Mixer and processes incorporating the same
10065157 ยท 2018-09-04
Assignee
Inventors
- Max M. Tirtowidjojo (Lake Jackson, TX, US)
- Hua Bai (Lake Jackson, TX, US)
- Edward M. Calverley (Midland, MI)
Cpc classification
B01F25/4335
PERFORMING OPERATIONS; TRANSPORTING
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
B01F25/102
PERFORMING OPERATIONS; TRANSPORTING
B01F25/4336
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
B01J4/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention relates to a mixer, an apparatus comprising the mixer and a reactor, and processes incorporating the same. The mixer comprises an inlet (104) to a chamber (102), wherein the chamber inlet angle is less than 90. The mixer further comprises an expander zone (106) that expands outwardly at an expander angle of less than 90. The mixer may be coupled to a reactor at its outlet, which may closely approximate the size of the reactor inlet due to the expander (106).
Claims
1. A mixer for use in a chemical process comprising; A first chamber having a first chamber inlet and a first chamber outlet A second chamber having a second chamber inlet and a second chamber outlet; A flow pattern development zone comprising a first tube within a second tube wherein the first tube is fluidly connected to the a first chamber outlet and the second tube is fluidly connected to the a second chamber outlet; and An expander zone having an outer diameter substantially equal to that of the second chamber outlet and/or second tube of the flow pattern development zone and an inner diameter that expands outwardly at an expander angle () of less than 90; Wherein the chamber inlet angle () of at least one of the first or second chamber inlet(s) is less than 90, the first chamber outlet is arranged concentrically within the second chamber outlet, the flow pattern development zone is upstream of the expander zone and the first tube of the flow pattern development zone ends at an inlet of the expander zone; wherein the chamber-inlet angle () is from 30 to 80; wherein the angle () between the chamber inlet and a line tangential to the chamber projected on a cross sectional plane to the chamber intersecting the point where the longitudinal axis of the inlet line meets the chamber's wall is 20 to 60; and wherein the mixer further comprising a mixing zone downstream of the flow pattern development zone and upstream of the expander zone, wherein the mixing zone has an outer diameter substantially equal to that of the flow pattern development zone and the first tube of the flow pattern development zone ends at the outlet of the mixing zone.
2. The mixer of claim 1, wherein the expander angle () is less than 20.
3. The mixer of claim 1, wherein the inner diameter of the at least one of the first or second chambers is at least 1.25 times greater than the inner diameter of its respective chamber inlet.
4. The mixer of claim 1, wherein the inner diameter of at least one of the first or second chamber is greater than the inner diameter of its respective outlet.
5. The mixer of claim 1, wherein an annular space is created by the first and second chamber outlets and the ratio of the cross sectional area of the first chamber outlet to the cross sectional area of the annular space is between 1 and 3.
6. The mixer of claim 1, wherein the length of the flow pattern development zone is at least 0.5 times the diameter of the second chamber outlet.
7. The mixer of claim 1, wherein the inner diameter of the mixing zone is less than or equal to the inner diameter of the second tube of the flow pattern development zone.
8. The mixer of claim 4, wherein the inner chamber of at least one of the first or second chambers is tapered to provide its respective chamber outlet.
9. The mixer of claim 1, wherein the mixing zone comprises a single tube fluidly connected to the outermost chamber outlet and/or outermost tube of the flow pattern development zone, wherein the length of the mixing zone is substantially the same as or greater than the inner diameter of the mixing zone.
10. An apparatus comprising A reactor having an inner diameter of greater than 0.1 feet and less than 36 feet; and the mixer according to claim 1 having an inlet with an inner diameter of less than the reactor inner diameter.
11. The apparatus of claim 10, wherein the ratio of the inner diameter of the chamber outlet of the mixer to the inner diameter of the reactor is from 2 to 5.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings, wherein:
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DETAILED DESCRIPTION
(16) The present specification provides certain definitions and methods to better define the present invention and to guide those of ordinary skill in the art in the practice of the present invention. Provision, or lack of the provision, of a definition for a particular term or phrase is not meant to imply any particular importance, or lack thereof. Rather, and unless otherwise noted, terms are to be understood according to conventional usage by those of ordinary skill in the relevant art.
(17) The terms first, second, and the like, as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Also, the terms a and an do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item, and the terms front, back, bottom, and/or top, unless otherwise noted, are merely used for convenience of description, and are not intended to limit the part being described limited to any one position or spatial orientation.
(18) If ranges are disclosed, the endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of up to 25 wt. %, or, more specifically, 5 wt. % to 20 wt. %, is inclusive of the endpoints and all intermediate values of the ranges of 5 wt. % to 25 wt. %, etc.). As used herein, percent (%) conversion is meant to indicate change in molar or mass flow of reactant in a reactor in ratio to the incoming flow, while percent (%) selectivity means the change in molar flow rate of product in a reactor in ratio to the change of molar flow rate of a reactant.
(19) The mixer provided herein may incorporate one or more angles between components, zones, or longitudinal axes thereof that provide the mixer with improved performance relative to mixers not incorporating the angle. In each instance, the angles are defined as the lesser angle of the linear pair created by, or that would be created by, the intersection of the components, zones, or axes. For example, the chamber-inlet angle (denoted in
(20) The present invention provides a mixer for use in a gas-phase process, such as processes for the production of chlorinated propenes and/or higher alkenes. The mixer incorporates one or more design features that can i) provide for reduced backmixing of the reactants, and/or ii) minimize or eliminate plugging within the mixer. As a result, desired conversions may be substantially maintained, formation of secondary products may be minimized and/or fouling may be reduced or eliminated. Further, the advantages provided by one design feature may be leveraged, perhaps even synergistically, by combining the same with others.
(21) More specifically, the mixer comprises an inlet fluidly connected to a chamber, wherein the chamber-inlet angle () is less than 90. Desirably, the chamber-inlet angle, , is less than 15, or less than 80. In some embodiments, the chamber-inlet angle () may be greater than 20, or greater than 30. In some embodiments, the chamber-inlet angle () may be from 30-80. The mixer also comprises an expander zone, wherein the inner diameter thereof expands outwardly along the length thereof at an expander angle () of less than 90, or less than 45, or less than 20, or less than 15, or less than 10. Desirably, expander angle is greater than 1, or greater than 2, or greater than 3, or greater than 4, or greater than 5. In some embodiments, expander angle may be from 1 to 90, or from 2 to 45, or from 3 to 20, or from 4 to 15, or from 5 to 10. At its outlet, the expander may have an inner diameter (D.sub.e) of less than 100 feet, or less than 80 feet, or less than 50 feet, or less than 20 feet. In some embodiments, the expander zone outlet inner diameter (D.sub.e) may be substantially equal to the reactor inlet inner diameter (D.sub.r)
(22) The combination of these two features has been discovered to provide a mixer that not only provides the desired flow pattern and efficient mixing, but also is inexpensive to manufacture and robust in the challenging environments created by processes for the production of chlorinated propenes. More particularly, the provision of a chamber inlet angle less than 90, or from 30-80 has been found to render the mixer more robust against fouling from contaminants and secondary products that may already be present in the reactants as they are presented to the mixer. And, the provision of an expander zone, incorporating an expander angle of less than 90, allows the mixer to include an inlet close in size to the typical size of feedstreams used in commercial chemical processes, but yet, an outlet that may more closely approximate the size of the inlet of a reactor to which the mixer may be coupled. As such, the pressure drop and/or backmixing that may otherwise be seen between mixers and feedstreams, or mixers and reactors, of disparate sizes can be minimized or avoided.
(23) In some embodiments, the chamber may exhibit substantially the same geometry as the inlet, and the geometries thereof may be selected to encourage a desired flow pattern. Any flow pattern can be established and encouraged by the mixer (with the exception of back mixed flow). In some embodiments, the mixer is desirably utilized to produce a swirling flow pattern. Swirling flow patterns can be advantageous for use in many chemical processes, but in particular in processes where backmixing can be an issue. This is because swirling flow patterns tend to produce high shear at internal surfaces that can assist in the prevention of the accumulation of solids thereon. Swirling flow patterns may also only require a small head mixing chamber in comparison to the reactor diameter in order to be established. A swirling flow pattern can be induced by introduction of a feedstream into a generally cylindrical inlet, and thereafter into a generally cylindrical chamber.
(24) The inlet and chamber may have the same, or a different, inner diameter. In some embodiments, advantage can be seen by providing the chamber with an inner diameter (D.sub.c) at least 1.25 times greater, or at least two times greater, than the inner diameter of the inlet (D.sub.ci). In some embodiments, the inner diameter of the chamber (D.sub.c) is desirably less than 20 times, or less than 10 times, the inner diameter of the chamber inlet (D.sub.ci). In some embodiments, the ratio of the inner diameter of the chamber (D.sub.c) to the inner diameter of the inlet (D.sub.ci) is from 2-10. Providing the chamber and inlet with such a dimensional relationship has been found to render the chamber and inlet robust to the presence of the particulates and/or secondary products that may be present in the feedstreams as introduced therein.
(25) The chamber also desirably comprises an outlet, which may desirably be of the same geometry as the chamber and/or inlet. The outlet may also have the same diameter, or cross sectional area, as the case may be, as the chamber and/or chamber inlet, or may have a different diameter. In some embodiments, the chamber outlet has an inner diameter (D.sub.co) that is at least 2 times greater than the inner diameter of the chamber inlet (D.sub.ci). The outlet has an inner diameter (D.sub.co) that is less than the chamber inner diameter (D.sub.c), e.g., the ratio of the chamber inner diameter (D.sub.c) to the outlet inner diameter (D.sub.co) may be at least 1, or at least 1.1, or at least 1.2. Desirably, the ratio of the inner diameter of the chamber (D.sub.c) to the inner diameter of its outlet (D.sub.co) is less than 10, or less than 8, or less than 6, or less than 5, or less than 4. In some embodiments, the ratio of the inner diameter of the chamber (D.sub.c) to the inner diameter of its outlet (D.sub.co) is from 1.1 to 8 or from 1.2-4.
(26) If two or more inlets/chambers are provided, the outlets of any provided proximate to each other are desirably provided as concentric rings. In this way, the innermost chamber outlet would act as an egress for one reactant. Each subsequent chamber outlet would provide an annular space between it and the chamber outlet immediately interior to it, through which an additional reactant may flow, and so forth. The ratio of the cross sectional area of each annular space (A.sub.a) to the area of the inner most chamber outlet (A.sub.co, innermost) is desirably between 1 and 3, i.e., A.sub.a/A.sub.co is between 1 and 3.
(27) In some embodiments more than one, more than two, or more than three, or even more than 4, inlet(s)/chamber(s) are provided. In some embodiments, at least two inlets/chambers are provided. In other embodiments, more than one inlet may be provided on one or more chambers. In such embodiments, the additional inlet(s) and/or chamber(s) can have the same configuration, i.e., shape, inner dimension, chamber inlet angle, tangential chamber inlet angle, or one or more different configuration(s). For purposes of manufacturing efficacy, in those embodiments wherein multiple inlets/chambers are used, they may have the same configuration, but this is not necessary to appreciate the advantages of the invention.
(28) In some embodiments, the mixer may be provided with additional features and/or dimensional relationships that further enhance its suitability for use in connection with processes comprising a limiting reagent. More particularly, in some embodiments, the mixer may further comprise an advantageous tangential chamber-inlet angle and/or a flow pattern development zone and/or a mixing zone.
(29) That is, it has now been discovered that an angle between the chamber inlet and a line tangential to the chamber projected on a cross sectional plane to the chamber intersecting the point where the longitudinal axis of the inlet line meets the chamber's wall of less than 90, or less than 80, or less than 70, or less than 60, provides a beneficial flow to the reactant provided through the inlet. Desirably, the tangential chamber inlet angle is greater than 5, or greater than 10, or greater than 15, or greater than 20. In some embodiments, the tangential chamber inlet angle is from 5 to 90, or 10 to 80, or 15 to 70, or 20 to 60.
(30) The flow pattern development zone, if provided, will desirably be of a shape and/or dimension that further encourages the formation and/or maintenance of the desired flow pattern of the reactant provided by the at least one inlet. In those embodiments wherein a swirling pattern is developed, the flow pattern development zone may comprise a tube within a tube design, wherein the number of tubes correspond to the number of reactants introduced via inlets/chambers upstream of the flow pattern development zone.
(31) If, for example, only one reactant is provided via an inlet/chamber upstream of the flow pattern development zone, the flow development zone may simply be a tube having an inner diameter (D.sub.fpd) approximately the same as the inner diameter of the chamber outlet (D.sub.co) and be fluidly connected thereto. As another example, if three reactants are to be used in the process, and all three are desirably introduced upstream of the flow pattern development zone, three tubes of differing inner diameters would be provided about the same longitudinal axis. The innermost tube could be fluidly connected to a first chamber outlet, the annular space provided between the innermost tube and the next outlying tube could be fluidly connected to a second chamber outlet, and the annular space created by the middle tube and the outermost tube could be fluidly connected to a third chamber outlet.
(32) In another embodiment wherein three reactants are used, two may be introduced via two inlet/chambers, and a third may be introduced according to any method known to those of ordinary skill in the art, and may be introduced, e.g., after a flow pattern development zone. This embodiment may be advantageous when a desired reactant has a lesser residence time within the mixer for any reason, e.g., the reactant is highly reactive, unstable at the temperature(s) at which the other reactants are introduced to the mixer, etc.
(33) In embodiments wherein a flow pattern development zone is desirably included, it can have any suitable length (L.sub.fpd) and inner diameter (D.sub.fpd). Desirably, the length and inner diameter of the flow pattern development zone will facilitate and/or accommodate the desired flow rate of the reactants, while also encouraging or enhancing the desired flow pattern. The inner diameter (D.sub.fpd) of the innermost tube of the flow pattern development zone may be greater than 0.25 inch, or greater than 0.5 inch, or greater than 0.75 inches, or greater than 1 inch. The inner diameter (D.sub.fpd) of the outermost tube of the flow pattern development zone may be less than 60 or less than 30 or less than 24 or less than 18. In some embodiments, the inner diameter (D.sub.fpd) of the innermost tube of the flow pattern development zone is from 0.25 to 60 of from 0.5-30, or from 0.75 to 24 inches, or from 1 to 18.
(34) Any flow pattern development zone can have a length (L.sub.fpd) such that the ratio of its length (L.sub.fpd) to the inner diameter (D.sub.fpd) of the innermost tube thereof is greater than 0.5, or greater than 0.75, or greater than 1.0, or greater than 1.25, or greater than 1.5. The ratio L.sub.fpd to D.sub.fpd, innermost, may be less than 50, or less than 40, or less than 30, or less than 20, and in some embodiments, may be less than 10. In some embodiments, L.sub.fpd/D.sub.fpd, innermost may be from 0.25-50, or from 0.5 to 40, or from 0.75 to 30, or from 1.0 to 20, or from 1.25 to 10.
(35) A mixing zone may also be provided in some embodiments, and can be used to mix one or more reactants prior to entry into the expander zone. The mixing zone may be fluidly connected to the chamber outlet, or the flow pattern development zone, at the upstream end thereof, and is desirably fluidly connected to the expander zone at its downstream end. The mixing zone may be used to bring the reactants, previously introduced into separate inlets, and in some embodiments, passed through the flow pattern development zone, into contact with each other. The mixing zone is desirably of a geometry that will allow the flow pattern to be substantially maintained, and in some embodiments, may be cylindrical.
(36) The mixing zone may advantageously have the same, or a lesser, inner diameter (D.sub.m) as the largest immediately preceding inner diameter, i.e., if fluidly connected to one or more chamber outlets, the mixing zone is desirably substantially the same or smaller, diameter as the outermost chamber outlet. If the mixing zone is fluidly connected to a flow pattern development zone, the mixing zone will desirably be of the same geometry, and have an inner diameter, or cross sectional area, as the case may be, substantially the same as the outermost tube of the flow pattern development zone.
(37) Any mixing zone may be of any suitable length (L.sub.m), which may be chosen based upon the flow rate and reactivity of the reactants. Any mixing zone may have a length, L.sub.m, of greater than 1 foot, or greater than 10 feet, or greater than 20 feet, or greater than 30 feet. Mixing zone length Lm may be less than 60 feet, or less than 50 feet, or less than 40 feet. In some embodiments, mixing zone length may be from 1 to 60 feet, or from 10 feet to 50 feet, or from 20 feet to 40 feet. The ratio of mixing zone length L.sub.m to D.sub.m may, e.g., be 1, or 2, or 6, or 10. Desirably, the ratio of mixing zone length L.sub.m to mixing zone diameter D.sub.m will be from 2 to 8.
(38) One or more of the described features and/or dimensions may advantageously be employed in the mixer, wherein their advantages are expected to be cumulative, and perhaps synergistic. Any two, any three, any four, any five or all of the design concepts may be employed. For example, the mixer may have an chamber-inlet angle of less than 90, an expander zone having an expander angle of 45, and/or i) a chamber inner diameter (D.sub.c) at least 1.25 times greater than the inner diameter of the chamber inlet (D.sub.ci), and/or ii) a chamber inner diameter (D.sub.c) that is at least the same or greater than the inner diameter of the chamber outlet (D.sub.co), and/or iii) a tangential chamber-inlet angle of less than 90, and/or iv) a flow pattern development zone, having a ratio of length (L.sub.fpd) to the inner diameter (D.sub.fpd) of at least 0.5 and/or a mixing zone having a ratio of length (L.sub.m) and inner diameter (D.sub.m) of at least 1.0.
(39) Tables 1 and 2 show the possible dimensional relationships that may be optimized in the present mixer and possible values/ranges for each. More particularly, Table 1 contemplates the addition of any number of reactants to the mixer, and Table 2 is directed to those embodiments wherein 2 reactants are introduced via inlets/chambers (although others may be introduced by other means, into other sections of the mixer, e.g., as via injection into a port, etc.)
(40) TABLE-US-00001 TABLE 1 Dimension Embodiment 1 Embodiment 2 Embodiment 3 Number of 2 or greater 2-10 2-5 inlets/chambers D.sub.c (inches) 0.5-120 0.75-90 1.25-60 D.sub.c/(D.sub.ci) 1.25-20 1.5-20.sup. 2-10 Chamber-inlet angle, 90 5-85 10-80 Tangential chamber- 0 or greater 60 to 85 70 to 80 inlet angle, D.sub.c/D.sub.co .sup.1-10 1.2-8 1.2-4 D.sub.fpd, innermost 0.5-60 0.5-30.sup. 1-24 L.sub.fpd/D.sub.fpd, innermost 0.5-30 1-20 1-10 D.sub.fpd, outermost NA-60.sup. NA-50 NA-40 L.sub.m (feet) .sup.0-60 0-50 0-40 D.sub.m (inches) 0.5-120 1.0-60.sup. 1.0-36.sup. Expander angle () 90 .sup.2-45 .sup.3-25 D.sub.e (feet) 100.sup. 50 20
(41) One exemplary embodiment of the mixer is shown in
(42) Another embodiment of the mixer is shown in
(43) Additional embodiments of the mixer are shown in
(44) As shown in
(45) In the embodiment shown in
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(47) In some embodiments, the outlet of the mixer may desirably be operably disposed relative to the reactor that would desirably receive the mixed reactants, i.e., the mixer outlet may be directly coupled to a reactor inlet, or may be coupled to any other conduit capable of fluidly coupling the mixer outlet with the reactor inlet. Any such conduit is desirably configured so as to be substantially the same shape as the fluid flow from the reactor, e.g., to be substantially tubular or conical. Any such conduit will also desirably be placed about the same longitudinal axis as the outlet of the mixer.
(48) Whether directly attached to the reactor, or to a conduit there between, the advantages provided may be realized or enhanced by using certain reactor features and/or dimensions to assist in the design of the mixer. The incorporation of the expander into the present mixer allows an advantageous inlet arrangement to be used, having an inner diameter that more closely approximates the inner diameter of the feedstream source line, while yet having an outlet that more closely approximates the reactor inlet inner diameter.
(49) Table 2, below, provides a correlation between dimensions and features of the mixer with common reactor sizes with which the mixer may advantageously be used, for an exemplary process wherein two reactants are introduced to two inlet/chambers. Table 2 is by no means exhaustive, and those of ordinary skill will be able to extrapolate the dimensions and ranges given to any type of reactor, having any dimensions, and to any type of process.
(50) TABLE-US-00002 TABLE 2 Approximate Reactor ID 4 8 Reactor Dimensions ID (D.sub.r), in 3.826 96 Length, in 70.87 231 Mixer Dimensions Chamber/inlet number 2 2 Mixer head ID (inch) 2 28 Inlet 1 ID (0.1-0.5) (4-12) Chamber 1 (central) outlet ID 0.25-0.75 4-12 Inlet 2 ID 0.1-0.5 4-12 Chamber 2 (outer) outlet ID 0.6-1.4 9-27 Flow pattern development zone, 3-9 12-48 Length (in) Mixing zone, Length (in) 6-18 12-72 Expander Zone Angle from longitudinal axis 1-20 1-20
(51) The mixer can be attached to a reactor with various configurations. In order to provide a desired residence time, a reactor for the production or chlorinated propenes may typically be quite long, and so one or more sections of the reactor and/or mixer may be nonlinear, i.e., one or more zones thereof may comprise bends of 45 or greater, or 90 or greater, or even 135 or greater. In some embodiments, the reactor and/or mixer may comprise multiple bends, and in such embodiments, may even take the form of a serpentine pattern. Incorporating bends into the reactor and/or mixer allows the desired lengths to be utilized for each zone, while yet minimizing the manufacturing footprint required for the reactor and the mixer.
(52) The present mixer/reactor apparatus provides significant advantages when used in connection with chemical processes comprising a limiting reagent for which it was designed, and such processes are also provided. Incorporating the present mixer or mixer/reactor apparatus into such a process can reduce, or even eliminate backmixing that may occur in conventional mixers, so that substantial variances in conversions are not seen. Indeed, processes performed using the present mixer and/or apparatus can be provided with minimized production of secondary products and/or decomposition products such that variances of less than 2%, or even less than 1%, from the desired conversion, are seen. A reactor provided with such mixer described here may be operated at substantially longer run-time and hence allowed larger capacity than otherwise. Selectivity may also be substantially maintained, or is expected to decrease by no more than 2%. Such reactions may also typically include at least one limiting reactant having desired conversions that are far from exhaustion, e.g., conversions of less than 80%, or less than 40%, or even less than 20%.
(53) The efficiencies provided by the present mixers and apparatus can be further leveraged by providing the chlorinated and/or fluorinated propene and higher alkenes produced therein to further downstream processes. For example, 1,1,2,3-tetrachloropropene produced using the described reactors can be processed to provide further downstream products including hydrofluoroolefins, such as, for example, 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf) or 1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze). Improved methods for the production of hydrofluoroolefins, 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf) or 1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze), are thus also provided herein.
(54) The conversion of chlorinated and/or fluorinated propene and higher alkenes to provide hydrofluoroolefins may broadly comprise a single reaction or two or more reactions involving fluorination of a compound of the formula C(X).sub.mCCl(Y).sub.n(C)(X).sub.m to at least one compound of the formula CF.sub.3CFCHZ, where each X, Y and Z is independently H, F, Cl, I or Br, and each m is independently 1, 2 or 3 and n is 0 or 1. A more specific example might involve a multi-step process wherein a feedstock of 1,1,2,3 tetrachloropropene is fluorinated in a catalyzed, gas phase reaction to form a compound such as 2-chloro-3,3,3-tri-fluoropropene. The 2-chloro-2,3,3,3-tetrafluoropropane is then dehydrochlorinated to 2,3,3,3-tetrafluoropropene via a catalyzed, gas phase reaction.
EXAMPLE 1
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(56) The results of a computational fluid dynamic simulation are also shown in