Patent Application
20160108173
The invention is related to novel thermosiphon esterifier designs and to systems and methods implementing such novel designs.
Poly(ethylene terephthalate) (PET) resins are widely produced and used, for example, in the form of fibers and in the form of bottle resin. PET is commonly used in the production of beverage and food containers, thermoforming applications, textiles, and as engineering resins. PET is a polymer based on the monomer unit bis-β-hydroxyterephthalate, which is commonly formed from ethylene glycol and terephthalic acid (or dimethyl terephthalate),
The manufacturing process for PET is generally conducted within a series of melt phase reactors, which may include an esterifier, up flow pre-polymerizer (UFPP) and finisher. These reactors typically operate at temperatures above 270° C., while the operating pressure reduces from super-atmospheric pressure in the first reactor (esterifier) to nearly full vacuum in the final reactor (finisher).
The raw materials for PET production are ethylene glycol and phthalic acids. The phthalic acids are typically 100% terephthalic acid for the production of polyester fibers, but may contain up to 5% isophthalic acid for bottle resins. Catalysts and other additives may be added to the process at any point, but are normally injected at some point before the first tray of the UFPP. In the esterifier, ethylene glycol is reacted with terephthalic acid via an esterification reaction to form an oligomer and water vapor as a byproduct. The oligomer is then polymerized in the UFPP and finisher to form the PET polymer product with ethylene glycol and water as byproducts.
Although both esterification and polymerization can occur to some extent in each of the reactors, typically, 85-95% of the esterification reaction is completed within the esterifier. The size (i.e., residence time) and cost of the esterifier for a given plant throughput is determined by the need to accomplish sufficient esterification at the required esterifier reaction conditions (i.e., temperature and feed molar ratio of ethylene glycol to phthalic acid). The esterifier generally can consume more than 70% of the energy input to the system because the esterifier has to heat the incoming reactants up to the temperature required for the esterification reaction, and this reaction requires the vaporization of the water byproduct and excess ethylene glycol used to drive the reaction forward.
Various esterifier designs have been implemented within PET production systems, including thermosiphon esterifiers. Thermosiphon esterifiers generally comprise a vapor separator in combination with a heat exchanger. The heat exchanger can have vertically extending passages for fluid and an upper fluid outlet and a lower fluid inlet, the upper outlet communicating with the side of the thermosiphon system and the lower inlet being connected with the bottom of the thermosiphon system by a conduit loop, overflow means in the vessel for continuous withdrawal of esterification product at a rate which maintains a constant liquid level, means in the upper part of the vessel for withdrawing vapors, and means for injecting cold reactant feed mixture into the lower fluid inlet of the heat exchanger. Such esterifier designs are provided, for example, in U.S. Pat. No. 3,927,982 to Chapman and Temple, which is incorporated herein by reference.
Although thermosiphon esterifiers provide for vigorous mixing and enhanced heat transfer as compared to other types of esterifiers, they can often experience unstable recirculation rates. Such instability can cause operating difficulties in maintaining inventory control within the esterifier. It would thus be advantageous to provide modified esterifier designs to provide increased recirculation rate stability and overall energy savings.
The present invention provides a thermosiphon esterifier for use in polyethylene terephthalate) production, which can provide for a more effective PET production process. It further provides systems and methods for the production of PET utilizing such esterifiers. The inventors have discovered surprising economic benefits associated with the control of certain features of the thermosiphon esterifier and overall PET production system utilizing such an esterfier.
In one aspect of the present invention is provided an improved thermosiphon esterifier design comprising a heat exchange member, a crossover pipe in fluid communication with the heat exchange member, a vapor separation member, and a riser baffle member positioned within the vapor separator and in fluid communication with the crossover pipe.
The specific parameters and features of the riser baffle, vapor separator, and remaining components of the thermosiphon esterifier design can vary; certain exemplary parameters that may be employed in certain embodiments of the systems described herein are as follows:
Having thus described the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the inventions are shown. Indeed, these inventions may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout. As used in the specification, and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise.
Briefly, the present invention provides systems and methods for the production of polyethylene terephthalate (PET). More specifically, the invention provides novel esterifier designs that can be used within such systems and methods. The novel esterifier designs provided herein can, in some embodiments, provide improved productivity and/or economic benefits,
The novel esterifier designs described herein provide improvements over known thermosiphon esterifiers, such as described in U.S. Pat. No. 3,927,982. to Chapman and Temple (hereinafter “the '982 patent), which is incorporated herein by reference. Thermosiphon esterifiers are generally systems for the esterification, e.g., of ethylene glycol and phthalic acids to form oligomers, wherein no mechanical pumping is required to circulate the esterification product.
The thermosiphon esterifiers described in the '982 patent generally comprise an esterification vessel in combination with a heat exchanger, having vertically extending passages for fluid and having an upper fluid outlet and a lower fluid inlet, the upper outlet communicating with the side of the reaction vessel and the lower inlet being connected with the bottom of the reaction vessel by a conduit loop, overflow means in the vessel for continuous withdrawal of esterification product at a rate which maintains a constant liquid level, means in the upper part of the vessel for withdrawing vapors and means for injecting cold reactant feed mixture into the lower fluid inlet of the heat exchanger. In use, the thermosiphon esterifier of the '982. patent is first prefilled with reaction product, heated to reaction temperature, e.g., 250° C. to 400° C., and then a cold slurry of reactants is pumped into the lower fluid inlet of the heat exchanger. In the inlet end of the heat exchanger, the cold reactant slurry feed is quickly mixed with the hot reaction product recycling between the reaction vessel and the heat exchanger, and thereby quickly brought to reaction temperature. Some reactants may vaporize within the heat exchanger and the vaporized components, including water and other volatile byproducts of the esterification reaction evolved in the heat exchanger, can form a liquid comprising a foam. The liquid/foam mixture is less dense than the liquid contained in the thermosiphon pipe on the opposing vertical side of the esterifier. This density difference makes the fluid circulate within the esterifier. Byproduct vapor and excess reactant vapor are removed from the reaction vessel, to maintain a constant pressure, through the means for withdrawing gaseous products, and liquid reaction product is continuously drawn off from the reaction vessel, through the overflow means provided, to maintain a constant liquid level. Typically, two types of recirculating flows are possible, and it is known that in certain situations, a given system can operate between the two types of recirculating flows. The foam in the heat exchanger can expand or collapse, giving the appearance of an overall inventory change in the esterifier. This can also result in instability, making it impossible to change the overall operating pressure within the esterifier significantly.
In certain embodiments, the present disclosure provides a thermosiphon esterifier that can address certain disadvantages associated with traditional thermosiphon esterifiers. Specifically, in some embodiments, a novel thermosiphon esterifier design is provided that can allow for a smaller inventory to be used with the same throughput. In some embodiments, this provides improved productivity as compared with traditional thermosiphon esterifiers (as significantly less residence time in the esterifier may be required, all other reaction conditions being equal). In some embodiments, a higher operating pressure within the thermosiphon esterifier is possible, as thermosiphon recirculation rates may, in some embodiments, not be significantly reduced at higher esterifying pressure. In turn, use of a higher operating pressure can, in certain embodiments, allow the same product to be made with lower excess ethylene glycol in the esterifier, leading to a reduction in plant operating costs. In some embodiments, it is possible to maintain inventory control within the esterifier.
According to one embodiment of the present disclosure, a novel thermosiphon esterifier design is provided, comprising a riser baffle in the vapor separation portion of the thermosiphon esterifier that is adapted to receive product flow from the crossover pipe. The riser baffle can, in some embodiments, reduce the instability commonly associated with the operation of thermosiphon esterifiers. Consequently, in some embodiments, the presence of a riser baffle can help to ensure that the inventory of the esterifier stays consistent. Surprisingly, the incorporation of such a riser baffle can provide a significant improvement to esterifier productivity. In some embodiments, the riser baffle can allow for the use of higher pressures within the thermosiphon esterifier, which can lead to faster reaction times (i.e., less residence time of reactants within the thermosiphon esterifier).
One exemplary thermosiphon esterifier comprising such a riser baffle is illustrated in
The recirculating oligomer product thus mixes with the freshly injected reactants, which begin to react and the mixture then flows upward through the heat exchanger 1, where the mixture is heated further to reaction temperature by heat transfer fluid contained in heat exchanger tubes 6 (effectively reversing the cooling effect caused by the injection of cool slurry to the recirculating oligomer). The heat transfer fluid is supplied to the heat exchanger 1 through heat transfer fluid inlet 11 and leaves the heat exchanger via the heat transfer fluid outlet 12. During residence within the heat exchanger, much of the excess ethylene glycol reactant added and byproduct water produced in the esterification reaction between ethylene glycol and a phathalic acid are vaporized. The formation of this vapor in heat exchanger 1 reduces the density of the oligomer mixture flowing through the heat exchanger 1. It is this density difference between the vapor-laden oligomer in heat exchanger 1 and the essentially vapor-free oligomer in the down flowing section of the thermosiphon pipe 3, which provides the motive force to drive recirculation of the contents within the thermosiphon esterifier.
After passing through heat exchanger 1, the recirculating reaction mixture (including the oligomer used to pre-fill the system, newly-formed product, excess reactants, and/or byproducts) leaves the heat exchanger via crossover pipe 4, entering vapor separator 2 by flowing upwards through and out over the top of riser baffle 5. As the reaction mixture passes out into vapor separator 2, most of the vapor separates from the oligomer by gravity. The vapor flows upwards and out through vapor outlet 9, while the oligomer flows downwards past riser baffle 5 into the main volume of vapor separator 2.
Vapor separator 2 provides additional residence time for further reaction and allows any vapor formed to flow counter-currently to the downward flowing oligomer. This vapor can exit the system with vapor escaping the oligomer at riser baffle 5. The oligomer flowing through vapor separator 2 exits via thermosiphon pipe 4 connected to the bottom of vapor separator 2. Thermosiphon pipe 4 connects the bottom of vapor separator 2 to the heat exchanger 1 inlet, to allow oligomer to recirculate around the esterifier. Several product discharge nozzles are provided at the lowest point of thermosiphon pipe 4 to allow product to be withdrawn from the esterifier before further slurry injection (e.g., by pumps which transfer oligomer to the UFPP for the next step of PET production, polymerization).
According to the present invention, the inclusion of a riser baffle as described herein can have certain advantages in the operation of a thermosiphon esterifier. A baffle generally is understood to be a fluid flow-directing component. The shape, size, and features of a riser baffle useful according to the present disclosure can vary. For example, in some embodiments, the riser baffle can have a height that is greater than or equal to half the diameter of the crossover pipe (e.g., 4 in the embodiment depicted in
D
CO/2≦HRB≦HU.
The shape of the riser baffle wall can be convex or concave with respect to the flow from the crossover pipe 4. A cross-sectional view showing the riser baffle 5 of
In some embodiments, the cross-sectional area of the upflow side of the riser baffle (ARu) is related to the diameter of the vapor separator above the top of the riser baffle (DVS) by the formula:
0.05π(DVSL)2/4≦ARu≦0.95π(DVSL)2/4
In some embodiments, the cross-sectional area of the upflow side of the riser baffle (ARu) is related to the diameter of the vapor separator below the bottom of the riser baffle (DVSL) by the formula:
0.05π(DVSL)2/4≦ARu≦0.95π(DVSL)24
The bottom of the riser baffle can, in some embodiments, form an angle between 0 and 80 degrees with the horizontal. Similarly, the top of the riser baffle can, in some embodiments, form an angle between 0 and 80 degrees. These angles can be understood with reference to the embodiment of
The specific shape and size of vapor separator 2, within which the baffle described herein is employed, can vary. The overall shape of the vapor separator in the embodiments illustrated in
The angles of the walls of the fightbulb-shaped vapor separator can be varied to provide a range of specific designs. For example, as shown in
In another embodiment, an alternative vapor separator design within a thermosiphon esterifier, as schematically illustrated in
In the embodiment of
The diameter of the vapor separator (either lightbulb or straight-sided design) can be, in some embodiments, selected such that the upward superficial vapor velocity in the vapor separator is less than about 2 meters/second, where the superficial vapor velocity is calculated assuming that the only gases present are steam and ethylene glycol vapor, the esterification reaction is 100% complete, all ethylene glycol in excess of stoichiometric requirements is vaporized and that the gases obey the ideal gas theory. In some embodiments, the vertical distance between the top of the riser baffle and the point at which the vapor separator cross-section starts to reduce (HFB) is between about 0 meters and about 5 meters.
The vapor separator and the baffle feature having been described above, the remaining components of the thermosiphon esterifier and the parameters thereof (e.g., diameters, heights, capacities, distances between components, etc.) can vary. Certain parameters can, however, be beneficial to the operation of the thermosiphon esterifiers described herein. The features described in the present application can be applied to a range of thermosiphon esterifier designs, which may, in some embodiments, provide farther benefits as compared with traditional thermosiphon esterifiers.
For example, in some embodiments, there is a minimum vertical distance HTS between the slurry injection point (e.g., 7) and the top of the riser baffle. This height can, in some embodiment, affect the recirculation rate obtained within the thermosiphon esterifier. Advantageously, in some embodiments, a minimal value for this height is about 8 meters or greater (e.g., between about 8 meters and about 20 meters), in some embodiments, there is a preferable range of horizontal distance between the center line of the downflowing leg of the thermosiphon pipe (4) and the center line of the upflowing leg of the thermosiphon pipe, WCLS, which can be defined with respect to the diameter of heat exchanger 1 and the diameter of the vapor separator 2. For example, in some embodiments, this horizontal distance is within a range represented by the following:
(DHE+DVS)/2≦WCLS≦(DHE+DVS)/2+5)
wherein DHE is the diameter of the heat exchanger (e.g., the maximum diameter of the heat exchanger), and DVS is the diameter (e.g., the maximum diameter) of the vapor separator.
The properties of the heat exchanger 1 and the components thereof can also vary. The heat transfer fluid utilized in the heat exchanger tubes 6 can be one of a number of heat transfer media which can operate up to temperatures of about 340 ° C. or greater in either the liquid or vapor phase. One exemplary heat transfer fluid used is a mixture of biphenyl and diphenyl oxide, commercially available as DOWTHERM™ A (Dow® Corning Corporation), operating in the vapor phase, In some embodiments, the diameter (DT) of the tubes 6 used in the heat exchanger can be between about 0.5 inches and about 4 inches. The ratio of operating liquid inventory to the heat transfer surface area, based on heat exchanger tube outside diameter, provided by the heat exchanger is, in some embodiments, advantageously greater than about 0.3 cubic meters of operating liquid inventory per square meter of heat transfer surface area.
In some embodiments, a catalyst can be used in the thermosiphon esterifier to promote the reaction. For example, one or more catalysts can be injected into the esterifler with the slurry feed (e.g., into inlet 7). The catalyst can be any type of catalyst known to promote esterification, oligomerization, and/or polymerization reactions between ethylene glycol and phthalic acids. For example, in certain embodiments, the catalyst can be an organic or inorganic compound (e.g., an antimony, tin, titanium, lanthanum, zinc, copper, magnesium, calcium, manganese, iron, cobalt, zirconium, or aluminum compounds, such as oxides, carbonates, acetates, phosphorus derivatives, alkyls, or alkyl derivatives) or a strong acid (e.g., sulfuric acid, sulfophthalic acid, sulfosalicylic acid, or antimonic acid). See, for example, EP 812818, WO 99/28033; U.S. Pat. No. 6,998,462 to Duan et al., U.S. Pat. No. 3,056,818 to Werber, U.S. Pat. No. 3,326,965 to Schultheis et al.; U.S. Pat. No. 5,981,690 to Lustig et al; and U.S. Pat. No. 6,281,325 to Kuruan, which are incorporated herein by reference. In some embodiments, use of a catalyst in the thermosiphon esterifiers described herein can result in increased productivity (e.g., faster reaction, shorter residence time of reactants and products in the esterifier, etc.).
In certain embodiments, the diameter of the crossover pipe 4, having a diameter DCO, has a minimum value, e.g., about 0.2 meters or greater. In sonic embodiments, the thermosiphon pipe 3 has a minimum diameter, e.g., the diameter of the thermosiphon pipe (DTS) can, in some embodiments, be greater than about 0.2 meters. In certain embodiments, the diameter of the thermosiphon pipe (D TS) can be relatively constant along its length. In certain embodiments, a thermosiphon esterifier according to the present invention comprises a thermosiphon pipe having one or more bulges therein’ (i.e., portions of the thermosiphon pipe having an enlarged diameter). Exemplary embodiments showing a bulge in the thermosiphon pipe are schematically illustrated in
In other embodiments, a distillation column can be positioned in fluid communication with the vapor outlet on the vapor separator. The vapor from the vapor separator passes through a one-way valve, or similar device that allows the esterifer vapor to pass into the distillation column and prevents liquid from entering the esterifier, and is distilled in the distillation column. The bottom of the distillation column can have a liquid discharge.
The thermosiphon esterifiers described herein can provide various advantages over traditional thermosiphon esterifiers. In use, the thermosiphon esterifiers of the present disclosure can, in some embodiments, be operated at higher operating pressures than traditional thermosiphon esterifiers and, in some embodiments, thermosiphon esterifier recirculation rates are not significantly reduced at such high operating pressures. This property is in contrast to traditional thermosiphon esterifiers, wherein the greater instability in the esterifier inventory results in greater system instability. In some embodiments, the operating pressure measured in the vapor space at the top of the vapor separator in the thermosiphon esterifiers described herein is greater than about 1,65 atmospheres absolute. Because, in some embodiments, the pressure at which the thermosiphon esterifiers described herein are operated can be increased as compared with traditional thermosiphon operation, a smaller inventory can be used for the same reaction throughput in certain embodiments. In some embodiments, for a given reaction capability, a then iosiphon esterifier as described herein can be smaller in size than a traditional thermosiphon esterifier for the same reaction capability.
The thermosiphon esterifiers described herein can be operated batch wise, semi-continuously, or continuously. A continuous process is preferred, wherein the reactants (i.e., terephthalic acid, isophthalic acid for bottle grade polyester resin at a ˜less than 5% of the total plithalic acids, and ethylene glycol) can be continuously introduced to the esterifier via inlet 7, and wherein oligomer product can he continuously withdrawn via product discharge outlet 8). Advantageously, the entire thermosiphon esterifier, or at least portions thereof is insulated to prevent undue heat loss while operating at high temperatures.
In use, the level of liquid on the downflow side of the riser baffle with respect to the cross-over pipe 4 can vary. In the figures, the liquid is illustrated as being above the level of crossover pipe 4 and as being at the same height as the maximum height of riser baffle 5. However, in practice, the liquid level on the downflow side of the riser baffle can be modified significantly and can range from a level below the bottom of the crossover pipe up to a level above the top of the riser baffle (e.g., up to the top of the (upper) cylindrical section of the vapor separator). For example, in some embodiments, the liquid level on the downflow side of the riser baffle can be at about the top of the crossover pipe or below or higher. Although in traditional thermosiphon esterifiers, having the liquid above the top of the crossover pipe can result in excessive vibration of the system and can lead to equipment damage, the novel thermosiphon esterifiers described herein may, in certain embodiments, be operated with varying liquid levels with little to no detrimental effect.
Various advantages of the riser baffle-containing thermosiphon esterifiers described herein are more evident in the examples provided in the Experimental discussion below.
The experimental data provided herein is based on the embodiments illustrated by the Figures. Computer modeling data based on these embodiments is provided.
A thermosiphon esterifier according to the present disclosure as illustrated in
It is apparent based on this modeling that the productivity of Traditional Thermosiphon Esterifier A is comparable to the productivity of inventive Thermosiphon Esterifier 1; however, the operating conditions required for Traditional Thermosiphon Esterifier A are more harsh. In the last column of the table, the productivity of Inventive Thermosiphon Esterifier 1 is modeled using the same conditions as Traditional Thermosiphon Esterifier A. It is clear that Inventive Thermosiphon Esterifier 1 is more productive than Traditional Thermosiphon Esterifier A when they are operated under the same conditions,
A thermosiphon esterifier according to the present disclosure (i.e., as illustrated in
It is apparent based on this modeling that the productivity of inventive Thermosiphon Esterifier 2 is higher than that of Traditional Thermosiphon Esterifier B even though the operating conditions for Inventive Thermosiphon Esterifier 2 are more mild. In the last column of the table, the productivity of Inventive Thermosiphon Esterifier 2 is modeled using the same conditions as those of Traditional Thermosiphon Esterifier B. Again, it is clear that Inventive Thermosiphon Esterifier 2 is more productive than Traditional Thermosiphon Esterifier B when they are operated under the same conditions.
The thermosiphon esterifiers described above in Examples 1 and 2 are compared to determine the heat exchange area requirement for each.
In the Inventive Thermosiphon Esterifier designs (1 and 2), a much larger operating volume can be supported by each square meter of heat transfer area. This means that, using the Inventive Thermosiphon Esterifier designs, a smaller heat exchanger can be used for a given esterifier volume, thus facilitating a reduced capital cost for a given esterifier capacity.
A thermosiphon esterifier according to the present disclosure (i.e., as illustrated in
Operation of a thermosiphon esterifier according to the present disclosure (i.e., as illustrated in
From the table, it can be seen that the esterifier temperature is lower and the slurry feed molar ratio is reduced when the catalyst is present. When the catalyst is present, the esterifier operating conditions require less energy to produce the same oligomer (as measured by the carboxyl content) in the same residence time, thereby making the esterifier more energy efficient.
Many modifications and other embodiments of the invention will come to mind to one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing description. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
| Number | Date | Country | |
|---|---|---|---|
| 61791920 | Mar 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2014/028958 | Mar 2014 | US |
| Child | 14854860 | US |
