ALCOHOLS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent

Application No. 62/677,415, filed May 29, 2018, which is hereby incorporated by reference in its entirety.

FIELD OF INVENTION

[0002] The present invention generally relates to diol ester production processes.

More specifically, the present invention relates to systems and methods for producing diesters of glycols from esters of mono alcohols via a coupling reaction.

BACKGROUND OF THE INVENTION

[0003] Diol esters, such as ethylene glycol diformate, are used as processing aids in chemical production processes. Some diol esters, for instance ethylene glycol diformate, are also used in embalming fluids. Conventionally, diol esters are produced via esterification of diols followed by various downstream separation and purification processes.

[0004] In general, esterification of diols requires high reaction temperature, which results in the esterification process consuming a lot of energy. Furthermore, esterification reactions for producing esters are equilibrium limited. Thus, the conversion rates for diol in esterification processes are low even with the presence of excessive amounts of catalyst, which adds to the production cost for diol esters. Moreover, the esterification processes result in the reactants, the products and the catalysts all being in a mixture, after the equilibrium of the esterification reaction is reached. As a result, the downstream separation and purification processes for esterification are generally complicated and energy intensive. Usually, multiple reactors, vessels, and/or separators are needed to purify the diol esters and to efficiently recycle catalysts and unreacted reactants, which results in requiring both high production cost and high capital expenditure.

[0005] Overall, while methods of producing diol esters exist, the need for improvements in this field persists in light of at least the aforementioned drawbacks for the methods. BRIEF SUMMARY OF THE INVENTION

[0006] A solution to at least some of the above-mentioned problems associated with the production process for diol esters has been discovered. The solution resides in a method of producing a diol ester by coupling reactions of monohydric alcohol ester molecules. This can be beneficial for at least improving conversion rate of the reactants and simplifying the product purification and recovery process. Notably, the product stream of this method can be separated to recover the purified product in a simple two-step process, thereby limiting capital expenditure for the reactors and separators. Furthermore, this method can be performed with or without the presence of catalyst. The process can lead to reduced production cost and/or simplified product and catalyst recovery process. Therefore, the methods of the present invention provide a technical advantage over at least some of the problems associated with the currently available methods for producing diol esters mentioned above.

[0007] Embodiments of the invention include a method of producing a diol ester. The method includes coupling monohydric alcohol ester molecules under reaction conditions sufficient to produce the diol ester.

[0008] Embodiments of the invention include a method of producing ethylene glycol diformate. The method includes coupling methyl formate molecules under reaction conditions sufficient to product the ethylene glycol diformate.

[0009] Embodiments of the invention include a method of producing ethylene glycol diformate. The method includes flowing a stream comprising primarily methyl formate into a reactor. The method further includes subjecting the stream comprising primarily methyl formate to reaction conditions in the reactor that include a temperature of 100 to 600 °C and a pressure of 1 bar to 40 bar such that compounds of methyl formate couple to form the ethylene glycol diformate. The method further includes flowing a product stream comprising the ethylene glycol diformate from the reactor.

[0010] Embodiments of the invention include a method of producing ethylene glycol diformate. The method includes flowing a stream comprising primarily methyl formate into a reactor. The method further includes subjecting the stream comprising primarily methyl formate to reaction conditions in the reactor that include a temperature of 100 to 600 °C and a pressure of 1 bar to 40 bar such that methyl formate molecules couple to form the ethylene glycol diformate. The method further still includes flowing a product stream comprising the ethylene glycol diformate from the reactor. The method further includes feeding the product stream from the reactor to a first separation unit that separates the product stream into a first stream comprising primarily ethylene glycol diformate and methanol collectively and a second stream comprising methyl formate, air and/or O2, CO2, CO, and H2. The method further still includes separating the second stream in a second separation unit into a third stream comprising primarily methyl formate and a fourth stream comprising air and/or any combination of O2, CO2, CO, and H2. The method further includes recycling the third stream back to the reactor.

[0011] The following includes definitions of various terms and phrases used throughout this specification.

[0012] The terms “about” or“approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.

[0013] The terms“wt.%,”“vol.%” or“mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component.

[0014] The term“substantially” and its variations are defined to include ranges within

10%, within 5%, within 1%, or within 0.5%.

[0015] The terms“inhibiting” or“reducing” or“preventing” or“avoiding” or any variation of these terms, when used in the claims and/or the specification, include any measurable decrease or complete inhibition to achieve a desired result.

[0016] The term“effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0017] The use of the words“a” or“an” when used in conjunction with the term

“comprising,”“including,”“containing,” or“having” in the claims or the specification may mean“one,” but it is also consistent with the meaning of“one or more,”“at least one,” and “one or more than one.”

[0018] The words“comprising” (and any form of comprising, such as“comprise” and

“comprises”),“having” (and any form of having, such as“have” and“has”),“including” (and any form of including, such as“includes” and“include”) or“containing” (and any form of containing, such as“contains” and“contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0019] The process of the present invention can“comprise,”“consist essentially of,” or“consist of’ particular ingredients, components, compositions, etc., disclosed throughout the specification.

[0020] The term“primarily,” as that term is used in the specification and/or claims, means greater than any of 50 wt. %, 50 mol. %, and 50 vol. %. For example,“primarily” may include 50.1 wt. % to 100 wt. % and all values and ranges there between, 50.1 mol. % to 100 mol. % and all values and ranges there between, or 50.1 vol. % to 100 vol. % and all values and ranges there between.

[0021] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: [0023] FIG. 1 shows a schematic diagram of a system for producing diol esters, according to embodiments of the invention.

[0024] FIG. 2 shows a continuous plug flow reactor used in a system for producing diol esters, according to embodiments of the invention; and

[0025] FIG. 3 shows a schematic flow chart for a method of producing diol esters, according to embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0026] Currently, diol esters can be produced by esterification of glycol and acids, which requires a lot of energy, has limited reactant conversion rate, and presents various challenges for downstream product recovery. The present invention provides a solution, at least in part, to the problems. The solution is premised on a method that includes coupling monohydric alcohol ester molecules. This process requires more simplified downstream separation and product recovery process compared to conventional esterification based methods, thereby reducing both production cost and capital expenditure for diol ester production. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. System for producing diol esters

[0027] In embodiments of the invention, the system for producing diol esters can include an integrated system for producing and recovering diol esters. With reference to FIG. 1, a schematic diagram is shown of diol ester production system 100 that is capable of producing diol esters via a coupling chemistry based process and separating the diol ester in simpler steps, as compared to conventional methods. According to embodiments of the invention, diol ester production system 100 includes coupling reactor 101 configured to react an ester of monohydric alcohol to form a diol ester. In embodiments of the invention, coupling reactor 101 may include a plug flow reactor, a batch reactor, or micro channel reactor.

[0028] According to embodiments of the invention, a catalyst may be disposed in coupling reactor 101 Additionally or alternatively, the catalyst may be mixed with feed stream 11 and or gas stream 12 flowing to coupling reactor 101 In embodiments of the invention, the catalyst may include VIII and VIB group metal oxides, and combinations thereof. Non-limiting examples of the catalyst may include Pd, Pt, Ru, Rh, or combinations thereof supported over a support material including molybdenum oxide or tungsten oxide. In embodiments of the invention, the support material may further contain phosphorous and/or silicon. In embodiments of the invention, the support material comprising molybdenum oxide and/or tungsten oxide may include up to 5 wt.% phosphorous. In embodiments of the invention, the support material may be derived from alumina, silica, titanium oxide, tungsten oxide, or combinations thereof.

[0029] In embodiments of the invention, coupling reactor 101 may include a first inlet adapted for receiving ester of monohydric alcohol of feed stream 11. Coupling reactor 101 may further include a second inlet adapted for receiving gas stream 12 comprising oxygen and/or air.

[0030] As shown in FIG. 2, coupling reactor 101 may be a continuous plug flow reactor that includes elongated tubular body 201. In embodiments of the invention, coupling reactor 101 includes mass flow controller 202 adapted to receive and control a flowrate of an air and/or oxygen stream. Coupling reactor 101 further includes feed pipe 203 comprising a thin tubular structure inserted in tubular body 201, where feed pipe 203 is adapted to release methyl formate of feed stream 11 in tubular body 201. As shown in FIG. 2, a releasing end of feed pipe is disposed deeper in tubular body 201 than an inlet of mass flow controller 202 for air and/or nitrogen.

[0031] In embodiments of the invention, an outlet of coupling reactor 101 may be in fluid communication with first separation unit 102 such that product stream 13 flows from coupling reactor 101 to first separation unit 102. In embodiments of the invention, product stream 13 may include carbon dioxide (CO2), carbon monoxide (CO), hydrogen, unreacted methyl formate, ethylene glycol diformate, methanol, or combinations thereof. In embodiments of the invention, product stream 13 may further include air and/or O2 when the second inlet of coupling reactor 101 is used to receive air and/or oxygen.

[0032] According to embodiments of the invention, first separation unit 102 is adapted to separate product stream 13 to form second stream 14 comprising carbon dioxide, carbon monoxide, hydrogen, methyl formate, and first stream 15 comprising primarily ethylene glycol diformate and methanol, collectively. In embodiments of the invention, second stream 14 may further include air and/or oxygen when the second outlet of coupling reactor is used to receive air or oxygen. In embodiments of the invention, first separation unit 102 may include a flash column, a distillation column, or combinations thereof.

[0033] According to embodiments of the invention, a first outlet of first separation unit 102 may be in fluid communication with an inlet of second separation unit 103 such that second stream 14 flows from first separation unit 102 to second separation unit 103. In embodiments of the invention, a second outlet of first separation unit 102 may be in fluid communication with an inlet of purification unit 104 such that first stream 15 flows from first separation unit 102 to purification unit 104. In embodiments of the invention, second separation unit 103 is adapted to separate second stream 14 into third stream 16 comprising primarily methyl formate and fourth stream 17 comprising primarily carbon dioxide, carbon monoxide and hydrogen. In embodiments of the invention, stream 17 may further include air and/or oxygen when air and/or oxygen is flowed in the coupling reactor 101.

[0034] In embodiments of the invention, second separation unit 103 may include flash column, distillation column, or combinations thereof. Second separation unit 103 may include a first outlet for releasing stream 17. Second separation unit 103 may further include a second outlet in fluid communication with coupling reactor 101 such that recycle stream 16 flows from second separation unit 103 to coupling reactor 101. In embodiments of the invention, purification unit 104 may include one or more distillation columns. Purification unit 104 may be adapted to purify ethylene glycol diformate.

B. Method for producing diol esters

[0035] As shown in FIG. 3, embodiments of the invention include method 300 for producing diol esters. Method 300 may be implemented by diol ester production system 100 as shown in FIG. 1. According to embodiments of the invention, method 300 may include flowing feed stream 11 into coupling reactor 101, as shown in block 301. Feed stream 11 may comprise primarily an monohydric alcohol ester.

[0036] In embodiments of the invention, method 300 may include coupling monohydric alcohol ester molecules under reaction conditions sufficient to produce the diol ester. In embodiments of the invention, the coupling may take place with or without the presence of a catalyst. In embodiments of the invention, the catalyst may include VIII and VIB group metal oxides, or combinations thereof. Non-limiting examples of the catalyst may include Pd, Pt, Ru, Rh, or combinations thereof supported over a support material including molybdenum oxide or tungsten oxide. In embodiments of the invention, the support material may further contain phosphorous and/or silicon. In embodiments of the invention, the support material comprising molybdenum oxide and/or tungsten oxide may include up to 5 wt.% phosphorous. In embodiments of the invention, the support material may be derived from alumina, silica, titanium oxide, tungsten oxide, or combinations thereof.

[0037] According to embodiments of the invention, gas stream 12 comprising oxygen and/or air may be flowed into coupling reactor 102 such that feed stream 11 mixes with oxygen and/or air. Therefore, the coupling step may take place with or without the presence of oxygen from gas stream 12. In embodiments of the invention, a molar ratio of the monohydric alcohol ester to oxygen may be in a range of 0.1 to 32 mol.% and all ranges and values there between including ranges of 0.1 to 0.2 mol.%, 0.2 to 0.4 mol.%, 0.4 to 0.6 mol.%, 0.6 to 0.8 mol.%, 0.8 to 1.0 mol.%, 1.0 to 2.0 mol.%, 2.0 to 4.0 mol.%, 4.0 to 6.0 mol.%, 6.0 to 8.0 mol.%, 8.0 to 10.0 mol.%, 10.0 to 12.0 mol.%, 12.0 to 14.0 mol.%, 14.0 to 16.0 mol.%, 16.0 to 18.0 mol.%, 18.0 to 20.0 mol.%, 20.0 to 22.0 mol.%, 22.0 to 24.0 mol.%, 24.0 to 26.0 mol.%, 26.0 to 28.0 mol.%, 28.0 to 30.0 mol.%, and 30.0 to 32.0 mol.%.

[0038] In embodiments of the invention, non-limiting examples of the monohydric alcohol ester may include methyl formate, ethyl formate, propyl formate, butyl formate, and combinations thereof. Non-limiting examples of the diol ester may include ethylene glycol diformate, corresponding substituted ethylene glycol diformate, and combinations thereof. A non-limiting example for the coupling may include:

[0039] In embodiments of the invention, as shown in block 302, the coupling step may include subjecting feed stream comprising primarily methyl formate to reaction conditions in coupling reactor such that methyl formate couples to form ethylene glycol diformate.

[0040] In embodiments of the invention, the reaction conditions include a reaction temperature of 100 to 600 °C and all ranges and values there between, including ranges of 100 to 125 °C, 125 to 150 °C, 150 to 175 °C, 175 to 200 °C, 200 to 225 °C, 225 to 250 °C,

250 to 275 °C, 275 to 300 °C, 300 to 325 °C, 325 to 350 °C, 350 to 375 °C, 375 to 400 °C,

400 to 425 °C, 425 to 450 °C, 450 to 475 °C, 475 to 500 °C, 500 to 525 °C, 525 to 550 °C,

550 to 575 °C, and 575 to 600 °C. In embodiments of the invention, the reaction conditions may include a reaction pressure of 1 to 40 bar and all ranges and values there between including ranges of 1 to 4 bar, 4 to 7 bar, 7 to 10 bar, 10 to 13 bar, 13 to 16 bar, 16 to 19 bar, 19 to 22 bar, 22 to 25 bar, 25 to 28 bar, 28 to 31 bar, 31 to 34 bar, 34 to 37 bar, and 37 to 40 bar. In embodiments of the invention, the reaction conditions may include a space time of 1 to 100 millisecond (ms) and all ranges and values there between including ranges of 1 to 2 ms, 2 to 3 ms, 3 to 4 ms, 4 to 5 ms, 5 to 6 ms, 6 to 7 ms, 7 to 8 ms, 8 to 9 ms, 9 to 10 ms, 10 to 20 ms, 20 to 30 ms, 30 to 40 ms, 40 to 50 ms, 50 to 60 ms, 60 to 70 ms, 70 to 80 ms, 80 to 90 ms, and 90 to 100 ms.

[0041] According to embodiments of the invention, method 300 may further include flowing product stream 13 comprising the diol ester, such as ethylene glycol diformate, from coupling reactor 101, as shown in block 303. In embodiments of the invention, product stream 13 may include 5 to 20 wt.% ethylene glycol diformate and all ranges and values there between including 5 to 6 wt.%, 6 to 7 wt.%, 7 to 8 wt.%, 8 to 9 wt.%, 9 to 10 wt.%, 10 to 11 wt.%, 11 to 12 wt.%, 12 to 13 wt.%, 13 to 14 wt.%, 14 to 15 wt.%, 15 to 16 wt.%, 16 to 17 wt.%, 17 to 18 wt.%, 18 to 19 wt.%, and 19 to 20 wt.%. Product stream 13 may further include methyl formate, methanol, air and/or oxygen, carbon dioxide, carbon monoxide, H ₂ , or combinations thereof. In embodiments of the invention, product stream 13 may further include water when oxygen and/or air is mixed with feed stream 11.

[0042] In embodiments of the invention, as shown in block 304, method 300 may further include feeding product stream 13 from coupling reactor 101 to first separation unit 102. As shown in block 305, method 300 may include separating product stream 13 to form first stream 15 comprising primarily ethylene glycol diformate and methanol collectively, and second stream 14 comprising methyl formate, air and/or oxygen, carbon dioxide, carbon monoxide, hydrogen, or combinations thereof. In embodiments of the invention, first stream 15 may include 1 to 99.5 wt.% ethylene glycol diformate and all ranges and values there between.

[0043] According to embodiments of the invention, as shown in block 306, method

300 may further include separating second stream 14 in second separation unit 103 into third stream 16 including primarily methyl formate, and fourth stream 17 comprising primarily air and/or oxygen, carbon dioxide, carbon monoxide, hydrogen, or combinations thereof. In embodiments of the invention, third stream 16 may include 80 to 100 wt.% methyl formate and all ranges and values there between including 80 to 82 wt.%, 82 to 84 wt.%, 84 to 86 wt.%, 86 to 88 wt.%, 88 to 90 wt.%, 90 to 92 wt.%, 92 to 94 wt.%, 94 to 96 wt.%, 96 to 98 wt.%, and 98 to 100 wt.%,. According to embodiments of the invention, as shown in block 307, method 300 may further include recycling third stream 16 back to coupling reactor 101. In embodiments of the invention, third stream 16 may be mixed with feed stream 11.

[0044] In embodiments of the invention, first stream 15 comprising primarily ethylene glycol diformate may be flowed to purification unit 104. In embodiments of the invention, method 300 may further include purifying stream 15 to form purified product stream 18. Purified product stream 18 may include 90 to 100 wt.% ethylene glycol diformate and all ranges and values there between including ranges of 90 to 91 wt.%, 91 to 92 wt.%, 92 to 93 wt.%, 93 to 94 wt.%, 94 to 95 wt.%, 95 to 96 wt.%, 96 to 97 wt.%, 97 to 98 wt.%, 98 to 99 wt.%, and 99 to 100 wt.%, .

[0045] Although embodiments of the present invention have been described with reference to blocks of FIG. 3, it should be appreciated that operation of the present invention is not limited to the particular blocks and/or the particular order of the blocks illustrated in FIG. 3. Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of FIG. 3.

[0046] As part of the disclosure of the present invention, a specific example is included below. The example is for illustrative purposes only and is not intended to limit the invention. Those of ordinary skill in the art will readily recognize parameters that can be changed or modified to yield essentially the same results.

EXAMPLE

(Methyl formate coupling reaction)

[0047] A methyl formate coupling reaction was carried out in a continuous plug flow reactor as shown in FIG. 2. In this example, the volume of the continuous plug flow reactor is 9.84x l0 ⁶ m ³ . The mixture of about 7 vol.% oxygen and 93 vol.% nitrogen was flowed through mass flow controller 202 at a flowrate of 144 ml/minute. Methyl formate was flowed into feed pipe 203 at a flowrate of 0.48 ml/min. As shown in Table 1, three sets of reaction conditions have been tested, including reaction temperature of 350 °C and reaction pressure of 20 bar, reaction temperature of 560 °C and reaction pressure of 20 bar, and reaction temperature of 560 °C and reaction pressure of 10 bar.

[0048] The product produced under each set of the reaction conditions was analyzed using on-line gas chromatography equipped with a FID (flame ionization detector) and two TCDs (thermal conductivity detector). A molecular sieve and carbo wax column was used in the gas chromatography. The effluents from the reactor were condensed and product identification was performed using mass spectrometry. The results in Table 1 show that ethylene glycol diformate was produced under 20 bar at 560 °C with a selectivity of 28.43%. Under reaction pressure of 20 bar and reaction temperature of 350 °C, no ethylene glycol diformate was obtained. For reaction conditions of 10 bar and 650 °C, the selectivity for ethylene glycol diformate formation was merely 3.79%.

Table 1. Product distribution of methyl formate coupling

[0049] In the context of the present invention, embodiments 1-19 are described.

Embodiment 1 is a method of producing a diol ester. The method includes coupling monohydric alcohol ester molecules under reaction conditions sufficient to produce the diol ester. Embodiment 2 is the method of embodiment 1, wherein the diol ester is ethylene glycol diformate, and the monohydric alcohol ester is methyl formate. Embodiment 3 is the method of embodiment 2, further including flowing a stream including primarily methyl formate into a reactor before the coupling. Embodiment 4 is the method of embodiment 3, wherein the coupling includes subjecting the stream including primarily methyl formate to reaction conditions in the reactor such that compounds of methyl formate couple to form the ethylene glycol diformate. Embodiment 5 is the method of any of embodiments 2 to 4, further including flowing a product stream including the ethylene glycol diformate from the reactor. Embodiment 6 is the method of embodiment 5, further including separating the product stream in a first separation unit to form a first stream including primarily ethylene diformate and methanol collectively and a second stream including methyl formate, air and/or any combination of O2, CO2, CO, and H2. Embodiment 7 is the method of embodiment 6, further including separating the second stream in a second separation unit to form a third stream including primarily methyl formate and a fourth stream including air and/or any combination of O2, CO2, CO, and Eh. Embodiment 8 is the method of embodiment 7, further including recycling the third stream back to the reactor. Embodiment 9 is the method of any of embodiments 1 to 8, wherein the reaction conditions include a reaction temperature in a range of 100 to 600 °C. Embodiment 10 is the method of any of embodiments 1 to 9, wherein the reaction conditions include a reaction pressure of 1 to 40 bar. Embodiment 11 is the method of any of embodiments 1 to 10, wherein the coupling takes place in the presence of a catalyst. Embodiment 12 is the method of embodiment 11, wherein the catalyst is selected from the group consisting of VIII and VIB group metal oxides, and combinations thereof. Embodiment 13 is the method of any of embodiments 1 to 10, wherein the coupling takes place without the presence of a catalyst. Embodiment 14 is the method of any of embodiments 1 to 13, wherein the coupling takes place with the presence of oxygen. Embodiment 15 is the method of embodiment 14, wherein the monohydric alcohol ester is mixed with oxygen at a molar ratio of 0.1 to 32 molar %. Embodiment 16 is the method of any of embodiments 14 and 15, wherein the coupling step produces a byproduct including water. Embodiment 17 is the method of any of embodiments 1 to 13, wherein the coupling step takes place without the presence of oxygen. Embodiment 18 is the method of embodiment 17, wherein the coupling step produces a byproduct including hydrogen.

[0050] Embodiment 19 is a method of producing ethylene glycol diformate. The method includes flowing a stream including primarily methyl formate into a reactor and subjecting the stream including primarily methyl formate to reaction conditions in the reactor that include a temperature of 100 to 600 °C and a pressure of 1 bar to 40 bar such that methyl formate forms ethylene glycol diformate via coupling reaction. The method further includes flowing a product stream including the ethylene glycol diformate from the reactor, then feeding the product stream from the reactor to a first separation unit and separating the product stream, in the first separation unit, into a first stream including primarily ethylene glycol diformate and methanol collectively and a second stream including methyl formate, air and/or any combination of O2, CO2, CO, and Eb. The method also includes separating the second stream in a second separation unit into a third stream including primarily methyl formate and a fourth stream including air and/or O2, CO2, CO, and H2, and recycling the third stream back to the reactor.

[0051] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.