Title of Invention

"PROCESS AND APPARATUS FOR THE CONTINUOUS POLYCONDENSATION OF POLYESTER MATERIAL IN THE SOLID PHASE"

Abstract

The present invention relates to a process and apparatus for the continuous polycondensation of polyester material in a solid phase, in the form of amorphous or partially crystallized granulate via post-crystallization at 140° C to 250° C and subsequent post-condensation at approx. 200° C to 250° C and final cooling to under 60° C, wherein conventional process gases are used as the heating and cooling medium, the heating-up to the post-crystallization temperature takes place during a time of 1-10 minutes, characterized in that a rapid heating takes place at a heating rate of 50° C/min- 100° C/min to a temperature range of between 200° C and near the melting point of the polyester material, wherein the thickness of the product layer o be traversed by process gas during post-crystallization measures 1-10 cm. The apparatus comprising a post-crystallizer (4, 21), a reactor (10, 27), a granulate cooler and a gas line, characterized in that the post-crystallizer (21) is situated directly over the reactor (27), with which it forms a single unit, a fluidized bed (1) is placed upstream from the post-crystallizer (4).

Full Text

The invention relates to a process and apparatus for the continuous polycondensation of polyester material in a solid phase, in particular of PET in the form of granulate or the like according to the preamble of claim 1, as well as a device for executing the procedure according to the preamble of claims. Depending on the intended use of polyester materials, special properties are necessary. If certain properties can already be modified in a targeted manner with the recipe of components, co-components or additives, other properties, e.g., a high molecular weight and high purity, can only be achieved via subsequent treatment in the solid phase (SSP). Since polyester production and subsequent treatment are most often separated in terms of time and location, granulate is fabricated as an intermediate product. These are precipitated in amorphous form due to a low crysl.allixat.ion rate and rapid cooling of the polyester melt. During granulation and storage, the granulate absorbs liquid, which can lead to hydrolysis during subsequent re melting. In addition, amorphous polyester granulate has a strong tendency to bond at higher temperatures (in particular above 100° C). Various procedures and devices are known for the conventional crystallization and post-condensation of polyester materials in a solid phase, e.g., according to EP-A-379684 or DE-AS-2559290 or US-PS-4238593. To prevent bonding, the granulate is intensively moved during crystallization and polycondensation according to US-A-4064122. Solutions are also kngwn here for keeping the ratio between inflowing process gas to outgoing product during post-condensation to less than 0.6 (EP-A-717061), in order to better control the thermal profile and effectively remove contaminants. The gas can flow in the same or opposite direction as the product stream. To prevent the granulate for subsequent treatment from being heated again, it has already been suggested that polyester material be extruded, ,pelleted and crystallized without cooling the melt (EP-A-822214). In this case/ a temperature of 160 °C to 220 °C is maintained, and only a slight temperature rise to approx. 170° to 230° is necessary for the ensuing SSP process. A similar solution is disclosed in WO-A-97/23543 and US-A-5510454, where melt drops get onto a hot metal plate and partially crystallize. Due to specific crystal structures, the achievable IV values are to be less than 0.3. Low IV values of 0.4 to 0.6 can also be gleaned from US-A-4154920. It is also known to provide a band (ROLLDROP) instead of a metal plate, or to have the material pass as a strand through a drying segment with a casting gutter, through which air streams, wherein granulation takes place after drying (WO'-A-94/25239) . US-A-4.271.287 also discloses a procedure for the continuous polymerization of PET in a solid state. In this case, a combination of fluidized bed crystallization and polycondensation is used, wherein the PET granulate is actively moved during polycondensation. US-A-4.584.366 discloses a procedure for crystallizing and post-condensing of polycondensates in a reactor, which is designed as a continuous shaft/ in which crystallization takes place in the upper section of the shaft and post-condensation takes place in the lower section of the shaft Agitating elements for moving the polycondensate granulate is provided in the upper crystallization section. WO-A-00/01754 discloses a procedure for crystallizing PEN copolymers without a step for removing volatile components. Heating rates ranging from 10 °C/min to 18 °C/min and above are used for heating in the crystallizer. JP-A-59025815 discloses a procedure for crystallizing polyester granulate. Crystallization takes place rapidly, e.g., at 110. °C in 1-2 min to 130 °C in 10 sec-1 min, or at 150 °C in 5-20 sec. Heating to near the melting point of the polyester does not take place. The object of the invention is to develop a procedure for the continuous polycondensation of polyester material in a solid phase, which enables a high throughput of polyester material. The object is achieved with the characterizing features of claim 1. The object of the invention is also to provide a device for executing such a procedure. Preferred execution variants are disclosed in the subclaims. The invention proceeds from the assumption that large quantities of polyester material can be subjected to an SSP treatment without damaging the crystal structures if rapid heating takes place. This rapid heating for recrystallization can take place both with cold and hot granulate. It is necessary to maintain small granulate layer heights to achieve a rapid heating given a high throughput (passing through hot process gas) "within a few minutes. This raid heating must simultaneously be controlled (heating rate) to prevent .the polyester material from melting on or open. The temperature must then be maintained and st in order t avoid a bonding during SSP treatment despite the usual retention times (up to approx. 40 hours) in the reactor. Only a low energy and gas outlay is required relative to the high product quantity. In accordance with the present invention it relates to a process for the continuous polycondcnsation of polyester material in a solid phase, in the form of amorphous or partially crystallized granulate via post-crystallization at 140° C to 250° C and subsequent post-condensation at approx. 200° C to 250° C and final cooling to under 60° C, wherein conventional process gases are used as the heating and cooling medium, the hcating-up to the posl-crystallization temperature takes place during a time of 1-10 minutes, characterized in thai a rapid heating takes place at a heating rate of 50° C/min- 100° C/min to a temperature range of between 200° C and near the melting point of the polyester material, wherein the thickness of the product layer to be traversed by process gas during post-crystallization measures 1-10 cm. In accordance with the present invention relates to an apparatus for the continuous 'polvcondensation of polyester material in a solid phase, preferably granulate, in particular for executing a procedure, comprising a post-crystallizcr (4, 21), a reactor (10, 27), a granulate cooler and a gas line, characterized in that the post-crystallizer (21) is situated directly over the reactor (27), with which it forms a single unit, a fluidized bed (1) is placed upstream from the post-crystallizer (4). The invention will be described in greater detail below in an example based on a drawing are: Fig: 1 a first form of execution in a basic diagram Fig: 2 a second form of execution in a basic diagram Fig 3: a third form of execution in a basic diagram Fig 4: another form of execution in a basic diagram According to fig 1, an amorphous or partially crystallized (approx. 0-50%) polycstcr granulatc with a IV of up to 0.7 and a low temperature (room temperature or higher) or in a hot state (up 10 approx. 200° C) gets into a fluidized bed 1 (type OTWG of the applicant). A hot process gas 2, e.g., air or nitrogen, is here passed through the granulate. The supplied high quantity of gas has a rate of 1.5-4 m/s. In 2-8 minutes, the granulate is heated to 200 °C to 250 °C, so that the layer h3ight measures only 1-30 cm, preferably 2-15 cm. .n known procedures, the heating and retention time measures 2-25 minutes, preferably 15 minutes (EP-A-379684) or 5-30 minutes (EP-A-822214). Instead of a single gas inlet 2, two gas inlets 2 and 3 with varying gas inlet temperatures can be used. The post-crystallizer 4, in which the granulate gets into a channel 5 from above, has a structure corresponding to that disclosed in DE-A-19743461 of the applicant. The channel can enlarge from a width of approx. 5-10 cm (top) to approx. 20-30 cm in the middle area, and to approx. 40-60 cm in the bottom area of the post-crystallizer 4. However, the channel 5 can also have a constant width of 10 cm to 60 cm, for example. Large quantities of gas are passed through the granulate in a cross flow, wherein gas flows in 6 and out 8. The gas can also enter at position 7, and correspondingly exit at position 6. As an alternative, the gas can also pass through the product in a parallel or counter flow. The disclosed configuration of the post-crystallizer 4 yields a uniform granulate throughput given short heating and retention times with ensuing heating (approx. 0.2 to 3 hours, preferably 0.5 to 1 hour) at temperatures of between 200 and 250 °C. The granulate passes directly into the reactor 10 through a channel 9, where it stays for up to approx. 40 hours at a constant temperature for purposes of SSP treatment. To make throughput more uniform and prevent bonding, the reactor 10 has internal parts 11 of the kind known from CH-A-689284 of the applicant. Correspondingly low quantities of gas can be used in a countercurrent. Inert gas, e.g., nitrogen, is used as the process gas. The product is pre-cooled where the gas flows in 12 with a gas entry temperature of less than or equal to 60 °C. The reactor gas exits at position 13, but can alternatively exit at position 8 too. When rapidly heating the product close to the melting point, which happens in the proposed mode of operation (in the fluidized bed 1 and post-crystallizer 4), crystallinity is limited, and it has been shown that this causes the SSP reactivity to rise,sharply (the IV buildup/h is significantly higher than for conventional heating). See Table 1. The SSP treated granulate exits the reactor 10 through a transfer canal 14 to be further cooled to under 60 °C product temperature in a fluidized bed cooler 15. A conventional roof dryer can also be used as the post-crystallizer. A two-stage crystallizer could also be used. In a second configuration according to Fig. 2, the again cold or hot granulate gets into a channel 22 of a system that incorporates a post-crystallizer 21 and reactor 27. The post crystallizer 21 has a similar design as that of the first configuration on Fig. 1 (post-crystallizer 4) . Heating to 200 °C to 250 °C is rapid, and takes place in the uppermost sections of the post-crystallizer 21. The gas rapidly passes through gas inlet 23 to the granulate in channel 22. The retention time in the post-crystallizer 21 measures between 0.5 and 8 hours. The product can again be easily cooled via the gas inlet 24 in the lowermost section of the post-crystallizer 21. The gas exits at position 25. The granulate passes via a channel 26 directly into the reactor 27, where it remains for up to approx. 36 hours at a constant temperature for purposes of SSP treatment. The description of the reactor 27 and the process explanations relating to form of execution 1 also apply to reactor 27. A gas inlet 29 is provided near the floor of the reactor 27, but above a cone. Another gas inlet 30 is located below the channel 26. See Table 1 for the individual data. The SSP-treated granulate exits the reactor 27 through a transfer canal 31, and is further cooled to below a product temperature of 60 °C in a fluidized bed cooler 32. A third form of execution is described according to Fig. 3. In this case, an amorphous or partially crystallized (approx. 0-50 %) polyester granulate with a IV of up to 0.7 and a low temperature (room temperature or higher) or in a hot state (up to approx. 200 °C) in a fluidized bed 41 (type OTWG of the applicant). A process gas 42, e.g., air or nitrogen, is there passed through the granulate, supplied via the gas inlet 42 and/or 43. The supplied high quantity of gas has a velocity of 1.5-4 m/s. Within 2-8 minutes, the granulate is heated to 200 °C to 250 °C, which is why the layer height only measures 1-30 cm, preferably 2-15 cm. The granulate then gets into a conditioner 44, which is provided with annular internal parts 45 made out of sheet. The internal parts 45 are arranged in such a way as to achieve a certain directional reversal and, at a low product pressure, a high granulate settling rate. The settling rate in the upper area of the conditioner 44 is higher than in the ensuing reactor 49, but at least about the same. The internal parts 45 can also be straight (vertical). The conditioner 44 is used to further heat the granulate to approx. 220 °C-250 °C, set and maintain the temperature, and cool as necessary in the event of overheating. The granulate is heated in a parallel or counter flow by means of process gas (gas inlet 46 and gas outlet 47 can be switched if necessary), and kept for 1-8 hours in the conditioner 44 The IV value is elevated in the process. The granulate then gets directly to the reactor 49 located under the conditioner 44 via the transfer section 48, wherein it stays at a constant temperature for up to 36 hours for purposes of SSP treatment. To even out throughput and prevent bonding, the reactor 49 has internal parts 50, as are also known from CH-A-689284 of the applicant. The process can be executed in the counter-flow mode with correspondingly low quantities of gas. Inert gas, e.g., nitrogen, is used as the process gas. The product is pre-cooled in the area of the gas inlet 51 at a gas inlet temperature of less than 60 °C. A ga outlet 52 is to be provided as in Fig. 2. When rapidly heating the product near the melting point, which happens during operations such as those proposed (in the fluidized bed 41 and conditioner 44), crystallinity development is limited, and it has been shown that the SSP reactivity increases sharply as a result (the IV buildup/h is significantly higher than during conventional heating). See also Table 1. The SSP treated granulate exits the reactor 49 through a transfer canal 53 to be cooled further in a fluidized bed cooler 54 to below 60 °C. In another form of execution according to Fig. 4, an amorphous or partially crystallized (approx. 0-50 %) polyester granulate wi|".h an IV of up to 0.7 and a low temperature (room temperature or higher) or in a hot state (up to 20'0 °C); gets into a fluidized bed 61 (type OTWG of the applicant). A hot process gas 62, e.g., air or nitrogen, is there passed through the granulate. The supplied high quantity of gas has a rate of 1.5-4 m/s. Within 2-8 minutes, the granulate is heated to 200 °C to 250 °C, so that the layer height only measures 1-30 cm, preferably 2-15 cm. Two gas inlets 62 and 63 with varying gas inlet temperatures can also be used in place of the ga's inlet 62. The granulate subsequently gets into a conditioner 65 via a distributor 64. The distributor distributes the product through 6 to 16 pipes over the entire ring surface of the cond-tioner 65; The conditioner 65 itself is designed as a hollow cylinder. The product moves from the top down in the outer ring. The inner ring 66 is free of product and gas. The outside diameter minus the inside diameter of the hollow ! cylinder measures a constant 80 to 200 cm, preferably 120-160 cm (product distance between the outer wall and inner wall therefore measures 40 to 100 cm, preferably 60-80 cm) . This results in a low product pressure and high granulate settling rate in the conditioner 65. The geometry of the conditioner 65 can also be similar to the post crystallizer 4 according to the first form of execution, i.e., in that the section of the conditioner filled with product increases in diameter from the top down, i.e., the product distance between the outer wall and inner wall incrementally or continuously increases from the top down, e.g., from 40 cm at the top to 100 cm at the bottom in the direction of product flow. As a result, the uppermost area of the conditioner has the lowest product pressure and highest settling rate, which then varies as the granulate treating time increases. Also provided is a gas inlet 68. The conditioner 65 is used to further heat the granulate to approx. 200-250 °C, preferably 220-235 °C, set and maintain the temperature, or, if needed, cool during overheating. In the parallel flow (gas inlet 68 and gas outlet 69) or counter flow (gas inlet 69 and gas outlet 68) , the granulate is heated with a process gas and kept in the conditioner 65 for 1-8 hours. The IV value is increased in the process. The product exits the conditioner 65 and enters a transfer section 70. the temperature is here set for the ensuing reactor 73. This is done using a gas supply system 72 with inert gas (counter flow heat exchange) , wherein the temperature can measure between 200 °C and 250 °C, depending on the product. As an alternative, the transfer section 70 can be omitted. The granulate exits the transfer section 70 and enters the reactor 73, where it remains for up to 40 hours at a constant temperature • for SSP treatment. To make throughput more uniform and prevent bonding, the reactor 73 has internal parts 74 of the kind known from CH-A-689284 of the applicant. Correspondingly low gas quantities can be used in the counter flow mode. Inert gas, e.g., nitrogen, is used as the process gas. The product is pre-cooled in the area of the gas inlet 75 at a gas inlet temperature of less than or equal to 60 °C. The reactor gas exits at position 69. While rapidly heating the product near the melting point, which happens in the proposed mode of operation (in the fluidized bed 61 and conditioner 65) , crystallinity formation is limited, and it has been shown that this causes the SSP reactivity to increase sharply (the IV buildup/h is significantly higher than during conventional heating). See Table 1. The SSP-treated granulate exits the reactor 10 through a transfer canal 76, and is further cooled in a fluidized bed cooler 177 to below a. 60 °C product temperature. It would additionally be conceivable to provide a central gas outlet 69 from the reactor 73 and/or conditioner 65. It would be a reversal of conventional, dome-shaped gas distributors 67, 71. To ensure the corresponding pressure conditions, the gas is then discharged via a central tube and four gas outlet tubes offset by 90°. One or two such gas outlets can be provided given a unidirectional throughput to conduct the large quantities of gas efficiently. In all forms of execution, the product can be passed through in a combined counter and parallel flow in order to achieve a low pressure, preferably under 1 bar. So that the process can again be used after leaving the reactor, post-crystallizer and/or pre-heater, it preferably passes through a gas cleaning system, a filter, a gas washer/scrubber or a catalyst and a molecular dryer. Table la: The influence of heating rate up to 200 °C (Table Removed) Table 1b: The influence of heating rate up to 230 °C (Table Removed) Table 1c: The influence of temperature (Table Removed) Table 1d: The influence of retention time (Table Removed) LIST OF REFERENCE NUMBERS 1 Fluidized bed 2 Gas inlet 3 Gas inlet 4 Post crystallizer 5 Canal 6 Gas inlet 7 Gas inlet 8 Gas outlet 9 Canal , 10 Reactor^ 11 Internal parts 12 Gas inlet 13 Gas outlet 14 Transfer canal 15 Fluidized bed cooler 21 Post crystallizer 22 Canal 23 Gas inlet 24 Gas inlet 25 Gas outlet 26 Canal / 27 Reactor ^ 28 Internal parts 29 Gas inlet 30 Gas outlet 31 Transfer canal 32 Fluidized bed cooler 41 Fluidized bed 42 Gas inlet 43 Gas inlet 44 Conditioner 45 Internal parts 46 Gas outlet 47 Gas outlet 48 Transfer section 49 Reactor N/ 50 Internal parts 51 Gas inlet 52 Gas outlet 53 Transfer canal 54 Fluidized bed cooler 61 Fluidized bed 62 Gas inlet 63 Gas inlet 64 Distributor 65 Conditioner 66 Inner ring 67 Gas distributor 68 Gas inlet 69 Gas outlet "70 Transfer section 71 Gas distributor 72 Gas supply 73 Reactor _74 Internal parts 75 Gas inlet 76 Transfer canal 77 Fluidized bed cooler WE CLAIM: 1 . A process for the continuous polycondensation of polyester material in a solid phase, in the form of amorphous or partially crystallized granulate via post crystallization at 140° C to 250° C and subsequent post-condensation at approx. 200° C to 250° C and final cooling to under 60° C, wherein conventional process gases are used as the heating and cooling medium, the heating-up to the post-crystallization temperature takes place during a time of 1-10 minutes, characterized in that a rapid heating takes place at a heating rate of 50° C/min-100° C/min to a temperature range of between 200° C and near the melting point of the polyester material, wherein the thickness of the product layer to be traversed by process gas during post-crystallization measures 1-10 cm. 2. A process as claimed in claim 1 wherein the thickness of the product layer to be traversed by process gas during post-crystallization in a canal measures 5-60 cm. 3. A process as claimed in claim 1, wherein the thickness of the product layer to be traversed by process gas during post-crystallization measures 3-8 cm. 4. A process as claimed in claim 1 or 2 wherein the heating up and retention time measures 28 minutes. 5. A process as claimed in claims 1 to 4 wherein a high quantity of gas with a flow rate of 1.5 to 4 m/s is used during post-crystallization. 6. A process as claimed in claim 1, wherein the initial IV (intrinsic velocity) of the polyester material measures up to approx. 0.7. 7. A process as claimed in claim 1 to 6 wherein the polyester material is traversed in a cross current or counter current and/or parallel current. 8. A process as claimed in claims 1 to 7 wherein the post-condensation polycster material is pre-cooled by the process gas in the area of the gas inlet. 9. A process as claimed in one of claims 1 to 8, wherein the nitrogen is used as the process gas. 10. An apparatus for the continuous polycondensation of polyester material in a solid phase, preferably granulate, in particular for executing a procedure as claimed in claim 1 or claim 2, comprising a post-crystallizer (4, 21), a reactor (10, 27), a granulate cooler and a gas line, characterized in that the post-crystallizer (21) is situated directly over the reactor (27), with which it forms a single unit, a fluidized bed (1) is placed upstream from the post-crystallizer (4). 11. An apparatus as claimed in claim 10, wherein the reactor (10, 27, 49, 73) has annular internal parts (4), which are preferably arranged in the same direction. 12. An apparatus as claimed in claim 10, wherein the conditioner (44) has annular internal parts (45) that are arranged in the opposite direction. 13. An apparatus as claimed in claim 10, wherein it has a filter, a gas washer/ scrubber or a catalyst and a molecular sieve dryer for gas purification. 14. A process for the continuous polycondensation of polyester material in a solid phase substantially as herein described with reference to the foregoing description and the accompanying tables and drawings. 1 5. An apparatus for the continuous polycondensation of polyester material in a solid phase substantially as herein described with reference to the foregoing description and the accompanying tables and drawings.

Documents:

1253-delnp-2003-abstract.pdf

1253-delnp-2003-claims.pdf

1253-DELNP-2003-Correspondence-Others (22-12-2009).pdf

1253-delnp-2003-correspondence-others.pdf

1253-delnp-2003-correspondence-po.pdf

1253-delnp-2003-description (complete).pdf

1253-delnp-2003-drawings.pdf

1253-delnp-2003-form-1.pdf

1253-delnp-2003-form-13.pdf

1253-delnp-2003-form-19.pdf

1253-delnp-2003-form-2.pdf

1253-DELNP-2003-Form-26-(22-12-2009).pdf

1253-delnp-2003-form-3.pdf

1253-delnp-2003-form-4.pdf

1253-delnp-2003-form-5.pdf

1253-delnp-2003-gpa.pdf

1253-DELNP-2003-PA.pdf

1253-delnp-2003-pct-210.pdf

1253-delnp-2003-pct-308.pdf

1253-delnp-2003-pct-409.pdf

1253-delnp-2003-petition-137.pdf