Processes for the removal and recovery of minor elements in wet-process phosphoric acid

Abstract

In alternative embodiments, the invention provides processes and methods for the recovery or the removal of the so-called Minor Elements consisting of iron, aluminum and magnesium (expressed as oxides), from wet-process phosphoric acid using a continuous ion exchange approach. In alternative embodiments, use of processes and methods of the invention allows for the reduction of these Minor Elements with minimal phosphate losses and dilution in order to produce a phosphoric acid that is suitable for the production of fertilizer products such as world-class diammonium phosphate (DAP), merchant-grade phosphoric acid, superphosphoric acid, and other phosphoric acid products. Further, use of the invention would allow the use of lower grade phosphate rock or ore, which would greatly expand the potential phosphate rock reserve base for phosphate mining activities, and allow for better overall utilization of resources from a given developed mine site.

Claims

1. A method or process for the removal of one or more cationic metal minor element (ME) components, a mixture of minor element components, and/or a cationic metal impurity or contaminant, from a wet-process phosphoric acid comprising use of a continuous ion exchange system, comprising: (a) providing a wet-process phosphoric acid comprising a pretreated phosphoric acid solution, or a pretreated solution comprising a phosphoric acid, or a pretreated phos-acid feedstock, comprising high levels of one or more minor cationic element (ME) components, or a mixture of minor cationic element components, and the pretreatment comprises reducing the amount of suspended solids content in an untreated wet-process phosphoric acid solution; (b) providing a continuous ion exchange system comprising a strong cationic exchange resin or equivalent material, wherein the strong cationic resin or equivalent material is in the H+form (c) providing a strong acid regeneration solution comprising a strong acid; (d) applying the solution comprising a phosphoric acid or the phosphoric acid solution or the phos-acid feedstock of (a) to the strong cation exchange resin or equivalent material under conditions such that substantially most of the cationic metal impurities, contaminants, or minor element (ME) components, remain on the cationic exchange resin, and an effluent acid solution is produced that has substantially lowered amounts of cationic metal impurities, contaminants, or minor element (ME) components, and substantially most of the cationic metal impurities, contaminants, or minor element (ME) components remain bound to the strong cation exchange resin or equivalent material; and (e) removing the cationic metal impurities, contaminants, or minor element (ME) components, or eluting the cationic metal impurities, contaminants, or minor element (ME) components, from the strong cationic exchange resin or equivalent material using the strong acid regeneration solution to produce a cationic metal impurity-, contaminant-and/or minor element-containing effluent acid solution comprising substantially most of the cationic metal impurities, contaminants, or minor element (ME) components as an eluate, further comprising treating the cationic metal impurity-, contaminant-and/or minor element-containing effluent acid solution with a ground phosphate rock or equivalent, to generate: an acid solution comprising a water soluble phosphate, wherein the phosphate is derived from the ground phosphate rock or equivalent, and a slow release phosphate material from the excess ground phosphate rock in a slurry form comprising the metallic impurities with the phosphate material.

2. The method or process of claim 1, wherein the treated ground phosphate rock or equivalent is used to produce a phosphate fertilizer product.

3. A method or process for the removal of one or more cationic metal minor element (ME) components, a mixture of minor element components, and/or a cationic metal impurity or contaminant, from a wet-process phosphoric acid comprising use of a continuous ion exchange system, comprising: (a) providing a wet-process phosphoric acid comprising a pretreated phosphoric acid solution, or a pretreated solution comprising a phosphoric acid, or a pretreated phos-acid feedstock, comprising high levels of one or more minor cationic element (ME) components, or a mixture of minor cationic element components, and the pretreatment comprises reducing the amount of suspended solids content in an untreated wet-process phosphoric acid solution; (b) providing a continuous ion exchange system comprising a strong cationic exchange resin or equivalent material, wherein the strong cationic resin or equivalent material is in the H+form (c) providing a strong acid regeneration solution comprising a strong acid; (d) applying the solution comprising a phosphoric acid or the phosphoric acid solution or the phos-acid feedstock of (a) to the strong cation exchange resin or equivalent material under conditions such that substantially most of the cationic metal impurities, contaminants, or minor element (ME) components, remain on the cationic exchange resin, and an effluent acid solution is produced that has substantially lowered amounts of cationic metal impurities, contaminants, or minor element (ME) components, and substantially most of the cationic metal impurities, contaminants, or minor element (ME) components remain bound to the strong cation exchange resin or equivalent material; and (e) removing the cationic metal impurities, contaminants, or minor element (ME) components, or eluting the cationic metal impurities, contaminants, or minor element (ME) components, from the strong cationic exchange resin or equivalent material using the strong acid regeneration solution to produce a cationic metal impurity-, contaminant-and/or minor element-containing effluent acid solution comprising substantially most of the cationic metal impurities, contaminants, or minor element (ME) components as an eluate, further comprising evaporating the strong acid regeneration solution to selectively crystallize the cationic metal minor element fractions, wherein the crystallizing results in or produces an ME-sulfate salt.

4. A method or process for the removal of one or more cationic metal minor element (ME) components, a mixture of minor element components, and/or a cationic metal impurity or contaminant, from a wet-process phosphoric acid comprising use of a continuous ion exchange system, comprising: (a) providing a wet-process phosphoric acid comprising a pretreated phosphoric acid solution, or a pretreated solution comprising a phosphoric acid, or a pretreated phos-acid feedstock, comprising high levels of one or more minor cationic element (ME) components, or a mixture of minor cationic element components, and the pretreatment comprises reducing the amount of suspended solids content in an untreated wet-process phosphoric acid solution, optionally by filtering; (b) providing a continuous ion exchange system comprising a strong cationic exchange resin or equivalent material, wherein the strong cationic resin or equivalent material is in the H+form; (c) providing a strong acid regeneration solution comprising a strong acid; (d) applying the solution comprising a phosphoric acid or the phosphoric acid solution or the phos-acid feedstock of (a) to the strong cation exchange resin or equivalent material under conditions such that substantially most of the cationic metal impurities, contaminants, or minor element (ME) components, remain on the cationic exchange resin or equivalent material, and an effluent acid solution is produced that has substantially lowered amounts of cationic metal impurities, contaminants, or minor element (ME) components, and substantially most of the cationic metal impurities, contaminants, or minor element (ME) components remain bound to the strong cationic exchange resin or equivalent material, and optionally the produced acid solution is suitable for the production of fertilizer materials or di-ammonium phosphate (DAP), which requires a phosphoric acid that has a limited amount of cationic impurities; and (e) removing the cationic metal impurities, contaminants, or minor element (ME) components, or eluting the cationic metal impurities, contaminants, or minor element (ME) components, from the strong cationic exchange resin or equivalent material using the strong acid regeneration solution to produce a cationic metal impurity-, contaminant-and/or minor element-containing effluent acid solution comprising substantially most of the cationic metal impurities, contaminants, or minor element (ME) components as an eluate, wherein the strong cationic resin or equivalent material is either: (a) designed as a continuous ion exchange system operated by restricting the flow of the strong acid regeneration solution in order to preferentially load one of the minor element materials on the resin, or (b) in the strong acid regeneration solution.

5. The method or process of claim 1, wherein the strong cationic resin or equivalent material is designed as a continuous ion exchange system having one or more zones, and the continuous ion exchange system is operated in an up-flow mode to allow for periodic resin bed expansion and flushing of any accumulated solids from the resin.

6. The method or process of claim 3, wherein the concentration of the strong acid in the strong acid regeneration solution is increased, wherein optionally the strong acid in the strong acid regeneration solution is increased to concentrations in excess of about 40% for the sulfuric acid H.sub.2SO.sub.4; optionally in excess of about 50% for the nitric acid or in excess of about 30% for the hydrochloric acid.

7. The method or process of claim 3, wherein: (a) the strong acid regeneration solution comprises a sulfuric acid (H.sub.2SO.sub.4), a nitric acid (HNO.sub.3) or a hydrochloric acid (HCI), (b) the method of (a), wherein the sulfuric acid has a strength from about 5% to up to 98%, or in the range of about 20% to about 40% ; (c) the strong acid regeneration solution comprises an acid having a strength from about 5% up to a concentrated level; or (d) the strong acid regeneration solution comprises a strength up to about 35% , 40% , 50% , 60% , 70% , 80% , 90% or 98% , optionally in the range of about 62% when the strong acid regeneration solution comprises a nitric acid and about 37% when the strong acid regeneration solution comprises a hydrochloric acid.

8. The method or process of claim 3, wherein: (a) the phosphoric acid strength can range from about 12% to about 30% P.sub.2O.sub.5; (b) the phosphoric acid strength can range from about 18% to about 25% ; (c) the phosphoric acid strength can range from about 42% P.sub.2O.sub.5up to about 54% P.sub.2O.sub.5; (d) the phosphoric acid strength can range from about 12% P.sub.2O5to about 18% P.sub.2O.sub.5; or (e) the phosphoric acid strength can range from about 25% P.sub.2O.sub.5to about 30% P.sub.2O.sub.5.

9. The method or process of claim 3, wherein the strong cationic exchange resin or equivalent material capable of binding the minor element (ME) components are selected from the group consisting of: (a) a Purolite SST-60 material, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, PA), or equivalents; (b) a Purolite C-100 resin, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, PA) , or equivalents; (c) a Dowex MSC 650 material (Dow Chemical, Midland, MI) , or equivalents; (d) a resin, a composition or a material, or a non-resin solid or a semi-solid material, comprising chelating groups, functionalities or moieties that can bind ME components, wherein optionally that comprise a sulfonic acid functional group, iminodiacetic groups, chelating aminomethyl phosphonic acid groups or aminophosphonic groups, or similar chelating functionalities or moieties, and optionally the compositions comprise beads, wires, meshes, nanobeads, nanotubes, nanowires or other nano-structures, or hydrogels; and (e) any combination thereof.

10. The method or process of claim 3, wherein a cationic calcium (Ca.sup.+2) is also removed from the acid phase onto the resin.

11. The method or process of claim 3, wherein the phosphoric acid solution, the solution comprising a phosphoric acid, or the phos-acid feedstock, is first treated, or pre-treated, with a clarification process or a filtering process, or a clarification aid, and optionally the clarification process, filtering process or clarification aid comprises an activated clay, an activated carbon, an activated silica, or equivalents, or any combination thereof.

12. The method or process of claim 3, further comprising subsequently recovering the ME-sulfate salt, optionally as a marketable secondary/minor element fertilizer material.

13. The method or process of claim 3, further comprising recycling the concentrated sulfuric acid (H.sub.2SO.sub.4) fraction to a primary extraction system.

14. The method or process of claim 3, wherein the method or process operates at a temperature: (a) in excess of about 140 F., but less than about 190 F., or (b) between about 145 F. and about 160 F., thereby resulting in a heated strong acid regeneration solution and a heated impurity-, contaminant- and/or minor element-containing effluent acid solution.

15. The method or process of claim 14, further comprising cooling the heated impurity-, contaminant- and/or minor element-containing effluent acid solution, wherein upon cooling sulfates crystallize from the solution as a mixed impurity-, contaminant- and/or minor element-sulfate product, thus producing a impurity-, contaminant- and/or minor element-free concentrated acid, or sulfuric acid (H.sub.2SO.sub.4) and sulfate crystals.

16. The method or process of claim 1, wherein the cationic metal minor element components, or impurities or contaminants, comprise a cationic iron, optionally as a Fe.sup.+2 or Fe.sup.+3, or a cationic aluminum, optionally in the Al.sup.+3 form, or a cationic magnesium, optionally as Mg.sup.+2.

17. The method or process of claim 1, wherein the phosphoric acid solution, the solution comprising a phosphoric acid, or the phos-acid feedstock, is first treated, or pre-treated, with a clarification process or a filtering process, or a clarification aid.

18. The method or process of claim 1, further comprising: (a) treating the cationic metal impurity-, contaminant- and/or minor element-containing effluent acid solution with a lime and/or a lime-limestone mixture to precipitate the eluted minor elements as a hydroxide material; or, (b) neutralizing the cationic metal impurity-, contaminant- and/or minor element-containing effluent acid solution to precipitate the eluted cationic metal impurity, contaminant, or minor elements as a hydroxide material, and optionally further comprising separating the precipitated material for disposal to generate a precipitate-free water phase, optionally further comprising recycling the precipitate-free water phase.

19. The method or process of claim 3, wherein the cationic metal minor element components, or impurities or contaminants, comprise a cationic iron, optionally as a Fe.sup.+2 or Fe.sup.+3, or a cationic aluminum, optionally in the Al.sup.+3 form, or a cationic magnesium, optionally as Mg.sup.+2.

20. The method or process of claim 3, wherein the phosphoric acid solution, the solution comprising a phosphoric acid, or the phos-acid feedstock, is first treated, or pre-treated, with a clarification process or a filtering process, or a clarification aid.

21. The method or process of claim 3, further comprising: (a) treating the cationic metal impurity-, contaminant- and/or minor element-containing effluent acid solution with a lime and/or a lime-limestone mixture to precipitate the eluted minor elements as a hydroxide material; or, (b) neutralizing the cationic metal impurity-, contaminant- and/or minor element-containing effluent acid solution to precipitate the eluted cationic metal impurity, contaminant, or minor elements as a hydroxide material, and optionally further comprising separating the precipitated material for disposal to generate a precipitate-free water phase, optionally further comprising recycling the precipitate-free water phase.

22. The method or process of claim 21, further comprising: separating the precipitated material for disposal to generate a precipitate-free water phase, and optionally further comprising recycling the precipitate-free water phase.

23. The method or process of claim 1, wherein the pretreatment to reduce the amount of suspended solids content in an untreated wet-process phosphoric acid solution comprises filtering.

24. The method or process of claim 1, wherein the produced acid solution in step (d) is suitable for the production of fertilizer materials or di-ammonium phosphate (DAP), which requires a phosphoric acid that has a limited amount of cationic impurities.

25. The method or process of claim 1, wherein the treated ground phosphate rock or equivalent is used to produce a phosphate fertilizer product, optionally comprising a fast release P.sub.2O.sub.5; a slow release P.sub.2O.sub.5; secondary nutrients; and/or minor element nutrients.

26. The method or process of claim 1, further comprising recycling of the substantially cationic metal impurity-, contaminant- and/or minor element-free acid solution for use as a phosphoric acid solution, or a solution comprising a phosphoric acid, or a phos-acid feedstock of step 1(a).

27. The method or process of claim 3, wherein the pretreatment to reduce the amount of suspended solids content in an untreated wet-process phosphoric acid solution comprises filtering.

28. The method or process of claim 3, wherein in step (d) the produced acid solution is suitable for the production of fertilizer materials or di-ammonium phosphate (DAP), which requires a phosphoric acid that has a limited amount of cationic impurities.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The drawings set forth herein are illustrative of embodiments of the invention and are not meant to limit the scope of the invention as encompassed by the claims.

(2) Figures are described and discussed herein.

(3) FIG. 1 schematically illustrates an exemplary process of the invention, an overall process flow diagram for an exemplary impurity reduction process of the invention, referred to as the Minor Element Reduction (MER) process. Also shown in FIG. 1 is two exemplary alternatives for the treatment of the regeneration solution from the continuation ion exchange (or CIX) regeneration stage.

(4) Like reference symbols in the various drawings indicate like elements.

(5) Reference will now be made in detail to various exemplary embodiments of the invention, examples of which are illustrated in the accompanying drawings. The following detailed description is provided to give the reader a better understanding of certain details of aspects and embodiments of the invention, and should not be interpreted as a limitation on the scope of the invention.

DETAILED DESCRIPTION

(6) In alternative embodiments, the invention provides processes and methods for the recovery or the removal of iron, aluminum and magnesium (as cationic species) the so-called Minor Elements, from a wet-process phosphoric acid stream using a continuous ion exchange approach. In alternative embodiments, processes and methods of the invention allow for phosphate rock mining operations to increase the recovery of potentially useable ore or rock by allowing for the processing of lower grade ore or rock sources, thus enabling an effective expansion of the phosphate rock source without the need for development of additional mining area. Thus, the producer can stay on a developed site and utilize lower grade materials for a longer period of time.

(7) In alternative embodiments, as illustrated in FIG. 1, the exemplary Minor Element Reduction (MER) reduction process of the invention comprises pretreating a phos-acid (e.g., by filtering), or receiving a pretreated phos-acid, e.g., a filtered phos-acid (a nominal 26% P.sub.2O.sub.5) (stream 1) from a main phos-acid plant, before its input into the continuous ion exchange system. The pretreatment can comprise, or the pretreatment can further comprise, the phos-acid being treated with a clarification aid (2) in order to reduce the suspended solids content in the acid stream. In alternative embodiments, this treatment can be modified according to specific needs, and results in the reduction of the suspended solids, along with some removal of the darker color to remove suspended solids from the acid phase, and to partially reduce longer-chain color body (organic) materials. The extent of pretreatment required is specific to each phosphoric acid source and will vary accordingly. In alternative embodiments, activated clay, e.g. calcium or sodium bentonite clays is suitable for this purpose.

(8) In alternative embodiments, the underflow solids materials (3) recovered in this step can be filtered and disposed of to a gypsum pond, or alternatively returned to the phos-acid plant and combined with a filter feed slurry, e.g., a mixture of gypsum and phos-acid. In alternative embodiments, return of the solids to the phos-acid plant is preferred, if possible, in order to minimize P.sub.2O.sub.5 losses and dilution of the phos-acid.

(9) In alternative embodiments, the pretreated acid (4) is then processed in a continuous ion exchange (CIX) system, where it is contacted with a specific ion exchange resin, or equivalent material capable of binding the ME components, in a continuous fashion. In general a strong acid cation exchange resin or equivalent material is used.

(10) Examples of such resins or equivalent materials include, and optionally the strong cationic exchange resins or equivalent materials or compositions capable of binding the minor element (ME) components comprise: a PUROLITE SST-60 material, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, Pa.), or equivalents; a PUROLITE C-100 resin, comprised of gel polystyrene crosslinked with divinylbenzene (DVB) and a sulfonic acid functional group (Purolite, Bala Cynwyd, Pa.), or equivalents; a DOWEX MSC 650 material (Dow Chemical, Midland, Mich.), or equivalents; a resin, a composition or a material, or a non-resin solid or a semi-solid material, comprising chelating groups, functionalities or moieties that can bind ME components, and optionally that comprise a sulfonic acid functional group, iminodiacetic groups, chelating aminomethyl phosphoric acid groups or aminophosphonic groups, or similar chelating functionalities or moieties, wherein optionally the compositions comprise beads, wires, meshes, nanobeads, nanotubes, nanowires or other nano-structures, or hydrogels;

(11) The primary requirement is that the resin or equivalent material be of the so-called strong cation form and be in the hydrogen (H+) form.

(12) The minor element (ME) components, along with other cations, are removed from the acid and exchanged for an H+ ion that is on the resin, (which converts the ME-phosphate salt to phos-acid). In alternative embodiments, the treated acid (5) with lowered minor elements (ME) is then directed to a surge tank and returned to the phos-acid plant for normal downstream processing.

(13) It is important to recognize that the ME-phosphate materials in the phos-acid are converted to the acid form. In this manner the P.sub.2O.sub.5 that would normally remain in the ME-phosphate form (which has little ammoniation potential) is now converted to an acid form which can be readily ammoniated.

(14) The general exchange mechanism involved in the ME removal stage is as follows:
3RH++ME-PO.sub.4.fwdarw.3R-ME+H.sub.3PO.sub.4,
where R is the solid ion exchange resin: note that the impurity ME is converted to H.sub.3PO.sub.4 which is the desired form for phosphate (P) in the acid stream.

(15) In alternative embodiments, the ion exchange resin, now loaded with the ME and other cationic materials, is then water washed (6) in a continuous fashion. In alternative embodiments, the water flows are controlled to minimize overall P.sub.2O.sub.5 dilution. The water can be obtained from recycled water originating in the spent regeneration solution treatment options (1 and 2). Make-up water can be provided via process water make-up from the phosphoric acid plant.

(16) In alternative embodiments, the ME-loaded resin is then continuously regenerated with a solution of an acid, e.g., a sulfuric acid or an equivalent (7). In alternative embodiments, the H.sub.2SO.sub.4 strength is in the 10% to 30% range, depending on the ultimate disposition of the spent ME-sulfate stream. Other acids can be used, depending on the acids that are used for the digestion of the phosphate rock at the wet-process phos-acid facility. In the case of other acids, the ME in the spent regeneration solution will be in the salt form of the acid used for regeneration. For example, with nitric acid the ME's in the spent regeneration solution will be in the nitrate form, i.e. magnesium nitrate, iron nitrate, etc. In alternative embodiments, exemplary processes that have the most attractive applicability for the phosphate operations are those that use sulfuric acid for digestion, thus, at least for these exemplary processes, the ME's would more than likely be in the sulfate form.

(17) In alternative embodiments the acid that removes the ME and other cationic materials from the resin is sulfuric acid, and to produce a ME/cationic-sulfate eluate solution, i.e. the so called Spent Regeneration Solution (SRS), the hydrogen component (H+) from the acid is loaded back onto the resin to allow for resin reuse. In alternative embodiments the regenerated resin is again washed with water, and then returned to ME/cation removal service as the cycle is repeated.

(18) In alternative embodiments, an exemplary cationic exchange mechanism involved in the resin regeneration stage is as follows:
R-ME+H.sub.2SO.sub.4.fwdarw.RH++ME-SO.sub.4

(19) In alternative embodiments, equivalents to sulfuric acid (H.sub.2SO.sub.4) are used to regenerate the cationic exchange resin, i.e., to elute the contaminants, metals and the like binding to the resin before elution with acid. Examples of these acids are nitric and hydrochloric.

(20) The SRS (8) now contains the ME/cationic sulfate impurities along with residual free H.sub.2SO.sub.4. It is transferred to the ME-loaded regeneration solution treatment stage for further processing. The invention provides several exemplary options or alternatives for the treatment of this solution, depending on the specific characteristics of the solution and the location of the facility. In many cases it may be that the solution can be converted to a saleable product.

(21) In the first exemplary option, Option 1, the regeneration solution is treated with a mixture of limestone and lime (9) and the ME-components are precipitated as insoluble salts (10). This solid material can then be removed from the aqueous phase, if desired, and the sludge disposed of to the existing gypsum stack system. The aqueous solution (10) resulting from the treatment step is reusable water and can be returned to the CIX system. This method allows for economic treatment of the solution and overall economic attractiveness for the MER process.

(22) In the second exemplary option, Option 2, the loaded regeneration solution is mixed with ground phosphate rock (11), and the rock itself used as the treatment agent. After reaction, the rock material can be sold as a partially acidulated rock (12), or PAR product, and used as a modified superphosphate material. This product would be a low P.sub.2O.sub.5 analysis material that would have both fast release (water soluble) as well as a slower release (low water solubility) P.sub.2O.sub.5 fractions, and would also contain sulfate as well as the other minor elements, which in themselves are vital plant nutrients, for example, the so-called secondary and minor nutrients.

(23) In alternative embodiments of the exemplary PAR Option 2, the regeneration of the resin is operated to produce a concentrated ME-sulfate solution, and the ME is eventually crystallized from the solution as ME slurry. The regenerated solution is heated to a level that is sufficiently high to allow for the minor element sulfates to stay in solution. The spent regeneration solution is cooled to allow for the crystallization of the ME-sulfate. The ME-sulfate would be removed and recovered, and the concentrated sulfuric acid returned to the continuous ion exchange system.

(24) In an exemplary Option 3, if the amount of recovered ME is sufficient then there is the possibility of recovering specific marketable ME materials such as magnesium sulfate (MgSO.sub.4) In some cases, these recovered ME-sulfates may have market value in their own right, thus the P.sub.2O.sub.5 impurity can be converted to a useable co-product.

(25) In FIG. 1, the exemplary Option 3 alternative embodiment is shown for the case where a mixed ME-Sulfate product would be produced. The spent regeneration solution (8) would be sent to ME-Salt Recovery System and the solution concentrated to crystallize the ME-sulfate from the solution. In this case, the system would also be operated with a higher sulfuric acid solution, and at higher temperature in order to minimize the resulting water handling requirements. In alternative embodiments, the resulting crystallized ME-salt is dried then sold as a secondary/minor element product (13). The free sulfuric acid resulting from the crystallization (14) can be recycled to the so-called exemplary CIX extraction process of the invention.

(26) A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.