefore, if do not allow the heat energy in the particle escape in the air, the integrated system that just can provide the energy consumption costs to reduce.For making the reduced minimum of particle temperature, keep pressure on the particle to be higher than on the particle between dry period or particle in the vapour pressure of liquid.Because a lot of liquid have high heat of gasification, absorb the heat energy in a lot of particles, therefore, thereby the pressure on the maintenance particle keeps on the particle or intragranular wet branch is in liquid state, can prevent the liquid evaporation and take away on the particle or the interior heat energy that stores of particle.The present embodiment provides the pressure of keeping between separation and dry period on the particle to be higher than the Another reason of vapor pressure liquid.
Reckon with at some heats of Disengagement zone meeting loss, especially when air-flow directly passes through on the particle.But if allowing the pressure on the particle to descend between separation and dry period, then such temperature descends can be more obvious.In the present embodiment, the temperature of (it is following that pressure has just been reduced to vapor pressure liquid) compared with the fluid temperature that enters the Disengagement zone when particle broke away from, at its 80 ℃, 60 ℃, 40 ℃, in the amplitude of 20 ℃ or 10 ℃, preferably when slurry enters the Disengagement zone and when breaking away between, do not use heat energy from thermal source beyond the liquid.In the preferred embodiment, the temperature that adds liquid in the slurry of Disengagement zone is at least 120 ℃, and breaks away from least 70 ℃ of the temperature of particle when breaking away from, or at least 90 ℃, or be higher than 100 ℃, or at least 110 ℃, when breaking away from, measure.In the another embodiment, the temperature that adds liquid in the slurry of Disengagement zone is at least 140 ℃, and breaks away from least 80 ℃ of the temperature of particle when breaking away from, or is higher than 100 ℃, at least 120 ℃.In each of these embodiments, do not consider decrease of temperature, the temperature of particle is higher than the normal boiling point of liquid during disengaging.
In case be dried to wet minute required degree, preferably be reduced to low pressure below the vapour pressure that is lower than liquid under this fluid temperature by pressure with particle, before decompression, make simultaneously and keep the high pressure that is higher than vapor pressure liquid under this fluid temperature on the particle, particle is broken away from from the Disengagement zone.Pressure in the Disengagement zone should not descend and keep the vapour pressure that is lower than liquid under this fluid temperature.The fluctuation of drier (or Disengagement zone) internal pressure is an acceptable, condition be separate or dry period between pressure do not descend continuously or keep the vapour pressure that is lower than liquid under this fluid temperature.More preferably the decline of Disengagement zone internal pressure is not brought down below the vapour pressure of liquid under this fluid temperature.But as following further explanation, pressure regulator and controller preferably are provided, in position easily with the compressed air injection system so that in Disengagement zone or drier, pressure is maintained more than the vapor pressure liquid, and more preferably make pressure maintain+/-steady state value of 20psig.
Therefore, another embodiment is provided, wherein make and contain the wet thermoplastic polymer particles that divides of certain quantity of fluid, the preferred polyester polymer beads breaks away from least under greater than the pressure of vapour pressure and under 130 ℃ the temperature, comprise that the pressure that makes particle is reduced to the following low pressure of 50psig, particle temperature when wherein breaking away from is higher than 100 ℃, preferably at least 110 ℃.
With known conventional equipment the particle of being discharged by the Disengagement zone is broken away from from the Disengagement zone, described equipment can be kept high pressure in a side in zone, and reduces the pressure of regional opposite side.For example; dried granules can be disposed in the groove by the Disengagement zone, hold jar in, in the vertical pipe or in any appropriate containers; make particle run up to certain altitude; afterwards; a series of valves such as gate valve or ball valve are opened with the interval of measuring; first gate valve or ball valve are opened so that dried granules is received in the air lock chamber, and second gate valve in downstream keeps closing simultaneously.In case air lock chamber is filled to required height, first gate valve or ball valve are closed, and second gate valve or ball valve open, thereby particle is broken away from from the Disengagement zone, keep the endocorpuscular pressure in Disengagement zone to be higher than vapour pressure simultaneously.Other suitable valve comprises rotary valve in the conventional line, the spitting image of revolving door, particle can be received in the quadrant during running, forms sealing with wall during this rotary valve rotation, continue to rotate to the low-pressure side of pipeline, but release particles.This rotary valve is divided into several chambers, and rotation continuously, thereby to be equivalent to the speed of rotor rotation, fast and continuously particle is received successively, seals and discharges.
The liquid that at least a portion is separated from the Disengagement zone recycles directly or indirectly, and particle is trapped in the liquid, to generate slurry.The liquid of recirculation adds fashionablely can pass through filter earlier, to remove fine powder and particle, can heat or cool off.
Reckon with that sealing can have some pressure losses and pressure leakage because of breaking away from structure on every side or in the Disengagement zone, thereby duplicate pressure can not kept in the both sides of this structure.Therefore, by in any position liquid being pressurizeed again, it is relatively stable that pressure in the Disengagement zone is kept, and pressing position is recirculation circuit, crystal region for example, pressurizes by making particle enter the used mode of liquid, perhaps pressurizes in the Disengagement zone.Providing pump on the liquid recirculation circuit, is the short-cut method that liquid is pressurizeed again.Perhaps, the air-flow in the Disengagement zone also can be used as forced air, thereby provides liquid pressing mode again.But compare with the method that slurry that allows pressurization before liquid and particle separation and atmosphere are connected, the inventive method only needs the energy of much less just can keep that the pressure of liquid is higher than vapor pressure liquid in the Disengagement zone.
The temperature of separated liquid is optional can be heated a little again, do not heat fully, or even cooling.For example, if force fused mass by mould and under liquid fused mass to be cut into particle, thereby make particle entrainment in slurry, the temperature of fused mass may substantially exceed required crystallization temperature.In this case, the temperature that newly joins the liquid in the cutter under the liquid must be lower than the temperature of fused mass, is enough to be cooled to required crystallization temperature with the particle of the fusion guaranteeing to cut under liquid.Therefore, the heat loss of whole system reduces the temperature that adds the recirculated fluid of cutter under the liquid, and this heat loss may enough also suitably make fused mass be cooled to required crystallization temperature.Perhaps, although the heat loss of whole system is arranged, the temperature of recirculated fluid may be still too high, considers that the heat of the molten polymer that cuts and be transferred to liquid under the liquid shifts, and fluid need be cooled off.When needs are cooled the liquid of recirculation, heat exchanger can be provided, some heats are shifted by recycled fluid, for other process in the workshop condition provides heat energy.
Centrifugal dryer as shown in Figure 1.Be fed to centrifugal drying container 10 at the slurry that is higher than under the pressure of vapor pressure liquid by pipeline 1.Slurry in the circuit 1 is optional can to go to agglomerate gatherer circuit, to remove the granuloplastic big agglomerate of condensation polymer or spheroid or other big particulate matter.Incipient stage, systematic parameter does not also reach stable mode of operation, and some thermoplastic synthetic polymers might agglomeration.The agglomerate gatherer can only be made up of the macrovoid screen cloth, has only the large volume agglomerate not pass through.Slurry continues to flow back to circuit 1, and flow to centrifugal dryer 10.
If slurry flow is bigger, preferably divide two stages to make liquid and particle separation, in first water smoking, under the situation of not using centrifugal force, make big quantity of fluid and particle separation; In second stage, use centrifugal force to make residual liquid and particle separation at least.As shown in Figure 1, provide the optional phase I, a large amount of water at drying zone 5 by gravity effect and particle separation.Drying zone 5 is parts of Disengagement zone and is in the Disengagement zone, because the pressure on drying zone 5 particles maintains more than the vapor pressure liquid.Slurry in the pipeline flow in the drying zone, and at drying zone, a large amount of liquid 6 flow in the container 8 that is sealed in pipeline 1 by screen cloth 7 because of gravity, thereby allows remaining particle and residual water flow in the centrifugal dryer 10.Perhaps, no matter whether slurry flow is big, and optional drying zone can be exempted fully, and all slurry stream can be introduced in the centrifugal dryer, and need not make a part of liquid and particle separation earlier.
To add drier by slurry inlet 9 by the slurry that pipeline 1 flows, described slurry inlet 9 can be positioned at any position easily, links to each other with drier enclosure 12 fluids, and drier enclosure 12 can be a vertical direction, but if desired, can be horizontal direction.In this diagram, the position of slurry inlet 9 is near the bottom, as the side entrance of drier enclosure 12.Perhaps, slurry can be added by the slurry of outer casing bottom inlet 11, the center by porous armature spindle 13 longitudinally is to the upper reaches, makes slurry and armature spindle tangent and along the length direction distribution of hollow rotor shaft.Any conventional method that slurry is added drier can be accepted.
Slurry enters drier enclosure, and drier is equipped with rotor 13 longitudinally, is connected the lifter 14 on the rotor 13, with cylindrical screen 15, screen cloth 15 has formed Nei Huan district 16 and outer zone 17, and Nei Huan district 16 is the spaces between rotor 13 and the screen cloth 15, and outer zone 17 is spaces of screen cloth 15 outsides.Rotor 13 and be connected epitrochanterian lifter and drive rotation at a high speed by pulley or sheave 18.More than one screen cloth can be provided.
Slurry enters Nei Huan district 16 in a usual manner.High speed rotation by rotor 13 applies centrifugal force to slurry, and lifter 14 is invested cylindrical screen 15 with slurry, and screen cloth 15 has a certain size hole, can keep particle, allow liquid to pass through simultaneously, the effect of above-mentioned centrifugal force and lifter 14 makes liquid and particle separation.Rotor can 200rpm to 4000rpm the rotating speed rotation.The liquid that is thrown away by particle is forced to by screen cloth and enters outer zone, as shown by arrows, is discharged into the bottom of shell 12, and discharges by any one or a plurality of outlet 19.Optional in the enclosure with the liquid of particle separation and in optional drying zone 5 and the liquid of particle separation be merged into 23, and be added in the water pot 32.If exist, preferably control the height 35 of water in the water pot by mode well known in the art.At water pot 32 with enter between the gas access 21 of shell equalization of pressure circuit 34 is provided.Merged with the liquid of particle separation with the liquid of particle separation with in optional drying zone 5 in the enclosure, and optional being recycled, as the source of liquid in the slurry of adding drier 10.If water pot 32 exists, egress line 33 optional recirculation.
Particle in the Nei Huan district rises to the top with the flow pattern of the designing institute qualification of lifter 14.Lifter is lobate or sheet, in order to particle is upwards promoted, generally when rotor 13 rotations, promotes particle with the helical form form.Usually, particle is thrown back and forth by centrifugal force between screen cloth and lifter, and applies power upwards by the lifting blade of configuration.Along with particle rises by the Nei Huan district, they are discharged by drier enclosure 12 by particle outlet 20.
In shell, add air pressurized or other gas by gas access 21 ideally, to keep pressure.Position, any gas access all is fit to.Add gas and can keep shell and be pressurized to requiredly, preferred stable, be higher than the level of vapor pressure liquid.Pressure in the container can be by the monitoring of the probe in the container, and this container leads to the controller 24 of opening compressor 25, enters shell 12 to force air communication piping 21.Owing to need hyperbaric environment in the shell, so preferred shell does not have exhaust fan or is used for the outlet of emission gases.If desired, gas can be added any position in pipeline 1, pipeline 23 or this closed-loop system, pressurize again and keep the vapour pressure that the pressure that adds on the grouting material is higher than liquid under this fluid temperature, thus the pressure of control shell.
In order to hold hyperbaric environment, conventional drier or relevant centrifuge are placed in ASME (or other the suitable pressure vessel code) pressure vessel.Preferably enter the hole according to the pressure vessel code design that is suitable for, in order to the cleaning screen cloth, and other maintenance or inspection.Suitable sealing mechanism is provided, hyperbaric environment and surrounding environment in the pressurization drier are isolated.The mechanical seal of gas lubrication can be preferred design, but many sealing devices can use.Engine has sufficient power to rotate the rotor in pressurization drier or the centrifuge.
In case particle is emitted from drier by circuit 20, as shown in Figure 1, they break away from from the Disengagement zone by the ball valve gas lock.As mentioned above, the granule dispenser of any routine as long as can keep the pressure of container or pipe side, and with the low-pressure area of particulate emission to the distributor opposite side, just can use.As shown in the figure, the dried particles of pressurization is added to first ball valve 26, and ball valve 26 has passage 27, and passage 27 is in the release position, allows grain flow cross this passage, enters air lock chamber 29.When particles filled air lock chamber 29, second ball valve 30 maintains the closed position, and drops to below the vapour pressure of the liquid that separates in drier to prevent the pressure on the dried particles.According to predetermined height, time, density, weight or any other measurement result, first ball valve 26 rotations also are sealed to the closed position, stop particle and further flow into air lock chamber, and keep the vapour pressure that the pressure on dried particles before first ball valve 26 is higher than the liquid that separates in the drier.After first ball valve 26 sealings, second ball valve opened, and makes the content of air lock chamber connect atmosphere.This moment or afterwards, the pressure on the particle is reduced to below the vapour pressure of the liquid that separates in the drier, particle breaks away from from the Disengagement zone effectively.In case the content of air lock chamber is drained, second ball valve rotated to the closed position, first ball valve 26 reopens then, allows more particles fill air lock chamber 29.This order is continuous.
Particle height in the air lock chamber 29 is unrestricted, and desirable situation is to fill air lock chamber, makes highly to surpass 80% of air lock chamber's height, to reduce the gas flow of escaping out when second ball valve 30 opened from system.
If desired, can between the valve of particle outlet 20 and first any kind, provide hold up vessel 31, be used for making particle to gather, provide continuous grain flow, grain flow can not increased sharply, and regulate the speed that particle breaks away to ball valve.
The each disengaging during the step, particle is received in gas lock or the air valve and is released into atmosphere, can cause a certain amount of pressure of loss on the particle.For remedying this loss, above-mentioned pressure regulator to system has been guaranteed to introduce compressed air stream in some positions of system, for example introduces air-flow to circuit 23, introduces air-flow at drier 10 to circuit 1, or introduces air-flow in any suitable position.
When particle when the Disengagement zone breaks away from, estimate on the particle or evaporation of remaining wet branch or flash distillation in the particle, especially as fruit granule be the hot this situation that more is prone to.This evaporation or flash distillation are acceptables, can expect at least some embodiments.Only separate under pressure with particle, be reduced to the dry method difference in back below the vapor pressure liquid at pressure, during the decompression, stayed on the particle a large amount of wet branches, thereby need ensuing drying steps, and this step is used external heat, generally uses hot-air convection.In addition, in such method, have fluid loss to atmosphere, maybe need to reclaim fluid.And as mentioned above, the wet branch of flash distillation is many more on the particle, and the heat loss of particle itself is big more, thereby needs the heat energy of a great deal of to put on particle, to carry out ensuing processing.
In the embodiment preferred, the endocorpuscular It.V. in Disengagement zone does not increase.The particle that breaks away from the back acquisition preferably has its final molecular weight.Therefore, provide an embodiment, the thermoplastic polymer particles of pressurization is provided in this scheme, under at least 130 ℃, and be higher than under the atmospheric pressure, this crystallization of polymer particle degree is at least 20%, It.V. be at least 0.70dL/g, contain the wet branch of certain quantity of fluid, be reduced to below the 50psig, the particle of pressurization is broken away from by pressure with particle, the particle that breaks away from is packed in the cask, wherein, particle before being loaded into cask, not polymerization under solid state.Preferably the high It.V. thermoplastic polymer of preparation in 0.70 to the 1.15dL/g scope in fusion mutually is being enough to make under the fluid temperature of particle crystallization, is being equal to or higher than under the pressure of vapor pressure liquid, contacts a period of time with the form of particle with liquid.In the Disengagement zone, under described pressure,, and with particle drying, produce dried granules stream with liquid and particle separation.Dried granules is broken away from from the Disengagement zone, preferably reach about atmospheric pressure.After this cask is transported to client or dealer.Except the solid-state polymerization, particle can experience many other treatment steps between any described step, for example break away from step and the step of cask that particle packed between other treatment step of experience.
Cask be used on land, the container of sea or air transport.Example comprises railcar, half container, Gaylord box and hull.
Particle is fit to make various article, comprises fiber, pipeline, film, sheet material and mechanograph, for example bottle and plate, especially water pot carbonated drink bottle.
Embodiment
Carried out a test, purpose is with water and approximately crystallizes to the mixture centrifugation and the drying of PETG (PET) particle of about 34-37%.The PET-aqueous mixtures contains the PET particle of 0.75% volume, under the pressure of 155psia this mixture is heated to 165 ℃.PET coating of particles subglobular, the about 2.8mm of diameter, inherent viscosity is 0.80.
Equipment is made up of the vertical centrifugal dryer of type shown in Figure 1, and the rotor running speed is 1750rpm.Add the PET-aqueous mixtures at the drier side bottom.With water from drier through row of conduits to link to each other with the end of drier jar in.The vapor space of jar links to each other with pipeline with the vapor space of drier, so that make the pressure balance between equipment two parts.In this pressure-equalizing passageway, inject pressure-air, so that the pressure of system is controlled at 155psia.Dried granules is come out from the side roof part of drier, enters disconnector, reduces pressure.Disconnector comprises Clothoid type gas lock (RAL).The PET particle be discharged under the atmospheric pressure by RAL and room temperature under the tube in.The temperature of the spheric granules that discharges is 132 ℃.It all is because the water evaporation of not removing causes that the temperature of supposing particle drops to 132 ℃ by 165 ℃, and we infer, before breaking away from the particle percentage of water mostly be 2.15% most.
Claims (56)
1. method, described method is included under the fluid temperature that is higher than described liquid standard boiling point and is equal to or higher than described liquid under the pressure of the vapour pressure under this fluid temperature, the slurry of the pressurization that comprises thermoplastic synthetic polymer's particle and liquid is provided, with the slurry feed of described pressurization to the Disengagement zone, with in this Disengagement zone, be equal to or higher than under the high pressure of this vapor pressure liquid:
A. separating liquid and particle and
B. dried particles.
2. the process of claim 1 wherein that described particle comprises condensation polymer.
3. the method for claim 2, wherein said particle comprises polyester polymers.
4. the method for claim 3, wherein said particle comprises:
A. carboxyl acid component, described carboxyl acid component contains at least 80% mole terephthalic acid residue, terephthaldehyde acid derivative residue, naphthalene-2,6-dioctyl phthalate residue, naphthalene-2,6-dicarboxylic acid derivatives residue or its mixture and
B. hydroxy component, described hydroxy component contains at least 60% mole glycol residue or propane diols residue,
Percentage wherein calculates based on 100% moles of carboxylic acids component residue in the polyester polymers and 100% mole of hydroxy component residue.
5. the method for claim 4, wherein said particle comprises:
A. carboxyl acid component, described carboxyl acid component contain at least 90% mole terephthalic acid residue or terephthaldehyde acid derivative residue and
B. hydroxy component, described hydroxy component contains at least 90% mole glycol residue,
Percentage wherein calculates based on 100% moles of carboxylic acids component residue in the polyester polymers and 100% mole of hydroxy component residue.
6. the method for claim 3, wherein said slurry comprises the condensation polymerization composition granule of degree of crystallinity at least 20%.
7. the method for claim 6, wherein said liquid comprises water.
8. the method for claim 3, wherein said liquid comprises water, and the temperature of described liquid is at least 130 ℃.
9. the process of claim 1 wherein that described Disengagement zone comprises centrifugal dryer or centrifuge.
10. the process of claim 1 wherein that described Disengagement zone comprises screen cloth sedimentation-type centrifuge or rotating cylinder sedimentation-type centrifuge.
11. the method for claim 10, wherein said liquid comprises at least 130 ℃ water.
12. the method for claim 1, described method further comprises by the pressure with polyester polymer particles and is reduced in the Disengagement zone low pressure below the vapor pressure liquid under this fluid temperature, polyester polymer particles is broken away from from the Disengagement zone, before decompression, make simultaneously and keep the high pressure that is higher than vapor pressure liquid under this fluid temperature on the particle.
13. the method for claim 12, wherein said Disengagement zone comprises centrifugal dryer or centrifuge.
14. the method for claim 12, wherein said particle are dried to 5% weight or lower water capacity before disengaging.
15. the method for claim 12, wherein said particle are dried to 2% weight or lower water capacity before disengaging.
16. the method for claim 12, wherein said particle are dried to 1.0% weight or lower water capacity before disengaging.
17. the method for claim 12, wherein said particle are dried to 0.65% weight or lower water capacity before disengaging.
18. the method for claim 12, wherein said particle breaks away from from the Disengagement zone by valve.
19. the method for claim 18, wherein said valve comprise ball valve, disconnecting link valve, cup valve, butterfly valve or rotary valve.
20. the method for claim 12, the pressure after the wherein said disengaging on the particle are reduced to and are lower than 50psig.
21. when the method for claim 12, wherein said disengaging the temperature of the temperature of particle and the liquid that enters the Disengagement zone relatively, in its amplitude of 60 ℃.
22. when the method for claim 21, wherein said disengaging the temperature of the temperature of particle and the liquid that enters the Disengagement zone relatively, in its amplitude of 40 ℃.
23. when the method for claim 22, wherein said disengaging the temperature of the temperature of particle and the liquid that enters the Disengagement zone relatively, in its amplitude of 20 ℃.
24. the method for claim 12, the temperature of liquid is at least 120 ℃ in the slurry of wherein said adding Disengagement zone, and the temperature of the particle that breaks away from is higher than 100 ℃.
25. the method for claim 10, the temperature of liquid is at least 120 ℃ in the slurry of wherein said adding Disengagement zone, and the temperature of the particle that breaks away from is at least 110 ℃.
26, the method for claim 10, the temperature of liquid is at least 140 ℃ in the slurry of wherein said adding Disengagement zone, and the temperature of the particle that breaks away from is higher than 100 ℃.
27. the process of claim 1 wherein at least between a part of separation period and at least between a part of dry period, particle applied centrifugal force at least.
28. the process of claim 1 wherein that at least a portion is recycled to producing the charging that described slurry provides directly or indirectly from the liquid of particle separation.
29. the method for claim 28 wherein described recycled liquid contacts the formation slurry with particle before, is cooled off recycled liquid.
30. the method for claim 28, wherein particle is carried secretly and is entered during the liquid, and the temperature of described liquid is lower than the temperature of particle.
31. the process of claim 1 wherein that described process with liquid and particle separation is divided into first water smoking and two stages of second stage carry out, in first water smoking, under the situation of not using centrifugal force, make big quantity of fluid and particle separation; In second stage, use centrifugal force to make residual liquid and particle separation at least.
32. the method for claim 31, wherein said particle comprises polyester polymers, and described liquid comprises water.
33. a method, described method are included under the fluid temperature that is higher than the liquid standard boiling point, the slurry feed of pressurization that will contain condensation polymerization composition granule and described liquid is to the Disengagement zone that comprises centrifugal dryer or centrifuge; With in the Disengagement zone, under the pressure that is equal to or higher than the vapor pressure liquid under this fluid temperature, make liquid and particle separation and dried particles, wherein,, particle is applied centrifugal force between separation period and between dry period.
34. the method for claim 33, wherein the Disengagement zone comprises the centrifugal dryer of vertical direction.
35. the method for claim 34, wherein said centrifugal dryer are equipped with rotor, the lifter that is connected in rotor, cylindrical screen longitudinally, described cylindrical screen forms the Nei Huan district between armature spindle and screen cloth, and forms outer zone outside screen cloth.
36. the method for claim 35, wherein said and liquid particle separation flows in the outer zone by screen cloth, leave centrifugal dryer by liquid outlet, be promoted to the top of drier with the particle of fluid separation applications, and during the lifting of at least a portion, be dried.
37. the method for claim 33, described method further comprise Compressed Gas is injected described procedure.
38. it is 0.5% weight or lower that the method for claim 33, wherein said particle are dried to water capacity.
39. the method for claim 33, described method further comprise dried granules is broken away to the low pressure that is lower than this vapor pressure liquid from high pressure, keep before breaking away from the vapour pressure of particle simultaneously and be equal to or higher than in the Disengagement zone vapour pressure of liquid under this fluid temperature.
40. the method for claim 39, wherein said liquid comprises water.
41. the method for claim 40, wherein said low pressure is lower than 50psig.
42. the method for claim 39, wherein said particle breaks away from by rotary valve, a series of gate valve or a series of ball valve.
43. the method for claim 39, the temperature of particle is higher than 100 ℃ after the wherein said disengaging.
44. the method for claim 33, described method comprises introduces air lock chamber with dried granules.
45. the method for claim 33, wherein said particle comprises polyester polymers, and described liquid comprises water, and the It.V of described particle is at least 0.70dL/g.
46. the method for claim 45, wherein said particle breaks away from the low pressure to the vapour pressure that is lower than water, is loaded into cask afterwards directly or indirectly, and before the packing, solid-state polymerization does not take place particle.
47. the method for claim 46, wherein said particle breaks away to atmospheric pressure.
48. a disengaging method, described method be included in be higher than under the atmospheric pressure and at least 130 ℃ temperature under, provide and contain the wet thermoplastic polymer particles that divides of certain quantity of fluid; Be reduced to low pressure below the 50psig with pressure with particle, particle is broken away from, the temperature when wherein said particle breaks away from is higher than 100 ℃.
49. the method for claim 48, wherein said particle comprises polyester polymer particles.
50. the method for claim 49, the temperature after wherein said particle breaks away from is at least 110 ℃.
51. the method for a Production and Packaging particle, described method is included under at least 130 ℃ the temperature and is higher than under the atmospheric pressure, provide degree of crystallinity to be at least 20%, It.V. is at least 0.70dL/g, contains the thermoplastic polymer particles of the wet pressurization that divides of certain quantity of fluid; Be reduced to below the 50psig by pressure, the particle of pressurization is broken away from particle; With the granule packaging that breaks away from cask, wherein, described particle before being loaded into cask, not polymerization under solid state.
52. the method for claim 51, wherein said particle comprises polyester polymer particles.
53. the method for claim 52, wherein said polyester polymers has 0.70 to 1.15dL/g the It.V. that obtains in melt phase polymerization, and be equal to or higher than under the pressure of vapor pressure liquid, the polyester polymers of particle form is contacted in the certain liq temperature and time with liquid, make it produce at least 20% degree of crystallinity.
54. the method for claim 53, wherein in the Disengagement zone, under described pressure, described liquid and particle separation and described particle are dried, and produce dried granules stream, and dried granules breaks away from from the Disengagement zone.
55. the method for claim 48, wherein said particle are under the pressure of 50psig at least.
56. the method for claim 55, wherein said particle are under the pressure of 75psig at least.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60672904P | 2004-09-02 | 2004-09-02 | |
| US60/606,729 | 2004-09-02 | ||
| US11/134,946 | 2005-05-23 |
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| CN101438116A true CN101438116A (en) | 2009-05-20 |
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| CNA2005800381727A Pending CN101438116A (en) | 2004-09-02 | 2005-08-29 | Process for separating and drying thermoplastic particles under high pressure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463320A (en) * | 2015-11-16 | 2018-08-28 | 玛格自动化有限责任公司 | A kind of preparation method of plastic granule |
| CN112577267A (en) * | 2020-12-07 | 2021-03-30 | 江苏欧亚环保科技有限公司 | Efficient alloy baking device and baking method thereof |
| CN115435579A (en) * | 2022-09-16 | 2022-12-06 | 鄂尔多斯市中钰泰德煤炭有限公司 | Combined drying process for drying coal |
-
2005
- 2005-08-29 CN CNA2005800381727A patent/CN101438116A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463320A (en) * | 2015-11-16 | 2018-08-28 | 玛格自动化有限责任公司 | A kind of preparation method of plastic granule |
| US11241665B2 (en) | 2015-11-16 | 2022-02-08 | Maag Automatik Gmbh | Method for producing a plastic granulate |
| CN112577267A (en) * | 2020-12-07 | 2021-03-30 | 江苏欧亚环保科技有限公司 | Efficient alloy baking device and baking method thereof |
| CN115435579A (en) * | 2022-09-16 | 2022-12-06 | 鄂尔多斯市中钰泰德煤炭有限公司 | Combined drying process for drying coal |
| CN115435579B (en) * | 2022-09-16 | 2024-04-30 | 鄂尔多斯市中钰泰德煤炭有限公司 | A combined drying process for coal drying |
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