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Title:
IMPROVED PROCESS-INTENSIFIED FLOW REACTOR
Document Type and Number:
WIPO Patent Application WO/2019/028002
Kind Code:
A1
Abstract:
A flow reactor has a module having a process fluid passage with an interior surface, a portion of the passage including a cross section along the portion having a cross-sectional shape, and a cross-sectional area with multiple minima along the passage. The cross-sectional shape varies continually along the portion and the interior surface of the portion includes either no pairs of opposing flat parallel sides or only pairs of opposing flat parallel sides which extend for a length of no more than 4 times a distance between said opposing flat parallel sides along the portion and the portion contains a plurality of obstacles distributed along the portion.

Inventors:
LAVRIC ELENA DANIELA (FR)
JEAN PATRICK (FR)
Application Number:
PCT/US2018/044572
Publication Date:
February 07, 2019
Filing Date:
July 31, 2018
Export Citation:
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Assignee:
CORNING INC (US)
LAVRIC ELENA DANIELA (FR)
JEAN PATRICK (FR)
International Classes:
B01J19/00; B01F5/06; B01F13/00
Domestic Patent References:
WO2010138676A12010-12-02
WO2010009239A22010-01-21
Foreign References:
US7939033B22011-05-10
EP2172260A12010-04-07
US20140290786A12014-10-02
US7939033B22011-05-10
Attorney, Agent or Firm:
BEAN, Gregory V. (US)
Download PDF:
Claims:
CLAIMS

What is claimed is:

1. A flow reactor comprising:

a module having a process fluid passage therein, the process fluid passage comprising an interior surface, the process fluid passage further comprising a portion thereof which portion further comprises:

(1) an input end at which process fluid is to flow into the portion during use and

(2) an output end at which process fluid is to flow out of the portion during use, and

(3) a cross section along the portion delimited by the interior surface of the passage along the portion, the cross section having a cross-sectional area and a cross-sectional shape, the cross-sectional area having multiple minima along the passage between the input end and the output end, the passage characterized in that (1) the cross-sectional shape of the portion varies continually along the portion, (2) the interior surface of the portion includes either no pairs of opposing flat parallel sides or only pairs of opposing flat parallel sides which extend for a length of no more than 4 times a distance between said opposing flat parallel sides along the portion, and (3) the portion contains a plurality of obstacles positioned along the portion between the input end and the output end.

2. The flow reactor according to claim 1 wherein the portion further comprises

successive chambers each with a nozzle-like entrance and a narrowing exit.

3. The flow reactor according to claim 2 wherein one chamber of said successive

chambers is nested with a next-succeeding chamber of said successive chambers such that the narrowing exit of the one chamber forms the nozzle-like entrance of the next adjacent succeeding chamber.

4. The flow reactor according to either of claims 2 and 3 wherein at least one of the plurality of obstacles is located within a first chamber and intersects a straight line having a first endpoint located at a center of the entrance of the first chamber and a second endpoint locate at a center of the exit of the first chamber.

5. The flow reactor according to claim 4 wherein the at least one of the plurality of obstacles intersects every straight line having a first end point within the entrance of the first chamber and a second endpoint within the exit of the first chamber.

6. The flow reactor according to either of claims 4 and 5 having one or more bypass paths, positioned between the at least one obstacle and an inside surface of the first chamber, around the at least one obstacle of the plurality of obstacles.

7. The flow reactor according to claim 6 wherein said one or more bypass paths have a total cross-sectional area greater than the total cross-sectional area of the exit of the first chamber.

8. The flow reactor according to claim 6 wherein said at least one obstacle has one or more openings extending through said at least one obstacle.

9. The flow reactor according to claim 6 wherein said at least one obstacle has no

openings extending through said at least one obstacle.

10. The flow reactor according to any of claims 4-9 wherein the plurality of obstacles comprises at least three or more obstacles.

11. The flow reactor according to claim 4-9 wherein the at least one obstacle of the

plurality of obstacles comprises at least one obstacle per chamber.

12. The flow reactor according to any of claims 4-9 further comprising two or more

obstacles in a single chamber.

13. The flow reactor according to any of claims 4-9 wherein said at least one obstacle has two or more bypass paths.

14. The flow reactor according to claim 13 wherein said at least one obstacle has three or more bypass paths.

15. The flow reactor according to either of claims 13 and 14 wherein said bypass paths are separated by the obstacle by a distance of at least twice a maximum diameter of the exit of the chamber.

16. The flow reactor according to any of claims 4-9 wherein said at least one obstacle has a single bypass path.

17. The flow reactor according to any of claims 4-9 wherein said at least one obstacle has a two bypass paths, said two bypass paths positioned on opposite sides of the process fluid passage relative to one another.

18. The flow reactor of any of claims 1-17 wherein the at least one of the plurality of obstacles comprises a flat or concave surface aligned generally perpendicularly to the process fluid passage.

19. The flow reactor of claim 18 wherein the flat or concave surface faces in a

downstream direction.

20. The flow reactor of claim 18 wherein the flat or concave surface faces in an upstream direction.

21. The flow reactor of claim of any of claims 1-18 wherein the at least one of the

plurality of obstacles comprises a tapering elongated end pointing in a downstream direction.

22. The flow reactor of claim of any of claims 1-18 wherein the at least one obstacle of the plurality of obstacles comprises a tapering elongated end pointing in an upstream direction.

23. The flow reactor of any of claims 1-22 further comprising an internal screw thread structure on an inner surface of the process fluid passage.

24. The flow reactor of any of claims 1-23 further comprising an internal screw thread structure on an inner surface of the portion of the process fluid passage.

25. A flow reactor comprising:

a body having a process fluid passage contained therein, the process fluid passage having a portion thereof, said portion comprising a fluid input end and a fluid output end and successive cross-sectional-area minima between the input end and the output end, the portion further having a cross-sectional shape defined, at any position along the portion, as a cross section of the process fluid passage, at that position of the portion, angularly oriented such that, for a fluid flowing from the input to the output end of the portion, a net fluid flow through said cross section is maximized; the portion further having a passage shape defined at any position along the portion as a planar cross section of the process fluid passage passage taken at that position in a plane perpendicular to the predominant flow direction at that position; the passage shape having both a width and a height, perpendicular to the width, each varying continually with position along the flow passage; the flow passage comprising successive chambers each with a narrow entrance and a narrowing exit which protrudes into the next adjacent chamber (if any) forming the narrow entrance thereof, and an internal screw thread structure on an inner surface of the portion of the process fluid passage.

Description:
IMPROVED PROCESS-INTENSIFIED FLOW REACTOR

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. ยง 119 of U.S. Provisional Application No. 62/539,541, filed July 31, 2017, the content of which is incorporated herein by reference in it entirety.

FIELD

[0002] The present disclosure relates generally to flow reactors and particularly to flow reactors having optimized channel structures.

BACKGROUND

[0003] Process intensification aims to produce highly efficient reaction and processing systems using configurations that simultaneously significantly reduce reactor sizes and maximize mass- and heat-transfer efficiencies. Interest in and application of process intensification in chemical engineering is continually increasing because of the potential to transform large-scale, environmentally unfriendly industrial processes into smaller, safer, more energy-efficient and environmentally friendly processes.

[0004] Process intensification consists in the development of novel apparatuses and techniques that, compared to those commonly used today, are expected to bring very significant, even order(s)-of-magnitude improvements in manufacturing and processing, in decreasing equipment-size/production-capacity ratio, energy consumption, and/or waste production, ultimately resulting in cheaper and sustainable technologies. Put another way, any chemical engineering development that leads to a substantially smaller, cleaner, and more energy-efficient technology is process intensification.

[0005] The whole field of process intensification can generally be divided into two areas: process-intensifying equipment, such as novel reactors and intensive mixing, heat- transfer and mass-transfer devices; and process-intensifying methods, such as new or hybrid separations, integration of reaction and separation, heat exchange, or phase transition (in so- called multifunctional reactors), techniques using alternative energy sources (light, ultrasound, etc.), and new process-control methods (like intentional unsteady-state operation). Obviously, there can be some overlap. New methods may require novel types of equipment to be developed and vice versa, while novel apparatuses already developed sometimes make use of new, unconventional processing methods.

[0006] In US7939033 is disclosed a "microreactor" or micro- to milli-meter scale flow reactor with a characteristic channel design producing good mixing performance relative to pressure drop in a given channel or device. It would be desirable to achieve even better performance, however, such as equal or better mixing with lower pressure drop.

SUMMARY

[0007] The following presents a simplified summary of the disclosure in order to provide a basic understanding of some exemplary embodiments described in the detailed description.

[0008] In some embodiments, a flow reactor has a module having a process fluid passage with an interior surface, a portion of the passage including a cross section along the portion having a cross-sectional shape, and a cross-sectional area with multiple minima along the passage. The cross-sectional shape varies continually along the portion and the interior surface of the portion includes either no pairs of opposing flat parallel sides or only pairs of opposing flat parallel sides which extend for a length of no more than 4 times a distance between said opposing flat parallel sides along the portion and the portion contains a plurality of obstacles distributed along the portion.

[0009] In some embodiments, the portion further comprises successive chambers each with a nozzle-like entrance and a narrowing exit.

[0010] In some embodiments, a chamber of said successive chambers is nested with a next-succeeding chamber of said successive chambers such that the narrowing exit of the one chamber forms the nozzle-like entrance of the next adjacent succeeding chamber.

[0011] In some embodiments, at least one of the plurality of obstacles is located within a first chamber and intersects a straight line having a first endpoint located at a center of the entrance of the first chamber and a second endpoint locate at a center of the exit of the first chamber.

[0012] In some embodiments, the at least one of the plurality of obstacles intersects every straight line having a first end point within the entrance of the first chamber and a second endpoint within the exit of the first chamber . [0013] In some embodiments, the reactor having an obstacles in the first chamber has one or more bypass paths positioned between the at least one obstacle and an inside surface of the first chamber, i.e., around the at least one obstacle of the plurality of obstacles.

[0014] In some embodiments, the at least one obstacle has no openings extending through said at least one obstacle.

[0015] In some embodiments, with two or more bypass paths around the obstacle, the bypass paths are separated by the obstacle by a distance of at least twice a maximum diameter of the exit of the chamber, or as much as at least 2.5, 3, 3.5, or even 4 times.

[0016] In some embodiments, the flow reactor further comprises an internal screw thread structure on an inner surface of the portion of the process fluid passage.

[0017] The above embodiments are exemplary and can be provided alone or in any combination with any one or more embodiments provided herein without departing from the scope of the disclosure. Moreover, it is to be understood that both the foregoing general description and the following detailed description present embodiments of the present disclosure, and are intended to provide an overview or framework for understanding the nature and character of the embodiments as they are described and claimed. The accompanying drawings are included to provide a further understanding of the embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments of the disclosure, and together with the description, serve to explain the principles and operations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] These and other features, embodiments, and advantages of the present disclosure can be further understood when read with reference to the accompanying drawings:

[0019] FIG. 1 (Prior Art) shows a three-dimensional perspective view of a portion of a process fluid passage according to a prior art flow reactor;

[0020] FIG. 2 (Prior Art) shows an individual chamber of the passage of FIG. 1;

[0021] FIG. 3 (Prior Art) shows, in perspective view, a cross-section of the chamber of FIG. 2;

[0022] FIG. 4 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure; [0023] FIG. 5 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0024] FIG. 6 shows a cross-sectional view of a the passage of FIG. 5;

[0025] FIG. 7 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0026] FIG. 8-10 each show a cross-sectional view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0027] FIG. 11 shows a translucent perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0028] FIG. 12 shows a cross-sectional view of a portion of a process fluid passage in accordance with embodiments of the present disclosure, such as the embodiment of FIG. 11;

[0029] FIG. 13 shows a cut-away perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0030] FIG. 14 shows an alternate cut-away perspective view of the portion of a process fluid passage in accordance with embodiments of the present disclosure of FIG. 13;

[0031] FIGS. 15-18 each show a cut-away perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0032] FIG. 19 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0033] FIG. 20 shows a cross-sectional view of a chamber of the passage of FIG. 19;

[0034] FIG. shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0035] FIG. 22 shows an individual chamber of the passage of FIG. 21;

[0036] FIG. 23 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0037] FIG. 24 shows a cross-sectional view of a chamber of the passage of FIG. 23;

[0038] FIG. 25 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0039] FIG. 26 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0040] FIG. 27 shows a transparent plan view of a portion of the process fluid passage in FIG. 26; [0041] FIG. 28 shows a translucent perspective view of a portion of the process fluid passage in FIG. 26;

[0042] FIG. 29 shows a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0043] FIG. 30 shows a cross-sectional view of a chamber of the passage of FIG. 29;

[0044] FIG. 31 shows a plan view of a portion of a process fluid passage in accordance with embodiments of the present disclosure;

[0045] FIG. 32 shows a plan view of a chamber of the passage of FIG. 31;

[0046] FIG. 33 is a graph of measured pressure drop as a function of flow rate as obtained from process fluid passages in accordance with embodiments of the present disclosure;

[0047] FIG. 34 is a graph of measured pressure drop as a function of flow rate as obtained from process fluid passages in accordance with embodiments of the present disclosure;

[0048] FIG. 35 is a graph of measured volumetric mass transfer coefficient as a function of specific power consumption as obtained from process fluid passages in accordance with embodiments of the present disclosure;

[0049] FIG. 36 is a graph of measured volumetric mass transfer coefficient as a function of specific power consumption as obtained from process fluid passages in accordance with embodiments of the present disclosure;

[0050] FIG. 37 each show a cut-away perspective view of walls of a portion of a process fluid passage in accordance with embodiments of the present disclosure; and

[0051] FIG. 38 shows a cross-sectional plan view of a chamber of a portion of a process fluid passage in accordance with embodiments of the present disclosure.

DETAILED DESCRIPTION

[0052] Methods and apparatus will now be described more fully hereinafter with reference to the accompanying drawings in which exemplary embodiments of the disclosure are shown. Whenever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts. However, this disclosure can be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. [0053] The present disclosure relates generally to flow reactors employing modules similar to the ones disclosed in US7939033, hereby incorporated in its entirety by reference. If desired, the modules of the present disclosure may, however, depart from the generally planar geometry of that reference.

[0054] Flow modules having passages as disclosed herein may be formed by machining, molding, 3-D printing, and the like. Modules may be unitary (not able to be disassembled) or may consists of plates or other parts that are mechanically compressed or otherwise sealed together in a removable fashion.

[0055] FIG. 1 (Prior Art) shows a three-dimensional perspective view of a portion of a process fluid passage according to a prior art flow reactor, while FIG. 2 (Prior Art) shows an individual chamber of the passage of FIG. 1, and FIG. 3 (Prior Art) shows, in perspective view, a cross-section of the chamber of FIG. 2.

[0056] With respect to FIGS. 1-3, a flow reactor of the general type disclosed herein comprises a module having a process fluid passage 20 therein, the process fluid passage comprising an interior surface 22, the process fluid passage 20 further comprising a portion 30 thereof, which portion further comprises an input end 32 at which process fluid is to flow into the portion 30 during use and an output end 34 at which process fluid is to flow out of the portion 30 during use.

[0057] The portion 20 also comprises a cross section 36 along the portion 30, delimited by the interior surface 22 of the passage 20 along the portion 30, the cross section 36 having a cross-sectional area and a cross-sectional shape 38, the cross-sectional area having multiple minima 40 along the passage 20 between the input end 32 and the output end 34.

[0058] FIGS. 4 and 5 each show a three-dimensional perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure, and FIG. 6 shows a cross-sectional view of a the passage of FIG. 5. With respect to the passages shown in FIGS. 4-6, and generally with respect to embodiments of the present disclosure, the reactor is characterized in that the portion 30 of the passage 20 has (1) a cross-sectional shape 38 which varies continually along the portion 30, (2) an interior surface 22 (along the portion 30) which includes either no pairs of opposing flat parallel sides 42 (as seen in FIG. 3) or only pairs of opposing flat parallel sides 42 which extend for a length of no more than 4 times a distance d between said opposing flat parallel sides 42 along the portion 30 (shown in FIG. 12, discussed below), and (3) a plurality of obstacles 50 positioned along (within) the portion between the input end 32 and the output end 34 (in this case, in the form of a curved wall with a concave surface facing upstream.

[0059] Various forms of curvature may be used for the interior surface 22 of the portion 30 of the passage 20. As seen in FIG. 4, the height of the portion 30 of the passage 20 may vary periodically with the chambers themselves, so that each successive chamber is essentially identical. Alternatively, a period of variation in the height of the portion 20 of the passage 20 may be shorter, in length along the portion 30, or longer, as in the embodiment of FIG. 5. This results in obstacles 50 having varying height, as shown in the cross section of FIG. 6. Cross sections of additional embodiments of portions 30 of passages 20 are shown in FIGS. 8-10, with obstacles 50 of varying heights in the successive chambers 52 of FIG. 8, or of the same height in the successive chambers 52 of FIG. 9. Obstacles 50 may also extend only partially across the height of the chambers 52, as shown in the embodiment of FIG. 10. (Such obstacles effectively have only a single bypass path, albeit with a complex shape and flow pattern.) Variation in the height of the portion 30 of the passage 20 may also be asymmetrical, or the curvature of the successive chambers 52 may be asymmetrical. In the embodiment of FIG.7 and as seen in the figure, every other chamber 52 has a larger "bulge" (or a smaller radius of curvature) on the upper inside surface of the chamber (relative to the lower inside surface), while the remaining chambers 52 have a a larger "bulge" (or a smaller radius of curvature) on the lower insider surface (relative to the upper).

[0060] In the case as in the embodiment of Figure 10 where the obstacle 50 extends only partially across the height of the chamber 52, a straight line 60 having a first endpoint located at a center of the entrance of the chamber 52 and a second endpoint locate at a center of the exit of the chamber is intersected by the obstacle 50. This insures that the less than full height obstacle is sufficiently tall to have a significant effect in displacing flow in the height direction. Desirably, the obstacle 50 intersects not just the line 60 from the center point of the entrance to the center point of the exit of the chamber 52, but every line segment originating within the entrance of the chamber and ending within the exit of the chamber. In other words, desirably, there is no "line-of-sight" from the entrance to the exit of the chamber 52 even in the case that the obstacle extends only partially across the height of the chamber.

[0061] The portions 30 of passages 20 herein include one or more bypass paths 64, as indicated, for example, in FIGS. 4 and 5. The bypass paths 64 are paths positioned between the obstacle 50 and an inside surface of the associated chamber 52, and which lead around the obstacle 50. Such bypass paths 64 are distinguished from openings extending through an obstacle 50. Such openings 70 are seen in the embodiment of FIGS. 21-22. In embodiments more generally as seen in most other figures herein, the obstacle 50 has no openings extending through the obstacle 50. According to embodiments, as shown in FIG. 4, the one or more bypass paths 64 have a total cross-sectional area 66 greater than the total cross-sectional area 68 of the exit of the associated chamber.

[0062] FIG. 11 shows a translucent perspective view of a portion of a process fluid passage in accordance with embodiments of the present disclosure while FIG. 12 shows a cross-sectional view of a portion of a process fluid passage in accordance with embodiments of the present disclosure, of the type of the embodiment of FIG. 11. In embodiments as shown here, one or more chambers 52 have both an obstacle 50 and a second obstacle 51 in the same chamber 52. Desirably, the obstacle 50 and second obstacle 52 extend only partially across the height of the chamber 52 (as seen most clearly in FIG. 12), and desirably they are attached alternately to the "floor" and "ceiling" of the chamber 52. In such embodiments, the obstacle or the second obstacle 52 may not, alone, intersect all lines of sight between the respective chamber's entrance and exit (or even the centerline between them), but it is desirable that they do so when considered together.

[0063] In some embodiments, the chambers 52 may have or almost have rotational symmetry, such that the height and width of the chambers are both considered instead as a diameter. FIGS. 13-18 each show a cut-away perspective view of a portion of a process fluid passage in which the portion 30 of the passage 20, as well as the successive chambers 51, have rotational symmetry. In embodiments such as these, three or more bypass paths may be used. In embodiments, the obstacles 50 comprise a flat or concave surface 72 aligned generally perpendicularly to the portion 30 of the process fluid passage 20. The surface 72 may preferably face in an upstream direction as shown in the embodiments of FIGS. 15, 16, and 18, but in alternative embodiments may face in a downstream direction as in the embodiment of FIG. 17.

[0064] FIGS. 19-32 show embodiments which were fabricated and performance tested in comparison to a reference embodiment (the embodiment of FIGS. 1-3). (The embodiment of FIG. 25 has chambers 52 similar to those of the embodiment of FIG. 19, except raised "ceilings" and lowered "floors" 78, relative to the embodiment of FIG. 19 Results are shown in FIGS. 33-36.

[0065] FIGS. 33 and 34 are graphs of measured pressure drop. FIG. 33 results are from relatively larger scale passages, FIG. 34 from relatively smaller scale passages. The numbers in the keys correspond to the numbers given for each embodiment in FIGS. 19-32. As seen in FIGS. 33 and 34, all tested embodiments outperformed the reference embodiment in achieving lower pressure drop.

[0066] FIGS. 35 and 36 are graphs of measured volumetric mass transfer coefficient as a function of specific power consumption, with FIG. 35 results from relatively larger scale passages and FIG. 36 results from relatively smaller scale passages. As seen in FIG. 35, all tested embodiments other than number 2 and 5 outperformed the reference on this measure and in FIG. 36 all other than number 2. Accordingly, it is believed to be desirable to have no openings extending through the obstacles (as in embodiment number 2). Similarly, it is believed to be desirable to have the bypass paths, when there are two (or possibly more) in a chamber, separated by the obstacle by a distance of at least 2, 2.5, 3, 3.5 or even 4 times a maximum diameter of the exit of the chamber, unlike in embodiment number 5 in which a post or wedge 80 separates two bypass paths by only a short distance.

[0067] According to embodiments, the interior surface 22 (of the portion 30) passage 20 may include an internal screw thread structure 76 to impart an additional, helical motion to the fluid moving in the portion of the passage.

[0068] It will be appreciated that the various disclosed embodiments can involve particular features, elements or steps that are described in connection with that particular embodiment. It will also be appreciated that a particular feature, element or step, although described in relation to one particular embodiment, can be interchanged or combined with alternate embodiments in various non-illustrated combinations or permutations.

[0069] It is to be understood that, as used herein the terms "the," "a," or "an," mean "at least one," and should not be limited to "only one" unless explicitly indicated to the contrary. Thus, for example, reference to "a component" includes embodiments having two or more such components unless the context clearly indicates otherwise.

[0070] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, embodiments include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0071] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred.

[0072] While various features, elements or steps of particular embodiments can be disclosed using the transitional phrase "comprising," it is to be understood that alternative embodiments, including those that can be described using the transitional phrases "consisting" or "consisting essentially of," are implied. Thus, for example, implied alternative embodiments to an apparatus that comprises A+B+C include embodiments where an apparatus consists of A+B+C and embodiments where an apparatus consists essentially of A+B+C.

[0073] It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure cover the modifications and variations of this disclosure provided they come within the scope of the appended claims and their equivalents.