In this century, the shortage of fresh water will surpass the shortage of energy as a global concern for humanity; and these two challenges are inexorably linked, as explained, for example, in the “Special Report on Water” in the 20 May 2010 issue of The Economist. Fresh water is one of the most fundamental needs of humans and other organisms; each human needs to consume a minimum of about two liters per day. The world also faces greater freshwater demands from farming and industrial processes.
The hazards posed by insufficient water supplies are particularly acute. A shortage of fresh water may lead to a variety of crises, including famine, disease, death, forced mass migration, cross-region conflict/war, and collapsed ecosystems. Despite the criticality of the need for fresh water and the profound consequences of shortages, supplies of fresh water are particularly constrained. 97.5% of the water on Earth is salty, and about 70% of the remainder is locked up as ice (mostly in ice caps and glaciers), leaving only a fraction of all water on Earth as available fresh (non-saline) water.
Moreover, the earth's water that is fresh and available is not evenly distributed. For example, heavily populated countries, such as India and China, have many regions that are subject to scarce supplies. Further still, the supply of fresh water is often seasonally inconsistent. Meanwhile, demands for fresh water are tightening across the globe. Reservoirs are drying up; aquifers are falling; rivers are dying; and glaciers and ice caps are retracting. Rising populations increase demand, as do shifts in farming and increased industrialization. Climate change poses even more threats in many regions. Consequently, the number of people facing water shortages is increasing. Naturally occurring fresh water, however, is typically confined to regional drainage basins; and transport of water is expensive and energy-intensive.
Additionally, water can be advantageously extracted from contaminated waste streams (e.g., from oil and gas production) both to produce fresh water and to concentrate and reduce the volume of the waste streams, thereby reducing pollution and contamination and reducing costs.
Nevertheless, many of the existing processes for producing fresh water from seawater (or from brackish water or contaminated waste streams) require massive amounts of energy. Reverse osmosis (RO) is currently the leading desalination technology. In large-scale plants, the specific electricity required can be as low as 4 kWh/m3 at 30% recovery, compared to the theoretical minimum of around 1 kWh/m3; smaller-scale RO systems (e.g., aboard ships) are less efficient.
Other existing seawater desalination systems include thermal-energy-based multi-stage flash (MSF) distillation, and multi-effect distillation (MED), both of which are energy- and capital-intensive processes. In MSF and MED systems, however, the maximum brine temperature and the maximum temperature of the heat input are limited in order to avoid calcium sulfate, magnesium hydroxide and calcium carbonate precipitation, which leads to the formation of soft and hard scale on the heat transfer equipment.
Humidification-dehumidification (HDH) desalination systems include a humidifier and a condenser as their main components and use a carrier gas (e.g., air) to desalinate brine streams. A simple version of this technology includes a humidifier, a condenser, and a heater to heat the brine stream. In the humidifier, hot brine comes in direct contact with dry air, and this air becomes heated and humidified. In the condenser, the heated and humidified air is brought into (indirect) contact with a coolant (for example, cold brine) and gets dehumidified, producing pure water and dehumidified air. The HDH process operates at lower top brine temperatures than MSF and MED systems, precipitation of scaling components is hence avoided to some extent.
Another approach, described in U.S. Pat. No. 8,119,007B2 (A. Bajpayee, et al.), uses directional solvent that directionally dissolves water but does not dissolve salt. The directional solvent is heated to dissolve water from a salt solution into the directional solvent. The remaining highly concentrated salt water is removed, and the solution of directional solvent and water is cooled to precipitate substantially pure water out of the solution.
The present inventor was also named as one of the inventors on the following patent applications that include additional discussion of HDH and other processes for purifying water: U.S. application Ser. No. 12/554,726, filed 4 Sep. 2009; U.S. application Ser. No. 12/573,221, filed 5 Oct. 2009; U.S. application Ser. No. 13/028,170, filed 15 Feb. 2011; and U.S. application Ser. No. 13/241,907, filed 23 Sep. 2011; U.S. application Ser. No. 13/550,094, filed 16 Jul. 2012; U.S. application Ser. No. 13/916,038, filed 12 Jun. 2013; and U.S. application Ser. No. 13/958,968, filed 5 Aug. 2013.
Apparatus and methods for counter-flow simultaneous heat and mass exchange are described herein. Various embodiments of the apparatus and methods may include some or all of the elements, features and steps described below.
In an embodiment of the method, a counter-flow simultaneous heat and mass exchange device is operated by directing flows of two fluids into a heat and mass exchange device at initial mass flow rates where ideal changes in total enthalpy rates of the two fluids are unequal. At least one of the following state variables in the fluids is measured by one or more sensors: temperature, pressure and concentration, which together define the thermodynamic state of the two fluid streams at the points of entry to and exit from the device. The flow rates of the fluids at the points of entry and/or exit to/from the device can be measured; and the mass flow rate of at least one of the two fluids is changed such that the ideal change in total enthalpy rates of the two fluids through the device are brought closer to being equal.
The methods and apparatus allow operation of a heat and mass exchange device so that it always operates optimally or near optimally from the perspective of thermodynamic efficiency by controlling flows of the fluids by controlling flow controllers, such as pumps, blowers and valves in the system. These methods and apparatus can be used, e.g., for heat and mass exchange in a humidification-dehumidification process for producing fresh water from an aqueous source composition that includes dissolved species.
In the accompanying drawings, like reference characters refer to the same or similar parts throughout the different views; and apostrophes are used to differentiate multiple instances of the same or similar items sharing the same reference numeral. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating particular principles, discussed below.
The foregoing and other features and advantages of various aspects of the invention(s) will be apparent from the following, more-particular description of various concepts and specific embodiments within the broader bounds of the invention(s). Various aspects of the subject matter introduced above and discussed in greater detail below may be implemented in any of numerous ways, as the subject matter is not limited to any particular manner of implementation. Examples of specific implementations and applications are provided primarily for illustrative purposes.
Unless otherwise defined, used or characterized herein, terms that are used herein (including technical and scientific terms) are to be interpreted as having a meaning that is consistent with their accepted meaning in the context of the relevant art and are not to be interpreted in an idealized or overly formal sense unless expressly so defined herein. For example, if a particular composition is referenced, the composition may be substantially, though not perfectly pure, as practical and imperfect realities may apply; e.g., the potential presence of at least trace impurities (e.g., at less than 1 or 2%) can be understood as being within the scope of the description; likewise, if a particular shape is referenced, the shape is intended to include imperfect variations from ideal shapes, e.g., due to manufacturing tolerances. Percentages or concentrations expressed herein can represent either by weight or by volume. Processes, procedures and phenomena described below can occur at ambient pressure (e.g., about 50-120 kPa—for example, about 90-110 kPa) and temperature (e.g., −20 to 50° C.—for example, about 10-35° C.).
Although the terms, first, second, third, etc., may be used herein to describe various elements, these elements are not to be limited by these terms. These terms are simply used to distinguish one element from another. Thus, a first element, discussed below, could be termed a second element without departing from the teachings of the exemplary embodiments.
Spatially relative terms, such as “above,” “below,” “left,” “right,” “in front,” “behind,” and the like, may be used herein for ease of description to describe the relationship of one element to another element, as illustrated in the figures. It will be understood that the spatially relative terms, as well as the illustrated configurations, are intended to encompass different orientations of the apparatus in use or operation in addition to the orientations described herein and depicted in the figures. For example, if the apparatus in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary term, “above,” may encompass both an orientation of above and below. The apparatus may be otherwise oriented (e.g., rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
Further still, in this disclosure, when an element is referred to as being “on,” “connected to,” “coupled to,” “in contact with,” etc., another element, it may be directly on, connected to, coupled to, or in contact with the other element or intervening elements may be present unless otherwise specified.
The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of exemplary embodiments. As used herein, singular forms, such as “a” and “an,” are intended to include the plural forms as well, unless the context indicates otherwise. Additionally, the terms, “includes,” “including,” “comprises” and “comprising,” specify the presence of the stated elements or steps but do not preclude the presence or addition of one or more other elements or steps.
Additionally, the various components identified herein can be provided in an assembled and finished form; or some or all of the components can be packaged together and marketed as a kit with instructions (e.g., in written, video or audio form) for assembly and/or modification by a customer to produce a finished product.
Dependent heat and mass exchange devices are described herein.
An “independent” heat and mass exchange device has inlet states that do not depend on the operation of the device (e.g., choice of flow rates). In other words, an independent heat and mass exchange device has inlet states that depend only on external conditions.
A “dependent” heat and mass exchange device, in contrast, has inlet states that depend on the operation of the device (e.g., the choice of flow rates). This dependency usually exists because the outlets of the heat-and-mass-exchange (HME) apparatus serve as or are coupled with the inlets to other HME devices, and the outlets of the coupled HME devices can serve as or be coupled with the inlets of the HME device in question. For example, in a humidification-dehumidification (HDH) system, the condenser and humidifier are dependent HME devices as, for example, varying the flow rate of air in the condenser affects the operation of the humidifier (as it is the same flow rate) and so affects the outputs at the outlets of the humidifier, in particular, at the air outlet. The air leaving the humidifier enters the condenser; so the input at the inlet to the condenser changes with a changing of the flow rate of air in the condenser.
When controlling an independent HME device, one need only determine the states of the inputs and calculate the heat capacity ratio (HCR), and set the new mass flow rate ratio (MR) to MRnew=MRold/HCRd·HCRd is the modified heat capacity rate ratio and is further defined, below
There is no need for iteration, as changing the flow rate will not affect the inlet states. In contrast, when controlling a dependent HME device, the process is carried out iteratively, as changing the flow rate will change the inlet states, and so will affect the value of HCRd.
In the illustration of
In the illustration
A flow chart of the control operation is shown in
The target for the flow control is to achieve the following condition: Δ{dot over (H)}max,1=Δ{dot over (H)}max,2, where Δ{dot over (H)}max,1 and Δ{dot over (H)}max,2 represent the maximum possible change in total enthalpy rates for the first and second fluids. Accordingly, for the heat and mass exchange device in
Next, we consider a counter-flow cooling tower serving as the heat and mass exchanger and as a control volume, CV (shown in
{dot over (m)}da={dot over (m)}da,i={dot over (m)}da,o, (1)
where m is mass; da is dry air; I is input; and o is output.
A mass balance on the water in the cooling tower 10 gives the mass flow rate of the water leaving the humidifier in the water stream 34 via the following equation:
{dot over (m)}w,o={dot over (m)}w,i−{dot over (m)}da(ωa,o−ωa,i), (2)
where w is the water; a is the air stream; and ω is the humidity ratio (i.e., kg of vapor per kg of dry air in the moist air mixture).
In order to determine the maximum possible change in enthalpy rate, we determine whether the air stream 36 or the water stream 34 is the hot (warmer) stream.
When the water 34 enters hotter than the air 36, the ideal condition that the water stream 34 can attain is that the temperature at the exit of the water stream equals the wet-bulb temperature of the air stream 36 at the air-stream inlet 37. This equivalence corresponds to the enthalpy driving force, which is just the enthalpy potential difference between the two streams 34 and 36 driving the heat and mass transfer, becoming zero at the exit 33 of the water stream 34. The ideal condition that the moist air stream can reach is saturation at the inlet temperature of the water stream 34 and is a limit imposed by the rate processes (Ta,o≤Tw,i). When the air stream 36 enters the condenser 10 hotter than the water stream 34, the ideal conditions that can be attained by the air stream 36 and the water stream 34 differ from those in the case with hot water entering the heat and mass exchanger 10. These conditions again correspond to the driving enthalpy difference becoming zero for the respective streams.
Based on the above discussion, the effectiveness definition of a counter-flow direct contact heat and mass exchange (HME) device with hot water entering is written as follows. The denominator of the term on the right hand side represents the ideal change in total enthalpy rate.
Case I, Δ{dot over (H)}max,w<Δ{dot over (H)}max,a:
Case II, Δ{dot over (H)}max,w>Δ{dot over (H)}max,a:
Note that the First Law for the cooling tower 10 gives:
where Δ{dot over (H)}w is the change in total enthalpy rate for the feed water stream 34 and Δ{dot over (H)}a is the change in total enthalpy rate of the moist air stream 36. One can similarly derive the effectiveness definition when at the inlet 37 where the hot air stream 36 enters the cooling tower 10.
Now consider a counter-flow condenser serving as the heat and mass exchanger 10 (as shown in
{dot over (m)}da={dot over (m)}da,i={dot over (m)}da,o, and (6)
{dot over (m)}w,o={dot over (m)}w,i. (7)
The mass flow rate of the condensed water 38 can be calculated using the following simple mass balance:
{dot over (m)}pw={dot over (m)}da(ωa,i−ωa,o). (8)
To calculate the maximum total enthalpy rate change possible, the inlet temperatures and mass flow rates are determined. As explained before, the ideal condition corresponds to the enthalpy driving force becoming zero at the exit of the water stream 34 or at the exit of the air stream 36. The ideal condition that the air stream 36 can reach at the exit 39 is saturation at the inlet temperature of water. The water can at best reach the dry bulb temperature of the air at its inlet 37. Again, this corresponds to the enthalpy driving force reaching zero at the air inlet 37.
Based on the above discussion, the effectiveness definition of a counter-flow indirect contact HME device 10 is as follows. The denominator of the term on the right-hand side represents the ideal change in enthalpy rate in the following equations:
Case I, Δ{dot over (H)}max,w<Δ{dot over (H)}max,a:
Case II, Δ{dot over (H)}max,w>Δ{dot over (H)}max,a:
Note that the First Law for the condenser can be expressed as follows:
where Δ{dot over (H)}w is the change in total enthalpy rate for the feed water stream 34, and Δ{dot over (H)}a is the change in total enthalpy rate of the moist air stream 36.
In the embodiment, as shown in
Ambient air 62 is also pumped via a flow controller, such as a fan or pump, through the humidifier stages 58 and 60 and serves as a carrier gas for the vaporized water in the humidifier stages 58 and 60. The humidified carrier gas is then passed through a carrier-gas conduit and fed through a two-stage bubble-column condenser 64 and 66, as described in US 2013/0074694 A1, and cooled therein to precipitate the water. In the embodiment of
Meanwhile, the brine 76 remaining in the humidifier 68 from the aqueous feed 50 after water is evaporated therefrom is discharged from the humidifier via a brine outlet and fed through a crystallizer, a sludge thickener, and a filter press to produce a salt product that is removed from the system and a brine discharge that is directed into the brine holding tank 52 (and recirculated).
The humidifier 68, in this embodiment, is a dual-column bubble-column humidifier, and the condenser 70 is a bubble-column dehumidifier. The humidified carrier gas 62 from the humidifier 68 is fed into the condenser 70 at the lowest section of the condenser 70 (from the top of the humidifier 68) and at an intermediate exchange conduit 72 (from an intermediate position of the humidifier 68). Water is precipitated from the carrier gas 62 as it cools while rising through the stages 66 and 64 of the bubble-column condenser 70 and collected for productive use or for release. Meanwhile, the dehumidified carrier gas is released from the top of the condenser 70 after passing through stage 66.
With reference to
The following thermophysical properties of these two points are evaluated 84 in the next step:
From these values, the mass flow rates, {dot over (m)}, were calculated 86 as follows:
{dot over (m)}H1=ρH1×FW1;
{dot over (m)}A3=ρA3×FA3;
{dot over (m)}da,A3={dot over (m)}A3/(1+ωA3);
The modified heat capacity ratio, HCRd, in the bubble column dehumidifier is then calculated 88 according to the following equation:
HCRd is compared 89 with the value 1. If HCRd is to be greater than 1, the flow rate of air is increased 90. If HCRd is less than 1, the flow rate of air is decreased 92. After waiting 94 for the system to reach steady operation, the process is repeated with the measurements 82. If HCRd is very close to 1 (within error due to measurements), then this is the optimal operating point for these conditions; and, after waiting 96 for a sampling time specified by the user, the process is repeated with the measurements 82.
In this embodiment, system specifications are as follows
Results in the system from sequence of iterations (steps) of the process are presented in the following table:
As shown in the specific flowchart of
The flowchart of
This exemplification is carried out with three trays in stage 66 and with three trays in stage 64. The height for each humidifier stage 58/60 is 1.5 meters.
First, the system is operated as a single stage (i.e., the extracted stream duct to intermediate conduit 72 is closed); and the algorithm, above, is used to find 98 the appropriate mass flow rate of air 62 such that HCRd=1.
Next, the following measurements are taken 100 by sensors to determine the thermodynamic states of points W20 and A3:
Next, the following thermophysical properties to determine the thermodynamic states of W20 and A3 are evaluated 102:
From these values, the mass flow rates, {dot over (m)}, were calculated 104 as follows:
{dot over (m)}W20=ρW20×FW20;
{dot over (m)}A3=ρA3×FA3; and
{dot over (m)}da,A3{dot over (m)}A3/(1×ωA3).
The modified heat capacity ratio, HCRd,2, in the bubble column dehumidifier is then calculated 106 according to the following equation:
HCRd,2 is then compared 107 with the value, 1; and if HCRd,2 is 1 (or within a margin of error of 1), the following additional measurements are taken in step 112:
If HCRd,2≠1, the mass flow rate ratio, MR, in the second (hot) stage 64 is modified 108 before step 112 such that the new mass flow rate ratio, MR2=(previous mass flow rate ratio, MR2,previous)/(calculated HCRd.2).
Next, as shown in the flowchart of
From these values, the mass flow rates, {dot over (m)}, were calculated 116 as follows:
{dot over (m)}W1=ηW1×FW1;
{dot over (m)}A8=ηA8×FA8;
{dot over (m)}da,A8={dot over (m)}A8/(1+ωA8);
The modified heat capacity ratio, HCRd,1, in the bubble column dehumidifier is then calculated 118 according to the following equation:
HCRd,1 and HCRd,2 are compared 119 with the value 1; and if HCRd,1≠1, the mass flow rate ratio in the first (cooler) stage 66 is modified 120 such that the new mass flow rate ratio, MR1=(previous mass flow rate ratio, MR1,previous)/(calculated HCRd,1).
The process is repeated from the measurement 100 of properties of H20 and A3 until HCRd,1=HCRd,2=1 (or as close as possible), or until the change in the gained output ratio (GOR) and recovery ratio (RR) between iterations becomes negligible.
Results in the system from sequence of iterations (steps) of the process are presented in the following table:
In the above table and elsewhere herein, [-] indicates a non-dimensional number.
The following equations can be used for process optimization in a humidification-dehumidification cycle for producing fresh water and/or for concentrating and removing contaminants from an aqueous composition using the apparatus of
The thermodynamic balancing of the preheater 54 (where cp,W2 is the specific heat in the hot stage) can be expressed as follows:
The non-dimensional number for the heat capacity ratio (HCR) for the hot humidifier stage 58 (where WB is the wet bulb temperature and where the hot stage 58 is referenced as H2) can be expressed as follows:
The non-dimensional number for the cold humidifier stage 60, referenced as H1, can be expressed as follows:
The non-dimensional numbers for the hot and cold stages 64 and 66 of the bubble column condenser 70 can be expressed as follows:
where D1 represents the first stage 66 of the condenser 70, and where D2 represents the second stage 64 of the condenser 70.
The optimal system conditions for the cold stage 66 of bubble-column condenser 70 can be expressed as follows:
HCRD1=1[-] at steady state. (17)
Finally, the optimal system conditions for the hot stage 64 of the bubble-column condenser 70 can be expressed as follows:
HCRD2=1[-] at steady state. (18)
Specifically,
The systems and methods of this disclosure (including controlling the flows of the fluids through the system) can be implemented using a computing system environment. Examples of well-known computing system environments and components thereof that may be suitable for use with the systems and methods include, but are not limited to various forms of automated controllers, such as microcontrollers, personal computers, server computers, hand-held or laptop devices, tablet devices, multiprocessor systems, microprocessor-based systems, set top boxes, programmable consumer electronics, network PCs, minicomputers, mainframe computers, distributed computing environments that include any of the above systems or devices, and the like. Typical computing system environments and their operations and components are described in many existing patents (e.g., U.S. Pat. No. 7,191,467, owned by Microsoft Corp.).
The methods may be carried out via non-transitory computer-executable instructions, such as program modules. Generally, program modules include routines, programs, objects, components, data structures, and so forth that perform particular tasks or implement particular types of data. The methods may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be nontransitorally stored in both local and remote computer storage media including memory storage devices.
The systems and methods of this disclosure may utilize a computer (e.g., in the form of a microcontroller) to carry out the processes described herein. Components of the computer may include, but are not limited to, a computer processor, a computer storage medium serving as memory, and coupling of components including the memory to the computer processor. A microcontroller is a small computer including a single integrated circuit containing a processor core, non-transitory computer storage media (memory), and programmable input/output peripherals and can be used as an embedded system. The microcontroller memory can include both permanent (nonvolatile) read-only memory (ROM) storing pre-programmed software in the form of a compact machine code as well as volatile read-write memory for temporary data storage. The microcontroller can also include an analog-to-digital converter if the light detector to which it is electronically coupled transmits its illumination data in analog format as well as a programmable interval timer to control, e.g., the duration of activation of the indicator LED's.
The various processes described in the descriptions of this disclosure can be encoded as software instructions in memory and executed by a processor to carry out the processes.
In describing embodiments of the invention, specific terminology is used for the sake of clarity. For the purpose of description, specific terms are intended to at least include technical and functional equivalents that operate in a similar manner to accomplish a similar result. Additionally, in some instances where a particular embodiment of the invention includes a plurality of system elements or method steps, those elements or steps may be replaced with a single element or step; likewise, a single element or step may be replaced with a plurality of elements or steps that serve the same purpose. Further, where parameters for various properties or other values are specified herein for embodiments of the invention, those parameters or values can be adjusted up or down by 1/100th, 1/50th, 1/20th, 1/10th, ⅕th, ⅓rd, ½, ⅔rd, ¾th, ⅘th, 9/10th, 19/20th, 49/50th, 99/100th, etc. (or up by a factor of 1, 2, 3, 4, 5, 6, 8, 10, 20, 50, 100, etc.), or by rounded-off approximations thereof, unless otherwise specified. Moreover, while this invention has been shown and described with references to particular embodiments thereof, those skilled in the art will understand that various substitutions and alterations in form and details may be made therein without departing from the scope of the invention. Further still, other aspects, functions and advantages are also within the scope of the invention; and all embodiments of the invention need not necessarily achieve all of the advantages or possess all of the characteristics described above. Additionally, steps, elements and features discussed herein in connection with one embodiment can likewise be used in conjunction with other embodiments. The contents of references, including reference texts, journal articles, patents, patent applications, etc., cited throughout the text are hereby incorporated by reference in their entirety; and appropriate components, steps, and characterizations from these references may or may not be included in embodiments of this invention. Still further, the components and steps identified in the Background section are integral to this disclosure and can be used in conjunction with or substituted for components and steps described elsewhere in the disclosure within the scope of the invention. In method claims, where stages are recited in a particular order—with or without sequenced prefacing characters added for ease of reference—the stages are not to be interpreted as being temporally limited to the order in which they are recited unless otherwise specified or implied by the terms and phrasing.
This application is a continuation of U.S. application Ser. No. 16/268,643, filed 6 Feb. 2019, which is a continuation of U.S. application Ser. No. 15/401,948, filed 9 Jan. 2017, which is a continuation of U.S. application Ser. No. 14/574,968, filed 18 Dec. 2014, the entire contents of which are incorporated herein by reference. This application also claims the benefit of U.S. Provisional Application No. 61/917,847, filed 18 Dec. 2013, the entire content of which is incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
5724828 | Korenic | Mar 1998 | A |
6911121 | Beckman | Jun 2005 | B1 |
8252092 | Govindan et al. | Aug 2012 | B2 |
8292272 | Elsharqawy | Oct 2012 | B2 |
8496234 | Govindan et al. | Jul 2013 | B1 |
8523985 | Govindan et al. | Sep 2013 | B2 |
8647477 | Govindan et al. | Feb 2014 | B2 |
9266747 | Sparrow et al. | Feb 2016 | B1 |
9579590 | Govindan et al. | Feb 2017 | B2 |
10239765 | Govindan et al. | Mar 2019 | B2 |
10688409 | Govindan et al. | Jun 2020 | B2 |
20140367871 | Govindan et al. | Dec 2014 | A1 |
Number | Date | Country |
---|---|---|
2005033585 | Apr 2005 | WO |
2012159203 | Nov 2012 | WO |
Number | Date | Country | |
---|---|---|---|
20200384381 A1 | Dec 2020 | US |
Number | Date | Country | |
---|---|---|---|
61917847 | Dec 2013 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 16268643 | Feb 2019 | US |
Child | 16882608 | US | |
Parent | 15401948 | Jan 2017 | US |
Child | 16268643 | US | |
Parent | 14574968 | Dec 2014 | US |
Child | 15401948 | US |