SYSTEM AND METHOD FOR SEPARATING AIR GASES AT LOW PRESSURE

Abstract

An air gas separation plant comprising, in the direction of circulation of the air stream: a compression means that makes it possible to compress the air stream to a pressure P1 of between 1.15 bar abs and 2 bar abs, an adsorption unit of TSA type, and a cryogenic distillation unit, with the adsorption unit comprising at least two adsorbers A and B each having a parallelepipedal casing arranged horizontally and comprising: an air stream inlet and an air stream outlet, a fixed bed adsorbent mass, likewise of parallelepipedal shape, the faces of which are parallel to the faces of the casing; and a set of volumes allowing the air stream to pass through the adsorbent mass horizontally, over the entire cross-section and throughout the entire thickness thereof.

Claims

1-16. (canceled)

17. An air gas separation plant comprising, in the direction of circulation of the air stream: a) a compressor configured to compress the air stream to a pressure P1 of between 1.15 bar abs and 2 bar abs; b) a cryogenic distillation unit; c) an adsorption unit of TSA type comprising at least two adsorbers A and B each having a parallelepipedal casing arranged horizontally, wherein the adsorption unit further comprises: an air stream inlet and an air stream outlet; a fixed bed adsorbent mass, likewise of parallelepipedal shape, the faces of which are parallel to the faces of the casing; and a set of volumes allowing the air stream to pass through the adsorbent mass horizontally, over the entire cross-section and throughout the entire thickness thereof.

18. The plant as claimed in claim 17, wherein said plant comprises, between the compression means and the cryogenic distillation unit, a single adsorption unit.

19. The plant as claimed in claim 17, wherein the set of volumes comprises: a) a first volume V1 for the introduction and distribution of the air stream; b) a second volume V2 comprising the adsorbent mass; and c) a third volume V3 for recovering the purified air stream; wherein the three volumes are contiguous and in fluidic communication via the faces they have in common.

20. The plant as claimed in claim 19, wherein the second volume V2 comprises at least two sub-volumes containing different adsorbents.

21. The plant as claimed in claim 19, wherein the volume V1 and/or the volume V3 respectively comprise sub-volumes V11-V12 and V31-V32 which are separated by a perforated wall that improves the distribution of the fluids.

22. The plant as claimed in claim 19, wherein the volumes V1 or V11 and V3 or V32 each have at least one face that is permeable to the fluids, and the adsorber comprises fluid-distribution and fluid-recovery header tanks contiguous with the permeable faces.

23. The plant as claimed in claim 17, wherein the adsorption unit comprises N pairs of adsorbers where N≥1, each pair comprising an adsorber A and an adsorber B which are positioned contiguously so as to form a single parallelepiped.

24. The plant as claimed in claim 23, wherein each pair of adsorbers comprises an adsorber A in adsorption mode and an adsorber B in regeneration mode, with all the adsorbers in adsorption mode operating in parallel and all the adsorbers in regeneration mode operating in parallel.

25. The plant as claimed in claim 23, wherein each adsorber A or B, or the A/B adsorber pair, is installed inside an ISO container or inside a container having dimensions and lifting arrangements compliant with ISO standards.

26. The plant as claimed in claim 23, wherein the adsorbers A and B comprise external or internal thermal insulation over at least part of their faces.

27. The plant as claimed in claim 23, wherein the casing of the adsorber A and/or of the adsorber B comprises: a) a length L of between 2 and 15 meters; b) a height H of between 1 and 3 meters; and c) a width I of between 0.5 and 3 meters, preferably of between 0.8 and 1.2 meters.

28. A method for separating air gases from an air stream containing at least one impurity selected from water vapor, carbon dioxide, nitrogen oxides and hydrocarbons, the method comprising using the plant as defined in claim 17 and further comprising the following successive steps: a) compressing the air stream to a pressure P1 of between 1.15 bar abs and 2 bar abs; b) purifying the compressed air stream, by adsorption using the TSA unit so as to remove at least one impurity contained in the air stream; and c) separating the constituents of the air stream by cryogenic distillation using the unit, wherein all of step b) is carried out at the pressure P1.

29. The method for separating air gases as claimed in claim 28, wherein the pressure P1 is between 1.15 bar abs and 1.5 bar abs, preferably between 1.20 bar abs and 1.30 bar abs.

30. The method for separating air gases as claimed in claim 28, wherein the set of volumes comprises: a) a first volume V1 for the introduction and distribution of the air stream; b) a second volume V2 comprising the adsorbent mass; and c) a third volume V3 for recovering the purified air stream; wherein the three volumes are contiguous and in fluidic communication via the faces they have in common, wherein the method further comprises the steps of introducing, in step b), the air stream into the volume V1 or the sub-volume V11 and withdrawing the purified air stream from the volume V3 or from the sub-volume V32.

31. The method for separating air gases as claimed in claim 30, wherein: a) the plant employed comprises in its adsorption unit N pairs of adsorbers A and B, where N≥1, with the adsorbers of each pair being positioned contiguously so as to form a single parallelepiped, and with each pair of adsorbers comprising one adsorber A in adsorption mode and one adsorber B in regeneration mode, b) the method comprises an additional step d) of regenerating the adsorber B, and c) in step b), in each adsorber A in adsorption mode, the air stream is introduced into each volume V1 or sub-volume V11 and the purified air stream is withdrawn from each volume V3 or sub-volume V32, and in step d), in each adsorber B in regeneration mode, a regeneration stream is introduced into each volume V3 or sub-volume V32 then withdrawn from each volume V1 or sub-volume V11.

32. The method for separating air gases as claimed in claim 28, wherein the air or regeneration streams are introduced into or withdrawn from the various volumes V1, V11, V3 and V32 preferably via the sides thereof which are situated in the lateral faces of the parallelepipedal shape of the adsorber A or B, or via the sides thereof which are situated in the bases of the parallelepipedal shape of the adsorber A or B.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0060] These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the invention and are therefore not to be considered limiting of the invention's scope as it can admit to other equally effective embodiments.

[0061] FIG. 1 shows an embodiment of the prior art.

[0062] FIG. 2 provides an embodiment of the present invention.

[0063] FIG. 3 provides an embodiment of the present invention.

[0064] FIG. 4 provides a transverse section through the two adsorbers in accordance with an embodiment of the present invention.

[0065] FIG. 5 provides a longitudinal section through the two adsorbers in accordance with an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0066] The adsorber A of the plant according to invention will be described in greater detail by means of FIG. 3. Specifically, that figure shows the various volumes V1, V2 and V3 and any sub-volumes there might be. A “parallelepipedal shape” is given to mean that in practice, the adsorber casing has six flat faces and has the appearance of a parallelepiped, but that it may have reinforcements, locally at least one internal or external layer of insulation, and obviously pipes or tanks for introducing and withdrawing air and regeneration gas. With the adsorber laid down flat, its longest length is denoted as L, its width as l and its height as H. In the context of the invention, it is not important whether these are external or internal dimensions.

[0067] FIG. 3 clearly shows that the volumes and sub-volumes are all of parallelepipedal shape and all have the same length L and the same height H. The parallelepipeds that they form differ from one another only in terms of their width.

[0068] As previously indicated, the volume V2 may comprise a plurality of sub-volumes with each of said sub-volumes being able to contain a different adsorbent.

[0069] From the inlet toward the outlet it is thus possible to use activated alumina, doped activated alumina or silica gel to capture most of the water, a 13X zeolite to capture most of the CO2, an exchanged zeolite to capture the nitrogen oxides and certain hydrocarbons, etc. The configuration adopted here is easier than in the usual solutions for implementing multi-layer purification with a clearly determined geometric volume for each of the beds. The widths l2i may be of different dimensions. This configuration preferably corresponds to the use of adsorbent in particulate (bead, stick, etc.) form. It would also be possible to use monoliths or, more generally, structured adsorbents, this being with or without the need to have distinct sub-volumes. Indeed, depending on the geometric shape of the structured adsorbents, there is no need to systematically provide separation between elements of different natures which can be placed directly in series.

[0070] [FIG. 3] shows a scenario corresponding to 2 sub-volumes V21 and V22. According to another embodiment, the volume V1 and/or the volume V3 respectively comprise sub-volumes V11-V12 and V31-V32 which are separated by a perforated wall that improves the distribution of the fluids. This embodiment is aimed at ensuring good distribution of the air, and likewise of the regeneration gas, across the entire cross-section of the adsorbent. The perforated part between the volumes V11 and V12 on the one hand, and/or between the volumes V31 and V32 on the other hand, allows, at the expense of a slight head loss, an appreciable improvement in the distribution of the fluids entering and/or leaving the layers of adsorbent. The fluidic resistance of the layers of adsorbent themselves thus allows a near-perfect distribution of the flow rates (to within + or −1% if necessary) to be achieved very quickly, after just 1 or 2 centimeters.

In order to ensure the thermal efficiency of the adsorption unit, that is to say in order to limit thermal losses therefrom, one preferred embodiment corresponds to the following feature: [0071] at least certain faces of an adsorber or of an adsorber pair have thermal insulation on the outside or on the inside of the adsorber.
This thermal insulation may employ any one of the conventional insulation materials (perlite, rockwool, expanded foam, etc.) but may also employ measures such as an air film or preferably a double air film system as is conventionally used in adsorbers upstream of cryogenic air separation units. In that case, it is the fluid itself that acts as the insulation.
According to another embodiment, the adsorber A, or the A-B adsorber pair, is installed inside an ISO container or inside a container having dimensions and lifting arrangements compliant with ISO standards.
The adsorber or the two adsorbers are assembled into a specific structure produced in a workshop, which can optionally use part of a standard ISO container. The benefit of complying with ISO standards is that it greatly facilitates handling and transportation. Any reinforcements making the assembly mechanically pressure resistant will be contained within the standard dimensions of the containers.

[0072] Bearing in mind the fact that large-sized containers exist, it may be beneficial, in both of the above instances, for the distribution header tanks, some of the piping or valves, the electric heater, etc. to be likewise housed in the container. At least one of the walls of the container (lateral, bottom or top wall) can act directly as a wall for the adsorber itself. In particular, the lateral walls may be incorporated into the distribution volumes V1 and/or V3. More generally, at least part of the structure of the container is used directly as a structure for the adsorber.

[0073] The materials used for the adsorbers and their internals are, for example, carbon steel, stainless steel, aluminum, or materials having low thermal expansion, such as INVAR. The present invention also relates to a method for separating air gases from an air stream containing at least one impurity selected from water vapor, carbon dioxide, nitrogen oxides and hydrocarbons, using a plant as defined above and comprising the following successive steps: [0074] compressing 1 the air stream to a pressure P1 of between 1.15 bar abs and 2 bar abs, [0075] purifying the compressed air stream, by adsorption using the TSA unit 2 so as to remove at least one impurity contained in the air stream, and [0076] separating the constituents of the air stream by cryogenic distillation using the unit (3), with all of step b) carried out at the pressure P1.
Depending on the case, the method according to the invention may have one or more of the features below: [0077] the pressure P1 is between 1.15 bar abs and 1.5 bar abs, preferably between 1.20 bar abs and 1.30 bar abs; [0078] the method uses a plant as defined hereinabove, and in step b) the air stream is introduced into the volume V1 or the sub-volume V11 and the purified air stream is withdrawn from the volume V3 or from the sub-volume V32. Note that this introduction and/or this withdrawal are preferably performed either horizontally via one or both lateral sides of the casing, or vertically via one or both horizontal faces of the casing, in other words via the top and the bottom of the casing, or via a large face of the casing; [0079] the plant employed comprises in its adsorption unit N pairs of adsorbers A and B, where N≥1, with the adsorbers of each pair being positioned contiguously so as to form a single parallelepiped, and with each pair of adsorbers comprising one adsorber A in adsorption mode and one adsorber B in regeneration mode, the method comprises an additional step d) of regenerating the adsorber B, and in step b), in each adsorber A in adsorption mode, the air stream is introduced into each volume V1 or sub-volume V11 and the purified air stream is withdrawn from each volume V3 or sub-volume V32, and in step d), in each adsorber B in regeneration mode, a regeneration stream is introduced into each volume V3 or sub-volume V32 then withdrawn from each volume V1 or sub-volume V11; [0080] the air or regeneration streams are introduced into or withdrawn from the various volumes V1, V11, V3 and V32 preferably via the sides thereof which are situated in the lateral faces of the parallelepipedal shape of the adsorber A or B, or via the sides thereof which are situated in the bases of the parallelepipedal shape of the adsorber A or B. In fact, the streams may theoretically be introduced/withdrawn via at least one of the 5 faces of the different volumes facing onto the external surroundings (the 2 lateral faces, the top or bottom face, or possibly the main L×H face). As a preference, the lateral faces or via the base. The main face does not encourage distribution and the inside face is not available if 2 adsorbers are positioned contiguously. As the adsorber is filled from the top, the obstacles in the upper part will be avoided.

[0081] The method according to the invention is illustrated by [FIG. 2]. The atmospheric air 10 containing the various pollutants to be removed is compressed by means of the compressor 1 to the pressure P1, of the order of 1.5 bar abs, and this compressed air 11 is introduced into the adsorber A of the TSA. After purification this purified air 12 is sent into the downstream part of the unit 3, which comprises in particular the cryogenic distillation unit. The regeneration gas 14 originates from this latter unit. It is generally impure nitrogen (that is, containing argon and oxygen) at low pressure, close to atmospheric pressure. This gas—or a fraction of this gas—is heated using one or more heat exchangers (steam, electric, by heat recovery from other fluids, etc.) during the heating step and is then used for cooling the adsorber. The output 13, generally impure oxygen (90-98%) in the case under consideration here, is sent to a downstream unit, not shown.

[0082] Regarding the admission and withdrawal of the fluids, one or more of the following features may be present: [0083] the fluids are introduced into or withdrawn from the volume V1—or, as the case may be, the sub-volume V11—horizontally via one or both lateral sides. [0084] the fluids are introduced into or withdrawn from the volume V3—or, as the case may be, the sub-volume V32—horizontally via one or both lateral sides. [0085] the fluids are introduced into or withdrawn from the volume V1—or, as the case may be, the sub-volume V11—vertically via one or both horizontal faces constituting the top or the bottom of the parallelepiped. [0086] the fluids are introduced into or withdrawn from the volume V3—or, as the case may be, the sub-volume V32—vertically via one or both horizontal faces constituting the top or the bottom of the parallelepiped.

[0087] In another variant, the fluids are introduced or withdrawn via the large faces (of cross-section L*H) of the parallelepiped. In the latter instance, the circulation of the fluids through the adsorber (V1, V2, V3) is essentially in a straight line from the inlet to the outlet. What that means in particular is that there is no abrupt change in direction, at around 90°, for the fluid between it entering the adsorber and it passing horizontally through the adsorbent volume.

[0088] As the fluids circulate horizontally in the adsorbers, some of the constraints specific to radial adsorbers are experienced, and in particular the need to avoid the premature breakthrough of the impurities in the top part of the adsorber. Said breakthrough can originate from a bypass or a local air flow and/or a regeneration fault.

[0089] The bypass itself can originate from the compaction of the adsorbent. These problems are well known to a person skilled in the art, and previously developed solutions will be applied here. In particular, as indicated above, due to its geometry, using a parallelepipedal adsorber simplifies the implementation of the solutions envisaged for radial beds (dead zone filled to a sufficient height with adsorbent, equivalent to the cones, etc.). Again, it must be noted that filling is also simplified and that it is easy here to obtain dense, uniform filling by sprinkling, limiting both the compaction and the risk of uneven density in the beds.

[0090] Due to the simple geometry, a balloon can for example be used, inflated to a pressure greater than P1, forming a seal above the free surface of the adsorbents. A membrane can also be applied permanently to the free surface of the adsorbents through slight overpressure relative to the operating pressure. This overpressure can originate from a fluid, for example instrument air, or a heavy material. Once again, the solutions developed for the radial adsorbers of units that produce oxygen using adsorption should be adapted to suit.

[0091] The following example will illustrate the invention as has just been described.

[0092] It relates to an oxygen production unit producing of the order of 100 t/d (tonnes/day) for which an air flow rate of 15,000 Nm3/h is used. The pressure P1 on leaving the first compression stage is 1.3 bar abs. This air is cooled to 3° C. by means of a refrigerating unit in order to limit the quantity of water vapor carried to purification and in order to reduce the adsorption temperature. Here, this temperature is in the low range of the temperature levels used. It was selected mainly due to the low value of P1. Temperatures of 5 to 8° C. could be adopted, particularly if the pressure P1 was slightly higher. The final decision is based on a general cost analysis. The adsorption time applied is 150 minutes, resulting in a cycle time of 5 hours given that the purification unit usually comprises 2 adsorbers, one being in production while the other is in regeneration. Here, these conventional times could be reduced. The cryogenic process applied results in the availability of a significant waste gas flow that can be used for regeneration, which would potentially make it possible to shorten the usual heating and cooling times. In addition, the depressurization and repressurization steps are almost unnecessary given the respective production (1.3 bar abs) and regeneration (1.03 bar abs) pressures. However, the small thickness of the beds of activated alumina and of zeolite, of the order of 0.25 m, did not result in possible optimization being taken further. Production times of 120, 90 or even 60 minutes can be envisaged with air to be purified optionally introduced at a temperature greater than the 3° C. applied in this example. Given the large amount of energy involved in head losses at low pressure, installing an element for regulating the regeneration flow rate based on optimization of the head loss throughout said step can be envisaged. In other words, a higher flow rate is taken when the adsorber is relatively cold, for example at the start of heating and the end of cooling, and a lower flow rate when conversely it is, on average, hottest. It is also, more simply, possible to impose a first flow rate for heating and a lower second flow rate during cooling.

[0093] The total volume of adsorbent is of the order of 6 m3 split practically half and half between activated alumina and zeolite X exchanged with calcium and barium, a particularly effective adsorbent for capturing traces of hydrocarbons and nitrogen oxides.

[0094] According to the invention, each adsorber is in the form of a parallelepiped with a length L equal to 5.75 m, a height H equal to 2.9 m, and a width l equal to 1.00 m.

[0095] The working height of adsorbent is 2.1 m. An anti-pollution system is provided in the top part with an adsorbent reserve in order to compensate for compaction and 10 pipes for filling the volumes V21 and V22 with activated alumina and with zeolite respectively. The fluids are admitted and discharged by the sides. In this instance, what is present is box structures, themselves parallelepipedal, arranged contiguously on each side of the actual adsorber proper.

[0096] The inlet and outlet volumes V1 and V3 are not in this instance divided into sub-volumes. The widths available for each of them (0.25 m) allow for direct introduction as the velocity of the fluids is sufficiently low.

[0097] The two adsorbers are positioned adjacently with a thermal insulation barrier between the surfaces that face one another. This barrier may consist simply of an air film. One variant might be to retain only a common dividing wall separating the two adsorbers and to use internal insulation on each side. This type of insulation is favored because the circulating fluids in contact with the insulation are dry (purified air, regeneration nitrogen). The adsorbers are created symmetrically so that the volumes V3A of the first adsorber and V3B of the second adsorber are adjacent (discounting the insulation barrier, if that solution is adopted) in the central part.

[0098] This description will be explained using [FIG. 4] and [FIG. 5] which respectively depict a transverse section and a longitudinal section through the two adsorbers as installed.

[0099] [FIG. 4] thus depicts the two adsorbers A and B. The various references 1′ correspond to their exterior casing. They are separated by a barrier 2′ that provides thermal insulation. This barrier limits losses of heat from the regeneration stream and the heating of the purified air. Depending on the pressure P1 and the dimensions of the adsorber, it may have mechanical reinforcements to increase the stiffness of the large (L*H) faces of the adsorbers. As has already been described, there are a number of other variant ways in which to achieve this insulation. The references 3′ correspond to the volumes V1A and V1B intended for supplying air that is to be purified and extracting the regeneration gas. Likewise, the references 4′ apply to the purified-air outlet and the regeneration-gas inlet. The volumes V21A and V21B 5′ contain the activated alumina, the volumes V22A and V22B 6′ the exchanged zeolite. The walls (7′, 8′, 9′) are permeable to the gases but sealed with respect to particles of adsorbent. These are screens or perforated sheets covered with a metal gauze with a mesh size smaller than the minimum diameter of the particles It is also possible to select screens specially developed for this type of application, of the “wedge wire screen” type, also commonly referred to as Johnson screens after the name of a supplier. The references 10′, 11′, 12′ and 13′ correspond to the system intended to compensate for the compaction of the adsorbent and avoid local bypassing of the impurities. A rectangular metal sheet 10′ extending from one end of the adsorber to the other delimits a guard bed 11′ filled with adsorbent. The angle of the sheet to the horizontal allows the particles passing through the empty space 13′ to completely fill the volume situated below this sheet. The adsorbers are filled via the pipes 12′ which have a sealing flange at their top end.

[0100] [FIG. 5] is a longitudinal section through the adsorbers A and B, the adsorber B being an adsorber A in regeneration mode. It can be used to track the paths followed by the various fluids. It is assumed that the adsorber A is in the production phase. The air that is to be purified 20′ enters via the header tank 14′ attached to one end of the adsorber A. This air is distributed, partly because of the deflector effect caused by the lateral exterior wall of the adsorber, into the volume VIA. From there, it passes in succession through the exterior permeable wall, the bed 5′ of activated alumina, the permeable middle wall, the bed 6′ of zeolite and the permeable internal wall. The purified air 21′ is collected in the volume V3A then enters the header tank 15′ before leaving the system. The other adsorber B is at this time in the regeneration phase. The regeneration gas 30′ enters this adsorber via the header tank 15′, and follows a path that is the reverse of that of the air, and exits via the header tank 14′. It has been elected here to have the hot regeneration gas enter via the center of the device made up of the two adsorbers. This configuration is not compulsory and, bearing in mind the unavoidable thermal expansions, another arrangement could be adopted. Just one pipe for letting the fluids into and out of the adsorber has been depicted. Depending on the installation, it may be more sensible to provide two distinct pipes, one for the air and the other for the regeneration fluid.

[0101] Note that no filter on the outlet side of the adsorbers has been depicted in these drawings. Usually, in this type of application, this would be incorporated into the adsorbers. It is recalled that this is possible because, given the way the fluids circulate between adsorption and regeneration, these filters are self-cleaning, which is to say that they automatically unclog themselves during each cycle. As a preference, the filter is situated in the header tank 15′. It is preferably planar.

[0102] One of the benefits of using a low-pressure technology in the construction of the adsorbers is ease of transport between the workshop and the installation site. This facility nevertheless imposes a number of dimensional constraints. Thus, an adsorber will preferably have the following features: [0103] a length L of between 2 and 15 meters; a height H of between 1 and 3 meters; and a width l of between 0.5 and 3 meters, preferably of between 0.8 and 1.5 meters.

[0104] In theory, the width of the adsorber and more particularly the thickness of the layers of adsorbent should be limited so that the head losses across said adsorbents remain very small, of the order of a few millibar, possibly of around ten millibar or so.

[0105] That means that the two adsorbers can actually be positioned continuously without the overall length exceeding around 3 m.

[0106] These constraints that need to be complied with regarding the maximum dimensions of an adsorber mean that the flow rate of air purified by the TSA unit that has just been described is limited, probably to around 30 to 50,000 Nm3/h depending on the exact conditions adopted for the purification. To increase beyond that, it would therefore be necessary to install a number of identical units in parallel.

[0107] As indicated hereinabove, this adsorption unit is situated upstream of a cryogenic distillation unit. This unit can in particular be well suited to low-pressure oxygen production, and in particular to the production of oxygen with a purity of between 90 and 98%.

[0108] The plant according to the invention also makes it possible to produce small units, that is, from several tens to several hundreds of tonnes per day of oxygen competitively. The compression means 1 could then be common to several units, optionally of different types (boosted air for combustion, for ventilation, etc.).

[0109] While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.

[0110] The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.

[0111] “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.

[0112] “Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.

[0113] Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.

[0114] Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.

[0115] All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.