This disclosure relates to an apparatus and a process for heating or cooling high viscosity solutions that contain polymers.
Polymers and polymeric products (hereinafter referred to as “polymers”) are often manufactured in the presence of solvents and other volatile components (e.g., monomers and by-products) (solvents and volatile components will hereinafter be referred to as “volatiles”). The combination of a polymer with a solubilizing solvent is referred to as a polymer solution. During the production of the polymer, heat may need to be added or removed from the polymer solution.
Solution polymerization may be accomplished in adiabatic or non-adiabatic reactors, where part of the heat of reaction is removed through the use of heat exchangers. One advantage of the latter is that the production rate can be increased when compared with processes where no heat exchanger is present. After the desired polymer is obtained, it is desirable to remove the volatiles from the polymer. The removal of volatiles from the polymer is referred to as “devolatilization”. The separation of the volatiles from the polymer solution is generally accomplished by evaporation, where the polymer solution is heated to a temperature higher than the boiling point of the volatiles while simultaneously (concurrent with the heating) or sequentially (after the heating) extracting evolved volatiles from the polymer solution.
Heat exchangers used for this purpose are shell-and-tube heat exchangers, which comprise a plurality of tubes in a vessel where the heat is removed by circulating cooling water on the shell side of the heat exchangers. One of the potential issues with these exchangers is the high pressure drop used for the amount of heat that needs to be removed from the process. It is desirable to remove the heat of reaction while keeping the pressure drop to a minimum.
In addition, shell-and-tube heat exchangers are incapable of handing polymer solutions that have high viscosities of 10,000 to 1,000,000 centipoise due to high pressure drops incurred and reduced heat transfer rates. It is therefore desirable to have a heat exchanger that can handle the aforementioned high viscosity polymer solutions at temperatures of greater than 150° C., while keeping the polymer and the solvent in a single phase.
Disclosed herein is an apparatus comprising a shell; the shell having an inlet port for introducing a polymer solution into the shell and an outlet port for removing the polymer solution from the shell; wherein the polymer solution comprises a polymer and a solvent that is operative to dissolve the polymer; a plurality of plates in the shell; where the plurality of plates is stacked one atop the other to define a central passage that is in fluid communication with the inlet port of the shell; where the plurality of plates further defines a plurality of conduits, each conduit extending radially outwards from the central passage, where the plurality of conduits is in fluid communication with the central passage; and where the apparatus is operated at a pressure and a temperature effective to maintain the polymer solution in a single phase during its travel through the apparatus from the inlet port of the shell to an outlet port of the shell.
Disclosed herein too is a method comprising discharging a polymer solution in a single phase to an apparatus comprising a shell; the shell having an inlet port for introducing a polymer solution into the shell and an outlet port for removing the polymer solution from the shell; a plurality of plates disposed in the shell; where the plurality of plates is stacked one atop the other to define a central passage that is in fluid communication with the inlet port to the shell; where the plurality of plates further defines a plurality of conduits, each conduit extending radially outwards from the central passage, where the plurality of conduits is in fluid communication with the central passage; operating the apparatus at a pressure and a temperature effective to maintain the polymer solution in a single phase during its travel through the apparatus from the inlet port to the outlet port of the shell; and removing from the outlet port of the apparatus the polymer solution in the single phase; the polymer solution being at a higher temperature than a temperature at the inlet port, the polymer solution being at a lower temperature than the temperature at the inlet port, or the polymer solution remaining at the same temperature at the inlet and outlet port but with heat of reaction being removed from the polymer solution.
Disclosed herein is an apparatus and a process for increasing or reducing the temperature or removing the heat of reaction of high viscosity solutions that comprise polymers. The apparatus is effectively designed to maintain the polymer solution in a single phase during its transport through the apparatus while raising or lowering its temperature by an amount of greater than 10° C. from its initial temperature (e.g., the temperature at the inlet port of the apparatus), or alternatively, maintaining the polymer at a constant temperature (in a reactive polymer solution system), while simultaneously decreasing its pressure by as small an amount as possible.
In short, it facilitates increasing, reducing or maintaining constant the temperature of the polymer solution while simultaneously reducing the pressure of the polymer solution by as small an amount as possible. The disclosed apparatus can be used to heat, cool, or to maintain at a constant temperature (from inlet port to outlet port) a polymer solution that is transported through the apparatus, while facilitating a change in the pressure of the polymer solution.
In an embodiment, the apparatus is a shell and plate heat exchanger. In an embodiment, the apparatus comprises a shell within which is disposed a plurality of plates stacked one over the other, where a pair of neighboring plates (along with the associated walls) when in contact with one another form a plurality of radially disposed conduits that facilitate transporting the polymer solution from the center of the shell to the outside of the shell or alternatively from the outside to the center of the shell while raising its temperature and simultaneously reducing its pressure. The apparatus may alternatively be described as a flat plate heat exchanger where the plates are suspended in a cylindrical shell.
The apparatus therefore comprises a pressure controllable system where the polymer solution is increased in temperature from 120° C. to 300° C., preferably 180° C. to 260° C.; the pressure is decreased by less than 70 kilogram force per square centimeter (kgf/cm2), preferably by less than 35 kgf/cm2 from the inlet pressure all while maintaining the polymer in a single phase with the solvent. In an embodiment, the inlet pressure is 35 to 250 kgf/cm2, while the outlet pressure is 20 to 200 kgf/cm2. The single phase is a liquid phase. The polymer solution is a high viscosity solution having a solution viscosity of 100 to 2,000,000 centipoise, preferably 50,000 to 1,000,000 centipoise, and more preferably 100,000 to 600,000 centipoise measured as detailed below towards the end of this disclosure.
In another embodiment, the apparatus comprises a pressure controllable reactive exothermic system, such as polymerization, where the polymer solution is kept at a desired temperature ranging from 120° C. to 300° C., preferably 150° C. to 230° C.; the pressure is decreased by less than 50 kilogram force per square centimeter (kgf/cm2), preferably by less than 25 kgf/cm2 from the inlet pressure all while maintaining the polymer in a single phase with the solvent. In an embodiment, the inlet pressure is 35 to 250 kgf/cm2, while the outlet pressure is 20 to 200 kgf/cm2. The single phase is a liquid phase. The polymer solution is a high viscosity solution having a solution viscosity of 500 to 20,000 centipoise, preferably 1,000 to 10,000 centipoise measured as detailed below towards the end of this disclosure. One or more of these apparatuses can be part of a polymerization reactor system.
Detailed herein too is a devolatilization apparatus that comprises the apparatus in fluid communication with a pressure control device and a separate low pressure flash vessel that permits the devolatilization of volatiles (e.g., solvent, volatile by-products, volatile reactants, and the like) from the polymer solution. In an embodiment, the pressure control device is a valve that can be variably opened to control the pressure in the apparatus to keep the polymer solution in a single phase. In an embodiment, the devolatilization apparatus may further comprise a pump that facilitates charging the high viscosity polymer solution to the apparatus.
In the
It is to be noted that while the flow of the polymer solution is depicted and detailed in this application as being from top-to-bottom or from bottom-to-top, the apparatus can be mounted horizontally (instead of vertically as depicted in the
In another embodiment, the polymer solution is introduced into the apparatus at inlet port 120 in a single phase and leaves the apparatus at the outlet port 130 in a single phase. During the travel of the polymer solution through the apparatus, the polymer solution always is in a single phase because of the pressure in the apparatus which is maintained at greater than 20 kgf/cm2, preferably greater than 40 kgf/cm2, preferably greater than 60 kgf/cm2, preferably greater than 70 kgf/cm2, and more preferably greater than 80 kgf/cm2. The pressure in the apparatus is maintained so that the solvent, unreacted monomers and reactant by-products never vaporize in the apparatus.
In the
In the configuration depicted in the
In the configuration depicted in
As is detailed below, when the plates are stacked vertically, they form a passage 300 through which the polymer solution is transported. The support tube 158 is located in the passage 300 in the center of the apparatus and contacts the end plate 152, providing structural support to it.
The support tube 158 comprises a tubular shell 157 having openings 156 disposed therein. The openings 156 permit the polymer solution to flow into the annulus 159 which fills with polymer solution and helps distribute it to the conduits from the passage 300 (See
The following paragraphs detail the top-down flow of the polymer solution as seen in the
The term “top-down” flow is used to detail the flow of the polymer solution flow in the
In the
The shell 102 may have any cross-sectional geometry, but is preferably circular in its cross-sectional area when viewed from the top. In an exemplary embodiment, the shell 102 is preferably a cylinder having a height of 200 to 700 centimeters, preferably 250 to 400 centimeters and having an inner diameter d1 of 120 to 400 centimeters, preferably 150 to 180 centimeters. The inner diameter d1 referred to herein is the diameter measured at the shell inner surface. An exemplary material of construction for the shell 102 is a metal. Examples of suitable metals are carbon steel, stainless steel or other metal alloys.
Each plate 104 (See
The opening 112 in the plate 104 has a diameter d2 of 10 to 150 centimeters, preferably 40 to 100 centimeters. The annular space 159 has a width of 10 to 60 centimeters, preferably 20 to 50 centimeters. The support tube 158 has a thickness of 5 to 50 centimeters, preferably 5 to 20 centimeters. There can be 2 to 40 openings 156 along the length and surface of the support tube 158, preferably 6 to 36 openings.
An exemplary material of construction for the plate 104 is a metal. Examples of suitable metals for use in the plate 104 are aluminum, carbon steel, stainless steel or other metal alloys. In an embodiment, the inner circumference 107 and the outer circumference 109 of the plates 104 are both concentric with each other and are also concentric with an inner surface of the shell 102.
With reference now to the
The polymer solution 200 that enters the apparatus from the inlet port 120 travels along the passage 300 to contact the plurality of plates 104 where it travels radially outwards along the plurality of channels 106. Disposed in the plate 104 between each successive pair of channels 106 is a wall 108 that contains holes 110 to house banks of tubes 140 through which a heat transfer fluid 150 is transported (See
The heat transfer fluid 150 facilitates the heating or cooling of the polymer solution as it is transported through the apparatus 100 (See
As seen in the
In the embodiment depicted in the
The channel width at the inner circumference “d5” is less than the channel width “d6” at the outer circumference. The ratio of d6 to d5 is 2:1 to 6:1, preferably 2.2:1 to 3.5:1. In an embodiment, the distance d6 is 4 to 8 centimeters, preferably 5 to 7 centimeters, while the distance d5 is 1 to 4 centimeters, preferably 2 to 3 centimeters. The channel 106 has a floor that has a depth of 0.10 to 0.75 centimeters, preferably 0.2 to 0.4 centimeters from the top of the walls 108.
The polymer solution therefore contacts an ever widening channel as it travels from the opening 112 (See
The walls 108 are situated between the channels 106 and separate successive channels on a particular plate from one another. The walls 108 and the channels 106 are evenly distributed across the surface of the plate 104 (See
In an embodiment, a single plate 104 comprises 30 to 90, preferably 55 to 65 channels, and 30 to 90, preferably 55 to 65 walls 108, with the walls and channels alternating with each other evenly around the plate 104. Each wall 108 contains a bank of tubes 140. Each wall 108 contains 8 to 40 tubes, preferably 10 to 35 tubes. In an embodiment, the tubes are metal tubes and may comprise carbon steel.
The wall 108 has a thickness “t” of 1.5 to 3 centimeters, preferably 2 to 2.5 centimeters. In an embodiment, the wall thickness is 2 to 10% larger, preferably 3 to 5% larger than the outer diameter of the tube 140 in the tube bundle. Each tube 140 in the tube bundle has an inner diameter of 1 to 3 centimeters and an outer diameter of 1.5 to 4.0 centimeters. A preferred inner diameter for the tube is 1.5 to 2 centimeters and a preferred outer diameter is 2.0 to 2.2 centimeters.
The
In
With reference now to the
The second zone 404 begins at the terminus of the first zone and varies in length from about 1.0% to 40% of the total length of the channel connecting with the entrance of the third zone. The width of the second zone may remain constant for its entire length, decrease to a minimum and then remain constant or decrease to a minimum and thereafter increase again. Preferably at its narrowest point the second zone is 0.25 to 4.00 centimeters wide, more preferably 1 to 2 centimeters wide. The ratio of the width of the widest point of the zone to the width of the narrowest point of the zone is preferably from 1.0:1 to 1.5:1. Also preferably, the ratio of the widest width of the first zone to the narrowest width of the second zone is greater than 2:1, and preferably greater than 3:1.
The third zone 406 begins at the terminus of the second zone and terminates with an exit 420 for discharge of the polymer solution. The length of the third zone is from about 40 to 85% of the total length of the channel. The ratio of the width of the third zone at its terminus to that at its entrance is preferably from 1.75:1 to 10:1. The width of the zone need not be constantly increasing from entrance to terminus but may follow a sinusoidal or other curved shape. Also preferably, the ratio of the maximum width of the third zone to the minimum width of the restrictive zone is greater than 2:1.
As seen in the
Each conduit may have a constant width over its entire length or a varying width over its entire length. As discussed above for the respective channels, the width can gradually increase in length from the inner circumference to the outer circumference of the plate. In an embodiment, it can increase in width over a portion of the length and decrease in width over the remaining length of the conduit. In another embodiment, it can decrease in width over a portion of the length and increase in width over the remaining length of the conduit.
Tubes 140 (not shown) pass through holes 110 in the wall 108, and are adapted to transfer heat into the channels 106. In one embodiment, the tubes 140 secure the plates 104 together to form a stack (when the walls 108 and the plate 104 are a single integral component). In another embodiment, the tubes 140 secure the walls 108 and the plates 104 together to form the stack (when the walls 108 are a separate component from the plate 104). The heat is transferred by the fluid 150 in the tubes 140 to the walls 108 and from the walls to the floor 160 of the channel 106 and the roof of the channel 150.
As noted above, the plates 104 are stacked vertically above each other in the shell 102. Each plate is separated from a neighboring plate by a space of 0.1 to 1.0 centimeters, preferably 0.2 to 0.3 centimeters. The total number of plates (in a stack) in the shell 102 (and hence in the apparatus) is 50 to 1000, preferably 700 to 800. In an embodiment, the total number of channels in the shell is 1,000 to 100,000 and the total number of walls in the shell is 1,000 to 100,000.
With reference now to the
It is to be noted that the apparatus may also be used as a cooler. In the event that the apparatus is used to effect cooling, the temperature of the polymer solution is reduced during its transport through the apparatus. In another embodiment, if the cooler is used in a reactive system, it can be used to extract heat generated during a reaction (e.g., an exothermic reaction), and the temperature of the polymer solution can either increase or decrease, depending on the amount of heat released from the reaction versus the amount of heat removed. The polymer solution is still in a single phase during its travel through the plate stack. In an embodiment, the single phase is a liquid phase.
The polymer solution emanating from the outer circumference 109 of the plurality of channels 106 travels in the space between the shell and the outer circumference of the plate stack along path 200C to the bottom of the apparatus. It is then transported from the bottom of the apparatus to outlet port 130 along path 200D and then out of the apparatus via outlet port 130 along path 200E while still being in a single phase.
The polymer solution exiting the apparatus has an outlet temperature T2, which can be either higher, lower or the same as (in a reactive, exothermic system) the inlet temperature T1 and an outlet pressure P2, which is lower than the inlet pressure P1.
The term “bottom-to-top” flow is used to detail the flow of the polymer solution flow in the
During the travel through the plate stack, the temperature of the polymer solution is increased to a temperature greater than T1 while the pressure is simultaneously reduced to a pressure of less than P1. In another embodiment, the temperature of the polymer solution is reduced to a temperature lower than T1 while the pressure is simultaneously reduced to a pressure of less than P1. In an embodiment, the polymer solution is still in a single phase (e.g., a liquid phase) during its travel through the plate stack. In another embodiment, the single phase is a liquid phase.
It is to be noted that the apparatus may also be used as a cooler. In the event that the apparatus is used to effect cooling, the temperature of the polymer solution is reduced during its transport through the apparatus. In another embodiment, if the cooler is used in a reactive system, it can be used to extract heat generated during a reaction (e.g., an exothermic reaction), and the temperature can be going either up or down, depending on the amount of heat released from the reaction versus the amount of heat removed.
The polymer solution emanating from the plate stack enters the passage 300 at the center of the apparatus 100 via path 500D. From the center it is transported to the outlet 130 of the apparatus via path 500E. In one embodiment, the outlet 130 can be connected with a conduit that further transports the polymer solution. The conduit can be part of reactor system. In another embodiment, the outlet 130 is connected to a conduit which is then connected to the valve at which the polymer solution is subjected to depressurization to undergo phase separation.
In an exemplary embodiment, the inlet temperature T1 is 120 to 230° C. and inlet pressure P1 is 35 to 250 kgf/cm2, while the outlet temperature T2 is 150 to 300° C. and the outlet pressure P2 is 20 to 200 kgf/cm2.
The polymer solution generally contains 10 to 95 weight percent (wt %), preferably 20 to 85 wt % of a polymer, based on the total weight of the polymer solution. The solution has a viscosity of 1,000 to 2,000,000 centipoise, preferably 50,000 to 1,000,000 centipoise, and more preferably 100,000 to 600,000 centipoise. The average solution viscosity may be 300,000 to 350,000 centipoise measured as detailed below. The polymer solution is transported through the apparatus at a flow rate of 40,000 to 2,000,000 kilograms per hour, preferably 100,000 to 200,000 kilograms per hour, and more preferably 50,000 to 150,000 kilograms per hour. The flow is 0.5 to 50 kilograms/hr/conduit, preferably 1 to 5 kilograms/hr/conduit, and more preferably 3 to 4.5 kilograms/hr/conduit.
The fluid 150 has a maximum inlet temperature of 280 to 300° C. and a minimum outlet temperature of 200 to 220° C. The fluid generally decreases by a temperature of 5 to 10° C. during heating of the polymer solution. When the apparatus is used as a heater, the maximum inlet temperature for the fluid is always greater than the minimum outlet temperature. The apparatus may alternatively be used as a cooler, in which case, the minimum outlet temperature for the fluid is always greater than the maximum inlet temperature and the cooling fluid generally increases by a temperature of 5 to 10° C.
The polymer that is mixed with the solvent may be a thermoplastic polymer, a lightly crosslinked polymer, or a blend of a thermoplastic polymer with a lightly crosslinked polymer. The polymer can be an oligomer, a homopolymer, a copolymer, a block copolymer, an alternating copolymer, a random copolymer, a graft copolymer, a star block copolymer, a dendrimer, or the like, or a combination thereof.
Examples of the polymers that can be mixed with the solvent include a polyolefin, a polyacetal, a poly acrylic, a polycarbonate, a polystyrene, a polyester, a polyamide, a polyamideimide, a polyarylate, a polyarylsulfone, a polyethersulfone, a polyphenylene sulfide, a polyvinyl chloride, a polysulfone, a polyimide, a polyetherimide, a polytetrafluoroethylene, a polyetherketone, a polyether etherketone, a polyether ketone, a polybenzoxazole, a polyoxadiazole, a polybenzothiazinophenothiazine, a polybenzothiazole, a polypyrazinoquinoxaline, a polypyromellitimide, a polyquinoxaline, a polybenzimidazole, a polyoxindole, a polyoxoisoindoline, a polydioxoisoindoline, a polytriazine, a polypyridazine, a polypiperazine, a polypyridine, a polypiperidine, a polytriazole, a polypyrazole, a polypyrrolidine, a polycarborane, a polyoxabicyclononane, a polydibenzofuran, a polyphthalide, a polyanhydride, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyvinyl ketone, a polyvinyl halide, a polyvinyl nitrile, a polyvinyl ester, a polysulfonate, a polynorbornene, a polysulfide, a polythioester, a polysulfonamide, a polyurea, a polyphosphazene, a polysilazane, a polyurethane, a polysiloxane, or the like, or a combination thereof.
Exemplary polymers are polyolefins. Examples of polyolefins include homopolymers and copolymers (including graft copolymers) of one or more C2 to C10 olefins, including polypropylene and other propylene-based polymers, polyethylenes and other ethylene-based polymers, and olefin block copolymers. Such olefin-based polymers include high density polyethylenes (HDPE), low density polyethylenes (LDPE), linear low density polyethylenes (such as the LLDPE marketed by The Dow Chemical Company under the trademark “DOWLEX”), enhanced polyethylenes (such as those marketed by The Dow Chemical Company under the trademark “ELITE”), polymers made via molecular or single-site catalysts, such as metallocene, constrained geometry, polyvalent aryloxy ether, and the like. Examples of such polymers are linear or substantially linear ethylene copolymers (such as those marketed by The Dow Chemical Company under the trademarks “AFFINITY” and “ENGAGE” and those marketed by ExxonMobil Chemical Company under the trademarks “EXACT” and “EXCEED”), propylene-based copolymers (such as those marketed by The Dow Chemical Company under the trademark “VERSIFY” and those marketed by ExxonMobil Chemical Company under the trademark “VISTAMAXX”), and olefin-block copolymers (such as those marketed by The Dow Chemical Company under the trademark “INFUSE”), and other polyolefin elastomers (such as the EPDM marketed by The Dow Chemical Company under the trademark “NORDEL” or “NORDEL IP”).
The solvent will vary depending upon the manufactured polymer. Aprotic polar solvents such as water, propylene carbonate, ethylene carbonate, butyrolactone, acetonitrile, benzonitrile, nitromethane, nitrobenzene, sulfolane, dimethylformamide, N-methylpyrrolidone, or the like, or combinations thereof may be used to solvate some polymers. Polar protic solvents such as methanol, acetonitrile, nitromethane, ethanol, propanol, isopropanol, butanol, or the like, or combinations thereof may also be used. Other non-polar solvents such a benzene, toluene, methylene chloride, carbon tetrachloride, hexane, diethyl ether, tetrahydrofuran, or the like, or combinations thereof may be used to solvate some polymers. Co-solvents comprising at least one aprotic polar solvent and at least one non-polar solvent may also be utilized to modify the swelling power of the solvent and thereby adjust the solvating power of the solvent. An exemplary solvent for polyolefins is Isopar™ E from ExxonMobil.
The aforementioned polymers are manufactured in a solution, high pressure, or slurry polymerization reactor in which the monomers and produced polymers are entrained in a solvent or diluent. Other polymer solutions may also be manufactured (intentionally or unintentionally) containing large or small amounts of volatile components. Typical volatile components include solvents (such as aromatic or aliphatic inert diluents), unreacted monomers and/or comonomers and low molecular weight reaction by-products. The amount of solvent, unreacted monomers, unreacted comonomers, and/or other volatile components to be removed from the polymer solution may range from a large excess to a mere contaminating amount. Molten polymers produced in solution, high pressure, or in slurry polymerization plants, even after an initial flash-devolatilization stage, often contain from 10 to 60 weight percent or more of dissolved or entrained volatile components at the point they are processed in the apparatus. Typically, the amount of residual volatile components remaining in the devolatilized polymer should be less than about 0.5 wt %, preferably less than 0.1 wt %, and more preferably less than 0.05 wt %, based on the total weight of the devolatilized polymer as measured by ASTM D-4526.
Depending upon the starting concentration of volatile components in the flowable material to be devolatilized, and the level of residual volatiles that are acceptable in the devolatilized product, more than one stage (such as two or three stages) of devolatilization apparatus may be used. In addition, the devolatilization apparatus may be used in combination with other known devolatilization techniques, such as simple flash-devolatilization, ionic fluid extraction, extraction using a super-critical fluid, distillation, steam-stripping or carbon-dioxide-stripping, either in separate devolatilization stages or (in the case, for example, of steam-stripping or carbon-dioxide stripping) in combination with the apparatus of this invention within the same devolatilization stage.
In an embodiment, the apparatus detailed above may be used in conjunction with a pump and a pressure regulating device to form a devolatilization apparatus. This is depicted in the
The pressure regulating device is located downstream of the apparatus and is operative to keep the polymer solution in single phase throughout the apparatus. The polymer with a now substantially reduced volatile content is collected in a first tank (not shown) and may be subjected to further downstream process while the solvent is collected and recycled. In an embodiment, the devolatilization apparatus may include a flashing vessel (not shown) located downstream of the pressure regulation device.
In an embodiment, the pump 402 is a positive displacement pump. The pressure regulating device is preferably a valve. The pressure regulating device is used to keep the polymer solution in a single phase until it is desirable to separate the volatiles from the polymer. Exemplary valves 406 are gate valves, ball valves, sluice valves, or the like. In an embodiment, the pressure regulating device may be a nozzle or an orifice.
In some embodiments for the removal of solvents, unreacted monomers and comonomers from molten polymers, where the concentration of volatile components in the molten polymer is very high, adequate devolatilization may necessitate the use of more than one apparatus in series to reduce the volatile content in the molten polymer in two or more steps.
Although most of the description herein applies to a heating apparatus, it should be obvious to those familiar in the art that the same type of design could be used for cooling a polymer solution or for the removal of the heat of polymerization from a polymer reaction. This cooling apparatus would be operated in a similar fashion except that instead of a heating fluid, a cooling fluid would be used in the tubes 150 (See
This is an example that demonstrates the apparatus disclosed herein. A flat plate heat exchanger is designed in a cylindrical shell configuration with an outer diameter d1 of 160.2 centimeters (See
A bank of tubes carries the fluid and is placed perpendicular to the layers of the heat exchanger. The heat exchanger contains 60 banks of tubes. Each bank of tubes comprises 13 carbon steel tubes with an internal diameter of 1.42 centimeters and an external diameter of 2.23 centimeters. Each wall is 2.28 centimeters thick. Each channel has a width at the inner circumference of 2.5 centimeters and a width at the outer circumference of 6.3 centimeters and a height of 0.254 centimeters. The total number of conduits is 60 per layer, comprising a total of 43,200 total conduits.
Using standard heat transfer calculations for convection through the fluid and conduction across the tube walls, an overall heat transfer coefficient, U, for this exchanger is calculated to be U=130 W/m2·K. The total internal heat transfer area (A) for 43,200 channels is 1,430 m2 resulting in a heat exchanger with the product of U times A (UA) value of 185,900 W/K.
Given a polymer solution flowing through this apparatus at 159,000 kg/hr and a solution temperature increasing from 160 to 250° C. and a fluid temperature reduction from 290 to 283° C. (during the course of the polymer solution in the apparatus), the log mean temperature difference for this exchanger is 74° C. and the total heat duty is calculated as 13.8 million Watts.
The total flow through each conduit is approximately 3.7 kilograms/hr. Assuming a solution viscosity of 330,000 cP and using standard pressure drop (Bernoulli) calculations, the pressure drop is calculated as 31.5 kgf/cm2 through the exchanger.
Without being limited to theory, the detailed apparatus design functions effectively because the polymeric solution is kept at a single-phase inside the heater, allowing for maximum heat transfer rate, which is calculable. If the solution were to change phases, the heat transfer rate would drop substantially and the solution would lose heat due to vaporization. Both of these are avoided ensuring that the polymer solution in the apparatus remains in a single-phase throughout its residence time in the apparatus. The polymer solution in the apparatus never separates into two (or more) phases.
This design is advantageous in that it can handle high solution viscosities of 100,000 to 2,000,000 centipoise, with an average solution viscosity of 325,000 to 375,000 centipoise. It can also handle high flow rates of 140,000 to 170,000 kilograms/hour at polymer concentrations of greater than 30 wt %, preferably greater than 40 wt % and more preferably greater than 50 wt %, based on the total weight of the polymer and the solvent. The design permits a pressure drop in the polymer solution of 35 to 200 kgf/cm2 from the inlet port to the outlet port, while at the same time raising the temperature of the polymer solution by an amount of greater 40° C., preferably greater than 50° C., and more preferably greater than 60° C., from the initial inlet temperature.
One of the advantages of this design that pressure drops in the polymer solution of 14 to 50 kgf/cm2 from the inlet port to the outlet port can be handled by existing positive displacement pumps (e.g., gear pumps or screw pumps).
This is a comparative example and is performed on a shell and tube heat exchanger with the same fluid and flow rates as the above example. For the shell and tube exchanger, a standard design is used with the polymer solution flowing through the tubes and the medium flowing through the shell. Each tube is designed with an internal diameter of 2.0 centimeters, an outer diameter of 2.5 centimeters and a total length of 260 centimeters. Each tube is filled with twisted-tape type mixing elements with an aspect ratio of 1.5. A total of 8,000 tubes are fit inside a shell of diameter 300 centimeters.
Both heat transfer and pressure drop calculations for these mixers are calculated by the method of Joshi. In this manner, the Nusselt number is calculated to be 18.0, giving an overall heat transfer coefficient, U, of 115 W/m2·K. The total internal heat transfer area for 8,000 tubes is 1,630 m2 resulting in a heat exchanger UA value of 187,450 W/K. The log mean temperature difference for this exchanger is 74° C. and the total heat duty is calculated to be about 12.7 million Watts.
Pressure drop through the tubes is calculated using different correlations to give pressure drops ranging from 60 to 110 kgf/cm2, with the most likely value being approximately 75 kgf/cm2. Therefore, this exchanger type would have too high a pressure drop. As the outlet pressure of the exchanger has to be at least 20 kgf/cm2 in order to keep the polymer solution single-phase, the total pressure drop is likely to exceed the capability of a screw pump or even a gear pump. That is why this type of exchanger is not preferred for this unit operation.
The tube diameter can be increased to alleviate the pressure drop issue. However, at the pressures required for this unit operation to keep the same number of tubes, the shell size will become difficult to manufacture. A smaller number of larger diameter tubes increases the pressure drop (higher velocity through them) and it requires a longer length to provide the heat transfer area needed for the heat transfer, thereby again increasing pressure drop. That is why this type of exchanger has inherent limitations for this application.
The higher pressure drop makes it very difficult to keep the polymer solution single-phase towards the exit of the exchanger. If the solution is not single-phase but it reaches its bubble point, it will lose heat transfer rate and make it very difficult to heat up the solution to the desired temperature. In addition, the system would be unpredictable.
This is also a comparative example. If the flat plate heater described in (a) above were installed inside a devolatilizer vessel (a vessel where the polymer solution would actually phase separate into two phases), then there would be a few major issues.
1) The polymer solution would become two-phase inside the channel. This would decrease the heat transfer rate.
2) The size of this exchanger would be too large—it is unlikely that such an apparatus can be constructed due to stresses.
3) The fluid temperature could not be as high as 290° C. because that would cause the solution to reach the bubble point inside the flat plate heater (FPH) core or at the entrance of the channel, thus again reducing heat transfer effectiveness. In addition, lower fluid temperature would dramatically reduce the driving force for heat transfer. Therefore, the example as demonstrated in Example 1 is the preferred example.
This is an inventive theoretical example that details the use of the apparatus in a cooling mode to remove the heat of polymerization from the polymer solution. A flat plate cooler is designed in a cylindrical shell configuration with an outer diameter d1 of 282 centimeters (See
A bank of tubes carries the fluid and is placed perpendicular to the layers of the heat exchanger. The heat exchanger contains 65 banks of tubes. Each bank of tubes comprises 25 carbon steel tubes with an internal diameter of 1.58 centimeters and an external diameter of 1.91 centimeters. Each wall is 1.65 centimeters thick. Each channel has a width at the inner circumference of 2.5 centimeters and a width at the outer circumference of 11.1 centimeters and a height of 0.381 centimeters. When the plates are assembled, the total number of conduits is 65 per layer, comprising a total of 37,800 total conduits.
Using standard heat transfer calculations for convection through the fluid and conduction across the tube walls, an overall heat transfer coefficient, U, for this exchanger is calculated to be U=73 W/m2·K. The total internal heat transfer area (A) for 37,800 conduits is 4,852 m2 resulting in a heat exchanger with the product of U times A (UA) value of 354,200 W·K.
Given a polyethylene production rate of 22,000 kg/hr and a polyethylene heat of polymerization of 94.5 kJ/mol, the required heat removal is calculated as 21.8 million Watts. Assuming a polymer solution temperature of 190° C. and an average cooling fluid temperature of 130° C., the log mean temperature difference for this exchanger is 60° C., and the designed exchanger will be able to remove the heat of polymerization.
The total flow through each conduit is approximately 44 kilograms/hr at an average viscosity of 6300 cP. Using standard pressure drop (Bernoulli) calculations, the pressure drop is calculated as 3.66 kgf/cm2 through the exchanger.
By “substantially uniform,” as used with respect to a dimension (such as width or height) or a cross-sectional area of zone within a channel, is meant that the same is either not converging nor diverging at all, or is converging and/or diverging by no more than ten percent of the average of that dimension.
“Polymer” refers to a compound prepared by polymerizing monomers, whether of the same or a different type of monomer. The generic term “polymer” embraces the terms “oligomer,” “homopolymer,” “copolymer,” “terpolymer” as well as “interpolymer.”
“Interpolymer” refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term “interpolymer” includes the term “copolymer” (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term “terpolymer” (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
“Oligomer” refers to a polymer molecule consisting of only a few monomer units, such as a dimer, trimer, or tetramer.
“Bubble point pressure” means the highest pressure at which the first bubble of vapor is formed at a given temperature.
“Polymer solution” means a solution containing a dissolved polymer where the polymer and the volatiles are in a single phase—a liquid phase.
“Fluid” means a fluid useful to convey heat from a source, and transfer that heat by indirect heat exchange to a plate of the apparatus. Suitable thermal-fluids include steam, hot oils, and other thermal-fluids, such as those marketed by The Dow Chemical Company under the trademark “DOWTHERM™.”
Solution viscosities are measured using an Anton Paar MCR 102 rheometer made by Anton Paar Germany GmbH. The rheometer is equipped with a C-ETD300 electrical system. The cup-and-bob system (combination of concentric cylinders) comprises a 27 millimeter (mm) diameter cup and a 25 mm diameter bob to allow for 1 mm gap between the two. The bob is operated in rotational mode inside a 150 bar (approximately 153 kgf/cm2) pressure cell. Viscosity measurements are obtained at a pressure of 30 bar (approximately 31 kgf/cm2—obtained with a nitrogen atmosphere), a range of temperatures (150 to 250° C.), a range of polymer concentrations (20 to 90 weight percent), a range of shear rates (0.1 to >100 reciprocal seconds (s−1)), and range of polymer molecular weights (15,000 to 200,000 g/mole). The solvent in all cases is Isopar™ E by ExxonMobil. The viscosity measurements obtained range from 800 to greater than 2,000,000 centipoise.
While the invention has been described with reference to some embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Filing Document | Filing Date | Country | Kind |
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PCT/US2019/034607 | 5/30/2019 | WO | 00 |
Number | Date | Country | |
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62678597 | May 2018 | US |