Patent ID: 12196487

DETAILED DESCRIPTION OF THE INVENTION

FIG.2is a schematic representation of the hot part of the air separation unit. The atmospheric air10containing the various pollutants to be removed is compressed by means of the compressor C to the pressure P1, of the order of 1.5 bar abs, and this compressed air11is introduced into one of the adsorbers of the TSA (A1or A2). After purification this purified air12is sent into the downstream part of the unit, which comprises in particular the cryogenic fractionation unit D. The regeneration gas14originates from this fractionation 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 output13, generally impure oxygen (90-98%) in the case under consideration, is sent to a downstream unit, not shown.

Here, fixed bed is given to mean that the adsorbent, whether in the form of particles (beads, sticks, granules, wafers, etc.) or structured adsorbent such as for example monolithic, is immobile in a casing that is itself immobile. This excludes any solution in which the adsorbent is mobile and in particular any rotary system such as rotary contact or barrel systems (process in which it is the casings containing the adsorbent that are mobile).

Another essential point according to the invention is that the fluids circulate horizontally through the adsorbent mass. The mass can thus be held between two gas-porous vertical walls for which the spacing tolerances can be very small. Very thin, very uniform bed thicknesses can thus be obtained. As already indicated, it is practically impossible to reach this level of precision with a flat adsorbent bed having a large free surface.

Likewise, with this geometric configuration, it can be easy to obtain dense, uniform filling of the adsorber without having to use a complex filling system.

It will also be noted that in our case, the gas circulation in the inlet/outlet zones can equally well be vertical, horizontal or even more complex, for example with multiple inlet points. In any case, after distribution, circulation is necessarily horizontal through the adsorbent layers. Due to the design of the adsorber, the direction of circulation in the free volumes and through the adsorbent mass are completely unrelated.

FIG.3illustrates an example of an arrangement of the set of volumes used in the plant according to the invention. The external adsorber casing1is shown in thin lines, while the internal part of the set of volumes (internal part)2is arbitrarily shown in thick lines. The adsorber casing is essentially parallelepipedal. “Essentially parallelepipedal” is given to mean that in practice, the adsorber casing and the internal part have six flat faces and have the appearance of a parallelepiped with faces at right angles, but that there can be reinforcements, locally at least one internal or external layer of insulation, and obviously pipes or boxes for introducing and withdrawing air and regeneration gas. The adsorber is placed flat on the ground in its operating position, and the length thereof is denoted as L, the width l and the height H. In the context of the invention, it is not important whether these are external or internal dimensions.

Each of the parallelepipeds used is therefore defined by its three dimensions, namely H*L*l for the external adsorber casing and H′*L′*l′ for the internal part. The horizontal faces, floor and ceiling, are therefore identified by their dimensions L*l and L′*l′ (reference sign3, for example). The larger vertical faces are respectively identified as H*L and H′*L′ (reference sign4, for example). For the internal part, these faces H′*L′ are fluid-porous (reference sign5, for example). The other smaller vertical other faces are then denoted H*l and H′*l′ (reference sign6, for example).

The parallelepiped H′*L′*l′ forming the internal part is itself divided into three sub-volumes, all parallelepipedal. The central volume V17is a free volume suitable for the circulation of the fluids. On either side of V1are the adsorbent masses housed in the two parallelepipeds V2and V38and9. The internal part is symmetrical relative to its vertical mid-plane, which is shown schematically to the right of the sketch of the adsorber and has reference sign10. This mid-plane10is also the mid-plane of the adsorber casing. The adsorber as a whole therefore has a plane of symmetry10. As a result, each of the adsorbent masses will treat 50% of the air flow and be regenerated by 50% of the regeneration gas flow. All of the fluids circulate horizontally through the adsorbent through the faces H′*L′, which are the only porous faces. This circulation takes place from the central free volume V1of the internal part towards the free volumes V4and V5of the casing (reference sign11, for example) and vice versa.

In the arrangement applied inFIG.3, the internal part is the same length as the casing (L′=L) but lower (H′<H). The top face of said internal part adjoins the top face of the casing, that is, they have a common ceiling. There is therefore a space between the floor of the internal part and the floor of the casing that places the volumes V4and V5in fluid communication, this assembly then forming the free volume of the casing. This is one of the possible configurations between the casing and the internal part. Other options will be described below.FIG.3is therefore merely a non-limiting example of the possible configuration of the adsorber according to the invention, selected to explain the embodiment principle.

According to a preferred variant, volumes V2and V3of the internal part each include a plurality N (N between 1 and 4, preferably N=2) of adjacent sub-volumes, and each of these volumes can contain an adsorbent with a different property, all of these adsorbents being arranged symmetrically relative to the mid-plane of the adsorber. Very generally, the different adsorbents are separated by fluid-porous vertical walls (H′*L′) that hold them and prevent them from mixing. It will however be noted that it is possible to put the different adsorbents in place with a movable wall that is gradually raised during filling and that is, as appropriate, removed or left in place at the end.

In the context of the invention, a first adsorbent will for example be used that is suitable for removing the great majority of the water and optionally some of the CO2 (activated alumina, silica gel, doped alumina, etc.) and a second adsorbent suitable for removing the remaining CO2, the nitrogen oxides and certain hydrocarbons (X zeolites, preferably exchanged particularly with calcium and/or barium). A single bed (doped alumina, X zeolite) or three successive beds (for example alumina, X zeolite, exchanged zeolite) can equally be used.

In a first configuration, shown schematically in the cross-section4A inFIG.4(which is a side view of the adsorber cut in half vertically), the adsorber is produced so that the vertical walls (H′*L′) relative to the adsorbent volumes are sealably fixed, at the top and bottom, to the top wall and the bottom wall of the adsorber casing respectively. This configuration is simple and gives the assembly rigidity, but it must be checked whether the operating conditions result in excessive mechanical stresses. This will depend mainly on the materials used, the type of fixing between the walls and the temperature used during regeneration. This temperature depends on the adsorbents used, the regeneration flow available and the residual impurity content in the adsorbent selected for the design. With a regeneration temperature of 60 to 90° C. for example, such a configuration can be possible. It will be less easy to implement with temperatures of 150 to 250° C.

It will be noted that a single bed of adsorbent has been shown for the sake of simplicity. In most cases, there will be an intermediate porous wall on each side, suitable for separating two different adsorbents.

For any problems linked to the temperature, it might be necessary to provide a degree of freedom to permit vertical movements of the porous vertical walls holding the adsorbents.

According to other embodiments, the adsorber is thus produced so that the vertical walls (H′*L′) of the adsorbent volumes are sealably fixed at the top to the top wall of the adsorber casing and at the bottom to a solid end—or floor—going from the external wall of one adsorbent volume to the external wall of the other volume as shown in cross-section4B.

It can then be seen that there is a space between said solid end and the bottom wall of the adsorber casing forming an additional free volume in fluid communication with the two lateral free volumes (V4and V5) and contributing to the formation of the free volume of the adsorber.

In a reverse configuration (cross-section4C), the vertical walls (H′*L′) of the adsorbent volumes are sealably fixed at the top to a solid end—or ceiling—going from the external wall of one adsorbent volume to the external wall of the other volume and at the bottom to the bottom wall of the adsorber casing and there is then a space between said ceiling and the top wall of the adsorber casing forming an additional free volume V2din fluid communication with the two lateral free volumes (V4and V5) and contributing to the formation of the free volume of the adsorber.

Finally, according to another embodiment (4D), the vertical walls (H′*L′) of the adsorbent volumes are sealably fixed at the top and bottom to solid ends—ceiling and floor respectively—going from the external wall of one adsorbent volume to the external wall of the other volume and at the bottom to the bottom wall the adsorber casing. In this case, there is a space between said ceiling and the top wall of the adsorber casing and between said floor and the bottom wall of this same casing forming an additional free volume in fluid communication with the two lateral free volumes (V4and V5) and contributing to the formation of the free volume of the adsorber.

The mechanical strength of the internal part in the casing can be improved by supports, for example on the bottom part, or hanger systems, for example on the top part. These holding means can have a certain flexibility in order to follow any movements linked to the thermal expansion and contraction mentioned above. Said means can preferably be discrete or, at least, discontinuous, and not prevent fluids from passing from one zone to the other.

Likewise, there are different configurations with respect to the lateral walls (H′*l′) of the internal part.

According to a first embodiment, at least on one side, the lateral ends of the vertical walls of the adsorbent volumes are sealably fixed over their entire height (H′) to the lateral walls (H*l) of the adsorber casing.

According to a second embodiment, at least on one side, the lateral ends of the vertical walls of the adsorbent volumes are sealably fixed over their entire height (H′) to a solid plate (H′*l′).

A series of longitudinal cross-sections is shown schematically inFIG.5. The internal part, shown arbitrarily in thick lines, is assumed to be fixed to the casing by its top part but to have its own floor. Cross-section5A shows an internal part adjoined to the casing by its two lateral sides,5B by a single side, the other being closed by a flat end, and5C an internal part having its own two ends.

As above, there is a space between each solid plate fixed to the internal part and the adjacent lateral wall of the adsorber casing forming an additional free volume in fluid communication with the two lateral free volumes (V4and V5) and contributing to the formation of the free volume of the adsorber.

These free volumes allow the fluids to circulate and promote a good balance between the flows going to each of the two adsorbent masses. In addition, these free volumes can make it possible to house very efficient distribution systems, allowing almost perfect distribution of all of the streams through the adsorbents. An example of this type of device will be given below.

According to a preferred variant, volumes V2and V3containing the adsorbent mass include, over the entire length of their top end, a system suitable for avoiding the local potential pollution of the purified air linked to a bypass or to a local excess flow or to a regeneration fault.

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 excess air flow and/or a regeneration fault.

The bypass can originate from the compaction of the adsorbent. These problems are well known to a person skilled in the art and previously developed solutions can be applied here. In particular, due to its geometry, using a parallelepipedal adsorber simplifies the implementation of the solutions devised for radial beds (dead zone filled to a sufficient height with adsorbent, equivalent system 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 spraying, limiting both the compaction and the risk of uneven density in the beds. 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. Again, the solutions developed for the radial adsorbers of units for the production of oxygen by adsorption, which are described in the literature or patents filed, must be adapted. One of these solutions is described in greater detail in the example given at the end of this document.

As the implementation of sealing systems in the top part and filling are simplified, the use of adsorbents in their most common form, namely sticks, beads, crushed material, pellets and more generally particles, will preferably be applied. It must however be noted that the geometry of the parallelepipedal beds is particularly well suited to the use of monoliths in the form of bricks. Although this solution does not seem technically and economically beneficial at present, it could advantageously be used in the future.

Currently, at least one and preferably all of the adsorbents used in the process will be in the form of particles.

Given the geometry adopted for the adsorber, the process according to the invention will be such that both the central volume V1of the internal part and the free volume of the casing have means making it possible to introduce and extract the different fluids circulating in the adsorber (air to be purified, treated air intended for the cryogenic separation unit, regeneration gas originating from said unit, very generally low-pressure nitrogen).

More specifically, the arrangement of the internal part in the casing with its optional flat ends, and the layout of the means making it possible to introduce and extract the different fluids circulating in the adsorber requires that said fluids only circulate horizontally through the adsorbent masses between the inlet and the outlet of said adsorber.

As in all adsorbers intended to remove almost all of the impurities from a fluid, it must be ensured that the connections between elements are fluid-tight by applying the appropriate technologies (welding, flanges, gaskets, etc.).

According to a preferred arrangement, the air to be treated enters via volumes V4and V5and the purified air leaves via volume V1and as a result, the regeneration gas enters via volume V1and leaves via volumes V4and V5. The benefit of this arrangement comes from the TSA process as currently implemented at least in air purification units upstream of cryogenic separation units. Without wishing to go into detail here, it should be known that in this type of unit, during regeneration it is usual to only input the quantity of heat strictly necessary for the desorption of the impurities so that the heat front does not leave the adsorbent. Reference can for example be made in this regard to EP 1 080 773 for a more comprehensive explanation of the control of the heating time. This means that the entire (or almost the entire) external casing remains at a temperature close to that of the incoming air and the heat front only passes through the internal part. In the configurations in which one face of the internal part adjoins the wall of the casing or is very close to it, it can be beneficial to use insulating means in order to limit the heat transfers. These means could be on the side of the internal part, and/or on the side of the casing and/or optionally between the internal part and the casing. Such insulation will not always be necessary, in particular if there is a significant flow of regeneration gas. In this case, a regeneration temperature substantially lower than 100° C. is acceptable, of the order of 50 to 80° C. In this case, the heat losses will be naturally low and the thermal stresses linked to expansion will be limited. Conversely, the use of regeneration temperatures of 150° C. and more will require a more detailed examination of the resulting stresses. Depending on the location of the inlet for the air to be purified, and in particular if it has been substantially cooled in order to facilitate the adsorption of the impurities, some parts of the adsorber could optionally be insulated in order to retain this advantage.

According to a preferred embodiment, the central volume V1of the internal part comprises a filter that makes it possible to treat the purified air before sending it to the cryogenic separation unit. This filter makes it possible to remove any dust generated by the adsorbent(s). This filter will preferably be self-cleaning, that it, the regeneration gas will pass through it counter-currently and dislodge any dust captured during the preceding step. There is then generally a purge valve at the low point that makes it possible to discharge said dust periodically. This filter can be produced in a number of ways. Taking the arrangement inFIG.5B,FIG.6shows some of these options. These are cross-sections along the mid-plane of symmetry of the adsorber. Reference sign (20) corresponds to the casing, (21) to the internal part, (22) to the purified air outlet and regeneration gas inlet pipe, (23) to the part of this pipe that passes sealably through the free volume of the casing, (24) to the part of this pipe belonging to the internal part and (25) to the filtration zone(s).

The pipe and filter are shown in thick lines. The cross-section of the pipe can be any shape (circular, triangular, rectangular, etc.).

InFIG.6A it is the pipe itself that passes through the free volume V1(26) that acts as a filter. In this zone, it is for example perforated and surrounded by a fabric allowing filtration to 50 microns. It can also be a commercial filter fixed in the extension of the pipe, which then stops when it emerges into the volume V1. The pipe, or the commercial filter, can have a tapered internal packing element in order to improve the distribution of the fluids over their entire length.

In the case shown inFIG.6B, a plurality of commercial filters (25) fixed to the pipe (24) is used. This can make it possible to improve the distribution of the fluids through the adsorbent masses by distributing the fluid injection points in the free volume V1. Finally, inFIG.6C, an efficient fluid distribution system is associated with filtration. It will be noted that such a distribution system can be installed independently of the filtration function. There can be two perforated walls installed on either side of the vertical mid-plane, in the free volume V1and a certain distance from the porous walls holding the adsorbent. By creating an additional head loss, this system can allow almost perfect distribution of the gas in the adsorbent masses.

In a further preferred configuration, the means for introducing and extracting the fluids into and from the volumes V1, V4and V5are on a single face (H*l) of the parallelepipedal adsorber casing. This makes it possible to group together all of the adsorber inlets and outlets in order to facilitate connections to the equipment external to the adsorber itself (valves, exchanger, etc.).

FIG.7shows such a layout. The arrangement inFIG.5B is applied again, namely an internal part adjoining the casing by its top face and one side, with a simple pipe entering the free volume V1as shown inFIG.6A. The same reference signs as in this cross-section are used. InFIG.7A, which is a cross-section along the vertical mid-plane of the adsorber, the air to be purified arrives through the pipe27and enters the adsorber casing. The end28of the internal part acts as a deflector and distributes the air stream in the free volume29between the wall of the casing and said end.FIG.7B is a schematic top view illustrating the circulation of the air in the adsorber. After circulating in the free volume29, the air enters the two free volumes V4and V5, identified by reference sign30, passes through the porous walls holding the adsorbent, then the adsorbent masses, comes back out through the central porous walls, enters the discharge pipe and leaves the adsorber22.

The most conventional TSA purification units include two identical adsorbers, one being in the production phase while the second is in the regeneration phase. The various flows are then guided and extracted from the adsorbers by a set of valves that make it possible to carry out the purification cycle in accordance with the process used. All of these elements are connected by pipes. The valves, pipes and other ancillary equipment such as instrumentation, connecting cables, instrument air inlet, etc., are often supported by a single structure generally known as a “valve skid”.

According to the invention, the TSA unit implemented comprises, on either side of a central zone, two adsorbers as described above, installed symmetrically, with their inlets/outlets facing the central zone, and said central zone comprises means for distributing or recovering the various flows of the process such as valves, pipes, etc., that is, this central zone corresponds to what has been named the valve skid.

In a preferred variant embodiment, the two adsorbers and the valve skid of the central zone are aligned and form a single large parallelepiped with a height Ht and a width lt, and the length Lt of which is equal to the sum of the lengths of the two adsorbers and the length of the central zone.

More specifically, provision is made for the height Ht of this large parallelepiped to be essentially equal to the height H of one adsorber and for its width lt to be essentially equal to the width l of one adsorber. As a result, a compact unit is obtained that can form a whole and the full benefits of which will be disclosed below.FIG.8shows in thick lines the large parallelepiped40corresponding to the complete purification unit and comprising a first adsorber41as described above with its inlets and outlets through its lateral face44. On the opposite side is the second adsorber42, produced symmetrically to the first and the inlets and outlets of which are therefore through its lateral face identified by reference sign45. The central part43corresponds to the valve skid, the role of which was explained above.

In a further preferred embodiment, the central part also contains the regeneration heater. According to the method applied for purification, said central part can also house the aftercooler of the air to be purified and a separator vessel for separating and then removing the condensates so that all of the equipment corresponding to the “air purification” function is in the large parallelepiped.

The benefit of producing an air purification unit as described above relates to the possibility of having at least one common base for the different parts (the two adsorbers and the valve skid) and being able to transport it as a whole after construction in a workshop, for example. To this end, and depending on the size of the associated air separation unit, the parallelepiped therefore comprising the two adsorbers and the central zone has a length of between 3 and 12 meters, a height H of between 1 and 3 meters and a width l of between 1 and 3 meters.

Due to its dimensions, the TSA can have the following additional features:the parallelepiped comprising the two adsorbers and the central zone is contained in a structure in accordance with the ISO standards relating to containers and also including the handling systems in accordance with these ISO standards (often referred to as “ISO corners”). The TSA is then in a specific structure to be 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.the parallelepiped comprising the two adsorbers and the central zone is contained in an ISO container.at least part of the structure of the container acts directly as a structure for the adsorbers and/or the central zone.

The external structure of the TSA is then an actual container. At least one of the walls of the container (lateral, bottom or top wall) can act directly as a wall for the external adsorber casing. Preferably, several walls of the container are used in this way.

Given the low pressures at play in purification and in some cases temperatures remaining close to ambient temperature, a variety of materials can be used for the TSA. These will mainly be metallic materials (carbon steel, stainless steel, aluminum, etc.) and/or polymeric materials. In some parts, low thermal expansion materials such as Invar can be used. Construction will take place entirely in the workshop, with only the connections of the different fluids being made on site. The adsorbent filling will preferably also take place in the workshop.

The invention will now be illustrated using the example below.

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 P1on 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., or even more, could be adopted, particularly if the pressure P1was 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 two 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 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, more flow is taken when the adsorber is relatively cold, for example at the start of heating and the end of cooling, and less flow is taken when conversely it is, on average, hottest. In a simpler manner, a first heating flow rate and a second higher flow rate during cooling can be imposed, or in a slightly more complex manner, the regeneration time can be divided into three or four steps for example with changes in flow rate (start of heating/heating-start of cooling/end of cooling).

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

According to the invention, each adsorber is parallelepipedal, with a length L equal to approximately 3 m, a height H equal to approximately 3 m, and a width l equal to approximately 2.00 m.FIG.9shows a perspective cross-section of said adsorber. In the center is the volume V0suitable for the distribution of the fluids50with the purified air outlet and regeneration gas inlet pipe51. The bottom part of this pipe, which passes through the adsorber, is open and communicates with the filter52. This filter also acts as a flow divider. On either side of the filter is the first porous wall53that holds the zeolite bed. The zeolite bed54is approximately 0.25 m deep (wide). It is separated from the activated alumina by a second porous wall55. The alumina bed56is approximately 0.25 m wide. It is held by the last porous wall57, which separates it from the free volume of the casing.

The working height of adsorbent is 2.1 m. An anti-pollution system58is provided in the top part with an adsorbent reserve59in order to compensate for compaction and a series of pipes60for filling the adsorbent volumes with activated alumina and zeolite respectively. The anti-pollution system applied here is directly transposed from solutions developed for radial adsorbers. Without going into detail, it can be said that it is an upwardly-sloping metal sheet58welded all along one side to a porous wall and leaving a space of a few centimeters on the other side allowing the flow of the adsorbent particles.

A solid wall (not shown) must be imagined where the pipe passes through, isolating the internal part from the free volume of the external casing. The air to be purified is introduced into the casing in the center of the wall of the casing and strikes the solid wall (not shown) just mentioned. This acts as a deflector and ensures distribution in all directions. The actual principle of the circulation of the fluids was described above.

As initially stated, this purification unit is situated upstream of a cryogenic air separation unit. This unit can in particular be well suited to low-pressure oxygen production, and in particular to impure oxygen with a purity rate of between 90 and 98%.

Given the footprint constraints that are set in this case in order to take full advantage of the principle of the invention, such a TSA will only be suited to oxygen production of a maximum of a few hundred tonnes. It could however be cost-effective to use several TSA modules of this type to feed a larger cryogenic unit. These modules could then operate in parallel or, if beneficial, with phase offset.

The process described in this application is limited to the stated use, namely aerial gas separation. However, the principle of an adsorber of the type described herein and operating at low pressure, of the order of 1.10 to 1.5 bar abs for example, could have other applications, in particular in the field of CO2 capture.

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.).

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.

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

“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.

“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.

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.

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.

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.