Adsorbents and methods of making and using adsorbents

Abstract

An adsorbent composition having a bismuth material on a support containing at least one of a metal oxide, a metalloid oxide or an activated carbon and methods of making and using the same. The adsorbent composition is useful for adsorbing arsine from a fluid stream.

Claims

1. An adsorbent composition, comprising: a bismuth material on a support, the support comprising at least one of a metal oxide, a metalloid oxide or an activated carbon, wherein the support comprises pores that are substantially filled by the bismuth material; and an arsenic material adsorbed onto the bismuth material, wherein the adsorbent composition comprises about 5% to about 15% be mass of the bismuth material, and wherein the support has a moisture content of about 15% by mass or less.

2. The adsorbent composition of claim 1, wherein the bismuth material is selected from a group consisting of elemental bismuth and a bismuth compound.

3. The adsorbent composition of claim 1, wherein the bismuth material comprises a bismuth oxide.

4. The adsorbent composition of claim 3, wherein the bismuth oxide is bismuth (III) oxide (Bi.sub.2O.sub.3).

5. The adsorbent composition of claim 1, wherein the support comprises the metal oxide.

6. The adsorbent composition of claim 5, wherein the metal oxide has a surface area of about 20 m.sup.2/g to about 600 m.sup.2/g.

7. The adsorbent composition of claim 5, wherein the metal oxide is selected from a group consisting of a titanium oxide, a cerium oxide, an aluminum oxide, a silicon oxide, zirconium oxide, magnesium oxide, zeolites, activated carbon and mixtures thereof.

8. The adsorbent composition of claim 5, wherein the metal oxide comprises titanium dioxide.

9. The adsorbent composition of claim 5, further comprising silicon dioxide (SiO.sub.2).

10. The adsorbent composition of claim 1, wherein the arsenic material is selected from a group consisting of elemental arsenic and an arsenic-containing compound.

11. The adsorbent composition of claim 1, wherein the adsorbent composition comprises a lead content of about 5% by mass or less.

12. The adsorbent composition of claim 1, wherein the adsorbent composition is lead-free.

13. The adsorbent composition of claim 1, comprising about 0.01% to about 20% by mass of the arsenic material.

14. The adsorbent composition of claim 1, wherein the support comprises a moisture content of about 5% by mass or less.

15. The adsorbent composition of claim 14, wherein the support is moisture-free.

16. The adsorbent composition of claim 1, wherein a surface area of the support is about 50 m.sup.2/g to about 600 m.sup.2/g.

17. The adsorbent composition of claim 1, wherein the adsorbent composition is in a form selected from a group consisting of a tablet, an extrudate, a pellet, a rod, a molding and a monolith.

18. The adsorbent composition of claim 1, wherein the adsorbent composition has an arsine removal efficiency of about 90% or more as measured by a dry colorimetry method using an arsine analyzer.

19. The adsorbent composition of claim 1, wherein the adsorbent composition further comprises on the support at least one compound selected from a group consisting of a silver oxide, an iron oxide, a manganese oxide, a cerium oxide, a vanadium oxide, a tin oxide and mixtures thereof.

20. The adsorbent composition of claim 1, wherein the support comprises a pore volume of about 0.01 cc/g to about 5 cc/g.

21. The adsorbent composition of claim 1, wherein the support comprises a pore size of about 1 to about 750 .

22. An adsorbent composition, comprising: a bismuth material that substantially fills pores of a porous support, the support comprising at least one of a metal oxide, a metalloid oxide or an activated carbon, the support having a pore size of about 1 to about 750 ; and an arsenic material.

23. An adsorbent composition, comprising: a bismuth material that substantially fills pores of a porous titanium dioxide support; and an arsenic material.

24. The adsorbent composition of claim 1, wherein the support comprises at least one of a metal oxide or a metalloid oxide.

25. The adsorbent composition of claim 1, wherein the bismuth material is the sole active agent in the adsorbent composition.

26. The adsorbent composition of claim 25, wherein the bismuth material is bismuth (III) oxide (Bi.sub.2O.sub.3).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a comparison of a bismuth oxide on titanium oxide adsorbent with a lead oxide on aluminum oxide adsorbent for removing arsine in accordance with various example aspects of the disclosure.

(2) FIG. 2 shows a comparison of bismuth oxide on titanium oxide adsorbents with a lead oxide on aluminum oxide adsorbent for removing arsine in accordance with various example aspects of the disclosure.

(3) FIG. 3 shows a comparison of a titanium oxide adsorbent with a bismuth oxide on titanium oxide adsorbent for removing arsine in accordance with various example aspects of the disclosure.

(4) FIG. 4 shows a comparison of bismuth on titanium oxide adsorbents with a lead oxide on aluminum oxide adsorbent for removing arsine in accordance with various example aspects of the disclosure.

DETAILED DESCRIPTION

(5) Example aspects are described herein in the context of adsorbents and methods of making and using adsorbents. Those of ordinary skill in the art will recognize that the following description is illustrative only and is not intended to be in any way limiting. Other aspects will readily suggest themselves to those of ordinary skill in the art having the benefit of this disclosure. Reference will now be made in detail to implementations of the example aspects as illustrated in the accompanying drawings. The same reference indicators will be used to the extent possible throughout the drawings and the following description to refer to the same or like items.

(6) According to various example aspects, the disclosure is directed to adsorbents (for both liquids and gases) having an active material such as an active metal oxide on a support containing an activated carbon, a metalloid oxide or a metal oxide, for example, a high surface area metal oxide. Suitable active metal oxides include, but are not limited to a bismuth oxide (Bi.sub.xO.sub.y), a silver oxide (Ag.sub.xO.sub.y), an iron oxide (Fe.sub.xO.sub.y), a manganese oxide (Mn.sub.xO.sub.y), a cerium oxide (Ce.sub.xO.sub.y), a vanadium oxide (V.sub.xO.sub.y), a tin oxide (Sn.sub.xO.sub.y) and mixtures thereof, wherein x and y are integers. Suitable metal oxides (e.g., high surface area metal oxides) for the support include, but are not limited to, a titanium oxide (Ti.sub.xO.sub.y), a cerium oxide (Ce.sub.xO.sub.y), an aluminum oxide (Al.sub.xO.sub.y), a silicon oxide (Si.sub.xO.sub.y), magnesium oxide, alumo-silicates/zeolites and combinations thereof, wherein x and y are integers. For example, the adsorbent may contain a bismuth material, for example, elemental bismuth or a bismuth oxide (Bi.sub.xO.sub.y) on a support containing a titanium oxide (Ti.sub.xO.sub.y). In certain aspects, the adsorbent may contain bismuth (III, V) oxides on a support containing titanium dioxide (TiO.sub.2), for example. In yet further example aspects, the adsorbent may contain bismuth (III) oxide (Bi.sub.2O.sub.3) as the sole active agent on a support containing TiO.sub.2.

(7) The amount of the active material, for example, active metal oxide, per total weight of the adsorbent may vary depending on the type and anticipated concentration (in the process stream) of the reactive compound(s) to be adsorbed. The concentration of active material, for example, active metal oxide, per total weight of the adsorbent may be, for example, about 2 wt % to about 50 wt %. In certain example aspects, the concentration of the active material, for example, active metal oxide may be about 5 wt % to about 40 wt %, about 5 wt % to about 15 wt %, or about 8 wt % to about 11 wt %. In certain aspects, the concentration of the active agent may be about 9.4 wt %.

(8) In accordance with various example aspects of the disclosure, the adsorbent may contain about 5 wt % or less of lead oxide as the active material, for example, active metal oxide. In certain example aspects the lead content may be about 4 wt %, about 3 wt %, about 2 wt % or about 1 wt %. The adsorbent may also be lead-free. The term lead-free will be understood to mean that the adsorbent contains only trace amounts of lead e.g., about 10,000 ppm or less, or about 5,000 ppm or less, or about 1000 ppm or less, or about 500 ppm or less, such that the lead content may be zero or undetectable as measured by, for example, an X-ray fluorescence (XRF) spectrometer. Other techniques and instruments known to those of ordinary skill in the art for measuring trace amounts of lead may also be used.

(9) The support may be formed from one or more metal oxide, metalloid oxide or activated carbon. For example, where the active material is an active metal oxide and is on a support containing a titanium oxide, the support may be formed from only the titanium oxide. In certain example aspects, the support may contain the titanium oxide in addition to one or more other metal oxide. For example, the support may contain at least 50 wt % of a titanium oxide (Ti.sub.xO.sub.y), or the support may contain at least 75 wt % of a titanium oxide (Ti.sub.xO.sub.y) with the balance being one or more other metal oxide, for example, a silver oxide (Ag.sub.xO.sub.y), an iron oxide (Fe.sub.xO.sub.y), a manganese oxide (Mn.sub.xO.sub.y), a cerium oxide (Ce.sub.xO.sub.y), a vanadium oxide (V.sub.xO.sub.y), a tin oxide (Sn.sub.xO.sub.y) and combinations thereof. The metal oxide for the support may be in any crystalline form. For example, the titanium oxide may be titanium dioxide in anatase, brookite or rutile form. In certain aspects, the titanium oxide may be in anatase form. In certain embodiments, the metalloid oxide may be silicon dioxide (SiO2). In other embodiments, the support may comprise activated carbon.

(10) The characteristics of the support may have a significant effect on the performance of the adsorbent to remove a reactive compound from a process stream. The support characteristics may facilitate high dispersion of the active material on a surface of the support and may maintain such dispersion through the adsorption process. In various example aspects of the disclosure, the support may have a surface area of about 10 m.sup.2/g to about 600 m.sup.2/g, about 20 m.sup.2/g to about 300 m.sup.2/g or about 250 m.sup.2/g to about 350 m.sup.2/g. For example, the surface area may be about 290 m.sup.2/g (e.g., for TiO.sub.2 G5). The support may have a pore volume of about 0.01 cc/g to about 5 cc/g, or about 0.2 cc/g to about 1 cc/g. For example, the pore volume may be about 0.4 cc/g (e.g., for TiO.sub.2 G5). Additionally, the support may have a pore size of about 1 to about 750 , or about 10 to about 500 . For example, the support may have a pore size of about 55 (e.g., for TiO.sub.2 G5). These and other characteristics can be optimized by those of ordinary skill in the art based on the type and concentration of the reactive compounds to be adsorbed and the composition of the adsorbent.

(11) The moisture content of the support may also critically affect the performance of the adsorbent to adsorb a reactive compound from a process stream. In accordance with various example aspects, the support may have a moisture content of about 15 wt % or less. In certain aspects, the support may be moisture-free. The term moisture-free will be understood to mean that the support contains only trace amounts of water, e.g., about 5 wt % or less, or about 1 wt % or less, or about 0.5 wt % or less or about 0.1 wt % or less such that the moisture content may be zero or undetectable as measured by, for example, a Thermogravimetric analyzer (TGA). Other techniques and instruments known to those of ordinary skill in the art for measuring trace amounts of water may also be used.

(12) According to various example aspects of the disclosure, adsorbent compositions containing bismuth oxide (e.g., about 9.4 wt % bismuth (III) oxide derived from a citrate precursor) on a titanium oxide support may have a removal efficiency of arsine of about 100% for a period of about 45 hours or longer. Even after about 80 hours, the removal efficiency of the adsorbent may be about 85% or more. For an adsorbent containing bismuth oxide (e.g., about 9.4 wt % bismuth (III) oxide) derived from a nitrate precursor on a titanium oxide support, the arsine removal efficiency may be 100% for about 36 hours or longer and may be at about 78% even after about 56 hours.

(13) The adsorbents described herein may be manufactured by any suitable means known to those of ordinary skill in the art. For example, active material, for example, active metal oxide, particles may be formed in pores of the support by active material, for example, metal oxide, precursor impregnation, precipitation, deposition or strong electrostatic adsorption and/or any other method known to those of ordinary skill in the art, followed by calcination to decompose the active material, for example, metal oxide, precursor. Alternatively, the active material, for example, active metal oxide, can comprise some fraction of a physical mixture of active material, for example, active metal oxide, and a high surface area substrate and/or a binder. Where the adsorbent is intended to contain a bismuth material such as elemental bismuth or bismuth oxide as the active material, for example, active metal oxide, any suitable bismuth precursor can be used. For example, a bismuth precursor derived from organic acid salts/complexes (e.g., citrates, nitrates, etc.) and inorganic acid salts can be used. A bismuth citrate precursor, in particular, can lower the calcination temperature and suppress the sintering of the bismuth oxide at high temperatures (e.g., during high temperature calcination). The adsorbents can be manufactured in any suitable form, for example, as tablets, extrudates, pellets, rod, moldings, monoliths, etc. in various shapes and sizes.

(14) According to various example aspects, also disclosed are methods for removing impurities, for example, an arsenic material such as arsine, elemental arsenic and arsenic derivatives from a process stream (liquid or gas) using the adsorbents. The process stream may be from, for example, a petroleum, petrochemical, polymerization, synthesis gas (Syngas) and semiconductor process. For instance, the process may be a refinery off gas (ROG) process, a fluid catalytic cracking (FCC) off-gas process, a stem cracker off-gas process, a natural gas process and/or a shale gas process. The process streams may contain one or more reactive compounds including, but not limited to, acetylene and propadiene (MAPD) or components with significant reducing capacity such as hydrogen. The process streams may contain alkenes, carbon monoxide, carbon dioxide, nitrogen oxides (NO.sub.x), oxygen, thiol, hydrogen sulfide and sulfur oxides (SO.sub.x), carbonyl sulfide (COS), mercaptans and other sulfur compounds. In certain example aspects, a process stream may contain, for example, arsine at a concentration of about 0.1 ppmw to about 100 ppmw, or about 0.1 ppmw to about 0.5 ppmw.

(15) According to various example aspects, the adsorbents may be used as materials in any suitable equipment, including, but not limited to packed bed columns, fluidized beds, monoliths, cartridge filters, semiconductor process tools, and other equipment known to those of ordinary skill in the art. Methods for removing a reactive compound from a process stream using the adsorbents (e.g., adsorption processes) may be operated at any suitable temperature. For example, an adsorption process may operate at about 10 C. to about 150 C., about 20 C. to about 100 C., or about 20 C. to about 80 C. In certain aspects, if the process stream is a liquid, the adsorption process may operate at a temperature of about 50 C.; for a gas stream the adsorption process may operate at a temperature of about 130 C. The operating pressure of the adsorption process may be, for example, about 1 bar to about 100 bar, about 1 bar to about 50 bar, or about 1 bar to about 20 bar. For a liquid phase process stream the gas hourly space velocity (GHSV) may be about 20 h.sup.1 or less and for a gas phase process stream the GHSV may be about 10,000 h.sup.1.

EXAMPLES

Example 1A

Synthesis of Bismuth Oxide on Titanium Oxide (Bi/TiO.SUB.2.) Adsorbent Derived from Bismuth Citrate

(16) Bi/TiO.sub.2 adsorbent was prepared using an incipient wetness impregnation method. More specifically, 4.95 grams of bismuth citrate was dissolved in 30 grams of ammonium hydroxide (29% NH.sub.4OH) and resultant solution was mixed for about 30 minutes until full dissolution of the bismuth citrate has been observed. An amount of this solution was impregnated on a dry titanium oxide (Anatase) powder to achieve 97% pore volume fill of the carrier. The resultant powder was dried overnight at 110 C. and calcined at 400 C. for 2 hours to yield a Bi loading of about 9.4 wt % as determined by inductively coupled plasma spectrometry (ICP). Thermogravimetric Analysis (TGA) measurements confirmed full decomposition of the bismuth citrate in a calcined powder while x-ray photoelectron spectroscopy (XPS) indicated the presence of Bi in+3 oxidation state suggesting Bi.sub.2O.sub.3 as a primary compound of Bi in a material.

Example 1B

Synthesis of Bismuth Oxide on Titanium Oxide (Bi/TiO.SUB.2.) Adsorbent Derived from Bismuth Nitrate

(17) Bi/TiO.sub.2 adsorbent was prepared using an incipient wetness impregnation method. Bismuth nitrate stock solution (22.3 wt % Bi) was used as the Bi source. An amount of this solution was impregnated on a dry titanium oxide (Anatase) powder to achieve 97% pore fill of the carrier. The resultant powder was dried overnight at 110 C. and calcined at 400 C. for 2 hours to yield Bi loading of about 9.7 wt % as determined by ICP. Complete decomposition of the bismuth nitrate precursor in the calcined material was confirmed with TGA. XPS measurements also confirmed Bi+3 as a major form of Bi in a resultant material.

Example 1C

Comparison of a Bismuth Oxide on Titanium Oxide Adsorbent (Bi/TiO.SUB.2.) with a Lead Oxide on Aluminum Oxide Adsorbent (Pb/Al.SUB.2.O.SUB.3.)(Prior Art) for Removing Arsine

(18) Experimental Conditions:

(19) About 1 cubic centimeter of an adsorbent containing bismuth oxide on titanium dioxide (prepared as described above) was loaded into a reactor. A fluid containing about 100 ppmw of arsine in propane was passed through the reactor and over the adsorbent for a period of time at a liquid hourly space velocity (LHSV) of 10 h.sup.1. The fluid was at ambient temperature, liquid phase about 220 psig. Arsine was adsorbed onto the adsorbent from the fluid. The experiment was repeated at the same conditions with about 1 cubic centimeter of an adsorbent containing lead oxide on aluminum oxide (approximately 20 wt % PbO) loaded into the reactor. The results are shown in FIG. 1.

(20) As shown in FIG. 1, the removal efficiency (%) of arsine as a function of time was comparable for both adsorbents at 100% for about 22 hours. However, thereafter, the removal efficiency of the Pb/Al.sub.2O.sub.3 began to decline while the removal efficiency of the Bi/TiO.sub.2 remained at 100% until about 45 hours. At about 52 hours, the removal efficiency of the Pb/Al.sub.2O.sub.3 decreased to about 83% whereas the removal efficiency of the Bi/TiO.sub.2 remained high at about 99%. Even after another about 30 hours, the removal efficiency of the Bi/TiO.sub.2 not declined to that of the Pb/Al.sub.2O.sub.3. The arsenic content was measured in spent Bi/TiO.sub.2 and Pb/Al.sub.2O.sub.3 materials and was found to be 4.2 wt % and 2.4 wt %, respectively.

Example 2

Comparison of a Bismuth Oxide (Derived from a Citrate Precursor) on Titanium Oxide Adsorbent (Bi/TiO.SUB.2 .(Citrate)) with a Bismuth Oxide (Derived from a Nitrate Precursor) on Titanium Oxide Adsorbent (Bi/TiO.SUB.2 .(nitrate)) and a Lead Oxide on Aluminum Oxide Adsorbent (Pb/Al.SUB.2.O.SUB.3.)(Prior Art) for Removing Arsine

(21) Experimental Conditions:

(22) About 1 cubic centimeter of an adsorbent containing bismuth oxide derived from a citrate precursor on titanium oxide was loaded into a reactor. A fluid containing about 100 ppmw of arsine in propane was passed through the reactor and over the adsorbent for a period of time at a liquid hourly space velocity (LHSV) of 10 h.sup.1. The fluid was at ambient temperature (25 C.), liquid phase about 220 psig. Arsine was adsorbed onto the adsorbent from the fluid. The experiment was repeated at the same conditions with about 1 cubic centimeter of an adsorbent containing bismuth derived from a nitrate precursor on titanium oxide and again with about 1 cubic centimeter of an adsorbent containing lead on aluminum oxide. The results are shown in FIG. 2.

(23) As shown in FIG. 2, the removal efficiency (%) of arsine as a function of time was comparable for all three adsorbents for about 22 hours. However, thereafter, the removal efficiency of the Pb/Al.sub.2O.sub.3 began to decline while the removal efficiency of the Bi/TiO.sub.2 (citrate) and the Bi/TiO.sub.2 (nitrate) remained at 100% until about 38 hours. At this time, the removal efficiency of the Bi/TiO.sub.2 (nitrate) began to decline, while the removal efficiency of the Bi/TiO.sub.2 (citrate) remained at 100% until about 45 hours. At about 52 hours, the removal efficiency of the Pb/Al.sub.2O.sub.3 decreased to about 83% while at about 56 hours the removal efficiency of the Bi/TiO.sub.2 (nitrate) decreased to about 79%. However, the removal efficiency of the Bi/TiO.sub.2 (citrate) remained high at about 99% at 52 hours and was at about 97% at about 56 hours. Even after another about 25 hours, the removal efficiency of the Bi/TiO.sub.2 (citrate) had not declined to that of the Pb/Al.sub.2O.sub.3 or the Bi/TiO.sub.2 (nitrate). The arsenic content in a spent Bi/TiO.sub.2 (nitrate) sample was measured to be 3.1 wt %.

Example 3

Comparison of a Titanium Oxide Adsorbent (TiO.SUB.2.) with a Bismuth Oxide on Titanium Oxide Adsorbent (Bi/TiO.SUB.2.) for Removing Arsine

(24) Experimental Conditions:

(25) About 1 cubic centimeter of a titanium oxide adsorbent was loaded into a reactor. A fluid containing about 100 ppmw of arsine in propane was passed through the reactor and over the adsorbent for a period of time at a liquid hourly space velocity (LHSV) of 10 h.sup.1. The fluid was at ambient temperature (25 C.), liquid phase about 220 psig. Arsine was adsorbed onto the adsorbent from the fluid. The experiment was repeated at the same conditions with about 1 cubic centimeter of an adsorbent containing bismuth oxide on titanium dioxide. The results are shown in FIG. 3.

(26) As shown in FIG. 3, the removal efficiency (%) of arsine as a function of time of the Bi/TiO.sub.2 was significantly higher than the TiO.sub.2. The addition of bismuth oxide to titanium dioxide extended the adsorbent life by about 77 hours or more. This example indicates that titanium oxide (TiO.sub.2) alone is inactive in removal of arsine from a fluid while a Bi/TiO.sub.2 adsorbent system exhibits high activity in arsine capture.

Example 4

Comparison of Bismuth Oxide on Titanium Oxide Adsorbents (Bi/TiO.SUB.2.) with a Lead Oxide on Aluminum Oxide Adsorbent (Pb/Al.SUB.2.O.SUB.3.)(Prior Art) for Removing Arsine

(27) Experimental Conditions:

(28) About 1 cubic centimeter of an adsorbent containing about 2 wt % bismuth oxide on titanium dioxide (Bi/TiO.sub.2 (2 wt %)) was loaded into a reactor. A fluid containing about 100 ppmw of arsine in propane was passed through the reactor and over the adsorbent for a period of time at a liquid hourly space velocity (LHSV) of 10 h.sup.1. The fluid was at ambient temperature (25 C.), liquid phase about 220 psig. Arsine was adsorbed onto the adsorbent from the fluid. The experiment was repeated at the same conditions with about 1 cubic centimeter of an adsorbent containing about 9.4 wt % bismuth on titanium dioxide (Bi/TiO.sub.2 (9.4 wt %)), an adsorbent containing about 20 wt % bismuth on titanium dioxide (Bi/TiO.sub.2 (20 wt %)) and an adsorbent containing lead oxide on aluminum oxide (Pb/Al.sub.2O.sub.3 (about 20 wt % PbO)) loaded into the reactor. The results are shown in FIG. 4.

(29) As shown in FIG. 4, the removal efficiency (%) of arsine as a function of time was comparable for all adsorbents for about 13 hours. However, thereafter, the removal efficiency of the Bi/TiO.sub.2 (2 wt %) began to sharply decline as compared to the other adsorbents. At about 22 hours the removal efficiency of Pb/Al.sub.2O.sub.3 began to decline while the removal efficiency of the Bi/TiO.sub.2 (9.4 wt %) and the Bi/TiO.sub.2 (20 wt %) remained at 100% until about 34 hours. Thereafter, the removal efficiency of the Bi/TiO.sub.2 (9.4 wt %) remained at 100% until about 45 hours whereas the removal efficiency of the Bi/TiO.sub.2 (20 wt %) began to decline at about 35 hours. At about 52 hours, the removal efficiency of the Pb/Al.sub.2O.sub.3 decreased to about 83% whereas the removal efficiency of the Bi/TiO.sub.2 (9.4 wt %) remained high at about 99%. Even after another about 30 hours, the removal efficiency of the Bi/TiO.sub.2 (9.4 wt %) had not declined to that of the Bi/TiO.sub.2 (20 wt %) or the Pb/Al.sub.2O.sub.3. The resulting uptake of arsenic in the Bi/TiO.sub.2 (20 wt %) and Bi/TiO.sub.2 (2 wt %) samples was found to be about 3.7 wt % and about 1.2 wt %, respectively. This finding suggests that a bismuth oxide supported on titanium dioxide adsorbent system is active in arsine removal at a very small loading of the bismuth, for example, at least a Bi content of as low as about 2 wt %.

(30) It is to be understood that the phraseology or terminology used herein is for the purpose of description and not of restriction, such that the terminology or phraseology of the present specification may be interpreted by those of ordinary in the art in light of the teachings and guidance presented herein, in combination with the knowledge of those of ordinary skill in the relevant art(s).

(31) The various aspects disclosed herein encompass present and future known equivalents to the known components referred to herein by way of illustration. Furthermore, while aspects and applications have been shown and described, it will be apparent to those of ordinary skill in the art having the benefit of this disclosure that many more modifications than mentioned above are possible without departing from the inventive concepts disclosed herein.