The present invention relates to falling film apparatus, tube inserts for falling film apparatus, and methods for using a falling film apparatus, including separating a crude mixture of isocyanates in a falling film evaporator.
Falling film apparatus are in widespread industrial use as heat exchangers. They are useful as evaporators, for performing separations, for performing crystallizations, as well as in other applications. Falling film apparatus have multiple vertical tubes supported at each end by a tube sheet. The tubes are contained in a shell, through which a heat exchange fluid is circulated into contact with the vertical tubes to provide or remove heat from the tubes. A liquid to be so treated is passed downwardly through the interior of the tubes, where the liquid is heated or cooled, as the case may be.
Optimal operation of a falling film apparatus depends on forming a film of the liquid on all interior surfaces of the tubes. The liquid should wet all internal surfaces of each tube and in addition wet those surfaces uniformly and continuously throughout the operation of the device. Non-uniform distribution of the liquid can cause various problems, including reduced operating efficiencies. Unwanted reactions and fouling are common problems caused by improper liquid distribution in falling film apparatus.
For any liquid, there exists a theoretical minimum flow rate per tube that is necessary to maintain a film on the interior tube surfaces. Practically, it is necessary to operate at several times this theoretical minimum flow rate per tube. This constrains the range of operating rates that can be employed. Using higher flow rates promotes uniform wetting, but creates thicker films and can result in less efficient operation. Fluid passing through the device often must be recirculated one or more times to achieve the desired result, thereby increasing operating costs. Residence times are also increased, which can be problematic when, for example, the liquid is sensitive to time-temperature effects. Design improvements which allow a falling film apparatus to operate at flow rates closer to the theoretical minimum flow rate would be desirable.
This invention is in one aspect a falling film apparatus comprising:
Turning to
Hollow tubes 4 typically are cylindrical, with a circular cross-section, although hollow tubes 4 can assume other cross-sectional shapes if desired.
Hollow tubes 4 are vertically oriented, by which is it meant hollow tubes are oriented within 3 degrees of vertical, preferably within 1 degree of vertical.
Tube inserts 12 each are located at the top end of the associated hollow tube 4. As shown in
Lower section 21 has outer cross-sectional dimensions equal to or smaller than the inside cross-sectional dimension of the associated hollow tube 4, so lower section 21 can extend into associated hollow tube 4. Lower section 21 may (as shown in
Tube inserts 12 each have one or more process fluid openings 24 in upper section 25 for admitting a process fluid into the tube insert. “Process fluid” means any fluid or mixture of fluids (which may further contain a dispersed solid phase) that is passed through tube inserts 12 and hollow tubes 4, including a starting feed fluid introduced into tube inserts 12 and hollow tubes 4 as well as evaporated materials, reaction product or other products produced within hollow tubes. The process fluid contains at least one component that is liquid under the conditions that exist at the locations of circumferential ribs 22 of each tube insert 12. The composition of the process fluid may change as it travels through tube insert 12 and/or hollow tube 4.
In one embodiment, the process fluid opening is simply the open upper end of tube insert 12. In other embodiments, multiple process fluid openings 24 are provided in the wall of upper section 25 of tube insert 12, as shown in each of
In the embodiment shown in
Tube inserts 12 also each have an open bottom end 27 (
Tube inserts 12 have one or more circumferential ribs 22 residing on the interior surface of tube inserts 12, below the process fluid opening(s). Circumferential ribs 22 may reside in upper section 25 of tube insert 12 (as is the case in
Any arbitrary number of circumferential ribs may be provided. For example, the number of circumferential ribs is up to 10, up to 5 or up to 3, and only a single circumferential rib may be present.
By “circumferential”, it is meant that the rib extends entirely around the interior wall of tube insert 12, forming a circle (if oriented perpendicular to longitudinal central axis 60 of tube insert 12, as shown in
Each circumferential rib 22 projects radially inward (i.e., toward the central longitudinal axis) from the interior surface of tube insert 12. The radial width WRib (see
Each circumferential rib 22 has a longitudinal width δRib (
The inward edges 42 of circumferential ribs 22 may be curved, and when curved the inward edges 42 may have a radius of curvature RRib such that RRib≤δRib/2. When RRib=δRib/2 the inward edge 42 will have a semi-circular cross-section. RRib may be ≤δRib/4, ≤δRib/8, or ≤βRib/12 and in some embodiments RRib>δRib/32, preferably >δRib/24 or >δRib/16.
Circumferential ribs 22 may be integral with sidewall 40 of tube insert 12, or may be a separately-produced member that is affixed into position within tube insert 12. If separately-produced, circumferential ribs 22 may be affixed to sidewall 40 by, for example, welding or gluing, such as weld or adhesive 50 (
Integral circumferential ribs 22 may be produced by machining the interior of sidewall 40 of precursor tube 12A to remove wall material above and below the location of each circumferential rib 22, as shown in
The interior surface of sidewall 40 may be of uniform interior diameter (except for the ribs). In embodiments such as shown in
In operation, a process fluid is introduced onto the upper surface of tube sheet 5 and upon reaching a certain height (such as indicated by liquid interface 28 in
Tube inserts 12 may further include one or more features such as flow deflectors that produce a tangential flow of process fluid entering the tube insert. The process fluid openings may be machined to produce a tangential flow of process fluid entering the tube insert.
Turning to
Falling film heat apparatus 1 further includes at least one process fluid inlet port 10 for introducing a process fluid into upper portion 26 of the interior space enclosed by shell 2. Multiple process fluid inlet ports 10 may be provided. Falling film apparatus 1 further includes at least one process fluid outlet port 11 for removing process fluid(s) from lower portion 7 of the interior space enclosed by shell 2. Multiple process fluid outlet ports 11 may be provided. In the embodiment shown in
Falling film apparatus 1 further includes at least one heat exchange fluid inlet port 8 for introducing a heat exchange fluid into interior space 3 and at least one heat exchange fluid outlet port 9 for removing heat exchange fluid from interior space 3.
In addition to the foregoing features, falling film apparatus 1 may include various optional components. A distributor may be provided to distribute process fluid onto upper tube sheet 5. A wide variety of distribution systems are available to ensure the uniformity of the liquid level on the top tube sheet. One type of distributor is a flat-bottomed container installed above upper tube sheet 5. The container has holes that allow the process fluid to flow onto upper tube sheet 5 between tube inserts 12. A spray distribution system sprays droplets of process fluid over upper tube sheet 5 and/or a flat-bottomed container installed above upper tube sheet 5. Other useful distributors include, for example, any of those described in U.S. Pat. Nos. 4,154,642, 4,199,537 and 9,101,852, and US Published Patent Application No. 2020/0030712. Other optional components include various valves, pumps, automated process control devices, and the like.
In operation, a process fluid is introduced into upper portion 26 via one or more inlet ports 10. The process fluid pools on the upper surface of upper tube sheet 5 and upon reaching a certain height (reference numeral 28 in
In heat exchange operations, hollow tubes 4 are maintained at a different temperature than the process fluid introduced via feed inlet port(s) 10, and thus heat is exchanged between hollow tubes 4 and the process fluid. The hollow tube temperature may be higher or lower than that of the incoming process fluid. The hollow tube temperature typically is higher for operations such as evaporations, pasteurizations and performing chemical reactions, and lower for operations such as crystallizations.
Heat is supplied or removed from hollow tubes 4 via a heat exchange fluid that is introduced into middle portion 3 via heat exchange fluid inlet port 8. The heat exchange fluid circulates within interior space 3, between upper tube sheet 5 and lower tube sheet 6 and in contact with hollow tubes 4, heating or cooling hollow tubes 4 (as the case may be), and is withdrawn through heat exchange fluid outlet port 9. The heat exchange fluid may be a liquid and/or a gas. Some or all of the heat exchange fluid may undergo a phase change within the vessel; steam, for example, may partially or entirely condense within the vessel. Heat exchange fluids are selected at least partially with the desired operating temperatures in mind. Examples of other heat exchange fluids include liquid water, air, nitrogen, argon, helium, liquid and/or gaseous halocarbons (including hydrohalocarbons), silicone fluids, ethylene glycol, propylene glycol and other alkylene glycols and polyalkylene glycols, various alkylated aromatic compounds, various polyester compounds, and the like.
In some embodiments, the falling film apparatus of the invention is used to perform evaporations. In such embodiments, the process fluid is a single-component liquid, which is to be evaporated within hollow tubes 4 or, more typically, a multi-component fluid containing at least one component that is to be separated from at least one other component by fractional distillation within hollow tubes 4. Evaporations typically produce one or more gaseous products representing component(s) of the process fluid that become evaporated within hollow tubes 4, and one or more liquid products which are components of the process fluid that pass through hollow tubes 4 without evaporating. It is generally preferred to establish a flow of gases downward through hollow tubes 4 so that gaseous products are removed from the bottom of hollow tubes 4; however it is within the scope of the invention to remove gaseous products from the top of hollow tubes 4.
The falling film apparatus shown in
In the embodiment shown in
Non-volatilized component(s) of the process fluid are removed from lower portion 7 of the vessel via outlet port 11 and line 15. In the optional arrangement shown, non-volatilized component(s) removed via line 15 are combined with additional quantities of non-volatilized component(s) removed from gas-liquid separator 14 via line 16. A non-volatilized product stream is withdrawn via recovery line 20.
All or a portion of the non-volatilized components recovered from falling film apparatus 1 may be recycled back into falling film apparatus 1 if desired, as is the case, for example, of incomplete evaporation of volatile components of the process fluid. In
An important advantage of this invention is that annular films of liquid components of the process fluid can be formed without dry spots on all internal surfaces of tube inserts 12 and hollow tubes 4, even at low liquid flow rates. Lower liquid flow rates produce thinner films. Thinner films allow for faster and more uniform heating or cooling of the process fluid and, in the case of evaporations, more complete removal of volatile components from the process fluid. As a result, less material needs to be recycled. Recycled material experiences a more severe thermal history than material processed in a single pass, as the recycled material is exposed to the elevated temperatures for a much longer time period. When the recycled material contains heat-sensitive components, the ability to reduce recycling, thereby reducing exposure times to elevated temperatures, is often a significant advantage.
The ability to produce annular films without dry spots at low flow rates also extends the range of conditions at which the falling film apparatus can be operated. For example, it may be desirable or necessary to operate at relatively low flow rates at certain times, such as during start-ups or shutdowns, without fouling the apparatus or producing non-prime material. The falling film apparatus of the invention permits operation over a wide range of flow rates.
Flow rates though a hollow tube apparatus can be expressed in terms of a minimum wetting rate Γmin, which is a function of the contact angle θ (between the entering process fluid and the tube or insert), and the surface tension σ, viscosity μ, gravitational constant g and density ρ of the process fluid, as follows:
Previous falling film apparatus with tube inserts typically operate at a flow rate of 5 or more times Γmin; they do not produce uniform annular films at lower flow rates. By contrast, the falling film apparatus of this invention operates well at flow rates as low as 1.5 Γmin or even lower, and also operate well at much greater flow rates. Thus, in some embodiment of the invention, the falling film apparatus of the invention is operated at a flow rate of 1.5 Γmin to 10 Γmin, 1.5 Γmin to 5.0 Γmin or 1.5 to 3 Γmin.
The falling film apparatus of the invention is useful for performing many types of separations, including producing concentrated foods such as concentrated fruit juices and evaporated and/or condensed milk, manufacturing alcoholic beverages such as whiskeys, as well as in many chemical and/or petrochemical processes.
Among the many chemical separations for which the falling film apparatus is useful is the separation of a crude isocyanate mixture produced by phosgenating a mixture of methylene dianiline with higher polymethylene polyanilines. In such a separation, diphenyl methylene diisocyanate (MDI) is separated from higher polymethylene polyphenylene polyisocyanates (having three or more phenyl isocyanate groups) by passing the crude mixture through the falling film apparatus operated at a tube temperature sufficient to volatilize the MDI but not the higher polymethylene polyphenylene polyisocyanates. This produces an MDI-rich vapor stream that may contain, for example, at least 98% by weight MDI, and a liquid stream of polymethylene polyphenylene polyisocyanates that is, relative to the starting crude mixture, enriched in polymethylene polyphenylene polyisocyanate and depleted in MDI.
A hollow stainless steel tube having an inner diameter of 4.47 cm is fitted in a tube sheet positioned in the bottom surface of a container. A tube insert having an outer diameter of 4.47 cm and wall thickness of 0.018 cm is inserted into the hollow tube such that an upper section resides above the level of the tube sheet and a lower section resides within the hollow tube below the level of the tube sheet. Eight process fluid openings in the form of longitudinal slots 3 cm in width are spaced evenly about the circumference of the upper section of the tube insert. Associated with each of the process fluid openings is a flow deflector positioned at an angle of about 20 degrees to the open face of the slot. The flow deflectors produce a tangential flow entry of the process fluid into the tube insert. The interior surface of the tube insert below the process fluid openings is smooth and of a constant diameter.
A fluid having (at the temperature of the experiment) a density of 1106 kg/m3, a viscosity of 1.9 cP, a surface tension of 31 mN/m and an advancing contact angle with stainless steel of 60 degrees is poured into the container to create a flow rate of 82 kg/h, yielding a wetting rate Γ of 0.162 kg/m-s. The minimum wetting rate Γmin for this fluid is 0.099 kg/m-s, as calculated according to Equation 1 above. The operating ratio Γ/Γmin is 1.64. Under these conditions, the liquid forms rivulets on the inner walls of the tube insert and does not uniformly wet the walls. A uniform annular film is produced only when the flow rate is increased to produce an operating ratio Γ/Γmin of greater than 4.
Comparative Sample A is repeated, except this time the tube insert has 2 circumferential ribs in the inner wall beneath the process fluid openings. RRib is 0.762 mm, WRib is 2.03 mm, and δRib is 1.52 mm. A uniform film forms as the process fluid passes downwardly past the circumferential ribs, wetting all interior surfaces of the tube insert, at the operating ratio Γ/Γmin=1.64.
Comparative Sample A is again repeated, except this time the tube insert lacks the flow deflectors and there are three circumferential ribs. The circumferential ribs have the same dimensions as those described in Example 1. At the operating ratio Γ/Γmin=1.64, a uniform film forms as the process fluid passes downwardly past the 33 circumferential ribs, even without the benefit of tangential fluid entry. All interior surfaces of the tube insert become wetted.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US2022/042001 | 8/30/2022 | WO |
Number | Date | Country | |
---|---|---|---|
63245906 | Sep 2021 | US |