PROCESS AND APPARATUS FOR DIRECT CRYSTALLIZATION OF POLYCONDENSATES

Abstract

The present invention relates to a process for continuous production of partly crystalline polycondensate pellet material, comprising the steps of forming a polycondensate melt into pellet material; separating the liquid cooling medium from the pellet material in a first treatment space, wherein the pellets after exit from the first treatment space exhibit a temperature T.sub.GR, and crystallizing the pellet material in a second treatment space, wherein in the second treatment space fluidized bed conditions exist, and in the second treatment space the pellets are heated by supply of energy from the exterior by means of a process gas.

Claims

1. Process for continuous production of partly crystalline polycondensate pellet material, comprising the steps of a) forming a polycondensate melt into pellet material by adding a liquid cooling medium, which has a temperature below the glass transition temperature (Tg) of the polycondensate, and cooling to an average pellet temperature within the range of temperature of crystallization of the polycondensate, wherein cooling takes place before or during or after forming to pellets; b) separating the liquid cooling medium from the pellet material in a first treatment space, wherein the pellets after exit from the first treatment space exhibit a temperature T.sub.GR, c) crystallizing the pellet material in a second treatment space, wherein in the second treatment space fluidized bed conditions exist, and in the second treatment space the pellets are heated by supply of energy from the exterior by means of a process gas, wherein the process gas has a temperature T.sub.Gas, which is higher than the sum of the pellet temperature T.sub.GR and the temperature increase T.sub.KR which occurs due to heat of crystallization released in the second treatment space, i.e. T.sub.Gas>(T.sub.GR+T.sub.KR) and wherein the pellets at the exit from the second treatment space have an average temperature T.sub.PH, which is 5 to 70° C. higher than the sum of the temperature of the pellets T.sub.GR and the temperature increase T.sub.KR which occurs due to heat of crystallization released in the second treatment space, i.e. (T.sub.GR+T.sub.KR70° C.)≧T.sub.RH≧(T.sub.GR+T.sub.KR+5° C.).

2. Process according to claim 1, wherein the polycondensate is selected from the group consisting of polyesters and polyamides.

3. Process according to claim 2, wherein the polycondensate is a polyethylene terephthalate homopolymer of copolymer.

4. Process according to claim 3, wherein drying of the pellets occurs in the first treatment space, and wherein after exit from the first treatment space the pellets have a temperature T.sub.GR in the range from 100 to 180° C.

5. Process according to claim 1, wherein the cooling medium is water.

6. Process according to claim 5, wherein the water has a temperature in the range from 50° C. to 80° C.

7. Process according to claim 1, wherein the ratio X of the mass flows of gas (m.sub.G) and pellets (m.sub.P) (X=m.sub.G/m.sub.P) is adjusted in the second treatment space such that 1≦(T.sub.Gas−T.sub.KR−T.sub.GR)*X≦80.

8. Process according to claim 1, wherein the residence time of the pellets in the second treatment space is in the range from 1 to 15 minutes.

9. Device for performing the process according to claim 1, comprising a unit for forming pellets with a line for supply of a cooling medium and a line for discharge of a mixture of pellets/cooling medium, a drying unit located downstream of the unit for forming pellets, providing a first treatment space, and a crystallizer located downstream of the drying unit, providing a second treatment space and being provided with each an inlet and outlet for the pellets and a gas, so that in the second treatment space the gas can be led through the pellets under fluidized bed conditions, wherein the crystallizer is provided at the outlet for the pellets with a shut-off device with a housing and a rotor movably arranged therein and having a gap between the rotor and the housing which is larger than the average diameter of the pellets.

10. Device according to claim 9, wherein there is provided, downstream of the shut-off device, a second shut-off device with a housing and a rotor movably provided therein, which has a gap between rotor and housing which is smaller than the average pellet diameter.

11. Process for continuous production of partly crystalline polycondensate pellet material, comprising the steps of a) forming a polycondensate melt into pellet material by adding a liquid cooling medium, which has a temperature above 50° C., but at least 10° C. below its pressure-dependent boiling point, and cooling to an average pellet temperature within the range of temperature of crystallization of the polycondensate, wherein cooling takes place before or during or after forming to pellets; b) separating the liquid cooling medium from the pellet material in a first treatment space, c) crystallizing the pellet material in a second treatment space, wherein the liquid cooling medium is guided in a circular system, and wherein the liquid cooling medium before addition to step a) has a pH Value of more than 4.

12. Process according to claim 11, wherein the liquid cooling medium has a temperature below the glass transition temperature (Tg) of the polycondensate.

13. Process according to claim 11, wherein the liquid cooling medium is supplemented with a basic medium or a pH buffer medium.

14. Process according to claim 12, wherein the liquid cooling medium is supplemented with a basic medium or a pH buffer medium.

15. Process according to claim 11, wherein the amount of liquid cooling medium in the circular system is kept essentially constant by addition of fresh cooling medium, and wherein the fresh cooling medium contains a basic medium or a pH buffer medium.

16. Process according to claim 12, wherein the amount of liquid cooling medium in the circular system is kept essentially constant by addition of fresh cooling medium, and wherein the fresh cooling medium contains a basic medium or a pH buffer medium.

17. Process according to claim 13, wherein the pH buffer medium is present in form of hydrogencarbonate.

18. Process according to claim 14, wherein the pH buffer medium is present in form of hydrogencarbonate.

19. Process according to claim 15, wherein the pH buffer medium is present in form of hydrogencarbonate.

20. Process according to claim 16, wherein the pH buffer medium is present in form of hydrogencarbonate.

Description

[0152] The present invention will now be further elucidated using a non-limiting drawing, where

[0153] FIG. 1 shows a schematic depiction of a preferred embodiment of an apparatus according to the present invention.

[0154] The apparatus according to FIG. 1 has a reactor 1 for producing a polymer melt. This can be a reactor in which a melt polymerization is carried out to thus produce a prepolymer from the monomers. Alternatively, reactor 1 can also be an apparatus for melting a solid product, for example a prepolymer. Reactor 1 can in this case be an extruder for example.

[0155] The molten material is transferred into a pelletization apparatus 2. In the pelletization apparatus 2, a pellet material is produced from the molten material in a known manner. This may involve, for example, an underwater pelletizer (as shown in FIG. 1) or an underwater strand pelletizer. Pelletization takes place under water in this case. The pellets obtained are concurrently cooled down in pelletizer 2. As noted, however, cooling must not be so severe as to cool the pellets to below their crystallization temperature range. This can be achieved via the use of heated water having a temperature above 50° C., but at least 10° C. below it pressure-dependent boiling point, in particular having a temperature below the Tg of the polycondensate, especially having a temperature from 60 to 80° C. The pellet material should in the case of polyethylene terephthalate (PET) be cooled to a temperature in the range from 110 to 180° C., preferably 115 to 160° C. and especially 120 to 150° C.

[0156] The pellet material is transferred via a connection line 3 directly into the unit for drying the pellet material (drying unit) 4. To stop the pellet material from cooling down too much, this pellet material should be conducted as quickly as possible out of the pelletization apparatus 2 and through the connection line 3. Preferably, the flow velocity in connection line 3 can be increased by passing a gas stream (preferably air) into it.

[0157] The pellet material is separated from the liquid cooling medium (water) and dried in the unit for drying the pellet material (drying unit) 4. The cooling medium separated off is conducted via a pipework line 9a back into the stock reservoir vessel (tank) 9b for the cooling medium. The stock reservoir vessel 9b has an inlet 9e for importation of cooling medium. From the stock reservoir vessel 9b, the cooling medium is transferred into the pelletization apparatus 2 by means of a circulation apparatus (pump) 9c. In the course of the transfer, the cooling medium preferably traverses a heat exchanger 9d. In the heat exchanger 9d, the cooling medium can be heated or cooled down, as required. Especially cooling medium returned from the drying unit 4 can have an excessive temperature because of the contact with hot pellet material and has to be cooled before entry into the pelletization apparatus 2.

[0158] The fresh cooling medium, which is added via the inlet 9e, can contain a basic medium or a pH buffer medium. In particular, the use of water with a neutralising or buffer effect which is adjusted within a narrow range is provided herein. Alternatively, the addition of a basic medium or of a pH buffer medium can also be effected directly into the cooling circular system, e.g. into the storage container 9b.

[0159] The drying of the pellet material in the first treatment space of unit 4 is effected at a temperature of 100 to 200° C., preferably 120 to 160° C., by means of air, or a gas atmosphere comprising essentially air, as well as a mechanical drying apparatus. In the apparatus of FIG. 1, the air is conducted into drying unit 4 via an air inlet 10a. The air inlet 10a can be situated in the housing of drying unit 4 or in the connection line 5 or in both locations. Optionally, an aspirating filter (not illustrated) can be disposed in the air inlet line 10a. The air leaves the drying unit 4 through the air outlet 10b. A ventilator 10c for circulating the air through the drying unit 4 is disposed in the air outlet line 10b in the apparatus of FIG. 1. However, the ventilator could alternatively also be disposed in the air inlet line 10a. Furthermore, air inlet 10a and air outlet 10b can be connected to each other to form a circuit system. A condenser would then have to be provided in this circuit system.

[0160] The pellet material is transferred from the dryer 4 via a connection line 5 directly into a crystallizer 6. To avoid pellet adherence and agglomeration, connection line 5 is not equipped with shut-off devices. The pellet material can transition unimpeded from dryer 4 into crystallizer 6.

[0161] In crystallizer 6, the essentially amorphous pellet material is at least partially crystallized. Within crystallizer 6, the pellets are kept moving by a gas stream passing through crystallizer 6. Within crystallizer 6, the conditions are those of a fluidized bed. Additionally, an apparatus for mechanical movement of the particles could also be provided in crystallizer 6.

[0162] The pellets are crystallized by external heat supply, wherein for external heat supply a process gas in counter current to the pellet flow is led through the second treatment space, said process gas having a temperature T.sub.Gas which is higher than the pellet temperature T.sub.GR and the temperature increase T.sub.KR in the second treatment space which occurs due to released heat of crystallization, i.e. T.sub.Gas>(T.sub.GR+T.sub.KR). In the case of polyethylene terephthalate (PET) crystallization occurs at a temperature of 140 to 220° C., wherein at temperatures above 180° C. there is preferably used an inert gas, essentially nitrogen, as process gas. The crystallized pellet material departs the crystallizer via a discharge apparatus 7, for example a shut-off device such as a cellular wheel lock. Said cellular wheel lock is provided with a housing and a rotor movably arranged therein, which has a gap between rotor and housing which is larger than the average pellet diameter.

[0163] Alternatively, downstream of the cellular wheel lock there can be provided a second rotary air lock unit (such as a cellular wheel lock) with a housing and a rotor movably arranged therein, which has a gap between rotor and housing which is smaller than the average pellet diameter.

[0164] The pellets can be subjected to a subsequent thermal treatment such as a de-aldehydization or SSP reaction. Alternatively, the pellets can also be sent into a cooling step.

[0165] The process gas used in crystallizer 6 is conducted through a closed-loop circuit system of pipework lines 8a. The process gas enters crystallizer 6 through an inlet 6a and departs crystallizer 6 through the outlet 6b. The circuit system for the process gas contains a ventilator 8b for circulating the gas. A heat exchanger 8c is provided upstream of inlet 6a to bring the gas to the desired temperature before entry into crystallizer 6. Preferably, the gas is heated in heat exchanger 8c.

[0166] The circuit system of FIG. 1 further comprises a blocking device 8d (a valve, for example) to conduct a portion of the gas in a secondary circuit.

[0167] The circuit system of FIG. 1 further contains a condenser 8e to remove cooling medium from the gas, absorbed by the gas during passage through crystallizer 6. Since, according to the present invention, little cooling medium transitions into crystallizer 6, the dimensions of condenser 8e can be comparatively small.

[0168] The apparatus of FIG. 1 has a feed line 11 for fresh process gas, via which process gas can be fed into the above-described circuit system from an inert gas tank (not illustrated) or be let off out of the circuit system.

[0169] The present apparatus of the present invention is very useful for continuous pelletization and crystallization of a polymer, especially a polycondensate, preferably a polyester such as polyethylene terephthalate.